Table of Contents Page #

Floor Plan of the Henry Inside

Front
Cover
Table of Contents 1
Welcome Letter from the Chair 2
Oakland University Advertisement 3
Letter from President 4
CERM-2017 Organizing Committee: 5
Central Regional ACS Officers 5
Detroit Section ACS Executive Committee, Officers 5
Detroit Section ACS Committee Chairs 6
Things To Do 7
Dining Near CERM 9
Central Region Awards 11
Detroit Section Awards 15
Social Events (SE1-8) 19
Keynote Addresses (KN1-3) 22
Workshops (WS1-4) 25
Technical Program 27
Abstracts 46
Author Index 181
Our Sponsors and Exhibitors 186
Exposition Table Assignments 194
CERM Exhibitor Floor Plan Inside
Back
Cover
At a Glance Program Grid Outside
Back
Cover

1
Dear Participants and Friends:
On behalf of the Organizing Committee and the Detroit Section of the
ACS, we are very pleased to welcome you to the 2017 Central Regional
Meeting of the American Chemical Society (CERM), the 48th since the
beginning.
We have what we believe is a wonderful technical program. Please take a
look inside, where you will find symposia on such topics as, Optical
Chemistry and Optogenetics, Catalysis by Metal Complexes and
Nanomaterials: Fundamentals and Applications, and Applications in
Electronic Structure Theory and Molecular Dynamics along with some
exciting half-day symposia including Chemometrics of Computer
Simulations, Exploration of New Chemical Classes as Innovative
Therapies for Neurological Disorders, and Environmental Chemistry:
Water, Air & Health. There are also specialized symposia in Chemical
Education such as Active Learning - Students Performance &
Classroom Engagement and Undergraduate Teaching in Inorganic
Chemistry- an IONiC VIPEr Symposium, nestled cheek by jowl with
the traditional five branches of chemistry. Additionally, and importantly,
a highlight of CERM 2017 will be the keynote speakers on each morning
of the conference. Speakers from Ford Motor Company, BASF and the
University of Michigan-Ann Arbor will discuss chemistry applications in
industry in subjects ranging from coatings to high energy materials. By
all means, take a look and attend what you find to be of interest.
We are meeting at the Henry, in Dearborn, Michigan, a stones throw
from the Henry Ford Greenfield Village, and near to quite a few other
attractions. If you have never been to the Henry Ford Greenfield Village,
see if you can make the time in the next few days for a visit. The indoor
museum is a world class one, and the outdoor Greenfield Village is
unique, and filled with demonstrations, buildings, and events that are of
interest to chemists and chemical engineers. Mr. Ford was actually able
to purchase Thomas Edisons Menlo Park building. It is an ACS
National Historic Chemical Landmark, and open to the public.
We wish to offer a big thank you to the staff of the Henry. We have
found them to be amazingly helpful, and willing to work with us on the
many requirements we found that we had as the meeting developed. A
special thanks goes to Brooke Peterson, our primary contact. She is truly
wonderful.
We also wish to thank Michelle Stevenson, Wendy Jackson, and Joshua
Blair of the ACS Headquarters Staff for all their help in making this

2
meeting happen. Michelle, Wendy, Josh, all of you have been a wealth of
information as we developed each aspect of this gathering.
Additionally, we wish to thank our sponsors for their financial support of
the meeting. You can see their logos in this program booklet, and see
them in various places about the meeting areas. Please stop by our
vendors tables to see the latest the industry has to offer.
Finally, we would be foolish not to stop and thank the many volunteers
who have brought together all the threads that make up the meeting.
Anthony Sky has been ceaseless in finding people and organizations to
help sponsor this meeting. Klaus Friedrich has done a masterful job as
our webmaster. Sue White has worked tirelessly to ensure we have a
top-notch awards program. Jim Landis has been fantastic in putting out
plenty of advertising, and in putting together this program, and our
Treasurer, Mary Kay Heidtke, has done a truly stellar job of ensuring that
attendees and organizers have been in contact and that we are not
awash in a river of red ink. There are many others who deserve a special
thank you. We apologize if we have forgotten anyone, and take the
blame for that ourselves.
Please enjoy the meeting!
Mark A. Benvenuto Daniel Lawson Matthew J. Mio
General Chair, Program Chair Detroit Section
2017 CERM 2017 CERM Chair

3
American Chemical Society

1155 SIXTEENTH STREET, N.W.

OFFICE OF THE PRESIDENT WASHINGTON, D.C. 20036
Phone 202-872-4461
Allison A. Campbell, Ph.D. Fax 202-872-6338
President-Elect, 2016
President, 2017
Immediate Past President, 2018

June 6, 2017

Dear Central Regional Meeting participants,

On behalf of the more than 156,000 members of the American Chemical Society, I am
happy to extend my best wishes to all of you attending the 48th Central Regional Meeting in
Dearborn, Michigan.

Many symposia reflect the meeting theme of Diversity in Chemistry. Symposia will include
topics in catalysis as well as optical, computational, environmental, medicinal, and
pedagogical chemistry. Keynote speakers are Michael J. Pcolinski, North American vice
president for innovation and technology at BASF, and Mark Fields, technical leader of paint
research at Ford Motor and editor-in-chief of the Journal of Coatings Technology &
Research.

In addition to ACS workshops of careers and resum review, there will be workshops on
career planning, innovations in teaching, and instrumentation and a series of seminars on
Designing a better experiment with Chemometrics. Join your colleagues at the awards
ceremony and dinner to honor the recipients of the E. Ann Nalley Regional Award for
Volunteer Service to the ACS, the Stanley C. Israel Award for Advancing Diversity on the
Chemical Sciences, the Regional Award for Excellence in High School Teaching, and the
Partners for Progress and Prosperity Award. As well, 50 year and 60 year ACS members
will be recognized.

With all these events and great symposia, I want to express my special thanks to the
CERM chair Mark Benevenuto and to our host the Detroit Section for their hard work and
dedication to create a great experience here in Dearborn.

Best wishes for a most successful CERM 2017!

Sincerely,

Allison A. Campbell, Ph.D.

2017 President
American Chemical Society

4
CERM
Central Regional Meeting of the American Chemical Society
Dearborn, Michigan
6 10 June, 2017

Organizers of the2017 Central Regional Meeting of the American

Chemical Society
General Chair: Dr. Mark Benvenuto, University of Detroit Mercy
Program Chair: Dr. Dan Lawson, University of Michigan - Dearborn
Treasurer: Ms. Mary Kay Heidtke, Magni Industries
Publicity Chair: Mr. James Landis, Henkel Corporation (retired)
Workshops Coordinator: Dr. Amy Hamlin, Ash Stevens
Awards Chair: Ms. Sue White, Wayne State University
Fundraising Coordinator: Dr. Anthony Sky, Lawrence Technological
University
Web Site Development: Dr. Klaus Friedrich, University of Detroit Mercy

Central Region Board

Past Chair: Barry Farmer
Chair: Jeannie Phillips, Dow Chemical
Chair-Elect: Dr. Mark Benvenuto, University of Detroit Mercy
Treasurer: Dr. Roger Parker
Secretary: Dr. Roger Parker

Officers of the Detroit Section, American Chemical Society

Chair: Dr. Matt Mio, University of Detroit Mercy
Secretary: Dr. Amy Hamlin, Ash Stevens
Treasurer: Mr. Matthew S. Smith, Beckman
Chair-Elect: Ms. Denise Grimsley, BASF
Councilors: Dr. Mark Benvenuto, University of Detroit Mercy
Mr. James Landis, Henkel Corporation (retired),
Dr. Anthony Sky, Lawrence Technological University,
Alternate Councilors: Dr. Charlene Hayden Oakland University
Ms. Mary Kay Heidtke, Magni Industries
Ms. Meghann Murray, University of Detroit Mercy
Trustee Board: Dr. Kurt Reimann, BASF(retired)

5
Committee Chairs of the Detroit Section, American Chemical
Society

Awards & Recognition Sue White

Budget Committee Anthony Sky
Career Development Heinz Plaumann
Education Committee Katelyn Cottone
Environmental and Safety Chris Jock
Fundraising Laurie Dubin
Government Affairs Kevin J. O'Mara
Kids and Chemistry Co-chairs (5) Denise Grimsley, Mary Kay
Heidtke, Gina Ludwig, Felix
Schneider & Walter Siegl
Long Range Planning Committee Mary Kay Heidtke
Membership Committee Courtney Bialczyk
Midgley Award Galen Fisher
Minority Affairs Michele Williams-Harry
NCW/CCED Coordinator Denise Grimsley
Newsletter Mary Kay Heidtke
Program Committee Matt Mio
Project SEED Keith Williams
Public Relations & Facebook Gina Ludwig & Matthew S.
Smith
Social Media & Photography Matthew S. Smith
Student Members Kendra Evans & Matt Allen
USNCO (Chemistry Olympiad) Mark DeCamp
Webmaster (2) Joe Piechocki
Kevin L. Perry
Women Chemists Committee Hulya Ahmed
Younger Chemists Committee Meghann Murray
Industrial Liaison Hulya Ahmed
Liaisons:
ANACHEM L. Felix Schneider
Flint Sub-Section Jessica Tischler
Port Huron Sub-Section Larry Mavis

6
Things To Do Near CERM

The Henry Ford Museum and Greenfield Village is a

remarkable destination that brings American ideas and innovations
to life. The sheer scope and design of Henry Ford Museum is as
grand as the vision that inspired it. Its impossible not to feel a
sense of awe as your mind adjusts to a different sense of scale
more vast, more expansive and more diverse by far than
anything you'll encounter in everyday life. The sweeping, single-
floor space with its soaring 40-foot ceilings covers nine acres
dedicated to showcasing the finest collection of its kind ever
assembled. Entering Greenfield Village is like stepping into an 80-
acre time machine. It takes you back to the sights, sounds and
sensations of Americas past. There are 83 authentic, historic
structures, from Noah Websters home, where he wrote the first
American dictionary, to Thomas Edisons Menlo Park laboratory,
to the courthouse where Abraham Lincoln practiced law. The
buildings and the things to see are only the beginning. Theres the
fun stuff, too. In Greenfield Village, you can ride in a genuine
7
Model T or pull glass with world-class artisans; you can watch
1867 baseball or ride a train with a 19th-century steam engine. Its
a place where you can choose your lunch from an 1850s menu or
spend a quiet moment pondering the home and workshop where
the Wright brothers invented the airplane. Greenfield Village is a
celebration of people people whose unbridled optimism came to
define modern-day America. 20900 Oakwood Boulevard |
Dearborn | 313.982.6001

Ford Factory Tour: Journey into the factory where automobile

manufacturing came of age and where the technology of tomorrow
is on display.
20900 Oakwood Boulevard | Dearborn | 313-982-6001

Detroit Zoo: Home to more than 3,300 different animals and

features unique animal exhibits such as the butterfly garden and the
new penguin exhibit.
8450 W 10 Mile Road | Royal Oak | 248-541-5717

Detroit Institute of the Arts: One of the largest and most

significant art collections in the United States
5200 Woodward Avenue | Detroit | 313-833-3237

Downtown Birmingham: Filled with fabulous art galleries,

boutiques, restaurants, coffee shops and movie theaters. It's a
delightful place to browse, shop, walk, eat and spend free time.

The Somerset Collection: The premier shopping center includes:

Ne1man Marcus, Saks, Nordstrom, Tiffany, Gucci and more | 248-
689-7798

The Cranbrook Educational Community: Visit art and science

museums. World renowned architecture, sculpture and magnificent
gardens | 248-645-3149

8
Dining Near CERM
In the Henry: TRIA - An American Brasserie
Inspired American cuisine uniquely prepared and presented in a casual and
engaging atmosphere. Taste. Savor. Share.
American Phone: 1-313-253-4475 Dress code: Casual Open for
breakfast, lunch and dinner
Benihana
The original Japanese steak house. Chefs will have you craving for more as they
entertain you as they cook such favorites as steak, chicken, seafood and fresh
vegetables in traditional Japanese style on a hibachi table.
0.5 mile(s) from the hotel Phone: 1-313-593-3200 Japanese Open for
lunch and dinner
Big Fish Seafood Bistro
Offering bright, open settings and a menu of fresh fish and seafood that may be
prepared in many styles, from chargrilled and blackened to broiled, sauted or
deep-fried, with usually eight to 10 fresh catch selections.
0.7 mile(s) Phone: 1-313-336-6350 Seafood Open for lunch
and dinner
Andiamo Dearborn
Centrally located in the heart of downtown Dearborn, Andiamo - Dearborn
features all of chef Aldo's famous Italian dishes served in a contemporary,
elegant atmosphere. Live entertainment offered throughout the year.
2.2 mile(s) Phone: 1-313-359-3300 Italian Open for lunch and dinner
Osteria 222
Michael Chamas' small, refined spot is handsomely appointed, and the herb-
dappled fare, ranging from fresh salads to thin-crusted pizzas and full-scale
entrees, is carefully prepared and presented with style.
2.8 mile(s) Phone: 1-313-792-7500 American Open for lunch &
dinner
Kabuki Dearborn Restaurant
Kabuki is Dearborn's newest family-style restaurant owned and operated by
Michelle Lee, who started the business in Farmington Hills, Michigan. Kabuki
offers an interesting atmosphere combined with a highly rated menu.
2.7 mile(s) Phone: 1-313-278-6840 Japanese Open for lunch and dinner
Dress code: Casual
Al-Ameer Restaurant Serving hot, flavorful dishes at reasonable prices has
made them a favorite with local Middle Eastern food fans. A perfect place to
give this cuisine a first try, they offer a two-person sampler platter with a taste of
the best traditional dishes.
4.3 mile(s) Phone: 1-313-582-8185 Middle Eastern Open for lunch and
dinner
9
Dining at Fairlane Town Center:

Chick Chick Inn: Food Court serving traditional fried chicken and fish by the
piece, along with chicken tenders, BBQ chicken wings, chicken and fish wraps
and sandwiches, popcorn chicken and shrimp, soup, mac and cheese and all the
trimmings!

Kerby's Koney Island serves breakfast, lunch and dinner selections from a
classic koney island-style menu in the Food Court.

Fuji Hibachi Japan

Fresh made-to-order Japanese cuisine that is healthy and fast in the Food Court.

China Wok serves authentic Chinese food including vegetarian, chicken and
beef entrees in the Food Court.

P.F. Chang's provides contemporary, bistro-style restaurant setting, offering a

unique blend of high quality, authentic Chinese cuisine in a sophisticated
setting.

Sbarro serves Italian cuisine. Sbarro is known for its freshly made, hand-
stretched pizza, wide selection of pasta and fresh salads in the Food Court.

Shawarma Express serves delicious Middle Eastern cuisine, juice drinks and
appetizers in the Food Court.

Starters Bar & Grill offers an extensive menu, including steak and seafood
entrees, as well as a full bar and 20 HDTVs.

Subway serves fresh, nutritious, made-to-order sandwiches that are prepared to

taste in the Food Court.

Taco Bell Think outside the bun at Taco Bell. Enjoy many delicious Mexican
style dishes at low low prices in the Food Court.

Great Steak and Potato Co. Is renowned for serving the finest cheesesteak
sandwiches. The menu has grown to a complete line of specialty sandwiches,
fries and baked potatoes in the Food Court.

Troi Burger is a fast, casual eatery that serves fresh, never frozen, hamburgers,
organic shakes and fresh cut fries produced from local farms and small
businesses. Troi Burgers antibiotic and hormone free beef is ground daily in
house for optimal freshness.

10
Central Region Awards
Stan Israel Award: Cory Valente joined
the Dow Chemical Company in 2011 after
completing a postdoctoral fellowship at
Northwestern University in the laboratory
of 2016 Nobel Laureate in Chemistry Sir
Fraser Stoddart. He holds a PhD in Organic
Chemistry from York University in
Toronto.
Cory is currently the R&D leader for
Strategic Recruiting and Research
Assignments Program at Dow. He is
responsible for setting and implementing
the PhD campus recruiting strategy for
R&D, and managing a group of new Dow
scientists and engineers in a specialized
research assignments program.
In 2011, and in addition to his R&D role, Cory joined Dows employee diversity
network focused on Gays, Lesbians and Allies (GLAD) and inaugurated a
chapter in one of Dows largest and most critical innovation centers in Spring
House, PA. Cory then proceeded to take on the leadership of Dow's global
GLAD network in 2015 and has made a tremendous impact in GLADs strategic
direction and employee engagement at Dow, driving network membership to
new highs while educating and motivating the global employee base of 56,000
around the fundamental principles that ALL employees without regard to race,
gender, religion, ethnicity, or sexual orientation should be given an equal
opportunity to reach their full potential at Dow. This new strategy built the
global participant base to over 3,000, which now makes GLAD the largest of
Dows eight employee networks with new chapters launched around the world
under Corys leadership.
2016 was a monumental year for LGBT rights within the United States. Corys
passion for influencing outside of Dow, led the Company to vocally support
legislation that protects inclusion for all. Dow was one of the first business
community leaders to support the U.S. Supreme Courts decision on marriage
equality and the introduction of the federal Equality Act.
Cory also influenced Dows public opposition to discriminatory state legislation
in North Carolina, Missouri, Indiana, Louisiana and Texas. Dows live tweets
during a Missouri Senate debate garnered a mention of the company on the
Senate floor. As a Company, Dow believes a culture that is inclusive, celebrates
differences, and respects and welcomes everyone, unites its people enabling
individuals and families to thrive, businesses to prosper and economies to grow.
Corys actions and dedication over the past few years set the example for all
Dow employees straight or LGBT to not sit on the sidelines but instead
11
become active in these business critical issues. His results speak for themselves
and he truly is an inspirational figure within Dow and the Chemical profession,
and Cory was named by the Financial Times & OUTstanding to their top Future
LGBT leaders list in 2015 and 2016.

Excellence in HS Teaching Award:

Jamie Benigna has been a Chemistry
teacher for 16 years, teaching Intro and
AP Chemistry, as well as electives like
Organic Chemistry, Forensic Science, and
the Science of Food and Cooking. He
currently teaches at the Roeper School in
Birmingham, MI. He has a B.S. in
Chemistry (Honors) and a Masters in
Teaching from Wayne State University.
Jamie was a former co-chair of the AP
Chemistry Test Development Committee,
served on the Curriculum Development
and Assessment Committee, worked as a reader for the AP Chemistry exam
grading, and continues to write items for the exams. He has presented for the
Flinn Scientific Foundation Summer Chemistry Workshops and eLearning
series, and he currently leads training workshops for AP Chemistry teachers. He
has presented at numerous conferences, including NSTA, ChemEd, and the AP
Annual Conference; additionally, he has been published in the Journal of
Chemical Education. He received the Teacher of Promise award from the
Michigan Science Teachers Association in 2004. Outside of teaching
Chemistry, Jamie is a foodie and avid cook, and he worked on recipe
development and food styling for the VizChef app.

Ann Nalley Regional ACS Award:

Monique Wilhelm has been dedicated to
sharing her knowledge of chemistry to the
community in many different ways. She has
put a lot of focus on improving and
implementing safety guidelines both in the
classroom/laboratory setting as well as the
community setting during chemical
demonstrations.
Monique is deeply involved with ACS
including her involvement in the Chemical
Health and Safety (CHAS) and Education
(CHED) Divisions, and Co-Advisor for UM-
Flint ACS Student Chapter. By working with
CHAS she has been able to use her
12
experiences as the Lab Supervisor at UM-Flint to pass on what she has learned
to other colleagues. Monique doesnt only want to make sure that students and
faculty are safe in their chemical safety but also understand why it is important.
CHED has allowed Monique to share her perspectives on chemical education as
well as learn about what others are doing in Chemical Education. Once working
with CHED she once again took on another role and joined the CHED safety
committee. While on the safety committee she was able to use her vast
knowledge in chemical safety to revise the Guidelines for Chemical
Demonstrations.
Monique has also served as a mentor to many students as both an advisor of
Curiosity Academy (an after school program for girls in middle school designed
to show them a variety of science topics) as well as the Chemistry Club at UM-
Flint for many years. Both of these positions have allowed Monique to work
directly with young girls as well as college students. These roles allow her to
share her knowledge of science with the students as well as provide them with
support depending on where the student is in their education. Monique serves as
a great person to advocate for scientific work as well as a role model for future
scientists. Monique is a supporter of ACS and what they can provide to both
students and the community.
Moniques work in the science field has gone beyond ACS and at UM-Flint.
Monique has designed a hands-on experiment that can be used to help people
understand what occurred during the Flint Water Crisis. The experiment uses
pennies and household chemicals to be able to visually show what happened to
the water system. Monique has been able to use this demonstration to teach
children, community members, as well as other ACS members about the Flint
Water Crisis. Monique has provided talks to the local Detroit ACS section and
other Universitys providing a scientific approach to the Flint Water Crisis.
Moniques passion for community involvement has allowed her to be able to
explain something very complex to the community through a way they can
understand and then tell others.

The Partners for Progress and Prosperity Regional Award has been
established to reward collaborations that result in:
Improving the public perception and appreciation for
chemistry
Promoting career advancement opportunities and/or
supporting entrepreneurship in the chemistry enterprise
Advancing advocacy efforts with government and
other thought leaders
Supporting STEM (Science, Technology,
Engineering & Mathematics) education and/or research.
West Virginia State University (WVSU), Kanawha Valley Section of the ACS
and the Chemical Alliance Zone have worked extensively with the science
13
department at Herbert Hoover High School to support its STEM education since
the school was significantly damaged and ultimately condemned after the Elk
River floods in June of 2016. Everything in the chemistry and several other labs
as well as the classrooms supplies were lost and they
were forced to start from scratch this year. ACS and
Chemical Alliance Zone were instrumental in
organizing donation and mobilizing help to get
sciences classes started again. They helped procure
for us over $130,000 worth of funds and equipment.
The value of these donations were recorded and
reported to FEMA as part of the recovery effort.
By working directly with the science department at
Herbert Hoover High School, they have helped six
teachers get back on the feet and equipped to impact
about 780 kids! This is in addition to other support they provided to other
schools along the Elk River. The local impact has been huge. The local ACS has
also started an initiative to set up an aid program for helping schools in the
future that are damaged by catastrophic natural disasters and find themselves in
the same situation. This initiative takes the scope of their impact from the local
level to the national level and brings awareness help to a very noble cause.

The WVSU, ACS and Chemical Alliance Zone were heavily involved in
procuring donations. They were in contact weekly and sometimes daily with
staff at Herbert Hoover High school to get the equipment the teachers needed.
They helped set up meetings with company representatives and provided storage
for equipment. WVSU, ACS and Chemical
Alliance Zone have gone above and beyond and
exhibited exemplary dedication and
commitment to ensuring that the science
program not only recovers but thrives. ACS has
extended invitations to Hoover to participate in
the ACS Chemistry Olympiad, the Science
Coaches program and the Project SEED. Last
year, students participated and through
Olympiad earned scholarships to WVSU.
Herbert Hoover High School looks forward to a continued friendship and
partnership with WVSU, KVS ACS, and Chemical Alliance Zone.

14
Detroit Local Section Awards
Salutes to Excellence is a recognition award that gives ACS members an
opportunity to underscore outstanding accomplishments, achievements or
service for individuals who have made a positive impact on everyday life. In
2017, the Detroit Section of the American Chemical Society has selected Denise
Grimsley, Megan Klein and BASF to receive Salutes to Excellence Awards.
Denise Grimsley has served at the Detroit
Section National Chemistry Week chair
since 2001, where she has done an
exemplary job of raising public awareness of
the role of chemistry and chemists in society.
Her hands-on activity programs have
engaged dozens of volunteers with thousands
of kids to help them learn a bit of chemistry.
As co-chair of the Detroit Kids & Chemistry
group (since 2002) Denise has been largely
responsible for organizing the hands-on
chemistry activities that resulted in the
Section receiving six Chemluminary
Awards. She is always looking for new and
better experiments to enhance the message to
young people that chemistry can be fun. Many thousands of kids have been
reached. Denise has been a great ambassador to the student chapters at local
universities. She has brought student members into active participation in the
Section by engaging them in her hands-on programs and by arranging and
hosting their groups for laboratory tours at BASF. In 2013 alone, at least 6
different student chapters were involved in Detroit Section activities.
Denise is also the Detroit Chemists Celebrate Earth Day Chair. In her leadership
roles with CCED, NCW and K&C she has established working relationships
with the Detroit Zoo, the Michigan Science Center, and Cranbrook Science
Museum. Through her leadership, Detroit ACS outreach programs are not only
welcomed but are requested for return visits. Denise has been an active member
of the Detroit ACS Executive Committee for the last 15 years. She has served as
Section Treasurer and Secretary and is currently the Sections Chair-Elect. From
her recruiting of new employees and co-workers at BASF to her role-modeling
on the Detroit ACS Executive Committee, Denise encourages others to become
engaged and to step their own volunteer efforts.

15
Megan Klein has been serving the
community as a volunteer with the Detroit
Section of the American Chemical Society
(ACS) since 1998 and joined Ash Stevens
in 2002. Her various roles on the with the
ACS included Chair, Secretary, Treasurer,
Program Chair, Career Services
Coordinator Other Meghann, and Kids in
Chemistry volunteer, making it possible
for her to reach out to students of every
age, chemical professionals and even
foster some international relations with the
Chemical Institute of Canada. Her efforts to promote and encourage scientific
inquiry with hands-on experiments for children have enriched the lives of many
students over the years. Megan is particularly proud of her involvement with
developing and assisting a large annual merit badge program for 300 Girl
Scouts, initiated in 2004. She has supported dozens of chemical professionals
careers each year of her tenure as Career Coordinator with assistance through
seminars, networking and personal consultations. Megan is always a dependable
"behind the scenes catalyst for countless outreach events, all in an effort to
improve and enhance the understanding of chemistry at work and in the world
around us.

BASF Corporation has

been one of the leaders in
promoting chemistry in the
greater Detroit community
for many years. BASF had
its educational outreach
committee that offered training and the materials for the BASF volunteers who
were interested in participating in outreach activities. The ACS, Detroit Section
and BASF shared the same vision, and they partnered to improve the perception
and appreciation for chemistry in the greater Detroit area. BASF has been a
great source for volunteers, speakers, supplies, and financial support for the
Detroit Section activities for decades. Several BASF employees who have been
active members of the Detroit Section over the years helped to strengthen this
partnership. In 2016, BASF has partnered especially in the Chemist Celebrate
Earth Day (CCED) program. The 2016 CCED event was held on April 16 and
17.
More than 30 BASF employees from the Wyandotte and Southfield sites
volunteered for the 2016 CCED event!
The event was attended by about 1000 participants. The scientists were able to
spent more time with the participants, and left a great impression on them and
the hosts. Interns from BASF prepared posters on how chemists can reduce the
16
amount of pollution and landfill materials which were displayed at the event.
The BASF Wyandotte and Southfield sites put announcements about the CCED
program in the company newsletters in advance to solicit volunteers and interest.
The supplies for the hands-on experiments was prepared and stored at BASF for
future events.
Distinguished Service Award: Felix
Schneider retired after a 42 year career with
the U.S. Food and Drug Administration
(FDA). He held positions as an Analytical
Chemist, Supervisory Chemist, Research
Coordinator and Laboratory Director with
FDA. He served in the Cincinnati, Chicago
and Detroit Laboratories and temporary
assignments in Philadelphia and Washington
D.C. Mr. Schneider received a BS degree in
Chemistry and Mathematics from Western
Kentucky University, Bowling Green KY.
He is a long time active member of the
Detroit Section ACS and Anachem. Felix
has been involved in many section activities and programs either in a volunteer
or the leading role, including as a Co-Chair of Kids and Chemistry. He is a
mentor to so many of us who know him. He has been organizing and presenting
seminars for many years including serving on the CERM 2012 and 2017
Organizing Committees and helping with the annual ANACHEM Symposium.
Felix has many wonderful attributes and has contributed to the section in many,
many ways through his many years of service.
Outreach Volunteer of the Year: Ms.
Hulya D. Ahmed: Ms. Ahmed graduated
from Hacettepe University in Ankara, Turkey
in 1978 with an M.S. in Chemistry. She
worked as an analytical chemist at the United
German Pharmaceutical Companies in
Istanbul for 5 years before coming to the
United States. She received an M.S. in
Analytical Chemistry working in the area of
HPTLC under Professor Colin Poole at
Wayne State University. Since then, Hulya
has worked at BASF as a member of the
Chromatography and Spectroscopy Group.
She has extensive experience in polymer characterization by size exclusion
chromatography and has been leading the GPC lab since 2003. Ms. Ahmed is
very active in the Section where she participates in outreach activities, was a
member of the National Chemistry Week Committee (1993-97) and was co-
organizer of the Women Chemists' Committee for the Section. She served as
17
Treasurer-elect (1995), Treasurer (1996), Alternate Councilor (1998) and
Councilor (2001) for the Section. She has been serving as the Chair for the
Women Chemists Committee since 2001. Hulya has been involved in a safety
program that is geared toward teachers and volunteers for Kids & Chemistry
events.
Past Chair: The Section would like to recognize Matt Mio for his service as
Section Chair during 2016. He is the former Chair of the Education Committee,
a position he held for over 10 years. Matt has
volunteered for Local Section Kids &
Chemistry events and also presently serves
on the Society Committee on Education
Advisory Board for Undergraduate
Programming at national meetings. He is a
member of the Division of Education and the
Division of Organic Chemistry. Matt is also
co-advisor to the Student Member Chapter at
the University of Detroit Mercy. Matt is
active on committees for the Division for
Chemical Education Examinations Institute
and the Society Committee on Education.
Matt received his B.S. in chemistry from the
University of Detroit Mercy in 1997 and his
Ph.D. in organic chemistry from the
University of Illinois at Urbana-Champaign
in 2001. After post-doctoral study at Macalester College in St. Paul, MN, Matt
joined the faculty of the Department of Chemistry and Biochemistry at the
University of Detroit Mercy in 2002 where he currently serves as a Professor

Service Awards: The Detroit Section would like to honor its:

50 YEAR MEMBERS 60 YEAR MEMBERS
Dr. Paul Michael Beckwith Dr. Marcel Leon Halberstadt
Mr. George John Beyer Mr. Leo A. Homicz, Jr
Dr. Walter Keith Dean, Jr Dr. David Kessel
Dr. Douglas Leon Denton Mr. John Pappas
Mr. Thomas Byron Donahue Prof. David B. Rorabacher
Dr. Duane Allan Heyman Prof. Erhard William Rothe
Dr. John M. Kokosa Dr. David James Wilson
Mr. Ronald Joseph Lash
70 YEAR MEMBER
Dr. Gene Paul Reck
Dr. C. E. Anagnostopoulos
Dr. Stephen John Swarin
Mr. Walter Edward Szpunar

18
Social and Governance Events

SE1. Opening Mixer The Gallery, Tuesday, 5:30 PM 8:30 PM No Charge

Kick off your meeting in The Gallery and join attendees, exhibitors and staff in
an informal get-together.
SE2. Women Chemists Committee Luncheon, The Gallery, Wednesday,
12:30 N 2:00 PM - $30. For tickets, sign up at the Registration Desk.
The Women Chemists Committee will meet for lunch with Denise Hartmann
from BASF, who will discuss how we can create opportunities for success in our
careers in her talk.
Creating Luck in the Workplace
Denise Hartmann is responsible for the North
American Resins & Additives business by
leading regional teams working in
Transportation, Industrial, Furniture & Floor
Coatings, Printing, Packaging & Adhesives and
Formulation Additives. She assumed the role
on January 1, 2016 and is responsible for sales,
marketing, technical service and product
management for this portfolio of raw materials
for the coatings and printing and packaging
industries.
Denise earned a bachelors degree in chemical engineering from Michigan
Technological University and an MBA, with emphasis in Finance and
Marketing from the University of Michigan.
SE3. Ice Cream Social, Presidential Ballroom Prefunction Area, Thursday,
3:30 PM 5:00 PM No Charge
Join us for an old-fashioned Ice Cream Social at the Central Regional Meeting
for the ACS Governance Meeting. Members of the Board of Directors will be
on hand to give you the scoop on the American Chemical Society. Everyone is
encouraged to attend this event. This occasion is an excellent opportunity to ask
questions, offer suggestions, and learn about the daily activities of the ACS. On
Thursday, June 8th, the meeting will start at 4:00 PM followed by ice cream and
toppings until 5:00 PM. The location is the Prefunction area outside the
Presidential Ballroom of The Henry Hotel in Dearborn, Michigan. It is being
hosted by the American Chemical Society. We hope to see you there!

19
Social and Governance Events

SE4. Awards Dinner, Plaza Ballroom, Thursday, 6:00 PM 9:00 PM- $50.
For tickets, sign up at the Registration Desk.
Celebrate with our Regional and Detroit Section Award Winners and hear a
presentation by Jeffrey Moore:
Self-Healing Polymers
Damage in everyday synthetic materials is difficult to detect and even harder to
repair. It is desirable to develop methods to initiate without human
intervention chemical transformations that respond to damage where and when
repair is needed. This talk will review the field of self-healing polymers with
emphasis on achieving lifecycle control for light-weight, high-strength polymer
composites.
Jeffrey Moore received his B.S. in chemistry
(1984) and Ph.D. in Materials Science and
Engineering with Samuel Stupp (1989), both from
the University of Illinois. He then went to Caltech
as an NSF postdoctoral fellow working with
Robert Grubbs. In 1990, he joined the faculty at
the University of Michigan in Ann Arbor and then
in 1993 returned to UIUC where he is currently the
Murchison-Mallory Chair in the Department of
Chemistry. Jeff is a Fellow of the American
Academy of Arts & Sciences and the American
Chemical Society; he received the Campus Award
for Excellence in Undergraduate Teaching and has
been recognized as a Faculty Ranked Excellent by their Students. For 14 years
he served as an Associate Editor for the Journal of American Chemical Society.
In 2014, he was selected as an HHMI Professor. He has published over 300
articles covering topics from technology in the classroom to self-healing
polymers, mechanoresponsive materials and shape-persistent macrocycles. He is
currently serving as the Interim Director of the Beckman Institute for Advanced
Science and Technology at the University of Illinois.
SE5. Younger Chemists Committee Luncheon, The Gallery, Thursday, 12:30
N 2:00 PM - $25. For tickets, sign up at the Registration Desk.
Join the Younger Chemists Committee for Lunch and to hear Guy Wicker,
Ph.D, CEO at Ovshinsky Innovation LLC speak on:
A Modern Appreciation of Chemical Bonding
20
Social and Governance Events

Historically chemical bonding has been expressed in a simplified way. The

traditional covalent and ionic bond families based on Pauling's scheme are
almost 100 years old. Quantum mechanics and computer simulation can now
give us a very detailed description of chemical interactions.
This talk will review the changes in our
understanding of chemical bonding and ask
whether our basic teaching and understanding of
chemistry needs to be updated.
Guy Wicker was a former employee of Stan
Ovshinsky at Energy Conversion Devices and
Ovshinsky Solar LLC. Wicker has a doctorate in
electrical engineering from Wayne State
University. He worked for ECD from 1985-1990,
then with Rochester Hills-based Ovonyx Inc., a
joint venture between ECD and Intel Corp., from
1990-2008, specializing in phase-change memory.
SE6. Vendor Breakfast, The Gallery, Friday, 8:00 AM 10:00 AM No
Charge for Exhibitors Only
In thanks to our Exhibitors, they are invited to a free breakfast in the Gallery on
Friday, June 10 from 8:00 AM to 10:00 AM.
SE7. Central Region Governance Meeting, The Gallery, Friday, 1:00 PM
3:00 PM
Central Region Officers and representatives of Central Regional Meeting
Planning Committees will meet for the regions annual meeting on Friday, June
10 from 1:00 PM to 3:00 PM.
SE8. Multi-Section Mixer at CERM, The Gallery, Friday, 4:00 PM No
Charge, but please RSVP by signing up at the Registration Desk.
The Midland, Kalamazoo, Western Michigan, and Detroit Local Sections invite
you to a Multi-Section Mixer during CERM. Executive Board Members or any
interested local section members from any local section can:
Meet & exchange ideas with other local section leaders.
Create & plan new multisection events.
Learn best practices & new ideas from other local section leaders.
Network & make new connections in other ACS sections.

21
Keynote Addresses
KN1. Wednesday, Plaza Ballroom, 11:00 AM 12:00 Noon
Functional Coatings for Vehicle Sensors
Mark Nichols, Ford Research and Advanced Engineering, Ford Motor Company
Future semi- and fully autonomous vehicles
(AVs) will require additional sensors to
provide the necessary data for the automobile
to function appropriately. The additional
sensors will likely include radar, LIDAR,
multiple cameras, and ultrasonic sensors in
addition to highly detailed maps and their
associated GPS systems. The LIDAR and
camera systems, in particular, require precise
optics to provide high fidelity signals to their
sensors. Certain environmental conditions
degrade the performance of these sensors due
to fouling of the optics by dirt, de-icing salt
residues, water, snow, and frost.
Superhydrophobic, superhydrophilic, and omniphobic coatings for these optical
elements all show promising performance by reducing the amount of foulant
present on the optics and by easing the cleaning of the foulants. Omniphobic
and superhydrophilic coatings were synthesized, and a variety of
superhydrophobic coatings were obtained. The performance of these coatings
was quantified via contact angle with water and other fluids, transmitted optical
haze, and surface analysis. In addition, the durability of the coatings was
assessed via accelerated weathering testing and the change in properties
evaluated. The degradation in sensor performance before and after fouling, as
well as after a prescribed cleaning cycle was evaluated by transmitted haze and
an imaging algorithm to assess the quality of images for both cameras and
LIDAR. The prospects as well as future directions for these functional coatings
will also be discussed.
Biography of Dr. Mark Nichols
Dr. Nichols received his B.S. from the University of Michigan in 1987, his M.S.
from the University of Illinois in 1989, and his Ph.D. from the University of
Michigan in 1992. All his degrees are in Materials Science and Engineering.
Dr. Nichols joined Ford Research Laboratory in 1992 to work on the durability
of elastomers. His current research is focused on automotive coatings. Topics
of particular interest include: coating weatherability, corrosion, the fracture
behavior of coatings and films, color science, and functional surfaces. He is
currently a Technical Leader and heads the Paint and Corrosion Research group
in Ford's Stamping and Structures Research Department. In addition, Dr.
Nichols is the Editor-in-Chief of the Journal of Coatings Technology and
Research. Dr. Nichols is the co-author of the books; Mechanical Properties of
Coatings, 2nd ed., and Organic Coatings: Science and Technology, 4th ed.; has
22
Keynote Addresses
published over 65 peer-reviewed research papers; and holds 8 U.S. patents. Dr.
Nichols was a 2008 recipient of the Henry Ford Technology Award for his role
in the implementation of a 3-wet paint process at Ford.
KN2. Thursday, Plaza Ballroom, 11:00 AM 12:00 Noon
Sustainability at BASF
Michael J. Pcolinski, Vice President,
Advanced Materials & Systems Research, BASF
To address the challenges of sustainability &
improving efficiencies in transportation, the
automotive industry is already leveraging
durable, light-weight materials to reduce
emissions and improve fuel economy. One
further sought after goal is for design of
materials & systems which heighten the
personal experience while driving. Humans
sense oscillations as noise, vibrations and
harshness. Depending on their structure,
polymeric foams and elastomers influence
the reflectance & transmission of noises. Dr.
Pcolinskis talk will provide insight into tools
& strategies BASF experts are deploying to
meet the NVH reduction targets of its
customers.
By 2050 there will be more than 9 billion people on our earth and all will need a
livable environment & stable climate. New materials and products that provide
for clean water, sufficient food or that enhance our personal experiences in day
to day objects are also in high demand. Chemistry & biology technologies to
help shape our world & improve individual quality of life is translated by BASF
into products that use resources wisely, reduce emissions, & increase crop
yields.
At BASF we use the curated body of established principles and observations of
science to further communicate the value of chemistry & biology in order
improve the public appreciation of science in helping consumers & communities
achieve their goals.
Biography of Dr. Michael Pcolinski
Dr. Michael Pcolinski is Vice President of Advanced Materials & Systems
Research at BASF in North America. His responsibilities include leading
multiple research groups in polymer & materials science, modelling &
formulation, amphiphilic systems and analytical chemistry as well as supporting
BASF through expanding innovation capabilities & innovation management.
He also serves as a liaison with universities, government laboratories and other
external partners at all levels.
23
Keynote Addresses
Dr. Pcolinski joined BASF in 1992 and has served the company in a variety of
capacities and disciplines including research, strategic planning, sales &
business management. Most recently, he led the Office of Innovation &
Technology for BASF NA focusing on assisting business units in further
developing and leveraging their innovation capabilities for growth. He is an
executive sponsor for BASFs Journey to Innovation Excellence and serves on
the NA Research Executive Team.
Dr. Pcolinski holds a bachelors degree from Purdue University (1986) and a
doctorate in Medicinal Chemistry & Pharmacognosy from The Ohio State
University (1992).

KN3. Friday, Plaza Ballroom, 11:00 AM 12:00 Noon

Modern Approaches to Explosives Development
Adam J. Matzger, Department of Chemistry, University of Michigan
Energetic materials, a class that includes explosives and propellants, are essential
components in military and civilian applications
from defense to oil exploration. Traditional
approaches to produce improved energetic materials
have relied heavily on the synthesis of new
compounds using the tools of organic synthesis. This
process has proven only modestly productive with
very few new materials fielded in the last several
decades. Alternative approaches that utilize
supramolecular chemistry to produce
multicomponent crystals and energetic coordination
polymers are rapidly developing and have the
potential to shape modern discovery methods.
Recent progress will be discussed with an emphasis
on property tuning of detonation parameters through
design.
Biography of Dr. Adam Matzger
Adam Matzger received his B.A. degree in 1992 from Oberlin College. His
Ph.D. was completed at the University of California at Berkeley in the group of
K. Peter C. Vollhardt, where he conducted theoretical and experimental
investigations of dehydrobenzoannulenes and phenylenes. He went on to
postdoctoral work jointly with Nathan S. Lewis and Robert H. Grubbs at the
California Institute of Technology investigating a novel class of chemical
sensors. In 2000, he joined the faculty at the University of Michigan at Ann
Arbor, where he is now the Charles G. Overberger Collegiate Professor of
Chemistry and Professor of Macromolecular Science and Engineering. His
current research interest focus is on organic materials in the solid state and
encompasses crystalline polymorphs, explosive cocrystals, and porous materials.
24
Workshops
WS1. Finding Your Pathway
Wednesday, June 7 8:00 AM 11:00 AM Presidential Ballroom III
Learn about the four main career pathways available to chemical professionals:
Higher education, industry, government, and entrepreneurial careers and why
each one may or may not be the right choice for you. This workshop is not only
ideal for graduate students and recent grads, but also experienced professionals
who are considering a career change. In addition to learning about which types
of careers are available in each pathway, you'll also learn about the job market
and hiring trends to help you make your choice. The workshop allows time for
you to inventory your own values, interests, background, strengths and
weaknesses so that you can select which career pathway you'd like to explore in
detail.

WS2. Resume Review

Wednesday, June 7 1:00 PM 5:00 PM Presidential Ballroom III
A rsum serves a single-but-key purpose: To grant you an audience with a
potential employer. Its essential, then, that your rsum makes it clear how and
why your skills and experience meet the requirements of the job description.
Meet one-on-one with an ACS Career Councilor to go over your rsum.

WS3. What then? What now? What next? A Primer in Career and Life
Planning
Thursday, June 8 8:00 AM 11:00 AM Presidential Ballroom III
QuantumQik Careers purpose: Help you design a career and life roadmap so
that you will EXCEED YOUR OWN PERCEIVED POTENTIAL for a FULLY
LIVED LIFE!
We will coach you to identify YOUR LIFE PASSION, LIFE PURPOSE!
This will lead you CREATE CAREER OPTIONS
You will make a PLAN
One you will be able to ACT on!
By the end of the CERM Workshop, you will have a fully actionable Career
Planand on your way to your Life Fully Lived!
The Best Way to Predict YOUR Future is to CREATE IT!

WS4. Designing a Better Experiment with Chemometrics, Parts A, B and C

Friday, June 9 8:00 AM 11:00 PM Presidential Ballroom III
Whether you are dealing with Quality by Design (QbD) in a pharmaceutical
setting, Six Sigma quality improvement or you work in a large chemical facility,
at some point, you will use methodologies from a branch of statistics called
25
Design of Experiments. These methods for designing and analyzing data are just
as old, if not older than the t-test we all learned about in analytical chemistry.
However, the methods in Design of Experiments are far more efficient and
powerful than t-tests could ever be. Sadly, what is a staple of good industrial
research is mostly ignored in academic work. In these talks, we will cover 3
different methods from Design of Experiments, explain how to design them and
why you can't use a "One Size Fits All" approach.
Chemometrics WorkShop Part A: Definitive Screening Designs - Definitive
Screening Designs (DSD) are a new type of design for testing the effects of
multiple continuous factors simultaneously at 3 different levels and multiple
categorical factors at 2 levels. DSD were created for the express purpose of
helping laboratory scientists gain deep insight into what has an effect on the
results of the experiments.
DSD use a subset of the design points in a traditional factorial designed
experiment. The design points in the DSD allow the researcher to see the effect
of every factor they tested, independently from the other factors. These designs
can accommodate between 3 and 30 continuous factors and 0 to 4 categorical
factors simultaneously, while only requiring about 2N + 5 samples. This means
he researcher can test 10 factors for their effect on the result of the experiment
with 25 samples total. That makes DSD highly efficient in turning samples into
data. Compared to a typical t-test method, those same 10 factors would require
at least 60 samples, and still not give as good nor reliable results as DSD.
Chemometrics WorkShop Part B: Mixture Designs - For anyone that works
with formulations, whether it is in Pharma or if you just want to make the best
cup of coffee, the best blend of solvents for your reaction, Mixture Designs are
for you. The factorial based experiments, like the DSD, assume that more is
better. Mixture Designs assume that the proportions matter. Because of that
small change in terminology, factorial based experiments will not work well, if
at all, for formulations. This talk is for anyone that need to make the best blends,
alloys, formulations for their work or anyone that has ever wanted to make their
best blend of coffee for their morning cup.
Chemometrics WorkShop Part C: Optimal Response Surfaces - In a typical
Design of Experiments class, the student will learn that experimentation is an
iterative process. They are taught to start with a "screening design" like the
DSD. Test multiple factors for their effect on the outcome, then use a more in
depth design of experiment, like a response surface. Optimal Response Surfaces
are the most customizable types of response surfaces available. With the typical
factorial designed experiment or a mixture design, you have to change your
experiment to suit your design. With Optimal Response Surfaces, you change
your design to suit your experiment. You can combine the aspects you need
from a factorial designed experiment and mixture designs and combine them
into one, compact, experiment. There is no experiment that can't benefit from
the use of Optimal Response Surfaces.

26
TECHNICAL PROGRAM WEDNESDAY MORNING 27

Note: Index letters for Sessions are keyed to the Program Grid(Back Cover)
A. Academic Drug Discovery for the Central Nervous System, I. T.
Schiefer, Organizer, Presiding, Salon II
8:30 1. Identification and characterization of small molecule proteasome
activators: Implication in neurodegenerative disorders. E. Njomen, C.
Jones, B. Sjgren, J.P. Tepe
9:00 2. Development of CNS-permeable inhibitors of glucosylceramide
synthase for neuronopathic lipid storage diseases. S.D. Larsen, J.A.
Shayman
9:30 3. Discovery of 2-aminoquinoline-based scaffolds for potent and
selective neuronal nitric oxide synthase (nNOS) inhibition. M. Cinelli, A.V.
Pensa, H. Li, G. Chreifi, P. Martsek, L.J. Roman, A. Hikima, S. Salvage,
T.L. Poulos, R.B. Silverman
10:00 Intermission.
10:15 4. Novel attenuated furoxans (oxadiazole-4N-oxides) as potential
therapies for Alzheimers disease: proof-of-concept studies. I.T. Schiefer,
A. Horton, K.M. Nash, A. Kostrevski, A. Novak, A. Raghavan, Q.
Alhadidi, N. Wamer, B. Langenderfer, K. Royster, M. Ducharme, K.
Hagood, M. Post, E. Tackie-Yarboi, Z. Shah
10:45 5. Exploring the benefits and limitations of modulating NO/cGMP
signaling in MCI, Alzheimer's, and migraine. G.R. Thatcher
11:15 6. Multifunctional dopamine agonist as potential symptomatic and
neuroprotective treatment agents for Parkinsons disease. A.K. Dutta, B.
Das, D. Yedlapudi, D. Luo, S. Rajagopalan, J. Gnanada, M. Reith, J.
Andersen, S. Todi
B. Biochemistry, D. B. Lawson, Organizer, J. Hovey, Presiding, Salon VII
8:30 7. Targeting cancer cell metabolism using sugar-based small
molecules. F. Ndombera
9:00 8. Role of single disulfide linkages in the folding and activity of
scyllatoxin-based BH3 domain mimetics. J.M. Holub
9:30 9. Structural effects of platinum compounds on DNA. B. Jacob, S.
Thalalla Gamage, A. Sonousi, D. Crich, C.S. Chow
10:00 Intermission.
10:15 10. A clickable glutathione approach for identification of protein
glutathionylation in response to glucose metabolism. K.T. Samarasinghe
TECHNICAL PROGRAM WEDNESDAY MORNING 28

10:45 11. Insights into the structure, functions and malfunctions of

APOBEC3 Family DNA-cytosine deaminases. S.U. Siriwardena, A.S.
Bhagwat
C. Chemometrics & Computer Simulations, A. L. Ekstrom, Organizer,
Presiding, Salon V
8:30 12. Modeling chemical reactions with probabilistic models. A.L.
Ekstrom
9:00 13. Modifying ELISA standard curve fitting process to reduce
uncertainty in estimated microcystin concentrations. S. Qian, A. Weeden
9:30 Intermission.
9:45 14. Technology forecasting: Can you really believe that stuff?. H.P.
Plaumann, M.A. Benvenuto
10:15 15. Omissions and misrepresentations of statistics in my quantitative
analysis textbook. A.L. Ekstrom
D. Inorganic Chemistry, D. B. Lawson, Organizer, A. Grass, Presiding,
Salon VI
8:30 16. Preparation and characterization of nanostructured nickel tungstate
for energy conversion. S. Hosseini, A. Riley, Z. Li
9:00 17. Sensing redox using Eu(II)-containing complexes. L. Basal, M.D.
Bailey, J. Romero, R.G. Pautler, M.J. Allen
9:30 18. Thermodynamic stability and kinetic inertness of EuII-containing
complexes. C. Lenora
10:00 Intermission.
10:15 19. Low cost electrodeposited nickel phosphide as hydrogen
evolution reaction catalyst with enhanced activity and stability in acidic
electrolyte. R. Wasalathanthri, S. Jeffrey, N. Su, K. Sun, D.M. Giolando
10:45 20. Atomic layer deposition of tungsten carbide thin films. K.J.
Blakeney, C.H. Winter
11:15 21. Formamidinate-bridged Rh2(II,II) dimers with chelating
naphthyridine as photosensitizers for photocatalytic proton reduction. H.
Sayre, C. Turro
E. Advances in Electronic Structure Theory & Molecular Dynamics, J.
Song, Organizer, L. H. Hernandez de la Pena, Presiding, Salon I
9:00 24. Fuel cell membrane polymer degradation mechanisms by density
functional theory. J.E. Stevens
TECHNICAL PROGRAM WEDNESDAY MORNING 29

9:30 36. Multiple excitons on the road to strong correlation. A. Chien,

P.M. Zimmerman

10:00 Intermission.

