流动注射化学发光法测定氨苄西林的研究

氨苄西林在NaOH溶液中降解后,其产物可在酸性条件下与KMnO4发生化学发光反应,甲醛的存在可使发光强度增强。据此,采用流动注射技术,建立了一种测定氨苄西林的化学发光分析法。方法的检出限为9.1×10-9g/mL,相对标准偏差为1.8%(n=11,ρ=3.4×10-6g/mL),线性范围为4.0×10-8~2.0×10-5g/mL。利用该法测定了氨苄西林胶囊中的氨苄西林,其回收率在87%~106%。     

流动注射化学发光法测定佐米曲谱坦

在碱性条件下,佐米曲谱坦对鲁米诺-K3[Fe(CN)6]化学发光体系有较强的抑制作用,据此建立了佐米曲谱坦的流动注射化学发光分析法。该法的化学发光抑制值ΔI与佐米曲谱坦质量浓度在2.0×10-6~1.2×10-4g/mL范围内,呈良好的线性关系,检出限为7.6×10-7g/mL。对2.5×10-5g/mL佐米曲谱坦测定的相对标准偏差为1.2%(n=11)。方法适用于佐米曲谱坦片中佐米曲谱坦的测定。     

流动注射化学发光法测定那格列奈

在碱性介质中,那格列奈对Luminol-H2O2体系的化学发光有很强的抑制作用,据此建立了流动注射化学发光抑制法测定那格列奈的新方法.该法的化学发光抑制值△I与那格列奈的质量浓度在2.0×10-8～1.0×10-6 g/mL范围内,呈良好的线性关系,检出限为1.4×10-8 g/mL;对4.0×10-7 g/mL那格列奈连续进行11次平行测定,相对标准偏差为1.0%;通过对荧光光谱的研究,对机理进行了初步探讨.     

流动注射化学发光法测定司帕沙星的研究

在酸性介质中,司帕沙星对NaNO2-H2O2发光体系有很强的增强作用,并且其增强化学发光强度与司帕沙星的物质的量浓度在一定范围内呈线性关系。基于此,采用流动注射技术,建立了一种简单、快速测定司帕沙星的方法。线性范围为1.0×10-7~8.5×10-4mol/L,检出限为6.5×10-8mol/L。利用该法测定了司帕沙星片剂中的司帕沙星,回收率在98.8%~104.4%之间。     

Reversed flow injection and sandwich sequential injection methods for the spectrophotometric determination of copper(II) with cuprizone

Two new flow methods, flow injection analysis (FIA) and sequential injection analysis (SIA), for the spectrophotometric determination of Cu(II) in water at trace levels have been developed and optimised. Both methods are based on the reaction with oxalic acid bis(cyclohexylidene hydrazide) (cuprizone) in alkaline media. The two procedures have been developed for the final aim to compare their performances and to offer new rapid heavy metals analysis tools, avoiding the use of extraction steps. A detailed study of the physico-chemical parameters affecting the systems performances has been carried out. The reversed FIA and sandwich SIA approaches offered the best sensitivity. In both cases, an extremely good linearity has been obtained within the range 0.06-4 μg ml⁻¹ (correlation coefficient r=0.9999), whereas the observed detection limits were 0.013 and 0.004 μg ml⁻¹, for FIA and SIA, respectively. Furthermore, due to the great similarity of the diffusion zones in the reaction slugs, our approach offers the opportunity to compare the two methods in analogous conditions. This SIA method, besides keeping its typical reagent saving features, offered analytical performances equivalent to those of FIA. To obtain these results, an original “stop-flow like” method was successfully employed in the SIA approach. Both methods were validated by analysis of real water samples, after copper addition, and certified reference samples of fortified and waste waters.     

Chemiluminescence determination of bufrenorphine hydrochloride by flow injection analysis

A direct, simple and rapid flow-injection method is described for determining buprenorphine hydrochloride (10^?8–10^?4 M) based on its chemiluminescent oxidation with potassium permanganate in polyphosphoric acid. The limit of detection is 1 × 10^?8 M (0.5 pmol per injection) and the log-log calibration is linear up to 1 × 10^?4 M; the r.s.d. is 0.7% for a 10 μg ml^?1 solution (n = 10). The method is directly applicable to aqueous solutions of tablets containing the drug (0.2 mg/tablet).     

Chemiluminescence determination of iron(II) and titanium(III) by flow injection analysis based on reactions with and without luminol

Titanium(III) and iron(II) are shown to stimulate luminol chemiluminescence in the absence of added oxidant. Down to 10^?9 M titanium can be determined. Both metal ions also produce chemiluminescence when injected into 0.1 M carbonate buffer (pH 10.4), allowing >10^?6 M of each to be determined. The intensities are greater when the solutions have been deoxygenated by a stream of nitrogen, and when rhodamine B is used as a sensitizer.     

