Programmable self-assembly of a cystamine-block copolymer in response to pH and progressive reduction–ionization–oxidation

Programmable self-assembly of a cystamine-block copolymer in response to pH and progressive reduction–ionization–oxidation
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胱胺嵌段共聚物响应 pH 值和逐步还原-电离-氧化的可编程自组装

DOI:
10.1039/c5py01092f
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发表时间:
2015-10
期刊:
影响因子:
4.6
通讯作者:
Cai Yuanli
Cai Yuanli
中科院分区:
化学2区
文献类型:
--
作者:
Shi Hui;Zhou Kaiyi;Yu Qiuping;Cui Zhigang;Jiang Yanyan;Lu Xinhua;Cai Yuanli

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本文介绍了直接水性合成和可编程的自组装和可编程的自组装和重建,响应于水环境的条件(例如空气和溶液pH)的响应良好的反应性cystamine-block共聚物。各种各样
Direct aqueous synthesis and programmable self-assembly and reconstructions of a well-defined reactive cystamine-block copolymer in response to conditions of the aqueous environment, such as air and solution pH, are presented in this article. A variety of well-defined poly(cystamine methacrylamide hydrochloride) (PCysMA) polymers and copolymers with 2-hydroxypropylmethacrylamide (HPMA) and 2-aminoethylmethacrylamide hydrochloride (AEMA) can be achieved via fast and well-controlled aqueous RAFT under visible light irradiation at 25 °C. PHPMA-b-PCysMA assembles into spherical PCysMA-core micelles upon NH3+-to-NH2 conversion. Moreover, progressive reactions in the PCysMA block, including reduction, ionization and oxidation, can be induced stepwise by reduction in argon gas saturated acidic water, exposure to air and stepwise alkalization. These reactions lead to the stepwise conversion of the intermolecular interactions from electrostatic repulsion (ionized PCysMA block) into hydrogen-bonding associations (reduction-generated thiol block), electrostatic repulsion (as-ionized thiolate block), and hydrophobic cross-linking (oxidation-generated disulfides), leading to the programmable self-assembly and reconstruction of a water-soluble block copolymer into compound-encapsulated nanowires, compound-released nanowires, shortened nanorods/spheres, swollen nanowires, nanorods, and branched nanowires/networks. All the phase transformations stem from the environment-mediated reaction complexity of the CysMA unit, and hold potential for biological and other emerging fields.
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