Pham Thu Thao, Pham Tien Duc, Yusa Shin-Ichi
Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji 671-2280, Hyogo, Japan.
Faculty of Chemistry, University of Science, Vietnam National University, Hanoi, 19 Le Thanh Tong, Hoan Kiem, Hanoi 100000, Vietnam.
Polymers (Basel). 2022 Apr 20;14(9):1659. doi: 10.3390/polym14091659.
A diblock copolymer (P(VBTAC/NaSS)--PAPTAC; P(VS)A) composed of amphoteric random copolymer, poly(vinylbenzyl trimethylammonium chloride--sodium -styrensunfonate) (P(VBTAC/NaSS); P(VS)) and cationic poly(3-(acrylamidopropyl) trimethylammonium chloride) (PAPTAC; A) block, and poly(acrylic acid) (PAAc) were prepared via a reversible addition-fragmentation chain transfer radical polymerization. Scrips V, S, and A represent VBTAC, NaSS, and PAPTAC blocks, respectively. Water-soluble polyion complex (PIC) vesicles were formed by mixing P(VS)A and PAAc in water under basic conditions through electrostatic interactions between the cationic PAPTAC block and PAA with the deprotonated pendant carboxylate anions. The PIC vesicle collapsed under an acidic medium because the pendant carboxylate anions in PAAc were protonated to delete the anionic charges. The PIC vesicle comprises an ionic PAPTAC/PAAc membrane coated with amphoteric random copolymer P(VS) shells. The PIC vesicle showed upper critical solution temperature (UCST) behavior in aqueous solutions because of the P(VS) shells. The pH- and thermo-responsive behavior of the PIC vesicle were studied using H NMR, static and dynamic light scattering, and percent transmittance measurements. When the ratio of the oppositely charged polymers in PAPTAC/PAAc was equal, the size and light scattering intensity of the PIC vesicle reached maximum values. The hydrophilic guest molecules can be encapsulated into the PIC vesicle at the base medium and released under acidic conditions. It is expected that the PIC vesicles will be applied as a smart drug delivery system.
通过可逆加成-断裂链转移自由基聚合制备了一种由两性无规共聚物聚（乙烯基苄基三甲基氯化铵-苯乙烯磺酸钠）（P(VBTAC/NaSS)；P(VS)）和阳离子聚（3-(丙烯酰胺基丙基)三甲基氯化铵）（PAPTAC；A）嵌段以及聚丙烯酸（PAAc）组成的双嵌段共聚物（P(VBTAC/NaSS)--PAPTAC；P(VS)A）。下标V、S和A分别代表VBTAC、NaSS和PAPTAC嵌段。在碱性条件下，通过阳离子PAPTAC嵌段与去质子化的侧链羧酸根阴离子的PAA之间的静电相互作用，将P(VS)A和PAAc在水中混合形成水溶性聚离子复合物（PIC）囊泡。由于PAAc中的侧链羧酸根阴离子被质子化以消除阴离子电荷，PIC囊泡在酸性介质下会塌陷。PIC囊泡由涂有两性无规共聚物P(VS)壳的离子型PAPTAC/PAAc膜组成。由于P(VS)壳的存在，PIC囊泡在水溶液中表现出上临界溶液温度（UCST）行为。使用核磁共振氢谱、静态和动态光散射以及百分透光率测量研究了PIC囊泡的pH和热响应行为。当PAPTAC/PAAc中带相反电荷的聚合物比例相等时，PIC囊泡的尺寸和光散射强度达到最大值。亲水性客体分子可以在碱性介质中被封装到PIC囊泡中，并在酸性条件下释放。预计PIC囊泡将作为一种智能药物递送系统得到应用。
