Mediated Electrochemistry to Mimic Biology's Oxidative Assembly of Functional Matrices
Mediated Electrochemistry to Mimic Biology's Oxidative Assembly of Functional Matrices
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DOI：
10.1002/adfm.202001776
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发表时间：
2020-06-02
影响因子：
19
通讯作者：
Payne, Gregory F.
中科院分区：
文献类型：
--
作者：
Li, Jinyang;Kim, Eunkyoung;Payne, Gregory F.
生物学使用可扩散的氧化剂来执行从信号传导到基质组装的功能，并且这些氧化化学提供了令人惊讶的选择性。在这里，据报道，介导的电化学可以访问这样的氧化化学的丰富。具体地，电极施加的电压输入用于局部产生氧化介体，其可以扩散到聚合物溶液中并诱导共价键的形成，用于在电极表面处的水凝胶的沉积和官能化。取决于介体的氧化还原电位（E-0），可以“门控”电压输入以靶向特定残基（例如，硫醇或胺）和氧化化学。此外，不同E-O的介体提供不同的反应性，从而允许控制反应-扩散速率以调节水凝胶的交联密度和机械性能。重要的是，这种介导的氧化可以在生理学相关条件下进行，以保持不稳定的生物功能（例如，细胞活力和蛋白质功能）。最后，它表明，蛋白质融合标签可以被改造为具有“靶向”氨基酸残基，使蛋白质功能被氧化偶联到电沉积的水凝胶。总之，介导的电化学可以参与正交氧化化学以产生功能化的基质，因此介导的电化学应该为电制造工具箱增加重要的能力。
Biology uses diffusible oxidants to perform functions that range from signaling to matrix assembly, and these oxidation chemistries offer surprising selectivities. Here, it is reported that mediated electrochemistry can access the richness of such oxidation chemistries. Specifically, electrode-imposed voltage inputs are used to locally generate oxidized mediators that can diffuse into polymer solutions and induce the formation of covalent bonds for the deposition and functionalization of hydrogels at the electrode surface. Depending on the mediator's redox potential (E-0), it is possible to "gate" the voltage inputs to target specific residues (e.g., thiols or amines) and oxidation chemistries. Further, mediators of varying E-0 offer different reactivities and thus allow control of reaction-diffusion rates to modulate the hydrogel's crosslink density and mechanical properties. Importantly, this mediated oxidation can be performed under physiologically relevant conditions to preserve labile biological functionalities (e.g., cell viability and protein function). Finally, it is demonstrated that protein fusion tags can be engineered to have "targetable" amino acid residues that enable protein function to be oxidatively conjugated to electrodeposited hydrogels. In summary, mediated electrochemistry can engage orthogonal oxidation chemistries to create functionalized matrices and thus mediated electrochemistry should add important capabilities to the electrofabrication toolbox.