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CARBOHYDRATES AND GLYCOBIOLOGY # of Carbons Aldose Ketose
● Sugar - known as carbohydrate or hydrate of
carbon. 3 Aldotriose Ketotriose
● Most abundant biomolecule on earth.
4 Aldotetrose Ketotetrose
● Oxidation - central energy yielding pathway
in most non-photosynthetic cells. 5 Aldopentose Ketopentose
● Complex carbohydrate polymers act as
6 Aldohexose Ketopentose
signals.
● Has three major classes: monosaccharides, 7 Aldoheptose Ketoheptose
oligosaccharides and polysaccharides.
● Monosaccharides also exhibit
● Polyhydroxyaldehydes (aldose) or
stereoisomerism. The simplest
polyhydroxyketones (ketose)
monosaccharide that exhibits stereoisomerism
● Name ends in -ose.
is glyceraldehyde.
● Most have the empirical formula (CH2O)n -
● Mirror-image stereoisomers are called
number of molecules attached. Some contain
enantiomers.
nitrogen, phosphorus or sulfur.
● Non-mirror image stereoisomers are called
● Play a number of important roles in
diastereomers.
biochemical processes.
● Configuration: three-dimensional arrangement
- Major sources of energy
of groups around the chiral carbon.
- Have a key role in cell surfaces such
as cell-cell interactions and immune
recognition.
- Essential structural components
Sugars
● Monosaccharides: monomers (building
blocks) of all carbohydrates.
● Called differently depending on the number of
carbons and main functional group.
D. Glyceraldehyde and L. Glyceraldehyde. Notice the
● The simplest monosaccharides contain three
positions of both OH.
carbons (triose).
- Glyceraldehyde (aldotriose)
● Stereoisomers differ from each other in
- Dihydroxyacetone (aldoketose)
configuration.
● Glyceraldehyde and Dihydroxyacetone
- D & L systems are widely used.
- R & S systems are also used. This is a
more recent system.
There is no one-to-one correspondence
between the two systems.
● Possibilities for stereoisomerism increase as
the number of carbon atoms increase.
● Fischer projection - shows the structure of
molecules (two-dimensional perspective)
- In a Fischer projection, the orientation
of the bonds represents the direction of
Functional Group Name the bond.
Aldehyde (-COH) Aldose - Vertical bonds: directed behind the
plane. Away from the viewer.
Ketone (CH-CO-CH) Ketose - Horizontal bonds: directed in front of
the plane. Towards the viewer.
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The Fischer projection formulas of three forms of

glucose. The alpha and beta forms can be converted
to each other through the open-chain form. The
configuration at carbon 5 determines the D
designation.

Numbering of carbon atoms in sugars. D and L Fischer projection formulas - useful for describing
Glucose - enantiomers stereochemistry of sugars in their linear forms.
Haworth projection formulas - describing cyclic
structures.
- Structures are viewed from the edge of the
plane.
- Furanose - five-membered rings
- Pyranose - six-membered rings

REACTIONS OF MONOSACCHARIDES
Redox reaction of sugars
Stereoisomers of an aldotetrose • Oxidation: releases the energy stored in
The designation of D or L depends on the carbohydrates, takes place in cellular respiration.
configuration at the highest-numbered chiral carbon • Reduction: forms the carbohydrate, takes place in
atom. photosynthesis.
Epimers - diastereomers that differ from each other at • Oxidation reactions of sugars are used to identify
only one chiral carbon. the sugar.
• Aldehydes can be oxidized to give carboxyl group
When sugar forms a cyclic molecule… of acids (-COO- ), used to test for aldoses
● Sugars (esp. 5-6 C) normally exist as cyclic • Aldoses are called reducing sugars
molecules. • In the cyclic form, the compound formed by the
● Cyclization is a result of interaction between oxidation of aldose is called a lactone.
functional groups.
- C1 (aldehyde) and C5 (alcohol) forms • Two types of reagents are used to detect the
cyclic hemiacetal (aldohexoses). presence of reducing sugars: silver ammonia complex
- C2 (ketone) and C5 (alcohol) forms ion, Ag(NH3 )2 + (Tollen’s test) and glucose oxidase
cyclic hemiketal (ketohexoses) (which is specific only for glucose).
● Carbonyl carbon becomes a new chiral center:
anomeric carbon. Oxidation-reduction reactions of sugars
● Cyclic sugar can take two different forms (a • A deoxy sugar, L-fucose, is found in the
and B) - anomers of each other. carbohydrate portions of glycoproteins including the
ABO blood-group antigens. Another deoxy sugar, 2-
deoxyribose, is found in DNA.
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Alditol - carbonyl group reduced to a hydroxyl • Glycosidic bonds formed through the linkage of the
group. Oxygen atom of one sugar to another are called O-
C=O→ C-OH glycosidic bonds.
Examples: xylitol and sorbitol (artificial sweeteners) • N-glycosidic bonds can be found in nucleic acids,
Reducing - a hydrogen is added. especially between the nitrogenous bases and the
five-carbon sugar.
• S-glycosidic bonds are found in thioglycosides,
where O is replaced by sulfur.
• Glycosides derived from furanose (5 C):
furanosides.
• Glycosides derived from pyranose (6 C):
pyranosides.

