File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Hypersensitive radical probe studies of chloroperoxidase-catalyzed hydroxylation reactions

TitleHypersensitive radical probe studies of chloroperoxidase-catalyzed hydroxylation reactions
Authors
Issue Date1998
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/crt
Citation
Chemical Research In Toxicology, 1998, v. 11 n. 7, p. 816-823 How to Cite?
AbstractThe oxidation of hypersensitive radical probes by chloroperoxidase from Caldariomyces fumago (CPO) was studied in an attempt to 'time' a putative radical intermediate. Oxidation of (trans-2-phenylcyclopropyl)methane, previously studied by Zaks and Dodds [Zaks, A., and Dodds, D. R. (1995) J. Am. Chem. Soc. 115, 10419-10424] was reinvestigated. Unrearranged oxidation products were found as previously reported, and control experiments demonstrated that the cyclic alcohol from oxidation at the cyclopropylcarbinyl position, while subject to further oxidation, survives CPO oxidation as detectable species. However, in contrast to the report by Zaks and Dodds, the rearranged alcohol product expected from ring opening of a cyclopropylcarbinyl radical intermediate was shown to be unstable toward the enzyme oxidation reaction. Because of this instability, two new hypersensitive radical probes, (trans-2-phenylcyclopropyl)ethane and 2- (trans-2-phenylcyclopropyl)propane, and their potential cyclic and acyclic products from oxidation at the cyclopropylcarbinyl position were synthesized and tested. Oxidation of both of these probes at the cyclopropylcarbinyl position by CPO gave unrearranged alcohol products only, but control experiments again demonstrated that the rearranged alcohol products were unstable toward CPO oxidation conditions. From the combination of the probe and control studies, the lifetime of a putative radical intermediate must be less than 3 ps. Whereas the results are consistent with an insertion mechanism for production of alcohol product, they do not exclude a very short-lived intermediate.
Persistent Identifierhttp://hdl.handle.net/10722/167583
ISSN
2015 Impact Factor: 3.025
2015 SCImago Journal Rankings: 1.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorToy, PHen_US
dc.contributor.authorNewcomb, Men_US
dc.contributor.authorHager, LPen_US
dc.date.accessioned2012-10-08T03:08:47Z-
dc.date.available2012-10-08T03:08:47Z-
dc.date.issued1998en_US
dc.identifier.citationChemical Research In Toxicology, 1998, v. 11 n. 7, p. 816-823en_US
dc.identifier.issn0893-228Xen_US
dc.identifier.urihttp://hdl.handle.net/10722/167583-
dc.description.abstractThe oxidation of hypersensitive radical probes by chloroperoxidase from Caldariomyces fumago (CPO) was studied in an attempt to 'time' a putative radical intermediate. Oxidation of (trans-2-phenylcyclopropyl)methane, previously studied by Zaks and Dodds [Zaks, A., and Dodds, D. R. (1995) J. Am. Chem. Soc. 115, 10419-10424] was reinvestigated. Unrearranged oxidation products were found as previously reported, and control experiments demonstrated that the cyclic alcohol from oxidation at the cyclopropylcarbinyl position, while subject to further oxidation, survives CPO oxidation as detectable species. However, in contrast to the report by Zaks and Dodds, the rearranged alcohol product expected from ring opening of a cyclopropylcarbinyl radical intermediate was shown to be unstable toward the enzyme oxidation reaction. Because of this instability, two new hypersensitive radical probes, (trans-2-phenylcyclopropyl)ethane and 2- (trans-2-phenylcyclopropyl)propane, and their potential cyclic and acyclic products from oxidation at the cyclopropylcarbinyl position were synthesized and tested. Oxidation of both of these probes at the cyclopropylcarbinyl position by CPO gave unrearranged alcohol products only, but control experiments again demonstrated that the rearranged alcohol products were unstable toward CPO oxidation conditions. From the combination of the probe and control studies, the lifetime of a putative radical intermediate must be less than 3 ps. Whereas the results are consistent with an insertion mechanism for production of alcohol product, they do not exclude a very short-lived intermediate.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/crten_US
dc.relation.ispartofChemical Research in Toxicologyen_US
dc.subject.meshCatalysisen_US
dc.subject.meshChloride Peroxidase - Metabolismen_US
dc.subject.meshCyclopropanes - Chemistryen_US
dc.subject.meshFree Radicalsen_US
dc.subject.meshHydroxylationen_US
dc.subject.meshIndicators And Reagentsen_US
dc.subject.meshMagnetic Resonance Spectroscopyen_US
dc.subject.meshMitosporic Fungi - Enzymologyen_US
dc.subject.meshOxidation-Reductionen_US
dc.titleHypersensitive radical probe studies of chloroperoxidase-catalyzed hydroxylation reactionsen_US
dc.typeArticleen_US
dc.identifier.emailToy, PH:phtoy@hkucc.hku.hken_US
dc.identifier.authorityToy, PH=rp00791en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/tx9800295en_US
dc.identifier.pmid9671545-
dc.identifier.scopuseid_2-s2.0-0031823396en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0031823396&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume11en_US
dc.identifier.issue7en_US
dc.identifier.spage816en_US
dc.identifier.epage823en_US
dc.identifier.isiWOS:000074983800019-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridToy, PH=7006579247en_US
dc.identifier.scopusauthoridNewcomb, M=7101865783en_US
dc.identifier.scopusauthoridHager, LP=7004432356en_US

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats