摘要
兴奋剂是国际上体育界对违禁药物的总称。兴奋剂的服用不仅使竞技体育失去了公平竞争、催人奋发向上的本质，而且严重地威胁着运动员的身心健康。因此，研究灵敏度高、选择性好的兴奋剂检测新方法具有十分重要的意义。本论文详细研究了几种兴奋剂的光谱性质，以荧光法和瑞利散射光谱法研究并建立了分析测定这几种兴奋剂的新方法。主要内容如下：
1．利用盐酸普萘洛尔的内源荧光特性建立了一种简单、快速、灵敏的分析方法。考察了溶剂、表面活性剂和酸度等对其荧光特性的影响。在最佳实验条件下，盐酸普萘洛尔的线性范围和检测限分别为1.0×10~(-8)～3.0×10~(-6)mol／L和1.5×10~(-9)mol／L。用于片剂及尿样中盐酸普萘洛尔的测定，获得满意的结果。
2．利用瑞利散射光谱和紫外-可见吸收光谱，并结合透射电子显微技术研究了盐酸普萘洛尔与纳米金的相互作用。基于盐酸普萘洛尔诱导纳米金团聚并使溶液瑞利散射光(RLS)强度显著增强的现象，提出了瑞利散射光谱分析盐酸普萘洛尔的新方法。讨论了不同缓冲溶液，pH值，纳米金粒子浓度以及反应时间对体系RLS强度的影响。并考察了其它物质对此反应体系RLS强度的影响。采用固相微萃取技术处理尿样，可对盐酸普萘洛尔进行定性测定。
3．通过考察8种兴奋剂与Triton X-100的相互作用，发现睾酮、甲基睾酮、安体舒通和苄硫噻嗪等四种兴奋剂使Triton X-100的荧光显著下降，且荧光下降程度与这四种兴奋剂浓度成一定的线性关系。在此基础上，建立了这四种兴奋剂荧光猝灭分析的新方法。吸收光谱研究表明四种兴奋剂对Triton X-100的荧光猝灭为动态猝灭类型，并测定了猝灭常数。本法用于合成样品中上述四种兴奋剂的测定，获得满意的结果。
4．将四丁基溴化铵加入到Pb~(2+)的N，N-二甲基甲酰铵溶液中，形成强发光的簇状配合物Pb_4Br_(11)~(3-)，且荧光强度与Pb~(2+)的浓度成正比。在此基础上，建立了一种检测痕量铅离子的荧光分析新方法。在最佳实验条件下，Pb~(2+)的线性范围和检测限分别为1.0×10~(-7)～1.0×10~(-5)mol／L和7.6×10~(-9)mol／L。对1.0×10~(-6)mol／L的标准溶液11次平行测定的相对标准偏差为1.6％。此法用于合成样品中铅的测定，得到了满意的结果。同时探讨了簇状配合物Pb_4Br_(11)~(3-)的形成及发光机理。
Doping agent is the total name of the forbidden substances in sport field in the world. The intake of doping agents will not only make the sport spirit lose justice, competition and encouragement, but also greatly threaten the health of athletes. Therefore, the studies of establishing sensitive and selective analytical methods to determine doping agents are of great importance. The optical properties of doping agents have been studied in this thesis, based on which, novel methods for their analysis and determination by fluorescence spectrum and Rayleigh light scattering spectrum were proposed. The main work are summarized as following:
1. Based on the native fluorescence of propranolol, a simple and sensitive method for its determination was proposed. The effects of solvent, surfactant and acidity on the fluorescence intensity of propranolol were studied. Under the optimized conditions, the fluorescence intensity was proportional to the concentration of propranolol in the range 1.0×10-8~ 3.0xl0-6mol1-1. The limit detection was 1.5×10-9 mo11-1. The proposed method has been successfully applied to the determination of propranolol in tablet and urine.
2. The interaction between propranolol and gold nanoparticle was studied by Rayleigh light scattering spectrum, ultraviolet-visible spectrum and transmission electron microscopy. The addition of propranolol to the solution of gold nanoparticle could induce its aggregation and the RLS intensity would increase quickly, based on which, a novel approach for the determination of propranolol by RLS spectrum was proposed. The effects of different buffer solution, pH, concentration of gold nanoparticle and reaction time on the intensity of RLS were discussed. Prorpanolol could be qualitatively determined in urine with the combination of solid phase microextraction.
3. Through the interaction of eight doping agents with Triton X-100, it was found that testosterone, methyltestosterone, spironolactone and benzthiazide could quench the fluorescence of Triton X-100. The fluorescence intensity of Triton X-100 decreased proportionally to the concentration of them, based on which, a novel, simple approach for the determination of the four doping agents was proposed. The studies of absorbance spectra indicated that the fluorescence quenching belonged to dynamic quenching type; the constants of quenching were also calculated. The proposed method has been applied to their determination in the synthetic samples with
satisfactory results.
4. Adding bromide to Pb solution of N,N'-dimethylformamide (DMF), the highly emissive cluster Pb4Br could be formed and the fluorescence intensity of the formed cluster was proportional to the concentration of Pb, based on which, a novel, simple approach that used the emission from itself as the sensor for determination of Pb was proposed. Under the optimum conditions, the linear range and detection limit were mol and 7.6xlO mol, respectively. The relative standard deviation (R.S.D.) of determining 11 samples containing 1.0 10 mol Pb was 1.6%. The proposed method has been successfully applied to the determination of lead in the synthetic samples. The mechanisms of the formation and luminescence of Pb4Br were also studied.
引文
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