Deoxynucleosides reversible alkylation

REVERSIBLE ALKYLATION OF DEOXYNUCLEOSIDES BY A SIMPLE QUINONE METHIDE... 

The reversibility of dA alkylation by QM3 creates both problems and opportunities. For example, an accurate profile of products formed by initial exposure of DNA to QMs may not be easily determined since labile products such as the N1 adduct of dA would not persist through the typical procedures of enzyme digestion and analysis of the subsequent deoxynucleoside products by reverse phase HPLC. Thus, the full extent of DNA alkylation by QMs may be severely underestimated. 

Detection of the dA N1 and dC N3 adducts may not in one sense be particularly important for DNA based on their central position within the helical conformation and hydrogen bonding network.37,38 Still, the deoxynucleoside studies helped to focus attention on the reversibility of alkylation by QM and provided insight into the reactions of duplex DNA described below in Section 9.3. Reaction at the deoxynucleoside level also provided an essential system for developing a theoretical treatment of QM reaction.50-52 Computations based on density functional theory well rationalized the published results on d A and correctly anticipated the results on dG and dC reviewed above and described in more detail in Chapter 2 (Freccero). 

---