Non-enzymatic hydrolyses of aryl esters of thymidine 3'-monophosphate as probes for the rate-determining step in DNA hydrolysis.

In order to shed light on the rate-limiting step in DNA hydrolysis, non-enzymatic hydrolyses of aryl esters of thymidine 3'-monophosphate have been kinetically examined. In alkaline solutions, these dinucleotide analogues were hydrolyzed far faster than was thymidylyl(3'-5')thymidine (TpT), indicating that the departure of the leaving group from the phosphorus atom is rate-limiting. The CeIV- and CeIV/PrIII combination-mediated hydrolyses of these analogues were also faster than the corresponding hydrolysis of the dinucleotide.