Low energy tandem mass spectrometry of deoxynucleoside adducts of polycyclic aromatic hydrocarbon dihydrodiol-epoxides.
The use of fast-atom bombardment ionization-tandem mass spectrometry approaches, with collision energies on the order of 30-50 eV, was developed for the analysis of low picomole quantities of polycyclic aromatic hydrocarbon dihydrodiol-epoxide deoxynucleoside adducts. This strategy combines three experimental techniques: (1) product ion scans, (2) constant neutral loss scans, and (3) precursor ion scans. Product ion scans of the protonated molecule or the BH 2 (+) ion that results from loss of the deoxyribose were dominated by fragments associated with cleavage of the sigma bond between the dihydrodiol-epoxide moiety and the nucleobase. Constant neutral loss scans were based upon the loss of deoxyribose (116 u) or the combined loss of the deoxynucleoside, water, and carbon monoxide (313 u); precursor ion scans utilized the latter fragment. The formation of trimethylsilyl derivatives increased the sensitivity of analysis, which allowed the simultaneous detection of DNA adducts in a mixture.
National Center for Toxicological Research, Jefferson, Arkansas, USA.
P S
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Branco
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MP
Chiarelli
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JO
Lay
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FA
Beland