四价锰的化学发光行为的研究

【作者】 祝兴华；

【导师】 吕九如；

【作者基本信息】 陕西师范大学 ， 分析化学， 2004， 硕士

【摘要】 化学发光（Chemiluminescence，CL）是指通过化学反应而产生的发光现象。根据化学发光反应在某一时刻的发光强度或发光总量来确定反应中相应组分含量的分析方法叫化学发光分析法。化学发光分析法因其灵敏度高、测量装置简单、线性范围宽、分析速度快和容易实现自动化等优点吸引着广大分析工作者的注意，已被成功地应用于生命科学、地质分析、药物分析、临床检验、环境监测等领域。目前化学发光分析研究主要集中在两个方面：1．寻找新的化学发光反应体系，并将其应用于实际样品中的测定：2．将已有的化学发光反应体系与分离技术如高效液相色谱、毛细管电泳等联用，以期提高化学发光分析法的选择性。 本论文由综述和研究报告两部分组成。在综述部分，对不同价态锰的化学发光行为进行了综述，着重介绍了它们所涉及化学发光体系的反应机理以及分析应用。在研究报告部分，本文对以可溶性锰（Ⅳ）为氧化剂的化学发光反应体系进行了比较广泛的研究，发现在甲醛存在时，可溶性锰（Ⅳ）可以氧化许多有机物产生化学发光，对其反应机理进行了初步的探讨；同时，优化了反应条件，建立了测定抗坏血酸、磺胺类药物和头孢菌素类药物的化学发光分析法，从而从理论和实践上构建了一个以可溶性锰（Ⅳ）为氧化剂的化学发光分析新体系。 一、可溶性锰（Ⅳ）-甲醛-有机物化学发光反应体系机理的研究 本文对可溶性锰（Ⅳ）-甲醛-有机物化学发光反应的化学发光反应动力学性质和化学发光光谱的研究表明：1．可溶性锰（Ⅳ）-甲醛-有机物反应皆为快速化学发光反应；2．可溶性锰（Ⅳ）-甲醛-有机物化学发光体系的化学发光光谱的最大发射波长出现在640 nm处，这与发光体为单线态氧的二分子复合物的CIO^--H₂O₂-OH^-体系的化学发光光谱（λmax=635 nm）相似，因此我们推测可溶性锰（Ⅳ）-甲醛-有机物化学发光体系中的发光体是激发单线态氧分子的二分子复合物。可溶性锰（Ⅳ）-甲醛-有机物化学发光反应的可能发光机理表述如下： Mn（Ⅳ）+HCHO+H⁺+有机物→¹O₂（¹△g）+H₂O+其它产物 （1） 二、流动注射化学发光分析法测定抗坏血酸、磺胺类药物和头孢菌素类药物 本文发现，在甲醛存在条件下，抗坏血酸、磺胺类药物（磺胺甲基异噁唑、磺胺嚓睫和磺胺眯）和头抱菌素类药物（头抱曲松钠、头抱哇琳钠、头抱拉定和头抱呱酮钠）均与可溶性锰（IV）反应产生较强的发光信号，据此，对实验条件进行了优化，建立了测定抗坏血酸、磺服类药物和头抱菌素类药物的流动注射化学发光分析法。方法测定抗坏血酸、磺胺类药物和头饱菌素类药物的线性范围分别为6.oxlo一8一2.oxlo一，mol/L抗坏血酸、6.oxlo一8一8.oxlo一6gzmL磺胺甲基异嗯哇、一oxlo一7一8.oxlo一69/mL磺胺嚓睫、4.oxlo一8一s.oxlo一79/mL磺胺眯、l.oxlo一‘一2.oxlo一6gzmL头抱曲松钠、8.oxlo一，一6.oxlo一，gzmL头抱哇琳钠、4.0xl0一8一8.0K10一“g/mL头抱拉定和4.0、10一7一2.0xl0一，g/mL头抱呱酮钠。检出限分别为2、10一smol/L抗坏血酸、Zxlo一8 g/mL磺胺甲基异嗯哇、3 K10一89/ mL磺胺嚓睫、2义10一89/mL磺胺眯、Zxlo一”g/mL头抱曲松钠、2x10一79/mL头抱哇琳钠、lxlo一“g/mL头抱拉定和2义10一，g/mL头抱呱酮钠。H次平行测量的相对标准偏差均小于3%。 本论文对可溶性锰(IV卜甲醛一有机物化学发光反应体系的机理及其分析应用的研究有助于拓宽化学发光分析的研究领域，为深入地探讨化学发光反应机理提供了可靠的实践依据和有益的思路。更多还原

