School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A Raja SC Mullick Road, Kolkata, WB India 700032.
J Am Chem Soc. 2022 May 18;144(19):8402-8429. doi: 10.1021/jacs.2c01842. Epub 2022 May 3.
One of the major goals of bioinorganic chemistry has been to mimic the function of elegant metalloenzymes. Such functional modeling has been difficult to attain in solution, in particular, for reactions that require multiple protons and multiple electrons (H/e). Using a combination of heterogeneous electrochemistry, electrode and molecule design one may control both electron transfer (ET) and proton transfer (PT) of these H/e reactions. Such control can allow functional modeling of hydrogenases (H + e → 1/2 H), cytochrome c oxidase (O + 4 e + 4 H → 2 HO), monooxygenases (RR'CH + O + 2 e + 2 H → RR'CHOH + HO) and dioxygenases (S + O → SO; S = organic substrate) in aqueous medium and at room temperatures. In addition, these heterogeneous constructs allow probing unnatural bioinspired reactions and estimation of the inner- and outer-sphere reorganization energy of small molecules and proteins.
生物无机化学的主要目标之一是模拟精致的金属酶的功能。在溶液中，特别是对于需要多个质子和多个电子 (H/e) 的反应，这种功能模拟一直难以实现。通过组合使用非均相电化学、电极和分子设计，人们可以控制这些 H/e 反应的电子转移 (ET) 和质子转移 (PT)。这种控制可以允许在水相中和室温下对氢化酶 (H + e → 1/2 H)、细胞色素 c 氧化酶 (O + 4 e + 4 H → 2 HO)、单加氧酶 (RR'CH + O + 2 e + 2 H → RR'CHOH + HO) 和双加氧酶 (S + O → SO；S = 有机底物) 进行功能模拟。此外，这些非均相构建体允许探测非天然的仿生反应，并估计小分子和蛋白质的内球和外球重组能。
