自动化流动注射停流动力学分析仪的研制及其性能测试

本文研制了一套自动化流动注射停流动力学分析仪，该仪器由苹果Ⅱ型微机通过１２位ＡＤ／ＤＡ卡，流动注射停流控制仪及用ＢＡＳＩＣ语言编制的软件控制泵的起动和停止，试样的输送和混合，数据采集和处理，结果显示和打印，通过以铁（Ⅲ）与硫氰酸盐的反应体系采用固定时间法和以钒（Ｖ）的胶束催化反庆体系采用安始速法的现场测试证明，该仪器具有结构简单，操作方便，恒温性能好，通用性强等特点。     

Determination of norfloxacin in pharmaceuticals,human serum,and urine using a luminol—dissolved oxygen chemiluminescence system

A sensitive chemiluminescence method, based on the enhancive effect of norfloxacin on the reaction between luminol and dissolved oxygen in a flow injection system, was proposed for the determination of norfloxacin. The increment of the chemiluminiscence intensity was proportional to the concentration of norfloxacin, giving a calibration graph linear over the concentration from 0.4 ng mL⁻¹ to 400.0 ng mL⁻¹ (r ² = 0.9988) with the detection limit of 0.1 ng mL⁻¹ (3 × σ _noise). At the flow rate of 2.0 mL min⁻¹, a complete determination of norfloxacin, including sampling and washing, could be accomplished in 30 s with the relative standard deviation lower than 3.0 %. The proposed method was applied successfully to determine norfloxacin in pharmaceuticals, human urine, and serum. Possible mechanism of the reaction was also discussed.     

Biocatalysis and biorecognition in nonaqueous media. Some perspectives in analytical biochemistry

Biocatalysis and, to a lesser extent, biorecognition in non-aqueous media (including organic solvents as well as supercritical fluids and gases) constitute at present an exciting research area which has already demonstrated its biotechnological potential in numerous, varied applications. Less attention, however, has been paid to its analytical possibilities, even though many advantages have been postulated and a wide range of poorly water-soluble analytes are present in samples (or waste materials) from food and drink, petrochemical, pharmaceutical, military and other industries. The main approaches, developed in recent years to exploit the use of enzymes, antibodies or antibody mimics in water-restricted environments for analytical purposes, as well as possible future directions are briefly discussed.     

Determination of Picogram-Levels of Acetylspiramycin in Human Urine and Serum by Flow Injection Chemiluminescence

A sensitive chemiluminescence method for the determination of acetylspiramycin is presented. It is based on the greatly enhancive effect of acetylspiramycin on the chemiluminescence reaction between luminol and hydrogen peroxide in the flow system. The increase in chemiluminescence intensity was linearly proportional to the acetylspiramycin concentration in the range from 10pg·mL^–1 to 2.0ng·mL^–1 (r²=0.9979). The detection limit was 3pg·mL^–1 (3). At a flow rate of 2.0mL·min^–1, the process of determination, including sampling and washing, could be performed in 0.5 min, and the relative standard deviations of seven replicates are less than 5.0%. The proposed method was applied successfully to the determination of acetylspiramycin in pharmaceutical preparations, human urine and serum without pre-treatment. It was found that the excretive ratio of acetylspiramycin reached its maximum 2.0 hours after having been administered orally, and the excretive ratio in 12.0 hours was 8.4.     

A Highly Sensitive and Selective Assay for Cysteine Using the Chemiluminescence Reaction of Luminol and Hydrogen Peroxide

A very simple, highly sensitive and selective chemiluminescence (CL) method was established for the determination of cysteine. This method is based on the fact that the CL reaction of luminol and hydrogen peroxide can be greatly enhanced by cysteine. The CL intensities at maximum light emission were linearly correlated with the concentration of cysteine over the range of 2.0×10^–8–6.0×10^–6molL^–1 with a detection limit of 7.5×10^–9molL^–1. The relative standard deviation was 1.7% for the determination of 1.0×10^–7molL^–1 cysteine (n=9). The feasibility of utilizing the proposed method for the determination of total concentration of cysteine in human serum was examined.     

