| The thesis focuses on flow injection (FI) chemiluminescene (CL) & its applications in pharmaceutical and environmental analysis. The main content consisted of two parts:Part I A review of FI-CL analysisRecently, CL has been proven to be valuable for pharmaceutical, environmental and biological analysis. The most characteristic property of CL is remarkable sensitivity. Certain compounds can be detected in femtomole levels. Therefore, as an alternative to radiometric analysis, interest in chemiluminescent systems has focused on their utility for the determination of trace amounts of organic compounds in pharmaceutical preparation and environmental samples. In this part, based on the fundamental theory of CL quantificational analysis, the applications of various CL detection methods combined with FI analysis in the pharmaceutical, environmental and biological analysis was described, including more than 120 references during 2006-2008.Part II Research reportsSince the phenomenon of luminol CL was found by Albrecht in 1928, the application of CL had a great many grow. Luminol as one of the most important and familiar chemiluminescent compounds, its chemiluminescent system had been extensively studied. In this part, based on the CL reaction of luminol-H2O2, luminol-myoglobin and luminol-dissolved oxygen in alkaline medium combined with flow injection, amoxicillin, risperidone, matrine, chlorogenic acid, carbon monoxide and formaldehyde have been determined in pharmaceutical preparations, water sample or body fluids by the proposed method, respectively.1. Applications of FI-CL system in pharmaceutical analysis (1) It was found that amoxicillin could greatly enhance the CL intensity generated from the reaction between luminol and hydrogen peroxide. The increment CL signal was linearly dependent on amoxicillin concentration in the range from 10 pg·mL-1 to 2 ng·mL-1 (R2 = 0.9978) offering a detection limit as low as 3.5 pg·mL-1 (3σ). At a flow rate of 2.0 mL·min-1, one analysis cycle, including sampling and washing, could be accomplished in 20 s with a relative standard deviation of less than 5%. The sensitive FI method was applied successfully to determine of amoxicillin in pharmaceutical preparations, human urine and serum without any pretreatment procedure, with recovery from 90.0% to 110.0% and relative standard deviations of less than 5.0%.(2) A simple FI-CL method with synergistic enhancement has been investigated for the rapid and sensitive determination of the antipsychotic risperidone. The synergistic action was significant in the CL system of luminol-hydrogen peroxide with risperidone as an enhancer. The increased CL intensity was correlated with risperidone concentration in the range from 10 pg·mL-1 to 1.0 ng·mL-1 with relative standard deviations of less than 5.0% (n = 11); and the limit of detection was 4 pg·mL-1 (3σ). At a flow rate of 2.0 mL·min-1, the FI-CL method exhibited both high sensitivity and excellent selectivity giving a throughput of 120 times per hour. The proposed method was first applied successfully to monitor of risperidone in human urine without any pre-treatment process. It was found that the excretive amounts of risperidone reached its maximum after taking 2.0 mg risperidone for one hour, with a total excretive ratio of 17.37% in 8.5 hours.(3) A novel green method using FI-CL has been investigated for the rapid and sensitive determination of matrine. It was found that matrine could greatly inhibit the CL intensity generated from the reaction between luminol and myoglobin(Mb). The decrement CL signal was linearly the logarithm of the matrine concentration over the range from 10 ng·mL-1 to 3μg·mL-1 (R2= 0.9973) offering a detection limit as low as 3.5 ng·mL-1 (3σ). At a flow rate of 2.0 mL·min-1, one analysis cycle, including sampling and washing, could be accomplished in 20 s with a relative standard deviation of less than 5%. The sensitive FI method was applied successfully to determine of matrine in pharmaceutical injection, human urine and serum without any pretreatment procedure, with recovery from 90.0% to 110.0% and relative standard deviations of less than 5.0%.(4) A sensitive FI- CL method, based on the inhibitory effect of chlorogenic acid on the CL reaction between luminol and dissolved oxygen, was presented to determine chlorogenic acid. The decrement of CL intensity was linear with the logarithm of chlorogenic acid concentration over the range from 1.0 ng·mL-1 to 100 ng·mL-1 (R2 = 0.9978), with the detection limit of 0.3 ng·mL-1 (3σ). At a flow rate of 2.0 mL·min-1 for each line, a complete analytical process could be performed within 0.5 min, including sampling and washing, with a relative standard deviation of less than 3.0% (n = 5). The proposed procedure was applied successfully to determine chlorogenic acid in Flo Lonicerae for different dunking times and monitor the excretion of chlorogenic acid in human urine and it was found that chlorogenic acid in urine reached its maximum after drunk for 2 hours, presenting an excretive ratio of 63.82% in 6 hours. With urinary excretion rate method, the total elimination rate constant k and half-life time t1/2 of chlorogenic acid was calculated, which were 0.7667 and 0.91 hours, respectively.2. Applications of FI-CL system in environmental analysis(1) A novel CL method combined with FI technique for determination of carbon monoxide is presented in this paper. The CL signal based on the reaction between myoglobin and luminol in alkaline medium was remarkably enhanced by carbon monoxide. The enhanced CL intensity was linear with carbon monoxide concentration in the range from 0.01 to 10.0 pmol·L-1, and the detection limit was 3×10-3 pmol·L-1 (3σ). The whole process, including sampling and washing, could be completed in 0.5 min with a relative standard deviation of less than 4.0%. The proposed method was applied successfully in the assay of carbon monoxide in human serum and artifical samples without any pretreatment procedure.(2) A rapid and sensitive CL determination of formaldehyde with the FI technique was presented. It was found that the specific binding of myoglobin with formaldehyde could accelerate the electron transfer between myoglobin and luminol, thus producing quicker and more efficient CL at 425 nm than that of myoglobin-luminol reaction. The increased CL intensity was linear with the formaldehyde concentration in the range from 1 to 3000 pmol·L-1, and the limit of detection was 0.3 pmol·L-1 with a relative standard deviation of less than 5.0% (3a). At a flow rate of 2.0 mL·min-1, including sampling and washing, the assay could be accomplished in 0.5 minute. It was also found that there exists a linear relationship of vapor pressure for formaldehyde and temperatures from 291.5-315.0 K. The proposed method has been applied successfully to the determination of formaldehyde in air and human serum. |
PDF Full Text Request