10:15 22. New advances in density functional theory: practicing range

separation on the meta-GGA rung. M. Szczesniak, M. Modrzejewski
10:25
10:55 25. Computational exploration of reaction mechanism and
regioselectivity of alkyne cyclotrimerization by a dinickel iminopyridine
catalyst. T.C. Pankratz, J.R. Lindale, R. Hollingsworth, S. Groysman, R.L.
Lord
WEDNESDAY AFTERNOON
F. Active Learning - Students Performance & Classroom Engagement, D.
G. Kovacs, S. Marincean, Organizers, Presiding, Salon II
1:30 Introductory Remarks.
1:40 26. Creating and sharing molecular animations with Animator: a new
mobile learning tool for chemistry instruction. J. Winter
2:00 27. Molecular sciences made personal. J.S. Moore, J. Zavala, C. Ray,
D. Steele, R. Chadha
2:20 28. Augmentation of face-to-face lecture with online tools and students
involvement. S. Marincean
2:40 29. Observations from nearly four years of teaching with the flipped
pedagogy. V.M. Maloney
3:00 30. Career oriented performance task to enhance engagement in
learning organic chemistry. D.G. Kovacs, W.R. Winchester
3:20 Panel Discussion.
3:45 Intermission.
3:50 31. Authentic/ alternative assessment, V: classification of organic
compounds, reactions/mechanisms by science majors. M. Camacho
4:10 32. Authentic/ alternative assessment, V: performance of science
majors/non-majors on the categorizing grid. M. Camacho
4:30 33. Authentic/ alternative assessment in chemistry/ science education
V: the effect of the auto quiz on the achievement of science college
students. M. Camacho
TECHNICAL PROGRAM WEDNESDAY AFTERNOON 30

G. Advances in Electronic Structure Theory & Molecular Dynamics, J.

Song, Organizer, J.E. Stevens Presiding, Salon I
1:30 34. Assessing the quality of approximate quantum dynamics in
condensed phase. L.H. Hernandez de la Pena
2:00 35. Factors that influence stereoselectivity in the synthesis of
substituted pyrrolidines. M. Milletti
2:30 Intermission.
2:45 23. Determination of thermodynamic and spectroscopic properties of
small molecules. G. Schoendorff
3:15 37. Nuclear quantum effects are instrumental to vibrational broadening
of organic chromophores. Y. Law, A.A. Hassanali
3:45 Concluding Remarks.
H. Inorganic Chemistry, D. B. Lawson, Organizer, N. El Harakeh, Presiding,
Salon VI
1:30 38. Synthesis of low-coordinate transition metal bis(alkoxide)
complexes and their reactivity toward small molecule activation. M.
Yousif, R.L. Lord, S. Stoian, S. Groysman
2:00 39. Synthesis, structural characterization, and volatility evaluation of
zirconium and hafnium amidate complexes. M.C. Karunarathne, J.W.
Baumann, P.D. Martin, C.H. Winter
2:30 40. Visible light photoionization of the triplet metal to ligand charge
transfer excited state of tris-bipyridine-ruthenium(II). M. Alnaed, J.F.
Endicott
3:00 Intermission.
3:15 41. Fluorine doped tin oxide as corrosion protection on low cost water
oxidation electrodes. K.J. Lambright, D. Barrenbrugge, C. Alexander,
D.M. Giolando
3:45 42. Zinc complexes of a bulky dipyrromethene ligand and application
to the ring-opening polymerization of -caprolactone. M. Jandaghi, C.
Gianopoulos, M.R. Mason
4:15 43. Low-symmetry boron subphthalocyanines as fluorescent imaging
probes and precursors for designer metallophthalocyanines. L. Sejdarasi,
M.A. Kaster, K.J. McAuliffe, R. Szlag, E.R. Trivedi
I. Entrepreneurs Tool Kit: Resources & Success Stories, J. E. Sabol,
Organizer, Presiding, Salon VII
TECHNICAL PROGRAM WEDNESDAY AFTERNOON 31

1:30 187. ACS Division of Small Chemical Businesses: opportunities and

benefits. J.E. Sabol
2:00 188. The role of the expert in data-centric research. E.X. Esposito
2:30 Intermission.
2:45 189. Chemistry meets metallurgy: one chemists journey into the
industry of molten salts. L. Pignotti
3:15 190. Sustaining a service-based business in the chemical sector. J.E.
Sabol

J. Organic Chemistry Poster Session, D. B. Lawson, Organizer 2:00 - 4:00,

Salon IV and Plaza A
44. Sister Miriam Michael Stimson, OP and the development of the KBr
pellet method for IR spectroscopy. S.P. Wathen
45. Mild and highly efficient copper (I) mediated activation of simple and
hindered anhydrides in the acylation of alcohols and polyols. E. Mensah, L.
Earl
46. Computational and synthetic studies of aldimine synthesis. C.
Greenwalt, B. Knettle
47. Method for Von Baeyer naming of polycyclic cage-shaped
hydrocarbons: applications to bishomocubanes. W.L. Dilling, A.W. Jensen,
T. Xu, J. Liang, L. Zhao
48. Development of photoactivatable (2-quinolinyl)methyl-based nitroxyl
(HNO)-releasing compounds. M. Rahman, Y. Zhou, N.E. Brasch, A.J.
Seed, P. Sampson
49. Synthesis and photolysis of p-hydroxyphenacyl-based HNO donors. J.
Zhang, P. Sampson, A.J. Seed
50. Synthesis of N-benzyl amides via oxypyridinium salt promoted Ritter
reaction. M. Baniasad, P.A. Albiniak
51. Synthesis and evaluation of recently isolated immunologically active
glycolipids. S. Sadraei, E. Igbokwe, J.F. Trant
52. Synthesis of cationic contrast agents for the study of degenerative disc
disease. E. Davenport, M.D. Newton, S.E. Hartner, K. Gawronski, K.C.
Baker, T. Maerz, S.C. Timmons
53. Cosolvent effects of dissolved organic matter on the aqueous solubility
of organochlorine pesticides in the presence of ethanol. L. Ma, M. Otero, B.
Woo, N. Bhattacharyya, A. Demond
TECHNICAL PROGRAM WEDNESDAY AFTERNOON 32

54. Halogen-bonded complexes of bromosubstituted electrophiles with 1,4-

diazobicyclo[2,2,2]-octane. C. Weinberger, R. Hines, S.V. Rosokha
55. Synthesis of functionalized dibenzimidazole precursor of telmisartan.
M. Botti, J. England, C. Masell, N. Palushaj, A. Salman, A. Martin
56. Halogen bonding of iodoform with neutral and anionic nucleophiles. O.
Grounds, B. Watson, S.V. Rosokha
57. Solvent effects on the stereoselectivity of aprotic glycosylations. S.
Sadraei, A. Sadiq Ahmed, G. Yousif, A. Desai, J.F. Trant
58. Phosphinated itaconic acid/isosorbide oligomers. V. Hill, B. Howell, Y.
Daniel
59. Charing plasticizers from pentaethryitol. A. Alrubayyi, B. Howell
60. Pseudopeptides: A new biocompatible self-immolative material. D.M.
Leckie, J.F. Trant
61. High phosphorus content derivatives of deoxybenzoin. G.W. Lienhart
62. Incorporation of secondary monomer into polysulfides formed by
inverse vulcanization. C. Westerman, C. Jenkins
63. Biobased polymer additives from diphenolic acid. H. Fulco, B. Howell
64. Platinum(IV)-containing succinate oligomers. U.G. Huynh, B.A.
Howell
65. Glycerol/ adipic acid hyperbranched poly(ester)s for the release of
active organoplatinum antitumor agent. U.G. Huynh, R. Schumaker, B.A.
Howell
66. Synthesis of novel aspirin analogs for medicinal testing. H.K.
Albasrawi, S.C. Timmons
67. Phosphorous esters of biobased gallic acid. K. Oberdorfer, B.A.
Howell
68. Chirality transfer intramolecular [2+2] cycloaddition of electron
deficient allenes and alkenes. Y. Xu, M.K. Brown
69. Strategic flexibility in the controlled folding of disulfide rich peptides:
Progress toward controlled disulfide formation to access neuroactive
conotoxins. T. Kondasinghe
70. Progress towards the synthesis of derhodinosylurdamycin A analogues
bearing diverse 2-deoxy sugar subunits. P. Acharya, H. Khatri, J. Zhu
71. Synthesis of the 2-deoxy trisaccharide subunit of antitumor antibiotics
landomycin A/E. J. Woodward, X. Li
TECHNICAL PROGRAM WEDNESDAY AFTERNOON 33

72. Mechanistic studies of -mannosylation via Cs2CO3-mediated anomeric

O-alkylation. B. Bhetuwal, H.P. Nguyen, X. Li, J. Zhu
73. Stereoselective -mannosylation involving various electrophiles A. K.
Saybolt, N. Berry, U. Ahmed, X. Li
74. Riboflavin-biotin conjugate synthesis. T. Bazzi, B. Nasser, E. James, S.
Marincean
75. Synthesis of 2-C-methyl pseudouridines for the inhibition of HCV
RNA-Polymerase. I. Sappy
76. Work in preparation for the selective generation of a C5 prime uridine
monophosphate radical. M.A. Pasternak, M. Ellis, A.C. Bryant-Friedrich
77. Exploiting the Curtin-Hammett principle in the intramolecular
cyclization of heteroenyne allenes. S. Rayat, P. Filby
K. Physical Chemistry Poster Session, D. B. Lawson, Organizer 2:00 - 4:00,
Salon IV and Plaza B
78. Size control of the silver-glutathione nanoparticles during their
formation. Y. Zaker, N. Diemlar, B. Ashenfelter, B. Bhattarai, T.P. Bigioni
79. Kinetic and thermodynamic comparison of an aza-Cope [3,3]
sigmatropic rearrangement and an aza-Prins cyclization of a homoallylic
activated imine. M. Inaba, M. Milletti
80. Effect of two methyl substituents on the stereoselectivity of an aza-Cope
Mannich reaction. T. Stahl, M. Milletti
81. Spectroscopic studies on the interactions between vitamins and
nanoparticles. T.R. Brewer, T. Resh, R. Sheets, C. Bourne
82. Density Functional Theory study of the interaction of methane with the
prism structure of the water hexamer cluster. D.B. Lawson
83. A theoretical study of oxidation of ascorbic acid and its antioxidant
mechanism. Y. Tu, D. Njus, H. Schlegel
84. Computational simulations of hydrogen circular migration in protonated
acetylene induced by circularly polarized light. X. Shi, W. Li, H. Schlegel
85. Computational investigation into the competition between thymine and
carbonate addition to the guanine radical. S. Hebert, H. Schlegel
86. Photodegradation of p-nitrophenolate in solution phase and at the air-
aqueous interface. R. Young, D. Headley, M. Schmits, M. Subir
87. Nanostructured nickel tungstate (NiWO4) doped with silver and copper
for power conversion efficiency studies in photovoltaic cells. A. Riley, S.
Hosseini, Z. Li
TECHNICAL PROGRAM WEDNESDAY AFTERNOON 34

88. Vibrational Sum Frequency spectra of low concentrations of surfactant

show large interference effects in the in the CH stretching region which
suggests that acquiring a wide spectral range is necessary for accurate data
analysis. M.R. Watry, B. Felliger
89. Vibrational Sum Frequency intensities from terminal methyl groups are
significantly different in compact monolayers of long chain N-acylated
(stearoyl) amino acids due to amino acid head-group effects on chain
ordering. M.R. Watry, J. Fera

THURSDAY MORNING
L. Catalysis by Metal Complexes & Nanomaterials: Fundamentals &
Applications, M. Zhou, Organizer, F. A. Chavez, Presiding, Salon VII
8:30 90. Iron-catalyzed selective oxyfunctionalization of C-H bonds in
amines. C. Mbofana, E. Chong, J. Lawniczak, M.S. Sanford
9:00 91. Model compounds for class III dioxygenase iron-nitrosyl {FeNO}7
adducts. F.A. Chavez
9:30 92. Temporal separation of catalytic activities: a new way to design
tandem reactions. L. Li
10:00 Intermission.
10:15 93. Iridium-catalyzed dehydrogenative coupling of ethylene to form
1,3-butadiene. Y. Gao, A.S. Goldman
10:45 94. Towards improved catalyst designs: probing the deactivation of a
cobalt catalyst for water reduction. H. Baydoun, S. Mazumder, H. Schlegel,
C.N. Verani
11:15 95. Electrochemical CO2 reduction by polymer-encapsulated co-
based molecular electrocatalysts. C.C. McCrory
M. Salon I: Optical Chemistry & Optogenetics, A. Karunarathne, Organizer,
Presiding
8:30 Introductory Remarks.
8:35 96. Subcellular optogenetics: the search light for hidden treasures. A.
Karunarathne, D. Kankanamge, P. Siripurapu, K. Ratnayake, K. Senarath
9:05 97. Towards systematic (high throughput) quantum chemical studies
of microbial and animal rhodopsins. M. Olivucci, F. Melaccio, A.
Valentini, M. Del Carmen Marin
9:35 Intermission.
TECHNICAL PROGRAM THURSDAY MORNING 35

9:50 98. Broadband 2DES studies of excited-state dynamics of the orange

carotenoid protein. W.F. Beck
10:20 99. Achieving surface sensitivity in XUV spectrosocpy:
Understanding electron dynamics in metal oxide catalysts showing high
selectivity for CO2 reduction. L. Baker
N. Organic Chemistry, D. B. Lawson, Organizer, K. Kpogo, Presiding, Salon
V
8:30 100. Polymer analysis applications of thermo fisher scientific picospin
NMR spectrometers. D. Frasco
9:00 101. Supramolecular-inspired strategies for directing group-mediated
synthetic methodology. M. Young
9:30 102. Synthesis of Oligo-(3,5-dithio--D-glucopyranosides) as -
(13)-glucan mimetics. X. Liao
10:00 Intermission.
10:15 103. Synthesis of multifunctional fluoresceins by enzyme-catalyzed
Michael Addition. G. Shrikhande, S. Sen, J.E. Puskas
10:45 104. The synthesis of highly stable peptide and carbohydrate mimics:
Applications to anti-cancer and targeting autoimmune diseases. J.F. Trant
11:15 105. The synthesis of biostable acetal-free TF antigens. S. Sadraei,
A. Desai, G. Yousif, J.F. Trant
O. Undergraduate Teaching in Inorganic Chemistry: An IONiC VIPEr
Symposium, S. R. Smith, Organizer, Presiding, Salon VI
8:30 Introductory Remarks.
8:35 106. IONiC/VIPEr: A brief history of time. S.R. Smith, J.L. Stewart
8:55 107. Teaching nanomaterials to undergraduate students using VIPER.
M. Zhou
9:15 108. Crowdsourcing the development of an inorganic and
computational chemistry course using VIPEr resources. J.L. Stewart
9:35 Intermission.
9:45 109. Using and adapting VIPEr learning objects at Albion College.
V.P. McCaffrey
10:05 110. Using opening and closing questions to increase long-term
retention of inorganic chemistry. D.E. Benson
TECHNICAL PROGRAM THURSDAY MORNING 36

10:25 111. Using the primary literature in the undergraduate inorganic

classroom: showcasing the products of the NSF TUES funded IONiC
VIPEr workshops. S.R. Smith
10:45 Concluding Remarks.

THURSDAY AFTERNOON
P. Catalysis by Metal Complexes & Nanomaterials: Fundamentals &
Applications, M. Zhou, Organizer, S. Groysman, Presiding, Salon VII
1:30 112. Manipulating redox chemistry at the bottom of the periodic table:
insights into mechanisms and catalysis. S.C. Bart
2:30 114. Xanthene-bridged bimetallics for cooperative activation of small
molecules and catalysis. S. Groysman, T. Hollingsworth, R.L. Lord, R.
Hollingsworth
3:00 Intermission.
3:15 115. Assessing the impact of hydrothermal process parameters on the
bandgap energy and crystalline phases of titanium dioxide (TiO2). T. Peng,
S. Ray, J.A. Lalman, F. Arefi-Khonsari
3:45 116. Surface-enhanced Raman investigation of a plasmon-catalyzed
reaction on Ag nanoparticle surfaces. M.A. Young
4:15 117. Synthesis, stabilization and characterizations of Co3O4
nanoparticles. M. Zhou, S. Folkman, M. Nicki, R. Finke
Q. Optical Chemistry & Optogenetics, A. Karunarathne, Organizer,
Presiding, Salon I
1:30 118. Optogenetic activation of RhoA polarizes membrane trafficking
and drives immune cell migration from the rear. P. O'Neill, X. Meshik, J.
Castillo-Badillo, V. Kalyanaraman, N. Gautam
2:00 119. Single cell imaging reveals Ca2+ induced feedback activation of
PLC isoforms enhancing the Gq mediated PIP2 hydrolysis. K. Ratnayake,
J.L. Payton, A. Karunarathne
2:30 Intermission.
2:45 120. Retinal: Light switch or broken molecule?. J.L. Payton, K.
Ratnayake, N. Weis, A. Karunarathne
3:15 121. P-type dye-sensitized solar cells and fuels: challenges and
opportunities. Y. Wu
TECHNICAL PROGRAM THURSDAY AFTERNOON 37

R. Organic Chemistry, D. B. Lawson, Organizer, M. Hawasawi, Presiding,

Salon V
1:30 122. Relative stability of hexacarbonyldicobalt propargylic
carbocations: effect of remote substitution. B. St. Onge, P. Penner, J.
Skieneh, S. Adams, V. Pouget, J.R. Green
2:00 123. Kinetic, and computational study of retro-DielsAlder reactions
of -furfuryl alcohol/maleimide constructs as tunable end-caps for self-
immolative materials. N.A. Taimoory, R. Fayoumi, S. Nasri, J. Trant
2:30 124. Progress toward the synthesis of daphniphyllum alkaloids. A.M.
Lopez
3:00 Intermission.
3:15 125. Nontoxic flame retardants from biosources. B.A. Howell
3:45 126. Strategies for controlled disulfide formation to access neuroactive
conotoxins. H. Saraha
4:15 127. Phosphorus derivatives of methyl 3,5-dihydroxybenzoate. E.
Ostrander
S. Chemical Education Poster Session, D. B. Lawson, Organizer, 2:00 -
4:00, Salon IV and Plaza B
128. Acid neutralizing capacity of over-the-counter antacids and natural
supplements. H. Johns, C. Catanescu, M. Han
129. Digital Scholarship: Instructional videos for introductory chemistry
laboratory class. V.C. Ezeh
130. Environmental chemistry course content at Thiel College. A.M.
Reinsel
131. Screencasts and simulations in the learning of solubility. B.L.
Martinez, R.D. Sweeder, D.G. Herrington, J.R. Vandenplas
132. Screencasts and simulations in the learning of atomic interactions.
A.D. Shrode, R.D. Sweeder, D.G. Herrington, J.R. Vandenplas
133. Exploration of emission spectroscopy and absorption
spectrophotometry in introductory chemistry. P.S. Szalay, L.A. Zook-
Gerdau, E.J. Schurter, D.V. Perera
134. Investigation of the structural features necessary for a positive THC
assay. B. Martinez, Y. Zhou, C. Lassiter
135. Organic chemistry educational resources: Community of organic
chemistry educators. V.M. Maloney
TECHNICAL PROGRAM THURSDAY AFTERNOON 38

136. Philatelic fantasies: Enriching the teaching of chemistry by using

illustrations in postage stamps. P. Di Raddo
137. How to report results of ACS preferential elections. W.L. Dilling
T. Inorganic Chemistry Poster Session, D. B. Lawson, Organizer, 2:00 -
4:00, Salon IV and Plaza A
138. Synthesis of a series of long-chain aliphatic ligands for complexation
and water remediation. J. Pothoof, G. Nguyen, M. Bhagwagar, S. Makki,
M.A. Benvenuto
139. Deposition of phosphonium phosphate ionic liquids onto iron
substrates: Formation of iron polyphosphate films. D.W. Johnson, J.
Hancock
140. Aerobic oxidation of bulky dipyrromethanes to dipyrromethenes. F.
Saleh, C. Gianopoulos, M. Mason
141. Characterization of a luminescent EuII-containing azacryptate. T.
Jenks, M.D. Bailey, M.J. Allen
142. Bifunctional electrocatalytic water splitting under neutral conditions by
a mononuclear cobalt(II) molecular catalyst. K.M. Kulesa, D. Padilha, M.
Scarpellini, C.N. Verani
143. Investigating the reduction of a liposomal EuIII-tetraglycinate complex.
A. Zuhl, M.J. Allen
144. Synthesis, structural characterization, and room temperature
photoluminescence of scheelite phosphors. S. Perera, F.A. Rabuffetti
145. NIR-to-visible upconversion luminescence in Er:Yb:SrFX
nanocrystals. K.T. Dissanayake, F.A. Rabuffetti
146. Visible light induced photocatalytic hydrogen evolution using a CdS-
Ni2P hybrid aerogel system. D. Li, S. Brock
147. Crystallochemical study of monometallic A(CF3COO)2.nH2O (A =
Mg, Ca, Sr, Ba, Mn) as a tool for the synthesis of MgMn and CaMn
bimetallic trifluoroacetates. B.D. Dhanapala, H.N. Munasinghe, F.A.
Rabuffetti
148. Synthesis and characterization of a stable high-valent cobalt carbene
and the reduced carbene complexes and the reactivity toward carbene
transfer reactions. A. Grass, S. Groysman
149. Synthesis of new divalent zinc complexes and their reactivity toward
ring-opening polymerization reactions. T. Hollingsworth, S. Groysman
TECHNICAL PROGRAM THURSDAY AFTERNOON 39

150. Average and local crystal structure of -Er:Yb:NaYF4 upconverting

nanocrystals probed by X-ray total scattering. D.K. Amarasinghe, S.
Perera, F.A. Rabuffetti
151. Water splitting using cobalt-based amidopyridine ligands. H.
Baydoun, S. Mazumder, J. Burdick, H. Schlegel, C.N. Verani
152. Synthesis and characterization of new europium cryptates. M. Bailey,
G. Jin, M.J. Allen
153. Dendrimer-based MRI contrast agent for noninvasive brain tumor
imaging. S. Jayasundara Mudiyanselage
154. Photo/electrocatalytic hydrogen generation from water by a novel
nickel-based polypyridine catalyst. P. H. A. Kankanamalage, S.
Mazumder, K.K. Kpogo, H. Schlegel, C.N. Verani
155. Investigation of mechanistic pathways by versatile nitrogen-rich cobalt
and dicobalt catalysts for water splitting. K.K. Kpogo, S. Mazumder, D.
Wang, H. Schlegel, A. Fiedler, C.N. Verani
156. Optimization of the catalytic activity in cobalt-oxime complexes by
modulating ligand substituents towards water reduction. N. El Harakeh, D.
Basu, C.N. Verani
157. Development of molecular copper catalyst based on a polypyridine
ligand framework towards electrochemical water reduction. D.M.
Ekanayake, K.M. Kulesa, S. Mazumdar, K.K. Kpogo, H. Schlegel, C.N.
Verani
158. Production of a new series of ligands with potential to act as water
remediators. B. Sosnowski, B. Sliwinski, M. Ruprecht, P. Fitzgerald, S.P.
Kosmas, J. Pothoof, C. Niedek, M.A. Benvenuto
159. Towards molecular rectification: nanoscale devices based on
Langmuir-Blodgett monolayers of asymmetric oxovanadium(iv) and
chromium(iii) complexes. A. Weeraratne, C.N. Verani
160. Analysis of mineral cosmetics with a handheld X-ray fluorescence
analyzer. S. Thomas, T. Tieu Ngo, M.A. Benvenuto, E. Roberts-Kirchhoff
161. Synthesis of a tethered bis(iminopyridine) di-nickel complex and its
divergent reactivity with monosubstituted alkynes. R.L. Hollingsworth, S.
Groysman, R.L. Lord
162. Synthesis of silicon phthalocyanine and silicon naphthalocyanine
compounds. V. Kennedy, L. Erdmann, M. Siddihiki
163. Development of aluminophosphonate catalysts for ring-opening
polymerization of cyclic monomers. M. Jandaghi, M.R. Mason
TECHNICAL PROGRAM THURSDAY AFTERNOON 40

164. Promotion of the hydrogen evolution reaction using electrodeposited

nickel phosphide: Optimization of electrodeposition parameters. S. Jeffrey,
R. Wasalathanthri, N. Su, K. Sun, D.M. Giolando
165. Synthesis and magnetic properties of colloidal MnAsxSb1-x (x=0.1-0.9)
nanoparticles: Towards nanostructured magnetic refrigerants. M.A.
Hettiarachchi, S. Brock, E. Abdelhamid, B. Nadgorny
166. Developing metal organic frameworks for catalysis applications. A.M.
Rabon, M. Young
167. Synthesis and characterization of new classes of metal precursors for
atomic layer deposition. W. Iwadunna_Waduge, C.H. Winter, P.D. Martin
168. Oxygen evolution reaction catalyst incorporation into fluorine-doped
tin oxide films. D. Barenbugge, K.J. Lambright, C. Alexander, D.M.
Giolando
169. Synthesis and characterization of low symmetry subphthalocyanine
analogues. L. Sejdarasi, E.R. Trivedi
170. Low-symmetry subphthalocyanines as fluorescent probes and
precursors for low symmetry phthalocyanines. K. McAuliffe, E.R. Trivedi
171. Redox-active silver N-heterocyclic carbene complexes: A dual
targeting anti-bacterial drug. K. Malek
172. Iron-bis(dithiolene) N-heterocyclic carbene adducts as pre-catalysts for
organocatalysis. S. Jayaraman
173. Development of N-heterocyclic carbene-gold(I) complexes for
therapeutic applications. M. Miles, K. Arumugam
241. Synthesis and Properties of Nanofibers of Platinum(II) Complexes. S.
Barzegar, M. K. Abdolmaleki, G. Absalan, W. B. Connick
242. Synthesis of arylimidamide-azole hybrids as antileishmanial agents. A.
M. Abdelhameed, A. C. Joice, E. Zywot, H. L. Meeds, X. Liao, K. A.
Werbovetz

FRIDAY MORNING
U. Environmental Chemistry: Water, Air & Health, J. Westrick, Organizer,
Presiding, Salon I
8:00 174. The state of chemical analysis at great lakes water authority. S.
Simoliunas
TECHNICAL PROGRAM FRIDAY MORNING 41

8:25 175. Partitioning of pesticides between water and gasoline as a

function of ethanol content. M. Otero, N. Bhattacharyya, B. Woo, L. Ma,
A. Demond
8:50 176. A multidisciplinary assessment of the impact of acid spill
accidents on geoecosystems. S.P. Hyun, S. Ha, Y. Lee, H. Moon, D. Shin,
E. Lee, Y. Han, H. Jung, Y. Hwang
9:15 177. Understanding mechanisms underlying the rate of recovery of
mercury-contaminated lakes in Northern Michigan. M.M. Lynam, P.
Drevnick, J. Demers, J.T. Dvonch
9:40 Intermission.
9:55 178. Rapid detection of toxic heavy metals with boron doped diamond
microelectrode arrays. C.A. Rusinek, M. Ensch, M.F. Becker, R.
Rechenberg, A. Hardy, T. Schuelke
10:20 179. An investigation of the atmospheric deposition of phosphorus
across the Great Lakes Region. T. Mann, M.M. Lynam, J.T. Dvonch
10:45 180. Cadmium sorption mechanism by ferrous sulfide under a sulfate
reducing condition. S.P. Hyun, B. Kim, K.F. Hayes
11:10 181. Ramifications of permanganate pretreatment on the destruction
of microcystins. D. Szlag
V. Chemical Education, D. B. Lawson, Organizer, B. Corbin, Presiding,
Salon VII
8:30 182. Teaching general chemistry is not enough: Teaching students
metacognitive learning strategies. T.M. Clark
9:00 183. Improving student outcomes in general chemistry 1, organic 1
and anatomy and physiology 1 with extra chemistry and mathematics. A.L.
Ekstrom
9:30 184. Redox reactions and the automobile. C.J. Donahue
10:00 Intermission.
10:15 185. Students use of online chemistry simulations and their
conceptual learning. R.D. Sweeder, D.G. Herrington, J.R. Vandenplas
10:45 186. Natural gas chemistry. C.J. Donahue
W. Organic Chemistry, D. B. Lawson, Organizer, P. Adero, Presiding, Salon
V
8:00 113. Divalent europium in visible-light-promoted photoredox
catalysis. M.E. Cross, T.C. Jenks, M.D. Bailey, M.J. Allen
TECHNICAL PROGRAM FRIDAY MORNING 42

8:30 191. Stereoselective synthesis of potent calcium signal modulator

acremomannolipin A. X. Li
9:00 192. Amino acid-derived chelants for radionuclide decorporation. K.J.
Friedrich, B. Jones, C. Niedek, J. Mosley
9:30 193. C3-alkylation of 2,3-disubstituted indoles with
trichloroacetimidates. J.D. Chisholm
10:00 Intermission.
10:15 194. Synthesis of new nucleoside analogs: Possible HCV NS5B
inhibitors. B. Alabdullah, A.C. Bryant-Friedrich
10:45 195. Reduction of amides to amines using Na-SG and Na-AG. F.
Jalloh, J.E. Jackson, J. Dye
11:15 196. Fate of C5' oxidation and its adducts as a potential biomarker.
S.H. Cho, A.C. Bryant-Friedrich
FRIDAY AFTERNOON
X. Analytical Chemistry, D. B. Lawson, Organizer, J. Hovey, Presiding,
Salon II
1:30 197. Energy-resolved dissociation behaviors and gas-phase ion
structures of protonated and sodium cationized pseudouridine. Z.
Devereaux, Y. Zhu, Y. Nei, N. Cunningham, G. Berden, J. Oomens, M.T.
Rodgers
2:00 198. Cloud point extraction (CPE) in combination with tangential flow
filtration (TFF) for the isolation of silver nanoparticles and ionic silver. M.
Akbar, G. Bowers, S. Paluri, I. Sizemore
2:30 Intermission
2:45 199. Determination of manganese in whole blood by cathodic stripping
voltammetry with indium tin oxide. C.A. Rusinek, W. Kang, W.R.
Heineman, I. Papautsky, B. Wehring, M. Petzold, M.F. Becker, T. Schuelke
3:15 240. High-Affinity Binding and Detection of Pyrophosphate in Water
by a Resorcinarene Tetra-Salt Receptor. N. K. Beyeh, I. Dez, P. Inkinen, S.
MD. Taimoory, D. Meister, A. Peuronen, J. F. Trant, R. H. A. Ras, and K.
Rissanen
Y. Chemical Education, D. B. Lawson, Organizer, T. C. Jenks, Presiding,
Salon VII:
1:30 200. Incorporation of course-based undergraduate research experiences
in the organic chemistry and biochemistry laboratory. D.N. Large, H.K.
Albasrawi, S.C. Timmons
TECHNICAL PROGRAM FRIDAY AFTERNOON 43

2:00 201. Green chemistry: STEM connections to our world. K. Blue

Hetter
2:30 Intermission.
2:45 202. Prerequisite knowledge and success in general chemistry. Y.
Law, E.G. Olmstead, K.A. Campbell, R.L. Roswell, N. Wilson
3:15 203. #Twitter uses in #chem and #highered. K.S. Anliker
Z. Physical Chemistry, D. B. Lawson, Organizer, H. Baydoun, Presiding,
Salon V
1:30 204. Electron-transfer reactions via halogen-bonded complexes. S.V.
Rosokha
1:55 205. Gas phase structure of protonated and sodiated 5-halouridines
determined by infrared multiple photon dissociation action spectroscopy.
H.A. Roy, L. Hamlow, Y. Zhu, N. Cunningham, Z. Devereaux, J. Lee, G.
Berden, J. Oomens, M.T. Rodgers
2:20 206. Surface coverage dependent variation in molecular orientation of
an organic anion at the air-aqueous interface. M. Subir, D. Headley, R.
Young, M. Schmits, M. Quiroz
2:45 207. Theoretical calculation of pKas of bio-organic molecules in
aqueous medium using polarizable continuum and explicit water molecule.
B. Thapa, H. Schlegel
3:10 Intermission.
3:25 208. Predictions of pH-dependent binding affinities of host-guest
systems. M. Jones, A.K. Wilson
3:50 209. Light induced color changes in the purple protein
Bacteriorhodopsin. C. McGrath, M. Masthay, A. Mammana
4:15 210. Eigenstatespecific temperatures in twolevel paramagnetic spin
lattices. M. Masthay, C.N. Eads, A.N. Johnson, R.G. Keil, J.D. Mashburn,
H.B. Fannin
AA. Analytical Chemistry Poster Session, D. B. Lawson, Organizer, 2:00 -
4:00, Salon IV and Plaza B
211. Enzymatic hydrolysis of model glucuronide metabolites in wastewater:
Electronic and pH effects. J.M. Buth, M. Stockton, S. Yee, A. Tomsho
212. Analysis of roasted coffee for caffeine and chlorogenic acid using
liquid-chromatography mass spectrometry (LC-MS). S. Kiledal, L.A.
Baron, M.A. Nussbaum
TECHNICAL PROGRAM FRIDAY AFTERNOON 44

213. Investigating atrazine accumulation and histological changes in the

hepatopancreas of crayfish post-exposure. D.J. Dayfield, D.N. Maxwell,
V.C. Torres, K. Yacoo, N.K. Abraham, K.M. Barawi, K.S. Lambert, I.
Sayed, R.M. Belanger, K.R. Evans, E. Roberts-Kirchhoff
214. Quantifying diffusion of a model analyte set via capillary
electrophoresis. C. Arrasmith, C. Brown, A. Porter, R. Pozo, C. Daniels
215. Chemical analysis and radiocarbon dating of archaeological textile
fragments from the seip mound. M. Repaska, K.A. Jakes, R. Armitage
216. Robust diamond electrodes for electrochemical applications. C.A.
Rusinek, M. Ensch, M.F. Becker, A. Hardy, R. Rechenberg, T. Schuelke
217. Identifying fibers in South American Paracas period mummy textiles
by peptide mass fingerprinting. D. Bailey, M. Repaska, R. Armitage
218. Mass spectrometry for differentiating blue dyes in archaeological
textiles. P. Humphrey, R. Armitage
219. CNT modified working electrodes: detection of heavy metals and 1,2-
dihydroxybenzenes. S. Tolias, C. Spradlin, M. Sullivan, J. Lee, D. Dodson,
L. Zhai, S.K. Lunsford
BB. Biochemistry Poster Session, D. B. Lawson, Organizer, 2:00 - 4:00, Salon
IV and Plaza A:
220. Functional investigation of indirect tRNA aminoacylation in human
pathogens. W.N. Wood, U. Rathnayake, G. Silva, T.L. Hendrickson
221. Reactive oxygen species formation by metallo-tau peptides. S. Anwar,
S. Martic
222. Single-molecule studies of the FANCJ helicase reveal a dynamic
activity that dissolves G-quadruplexes and supports DNA replication. C.
Wu
223. Novel ROS-Sensitive NOS inhibitor for the treatment of ischemic
stroke. K.M. Nash, I.T. Schiefer, Z. Shah
224. Insight into the assembly and function of the Saccharomyces
cerevisiae GPI transamidase. T.J. Ness, T.L. Hendrickson
225. Evaluating the antimicrobial and antioxidant profiles of walnut husks
extracted by different methods and drying conditions. E. Ward, T. Kayla,
A. Gradl, M. Alzahabi, C. Samaniego, M. Ammerman, L. Wang, J. Wenzel
226. Tuning the substrate specificity of the glutathione transferase GstB
from Escherichia coli via site-directed mutagenesis. N.V. Stourman, J.
Moore
TECHNICAL PROGRAM FRIDAY AFTERNOON 45

227. Understanding the redox regulation of the cell by developing peptide

inhibitors to control the function of redox enzymes. D.N. Kekulandara
228. Exploration of cytotoxicity of Ruthenium(II)-mono-arene complexes
to human cancer cell lines. S. Hillaker, L. Wang, C. Samaniego
229. Versatile new method to map uracil rich regions in the genome. V.
Asgiriya Senevirathne
230. Using the MARTINI forcefield to model the self-assembly behavior of
amphiphilic dendron-lipid hybrids. N.A. Taimoory, A. Rahimi, J.F. Trant
231. Rational design of altered peptide ligands for treatment of celiac
disease. D. Meister, N.A. Taimoory, J.F. Trant
232. Indirect tRNA aminoacylation and Asn-transamidosome formation in
bacteria. U. Rathnayake, G. Silva, T.L. Hendrickson
233. Kinetic study of cytochrome c reduction by various polyphenolic
compounds. M. Rabago-Smith, D. Do, A. Baker, L. Wang, V.R. Moorman
234. Investigation of fluorescently tagged catechins in mouse embryonic
fibroblast cells. M. Rabago-Smith, M. Thomas, C. Samaniego, V.R.
Moorman, L. Wang
235. FANCJ repairs DNA helicases with REV1 and the BRCT supressor
gene. F.M. Iscovo, C. Wu, M. Jirjees
236. SMYD2 glutathionylation controls sarcomere stability and myofibril
integrity. D.N. Munkanatta Godage, K.T. Samarasinghe, Z. Yang, M.
Luo, Y. Ahn
237. Engineering optical actuators for G proteins. D. Kankanamge, A.
Karunarathne
238. Role of Amot coiled-coil homology domain residues in lipid binding
specificity. R. Thakkar, A.C. Kimble Hill
239. Copper transport in chickens; evidence of a role for riboflavin binding
protein. S.R. Smith, N. Bell, M. Benore
Abstracts 46
1. Identification and characterization of small molecule proteasome
activators: Implication in neurodegenerative disorders
Evert Njomen2, [email protected], Corey Jones2, Benita Sjgren3,
Jetze P. Tepe1. (1) Michigan State University, East Lansing, Michigan, United
States (2) Chemistry, Michigan State University , Ypsilanti, Michigan, United
States (3) Pharmacology and Toxicology, Michigan State University, East
Lansing, Michigan, United States
Constant flux of the cellular protein pool is crucial for maintaining cellular
homeostasis and cell function. One of the main intracellular proteolytic
pathways involves the proteasome, which is responsible for the degradation of
short-lived, misfolded, and damaged proteins. Declined proteasome activity is
associated with aging, and results in the accumulation of misfolded and
oxidatively damaged proteins. When protein accumulation exceeds cellular
clearance in neurons, aggregation occurs, which is the hallmark of several
neurological disorders, including Parkinsons disease (PD), Alzheimers disease
(AD), Huntingtons disease (HD) and amyotrophic lateral sclerosis (ALS, Lou
Gehrigs disease). These intrinsically disordered and damaged proteins are
mainly targeted by the 20S proteasome for degradation to detoxify the cell.
However, the 20S mainly exists in a latent closed-gate form; thus, proteasome
activation has emerged as a novel research area for potential therapeutic
intervention in these disorders. In a HTS, we discovered phenothiazines,
clinically used neuroleptic drugs, as one of the first drug-like molecules capable
of directly enhancing 20S proteolytic activity. This talk will focus on efforts in
improving potency and eliminating neuroleptic activity, for better understanding
of the biochemical mechanics of the still unclear 20S-gate regulation and
proteolysis.
2. Development of CNS-permeable inhibitors of glucosylceramide synthase
for neuronopathic lipid storage diseases
Scott D. Larsen1,3, [email protected], James A. Shayman2. (1)
Medicinal Chemistry, University of Michigan, South Lyon, Michigan, United
States (2) Internal Medicine, University of Michigan, Ann Arbor, Michigan,
United States (3) Vahlteich Medicinal Chemistry Core, University of Michigan,
Ann Arbor, Michigan, United States
Lysosomal storage diseases (LSDs) result from genetic mutations in one of 42
different lysosomal proteins, 12 of which are involved in the enzymatic
catabolism or degradation of sphingolipids and glycosphingolipids (GSLs).
Although fully two-thirds of all LSDs have some CNS involvement (e.g.
Sandhoff and Gaucher type 3) that can result in progressive cognitive and motor
decline, there are currently no effective therapies. There are, however, two
clinically effective approaches to treating LSDs in the periphery. The first is
enzyme replacement therapy (e.g. Cerezyme), in which the defective enzyme
is supplemented with recombinant protein that has been terminally modified to
Abstracts 47
be taken up into the lysosome. The second approach entails inhibition of GSL
synthesis with small molecules (substrate reduction therapy). This strategy was
most recently validated with the approval of eliglustat tartrate (Cerdelga), a
potent substrate-based inhibitor of glucosylceramide (GlcCer) synthase, for the
treatment of Gaucher type 1. Unfortunately, eliglustat has not proven effective
in pre-clinical models of CNS-based LSDs. In this presentation we will
summarize our efforts to employ a property-based approach to the design of
eliglustat analogs that can reduce GSL levels in the brain.
3. Discovery of 2-aminoquinoline-based scaffolds for potent and selective
neuronal nitric oxide synthase (nNOS) inhibition
Maris Cinelli1,3, [email protected], Anthony V. Pensa1,3, Huiying
Li2, Georges Chreifi2, Pavel Martsek4,5, Linda J. Roman5, Atsuko Hikima6,
Sarah Salvage6, Thomas L. Poulos1, Richard B. Silverman3,1. (1) Chemistry,
Northwestern University, Evanston, Illinois, United States (2) Departments of
Molecular Biology and Biochemistry, Pharmaceutical Sciences, and Chemistry,
University of California at Irvine, Irvine, California, United States (3)
Chemistry of Life Processes Institute, Northwestern University, Evanston,
Illinois, United States (4) Department of Pediatrics and Center for Applied
Genomic, First School of Medicine, Charles University, Prague, Czech Republic
(5) Department of Biochemistry, University of Texas Health Science Center, San
Antonio, Texas, United States (6) Institute of Pharmaceutical Sciences, King's
College London, London, United Kingdom
Although nitric oxide (NO) is an important biological second messenger, disease
can result from dysregulation of NO production. High levels of NO and the
neuronal isoform of nitric oxide synthase (nNOS) are associated with
neurodegenerative disorders. Although inhibition of nNOS is therapeutically
desirable, designing nNOS inhibitors is challenging. First, nNOS inhibition must
be isoform-specific, as inhibition of the related isoforms iNOS and eNOS can
result in immune system or cardiovascular side effects, respectively. Second,
most nNOS inhibitors mimic the enzymes substrate, L-arginine, and these
compounds are polar, ionizable (high pKa), and have poor blood-brain-barrier
permeation and low oral bioavailability.
From a screen of low pKa guanidine isosteres, we identified a 2-aminoquinoline-
based scaffold with good nNOS inhibitory activity (50-70 nM, rat nNOS) and
selectivity >100-fold over both bovine eNOS and murine iNOS. X-ray
crystallography of these inhibitors bound to nNOS reveals that 2-
aminoquinolines act as competitive arginine mimics. Several compounds have
high cellular permeability, oral bioavailability and long half-life in mice, and
good brain permeation in both mice and rats. Nonetheless, these compounds
have lower activity against human nNOS, poor selectivity over human eNOS,
low therapeutic index in rats, and are promiscuous in CNS counterscreening,
likely due to a GPCR-like pharmacophore.
Abstracts 48
Two strategies were used to reduce off-target binding and improve human
nNOS activity and selectivity. First, we employed a truncation-and-inversion
strategy to disrupt the promiscuous pharmacophore, which greatly reduced off-
target binding. We then took advantage of a newly discovered auxiliary pocket
in nNOS to optimize this scaffold into very potent dual rat/human nNOS
inhibitors, with selectivity over human eNOS approaching 500-fold. In the
second strategy, the original pharmacophore was preserved, but hydrophilic
groups were introduced to reduce off-target binding and bind a histidine specific
to human nNOS. These inhibitors were also potent and selective, with excellent
cellular permeability and modest attenuation in unwanted binding. These results
highlight the promise of 2-aminoquinolines as readily optimized scaffolds for
further nNOS inhibitor development.
4. Novel attenuated furoxans (oxadiazole-4N-oxides) as potential therapies
for Alzheimers disease: proof-of-concept studies
Isaac T. Schiefer1, [email protected], Austin Horton1, Kevin M.
Nash2, Alexander Kostrevski1, Adam Novak1, Aparna Raghavan1, Qasim
Alhadidi1, Nathan Wamer1, Bryn Langenderfer1, Kalee Royster1, Maxwell
Ducharme1, Katelyn Hagood1, Megan Post1, Ethel Tackie-Yarboi1, zahoor
shah1,2. (1) Medicinal and Biological Chemistry, University of Toledo, Toledo,
Ohio, United States (2) Pharmacology, The University of Toledo, Toledo, Ohio,
United States
Nitric oxide (NO) mimetics capable of enhancing cGMP/CREB signaling have
demonstrated efficacy as potential novel therapies for neurodegeneration. We
are developing a class of thiol-dependent NO mimetics known as furoxans,
oxadiazole-4N-oxides. Furoxans are unique because they exhibit tunable NO
mimetic effects. Rate of furoxan NO mimetic effects can be significantly
attenuated to produce slow-onset NO mimetics. We have reported furoxan
efficacy in multiple in vitro and ex vivo systems, including reversal of A42
induced synaptic dysfunction in LTP and protection against oxygen glucose
deprivation (OGD), a cellular model of ischemia. The present study describes
the design, synthesis, and screening of a focused furoxan library resulting in the
identification of a prototype furoxan, IS-1-41, which was profiled for in vivo.
Analogues were designed with rigorous consideration of physiochemical
properties for optimal CNS bioavailability. Incorporating electron donating or
electron withdrawing groups probed electronic sensitivity of the thiophilic
furoxan ring with the goal of fine-tuning reactivity towards endogenous thiols,
and thus the rate of NOx release. The hit furoxan demonstrated significantly
attenuated reactivity- with negligible reactivity toward generic cellular thiols
under physiological conditions. Nonetheless, NO/cGMP dependent
neuroprotection was observed and a hyperbolic concentration response curve
revealed both EC50 and IC50 values- reflecting the notion that enhancing NO
signaling is beneficial to a certain point and then becomes counter-productive.
One furoxan was shown to be brain bioavailable via multiple administration
Abstracts 49
routes and was capable of reversing pCREB dependent cholinergic memory
deficits in a mouse model of contextual fear memory.

5. Exploring the benefits and limitations of modulating NO/cGMP signaling

in MCI, Alzheimer's, and migraine
Gregory R. Thatcher, [email protected]. Univ Of Illinois At Chicago, Chicago,
Illinois, United States
Substantial evidence implicates dysfunction in NO/cGMP/CREB signaling in
Alzheimer's disease and mixed pathology dementia, including network analysis
of signaling via CREB and levels of cGMP in human brains. Enhancement of
NO/cGMP signaling via activation of the enzyme soluble guanylyl cyclase
(sGC) can be achieved by nitric oxide donors, direct activators of sGC, or
phosphodiesterase (PDE) inhibitors. Comparative data on these approaches in
animal and in vitro models will be discussed; in addition to examination of the
animal models themselves, with reference to the search for mouse models that
mimic aspects of human disease that are not driven by isolated, rare, genetic
mutations. Activation of NO/cGMP restores long term potentiation and memory
in models of synaptic dysfunction, but in mouse models without such
dysfunction, activation of this pathway is able to potentiate systems that
reinforce hyperalgesia, providing an opportunity to discover therapeutic
interventions for migraine.
6. Multifunctional dopamine agonist as potential symptomatic and
neuroprotective treatment agents for Parkinsons disease
Aloke K. Dutta1, [email protected], Banibrata Das2, Deepthi yedlapudi1, Dan
Luo1, Subramanian Rajagopalan3, Joshi Gnanada4, Maarten Reith5, Julie
Andersen3, Sokol Todi4. (1) pharmaceutical Sciences, Wayne State University,
Troy, Michigan, United States (2) wayne state university, Madison Heights,
Michigan, United States (3) Buck Institute for Research on Aging, Novato,
California, United States (4) Pharmacology, Wayne State University, Detroit,
Michigan, United States (5) Psychiatry, New York University, New York, New
York, United States
Abstracts 50
Although the etiology of Parkinsons disease (PD) is not completely understood,
recent research has provided insights on pathogenic factors such as aggregation
of -synuclein protein, oxidative stress, and iron dysregulation. Current
therapies for PD are mainly symptomatic in nature and consequently the disease
progression continues. Thus, there is an unmet need for development of
symptomatic and disease modifying drugs which will provide greater benefit
and a paradigm shift over the current treatment options. In our overall goal to
develop D2/D3 agonists as possible symptomatic and neuroprotective agents, we
undertook a hybrid drug development approach by combining known dopamine
agonists moiety with a substituted piperazine fragment. Our hybrid molecular
template allows us to introduce a unique set of relevant multifunctional
properties without compromising agonist potency. Our overall goal is to develop
suitable multifunctional dopamine agonists to address both symptomatic relief
(e.g. motor dysfunction) and disease modifying neuroprotective effects to slow
or stop the progression of PD. Our drug development effort resulted in
production of number of lead molecules, which showed variable selectivities for
D3 over D2 receptor subtypes. Some of our lead multifunctional dopamine
agonists e.g. D-607, D-512 and D-520, developed as neuroprotective treatment
agents for PD, have been pharmacologically characterized and were found to
addresses some underlying pathogenesis factors in PD including chelation of
iron to reduce oxidative stress and inhibition of aggregation of -Syn protein as
well as potent antioxidant activity. These molecules exhibit potent efficacy in a
reserpinized PD animal model, which indicates efficient brain penetration to
provide symptomatic effect. These molecules also rescued PC12 and
dopaminergic MN9D cells from toxicity induced by neurotoxin 6-OHDA in a
dose-dependent manner. In an in vivo, Drosophila melanogaster model
expressing a disease-causing variant of -Syn protein in fly eyes, the compound
suppressed toxicity significantly compared to controls by reducing levels of
aggregated -Syn. Finally, these compounds were able to rescue DAergic
neurons from toxicity of MPTP in mice, a well-known PD neuroprotection
model. These observations strongly suggest that our multifunctional drug
development strategy could lead to viable symptomatic and disease modifying
therapy of PD. This work is supported by NIH/NINDS (NS 047198, AKD).
7. Targeting cancer cell metabolism using sugar-based small molecules
Fidelis Ndombera, [email protected]. CHEMISTRY, Wayne State
University, DETROIT, Michigan, United States
Metabolic reprogramming occurs in cancer cells leading to an altered
metabolism. Small molecules that block this altered metabolism in cancer or that
increase the production of reactive oxygen species (ROS) are emerging as
potential anti-cancer agents. This is because increased generation of ROS
observed in most cancer cells relative to normal cells suggest that this
biochemical property provide a therapeutic window for selective killing of
cancer cells using ROS-modulating small molecules. ROS-modulating small
Abstracts 51
molecules such as phenethyl isothiocyanate, piperlongumine and 2-deoxy-D-
glucose exploit cancer cell vulnerability to reach lethal ROS levels above the
antioxidants protective threshold.
To explore the generality of these observations, we hypothesized that
carbohydrate based ROS-modulating molecules would more selectively enhance
ROS levels in cancer cells relative to normal cells. Furthermore, cancer cells
overexpress glucose (GLUT-1) transporters in order to facilitate enhanced sugar
entry necessary to fuel high cancer-cell metabolism. Previous studies have
demonstrated that GLUT-1 tolerates substitution at positions 1, 2 and 6 of a
glucose molecule Consequently, we ensured our sugar-conjugated small
molecules maintained vital structure-activity relationships with GLUT-1.
Considering that various carbohydrates can be used for cellular energetics or
protein N-glycosylation of which interruption can lead to cellular stress, we
synthesized and evaluated a library of N-aryl glycosides for induction of ROS
and cytotoxicity in H1299 lung cancer cell line. Two N-aryl glycosides (K8 and
H8) were identified that induce about 2-fold ROS levels and cytotoxicity in
H1299 cells. K8A was recently evaluated in 60 cell lines by the National Cancer
Institute and found to inhibit growth in UO-31, NCI H522 and CCRF-CEM. We
further showed that the acetylated form of K8 (K8A) activates AMPK, and
stabilizes p53 and induce a higher cytotoxicity than 2-deoxy-D-glucose in
H1299 cell line. In addition, K8A induces ER stress indicated by upregulation of
glucose-regulated protein-78 (GRP-78). Interestingly, initial mechanistic studies
using click chemistry suggest that K8A blocks global protein glycosylation in
H1299 cells.
8. Role of single disulfide linkages in the folding and activity of scyllatoxin-
based BH3 domain mimetics
Justin M. Holub, [email protected]. Chemistry and Biochemistry, Ohio
University, Athens, Ohio, United States
Anti-apoptotic Bcl-2 proteins are implicated in pathogenic cell survival and have
attracted considerable interest as therapeutic targets. We recently developed a
new class of synthetic peptide based on scyllatoxin (ScTx) designed to mimic
the helical BH3 interaction domain of the pro-apoptotic Bcl-2 protein Bax.
Notably, fully oxidized ScTx-Bax BH3 domain mimetics containing three
disulfides did not bind Bcl-2 in vitro, while fully reduced isoforms bound Bcl-2
with high affinity. In this study, the contribution of single disulfides in the
folding and function of ScTx-Bax peptides was investigated. We synthesized
five ScTx-Bax variants, each presenting a different combination of native
disulfide linkage and evaluated their ability to directly bind Bcl-2 in vitro. It was
determined that the position of the disulfide linkage had significant implications
on the structure and function of ScTx-Bax peptides. This study underscores the
importance of structural dynamics in BH3:Bcl-2 interactions and further
Abstracts 52
validates ScTx-based ligands as potential modulators of anti-apoptotic Bcl-2
function.

9. Structural effects of platinum compounds on DNA

Brigid Jacob, [email protected], Supuni Thalalla Gamage, Amr
Sonousi, David Crich, Christine S. Chow. Wayne State University, Livonia,
Michigan, United States
Cisplatin, or cis-diamminedichloridoplatinum(II), is a known anticancer drug.
Cisplatin preferentially coordinates to guanosine residues in DNA and makes
1,2-intrastrand d(GpG) adducts. Formation of these adducts causes the DNA
helix to be bent, which is detrimental to replication, transcription, and DNA
repair, and ultimately leads to apoptosis. Despite successful clinical use of the
drug, certain cancers have shown resistance to cisplatin. Carbohydrate-linked
platinum compounds, such as cis-dichlorido[(2-b-D-glucopyranosidyl)propane-
1,3-diammine]platinum(II) (1), have antitumor activity with comparable
efficacy to cisplatin against certain cancer cell lines. We seek to understand how
this carbohydrate-linked platinum compound affects the structure of DNA,
specifically the bending angle induced as a result of its binding. DNA was
platinated with either cisplatin or 1 at one binding site. An electrophoretic
mobility shift assay was used to analyze the effects of platination on DNA
compared to a control DNA without platination. Platination caused a gel
mobility retardation, which allowed for the quantification of the bending angles.
By comparing the results of cisplatin with 1, we hope to correlate the varying
structural effects caused by different platinum compounds with their biological
functions.
Abstracts 53
10. A clickable glutathione approach for identification of protein
glutathionylation in response to glucose metabolism
Kusal T. Samarasinghe, [email protected]. Chemistry, Wayne State
University, Detroit, Michigan, United States
Mitochondrial ROS (mROS) are the key component of cellular damage and
redox signaling. Many cancer, ischemic conditions and other pathological
conditions always accompanied by elevated levels of mROS. Even though
glucose metabolism known to associate with redox regulation, which controls
the levels of mROS, the dynamics of glutathionylation in response to glucose
metabolism remain unknown. To address this, we employed the metabolic
synthesis of clickable glutathione in HEK293/GSM4 cell line which stably
overexpress the mutant of glutathione synthetase (GSM4). Glutathionylation
levels did not significantly increase when treated with antimycin A (AMA) or
glucose starvation alone. In contrast, glutathionylation was readily induced even
at shorter time period when we treated AMA and glucose starvation together.
Interestingly, glutathionylation was reversed by the addition of glucose or
pyruvate proving that reversibility of glutathionylation is regulated by glucose
metabolism. We identified over 1200 glutathionylated proteins by LCMS/MS
analysis including several new glutathionylated proteins including PP2C.
PP2C is a metal ion dependent protein phosphatase involved in metabolic
stress sensing AMPK signaling. We found PP2C modified at C314 position in
response to metabolic stress and glutathionylation of PP2C disrupted the
interaction with mGluR3, a membrane bound protein associated with
neurological disorders. All together study of protein oxidation in response to
glucose metabolism broadens the knowledge of glutathionylation.

