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聚合物胶束在水中的多组分自组装与自分类:通过动力学或热力学控制实现选择性和可切换的缔合

Multicomponent Self-Assembly and Self-Sorting of Polymer Micelles in Water: Selective and Switchable Association by Kinetic or Thermodynamic Control.

作者信息

Kanno Rikuto, Kono Hiroyuki, Ryoki Akiyuki, Ouchi Makoto, Terashima Takaya

机构信息

Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.

出版信息

J Am Chem Soc. 2024 Nov 13;146(45):30848-30859. doi: 10.1021/jacs.4c08778. Epub 2024 Oct 15.

DOI:10.1021/jacs.4c08778
PMID:39404465
Abstract

Herein, we report multicomponent self-assembly and self-sorting of polymer micelles in water using mixtures of an anionic random copolymer bearing sodium sulfonate and dodecyl groups and random copolymers carrying poly(ethylene glycol) (PEG) and alkyl groups. In pure water, the anionic copolymer is co-self-assembled with the PEG copolymers to form anion/PEG-fused micelles with a controlled aggregation number. By designing the composition or alkyl groups of PEG copolymers, the fused micelle is reversibly self-sorted into discrete anion or PEG micelles in the presence of NaCl. Co-self-assembly of the anionic copolymer and PEG copolymers is kinetically or thermodynamically controlled, depending on the dynamic properties of the PEG copolymer micelles. Thus, the selective self-assembly of ternary copolymers is also controllable and switchable by temperature: A kinetically favored anion/PEG-fused micelle is predominantly formed in the presence of a kinetically frozen PEG micelle at low temperature, whereas the fused micelle is transformed via polymer chain exchange upon heating into a thermodynamically more stable anion/PEG-fused micelle.

摘要

在此,我们报道了在水中使用带有磺酸钠和十二烷基的阴离子无规共聚物与带有聚乙二醇(PEG)和烷基的无规共聚物的混合物进行聚合物胶束的多组分自组装和自分类。在纯水中,阴离子共聚物与PEG共聚物共同自组装形成具有可控聚集数的阴离子/PEG融合胶束。通过设计PEG共聚物的组成或烷基,在NaCl存在下,融合胶束可逆地自分类为离散的阴离子或PEG胶束。阴离子共聚物和PEG共聚物的共同自组装受动力学或热力学控制,这取决于PEG共聚物胶束的动力学性质。因此,三元共聚物的选择性自组装也可通过温度进行控制和切换:在低温下,在动力学冻结的PEG胶束存在下主要形成动力学有利的阴离子/PEG融合胶束,而加热时融合胶束通过聚合物链交换转变为热力学更稳定的阴离子/PEG融合胶束。

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