Protein structure plays an essential role on their stability, functionality, and catalytic activity. In this work, the interplay between the β-sheet structure and its catalytic implications to the design of enzyme-inspired materials is investigated. Here, inspiration is drawn from the active sites and β-sheet rich structure of the highly efficient multicopper oxidase (MCO) to engineer a bio-inspired electrocatalyst for water oxidation utilizing the abundant metal, copper. Copper ions are coordinated to poly-histidine (polyCuHis), as they are in MCO active sites. The resultant polyCuHis material effectively promotes water oxidation with low overpotentials (0.15 V) in alkaline systems. This activity is due to the 3D structure of the poly-histidine backbone. By increasing the prevalence of β-sheet structure and decreasing the random coil nature of the polyCuHis secondary structures, this study is able to modulates the electrocatalytic activity of this material is modulated, shifting it toward water oxidation. These results highlight the crucial role of the local environment at catalytic sites for efficient, energy-relevant transformations. Moreover, this work highlights the importance of conformational structure in the design of scaffolds for high-performance electrocatalysts.

中文翻译：

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酶启发聚合物催化剂中的二级结构影响水氧化效率

蛋白质结构对其稳定性、功能性和催化活性起着至关重要的作用。在这项工作中，研究了β-折叠结构之间的相互作用及其对酶启发材料设计的催化影响。在这里，我们从高效多铜氧化酶 (MCO) 的活性位点和富含β片层的结构中汲取灵感，设计了一种仿生电催化剂，利用丰富的金属铜进行水氧化。铜离子与多聚组氨酸 (polyCuHis) 配位，因为它们位于 MCO 活性位点。所得的聚铜组氨酸材料在碱性系统中以低过电势（0.15 V）有效促进水氧化。该活性归因于多组氨酸主链的 3D 结构。通过增加β-折叠结构的普遍性和减少多聚铜组氨酸二级结构的无规卷曲性质，本研究能够调节该材料的电催化活性，将其转向水氧化。这些结果凸显了当地环境在催化位点对于高效、能源相关转化的关键作用。此外，这项工作强调了构象结构在高性能电催化剂支架设计中的重要性。