11. Insights into the structure, functions and malfunctions of APOBEC3

Family DNA-cytosine deaminases
Sachini U. Siriwardena1, [email protected], Ashok S. Bhagwat1,2. (1)
Chemistry, Wayne state university, Detroit, Michigan, United States (2)
Immunology and Microbiology, Wayne state university, School of Medicine,
Detroit, Michigan, United States
Abstracts 54
The APOBEC3 family of DNA-cytosine deaminases provide innate immunity
against viral infections. Their biological function is to introduce mutations in the
genome of viruses, clear foreign DNA, and to block retrotransposition of
endogenous retroelements. However there is an emerging consensus that these
enzymes impact the integrity of cellular genomes and contribute to cancer
development, with the strongest evidence supporting a role for APOBEC3B in
cancer-associated mutations. To characterize its enzymatic activity, we
constructed several derivatives of the catalytic domain of APOBEC3B and the
one with optimal activity was purified to homogeneity and its kinetic parameters
and substrate specificity were determined. During this analysis, a methionine
residue at the junction of amino- and carboxy terminal domains was found to be
essential for high catalytic activity and structural stability of the protein. Then
we expanded our study towards the consequences of APOBEC3 upregulation on
normal cells. Since many APOBEC3 family members are inducible by
inflammatory stimuli such as various cytokines and certain chemicals, phorbol
12-myristate 13-acetate (PMA, a.k.a. TPA) was used to induce expression of
APOBEC3 enzymes in a keratinocyte cell line. We found that both APOBEC3A
and APOBEC3B were responsive to PMA treatment. To study the effects of this
expression on genomic DNA we are quantifying genomic damage caused by
these enzyme such as uracils, abasic sites, strand breaks and mutations.
CRISPR/Cas9 genome editing was used to generate an UNG-/- keratinocyte cell
line in order to address the role of UNG (uracil DNA glycosylase) in repairing
DNA damage. We are testing a model in which cytokine-induced expression of
APOBEC3 proteins causes genome-wide mutations and strand breaks, and may
emerge as a key link between inflammation and malignant transformation.
12. Modeling chemical reactions with probabilistic models
Andrew L. Ekstrom1,2, [email protected]. (1) Henry Ford College ,
Madison Heights, Michigan, United States (2) Oakland University, Rochester,
Michigan, United States
In a typical chemical kinetics class, chemical reactions are treated as
deterministic models. This makes modeling long chain polymer reactions
(5,000+ steps) quite cumbersome and computationally greedy. However, we can
change our view of chemical reactions to one that is more probabilistic in nature
and model long chain polymer growth (25,000+ steps) faster and easier.
In this talk, we will discuss how we can transform deterministic models into
probabilistic models, why this modeling technique works, how to impliment it
on a traditional laptop/desktop and some issues that will come up in modeling
deterministic and probabilistic models.
13. Modifying ELISA standard curve fitting process to reduce uncertainty
in estimated microcystin concentrations
Song Qian, [email protected], Alexandra Weeden. Environmental
Science, University of Toledo, Toledo, Ohio, United States
Abstracts 55
ELISA is a commonly used method for measuring cyanobacterial toxin
(microcystin). However, ELISA-measured microcystin concentrations are highly
variable, hindering decision-making process to protect public health. We present
a study aimed at ex- ploring the optimal ELISA standard curve fitting process
for reducing measurement uncertainty. Using an ELISA kit for measuring
microcystin, we show that uncertainty associated with the estimated microcystin
concentrations can be reduced by nearly 50% simply by replacing the currently
used standard curve with a four-parameter logistic function defined on the log
concentration scale. We also experimented with the effects of adding additional
standard solutions to the curve-fitting process and determined that increasing the
number of standard solution beyond the six distinct concentration levels
currently used is likely unnecessary. However, the zero-concentration solution
should be replaced by a solution with a low concentration, e.g., 0.05 g/L.
14. Technology forecasting: Can you really believe that stuff?
Heinz P. Plaumann2, [email protected], Mark A. Benvenuto1. (1)
Department of Chemistry and Biochemistry, University of Detroit Mercy,
Detroit, Michigan, United States (2) Chemical Engineering, Wayne State
University, Detroit, Michigan, United States
The on-going development and introduction of new technologies often seem
overwhelming, with no field of human endeavor excluded from this burgeoning
activity! In this survey presentation, we review some of methods to analyze
trends in development and market introductions. The subjects range from
agricultural trends, consumer in-home goods, automotive and transportation
topics, even dishwashing detergents! Trends in publications and patents are not
excluded from our review! Several popular models are applied and compared.
As with weather forecasting, a forecast is a prediction, often embodying many
assumptions, incomplete data, oft suffering from other pitfalls.
It is just a forecastnot a prophecy!
15. Omissions and misrepresentations of statistics in my quantitative
analysis textbook
Andrew L. Ekstrom1,2, [email protected]. (1) Henry Ford College ,
Madison Heights, Michigan, United States (2) Industrial and Systems
Engineering, Oakland University, Rochester, Michigan, United States
If you look through a typical Analytical Chemistry or Quantitative Analysis
textbook, there are sections that deal with statistics. If you compare what these
sections teach the reader and compare that to what is found in a typical statistics
textbook that covers the same topics, the differences are significant. Often, the
chemistry textbooks leave out a lot of important information. This talk is
dedicated to discussing important aspects about t-tests, sampling methods,
significant digits, ANOVA and simple linear regression that are not covered or
poorly covered in the chemistry textbooks.
Abstracts 56
16. Preparation and characterization of nanostructured nickel tungstate for
energy conversion
SeyyedAmirhossein Hosseini, Andrew Riley, Zhihai Li, [email protected]. Ball State
University, Muncie, Indiana, United States
Semiconductors have demonstrated great capacity for application in energy
storage devices and solar light conversion. The semiconductor to be utilized in
the solar energy conversion must hold appropriate physio-chemical properties
such as suitable band gap, proper mechanical and electrochemical resistance,
and relatively stable excitation state. Owing to its small band gap value and low
cost, Nickel Tungstate (NiWO4) nanomaterials are promising candidates for
application in solar cells.
In this work, the preparation and application of nickel tungstate in photovoltaic
cell have been studied and structural modification including nickel tungstate
incorporation into graphene structure and particle size modification via
particular chemical synthesis have been performed. Nanoscale particles of
NiWO4 were prepared using different chemical approaches (thermal
decomposition, co-precipitation, and sol-gel method). Then, NiWO4-
nanoparticles will be doped with different tailored metal ions to understand the
effect of doping on bandgap and light conversion.
Prepared nanomaterials will be characterized with different techniques, such as
TEM, atomic force microscopy (AFM), scanning tunneling microscopy (STM),
XRD, UV-Vis. Solar cell modules/devices will be fabricated and their
photoelectrical properties will be studied. The overall solar cell efficiency of
each compound will be studied using photo-electrochemical techniques in the
presence and absence of light.
17. Sensing redox using Eu(II)-containing complexes
Lina Basal1, [email protected], Matthew D. Bailey1, Jonathan Romero3,
Robia G. Pautler3, Matthew J. Allen2. (1) Department of Chemistry, Wayne State
University, Sterling Heights, Michigan, United States (2) Department of
Chemistry, Wayne State University, Detroit, Michigan, United States (3)
Department of Molecular Physiology and Biophysics, Baylor College of
Medicine, Houston, Texas, United States
Because oxygen-deficient tumors have been demonstrated to be resistant to
radiotherapy, there has been investigation for noninvasive methods to detect
dissolved oxygen concentration (pO2) using magnetic resonance imaging (MRI).
Current 1H-MRI techniques for quantitation of pO2 require intensive data
acquisition and are not practical for clinical settings. Eu(II) has interesting redox
and magnetic properties that can be tuned by changing the coordination
environment around Eu(II). We hypothesized that by introducing paramagnetic
Eu(II) cations near 19F nuclei, line-broadening caused by shortening of
transverse relaxation times becomes so severe that there is no observable signal.
Abstracts 57
Once oxidized to Eu(III), signal is restored. Here, we present fluorinated ligands
that coordinate Eu. These fluorinated Eu-containing complexes act as bimodal
contrast agents for magnetic resonance imaging that turn-on upon oxidation with
oxygen. We envision that these oxidation-responsive contrast agents for
multinuclear 1H- and 19F-MRI have the potential to provide quantitative
information about oxygen concentration.
18. Thermodynamic stability and kinetic inertness of EuII-containing
complexes
Chamika Lenora, [email protected]. Chemistry, Wayne State
University, Detroit, Michigan, United States
The purpose of this research is to study the thermodynamic stability and kinetic
inertness of EuII-containing complexes that have potential applications in
catalysis, sensors, and imaging. Toward this goal, we have synthesized nine
ligands with different donor atoms (oxygen, sulfur, and nitrogen) and electron
donating or withdrawing groups adjacent to the donor atoms to study the
potential synergistic effect of these properties on the stability and inertness of
EuII-containing complexes. Protonation constants of the ligands were assessed
by pH-potentiometric titrations. Thermodynamic complexation of EuII with
cryptands were monitored using pH-potentiometric titrations and
electrochemical techniques. Kinetic inertness of complexes was characterized by
rate of dissociation in acidic or neutral solutions using electrochemical
techniques, inductively coupled plasma mass spectrometry, or fluorescence
spectroscopy. We compare our results with those of reported complexes with
different physio-chemical properties and we expect that our results will provide
strategies for the rational design of ligands for EuII ions.
19. Low cost electrodeposited nickel phosphide as hydrogen evolution
reaction catalyst with enhanced activity and stability in acidic electrolyte
Ruwani Wasalathanthri1,4, [email protected],
Samuel Jeffrey1,4, Naheya Su2,4, Kai Sun3, Dean M. Giolando1,4. (1) Chemistry
and Biochemistry, The University of Toledo, Toledo, Ohio, United States (2)
Department of Chemical Engineering, The University of Toledo, Toledo, Ohio,
United States (3) Department of Materials Science and Engineering, University
of Michigan, Ann Arbor, Michigan, United States (4) School of Green Chemistry
and Engineering, The University of Toledo, Toledo, Ohio, United States
As fossil fuels deplete, finding an alternative energy source has become a crucial
issue to be solved in todays society. Dihydrogen, produced from water, has the
potential to be such an alternative energy carrier. As water splitting is generally
performed with precious metal electrodes, a goal would be to find cost effective
non-noble metal catalysts for the Hydrogen Evolution Reaction (HER).
Recently, much attention is given to metal phosphides as highly active and
stable catalysts for HER. This research investigates the merits of
electrodeposited amorphous nickel phosphide (Ni-P) materials as potential
Abstracts 58
catalysts for the HER in 0.5 M H2SO4. The Ni-P catalyst investigated in this
research exhibits good activity and long term stability in acidic medium, with an
overpotential of -198 mV (without iR correction) to achieve 1 mA/cm2 current
density. This overpotential is comparable to that of electrodeposited Pt (-111
mV), and much better than that of electrodeposited Ni (-429 mV). This
overpotential remained nearly the same after 5000 cyclic voltammetry sweeps of
electrolysis in 0.5 M H2SO4, indicating the long-term stability in acidic
electrolytes. Additionally, with some modifications to the electrodeposition
conditions, an atomic % of phosphorous to ~ 24% could be achieved, which is
higher than that is generally reported with electrodeposited Ni-P materials.
Electrodeposited amorphous Ni-P can therefore be used as active and stable
earth abundant metal catalyst for HER in acidic electrolyte.
20. Atomic layer deposition of tungsten carbide thin films
Kyle J. Blakeney, [email protected], Charles H. Winter. Chemistry,
Wayne State University, Detroit, Michigan, United States
Atomic Layer Deposition (ALD) is a gas phase thin film deposition technique
with a very high degree of control of film thickness and conformality. It is based
on self-limiting surface reactions between two or more volatile and thermally
stable precursors which deposits the film approximately one monolayer at a
time. It is generally challenging to deposit highly conductive early transition
metal-containing films by ALD without plasma enhancement; however,
reasonably low resistivity carbides of Nb, Hf, and Ti have been deposited by
thermal ALD from the corresponding metal chloride with trimethylaluminum
(TMA) as both a reducing agent and carbon source. Although there are several
related patents, details for the other early transition metals have not been
reported and should be evaluated for potential industrial uses.
The most common tungsten ALD precursor is the gaseous and dangerous WF6.
Herein, we will present the results of an ALD film deposition study using the
solid precursor WCl6 and TMA for the growth of WCx films. These include
demonstration of self-limiting surface reactions for both precursors, dependence
of growth rate on temperature, and linear film growth with increasing number of
ALD cycles. Electrical and compositional film characterization will also be
discussed.
Abstracts 59

21. Formamidinate-bridged Rh2(II,II) dimers with chelating naphthyridine

as photosensitizers for photocatalytic proton reduction
Hannah Sayre2, [email protected], Claudia Turro1. (1) Ohio State Univ,
Columbus, Ohio, United States (2) Chemistry and Biochemistry, The Ohio State
University, Columbus, Ohio, United States
Formamidinate-bridged Rh2(II,II) dimers have promising excited-state
properties for photocatalytic proton reduction. Ligand modifications of
[Rh2(DTolF)2(np)2]2+ (DTolF = N,N'-di-p-tolylformamidinate; np = 1,8-
naphthyridine) yield compounds which absorb low energy visible light and have
extended excited-state lifetimes. Photoinitiated electron transfer to
methylviologen has been observed. Hydrogen production in a multicomponent
system will be discussed.
22. New advances in density functional theory: practicing range separation
on the meta-GGA rung
Maria Szczesniak1, [email protected], Marcin Modrzejewski2. (1)
Department of Chemistry, Oakland University, Rochester, Michigan, United
States (2) Faculty of Chemistry, University of Warsaw, Warsaw, Poland
Strategies of designing new meta-GGA functionals suitable for both
thermochemistry and noncovalent interactions will be presented. In contrast to
the existing approaches involving fitting large numbers of adjustable parameters
to benchmark sets, a strategy of constraint satisfaction is pursued. Most of the
Abstracts 60
existing exchange and correlation functionals often depend on the mutual error
cancellations. Thus, attempts to improve one of the components may result in
worsening of the overall performance. The solution is to avoid the error
cancellation in the first place. Most errors in density functional approximations
reside in the exchange part. One idea involves designing a new scheme for
converting existing exchange functionals into range-separated hybrids. The
scheme is based on the underlying Becke-Roussel exchange hole that has the
exact second-order expansion in the inter-electron distance. The resulting range-
separated exchange functional depends on the kinetic energy density and
Laplacian even if the base functional lacks the dependence on these variables. A
very successful variant containing only two parameters adjustable will be
presented. The performance of this functional on a variety of test sets will be
evaluated and the merits of each component will be discussed. The superiority
of this 2-parameter functional compared to 11-parameter combinatorial and 51-
parameter empirically-optimized meta-GGAs will be shown.
23. Determination of thermodynamic and spectroscopic properties of small
molecules
George Schoendorff, [email protected]. Department of Chemistry,
Michigan State University, East Lansing, Michigan, United States
The ground and low-lying excited states have been computed for a number of
small molecules that span the main group, transition metals, and lanthanides.
Bond dissociation energies, spectroscopic constants, and minimum energy
crossing points are computed with a range of computational methods including
both single- and multi-reference methods. The nature of the ligand-transition
metal and ligand-lanthanide bonds are also characterized.
24. Fuel cell membrane polymer degradation mechanisms by density
functional theory
Jonathan E. Stevens, [email protected]. Univ of Detroit Chem Dept,
Detroit, Michigan, United States
Polymer Electrolyte Membrane Fuel Cells (PEFMCs), or simply Fuel Cells,
are expected to continue to play a role in the development of alternative energy
sources. Sulfonated polyether (ether) ketone, or sulfonated PEEK (sPEEK)
membranes are one possible candidate for fuel cell membranes. In this work, the
reactivity of the sulfonated PEEK long chain molecule with H radicals is studied
by M062X hybrid density functional calculations. Results suggest a simple
degradation process in which the ready addition of H or OH radicals to aromatic
rings within the polymer is followed by rapid bond-breaking processes within
the polymer chain. The energetics of relevant reaction paths energetics are
computed in both gas-phase and in a water environment as modeled by polarized
continuum model (PCM) calculations.
Abstracts 61
25. Computational exploration of reaction mechanism and regioselectivity
of alkyne cyclotrimerization by a dinickel iminopyridine catalyst
Trey C. Pankratz1, Jacob R. Lindale1, Ryan Hollingsworth3, Stanislav
Groysman2, Richard L. Lord1, [email protected]. (1) Department of Chemistry,
Grand Valley State University, Allendale, Michigan, United States (2)
Chemistry, Room 123, Wayne State University, Detroit, Michigan, United States
(3) Department of Chemistry, Wayne State University, Detroit, Michigan,
United States
Recent reports by Uyeda (J. Am. Chem. Soc. 2015, 137, 8042-8045) and
Groysman (Dalton Trans. 2017, ASAP) have shown that iminopyridine
supported dinickel catalysts allow for selective alkyne cyclotrimerization. In this
work, we explore the reaction mechanism of the xanthene-bridged dinickel
catalyst using density functional theory. The origin of regioselectivity for 1,2,4-
vs. 1,3,5-substituted benzenes will be discussed for model monosubstituted
alkynes, along with progress toward an understanding of why this catalyst
allows for more cyclooctatetraene formation.
26. Creating and sharing molecular animations with Animator: a new
mobile learning tool for chemistry instruction
Julia Winter, [email protected]. Alchemie , Troy, Michigan, United States
This work presents the Animator, an app for smartphone and tablet, which
would provide students and instructors a means to create molecular animations.
The Animator app will be used by students and instructors to construct, share,
and discuss dynamic processes and in doing so, aid students in developing a
deeper understanding of chemical processes. This app provides instructors a
measure of their students understanding of phenomenon on a molecular level.
By leveraging readily accessible mobile technology, the sharing of the student-
generated animations gives instructors a new tool for facilitating dialog between
students and can be used to identify student misconceptions. Furthermore, this
tool will be particularly useful for instructors who need to create digital content
for their online, blended-learning, or flipped classes. Feedback and use data
from a pilot study of the app in college and high school classrooms will be
presented.
Abstracts 62

27. Molecular sciences made personal

Jeffrey S. Moore1, [email protected], Jose Zavala2, Christian Ray2, Diana
Steele3, Rajat Chadha4. (1) MC 251, Beckman Institute, Urbana, Illinois, United
States (2) Chemistry, University of Illinois, Urbana, Illinois, United States (3)
University of Illinois, Urbana, Illinois, United States
The premedical competencies as outlined in a recent American Association of
Medical Colleges HHMI Scientific Foundation for Future Physicians report call
for stronger connections between course content and the underlying principles in
health and medicine. To meet this need, chemistry courses for pre-health
professionals have been developed at the University of Illinois to teach concepts
and content in a personally meaningful way, thereby stimulating deep student
interest and promoting curiosity-driven learning. Scientific evidence shows that
people who feel curious devote more attention to an activity, process
information more critically, remember information more effectively, and persist
on task until goals are met.
Abstracts 63
In these courses, learning is made personally meaningful by enabling the
students, if they so choose, to investigate their own molecular make-up and
helping them understand how their own phenotype relates to their own personal
genetic data. Acquiring personal genetic data is affordable and is becoming an
important part of the healthcare industry. For this reason, there is a growing
need to educate prospective healthcare professionals in the interpretation of
genetic data and the role of genotype-phenotype association in the molecular
etiology of human conditions.
After a brief introduction on the pedagogy of this approach, especially as it
applies to chemical education, this talk will present examples of how genetic
data acquired from direct-to-consumer services are used in the classroom.
Specific instances of integrating this information into General and Organic
Chemistry will be given, along with assessment data collected to date.
28. Augmentation of face-to-face lecture with online tools and students
involvement
Simona Marincean, [email protected]. Department of Natural Sciences,
University of Michigan - Dearborn, Dearborn, Michigan, United States
At University of Michigan-Dearborn there is one organic chemistry sequence
aimed at students with interest in chemistry, biochemistry or health related
careers. Thus the constituency of the student body is quite diverse with respect
to background knowledge as well as the type of interest in the material.
Students participation during face-to-face time with the instructor and outside
of classroom plays a vital role in the learning process and its effect can be
evaluated through assessment. This presentation will discuss the efforts that
have been made at our school to promote student engagement in the organic
chemistry courses and the outcome with respect to material retention. The effect
of using teaching methods such as just-in-time, flipped lecture, online forums,
and on-the-fly online quizzes on the student performance will be surveyed.
29. Observations from nearly four years of teaching with the flipped
pedagogy
Vincent M. Maloney, [email protected]. Purdue Univ at Ft Wayne, Fort
Wayne, Indiana, United States
The flipped pedagogy has been applied to a two semester organic chemistry
sequence for biology and pre-professional majors (80-100 students) and to a
general education chemistry course (60-100 students) for non-science majors.
Previously for organic chemistry, a more traditional lecture with significant
amounts of active learning had been used. In fall 2013, all content was moved
outside of the face to face classroom in the format of lecture capture videos. In
class, nearly all of the time was devoted to group problem solving. Student
attitude surveys were conducted both semesters with students expressing overall
positive responses about the class format. However, no significant differences in
Abstracts 64
ACS organic chemistry exam scores or DFW rates were observed.
Subsequently, a partially flipped class was given four times for freshman non-
science majors with improvements in grades with each subsequent course.
Adjustments made in each course gave indications as how to improve scores and
learning for the organic sequence for the next time it will be taught.
30. Career oriented performance task to enhance engagement in learning
organic chemistry
Dalila G. Kovacs1, [email protected], William R. Winchester2. (1) Grand
Valley State Univ, Allendale, Michigan, United States (2) Chemistry, Grand
Valley State University, Grand Rapids, Michigan, United States
It is a requirement of my major" is a response that demonstrates a mindset that
undermines enthusiasm and self-motivation necessary for successful completion
of the course and is too commonly the answer found on course evaluation forms
asking non-chemistry major students why are they enrolled in organic
chemistry. Students taking this course are either focused on a high score on
MCAT or the letter grade of a B+ or better, required for admission to
professional or graduate School. Because of this mindset, the long-term
significance of organic chemistry in the future profession of these students is
lost. For the last four years, our approach to overcome this challenge was to
introduce to the 2nd semester non-majors Organic Chemistry course a choice of
a special writing and oral presentation assignment, to allow us to estimate the
students capacity to transfer knowledge from the organic chemistry to their
profession and personal life. Students are challenged to develop a presentation
of scientifically sound information on a molecule of interest in a written format
with an option for public presentation. Work is completed primarily outside the
lecture throughout the entire semester, with specific milestone mini-assignments
submitted on line and open for colleagues review and critique. An overview of
the assignment and its components, grading rubric, and samples of the student
efforts along with their comments will be presented.
31. Authentic/ alternative assessment, V: classification of organic
compounds, reactions/mechanisms by science majors
Moises Camacho, [email protected]. Extension Division, University
of Puerto Rico Mayaguez Campus, Mayaguez, Puerto Rico, United States
The purpose of this study was to investigate the ability to complete, identify and
classify common organic reactions, the mechanisms by which they take place
and the major organic reactants/products.
A pilot study was made with majors/non-majors to observe their classification
skills with a sample of 50 reactions which were taken from well known organic
chemistry texts like Mc Murry Organic Chemistry.
The instrument was administrated to about 60 chemistry majors and non-majors
(Biology) who had approved from 16 to 40 chemistry semester hours. The
Abstracts 65
results demonstrated that 98.0% of the subjects had forgotten almost 100% of
the type of classes (e.g. compounds, reactions, mechanisms involved in the
reactions). Only about 2% remembered very few concepts.
The study was repeated for several semesters with the purpose of
reproductibility. The results were very similar. There was no significant
statistical difference between the mean scores of majors and non-majors.
These findings have been observed in several classification studies (e.g.
compounds, reactions, equations, problems) of the author and others. The
implications for chemical education, science and mathematics in general are
relevant since these findings reflected rote-memorization not genuine
understanding, permanent learning, nor long term memory (LTM).
32. Authentic/ alternative assessment, V: performance of science
majors/non-majors on the categorizing grid
Moises Camacho, [email protected]. Extension Division, University
of Puerto Rico Mayaguez Campus, Mayaguez, Puerto Rico, United States
The purpose of this study was to investigate the categorization capacity of
college students in a categorizing grid of general chemistry compounds and to
compare their classification ability with other categorization schemes like
conceptual maps and tables. These studies have been done for several semesters
with about 50-60 subjects for reproducibility. Almost all students have showed
very little knowledge of the classes of compounds and taxonomic rules. There
was not significant statistical difference between the mean scores of majors/non-
majors. Since classification is pervasive in nature and science this study is
relevant in science education.
33. Authentic/ alternative assessment in chemistry/ science education V: the
effect of the auto quiz on the achievement of science college students
Moises Camacho, [email protected]. Extension Division, University
of Puerto Rico Mayaguez Campus, Mayaguez, Puerto Rico, United States
The auto quiz is an assessment technique in which the students read, understand,
analyze, synthesize and evaluate the assigned topics (e.g. chapter). Then they
prepared 15 questions of the most relevant content of the chapter. After they
have learned the answers (and reasons for the best or most correct of them) they
presented the auto quiz orally to the class. The professor evaluated both the
quality of the questions, answers, reasons and examples provided by each
student according to the written instructions.
The sample had consisted of about 50 students per semester during several
semesters. The students, who prepared, presented and approved one auto quiz
per chapter also approved the regular quiz and three exams of the professor with
80% to 100%.
Abstracts 66
In addition, the auto quiz students also approved the course with 90 to 100%.
This constructivist technique was invented and applied by the author and has
been very effective in demonstrating the extent of understanding of a topic.
There was a significant statistical difference between the mean scores of regular
and auto quiz students. This study is relevant for chemical, science education
and science in general since this constructivist technique promotes the
development of higher cognitive skills, and is relevant for science and science
education.
34. Assessing the quality of approximate quantum dynamics in condensed
phase
Lisandro H. Hernandez de la Pena, [email protected]. Kettering
University, Flint, Michigan, United States
Time correlation functions provide a convenient language for analyzing the rich
variety of dynamical processes in condensed phase, including the rate of
electron or proton transfer processes, vibrational relaxation, molecular diffusion,
etc. However, the calculation of the corresponding time correlation function of
systems where quantum behavior is significant is particularly challenging due to
the intractability of the underlying quantum dynamics of a multidimensional
system. As a result, approximate methods become in this context unavoidable.
In this talk, we discuss a general protocol for analyzing the quality of
approximate quantum time correlation functions of non-trivial systems in many
dimensions. This approach is motivated by the generalized deconvolution of the
Kubo transformed correlation function onto a time correlation function at a
given value of in imaginary time (0 < < h), which leads to a series of sum
rules that allow us to link derivatives of different order in the corresponding
correlation functions. We focus on the case when = h/2 for which all
deconvolution kernels become real valued functions and their asymptotic
behavior at long times exhibit a polynomial divergence. It is then shown that
thermally symmetrized static averages, and the averages of the corresponding
time derivatives, are ideally suited to investigate the quality of approximate
correlation functions at successively larger, and up to arbitrarily long, times.
This overall strategy is illustrated analytically for a harmonic system, and
numerically for a multidimensional double-well potential and a Lennard-Jones
fluid representing liquid neon at 30 K.
35. Factors that influence stereoselectivity in the synthesis of substituted
pyrrolidines
Maria-Clelia Milletti, [email protected]. Chemistry, Eastern Michigan
University, Detroit, Michigan, United States
We use Density Functional methods to model the synthesis of substituted
pyrrolidines via the aza-Cope Mannich reaction. Specifically, we investigate
the effect of several variables on reaction stereoselectivity, including bulk and
Abstracts 67
electron withdrawing effects of a protecting group at the nitrogen position,
identity of the Lewis acid catalyst, and the presence of substituents at the alpha
position to the nitrogen center. Stereoselectivity is predicted by comparing
relative stability of intermediates and activation barriers in the multi-step
reaction pathway. Particular challenges to achieving a high level of
stereoselectivity in the substrates examined here include conformational
mobility in the iminium cation intermediates and the similarity in stability of
intermediates among the possible stereochemical pathways.
36. Multiple excitons on the road to strong correlation
Alan Chien2, Paul M. Zimmerman1, [email protected]. (1) University of
Michigan, Ann Arbor, Michigan, United States (2) Chemistry, University of
Michigan, Ann Arbor, Michigan, United States
In advanced solar cell materials, management of excited electron-hole pairs
(excitons) is a central theme that unites theoretical and experimental studies.
When separated, these pairs generate electrical current to do useful work. In
singlet fission, a single exciton is divided into a double exciton, permitting
double the charge generation compared to typical photovoltaic materials. This
talk will focus on our ongoing efforts to characterize and control singlet fissions
multi-exciton states, and prospects for developing high efficiency solar-to-
chemical-energy storage processes that store the excited electrons in redox
active molecules. This will include a discussion of quinoidal oligothiophenes,
one of the few materials where intramolecular double exciton states are known,
as well as details of new electronic structure methods (Chien and Zimmerman, J.
Chem. Phys. 2017) that are uniquely powerful for handling the strongly
correlated multiexciton states of fission.
37. Nuclear quantum effects are instrumental to vibrational broadening of
organic chromophores
Yu Kay Law1, [email protected], Ali A. Hassanali2. (1) School of Natural Science
and Mathematics, Indiana University East, Richmond, Indiana, United States
(2) Condensed Matter and Statistical Physics Section, The Abdus Salam
International Center for Theoretical Physics, Trieste, Italy
We have studied the electronic spectrum of a number of different organic
chromophores in different solvent conditions by calculating the spectrum based
on conformational sampling using both the GAFF force field and ab initio
molecular dynamics simulations. In addition, as well as simulating molecules
with classical nuclei, we have used ring-polymer molecular dynamics
simulations and the PIGLET simulations to incorporate nuclear quantum effects
in our simulations. We show in a range of different systems that much of the
vibrational broadening of chromophores, regardless of the functional groups
present, cannot be found in the absence of nuclear quantum effects. This
suggests that simulations that do not take into account nuclear quantum effects
Abstracts 68
may omit significant portions of the accessible conformational space relevant to
the prediction of vibrational broadening of chromophores.
38. Synthesis of low-coordinate transition metal bis(alkoxide) complexes
and their reactivity toward small molecule activation
Maryam Yousif2, [email protected], Richard L. Lord1, Sebastian
Stoian4, Stanislav Groysman3. (1) Department of Chemistry, Grand Valley State
University, Allendale, Michigan, United States (2) Wayne State University ,
Detroit , Michigan, United States (3) Chemistry, Room 123, Wayne State
University, Detroit, Michigan, United States (4) National High Magnetic field
laboratory, Tallahassee, Florida, United States
We are exploring the reactivity of low-coordinate metal complexes in
bis(alkoxide) ligand environments in the activation of small molecules and
catalysis. Our current research focuses on bond activation and bond formation
reactions involving azide precursors, carbonyl compounds, and CO2 with the
goal to develop new catalysts for N-N and C-N bonds formation. We have
reported synthesis of the first-generation quasi-two-coordinate complexes
M(OR)2(THF)2 (OR = OC(tBu)2Ph, M = Mn, Fe, Co). For Cr, a dimeric
[Cr(OR)2]2 was obtained. [Cr(OR)2]2 leads to the stable Cr(OR)2(NR) complexes
featuring trigonal planar metal centers. Cr(OR)2(NR) complexes serve as
catalysts for the nitrene transfer to isocyanides to form carbodiimides. Aiming to
improve our system, we have recently begun exploring the chemistry of the
second generation transition metal complexes using bulkier alkoxide ligand
M(OR)2(THF)2 (OR = OC(tBu)2(3,5-Ph2Ph), M = Cr, Co, Fe). The reaction of
the second generation iron(II) precursor with non-sterically hindered aromatic
azides ArN3 leads to the formation of tetrazene complexes
(OR)2Fe(ArNNNNAr). DFT and Mssbauer spectroscopy revealed a high spin
iron(III) center. Catalytic formation of azoarenes and carbodiimides by this
system will be reported. The scope and the mechanism of these transformation
will be discussed.
39. Synthesis, structural characterization, and volatility evaluation of
zirconium and hafnium amidate complexes
Mahesh C. Karunarathne4, Joseph W. Baumann2, [email protected],
Philip D. Martin3, Charles H. Winter1. (1) Wayne State Univ, Detroit, Michigan,
United States (2) Wayne State University, Detroit, Michigan, United States (3)
61 Chemistry, Wayne State University, Detroit, Michigan, United States (4)
Chemistry, University of Sri Jayewardenepura, Gangodawila, Sri Lanka
Treatment of tetrakis(dimethylamido)zirconium or
tetrakis(dimethylamido)hafnium with four equivalents of N-tert-butylacetamide,
N-isopropylisobutyramide, N-isopropylacetamide, N-methylacetamide, or N-
tert-butylformamide in refluxing toluene, followed by sublimation of the crude
products at 105-125 C/0.05 Torr, afforded tetrakis(N-tert-
butylacetamido)zirconium (81%), tetrakis(N-isopropylisobutyramido)zirconium
Abstracts 69
(87%), tetrakis(N-isopropylacetamido)zirconium (51%), tetrakis(N-tert-
butylacetamido)hafnium (83%), tetrakis(N-isopropylisobutyramido)hafnium
(79%), tetrakis(N-isopropylacetamido)hafnium (67%), tetrakis(N-
methylacetamido)zirconium (5%), and tetrakis(N-tert-
butylformamido)zirconium (1%) as colorless crystalline solids. The structural
assignments for the new complexes were based upon spectral and analytical data
and by X-ray crystal structure determinations for tetrakis(N-tert-
butylacetamido)zirconium, tetrakis(N-isopropylacetamido)zirconium,
tetrakis(N-isopropylacetamido)hafnium, tetrakis(N-methylacetamido)zirconium,
and tetrakis(N-tert-butylformamido)zirconium. These complexes are monomeric
in the solid state, with eight-coordinate metal centers surrounded by four 2-
N,O-amidate ligands. Six of the eight new complexes undergo sublimation on a
preparative scale from 130-140 C at 0.05 Torr, with 84.5-95.8% sublimed
recoveries and 0.68-3.06% nonvolatile residues. Tetrakis(N-
methylacetamido)zirconium, and
tetrakis(N-tert-butylformamido)zirconium decompose extensively upon
attempted sublimation. Solid state decomposition temperatures for the zirconium
complexes range between 218-335 C and 290-360 C for the hafnium
complexes. Tetrakis(N-isopropylisobutyramido)zirconium and tetrakis(N-
isopropylacetamido)hafnium exhibit the highest solid state decomposition
temperatures among the series, good volatility, and have useful properties for
application as chemical vapor deposition and atomic layer deposition precursors.

40. Visible light photoionization of the triplet metal to ligand charge

transfer excited state of tris-bipyridine-ruthenium(II)
Marim Alnaed, [email protected], John F. Endicott. Wayne State Univ,
Detroit, Michigan, United States
We find that the triplet metal to ligand charge transfer excited state, 3MLCT, of
tris-bipyridineruthenium(II), [Ru(bpy)3]2+, is photoionized with 405 nm light
with moderate efficiency. Previous work has shown that ultraviolet irradiations
of this excited state produce solvated electrons, also with moderate efficiency
(Goez, et al. 2004), and our observations show that this is an important issue for
visible wavelength irradiations as well. We have used radiation from a 100 mW
Abstracts 70
3
532 nm diode laser to generate the MLCT excited state and the superimposed
beam of a 50 mW 405 nm diode laser to carry out the photolysis. Depending on
the conditions, more than half of the substrate in the photolysis region could be
transformed into products in less than 15 min. The optimization of the
observations in continuous photolysis experiments requires: chemical
scavenging for the primary solvated electron photoproduct (which is very
reactive); the minimization of back reactions; and the minimization and/or
evaluation of diffusion effects. Simple thermodynamic considerations indicate
that the threshold energy for dissociation of an electron from the [Ru(bpy)3]2+
3
MLCT excited state is about 2.1 eV (ca. 600 nm) while the excited state has
appreciable visible and near ultraviolet absorption bands, so its photoionization
is consistent with what is known about other photoionizable systems, such as
[Ru(NH3)6]2+ (Matsubara and Ford, 1978). Our use of 532 nm irradiations to
generate the 3MLCT excited state followed by its photoionization with 405 nm
irradiations models the photoprocesses that can occur with broadband visible
light irradiations. Related photoionization processes are likely for many
potential photosensitizers whose excited states are good electron donors.
41. Fluorine doped tin oxide as corrosion protection on low cost water
oxidation electrodes
Kelly J. Lambright1,2, [email protected], Derrick Barrenbrugge1,2,
Chris Alexander3,2, Dean M. Giolando1,2. (1) Chemistry and Biochemistry, The
University of Toledo, Gibsonburg, Ohio, United States (2) School of Green
Chemistry and Engineering, University of Toledo, Toledo, Ohio, United States
(3) Department of Chemical Engineering, University of Toledo, Toledo, Ohio,
United States
Hydrogen gas, created through the process of water electrolysis, has the
potential to be an emission-free fuel for energy production. To be feasible for
large-scale production, the cost to produce hydrogen gas should be driven as low
as possible. Water electrolysis is very corrosive towards inexpensive electrode
materials, and therefore a cost-effective corrosion protection layer is needed.
This research focuses on depositing fluorine-doped tin oxide thin films as a
corrosion resistant layer over inexpensive electrode materials. Dibutyltin
diacetate is synthesized in-house using a solvent-free green synthesis and is the
precursor material for the tin oxide films. For comparison, tin tetrachloride is
also used as a precursor for the tin oxide thin films. The precursor solution
contained either tin tetrachloride or dibutyltin diacetate with ammonium
bifluoride, as the fluoride dopant, in 200 proof ethanol. This solution was used
in a spray pyrolysis deposition technique for depositing tin oxide thin films.
Resultant films were characterized using scanning electron microscopy, energy
dispersive X-ray spectroscopy, UV-Vis-NIR spectroscopy, Hall measurements
and powder X-ray diffraction. Stability tests were performed via constant
potential electrolysis and cyclic voltammetry. The tin oxide thin films created
from the dibutyltin diacetate precursor lasted much longer under electrolysis
Abstracts 71
than films created by the tin tetrachloride precursor. The longest lasting film
withstood constant potential electrolysis for more than 3 months.
42. Zinc complexes of a bulky dipyrromethene ligand and application to the
ring-opening polymerization of -caprolactone
Morteza Jandaghi1, [email protected], Christopher
Gianopoulos3, Mark R. Mason2. (1) Chemistry, University of Toledo, Toledo,
Ohio, United States (2) MS 602 Dept of Chemistry, University of Toledo,
Toledo, Ohio, United States
Bulky dipyrromethene ligands exhibit a close analogy to popular -diketiminate
ligands, which are known for providing steric protection in complexes of
transition and main group metals. For example, both of these bidentate,
monoanionic nitrogen-donor ligand systems form a six-membered chelate ring
with the metal. Previous developments in homogeneous, single-site
polymerization catalysts demonstrate the utility of a bulky ligand on a metal
center. Zinc complexes of -diketiminate ligands have been shown to catalyze
the ring-opening polymerization of lactides and copolymerization of epoxides
and CO2. In contrast, the dipyrromethene chemistry of zinc has not been
thoroughly studied. In this context, we have prepared and characterized several
zinc complexes of a bulky dipyrromethene ligand. The new complexes have
been characterized by X-ray crystallography and NMR spectroscopy. Details of
the synthesis and characterization of these compounds, as well as preliminary
results on the ring-opening polymerization of -caprolactone using zinc
dipyrromethene complexes, will be presented.
43. Low-symmetry boron subphthalocyanines as fluorescent imaging
probes and precursors for designer metallophthalocyanines
Leart Sejdarasi, Megan A. Kaster, Katherine J. McAuliffe, Regina Szlag, Evan
R. Trivedi, [email protected]. Department of Chemistry, Oakland
University, Farmington Hills, Michigan, United States
Subphthalocyanines (SPcs) are 14 -electron systems containing a central boron
atom with an axial ligand. Much like their larger phthalocyanine (Pc) cousins,
SPcs have intense electronic absorption and emission across the visible
spectrum, warranting their study for a wide variety of applications, including
fluorescence imaging of biological targets. Visibly emitting SPcs may well be
applied as cell labelling probes as an in vitro tool, however application in vivo
requires absorption and emission in the near-infrared (NIR) window of
maximum tissue penetration; synthetic efforts are required to shift absorption
into the NIR region. Herein we report a synthetic approach involving mixed
cyclization of dinitrile derivatives, with varying aromaticity and heteroatom
substitution, to produce low-symmetry SPcs with optical properties that are
tunable by design. Intracellular fluorescence in MDA-MB-231 breast tumor
cells was observed from SPcs and negative effects on cell viability were found
to be mitigated by exchanging the axial ligand of boron. Low-symmetry SPcs
Abstracts 72
show promise as standalone optical probes, but also as synthetic precursors to
designer NIR absorbing Pcs via the Kobayashi ring expansion reaction.
Synthetic strategies, optical characterization, and initial tests of biocompatibility
of new SPcs and Pc probes will be discussed.
44. Sister Miriam Michael Stimson, OP and the development of the KBr
pellet method for IR spectroscopy
Steven P. Wathen, [email protected]. Chemistry, Siena Heights
University, Adrian, Michigan, United States
Historically, obtaining the IR spectrum of a solid material posed difficulties and
a preparing a mull with mineral oil was not always a satisfactory solution. The
method of forming a disc of KBr mixed with the solid sample was developed by
Sr. Miriam Michael Stimson, a Dominican sister and Ph.D. chemist. Sr. Miriam
was on the faculty at Siena Heights College in Adrian, Michigan where she did
research on the spectroscopy of nucleic acids. The KBr method was developed
to obtain better quality IR spectra of solid samples. The background of this work
wll be presented.
45. Mild and highly efficient copper (I) mediated activation of simple and
hindered anhydrides in the acylation of alcohols and polyols
Enoch Mensah, [email protected], Lindsey Earl. School of Natural Sciences ,
Indiana University Southeast , Charlestown , Indiana, United States
A new and highly efficient copper (I) mediated protocol for activating both
simple and highly hindered anhydrides in the acylation of alcohols and polyols
is described. This method of acylation of alcohols is mild and mostly proceed at
room temperature with low catalyst loading. The method has been extended to a
variety of different alcohol substrates with different steric encumbrance to afford
the corresponding esters in good to excellent yields.
46. Computational and synthetic studies of aldimine synthesis
Cody Greenwalt, [email protected], Brian Knettle. Department of
Chemistry, Hiram College, Hiram, Ohio, United States
Aldimine synthesis from aldehyde and amine starting materials is known to
commence with a nucleophilic attack by the amine nitrogen upon the electron-
deficient carbon of the aldehyde. One potential way to assist this process is to
provide a carbon with increased positive charge. In this work, a range of
electron donor/withdrawing groups effects upon the ability to synthesize
aldimines are studied by obtaining computationally derived values for the
amount of positive charge upon the aldehyde carbon and attempting to correlate
those to the experimentally obtained synthetic yields. Results suggest that the
prediction of increased positive charge upon the aldehyde carbon as a better
electron withdrawing group is added is flawed and that substituents actually play
a far lesser role in the synthesis than might be expected.
Abstracts 73
47. Method for Von Baeyer naming of polycyclic cage-shaped
hydrocarbons: applications to bishomocubanes
Wendell L. Dilling, [email protected], Anton W. Jensen, Tianzuo Xu, Jing
Liang, Linlin Zhao. Chemistry and Biochemistry, Central Michigan University,
Midland, Michigan, United States
Originally Eckroth (J. Org. Chem. 1967, 32, 3362-3365; J. Chem. Educ. 1993,
70, 609-611), and more recently extended by Zhang and coworkers [Daxue
Huaxue (Univ. Chem.) 2014, 29, No. 3, 35-40] have developed a simplified
method for Von Baeyer naming of polycyclic cage-shaped hydrocarbons by
converting the three-dimensional structures into two-dimensional structures by
expanding one ring and keeping the other atoms inside that ring. We have
applied this method to the five bishomocubanes. For example 1,3-
bishomocubane (below) is named pentacyclo[5.3.0.02,5.03,9.04,8]decane.

48. Development of photoactivatable (2-quinolinyl)methyl-based nitroxyl

(HNO)-releasing compounds
Mohammad Rahman1, [email protected], Yang Zhou 1, Nicola E. Brasch2,
Alexander J. Seed1, Paul Sampson1. (1) Chemistry & Biochemistry, Kent State
University, Kent, Ohio, United States (2) Chemistry, Auckland University of
Technology, Auckland, New Zealand
Nitroxyl (HNO) has received recent attention as a potential pharmacological
agent. It improves vasorelaxation and myocardial contractility, and is a
promising therapeutic agent for the treatment of acute congestive heart failure.
Studying the chemical and biological effects of HNO remains challenging due to
its short lifetime, requiring the use of HNO donors. However, the slow release of
nitroxyl from common HNO donors limits kinetic and mechanistic studies with
biologically relevant molecules. To address these limitations, a new family of
HNO donors of general structure 1 has been developed which exploit the (2-
quinolinyl)methyl phototrigger for releasing HNO. The synthesis of several
HNO donors of general structure 1 is presented and preliminary photochemical
studies aimed at rapid and selective HNO generation from these targets are
described.
Abstracts 74

49. Synthesis and photolysis of p-hydroxyphenacyl-based HNO donors

Jiuhong Zhang, [email protected], Paul Sampson, Alexander J. Seed.
Chemistry & Biochemistry, Kent State University, Kent, Ohio, United States
Due to the great potential of nitroxyl (HNO) for the treatment of acute
congestive heart failure, the synthesis of various HNO donors has been of
interest to both the scientific and clinical research communities. The application
of photo-removable protecting groups (PPGs) for the release of chemically or
biologically active species with precise spatial and temporal resolution is a well-
established general strategy that remains underdeveloped in the HNO field. The
biocompatible p-hydroxyphenacyl chromophore has been studied as a rapid and
efficient photo-trigger, but it has not been explored as a tool for photoactivated
HNO release. In the present work, we report the synthesis of two p-
hydroxyphenacyl-based HNO donors 1 and describe their photolytic properties.
The mechanism of HNO generation will also be discussed.

50. Synthesis of N-benzyl amides via oxypyridinium salt promoted Ritter

reaction
Maryam Baniasad, [email protected], Philip A. Albiniak. Ball
State University, Muncie, Indiana, United States
Abstracts 75
The Ritter reaction is one of the most useful synthetic routes for the conversion
of nitriles to the corresponding N-alkyl amides. However, despite its obvious
utility, traditional Ritter reactions suffer from several disadvantages such as
requiring an excess amount of corrosive acid and potentially hazardous
catalysts/additives. Due to the importance of amides as building blocks in
organic and medicinal chemistry several variations have been reported for the
Ritter reaction to synthesize amide groups under milder and environmentally
acceptable conditions. However, almost all of these methods suffer from
disadvantages such as high cost, poor availability or toxicity of the reagents, and
extended reaction times. In this project we are investigating the utility of the
compound 2-Benzyloxy-1-methylpyridinium triflate (BnOPT) as an effective
reagent for the benzylation of nitrile functional groups to create N-
benzylamides. BnOPT has been shown to be an effective reagent for the
benzylation of various nucleophiles such as alcohols, carboxylic acids, and
electron-rich aromatic rings. The proposed mechanism of benzyl transfer using
BnOPT involves an SN1-like pathway where this reagent decomposes to a
benzyl cation upon warming followed by trapping with the nitrile. Upon
quenching of the resultant nitrilium ion with water, an N-benzyl amide would be
generated. The primary advantage of BnOPT is that there is no need for the
addition of strongly acidic reagents required for traditional methods. This poster
will focus on the initial reactivity investigation and optimization of BnOPT-
promoted Ritter reactions.
51. Synthesis and evaluation of recently isolated immunologically active
glycolipids
Seyed Iraj Sadraei, [email protected], Emmanuel Igbokwe, John F. Trant.
Chemistry and Biochemistry, University of Windsor, LaSalle, Ontario, Canada
Invariant natural killer T cells (iNKT), a subclass of white blood cells, are potent
producers of non-specific cytokines whose activation can lead to a systemic
immune response. They are unique in having a monospecific T-cell receptor that
recognizes glycolipid antigens; however the true natural glycolipid antigen was
unidentified until recently, when it was isolated from S. pneumoniae, the leading
cause of neonatal sepsis and meningitis. Two main fractions of antigenic S.
pneumoniae glycolipids were identified, one contains a monosaccharide glucose
sugar linked to diacylglycerol (DAG), the second fraction is identical except it
has a disaccharide moiety attached to the DAG. Both the monosaccharide and
the disaccharide appear capable of activating iNKT cells. However, these tests
were done using very small amounts of isolated glycolipids, and consequently it
is difficult to ascertain whether the activity is due to these compounds or to
some minor impurity. There are also questions about the unusual structures of
the glycolipids. Consequently, we aim to synthesize both classes of glycolipids
to both allow for a quantitative biological evaluation of their activity, and to
allow for a confirmation of their structure by synthesis. This poster will discuss
Abstracts 76
the importance of these S. pneumoniae glycolipids, and our progress towards
their total synthesis, and preliminary immunological results.

