Characterization of a 5'-aldehyde terminus resulting from the oxidative attack at C5' of a 2-deoxyribose on DNA.
The 5'-aldehyde terminus is a DNA oxidative damage resulting from attack at C5' of 2-deoxyriboses by some potent natural or chemical DNA cleavers. To offer a fast and specific method for characterization of this type of damage, we used on-line electrospray ionization mass spectrometry (ESI-MS) detection during liquid chromatography analyses. The intrinsic reactivity of 5'-aldehyde terminus with nucleophiles (formation of hydrate with water, of a Tris adduct with Tris buffer) or through beta-elimination reaction resulted in complex LC profiles and MS data. We showed that derivatization of the aldehyde function as an oxime ether gives a stable derivative easy to characterize during on-line ESI-MS analyses. Complete structural characterization of the Tris adduct and the oxime ether derivative were obtained from MS and detailed NMR studies performed on derivatized 5'-aldehyde thymidine models.
Angeloff
A
A
Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, F-31077 Toulouse Cedex 4, France.
Dubey
I
I
Pratviel
G
G
Bernadou
J
J
Meunier
B
B
D000447:Aldehydes / Q000737:chemistry*; D002851:Chromatography, High Pressure Liquid; D018736:DNA Adducts / Q000032:analysis / Q000737:chemistry*; D004249:DNA Damage; D003855:Deoxyribose / Q000737:chemistry*; D010084:Oxidation-Reduction; D010091:Oximes / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
D000447:Aldehydes; D018736:DNA Adducts; D010091:Oximes; D003855:Deoxyribose