Double proton transfer dynamics of model DNA base pairs in the condensed phase.

Abstract:

:The dynamics of excited-state double proton transfer of model DNA base pairs, 7-azaindole dimers, is reported using femtosecond fluorescence spectroscopy. To elucidate the nature of the transfer in the condensed phase, here we examine variation of solvent polarity and viscosity, solute concentration, and isotopic fractionation. The rate of proton transfer is found to be significantly dependent on polarity and on the isotopic composition in the pair. Consistent with a stepwise mechanism, the results support the presence of an ionic intermediate species which forms on the femtosecond time scale and decays to the final tautomeric form on the picosecond time scale. We discuss the results in relation to the molecular motions involved and comment on recent claims of concerted transfer in the condensed phase. The nonconcerted mechanism is in agreement with previous isolated-molecule femtosecond dynamics and is also consistent with the most-recent high-level theoretical study on the same pair.

authors

Kwon OH,Zewail AH

doi

10.1073/pnas.0702944104

subject

Has Abstract

pub_date

2007-05-22 00:00:00

pages

8703-8

issue

21

eissn

0027-8424

issn

1091-6490

pii

0702944104

journal_volume

104

pub_type

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