Simultaneous determination of cobalt(III)-copper(II) and cobalt(III)-nickel(II) mixtures by differential kinetic methods

A procedure is reported for the simultaneous determination of binary mixtures of cobalt(III)-copper(II) and cobalt(III)-nickel(II) by differential kinetic methods based on complex formation reactions with 3-(1H-1,2,4-triazolyl-3-azo)-2,6-diaminotoluene. The single-point method is used in both cases. The simultaneous determination of Co-Cu and Co-Ni is possible in the concentration range from 10/1 to 1/1. The interference caused by various ions is also studied. The method has been used to determine cobalt-copper and cobalt-nickel mixtures in synthetic samples, hydrofining catalysts and low alloy steels.     

Chemiluminescence flow system for the determination of Fe(II) and Fe(III) in water

A novel chemiluminescence (CL) flow system has been developed for the sequential determination of Fe(II) and Fe(III) in water. Fe(II) was detected by its catalytic effect on the CL reaction between luminol immobilized on an anion exchange resin column and dissolved oxygen; Fe(III) was determined by difference measurement after on-line conversion to Fe(II) in a reducing mini-column packed with Cu plated Zn granules. For both ions, the calibration graph was linear in the range 1 × 10^–9 to 1 × 10^–6 g/mL, and the detection limit was 4 × 10^–10 g/mL. A complete analysis could be performed in 1.5 min with a relative standard deviation of less than 5%. The system could be reused for over 200 times and has been applied successfully to the determination of Fe(II) and Fe(III) in natural water samples.     

Chemiluminescence flow system for the determination of Fe(II) and Fe(III) in water

A novel chemiluminescence (CL) flow system has been developed for the sequential determination of Fe(II) and Fe(III) in water. Fe(II) was detected by its catalytic effect on the CL reaction between luminol immobilized on an anion exchange resin column and dissolved oxygen; Fe(III) was determined by difference measurement after on-line conversion to Fe(II) in a reducing mini-column packed with Cu plated Zn granules. For both ions, the calibration graph was linear in the range 1 × 10^–9 to 1 × 10^–6 g/mL, and the detection limit was 4 × 10^–10 g/mL. A complete analysis could be performed in 1.5 min with a relative standard deviation of less than 5%. The system could be reused for over 200 times and has been applied successfully to the determination of Fe(II) and Fe(III) in natural water samples. Received: 13 March 1997 / Revised: 3 June 1997 / Accepted: 6 June 1997     

Catalytic determination of traces of cobalt by the protocatechuic acid — Hydrogen peroxide reaction in a flow injection system

Summary A catalytic method in a flow injection system is proposed for the simple, rapid and sensitive determination of trace amounts of cobalt; the method is based on the cobalt-catalyzed oxidation of protocatechuic acid by hydrogen peroxide. The reported method has a limit of detection of 0.2 ppb by injecting 75l of sample, corresponding to 15 pg cobalt, and permitsca. 50 determinations per hour with a relative standard deviation of 1.5%. Relatively good selectivity is also obtained.

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Katalytische Bestimmung von Kobalt-Spuren mit der Protocatechusäure-Wasserstoffperoxid-Reaktion in einer Flie-Injektions-Vorrichtung

Zusammenfassung Eine einfache, schnelle und empfindliche Bestimmung von Kobaltspuren wurde beschrieben. Sie beruht auf der durch Kobalt katalysierbaren Oxydation von Protocatechusäure durch Wasserstoffperoxid. Bei Injektion von 75l Probe (entsprechend 15 pg Co) beträgt die Erfassungsgrenze des Verfahrens 0,2 ppb. 50 Bestimmungen sind pro Stunde durchführbar; die relative Standardabweichung beträgt 1,5%. Die Selektivität ist relativ gut.

     

Voltammetric determination of traces of cobalt(II) with a chemically modified carbon paste electrode

Summary A new preconcentration and voltammetric determination method for cobalt(II) in aqueous solution with a chemically modified electrode is proposed. The accumulation behaviour and voltammetry of cobalt(II) has been investigated with a carbon paste electrode modified with cationexchanger and 1,10-phenanthroline. The electrochemical response is characterized with respect to carbon paste composition, pH, preconcentration time, cobalt(II) concentration and other variables. For a 3-min preconcentration time, the electrode gives good linearity for 1×10^–7 to 4×10^–6 mol/l Co(II), a detection limit of 8×10^–8 mol/l. The response can be reproduced with a 4.0% relative standard deviation. The method is fairly free from many coexisting ions interferences. A rapid and convenient renewal procedure allows the use of a single electrode in multiple analytical determinations over several days. Satisfactory results are obtained for the determination of cobalt in a variety of certified standard reference materials.     

On-line determination of mercury(II) by membrane separation flow injection analysis

A rapid and inexpensive gas-diffusion (GD) flow injection method for the on-line determination of Hg(II) in aqueous samples is described. The analytical procedure involves the injection of a Hg(II) sample into a 1.5 M H₂SO₄ carrier stream which is merged with a reagent stream containing 0.6% SnCl₂ and 1.5 M H₂SO₄. Under these conditions Hg(II) is reduced to metallic mercury which partially evaporates through a Teflon membrane into an acceptor stream containing 1.75×10⁻⁴ M KMnO₄ in 0.3 M H₂SO₄. The decrease in the absorbance of the acceptor stream at 528 nm corresponding to the absorption maximum of the permanganate anion can be related to the original concentration of Hg(II) in the sample. The method is characterized by a detection limit of 4 μg l⁻¹ and a sampling frequency of 8 h⁻¹. The flow system was successfully applied to the analysis of river samples spiked with Hg(II).     

