Watson-Crick Base Pairing Controls Excited-State Decay in Natural DNA

被引:60
作者
Bucher, Dominik B. [1 ,2 ,3 ]
Schlueter, Alexander [1 ,2 ]
Carell, Thomas [3 ]
Zinth, Wolfgang [1 ,2 ]
机构
[1] Univ Munich, D-80538 Munich, Germany
[2] Univ Munich, Ctr Integrated Prot Sci CIPSM, D-80538 Munich, Germany
[3] Univ Munich, Dept Chem, Ctr Integrated Prot Sci, D-81377 Munich, Germany
关键词
base pairing; DNA photochemistry; excited-state decay; femtosecond IR spectroscopy; proton transfer; CENTER-DOT-C; PROTON-TRANSFER; ULTRAFAST DEACTIVATION; THYMINE DIMERIZATION; ENERGY-TRANSFER; UV EXCITATION; DYNAMICS; FEMTOSECOND; DELOCALIZATION; PHOTOPHYSICS;
D O I
10.1002/anie.201406286
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Excited-state dynamics are essential to understanding the formation of DNA lesions induced by UV light. By using femtosecond IR spectroscopy, it was possible to determine the lifetimes of the excited states of all four bases in the double-stranded environment of natural DNA. After UV excitation of the DNA duplex, we detected a concerted decay of base pairs connected by Watson-Crick hydrogen bonds. A comparison of single- and double-stranded DNA showed that the reactive charge-transfer states formed in the single strands are suppressed by base pairing in the duplex. The strong influence of the Watson-Crick hydrogen bonds indicates that proton transfer opens an efficient decay path in the duplex that prohibits the formation or reduces the lifetime of reactive charge-transfer states.
引用
收藏
页码:11366 / 11369
页数:4
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