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Spectroscopic Definition of the CuZĀ° Intermediate in Turnover of Nitrous Oxide Reductase and Molecular Insight into the Catalytic Mechanism

2017-03-29Artigo cientĆ­fico Acesso aberto
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dc.contributor.authorJohnston, Esther M.
dc.contributor.authorCarreira, CĆ­ntia
dc.contributor.authorDell'Acqua, Simone
dc.contributor.authorDey, Somdatta Ghosh
dc.contributor.authorPauleta, Sofia R.
dc.contributor.authorMoura, Isabel
dc.contributor.authorSolomon, Edward I.
dc.contributor.institutionDQ - Departamento de QuĆ­mica
dc.contributor.institutionUCIBIO - Applied Molecular Biosciences Unit
dc.contributor.pblACS - American Chemical Society
dc.date.accessioned2022-02-24T23:13:32Z
dc.date.available2022-02-24T23:13:32Z
dc.date.issued2017-03-29
dc.descriptionFundacao para a Ciencia e Tecnologia - PTDC/QUI-BIQ/116481/2010, PTDC/BBB-BQB/0129/2014, SFRH/BD/87898/2012 ; Unidade de Ciencias Biomoleculares Aplicadas-UCIBIO - FCT/MEC - UID/Multi/04378/2013 ; ERDF - POCI-01-0145-FEDER-007728
dc.description.abstractSpectroscopic methods and density functional theory (DFT) calculations are used to determine the geometric and electronic structure of CuZĀ°, an intermediate form of the Cu4S active site of nitrous oxide reductase (N2OR) that is observed in single turnover of fully reduced N2OR with N2O. Electron paramagnetic resonance (EPR), absorption, and magnetic circular dichroism (MCD) spectroscopies show that CuZĀ° is a 1-hole (i.e., 3CuICuII) state with spin density delocalized evenly over CuI and CuIV. Resonance Raman spectroscopy shows two Cu-S vibrations at 425 and 413 cm-1, the latter with a -3 cm-1 O18 solvent isotope shift. DFT calculations correlated to these spectral features show that CuZĀ° has a terminal hydroxide ligand coordinated to CuIV, stabilized by a hydrogen bond to a nearby lysine residue. CuZĀ° can be reduced via electron transfer from CuA using a physiologically relevant reductant. We obtain a lower limit on the rate of this intramolecular electron transfer (IET) that is >104 faster than the unobserved IET in the resting state, showing that CuZĀ° is the catalytically relevant oxidized form of N2OR. Terminal hydroxide coordination to CuIV in the CuZĀ° intermediate yields insight into the nature of N2O binding and reduction, specifying a molecular mechanism in which N2O coordinates in a Ī¼-1,3 fashion to the fully reduced state, with hydrogen bonding from Lys397, and two electrons are transferred from the fully reduced Ī¼4S2- bridged tetranuclear copper cluster to N2O via a single Cu atom to accomplish N-O bond cleavage.en
dc.description.versionauthorsversion
dc.description.versionpublished
dc.format.extent15
dc.format.extent6067459
dc.identifier.doi10.1021/jacs.6b13225
dc.identifier.issn0002-7863
dc.identifier.otherPURE: 2516877
dc.identifier.otherPURE UUID: 27299af1-5a6d-4f4a-a58b-b626a309d0e2
dc.identifier.otherScopus: 85016297320
dc.identifier.otherPubMed: 28228011
dc.identifier.otherWOS: 000398247100043
dc.identifier.otherORCID: /0000-0002-2149-9416/work/55386477
dc.identifier.urihttp://hdl.handle.net/10362/133538
dc.identifier.urlhttps://www.scopus.com/pages/publications/85016297320
dc.language.isoeng
dc.peerreviewedyes
dc.subjectCOPPER-SULFUR CLUSTER
dc.subjectN2O REDUCTASE
dc.subjectELECTRONIC-STRUCTURE
dc.subjectPSEUDOMONAS-NAUTICA
dc.subjectRESONANCE
dc.subjectCatalysis
dc.subjectGeneral Chemistry
dc.subjectBiochemistry
dc.subjectColloid and Surface Chemistry
dc.titleSpectroscopic Definition of the CuZĀ° Intermediate in Turnover of Nitrous Oxide Reductase and Molecular Insight into the Catalytic Mechanismen
dc.typejournal article
degois.publication.firstPage4462
degois.publication.issue12
degois.publication.lastPage4476
degois.publication.titleJournal of the American Chemical Society
degois.publication.volume139
dspace.entity.typePublication
rcaap.rightsopenAccess

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