VITAMIN C • Glycosidic bonds between monosaccharides are the

• Vitamin C is related to sugars basis for the formation of oligosaccharides and
• Also known as ascorbic acid polysaccharides.
• Vitamin C is an unsaturated lactone with a five • Glycosidic linkage can take various forms;
membered ring structure. numerous combinations are found in nature.
• Most animals synthesize Vit. C except for guinea • The hydroxyl groups (-OH) are numbered so that
pigs and primates, including humans. they can be distinguished; the numbering follows the
• Ascorbic acid is taken through diet; deficiency leads carbon atoms.
to scurvy

Scurvy: collagen (protein) has structural defects,

causing skin lesions and fragile blood vessels.
Hydroxyproline (amino acid derivative) is important
for the stability of collagen.

• Chemical nature of oligosaccharides and

Ascorbic acid is essential for the activity of prolyl
polysaccharides depend on
hydroxylase, which converts proline to
1. the monosaccharides that are linked together
hydroxyproline.
2. the particular glycosidic bond formed
• Example: the difference between cellulose and
Lack of ascorbic acid affects this activity, leading to
starch depend on the glycosidic bond formed between
the fragile collagen responsible for the symptoms of
glucose monomers.
scurvy.
• Variation in glycosidic linkages can form linear and
branchedchain polymers.
Esterification reactions of sugars
• Hydroxyl groups of sugars can react with acids and
GLYCOSIDES
derivatives of acids to form esters.
• In testing the presence of reducing sugars, anomeric
• Phosphate esters are important because they are the
carbon is usually involved in the reaction. It is also
usual intermediates in the breakdown of
frequently involved in the glycosidic linkage.
carbohydrates to provide energy.
• Note that the internal anomeric carbon in an
• Formed by the transfer of phosphate from ATP to
oligosaccharide or a polysaccharide is not free to give
give phosphorylated sugar and ADP.
a positive result for reducing sugar.
• These reactions are important in carbohydrate
• Only if the end residue is a free hemiacetal rather
metabolism.
than a glycoside will there be a positive test for
reducing sugar.
• It is possible for a sugar hydroxyl group (ROH)
Derivatives of sugars
bonded to the anomeric carbon to react with another
• Amino sugars: carbohydrates that contain amino
hydroxyl group (R’-OH) to form a glycosidic linkage
group or its derivatives that substitutes for the
(R’-O-R), or a compound known as a glycoside.
hydroxyl group of the parent sugar.
• Glycosidic linkage is not an ether
• In N-acetyl amino sugars, the amino group itself
• The hydrolysis of glycosidic linkages results in the
carries the acetyl group (CH3 -CO-) as a substituent
original alcohol, not a new compound.
• Important examples of amino sugars: N-acetyl-β-
• The bond formed is called a glycosidic bond.
Dglucosamine and N-acetyl-βmuramic acid. These
are components of bacterial cell walls.
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Some hexose derivatives important in biology. In LACTOSE

amino sugars, an -NH2 group replaces one of the
-OH groups in the parent hexose. Substitution of -H
for -OH produces a deoxy sugar; note that the deoxy
sugars shown here occur in nature as the L-isomers.
The acidic sugars contain a carboxylate group, which
confers a negative charge at neutral pH. D-glucono-δ-
lactone results from formation of an ester linkage
between the C-1 carboxylate group and the C-5 (also • Lactose: made up of β-Dgalactose and D-glucose
known as the carbon) hydroxyl group of Dgluconate. linked at β(1→4)
• A reducing sugar because the anomeric carbon of
OLIGOSACCHARIDES glucose is free.
• Oligomers (Grk. oligos = few) of sugars are usually • Have two anomeric forms, each must have the β-D-
disaccharides formed by linking two galactose while the D-glucose can be either α or β.
monosaccharides units.
• Three of the most important examples of MALTOSE
oligosaccharides are disaccharides
• Sucrose
• Lactose
• maltose

• Maltose is obtained from the hydrolysis of starch

• Consist of two residues of Dglucose in an α(1→4)
linkage.
• Differs from cellobiose (from cellulose) only in the
glycosidic linkage which is β(1→4)
SUCROSE • Mammals can digest maltose but not cellobiose.
• Yeast contains enzymes that hydrolyze starch to
maltose and glucose, which is fermented during
brewing.

