Product ion studies of some novel arylamine adducts of deoxyguanosine by matrix-assisted laser desorption/ionization and post-source decay.
The product ions of the BH(2)(+) ions formed by the glycosidic cleavage of N-(deoxyguanosin-O(6)-yl)-2-methylaniline, 4-(deoxyguanosin-8-yl)-2-methylaniline, and N-(deoxyguanosin-1-yl)-2-methylaniline have been studied using matrix-assisted laser desorption/ionization (MALDI) and post-source decay (PSD) to identify fragment ions and pathways that may be used to differentiate their structures. All three isomers may be distinguished based on their PSD product ion spectra using only femtomole quantities of sample. N-(Deoxyguanosin-O(6)-yl)-2-methylaniline produces product ions at m/z 107 and 134 that are diagnostic for 2-methylaniline attachment to the O(6) position of guanine. The BH(2)(+) ion from 4-(deoxyguanosin-8-yl)-2-methylaniline yields a product ion formed by the consecutive losses of 17 and 42 u neutral fragments that may be regarded as specific for guanine-arylamine adducts that possess two primary amine groups. The BH(2)(+) ion from 4-(deoxyguanosin-8-yl)-2-methylaniline yields no product ions that correlate with specificity for guanine N1 substitution. However, the product ion abundance ratio of the protonated arylamine to that of the ammonia loss ion may be used to differentiate an adduct formed by N1 substitution from other arylamine adducts of guanine studied thus far.
Chiarelli
M P
MP
Dept. of Chemistry, Loyola University, 6525 N Sheridan Rd., Chicago, IL 60626 USA.
Wu
H P
HP
Antunes
A M
AM
Branco
P S
PS
D002273:Carcinogens / Q000737:chemistry*; D003849:Deoxyguanosine / Q000031:analogs & derivatives* / Q000737:chemistry*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D014052:Toluidines / Q000737:chemistry*
D002273:Carcinogens; D014052:Toluidines; C023622:2-toluidine; D003849:Deoxyguanosine