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Thermo/pH Responsive Star and Linear Copolymers Containing a Cholic Acid-Derived Monomer N-Isopropylacrylamide and Acrylic Acid: Synthesis and Solution Properties

机译:含有胆酸衍生单体N-异丙基丙烯酰胺和丙烯酸的热/ pH响应性星形和线型共聚物:合成和溶液性质

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摘要

In this work three CTAs trithiocarbonate-type were synthesized—bifunctional (with PEG), trifunctional (with glycerol), and tetrafunctional (PERT)—and used in the controlled polymerization of 2-(acryloyloxy)ethyl cholate (CAE) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The resulting macroCTAs containing a cholic acid-derived polymer were chain extended with -isopropylacrylamide with or without acrylic acid. The thermosensitive and/or pH properties of these copolymers were studied in PBS solutions. The copolymers synthesized without poly(acrylic acid) (PAAc) were unstable above the transition temperature. Similar behavior was observed for the copolymer solutions containing PAAc (2% in feed) at lower values of pH showing a faster precipitation above the LCST. On the contrary, copolymer solutions containing PAAc showed great stability at higher pH values for a longer time period at 37 °C. Interestingly, the of the aggregates ranged from 18 to 30 nm in all copolymers (with or without PAAc) below the transition temperature, although the topology and the block sequence in the chain were significantly different.
机译:在这项工作中,合成了三种CTA三硫代碳酸酯型-双官能(含PEG),三官能(含甘油)和四官能(PERT),并通过可逆加成将其用于受控的2-(丙烯酰氧基)乙基胆酸(CAE)聚合。断裂链转移(RAFT)聚合。将所得的含有胆酸衍生的聚合物的macroCTA与具有或不具有丙烯酸的-异丙基丙烯酰胺进行链增长。在PBS溶液中研究了这些共聚物的热敏性和/或pH特性。在转变温度以上,没有聚丙烯酸(PAAc)合成的共聚物是不稳定的。对于含有PAAc(进料中2%)的共聚物溶液,在较低的pH值下观察到类似的行为,表明在LCST上方有较快的沉淀。相反,含有PAAc的共聚物溶液在较高的pH值下在37°C的较长时间内显示出出色的稳定性。有趣的是,尽管链中的拓扑结构和嵌段顺序明显不同,但在低于转变温度的所有共聚物(有或没有PAAc)中,聚集体的聚集范围为18至30 nm。

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