Responsive Polymers with Contraction-arisen Helicity and Biomimetic Membrane-spanning Transport Functions

doi:10.1007/s40242-022-2031-z

高等学校化学研究 ›› 2022, Vol. 38 ›› Issue (3): 803-808.doi: 10.1007/s40242-022-2031-z

Responsive Polymers with Contraction-arisen Helicity and Biomimetic Membrane-spanning Transport Functions

MIN Jing, ZHANG Chenyang, QI Shuaiwei, WANG Liyan and DONG Zeyuan

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China

收稿日期:2022-01-26 修回日期:2022-02-12 出版日期:2022-06-01 发布日期:2022-02-17
通讯作者: WANG Liyan, DONG Zeyuan E-mail:wangliyan@vip.sina.com;zdong@jlu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (Nos.22071078, 92156012 and 21722403) and the Program for Jilin University Science and Technology Innovative Research Team(JLUSTIRT), China (No.2019TD-36).

Responsive Polymers with Contraction-arisen Helicity and Biomimetic Membrane-spanning Transport Functions

MIN Jing, ZHANG Chenyang, QI Shuaiwei, WANG Liyan and DONG Zeyuan

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China

Received:2022-01-26 Revised:2022-02-12 Online:2022-06-01 Published:2022-02-17
Contact: WANG Liyan, DONG Zeyuan E-mail:wangliyan@vip.sina.com;zdong@jlu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos.22071078, 92156012 and 21722403) and the Program for Jilin University Science and Technology Innovative Research Team(JLUSTIRT), China (No.2019TD-36).

摘要/Abstract

摘要： Responsive polymers have attracted increasing attention for prospective design of smart materials. The development of multifunctional responsive materials is very dependent on polymeric structures that can be manipulated with the change of microenvironment at the molecular level. Herein, we report a type of responsive coordination polymers(RCPs) consisting of dual phenanthroline-oxadiazole(DPO) units and metal Zn²⁺ ions, which can contract from linear structure into topologically helical structure driven by hydrophobic effect while changing the microenvironment from nonpolar solvent to aqueous media. The symmetry breaking of RCPs was confirmed by circular dichroism(CD) spectra and atomic force microscope(AFM) images, clearly demonstrating the intramolecularly contraction-arisen helicity. Moreover, RCPs can intelligently adapt different microenvironments by changing their conformations, as evidenced by a demonstration of biomimetic lipid bilayer-based vesicle experiments. Furthermore, RCPs show significant concentration-dependent transmembrane transport functions, implying that RCPs are able to span cellular membranes to form channels inside the hydrophobic lipid bilayers. At the same time, the electrophysiological conductance experiments further underpin the biomimetic transport functions and channel-based conduction mechanism of RCPs. This study demonstrates an important paradigm of responsive polymers performing microenvironment-induced conformational change and thereof unique functions, and thus provides valuable insights on the development of functional responsive materials.

关键词: Responsive polymer, Molecular contraction, Symmetry breaking, Helicity, Transmembrane transport

Abstract: Responsive polymers have attracted increasing attention for prospective design of smart materials. The development of multifunctional responsive materials is very dependent on polymeric structures that can be manipulated with the change of microenvironment at the molecular level. Herein, we report a type of responsive coordination polymers(RCPs) consisting of dual phenanthroline-oxadiazole(DPO) units and metal Zn²⁺ ions, which can contract from linear structure into topologically helical structure driven by hydrophobic effect while changing the microenvironment from nonpolar solvent to aqueous media. The symmetry breaking of RCPs was confirmed by circular dichroism(CD) spectra and atomic force microscope(AFM) images, clearly demonstrating the intramolecularly contraction-arisen helicity. Moreover, RCPs can intelligently adapt different microenvironments by changing their conformations, as evidenced by a demonstration of biomimetic lipid bilayer-based vesicle experiments. Furthermore, RCPs show significant concentration-dependent transmembrane transport functions, implying that RCPs are able to span cellular membranes to form channels inside the hydrophobic lipid bilayers. At the same time, the electrophysiological conductance experiments further underpin the biomimetic transport functions and channel-based conduction mechanism of RCPs. This study demonstrates an important paradigm of responsive polymers performing microenvironment-induced conformational change and thereof unique functions, and thus provides valuable insights on the development of functional responsive materials.

Key words: Responsive polymer, Molecular contraction, Symmetry breaking, Helicity, Transmembrane transport

MIN Jing, ZHANG Chenyang, QI Shuaiwei, WANG Liyan and DONG Zeyuan. Responsive Polymers with Contraction-arisen Helicity and Biomimetic Membrane-spanning Transport Functions[J]. 高等学校化学研究, 2022, 38(3): 803-808.

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Responsive Polymers with Contraction-arisen Helicity and Biomimetic Membrane-spanning Transport Functions

Responsive Polymers with Contraction-arisen Helicity and Biomimetic Membrane-spanning Transport Functions

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