In:
Angewandte Chemie, Wiley, Vol. 127, No. 49 ( 2015-12), p. 14985-14989
Abstract:
Ultrafast excited‐state deactivation dynamics of small cytosine (Cy) and 1‐methylcytosine (1mCy) microhydrates, Cy⋅(H 2 O) 1‐3 and 1mCy⋅(H 2 O) 1,2 , produced in a supersonic expansion have been studied by mass‐selected femtosecond pump–probe photoionization spectroscopy at about 267 nm excitation. The seeded supersonic expansion of Ar/H 2 O gas mixtures allowed an extensive structural relaxation of Cy and 1mCy microhydrates to low‐energy isomers. With the aid of electronic structure calculations, we assigned the observed ultrafast dynamics to the dominant microhydrate isomers of the amino‐keto tautomer of Cy and 1mCy. Excited‐state lifetimes of Cy⋅(H 2 O) 1‐3 measured here are 0.2–0.5 ps. Comparisons of the Cy⋅H 2 O and 1mCy⋅H 2 O transients suggest that monohydration at the amino Watson–Crick site induces a substantially stronger effect than at the sugar‐edge site in accelerating excited‐state deactivation of Cy.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v127.49
DOI:
10.1002/ange.201507524
Language:
German
Publisher:
Wiley
Publication Date:
2015
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