Department of Inorganic Spectroscopy, Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Angew Chem Int Ed Engl. 2020 Sep 14;59(38):16786-16794. doi: 10.1002/anie.202005208. Epub 2020 Jul 23.
[FeFe] hydrogenases are the most active H converting catalysts in nature, but their extreme oxygen sensitivity limits their use in technological applications. The [FeFe] hydrogenases from sulfate reducing bacteria can be purified in an O -stable state called H . To date, the structure and mechanism of formation of H remain unknown. Our 1.65 Å crystal structure of this state reveals a sulfur ligand bound to the open coordination site. Furthermore, in-depth spectroscopic characterization by X-ray absorption spectroscopy (XAS), nuclear resonance vibrational spectroscopy (NRVS), resonance Raman (RR) spectroscopy and infrared (IR) spectroscopy, together with hybrid quantum mechanical and molecular mechanical (QM/MM) calculations, provide detailed chemical insight into the H state and its mechanism of formation. This may facilitate the design of O -stable hydrogenases and molecular catalysts.
[FeFe]氢化酶是自然界中活性最高的 H2 转化催化剂，但它们对氧气的极度敏感性限制了它们在技术应用中的使用。来自硫酸盐还原菌的[FeFe]氢化酶可以在一种称为 H 的稳定状态下被纯化。迄今为止，H 的结构和形成机制仍不清楚。我们获得了这种状态的 1.65 Å 晶体结构，揭示了一个与开放配位位结合的硫配体。此外，通过 X 射线吸收光谱（XAS）、核共振振动光谱（NRVS）、共振拉曼（RR）光谱和红外（IR）光谱的深入光谱表征，以及混合量子力学和分子力学（QM/MM）计算，为 H 状态及其形成机制提供了详细的化学见解。这可能有助于设计对氧气稳定的氢化酶和分子催化剂。
