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Study On Chemiluminescent Reactions And Analytical Applications Of Two Ru(Ⅱ) Complexes

Posted on:2005-03-04Degree:DoctorType:Dissertation
Country:ChinaCandidate:J XiFull Text:PDF
GTID:1101360125955849Subject:Analytical Chemistry
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Chemiluminescence (CL) analysis is a simple, rapid, and sensitive analytical method, which is developed based on the CL phenomena. With many advantages, such as high sensitivity, wide linear range and relatively simple instrumentation, it has been widely used for determination of many kinds of substances in analytical chemistry. The chemiluminescent reagent is the basis of CL analysis and its properties are very important for increasing the sensitivity and extending the application of this method. As a kind of inorganic compound CL reagent, the ruthenium( II) complex is soluble, stable, high quantum efficiency and not destroyed in CL process, so it will be used more widely in analytical chemistry.In all of ruthenium( II) complex being used as CL reagent, tris-(2,2'-bipyridine) ruthenium( II)( Ru(bipy)32+ ) is the most widely used and the analytical application of this reagent is mainly based on its electrogenerated chemiluminescence (ECL) reactions. Some study results have indicated that compared with Ru(bipy)32+, tris-(l,10-phenanthroline)ruthenium(II) ( Ru(phen)32+ ) and tris-(4, 7-diphenyl-l,10-phenanthrolinedisulfonic acid)ruthenium(II) (RuBPS) are more sensitive for analysis. Furthermore, CL analysis is superior in many respects to ECL, such as rapidness, simple instrument, little wastage of the CL reagent, and so on.In this study, the CL reaction and mechanism of Ru(phen)32+ and RuBPS were investigated detailedly, based on which, several novel CL systems were developed and applied to determine babituric acid, amino acids, hydrazine and isoniazid and diuretics. The above CL methods are simple and sensitive, by which, the application of ruthenium( II) complex in CL analysis is expanded to a certain extent. The main contents of this study could be described as follows:1. The effects of babituric acid and its three derivatives on Ru(phen)32+-Cerium (IV) (Ce(IV)) CL system was investigated and the results showed that only barbituric acid could enhance CL intensity of that system. Then a novel CL method was developed for sensitive determination of barbituric acid, the linear range and detection limit of which were 5.0 x 10"3~ 2.0 # g ?mL-1 and 6.9 x 10-4 #. g ?mL-1, respectively. The detail mechanism of CL reaction was also presented.2. The direct and sensitive detection of amino acids is very important and significative for life sciences research. Based on investigating the effects of 20 amino acids existing as components of protein on Ru(phen)32+ CL system, two novel methods were developed to directly and sensitively detect amino acids.Based on their enhancement effects on CL intensity of Ru(phen)s +-Ce(IV) system, a novel method was developed to detect tryptophan and cysteine. Under their own optimum conditions, for tryptophan, the linear range and detection limit were 5.0 x 10~3 ~ 7.0 x 10"' n g ?mL"1 and 4.0 10"3 /i g ?mL"1, respectively; and for cysteine, 5.0 x 10"2 ~ 2.0/i g ?mL"1 and 3.2 x 10~2/ig ' mL"1, respectively. This method was selective to tryptophan and cysteine, respectively and could be used to determine the contents of these two amino acids in synthetic samples. The possible mechanism of CL reaction was studied.Based on its enhancement effect on CL intensity of Ru(phen)32+-SDBS-KMnO4 system, a novel method was developed to sensitively and selectively detect cysteine. The linear range and detection limit were 2.5 x 10"2 ~ 2.0 g ?mL1 and 2.1 x 10"2 n, g ?mL"1, respectively. The experimental results showed that the enhancement effect of cysteine on the CL system depended on its mercapto functional group.3. Hydrazine and isoniazid were determined by CL analysis based on their enhancement effects on Ru(phen)32+-Ce(IV) system, respectively. Under their own optimum conditions, for hydrazine, the linear range and detection limit were 2.0 x 10"3~ 2.0/ig ?mL"1 and 1.8 x 10"3/ig ?mL"1, respectively; and for isoniazid, 7.0 x 10~2~ 6.5 M g ?mL"1 and 2.5 x 10"2/g ?mL"1, respectively. The mechanism of CL reaction was also investigated.4. Using Ce(IV) as the oxidant, the effects...
Keywords/Search Tags:Ru(phen)s2+, RuBPS, Chemiluminescence analysis, Barbituric acid, Amino acid, Hydrazino compounds, Diuretics
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