Article: Influence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site
| Title | Influence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Authors | Guo, Z1 Xue, J1 Ke, Z2 Phillips, DL1 Zhao, C2 | ||||||||
| Issue Date | 2009 | ||||||||
| Publisher | American 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?] DOI: http://dx.doi.org/10.1021/jp8104584 | ||||||||
| Abstract | A 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. | ||||||||
| ISSN | 1520-6106 2011 Impact Factor: 3.696 2011 SCImago Journal Rankings: 0.299 | ||||||||
| DOI | http://dx.doi.org/10.1021/jp8104584 | ||||||||
| ISI Accession Number ID | WOS:000265687500042
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 | References in Scopus |
| dc.contributor.author | Guo, Z | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| dc.contributor.author | Xue, J | ||||||||
| dc.contributor.author | Ke, Z | ||||||||
| dc.contributor.author | Phillips, DL | ||||||||
| dc.contributor.author | Zhao, C | ||||||||
| dc.date.accessioned | 2010-05-31T03:28:12Z | ||||||||
| dc.date.available | 2010-05-31T03:28:12Z | ||||||||
| dc.date.issued | 2009 | ||||||||
| dc.description.abstract | A 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.nature | Link_to_subscribed_fulltext | ||||||||
| dc.identifier.citation | Journal 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.doi | http://dx.doi.org/10.1021/jp8104584 | ||||||||
| dc.identifier.epage | 6532 | ||||||||
| dc.identifier.hkuros | 160829 | ||||||||
| dc.identifier.isi | WOS:000265687500042
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.issn | 1520-6106 2011 Impact Factor: 3.696 2011 SCImago Journal Rankings: 0.299 | ||||||||
| dc.identifier.issue | 18 | ||||||||
| dc.identifier.pmid | 19358540 | ||||||||
| dc.identifier.scopus | eid_2-s2.0-66349134468 | ||||||||
| dc.identifier.spage | 6528 | ||||||||
| dc.identifier.uri | http://hdl.handle.net/10722/58318 | ||||||||
| dc.identifier.volume | 113 | ||||||||
| dc.language | eng | ||||||||
| dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journal/jpcbfk | ||||||||
| dc.publisher.place | United States | ||||||||
| dc.relation.ispartof | Journal of Physical Chemistry B | ||||||||
| dc.relation.references | References in Scopus | ||||||||
| dc.title | Influence of water hydrogen bonding on the reactions of arylnitrenium ions with guanosine: Hydrogen-bonding effects can favor reaction at the C8 site | ||||||||
| dc.type | Article |
Author Affiliations
- The University of Hong Kong
- Sun Yat-Sen University