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Study On The Chiral Discrimination Of Molecules By Time Resolved Phosphorescene And Fluorescence

Posted on:2004-11-10Degree:MasterType:Thesis
Country:ChinaCandidate:Y L WeiFull Text:PDF
GTID:2121360095953736Subject:Analytical Chemistry
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Chapter 1: The history of phosphorescence method had been reviewed, including low temperature phosphorescence and room temperature phosphorescence. The further developments in this field were also discussed.Chapter 2: The history and development of quinine and quinidine, which are used to treat Malaria have been introduced. And the characteristic, state, pharmacology and the excretion velocity in human body of them are all reviewed in detail.Chapter 3: Paper substrate room temperature phosphorescence (PS-RTP) of quinidine (QD) and quinine (QN) were investigated. The method is based on Whatman No.40 (medium fast speed quantitative) filter paper as substrate and Pb(Ac)2 as heavy atom perturber. Various factors affecting their RTP were discussed in detail, including heavy atom, pH effect and drying conditions, etc. Under the optimum experimental conditions, the linear dynamic range (LOD), limit of detection (LOD), and relative standard deviation (RSD) were 5.44-709.08 ng/spot and 4.10-786.54 ng/spot, 0.53 ng/spot and 0.14 ng/spot, 0.53% and 0.14% for QN and QD, respectively. The first analytical application for the determination of the two compounds was developed. The recovery of standard samples added to Quinine sulfate and quinidine sulfate is in the range 95-107%. The proposed method was successfully applied to real sample analysis without separation.Chapter 4: Based on the PS-RTP, which used Whatman No.40 (medium fast speed quantitative) filter paper as substrate and Pb(Ac)2 as heavy atom perturber, the time resolved phosphorescence of QN and QD was investigated. Various factors affecting their phosphorescence lifetime were discussed in detail, such as the concentration of heavy atom, pH and drying conditions. Under the optimum experimental conditions, the RTP lifetimes of QN and QD are 2066.41 s and 2155.86 s. The environmental factors have not effect of the RTP lifetime difference between QN and QD. After adding some chiral discriminators such as (+)-tartaric acid, cholic acid sodium salt, cyclodextrins and so on, there has something interesting change on them. It is shown that (+)-tartaric acid can discriminate QN and QD with the best result.Chapter 5: The approach for micellar stabilized room temperature phosphorescence (MS-RTP) of quinine and quinidine has been developed based on a technique of sodium sulfitechemical deoxygenation. The phosphorescence characteristics of QN and QD in SDS micelle were studied in detail in the presence of T1NO} as the heavy atom perterber. Various factors of effect on MS-RTP of QN and QD are discussed in detail including the concentration of heavy atom, the concentration of SDS, pH effect and deoxygenation condition. Analytical curves of QN and QD are linear in the range of 3 10-6-8 10-5mol/L and 1 10-6-8 10-5mol/L, respectively, and with the LOD of 3.99 10-7mol/L and 1.68 10-7 mol/L. The recovery of standard samples added to Quinine sulfate and quinidine sulfate is in the range 90-106%. The proposed method was successfully applied to real sample analysis without separation.Chapter 6: Various factors affecting the phosphorescence lifetime of QN and QD were investigated in detail, such as the concentration of heavy atom and the micelle, pH and deoxygenation. And the micro-environmental properties of various media were comparatively investigated. But the change of environmental conditions cannot discriminate QN and QD. After adding some chiral discriminators such as (+)-tartaric acid, (+)-10-camphorsulfonic acid, glycyrrhizic acid ammonium salt, digitonin, deoxycholic acid sodium salt, BSA, (R)-(-)-N-(3,5-dinitro benzoyl)- -phenylglycine and so on, the phosphorescence intensities of QN and QD were both to varying degree quenched and the phosphorescence lifetime decreased. The decay of them obeyed Stern-Volmer kinetic relationship and the Ksv (the constant of Stern-Volmer) were calculated. According the Ksv, the order of chiral discrimination ability of these additives are as following digitonin, glycyrrhizic acid ammonium salt > deoxycholic acid sodium...
Keywords/Search Tags:Discrimination
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