4.8 Article

UV-Induced Bond Modifications in Thymine and Thymine Dideoxynucleotide: Structural Elucidation of Isomers by Differential Mobility Mass Spectrometry

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ANALYTICAL CHEMISTRY
卷 82, 期 14, 页码 6163-6167

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AMER CHEMICAL SOC
DOI: 10.1021/ac100977b

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  1. Natural Sciences and Engineering Research Council of Canada

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Differential mobility spectrometry has been applied to reveal the occurrence of isomerization of thymine nucleobase and of thyrnine dideoxynucleotide d(5'-TT-3') due to bond redisposition induced by UV irradiation at 254 nm of frozen aqueous solutions of these molecules. Collision-induced dissociation (CID) spectra of electro-sprayed photoproducts of the thymine solution suggest the presence of two isomers (the so-called cyclobutane and 6,4-photoproducts) in addition to the proton-bound thymine dimer, and these were separated using differential mobility spectrometry/mass spectrometry (DMS/MS) techniques with water as the modifier. Similar experiments with d(5'-TT-3') revealed the formation of a new isomer of deprotonated thymine dideoxynucleotide upon UV irradiation that was easily distinguished using DMS/MS with isopropanol as the modifier. The results reinforce the usefulness of DMS/MS in isomer separation.

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