Abstract
The rate expression for the deamination of free cytosine base in unbuffered aqueous solution has been measured as In k = 8.301 - 75.230 kJ mol −1/ RT. Irradiation of similar solutions at 265 nm, followed by high performance liquid chromatography (HPLC) quantification of the uracil formed, allowed a quantum yield for uracil hydrate formation to be calculated as 4.9 × 10 −4. This result was used together with literature values of other rate constants to simulate a mechanism for the formation of uracil from UV-irradiated cytosine solutions. A value of 7.4 × 10 11 s −1 for the internal conversion of cytosine singlet to ground-state cytosine gave the best agreement between the experimental results and the simulation.
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