Matsuura I, Imaizumi M, Sugiyama M
Research Laboratories, Nippon Shinyaku Co., Ltd., Ktyo, Japan.
Chem Pharm Bull (Tokyo). 1990 Jun;38(6):1692-6. doi: 10.1248/cpb.38.1692.
A rate equation for photodegradation was derived from Lambert-Beer's law and Grotthus-Draper's law: -dc/dt=k1(1-exp(-(k2c+k3(c0-c))))k2c/(k2c+k3(c0-c)) where c is the concentration of reactant, c0 is the initial concentration of reactant, t is time, k1 is the rate constant, and k2 and k3 are the absorption coefficient of reactant and its photodegradation product, respectively. In a case where the photodegradation products have no photoabsorption, k3 assumes the value of zero in the above general equation. In a case where the photodegradation products have the same spectrum and molar absorptivity as that of the reactant, k3 assumes the value of k2, and hence the photodegradation is not a first-order reaction; however, the equation itself gives the pseudo-first-order reaction rate equation. In a case where the concentration of reactant is high enough, the equation approaches a zero-order reaction rate equation. The photodegradation rate of nifedipine in solutions under a germicidal lamp, near an ultraviolet fluorescent lamp and a fluorescent lamp was analyzed using the above equation. The photodegradation rate was directly proportional to the amount of light absorbed, and fitted well with the equation. The above theoretical equation was substantiated by the photodegradation of nifedipine, and hence is expected to apply to other photosensitive drugs.
根据朗伯-比尔定律和格罗特斯-德雷珀定律推导了光降解的速率方程:-dc/dt=k1(1-exp(-(k2c+k3(c0-c))))k2c/(k2c+k3(c0-c)),其中c为反应物浓度,c0为反应物初始浓度,t为时间,k1为速率常数,k2和k3分别为反应物及其光降解产物的吸收系数。在光降解产物无光吸收的情况下,上述通用方程中k3的值为零。在光降解产物与反应物具有相同光谱和摩尔吸光率的情况下,k3的值为k2,因此光降解不是一级反应;然而,该方程本身给出了准一级反应速率方程。在反应物浓度足够高的情况下,该方程趋近于零级反应速率方程。使用上述方程分析了硝苯地平在杀菌灯、近紫外荧光灯和荧光灯下溶液中的光降解速率。光降解速率与吸收的光量成正比,并且与该方程拟合良好。上述理论方程通过硝苯地平的光降解得到了证实,因此有望应用于其他光敏药物。