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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
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TitleInfluence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site
 
AuthorsGuo, Z1
Xue, J1
Ke, Z2
Phillips, DL1
Zhao, C2
 
Issue Date2009
 
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfk
 
CitationJournal Of Physical Chemistry B, 2009, v. 113 n. 18, p. 6528-6532 [How to Cite?]
DOI: http://dx.doi.org/10.1021/jp8104584
 
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.
 
ISSN1520-6106
2013 Impact Factor: 3.377
2013 SCImago Journal Rankings: 1.575
 
DOIhttp://dx.doi.org/10.1021/jp8104584
 
ISI Accession Number IDWOS:000265687500042
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).

 
ReferencesReferences in Scopus
 
DC FieldValue
dc.contributor.authorGuo, Z
 
dc.contributor.authorXue, J
 
dc.contributor.authorKe, Z
 
dc.contributor.authorPhillips, DL
 
dc.contributor.authorZhao, C
 
dc.date.accessioned2010-05-31T03:28:12Z
 
dc.date.available2010-05-31T03:28:12Z
 
dc.date.issued2009
 
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.
 
dc.description.naturelink_to_subscribed_fulltext
 
dc.identifier.citationJournal Of Physical Chemistry B, 2009, v. 113 n. 18, p. 6528-6532 [How to Cite?]
DOI: http://dx.doi.org/10.1021/jp8104584
 
dc.identifier.doihttp://dx.doi.org/10.1021/jp8104584
 
dc.identifier.epage6532
 
dc.identifier.hkuros160829
 
dc.identifier.isiWOS:000265687500042
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).

 
dc.identifier.issn1520-6106
2013 Impact Factor: 3.377
2013 SCImago Journal Rankings: 1.575
 
dc.identifier.issue18
 
dc.identifier.pmid19358540
 
dc.identifier.scopuseid_2-s2.0-66349134468
 
dc.identifier.spage6528
 
dc.identifier.urihttp://hdl.handle.net/10722/58318
 
dc.identifier.volume113
 
dc.languageeng
 
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfk
 
dc.publisher.placeUnited States
 
dc.relation.ispartofJournal of Physical Chemistry B
 
dc.relation.referencesReferences in Scopus
 
dc.titleInfluence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site
 
dc.typeArticle
 
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<contributor.author>Ke, Z</contributor.author>
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<contributor.author>Zhao, C</contributor.author>
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<description.abstract>A computational study was done for the reactions of the 2-fluorenylnitrenium ion (2FN) with guanosine (G) and its monohydrate tautomer (G&#183;H 2O) to form the key N7 or C8 intermediates that may then proceed to produce the C8 adduct product. The 2FN + G&#183;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&#183;H 2O in our case), so the C8 position of guanosine will become more nucleophilic than position N7. Computational results for the 2FN + G&#183;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 &quot;C8 intermediate&quot; 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. &#169; 2009 American Chemical Society.</description.abstract>
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Author Affiliations
  1. The University of Hong Kong
  2. Sun Yat-Sen University