A Density Functional Theory Investigation on the Mechanism of the Second Half-Reaction of Nitric Oxide Synthase.
Density functional theory methods have been employed to systematically investigate the overall mechanism of the second half-reaction of nitric oxide synthases. The initial heme-bound hydrogen peroxide intermediate previously identified is found to first undergo a simple rotation about its OO peroxi...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 11; pp. 3328 - 3335 |
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| Autores principales: | , , |
| Formato: | Artículo |
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American Chemical Society
3/19/2008
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=31445762&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 31445762 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 3/19/2008 vid: 130 iid: 11 pid: 997 pub: American Chemical Society artinfo: ui: 31445762 10.1021/ja072650+ ppf: 3328 ppct: 7 formats: tig: atl: A Density Functional Theory Investigation on the Mechanism of the Second Half-Reaction of Nitric Oxide Synthase. aug: au: Robinet, Jesse J. Kyung-Bin Cho Gauld, James W. affil: Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada su: Density functionals Nitric oxide Hydrogen peroxide Nitrogen compounds Functional analysis sug: subj: Density functionals Nitric oxide Hydrogen peroxide Nitrogen compounds Functional analysis ab: Density functional theory methods have been employed to systematically investigate the overall mechanism of the second half-reaction of nitric oxide synthases. The initial heme-bound hydrogen peroxide intermediate previously identified is found to first undergo a simple rotation about its OO peroxide bond. Then, via a "ping-pong" peroxidase-like mechanism the OH proton is transferred back onto the substrate's -NO oxygen then subsequently onto the outer oxygen of the resulting FeOOH species. As a result, O is released as HO with concomitant formation of a compound I-type (FeO) species. Formation of the final citrulline and NO products can then be achieved in one step via a tetrahedral transition structure resulting from direct attack of the FeO moiety at the substrate's guanidinium carbon center. The possible role of alternative mechanisms involving a protonated compound II-type species or an initial transfer of only the NH hydrogen of the NHOH group of N-hydroxy-L-arginine is also discussed. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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