Document Detail


Excited-state dynamics of dGMP measured by steady-state and femtosecond fluorescence spectroscopy.
MedLine Citation:
PMID:  20085298     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
The room-temperature fluorescence of 2'-deoxyguanosine 5'-monophosphate (dGMP) in aqueous solution is studied by steady-state and time-resolved fluorescence spectroscopy. The steady-state fluorescence spectrum of dGMP shows one band centered at 334 nm but has an extraordinary long red tail, extending beyond 700 nm. Both the fluorescence quantum yield and the relative weight of the 334 nm peak increase with the excitation wavelength. The initial fluorescence anisotropy after excitation at 267 nm is lower than 0.2 for all emission wavelengths, indicating an ultrafast S(2) --> S(1) internal conversion. The fluorescence decays depend strongly on the emission wavelength, getting longer with the wavelength. A rise time of 100-150 fs was observed for wavelengths longer than 450 nm, in accordance with a gradual red shift of the time-resolved spectra. The results are discussed in terms of a relaxation occurring mainly on the lowest excited (1)pi pi*-state surface toward a conical intersection with the ground state, in line with recent theoretical predictions. Our results show that the excited-state population undergoes a substantial "spreading out" before reaching the CI, explaining the complex dynamics observed.
Authors:
Francois-Alexandre Miannay; Thomas Gustavsson; Akos Banyasz; Dimitra Markovitsi
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  114     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2010 Mar 
Date Detail:
Created Date:  2010-03-04     Completed Date:  2010-05-21     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  3256-63     Citation Subset:  IM    
Affiliation:
Laboratoire Francis Perrin, CEA/DSM/IRAMIS/SPAM-CNRS URA 2453, CEA Saclay, F-91191 Gif-sur-Yvette, France.
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MeSH Terms
Descriptor/Qualifier:
Deoxyguanine Nucleotides / chemistry*
Quantum Theory*
Spectrometry, Fluorescence
Time Factors
Water / chemistry
Chemical
Reg. No./Substance:
0/Deoxyguanine Nucleotides; 7732-18-5/Water; 902-04-5/2'-deoxyguanosine 5'-phosphate

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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