LACTOSE INTOLERANCE

• Sucrose (table sugar) is extracted from sugar cane

and sugar beets.
• Monosaccharide units: α - D - glucose and β - D
-fructose.
• C -1 of the glucose is linked to the C -2 of the
fructose in a α, β(1 → 2) glycosidic linkage.
• Not a reducing sugar, but monomeric substituents
are.
• Glucose & fructose - reducing sugars.

• Consumption leads to hydrolysis of monomers

which are then used as energy sources.
• Humans consume large quantities; excessive
consumption contribute to health problems which led
to a search for other sweetening agents • Sugar intolerance results from the inability to either
• Fructose: sweeter than sucrose, but changes texture digest or metabolize certain sugars, usually due to
of food missing or defective enzymes.
• Saccharin and cyclamates: causes cancer in lab • Some adults have a deficiency in the enzyme lactase
animals in the intestinal villi.
• Aspartame: suspected to cause neurological • Build-up of lactose causes bacterial lactase to act on
problems it, releasing H, CO2 , and organic acids instead of
galactose and glucose.
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• The bacterial products lead to digestive problems
such as bloating and diarrhea; the products further • Starch are polymers of α-D-glucose. Has different
draw water via osmosis thus aggravating the diarrhea. forms; can be distinguished from one another by their
degrees of chain branching.
• Even if lactase is present, other people cannot • Amylose: linear polymer linked at α(1→4)
metabolize galactose. glycosidic bonds
• If an enzyme that catalyzes the reaction pathway for • Amylopectin: branched chain polymer with
galactose is absent, galactose builds up resulting in branches starting at α(1→6) linkages along the chain
galactosemia. of α(1→4)
• Severe problem in infants because galactose is
converted to galactitol, which cannot be excreted.
The accumulation draws in water and causes
swelling, edema causes damage.
Galactose build-up in the brain causes damage.
• Dietary therapy for lactose intolerance and
galactosemia are different.
• Lactose intolerant people must avoid taking in
lactose throughout their lives.
• Galactosemia-afflicted people must avoid milk Amylose and Amylopectin
during their childhood. The development of • Starch are storage molecules and therefore should
metabolic pathways for galactose during puberty have a mechanism for releasing glucose.
alleviates the problem in most individuals. • Enzymes can hydrolyze these different forms of
starch: α and β-amylase.
STRUCTURES AND FUNCTIONS OF POLYSACCHARIDES • β-amylase is an exoglycosidase, cleaves from the
• When many monosaccharides are linked together, non-reducing end of the polymer, produces maltose.
the result is a polysaccharide. • α-amylase is an endoglycosidase, cleaves anywhere
• Polysaccharides that occur in organisms are usually along the chain to produce glucose and maltose.
composed of a very few types of monosaccharide. • Amylose can be completely degraded to glucose
• Homopolysaccharide: polymer consisting of only and maltose by the two amylases; amylopectin is not
one type of monosaccharide. completely degraded because the branches are not
• Heteropolysaccharide: polymer consisting of more attacked.
than one type of monosaccharide. • Debranching enzymes that attack α(1→6) are used
• Complete characterization of a polysaccharide by plants and animals.
includes
• Specification of which monomers are HOW IS GLYCOGEN RELATED TO STARCH?
present • Starch is to plants as glycogen is to animals: both
• Sequence of monomers are storage polymers.
• Specific type of glycosidic linkage. • Glycogen is a branched-chain polymer of α-D-
glucose; similar to the amylopectin part in this regard.
DIFFERENCE BETWEEN CELLULOSE AND STARCH • Glycogen is more highly branched, every 10th
• Cellulose is the major structural component of plant residue is a branch compared to every 25th in
cell walls. amylopectin
• Linear homopolysaccharide of βD-glucose, with all • Average chain length is 13 glucose residue, and 12
residues linked in β(1→4) glycosidic bonds. layers of branching
• Individual polysaccharide chains are hydrogen- • Has glycogenin at its core, an enzyme that acts as a
bonded together. primer to convert glucose into glycogen.
• Animals are not capable of hydrolyzing cellulose • Found in animal cells in granules, observed in liver
because of the absence of cellulase. and muscle cells.
• Cellulase attack the β(1→4) glycosidic bonds
• Certain bacteria have cellulase, including bacteria • The number of branch points in the glycogen
found in termite gut and ruminants. structure is significant for two reasons:
1. a more branched polysaccharide is more water-
soluble; the more glycogen in a solution is, the faster
energy can be released.
2. When an organism needs energy quickly for
spontaneous reflexes, the enzyme glycogen
phosphorylase has more potential targets if there are
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more branches. This allows quicker mobilization of • Aside from being energy storage and structural
glucose materials, sugars are also information carriers:
• They serve as destination labels for some proteins
CHITIN • They serve as mediator of specific cell-cell
• Chitin: polysaccharide similar to cellulose in both interaction and interaction between cells and
structure and function. extracellular matrix
• Linear homopolysaccharide with all residues • Other roles of specific carbohydrate containing
linked in β(1→4) glycosidic bonds molecules include
• Differ from cellulose in the monomeric unit. • cell-cell recognition
• cellulose: β-D-glucose • cell adhesion
• chitin: N-acetyl-β-D-glucosamine • cell migration
• Plays a structural role, has a fair amount of • blood clotting
mechanical strength because of hydrogen bonds. • immune response
• Major component of the exoskeletons of • When an informational carbohydrate is covalently
invertebrates; cell walls of algae, fungi, and yeast. bonded to a protein or lipid, it forms a
glycoconjugate.
ROLE OF POLYSACCHARIDES IN THE WALLS OF CELLULOSE
• Heteropolysaccharides are major components of Glycoproteins: have one or several oligosaccharides
bacterial cell walls. covalently joined to a protein.
• They are also cross-linked by peptides in • The oligosaccharides have various complexity
prokaryotic cell walls. depending on the molecule.
• The repeating polysaccharide units consist of two • Outside cell: on the outer face of the plasma
residues held at β(1→4) like cellulose. membrane, in the extracellular matrix, and blood
• Residues are N-acetyl-D-glucosamine and N- • Inside cell: Golgi complexes, secretory granules,
acetylmuramic acid. lysosomes
• N-Acetylmuramic acid is found only in prokaryotic • Highly rich in information; forms specific sites for
cell walls; does not occur in eukaryotic cell walls. recognition and high-affinity binding by other
• Plant cell walls consist largely of cellulose. proteins.
• Pectin, another component of plant cell walls, is
composed mostly of Dgalacturonic acid residues. Proteoglycans: macromolecules of the cell surface of
• Extracted from plants; used as a gelling agent in extracellular matrix, a type of glycoprotein
yogurt fruit preserves, jams and jellies • Unique from other glycoproteins because of
• Lignin (L. lignum, “wood”) a nonpolysaccharide glycosaminoglycan.
component of plant cells walls; a polymer of • One or more glycosaminoglycan chains are joined
coniferyl alcohol, very tough and durable. covalently to a membrane protein
• Glycosaminoglycan moiety of the proteoglycan
POLYSACCHARIDES IN CONNECTIVE TISSUES dominates the structure; often the main site of
• Glycosaminoglycans: polysaccharide based on a biological activity
disaccharide in which one of the sugars is • Major components of connective tissues such as
• An amino sugar cartilage.
• One of the sugars has a negative charge because of
a sulfate or a carboxyl group Glycolipids: membrane lipids in which the
• Involved in a wide variety of cellular function and hydrophilic head groups are oligosaccharide
tissue. • Act as a specific site for recognition by
• Heparin: a natural anticoagulant that prevents blood carbohydrate-binding proteins.
clots • Gangliosides are a specific type of glycolipid and
• Hyaluronic acid: a component of vitreous humor of the carbohydrate moieties are available for signal
the eye and the lubricating fluid of the joints. transduction.

