Dynamic‐Covalent Crosslinking of Benzenetricarboxamide–Phenylboronate Conjugates
Dynamic‐Covalent Crosslinking of Benzenetricarboxamide–Phenylboronate Conjugates
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苯三甲酰胺与苯基硼酸酯缀合物的动态共价交联
DOI：
10.1002/mabi.202300001
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发表时间：
2023
影响因子：
4.6
通讯作者：
Webber, Matthew J.
中科院分区：
文献类型：
--
作者：
VandenBerg, Michael A.;Xian, Sijie;Xiang, Yuanhui;Webber, Matthew J.
为了增强超分子生物材料的功能，最近的努力探索了耦合超分子和共价成分的混合材料的创建。在这里，苯三甲酰胺（BTA）超分子聚合物基序被修饰以呈现苯基硼酸（PBA），以便通过添加多臂二醇交联剂促进PBA-二醇动态共价键的一维BTA堆叠的交联。有趣的是，这两个基序的组合阻碍了最终的组装过程，产生的水凝胶的机械性能比没有多臂二醇交联剂制备的水凝胶差。然而，无论有或没有交联剂，这两种系统都会对生理水平的葡萄糖的存在做出反应，从而降低其机械完整性。在这两种情况下，BTA 堆叠中的排斥静电相互作用都会在葡萄糖结合时发生，并且葡萄糖与 PBA-二醇键的竞争加剧，从而放大了混合材料中的葡萄糖响应。因此，目前的结果表明，当 BTA 超分子聚合和 PBA-二醇交联的两种不同的动态基序结合在一起时，水凝胶力学会降低，但葡萄糖响应会增加，这为未来制备葡萄糖响应性超分子生物材料提供了前景。
In an effort to augment the function of supramolecular biomaterials, recent efforts have explored the creation of hybrid materials that couple supramolecular and covalent components. Here, the benzenetricarboxamide (BTA) supramolecular polymer motif is modified to present a phenylboronic acid (PBA) in order to promote the crosslinking of 1D BTA stacks by PBA–diol dynamic‐covalent bonds through the addition of a multi‐arm diol‐bearing crosslinker. Interestingly, the combination of these two motifs serves to frustrate the resulting assembly process, yielding hydrogels with worse mechanical properties than those prepared without the multi‐arm diol crosslinker. Both systems with and without the crosslinker do, however, respond to the presence of a physiological level of glucose with a reduction in their mechanical integrity; repulsive electrostatic interactions in the BTA stacks occur in both cases upon glucose binding, with added competition from glucose with PBA–diol bonds amplifying glucose response in the hybrid material. Accordingly, the present results point to an unexpected outcome of reduced hydrogel mechanics, yet increased glucose response, when two disparate dynamic motifs of BTA supramolecular polymerization and PBA–diol crosslinking are combined, offering a vision for future preparation of glucose‐responsive supramolecular biomaterials.