(E)-5-[2-(methoxycarbonyl)ethenyl]cytidine as a chemical actinometer for germicidal UV radiation

(E)-5-[2-(Methoxycarbonyl)ethenyl]cytidine (S) was examined for use as a chemical actinometer for germicidal UV radiation. Its photoproduct, 3-beta-D-ribofuranosyl-2,7-dioxopyrido[2,3-d]pyrimidine (P), is strongly fluorescent with excitation and emission maxima at 330 and 385 nm, respectively. Experiments were conducted to characterize the dynamic behavior of aqueous solutions of S and P when subjected to UV radiation. UV sources used for these experiments included a low-pressure mercury lamp, a XeBr excimer lamp, and a KrCI excimer lamp; all three sources were mounted in collimating devices to provide incident beams that could be easily and accurately characterized by radiometry. These three sources each yielded essentially monochromatic outputwith characteristic wavelengths of 254, 282, and 222 nm, respectively. At practical concentrations, it was found that the absorbance of the actinometer solution was neither high enough to make the actinometer solutions optically opaque nor low enough to be optically transparent to UV. In addition, the photoproduct displayed a molar absorption coefficient that was similar in magnitude to that of the parent compound, thereby resulting in competitive absorption of UV energy between Sand Pduring irradiation. For purposes of evaluation of the results of irradiation, a mathematical model was developed to accountforthe nonideal optical characteristics of the system. The model is based on a description of local photochemical kinetics; predictions of overall reactor performance were developed by spatial and temporal integration of model results. The model was used to analyze the dynamic behavior of actinometer solutions during UV irradiation and to estimate the quantum yield for photoproduction of Pfrom S. This modeling approach is potentially applicable to other photochemical processes in which multiple compounds are present that absorb photoactive radiation; however, general application of this modeling approach to photochemical reactor systems will require inclusion of othertermsto describe relevanttransport behavior within the system.