Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside

doi:10.1021/acs.jpclett.7b01588

. 2017 Aug 17;8(16):3800-3804.

doi: 10.1021/acs.jpclett.7b01588. Epub 2017 Aug 2.

Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside

Sergey K Filippov¹, Bart Verbraeken², Petr V Konarev^{3

4

5}, Dmitri I Svergun³, Borislav Angelov⁶, Natalya S Vishnevetskaya⁷, Christine M Papadakis⁷, Sarah Rogers⁸, Aurel Radulescu⁹, Tim Courtin², José C Martins², Larisa Starovoytova¹, Martin Hruby¹, Petr Stepanek¹, Vitaly S Kravchenko¹⁰, Igor I Potemkin^{10

11}, Richard Hoogenboom²

Affiliations

¹ Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic CZ - 162 06 Praha 1, Czech Republic.
² Department of Organic and Macromolecular Chemistry, Ghent University , Krijgslaan 281-S4, 9000 Ghent, Belgium.
³ Hamburg Outstation, European Molecular Biology Laboratory c/o DESY, Notkestrasse 85, Hamburg 22607, Germany.
⁴ A.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre 'Crystallography and Photonics', Russian Academy of Sciences , Leninsky prospekt 59, Moscow 119333, Russian Federation.
⁵ National Research Centre "Kurchatov Institute" , Akademika Kurchatova Place 1, Moscow 123182, Russian Federation.
⁶ Institute of Physics, Academy of Sciences of the Czech Republic , 182 21 Praha 8, Czech Republic.
⁷ Technische Universität München, Physik-Department , Fachgebiet Physik weicher Materie, James-Franck-Straße 1, 85748 Garching, Germany.
⁸ ISIS Facility, STFC, Rutherford Appleton Laboratory , Harwell Oxford, Didcot, OX11 0QX, United Kingdom.
⁹ Forschungszentrum Jülich GmbH, Jülich Centre for Neutron Science JCNS, Outstation at Heinz Maier-Leibnitz Zentrum, Lichtenbergstraße 1, 85748 Garching, Germany.
¹⁰ Physics Department, Lomonosov Moscow State University , Moscow 119991, Russian Federation.
¹¹ National Research South Ural State University , Chelyabinsk 454080, Russian Federation.

PMID: 28759235
DOI: 10.1021/acs.jpclett.7b01588

Free article

Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside

Sergey K Filippov et al. J Phys Chem Lett. 2017.

Free article

. 2017 Aug 17;8(16):3800-3804.

doi: 10.1021/acs.jpclett.7b01588. Epub 2017 Aug 2.

Authors

Affiliations

¹ Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic CZ - 162 06 Praha 1, Czech Republic.
² Department of Organic and Macromolecular Chemistry, Ghent University , Krijgslaan 281-S4, 9000 Ghent, Belgium.
³ Hamburg Outstation, European Molecular Biology Laboratory c/o DESY, Notkestrasse 85, Hamburg 22607, Germany.
⁴ A.V. Shubnikov Institute of Crystallography, Federal Scientific Research Centre 'Crystallography and Photonics', Russian Academy of Sciences , Leninsky prospekt 59, Moscow 119333, Russian Federation.
⁵ National Research Centre "Kurchatov Institute" , Akademika Kurchatova Place 1, Moscow 123182, Russian Federation.
⁶ Institute of Physics, Academy of Sciences of the Czech Republic , 182 21 Praha 8, Czech Republic.
⁷ Technische Universität München, Physik-Department , Fachgebiet Physik weicher Materie, James-Franck-Straße 1, 85748 Garching, Germany.
⁸ ISIS Facility, STFC, Rutherford Appleton Laboratory , Harwell Oxford, Didcot, OX11 0QX, United Kingdom.
⁹ Forschungszentrum Jülich GmbH, Jülich Centre for Neutron Science JCNS, Outstation at Heinz Maier-Leibnitz Zentrum, Lichtenbergstraße 1, 85748 Garching, Germany.
¹⁰ Physics Department, Lomonosov Moscow State University , Moscow 119991, Russian Federation.
¹¹ National Research South Ural State University , Chelyabinsk 454080, Russian Federation.

PMID: 28759235
DOI: 10.1021/acs.jpclett.7b01588

Abstract

Herein, we provide a direct proof for differences in the micellar structure of amphiphilic diblock and gradient copolymers, thereby unambiguously demonstrating the influence of monomer distribution along the polymer chains on the micellization behavior. The internal structure of amphiphilic block and gradient co poly(2-oxazolines) based on the hydrophilic poly(2-methyl-2-oxazoline) (PMeOx) and the hydrophobic poly(2-phenyl-2-oxazoline) (PPhOx) was studied in water and water-ethanol mixtures by small-angle X-ray scattering (SAXS), small-angle neutron scattering (SANS), static and dynamic light scattering (SLS/DLS), and ¹H NMR spectroscopy. Contrast matching SANS experiments revealed that block copolymers form micelles with a uniform density profile of the core. In contrast to popular assumption, the outer part of the core of the gradient copolymer micelles has a distinctly higher density than the middle of the core. We attribute the latter finding to back-folding of chains resulting from hydrophilic-hydrophobic interactions, leading to a new type of micelles that we refer to as micelles with a "bitterball-core" structure.

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Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside

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Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside

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