2020.01.10《Nanomechanics of Anion−π Interaction in Aqueous Solution》

在《JACS》发表的研究中，聚焦海洋贻贝水下超强黏附行为背后的分子间相互作用机理，首次揭示阴离子-π和π-阳离子-π分子间作用在水下黏附中的重要贡献与微纳力学机制，解释了一直困扰人们的关于海洋生物如何实现在盐溶液条件下牢固黏附岩石表面的这个自然现象。具体而言，该工作设计合成出了仿海洋生物蛋白结构的邻苯二酚-磷酸酯基团模型分子，构建仿生水下黏附涂层。首次在实验上证实了两基团间阴离子-π相互作用的存在，并探明了其在海洋生物无惧高盐强黏附中的关键作用 为：通过阳离子盐在邻苯二酚一侧形成阳离子-π相互作用，协同促成了邻苯二酚另一侧与磷酸酯之间阴离子-π相互作用，形成牢固的阴离子-π-阳离子构型。因此，该黏附涂层的黏附强度不仅不因阳离子盐的存在而降低，反而因阳离子-π相互作用的协同而增强。该发现深化了高盐溶液条件下黏附理论的认知，为设计开发水下耐盐强黏附的修复材料提供了理论依据和技术支撑。

该文章为张嘉文和项力是共同第一作者，曾宏波教授为唯一通讯作者。

In a study published in the Journal of the American Chemical Society (JACS), researchers focused on the intermolecular interaction mechanisms underlying the exceptional underwater adhesion of marine mussels. For the first time, they revealed the significant contribution and micro-nanomechanical mechanisms of anion–π and cation–π interactions in underwater adhesion, explaining the long-standing natural phenomenon of how marine organisms achieve robust adhesion to rock surfaces in saline environments. Specifically, the work involved designing and synthesizing model molecules with catechol–phosphate ester groups that mimic the structure of marine adhesive proteins, which were then used to construct biomimetic underwater adhesive coatings. The study experimentally confirmed the existence of anion–π interactions between these two functional groups and elucidated their critical role in the salt-tolerant strong adhesion of marine organisms. The mechanism involves the formation of cation–π interactions on one side of the catechol group with cationic salts, which synergistically promotes anion–π interactions between the catechol group and the phosphate ester on the other side, resulting in a stable anion–π–cation configuration. Consequently, the adhesion strength of the coating is not diminished by the presence of cationic salts but is instead enhanced by the synergistic effect of cation–π interactions. This discovery deepens the understanding of adhesion mechanisms under high-salinity conditions and provides both a theoretical foundation and technical support for designing and developing salt-tolerant, high-strength underwater repair materials.

Co-First Authors: Jiawen Zhang and Lishi Xiang

Corresponding Author: Professor Hongbo Zeng

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Supporting Information Nanomechanics of Anion-π Interaction in Aqueous Solution