Vibrational spectroscopy reveals the initial steps of biological hydrogen evolution (original) (raw)
* Corresponding authors
a Institut für Chemie, Technische Universitaet Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany
E-mail: marius.horch@gmx.de, ingo.zebger@tu-berlin.de
b Fakultaet für Biologie und Biotechnologie, Lehrstuhl für Biochemie der Pflanzen, AG Photobiotechnologie, Ruhr-Universitaet Bochum, Universitaetsstrasse 150, D-44801 Bochum, Germany
c Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, Muelheim an der Ruhr, Germany
Abstract
[FeFe] hydrogenases are biocatalytic model systems for the exploitation and investigation of catalytic hydrogen evolution. Here, we used vibrational spectroscopic techniques to characterize, in detail, redox transformations of the [FeFe] and [4Fe4S] sub-sites of the catalytic centre (H-cluster) in a monomeric [FeFe] hydrogenase. Through the application of low-temperature resonance Raman spectroscopy, we discovered a novel metastable intermediate that is characterized by an oxidized [FeIFeII] centre and a reduced [4Fe4S]1+ cluster. Based on this unusual configuration, this species is assigned to the first, deprotonated H-cluster intermediate of the [FeFe] hydrogenase catalytic cycle. Providing insights into the sequence of initial reaction steps, the identification of this species represents a key finding towards the mechanistic understanding of biological hydrogen evolution.
This article is Open Access
Please wait while we load your content... Something went wrong. Try again?
Supplementary files
Article information
DOI
https://doi.org/10.1039/C6SC01098A
Article type
Edge Article
Submitted
09 Mar 2016
Accepted
29 Jun 2016
First published
11 Jul 2016
This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry
Download Citation
Chem. Sci., 2016,7, 6746-6752
Author version available
Permissions
Vibrational spectroscopy reveals the initial steps of biological hydrogen evolution
S. Katz, J. Noth, M. Horch, H. S. Shafaat, T. Happe, P. Hildebrandt and I. Zebger,Chem. Sci., 2016, 7, 6746DOI: 10.1039/C6SC01098A
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.
Read more about how to correctly acknowledge RSC content.