Robert Viviane, Monza Emanuele, Tarrago Lionel, Sancho Ferran, De Falco Anna, Schneider Ludovic, Npetgat Ngoutane Eloïne, Mekmouche Yasmina, Pailley Pierre Rousselot, Simaan A Jalila, Guallar Victor, Tron Thierry
Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
Joint BSC-CRG-IRB Research Program in Computational Biology, Barcelona Supercomputing Centre, Jordi Girona 29, 08034, Barcelona, Spain.
Chempluschem. 2017 Apr;82(4):607-614. doi: 10.1002/cplu.201700030. Epub 2017 Mar 2.
Systems featuring a multi-copper oxidase associated with transition-metal complexes can be used to perform oxidation reactions in mild conditions. Here, a strategy is presented for achieving a controlled orientation of a ruthenium-polypyridyl graft at the surface of a fungal laccase. Laccase variants are engineered with unique surface-accessible lysine residues. Distinct ruthenium-polypyridyl-modified laccases are obtained by the reductive alkylation of lysine residues precisely located relative to the T1 copper centre of the enzyme. In none of these hybrids does the presence of the graft compromise the catalytic efficiency of the enzyme on the substrate 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid). Furthermore, the efficiency of the hybrids in olefin oxidation coupled to the light-driven reduction of O is highly dependent on the location of the graft at the enzyme surface. Simulated Ru -Cu electron coupling values and distances fit well the observed reactivity and could be used to guide future hybrid designs.
具有与过渡金属配合物相关的多铜氧化酶的体系可用于在温和条件下进行氧化反应。在此，提出了一种在真菌漆酶表面实现钌 - 多吡啶接枝可控取向的策略。通过设计具有独特表面可及赖氨酸残基的漆酶变体。通过赖氨酸残基相对于酶的T1铜中心精确定位的还原烷基化反应，获得了不同的钌 - 多吡啶修饰的漆酶。在这些杂合体中，接枝的存在均未损害酶对底物2,2'- 联氮 - 双(3 - 乙基苯并噻唑啉 - 6 - 磺酸)的催化效率。此外，杂合体在与光驱动的O还原偶联的烯烃氧化中的效率高度依赖于接枝在酶表面的位置。模拟的Ru - Cu电子耦合值和距离与观察到的反应活性非常吻合，可用于指导未来的杂合体设计。
