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Main Title: X-ray Crystallography and Vibrational Spectroscopy Reveal the Key Determinants of Biocatalytic Dihydrogen Cycling by [NiFe] Hydrogenases
Author(s): Ilina, Yulia
Lorent, Christian
Katz, Sagie
Jeoung, Jae-Hun
Shima, Seigo
Horch, Marius
Zebger, Ingo
Dobbek, Holger
Type: Article
Abstract: [NiFe] hydrogenases are complex model enzymes for the reversible cleavage of dihydrogen (H2). However, structural determinants of efficient H2 binding to their [NiFe] active site are not properly understood. Here, we present crystallographic and vibrational‐spectroscopic insights into the unexplored structure of the H2‐binding [NiFe] intermediate. Using an F420‐reducing [NiFe]‐hydrogenase from Methanosarcina barkeri as a model enzyme, we show that the protein backbone provides a strained chelating scaffold that tunes the [NiFe] active site for efficient H2 binding and conversion. The protein matrix also directs H2 diffusion to the [NiFe] site via two gas channels and allows the distribution of electrons between functional protomers through a subunit‐bridging FeS cluster. Our findings emphasize the relevance of an atypical Ni coordination, thereby providing a blueprint for the design of bio‐inspired H2‐conversion catalysts.
Subject(s): biocatalysis
crystal structure
hydrogen activation
[NiFe] hydrogenase
vibrational spectroscopy
Issue Date: 25-Oct-2019
Date Available: 13-Feb-2020
Language Code: en
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, 390540038, EXC 2008: UniSysCat
DFG, 273919336, SPP 1927: Iron-Sulfur for Life
DFG, 53182490, EXC 314: Unifying Concepts in Catalysis
EC/H2020/810856/EU/Twin to Illuminate Metals in Biology and Biocatalysis through Biospectroscopy/TIMB3
TU Berlin, Open-Access-Mittel - 2019
Journal Title: Angewandte Chemie International Edition
Publisher: Wiley
Volume: 58
Issue: 51
Publisher DOI: 10.1002/anie.201908258
Page Start: 18710
Page End: 18714
EISSN: 1521-3773
ISSN: 1433-7851
TU Affiliation(s): Fak. 2 Mathematik und Naturwissenschaften » Inst. Chemie » FG Physikalische Chemie / Biophysikalische Chemie
Appears in Collections:Technische Universität Berlin » Publications

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