盐酸黄酮哌酯在碱溶液中的荧光增强反应及其分析应用  

Fluorescence enhancement of flavoxate hydrochloride in alkali solution and its application in pharmaceutical analysis

作　　者：李文红[1,2,3] 孙冲梅 魏永巨[1,2] 

机构地区：[1]河北师范大学生命科学学院,河北石家庄050024 [2]河北师范大学化学与材料科学学院,河北石家庄050024 [3]河北工业职业技术学院环境与化学工程系,河北石家庄050091

出　　处：《药学学报》2015年第10期1324-1329,共6页Acta Pharmaceutica Sinica

基　　金：国家自然科学基金资助项目(20975029;81173496);河北省自然科学基金资助项目(B2014205129)

摘　　要：研究了盐酸黄酮哌酯（FX）在强碱溶液中的荧光增强反应,探讨反应机制,建立了药物样品中FX的荧光分析新方法。FX无内源荧光,其强碱水溶液可缓慢产生荧光,加热促进荧光增强反应。FX分解产物的三维荧光图谱中呈现2个荧光峰,激发波长（λex）分别位于223 nm和302 nm,发射波长（λex）均为410 nm。以硫酸奎宁为参比,测得分解产物的荧光量子产率为0.50。FX分解产物的结构表征和光谱解析表明,FX强碱溶液在加热过程中首先发生酯键水解反应,生成3-甲基黄酮-8-羧酸,然后发生γ-吡喃酮环裂解反应,生成α,β-不饱和酮。该产物包含邻羟基苯甲酸结构,在碱性条件下形成分子内氢键,共轭程度增加,刚性增强,因而产生荧光。基于这一荧光增强反应,建立了测定FX的荧光分析方法。在0.020 3～0.487μg·m L-1内,荧光强度与浓度之间的回归方程为IF=23.9＋5 357.3 c,r=0.999 7（n=8）,检出限D=1.1 ng·m L-1。本法用于盐酸黄酮哌酯片中FX的测定,加标回收率为100.2%,测定结果与紫外分光光度法一致,表明方法可靠。Fluorescence enhancement reaction of flavoxate hydrochloride （FX） in strong alkali solution was studied, the mechanism of the reaction was investigated, and a novel fluorimetric method for analysis of FX in drug sample was established. FX has no intrinsic fluorescence, but it can slowly produce fluorescence in strong alkali solution. Heating can promote the fluorescence enhancement reaction. In 3D fluorescence spectra of the decomposition product of FX, two fluorescence peaks, located respectively at excitation wavelengths λem ission wavelength λcm=223/410 nm, and 302/410 nm, were observed. Using quinine sulfate as a reference, fluorescence quantum yield of the decomposition product was measured to be 0.50. The structural characteriza- tion and spectral analysis of the decomposition product reveal that ester bond hydrolysis reaction of FX is firstly occurred during heating process, forming 3-methylflavone-8-carboxylic acid （MFA）, then a cleavage reaction of the γ-pyrone ring of MFA occurred, producing a, β-unsaturated ketone. This product includes adjacent hydroxyl benzoic acid group in its molecule, which can form intramolecular hydrogen bond under alkaline condition, so that increase the conjugate degree and enhance the rigidity of the molecule, and thereby cause fluorescenceenhancement. Based on this fluorescence enhancement reaction, a fluorimetric method was proposed for the determination of FX. A linear calibration curve covered the concentration range 0.020 3-0.487 Bg·mL-1. The regression equation was IF=23.9＋5357.3C, with correlation coefficient r=0.999 7 （n=8）, detection limit D-- 1.1 ng·mL-1. The method was applied to the analysis of FX tablets, with a spiked recovery rate of 100.2%. The reliability of the method was verified by a UV-spectrophotometric method.

关 键 词：盐酸黄酮哌酯 3-甲基黄酮-8 羧酸 荧光增强 三维荧光 荧光分析法 

分 类 号：R917[医药卫生—药物分析学]