Enzyme Mimetic Active Intermediates for Nitrate Reduction in Neutral Aqueous Media.,Angewandte Chemie International Edition

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Enzyme Mimetic Active Intermediates for Nitrate Reduction in Neutral Aqueous Media.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-03-06 , DOI: 10.1002/anie.202002647
Yamei Li _{1,

2} , Yoo Kyung Go ₃ , Hideshi Ooka ₁ , Daoping He _{1,

4} , Fangming Jin ₄ , Sun Hee Kim ₃ , Ryuhei Nakamura _{1,

2}

Affiliation

Nitrate is a pervasive aquatic contaminant of global environmental concern. In nature, the most effective nitrate reduction reaction (NRR) is catalyzed by nitrate reductase enzymes at neutral pH, using a highly‐conserved Mo center ligated mainly by oxo and thiolate groups. Mo‐based NRR catalysts mostly function in organic solvents with a low water stability. Recently, an oxo‐containing molybdenum sulfide nanoparticle that serves as an NRR catalyst at neutral pH was first reported. Herein, in a nanoparticle‐catalyzed NRR system a pentavalent Mo^V(=O)S₄ species, an enzyme mimetic, served as an active intermediate for the NRR. Potentiometric titration analysis revealed that a redox synergy among Mo^V−S, S radicals, and Mo^V(=O)S₄ likely play a key role in stabilizing Mo^V(=O)S₄, showing the importance of secondary interactions in facilitating NRR. The first identification and characterization of an oxo‐ and thiolate‐ligated Mo intermediates pave the way to the molecular design of efficient enzyme mimetic NRR catalysts in aqueous solution.

中文翻译：

酶模拟活性中间体，用于中性水性介质中的硝酸盐还原。

硝酸盐是一种引起全球环境关注的普遍的水生污染物。在自然界中，最有效的硝酸盐还原反应（NRR）是由硝酸盐还原酶在中性pH条件下催化的，使用高度保守的Mo中心，主要由羰基和硫醇盐基团连接。钼基NRR催化剂主要在水稳定性低的有机溶剂中起作用。最近，首次报道了在中性pH值下可作为NRR催化剂的含氧基团的硫化钼纳米颗粒。在此，在纳米颗粒催化的NRR系统中，酶模拟物五价Mo ^V（= O）S ₄物种是NRR的活性中间体。电位滴定分析表明，Mo ^V -S，S自由基和Mo ^V（= O）S之间具有氧化还原协同作用₄可能在稳定Mo ^V（= O）S _4中起关键作用，显示出次级相互作用在促进NRR中的重要性。羰基和硫醇基连接的钼中间体的首次鉴定和表征为高效模拟酶的NRR水溶液分子设计铺平了道路。

更新日期：2020-03-06

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