摘要
本论文回顾了电化学发光分析法的发展历史,介绍了电化学发光反应的基本原理和电化学发光的主要反应体系及其反应机理,评述了电化学发光分析法与流动注射、高效液相色谱和毛细管电泳联用技术,在药物分析领域的应用。在已有文献的基础上,成功地建立了盐酸麻黄碱、苯海拉明及青霉素类抗生素等药物测定的新方法,摘要如下:
1.基于盐酸麻黄碱(EPH)对三联吡啶合钌(Ru(bpy)32+)电化学发光(ECL)的增敏作用,建立了流动注射?电化学发光(FIA?ECL)分析法测定EPH的新方法,并将本法应用于药品中EPH含量的测定。研究结果表明,在pH10.0的0.1 mol/L Na2B4O7-NaOH介质中,在电位1.10 V下进行恒电位电解,当Ru(bpy)32+的摩尔浓度为1.0×10-4 mol/L时,EPH对Ru(bpy)32+ECL强度的增敏效果较好。在上述优化条件下,本法测定EPH的线性范围为2.40-24.0 mg/L(r=0.9995),检出限为1.20 mg/L,相对标准偏差(RSD)小于1.60%(n=10),加标回收率为97.0-105%。
2.胺类物质对Ru(bpy)32+ECL强度的增敏能力,与胺本身的结构有关。对伯仲叔胺而言,由于它们氨基的第一级电离化所需能量为伯>仲>叔胺,使得它们增敏Ru(bpy)32+ECL强度的能力为伯<仲<叔胺。盐酸麻黄碱(EPH)和苯海拉明(DPH)结构式中的胺基分别属于仲胺和叔胺,即DPH增敏Ru(bpy)32+ECL强度的能力强于EPH。从而应用FIA?ECL分析法,实现了无需先分离,即可直接选择性测定含有EPH的复合药剂中DPH的含量。实验结果表明,在优化的实验条件下,测定DPH的线性范围为2.00-40.0 mg/L(r=0.9995),检出限为2.00 mg/L,相对标准偏差(RSD)小于4.6%(n=5),加标回收率为98.0-106%。此方法较之于高效液相色谱法的优势在于:分析速度快、方法简单、经济、安全。
3.应用高效液相色谱法?电化学发光(HPLC?ECL)联用技术,建立了同时测定青霉素、青霉素V、阿莫西林、氨苄西林等四种常用青霉素类抗生素的新方法。由于青霉素类抗生素的水解产物相比于其本身而言,对Ru(bpy)32+ECL强度有更强地增敏能力。这为实现电化学发光分析法测定青霉素类抗生素奠定了理论基础。本方法是通过同时测定四种青霉素类抗生素药物的水解产物,实现对四种青霉素类抗生素药物本身的间接测定。首先将四种青霉素类抗生素药物的NaOH溶液加热至其完全水解,再用流动相将其稀释至适当浓度进行HPLC?ECL分析。实验中采用XBP-C18色谱柱反相柱洗脱,以PBS缓冲溶液(pH值为8.0)-甲醇(85∶15)为流动相,于263 nm处检测,分离并测定了上述四种青霉素类抗生素药物。实验结果表明:四种青霉素类抗生素药物的水解产物均可在20 min内完全分离,且最低检出限低于0.1μg/mL。将本法用于尿样中药物含量的测定取得了满意的结果。四种青霉素类抗生素药物在尿样中的回收率平均为100.4%。实验证明该方法操作简便、快速灵敏、准确复性好,灵敏度高,适用于尿液中多组分青霉素类抗生素的确认和准确定量测定。
In the paper, the history of electrochemiluminesence (ECL) containing the principles, main reaction systems and mechanism of ECL and the application of ECL in pharmaceutical analytical field were reviewed. New methods based on ECL have been developed for determining ephedrine hydrochloride, diphenhydramine and penicillin-like antibiotics. Some chief results were shown as following:
1. A new flow-injection electrochemiluminescence (FIA-ECL) analytical method of ephedrine hydrochloride has been proposed in this paper. It is based on a fact that ephedrine could react with tris(2,2′-bipyridine)ruthenium(II)(Ru(bpy)32+) to enhance electrochemiluminescence signal. In the Na2B4O7-NaOH solution of pH10.0, The best ECL response was obtained at potential of 1.10 V in the present of 1.0×10-4 mol/L Ru(bpy)32+ The linear range of the method is from 2.40 to 24.0 mg/L with a correlation coefficient of 0.9995 and the detection limit of 2.00 mg/L. The method has successfully applied to the determination of ephedrine hydrochloride in ephedrine injection and nasal drop. The relative standard deviation (RSD) was less than 1.60% (n=10) and recoveries were from 96.0% to 103% for the determination of practical samples.
2. On the basis of the structural effect between diphenhydramine hydrochloride (DPH) and ephedrine hydrochloride (EPH) to enhance ECL intensity, FIA-ECL analysis of DPH in the present of EPH by utilizing Ru(bpy)32+. In the experimental conditions optimized, the linear ECL response to concentrations of DPH is from 2.00 to 40.0μg/L with a correlation coefficient of 0.9995 and a detection limit of 1.20μg/L. RSD was less than 4.6% (n=5) and recoveries were in the range of 98.0-106% for the determination of DPH in pharmaceutical samples. The method avoids triumphantly an interference of coexistent EPH in the compounding drug without prior separation. The method has advantages over HPLC method in terms of speed and convenience, economics and safe procedure, and could be an alternative for places where HPLC equipment is not available.
3. A highly selective and sensitive detection method of Penicillin-like antibiotics based on HPLC?ECL with Ru(bpy)32+ has been developed. The ECL emission is based on the reaction between the hydrolysis of Penicillin-like antibiotics and Ru(bpy)33+. The experimental results showed that maximum ECL intensities are obtained after hydrolyzing 30 min, because ECL on the Penicillin-like antibiotics were strongly dependent on the hydrolysis time. Under the optimal condition, the linear detection range from 1.0 to100.0μg/mL and the detection limits are estimate to 0.1μg/mL with S/N of 3 for four Penicillin-like antibiotics. The RSDs is less than 6.0% (n=10) and recoveries were in the range of 96.3%-105.3% for the determination of four Penicillin-like antibiotics in human urine samples. The results are satisfactory compared with HPLC method.
引文
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