52. Synthesis of cationic contrast agents for the study of degenerative disc
disease
Erik Davenport1, [email protected], Michael D. Newton2, Samantha E.
Hartner2, Karissa Gawronski2, Kevin C. Baker2,3, Tristan Maerz2,3, Shannon C.
Timmons1. (1) Department of Natural Sciences, Lawrence Technological
University, Southfield, Michigan, United States (2) Orthopaedic Research
Laboratory, Beaumont Health, Royal Oak, Michigan, United States (3)
Department of Orthopaedic Surgery, Oakland University William Beaumont
School of Medicine, Rochester, Michigan, United States
Degenerative disc disease is a term used to describe the changes that occur as
spinal discs degrade over time, often resulting in chronic pain. The diagnosis of
this affliction currently depends upon imaging techniques, such as MRI, which
detect morphological changes in discs. Unfortunately, these changes are usually
only detected at an advanced stage of the disease, limiting treatment options. In
an attempt to better understand degenerative disc disease, contrast agents are
Abstracts 77
used in micro-CT imaging applications to follow disease progression via the
quantification of the sulfated polymer glycosaminoglycan, which is directly
correlated to intervertebral disc health. Interestingly, only anionic contrast
agents are presently commercially available, which are repelled by the
negatively charged sulfated glycosaminoglycans present in intervertebral discs.
In this study, we aimed to prepare cationic contrast agents, which directly bind
to sulfated glycosaminoglycans and provide a more direct method of
quantification over the progression of degenerative disc disease. A positively
charged cationic contrast agent, CA4+, was successfully prepared over four
synthetic steps in 34% overall yield. The details of this synthetic scheme, as well
as progress toward the synthesis of novel cationic contrast agents will be
described. The use of CA4+ to successfully study the biomechanical properties of
intervertebral discs as they degenerate/regenerate indicates that this contrast
agent may be a strong non-destructive characterization tool for preclinical
studies.
53. Cosolvent effects of dissolved organic matter on the aqueous solubility
of organochlorine pesticides in the presence of ethanol
Lan Ma2, [email protected], Margarita Otero1, Brandon Woo2, Nirvan
Bhattacharyya2, Avery Demond2. (1) Environmental Engineering, University of
Michigan, Ann Arbor, Michigan, United States (2) University of Michigan, Ann
Arbor, Michigan, United States
In the effort to promote ethanol/gasoline blends as an alternative fuel, potential
negative impacts on the environment post-production have been overlooked.
Many ethanol spills occur in water bodies that have sediments that are
historically contaminated with persistent organic compounds such as
organochlorine pesticides. Ethanol can enhance the aqueous solubility of such
compounds by orders of magnitude. In addition, river sediment contains organic
matter that, if dissolved, can also act as a cosolvent, further increasing the
aqueous solubility of pesticides. Under natural conditions, the dissolved organic
matter (DOM) may be composed of humic substances. However, sediments in
urban rivers may contain other types of organic matter resulting from
anthropogenic activity, significantly altering the composition of DOM. This
research seeks to assess the impact of DOM on the aqueous solubility of
organochlorine pesticides in the presence of ethanol.
In the presence of humic-derived DOM, a significant increase in the aqueous
solubility of pesticides is observed only at low and high ethanol fractions. To
explain this behavior, 13C-NMR was used to characterize the composition of the
organic matter dissolved by water-ethanol mixtures at different ethanol mass
fractions. The spectra show that the DOM extracted by water contains higher
concentrations of carboxylic and aromatic carbons, while the DOM extracted by
ethanol contains higher concentrations of aliphatic carbon. In the case of an
urban river sediment (Anacostia River, MD), an enhancement of the pesticide
aqueous solubility by the DOM of approximately an order of magnitude was
Abstracts 78
observed at low and high ethanol fractions, greater than that observed for humic-
derived DOM. This increase could not be solely attributed to an increase in the
total organic carbon present. Consequently, it appears that the composition of
the organic matter present in the Anacostia River sediment is responsible for the
greater increase in the solubility of organochlorine pesticides in the presence of
ethanol.
54. Halogen-bonded complexes of bromosubstituted electrophiles with 1,4-
diazobicyclo[2,2,2]-octane
Craig Weinberger, [email protected], Rachel Hines, Sergiy V. Rosokha.
Ball State University, MUNCIE, Indiana, United States
Intermolecular interactions involving covalently-bonded halogen atoms, referred
to as halogen bonding, recently appeared as a powerful method for molecular
recognition and preparation of functional materials. A large number of crystal
structures showing halogen bonding and computational studies of the nature of
this interaction are reported in the literature. The experimental characteristics of
such complexes in solutions are rather scarce. This work presents spectral and
thermodynamic characteristics of the halogen-bonded complexes between
bromosubstituted electrophilic molecules R-Br (R-Br=CBr3F, CCl3Br, CBr3NO2,
CBr3COCBr3, CBr3CN, CBr3CONH2, etc.) and 1, 4-diazobicyclo[2,2,2]-octane
(DABCO). It is known that DABCO is a strong donor as well as a good
electrophile. Also, the transparency of its electronic spectrum in the UV makes it
a very suitable compound for studying this interaction. UV-Vis spectral
measurements showed that this donor forms moderately strong complexes with
the R-Br electrophiles which are characterized by intense absorption bands in
the UV-Vis range. The energy of these bands follows common Mulliken
correlation with the difference of the energies of highest occupied molecular
orbital of nucleophiles and lowest unoccupied molecular orbital of the R-Br
electrophile. The formation constants of the halogen-bonded [R-Br, DABCO]
complexes ranged from 0.1 to 10 M-1, which is common for intermolecular
associates. Interestingly, their dependence on the polarity of the solvent does not
follow predictions of the electrostatic models. These spectral and
thermodynamic data suggest that besides electrostatic, charge-transfer
interaction contribute significantly to the formation of [R-Br, DABCO]
complexes.
55. Synthesis of functionalized dibenzimidazole precursor of telmisartan
Matthew Botti, [email protected], Jessica England,
[email protected], Christine Masell,
[email protected], Nina Palushaj,
[email protected], Addallah Salman,
[email protected], Alex Martin. Concordia University Ann
Arbor, Ann Arbor, Michigan, United States
Abstracts 79
Telmisartan is a widely prescribed antihypertensive drug that lost patent
protection in 2014. The current commercial process uses a highly functionalized
dibenzimidazole precursor, which is a significant cost driver for the production
of telmisartan. Since the original process was reported by Uwe Ries et al. in
1993, only minimal improvements have been made to the synthesis of this major
precursor. We have designed a new synthetic approach that provides a direct
assembly of the dibenzimidazole moiety by utilizing a facile Suzuki cross-
coupling reaction to form the dibenzimidazole linker. This process avoids the
harsh conditions and impurities associated with the problematic condensation
reactions used in the original process. By improving the synthesis of the
functionalized dibenzimidazole precursor, the production cost could be
significantly reduced without changing the commercial process.
56. Halogen bonding of iodoform with neutral and anionic nucleophiles
Olivia Grounds, [email protected], Brandon Watson, Sergiy V. Rosokha.
Ball State University, Evansville, Indiana, United States
Halogen bonding is an intermolecular attraction between covalently-bonded
halogens atoms and electron-rich centers. The strongest halogen bonds are
formed by iodine, which is the most polarizable halogen atom. Therefore,
chemical literature contains a large number of the solid state X-ray structures
showing halogen bonds involving iodine atoms. However, the experimental data
about the strengths of halogen bonding and spectral properties of halogen
bonded complexes of iodinated molecules in solution are limited. For example,
while X-ray structures showing halogen bonding with iodoform were published
long ago, there are no spectral or thermodynamic characteristics of the halogen
bonded complexes of this one of the simplest halogenated molecule. The lack of
the experimental characteristic hinders reliable analysis of the nature of this
novel intermolecular bonding. To fill this gap, we carried out spectral
measurements of the complex formation of iodoform with anionic (Cl-, Br-, I- ,
N3-, NCS-, NCO-) and neutral (DABCO) nucleophiles. These studies revealed
that iodoform form relatively strong complexes with these nucleophiles. Their
formation constants are in the 5-20 M-1 range. All these complexes show intense
absorption bands in the 250 400 nm range. The energies of these absorption
bands show linear correlation with the energies of the highest occupied
molecular orbital of the nucleophiles. This Mulliken correlation is a typical
feature of the charge transfer complexes, and it suggest the charge-transfer
nature of the halogen-bonded associates involving iodoform.
57. Solvent effects on the stereoselectivity of aprotic glycosylations
Seyed Iraj Sadraei, Adan Sadiq Ahmed, [email protected], Greg Yousif,
Advait Desai, John F. Trant. Chemistry and Biochemistry, University of
Windsor, LaSalle, Ontario, Canada
Glycosylation, the anomeric functionalization of a carbohydrate, is one of the
best studied reactions in organic chemistry. There are myriads of methods
Abstracts 80
developed to accomplish this reaction, however none of them have proven
general and obtaining stereoselective reactions remains a significant challenge.
After the choice of leaving group and activating agent, the choice of solvent has
one of the largest impacts on the outcome of glycosylation. The two solvent
extremes are often taken to be diethyl ether and acetonitrile. The former favours
axial ()-glycosylation, while the latter generally favours -attack. There is
significant controversy about the exact mechanism by which acetonitrile
accomplishes this selectivity, but it has been proposed that there exists a solvent
network that delivers the nucleophile to the -face. However, there is no
experimental support for or against the proposition. Interestingly, this
mechanism should only be active when the nucleophile is protic, as most
glycosyl acceptors are (alcohols, thiols, amines); C-glycosylating agents (e.g.
furan) should not be capable of taking part in this network, and should not show
the -acetonitrile effect. Our preliminary experimental and computational results
will be discussed in this presentation.

58. Phosphinated itaconic acid/isosorbide oligomers

Victoria Hill1, [email protected], Bob Howell1, Yoseph Daniel2,1. (1)
Chemistry & Biochemistry, Central Michigan University, Saranac, Michigan,
United States (2) Department of Physics, Central Michigan University, Mount
Pleasant, Michigan, United States
Itaconic acid is a four-carbon diacid containing a methylene group at the 2-
position and is readily available from biosources. Michael addition of phosphites
to the methylene group provides a route to a variety of phosphorus compounds.
The phosphorus-containing itaconic acid may be subjected to melt
polymerization with isosorbide, a starch-derivd green diol, to generate
oligomeric materials suitable for use as non-toxic, non-migrating flame-
retardant additives for a variety of polymers.
59. Charing plasticizers from pentaethryitol
Aeshah Alrubayyi, [email protected], Bob Howell. Department of Chemistry
and Biochemistry, Central Michigan University, Mount Pleasant, Michigan,
United States
Pentaethryitol esters are of interest as bio-based plasticizers from polymeric
materials. Aliphatic esters are volatile and may contribute to the flammability of
Abstracts 81
the material into which they are incorporated. Esters that would promote char
formation when heated might reduce this effect and further might decrease the
flammability of the host polymer. A variety of pentaerythritol esters containing
char-forming aromatic units (benzoate, thiophenecarboxylate, furancarboxylate,
etc.) are being prepared for examination as non-flammable plasticizers form
polymeric materials.
60. Pseudopeptides: A new biocompatible self-immolative material
Dominique M. Leckie, [email protected], John F. Trant. Chemistry and
Biochemistry, University of Windsor, St Joachim, Ontario, Canada
Polymer science has undergone a significant renaissance in the last decade as
new "smart" materials and polymerization methodologies have created entirely
new biomedical applications. Many of these, including drug delivery, device
implantation, and post-surgical support would all benefit from new degradable
polymers. However, biodegradable polymers require multiple independent bond
cleavage events to complete depolymerization, resulting in slow, uncontrolled
degradation. This is undesirable for time sensitive applications. To overcome
this challenge, Shabat developed the first self-immolative polymer (SIP). These
materials propagate a single bond cleavage event, the removal of a stabilizing
end-cap, down the backbone leading to complete end-to-end depolymerization.
SIPs show great promise for drug delivery, "smart" coatings, and
environmentally sustainable applications. However, current examples of SIPs
often result in potentially toxic degradation products, such as quinones, which
render them unfit for biomedicine. Amino acid building blocks, including lysine,
ornithine and diaminobutyric acid, present a promising alternative to current
scaffolds to overcome this biocompatability challenge. Furthermore, the
trifunctional nature of these monomers readily permits side-chain
functionalization, allowing for fine-tuning of the polymers' physical and
mechanical properties. Our preliminary results into the synthesis of these
promising biomaterials, and our investigations into their depolymerization
kinetics will form the focus of this presentation.

Scaffold of self-immolative polymer built with amino acids

61. High phosphorus content derivatives of deoxybenzoin
Abstracts 82
Gavan W. Lienhart, [email protected]. Chemistry and Biochemistry,
Central Michigan University, Haslett, Michigan, United States
Deoxybenzoin may be generated from anisaldehyde. It has been utilized to
generate a variety of intrinsically flame retardant materials. This flammability
resistance is thought to arise through formation of alkyne linkages. The
introduction of phosphorus entities into this compound should produce an even
more effective flame retardant agent. Treatment of deoxybenzoin with phosphite
should generate a phosphorus adduct. Phosphorylation at the phenolic groups
may then be used to produce compounds containing three phosphorus-
containing moieties. These compounds have the potential to function as
effective flame retardants in a variety of polymeric systems.
62. Incorporation of secondary monomer into polysulfides formed by
inverse vulcanization
Clayton Westerman, [email protected], Courtney Jenkins. Chemistry, Ball
State University, Muncie, Indiana, United States
The petroleum industry is one of the largest around the world today. Many
products are yielded from this industry with different uses for fuels, oils, plastics
etc. Elemental sulfur is one of the waste products generated from the refining
step during a catalytic process called hydrodesulfurization. This cheap and
abundant source of reagent is recycled during inverse vulcanization which is a
new type of polymerization. Inverse vulcanization is use of a small amount of
monomer with large amounts of elemental sulfur that exists as an eight-
membered ring. The sulfur ring opens at 160 C, generating free radicals to bind
to the monomer. Our use of Divinylbenzene (DVB) and sulfur forms the
prepolymer, poly(S-r-DVB) after 30 minutes at 185 C. Incorporation of
monomer and sulfur is supported by the 1H-NMR spectrum and TLC. Our aim is
to include a second monomer, [1,4-Cyclohexanedimethanol divinyl ether
(CDE)], with a boiling point of 126 C, at a much lower temperature of 100 C
to generate a new polymer. This inclusion at a lower temperature regenerates
sulfur radicals to allow binding to CDE. Furthermore, the lower temperature
lowers the chance of rearrangement and degradation of the polymer. The process
occurs for an hour and the polysulfide is formed. Inclusion of the second
monomer is confirmed via 1H-NMR. We performed GPC and DSC to
investigate the chain length and material properties respectively as well as
examined reaction conditions for maximum incorporation of the second
monomer.
63. Biobased polymer additives from diphenolic acid
Harrison Fulco1, [email protected], Bob Howell2. (1) Chemistry and
Biochemistry, Central Michigan University, Houghton Lake, Michigan, United
States (2) Chemistry and Biochemistry, Central Michigan University, Mount
Pleasant, Michigan, United States
Abstracts 83
Polymer additives derived from renewable biosources are generally more
environmentally-friendly than those generated from petroleum sources and are
independent of fluctuations in petrochemical markets. Flame retardants based on
biomaterials are particularly attractive. Diphenolic acid is available from natural
sources and contains functionality to permit conversion to a variety of
phosphorous esters with flame-retarding potential. The carboxylic acid is first
converted to the corresponding anilide and then treated with appropriate
phosphorus reagents to generate difunctional phosphorus ester. The resulting
compounds contain both phosphorus and nitrogen and should display good
flame retardancy in a variety of polymeric materials.
64. Platinum(IV)-containing succinate oligomers
Uyen G. Huynh2, [email protected], Bob A. Howell1. (1) Central Michigan
Univ, Mount Pleasant, Michigan, United States (2) central michigan university,
Mount Pleasant, Michigan, United States
Organoplatinum antitumor agents have had a tremendously positive impact on
the treatment of cancer. However, administration of these drugs is accompanied
by rather severe side effects. A way to mitigate the side effects is to deliver the
drug at low concentrations such that antitumor activity is maintained but the
threshold for toxicity is not reached. To provide a release vehicle, platinum(IV)-
succinate oligomers are being prepared.
Enzymatic degradation of these materials will slowly release platinum into the
extracellular fluid. Once inside the tumor cell, the platinum(IV) species will be
reduced to an active platinum(II) entity.
65. Glycerol/ adipic acid hyperbranched poly(ester)s for the release of
active organoplatinum antitumor agent
Uyen G. Huynh2, [email protected], Rachel Schumaker2,
[email protected], Bob A. Howell1. (1) Central Michigan Univ, Mount
Pleasant, Michigan, United States (2) central michigan university, Mount
Pleasant, Michigan, United States
Glycerol/ adipic acid hyperbranched poly(ester)s may be prepared under
conditions in which both molecular weight and end-group functionality are
controlled. This polymer of approximately 2500 g/mol containing carboxyl end-
groups is an ideal carrier for active platinum species. For example, treatment of
the polymer with dichlorodiamineplatinum(II) in the presence of silver triflate
affords the polymer with platinumdiamine units coordinated to terminal
carboxylate groups. This platinum end-capped material should serve as a useful
platform for the controlled release of active drug.
66. Synthesis of novel aspirin analogs for medicinal testing
Abstracts 84
Hadeel K. Albasrawi, [email protected], Shannon C. Timmons. Department of
Natural Sciences, Lawrence Technological University, Southfield, Michigan,
United States
Aspirin is a common nonsteroidal anti-inflammatory drug used to treat pain,
fever, and inflammation. It is one of the most widely used medications in the
world with an estimated 40,000 tons produced and consumed annually. Recent
research has shown that this inexpensive age-old drug holds promise as an
anticancer agent. Studies have shown that aspirin has a remarkable ability to
inhibit the proliferation of colorectal cancer cells in vitro, for example. Although
the mechanism of action has not yet been established, it is clear that the
synthesis of aspirin analogs to further probe this finding is of interest. In this
study, a small library of novel aspirin analogs was synthesized using salicylic
acid as a molecular scaffold. Through the use of a variety of acyl chlorides,
aspirin analogs with varying degrees of hydrophobicity and steric hindrance
were successfully prepared. Using a panel of different cancer cell lines, the
medicinal activity of these aspirin analogs will be determined in future cell
proliferation assays to establish a structure-activity relationship.
67. Phosphorous esters of biobased gallic acid
Kendahl Oberdorfer2, [email protected], Bob A. Howell1. (1) Central
Michigan Univ, Mount Pleasant, Michigan, United States (2) Chemistry and
Biochemistry, Central Michigan University, Cedar Springs, Michigan, United
States
Gallic acid is a triphenolic acid available from natural sources. It represents a
good non-petroleum base for the preparation of phosphorus flame retardants.
Conversion of the carboxyl function to the corresponding anilide generates a
compound containing three reactive hydroxyl groups. These may be converted
to a variety of phosphate esters using the Atherton-Todd procedure
(phosphite/carbon tetrachloride). The esters may be characterized using
spectroscopic and thermal methods. They show promise as flame-retarding
additives for DGEBA epoxy resin.
68. Chirality transfer intramolecular [2+2] cycloaddition of electron
deficient allenes and alkenes
Yao Xu, [email protected], Michael K. Brown. Chemistry, Indiana University
Bloomington, Bloomington, Indiana, United States
Intramolecular chirality transfer [2+2] cycloaddition of electron deficient allenes
and alkenes is presented. Two variants are disclosed, one in which allenic esters
are used and the other involves allenic phosphonates. In both cases high levels
of chirality transfer are observed. The mechanistic details of these reactions are
also discussed.
Abstracts 85
69. Strategic flexibility in the controlled folding of disulfide rich peptides:
Progress toward controlled disulfide formation to access neuroactive
conotoxins
Thilini Kondasinghe, [email protected]. Chemistry, Wayne State University,
Detroit, Michigan, United States
Conotoxins are mini proteins that are isolated from venomous Conus snails.
They have exhibited a role as ion channel inhibitors of high specificity.
Therefore, they present an opportunity for use as potential therapeutic agents for
various neurological ailments. The goal of this research is to establish a tunable
chemical environment that will facilitate the consistent and reliable folding of
disulfide rich peptides, including conotoxins, into their active conformations.
Progress toward these endeavors will be presented.
70. Progress towards the synthesis of derhodinosylurdamycin A analogues
bearing diverse 2-deoxy sugar subunits
Padam Acharya, Hem Khatri, Jianglong Zhu, [email protected].
Department of Chemistry and Biochemistry, University of Toledo, Toledo, Ohio,
United States
Angucycline antibiotics are one class of bioactive natural products containing
angularly assembled tetracyclic ring frame and exhibit diverse biological
activities such as antitumor, enzyme inhibiting, and platelet aggregation
inhibiting activities. The urdamycins are a class of angucyclines produced by
Streptomyces fradiae first isolated by Drautz and co-workers in 1986. Among
urdamycins, derhodinosylurdamycin A was first reported as a bioactive natural
product derivative which showed significant anticancer activity against L1210
Leukemia cells with IC50 value of 0.75g/ml. We have recently completed the
first total synthesis of derhodinosylurdamycin A. In this presentation, we will
describe our efforts in the synthesis of analogues of derhodinosylurdamycin A
bearing diverse 2-deoxy sugar subunits for extensive SAR studies.
71. Synthesis of the 2-deoxy trisaccharide subunit of antitumor antibiotics
landomycin A/E
Justin Woodward, [email protected], Xiaohua Li. Department of Natural
Sciences, University of Michigan-Dearborn, Dearborn, Michigan, United States
The landomycins are a family of angucycline antitumor antibiotics isolated from
Streptomyces cyanogenus. Among the landomycins, landomycin A possesses a
broad spectrum of antitumor activity against a range of 60 cancer cell lines.
Structurally, landomycin A contains an angular tetracyclic core as well as a
hexassacharide subunit consisting of two repeat units of trisaccharide (-L-
rhodinose-(13)- -D-olivose-(14)- -D-olivose), while landomycin E
contains one copy of this trisaccharide subunit. Although it is known that
landomycin A inhibits DNA synthesis and G1/S cell cycle progression, the
specific mechanism of action on cancer cells has not yet been determined. In this
Abstracts 86
presentation, we will describe our concise synthesis of this 2-deoxy trisaccharide
subunit of landomycin A/E.
72. Mechanistic studies of -mannosylation via Cs2CO3-mediated anomeric
O-alkylation
Bishwa Bhetuwal1, Hai P. Nguyen1, Xiaohua Li2, Jianglong Zhu3,
[email protected]. (1) The University of Toledo, Bellefontaine, Ohio,
United States (2) Department of Natural Sciences, University of Michigan-
Dearborn, Dearborn, Michigan, United States (3) Department of Chemistry and
Biochemistry, University of Toledo, Toledo, Ohio, United States
Stereoselective construction of -mannopyranoside, one of the key glycosidic
linkages in biologically significant N-linked glycans, is a long-standing
challenge. Recently, we developed a direct and efficient method for the
synthesis of -mannosides via cesium carbonate mediated anomeric alkylation.
In this presentation, we describe our preliminary results during the mechanistic
studies of this reaction and propose a revised working model for the -
mannosylation.
73. Stereoselective -mannosylation involving various electrophiles
Kevin Saybolt, [email protected], Nader Berry, Uddin Ahmed, Xiaohua Li.
Department of Natural Sciences, University of Michigan-Dearborn, Dearborn,
Michigan, United States
Stereoselective -mannosylation has been one of the long-standing challenges in
synthetic carbohydrate chemistry. Recently, we developed a stereoselective -
mannosylation via cesium carbonate-mediated anomeric O-alkylation of D-
mannose-derived lactols with sugar-derived triflate electrophiles. In this
presentation, we will report our studies involving various electrophiles. In
addition, we will report a highly efficient formal synthesis of potent calcium
signal modulator acremomannolipin A using this -mannosylation method.
74. Riboflavin-biotin conjugate synthesis
Talal Bazzi, Batoul Nasser, Eric James, Simona Marincean,
[email protected]. University of Michigan - Dearborn, Dearborn, Michigan,
United States
Riboflavin, or B2 vitamin, is a precursor of coenzymes, Flavin Mononucleotide
and Flavin Adenine Dinucleotide, which are participants in fundamental cell
processes. Riboflavin has been linked to embryonic development and growth
and thus its qualitative and quantitative determination is of relevance. The
concentration of Riboflavin is typically determined by chromatography, or
indirect coupled assays. These methods are not useful in many applications such
as measuring its presence and concentration in critical biological samples or
studying nutrition-deficient populations. Progress towards synthesis of a biotin-
riboflavin conjugate that will constitute the core of a novel detection strategy
Abstracts 87
employing the well-established affinity and stability of the biotinavidin system,
will be presented.
75. Synthesis of 2-C-methyl pseudouridines for the inhibition of HCV
RNA-Polymerase
Immaculate Sappy, [email protected]. Medicinal &
Biological Chemistry, The University of Toledo, College of Pharmacy &
Pharmaceutical Sciences, Toledo, Ohio, United States
Studies of the structure and function of Hepatitis C Virus (HCV) RNA-
dependent RNA polymerase (RdRp)
have broaden our understanding of HCV viral RNA replication and the
mechanism of action of this RNA polymerase. These findings have encouraged
the development of inhibitors of this target for antiviral therapy. Anti-HCV
activity has been shown in-vivo with C-nucleosides containing a 2-C-methyl
(Me) substituent. The presence of the 2-C-Me group prevents the chain
elongation catalyzed by the RdRp NS5B. To further investigate this
phenomenon, the synthesis of modified pseudouridines was performed using
earlier developed strategies for the unmodified nucleoside. By coupling of the
protected pyrimidine to a likewise protected 2-C-methyl-D-ribono-lactone the
C-nucleoside was formed. Subsequent reduction and ring closure generated
alpha and/or beta- 2-C-Me pseudouridines. Through the work presented here,
this modified pseudouridine synthesis was optimized and will be utilized in the
synthesis of other modifications of this naturally occurring nucleoside and
evaluated for their antiviral activity. This will include conversion to substrates
suitable for the monophosphate prodrug strategy.
76. Work in preparation for the selective generation of a C5 prime uridine
monophosphate radical
Mariah A. Pasternak2, [email protected], Matthew Ellis1,
Amanda C. Bryant-Friedrich2. (1) Medicinal & Biological Chemistry, The
University of Toledo , Toledo, Ohio, United States (2) University of Toledo,
Toledo, Ohio, United States
Background: Various agents that cause RNA damage exist, such as reactive
oxygen species (ROS) and several other oxidants. Oxidative damage to RNA,
which involves free radicals, can impact ribosome function, alter protein
synthesis, and play a role in diseases such as Alzheimers and dementia. Indeed,
oxidative damage could be more prevalent in RNA than in DNA because RNA
is single-stranded, has less association with proteins, and is present in the
cytosol near mitochondria that produce ROS. Since RNA modifications are
detected in pathological states, it is important to understand how they are
produced.
Purpose / Objective: The goal of this research is to understand mechanisms of
RNA damage that could occur in vivo by using a site-specific radical produced
Abstracts 88
by photolysis on the C5 prime group of a C5 prime uridine monophosphate
molecule as a model of a specific type of oxidative damage that could occur to
RNA. A predicted product created by reactions occurring after the site-specific
radical is produced is C5 prime uridine monophosphate, so part of the overall
project involves determining the stability of C5 prime uridine monophosphate
and creating calibration curves for the C5 prime uridine monophosphate to
quantify amounts that may form from radical reactions.
Methods: Synthesis of C5 prime uridine monophosphate was completed by
protecting uridine 2 prime and 3 prime hydroxyl groups with an isopropylidene
group, adding the phosphate group onto the uridine 5 prime hydroxyl using
phosphoryl chloride, and de-protecting the 2 prime and 3 prime hydroxyl groups
with hydrolysis. Calibration curves for C5 prime uridine monophosphate were
generated on HPLC using known concentrations of that compound. Stability
testing of C5 prime uridine monophosphate under photolysis conditions was
done using a 500 W mercury bulb with cut-off filters and a focusing lens.
77. Exploiting the Curtin-Hammett principle in the intramolecular
cyclization of heteroenyne allenes
Sundeep Rayat1, [email protected], Pamela Filby2. (1) Department of Chemistry,
Ball State University, Muncie, Indiana, United States (2) Chemistry, Ball State
University, Muncie, Indiana, United States
Our laboratory is engaged in developing versatile methods for the synthesis of
medicinally relevant heterocycles based on quinazolinimine scaffold.Previously,
we have reported one pot Lewis acid assisted cascade/tandem cyclization of
heteroenyne-allenes, the 2-((biphenyl-2-ylimino)methyleneamino)benzonitriles
1 to functionalized phenanthridine-fused quinazoliniminium salts (PQ +X- ,
where X = Cl-, BF4- ). Based on a previous study from our research group, we
hypothesized that this reaction involves HX generated in situ from Lewis acid
and trace water. The cyclization of 1 to PQ + involves (a) C-N bond formation
and (b) a C-C bond formation. The sequence in which C-C and C-N bond
formations takes place was not clearly evident. We undertook a systematic
computational investigation of several mechanistic avenues that could be
invoked involving the cyclization of the heteroenyne allene 1 to the cation PQ +.
All calculations were carried out at B3LYP level of theory and employed 6-
311G* basis set. The solvent effects were considered using Polarized
Continuum Model with nitromethane as the solvent. Our primary goal was to
identify critical reactive intermediates and nature of transition states involved in
the formation of the final product. Our results show that C-C bond formation
precedes C-N bond formation. The reaction proceeds via the initial protonation
of carbodiimide nitrogen (N). The resulting protonated intermediate is trapped
by nucleophilic attack from the biphenyl ring (ring B) to leading to the
formation of the sigma complex I (C-C bond formation). The latter undergoes
proton migration from the ring B to the CN group that restores the aromaticity
of the phenanthridine ring, and activates the nitrile towards nucleophilic attack
Abstracts 89
(C-N bond formation) from the N resulting in the formation of the fused
heterocyclic cation PQ +. The Curtin-Hammett principle plays an important role
in guiding the overall reaction pathway. We also explored the potential energy
surface for the F and Me substituted 1 to gain insights into substituent effects
on the mechanism and the results will be presented.

78. Size control of the silver-glutathione nanoparticles during their

formation
Yeakub Zaker, [email protected], Nathan Diemlar, Brian
Ashenfelter, Badri Bhattarai, Terry P. Bigioni. Chemistry and Biochemistry,
University of Toledo, Toledo, Ohio, United States
Size control is a longstanding challenge in the production of single-sized water
soluble silver nanoparticles. For example, the silver-glutathione (Ag-SG) system
is known to produce polydisperse products (>20 different discrete molecular
species), therefore isolation of any particular size requires size fractionation of
the mixed-size products. It is possible to obtain singular Ag-SG nanoparticle
products by attrition, i.e. destroying all but the desired product, but this is a
laborious procedure with low yield. Here, we present a methodology for
producing nearly single-sized products of Ag-SG nanoparticles directly, with no
post-processing required, with good yield. By studying the consequences of
different reaction conditions on the size distribution, the effects of reduction
rate, pH, buffer composition, temperature, time, and precursor solubility could
be disentangled. The rate of the reaction was found to have the most significant
effect, with slower reaction rates producing small sizes and the narrowest
distributions. These results were used to develop a facile method for producing
Ag15(SG)11 and Ag32(SG)19 in high yield.
79. Kinetic and thermodynamic comparison of an aza-Cope [3,3]
sigmatropic rearrangement and an aza-Prins cyclization of a homoallylic
activated imine
Migeru Inaba, [email protected], Maria-Clelia Milletti. Chemistry, Eastern
Michigan University, Detroit, Michigan, United States
It is possible to obtain a piperidine with two chiral centers from an achiral
homoallylic imine via aza-Prins cyclization. Furthermore, an aza-Cope
rearrangement from the same achiral homoallylic imine leads to a chiral
homoallylic amine that can be easily converted to an amide. In this work we use
computational methods to investigate whether reaction conditions can be
Abstracts 90
modified to produce primarily one product or the other. In addition, we
determine whether either product can be obtained stereoselectively. The results
indicate that both pathways are endergonic, but aza-Cope products are favored.
The boat conformers of the imine are thermodynamically favored. In addition,
activation barriers for the reaction from the homoallylic imine to the aza-Cope
product are the lowest and especially so for the chair conformations. However, it
is possible for the aza-Cope products to convert to the aza-Prins product with
activation barriers that are not much higher.
80. Effect of two methyl substituents on the stereoselectivity of an aza-Cope
Mannich reaction
Terrence Stahl, [email protected], Maria-Clelia Milletti. Chemistry, Eastern
Michigan University, Detroit, Michigan, United States
Density functional methods are used to model key steps of the tandem aza-Cope
Mannich reaction leading to a substituted pyrrolidine using boron trifluoride as
the acid catalyst. The effect of two bulky methyl substituents at the alpha
position to the nitrogen center is considered with respect to optimizing
stereoselectivity in the pyrrolidine reaction product. The results are compared to
those for a substrate with no protecting group at the nitrogen and where zinc
chloride is used as the acid catalyst.
81. Spectroscopic studies on the interactions between vitamins and
nanoparticles
Timothy R. Brewer, [email protected], Tyler Resh, Russell Sheets,
Christopher Bourne. Chemistry, Eastern Michigan University, Ypsilanti,
Michigan, United States
The interactions between the main chemical components in vitamins such as
riboflavin, pyridoxine, and thiamine and silver nanoparticles were studied using
absoprtion and fluorescence spectroscopic techniques. The dependence of the
intensity of the absoprtion band on the amount of nanoparticle resulted in values
for the apparent association constant. The fluorescence dependence of the
riboflavin due to silver nanoparticles probed the quenching. Investigations into
the type (size and shape) of the nanoparticle will determine the molecular
interactions such as excited state reaction molecule rearrangement, energy
transfer, and collisional quenching that occur in these systems. Energy transfer
processes can be determined by the overlap between the donor emission and
acceptor absorption.
82. Density Functional Theory study of the interaction of methane with the
prism structure of the water hexamer cluster
Daniel B. Lawson, [email protected]. Natural Sciences, University of
Michigan-Dearborn, Dearborn, Michigan, United States
Abstracts 91
Density Functional Theory with MS3G basis are used to calculate energy
optimized geometries and ZPEs of the isomers of methane interacting with 8
different low lying water hexamers and compared with the resulting single point
MP2/aug-cc-pvtz and CCSD(T)/aug-cc-pvtz energies. Analysis of the 32
methane water hexamer structures is provided in terms of relative interaction
energy, NBOs perturbation theory analysis and orbital analysis. Addition of the
methane does not change the overall geometry of the hexamer geometry
however the relative energy levels of the original water hexamers are altered.
83. A theoretical study of oxidation of ascorbic acid and its antioxidant
mechanism
Yi-Jung Tu1, [email protected], David Njus2, H. Bernhard Schlegel1. (1)
Chemistry, Wayne State University, Detroit, Michigan, United States (2)
Biological Sciences, Wayne State University, Detroit, Michigan, United States
Ascorbic acid is a well known antioxidant and radical scavenger. It can be
oxidized by losing two protons and two electrons, but normally loses only one
electron at a time. The reactivity of the ascorbate radical is unusual, in that it can
either disproportionate or react with other radicals. To explore the oxidation
mechanism of ascorbic acid, the pKas and reduction potentials have been
calculated using the B3LYP/6-31+G(d,p) and CBS-QB3 levels of theory with
the SMD implicit solvent model and explicit waters. Calculations show that the
most stable form of dehydroascorbic acid in water is the bicyclic hydrated
structure, in agreement with NMR studies. The possible oxidation reactions at
different pH conditions can be understood by constructing a potential-pH
(Pourbaix) diagram from the calculated pKa and standard reduction potentials.
Under physiological pH the disproportionation of the intermediate radical is
thermodynamically favored. The calculations show that disproportionation
proceeds via dimerization of ascorbate radical and internal electron transfer, in
agreement with Bielskis proposed mechanism. Cyclization of one of the
ascorbate fragments in the dimer followed by protonation and dissociation yields
a pair of fully reduced and fully oxidized structures. Calculations show that this
mechanism also explains the reaction of the ascorbic acid radical with other
radical species such as superoxide. Ascorbate radical combines with the radical
and intramolecular electron transfer followed by hydrolysis yields
dehydroascorbic acid and converts the radical to its reduced form.
84. Computational simulations of hydrogen circular migration in
protonated acetylene induced by circularly polarized light
Xuetao Shi, [email protected], Wen Li, H. Bernhard Schlegel. Department
of Chemistry, Wayne State University, Detroit, Michigan, United States
The hydrogens in protonated acetylene are very mobile and can easily migrate
around the C2 core by moving between classical and non-classical structures of
the cation. The lowest energy structure is the T-shaped, non-classical cation with
a hydrogen bridging the two carbons. Conversion to the classical H2CCH+ ion
Abstracts 92
requires only 4 kcal/mol. The e ect of circularly polarized light on the migration
of hydrogens in oriented C2H3+ has been simulated by Born-Oppenheimer
molecular dynamics. Classical trajectory calculations were carried out with the
M062X/6-311+G(3df,2pd) level of theory using linearly and circularly polarized
32 cycle 7 m cosine squared pulses with peak intensity of 5.6 1013 W/cm2
and 3.15 1013 W/cm2, respectively. These linearly and circularly polarized
pulses transfer similar amounts of energy and total angular momentum to C2H3+.
The average angular momentum vectors of the three hydrogens show opposite
directions of rotation for right and left circularly polarized light, but no
directional preference for linearly polarized light. This di erence results in an
appreciable amount of angular displacement of the three hydrogens relative to
the C2 core for circularly polarized light, but only an insigni cant amount for
linearly polarized light. Over the course of the simulation with circularly
polarized light, this corresponds to a propeller-like motion of the three
hydrogens around the C2 core of protonated acetylene.
85. Computational investigation into the competition between thymine and
carbonate addition to the guanine radical
Sebastien Hebert, [email protected], H. Bernhard Schlegel. Wayne State
University, Pittsburgh, Pennsylvania, United States
DNA oxidative damage is known to cause various degenerative conditions,
including aging, Alzheimers, and cancer. Due to its relatively low oxidation
potential, the guanine nucleobase is widely studied as a suitable model for
biological DNA damage. Guanine oxidation can occur selectively using
carbonate radical anions, which are known to be produced under conditions of
oxidative stress. Under specific conditions, that is when the 5'-GCT-3' motif is
present, guanine oxidation can readily lead to formation of a covalently bound
guanine-thymine (GT) adduct. Experiments by Shavirovich and coworkers
found that GT formation was competitive with formation of 8-oxo-7,8-
dehydroguanine (8-oxo-G), a known 2-electron oxidation product of guanine.
While the production of GT and 8-oxo-G have been studied under a number of
conditions, the mechanism and reasoning behind their competitive nature has
only been speculated. In this study, density functional calculations are
performed using the G09 program to probe the reaction pathway with the SMD
implicit solvation model to account for the influence of the water solvent. In an
attempt to better understand these oxidation pathways, we also consider the
strong pH dependence on the product distribution noted by Shavirovich and
coworkers and account for solvent protonation/deprotonation events with
compounds having pKas close to the desired pH.
86. Photodegradation of p-nitrophenolate in solution phase and at the air-
aqueous interface
Abstracts 93
2 3 4
Ryan Young , [email protected], Daniel Headley , Margaret Schmits ,
Mahamud Subir1. (1) Chemistry, Ball State University, Muncie, Indiana, United
States (2) Ball State University, Muncie, Indiana, United States
In recent years, it has been shown that small organic anions, such as phenolate,
can exhibit surface affinity for the air-water interface. Given the surface
proclivity of these compounds, an important enquiry that emerges is relevant to
their rate of photolysis at the water surface. The focus of this study involves p-
nitrophenol (pNP), which has a pKa of 7.15 at room temperature. In our lab, we
have shown that pNP, the conjugate base of pNP, at pH 13, adsorbs at the air-
aqueous interface. The purpose of this study has been to elucidate the
differences (if any) in the photodegradation rate of pNP in the bulk aqueous
solution versus when adsorbed at the air-water interface. To this end, we have
performed systematic direct photolysis studies of pNP in the solution phase
using UV-Vis spectroscopy and monitored its surface photolysis using second
harmonic generation (SHG) spectroscopy. In the aqueous solution, the quantum
efficiency of pNP and pNP were found to be 3.31 ( 0.08) 105 mol einstein1
and 1.33 ( 0.04) 105 mol einstein1, respectively. This result indicated that
pNP is more photo-stable than pNP in the aqueous solution. Moreover, based
on SHG study, the pNP degradation at the surface appears to be much less
efficient. These findings, along with the influence of H2O2 on the surface
photodegradation of pNP, will be discussed. The challenges associated with
probing chemical reactions at a buried interface will also be emphasized.
87. Nanostructured nickel tungstate (NiWO4) doped with silver and copper
for power conversion efficiency studies in photovoltaic cells
Andrew Riley2, SeyyedAmirhossein Hosseini3, Zhihai Li1, [email protected]. (1) Ball
State University, Muncie, Indiana, United States (2) Chemitry, Ball State
University, Muncie, Indiana, United States (3) Chemistry, Ball State University,
Muncie, Indiana, United States
The development of clean energy resources represents an important task to meet
the future demand for renewable energy. Photovoltaic cells (PV) represent a
promising solution as an environmental benign system converting solar energy
(sun light) to electricity. Nickel Tungstate (NiWO4) has shown the capacity to
effectively convert sunlight to electricity. Using group 11 elements such as
copper (Cu) and/or silver (Ag) as a dopant, this effect may be magnified.
In this work, nanostructured NiWO4 has been prepared and characterized with
different techniques such as atomic force microscopy (AFM), TEM, XRD, etc.
The nanostructured NiWO4 are further doped with group 11 elements for the
application in photovoltaic. For the doping of NiWO4 with copper (Cu), a
precipitation method has been used to synthesize Cu(x)Ni(1-x)WO4. The
precipitation method was aided by Cetyltrimethylammonium Bromide (CTAB)
in an aqueous solution held between 7 and 7.5 pH, and synthesized Cu(x)Ni(1-
x)WO4 was washed and then annealed.
Abstracts 94
For preparation of photovoltaic cells, a paste was made by combining the
sample with polyethylene glycol (PEG) and acetic acid, and a counter electrode
was prepared using platinum ink. Iodine dye was injected and the electrode was
sealed. Our results showed an initial power conversion efficiency (PCE) for
NiWO4 of 0.15%, which increased dramatically to 0.86% with a 9% doping
level of copper. More work is being done to fine tune the synthesis and
preparation of electrodes to increase our PCE yield.
88. Vibrational Sum Frequency spectra of low concentrations of surfactant
show large interference effects in the in the CH stretching region which
suggests that acquiring a wide spectral range is necessary for accurate data
analysis
Mark R. Watry, [email protected], Braden Felliger,
[email protected]. Department of Chemistry and Physics,
Franciscan University of Steubenville, Steubenville, Ohio, United States
Vibrational Sum Frequency spectra of sub-monolayer coverages of N-acylated
(lauroyl) L-phenylalanine show strong interferences between the CH stretching
modes at the air/water interface. This result suggests that one should acquire a
wide spectrum when investigating surfaces that produce low signals so that the
interferences in the peaks can be fit properly.
89. Vibrational Sum Frequency intensities from terminal methyl groups are
significantly different in compact monolayers of long chain N-acylated
(stearoyl) amino acids due to amino acid head-group effects on chain
ordering
Mark R. Watry, [email protected], Joshua Fera,
[email protected]. Department of Chemistry and Physics,
Franciscan University of Steubenville, Steubenville, Ohio, United States
Vibrational Sum Frequency spectra of various N-acylated (stearoyl) L-amino
acids show different intensities in the terminal methyl group stretching modes
for different monolayers at the air/water interface. One could expect the chains
to be well ordered in a compact monolayer and that the signals would be the
same or very similar. These results suggest that the amino acid head group has
an effect on the orientation of the entire acyl chain.
90. Iron-catalyzed selective oxyfunctionalization of C-H bonds in amines
Curren Mbofana, [email protected], Eugene Chong, James Lawniczak,
Melanie S. Sanford. Department of Chemistry, University of Michigan, Ann
Arbor, Michigan, United States
Amines are found in numerous biologically active compounds. As such,
methods for the selective functionalization of CH bonds in these scaffolds are
highly desirable as they have the potential to streamline synthetic routes to
and/or enable late stage functionalization of these molecules. Under oxidizing
Abstracts 95
conditions, amines exhibit diverse reactivity with most of the transformations
occurring on or adjacent to the amine nitrogen. The electronic preference for
reactivity at C-H bonds proximal to the nitrogen makes attempts for distal
functionalization quite challenging. A regioselective iron-catalyzed oxidation of
aliphatic amines at distal benzylic C-H bonds under acidic conditions was
achieved. The synthetic utility of this method was demonstrated by targeting the
synthesis and derivatization of a variety of bioactive molecules.
91. Model compounds for class III dioxygenase iron-nitrosyl {FeNO}7
adducts
Ferman A. Chavez, [email protected]. Oakland Univ Chem Dept, Rochester
Hills, Michigan, United States
Class III dioxygenases, contains His3 iron(II) binding sites in contrast to Class I
and II sites possessing 2His-1-Carboxylate metal binding sites. The lack of a
carboxylate group renders the iron site more Lewis acidic altering the
mechanism for dioxygenase reactivity. Enzymes containing His3 metal binding
sites include gentisate 1,2-dioxygenases (GDO), salicylate 1,2-dioxygenase
(SDO), 3-hydroxyanthranilate 3,4-dioxygenases (HAD), 1-hydroxy-2-
naphthoate dioxygenase (HNDO), and cysteine dioxygenase (CDO) [1]. These
enzymes belong to the cupin superfamily characterized by two highly
conservative sequence motifs of G(X)5HXH(X)3,4E(X)6G and
G(X)5PXG(X)2H(X)3N [2]. Nitric oxide has been used to study ferrous active
sites since they are spectroscopically silent and do not exhibit low energy
absorption bands. Although many nonheme enzymes form stable Fe-NO
complexes, a number of them are known to react reversibly with formation of
paramagnetic nitrosyl-iron centers which according to the Enemark and Feltham
notation are of the {FeNO}7 type [3]. In our efforts to synthesize models that
reproduce the reversibility of iron-nitrosyl formation, we have synthesized
[Fe(T1Et4iPrIP)(OTf)2] (T1Et4iPrIP = tris(1-ethyl-4-isopropyl-imidazolyl)
phosphine) which reversibly binds nitric oxide to afford
[Fe(T1Et4iPrIP)(NO)(THF)-(OTf)](OTf) (1), the first example of a 6-coordinate
{FeNO}7 S = 3/2 complex containing a linear Fe-N-O group and exhibiting the
highest (NO) for compounds in this class (1831 cm-1). DFT studies reveal an
enhanced degree of electron transfer from the *(NO) to the iron d orbitals
accounting for the large stretching frequency. Reaction of 1 with 2 equiv water
affords [Fe(T1Et4iPrIP)(NO)(H2O)](OTf)2 (2) which is more electron rich and
has a lower n(NO) (1791 cm-1).
Abstracts 96

92. Temporal separation of catalytic activities: a new way to design tandem

reactions
Le Li, [email protected]. Sun Yat-Sen University, Columbus, Ohio, United
States
During the studies of ruthenium-catalyzed reductive functionalization of
terminal alkynes, we found that these catalytic reactions exhibited a unique
kinetic behaviour that two different catalytic activities were separated in time
domain. Therefore, we named it as temporal separation of catalytic activies.
Currently, our research focus on designing novel tandem reactions based on this
unprecedented phenomenon.
93. Iridium-catalyzed dehydrogenative coupling of ethylene to form 1,3-
butadiene
Yang Gao2, [email protected], Alan S. Goldman1. (1) Rutgers Univ,
Piscataway, New Jersey, United States (2) Chemistry, Rutgers, the State
University of New Jersey, Piscataway, New Jersey, United States
Formation of 1,3-dibutadiene directly from ethylene typically includes two
steps, dimerization of ethylene first and followed by dehydrogenation of the
butenes obtained, which usually requires high temperature and different catalyst
for each step. Herein, we report that 1,3-butadiene can be obtained under mild
reaction condition by using (Phebox)Ir(2-C2H4)2 as the only catalyst. For
example, 60 catalyst turnovers were achieved after 24 h under 8 atm C2H4 at 120
C. Experimental data support a mechanism involving an iridium
metallacyclopentane complex, which was characterized by NMR spectroscopy
during the reaction.
94. Towards improved catalyst designs: probing the deactivation of a cobalt
catalyst for water reduction
Habib Baydoun, [email protected], Shivnath Mazumder, H.
Bernhard Schlegel, Claudio N. Verani. Chemistry, Wayne State Univeristy,
Detroit, Michigan, United States
Hydrogen gas is a highly promising fuel that can be obtained from the water
splitting reaction. This overall reaction can be divided into two half reactions,
namely water oxidation and water reduction. Current methods of performing
Abstracts 97
water splitting require the use of expensive and rare metals. This requirement
places severe restrictions on the wide-spread application of hydrogen-based
technologies. Herein, we present the results obtained for the water reduction
catalyst [CoIII(L1)(pyrr)2]PF6 (1), where (L1)2- is a bis-amido pyridine ligand and
pyrr is pyrrolidine, is investigated. Complex 1 has an overpotential of 0.54 V
and has an observed turnover frequency 23/min. However, 1 was only
catalytically active for a relatively short time. With the aim of designing more
robust catalysts we investigated the deactivation mechanism
of 1 by performing a detailed structural and electronic study. Evidence from X-
ray crystallography and UV-VIS-NIR spectroscopy suggests that the metal-
reduced [CoI(L1)] species is in tautomeric equilibrium with the ligand-reduced
[CoII(L1)] species. Only [CoI(L1)] favors formation of a CoIII-H hydride
relevant for catalysis, while the [CoII(L1)]K leads to ligand protonation.
Structural distortions of the latter seem responsible for catalyst deactivation.
95. Electrochemical CO2 reduction by polymer-encapsulated co-based
molecular electrocatalysts
Charles C. McCrory, [email protected]. Chemistry, University of Michigan,
Ann Arbor, Michigan, United States
Designing new, electrocatalytic systems for the selective of CO2 to single
products remains a critical challenge in electrochemical CO2 conversion. In
biological systems, fast catalytic acitivty and high product selectivity are
achieved by carefully controlling both the ligands coordinating an active metal
site and the environment surrounding it. In our work, we have explored the
influence of the electrocatalyst environment surrounding molecular systems for
selective CO2 reduction. In particular, we have investigated the influence of a
catalyst's primary, secondary, and outer coordination sphere on it's activity for
CO2 to single products by coordinating Co-based macrocyclic metal complexes
within coordinating polymers with different functional moeities.
96. Subcellular optogenetics: the search light for hidden treasures
Ajith Karunarathne, [email protected], Dinesh Kankanamge,
Praneeth Siripurapu, Kasun Ratnayake, Kanishka Senarath. Chemistry and
Biochemistry, University of Toledo, Toledo, Ohio, United States
In cellular signaling Timing is everything. Temporal control of signaling in
spatially segregated domains of a cell is further challenging and governs
polarized cell behaviors, such as cell migration and neurite outgrowth. The
majority of such cell behaviors is controlled by G protein coupled receptors
(GPCRs) and their signaling is implicated in numerous pathological conditions
including cancer and heart disease. Classical signaling control methods usually
disrupt cells, only provide static information and irreversibly perturb the
molecular networks. While these methods afford information on genetic
contributions, they provide little to no spatial or temporal control. The rise of
Abstracts 98
optogenetics, primarily based on light-sensitive ion channels from the rhodopsin
family photoreceptors provided the answer to the temporal aspect of the
problem. However, the spatial control of GPCR signaling in single cells has not
been realized. We achieved the precise spatial and temporal control of GPCR
signaling and simultaneous visualization of molecular and cellular responses at
the single cell level by engineering optogenetic systems using non-rhodopsin
opsins, which are color-light sensing GPCRs. We also manipulate phototropin
and cryptochrome based optical triggers to gain optical control of a variety of
cell signaling processes and they provide varying levels of spatial and temporal
control at the single level. These optogenetics actuators allow us to unveil
intricate and subtle molecular processes that modulate cell signaling networks
and behaviors, which are otherwise difficult to decipher.

97. Towards systematic (high throughput) quantum chemical studies of

microbial and animal rhodopsins
Massimo Olivucci1,2, [email protected], Federico Melaccio1, Alessio Valentini1,
Maria Del Carmen Marin1. (1) Univ Siena Dept of Chem, Siena, Italy (2)
Department of Chemistry , Bowling Green State University, Bowling Green,
Ohio, United States
Biologists are intensively using computational methods for investigating
molecular-level diversity within protein families. However, these studies are
often limited to the alignment of protein sequences, which do not provide direct
information on structural or functional similarities. When focusing on the
rhodopsin family, this has the consequence that the mechanistic diversity of
certain processes, such as those regulating the absorption wavelength or the
photoisomerization timescale, remains unexplored. In this lecture, we report on
a prototype protocol for the fast construction and automation of relatively simple
but congruous sets of quantum chemistry-based models of rhodopsins, suitable
for the investigation of trends in spectroscopic and photochemical properties. [1]
By constructing models of evolutionarily distant and close rhodopsins [1,2] we
provide computational evidence that, in spite of high sequence diversities and
distinct double-bond selectivities, the retinal chromophore photoisomerization
invariably occurs via different implementations of the same space-saving
mechanism first proposed by Warshel. We also provide evidence that the
observed diversity in excited state lifetime, which spans a 50-500 fs range, may
be associated to the presence of an electronic near-degeneracy between the first
two electronically excited states of the chromophore. [3] We argue that this
Abstracts 99
factor contributes, in general, to make the excited state lifetime of animal
rhodopsin shorter (i.e. in a 100 fs timescale) and, therefore, react faster.

