10.14279/DEPOSITONCE-6230
Katz, Sagie
Noth, Jens
Horch, Marius
Shafaat, Hannah
Happe, Thomas
Hildebrandt, Peter
Zebger, Ingo
Vibrational spectroscopy reveals the initial steps of biological hydrogen evolution
Technische Universität Berlin
2016
540 Chemie und zugeordnete Wissenschaften
Technische Universität Berlin
Technische Universität Berlin
2017-10-24
2017-10-24
2016
en
Article
2041-6520
https://depositonce.tu-berlin.de//handle/11303/6891
2041-6539
28451119
[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 [(FeFeII)-Fe-I] 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.