流动注射化学发光法快速测定化学需氧量

基于酸性K2 Cr2 O7在消解水体中的有机污染物时被还原为Cr(Ⅲ ) ,而Cr(Ⅲ )可以催化Luminol H2 O2 体系产生强的化学发光 ,建立了一种测定COD的流动注射化学发光法。本方法不需要催化剂 ,不需要长的消解时间 ,可以采用较低的酸度 ,适合于在线连续检测水体COD。本方法检测COD的线性范围为 2 0～1 0 0 0 0mg L ,检出限为 1 0mg L ,对 1 0mg LCOD的 1 1次平行测定的RSD小于5 %。方法已用于地表水样COD的测定。     

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II)

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI.     

Efficient flow injection and sequential injection methods for spectrophotometric determination of oxybenzone in sunscreens based on reaction with Ni(II)

Spectrophotometric determination of a widely used UV-filter, such as oxybenzone, is proposed. The method is based on the complexation reaction between oxybenzone and Ni(II) in ammoniacal medium. The stoichiometry of the reaction, established by the Job method, was 1:1. Reaction conditions were studied and the experimental parameters were optimized, for both flow injection (FI) and sequential injection (SI) determinations, with comparative purposes. Sunscreen formulations containing oxybenzone were analyzed by the proposed methods and results compared with those obtained by HPLC. Data show that both FI and SI procedures provide accurate and precise results. The ruggedness, sensitivity and LOD are adequate to the analysis requirements. The sample frequency obtained by FI is three-fold higher than that of SI analysis. SI is less reagent-consuming than FI.     

Chemiluminescence determination of sodium 2-mercaptoethane sulfonate by flow injection analysis using cerium(IV) sensitized by quinine

A flow injection method with chemiluminescence (CL) detection is proposed for the determination of sodium 2-mercaptoethane sulfonate (MESNA), a drug often used to reduce the urotoxic effects of antineoplastic alkylating agents. The procedure is based on the reaction of the thiol with Ce(IV) in a sulfuric acid medium and measurement of the CL intensity produced by quinine used as a sensitizer. The optimum conditions for CL emission were investigated. Using the CL peak height as the analytical parameter, MESNA was determined over the concentration range 0.29–2.21 ng (1.97–9.85 μg·l⁻¹) with a detection limit of 0.21 ng (1.38 μg·l⁻¹) and a relative standard deviation (R.S.D.) of 4.1%. The method was applied satisfactorily to the determination of MESNA in pharmaceutical preparations with percentages of recovery between 94 and 105.     

Chemiluminescence determination of carbofuran and promecarb by flow injection analysis using two photochemical reactions

A flow injection-chemiluminescent method for the determination of carbofuran and promecarb is proposed. The assay was based on the on-line conversion of the pesticides into methylamine by irradiation with UV light. The methylamine generated was subsequently reacted with tris(2,2'-bipyridine)ruthenium(III), which was generated through the on-line photo-oxidation of tris(2,2'-bipyridine)ruthenium(II) with peroxydisulfate. The emitted light showed a linear relationship with the concentration of the pesticide over the ranges 0.22-11.2 microg ml(-1) for carbofuran and 0.41-16.6 microg ml(-1) for promecarb. The repeatability was 1.6% expressed as relative standard deviation (n = 10) and the reproducibility, studied on five different days, was 2%. The sample throughput was 200 injections per h. The reliability of the method for routine analysis of these pesticides in water, soil and grains is demonstrated.     

Spectrophotometric determination of fluoxetine by batch and flow injection methods

A rapid, simple, and accurate spectrophotometric method is presented for the determination of fluoxetine by batch and flow injection analysis methods. The method is based on fluoxetine competitive complexation reaction with phenolphthalein-beta-cyclodextrin (PHP-beta-CD) inclusion complex. The increase in the absorbance of the solution at 554 nm by the addition of fluoxetine was measured. The formation constant for fluoxetin-beta-CD was calculated by non-linear least squares fitting. Fluoxetine can be determined in the range 7.0 x 10(-6)-2.4 x 10(-4) mol l(-1) and 5.0 x 10(-5)-1.0 x 10(-2) mol l(-1) by batch and flow methods, respectively. The limit of detection and limit of quantification were respectively 4.13 x 10(-6) mol l(-1) and 1.38 x 10(-5) mol l(-1) for batch and 2.46 x 10(-5) mol l(-1) and 8.22 x 10(-5) mol l(-1) for flow method. The sampling rate in flow injection analysis method was 80+/-5 samples h(-1). The method was applied to the determination of fluoxetine in pharmaceutical formulations and after addition to human urine samples.