System-Level Network Analysis of a Catechol Component for Redox Bioelectronics
System-Level Network Analysis of a Catechol Component for Redox Bioelectronics
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DOI：
10.1021/acsaelm.2c00269
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发表时间：
2022-05
影响因子：
4.7
通讯作者：
Zhiling Zhao;Si Wu;Eunkyoung Kim;Chen‐yu Chen;J. Rzasa;Xiaowen Shi;W. Bentley;G. Payne
中科院分区：
文献类型：
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作者：
Zhiling Zhao;Si Wu;Eunkyoung Kim;Chen‐yu Chen;J. Rzasa;Xiaowen Shi;W. Bentley;G. Payne
氧化还原是一种普遍存在的生物信号传导方式，为生物电子学提供了机会。各种实验研究表明，儿茶酚为基于氧化还原的生物电子学提供了独特的分子电子特性，因为儿茶酚可以赋予氧化还原活性而不导电。在这里，我们在电极表面制造了含儿茶酚的水凝胶膜，并使用动态光谱电化学测量和基于物理的建模（即，反应扩散模型）。我们表明：（i）电子通过儿茶酚膜的流动涉及氧化还原反应网络;（ii）儿茶酚节点的氧化还原状态切换由可扩散电子载流子（即，介体）并且与电极处的电子转移同步;以及（iii）基于物理学的反应-扩散模型可以抽象为可以用于表征更复杂实验系统的响应特性的容易测量的度量（即，无法从第一原理描述的系统）。最后，我们进行了简单的扰动分析以说明理论如何指导能够检测儿茶酚涂覆的电极与氧化还原相互作用组的生物相关节点（即，对氧化还原网络拓扑敏感的度量）。总的来说，这项工作提供了一个统一的框架来理解基于儿茶酚的电极涂层，并建议理论如何指导氧化还原生物电子学新兴应用中数据驱动分析的指标选择。
Redox is a ubiquitous biological signaling modality that is providing opportunities for bioelectronics. Various experimental studies have demonstrated that catechols offer unique molecular electronic properties for redox-based bioelectronics because catechols can confer redox activity without conductivity. Here, we fabricated a catechol-containing hydrogel film at an electrode surface and characterized this film using dynamic spectroelectrochemical measurements and physics-based modeling (i.e., reaction–diffusion modeling). We show that (i) the flow of electrons through the catechol film involves a redox reaction network; (ii) the redox-state switching of the catechol node is gated by diffusible electron carriers (i.e., mediators) and synchronized to electron transfer at the electrode; and (iii) a physics-based reaction–diffusion model can be abstracted into readily measurable metrics that can be used to characterize the response characteristics of more complex experimental systems (i.e., systems that cannot be described from first principles). Finally, we performed a simple perturbation analysis to illustrate how theory can guide the selection of metrics capable of detecting interactions between the catechol-coated electrode and bio-relevant nodes of a redox interactome (i.e., metrics that are sensitive to redox network topology). Overall, this work provides a unifying framework to understand catechol-based electrode coatings and suggests how theory can guide the selection of metrics for data-driven analysis in emerging applications in redox bioelectronics.