【Abstract】 "Chemiluminescence(CL)" is defined as the production of electromagnetic (ultraviolet, visible or near-infrared) radiation as a result of a chemical reaction. The process by which CL is generated is the same as that for photoluminescence (fluorescence and phosphorescence) except that the former requires no light excitation source. Then, CL is now considered as a very sensitive analytical technique and applied to different fields such as biotechnology, pharmacology, molecular biology, clinical medicine and environmental detection owing to its advantages of high sensitivity, rapidity, low detection limits, wide linear ranges and low cost of instrumentation. Current research in CL is focused on two general directions. One direction is the discovery of new CL reactions and investigation of their applicability to real samples and the other direction is the combination of CL detection systems and newly developed separation techniques such as HPLC, CE and so on.This thesis consists of two parts: review and research reports. In the first part, it was focus on reviewing the CL mechanisms of the system including manganese with different valence values, and the analytical applications of the system. In the second part, we studied the CL system applied soluble manganese (IV) as oxidant extensively, then it was found that a range of organic compounds could be oxidised by soluble manganese (IV) to produce CL in the presence of formaldehyde. Furthermore, the CL mechanism was discussed in depth, and the experiment conditions were optimized. Based on the fact, a flow injection method has been developed to determine ascorbic acid, sulfa drugs (sulfamethoxazole, sulfadiazine, sulfaguannidine) and cephalosporins (ceftriaxone sodium, cefazolin sodium, cefradine and cefoperazone sodium). Then, a new CL system was established basedon the experimental phenomena.1. The mechanism of soluble manganese (IV)-formaldehyde-organic compounds systemsWith the aid of the study of the CL kinetic characteristics and the CL spectra of the systems, it was found as follows: l.The CL spectra of soluble manganese(IV)-formaldehyde-organic compound system revealed that the reaction was a rapid CL reaction; 2. the range of the spectra obtained were from 555 to 705 nm, which is similar to that of ClO- - H2O2 system, in which the ideal maximum emission wavelength appears at 643 nm and the emitter was regarded as excited 1O21O2(1Δg1Δg) molecules. Thus it may be proposed that the emission spectra recorded were attributed to the formation of excited 1O21O2(1Δg1Δg) molecules. The possible mechanism of the CL system was assumed as follows: Mn(IV) + HCHO + H+ + organic compounds→1 O2 (1Δg) + H2O+other products ( 1 ) 2. The determination of ascorbic acid, sulfa drugs and cephalosporins with flow injection analysis-chemiluminescence method.The experimental conditions of the CL reaction were optimized and the feasibility of application of the present reactions to the determination of ascorbic acid, sulfa drugs and cephalosporins was evaluated. With the soluble manganese (IV)-formaldehyde-organic compound system, the procedure allows the determination of 6.0×10-8 ~ 2.0×10-5mol/L ascorbic acid, 6.0×10-8 ~ 8.0×10-6 g/mL sulfamethoxazole, 1.0×10-7 ~ 8.0×10-6 g/mL sulfadiazine, 4.0×10-8 ~ 8.0×10-7 g/mL sulfaguannidine, 1.0×10-8 ~ 2.0×10-6g/mL ceftriaxone sodium, 8.0×10-7 ~ 6.0×10-5 g/mL cefazolin sodium, 4.0×10-8 ~ 8.0×10-6 g/mL cefradine and 4.0×10-7 ~ 2.0×10-5 g/mL cefoperazone sodium with the detection limits of 2xlO"8mol/L ascorbic acid, 2×10-8 g/mL sulfamethoxazole, 3×10-8 g/mL sulfadiazine, 2×10-8 g/mL sulfaguannidine, 2×10-9 g/mL ceftriaxone sodium, 2×10-7 g/mL cefazolin sodium, 1×10-8 g/mL cefradine and 2×10-7 g/mL cefoperazone sodium. The relative standard deviations are lower than 3%.Above all, the CL mechanism was discussed in depth, and the experiment conditions were optimized. A flow injection method has been developed to the determination of ascorbic acid, sulfa drugs (sulfamethoxazole, sulfad更多还原