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Functionally Releva...
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Bruschi, Maurizio
(författare)
Functionally Relevant Interplay between the Fe(4)S(4) Cluster and CN(-) Ligands in the Active Site of [FeFe]-Hydrogenases.
- Artikel/kapitelEngelska2010
Förlag, utgivningsår, omfång ...
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2010-03-19
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American Chemical Society (ACS),2010
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electronicrdacarrier
Nummerbeteckningar
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LIBRIS-ID:oai:lup.lub.lu.se:afd8b3c3-6907-425a-8bbc-fdc645f69963
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https://lup.lub.lu.se/record/1581786URI
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https://doi.org/10.1021/ja1008773DOI
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Språk:engelska
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Sammanfattning på:engelska
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Ämneskategori:art swepub-publicationtype
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Ämneskategori:ref swepub-contenttype
Anmärkningar
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[FeFe]-hydrogenases are highly efficient H(2)-evolving metalloenzymes that include cyanides and carbonyls in the active site. The latter is an Fe(6)S(6) cluster (the so-called H-cluster) that can be subdivided into a binuclear portion carrying the CO and CN(-) groups and a tetranuclear subcluster. The fundamental role of cyanide ligands in increasing the basicity of the H-cluster has been highlighted previously. Here a more subtle but crucial role played by the two CN(-) ligands in the active site of [FeFe]-hydrogenases is disclosed. In fact, QM/MM calculations on all-atom models of the enzyme from Desulfovibrio desulfuricans show that the cyanide groups fine-tune the electronic and redox properties of the active site, affecting both the protonation regiochemistry and electron transfer between the two subclusters of the H-cluster. Despite the crucial role of cyanides in the protein active site, the currently available bioinspired electrocatalysts generally lack CN(-) groups in order to avoid competition between the latter and the catalytic metal centers for proton binding. In this respect, we show that a targeted inclusion of phosphine ligands in hexanuclear biomimetic clusters may restore the electronic and redox features of the wild-type H-cluster.
Ämnesord och genrebeteckningar
Biuppslag (personer, institutioner, konferenser, titlar ...)
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Greco, Claudio
(författare)
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Bertini, Luca
(författare)
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Fantucci, Piercarlo
(författare)
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Ryde, UlfLund University,Lunds universitet,Beräkningskemi,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Computational Chemistry,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)teok-ury
(författare)
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Gioia, Luca De
(författare)
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BeräkningskemiEnheten för fysikalisk och teoretisk kemi
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Journal of the American Chemical Society: American Chemical Society (ACS)132:14, s. 4992-49921520-51260002-7863
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