Abstract

European Journal of Mass Spectrometry
Volume 12 Issue 5, Pages 283–289 (2006)
doi: 10.1255/ejms.825

Characterization of activation energy distribution for ultraviolet irradiation of T- rich oligonucleotide using high-performance liquid chromatography electrospray ionization mass spectrometry tandem mass spectrometry

Renfang Song,^a,b Jinzhong Liu,^a Wenbing Zhang,^a Huayong Chen,^a,b Huimin Ma,^a,b Guoying Sheng,^a Zhen Zhou^a and Jiamo Fu^a,*
aState Key Laboratory of Organic Geochemistry, Guangzhou Research Center of Mass Spectrometry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
^bGraduate School of the Chinese Academy of Sciences, Beijing, China

Exposure to solar UV radiation gives rise to mutations that may lead to skin cancer of human being. Series of experiments were carried out in order to reveal activation energy distribution of DNA mutation caused by UV radiation. The T-rich oligonucleotides were exposed to UV radiation with increasing intensity for different durations. Photoproducts of T-rich oligonucleotide were investigated using ion-pair reversed-phase high-performance liquid chromatography/tandem electrospray ionization mass spectrometry (IP-RP-HPLC/ESI-MS) at room temperature. Two photoproducts of T-rich oligonucleotide were cis-syn cyclobutane pyrimidine dimmer (T[c,s]T) and the pyrimidine(6,4)pyrimidone product (T[6,4]T). Activation energy distribution of DNA mutation was calculated using a commercial kinetics analysis programs by Robert L. Braun and Alan K. Burnham , Lawrance Livermore International Laboratory (version 2.4.1). To use the software for deriving the kinetics parameters, the factor T (temperature) in the software was substituted with k₁R, in which k₁ is a factor, R is radiation intensity. The activation energy derived ranges from 55 to 110kJ mol^–1. By the same software, those kinetics parameters were extrapolated to natural UV radiation process to predict DNA damage degree without the DNA repair process.

Keywords: T-rich oligonucleotides, photoproducts,activation energy distribution ,IP-RP-HPLC/ESI-MS

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