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Thermally Responsive Hyperbranched Poly(ionic liquid)s: Assembly and Phase Transformations
Macromolecules ( IF 5.1 ) Pub Date : 2018-06-25 00:00:00 , DOI: 10.1021/acs.macromol.8b00845 Volodymyr F. Korolovych 1 , Andrew Erwin 1 , Alexandr Stryutsky 2 , Hansol Lee 1 , William T. Heller 3 , Valery V. Shevchenko 2 , Leonid A. Bulavin 4 , Vladimir V. Tsukruk 1
Macromolecules ( IF 5.1 ) Pub Date : 2018-06-25 00:00:00 , DOI: 10.1021/acs.macromol.8b00845 Volodymyr F. Korolovych 1 , Andrew Erwin 1 , Alexandr Stryutsky 2 , Hansol Lee 1 , William T. Heller 3 , Valery V. Shevchenko 2 , Leonid A. Bulavin 4 , Vladimir V. Tsukruk 1
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A library of linear and branched amphiphilic poly(ionic liquid)s based on hydrophobic cores and peripheral thermally sensitive shells was synthesized and studied with regard to their ability to form stimuli-responsive, organized assemblies in aqueous media. The thermally responsive derivatives of poly(ionic liquid)s were synthesized by neutralizing 32 terminal carboxyl groups of functionalized polyester cores by amine-terminated poly(N-isopropylacrylamide)s (PNIPAM) (50% and 100%). We observed that these hyperbranched poly(ionic liquid)s possessed a narrow low critical solution transition (LCST) window with LCST for hyperbranched compounds being consistently lower than that for linear PNIPAM containing counterparts. We found that the poly(ionic liquid)s form spherical micellar assemblies with diverse morphologies, such as micelles and their aggregates, depending on the terminal compositions with reduced sizes for hyperbranched poly(ionic liquid)s. Increasing temperature above LCST promoted formation of network-like aggregates, large vesicles, and spherical micelles. Moreover, all PNIPAM-terminated compounds exhibited distinct unimolecular prolate nanodomain morphology in contrast to common spherical domains of initial cores. We proposed a multilength scale organized morphology to describe the thermoresponsive poly(ionic liquid)s micellar assemblies and discussed their morphological transformations during phase transitions associated with changes in hydrophobic–hydrophilic balance of poly(ionic liquid)s with distinct hydrophobic cores and variable peripheral shells.
中文翻译：
热响应性超支化聚（离子液体）：组装和相变
合成了基于疏水核和外围热敏壳的线性和支链两亲性聚离子液体库，并对其在水性介质中形成刺激响应性，有组织的装配体的能力进行了研究。聚（离子液体）的热响应衍生物是通过胺端基的聚（N）中和官能化聚酯核的32个末端羧基而合成的-异丙基丙烯酰胺）（PNIPAM）（50％和100％）。我们观察到，这些超支化聚离子液体具有狭窄的低临界溶液转化（LCST）窗口，其中超支化化合物的LCST始终低于含线性PNIPAM对应物的LCST。我们发现，聚（离子液体）形成具有多种形态的球形胶束组件，例如胶束及其聚集体，具体取决于超支化聚（离子液体）的尺寸减小的末端组成。高于LCST的温度升高促进了网络状聚集体，大囊泡和球形胶束的形成。此外，与初始核的常见球形结构域相反，所有PNIPAM封端的化合物均表现出不同的单分子扁长的纳米结构域形态。
更新日期：2018-06-25
中文翻译：
热响应性超支化聚（离子液体）：组装和相变
合成了基于疏水核和外围热敏壳的线性和支链两亲性聚离子液体库，并对其在水性介质中形成刺激响应性，有组织的装配体的能力进行了研究。聚（离子液体）的热响应衍生物是通过胺端基的聚（N）中和官能化聚酯核的32个末端羧基而合成的-异丙基丙烯酰胺）（PNIPAM）（50％和100％）。我们观察到，这些超支化聚离子液体具有狭窄的低临界溶液转化（LCST）窗口，其中超支化化合物的LCST始终低于含线性PNIPAM对应物的LCST。我们发现，聚（离子液体）形成具有多种形态的球形胶束组件，例如胶束及其聚集体，具体取决于超支化聚（离子液体）的尺寸减小的末端组成。高于LCST的温度升高促进了网络状聚集体，大囊泡和球形胶束的形成。此外，与初始核的常见球形结构域相反，所有PNIPAM封端的化合物均表现出不同的单分子扁长的纳米结构域形态。
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