eprintid: 1424789
rev_number: 30
eprint_status: archive
userid: 608
dir: disk0/01/42/47/89
datestamp: 2014-03-25 22:25:14
lastmod: 2021-10-04 01:43:31
status_changed: 2014-03-25 22:25:14
type: article
metadata_visibility: show
item_issues_count: 0
creators_name: Kubas, A
creators_name: De Sancho, D
creators_name: Best, RB
creators_name: Blumberger, J
title: Aerobic Damage to [FeFe]-Hydrogenases: Activation Barriers for the Chemical Attachment of O2.
ispublished: pub
divisions: UCL
divisions: B04
divisions: C06
divisions: F60
keywords: [FeFe]-hydrogenases, ab initio calculations, electron transfer, iron-sulfur clusters, oxygen activation
note: © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
abstract: [FeFe]-hydrogenases are the best natural hydrogen-producing enzymes but their biotechnological exploitation is hampered by their extreme oxygen sensitivity. The free energy profile for the chemical attachment of O2 to the enzyme active site was investigated by using a range-separated density functional re-parametrized to reproduce high-level ab initio data. An activation free-energy barrier of 13 kcal mol(-1) was obtained for chemical bond formation between the di-iron active site and O2 , a value in good agreement with experimental inactivation rates. The oxygen binding can be viewed as an inner-sphere electron-transfer process that is strongly influenced by Coulombic interactions with the proximal cubane cluster and the protein environment. The implications of these results for future mutation studies with the aim of increasing the oxygen tolerance of this enzyme are discussed.
date: 2014-04-14
official_url: http://dx.doi.org/10.1002/anie.201400534
vfaculties: VMPS
oa_status: green
full_text_type: pub
primo: open
primo_central: open_green
article_type_text: JOURNAL ARTICLE
verified: verified_manual
elements_source: PubMed
elements_id: 938503
doi: 10.1002/anie.201400534
language_elements: ENG
lyricists_name: Blumberger, Jochen
lyricists_name: Kubas, Adam
lyricists_id: JBLUM96
lyricists_id: AKUBA18
full_text_status: public
publication: Angew Chem Int Ed Engl
volume: 53
number: 16
pagerange: 4081-4084
citation:        Kubas, A;    De Sancho, D;    Best, RB;    Blumberger, J;      (2014)    Aerobic Damage to [FeFe]-Hydrogenases: Activation Barriers for the Chemical Attachment of O2.                   Angew Chem Int Ed Engl , 53  (16)   pp. 4081-4084.    10.1002/anie.201400534 <https://doi.org/10.1002/anie.201400534>.       Green open access   
 
document_url: https://discovery.ucl.ac.uk/id/eprint/1424789/1/4081_ftp.pdf