Multicopper models for the laccase active site: effect of nuclearity on electrocatalytic oxygen reduction.
Multicopper models for the laccase active site: effect of nuclearity on electrocatalytic oxygen reduction.
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DOI：
10.1021/ic501080c
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发表时间：
2014-07
影响因子：
4.6
通讯作者：
Edmund C. M. Tse;D. Schilter;Danielle L. Gray;T. Rauchfuss;A. Gewirth
中科院分区：
文献类型：
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作者：
Edmund C. M. Tse;D. Schilter;Danielle L. Gray;T. Rauchfuss;A. Gewirth
制备了2，2‘-二吡啶甲胺(DPA)的铜配合物，并考察了其对氧还原反应(ORR)的电催化性能。为了研究多核性对ORR的影响，用柔性连接物连接了两个铜-DPA单元，并在配体框架中安装了第三个金属结合口袋。DPA衍生物的二元和三元络合物的ORR起始电位和扩散极限电流密度与较简单的铜-DPA体系相当。电化学分析、结晶学数据和金属取代研究表明，DPA衍生物的铜配合物通过双核分子间途径与O2反应，但第三结合位的铜中心不参与ORR过程。这项研究强调了铜-DPA络合物模拟漆酶T3位点的可行性，并为设计未来的漆酶模型提供了指导。
Cu complexes of 2,2'-dipicolylamine (DPA) were prepared and tested as electrocatalysts for the oxygen reduction reaction (ORR). To study the effect of multinuclearity on the ORR, two Cu-DPA units were connected with a flexible linker, and a third metal-binding pocket was installed in the ligand framework. ORR onset potentials and the diffusion-limited current densities of di- and tricopper complexes of DPA derivatives were found to be comparable to those of the simpler Cu-DPA system. Electrochemical analyses, crystallographic data, and metal-substitution studies suggested that Cu complexes of DPA derivatives reacted with O2 via a binuclear intermolecular pathway but that the Cu center in the third binding site did not participate in the ORR process. This study highlights the viability of Cu-DPA complexes to mimic the T3-site of laccase, and serves as a guide for designing future laccase models.