Polymerization-Induced Electrostatic Self-Assembly Governed by Guanidinium Ionic Hydrogen Bonds
Polymerization-Induced Electrostatic Self-Assembly Governed by Guanidinium Ionic Hydrogen Bonds
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DOI：
10.1021/acs.macromol.2c01323
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发表时间：
2022-08
期刊：
影响因子：
5.5
通讯作者：
Weixing Xiong;Xiyu Wang;Yuanyuan Liu;Caihui Luo;Xinhua Lu;Yuanli Cai
中科院分区：
文献类型：
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作者：
Weixing Xiong;Xiyu Wang;Yuanyuan Liu;Caihui Luo;Xinhua Lu;Yuanli Cai
聚合诱导静电自组装(PIESA)是一种可伸缩合成各种形貌的聚离子络合物(PIC)纳米粒子的有效方法。以前的PIESA是由库仑相互作用驱动的。然而，仿生多价相互作用，例如蛋白质中无处不在的离子氢键，并有可能获得新材料，仍未被探索。在这里，我们使用类精氨酸的全光谱离子氢键来更新PIESA。动力学研究揭示，在缺乏Gen+/n-(0.84)的情况下，Gu的相互作用从相反电荷(转化率为6-73%)演变为同电荷的离子氢键(转化率为84-99%)，导致超小的团簇(2-5 nm，转化率为6-84%)和大小可调的“大化合物胶束”(14-25 nm，转化率为90->；99%)。较长的胍嵌段长度导致电荷中性蠕虫转变为带正电荷的微米级大面积单层片层到多层小片，再到管状网络到泡状聚集体，这表明类似电荷的离子氢键足够强，足以压倒库仑排斥相互作用，从而彻底改变我们的PIESA化学，用于精确合成下一代纳米结构仿生功能材料。
Polymerization-induced electrostatic self-assembly (PIESA) represents a powerful method for the scalable synthesis of polyion complex (PIC) nanoparticles with various morphologies. Previous PIESA was driven by Coulombic interactions. Yet, biomimetic multivalent interactions, e.g., ionic hydrogen bonds omnipresent in proteins and potentially enabling access to new materials, remain unexplored. Herein, we update PIESA using arginine-like full-spectrum guanidinium ionic hydrogen bonds. Kinetic studies unravel that, at guanidinium-starvingn+/n–(0.84), guanidinium interactions evolve from opposite-charge (6–73% conversion) into like-charge ionic hydrogen bonds (84 to >99% conversion), leading to ultrasmall clusters (2–5 nm, at 6–84% conversion) and size-tunable “large compound micelles” (14–25 nm, at 90 to >99% conversion). Longer guanidinium-block length results in the transformation of charge-neutral worms to positive-charge micron-scale large-area monolayer lamellae to multilayer platelets to tubular networks to vesicular aggregates, suggesting that the like-charge ionic hydrogen bonds are strong enough to overwhelm Coulombic repulsive interactions, and thus to revolutionize our PIESA chemistry for the precision synthesis of next-generation nanostructured biomimetic functional materials.