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

Sergey K Filippov, Bart Verbraeken , Petr V Konarev, Dmitri I Svergun, Borislav Angelov, Natalya S Vishnevetskaya, Christine M Papadakis, Sarah Rogers, Aurel Radulescu, Tim Courtin, José C Martins, Larisa Starovoytova, Martin Hruby, Petr...

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

Jazyk angličtina Země Spojené státy americké

Typ dokumentu práce podpořená grantem

Perzistentní odkaz   https://www.medvik.cz/link/bmc20016063

Grantová podpora
NV15-25781A MZ0 CEP - Centrální evidence projektů

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.

Citace poskytuje Crossref.org

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$a Block and Gradient Copoly(2-oxazoline) Micelles: Strikingly Different on the Inside / $c Sergey K Filippov, Bart Verbraeken , Petr V Konarev, Dmitri I Svergun, Borislav Angelov, Natalya S Vishnevetskaya, Christine M Papadakis, Sarah Rogers, Aurel Radulescu, Tim Courtin, José C Martins, Larisa Starovoytova, Martin Hruby, Petr Stepanek, Vitaly S Kravchenko, Igor I Potemkin, Richard Hoogenboom
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$a 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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