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Glycosidic Bond Hydrolysis So far as methods developed up to the present are concerned, chain scission has depended on the initial removal of a base residue. This is therefore a convenient place to discuss the hydrolysis of the glycosidic linkage. As is well known, ribonucleosides are more stable than deoxyribonucleosides and, in each class, the purine bases are lost much more rapidly than the pyrimidines. Recently rate measurements made over a wide pH range have deepened our understanding of the process [311-317].

Double-strand cleavage results from the application of hydrodynamic stress [255,256]. The mechanism of the shearing process is unknown and no work has been reported on the nature of the end groups in such sheared molecules. The process may be hydrolytic as above, but alterna­ tively sufficient strain could be localized in a bond to allow homolytic (radical) cleavage and calculation suggests that this is so [256]. C . POLYRIBONUCLEOTIDE HYDROLYSIS In the previous section the mechanism of base-catalyzed hydrolysis of ribonucleotide esters was discussed briefly.

A considerable number of estimates of deamination rates have been given, since it was felt that the variation of these with, for example, pH, might cast light on which bases are involved in mutations or inactivation. Some relative values are given in Table I [178, 185-187]. It is noticeable that the three bases (as nucleosides) only differ overall by a factor of 6, with G > A > C. 0 reduced the rate in TMV nucleic acid for A and C to 1/90 and that for 1. 2, 20°C Substrate Nucleoside tRNA (E. coli) TMV-RNA TMV DNA (calf thymus) DNA (heat-denatured) Ref.

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