酶促制备丝裂霉素类似物反应动力学模型研究

基于固定化T. laibacchii脂肪酶催化2-甲基-1,4-苯醌与正丁胺的Michael加成反应建立了酶促制备丝裂霉素类似物2-甲基-3-正丁胺酰-1-氢-4-醌的反应动力学模型.该反应在柠檬酸缓冲溶液(pH值为7.0)中进行,最终产率可达98%.该文提出了修正的有序双双和随机双双机理,采用King-Altman方法得到相关微分方程组以表示即时反应速率.通过联合解微分方程和最优化方法确定动力学模型参数,使用ode45程序解微分方程组,并运用Fmincon软件计算动力学常数.研究结果表明:模型拟合值与实验值的平均相对偏差为11.25%,且偏差服从关于y=0的轴对称分布.当固定化酶粒径为0.5 mm、搅拌转速为200 rpm时可以忽略内外扩散限制.该文建立的动力学模型为固定化酶固有动力学模型.

The Kinetic Modeling of the Enzymatic Preparation of Mitomycin Analogs

The reaction kinetic model for enzymatic preparation of mitomycin analogue 2-methyl-3-n-butylamino-1-hydro-4-quinone is established based on the Michael addition reaction of 2-methyl-1,4-benzoquinone and n-butylamine catalyzed by immobilized T. laibacchii lipase.The reaction is carried out in a citric acid buffer solution(pH=7.0),and the final yield reaches 98%.In this paper,the modified ordered bi-bi and random bi-bi mechanisms are proposed,and the relevant differential equations are obtained by the King-Altman method to express the instantaneous reaction rate.The kinetic model parameters are determined by the combined solution of differential equations and optimization methods,and ode45 is used to solve the differential equations and Fmincon is used to calculate the kinetic constants.The results show that the average relative deviation between the model fitted value and the experimental value is 11.25%,and the distribution is symmetrical with zero axis.When the particle size of the immobilized enzyme is 0.5 mm and the stirring speed is 200 rpm,the experimental results show that the internal and external diffusion limitations can be ignored.Therefore,it can be seen from the above that the established kinetic model is the inherent kinetic model of the immobilized enzyme.