98. Broadband 2DES studies of excited-state dynamics of the orange

carotenoid protein
Warren F. Beck, [email protected]. Department of Chemistry, Michigan
State University, East Lansing, Michigan, United States
Broadband two-dimensional electronic spectroscopy (2DES) affords an
unprecedented opportunity to follow the formation and decay of dark
intermediate states that are produced following optical excitation of carotenoids
in solution and when bound to proteins. We have applied 2DES for the first time
to study the light-induced dynamics associated with photoactivation of the
orange carotenoid protein (OCP), which performs nonphotochemical quenching
(NPQ) and singlet O2 quenching mechanisms in cyanobacteria. This talk will
discuss the first 2DES spectra from OCPO, the dark NPQ-inactive form of the
protein. The bound 3'-hydroxyechinenone carotenoid undergoes fast
nonradiative dynamics involving the formation of intramolecular charge transfer
(ICT) character due to large-amplitude torsional motions of the conjugated
polyene backbone following optical preparation of the S2 (11Bu+) state.
99. Achieving surface sensitivity in XUV spectrosocpy: Understanding
electron dynamics in metal oxide catalysts showing high selectivity for CO2
reduction
L. Robert Baker, [email protected]. University of California, Berkeley,
Columbus, Ohio, United States
The ability to probe electron dynamics with surface sensitivity on the ultrafast
time scale is critical for understanding processes such as charge separation,
interfacial charge transfer, and carrier trapping that mediate efficiency in
catalytic and energy conversion materials. Extreme ultraviolet (XUV)
spectroscopy is a powerful tool for probing electronic structure and charge
carrier dynamics because of its elemental-, oxidation-, coordination-, and
electronic spin-state sensitivity. To extend the benefits of this technique for
investigating charge carrier dynamics at surfaces, we have developed near
Abstracts 100
grazing-angle XUV reflection-absorption (RA) spectroscopy. Using this
technique we are investigating the ultrafast surface carrier dynamics in a series
of CO2 reduction and water oxidation metal oxide catalysts. In particular, we
have recently demonstrated that CuFeO2 is a selective catalyst for photo-
electrochemical CO2, converting CO2 to acetate with 80% Faradaic efficiency at
0.4 V bias vs. Ag/AgCl during visible light illumination. However, the role of
electronic structure and charge carrier dynamics in mediating catalytic
selectivity has not been well understood. XUV RA measurements probe the M2,3
edge of 3d transition metals, which provide oxidation and spin state resolution
with element specificity. In addition to chemical state specificity, these
measurements are also surface sensitive, and by independently simulating the
contributions of the real and imaginary components of the complex refractive
index, we can differentiate between surface and sub-surface contributions to the
excited state spectrum. These results allow us to observe the ultrafast dynamics
of exciton formation, surface localization, self-trapping (i.e. polaron formation),
and interfacial charge separation in a range of catalytically active metal oxides.
100. Polymer analysis applications of thermo fisher scientific picospin NMR
spectrometers
Daniel Frasco, [email protected]. Thermo Fisher Scientific, Columbus,
Ohio, United States
Nuclear magnetic resonance (NMR) spectroscopy has proven to be an
invaluable analytical tool for polymer analysis by elucidating molecular
structure, studying reaction dynamics, monitoring reaction progress, and
gauging product purity. When analyzing polymers using high-field NMR
spectrometers, resonance signals often coalesce as broad peaks due to poor
molecular rotation and the marginally different chemical environments the
polymer repeating units are situated in. To that end, low-field NMR such as the
Thermo Scientific picoSpin 80 NMR spectrometer readily lends itself as a
low-cost alternative to high-field instruments with significant savings on both
instrument procurement and upkeep, while still generating similar information to
what would be obtained from a high-field instrument. In this work, a picoSpin
NMR spectrometer was used to obtain a variety of critical polymer data from a
diverse group of applications. Information about polymer structure was
accomplished through the molecular weight determination of poly(ethylene
glycol) (PEG) acetyl triarm and compositional analysis of a polyol. The
picoSpin was also used to qualitatively and quantitatively monitor the
polymerization of t-butyl acrylate with a polystyrene reagent by identifying and
integrating the resonance signals associated with the t-butyl acrylate monomer.
Finally, the picoSpin was used determine the quality of cosmetic product
samples by quantitatively determining the percent of polydimethylsiloxane
present in the sample.
CERM 101. Supramolecular-inspired strategies for directing group-
mediated synthetic methodology
Abstracts 101
Michael Young, [email protected]. Chemistry & Biochemistry, University of
Toledo, Toledo, Ohio, United States
Directing groups are frequently required for site-selective C-H activation, as
well as regioselective and asymmetric functionalization of alkenes. A challenge
in the field is that many endogenous functional groups, such as amines, esters,
and amides, require additional synthetic steps to append and remove stronger or
chelating directing functionality, which adds significant cost and time to these
synthetic strategies. Our group is focused on using supramolecular strategies,
such as hydrogen bonding and dynamic covalent chemistry, to facilitate
directing-group mediated organometallic chemistry. The ultimate goal of our
work is to generate more sustainable methodology that makes use of simple
functionality and catalytic or recyclable directing groups that can be directly
applied in situ for the functionalization of both simple and complex feedstocks.
CERM 102. Synthesis of Oligo-(3,5-dithio--D-glucopyranosides) as -
(13)-glucan mimetics
Xiaoxiao Liao, [email protected]. chemistry, wayne state university,
Detroit, Michigan, United States
The -(13)-glucans are natural products well-known as immunostimulating
agent. Its common resources are Fugi, Seaweeds and Lichen. Biological study
reveals a hydrophobic interaction between the glucan and the lectin domains
of CR3 and Dectin-1. Here we synthesized Oligo-(3,5-dithio--D-gluco-
pyranosides) as -(13)-glucan mimetics. Replacement of pyranose ring
oxygen and glycosidic bond oxygen with more lipophilic sulfur will largely
increase the hydrophobicity of -(13)-glucan. This modification will largely
improve the binding affinity to receptors, making it possible to use short
mimetics instead of long polysaccharide as immunostimulating agent.

CERM 103. Synthesis of multifunctional fluoresceins by enzyme-catalyzed

Michael Addition
Gayatri Shrikhande2, [email protected], Sanghamitra Sen2, Judit E.
Puskas1. (1) ChemicalBiomolecular Engineering, The University of Akron,
Abstracts 102
Akron, Ohio, United States (2) Chemical & Biomolecular Engineering, The
University of Akron, Ohio, Akron, Ohio, United States
Tetrafunctional flouresceins were synthesized by very efficient Michael
additions catalyzed by Candida antarctica lipase B (CALB). First fluorescein
diacrylate (FL-DA) was prepared using a modified method. Subsequently
tetraethylacetate- and tetraallyl-fluoresceins were synthesized with the
corresponding functional secondary amines. The structure of the products was
confirmed using 13C and 1H-NMR. High resolution Mass Spectrometry
demonstrated the formation of very pure products without any additional
purification such as column chromatography. These multifunctional fluoresceins
are good candidates for the synthesis of imaging agents for a wide variety of
application.
CERM 104. The synthesis of highly stable peptide and carbohydrate
mimics: Applications to anti-cancer and targeting autoimmune diseases
John F. Trant, [email protected]. Chemistry and Biochemistry,
University of Windsor, LaSalle, Ontario, Canada
Peptide and carbohydrate chemists have historically worked separately from
both each other and the main community of organic chemists; this is apparent
from the different protecting groups used by the three groups of researchers and
the limited inroads that novel reactivity has made into the bioorganic fields,
although these barriers have finally started to dissolve in recent decades. As the
importance of the interplay between these two classes of biomolecules is
becoming increasingly clear, new methods for the synthesis of complex
glycoconjugates and peptides is of greater interest; however, a major challenge
that has limited pharmaceutical interest in these bioorganic molecules remains:
the poor biostability of carbohydrates and peptides in vivo. The rapid turnover of
these molecules is essential for their biological relevance, but it also makes them
unattractive drug targets. The Trant Group, recently established at Windsor, is
focused on the synthesis of synthetic mimics of these bioorganic targets for
applications in anti-cancer immunotherapy, autoimmune disease treatment, and
biomaterials. This presentation will present some of our early results, arising
from our combined arms approach of using computationally-aided rational
design with novel peptide architectures and synthetic chemistry. The discussion
will include the design of novel peptides for the treatment of multiple sclerosis;
the synthesis of acetal-free disaccharide analogues of the TF antigen for anti-
cancer applications; and the role of hyper-multivalency in biomedical research.
Abstracts 103
CERM 105. The synthesis of biostable acetal-free TF antigens
Seyed Iraj Sadraei, [email protected], Advait Desai, Greg Yousif, John F.
Trant. Chemistry and Biochemistry, University of Windsor, LaSalle, Ontario,
Canada
In recent decades, the central role of carbohydrates in biology has become more
widely acknowledged. Carbohydrate mediated interactions drive many
biological processes, including bacterial and viral infection (notably HIV and
influenza), immunogenic responses, and cancer pathogenesis/metastasis. These
conditions could be probed and/or treated using carbohydrate vaccines, enzyme
inhibitors and anti-tumour compounds. However, a key drawback to the
realization of this potential is the inherent low in vivo half-lives of
glycoconjugates due to the enzymatically labile glycosidic bond. The TF antigen
is a particularly interesting target as it is significantly overexpressed by many
different cancer strains including stomach, pancreas, lung, and breast; however,
it is never found in healthy cells. If the immune system could be trained to target
this molecule, then the immune system could be used to help cure cancer. This
project aims to remove the unstable acetal functionality in carbohydrates by
replacing the exocyclic or endocyclic anomeric oxygen with a methylene (C-
glycoside or carbasugar respectively) to make new acetal-free analogues of the
TF antigen for biological evaluation. Removing the labile functionality should
result in greatly enhanced lifetime, and bioavailability relative to the native
system with no likely loss in recognition specificity. This presentation will
discuss the importance of acetal-free carbohydrates, and our progress towards
the synthesis of these promising molecules.

CERM 106. IONiC/VIPEr: A brief history of time

Sheila R. Smith2, [email protected], Joanne L. Stewart1. (1) Dept of Chem,
Hope College, Holland, Michigan, United States (2) Dept of Nat Sci, University
of Michigan, Dearborn, Michigan, United States
In this introductory talk, by members of the Leadership Council of IONiC (the
Interactive Online Network of Inorganic Chemists), we will present the nuts and
bolts of the IONiC VIPEr platform in a brief introduction to the materials
Abstracts 104
available on the NSF funded Inorganic Chemistry website. We will present both
the curricular and the social aspects of the site and of the group.

107. Teaching nanomaterials to undergraduate students using VIPER

Meng Zhou, [email protected]. Department of Natural Sciences, Lawrence
Technological University, Southfield, Michigan, United States
Our recent implementation of course modules from VIPER (Virtual Inorganic
Pedagogical Electronic Resource) will be discussed. The course materials were
adopted to teach 1) solid state structure and electrochemistry in General
Chemistry I, offered to first-year science and engineering students, and 2) 1-D
nanomaterials in an undergraduate nanomaterials course for upperclassmen.
108. Crowdsourcing the development of an inorganic and computational
chemistry course using VIPEr resources
Joanne L. Stewart, [email protected]. Dept of Chem, Hope College, Holland,
Michigan, United States
VIPEr, the Virtual Inorganic Pedagogical Electronic Resource, has grown to
contain a bewildering array of outstanding teaching materials. How do we select
and adapt them for our teaching? An advanced undergraduate chemistry course
that integrates group theory, computational chemistry, and student-research
projects will be described. The course provides a case study on how to
crowdsource a course by using resources from various web-based collections
including VIPEr. These resources support active learning, visualization, and the
integration of the chemical literature with learning. The impact of the course on
students understanding of molecular orbital theory was tested by comparing
their learning gains to students in an introductory inorganic chemistry course
where molecular orbital theory was first introduced.
109. Using and adapting VIPEr learning objects at Albion College
Vanessa P. McCaffrey, [email protected]. Dept of Chemistry, Albion
College, Albion, Michigan, United States
The first topics covered in the Advanced Inorganic class at Albion College are
atomic structure, orbitals and bonding. These concepts were first covered in the
general chemistry curriculum, but are integral to a grounded understanding of
inorganic chemistry. After a brief review, significant time is spent on a deeper
exploration of some of the nuances that will better resonate with students now
that they are later in their academic career. For example, when discussing
electronic configurations in general chemistry, the exceptions encountered in
Abstracts 105
the first transition series are often glossed over, with hand-waving arguments
used to explain the configurations observed. This presentation will describe the
use of a Slaters Rule VIPEr Learning Object and its modifications that
effectively conveys these subtleties to undergraduate chemistry majors. Other
Learning Objects that have proven effective will also be described.
110. Using opening and closing questions to increase long-term retention of
inorganic chemistry
David E. Benson, [email protected]. Chemistry & Biochemistry, Calvin
College, Grand Rapids, Michigan, United States
A series of questions were generated for the start and end of a lecture period in
sophomore- and senior-level undergraduate inorganic chemistry courses. These
questions were focused on retrieval and assessment of students understanding of
material from previous courses or earlier in the semester. This knowledge recall
was also intended to interleave and connect previous concepts with the concepts
discussed in the lecture. Furthermore, the act of writing a response to the
opening and closing questions, for no point value, forced students to explain
background concepts before and after the material is discussed during the lecture
period. Concept explanation, presumably helps students form models for these
new concepts properly assembled with background concepts. These questions,
along with homework questions focused these concepts, was preliminarily found
to increase classroom performance of mid-level students. Additional sampling
and question development are necessary to draw significant conclusions,
however, this is one small tweak that can be made to improve concept retention
in inorganic chemistry. Example questions and responses will be discussed.
111. Using the primary literature in the undergraduate inorganic
classroom: showcasing the products of the NSF TUES funded IONiC
VIPEr workshops
Sheila R. Smith, [email protected]. Dept of Nat Sci, University of Michigan,
Dearborn, Michigan, United States
In this presentation, we will showcase some of the numerous Learning Objects
(LO), collaboratively developed at NSF TUES supported workshops over the
past five years. These LOs are designed to be manageable pieces of curricula
focused on specific student centered learning goals. Each comes with
implementation notes, assessment data,and where applicable, handouts and keys.
Active learning made easy-er.
Abstracts 106

112. Manipulating redox chemistry at the bottom of the periodic table:

insights into mechanisms and catalysis
Suzanne C. Bart, [email protected]. Department of Chemistry, Purdue
University, West Lafayette, Indiana, United States
Before catalytic chemistry can be developed for new metals, such as those in the
F block, there needs to be an underlying understanding of the available redox
chemistry and operative mechanisms for these metals . Redox-active ligands
have been demonstrated to mediate multi-electron chemistry on a variety of
transition metals and main group elements, promoting useful bond forming and
small activation chemistry. Our group has been exploring such frameworks for
the elements in the f-block, in hopes to extend this methodology to generate
elusive targets and observe new chemistry. Herein, we present our latest
findings on the synthesis and unique electronic structures, as well as how we
have been able to use these ligands to observe new redox processes for these
typically redox-restricted elements. These unusual species have interesting
chemical properties, and their study gives molecular insight into organometallic
chemistry and small molecule activation. Our complete study combining
characterization by spectroscopic, structural, and computational methods will be
presented, as well as a discussion of the role of the redox-active ligands in the
observed chemistry.
113. Divalent europium in visible-light-promoted photoredox catalysis
Michael E. Cross, Tyler C. Jenks, Matthew D. Bailey, Matthew J. Allen,
[email protected]. Department of Chemistry, Wayne State University,
Detroit, Michigan, United States
We present our studies focused on the use of a Eu(II)-containing complex as a
precatalyst for photoredox catalysis. The system to be presented uses low-
energy visible light that minimizes potential side reactions that can occur with
UV light. The studies described here are focused on establishing the boundries
of usefulness of the system and on elucidating the mechanism of catalysis. As
the first example, to the best of our knowledge, of a divalent lanthanide being
used for visible-light-promoted carbon-carbon bond-forming catalysis, we
expect this system to be of interest to synthetic chemists.
Abstracts 107
114. Xanthene-bridged bimetallics for cooperative activation of small
molecules and catalysis
Stanislav Groysman2, [email protected], Thilini Hollingsworth3,
Richard L. Lord1, Ryan Hollingsworth3. (1) Department of Chemistry, Grand
Valley State University, Allendale, Michigan, United States (2) Chemistry,
Wayne State University, Detroit, Michigan, United States
Our group is investigating cooperative bimetallic reactivity of homo- and
heterodinuclear complexes in the activation of small molecules and
homogeneous catalysis. We have recently synthesized new dinucleating ligands
bearing two identical or two different chelating units linked by a xanthene
bridge. In this presentation, syntheses and structures of new homo- and
heterobimetallic complexes will be described, and their reactivity will be
reported.
115. Assessing the impact of hydrothermal process parameters on the
bandgap energy and crystalline phases of titanium dioxide (TiO2)
Tao Peng1, [email protected], Srimanta Ray2, Jerald A. Lalman1,
Farzaneh Arefi-Khonsari3. (1) Department of Civil and Environmental
Engineering, University of Windsor, Windsor, Ontario, Canada (2) Department
of Chemical Engineering, National Institute of Technology Agartala, Tripura,
India (3) Department of Chemical Engineering / Laboratoire Interfaces et
Systemes Electrochimiques, Universit Pierre et Marie Curie, Paris, France
Among the various available methods for synthesis of nanostructured TiO2,
hydrothermal synthesis is a promising and well developed technique. The
current work is focused on examining the impact of synthesis temperature, alkali
concentration and mass of TiO2 on the properties of the nanostructure in
hydrothermal batch synthesis. The results showed that crystal phases varied with
change in synthesis parameter settings. The change in bandgap energy was
closely associated with the crystalline phases of TiO2. Decrease in the bandgap
energy was linked with lower alkali concentration and higher mass of TiO2. The
anatase crystalline phase was predominant at lower temperature (120oC)
conditions, whereas, brookite was the dominant phase at higher temperature
condition. The results showed that TiO2 with mixed phases had a lower bandgap
energy and higher photocatalytic activity. The impact of the parameters on the
bandgap is shown in the contour plots (Figure 1). The main effects and
optimality plots indicate the highest bandgap energy of 3.3 eV was recorded for
10M alkali concentration, 150oC treatment temperature with 3 g of TiO2
(Figures 2 and 3). Interaction between the variables is shown in Figure 4. The
novelty of the work is utilizing a systematic approach to examine the impact of
hydrothermal process parameters on the TiO2 bandgap energy.
Abstracts 108

116. Surface-enhanced Raman investigation of a plasmon-catalyzed

reaction on Ag nanoparticle surfaces
Matthew A. Young, [email protected]. Department of Chemistry, Hillsdale
College, Hillsdale, Michigan, United States
Plasmonic nanoparticles can be used to drive photochemical reactions of
adsorbed molecules. An example that has generated a lot of activity in the recent
literature is the photoreduction of 4-nitrobenzenethiol (4-NBT) to 4-
aminobenzenethiol (4-ABT) via plasmonically produced hot electrons. Surface-
enhanced Raman spectroscopy (SERS) can be used to monitor the progress of
the reaction of a self-assembled monolayer (SAM) of 4-NBT on Ag
nanostructures because the spectra generated by 4-NBT and 4-ABT are distinct.
The sensitivity of SERS allows the reaction to be monitored on the time scale of
1 second. In order to characterize this reaction, we have investigated the effect
of Ag nanostructure morphology on the relationship between the SERS intensity
of adsorbed molecules and the rate of the photoreduction reaction. We find that
for Ag nanoparticles (NPs) produced via the reduction of silver nitrate by
sodium citrate, the rate of the reaction is faster if the Ag NPs are aggregated
using NaCl prior to immobilizing them on glass for use as a SERS substrate.
However, we find that there is no clear correlation between the SERS intensity
and the photoreduction rate. For a different type of Ag nanostructure, Ag-coated
silica beads, we find a positive correlation between the SERS intensity and the
photoreduction rate. We have also used atomic layer deposition (ALD) of an
alumina spacer layer between the Ag nanostructures and the 4-NBT SAM in
order to probe the distance dependence of the plasmon driven reaction. We find
that the photoreduction reaction rate decreases as the thickness of the insulated
alumina layer increases. Finally, we measured the rate of this reaction with 532
Abstracts 109
nm and 785 nm laser excitation. We find that the reaction takes place at both
excitation wavelengths, but it is much more efficient at 532 nm.
117. Synthesis, stabilization and characterizations of Co3O4 nanoparticles
Meng Zhou1,2, [email protected], Scott Folkman2, Matthew Nicki2, Richard
Finke2. (1) Department of Natural Sciences, Lawrence Technological
University, Southfield, Michigan, United States (2) Department of Chemistry,
Colorado State University, Fort Collins, Colorado, United States
Co3O4 nanoparticles have broad applications. They have been used as battery
electrodes, supercapacitors, and superparamagnetic materials. In addition, they
are catalysts for electrochemical water splitting and Fischer-Tropsch chemistry.
I will present our recent studies on the synthesis, stabilization and
characterizations of Co3O4 nanoparticles that are made in an alcohol solvent.
118. Optogenetic activation of RhoA polarizes membrane trafficking and
drives immune cell migration from the rear
Patrick O'Neill1, [email protected], Xenia Meshik1, Jean Castillo-Badillo1,
Vani Kalyanaraman1, N Gautam1,2. (1) Anesthesiology, Washington University
School of Medicine, Saint Louis, Missouri, United States (2) Genetics,
Washington University School of Medicine, St. Louis, Missouri, United States
Although lamellipodia at the leading edge are widely thought to control cell
motility and directionality, there is evidence that in immune cells undergoing
amoeboid migration, the bulk of traction forces are at the cell rear. However,
approaches that rely on overexpression of mutant proteins or RNA knockdown
have not been able to identify signaling events at the cell rear to determine their
contributions to migration directly. To overcome this challenge, we used an
optogenetic approach to acutely control endogenous RhoA activity at the
subcellular level. We found that RhoA triggers persistent cell migration in the
opposite direction that is more rapid compared to GPCR or Rac/Cdc42 driven
migration. The migration is Rac-independent without prominent lamellipodia or
actin polymerization at the leading edge. I will present these results and show
additionally, that this migration is mediated by RhoA triggered polarized
membrane trafficking.
119. Single cell imaging reveals Ca2+ induced feedback activation of PLC
isoforms enhancing the Gq mediated PIP2 hydrolysis
Kasun Ratnayake, [email protected], John L. Payton,
Ajith Karunarathne. Chemistry and Biochemistry, University of Toledo, Toledo,
Ohio, United States
Phosphatidylinositol (4,5) bisphosphate (PIP2) is an important signaling
molecule involved in cellular signaling pathways, primarily by GPCR
activation, that leads to important aspects in cell physiology. In Gq mediated cell
signaling, downstream effector, phospholipase C (PLC) is required to induce
Abstracts 110
hydrolysis of PIP2 to inositol 1,4,5 triphosphate (IP3) and diacylglycerol (DAG)
to amplify and transduce the signals to the cell interior. The PLC has several
isoforms which are implicated in different PIP2 hydrolysis functionality under
different conditions. For example, PLC is mainly activated by heterotrimeric
G-proteins, and . Several PLC isoforms are activated differently based on
the type of G-protein subunit they interact. PLC is another major effector for
PIP2 hydrolysis mainly activated by calcium ions due to its unique calcium
binding domain at the active site. In cells, the calcium signaling arises due to
series of molecular events such as PIP2 hydrolysis, IP3 generation and binding
to IP3 receptors in endoplasmic reticulum that leads to opening of calcium ion
channels. Though it has been suggested that released calcium can activate
different PLC isoforms, the molecular basis of the process is not clear. By
employing live cell imaging, optogenetics and computational modeling of the
phosphoinositide signaling pathway, we show that Gq mediated PLC activation
and subsequent PIP2 hydrolysis are enhanced by calcium induced feedback
activation of PLC isoforms.
120. Retinal: Light switch or broken molecule?
John L. Payton, [email protected], Kasun Ratnayake, Nicole Weis, Ajith
Karunarathne. Chemistry and Biochemistry, University of Toledo, Toledo, Ohio,
United States
G-protein-coupled receptors (GPCRs) are one of the most diverse receptors in
eukaryotes that govern neurons activity, cell motility, heart regulation, and the
vision cycle. The isomerization of 11-cis-retinal in its bound state (i.e., retinal
protonated Schiff base, RPSB) is a key small molecule involved in activation of
light sensing GPCRs, opsins, which allows humans to perceive light. As the
photochemistry and photophysics of RPSB is being extensively studied, the
solution phase excited state surface of retinal is relatively unexplored in
comparison. Our recent studies suggest there is a significant difference in
photochemistry of retinal outside of the protein environment and the
photoproducts potential cytotoxicity. Presented will be our mechanistic studies
of the solvated retinal via a quantum mechanical study of the proposed
pathways. Our experimental HLPC study will analytically quantify the photo-
efficiency and photoproducts. The studies yield clues to the role of free retinals
photoproducts found in living cells.
121. P-type dye-sensitized solar cells and fuels: challenges and opportunities
Yiying Wu, [email protected]. Ohio State Univ, Columbus, Ohio,
United States
Dye-sensitization of a p-type semiconductor achieves charge separation through
photo-driven hole injection from the excited sensitizer to the p-type
semiconductor. It forms a photocathode that can be used for building tandem
dye-sensitized solar cells. It also provides an attractive platform for artificial
photosynthesis. I will talk about the materials design of molecular sensitizers
Abstracts 111
and nanostructured semiconductors to achieve the control of directional charge
transfer. I will also discuss our progress in molecular catalysts for hydrogen
generation and their use in p-type dye-sensitized photocatalytic water reduction.
Finally, I will present a hybrid device named solar battery, which possesses
the dual functions of solar energy harvesting and in situ storage, which is
desirable in the utilization of solar energy due to the intermittent nature of
sunlight.
122. Relative stability of hexacarbonyldicobalt propargylic carbocations:
effect of remote substitution
Brent St. Onge, [email protected], Page Penner, Jenna Skieneh, Scott
Adams, Victor Pouget, James R. Green. Chemistry and Biochemistry, University
of Windsor, Windsor, Ontario, Canada
The effect of remote substituents on the relative rates of Nicholas reactions has
been studied. Lewis acid- mediated competitive reactions of 1 (R = H, Ph, vinyl,
n-Bu) with multiple nucleophiles show that the presence of classically
conjugating substituents slow the reaction relative to alkyl groups, and give an
overall reaction rate order of n-Bu > vinyl Ph > H. With the assistance of DFT
calculations, the results will be discussed in term of conjugative and inductive
cation stabilization effects.

123. Kinetic, and computational study of retro-DielsAlder reactions of -

furfuryl alcohol/maleimide constructs as tunable end-caps for self-
immolative materials
Nazanin A. Taimoory, [email protected], Rose Fayoumi, Sarah Nasri, John F
Trant. Chemistry and Biochemistry, University of Windsor, Lasalle, Ontario,
Canada
Self-immolative polymers are materials that depolymerize monomer-by-
monomer when exposed to a defined stimulus (i.e. temperature, reduction, O2,
UV radiation, pH etc). Among all the responsive stimuli, heat shows significant
potential as a targeted stimulus. The Gillies group recently reported the
preparation of a thermally sensitive end-cap based on the Diels-Alder (DA)
cycloadduct of -furfuryl alcohol and substituted maleimides. At elevated
temperatures, the retro-Diels-Alder (rDA) reaction occurs breaking up the
cycloadduct. To increase the versatility of this approach, we have prepared a
number of different constructs by varying the HOMO/LUMO gap of the diene
and dienophile to provide tunable end-caps appropriate for a broad range of
temperatures. These particular reactions have never been reported in the
literature, and consequently we are carrying out a detailed experimental
Abstracts 112
(stereoisomeric ratio, kinetic study) study on both the forward and retro DA
reactions. Several of these materials also show an interesting tendency to form
significant amounts of the exo cycloadduct, despite the exceedingly favourable
secondary orbital overlap. To explore the origin of this endo/exo selectivity, and
to determine the precise mechanism of addition and reversion (concerted,
asynchronous and/or stepwise zwitterionic), a detailed potential energy surface
(PES) analysis is being investigated using advanced quantum chemical
calculations. The presentation will discuss the results of these studies, and their
implications for biomedically relevant self-immolative nanoparticles.

124. Progress toward the synthesis of daphniphyllum alkaloids

Alberto M. Lopez, [email protected]. Wayne State University, Detroit,
Michigan, United States
The promising biological activity and structural complexity of the
Daphniphyllum alkaloids has made this family of natural products a popular
target in the synthetic community. Retrosynthetic analysis of target compounds
suggests that these compounds can be accessed from a common tricyclic
intermediate, which, in turn is produced from a tandem N-centered radical
(NCR) cyclization. Little precedent for this specific type of reactivity was given
at the onset of this research, but it was successfully applied to the construction
of the core of our target molecules. N-containing substrates for our synthesis
were produced in our lab and applied to the total synthesis. The current status of
our syntheses is described as well as future plans for the completion of
daphniyunnine C.
125. Nontoxic flame retardants from biosources
Bob A. Howell, [email protected]. Central Michigan Univ, Mount
Pleasant, Michigan, United States
Abstracts 113
Traditionally, flame retardants for polymeric materials have been organohalogen
compounds generated from petroleum sources. These compounds are highly
effective and readily available but are stable in the environment, tend to
bioaccumulate and may pose a risk to human health. Consequently, they are
coming under increasing regulatory pressure worldwide and several have been
withdrawn from the market. Organophosphorus compounds derived from
renewable biosources (plant oils, fisheries byproducts, food waste, starch) offer
attractive alternatives. They are generally environmentally-friendly and are
independent of fluctuations in petrochemical markets.
126. Strategies for controlled disulfide formation to access neuroactive
conotoxins
Hasina Saraha, [email protected]. Chemistry, Wayne State University, Milan,
Michigan, United States
Disulfide bond linkages are important features in peptide folding and have been
observed in many biologically interesting peptides. Conotoxins are a large group
of peptides that typically exhibit disulfide linkages in their structure. They have
shown activity toward different ion channels and therefore, present potential as
pharmaceutical drugs for the treatment of neurological disorders. The aim of this
research is to establish a reliable method for consistently folding disulfide rich
proteins, including conotoxins, into their native structure. In order to work
toward this goal, a series of cysteine protecting groups are designed and
synthesized. The use of palladium-labile protecting groups was investigated for
the systematic deprotection of cysteine and followed by in situ oxidation. It is
expected that the impact of this research will advance both the field of
neuroscience and peptide chemistry.
127. Phosphorus derivatives of methyl 3,5-dihydroxybenzoate
Eric Ostrander, [email protected]. Chemistry and Biochemistry, Central
Michigan University, Mount Pleasant, Michigan, United States
For most applications, polymeric materials must be flame retardaed. Aromatic
compounds containing a high level of phosphorus are effective flame retardants.
A variety of phosphorus compounds derived from methyl-3,5-
dihydroxybenzoate have been prepared, fully characterized using spectroscopic
and thermal methods, and examined for flame-retardant effects in DGEBA
epoxy resin.
128. Acid neutralizing capacity of over-the-counter antacids and natural
supplements
Hannah Johns1,3, [email protected], Christian Catanescu1, Myung
Han2. (1) Biological and Physical Sciences, Columbus State Community Colle,
Columbus, Ohio, United States (2) Biological and Physical Sciences, Columbus
State Community College, Columbus, Ohio, United States (3) BSPS Program,
Ohio State University, Columbus, Ohio, United States
Abstracts 114
Assessing pros and cons of herbal medicines and weighing in safety concern
between synthetic drugs and naturally occurring ones are an important mission
of chemistry education to enlighten the public in the context of social and ethical
issues that medicinal chemistry often generates. In this regard acid neutralizing
capacity (ANC) of the over-the-counter (OTC) antacids (Tums, Alka Seltzer,
and Milk of Magnesia) was compared with that of the natural supplements
(Cardamom, Ginger, Chamomile, Mint, Licorice, Green Tea, and St. Johns
Wort). First order estimates show that Milk of Magnesia was the most effective
for its ANC. The natural supplements consistently exhibited less efficacy in their
ANC than the OTC antacids. The ANC of Tums (calcium carbonate) was less
effective than Milk of Magnesia. The need for adults to supplement dietary
calcium to prevent osteoporosis may give an edge for the popularity of Tums
over the magnesium containing OTC. A better control of each sample in terms
of size and texture would have rendered improved estimates for ANC, as an
integration of the buffer capacity (b) over a pH range observed, following the
formula, ANC = b d pH.
129. Digital Scholarship: Instructional videos for introductory chemistry
laboratory class
Vivian C. Ezeh, [email protected]. Department of Chemistry &
Biochemistry, Kenyon College, Gambier, Ohio, United States
With a goal to increase the transfer of key laboratory skills to upper level and
research laboratories, a series of instructional videos and digital tools was
desgined and produced. This report is a presentation of a colloborative efforts by
students that are teaching assistants for introductory chemistry and a digital
librarian to produce these digital resources for upcoming students
130. Environmental chemistry course content at Thiel College
Anna M. Reinsel, [email protected]. Thiel College, Greenville, Pennsylvania,
United States
Thiel College offers an environmental chemistry course required by all
environmental science and environmental chemistry majors. This course is
generally taken in their junior or senior year. In it we explore the relationships
between the fundamental principles of chemistry and the environment. The
course provides an introduction to the chemistry of the lithosphere, hydrosphere
and atmosphere. The details of the environmental chemistry course at Thiel
College will be presented.
131. Screencasts and simulations in the learning of solubility
Brianna L. Martinez3, [email protected], Ryan D. Sweeder3, Deborah G.
Herrington2, Jessica R. Vandenplas1. (2) Department of Chemistry, Grand
Valley State University, Allendale, Michigan, United States (3) Lyman Briggs
College, Michigan State University, East Lansing, Michigan, United States
Abstracts 115
As educators increasingly use the growing collection of online resources such as
animations and simulations in chemistry courses, it is becoming even more
important to understand the strengths and weaknesses of such resources on
students understanding of core chemistry concepts. In this study, a guided
simulation activity and screencast were developed, based around the simulation
designed by the PhET Interactive Simulations project, to help students from
general chemistry classes learn about the dissolution of ionic and covalent
compounds in water. Student understanding of the concepts were assessed
through pre- and posttests, answers to assignment questions, and near-transfer
follow-up questions. The simulation assignment involved students answering
guiding questions as they engaged with the simulation; the screencast consisted
of analogous instructions and guiding questions that the students answered as
they watched an expert manipulate the same simulation. Our initial study
indicated that students who engaged with the screencast gained a better
understanding of the dissolving process, more specifically, the particulate level
interactions with water. The initial study also suggested, based on eye tracking
analysis, that there were significant differences in the way the different
treatment groups used the electronic resources. Following the initial study, the
pre- and posttests were revised and the study repeated again. After revisions,
evidence of learning gains were demonstrated along with significant differences
between the two different treatment groups.
132. Screencasts and simulations in the learning of atomic interactions
Alec D. Shrode4, [email protected], Ryan D. Sweeder3, Deborah G.
Herrington2, Jessica R. Vandenplas1. (2) Department of Chemistry, Grand
Valley State University, Allendale, Michigan, United States (3) Lyman Briggs
College, Michigan State University, East Lansing, Michigan, United States (4)
Lyman Briggs College, Michigan State University, East Lansing, Michigan,
United States
Online learning resources, including simulations and illustrations, are becoming
more widespread in education. Their use is especially prevalent in chemistry
classes, where they can be used to visualize interactions at the molecular level.
To understand their use and impact on students, both a guided simulation
activity and a screencast were developed to be used with a PhET simulation.
These were developed for outside-of-class use, and was the students first
college exposure to the topic. The guided activity led students through a series
of questions while interacting with the simulation directly; the screencast was an
expert narrated short video demonstrating usage of the simulation which led
students to answer the same questions. General chemistry students at two
universities were split into two groups and each was given one of the learning
treatments. Pre-tests and follow-up questions were analyzed to identify learning
gains made by the students. An initial study indicated that neither treatment was
particularly effective nor were there notable differences between the two
treatments. After revisions, both treatments lead to student learning gains, but
Abstracts 116
few differences exist between them. This result highlights the importance of
revising and fine-tuning online learning materials to make them be the most
effective. The results of this study will help the efforts of educators in all
disciplines be able to use online resources and materials to their full potential.
133. Exploration of emission spectroscopy and absorption
spectrophotometry in introductory chemistry
Paul S. Szalay2, [email protected], Lois A. Zook-Gerdau1, Eric J.
Schurter2, Deepamali V. Perera2. (1) Muskingum University, New Concord,
Ohio, United States (2) Chemistry, Muskingum University, New Concord, Ohio,
United States
Emission spectroscopy experiments in larger enrollment introductory chemistry
courses have often been carried out utilizing handheld spectrographs or
spectroscopes. Technological advances have made devices like emission
spectrometers and absorption spectrophotometers more portable and affordable
thus providing expanded course incorporation opportunities.
The experiment presented here was developed for and implemented in offerings
of General Chemistry I. It is composed of six sections that in different ways
explore emission spectroscopy and the complementary technique of absorption
spectrophotometry. Parts I and II offer an introduction to the technique of
emission spectroscopy as an instrumental method of analysis. Parts III through
V emphasize applications of that technique including sample preparation and
analysis considerations. Part VI further characterizes emission spectroscopy via
comparison with absorption spectrophotometry.
All of the experiment sections could be carried out as independent exercises as
laboratory time allows or to emphasize a particular content point of instructor
interest. The learning objectives for the experiment are included along with
detailed overviews of the sections. These include a brief summary of the
procedure along with expected student learning outcomes. Typical student
experimental results and performance observations are also included.
134. Investigation of the structural features necessary for a positive THC
assay
Bonnie Martinez, [email protected], Yuxi Zhou, Casey Lassiter. Chemistry,
Marietta College, Marietta, Ohio, United States
The microplate assay for cannabinoids employs a polyclonal antibody that is
specific for identifying delta-9-tetrahydrocannabinol in urine, blood and saliva
samples. Testing of the microplate with small organic molecues at low
concentrations in place of biolgical smaples shows that the assay is positive
when key structural characteristics are present. Our group has been investigating
the assay with dihydroxyphenols and quinones and seen indication of the cross-
reactivity in the assay. The results from these studies will be presented.
Abstracts 117
135. Organic chemistry educational resources: Community of organic
chemistry educators
Vincent M. Maloney, [email protected]. Purdue Univ at Ft Wayne, Fort
Wayne, Indiana, United States
OrganicERs network of practitioners is created for the dissemination of teaching
materials for organic chemistry instruction at the college level and promoting
evidence-based active-learning pedagogies. The website (www.organicers.org)
allows college-level instructors with verified identity to network and to access,
share and develop curriculum materials developed by peer instructors. In
addition to online activity, members of the leadership board and previous
participants facilitate professional development workshops, symposia, outreach
and curriculum development activities.
136. Philatelic fantasies: Enriching the teaching of chemistry by using
illustrations in postage stamps
Pasquale Di Raddo, [email protected]. Chemistry, Ferris State, Big
Rapids, Michigan, United States
The hobby of philately, or stamp collecting, seems to have diminished in
popularity among the young. Yet it may offer a colorful learning tool for our
students in the teaching of chemistry. Postage stamps chosen from around the
world will be presented that illustrate the beauty and the history of chemistry
and chemists who have made it great.
137. How to report results of ACS preferential elections
Wendell L. Dilling, [email protected]. Chemistry and Biochemistry, Central
Michigan University, Midland, Michigan, United States
The results of the recent ACS election (C&EN, Nov. 7, 2016, p 7) reported vote
counts for elections of President-Elect, Directors of Districts II and IV, and one
of the Directors-at-Large (Schulz). The vote count/s for the election of the other
Director-at-Large (Phillips) was not reported. This election of Directors-at-
Large is one that involves the recently enacted preferential voting procedure
because two candidates were elected. The vote counts for the three rounds of
vote counting that are shown in C&EN show how Schulz was elected by a
majority of the voters, but the following steps showing how Phillips was elected
are not shown. The next step in the vote counting should involve adding the
second-choice votes on the ballots where Schulz was the first-choice to the first-
choices for the three remaining candidates. Subsequent steps, if needed, would
show how one of the three remaining candidates (Phillips) achieved a majority
of the votes. Problems with reporting the results of other ACS preferential
elections are shown and discussed.
138. Synthesis of a series of long-chain aliphatic ligands for complexation
and water remediation
Abstracts 118
Justin Pothoof, [email protected], Grace Nguyen, Michele Bhagwagar,
Sara Makki, Mark A. Benvenuto. Department of Chemistry and Biochemistry,
University of Detroit Mercy, Detroit, Michigan, United States
A series of aliphatic ligands has been produced, comprised of an aliphatic multi-
amine (2 - 6 nitrogen atoms) and two long chain aliphatic aldehydes (8 - 12
carbon atoms). Schiffs Base condensations at ambient temperature are used to
produce the ligands, and metal complexation trials have been performed using a
variety of metal salts. Synthetic routes and ligand characterizations will be
presented.
139. Deposition of phosphonium phosphate ionic liquids onto iron
substrates: Formation of iron polyphosphate films
David W. Johnson, [email protected], Joseph Hancock. Department of
Mechanical Engineering, University of Dayton, Dayton, Ohio, United States
The reactions of several oil soluble phosphonium phosphate ionic liquids with
iron substrates were investigated to determine their suitability as extreme
pressure lubricant additives. Extreme pressure additives must form a lubricious
film on the surface of the bearing and the film is a polyphosphate for the
phosphate ester additives. The ionic liquids, dissolved in ester based lubricant
base stocks were found to react with metal surfaces to form a phosphorus
containing film. Scanning electron microscopy showed the deposition of a layer
on the surface and x-ray fluorescence showed that the layer contained
phosphorus. The thickness of the layer depends on the reaction time and
teemperature, The SEM of an iron disk before and after reaction are shown in
Figure 1. Infrared analysis of the film demonstrated the formation of poly
phosphate chains on the material. Decomposition products from the ionic liquid
were identified by GC-MS.
Abstracts 119
140. Aerobic oxidation of bulky dipyrromethanes to dipyrromethenes
Fatemeh Saleh, [email protected],
Christopher Gianopoulos, Mark Mason. Chemistry, University of Toledo,
Toledo, Ohio, United States
Dipyrromethenes are important precursors to porphyrins and BODIPY dyes.
Deprotonated dipyrromethenes coordinate to main group and transition metals to
yield new complexes that are potential catalysts for a variety of polymerization
reactions and organic transformations. Synthesizing symmetrical
dipyrromethenes requires oxidation of dipyrromethanes with an oxidant such as
2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), which is expensive,
relatively toxic, and requires more separation steps and the use of solvents.
Based on a serendipitous observation of aerobic oxidation of a dipyrromethane
during a melting point observation, we investigated the oxidation of molten
bulky, aryl-substituted dipyrromethanes with air to yield dipyrromethenes. The
resulting compounds have been characterized by NMR spectroscopy and High-
Resolution Mass Spectrometry. Furthermore, the extent of dipyrromethane
conversion to dipyrromethene through air oxidation has been measured by NMR
spectroscopy. Details of synthesis and characterization, along with the air
oxidation of each dipyrromethane to the corresponding dipyrromethene, will be
discussed.
141. Characterization of a luminescent EuII-containing azacryptate
Tyler Jenks, [email protected], Matthew D. Bailey, Matthew J. Allen.
Department of Chemistry, Wayne State University, Detroit, Michigan, United
States
Luminescence has a wide array of uses including lighting, imaging, low-
concentration detection, and labelling, making it a desirable property to
understand and control. Luminescent materials can be plagued by issues such as
low quantum yield, air instability, and solvent selectivity. To this end, we have
synthesized a new, luminescent EuII-containing azacryptate. The crystal
structure of the new complex shows an 8-coordinate environment with six
methyl groups that create a cage-like structure, minimizing the interaction of
solvent molecules with the metal ion. The encapsulation of EuII is likely
responsible for the relatively high air- and solvent-stability of the complex
compared to other EuII-containing azacryptates. The structure is consistent with
the observed intense visible-light luminescence that persists in solution.
142. Bifunctional electrocatalytic water splitting under neutral conditions
by a mononuclear cobalt(II) molecular catalyst
Krista M. Kulesa3, [email protected], Diego Padilha1, Marciela
Scarpellini2, Claudio N. Verani3. (1) UFRJ, Rio de Janeiro, Brazil (2) Inorganic
Chemistry, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil (3)
Chemistry, Wayne State University, Farmington Hills, Michigan, United States
Abstracts 120
Splitting water into H2 and O2 offers great promise for renewable fuel sources.
Current methods for splitting water involve expensive and rare metals,
restricting widespread use. However, Earth-abundant transition metals provide
more economic and accessible alternatives. Here, the electrocatalyst
[CoII(L)Cl]PF6 (L = bisimidazole aminopyridyl framework) is investigated for
both reduction and oxidation of water in a wide range of pHs. The
electrocatalyst [CoII(L)Cl]PF6 can produce both H2 and O2 at neutral pH. Most
notable electrocatalytic O2 production occurs at pH 11.5, with an overpotential
of 0.38 V. Using 2.6 mol/L of [CoII(L)Cl]PF6 catalyst, a turnover number of
240 with a Faradaic efficiency of 90% was obtained following 3h of bulk
electrolysis. Post-catalysis solution and surface analysis demonstrates prolonged
molecular stability in the medium, and minimal decomposition after catalysis.
Scanning electron microscopy tentatively indicates a molecular mechanism in
play, with supportive DFT calculations underway.

a) 3h CPE/ pH 8, phosphate/FTO, Ag/AgCl, Pt coil. TON = 174 at 98%

Faradaic efficiency (Inset: [CoII(L)Cl]+); b) Before/after 3h CPE UV-Vis of
[CoII(L)Cl]+. Profiles with similar intensities after CPE indicate no significant
loss of catalyst (inset: CVs of working electrodes subjected to prolonged
solution exposure and CPE/ pH 8, 0.1 M phosphate)
143. Investigating the reduction of a liposomal EuIII-tetraglycinate complex
Alex Zuhl, [email protected], Matthew J. Allen. Department of Chemistry,
Wayne State University, Detroit, Michigan, United States
EuII and EuIII exhibit drastically different magnetic properties. Investigating this
redox couple is of paramount importance to Eu-based applications. Recently a
tetraglycinate complex of EuIII has been shown to be reduced from the trivalent
state to the divalent state in the presence of metallic Zn. Metallic Zn
nanoparticles form protective ZnO coatings that dissolve in aqueous solutions
below pH 7.4. Here, the pH-dependent reduction of EuIII-containing
tetraglycinate complex using ZnO-coated metallic Zn nanoparticles is reported
as a possible responsive contrast enhancing system for magnetic resonance
imaging.
Abstracts 121
144. Synthesis, structural characterization, and room temperature
photoluminescence of scheelite phosphors
Sameera Perera, [email protected], Federico A. Rabuffetti.
Chemistry, Wayne State University, Detroit, Michigan, United States
Owing to their compositional flexibility, amenability to crystal-chemical
thinking, and photoluminescent properties, double molybdates and tungstates of
formula ARE(MO4)2 (A = Li, Na, K; RE = rare-earth; M = Mo, W) and
scheelite-type structure are being intensively investigated as functional materials
in areas such as solid-state lighting, solid-state lasers, and optical thermometry.
Our group is interested in understanding compositional control of energy-
transfer processes in this family of materials, and on expanding the toolbox of
synthetic and spectroscopic techniques that enable such an understanding.
In this work, the NIR-to-NIR and NIR-to-visible light upconversion properties
of polycrystalline NaYb(MoO4)2 and NaYb(WO4)2 are investigated using a
combination of steady-state and time-dependent spectrofluorometry, elemental
analysis, and Rietveld analysis of synchrotron X-ray total scattering data. Both
metalates exhibit strong NIR and bright blue luminescence emission under 973
nm laser excitation. NIR emission results from Yb-sensitized Tm3+ ions, which
are found to be present at the trace level (~1 ppm) in both NaYb(MoO4)2 and
NaYb(WO4)2. In the case of the blue emission, power-dependence and time-
dependent spectrofluorometric studies favor cooperative luminescence of Yb-Yb
dimers, rather than three-photon energy-transfer upconversion. No signs of
structural modulation are observed, suggesting that clustering of Yb3+ ions to
yield dimers occurs on a local scale. The formation of Yb-Yb dimers that can
interact cooperatively under NIR excitation is feasible considering the Na+/Yb3+
substitutional disorder in NaYb(MoO4)2 and NaYb(WO4)2 and the shortest
distance between two adjacent Yb3+ ions.
145. NIR-to-visible upconversion luminescence in Er:Yb:SrFX nanocrystals
Kumuduni T. Dissanayake, [email protected], Federico A. Rabuffetti.
Chemistry, Wayne Sate University, Detroit, Michigan, United States
Upconverting nanocrystals, which sequentially absorb multiple near-infrared
(NIR) photons and emit higher-energy NIR or visible photons, offer several
potential advantages over molecular downconversion fluorophores traditionally
employed in biophotonic applications such as optical imaging and sensing.
Despite significant advances over the past decade, the search for new
upconverting materials featuring higher efficiency and full-spectrum color
tunability continues in order to further accelerate their implementation as optical
probes.
In this work, the ability of semiconducting SrFBr nanocrystals codoped with ~1
mol. % of Er and Yb to perform infrared-to-visible light upconversion is
demonstrated. The average and local crystal structures conform to those
Abstracts 122
expected on the basis of the P4/nmm tetragonal space-group. Excitation of Yb at
980 nm results in two-photon upconversion and green-yellow luminescence
from Er, highlighting the potential of alkaline-earth fluorohalides as hosts for
Yb-Er sensitizer-activator pairs. The excited states of the Er activator in the
SrFBr host exhibit a biexponential decay with lifetimes in the 0.1-0.2 and 0.3-
0.4 ms ranges. These findings prompt for an expansion of the library of
upconverting nanocrystals into novel materials containing heavy halide anions
(i.e., Cl-, Br-, and I-).
146. Visible light induced photocatalytic hydrogen evolution using a CdS-
Ni2P hybrid aerogel system
Da Li1, [email protected], Stephanie Brock2. (1) Chemistry, WAYNE
STATE UNIVERSITY, Detroit, Michigan, United States (2) Wayne State
University, Ferndale, Michigan, United States
It is essential to construct clean energy production and storage systems due to
the increasing global energy demand and the climate change impact of CO2 from
energy production. Evolution of hydrogen from water utilizing visible light
induced catalysis is a promising and appealing pathway. CdS nanoparticles are
good visible light absorbers but not efficient hydrogen evolution catalysts, while
Ni2P is shown to be an outstanding electrocatalyst for the hydrogen evolution
reaction (HER). Using sol-gel approach to integrate of CdS nanoparticles with
Ni2P nanoparticles is expected to yield a hybrid system in which photo
generated carriers on CdS are transferred to catalytically active Ni2P sites. In this
work, the assembly of preformed nanoparticles to make Ni2P-CdS hybrid
aerogels will be described and photocatalytic HER data will be presented. The
performance of these novel architectures will be compared to CdS-Ni2P
nanoparticles and CdS aerogels and the role of interparticle coupling, porosity
and surface passivation on catalytic efficiency will be discussed.

