Department of Molecular Chemistry, DCM, Univ. Grenoble Alpes , CNRS, 38000 Grenoble, France.
Univ. Grenoble Alpes , CNRS, CERMAV, 38000 Grenoble, France.
J Am Chem Soc. 2017 Nov 15;139(45):16076-16079. doi: 10.1021/jacs.7b09442. Epub 2017 Nov 7.
We demonstrate self-assembly, characterization and bioelectrocatalysis of redox-active cyclodextrin-coated nanoparticles. The nanoparticles with host-guest functionality are easy to assemble and permit entrapment of hydrophobic redox molecules in aqueous solution. Bis-pyrene-ABTS encapsulated nanoparticles were investigated electrochemically and spectroscopically. Their use as electron shuttles is demonstrated via an intraelectron transfer chain between neighboring redox units of clustered particles (D = 195 nm) and the mono- and trinuclear Cu sites of bilirubin oxidases. Enhanced current densities for mediated O reduction are observed with the redox nanoparticle system compared to equivalent bioelectrode cells with dissolved mediator. Improved catalytic stability over 2 days was also observed with the redox nanoparticles, highlighting a stabilizing effect of the polymeric architecture. Bioinspired nanoparticles as mediators for bioelectrocatalysis promises to be valuable for future biofuel cells and biosensors.
我们展示了具有氧化还原活性的环糊精包覆纳米粒子的自组装、表征和生物电化学。这些具有主客体功能的纳米粒子易于组装，并允许将疏水性氧化还原分子包埋在水溶液中。双芘-ABTS 包埋的纳米粒子进行了电化学和光谱学研究。通过相邻的簇状颗粒（D = 195nm）的氧化还原单元之间的电子转移链和胆红素氧化酶的单核和三核 Cu 位点，证明了它们作为电子穿梭体的用途。与含有溶解介体的等效生物电极相比，观察到氧化还原纳米粒子系统介导的 O 还原的电流密度增强。还观察到氧化还原纳米粒子具有 2 天以上的改进的催化稳定性，突出了聚合结构的稳定作用。作为生物电化学介体的仿生纳米粒子有望成为未来生物燃料电池和生物传感器的有价值的材料。