Flow-injection chemiluminescent determination of metoclopramide hydrochloride in pharmaceutical formulations and biological fluids using the [Ru(dipy)(3)(2+)]-permanganate system

A flow-injection (FI) methodology using (2,2′-dipyridyl) ruthenium(II) [Ru(dipy)₃²⁺] chemiluminescence (CL) was developed for the rapid and sensitive determination of metoclopramide hydrochloride. The method is based on the CL reaction of metoclopramide with Ru(dipy)₃²⁺ and KMnO₄ in a sulfuric acid medium. Under the optimum conditions, a calibration graph was obtained over the concentration range 0.005-3.5 μg ml⁻¹ with a limit of detection (S/N=2) of 1 ng ml⁻¹. The correlation coefficient was 0.99993 (n=8) with a relative standard deviation of 0.48% for 10 determinations of 1 μg ml⁻¹ of drug. The method was successfully applied to the determination of metoclopramide in pharmaceutical preparations and biological fluids after IP administration of 25 mg kg⁻¹ dose to rats. The elimination half-life was 2.5±0.4 h.     

Flow-injection determination of total iron in freshwater samples with neutralisation chemiluminescence

A flow-injection chemiluminescence method has been established for the determination of total iron in freshwater samples. The enhanced chemiluminescence emission was caused by the iron(II) from the neutralisation reaction of hydrochloric acid and sodium hydroxide without the use of any chemiluminescent reagent. The calibration graph was linear in the concentration range of 2.8–560 µg L^?1 (r ² = 0.9983, n = 8), with relative standard deviation (RSD; n = 4) in the range of 0.8–2.6%. The limit of detection (S/N = 3) was 0.56 µg L^?1 with injection throughput of 180 h^?1. The effect of common anions and cations were studied over their environmentally relevant concentrations in freshwaters. The method was successfully applied to determine total iron in freshwater samples. Iron(III) was reduced to iron(II) by using hydroxylammonium chloride. The proposed method was compared with spectrophotometric method and there was no significant difference between the two methods at the 95% confidence level (t-test). Analysis of river water (certified reference material SLRS-4) for iron(II), after reduction of iron(III) with hydroxylammonium chloride, gave good results (2.17 ± 0.22 µM compared with the certificate value of 1.85 ± 0.1 µM).     

Determination of phosphate in freshwater samples by flow-injection with lucigenin chemiluminescence

Lucigenin chemiluminescence (CL) in conjunction with flow-injection analysis (FIA) is used for the determination of phosphate in freshwater samples. The procedure is based on the formation of molybdophosphoric heteropoly acid (MoP–HPA) by the reaction of phosphate and ammonium molybdate under acidic conditions. CL emission was observed as a result of oxidation of lucigenin in aqueous sodium hydroxide solution in the presence of MoP–HPA. Calibration was linear up to 500?µg?L^?1 (r ^2?=?0.9998; n?=?8), with a detection limit (S/N?=?3) of 0.95?µg?L^?1. An injection throughput of 120 h^?1, and relative standard deviation (RSD; n?=?4) of 1.3–3.2% were achieved in the concentration range studied. An on-line chelating column was used to remove interfering cations. The method was applied to freshwater samples, and the results (51?±?1.0 – 107?±?2.0?µg?L^?1) did not differ significantly from results obtained using a spectrophotometric method (52.5?±?1.0 – 102?±?2.0?µg?L^?1) at 95% confidence level (t-test).     

Flow-Injection Analysis of Chloride in Milk with a Dialyzer and a Coated Tubular Inorganic Chloride-Selective Electrode

Abstract

A rapid and reliable automated procedure for the direct measurement of the chloride content in milk is described. The method is based on the principles of the flow-injection technique; a dialyzer is used to eliminate interferences and the dialyzed chloride is measured with a coated tubular chloride-selective electrode. With this system potential change caused by the interference of casein is obviated, giving a stable baseline. Results obtained for chloride in milk at a sampling rate of 120 samples per hour compared well with data obtained by the standard Volhard titration method. With 30-μl samples a working range of 250–5000 mg/1 chloride is covered with a coefficient of variation of better than 0.50%.     

Determination of risperidone at picogram level in human urine by luminol—H2O2 chemiluminescence

A simple flow-injection chemiluminescence method with synergistic enhancement has been investigated for the rapid and sensitive determination of antipsychotic risperidone. The synergistic action was significant in the chemiluminescence system of luminol—hydrogen peroxide with risperidone as an enhancer. The increased chemiluminescence intensity was correlated with risperidone concentration within the range from 10 pg mL⁻¹ to 1.0 ng mL⁻¹ with relative standard deviations lower than 5.0 % and the detection limit of 4 pg mL⁻¹. At a flow rate of 2.0 mL min⁻¹, the flow-injection chemiluminescence method exhibited both a high sensitivity and excellent selectivity giving a throughput of 120 times per hour. The proposed method was successfully applied to determine the risperidone content in human urine without any pretreatment. It was found that the excretive amounts of risperidone reached their maximum after taking 2.0 mg of risperidone for 1 h, with a total excretive ratio of 17.37 % in 8.5 h.