147. Crystallochemical study of monometallic A(CF3COO)2.nH2O (A = Mg,

Ca, Sr, Ba, Mn) as a tool for the synthesis of MgMn and CaMn bimetallic
trifluoroacetates
Abstracts 123
Bajjala D. Dhanapala, [email protected], Hashini N. Munasinghe , Federico
A. Rabuffetti. Chemistry, Wayne State University, Detroit, Michigan, United
States
Bimetallic trifluoroacetates have gained much attention as single-source
precursors for the synthesis of fluoride materials. However, the design of
bimetallic compounds through a crystallochemical study of their monometallic
counterparts remains limited. Here, we demonstrate that a systematic study of
the crystal-chemistry of A(CF3COO)2.nH2O (A = Mg, Ca, Sr, Ba, Mn), enables
the synthesis of MgMn and CaMn bimetallic trifluoroacetates. Chemical and
structural analyses include using variable-temperature single-crystal X-ray
diffraction, powder X-ray diffraction, and thermal analysis. Single-crystal and
powder X-ray diffraction analyses of Mnx(CF3COO)2x.4H2O reveal the existence
of both monomeric (x = 1) and trimeric (x = 3) structures. Mn(CF3COO)2.4H2O
is isostructural to Mg(CF3COO)2.4H2O, and Mn3(CF3COO)6.4H2O is
isostructural to Ca3(CF3COO)6.4H2O. These relationships enable the synthesis
of bimetallic Mg0.45Mn0.55(CF3COO)2.4H2O and Ca1.71Mn1.28(CF3COO)6.4H2O,
their crystal structures are also reported.
148. Synthesis and characterization of a stable high-valent cobalt carbene
and the reduced carbene complexes and the reactivity toward carbene
transfer reactions
Amanda Grass, [email protected], Stanislav Groysman. Chemistry,
Room 123, Wayne State University, Detroit, Michigan, United States
The formally CoIV carbene Co(OR)2(=CPh2) is formed upon the reaction of
diphenyldiazomethane with the cobalt bis(alkoxide) precursor Co(OR)2(THF)2.
Structural, spectroscopic, and theoretical studies demonstrate that
Co(OR)2(=CPh2) has significant high-valent CoIV=CPh2 character with non-
negligible spin density on the carbene moiety. Subsequent reduction of the high-
valent carbene with the one-electron reductant decamethylcobaltacene gives
[Co(OR)2(=CPh2)]-[CoCp*2]+. The reduced carbene features an elongated Co-
Ccarbene bond (from 1.773 to 1.923 ) and Co-O bond (from 1.765 to 1.852
), suggesting a metal-centered reduction. Theoretical studies will help to gain
insight into the oxidation state of the reduced carbene. The present data suggests
the unique ability of this novel carbene to be interconverted between Schrock
and Fisher type carbenes upon simple redox reactions. Our reactivity studies will
focus on the carbene transfer reactivity of both systems to form new C-C, C-N,
and C-O bonds.
149. Synthesis of new divalent zinc complexes and their reactivity toward
ring-opening polymerization reactions
Thilini Hollingsworth1, [email protected], Stanislav Groysman2. (1) Chemistry,
Wayne State University, Canton, Michigan, United States (2) Chemistry, Room
123, Wayne State University, Detroit, Michigan, United States
Abstracts 124
Over the years, metal-salen complexes have been investigated due to their
applications in the field of homogeneous catalysis, including polymerization of
lactides and epoxides, as well as copolymerization of epoxides with CO2.
Recently, polylactides (PLAs) and polycarbonates (PCs) have attracted interest
as a more biodegradable, renewable, and biocompatible substance than
conventional oil based materials. PLAs are prepared via ring-opening
polymerization of cyclic ester lactides, while PCs can be prepared via ring-
opening copolymerization of epoxides with CO2. Tacticity heavily influences
the nature of these polymers, thus stereoselective synthesis of PC and PLA
microstructures is of great importance. Recent studies have highlighted a
number of divalent, trivalent and tetravalent Lewis-acidic metal complexes,
featuring salen ligands, with the ability to polymerize lactides and/or
copolymerize epoxides with CO2 in a controlled and stereoselective manner.
These studies have shown that both metal and ligand structure influence
polymerization behavior. In this study, we specifically focus on the design and
synthesis of divalent zinc complexes, supported by a Schiff base ligand, with the
goal of performing selective ring-opening polymerization reactions.
150. Average and local crystal structure of -Er:Yb:NaYF4 upconverting
nanocrystals probed by X-ray total scattering
Dinesh K. Amarasinghe, [email protected], Sameera Perera,
[email protected], Federico A. Rabuffetti, [email protected].
Chemistry, Wayne State University, Detroit, Michigan, United States
Nanocrystalline-NaYF4 is widely employed as a host for upconverting
lanthanide ions. The efficient photoluminescence of lanthanide-doped
-NaYF4 is directly dependent on the crystal structure, which remains a subject
of debate. A detailed crystallographic investigation of the structure of -
Er:Yb:NaYF4 nanocrystals (~22 nm) was performed using Rietveld and pair
distribution function (PDF) analyses of synchrotron
X-ray total scattering data. The crystal structure was modeled using three
different space-groups: P-62m, P-6, and P63/m. Rietveld and PDF analyses
show that the average and local crystal structures are best modeled by the P63/m
space-group. This space-group yields physically meaningful structural
parameters with a minimum number of internal degrees of freedom.
151. Water splitting using cobalt-based amidopyridine ligands
Habib Baydoun, [email protected], Shivnath Mazumder, Jordyn
Burdick, H. Bernhard Schlegel, Claudio N. Verani. Chemistry, Wayne State
Univeristy, Detroit, Michigan, United States
As part of an ongoing search for alternative energy sources, splitting water into
oxygen and hydrogen has emerged as a source of alternative energy. To this end
we have been interested in developing catalysts capable of performing water
reduction and water oxidation. In this poster a variety of catalytic platforms
Abstracts 125
based on a bis amido pyridine framework are presented. A new monomeric
cobalt complex in an amido pyridine ligand ([CoIII(L1)(pyrr)2]PF6) is used and
found to have an onset overpotential of 0.54 V and an observed TOF of 23 per
minute. The catalytic decomposition pathway was explored with the aim of
designing more stable catalysts.
Following the initial catalytic design, we designed a modified catalyst in which
the bis amido pyridine framework is extended over a phenylene tetramine bridge
[(CoIII)2L2(pyrr)4](PF6)2. The bimetallic cobalt complex showed a significant
improvement in activity in which onset overpotential decreased to 0.45 V and
the TOF was found to be 55 5 min-1 per cobalt center. To the best of our
knowledge this is one of the first examples where a dimeric catalyst is more
active than its monomeric counterpart.
Finally, we demonstrate that we can drive water oxidation by the modification
of conductive carbon-based supports with a hydrophobic octadecyloxy
substituted catalyst in an N2N2 environment [CoIII(LOC18H37)(pyrr)2]ClO4. This
modification allowed us to prepare a catalyst that can be recycled.
152. Synthesis and characterization of new europium cryptates
Matthew Bailey1, [email protected], Guo-Xia Jin3, Matthew J. Allen2.
(1) Department of Chemistry, Wayne State University, Detroit, Michigan,
United States (3) College of Chemistry, Chemical Engineering and Materials
Science, Shandong Normal University, Jinan, China
Herein we present the synthesis of two new cryptands and their complexes with
EuI2 and EuCl2. The first new cryptand is a tribenzo derivative of an all
nitrogenous cryptand based on the 2.2.2-cryptand backbone. The splitting of the
cryptand into two sets of nitrogen donors with different Lewis basicity facilitates
a lopsided ligation and hypsochromically shifts the spectral profile in
comparison to a non-benzoated analogue. The second cryptand contains two
2.2.2-cryptand backbones joined by one tetrahydroxybenzo unit. The di-
europium complexes of this cryptand, having intermetallic distances of about 9.7
, are evaluated as contrast agents for magnetic resonance imaging.
153. Dendrimer-based MRI contrast agent for noninvasive brain tumor
imaging
Sunalee Gonawala Jayasundara Mudiyanselage, [email protected].
Henry Ford Health System, Detroit, Michigan, United States
Malignant brain tumors are among the most devastating tumors, with survival of
only one to three years after diagnosis even with the best of treatments. Invasive
biopsy is routinely utilized to assess histological type, classification, grade and
potential aggressiveness of brain cancer and also for determination of the type of
drug regimen employed for treatment. Imaging techniques include CT, PET,
ultrasound and, most importantly, MRI. Dendrimer-based T1 relaxation agents
have been used to image glioma tumor with a compromised blood brain tumor
Abstracts 126
barrier. One reservation about previous work is that the ligand motif used to
bind Gd3+ build the dendrimer-based nanostructures was DTPA, a less
thermodynamically stable linear acyclic ligand than macrocyclic chelators. In an
attempt to prepare clinical relevant MRI contrast agent for glioma imaging, we
synthesized a generation 3 (G3) dendrimer conjugated with thermodynamically
stable macrocyclic Gd-DOTA chelates. The synthesized G3-Gd-DOTA
nanoparticles were characterized using TEM and mass spectroscopic methods.
According to TEM analysis G3 nanoparticles were ~ 5 nm in size which
facilitate deeper tumor penetration across the blood brain tumor barrier. The
development of T1 relaxation based MRI probe for in vivo imaging of glioma is
unique to our laboratory.
154. Photo/electrocatalytic hydrogen generation from water by a novel
nickel-based polypyridine catalyst
Pavithra H. A. Kankanamalage3, [email protected], Shivnath
Mazumder3, Kenneth K. Kpogo2, H. Bernhard Schlegel2, Claudio N. Verani1. (1)
Wayne State Univ, Detroit, Michigan, United States (2) Chemistry, Wayne State
University, Detroit, Michigan, United States (3) Chemistry, Wayne state
Universty, Detroit, Michigan, United States
Limited fossil fuel reserves and excessive CO2 emission require an urgent search
for renewable energy sources. Dihydrogen is an ideal candidate due to its high
energy density and to the formation of water as the sole combustion product.
Nickel is considered an ideal metal for dihydrogen generation and we introduced
a new nickel-based complex [NiII(LN2Py3)(MeCN)](ClO4)2 that has been
synthesized and thoroughly characterized. This complex is active both as an
electrocatalyst, as well as a photocatalyst. The Ni complex has an onset
overpotential of 780 mV in phosphate buffer at pH 7. The Turnover number was
measured to be 1050 after 3h for electrocatalytic water reduction. A TON of
3500 was measured for photocatalytic hydrogen generation from water in
presence of fluorescein and TEA at pH 12. DFT calculations have shown that
the electrocatalytic mechanism of H2 generation involves a ligand-reduced NiIL.
intermediate that, upon addition of a proton, gives rise to a NiIIH complex thus
avoiding formation of the high energy trivalent NiIIIH species.
Abstracts 127
155. Investigation of mechanistic pathways by versatile nitrogen-rich cobalt
and dicobalt catalysts for water splitting
Kenneth K. Kpogo1, [email protected], Shivnath Mazumder1,2, Denan
Wang3, H. Bernhard Schlegel1, Adam Fiedler3, Claudio N. Verani1. (1)
Chemistry, Wayne State University, Detroit, Michigan, United States (2) Hofstra
University, Long Island, New York, United States (3) Marquette University,
Milwaukee, Wisconsin, United States
The development of water splitting catalysts that are affordable and made from
Earth-abundant transition metals is of immense scientific interest. Aiming to
develop efficient water splitting catalysts, a water-soluble [CoII-Qpy], and a
bimetallic [(bpy)CoIIL1CoII(bpy)] catalysts were prepared and characterized by
spectroscopic, spectrometric, and X-ray analysis. [CoII-Qpy] efficiently reduces
H2O to H2 at neutral pH, with a turnover frequency (TOF) of 967 H2/cat/h at an
overpotential of 0.63 V. The catalyst is efficiently versatile with sustained H2O
reduction producing H2 over 18 hours with a turnover number (TON) of 12,100
and Faradaic efficiency (%FE) of 97%. [CoII-Qpy] also efficiently oxidizes H2O
to O2 in 0.1 M borate buffer (pH 8.0), on a fluorine-doped tin oxide (FTO), with
a TOF of 64.3 mol O2 /molcat/h and a %FE of 84% with an applied potential of
1.50 VAg/AgCl. The bimetallic catalyst [(bpy)CoIIL1CoII(bpy)], efficiently reduces
H+ to H2 in MeCN in presence of 100 equiv. of HOAc with a TON of 18 and
(%FE) of 94 % after 3h at 1.6 VAg/AgCl. Experimental and DFT results show
that [(bpy)CoIIL1CoII(bpy)] undergoes two successive metal-based 1e reductions
to give the active species [CoICoI] which yields a CoIIH and releases H2 by a
cooperative 2e transfer. Post-catalytic scanning electron microscopy analysis
and spectral properties confirm molecular catalysts.

156. Optimization of the catalytic activity in cobalt-oxime complexes by

modulating ligand substituents towards water reduction
Abstracts 128
2 2
Nour El Harakeh , [email protected], Debashis Basu , Claudio N.
Verani1. (1) Wayne State Univ, Detroit, Michigan, United States (2) Wayne State
University, Detroit, Michigan, United States
The global demand for alternative energy sources is increasing while non-
renewable fossil fuel reserves are continuously decreasing. The generation of
hydrogen through proton reduction is a potential source of a clean energy.
Efforts have been made to design and synthesize catalytic complexes that could
efficiently convert water into hydrogen. Ideally, these molecular catalysts need
to be robust, functional at low overpotentials, and selective to H2 evolution. Our
efforts aim at the synthesis of cobalt-based oxime complexes for proton
reduction (2H+ + 2e- H2 ) which later can be coupled with compounds for
water oxidation to achieve water splitting. Here, four cobalt(III) oxime
complexes were synthesized and fully characterized. For all cases, the
electrocatalytic behavior was evaluated under the same experimental conditions
in order to effectively compare their catalytic activities. This will allow us to
understand how manipulating the ligand substituents can affect the catalytic
rates and the overpotentials of these catalysts.

157. Development of molecular copper catalyst based on a polypyridine

ligand framework towards electrochemical water reduction
Danushka M. Ekanayake2, [email protected], Krista M. Kulesa2,
Shivnath Mazumdar2, Kenneth K. Kpogo2, H. Bernhard Schlegel3, Claudio N.
Verani1. (1) Wayne State Univ, Detroit, Michigan, United States (2) Chemistry,
Wayne State University, Detroit, Michigan, United States
Transition metal complexes with suitable ligand frameworks can act as catalysts
for water splitting process by overcoming the activation barrier between the
water and the products. We have developed a water-soluble mononuclear copper
catalyst based on phenylenediamine-bridged pentadentate N2N3 ligand
framework aiming towards the development of efficient water reduction
catalysts. The complex showed a reversible wave at E1/2 = -460 mVFc/Fc+
attributed to the CuII/CuI couple. CuII-N2N3 complex showed turnover frequency
of 557 mol-1 h-1 with an overpotential of 780 mV and a faradaic efficiency of
87% during three hours of catalysis at pH 7 phosphate buffer at an applied
potential of -1700 mV. However, the catalytic behavior at pH 2.5 at an applied
potential of -1.4V shows an inflection in the charge vs time plot which might be
due to the pendant pyridine gets protonated and acts as a relay at acidic medium.
Abstracts 129
1
Experimental evidence for the relay mechanism was gathered by H NMR
titrations of the unmetallated ligand and in situ generated [Cu(I)L] with
trifluoroacetic acid. EPR and UV-Visible spectra were used to probe the changes
during the bulk electrolysis process. Scanning electron microscopic analysis was
performed to study the molecular nature of the catalyst. Mechanistic studies
were performed using density functional theory calculations to understand the
pathway for electrocatalytic hydrogen generation.
158. Production of a new series of ligands with potential to act as water
remediators
Benjamin Sosnowski2, Benjamin Sliwinski2, Michal Ruprecht2, Polly Fitzgerald2,
Steven P. Kosmas2, [email protected], Justin Pothoof1, Christopher
Niedek1, Mark A. Benvenuto1. (1) Department of Chemistry and Biochemistry,
University of Detroit Mercy, Detroit, Michigan, United States (2) Science,
Grosse Point North H.S., Grosse Point Woods, Michigan, United States
A series of molecules, all including tris- 2-amino-ethyleneamine (tris) has been
produced using a Schiffs base condensation and one of three long-chain,
aliphatic aldehydes. The syntheses are straightforward, and can be run in air at
ambient temperature. The ability of these molecules to complex with metal ions
makes them good candidates for water remediation. Their syntheses and
characterization will be presented.
159. Towards molecular rectification: nanoscale devices based on
Langmuir-Blodgett monolayers of asymmetric oxovanadium(iv) and
chromium(iii) complexes
A. D. K. Isuri Weeraratne2, [email protected], Claudio N. Verani1. (1)
Wayne State Univ, Detroit, Michigan, United States (2) Chemistry, Wayne State
University, Detroit, Michigan, United States
Rectifiers are devices that convert alternating current into direct current and are
necessary for information management. Molecular rectification was first
proposed by Aviram and Ratner, and can be achieved by using asymmetric
molecules that have electron donor and electron acceptor moieties with
accessible energy at the electrode|molecule|electrode junction. Our group has
successfully developed two nanoscale molecular rectifiers based on asymmetric
five-coordinate iron(III) trisphenolate and bisphenolate complexes. With an
increasing demand for molecular rectifiers we are aiming to understand the
mechanisms of rectification to reach higher current efficiency. This may be
achieved by matching the Fermi level of electrodes with the SOMO (Singly
Occupied Molecular Orbital) of the metallic ion in the surfactant. With that aim
in mind we have synthesized and characterized novel bisphenolate
chromium(III) and oxovanadium(IV) complexes to evaluate the redox,
amphiphilic properties and current voltage measurements of new devices.
Abstracts 130
160. Analysis of mineral cosmetics with a handheld X-ray fluorescence
analyzer
Sara Thomas, [email protected], Tiffany Tieu Ngo,
[email protected], Mark A. Benvenuto, Elizabeth Roberts-Kirchhoff.
Department of Chemistry and Biochemistry, University of Detroit Mercy,
Detroit, Michigan, United States
The sale and use of cosmetics is an enormous business throughout the world.
The Federal Food, Drug, and Cosmetic Act gives authority of the U.S. Food and
Drug Administration (FDA) to oversee the safety of food, drugs, and cosmetics.
The FDA does not approve cosmetic products in the same way as it monitors
food and food supplements. This study examines the components of powdered
cosmetics including foundation and eye shadows often referred to as mineral
makeup with a handheld X-ray fluorescence (XRF) analyzer to determine what
elements are present. Twenty-five cosmetic samples and standards were
evaluated by comparing the results from two instruments, the Bruker S1 Turbo
XRF analyzer and the Bruker S1 Titan XRF analyzer. In the makeup samples,
the presence of the different elements was verified by analyzing the XRF spectra
of each sample. Most samples contained titanium rubidium, and iron. Some
samples contained vanadium, cobalt, zinc, manganese. Future work will include
the analysis of other elements in the makeup samples.
161. Synthesis of a tethered bis(iminopyridine) di-nickel complex and its
divergent reactivity with monosubstituted alkynes
Ryan L. Hollingsworth2, [email protected], Stanislav Groysman3, Richard
L. Lord1. (1) Department of Chemistry, Grand Valley State University,
Allendale, Michigan, United States (2) Wayne State University, Canton,
Michigan, United States (3) Chemistry, Room 123, Wayne State University,
Detroit, Michigan, United States
Transition metal-catalyzed cyclotrimerization of alkynes provides an atom-
efficient method for the synthesis of aromatic compounds. The regioselectivity
(1,2,4- vs. 1,3,5-isomers) and chemoselectivity (cyclotrimerized products vs.
cyclotetramerized and/or oligomeric products) of these reactions are controlled
by the sterics and electronics of the transition metal complex. While many
monometallic catalysts are known, interests have shifted toward bimetallic
systems to improve upon and/or better understand regioselectivity,
chemoselectivity, and catalytic efficiency of these reactions. In this field,
bimetallic complexes incorporating late transition metals are uncommon and
general lack a stabilizing, dinucleating ligand, allowing for potential
decomposition into mononuclear species. A recently reported di-nickel system,
tethered by a rigid dinucleating ligand, served as a highly effective and selective
catalyst for terminal alkyne cyclotrimerization reactions. Our groups interest in
late-base-transition metal complexes geared toward cooperative activation of
small molecules, lead us to explore of metal-metal distance and ligand flexibility
Abstracts 131
as it pertains to cyclotrimerization reactions. Herein, we report synthesis,
structure, and cyclotrimerization reactivity of a new di-nickel system, supported
by a semi-rigid dinucleating ligand.
162. Synthesis of silicon phthalocyanine and silicon naphthalocyanine
compounds
Vance Kennedy, [email protected], Lindsey Erdmann, Mohammad
Siddihiki. Chemistry, Eastern Michigan University, Chelsea, Michigan, United
States
This research investigates the synthesis, separation, and characterization of new
Silicon Phthalocyanine (SiPc) and Silicon Naphthalocyanine (SiNc) compounds.
Different alcohol chains including heptanol, octanol, and nonanol were attached
to dihydroxysilicon or dicholrosilicon phthalocyanine and naphthalocyanine
compounds. The resulting products of the synthesis were dialkoxy silicon
phthalocyanines and napthalocyanines. The products were separated and
purified through column chromatography and characterized by UV-vis and H1
NMR spectroscopy.
163. Development of aluminophosphonate catalysts for ring-opening
polymerization of cyclic monomers
Morteza Jandaghi1, [email protected], Mark R. Mason2.
(1) Chemistry, University of Toledo, Toledo, Ohio, United States (2) MS 602
Dept of Chemistry, University of Toledo, Toledo, Ohio, United States
Ring-opening polymerization continues to receive great interest because it is
used for polymerization of a wide variety of cyclic monomers. With the
emergence of biomass-derived monomer conversion to biodegradable polymers,
ring-opening polymerization of cyclic monomers is even more highlighted. Our
group previously developed a catalyst system for polymerization of epoxides
based on reaction of an aluminum alkyl and a phosphonic acid. This catalyst is
structurally similar to Vandenbergs aluminoxane-based catalysts for epoxide
polymerizations. Presented herein are the results of continued investigation of
our catalyst system by looking into the effects of catalyst aging, presence of
water, and catalyst substituents on catalyst polymerization activity and polymer
properties. The aim of this research was to optimize the catalyst for
polymerization of epichlorohydrin to high molecular weight polyether
elastomers. The application of this catalyst system to the polymerization of other
monomers will also be mentioned briefly.
164. Promotion of the hydrogen evolution reaction using electrodeposited
nickel phosphide: Optimization of electrodeposition parameters
Samuel Jeffrey1,4, [email protected], Ruwani
Wasalathanthri1,4, Naheya Su2,4, Kai Sun3, Dean M. Giolando1,4. (1) Chemistry
and Biochemistry, The University of Toledo, Toledo, Ohio, United States (2)
Chemical Engineering, The University of Toledo, Toledo, Ohio, United States
Abstracts 132
(3) Materials Science and Engineering, The University of Michigan, Ann Arbor,
Michigan, United States (4) School of Green Chemistry and Engineering, The
University of Toledo, Toledo, Ohio, United States
A major problem facing the world in the coming years is the finite amount of
fossil fuels. A push for alternate energy sources is an answer to this problem,
and more specifically dihydrogen, which is considered a good alternate energy
carrier. The combustion of dihydrogen with dioxygen yields only water and
energy as its products. Thus, it is a clean form of generating energy. However,
currently most of the industrial generation of dihydrogen directly or indirectly
depends on fossil fuels. A different method, using solar water splitting offers a
clean alternative way of generating dihydrogen. In this research, our aim is to
use an in-situ solar device that splits water into dioxygen and dihydrogen.
Another challenge with water splitting is to find a highly active and stable
catalysts to lower the overpotential. Originally expensive, highly active
catalysts, such as platinum are considered as the best catalysts for Hydrogen
Evolution Reaction (HER). As an alternative to platinum, our research examines
electrodeposit nickel phosphide, which is found to be highly active and stable
for HER in acidic medium. Then optimizations were carried out on the
electrodeposited nickel phosphide coating using differences in deposition
current density, deposition temperature, and the phosphorus content of the
plating bath. The final goal is to design an in-situ solar device with a cost
efficient non-noble metal catalyst, in order to generate hydrogen for energy
usage.
165. Synthesis and magnetic properties of colloidal MnAsxSb1-x (x=0.1-0.9)
nanoparticles: Towards nanostructured magnetic refrigerants
Malsha A. Hettiarachchi2, [email protected], Stephanie Brock2, Ehab
Abdelhamid1, Boris Nadgorny1. (1) Department of Physics and Astronomy,
Wayne State University, Detroit, Michigan, United States (2) Department of
Chemistry, Wayne State University, Detroit, Michigan, United States
Magnetic materials with large Magneto-Caloric Effects (MCE) are recognized
as potential magnetic refrigerant (MR) materials. Bulk MnAs has been studied
as a prospective MR material owing to a large MCE associated with its First
Order Phase Transition (FOPT). However, MnAs undergoes a large thermal
hysteresis of 6 K during its magnetic transition. This large thermal hysteresis
prevents its efficient MR cycling. Further, the magnetic entropy change
associated with the FOPT of these MnAs compounds is limited to a narrow
temperature range, making the temperature control window very small. A range
of solid solutions of MnAs that can be synthesized by both cation and anion
doping, are reported to reduce the hysteresis, enabling tuning of the optimal
temperature range. Nano materials have the potential to enable the formation of
nano 3-D graded macrostructures. Therefore, the synthesis of nanomaterials of
these solid solutions are expected to greatly expand the temperature window
compared to their bulk counterparts.
Abstracts 133
In this work, we synthesized a range of target compositions of MnAsxSb1-x
(x=0.1-0.9) colloidal nanoparticles by a solution phase route. These narrow
polydispersed nanoparticles are of ca. 12-14 nm in diameter. The solid solutions
of target compositions x=0.1 to 0.8 are closely related to the MnSb phase, as
revealed by powder X-ray patterns, with a small shift towards higher 2-Theta
(degrees) with increasing As amounts. However, the solid solution phase of
target composition x=0.9 is closely related to the MnAs orthorhombic phase.
The consequences of the composition on the magnetic properties of these solid
solutions will be described and discussed in the context of materials for MCE.
166. Developing metal organic frameworks for catalysis applications
Allison M. Rabon, [email protected], Michael Young. Chemistry and
Biochemistry, University of Toledo, Toledo, Ohio, United States
Metal organic frameworks (MOFs) have potential for use in energy storage,
catalysis, and waste water treatment. Our work aims to develop new strategies to
access these applications, specifically catalysis, via a two-stage postsynthetic
method. Using 9,10 and 2,6-disubstituted anthracene derivatives, we have
worked to prepare novel frameworks in the UiO and IR MOF families, using
zirconium and zinc respectively. By incorporating the robust anthracene
fragment into these MOFs, we hope to show that postsynthetic modification of
even the more sensitive IR MOFs can be achieved using Diels-Alder chemistry.
Along the way, we have discovered many other binding modes as well,
including DMF-carboxylate adducts and 1D-coordination polymers.
167. Synthesis and characterization of new classes of metal precursors for
atomic layer deposition
Wathsala_Lakmali Iwadunna_Waduge3, [email protected], Charles
H. Winter1, Philip D. Martin2. (1) Wayne State Univ, Detroit, Michigan, United
States (2) 61 Chemistry, Wayne State University, Detroit, Michigan, United
States (3) Chemistry, Wayne State University, Detroit, Michigan, United States
Precursors for atomic layer deposition (ALD) must combine high volatility, high
thermal stability, and rapid reactivity towards the co-reagent to afford the
desired material. Herein, we describe the synthesis and characterization of a new
class of ligands L1-L5 and their corresponding nickel, cobalt, and chromium
complexes. Neutral ligands L1H-L5H were deprotonated with potassium hydride
to form the corresponding potassium salts. These potassium salts were treated
anhydrous NiCl2, CoCl2, and CrCl2 to obtain the metal complexes, which were
then purified by crystallization or sublimation. The spectral and analytical
characterization of these complexes will be presented. Many of the complexes
were characterized by X-ray crystallography. The volatility and thermal stability
of these complexes will also be described. Finally, the reactivity of these new
complexes toward reducing reagents will be overviewed.
Abstracts 134

168. Oxygen evolution reaction catalyst incorporation into fluorine-doped

tin oxide films
Derrick Barenbugge1,2, [email protected], Kelly J.
Lambright1,2, Chris Alexander3,2, Dean M. Giolando1,2. (1) Chemistry and
Biochemistry, The University of Toledo, Gibsonburg, Ohio, United States (2)
School of Green Chemistry and Engineering, University of Toledo, Toledo,
Ohio, United States (3) Department of Chemical Engineering, University of
Toledo, Toledo, Ohio, United States
Climate change, mainly brought about by the burning of fossil fuels for the
production of energy, is a pressing concern for todays society. One solution to
this concern is alternative energy from renewable sources. A possible alternative
energy is hydrogen gas produced from water electrolysis where a solar cell in
solution is used to drive the reaction. A triple junction amorphous silicon
photovoltaic (tj-a-Si PV) device has a large enough potential to drive the energy
intensive oxygen evolution reaction. The window layer of the tj-a-Si PV device
is the anode for water electrolysis and the site of the Oxygen Evolution
Reaction. The process of electrolysis corrodes the window layer of the tj-a-Si
PV device and, therefore, there is a need for a corrosion protection layer of
fluorine-doped tin oxide, which is deposited via spray pyrolysis using dibutyltin
diacetate as the tin oxide precursor. Once the anode is protected, a catalyst needs
to be incorporated to reduce the overpotential. This research focuses on the
addition of catalyst to the corrosion resistant layer on the anode using metal salts
and nanoparticles mixed into the dibutyltin diacetate precursor solution. The
addition of gold colloid, chromium (III), and cobalt (III) lowered the
overpotential and an increased response towards the Oxygen Evolution
Reaction. All films were characterized by scanning electron microscopy, powder
X-ray diffraction, cyclic voltammetry, and linear sweep voltammetry.
Sweep of what?
Abstracts 135
169. Synthesis and characterization of low symmetry subphthalocyanine
analogues
Leart Sejdarasi1, [email protected], Evan R. Trivedi2. (1) Chemistry,
Oakland University, Rochester, Michigan, United States (2) Department of
Chemistry, Oakland University, Farmington Hills, Michigan, United States
The serendipitous discovery of subphthalocyanines in 1972 established an
entirely new class of cyclic compounds that feature boron as the central atom.
These peculiar compounds were revisited more than a decade later and were
utilized in the synthesis of asymmetric phthalocyanine analogues. Admittedly,
this application is among the most popular for subphthalocyanines, but currently
they are an emerging class of standalone compounds that are suited for
numerous high technology applications. Subphthalocyanines exhibit a cone-
shaped trigonal structure that when unsubstituted, remain completely
symmetrical, but the axis of symmetry allows for, upon proper substitution, the
generation of chirality and low symmetry. Symmetrical subphthalocyanines do
not consistently provide the optimal properties for each niche application, but
focus is now on synthesis of designer low symmetry subphthalocyanines that
can be suited for any application. In addition to intrinsic chirality,
subphthalocyanines feature unique photophysical properties. Despite the robust
structural and chemical properties of subphthalocyanines, arguably the most
alluring characteristic of these compounds is that any given property is tunable.
The growing interest of subphthalocyanines stems from the synthetic point of
view to their applied physical properties. Contemporary research of these
compounds has led to my interest in developing a novel synthetic scheme that
can be used by researchers to synthesize designer subphthalocyanines that are
suited to meet the requirements of their respective fields. My unprecendented
approach utilizes bulky substituent groups on the subphthalocyanine and
exhibits low symmetry. Synthesis of these compounds has posed great difficulty,
but we report the complete synthesis and characterization of two entirely new
and exotic subphthalocyanines, nicknamed F4 SPc and F8 SPc. Compounds
have been characterized by LC/MS, 1H NMR, 19F NMR and UV/Vis
spectroscopy.
170. Low-symmetry subphthalocyanines as fluorescent probes and
precursors for low symmetry phthalocyanines
Katherine McAuliffe1, [email protected], Evan R. Trivedi2. (1) Oakland
University, Oxford, Michigan, United States (2) Department of Chemistry,
Oakland University, Farmington Hills, Michigan, United States
Phthalocyanines (Pcs) and their precursors, subphthalocyanines (SPcs) are
pyrrolic macrocycles, most commonly used for their optical properties in
applications such as photovoltaics, light emitting diodes, and fiber optic
telecommunication. Recent studies have shown that Pcs and SPcs also have
potential as cell imaging dyes. SPcs are converted into Pcs through a Kobayashi
Abstracts 136
ring expansion reaction. This has led to a shift in focus toward the development
of SPcs as reaction intermediates in a route to create highly unsymmetric Pcs.
Herein, we report low symmetry SPcs as cell imaging probes, made by cyclizing
2,3-naphthalenedicarbonitrile and tetrafluorophthalonitrile in the presence of
boron trichloride. In addition to potential as standalone fluorescent imaging
probes, these SPcs can be used as intermediates for low-symmetry Pcs. Strong
electron withdrawing groups impart stability for Kobayashi insertion reactions
and insertions with a number of isoindolines and dicyanides will be presented.
171. Redox-active silver N-heterocyclic carbene complexes: A dual
targeting anti-bacterial drug
Kotiba Malek, [email protected]. Chemistry, Wright State University,
Dayton, Ohio, United States
Bacterial resistance to current antibiotics necessitates new alternative therapeutic
drugs. Silver based drugs are promising in this realm. However, current silver-
based antibacterial drugs are limited in their bioavailability due to their rapid
release of silver ions. Recently, N-heterocyclic carbene containing silver
complexes have gained popularity due to slow release of silver ions under
biological conditions. As a result, two new potential antibacterial silver-NHC
complexes were synthesized and confirmed via analytical techniques, including
1
H and 13C NMR spectroscopy and x-ray crystallography.
172. Iron-bis(dithiolene) N-heterocyclic carbene adducts as pre-catalysts for
organocatalysis
Selvakumar Jayaraman, [email protected]. Chemistry, Wight
State University, Fairborn, Ohio, United States
The intriguing electronic and photophysical properties of transition metal
dithiolene complexes continue to remain an active research area. Donahue et al
demonstrated the reversible electrochemical release of triphenylphosphine from
five coordinated Iron bis(dithiolene)-triphenylphospine adducts. We envisioned
a similar reversible release of N-heterocyclic carbene (NHC) with Iron
bis(dithiolene)-NHC adducts would be possible under electrochemical
conditions. Since, NHCs are ubiquitous in homogeneous catalysis, particularly
in organocatalysis, a controlled reversible release is exceedingly attractive.
Herein, an electrogenerated NHC catalyzed cyclo-trimerization of
phenylisocyanate and synthesis of -butyrolactone from cinnamaldehyde is
discussed.
173. Development of N-heterocyclic carbene-gold(I) complexes for
therapeutic applications
Meredith Miles, [email protected], Kuppuswamy Arumugam. Chemistry,
Wright State University, Dayton, Ohio, United States
Abstracts 137
The tunable steric and electronic properties of N-heterocyclic carbenes (NHCs)
coupled with their -donating abilities allow for excellent coordination to
transition metal complexes. NHC-gold(I) complexes have shown promise as
cancer treatment drugs because of their ability to target thiol functional groups
found in the thioredoxin (Trx) system. Our previous work has proven that
generating reactive oxygen species (ROS) and inhibiting the Trx system
simultaneously induces apoptosis. Hence, modifying the N-substituents and
fusing the NHC-gold(I) complex with naphthoquinone further enhanced this
oxidative-stress pathway to kill the tumor cells. Three napththoquinone fused
NHC-gold(I) complexes were synthesized and confirmed structurally with 1H
and 13C NMR, UV-Vis spectroscopy, IR spectroscopy, and X-ray
crystallography. The redox properties of the complexes were confirmed with
various electrochemical techniques. Cell proliferation studies were also
performed to determine the efficacy of the complexes.
174. The state of chemical analysis at great lakes water authority
Saulius Simoliunas, [email protected]. Great Lakes Water Protection
Committee, Detroit, Michigan, United States
The atate of chemical analysis and monitoring is inadequate at Great Lakes
Water Authority, which was formed in 2016 after mediation in Detroit
bankruptcy court. The predecessor Detroit Water and Sewerage Department
transferred its management team to GLWA. As a cost saving measure, DWSD /
GLWA eliminated most chemists' jobs and gave them to operators. Thus out
through the window went Standard Methods for Water and Wastewater
Analysis. Pollution in Detroit River went up and drinking water was not fully
analyzed for toxic chlorination by products. The cost to the consumer is three
times higher than the national average. Great Lakes Water Protection Committee
was formed to address these issues to GLWA board and presented many
proposals without any reply from GLWA. The binational Great Lakes Water
Quality Agreement specifies that public will be involved in Great Lakes issues.
It is high time to return chemistry to GLWA.
175. Partitioning of pesticides between water and gasoline as a function of
ethanol content
Margarita Otero1, [email protected], Nirvan Bhattacharyya2, Brandon
Woo2, Lan Ma2, Avery Demond2. (1) Environmental Engineering, University of
Michigan, Ann Arbor, Michigan, United States (2) University of Michigan, Ann
Arbor, Michigan, United States
Negative environmental consequences of fossil fuel use and concerns about the
security of petroleum supplies have led to the implementation of policies to
increase the use of renewable energy. To date, this requirement has been met
primarily by blending conventional gasoline with ethanol in various proportions.
The coincidence of spills of gasohol and high pesticide usage in agricultural
watersheds, such as in the Midwest, raises the concern that the concentration of
Abstracts 138
regulated organochlorine pesticides in surface waters might increase. This
research aims to assess the partitioning behavior of pesticides between gasoline
and water as a function of ethanol content.
Measurements show that the aqueous solubility of organochlorine pesticides
increases by three to seven orders of magnitude in the presence of ethanol. The
relationship between the aqueous solubility of the pesticides and the ethanol
mass fraction can be described by a two-part log-linear model, with the
breakpoint occurring at an ethanol mass fraction of approximately 0.35 for the
pesticides examined. The solubility relationship is heavily influenced by
cosolvent-solvent interactions, with the breakpoint occurring due to a shift in
these interactions, and consequently in the solubilization mechanism.
The increase in the aqueous solubility of pesticides in the presence of ethanol
affects the partition coefficient, defined as the ratio of the concentration of the
compound in the organic phase to that in the aqueous phase. Results with
water/ethanol/iso-octane/dieldrin systems show that the presence of ethanol can
decrease the partition coefficient of dieldrin by over four orders of magnitude,
driven by the increasing solubility of the pesticide in the aqueous phase. The
relationship between the logarithm of the partition coefficient versus the
logarithm of the aqueous solubility of the pesticide follows a linear behavior,
with a slope of -1, suggesting that the partitioning behavior can be predicted
with a log-log model if aqueous solubility data are available.
176. A multidisciplinary assessment of the impact of acid spill accidents on
geoecosystems
Sung P. Hyun1, [email protected], Seonjin Ha1, Yoonho Lee1, Hee Sun
Moon1, Doyun Shin1, eunhee lee2, Young Soo Han1, hyun jung3, yu sik hwang3.
(1) Korea Institute of Geoscience & Mineral Resources, Daejeon, Please select,
Korea (the Republic of) (2) Korea Institute of Geoscience & Mineral Resources,
Daejeon, Korea (the Republic of) (3) Korea Institute of Toxicology, Jinju, Korea
(the Republic of)
The objective of this study was to identify and assess multiple aspects of the
impact of chemical accidents, specifically acid spills on geo-ecosystems. For
this purpose, we developed and used a multidisciplinary approach. First, we
carried out batch-type geomedia-acid reaction experiments to obtain acid
neutralizing capacity and surface acidity constants for different geomedia.
Second, we conducted column tests to investigate longer term, secondary effects
of sulfuric and hydrofluoric acid on geomedia. Third, we measured changes in
microbial communities before and after exposure to sulfuric and hydrofluoric
acid to investigate the effects of remnant acids on soil microbial ecology. Based
on the results, we suggest the gram-positive to gram-negative ratio as a
bioindicator for assessing the impact of the acids. Fourth, we designed a
visualization cell to simulate the reaction and transport of acid through
geomedia in subsurface environments. We observed clear distinction among
Abstracts 139
different geomedia in terms of the acid affected area and soil pH distribution.
Fifth, we performed ecotoxicological investigation of acid impact on geomedia.
In the controlled pH experiments, the extreme pH conditions caused by spilled
acids made the affected soils unsuitable habitat for worms and plants. We also
added the same amounts of acids to different geomedia and found that
depending on their acid neutralizing power, suitability of the geomedia as a
habitat deteriorated to different degrees. Based on the findings of this study, we
defined the vulnerability of a geo-ecosystem as the reciprocal of its acid-
neutralizing capacity against moving acid fronts to quantitatively assess the
impact of acid spills on geo-ecosystems, and to develop a prototype of a
vulnerability assessment system.
177. Understanding mechanisms underlying the rate of recovery of
mercury-contaminated lakes in Northern Michigan
Mary M. Lynam1, [email protected], Paul Drevnick2,3, Jason Demers4, J T.
Dvonch1. (1) University of Michigan Air Quality Laboratory, Ann Arbor,
Michigan, United States (2) Biological Station, University of Michigan , Ann
Arbor, Michigan, United States (3) Environmental Monitoring and Sceince
Division, Alberta Environment and Parks, Calgary, Alberta, Canada (4) Earth
and Environmental Sciences, University of Michigan, Ann Arbor, Michigan,
United States
Since the 1970s federal regulation of mercury, Hg, has resulted in considerable
declines in discharges to water bodies and emissions to the atmosphere in the
Great Lakes region of North America. Initially, reductions in mercury
concentrations in biota from the Great Lakes and smaller inland lakes were
apparent. More recently, increasing trends in mercury concentration in fish and
fish-eating birds have been reported. Research has shown that mercury
previously deposited to soils in watersheds may be mobilized and transported to
aquatic ecosystems thus attenuating recovery of mercury-contaminated lakes.
Therefore, improved understanding of the causal mechanisms driving the rate of
recovery requires knowledge of fluxes of mercury to lakes from atmospheric
deposition and watershed runoff.
To investigate this, sediment cores were collected from five inland lakes, in
Pellston, MI, spanning a range of watershed area to lake area ratios (AW:AL).
Mercury concentrations in sediment profiles for all lakes show (i) stable pre-
industrial (ii) logging/agricultural and (iii) industrialization periods. A recovery
period (iv) was evident in some lakes. Sediment dating is in progress, facilitating
the calculation of sediment mercury fluxes, estimates of net atmospheric
mercury flux and additional flux of mercury from watershed runoff.
Measurement of natural abundance mercury isotopes in sediments from each
lake will provide additional evidence of the contributions of mercury from
atmospheric deposition and watershed runoff. A decadal record (1998-2008) of
total mercury in event precipitation collected at Pellston, MI provides an
independent record of wet depositional flux during the industrialization and
Abstracts 140
recovery periods. Mercury concentration in precipitation decreased -2.02 %
year-1 (Sens slope, 95% confidence intervals -3.57, 0.22, p< 0.1), but mercury
wet deposition (flux) showed no significant trend. Findings from the
geochemical archive in combination with the decadal record of atmospheric
monitoring are used to lend insight into the mechanisms controlling recovery in
mercury-contaminated lakes.
178. Rapid detection of toxic heavy metals with boron doped diamond
microelectrode arrays
Cory A. Rusinek1, [email protected], Mary Ensch2,1, Michael F. Becker1,
Robert Rechenberg1, Aaron Hardy1, Thomas Schuelke1,3. (1) Center for
Coatings and Diamond Technologies, Fraunhofer USA, Inc., East Lansing,
Michigan, United States (2) Chemical Engineering, Michigan State University,
East Lansing, Michigan, United States (3) Electrical and Computer
Engineering, Michigan State University, East Lansing, Michigan, United States
Toxic heavy metals such as lead (Pb), cadmium (Cd), and mercury (Hg) cause
serious health complications and ingestion of these toxins through contaminated
drinking water, even at trace levels, has become a prominent issue. Chronic
exposure to toxic metals such as Pb, Cd, and Hg is carcinogenic while causing
other problems like kidney failure, severe neurotoxicity, and IQ loss. These
problems are only magnified in children as several stages of bodily development
can be severely hindered. Electroanalytical methods are an attractive technique
for trace detection of heavy metals due to low cost of experimental tools, low
limits of detection, multi-element analysis capability, and the possibility to
package them into sensing devices. Specifically, boron-doped diamond (BDD)
is a rugged, yet sensitive electrode material with significant potential in
electrochemical sensing. Using square-wave stripping voltammetry (SWSV), we
have developed BDD micro-electrode arrays (MEAs) as well as macro-electrode
disks, achieving detection limits as low as 160 parts-per-trillion (ppt) for Pb with
a deposition time of just 2 minutes. This is nearly 100x below the 15 ppb
maximum contaminant level (MCL) in drinking water set by the Environmental
Protection Agency (EPA). MEAs of various diameter and spacing were
investigated to find the optimum geometry for both single and multi-element
detection of Pb, Cd, Hg, and Cu where results were compared with those
obtained at macro-electrodes as well. The applicability of each electrode for the
determination of toxic heavy metal ions in drinking and environmental water
samples was studied as well.
Abstracts 141

179. An investigation of the atmospheric deposition of phosphorus across

the Great Lakes Region
Taylor Mann, [email protected], Mary M. Lynam, J T. Dvonch. University
of Michigan Air Quality Laboratory, Ann Arbor, Michigan, United States
Phosphorus, P, is a well-known limiting nutrient essential for photosynthetic
organisms residing in terrestrial, fresh-water and marine ecosystems. Excessive
levels of this nutrient in aquatic environments are characteristically manifested
by the presence of hypoxia and harmful algal blooms, HABs. The incidence of
HABs is on the rise and in the US alone at least 35 states have documented their
occurrence, moreover, satellite images reveal their extent in the Great Lakes
region especially in Lake Erie. While excessive runoff of P to water bodies has
long been recognized as driving the production of HABs, more recently, it has
been suggested that P deposited from the atmosphere may be an additional
transfer pathway whose significance has been largely overlooked. We are
investigating and assessing levels of P deposition from the atmosphere across
the Great Lakes Region. Wet deposition samples were collected at several sites
in Illinois and Michigan during different study periods from 2001 to 2009.
Annual averaged volume weighted mean concentrations, VWM, for P ranged
from 6 to 17 g L-1 across the sites while the range for average annual
deposition was 4 to 17 g m-2. Monthly mean concentrations and monthly
deposition amounts are greater during warmer months (March through October)
compared to colder months and consistent with greater scavenging of P in
rainfall compared to other types of precipitation (snow and rainfall/snow mix).
An increasing north to south gradient with much higher rainfall concentrations
and wet deposition is evident at the sites. The most southerly sites (in Illinois)
may be impacted either by point sources of P from fertilizer plants or from more
diffuse resuspended dust originating from agricultural activities that are
prevalent in this region.
180. Cadmium sorption mechanism by ferrous sulfide under a sulfate
reducing condition
Sung P. Hyun1,3, [email protected], Bo-A Kim1, Kim F. Hayes2. (1) Korea
Institute of Geoscience & Mineral Resources, Daejeon, Korea (the Republic of)
(2) University of Michigan, Ann Arbor, Michigan, United States (3) University
of Science and Technology, Daejeon, Korea (the Republic of)
Abstracts 142
Cadmium (II) was reacted with ferrous sulfide mackinawite (FeS) in an anoxic
chamber under a range of pH values, initial Cd and background electrolyte
concentrations, using wet chemical methods, thermodynamic modeling, X-ray
photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS).
The expected Cd removal mechanisms included simple adsorption by the
mackinawite surface, formation of either crystalline or amorphous Cd sulfide
solid phases following dissolution of FeS according to its solubility, formation
of (Fe,Cd)S solid solution, and adsorption by possible solid phase oxidation
products of FeS such as ferrihydrite or goethite. The batch sorption
measurements showed that cadmium removal by mackinawite suspensions was
greater than 99% under all experimental conditions tested, including pH
between 4 and 10, initial Cd concentration between 10-6 and 10-4M, and NaCl
background electrolyte concentration between 0.01 and 0.1M. Thermodynamic
calculations showed that Cd aqueous speciation changed as a function of pH and
background electrolyte concentration. CdCl+ was the predominant aqueous Cd
species in the absence of added ferrous sulfide, while Cd(HS)2(aq) species
became dominant once ferrous sulfide was added to the background electrolyte
solution containing Cd. XPS and XAS indicated that the formation of
greenockite (a hexagonal CdS phase) was the major Cd removal mechanism
among the possible processes in the reaction of mackinawite and dissolved Cd.
No evidence of Fe(III) solid phase oxidation products was found. Thus this
study shows that mackinawite is a good scavenger of Cd over wide ranges of
environmental conditions under reducing conditions.
181. Ramifications of permanganate pretreatment on the destruction of
microcystins
David Szlag, [email protected]. Chemistry, Oakland University, Rochester,
Michigan, United States
Oxidative pretreatment of water with permanganate is a useful tool for reducing
taste and odor compounds, controlling zebra mussels, and destroying
contaminants in source water that are not readily removed by the rest of the
drinking water purification process. Microcystins are a class of dangerous
toxins, produced by cyanobacteria, which can be treated by preoxidation. This
study describes the kinetics of microcystin destruction by permanganate ion.
Our work focused on microcystin LA which is one of the most common and
most toxic congeners, having an LD50 of 50/kg. We report rate constants,
activation energies, and discuss the mechanism of microcystin destruction, and
identify the major oxidation products. The oxidation products present challenges
for detection by the commonly used ELISA test and were assessed for toxicity
by the protein phosphatase inhibition assay.
182. Teaching general chemistry is not enough: Teaching students
metacognitive learning strategies
Abstracts 143
Ted M. Clark, [email protected]. Chemistry and Biochemistry, The Ohio State
University, Columbus, Ohio, United States
Teaching and learning practices in large enrollment STEM courses in higher
education dramatically differ from those in high school science classes since
many aspects of the course, such as class size, pace, depth of coverage,
homework assignments, are quite different. Even highly successful high school
students frequently have poor metacognition and struggle when their learning
strategies are found to be inadequate in a course like general chemistry.
Following the framework discussed by McGuire in Teach Students How to
Learn, interventions have taken place in several large enrollment (n > 300
students per class) general chemistry sections at OSU. The aims of these
interventions have been to convince students to improve their approach to
learning, communicate strategies proven to be effective, and establish a learning
community of students, instructor, and teaching assistants. After learning more
about metacognition in this session, student views of the course became more
positive, with >90% feeling more or much more positive about their future
performance. Such an attitudinal shift has implications for STEM retention. In
addition, a high proportion held that, to succeed in general chemistry, they
would need to study differently than they did in high school. In particular, using
resources before class to preview the material, like the textbook, was a strategy
most had never considered applicable for a science course. Students attending
metacognitive sessions outperformed their projected mid-term exam scores,
which were based on an initial pre-test. When a metacognition session was
included in a class with several other interventions, like peer-led sessions and
small group activities, ANOVA analysis showed the metacognition session to be
most statistically significant, (F(47, 504) = 2.118, p = 0.001). This is
encouraging, since this useful intervention (effect size = 0.50) is much easier to
implement than ones with extensive logistical needs, like PLTL. In this
presentation, the manner in which instructors have become aware of, and used,
McGuires work will be discussed, along with implications for further directions
for this approach at OSU.
183. Improving student outcomes in general chemistry 1, organic 1 and
anatomy and physiology 1 with extra chemistry and mathematics
Andrew L. Ekstrom1,2, [email protected]. (1) Henry Ford College ,
Madison Heights, Michigan, United States (2) Oakland University, Rochester,
Michigan, United States
General Chemistry 1 and Organic Chemistry 1 are important courses for
students who want to get into medical school. Anatomy and Physiology 1 is
important for students that want to get into nursing school. All of these courses
are considered by students to be "weeder" courses. Meaning, they tend to
remove ("weed out") students from pursuing future medical careers.
Abstracts 144
The pre-requisite classes for these courses differ by university/college. We will
discuss how student performance in these courses will differ based upon student
performance in various combinations of chemistry and math classes that are
taken as pre-requisites. We will also try to determine what courses should be
pre-req's and how to determine the effectiveness of current pre-requisites.
184. Redox reactions and the automobile
Craig J. Donahue, [email protected]. Department of Natural Sciences,
University of Michigan-Dearborn, Dearborn, Michigan, United States
This presentation presents a catalog of both inorganic and organic redox
reactions that can be connected to the automobile. The goal of this project was
to compile a catalog of redox reactions that showcase the importance of redox
reactions in the preparation of compounds and materials that go into the
manufacture of the automobile, that occur when the automobile is in operation,
or can be connected with the automobile in some other way. These redox
reactions are subdivided into subcategories including fuel preparation, fuel
additives, fuel combustion, metals (extractive metallurgy), batteries, corrosion,
air pollution, and the catalytic converter among others. This information has
been used by the presenter in his two-semester General Chemistry course for
undergraduate engineering students in order to make redox reactions and the
topic of electrochemistry more applied and more relevant to the audience.
185. Students use of online chemistry simulations and their conceptual
learning
Ryan D. Sweeder2, [email protected], Deborah G. Herrington1, Jessica R.
Vandenplas1. (1) Department of Chemistry, Grand Valley State University,
Allendale, Michigan, United States (2) Lyman Briggs College, Michigan State
University, East Lansing, Michigan, United States
Online educational materials are becoming more common given the
proliferation of online, flipped, or blended classes. Simulations are particularly
appealing as they allow students to manipulate variables and observe the
outcomes as a means to construct their understanding of course concepts. In
chemistry, simulations provide the added benefit of allowing students to make
connections between the behavior of particles, something that they cannot see,
and macroscopic observations. Although classroom use of such simulations have
led to improved student understanding, independent use of the simulations may
lead to unintended outcomes such as new misconceptions. This talk will discuss
students out of classroom use of simulations and screencasts (videos that point
out salient features of simulations) and the resultant impacts on student learning
of key general chemistry concepts. The research provides suggestions for
designing assignments and assessments to support student learning from
simulations in this setting.
186. Natural gas chemistry
Abstracts 145
Craig J. Donahue, [email protected]. Department of Natural Sciences,
University of Michigan-Dearborn, Dearborn, Michigan, United States
This presentation examines the composition of crude natural gas and traces how
the major components methane and C2-C4 hydrocarbons (or natural gas
liquids) and minor components (e.g. hydrogen sulfide and helium) are
isolated and used. The goal of this project was to produce a one-page flowchart
that shows in a general way how the components of crude natural gas are used to
made key inorganic compounds (e.g. sulfuric acid, ammonia, and nitric acid),
organic monomers from the natural gas liquids (e.g. ethylene, ethylene glycol,
propylene, and 1,3-butadiene) which are transformed to commodity plastics, and
how methane is converted via steam reforming and the water gas shift reaction
to synthesis gas that is converted to methanol and formaldehyde and is also used
in Fischer-Tropsch processes. This flowchart has been used by the presenter in
his two-semester General Chemistry course for undergraduate engineering
students.
187. ACS Division of Small Chemical Businesses: opportunities and benefits
Joseph E. Sabol, [email protected]. Chemical Consultant, Marquette,
Michigan, United States
The American Chemical Society ACS, Division of Small Chemical Businesses
SCHB was founded in 1978 and has continuously provided valuable member
benefits and informative programming at ACS national, regional, and local
meetings. SCHB's programming includes resources for entrepreneurs and
features start-up, small, and growing businesses in the chemical and related
sectors. SCHB member benefits include: business directory listing of products
and services; deeply discounted expo booth space at ACS national meetings;
scholarship to attend ACS Leadership Courses; monthly newsletters; advance
notice of meeting abstracts and events; lunch with speakers and members at
national meetings; the opportunity to shape and direct SCHB by holding office
or chairing a committee; a buddy/mentor system for sharing expertise; and - the
best of all - amazing networking opportunities, including in person at ACS
meetings and 24x365 virtual through SCHB's myriad of social media platforms,
including ACS Network, Linked-In, Twitter, and Facebook. Patron [corporate]
membership is also available. Join SCHB! Get involved! Stay involved! See
what SCHB can do for you - and what you can do for SCHB!
188. The role of the expert in data-centric research
Emilio X. Esposito, [email protected]. exeResearch LLC, East
Lansing, Michigan, United States
Today, a greater emphasis is being placed on gathering data and extracting
information from it. Ubiquitous access to the needed software and hardware has
reduced the perceived need for the computational expert. Unfortunately, the
experience of an in-field expert is often discounted. The difficulty is no longer
Abstracts 146
convincing others of the need or importance of the proposed research but the
need for an expert to perform the research and present the results. Unlike bench-
top chemistry experiments, computational studies always return a numerical
value. The skill of a computational expert comes from the knowledge of
knowing how to design the experiments, setting up the calculations,
interrogating and explaining the results. This talk focuses on the successes and
challenges for a computational and data-centric contract research organization.
189. Chemistry meets metallurgy: one chemists journey into the industry
of molten salts
Louis Pignotti, [email protected]. Kolene, Detroit, Michigan, United States
Molten salts represent an interesting intersection of industrial chemistry and
metallurgy. Molten salts are utilized to clean and modify the surface of metals,
and applications can be found anywhere from primary metal production to
engine rebuilding. The creation and application of molten salt requires a broad
base of knowledge, including solution-based chemistry, analytical chemistry,
solid-state physics, and metallurgy, among others. Presented here are several
case studies of the use and application of molten salts and the story of one
chemist's venture out of academia and into industry.
190. Sustaining a service-based business in the chemical sector
Joseph E. Sabol, [email protected]. Chemical Consultant, Marquette,
Michigan, United States
Most chemists are familiar with being an employee at a product-based employer.
What about a service-based company or being the owner? What are the
responsibilities, legal obligations, and benefits? Convincing customers/clients to
pay you money for "intangibles" is a challenge and most chemistry students do
not study business or marketing. Leveraging your skill-set and accentuating your
strengths is crucial and can compensate for your weaknesses. Cash is your
oxygen, but do not live for cash. Have fun, learn something, make money, make
a difference. Successful businesses know how to get and - more importantly -
keep customers. This presentation shares insight from the author's 17+ years of
providing technical and business development services to the chemical and
related industries.
191. Stereoselective synthesis of potent calcium signal modulator
acremomannolipin A
Xiaohua Li, [email protected]. Department of Natural Sciences, University of
Michigan-Dearborn, Dearborn, Michigan, United States
Acremomannolipin A, a novel glycoconjugate isolated from Acremonium
strictum, was found to be a potent calcium signal modulator. Structurally,
acremomannolipin A contains a D-mannopyranoside -linked to a polyol. In this
presentation, we will describe our synthesis of Acremomannolipin A in which
Abstracts 147
the key -mannopyranosidic likage has been successfully constructed via cesium
carbonate-mediated stereoselective anomeric O-alkylation.
192. Amino acid-derived chelants for radionuclide decorporation
Klaus J. Friedrich1, [email protected], Bianca Jones1, Christopher
Niedek1, Jaramys Mosley2. (1) Chemistry and Biochemistry, University of
Detroit Mercy, Detroit, Michigan, United States (2) University of Michigan, Ann
Arbor, Michigan, United States
Human exposure to radionuclides, whether from nuclear power plant incidents
or radiological or nuclear weaponry, is of growing concern. The currently
approved treatment of radionuclide exposure involves decorporation therapy by
complexation of the -, -, and -emitters with diethylenetriamine pentaacetic
acid (DTPA), an approach that is limited by the low solubility of the chelant in
physiological media and very limited transport through lipid membranes. While
derivatization of the complexing agent can improve lipophilicity and hence
make the treatment of large numbers of patients with an orally available drug
possible, effective therapy is still limited to a few isotopes and hampered by the
uncertain metabolic stability of the radionuclide complexes. The radionuclides
of concern are unstable isotopes of americium, thorium, uranium, and cobalt, to
name just a few.
Orally available prodrugs based on hydroxylated derivatives of DTPA and
DTPA homologues are being developed that promise to allow for the
decorporation of a wide range of radionuclide ions. While DTPA itself is a well
studied chelant, it is the side-chain hydroxy group of serine and serine
homologues incorporated into the DTPA motif that can function as a metabolic
site to form the corresponding glucuronidated and phosphorylated products.
These are expected to show low repartitioning into organs, through the blood-
brain-barrier or the placenta, increased renal passage, and little persistence in the
environment.
The synthesis of serine homologues and iminodiacetic and dipropionic acid
esters suitable as building blocks of DTPA derivatives will be described. L-
Serine and racemic 2-amino-7-hydroxy heptanoic acid derivatives have
successfully been combined with iminodiacetic and dipropionic acid esters to
arrive at new DTPA analogues. Testing of these new chelants is ongoing.
193. C3-alkylation of 2,3-disubstituted indoles with trichloroacetimidates
John D. Chisholm, [email protected]. Syracuse University, Syracuse, New
York, United States
Trichloroacetimidates are effective electrophiles for the C3-alkylation of 2,3-
disubstituted indoles. These reactions proceed rapidly using a Lewis acid
catalyst. This chemistry provides an efficient entry to 3,3'-disubstituted
indolenine systems. These indolenines are often used as intermediates in the
synthesis of many complex molecules. Effective reaction conditions have been
Abstracts 148
determined, and the scope of the reaction has been investigated. This chemistry
provides an alternative to base promoted and transition metal catalyzed methods
that are utilized to access these systems.

