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基于互补核碱基分子识别的热响应和pH响应微凝胶的制备

Preparation of Thermo- and pH-Responsive Microgels Based on Complementary Nucleobase Molecular Recognition.

作者信息

Pan Jiasheng, Wen Xin, Wang Mu, Li Jun, Li Xiangyu, Feng Anchao, Zhang Liqun, Thang San H

机构信息

State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China.

Beijing Key Laboratory of Preparation and Processing of New Polymer Materials, Beijing University of Chemical Technology, Beijing, 100029, China.

出版信息

Macromol Rapid Commun. 2022 Sep;43(17):e2200239. doi: 10.1002/marc.202200239. Epub 2022 Jun 15.

DOI:10.1002/marc.202200239
PMID:35526233
Abstract

Complementary interactions between the natural nucleobases is one of the important ways of biomolecular recognition. Although scientists have introduced such supramolecular noncovalent interactions into biomimetic materials through different approaches in recent years, further research is still needed to confer structural features of biomolecules into emerging stimuli-responsive microgels. In this study, a series of bis-thymine end decorated flexible poly (N-isopropyl acrylamide) (T-PNIPAM-T) are obtained through a thymine esterified RAFT agent. Meanwhile, a rigid polymeric backbone poly[1-(4-vinyl benzyl)] adenine (P A), including several pendant adenines on the side chain is prepared. Through nucleobase complementary pairing subtle supramolecular cross-linked 3D networks are constructed, and further self-assembled to form microgels under the balance between hydrophilicity and block flexibility. More importantly, such supramolecular 3D microgels show volumetric shrinkage in different water content environments and the assembly behavior under thermo and pH stimulated conditions. This exploration is expected to play an important value and significance in the field of biomimetic controlled release of soft matter in the future.

摘要

天然核碱基之间的互补相互作用是生物分子识别的重要方式之一。尽管近年来科学家们已通过不同方法将这种超分子非共价相互作用引入仿生材料中,但仍需要进一步研究,以便将生物分子的结构特征赋予新兴的刺激响应性微凝胶。在本研究中,通过胸腺嘧啶酯化的可逆加成-断裂链转移(RAFT)试剂获得了一系列双胸腺嘧啶末端修饰的柔性聚(N-异丙基丙烯酰胺)(T-PNIPAM-T)。同时,制备了一种刚性聚合物主链聚[1-(4-乙烯基苄基)]腺嘌呤(PA),其侧链上包含几个侧挂腺嘌呤。通过核碱基互补配对构建了精细的超分子交联三维网络,并在亲水性和嵌段柔韧性之间的平衡下进一步自组装形成微凝胶。更重要的是,这种超分子三维微凝胶在不同含水量环境中表现出体积收缩以及在热和pH刺激条件下的组装行为。预计这一探索在未来软物质的仿生控释领域将发挥重要价值和意义。

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