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dc.contributor.authorMeyer, Armin H.
dc.contributor.authorDybała-Defratyka, Agnieszka
dc.contributor.authorAlaimo, Peter J.
dc.contributor.authorGeronimo, Inacrist
dc.contributor.authorSanchez, Ariana D.
dc.contributor.authorCramer, Christopher J.
dc.contributor.authorElsner, Martin
dc.date.accessioned2016-02-02T08:48:22Z
dc.date.available2016-02-02T08:48:22Z
dc.date.issued2014
dc.identifier.citationDalton Transactions, Vol. 43, nr. 32, s. 12175-12186
dc.identifier.issn1477-9226
dc.identifier.urihttp://hdl.handle.net/11652/1040
dc.identifier.urihttp://pubs.rsc.org/en/content/articlelanding/2014/dt/c4dt00891j#!divAbstract
dc.description.abstractCytochrome P450 enzymes are responsible for a multitude of natural transformation reactions. For oxidative N-dealkylation, single electron (SET) and hydrogen atom abstraction (HAT) have been debated as underlying mechanisms. Combined evidence from (i) product distribution and (ii) isotope effects indicate that HAT, rather than SET, initiates N-dealkylation of atrazine to desethyl- and desisopropylatrazine by the microorganism Rhodococcus sp. strain NI86/21. (i) Product analysis revealed a non-selective oxidation at both the αC and βC-atom of the alkyl chain, which is expected for a radical reaction, but not SET. (ii) Normal 13C and 15N as well as pronounced 2H isotope effects (εcarbon: −4.0‰ ± 0.2‰; εnitrogen: −1.4‰ ± 0.3‰, KIEH: 3.6 ± 0.8) agree qualitatively with calculated values for HAT, whereas inverse 13C and 15N isotope effects are predicted for SET. Analogous results are observed with the Fe(IV)[double bond, length as m-dash]O model system [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin-iron(III)-chloride + NaIO4], but not with permanganate. These results emphasize the relevance of the HAT mechanism for N-dealkylation by P450.en_EN
dc.language.isoenen_EN
dc.publisherRoyal Society of Chemistryen_EN
dc.relation.ispartofseriesDalton Transactions, Vol. 43, nr. 32, 2014en_EN
dc.titleCytochrome P450-catalyzed dealkylation of atrazine by Rhodococcus sp. strain NI86/21 involves hydrogen atom transfer rather than single electron transferen_EN
dc.typeArtykułpl_PL
dc.typeArticleen_EN


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