194. Synthesis of new nucleoside analogs: Possible HCV NS5B inhibitors

Bader Alabdullah1,2, [email protected], Amanda C.
Bryant-Friedrich1. (1) University of Toledo, Toledo, Ohio, United States (2)
University of Basrah, Basrah, Iraq
Per the World Health Organization (WHO), hepatitis C affects chronically 130-
150 million people worldwide. Seven hundred thousand patients die each year
from hepatitis C-related liver diseases. The risk of death from liver cancer and
cirrhosis can be reduced by antiviral medications, but access to those
medications is limited due mainly to the high cost of treatment ($31,452 to
$410,548 per Quality-Adjusted-Life-Year (QALY) gained owing to the
individual patient characteristics such as fibrosis stage, comorbidities, estimated
life expectancy, and HCV genotype). The recent publication of the crystal
structure of the HCV RNA-dependent RNA-polymerase (RdRp) NS5B with an
inhibitor in the active site has enabled elegant development of new agents
targeting the NS5B enzyme. Nucleoside analogs modified at the 2 position have
been proven to be effective against the HCV RdRp NS5B as a chain terminator.
Herein, we present the design and synthesis of new nucleoside analogs starting
from unmodified nucleosides in a few steps. The synthesis is in the process of
optimization and will be extended to the synthesis of phosphoramidate prodrugs.
These modified nucleotides will be tested against HCV using the Replicon
assay.
195. Reduction of amides to amines using Na-SG and Na-AG
Fatmata Jalloh2, [email protected], James E. Jackson1, James Dye1. (1) Dept
Chemistry, Michigan State Univ, East Lansing, Michigan, United States (2) RM
11, Michigan State University, East Lansing, Michigan, United States
Amine constitute an important intermediate in pharmaceutical industries, and is
a key linking moiety in protein and peptide drug productions. Different reagents
have been used in the reduction of amides to amines, such as lithium aluminum
hydride (LiAlH4), Ir, Pt, Ru, Fe, Zn, etc. Although these reagents are effective,
they can be expensive, difficult to make or handle, air and moisture sensitive,
complex wake up and purification process, may also reduce other groups in the
compound of interest, or limited by other functional groups present. By applying
Abstracts 149
the Bouveault-Blanc reduction method, under similar reaction conditions,
amides have been successfully reduced to amine using both sodium
encapsulated in silica and alumina gel (Na-SG and Na-AG). These reagents are
commercially available free-flowing powders that are non-pyrophoric in dry air,
and cheap. We have seen significant progress in the reduction of tertiary amides
to amine, especially with Na-AG, giving a higher yield. We are currently
exploring a wide range of amides to show the versatility of our reagents.
196. Fate of C5' oxidation and its adducts as a potential biomarker
Shin H. Cho, [email protected], Amanda C. Bryant-Friedrich.
Medicinal and Biological Chemistry, University of Toledo, Toledo, Ohio, United
States
Endogenous exposome is any exposure from the internal environment within the
body which can have the propensity for developing various diseases throughout
lifetime. It includes metabolism of byproducts from mitochondria, infection,
inflammation, oxidative stress from reactive oxygen species, and so on.
Oxidative stress can have an impact on DNA, resulting in the strand breakage by
the abstraction of hydrogen at various carbon centers in deoxyribose moiety.
Among the 5 carbons in this moiety, the hydrogen at the 5' carbon is more
susceptible to abstraction compared to others. Nonetheless, the exact mechanism
to understand how these are degraded are yet to be investigated. Here we present
the investigation of oxidative damage products resulting from 5'-hydrogen
abstraction. The goal of this project is to prove whether the degradation of the
nucleoside modified at C5' position can be used as potential biomarkers to
monitor oxidative stress. Such task can be initiated by identifying the
degradation products derived from C5' oxidation of DNA. This involves the
multi-step synthesis of C5' modified nucleoside followed by incubation studies
using analytical techniques such as HPLC. Similar studies will be conducted in
oligonucleotides.
197. Energy-resolved dissociation behaviors and gas-phase ion structures of
protonated and sodium cationized pseudouridine
Zachary Devereaux2, [email protected], Yanlong Zhu2, Yuan-wei Nei2,
Nathan Cunningham2, Giel Berden1, Jos Oomens1, Mary T. Rodgers2. (1) IMM -
FELIX Laboratory, Radboud University, Nijmegen, Netherlands (2) Chemistry,
Wayne State University, Detroit, Michigan, United States
Nucleosides are the building blocks of RNA and DNA. Naturally occurring
nucleoside analogues have important roles in cellular processes and in the
overall health of organisms. Pseudouridine, an isomer of uridine, is the most
common naturally occurring modified nucleoside in RNA, but its function is still
not completely understood. Systematic studies of the intrinsic properties of
modified nucleosides compared with their canonical RNA and DNA nucleoside
counterparts aim to identify trends between structural features and biological
activity. In this work the intrinsic properties of protonated and sodium
Abstracts 150
cationized pseudouridine, uridine, and 2-deoxyuridine are investigated and
compared. Energy-resolved collision induced dissociation (ER-CID)
experiments in a quadrupole ion trap (QIT) mass spectrometer and high mass
accuracy measurements in a Fourier transform ion cyclotron resonance (FT-
ICR) mass spectrometer are used to determine relative glycosidic bond
stabilities and low-energy decomposition pathways. Infrared multiple photon
dissociation (IRMPD) action spectroscopy coupled with theoretical calculations
are used to determine favorable gas-phase ion structures. Results thus far show
increasing relative glycosidic bond stability following the order: pseudouridine
> uridine > 2-deoxyuridine. Additionally, protonation activates the glycosidic
bond more than sodium cationization. Low-energy pseudouridine fragmentation
does not occur at the glycosidic bond as it does in the other systems. Gas-phase
ion structures of uridine and 2-deoxyuridine are highly parallel, and
comparisons are to be made with pseudouridine structures. Experiments,
calculations, and data analysis are currently ongoing, particularly for protonated
and sodium cationized pseudouridine.
198. Cloud point extraction (CPE) in combination with tangential flow
filtration (TFF) for the isolation of silver nanoparticles and ionic silver
Md Ali Akbar, [email protected], Gregory Bowers, Sesha Paluri, Ioana
Sizemore. Chemistry, Wright State University, Fairborn, Ohio, United States
The increased use of silver nanoparticles (AgNPs) in a variety of consumer
products (e.g., 438) has amplified the environmental exposure to silver. This
exposure to AgNPs is associated with alarming in vitro and in vivo cytotoxicity
that mainly results from the release of Ag+ ions from AgNPs under favorable
redox conditions. In this study, we demonstrate the improvement in the isolation
efficiency of the two Ag species (AgNPs and Ag+) from colloidal and biological
matrices by combining for the first time cloud point extraction (CPE) with
tangential flow filtration (TFF). Briefly, a non-ionic surfactant (Triton X-114)
and sodium thiosulfate were added to the samples containing AgNPs and
incubated over the cloud point temperature of the surfactant to allow for the
micelle formation with AgNPs (surfactant phase) and the chelation of Ag+ with
thiosulfate (aqueous phase). The two CPE phases were then separated by
centrifugation, and the aqueous phase containing AgNPs was further processed
through a 1-kD filter. The total concentration of Ag in the two CPE phases and
the resulting TFF products, namely permeate (containing Ag+) and retentate
(containing AgNPs), were quantified by inductively coupled plasma optical
emission spectroscopy (ICP-OES). The incorporation of a rapid, one-step
filtration resulted in an increase of AgNP extraction efficiency from 80.65% to
87.59% for borohydride-capped, from 72.49% to 77.98% for PVP-capped, and
from 56.05% to 65.23% for Citrate-capped AgNPs. The total Ag recovery was >
92.89% in these original colloids. The Ag+ content in these colloids was found
to range from 9.04% to 27.46%, resulting in a total Ag loss ranging from 3.37%
to 7.11% in the process. CPE-TFF methodology was implemented to analyze the
Abstracts 151
+
fate of AgNPs in cells exposed with AgNPs, and the AgNPs and Ag extraction
efficiencies are found to be 70% and 11% respectively with an overall recovery
of 81%.
199. Determination of manganese in whole blood by cathodic stripping
voltammetry with indium tin oxide
Cory A. Rusinek1,4, [email protected], Wenjing Kang3, William R.
Heineman2, Ian Papautsky3, Bettina Wehring1, Michael Petzold1, Michael F.
Becker1, Thomas Schuelke1,5. (1) Center for Coatings and Diamond
Technologies, Fraunhofer USA, Inc., East Lansing, Michigan, United States (2)
Department of Chemistry, Univ of Cincinnati, Cincinnati, Ohio, United States
(3) Electrical and Computer Engineering, University of Cincinnati, Cincinnati,
Ohio, United States (4) Chemistry, University of Cincinnati, Cincinnati, Ohio,
United States (5) Electrical and Computer Engineering, Michigan State
University, East Lansing, Michigan, United States
Manganese (Mn) is a required trace metal in the body. In recent years however,
it has garnered significant attention as a developmental neurotoxin in children
with chronic exposure. It has been linked to complications such as memory loss
with negatively associated IQ scores, attention deficit hyperactivity disorder
(ADHD), and in extreme cases, the development of a Parkinsons disease
analogue- manganism. Cathodic stripping voltammetry has proven to be a
suitable method for electroanalytical determination of Mn. We have established
Mn CSV using indium tin oxide (ITO) as the working electrode for the
determination of Mn in bovine whole blood after an acid digestion. Reliable,
accurate, and precise results were obtained as only 9% variation in the digested
blood was observed. The CSV results were compared with graphite-furnace
atomic absorption spectroscopy (GF-AAS) and inductively coupled plasma-
mass spectrometry (ICP-MS) and favorable agreement across the methods was
observed. We also optimized the ITO film on non-optically transparent
substrates by altering the fabrication process where we observed better
performance than that seen with commercially available ITO. Due to ITOs
excellent positive potential window and stability under harsh environments, this
method could be applied to other oxide-forming transition metals detectable by
CSV.
Abstracts 152

Mn cathodic stripping voltammograms of 4 separate bovine blood digestions

200. Incorporation of course-based undergraduate research experiences in
the organic chemistry and biochemistry laboratory
Delaney N. Large, Hadeel K. Albasrawi, Shannon C. Timmons,
[email protected]. Department of Natural Sciences, Lawrence Technological
University, Southfield, Michigan, United States
Most chemistry laboratory courses are taught using a cookbook-style approach
in which students follow step-by-step instructions in an effort to produce a
prescribed result. While it is important to expose students to a wide variety of
scientific techniques, these skills can often be taught in the context of course-
based undergraduate research experiences (CURE), which allow students to
participate in an authentic research project in a classroom setting. Involving
undergraduate students in research experiences increases student ownership of
experiments and creates excitement for scientific research, while improving
critical thinking skills and impacting students career choices. Furthermore,
research project participation by undergraduate students has been shown to
improve the retention and graduation rates of underrepresented minority
students, strengthening the STEM pipeline and enhancing diversity in scientific
fields. At Lawrence Technological University, two novel CURE-inspired
modules have been developed and incorporated into our sophomore-level
organic chemistry laboratory and junior-level biochemistry laboratory courses.
In the organic chemistry laboratory, students attempt to synthesize novel aspirin
analogs for medicinal testing, whereas in the biochemistry laboratory, students
aim to identify possible chemical mutagens using a modified Ames test. Lessons
learned from the development and implementation of these discovery-based
laboratory modules will be discussed along with assessment results.
201. Green chemistry: STEM connections to our world
Kathe Blue Hetter1,2, [email protected]. (1) Science Chair, Skyline High
School, Ann Arbor, Michigan, United States (2) Beyond Benign, Wilmington,
Massachusetts, United States
Green chemistry provides a framework and lens for learning, teaching and
investigating the STEM skill set. What if we were able to grow our own
packaging? How does the surface chemistry of shark scales prevent bacteria
Abstracts 153
growth? Can we still have vibrant colors and hues without using harmful
chemicals in the process?
Highlighting industrial examples of sustainable design is one way to engage
students and provide an opportunity to demonstrate how chemistry concepts
connect to our world. Learn how innovative green chemistry technologies are
serving as tools to capture the imagination of the next generation of problem
solvers. Teachers and students alike, delight in the interactive and engaging
activities that bring these innovative ideas, designs and applications to life.
202. Prerequisite knowledge and success in general chemistry
Yu Kay Law2, [email protected], Edwin G. Olmstead1, Kayla A. Campbell2,
Roberta L. Roswell2, Neena Wilson2. (1) Chemistry Department, Fort Hays State
Univ, Hays, Kansas, United States (2) School of Natural Science and
Mathematics, Indiana University East, Richmond, Indiana, United States
We have studied the efficacy of a number of different placement instruments on
predicting success in general chemistry. When doing so, we found that the grade
on the previous mathematics course is one of the best predictors of success in
chemistry, although the level of the mathematics course does also play a role in
helping predict success. We find, moreover, that placement tests and previous
coursework grades predict different aspects of success, as shown by their
capacity for predicting laboratory versus examination scores. When we
attempted to remediate students that were predicted to encounter hardship based
on previous high school coursework and grade by integrating the teaching of
college algebra with general chemistry, we were not successful in enabling most
of the students to succeed. This suggests that success in general chemistry due to
students who are underprepared may not be remediated simply by developing
mathematics skills on a just-in-time basis.
203. #Twitter uses in #chem and #highered
Keith S. Anliker, [email protected]. Chemistry and Chemical Biology, IUPUI,
Indianapolis, Indiana, United States
Should you be on Twitter? Thats hard to say, but I will talk with session
participants about what I get out of it, and why you might want to give it a try.
I'll share my own Twitter story that goes back to when I created an account and
started tweeting for ACS-
CERM 2011 in Indianapolis, and the launch of my class Twitter account in
March of that year. Well also look at my recent, heavier engagement in Twitter
with my personal/professional account and my experience as the co-curator of
content for our departmental Twitter account.
In addition, I'll share my thoughts on the varied Twitter approaches Ive
observed in chemistry, the sciences and in higher education, and provide some
data on what individuals, research groups, departments and universities do with
Abstracts 154
Twitter. We'll also cover some Twitter basics in the processjust in case I
convince you to take the plunge.
204. Electron-transfer reactions via halogen-bonded complexes
Sergiy V. Rosokha, [email protected]. Chemistry, Ball State University,
Muncie, Indiana, United States
During the last decade, an attractive interaction between electrophilic halogen
atoms and electron-rich centers, i.e. halogen bonding, has been fruitfully used
for molecular recognition and crystal engineering. In this work, we discuss the
effects of this novel supramolecular interaction in chemical reactions of
halogenated species. Specifically, while rates of oxidation of sterically-protected
ferrocenes by brominated molecules R-Br (CBr3CN, CBr4, CBr3NO2,
CBr3COCBr3, CBr3CONH2, CBr3F, and CBr3H) were consistent with the
predictions of the outer-sphere dissociative electron-transfer theory, the similar
redox-reactions of typical halogen-bond acceptors tetramethyl-p-
phenylenediamine (TMPD) were 3 to 6 order of magnitude faster than
calculated using the same model. The fast oxidation of TMPD molecules was
related to the involvement of the transient halogen-bonded [R-Br, TMPD]
complexes in which barriers for electron transfer were lowered by the strong
electronic coupling of reactants. The Mulliken-Hush treatment of the spectral
and structural characteristics of these complexes afforded the values of coupling
elements Hab of 0.2 0.5 eV. The rates of the inner-sphere electron-transfer
reactions calculated using these coupling elements and formation constants of
the [R-Br, TMPD] associates were consistent with the experimental kinetic data.
This confirmed participation of these halogen-bonded associates as the precursor
in the redox-reactions of the brominated electrophiles. More generally, the
decrease of the barrier for electron transfer between the halogen-bonded
reactants demonstrated in the current work points out that halogen bonding
should be taken into account in the mechanistic analysis of the reactions of
halogenated species.

Figure. Energy diagram for the electron transfer via halogen-bonded complex
Abstracts 155
205. Gas phase structure of protonated and sodiated 5-halouridines
determined by infrared multiple photon dissociation action spectroscopy
Harrison A. Roy1, [email protected], Lucas Hamlow1, Yanlong Zhu1,
Nathan Cunningham1, Zachary Devereaux1, Justin Lee1, Giel Berden2, Jos
Oomens2, Mary T. Rodgers1. (1) Wayne State University, Detroit, Michigan,
United States (2) IMM - FELIX Laboratory, Radboud University, Nijmegen,
Netherlands
Nucleic acids store and transfer genetic information and are therefore essential
in the central dogma of biology. Of the 112 naturally occurring modified
nucleosides in the RNA modification database, 44 of these are modified
uridines. Halogenation is a common synthetic modification for drug targets that
enables the systematic variation of the size, dipole moment, polarizability, and
electron withdrawing character of molecules. Several synthetic 5-halouridines
and their derivatives have been shown to have bioactivity. Incorporation of these
modifications into RNA is believed to be one mechanism of their mutagenicity.
5-Bromouridine has also found use as a tool for the study of RNA by increasing
its photosensitivy and allowing crosslinking to proteins. This study probes the
intrinsic effect of 5-halogenation on the gas phase structure and reactivity of
protonated and sodium cationized 5-halouridines, [x5Urd+H]+ and [x5Urd+Na]+,
where x5Urd = 5-fluorouridine (f5Urd), 5-chlorouridine (cl5Urd), 5-bromouridine
(br5Urd), and 5-iodouridine (i5Urd). Complementary methods of theory and
experiment were employed in this study. Spectra were measured by infrared
multiple photon dissociation (IRMPD) action spectroscopy performed in a
Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) in
the fingerprint region (~700-1900 cm-1) using a free electron laser and the
hydrogen-stretching region (~3300-3800 cm-1) using an OPO/OPA laser. Results
were compared to linear IR spectra predicted from density functional theory
calculations to determine of the gas-phase structures generated by electrospray
ionization. A mixture of O4 and 2,4-dihydroxy tautomers (T) of [x5Urd+H]+ are
accessed in the experiments. Changes in the appearance of the IRMPD spectra
suggest that the relative populations of the O4 and T conformers varies with the
size of the halogen substituent, with T conformers favored for [Urd+H]+ and
[f5Urd+H]+. However, as the size of the halogen substituent increases, O4
protonated conformers become increasingly favorable and the dominant
conformers for [br5Urd+H]+ and [i5Urd+H]+. A mixture of O2,O2'-bidentate and
O2,O4',O5'-tridentate conformers of the [x5Urd+Na]+ are accessed in the
experiments, with both modes of binding competitive for the entire series.
206. Surface coverage dependent variation in molecular orientation of an
organic anion at the air-aqueous interface
Mahamud Subir, [email protected], Daniel Headley, Ryan Young, Margaret
Schmits, Milina Quiroz. Chemistry, Ball State University, Muncie, Indiana,
United States
Abstracts 156
Molecular coverage and its relative orientation at a given surface can influence
its photochemical reactivity. This is particularly important in elucidating the
interfacial photo-degradation rate of organic compounds relevant to petroleum
weathering and aerosol science. Using a combination of second harmonic
generation spectroscopy and surface tension measurements, we have explored
the surface affinity and orientation of p-nitrophenolate (pNP), an aromatic
anion, at the air aqueous interface of various electrolyte solutions. It is revealed
that irrespective of the ionic strength, the adsorbed pNP experiences a change in
its relative orientation with respect to the surface normal as its surface coverage
is increased. The orientation varies from an upright position to a flat
configuration. Furthermore, our study show that in the presence of a zwitterionic
lipid monolayer, the pNP molecule exhibits a greater degree of vertical
alignment and its orientational variation is restricted with increasing surface
pNP coverage. This molecular behavior will be discussed in the context of
electrostatic and intermolecular interactions at the air-aqueous interface. The
implication of this finding on surface photodegradation rate of pNP will also be
highlighted.
207. Theoretical calculation of pKas of bio-organic molecules in aqueous
medium using polarizable continuum and explicit water molecule
Bishnu Thapa, [email protected], H. Bernhard Schlegel. Wayne State
University, Detroit, Michigan, United States
Knowledge of acid dissociation constants (pKas) is useful for the understanding
of the stability and reactivity of chemical compounds. It is also useful for
designing experiments and exploring the mechanism of chemical reactions.
Accurate experimental determination of acid dissociation constants of chemical
compounds is always desired but can sometimes be very challenging due to the
various reasons e.g. low stability of the compounds, interference from the
compounds in solution and the solvent itself, etc. Theoretical calculation of
pKas can be very useful in cases where there are experimental difficulties or
where experimental values have not yet been measured. In this study, we have
developed a computational method for calculating the pKas of bio-organic
molecules to within pKas 1 pKa unit. We have used this method to calculate
the pKas of nucleobases, and a wide range of substituted alcohols,
hydroperoxides, thiols, and selenols with the known and unknown experimental
pKas.
208. Predictions of pH-dependent binding affinities of host-guest systems
Michael Jones1, [email protected], Angela K. Wilson2. (1) Chemistry,
Michigan State University, Dearborn, Michigan, United States (2) Division of
Chemistry, National Science Foundation, Denton, Texas, United States
Cells are open systems that are consistently exchanging energy and matter with
the environment to maintain homeostasis. As the function is determined by the
structure and the structure is determined by the environment, the activity of
Abstracts 157
proteins is sensitive to changes in the environment. Specifically, changes in the
temperature, pressure, pH, and ionic strength influence how small molecules
bind to proteins. Computer simulation and modeling techniques have been
employed to determine how sensitive the binding of several guest molecules to a
host system are to pH and ionic strength.
209. Light induced color changes in the purple protein Bacteriorhodopsin
Carlie McGrath2, [email protected], Mark Masthay3,1, Angela
Mammana2,1. (1) University of Dayton, Dayton, Ohio, United States (2)
Chemistry Department, University of Dayton, Dayton, Ohio, United States (3)
Department of Chemistry SC 178, University of Dayton, Dayton, Ohio, United
States
This research provides new insights into the mechanisms associated with light-
induced color changes in the bacteriorhodopsin (BR)-containing halobacterial
purple membrane (PM). BR is a purple, 26kDa transmembrane protein which is
structurally similar to the human visual proteins rhodopsin and iodopsin.
This research focuses on the influences of light scattering and spectral
distortions induced by the solvent in which PM is suspended. Varying volume
ratios of water and glycerol were used as the solvent for PM samples. A ratio of
60% glycerol:40% water produced spectra with the least scattering, as
demonstrated by a low absorbance region (300-420 nm) in the UV-visible
absorption spectra and equal intensities of the positive and negative bands in the
circular dichroism (CD) spectra. Suspensions of native PM, calcium saturated
purple membrane (CSPM) and cation free blue membrane (CFBM) were
irradiated with intense 532 nanometer (nm) laser pulses or the 254 nm line from
a mercury lamp. During irradiation the absorption and CD spectra were
monitored; the spectral changes observed in pure water and glycerol:water
suspensions were similar, but faster in pure water.
PM, CSPM, and CFBM each produced a UV product with max ~360 nm; each
species experienced unique changes in the CD spectra as well. With both the
laser and the lamp, the absorption spectra of both PM and CSPM crossed over
(i.e., the long wavelength edge of the main absorption band shifted
bathochromically) during the early stages of irradiation; this crossing over was
absent in CFBM. PM also underwent a later bathochromic shift of its absorption
max with a concomitant purple-to-blue color changebut only with the laser.
With both light sources CSPM and CFBM underwent a color loss but no color
change. The structural and mechanistic implications of these spectral changes
are detailed below.
210. Eigenstatespecific temperatures in twolevel paramagnetic spin
lattices
Mark Masthay1, [email protected], Calley N. Eads2, Amber N.
Johnson1, Robert G. Keil1, Joe D. Mashburn3, Harry B. Fannin4. (1) Department
Abstracts 158
of Chemistry SC 178, University of Dayton, Dayton, Ohio, United States (2)
Department of Chemistry and Biochemistry, University of Arizona, Tucson,
Arizona, United States (3) Department of Mathematics, University of Dayton,
Dayton, Ohio, United States (4) Department of Chemistry, Murray State
University, Murray, Kentucky, United States
Increasing interest in the thermodynamics of small and/or isolated systems, in
combination with recent observations of negative temperatures of atoms in
ultracold optical lattices, have stimulated the need for estimating the
conventional, canonical temperature Tcconv of systems in equilibrium with heat
baths using eigenstatespecific temperatures (ESTs). Four distinct ESTs
continuous canonical, discrete canonical, continuous microcanonical, and
discrete microcanonicalare accordingly derived from Boltzmann entropies for
twolevel paramagnetic spin lattices (PSLs) in external magnetic fields. At large
N, the four ESTs are intensive, equal to Tcconv, and obey all four laws of
thermodynamics. In contrast, for N < 1,000, the ESTs of most PSL eigenstates
are nonintensive, differ from Tcconv, and violate each of the thermodynamic
laws. Hence, in spite of their similarities to Tcconv at large N, the ESTs are not
true thermodynamic temperatures. Even so, each of the ESTs manifests a unique
functional dependence on energy which clearly specifies the magnitude and
direction of their deviation from Tcconv; the ESTs are thus good temperature
estimators for small PSLs. The thermodynamic uncertainty relation is obeyed
only by the ESTs of small canonical PSLs; it is violated by large canonical PSLs
and by microcanonical PSLs of any size. The ESTs of populationinverted
eigenstates are negative when calculated using Boltzmann entropies, but positive
when calculated using Gibbs entropies; the origin and thermodynamic
implications of these entropicallyinduced differences in sign, as well as
potential applications of the four ESTs to nanothermometers and to systems with
longrange interactions will be discussed.
211. Enzymatic hydrolysis of model glucuronide metabolites in wastewater:
Electronic and pH effects
Jeffrey M. Buth1, [email protected], Miranda Stockton2, Seokyeong
Yee3, Andrea Tomsho1. (1) Chemistry & Biochemistry, University of Mount
Union, Alliance, Ohio, United States (2) Penn State University, University Park,
Pennsylvania, United States (3) Philadelphia College of Osteopathic Medicine-
Georgia Campus, Suwanee, Georgia, United States
In the last decade, pharmaceutical compounds have received much attention as
aquatic pollutants following discharge from wastewater treatment plants
(WWTPs). Designed to elicit potent biological effects, they may negatively
impact the health of aquatic ecosystems and humans who obtain their potable
water from contaminated sources. Compared to parent compounds, relatively
little research has explored the environmental fate of drug metabolites, which
often constitute a large percentage of the total pharmaceutical load. Because
conjugated phase II metabolites such as glucuronides may undergo enzymatic
Abstracts 159
hydrolysis and reform the active forms of drugs, it is important to assess their
fate during wastewater treatment and after discharge. This study examined the
pH dependence of glucuronide hydrolysis rates in wastewater influent, effluent,
and downstream river water using five model glucuronides (phenyl--D-
glucuronide, 4-nitrophenyl--D-glucuronide, 4-aminophenyl--D-glucuronide,
8-hydroxyquinoline--D-glucuronide, and benzyl--D-glucuronide). The
substrates were chosen to explore the electronic effects of structure on
hydrolysis rates. Water samples were spiked with target glucuronides to initiate
reactions, and periodic subsamples were removed for high performance liquid
chromatography analysis. In each matrix, the hydrolysis rate of every
glucuronide peaked at circumneutral pH. Rates were consistently higher in
influent than in effluent and downstream river water, which can be explained by
the higher level of E. coli in the influent, which is known to produce the
hydrolytic enzyme, -glucuronidase. Additionally, hydrolysis rates were higher
for glucuronides whose aglycones exhibited greater resonance stabilization
during the nucleophilic reaction. While further research is warranted, the results
obtained using model compounds provide a starting point to predict the relative
hydrolysis rates of structurally similar pharmaceutical glucuronides in aquatic
media.
212. Analysis of roasted coffee for caffeine and chlorogenic acid using
liquid-chromatography mass spectrometry (LC-MS)
Sigrid Kiledal1, [email protected], Lee A. Baron1, Mark A. Nussbaum2. (1)
Hillsdale College, Hillsdale, Michigan, United States (2) Chem Dept, Hillsdale
College, Hillsdale, Michigan, United States
Coffee is one of the most consumed beverages in the world. It is known to
contain compounds that have biological effects, the most notable being caffeine.
Coffee contains chlorogenic acids that can be harmful to those suffering from
Gastroesophageal Reflux Disease (GERD), and it also contains cafestol which
has been found to increase levels of cholesterol. In this study, coffees from
Guatemala, Kenya, Maui, and Papua New Guinea were examined at light,
medium, and dark roasting levels based on time in the roaster and color of the
beans in order to determine which coffee contains the largest amount of caffeine
while containing the least amount of chlorogenic acids and cafestol.
A quantitative method was developed to determine the concentrations of
caffeine, 3-o-caffeoylquinic acid (3-CQA), a specific derivative of chlorogenic
acid, and cafestol in the coffee samples using LC-MS with selected ion
monitoring (SIM); the pH was also measured to determine the total acidity.
Unfortunately, while the method developed could separate, identify, and
quantify all three compounds, the cafestol levels present in the coffee samples
were below the limit of detection for the instrument. The highest concentrations
of caffeine were found in the dark roasts, and the highest levels of chlorogenic
acid were found in the light roasts of the coffee samples from all four regions.
Abstracts 160
The samples of coffee were also analyzed qualitatively by comparison to a
Coffee Brewing Control Chart (CBCC), which plots coffee based on certain
characteristics such as weak, underdeveloped, strong, and bitter. These
characteristics were determined by calculating the percent total dissolved solids
versus the percent extracted. All three roasts of the Guatemalan coffee, the
medium and dark roast of the Kenyan coffee, and the medium roast of the coffee
from Maui were considered to be within the ideal range for both the European
and the Norwegian Specialty Coffee Associations. The coffee that was found to
be the best choice for GERD sufferers through both analyses was the dark roast
of the Guatemalan coffee; it contained the highest concentration of caffeine, the
lowest concentration of acid, and fell within the ideal range on the CBCC.
213. Investigating atrazine accumulation and histological changes in the
hepatopancreas of crayfish post-exposure
Daniel J. Dayfield3, [email protected], Danielle N. Maxwell1,
[email protected], Victoria C. Torres1, [email protected],
Kathrine Yacoo1, [email protected], Noor K. Abraham2, Kaldoun M.
Barawi2, Kaitlin S. Lambert1, Ila Sayed2, Rachelle M. Belanger2, Kendra R.
Evans1, Elizabeth Roberts-Kirchhoff1. (1) Department of Chemistry and
Biochemistry, University of Detroit Mercy, Detroit, Michigan, United States (2)
Biology Department, University of Detroit Mercy, Detroit, Michigan, United
States (3) Division of Natural Sciences and Mathematics, Marygrove College,
Detroit, Michigan, United States
Many pesticides are known to have long-term adverse effects on aquatic
organisms, and thus it is of interest to explore the effects of pesticide
accumulation in these species. We are investigating the accumulation of atrazine
(ATR) in the hepatopancreas of the virile crayfish, Orconectes virilis. Crayfish
were treated with environmentally-relevant ATR concentrations (80 and 300
ppb) and control concentrations (0 ppb (negative control) and 1000 ppb ATR
(positive control)) for 15 days. Histological changes, including increased
vacuolization, were visualized in the hepatopancreas following sectioning and
staining with hematoxylin and eosin (H & E). It is of interest to correlate
physiological changes with the level of accumulation of ATR, so we have
developed and are evaluating a method to extract and quantitate the amount of
ATR in the hepatopancreas. Hepatopancreas tissue was isolated from the
crayfish, and ATR was extracted using a quick, easy, cheap, effective, rugged,
and safe (QuEChERS) method. Following the extraction, the ATR was
analyzed using liquid chromatography-mass spectrometry (LC-MS), which
allows for the quantitation of ATR, its metabolites, and other pesticides that may
accumulate in the tissue. A stable-isotope internal standard, ATR-d5, was
included in the analysis and will be used to improve the accuracy and precision
of the ATR quantitation.
214. Quantifying diffusion of a model analyte set via capillary
electrophoresis
Abstracts 161
1 1 1
Corbin Arrasmith , [email protected], Cassidy Brown , Ariel Porter ,
Rodrigo Pozo2, Charlisa Daniels1. (1) Chemistry, Northern Kentucky University,
Highland Heights, Kentucky, United States (2) Environmental Engineering,
Universidad de San Francisco Quito, Cumbay, Ecuador
The goal of this project was to determine the relationships between the
temperature, analyte, and concentration of the analyte within a capillary. This
was investigated using Capillary Electrophoresis (CE). An alkyl series (toluene
through 1-phenyl octane), and thoiurea were used to analyze the kinetics in an
open capillary at room temperature and an adjusted temperature of 25C, and
mobile phase concentration of 75% acetonitrile:25% Tris base. This series and
mobile phase were selected based on their use in previous studies in other
publications.
The second goal on the project was to try to fabricate a micro CE machine that
will cut down on both size and waste. This was investigated by using a Labsmith
HVS 448 High Voltage Sequencer by using a voltage differential to make salt
particles found in the 75% acetonitrile: 25% Tris base flow from point to point.
Also, different porogens were added to a 50/50 polymeric ratio of GMA:
EDMA. The purpose of this was to see how different porogens affected the pore
sizes of the polymer. This was observed using a Scanning Electron Microscope
(SEM).
215. Chemical analysis and radiocarbon dating of archaeological textile
fragments from the seip mound
Mishka Repaska1, [email protected], Kathryn A. Jakes2, Ruth Ann
Armitage1. (1) Department of Chemistry, Eastern Michigan University, Dundee,
Michigan, United States (2) Ohio State University, Professor Emerita,
Columbus, Ohio, United States
The few textile artifacts that are found in archaeological sites often are preserved
by impregnation with copper or by charring; either route makes these organic
materials less susceptible to microbial degradation. Fragments of fabric made of
plant stem fiber excavated from the Seip Mound complex in Ohio (ca. 2100
1500 BP) show green coloration in repeating patterns of decoration. It remains
unclear how the material was decorated; whether it was painted with a pigment
suspended in a binding medium or dyed with a colorant that binds at the
molecular level. Minute samples taken from small bits of yarn that have fallen
away from the fabric fragments were provided to determine if a binding medium
could be identified, and to measure the radiocarbon age. To facilitate this study,
we prepared mockups of potential binding media on milkweed fibers and built a
database of their compositions based on our examination with direct analysis in
real time mass spectrometry (DART-MS). Comparison of the compositions of
the archaeological samples to the database will be presented. Minimally-
destructive radiocarbon dating was carried out on a fragment of the textile as
well as on a small sample of a charred textile also from the Seip complex. The
Abstracts 162
process involved removing burial environment contamination from fibers with a
pH 8 phosphate buffer pre-treatment followed by plasma-chemical oxidation
(PCO) to produce carbon dioxide for accelerator mass spectrometric (AMS)
radiocarbon analysis. The radiocarbon age of the green stained textile was found
to be consistent with previous dates for Seip, though that obtained for the
charred textile was not, perhaps indicating that it either was not fully cleaned by
the phosphate treatment or was from a later intrusion in the archaeological site.
216. Robust diamond electrodes for electrochemical applications
Cory A. Rusinek1, [email protected], Mary Ensch2,1,
[email protected], Michael F. Becker1, Aaron Hardy1, Robert
Rechenberg1, Thomas Schuelke1,3. (1) Center for Coatings and Diamond
Technologies, Fraunhofer USA, Inc., East Lansing, Michigan, United States (2)
Chemical Engineering, Michigan State University, East Lansing, Michigan,
United States (3) Electrical and Computer Engineering, Michigan State
University, East Lansing, Michigan, United States
With one of the widest potential windows of any solid electrode material, boron
doped diamond (BDD) has proven excellence as an electrochemical tool. From
water treatment and chemical synthesis to electrochemical analysis and sensing,
BDD has applications in a variety of sample media. This combined with its
stability, low background current, and low double layer capacitance make BDD
specifically useful in trace detection, such as the determination of toxic heavy
metals and polycyclic aromatic hydrocarbons (PAHs) in water. We have
developed several BDD electrode technologies, each tailored to a specific
electroanalytical application. With a Nafion coated BDD optically transparent
electrode (OTE) we engineered a fluorescence based spectroelectrochemical
sensor for a common PAH, 1-hydroxypyrene, achieving a detection limit of 80
nM (17 ppb). With this, we fabricated BDD microelectrode arrays (MEAs) for
the detection of both toxic heavy metal ions and neurotransmitters, achieving
good sensitivity with low limits of detection. We also designed and produced
BDD disk electrodes for general electroanalytical applications. These BDD disk
electrodes exhibit superb electrochemical redox processes where we observed
peak separations of 65 mV or less in cyclic voltammetry (CV) of potassium
ferricyanide. Lastly, we have developed a BDD electrode stack for applications
in wastewater treatment using anodic oxidation. The electrode stacks are capable
of COD and TOC removal/reduction as well as the destruction of per- and poly-
fluoroalkyl substances (PFASs). This work further exemplifies BDD as an
excellent electrode material while broadening its sensing applications and
electrochemical capability.
Abstracts 163

217. Identifying fibers in South American Paracas period mummy textiles

by peptide mass fingerprinting
David Bailey, [email protected], Mishka Repaska, Ruth Ann Armitage.
Department of Chemistry, Eastern Michigan University, Dundee, Michigan,
United States
Analyzing ancient textiles is valuable in the study of human culture as it allows
us to understand past cultures exploitation of resources, trading practices, and
ritual traditions. Since ancient textiles are easily degraded and contaminated
over time, answering archaeological questions pertaining to these artifacts can
be difficult, when the survive into the present at all. Identifying the species from
which animal fibers originate is often done using microscopy, though in the case
of camelid fibers, the fiber morphology is insufficient for species identification.
Previous studies indicated that camelid fibers are prevalent in the textiles
associated with burials from the Paracas Necropolis of Northern Peru. We report
here on our efforts to determine if the species can be identified with
archaeological proteomics methods. We are first generating peptide mass
fingerprints (PMF) for the trypsin digests of a library of reference camelid wool
fibers including alpaca (suri and huacayo), llama, camel, guanaco, and vicua
Abstracts 164
with paper spray ionization and time-of-flight mass spectrometry. Once the
method is shown to produce reliable sequence information, we will prepare
small fibers from the Paracas textiles for comparison. The work is ongoing;
preliminary results will be presented.
218. Mass spectrometry for differentiating blue dyes in archaeological
textiles
Precious Humphrey, [email protected], Ruth Ann Armitage. Department
of Chemistry, Eastern Michigan University, Dundee, Michigan, United States
Indigo has a long and prestigious history from the ancient past to our blue jeans
today. Indigotin is a dark blue colorant molecule that is produced from many
plants, including indigo (Indigofera), woad (Isatis), and knotweed (Polygonum)
when the leaves are crushed, fermented, and then reacted with oxygen. All of the
indigo-producing plants undergo the same chemistry, so they are difficult to
differentiate from each other in archaeological textiles. There are many
analytical approaches to the characterization of blue dyes in conservation
science, though few are able to reliably distinguish between blues obtained from
the various plant sources. Archaeologists and conservators are interested in
sourcing the colors that ancient people used, as this provides insight into their
selection of materials and the chemical technology necessary to produce dyes.
We present here the initial stages of work to use direct analysis in real time
(DART) mass spectrometry (as well as other ionization methods) to differentiate
blue dyes made from indigo, woad, and knotweed on a variety of fiber
substrates. Based on the results for the lab-prepared materials, we will apply the
best method to archaeological fibers previously shown to contain indigotin.
219. CNT modified working electrodes: detection of heavy metals and 1,2-
dihydroxybenzenes
Stamatina Tolias2, [email protected], Corrie Spradlin2, Mary
Sullivan2, Justin Lee2, Dolores Dodson2, Lei Zhai1, Suzanne K. Lunsford3. (1)
Nanoscience Tech Center, Univ of Central Florida, Orlando, Florida, United
States (2) Chemistry, Wright State University, Dayton, Ohio, United States
Over the last decade, Carbon nanotubes have attracted great interest and
recognition due to their excellent electronic/ conductive properties and
minuscule functional size. Due to these electronically optimal features, carbon
nanotubes (CNT) have expanded their appliance to electrochemical electrodes.
Through much research in the field of electrochemistry, these electrodes are now
being implemented as biosensors in the detection of various medicinal and
environmental compounds of interest. CNTs have opened a new era in materials
science as they can be used to enhance material conductivity while using
selective polymers as electrochemical sensors to detect common
neurotransmitters (1,2-dihydroxybenzenes) and heavy metals such as lead and
cadmium. Results of the following CNT modified electrodes: CNT-polyvinyl
alcohol (PVA) to detect 1,2-dihydroxybenzenes in the presence of ascorbic acid,
Abstracts 165
poly-3-hexylthiophene (P3HT) modified CNT electrode to detect heavy metal
lead and polystyrene sulfonate (PSS) modified CNT electrode to detect lead and
cadmium simultaneously will be shown. Our understanding of CNT dispersed
with certain polymers to selectively detect the chemical of interest has provided
efficient hole or electron transport to successfully detect the compounds of
interest. These research experiences have been beneficial in expanding content
knowledge in the applications of CNTs while utilizing electrochemical
techniques such as cyclic voltammetry (CV), differential pulse voltammetry
(DPV) and square wave anodic stripping voltammetry (SWASV). This
presentation will further illustrate some novel aspects of integrating CNT-PSS
with nanoparticle incorporation to possibly further enhance the electrocatalytic
activity of the electrode surface for heavy metal detection.
220. Functional investigation of indirect tRNA aminoacylation in human
pathogens
Whitney N. Wood1, [email protected], Udumbara Rathnayake1,
Gayathri Silva1, Tamara L. Hendrickson2. (1) Chemistry, Wayne State
University , Detroit, Michigan, United States (2) Chemistry, Wayne State
University, Detroit, Michigan, United States
Helicobacter pylori, Staphylococcus aureus and many other pathogens lack one
or more aminoacyl-tRNA synthetase (aaRS), the enzymes that typically
aminoacylate tRNAs for ribosomal translation. These organisms must use an
indirect pathway to aminoacylate some tRNAs. Specifically, H. pylori lacks the
genes that encode for asparaginyl- and glutaminyl-tRNA synthetases (AsnRS
and GlnRS, respectively). Instead H. pylori uses a two-step, indirect pathway to
synthesize Asn-tRNAAsn and Gln-tRNAGln. This process requires two
misacylating tRNA synthetases (a non-discriminating aspartyl-tRNA synthetase,
ND-AspRS, and glutamyl-tRNA synthetase 2, GluRS2) and a glutamine-
dependent amidotransferase called AdT. We have recently discovered a protein
called Hp0100 that promotes formation of a stable complex between ND-
AspRS, Hp0100, and AdT in vitro called the Asn-transamidosome. Hp0100
enhances AdTs ability to produce both Asn-tRNAAsn and Gln-tRNAGln and it
hydrolyzes ATP in the presence of either Asp-tRNAAsn or Glu-tRNAGln, the
precursors to Asn-tRNAAsn and Gln-tRNAGln, respectively. Full-length orthologs
of Hp0100 are restricted to the e-proteobacteria. However truncated orthologs
are found outside of this clade that comprise the N-terminal 2/3 of Hp0100.
Notably, this truncated protein was found in Neisseria gonorrhoeae and S.
aureus, organisms that have been identified by the Centers for Disease Control
as biggest threats to the US because of their high rates of antibiotic resistance.
We have overexpressed and purified the S. aureus protein Sa2591, an example
of a truncated ortholog of Hp0100. Like Hp0100, Sa2591 hydrolyzes ATP in the
presence of either Asp-tRNAAsn or Glu-tRNAGln. Both Hp0100 and Sa2591
contain a putative metal binding site (a CXXC motif) and when metal is present
both enzymes hydrolyze ATP in the absence of either Asp-tRNAAsn or Glu-
Abstracts 166
Gln
tRNA . Our efforts to determine the metal of choice for Sa2591 will be
presented along with a hypothesis for why metal-sensing may be important.
221. Reactive oxygen species formation by metallo-tau peptides
Saba Anwar, [email protected], Sanela Martic. Chemistry, Oakland
University, Sterling Heights , Michigan, United States
In the presence of a biological reductant, metal ions may form reactive oxygen
species (ROS) which lead to oxidative stress. Elevated levels of these metal ions
were found in peptide plaques or filaments, in the brain, associated with
Alzheimers Disease. One biomarker of neurodegeneration is tau protein, a
structural protein which is key for maintaining neuronal cell function. The role
of metal ions and tau, in the context of ROS, has not been fully identified. The
R1-R4 domain of tau (Fig. 1) are critical domains for post-translational
modifications and aggregation. Herein, the tau peptides R1, R2, R3, and R4
(Fig. 1), were evaluated for their ability to participate in metal-catalyzed ROS
production in the presence of metal ions (Cu(II), Zn(II), Fe(II) and Fe(III)) and
ascorbic acid. Using fluorescence spectroscopy, hydrogen peroxide levels were
measured. UV-vis spectroscopy was used to evaluate the oxidation of ascorbic
acid. The presence of R-peptides modulated hydrogen peroxide levels depending
on the R-peptide sequence (Fig. 2). Low catalytic activity was observed for
peptides with metal ions in the absence of a reducing agent.

Fig. 1. Primary sequence of Tau peptides R1 through R4 (the main metal

binding sites are circled).

Fig. 2. Plot of fluorescence intensities, related to hydrogen peroxide production,

for R-peptides with metal ions (Cu(II)) in the absence and presence of ascorbic
acid.
Abstracts 167
222. Single-molecule studies of the FANCJ helicase reveal a dynamic
activity that dissolves G-quadruplexes and supports DNA replication
Colin Wu, [email protected]. Chemistry, Oakland University, Rochester,
Michigan, United States
The FANCJ (Fanconi anemia complementation group J) DNA helicase
participates in the repair of cytotoxic interstrand DNA crosslinks (ICLs).
Defects in FANCJ can give rise to either Fanconi anemia (FA), a chromosomal
instability disorder characterized by progressive bone marrow failure, or to
increased susceptibility to breast cancer, ovarian cancer, and acute myeloid
leukemia. As an interaction partner of the BRCA1 tumor suppressor and of the
MLH1 mismatch repair protein, FANCJ also participates in double strand break
(DSB) repair via homologous recombination and may play a supporting role in
DNA replication. These essential cellular processes depend on the multiple
biochemical functions of FANCJ which include dsDNA unwinding and the
remodeling of nucleoprotein complexes and of non-canonical DNA structures
such as G-quadruplexes (G4s). In order to obtain a thermodynamic and kinetic
understanding of these various properties, we employed TIRF microscopy to
visualize the DNA binding, ssDNA translocation, duplex unwinding, and G4
melting activities of individual FANCJ molecules. We show that FANCJ
monomers can readily translocate along ssDNA with the expected 5 to 3
directionality, unwind dsDNA, and resolve G4s. To our surprise, the FANCJ-
ssDNA interaction is modulated by the incoming nucleotide such that ATPS
binding promotes FANCJ dissociation from the ssDNA; however, its interaction
with G4s is not influenced by ATPS. This suggests that FANCJ may have a
different DNA binding site outside of its canonical helicase core. Consistent
with this hypothesis, we show that during ssDNA translocation and DNA
unwinding, the FeS cluster subdomain within FANCJ is positioned in front of
the helicase subdomains and poised to quench the incoming Cy3 fluorescence
from the labeled DNA substrate. On the other hand, our smFRET experiments
reveal that during FANCJ mediated G4 bypass, the quadruplex undergoes
iterating cycles of opening and refolding, resulting in anti-correlated changes to
Cy3 and Cy5 fluorescence intensities that are not sensitive to FeS quenching.
This observation indicates that the G4-containing translocation strand within
FANCJ is positioned away from the FeS cluster during G4 remodeling. Taken
together, we propose that FANCJ has an alternative DNA binding site involved
in G4 recognition and targets FANCJ to resolve these structures in order to
support DNA replication.
223. Novel ROS-Sensitive NOS inhibitor for the treatment of ischemic
stroke
Kevin M. Nash1, [email protected], Isaac T. Schiefer2, Zahoor
Shah2. (1) Pharmacology, The University of Toledo, Toledo, Ohio, United States
(2) MS 1015, University of Toledo, Toledo, Ohio, United States
Abstracts 168
Ischemic stroke is one of the leading causes of death in the United States, and is
characterized by hypoxia leading to inflammatory and free-radical mediated cell
death. Reactive oxygen species (ROS) such as superoxide (O2.-) are formed in
excess under hypoxic conditions which cause protein, DNA and lipid oxidation.
Nitric oxide (NO) formed by NO synthase (NOS) is necessary to restore blood
flow, and has been shown to be protective in ischemic stroke, however NO can
react with O2.- to form the highly oxidizing peroxynitrite (ONOO-).
Additionally, NOS has been shown to uncouple under oxidative conditions to
instead produce O2.-, further exacerbating the initial insult. Nitrones are
antioxidant molecules that are shown to be protective in stroke and other
oxidative pathologies through the spin-trapping of free radicals. After reacting
with ROS, nitrones are observed to decompose to release NO. A novel nitrone
(KN-1-35) was designed and synthesized such that its decomposition product is
a competitive NOS inhibitor, effectively leading to NOS inhibition specifically
at the site of ROS production while simultaneously neutralizing ROS and
releasing NO. An efficient synthesis yielded the reverse-engineered nitrone, and
its ability to spin-trap radicals and decompose into the putative NOS inhibitor
was observed using electron paramagnetic resonance (EPR) and liquid
chromatography-tandem mass spectrometry (LC-MS/MS). The pro-drug ability
of KN-1-35 was tested in an in vitro model of ischemic stroke by measuring cell
viability, inhibitor formation, and NOS activity in neuroblastoma cells subjected
to oxygen glucose deprivation (OGD). Lastly, the efficacy of tKN-1-35 in
reducing ischemic damage will be tested in an in vivo mouse model of
permanent ischemia.

