应用化学

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α1受体阻滞剂类药物与某些同多酸根的共振瑞利散射光谱及其分析应用

张敏1,周尚2,朱乾华2,杨琼2,杨季冬1,3*   

  1. (1.西南大学化学化工学院 重庆 400715;2.长江师范学院化学化工学院 重庆 408100;
    3.重庆三峡学院化学与环境工程学院 重庆 404100)
  • 收稿日期:2012-05-17 修回日期:2012-06-27 出版日期:2013-03-10 发布日期:2013-03-10
  • 通讯作者: 杨季冬,教授; Tel:023-72790666; Fax:023-58106710; E-mail:flyjd6400@sina.com; 研究方向:分子光谱分析
  • 基金资助:
    国家自然科学基金(21175015)资助项目;教育部基金项目春晖计划(Z2009-1-63003)

Resonance Rayleigh Scattering Spectra of α1-Receptor Blocker Drugs and Some Isopoly Acids and Their Analytical Application

ZHANG Min1, ZHOU Shang2, ZHU Qianhua2, YANG Qiong2, YANG Jidong1,3*   

  1. (1.School of Chemistry and Chemical Engineering,Southwest University,Chongqing 400715,China;
    2.School of Chemistry and Chemical Engineering,Yangtze Normal University,Chongqing 408100,China;
    3.School of Chemical and Environmental Engineering,Three Gorges Univeisity,Chongqing 404100,China)
  • Received:2012-05-17 Revised:2012-06-27 Published:2013-03-10 Online:2013-03-10

摘要: 在酸性介质中,钼酸根、钨酸根等同多酸根与盐酸哌唑嗪(PRH)和甲磺酸多沙唑嗪(Dox)等α1受体阻滞剂反应形成离子缔合物时,会导致体系的共振瑞利散射(RRS)显著增强并出现新的RRS光谱,最大散射峰分别位于367 nm(钼酸根体系)和290 nm(钨酸根体系)。 PRH和Dox与同多酸根的反应产物具有相似的RRS光谱特征。 其反应的适宜酸度分别为pH值2.1~2.3(钼酸根-PRH体系)和pH值3.1~3.3(钨酸根-PRH体系)。 在一定浓度范围内,不同的反应体系RRS强度增强程度与药物浓度成正比,均可用于痕量药物的测定。 反应具有很高的灵敏度,不同同多酸对PRH的检出限(3σ/s)分别为4.76 μg/L(钼酸根-PRH体系)和9.88 μg/L(钨酸根-PRH体系)。 方法也具有较好的选择性,用于片剂和人尿液中的α1受体阻滞剂的测定,结果满意。 此外,本文还应用计算化学软件Gaussview3.07和Gaussian03W,采用密度泛函法,在B3LYP/6-31G基组水平上计算了盐酸哌唑嗪的电荷分布,对反应机理和RRS增强的原因进行了讨论。

关键词: 盐酸哌唑嗪, 甲磺酸多沙唑嗪, 共振瑞利散射, 钼酸盐, 钨酸盐

Abstract: In an acid solution, an isopoly-acid anion such as isopoly-molybdic acid or isopoly-tungstic acid could react with prazosin hydrochloride(PRH) and doxazosin mesyllate(Dox)α1-receptor blocker drugs to form ion-association complexes respectively. It resulted in the great enhancement of resonance Rayleigh scattering(RRS) intensities and new RRS peaks. The maximum RRS wavelength was located at 367 nm for isopoly-molybdic acid system and 290 nm for isopoly-tungstic acid system. The reaction products of the two drugs had similar spectral characteristics. The optimum pH ranges were 2.1~2.3 for isopolymolybdic acid-PRH system and 3.1~3.3 for isopoly-tungstic acid-PRH system. In a certain range, the intensities of RRS were directly proportional to the concentration of drugs for the two different reaction systems. The reactions exhibited a high sensitivity, with a detection limit (3σ/s) of 4.76 μg/L(isopoly-molybdic acid-PRH system) and 9.88 μg/L(isopoly-tungstic acid-PRH system) for PRH, and also showed a good selectivity. The method was applied to the determination of α1-receptor blocker drugs in tablets and human urine samples. Density functional theory(DFT) calculations with Gaussian 03W at B3LYP/6-31G level were performed to calculate the charge distribution of PRH for investigating the reaction mechanism; in addition, the reasons for the RRS enhancement of the system were discussed.

Key words: prazosin hydrochloride, doxazosin mesyllate, Resonance Rayleigh Scattering, molybdate, tungstate

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