THE DEWAR VALENCE ISOMER OF THE (6-4) PHOTOADDUCT OF THYMIDYLYL-(3'-5')-THYMIDINE MONOPHOSPHATE - FORMATION, ALKALINE LABILITY AND CONFORMATIONAL PROPERTIES

被引:33
作者
KAN, LS
VOITURIEZ, L
CADET, J
机构
[1] CEN,SESM,DRFMC,LES ACIDES NUCL LAB,85X,F-38041 GRENOBLE,FRANCE
[2] JOHNS HOPKINS UNIV,DEPT BIOCHEM,BALTIMORE,MD 21205
关键词
TPT PHOTOPRODUCTS; PYRIMIDINE(6-4)PYRIMIDONE PHOTOADDUCTS; DEWAR ISOMER; PHOTOISOMERIZATION;
D O I
10.1016/1011-1344(92)85040-2
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The formation of the Dewar valence isomer of the pyrimidine(6-4)pyrimidone photoadduct of thymidylyl-(3'-5')-thymidine monophosphate (TpT) was investigated under different irradiation conditions. This photoproduct was generated on exposure of TpT to far-UV radiation. However, no detectable amount of the Dewar isomer or its precursor (pyrimidine(6-4)pyrimidone photoadduct) was observed following acetone photosensitization of TpT. The Dewar valence isomer was much more unstable than the pyrimidine(6-4)pyrimidone photoproduct when treated with hot piperidine. A detailed conformational analysis of the TpT Dewar isomer photoproduct is reported as inferred from extensive one- and two-dimensional 300 and 620 MHz proton nuclear magnetic resonance (H-1 NMR) measurements and molecular mechanics calculations.
引用
收藏
页码:339 / 357
页数:19
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