Nitric Oxide Synthase (NOS) becomes uncoupled under ischemic conditions to

instead produce reactive oxygen species (ROS). The novel nitrone KN-1-35 is
proposed to neutralize ROS to yield a NOS inhibitor and effectively inhibit
uncoupled NOS at the site of ischemia.
Abstracts 169
224. Insight into the assembly and function of the Saccharomyces cerevisiae
GPI transamidase
Travis J. Ness, [email protected], Tamara L. Hendrickson. Wayne State
University, Grosse Pointe, Michigan, United States
Glycosylphosphatidylinositol (GPI) anchoring of proteins is a complex post-
translational modification. Approximately 0.5% of all eukaryotic proteins
undergo this process to become associated with the cell surface. GPI-anchored
proteins (GPI-APs) play important roles in parasitic infection, embryogenesis,
and signal transduction pathways.This modification is catalyzed by GPI
transamidase (GPI-T), a complex, multi-subunit, membrane-bound enzyme in
the endoplasmic reticulum.
There are five subunits that assemble to form Saccharomyces cerevisiae GPI-T:
Gaa1, Gpi8, Gpi16, Gpi17, and Gab1. In yeast, Gaa1, Gpi8, and Gpi16 purify as
one complex. Each subunit contains 1 to ~10 transmembrane domains,
contributing to the complexity of this enzyme, and hindering activity and
functional studies. To overcome challenges arising from solubilization and
purification from the membrane, the putative soluble domains of the subunits
that purify from yeast, Gpi8:Gpi16:Gaa1, termed the GPI-T heterotrimer, were
over-expressed. Gaa1s TAP-tagged soluble domain was purified and Gpi8 and
Gpi16 were successfully co-purified in a complex with Gaa1. This result
demonstrates that the transmembrane domains are not necessary for the subunits
to form a complex. While the overall reaction catalyzed by GPI-T is understood,
the role of each individual subunit in GPI anchoring of proteins is necessary to
understand this modifications impact in healthy and disease states of the cell.
An in vitro fluorescence resonance energy transfer (FRET) assay developed in
our lab allows for measuring the activity of the purified, full-length GPI-T and
the soluble domains of the heterotrimer. It was previously reported that GPI-T
could use nucleophiles such as hydroxylamine and hydrazine in place of the GPI
anchor. Our FRET assays demonstrate that full-length and soluble GPI-T
heterotrimer activities are nucleophile-dependent. Efforts are currently
underway to analyze the peptide products by HPLC-MS.
225. Evaluating the antimicrobial and antioxidant profiles of walnut husks
extracted by different methods and drying conditions
Elijah Ward, [email protected], Topping Kayla,
[email protected], Alec Gradl, Majed Alzahabi, Cheryl Samaniego,
Michelle Ammerman, Lihua Wang, Jonathan Wenzel. Kettering University,
Flint, Michigan, United States
Walnut husks are typically discarded by the walnut processing industry, but
these husks offer previously uncharacterized phytochemical value which
warrants exploration. To extract the potential phytochemicals, a supercritical
fluid extraction method using environmentally friendly ethanol and a CO2
Abstracts 170
modifier was compared with a traditional ultrasonic extraction method. Prior to
performing the extractions, a portion of the extracts were dried while another set
remained in their hydrated forms. These samples were then assessed to
determine the overall effects of drying processes as these are often employed by
industries to preserve materials. Our research team was interested particularly in
assessing antioxidant and antimicrobial values for these husks. The Total
Phenolic Content (TPC), or Folin-Ciocalteu assay, was used to determine the
antioxidant power of the extracts , and HPLC-MS was performed to identify
compounds enriched in the extracts. Prior to adding extracts to antimicrobial
assays, the volumes used were normalized to antioxidant values derived from
the TPC assay. Disc diffusion assays as well as liquid culture assays were used
to test the impact of extracts on the growth of several bacterial strains.
Antimicrobial assays showed the ability of supercritical and ultrasonic walnut
husk extracts to inhibit growth of gram negative bacteria. Following the
profiling of the extracts on antimicrobial activities, the extracts will be tested for
anti-proliferative effects on mammalian cells so that the compounds can be
excluded which exhibit toxic effects to both microbes and mammalian cells.
226. Tuning the substrate specificity of the glutathione transferase GstB
from Escherichia coli via site-directed mutagenesis
Nina V. Stourman2, Jennifer Moore1, [email protected]. (1)
Youngstown State University, Youngstown, Ohio, United States (2) Chemistry,
Youngstown State University, Youngstown, Ohio, United States
Glutathione transferases (GSTs) are detoxication enzymes that are widely
distributed in nature. They fulfill their protective roles by catalyzing the
conjugation of the tripeptide glutathione to both endogenous and xenobiotic
electrophiles. GstB is a glutathione transferase from Escherichia coli that is
known to detoxify bromoacetate, a water disinfection by-product. This work has
established an expanded substrate scope for wild type GstB, and kinetic
parameters have been obtained for bromoacetate, chloroacetate, iodoacetate,
iodoacetamide, and 2-bromobutyrate. Site-directed mutagenesis of the
electrophile-binding site residue arginine 119 was performed, generating the
alanine, glutamine, histidine, and serine enzyme variants. The activities of the
mutants toward a range of electrophiles were evaluated to investigate the impact
of the amino acid substitutions on the enzyme's substrate specificity. Preliminary
results indicate that the serine mutant affords rate enhancement for
iodoacetamide conjugation compared to wild type GstB. The finding that amino
acid substitution at position 119 can modify substrate specificity provides
support for pollutant-targeted bioremediation strategies.
227. Understanding the redox regulation of the cell by developing peptide
inhibitors to control the function of redox enzymes
Dilini N. Kekulandara, [email protected]. Chemistry, Wayne State
University, Detroit, Michigan, United States
Abstracts 171
Glutaredoxin (Grx) and thioredoxin (Trx), are members of oxidoreductase
enzyme family, involved in the regulation of thiol redox state of the cell by
catalyzing the reduction of protein- glutathionyl mixed disulfides (protein-SSG)
and protein-protein disulfides. Grx1 and Trx1 are also regulate the cell apoptosis
and/or proliferation through stress activated protein kinase (SAPK) pathway by
functioning as an endogenous inhibitor of apoptosis signaling-regulating kinase
1 (ASK1). Selective inhibitors of redox enzymes can be tools for elucidating the
functions in regulating critical cellular processes via protein modification and
cell apoptosis. Such information may lead to new therapeutic approaches in
cancer, cardiovascular diseases and neurodegenerative diseases. However, there
are only a very few inhibitors discovered as redox enzyme inhibitors. Most of
them are identified as chemically thiol-reactive and non-selective compounds.
Herein, we report a selective peptide inhibitor and evaluate its effects on human
Grx1 and Trx1 over other related redox enzymes. The phage display technique
was used to select ETRWPNT peptide as a potential candidate that binds to
Grx1/Trx1 from M13 Ph.D.-7 phage library. Selected peptide was synthesized
with and without cell permeable TAT tag and in vitro binding, inhibition of the
redox enzymes and the cell viability were evaluated. To understand the effects
of redox enzymes inhibition on cell apoptosis, regulation mechanism(s)
associated with SAPK pathway was evaluated.
228. Exploration of cytotoxicity of Ruthenium(II)-mono-arene complexes to
human cancer cell lines
Seth Hillaker, [email protected], Lihua Wang, Cheryl Samaniego.
Kettering University, Flint, Michigan, United States
Cisplatin (and related platinum compounds) is the most commonly used
chemotherapy drug. It targets DNA and potentially Hsp90 in hormone based
cancers. Unfortunately, cisplatin is very toxic and has severe side effects.
Ruthenium complexes have been extensively studied as potential anticancer
agents, including Ru(II) mono-arene complexes. Ru(II) mono-arene complexes
are effective against cisplatin resistant ovarian cancer cells and may have less
side effects than cisplatin. Enhanced drug delivery can be accomplished using
passive targeting via the enhanced permeability and retention effect of tumors or
active targeting by connecting anticancer agents with molecules or drug delivery
platforms that can selectively bind to cancer cells. This work studies the
cytotoxicity of Ru(II)-mono-arene complexes on various cancer cell lines and
explores potential delivery platforms using nanostructures.
229. Versatile new method to map uracil rich regions in the genome
Vimukthi Asgiriya Senevirathne, [email protected]. Chemistry,
Wayne State University, Detroit, Michigan, United States
Uracil, which is a nucleotide base normally found in RNA, can also occur in
DNA. One such mechanism is during cytosine deamination by activation-
induced DNA cytosine deaminase (AID) during the antibody maturation process
Abstracts 172
in the germinal center of B cells. However, AID off-targeting activity can result
in mutations in non-immunoglobulin targets resulting in B cell lymphoma. Here
we introduce a novel method, based on a biotin linker (SS-ARP) that can be
effectively used to enrich the uracil containing regions of the genome.
In this study, by using a bacterial strain CJ236, we have optimized the
conditions for the uracil containing genomic DNA enrichment and Illumina
library preparation with the enriched DNA.
This method provides a direct and a convenient approach to map the uracil rich
genomic regions and we believe that it would help in identifying the AID off-
targeting activity in a genome wide fashion in B cell lymphoma.
230. Using the MARTINI forcefield to model the self-assembly behavior of
amphiphilic dendron-lipid hybrids
Nazanin A. Taimoory1, [email protected], ali Rahimi2, John F. Trant1. (1)
Chemistry and Biochemistry, University of Windsor, Lasalle, Ontario, Canada
(2) Department of Chemical Engineering , Amirkabir University of Technology,
Tehran, Tehran, Iran (the Islamic Republic of)
Self-assembling multivalent amphiphilic compounds that can mimic biological
membranes are promising tools to probe biological systems, and may provide
the basis for future therapeutic tools. Recently, Trant and Gillies reported the
synthesis and behavior of a new class of amphiphilic glycodendron-lipid
hybrids; however, it was difficult to understand the underlying factors that drove
the observed self-assembly behavior. In this current study, building on these
results, the molecular dynamics simulation of functionalized dendron-lipid
hybrids (0-4 generations, -galactose, amine and hydroxyl functionalized) and
their self-assembled architectures were carried out using the Gromacs software
package. The nano-aggregation profile of these materials is very complex and
depends, amongst other factors, on the molecular weight and flexibility; the
mass fraction and partition coefficients of the hydrophobic and hydrophilic
components; the precise non-covalent interactions between molecules; the
nature of the hydration sphere; and the method of self-assembly used to create
the nanoparticles. The molecules and nanoparticles were analyzed at two
computational resolutions: fully atomistic (highly computationally intensive),
and coarse grain (CG, substantially less computationally intensive) using the
MARTINI forcefield to provide greater insight and to compare the accuracy of
two approaches. This presentation will discuss our computational results, the
MARTINI forcefield, and our future directions towards the modelling of new
complex cell membrane mimicking systems being developed in the Trant
Group.
Abstracts 173

231. Rational design of altered peptide ligands for treatment of celiac

disease
Daniel Meister, [email protected], Nazanin A. Taimoory, John F. Trant.
Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, Canada
Celiac disease (CD) is an autoimmune disorder that affects the digestive tract,
damaging the small intestine and inhibiting nutrient absorption. It affects 1 in
100 Canadians and there is no cure. CD stems from the misrecognition of
peptide fragments of gluten by human leukocyte antigen (HLA) receptors which
are in turn identified by T-cells leading to an immune response. Use of altered
peptide ligands has been proposed as a possible treatment method (to
outcompete and displace gluten and prevent T-cell recognition), however this
approach has not been successful due to low binding affinity of peptides, poor
biostability and inability to prevent T-cell activation. Previous attempts were
limited in using only natural amino acids in their attempt to improve binding
affinity. We propose the use of rationally designed artificial amino acids
incorporated into altered peptide ligands (APL). These residues will be able to
take advantage of various binding sites within the large HLA receptor pocket to
increase affinity by orders of magnitude. We are developing a computational
method for use in screening potential candidates by combining docking,
molecular dynamics and MM-PB/GBSA techniques. Our first step is a
benchmarking study correlating experimental and computational data for
peptides with known binding affinities to the HLA-DQ2 receptor. Once
optimized, this approach will then be utilized to screen large numbers of APLs,
the most promising of which will then be synthesized and utilized for further
studies. This poster will provide an update on our progress towards this goal.
Abstracts 174

232. Indirect tRNA aminoacylation and Asn-transamidosome formation in

bacteria
Udumbara Rathnayake, [email protected], Gayathri Silva, Tamara
L. Hendrickson. Chemistry, Wayne State University, Detroit, Michigan, United
States
Most bacteria and archaea do not have genes encoding asparaginyl-tRNA
synthetase (AsnRS) or glutaminyl-tRNA synthetase (GlnRS), and consequently
rely on an indirect pathway to produce Asn-tRNAAsn and Gln-tRNAGln. Indirect
tRNA aminoacylation occurs in two steps. The first step for Asn-tRNAAsn
synthesis involves the misacylation of tRNAAsn with aspartate to form Asp-
tRNAAsn; this reaction is catalyzed by a non-discriminating aspartyl-tRNA
synthetase (ND-AspRS). Next, an amidotransferase called GatCAB converts
Asp-tRNAAsn into Asn-tRNAAsn. Mechanism/s for the quick delivery of Asp-
tRNAAsn, from ND-AspRS to GatCAB must exist to ensure the fidelity of
protein synthesis. For example, Thermus thermophilus assembles a stable
ribonucleoprotein complex called the Asn-transamidosome, from tRNAAsn,
GatCAB and ND-AspRS. This complex prevents premature release of Asp-
tRNAAsn prior to transamidation by GatCAB.
Unlike T. thermoplilus, Helicobacter pylori, require another protein partner,
Hp0100, to form a stable, tRNA-independent Asn-transamidosome. Hp0100
accelerates the GatCAB catalyzed transamidation of Asp-tRNAAsn into Asn-
tRNAAsn ~35 fold. Our preliminary evidence suggests that Hp0100 contains two
mutually exclusive ATP binding domains, which are activated by Asp-tRNAAsn
and Glu-tRNAGln. Further, Hp0100 also has a putative metal binding motif that
preferentially binds to divalent metal ions.
The Asn-transamidosome from Mycobacterium smegmatis, has been isolated.
The overexpression of GatCAB subunits in M. smegmatis result in the co-
purification of ND-AspRS and other unknown proteins. In the presence of
tRNAAsn, yield of purified Asn-transamidosome roughly tripled, suggesting that
the M. smegmatis Asn-transamidosome is more robust in the presence of
Abstracts 175
Asn
tRNA . To our knowledge, this purification represents the first successful
purification of any Mycobacterial Asn-transamidosome from its native
organism. Two of the unknown proteins that reproducibly co-purified with
GatCAB were identified as a universal stress protein (UPS) and superoxide
dismutase (SOD).
We hypothesize that the disruption of Asn-transamidosome causes low levels of
mistranslation of Asp into Asn codons of proteins, and the accessory proteins
like Hp0100, USPs and SOD might interfere with the Asn-transamidosome
assembly in response to external stressors leading to bacterial persistence and
antibiotic tolerance.
233. Kinetic study of cytochrome c reduction by various polyphenolic
compounds
Montserrat Rabago-Smith2, [email protected], Duyen Do2, Austin
Baker2, Lihua Wang1, Veronica R. Moorman2. (1) Kettering Univ, Flint,
Michigan, United States (2) Kettering University, Flint, Michigan, United States
In addition to being an important mitochondrial electron transfer protein,
cytochrome c plays a central role in apoptosis, the process of programed cell
death that is involved in cancer, heart failure, etc. Previously, it has been found
that polyphenolic antioxidants, such as green tea catechins, are able to bind and
reduce cytochrome c, which may contribute to the mechanism of the various
health benefits of green tea catechins and other dietary polyphenolic
antioxidants.
This work studies the kinetics of cytochrome c reduction by various
polyphenolic compounds (such as catechol, caffeic acid, and 3,4-
dihydroxybenzoic acid) to investigate the relationship between the structural
features of the compounds and their reactivity. Specifically, the effects of the
locations of the hydroxyl groups on the benzene ring and the nature of other
substituents were examined.
234. Investigation of fluorescently tagged catechins in mouse embryonic
fibroblast cells
Montserrat Rabago-Smith, [email protected], Micheal Thomas, Cheryl
Samaniego, Veronica R. Moorman, Lihua Wang. Kettering University, Flint,
Michigan, United States
Green tea is one of the most popular drinks in the world and its health benefits
are well known. These benefits are attributed to its strong antioxidants
properties. Catechins such as epigallochatechin gallate (ECGC) and epicatechin
(EC) account for 9%- 48% percent of teas dry weight; and are the major source
for its antioxidant activity. Recent studies done in our group suggest that
catechins have additional interactions with cellular proteins such as cytochrome
c. Such interactions suggest additional modes for cell protection. This
presentation will discuss the preparation of ECGC and EC fluorescent
Abstracts 176
derivatives. Additionally, studies between mouse embryonic fibroblast cells and
the synthesized fluorescent probes will be discussed. Preliminary results using
EC and EGCG derivatives suggest that these catechins are transported through
the membrane into the cytoplasm and the nucleus.
235. FANCJ repairs DNA helicases with REV1 and the BRCT supressor
gene
Francesca M. Iscovo, [email protected], Colin Wu, Mena Jirjees,
[email protected]. Chemistry, Oakland University, Rochester, Michigan,
United States
Accumulated DNA damage and oxidative stress are common precursors to
cancer, cardiovascular disease, and stroke. FANCJ is a DNA helicase that
repairs damaged DNA in human cells, and it coordinates with the REV1
polymerase and the BRCA1 tumor suppressor to participate in separate DNA
repair pathways. How these genomic caretakers target damaged DNA is not
known. This work aims to bridge this knowledge gap by determining the
substrate binding preferences of FANCJ, REV1, and BRCA1. Recombinant
proteins are purified for fluorescence spectroscopy and quartz crystal
microbalance based DNA binding assays. These experimental outcomes will
provide a detailed description of the intricate DNA damage response network
maintained by FANCJ, REV1, and BRCA1; this data will be especially helpful
for understanding how malfunctions in these proteins give rise to genetic
instability, and also for designing new anticancer treatments that target their
corresponding DNA repair pathways in malignant cells.
236. SMYD2 glutathionylation controls sarcomere stability and myofibril
integrity
Dhanushka N. Munkanatta Godage2, [email protected], Kusal T.
Samarasinghe2, Zhe Yang3, Minkui Luo1, Young-Hoon Ahn2. (1) Box 248,
Memorial Sloan-Kettering Cancer Center, New York, New York, United States
(2) Chemistry, Wayne State University, Detroit, Michigan, United States (3)
Biochemistry and Molecular Biology, Wayne state university, School of
Medicine, Detroit, Michigan, United States
The reactive oxygen species (ROS) are important signaling molecules that
contribute to etiology of multiple muscle-related diseases, including
cardiomyopathy and heart failure. However, it remains yet incompletely
understood how ROS or cellular stress make an impact on structural stability of
sarcomere or myofibril, a contractile unit of muscle. Protein glutathionylation is
one of major protein cysteine oxidative modifications that play an important role
in redox signaling and oxidative stress. In this report, we used a clickable
glutathione approach in cardiomyocytes, finding that SET and MYND Domain
Containing 2 (SMYD2), a lysine methyltransferase, can be selectively
glutathionylated at C13 residue. Functional studies showed that SMYD2 C13
glutathionylation serve as a key molecular event that leads to a loss of myofibril
Abstracts 177
integrity and degradation of sarcomeric proteins mediated by matrix
metalloprotease 2 (MMP-2) and calpain 1. Biochemical analysis demonstrated
that SMYD2 glutathionylated at a C13 residue loses its interaction with Hsp90
and N2A, a domain of titin that is important for stress-sensing. Further analysis
showed that N2A can be degraded by MMP-2 upon its dissociation from
SMYD2, suggesting the protective role of SMYD2 in sarcomere stability. Our
results uncover SMYD2 glutathionylation as a novel molecular mechanism by
which ROS contribute to sarcomere destabilization and muscle dysfunction.
237. Engineering optical actuators for G proteins
Dinesh Kankanamge, [email protected], Ajith
Karunarathne. Chemistry and Biochemistry, University of Toledo, Toledo, Ohio,
United States
Insulated activation of G proteins is necessary for identification of their
exclusive contribution to the overall pathway function without interfering
signals from the G Protein Coupled Receptor (GPCR). Activators of G protein
Signaling (AGS) family proteins can serve as a library of biological regulators to
manipulate signaling of G and G independent of GPCR activation.
Combining minimum activation domains of AGS and blue light sensing
cryptochrome and phototropin photoreceptor domains, we engineer optically
triggered activators of G proteins. We show that the spatial and temporal
controllability, especially the reversibility and the repeatability of signaling
elicited by our actuators on optical command make them powerful tools for
interrogating signaling networks in living cells.
238. Role of Amot coiled-coil homology domain residues in lipid binding
specificity
Rut Thakkar2, [email protected], Ann C. Kimble Hill1. (1) Dept. of
Biochemistry & Molecular Biology, Indiana University School of Medicine,
Indianapolis, Indiana, United States (2) Department of Neuroscience,
Vanderbilt University, Nashville, Tennessee, United States
Angiomotins (Amots) are adaptor proteins that regulate pathways involved in
protein sorting and downstream signaling events such as cellular differentiation,
proliferation, and migration. The Amot coiled-coil homology (ACCH) domain
has been described as the region for selectively binding monophosphorylated
phosphatidylinositols (PI) as well as for guiding specific transcription factors
away from or towards the nucleus. As previous research has suggested that three
arginine, four lysine, and three tyrosine residues within the ACCH domain drive
the lipid binding affinity of Amot to non- and mono-phosphorylated PIs, the
goal of this study is to determine whether these residues further influence lipid
selectivity. A protein containing mutations of these specific arginine, lysine, and
tyrosine residues within the ACCH domain were screened for changes in affinity
to mono-, di-, and tri-phosphorylated PIs in addition to other negatively charged
lipids by using lipid pull down and protein pull down assays. To investigate the
Abstracts 178
hypothesized mechanism, ACCH domain fragments cleaved by Asp-N, NTCB,
and Formic Acid were then screened for affinity to mono-phosphorylated lipids,
as well as their ability to discriminate for specific lipid head groups. Through
these experiments, we intend to distinguish whether these ACCH domain
residues drive affinity for or association with the PI head group.
239. Copper transport in chickens; evidence of a role for riboflavin binding
protein
Sheila R. Smith, [email protected], Natasha Bell, Marilee Benore. Dept of
Nat Sci, University of Michigan, Dearborn, Michigan, United States
Copper is an essential metal in fetal development. In the avian embryo, transport
and storage of copper is complicated by the need to deliver a full complement of
copper to the egg before laying and to store it safely in the unfertilized egg until
it is required. Several egg proteinsinvolved in copper storage have been
previously identified, particularly, phosvitin. It is not known how copper is
transported from the mother to the egg. Riboflavin Binding protein (RBP), the
primary transport system for the essential vitamin riboflavin, will also bind
copper in vitro. In the current work, we apply a new competitive binding assay
to determine the binding affinities of copper to both RBP and to phosvitin. The
implications of these affinities for the transport of copper in eggs will be
examined.
240. High-Affinity Binding and Detection of Pyrophosphate in Water by a
Resorcinarene Tetra-Salt Receptor
N. K. Beyeh,a,b I. Dez,a P. Inkinen,a S. MD. Taimoory,b D. Meister,b A.
Peuronen,c J. F. Trant,b R. H. A. Ras,a and K. Rissanenc , a Aalto University,
Espoo, Finland, b University of Windsor, Windsor, Canada, c University of
Jyvskyl, Jyvaskyla, Finland
Pyrophosphates are very important biological anions formed by the hydrolysis
of adenosine triphosphate (ATP) into adenosine monophosphate (AMP) in
cells.1 In all organisms from bacteria to humans, inorganic pyrophosphate (PPi)
is hydrolyzed to phosphate which in turn helps the DNA, RNA and protein
synthesis processes.2 Alendronate, a PPi analog, is currently being used as a
drug for osteoporosis, Pagets disease, and for complications of prostate cancer.3
In addition, phosphate anions such as PPi and ATP play key roles in energy
transduction and several major metabolic processes such as DNA replication.1
The PPi concentrations can provide critical information on these processes and
therefore, the detection and quantification of PPi can help identify diseases such
as chondrocalcinosis or calcium pyrophosphate dihydrate (CPPD) crystal
deposition disease.2,4
N-alkyl ammonium resorcinarene chloride,5 a macrocyclic tetra-salt receptor,
binds PPi with a remarkably high binding constant (K1=1.15106 M-1). The
results was compared with a monophosphate in potassium phosphate (K3PO4)
Abstracts 179
and a triphosphate in adenosine triphosphate (ATP). The binding processes were
studied in all phases via Mass Spectrometry, NMR spectroscopy, Isothermal
Titration Calorimetry (ITC), UV-Vis/Fluorescence spectroscopy and supported
through detailed conformational analysis and DFT based computational
modeling.

241. Synthesis and Properties of Nanofibers of Platinum(II) Complexes

S. Barzegar, M. K. Abdolmaleki, G. Absalan, W. B. Connick *, Department of
Chemistry, University of Cincinnati, Cincinnati, Ohio, USA, Department of
chemistry, College of Sciences, Shiraz University, Shiraz, Iran
Luminescent platinum(II) complexes have attracted much attention due to their
potential practical use as photocatalysts, luminophore in LEDs and components
in sensors. Platinum(II) salts often are intensely colored in the solid-state
because short PtPt interactions that result in low-lying charge transfer states.
In this presentation we will discuss different methods for preparing nanofibers
of a metal complex. We also will discuss the factors influencing the
morphology and size of these particles, as well as other properties of these
unusual materials.
242. Synthesis of arylimidamide-azole hybrids as antileishmanial agents
A. M. Abdelhameed, A. C. Joice, E. Zywot, H. L. Meeds, X. Liao, K. A.
Werbovetz, Division of Medicinal Chemistry & Pharmacognosy, The Ohio State
University
Leishmaniasis, a neglected tropical disease with visceral and cutaneous
manifestations, is prominent in regions of Africa, South America and the Indian
subcontinent. Cutaneous leishmaniasis can lead to lifelong scars while visceral
leishmaniasis is lethal if left untreated. There is a critical need for new drugs
since current medications show resistance or display serious adverse effects.
DB766 is an antileishmanial lead compound that shows potent antileishmanial
activity, displaying IC50 values below 0.1 M against intracellular Leishmania
and good selectivity against J774 macrophages with a CC50 value of 2.8 M.
Abstracts 180
However, administration of DB766 at an oral dose of 100 mg/kg/day for 5 days
resulted in only 71% reduction in liver parasitemia in a murine visceral
leishmaniasis model. Thus, further modification is needed to improve the
antileishmanial efficacy of arylimidamide molecules. Additional studies
implicated ergosterol metabolism in the mechanism of action of DB766, and
recent studies showed that a combination of DB766 with the azole drug
posaconazole displayed synergistic activity in a mouse model of visceral
leishmaniasis. Thus, synthesis of hybrid compounds containing both the
arylimidamide and azole scaffolds might provide a more effective
antileishmanial agent. A series of hybrid compounds were synthesized where
the arylimidamide and azole groups are separated by phenoxyalkyl linkers of
different chain lengths. Improved antileishmanial activity was observed with an
increase in chain length. The best antileishmanial activity in a series of
unsubstituted phenoxyalkyl hybrids was seen for a compound with an octyloxy
phenyl linker which displayed an IC50 value of 1.0 M against intracellular L.
donovani. Further increase in the hydrocarbon chain length led to slight drop in
antiparasitic activity. Substitution of the phenyl ring of the linker with an
isopropoxy group lead to improvement in the antileishmanial activity, especially
when this group was in the position ortho to the arylimidamide group (IC50 =
0.50 M vs. L. donovani). This compound also displayed >10 fold selectivity
towards L. donovani compared to J774 macrophages. Further modifications
were performed by replacing the imidazole group with either triazole or pyrrole.
The pyrrole analog was slightly less potent against L. donovani compared to its
corresponding imidazole derivative, while replacement of imidazole with
triazole caused a decrease in the antileishmanial activity.

Come to Toledo
for the
Central Regional Meeting
in 2018
Guide to Authors (Presenters in Bold) 181
Abdelhameed, A.M. 242 Barenbugge, D. 168 Buth, J.M. 211
Abdelhamid, E. 165 Baron, L.A. 212 Camacho, M. 31, 32, 33
Abdolmaleki, M.K. 241 Barrenbrugge, D. 41 Campbell, K.A. 202
Abraham, N.K. 213 Bart, S.C. 112 Castillo-Badillo, J. 118
Absalan, G. 241 Barzegar, S. 241 Catanescu, C. 128
Acharya, P. 70 Basal, L. 17 Chadha, R. 27
Adams, S. 122 Basu, D. 156 Chavez, F.A. 91
Ahmed, U. 73 Baumann, J.W. 39 Chien, A. 36
Ahn, Y. 236 Baydoun, H. 94, 151 Chisholm, J.D. 193
Akbar, M. 198 Bazzi, T. 74 Cho, S.H. 196
Alabdullah, B. 194 Beck, W.F. 98 Chong, E. 90
Albasrawi, H.K. 66, 200 Becker, M.F. 178, 199, Chow, C.S. 9
Albiniak, P.A. 50 216 Chreifi, G. 3
Alexander, C. 41, 168 Belanger, R.M. 213 Cinelli, M. 3
Alhadidi, Q. 4 Bell, N. 239 Clark, T.M. 182
Allen, M.J. 17, 113, 141, Benore, M. 239 Connick, W.B. 241
143, 152 Benson, D.E. 110 Crich, D. 9
Alnaed, M. 40 Benvenuto, M.A. 14, Cross, M.E. 113
Alrubayyi, A. 59 138, 158, 160 Cunningham, N. 197,
Alzahabi, M. 225 Berden, G. 197, 205 205
Amarasinghe, D.K. 150 Berry, N. 73 Daniel, Y. 58
Ammerman, M. 225 Beyeh, N. K. 240 Daniels, C. 214
Andersen, J. 6 Bhagwagar, M. 138 Das, B. 6
Anliker, K.S. 203 Bhagwat, A.S. 11 Davenport, E. 52
Anwar, S. 221 Bhattacharyya, N. 53, Dayfield, D.J. 213
Arefi-Khonsari, F. 115 175 Del Carmen Marin, M.
Armitage, R. 215, 217, Bhattarai, B. 78 97
218 Bhetuwal, B. 72 Demers, J. 177
Arrasmith, C. 214 Bigioni, T.P. 78 Demond, A. 53, 175
Arumugam, K. 173 Blakeney, K.J. 20 Desai, A. 57, 105
Asgiriya Senevirathne, Blue Hetter, K. 201 Devereaux, Z. 197, 205
V. 229 Botti, M. 55 Dhanapala, B.D. 147
Ashenfelter, B. 78 Bourne, C. 81 Di Raddo, P. 136
Bailey, D. 217 Bowers, G. 198 Diemlar, N. 78
Bailey, M. 152 Brasch, N.E. 48 Dez, I. 240
Bailey, M.D. 17, 113, Brewer, T.R. 81 Dilling, W.L. 47, 137
141 Brock, S. 146, 165 Dissanayake, K.T. 145
Baker, A. 233 Brown, C. 214 Do, D. 233
Baker, K.C. 52 Brown, M.K. 68 Dodson, D. 219
Baker, L. 99 Bryant-Friedrich, A.C. Donahue, C.J. 184, 186
Baniasad, M. 50 76, 194, 196 Drevnick, P. 177
Barawi, K.M. 213 Burdick, J. 151 Ducharme, M. 4
Guide to Authors (Presenters in Bold) 182
Dutta, A.K. 6 Groysman, S. 25, 38, Igbokwe, E. 51
Dvonch, J.T. 177, 179 114, 148, 149, 161 Inaba, M. 79
Dye, J. 195 Ha, S. 176 Inkinen, P. 240
Eads, C.N. 210 Hagood, K. 4 Iscovo, F.M. 235
Earl, L. 45 Hamlow, L. 205 Iwadunna_Waduge, W.
Ekanayake, D.M. 157 Han, M. 128 167
Ekstrom, A.L. 12, 15, Han, Y. 176 Jackson, J.E. 195
183 Hancock, J. 139 Jacob, B. 9
El Harakeh, N. 156 Hardy, A. 178, 216 Jakes, K.A. 215
Ellis, M. 76 Hartmann, D. SE2 Jalloh, F. 195
Endicott, J.F. 40 Hartner, S.E. 52 James, E. 74
England, J. 55 Hassanali, A.A. 37 Jandaghi, M. 42, 163
Ensch, M. 178, 216 Hayes, K.F. 180 Jayaraman, S. 172
Erdmann, L. 162 Headley, D. 86, 206 Jayasundara
Esposito, E.X. 188 Hebert, S. 85 Mudiyanselage, S. 153
Evans, K.R. 213 Heineman, W.R. 199 Jeffrey, S. 19, 164
Ezeh, V.C. 129 Hendrickson, T.L. 220, Jenkins, C. 62
Fannin, H.B. 210 224, 232 Jenks, T. 141
Fayoumi, R. 123 Hernandez de la Pena, Jenks, T.C. 113
Felliger, B. 88 L.H. 34 Jensen, A.W. 47
Fera, J. 89 Herrington, D.G. 131, Jin, G. 152
Fiedler, A. 155 132, 185 Jirjees, M. 235
Filby, P. 77 Hettiarachchi, M.A. 165 Johns, H. 128
Finke, R. 117 Hikima, A. 3 Johnson, A.N. 210
Fitzgerald, P. 158 Hill, V. 58 Johnson, D.W. 139
Folkman, S. 117 Hillaker, S. 228 Joice, A.C. 242
Frasco, D. 100 Hines, R. 54 Jones, B. 192
Friedrich, K.J. 192 Hollingsworth, R. 25, Jones, C. 1
Fulco, H. 63 114 Jones, M. 208
Gao, Y. 93 Hollingsworth, R.L. 161 Jung, H. 176
Gautam, N. 118 Hollingsworth, T. 114, Kalyanaraman, V. 118
Gawronski, K. 52 149 Kang, W. 199
Gianopoulos, C. 42, 140 Holub, J.M. 8 Kankanamalage, P.H.A.
Giolando, D.M. 19, 41, Horton, A. 4 154
164, 168 Hosseini, S. 16, 87 Kankanamge, D. 96, 237
Gnanada, J. 6 Howell, B. 58, 59, 63 Karunarathne, A. 96,
Goldman, A.S. 93 Howell, B.A. 64, 65, 67, 119, 120, 237
Gradl, A. 225 125 Karunarathne, M.C. 39
Grass, A. 148 Humphrey, P. 218 Kaster, M.A. 43
Green, J.R. 122 Huynh, U.G. 64, 65 Kayla, T. 225
Greenwalt, C. 46 Hwang, Y. 176 Keil, R.G. 210
Grounds, O. 56 Hyun, S.P. 176, 180 Kekulandara, D.N. 227
Guide to Authors (Presenters in Bold) 183
Kennedy, V. 162 Luo, D. 6 Moore, J. 226
Khatri, H. 70 Luo, M. 236 Moore, J.S. 27, SE4
Kiledal, S. 212 Lynam, M.M. 177, 179 Moorman, V.R. 233, 234
Kim, B. 180 Ma, L. 53, 175 Mosley, J. 192
Kimble Hill, A.C. 238 Maerz, T. 52 Munasinghe, H.N. 147
Knettle, B. 46 Makki, S. 138 Munkanatta Godage,
Kondasinghe, T. 69 Malek, K. 171 D.N. 236
Kosmas, S.P. 158 Maloney, V.M. 29, 135 Nadgorny, B. 165
Kostrevski, A. 4 Mammana, A. 209 Nash, K.M. 4, 223
Kovacs, D.G. 30 Mann, T. 179 Nasri, S. 123
Kpogo, K.K. 154, 155, Marincean, S. 28, 74 Nasser, B. 74
157 Martsek, P. 3 Ndombera, F. 7
Kulesa, K.M. 142, 157 Martic, S. 221 Nei, Y. 197
Lalman, J.A. 115 Martin, A. 55 Ness, T.J. 224
Lambert, K.S. 213 Martin, P.D. 39, 167 Newton, M.D. 52
Lambright, K.J. 41, 168 Martinez, B. 134 Nguyen, G. 138
Langenderfer, B. 4 Martinez, B.L. 131 Nguyen, H.P. 72
Large, D.N. 200 Masell, C. 55 Nichols, M. KN1
Larsen, S.D. 2 Mashburn, J.D. 210 Nicki, M. 117
Lassiter, C. 134 Mason, M. 140 Niedek, C. 158, 192
Law, Y. 37, 202 Mason, M.R. 42, 163 Njomen, E. 1
Lawniczak, J. 90 Masthay, M. 209, 210 Njus, D. 83
Lawson, D.B. 82 Matzger, A.J. KN3 Novak, A. 4
Leckie, D.M. 60 Maxwell, D.N. 213 Nussbaum, M.A. 212
Lee, E. 176 Mazumdar, S. 157 Oberdorfer, K. 67
Lee, J. 205, 219 Mazumder, S. 94, 151, Olivucci, M. 97
Lee, Y. 176 154, 155 Olmstead, E.G. 202
Lenora, C. 18 Mbofana, C. 90 O'Neill, P. 118
Li, D. 146 McAuliffe, K. 170 Oomens, J. 197, 205
Li, H. 3 McAuliffe, K.J. 43 Ostrander, E. 127
Li, L. 92 McCaffrey, V.P. 109 Otero, M. 53, 175
Li, W. 84 McCrory, C.C. 95 Padilha, D. 142
Li, X. 71, 72, 73, 191 McGrath, C. 209 Paluri, S. 198
Li, Z. 16, 87 Meeds, H.L. 242 Palushaj, N. 55
Liang, J. 47 Meister, D. 231, 240 Pankratz, T.C. 25
Liao, X. 102, 242 Melaccio, F. 97 Papautsky, I. 199
Lienhart, G.W. 61 Mensah, E. 45 Pasternak, M.A. 76
Lindale, J.R. 25 Meshik, X. 118 Pautler, R.G. 17
Lopez, A.M. 124 Miles, M. 173 Payton, J.L. 119, 120
Lord, R.L. 25, 38, 114, Milletti, M. 35, 79, 80 Pcolinski, M.J. KN2
161 Modrzejewski, M. 22 Peng, T. 115
Lunsford, S.K. 219 Moon, H. 176 Penner, P. 122
Guide to Authors (Presenters in Bold) 184
Pensa, A.V. 3 Roman, L.J. 3 Shah, Z. 4, 223
Perera, D.V. 133 Romero, J. 17 Shayman, J.A. 2
Perera, S. 144, 150 Rosokha, S.V. 54, 56, Sheets, R. 81
Petzold, M. 199 204 Shi, X. 84
Peuronen, A. 240 Roswell, R.L. 202 Shin, D. 176
Pignotti, L. 189 Roy, H.A. 205 Shrikhande, G. 103
Plaumann, H.P. 14 Royster, K. 4 Shrode, A.D. 132
Porter, A. 214 Ruprecht, M. 158 Siddihiki, M. 162
Post, M. 4 Rusinek, C.A. 178, 199, Silva, G. 220, 232
Pothoof, J. 138, 158 216 Silverman, R.B. 3
Pouget, V. 122 Sabol, J.E. 187, 190 Simoliunas, S. 174
Poulos, T.L. 3 Sadiq Ahmed, A. 57 Siripurapu, P. 96
Pozo, R. 214 Sadraei, S. 51, 57, 105 Siriwardena, S.U. 11
Puskas, J.E. 103 Saleh, F. 140 Sizemore, I. 198
Qian, S. 13 Salman, A. 55 Sjgren, B. 1
Quiroz, M. 206 Salvage, S. 3 Skieneh, J. 122
Rabago-Smith, M. 233, Samaniego, C. 225, 228, Sliwinski, B. 158
234 234 Smith, S.R. 106, 111,
Rabon, A.M. 166 Samarasinghe, K.T. 10, 239
Rabuffetti, F.A. 144, 145, 236 Sonousi, A. 9
147, 150 Sampson, P. 48, 49 Sosnowski, B. 158
Raghavan, A. 4 Sanford, M.S. 90 Spradlin, C. 219
Rahimi, a. 230 Sappy, I. 75 St. Onge, B. 122
Rahman, M. 48 Saraha, H. 126 Stahl, T. 80
Rajagopalan, S. 6 Saybolt, K. 73 Steele, D. 27
Ras, R.H.A. 240 Sayed, I. 213 Stevens, J.E. 24
Rathnayake, U. 220, 232 Sayre, H. 21 Stewart, J.L. 106, 108
Ratnayake, K. 96, 119, Scarpellini, M. 142 Stockton, M. 211
120 Schiefer, I.T. 4, 223 Stoian, S. 38
Ray, C. 27 Schlegel, H. 83, 84, 85, Stourman, N.V. 226
Ray, S. 115 94, 151, 154, 155, 157, Su, N. 19, 164
Rayat, S. 77 207 Subir, M. 86, 206
Rechenberg, R. 178, 216 Schmits, M. 86, 206 Sullivan, M. 219
Reinsel, A.M. 130 Schoendorff, G. 23 Sun, K. 19, 164
Reith, M. 6 Schuelke, T. 178, 199, Sweeder, R.D. 131, 132,
Repaska, M. 215, 217 216 185
Resh, T. 81 Schumaker, R. 65 Szalay, P.S. 133
Riley, A. 16, 87 Schurter, E.J. 133 Szczesniak, M. 22
Rissanen, K. 240 Seed, A.J. 48, 49 Szlag, D. 181
Roberts-Kirchhoff, E. Sejdarasi, L. 43, 169 Szlag, R. 43
160, 213 Sen, S. 103 Tackie-Yarboi, E. 4
Rodgers, M.T. 197, 205 Senarath, K. 96
Guide to Authors (Presenters in Bold) 185
Taimoory, N.A. 123, Wehring, B. 199
230, 231 Weinberger, C. 54
Taimoory, S.MD. 240 Weis, N. 120
Tepe, J.P. 1 Wenzel, J. 225
Thakkar, R. 238 Werbovetz, K.A. 242
Thalalla Gamage, S. 9 Westerman, C. 62
Thapa, B. 207 Wicker, G. SE5
Thatcher, G.R. 5 Wilson, A.K. 208
Thomas, M. 234 Wilson, N. 202
Thomas, S. 160 Winchester, W.R. 30
Tieu Ngo, T. 160 Winter, C.H. 20, 39, 167
Timmons, S.C. 52, 66, Winter, J. 26
200 Woo, B. 53, 175
Todi, S. 6 Wood, W.N. 220
Tolias, S. 219 Woodward, J. 71
Tomsho, A. 211 Wu, C. 222, 235
Torres, V.C. 213 Wu, Y. 121
Trant, J. 123 Xu, T. 47
Trant, J.F. 51, 57, 60, Xu, Y. 68
104, 105, 230, 231, 240 Yacoo, K. 213
Trivedi, E.R. 43, 169, Yang, Z. 236
170 yedlapudi, D. 6
Tu, Y. 83 Yee, S. 211
Turro, C. 21 Young, M. 101, 166
Valentini, A. 97 Young, M.A. 116
Vandenplas, J.R. 131, Young, R. 86, 206
132, 185 Yousif, G. 57, 105
Verani, C.N. 94, 142, Yousif, M. 38
151, 154, 155, 156, 157, Zaker, Y. 78
159 Zavala, J. 27
Wamer, N. 4 Zhai, L. 219
Wang, D. 155 Zhang, J. 49
Wang, L. 225, 228, 233, Zhao, L. 47
234 Zhou, M. 107, 117
Ward, E. 225 Zhou, Y. 48, 134
Wasalathanthri, R. 19, Zhu, J. 70, 72
164 Zhu, Y. 197, 205
Wathen, S.P. 44 Zimmerman, P.M. 36
Watry, M.R. 88, 89 Zook-Gerdau, L.A. 133
Watson, B. 56 Zuhl, A. 143
Weeden, A. 13 Zywot, E. 242
Weeraratne, A. 159
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

ACS Publications, a
division of the American
Chemical Society, is a
nonprofit scholarly
publisher of nearly 50 peer-reviewed journals and a range of e-
books at the interface of chemistry and related sciences, including
physics and biology, which are consistently ranked among the
most cited, most trusted, and most read in scientific literature. The
Division offers high quality, rapid time to publication, a range of
channels to access the publishers cutting-edge digital platform,
and a comprehensive program of Open Access initiatives. ACS
Publications also publishes Chemical & Engineering Newsa
news magazine covering science and technology, business and
industry, government and policy, education, and employment
aspects of the chemistry field. (15)

Advion is the partner of choice for biopharmaceutical,

academic/government researchers, and industrial chemists seeking
to enhance their chemical synthesis knowledge, workflow and
mass spectrometry results. Using our deep scientific and
engineering expertise, we develop a broad portfolio of chemist-
centric, purpose-built mass spectrometers, nanoelectrospray
ionization sources, flow-chemistry synthesis systems and
consumables characterized by their reliability, high quality and
flexibility. (13)

186
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

A special thank you to the Amalgamated Tuna Company of

Highland Heights, Ohio, for their generous support of CERM
2017.

At BASF, we create
chemistry for a sustainable
future. We combine
economic success with
environmental protection
and social responsibility.
Through science and
innovation we enable our customers in nearly every industry to
meet the current and future needs of society.

BASF Corporation is the largest affiliate of BASF SE and the

second largest producer and marketer of chemicals and related
products in North America. (11)

187
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

Biotage offers solutions,

knowledge and experience in the
areas of analytical chemistry,
medicinal chemistry, peptide
synthesis, separation and
purification. The customers
include pharmaceutical and biotech companies, companies within
the food industry and leading academic institutes. The company is
headquartered in Uppsala and has offices in the US, UK, China,
Korea and Japan. (3)

Bruker designs and manufactures

analytical instrumentation for
materials research, structural and
surface investigations. Brukers
range of technologies contain FT-
IR, NMR and mass spectrometry.
Our portfolio also includes compact, powerful, robust, yet easy-to-
use instrumentation specially developed for scientific education
purposes. We are strongly committed to meet costumers needs
and continue to develop innovative solutions for todays analytical
questions. (10)

Gamry Instruments is the recognized leader in instrumentation

for electrochemical impedance spectroscopy. We have also
developed a laboratory course in electrochemistry for
undergraduate facilities. Stop by the booth to see our educational
bundle which includes the instrument, teaching and student
manuals, cells, and electrodes needed to complete a semester
course. (6)
188
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

The HORIBA Group of worldwide companies provides an

extensive array of instruments and systems for applications ranging
from automotive R&D, process and environmental monitoring, in-
vitro medical diagnostics, semiconductor manufacturing and
metrology, to a broad range of scientific R&D and QC
measurements. Proven quality and trustworthy performance have
established widespread confidence in the HORIBA Brand. (5)

Nanalysis manufactures portable NMR spectrometers. The

NMReady is the first portable NMR spectrometer in a single
compartment enclosure. It is used by chemists in many
industries and in university labs. (1)

Netzsch Instruments North

America, LLC Make your
choice from among our
diverse variety of instruments for Thermal Analysis. NETZSCH
Analyzing & Testing has consistently invested its long-time
experience into innovative new developments and advanced
technologies conceived for state-of-the-art application tasks in
materials research and development, quality assurance and process
optimization. Our products and services embody technological
leadership, expertise, and reliable quality for the users benefit. (7)

189
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

Rigaku Oxford Diffraction provides tools which drive

discoveries and increase our understanding of the universe at a
molecular level. Our products include instrumentation and
software for chemical crystallography, macromolecular
crystallography and biological solution scattering. Additionally,
our group includes Rigaku Reagents, which provides reagents and
tools for macromoleculer crystallization and cryo-
crystallography.(2)

"Contributing to Society through Science and Technology"

Based on this corporate philosophy that represents the pioneering
spirit inherited from our founder, Shimadzu Corporation has
continued to develop all our businesses for the past 140 years since
its foundation in Kyoto in 1875.
Our analytical and measuring instruments, and industrial
machinery are now used for a broad range of applications in a wide
variety of industries, where they serve society by providing
confidence and convenience through the business operations of our
customers. (8)

190
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

ACS Division of Small Chemical Businesses (SCHB) helps

chemists working in small enterprises, including self-employed,
with the legal, social, educational, legislative, regulatory, and
economic aspects of their unique professional status.

Innovative analytical instruments, lab equipment and specialty

diagnostics that provide rapid and accurate results for customers in
research, clinical and applied markets. (14)

Vernier Software &

Technology is the leading
worldwide innovator of real-
time data-collection, graphing
and analysis tools for science
education. Vernier chemistry
offerings range from a benchtop gas chromatograph and
spectrophotometers to pH and temperature probes, all controlled
using our award-winning software Logger Pro or our stand-alone
LabQuest 2 lab interface. (4)

191
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

Central Michigan University: We

emphasize high-quality education by
maintaining a high teacher/student ratio to
ensure adequate mentoring. We offer
undergraduate programs in Chemistry and
Biochemistry and MS in Chemistry and MA in Teaching College
Chemistry. Faculty also participate in PhD programs in the Science
of Advanced Materials and in Biochemistry, Cell and Molecular
Biology. (27)

(23)

See our advertisement on page 3. (22)

University of Cincinnati (21)

(23)
192
Our Sponsors and Exhibitors
Note: Exhibit Table Numbers follow each entry (in parenthesis).

(28)

University of
Michigan,
Dearborn
(26)

Wayne State University: With a research pedigree dating to well

before the 1944 establishment of the Ph.D. program by Neil E.
Gordon, and a teaching mission embracing diversity and modern
methodology, the department of Chemistry provides a supportive
yet competitive atmosphere for faculty and students alike. We have
over 150 graduate students and 30 postdoctoral fellow researchers
in the Department. In the last three years nearly 60 Ph.D.s and 150
Bachelor's degrees in Chemistry have been awarded. ((29)

Wright State University: The

Masters program in
Chemistry at Wright State
University provides a
well-rounded curriculum
in a setting that is large
enough to afford the
advantages of a modern chemistry program, yet small enough to
allow personal attention. We offer coursework and faculty-directed
research in traditional and applied chemistry. Visit
chemistry.wright.edu to learn more. (25)
193
Exhibition Table Assignments

Table #
1 Nanalysis
2 Rigaku Corporation
3 Biotage
4 Vernier
5 Horiba Scientific
6 Gamry
7 Netzsch Instruments North America, LLC
8 Shimadzu
9
10 Bruker Optics
11 BASF
12
13 Advion
14 Thermo-Scientific
15 ACS publications
16
17
18
19
20
21 University of Cincinnati
22 Oakland University
23 Lawrence Technological University
24 University of Detroit - Mercy
25 Wright State University
26 University of Michigan - Dearborn
27 Central Michigan University
28 University of Michigan
29 Wayne State University

194
CERM 2017 Program Grid

Tuesday, June 6 Wednesday, June 7 Thursday, June 8 Friday, June 9

MEETING
PM WED AM WED PM THUR AM THUR PM FRI AM FRI PM
ROOM
Presidential EXHIBIT SET-UP (8 am - 3
E X H I B I T D I S P L A YS SE3. 4:00 pm Ice Cream Social EXHIBIT TEARDOWN
Prefunction pm)

Presidential EXHIBIT SET-UP (8 am - 3

E X H I B I T D I S P L A YS EXHIBIT TEARDOWN
Salon IV pm)
E & G. Electronic Structure Theory & Molecular
Salon I M & Q. Optical Chem & Optogenetics U. Environmental Chemistry
Dynamics

Salon II A. Academic Drug Discovery F. Active Learning X. Analytical Chemistry

WS1. Finding Your Pathway WS3. Career Planning WS4. Chemometrics SE7. 1:00 pm Governance /
Salon III WS2. Resume Review
Workshop Workshop Workshop SE8. 4:00 pm Science Mixer

Salon V C. Chemometrics N & R. Organic Chemistry W. Organic Chemistry Z. Physical Chemistry

O. Undergrad Teaching in
Salon VI D &H. Inorganic Chemistry
INORGN Chem

Salon VII B. Biochemistry I. Entrepreneurs Tool Kit L & P. Catalysis by Metal Complexes & Nanomaterials V & Y. Chemical Education

Plaza Ballroom KN1. Keynote Address KN2. Keynote Address SE4. 6:00 pm Award Dinner KN3. Keynote Address

Plaza
Prefunction
R E G I S T R A T I O N
T. Inorganic Poster Session BB. Biochemistry Poster
Plaza A J. Organic Poster Session (2)
(2) Session (2)
K. Physical Chemistry Poster S. Chemical Education Poster AA. Analytcal Poster Session
Plaza B
Session (2) Session (2) (2)

The Gallery SE1. Opening Reception SE2. WCC Luncheon SE5. YCC Luncheon SE6. Vendor Breakfast

Key: Exhibit Keynote Address Poster Session (2) Registration Social Event Workshop
Notes: 1. Index key letters in the grid correspond to Index key IDs listed in the Mobile App and Program book.
2. Primary Poster Locations will be in the Exposition (Presidential Ballroom Salon IV) with overflow in the Plaza Ballroom.