Estimation of Gas-Phase Acidities of Deoxyribonucleosides: An Experimental and Theoretical Study

We determined the gas-phase acidities (Delta H-acid) of four deoxyribonucleosides, i.e., 2'-deoxyadenosine (dA), 2'-deoxyguanosine (dG), 2'-deoxycytidine (dC), and 2'-deoxythymidine (dT) by applying the extended kinetic method. The negatively charged proton-bound hetero-dimeric anions, [A - H - B](-) of the deoxyribonucleosides (A) and reference compounds (B) were generated under electrospray ionization conditions. Collision-induced dissociation spectra of [A - H - B](-) were recorded at four different collision energies using a triple quadrupole mass spectrometer. The abundance ratios of the individual monomeric product ions were used to determine the Delta H-acid of the deoxyribonucleosides. The obtained Delta H-acid value follows the order dA > dC > dT > dG. The Delta G(acid) (298 K) values were determined by using Delta G(acid) = Delta H-acid -T Delta S-acid where the Delta H-acid and Delta S-acid values were determined directly from the kinetic method plots. The Delta H-acid values were also predicted for the deoxyribonucleosides at the B3LYP/6-311+G(star star)//B3LYP/6-311G(star star) level of theory. The acidity trend obtained from the computational investigation shows good agreement with that obtained experimentally by the extended kinetic method. Theoretical calculations provided the most preferred deprotonation site as C5'-OH from sugar moiety in case of dA, and as -NH2 (dC and dG) or -NH- (dT) from nitrogenous base moiety in the case of other deoxyribonucleosides. (J Am Soc Mass Spectrom 2010, 21, 136-143) (C) 2010 American Society for Mass Spectrometry