Post-chemiluminescence phenomenon of NBS-luminol reactions and their applications to flow injection analysis of piroxicam.

A new post-chemiluminescence (PCL) reaction was observed when piroxicam was injected into the reaction mixture after the CL reaction of N-bromosuccinimide (NBS) and luminol. A possible reaction mechanism was proposed based on the studies of the CL kinetic characteristics, the CL spectra, fluorescence spectra and other experiments. A new flow injection CL method for the determination of piroxicam was established based on the PCL reaction. The relative standard deviation (RSD) for the determination of piroxicam was 1.2% (n = 11, c = 2.0 x 10(-6) g/ml). The CL intensity responded linearly to the concentration of piroxicam in the range 1.0 x 10(-7) - 1.0 x 10(-5) g/ml (r = 0.9991). The detection limit was 4.0 x 10(-8) g/ml. The method had been applied to the determination of piroxicam in tablets with satisfactory results.     

Flow-injection chemiluminescence determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids.

A novel, rapid and sensitive analytical method is described for determination of ofloxacin and levofloxacin by enhanced chemiluminescence (CL) with flow-injection sampling. The method is based on the CL reaction of the Ce(IV)-Na2S2O4-ofloxacin/levofloxacin-H2SO2 system. The enhanced CL mechanism was developed and the optimum conditions for CL emission were investigated. The CL intensity was correlated linearly (r = 0.9988) with the concentration of ofloxacin (or levofloxacin) in the range of 1.0 x 10(-8) - 1.0 x 10(-7) g ml(-1) and 1.0 x 10(-7) - 6.0 x 10(-6) g ml(-1). The detection limit (S/N = 3) is 7 x 10(-9) g ml(-1). The relative standard derivation (RSD, n = 11) is 2.0% for ofloxacin at 4 x 10(-7) g ml(-1) and for levofloxacin at 6 x 10(-7) g ml(-1). This method has been successfully applied for the determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids with satisfactory results.     

Molecular imprinting-chemiluminescence determination of trimethoprim using trimethoprim-imprinted polymer as recognition material

A new molecular imprinting-chemiluminescence method for the determination of trimethoprim was developed, in which trimethoprim-imprinted polymer was used as the molecular recognition material and the CL reaction of trimethoprim with potassium permanganate in acidic medium was used as the detection system. The CL intensity responds linearly to the concentration of trimethoprim within the 5.0 x 10(-8)-5.0 x 10(-6) g mL(-1) range (r= 0.9983) with a detection limit of 2 x 10(-8) g mL(-1). The relative standard deviation for the determination of 1.0 x 10(-7) g mL(-1) trimethoprim solutions is 4.8% (n= 9). The method has been applied to the determination of trimethoprim in pharmaceutical preparations and body fluids, and satisfactory results were obtained.     

Sensitive assay for catecholamines in pharmaceutical samples and blood plasma using flow injection chemiluminescence analysis.

A rapid and sensitive chemiluminescence (CL) method using flow injection analysis was described for the determination of three catecholamines: dopamine, adrenaline and dobutamine, based on their greatly enhancing effects on the CL reaction of luminol-potassium periodate in basic solutions. Under the optimized conditions, the calibration graphs relating the increase of CL intensity to the concentration of the analytes were linear. The present method allows for the determination of dopamine, adrenaline, and dobutamine over the range of 1.0 x 10(-10) - 1.0 x 10(-7) g/ml. The relative standard deviations for measurements (n=11) of dopamine, adrenaline and dobutamine were 2.9, 2.3 and 1.8% when the concentrations of three catecholamines were at 1.0 x 10(-9) g/ml, respectively. The detection limits of the method were 2.0 x 10(-11) g/ml dopamine, 1.0 x 10(-11) g/ml adrenaline and 4.0 x 10(-11) g/ml dobutamine. The method was successfully applied to the determination of three catecholamines in pharmaceutical samples and blood plasma.     

纳米银催化的鲁米诺化学发光体系测定呋喃硫胺的研究

基于纳米银能够增强鲁米诺-H2O2-呋喃硫胺体系化学发光的现象,建立了测定呋喃硫胺的流动注射化学发光新方法.对体系的化学发光机理进行了初步探讨,发现该体系的化学发光光谱的最大发射波长为425nm,该体系的发光体为激发态的3-氨基邻苯二甲酸根离子.该方法测定呋喃硫胺的线性范围为1.0×10-8～1.0×10-5g/mL,检出限4×10-9g/mL,对1.0×10-6g/mL呋喃硫胺连续9次测定的相对标准偏差(RSD)为1.9％.方法已用于药物呋喃硫胺片中呋喃硫胺的测定.     

