生物样品中小檗碱的电化学分析新方法  

A Novel Electrochemical Method for Berberine Detection in Biological Fluids

作　　者：周锐 张自品 ZHOU Rui;ZHANG Zi-Pin(School of Pharmacy,Anhui University of Chinese Medicine,Hefei 230012,China)

机构地区：[1]安徽中医药大学药学院,合肥230012

出　　处：《应用化学》2023年第4期518-526,共9页Chinese Journal of Applied Chemistry

基　　金：安徽省自然科学基金面上项目(No.2008085MH293);安徽省留学人员创新项目择优资助基金(No.19);安徽省教育厅高校自然科学研究重点项目(No.2022AH050459)资助。

摘　　要：由于小檗碱氧化电位较高(>1.1 V vs. Ag/AgCl),进行生物样品中小檗碱的选择性电化学分析具有挑战性。基于溴百里酚蓝(BTB)和小檗碱的分子间非共价作用,通过单壁碳纳米管(SWNTs)将BTB修饰在电极表面并通过电化学聚合产生poly-BTB,利用聚BTB(poly-BTB)电极过程可逆以及氧化还原电位低的特点,以poly-BTB同时作为小檗碱的识别元件和电化学探针建立了小檗碱的电化学分析新方法。循环伏安和电化学阻抗谱结果表明,poly-BTB和小檗碱的分子间作用导致小檗碱结合在poly-BTB/SWNTs修饰电极表面,从而引起修饰电极的峰电流下降。在最优化的实验条件下,poly-BTB/SWNTs修饰电极的电流下降率和小檗碱的浓度在0.05~1μmol/L和1~100μmol/L范围内呈良好线性关系,检测限为0.022μmol/L。动物实验结果表明,该方法对生物样品具有很好的选择性,可用于血浆和肝脏匀浆中小檗碱含量的测量,为小檗碱相关的生理病理研究提供了一种简单有效的方法。Selective electrochemical detection of berberine in biological fluids is challenging due tothe high overpotential for berberine electrooxidation(>1.1 V vs.Ag/AgCl).By taking advantage of the non-covalent interactions between bromothymol blue(BTB)and berberine,and the reversible and low-potential electrochemical redox properties of polymerized BTB(poly-BTB),we report a new electrochemical method for berberine detection using poly-BTB as both the recognition unit for berberine and electrochemical probe,in which poly-BTB is generated by electropolymerization of BTB immobilized onto the GC electrode surface via single-walledcarbon nanotubes (SWNTs). The strong affinity of poly-BTB toward berberine leads to the binding of berberineonto the electrode surface and consequently causes the decrement in the peak current of poly-BTB/SWNTsmodifiedelectrode upon berberine being introduced, which validates berberine detection using the currentdecrease of the poly-BTB/SWNTs/GC electrode as the signal readout. Under the optimized conditions, themethod shows linear concentration of berberine in the range of 0. 05~1 μmol/L and 1~100 μmol/L with adetection limit of 0. 022 μmol/L based on 3σ. As for the animal experiments, the electrochemical method hasbeen demonstrated to be selective and effective for berberine level qualification in rat plasma and liverhomogenates. This study offers a facile electrochemical method for berberine detection in biological fluids withless technical demanding and simple operating procedures, which holds a great promise for more applicationsin physiological and pathological researches associated with berberine.

关 键 词：小檗碱 溴百里酚蓝 非共价作用 电化学分析方法 

分 类 号：O657.1[理学—分析化学]