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

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• 作者：Antony St-Jacques ; Janna Anichina ; Bradley B. Schneider ; Thomas R. Covey ; Diethard K. Bohme
• 刊名：Analytical Chemistry
• 出版年：2010
• 出版时间：July 15, 2010
• 年：2010
• 卷：82
• 期：14
• 页码：6163-6167
• 全文大小：190K
• 年卷期：v.82,no.14(July 15, 2010)
• ISSN：1520-6882

文摘

Differential mobility spectrometry has been applied to reveal the occurrence of isomerization of thymine nucleobase and of thymine 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 electrosprayed 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.