Flow-injection chemiluminescence determination of polyphenols using luminol-NaIO4-gold nanoparticles system

It was found that gold nanoparticles with different sizes could enhance the chemiluminescence (CL) of the luminol-NaIO4 system in alkaline solution. The most intensive CL signals were obtained with gold nanoparticles in diameter of 4 nm and the CL intensity increased linearly with the concentration of gold nanoparticles. The studies of UV-vis spectra, CL spectra, effects of concentrations of luminol and periodate solution were carried out to explore the CL enhancement mechanism. Catechol, hydroquinone and resorcinol were found to inhibit the CL signals of the luminol-NaIO4 reaction catalyzed by gold nanoparticles, which made it applicable for the determination of these polyphenols. Under the selected experimental conditions, the detection limits (3sigma) were in the range of 2.1 x 10(-9) to 1.0 x 10(-10) g ml(-1), the relative standard deviation (R.S.D., n=11) were in the range of 1.7-2.9%. The method has been successfully applied to the determination of catechol in tap water and synthesized samples with satisfactory results.     

纳米银增强化学发光法测定塑料中的双酚A

研究发现在碱性介质中,纳米银对luminol-KMnO4化学发光体系的发光信号具有强烈的增敏作用,而双酚A对该体系具有明显的抑制作用,据此结合流动注射技术,建立了流动注射化学发光分析法测定塑料中双酚A的方法。该方法测定双酚A的线性范围为8.0×10-11～1.0×10-8g.mL-1(0.9926)和1.0×10-8～8.0×10-8g.mL-1(0.9916),检出限(3σ)为6.5×10-11g.mL-1。对5.0×10-10g.mL-1和5.0×10-8g.mL-1双酚A平行测定11次,其相对标准偏差为1.4%和1.0%。对反应机理进行了讨论。该方法简单、快速、灵敏度高,用于塑料制品中双酚A的测定,回收率为97.0%～105.0%。     

Determination of lomefloxacin by terbium sensitized chemiluminescence method

A simple, rapid and sensitive chemiluminescence (CL) method was proposed for the determination of lomefloxacin (LFX). This method is based on the fact that the weak CL from the redox reaction of Ce(4+)-Na(2)SO(3) can be greatly enhanced by the complex of Tb(3+)-LFX. The CL intensity is directly proportional to the concentration of LFX in the range 2.0x10(-9) to 1.0x10(-5) mol L(-1), and the detection limit (S/N=3) is 1.1x10(-9) mol L(-1). This method has been applied to the detection of LFX in pharmaceutical preparation, urine and serum samples. Recoveries were in the range 95-105%. The CL mechanism of Ce(4+)-Na(2)SO(3)-Tb(3+)-LFX system was proposed to be an intermolecular energy transfer from excited SO(2)(*) to LFX and an intramolecular energy transfer from LFX to Tb(3+).     

流动注射后化学发光法测定盐酸阿比朵尔

研究了盐酸阿比朵尔在鲁米诺-K3Fe(CN)6化学发光反应体系中的后化学发光反应. 据此建立了测定盐酸阿比朵尔的流动注射后化学发光分析法. 方法的线性范围为6.0×10-9～1.0×10-7 g/mL, 检出限(3σ)为2×10-9 g/mL. 对4.0×10-8 g/mL的盐酸阿比朵尔溶液连续11次平行测定, RSD=1.3%. 方法已用于盐酸阿比朵尔胶囊及尿样中盐酸阿比朵尔含量的测定. 在对这一后化学发光反应的动力学性质、化学发光光谱、紫外可见吸收光谱以及一些相关问题研究的基础上, 提出了可能的反应机理.     

Determination of trace aluminum (III) using a novel cerium (IV)-calcein chemiluminescence detection

A simple, sensitive and selective chemiluminescence (CL) method was developed for the direct determination of aluminum (Al). This method is based on that the weak CL of cerium (IV)-calcein can be greatly enhanced by Al(III). The calibration curve was linear over the range 2.0 x 10(-10) to 4.0 x 10(-8)g mL(-1) with a detection limit of 8 x 10(-11)g mL(-1) (3sigma). The R.S.D. was 2.5% by 11 replicated determinations of 1.0 x 10(-9)g mL(-1) Al(III). The proposed method has been used to determine the concentration of Al(III) in real water samples with satisfactory results. The mechanism of the CL reaction was also discussed.     

Chemiluminescence of chlorpromazine hydrochloride based on cerium(IV) oxidation sensitized by rhodamine 6G

A new chemiluminescence (CL) method is proposed for the determination of chlorpromazine hydrochloride, a drug often used to treat the psychiatric patients suffering from clinical depression. The method is based on the reaction between studied drug and Ce(IV) in a nitric acid medium and measurement of the CL intensity produced by rhodamine 6G used as a sensitizer. In the optimum conditions, CL intensities are proportional to concentrations of the studied drug over the range 0-1x10(-5) g ml(-1) with a detection limit of 6.5x10(-9) g ml(-1). The relative standard deviation (R.S.D.) is 4.1% for 1.5x10(-6) g ml(-1) chlorpromazine hydrochloride (n=11). The method has been applied to the determination of studied drug in tablets and biological fluids with satisfactory results.     

