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Tetravalent Manganese Chemiluminescence Behavior

Posted on:2005-12-18Degree:MasterType:Thesis
Country:ChinaCandidate:X H ZhuFull Text:PDF
GTID:2191360122494932Subject:Analytical Chemistry
Abstract/Summary:PDF Full Text Request
"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 compoundsâ†'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...
Keywords/Search Tags:flow injection, chemiluminescence, soluble manganese(IV), formaldehyde
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