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Block and gradient copoly(2-oxazoline) micelles : strikingly different on the inside

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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 H-1 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.
Keywords
COPOLYMER AQUEOUS-SOLUTIONS, ANGLE NEUTRON-SCATTERING, MICELLIZATION, TRANSITION, POLYMERIZATION, ARCHITECTURES, SOLVENT

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Chicago
Filippov, Sergey K, Bart Verbraeken, Petr V Konarev, Dmitri I Svergun, Borislav Angelov, Natalya S Vishnevetskaya, Christine M Papadakis, et al. 2017. “Block and Gradient Copoly(2-oxazoline) Micelles : Strikingly Different on the Inside.” Journal of Physical Chemistry Letters 8 (16): 3800–3804.
APA
Filippov, S. K., Verbraeken, B., Konarev, P. V., Svergun, D. I., Angelov, B., Vishnevetskaya, N. S., Papadakis, C. M., et al. (2017). Block and gradient copoly(2-oxazoline) micelles : strikingly different on the inside. JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 8(16), 3800–3804.
Vancouver
1.
Filippov SK, Verbraeken B, Konarev PV, Svergun DI, Angelov B, Vishnevetskaya NS, et al. Block and gradient copoly(2-oxazoline) micelles : strikingly different on the inside. JOURNAL OF PHYSICAL CHEMISTRY LETTERS. 2017;8(16):3800–4.
MLA
Filippov, Sergey K, Bart Verbraeken, Petr V Konarev, et al. “Block and Gradient Copoly(2-oxazoline) Micelles : Strikingly Different on the Inside.” JOURNAL OF PHYSICAL CHEMISTRY LETTERS 8.16 (2017): 3800–3804. Print.
@article{8534833,
  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 H-1 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 {\textacutedbl}bitterball-core{\textacutedbl} structure.},
  author       = {Filippov, Sergey K and Verbraeken, Bart and Konarev, Petr V and Svergun, Dmitri I and Angelov, Borislav and Vishnevetskaya, Natalya S and Papadakis, Christine M and Rogers, Sarah and Radulescu, Aurel and Courtin, Timothee and Martins, Jos{\'e} and Starovoytova, Larisa and Hruby, Martin and Stepanek, Petr and Kravchenko, Vitaly S and Potemkin, Igor I and Hoogenboom, Richard},
  issn         = {1948-7185},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY LETTERS},
  keyword      = {COPOLYMER AQUEOUS-SOLUTIONS,ANGLE NEUTRON-SCATTERING,MICELLIZATION,TRANSITION,POLYMERIZATION,ARCHITECTURES,SOLVENT},
  language     = {eng},
  number       = {16},
  pages        = {3800--3804},
  title        = {Block and gradient copoly(2-oxazoline) micelles : strikingly different on the inside},
  url          = {http://dx.doi.org/10.1021/acs.jpclett.7b01588},
  volume       = {8},
  year         = {2017},
}

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