Supramolecular copolymerization through self-correction of non-polymerizable transient intermediates |
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Authors: | Ganyu Chen Peichen Shi Longhui Zeng Liubin Feng Xiuxiu Wang Xujing Lin Yibin Sun Hongxun Fang Xiaoyu Cao Xinchang Wang Liulin Yang Zhongqun Tian |
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Institution: | State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 P. R. China.; School of Electronic Science and Engineering (National Model Microelectronics College), Xiamen University, Xiamen 361005 P. R. China |
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Abstract: | Kinetic control over structures and functions of complex assembly systems has aroused widespread interest. Understanding the complex pathway and transient intermediates is helpful to decipher how multiple components evolve into complex assemblies. However, for supramolecular polymerizations, thorough and quantitative kinetic analysis is often overlooked. Challenges remain in collecting the information of structure and content of transient intermediates in situ with high temporal and spatial resolution. Here, the unsolved evolution mechanism of a classical self-sorting supramolecular copolymerization system was addressed by employing multidimensional NMR techniques coupled with a microfluidic technique. Unexpected complex pathways were revealed and quantitatively analyzed. A counterintuitive pathway involving polymerization through the ‘error-correction’ of non-polymerizable transient intermediates was identified. Moreover, a ‘non-classical’ step-growth polymerization process controlled by the self-sorting mechanism was unraveled based on the kinetic study. Realizing the existence of transient intermediates during self-sorting can encourage the exploitation of this strategy to construct kinetic steady state assembly systems. Moreover, the strategy of coupling a microfluidic technique with various characterization techniques can provide a kinetic analysis toolkit for versatile assembly systems. The combined approach of coupling thermodynamic and kinetic analyses is indispensable for understanding the assembly mechanisms, the rules of emergence, and the engineering of complex assembly systems.Polymerization through the ‘error-correction’ of non-polymerizable transient intermediates was identified in a classical self-sorting supramolecular copolymerization system by employing NMR coupled with a microfluidic technique. |
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