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Article: Influence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site

TitleInfluence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site
Authors
Issue Date2009
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfk
Citation
Journal Of Physical Chemistry B, 2009, v. 113 n. 18, p. 6528-6532 How to Cite?
AbstractA computational study was done for the reactions of the 2-fluorenylnitrenium ion (2FN) with guanosine (G) and its monohydrate tautomer (G·H 2O) to form the key N7 or C8 intermediates that may then proceed to produce the C8 adduct product. The 2FN + G·H 2O reactions with the transition state of the C8 pathway being noticeably lower than that of the N7 pathway are very different from those found for the 2FN + G reactions where the transition states for the N7 pathway are lower than those for the C8 pathway. This is due to the lone pair of N7 being protected by hydrogen bonding in a protic solvent (G·H 2O in our case), so the C8 position of guanosine will become more nucleophilic than position N7. Computational results for the 2FN + G·H 2O reactions predict that the C8 intermediate, rather than the N7 intermediate, is the predominant intermediate formed from the reaction. Our results are consistent with time-resolved absorption and time-resolved resonance Raman experiments that found a very fast reaction of 2FN with guanosine to produce a "C8 intermediate" with a common time constant for the decay of 2FN and the formation of the C8 intermediate. The results here suggest that explicit hydrogen-bonding effects on the chemical reactivity of guanosine may contribute to arylnitrenium ions reacting with guanine derivatives to produce predominantly C8 adducts rather than N7 adducts. © 2009 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/58318
ISSN
2015 Impact Factor: 3.187
2015 SCImago Journal Rankings: 1.414
ISI Accession Number ID
Funding AgencyGrant Number
Research Grants Council of Hong KongHKU-7040/06P
Croucher Foundation
University of Hong Kong
Funding Information:

This research has been supported by Grants from the Research Grants Council of Hong Kong (HKU-7040/06P) to D.L.P. D.L.P. thanks the Croucher Foundation for the award of a Croucher Foundation Senior Research Fellowship (2006-07) and the University of Hong Kong for an Outstanding Researcher Award (2006).

References

 

DC FieldValueLanguage
dc.contributor.authorGuo, Zen_HK
dc.contributor.authorXue, Jen_HK
dc.contributor.authorKe, Zen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorZhao, Cen_HK
dc.date.accessioned2010-05-31T03:28:12Z-
dc.date.available2010-05-31T03:28:12Z-
dc.date.issued2009en_HK
dc.identifier.citationJournal Of Physical Chemistry B, 2009, v. 113 n. 18, p. 6528-6532en_HK
dc.identifier.issn1520-6106en_HK
dc.identifier.urihttp://hdl.handle.net/10722/58318-
dc.description.abstractA computational study was done for the reactions of the 2-fluorenylnitrenium ion (2FN) with guanosine (G) and its monohydrate tautomer (G·H 2O) to form the key N7 or C8 intermediates that may then proceed to produce the C8 adduct product. The 2FN + G·H 2O reactions with the transition state of the C8 pathway being noticeably lower than that of the N7 pathway are very different from those found for the 2FN + G reactions where the transition states for the N7 pathway are lower than those for the C8 pathway. This is due to the lone pair of N7 being protected by hydrogen bonding in a protic solvent (G·H 2O in our case), so the C8 position of guanosine will become more nucleophilic than position N7. Computational results for the 2FN + G·H 2O reactions predict that the C8 intermediate, rather than the N7 intermediate, is the predominant intermediate formed from the reaction. Our results are consistent with time-resolved absorption and time-resolved resonance Raman experiments that found a very fast reaction of 2FN with guanosine to produce a "C8 intermediate" with a common time constant for the decay of 2FN and the formation of the C8 intermediate. The results here suggest that explicit hydrogen-bonding effects on the chemical reactivity of guanosine may contribute to arylnitrenium ions reacting with guanine derivatives to produce predominantly C8 adducts rather than N7 adducts. © 2009 American Chemical Society.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfken_HK
dc.relation.ispartofJournal of Physical Chemistry Ben_HK
dc.titleInfluence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 siteen_HK
dc.typeArticleen_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jp8104584en_HK
dc.identifier.pmid19358540-
dc.identifier.scopuseid_2-s2.0-66349134468en_HK
dc.identifier.hkuros160829en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-66349134468&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume113en_HK
dc.identifier.issue18en_HK
dc.identifier.spage6528en_HK
dc.identifier.epage6532en_HK
dc.identifier.isiWOS:000265687500042-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridGuo, Z=36554069300en_HK
dc.identifier.scopusauthoridXue, J=23007272500en_HK
dc.identifier.scopusauthoridKe, Z=14048262500en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridZhao, C=7403563836en_HK

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