Caught in the Hinact: Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O2-stable State of [FeFe] Hydrogenase

Rodriguez-Macia P, Galle LM, Bjornsson R, Lorent C, Zebger I, Yoda Y, Cramer SP, Debeer S, Span I, Birrell JA (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 59

Pages Range: 16786-16794

Journal Issue: 38

DOI: 10.1002/anie.202005208

Abstract

[FeFe] hydrogenases are the most active H2 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 O2-stable state called Hinact. To date, the structure and mechanism of formation of Hinact 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 Hinact state and its mechanism of formation. This may facilitate the design of O2-stable hydrogenases and molecular catalysts.

Authors with CRIS profile

Ingrid Span

Involved external institutions

Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion DE Germany (DE) Heinrich-Heine-Universität Düsseldorf DE Germany (DE) Technische Universität Berlin DE Germany (DE) Japan Synchrotron Radiation Research Institute (JASRI) JP Japan (JP) SETI Institute US United States (USA) (US)

How to cite

APA:

Rodriguez-Macia, P., Galle, L.M., Bjornsson, R., Lorent, C., Zebger, I., Yoda, Y.,... Birrell, J.A. (2020). Caught in the Hinact: Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O2-stable State of [FeFe] Hydrogenase. Angewandte Chemie International Edition, 59(38), 16786-16794. https://doi.org/10.1002/anie.202005208

MLA:

Rodriguez-Macia, Patricia, et al. "Caught in the Hinact: Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O2-stable State of [FeFe] Hydrogenase." Angewandte Chemie International Edition 59.38 (2020): 16786-16794.

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