• Chondroitin sulfates and keratan sulfate: component CARBOHYDRATES AND THE IMMUNE RESPONSE
of connective tissues • Some of the most important examples of
• Glucosamine sulfate and chondroitin sulfate: OTC glycoproteins are involved in the immune response
drugs that help repair damaged cartilage. (e.g., antibodies)
• Antibodies bind to immobilize antigens that attack
the organism.
GLYCOCONJUGATES: Proteoglycans, Glycoproteins, • Carbohydrates also play an important role as
and Glycolipids antigenic determinants:
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• portions of an foreign molecule that
antibodies recognize and to which they bind.
ABO Blood Groups
• The four blood groups are distinguished based on
the oligosaccharide portion of the glycoprotein on the
surface of red blood cells.
• In all blood types, L-fucose (6-deoxy-L-
galactose) is found
• N-Acetylgalactosamine is found at the
nonreducing end of the oligosaccharide in the
type-A blood-group antigen
• In type-B blood, α-D-galactose takes the
place of Nacetylgalactosamine
• In type-O blood, neither of these terminal
residues is present
• In type-AB blood, both kinds of
oligosaccharide are present.
• If a blood transfusion is attempted with
incompatible blood type, an antigen antibody reaction
takes place
• The antibodies on the recipient recognize the
antigen specific for the introduced blood from
the donor.
• The characteristic oligosaccharide residues
on the introduced blood serve as the
antigen
• A cross-linking reaction occurs; cells will clump
together
• Wrong blood transfusion can result in life-
threatening severe reactions.