流动注射-电化学发光法测定煤灰中痕量钼(Ⅵ)

基于钼(Ⅵ)在-0.60V(vs.Ag/AgCl)电位下在线还原为钼(Ⅲ),且在碱性条件下钼(Ⅲ)与鲁米诺发生化学发光反应,据此提出了流动注射-电化学发光法测定煤灰中痕量钼(Ⅵ)的方法。钼(Ⅵ)的质量浓度与化学发光强度的增加值在5.0×10-7～5.0×10-4g.L-1范围内呈线性关系,检出限(3s/k)为5×10-8g.L-1。对1.0×10-6g.L-1钼(Ⅵ)标准溶液进行11次测定,测定值的相对标准偏差为2.6%。方法可用于煤灰中痕量钼(Ⅵ)的测定,测定值与国标方法测定值相符。     

Electrogenerated chemiluminesence method for the determination of riboflavin at an ionic liquid modified gold electrode

A highly sensitive electrogenerated chemiluminescence (ECL) method for the determination of riboflavin was developed based on the enhancement of ECL intensity of lucigenin at room temperature ionic liquids (RTILs) modified gold electrode. RTILs modified gold electrode exhibited excellent electrochemical and ECL property to lucigenin system and the ECL intensity of lucigenin was greatly enhanced by riboflavin. The characterization of the RTILs modified electrode and the attractive performance of the sensitive ECL method for the determination of riboflavin were investigated. Under the optimized conditions, the ECL intensity was directly proportional to the concentration of riboflavin in the range from 5.0×10(-10) g/mL to 1.0×10(-8)g/mL with the detection limit of 1×10(-10) g/mL. The method has been applied to the determination of riboflavin in the pharmaceutical preparations with satisfactory recovery from 96% to 101%. This work demonstrates that the incorporation of ECL method with RTILs modified electrode is a promising strategy for the determination of organic compounds with high sensitivity and good reproducibility.     

基于纳米TiO2的化学发光法检测核黄素

纳米TiO2与NaOH溶液作用能产生化学发光辐射,在表面活性剂十六烷基三甲基溴化铵(CTAB)的存在下,核黄素的加入能增强纳米TiO2-NaOH溶液的化学发光强度。基于此,构建了纳米TiO2-NaOH溶液化学发光新体系,建立了纳米TiO2-NaOH-核黄素体系检测核黄素的化学发光新方法。在优化实验条件下,核黄素质量浓度在5.0×10-6～3.5×10-4g/mL范围内与化学发光强度呈良好的线性关系,检出限为3.0×10-6g/mL,对2.5×10-5g/mL的核黄素进行11次平行测定,相对标准偏差为2.9%。该方法用于维生素B2片剂的测定,其结果与药典方法测得一致。该文同时对化学发光反应的机理进行了初步探讨。     

Ru(phen)3 2+-SDBS-KMnO4化学发光体系检测半胱氨酸的研究

在20mmol·L-1硫酸-1.2mmol.L-1十二烷基苯磺酸钠(SDBS)介质中,半胱氨酸可以增强三(1,10-菲咯啉)钌(Ⅱ)[Ru(phen)32+]-KMnO4化学发光体系的发光强度.基于此,建立了一种化学发光直接检测半胱氨酸的新方法.在优化的实验条件下,该方法的线性范围和检测限分别为2.5×10-2-2.0μg·mL-1和2.1×10-2μg·mL-1,对11份含半胱氨酸0.5μg·mL-1的溶液平行测定的相对标准偏差(R.S.D.)为5.3%.将其用于合成样品中半胱氨酸含量的测定,结果令人满意.并提出了可能的化学发光机理.     

Chemiluminescence flow injection analysis of 1,3-dichloro-5,5-dimethylhydantoin in swimming pool water

A new chemiluminescence (CL) flow-injection method is proposed for the determination of 1,3-dichloro-5,5-dimethylhydantoin (DDH). The method is based on the chemiluminescent reaction of DDH and luminol-H(2)O(2) in an alkaline medium (pH 12.0-12.5). The concentration of the analyte shows a good linear relationship with the produced luminescence intensity in the range of 3.0x10(-8) to 8.0x10(-6) mol l(-1). The detection limit of the proposed method is 1.0x10(-8) mol l(-1) and the relative standard deviation (R.S.D.) is 4.7% (n=5) at 5.0x10(-7) mol l(-1). This method was successfully applied to the determination of trace amounts of this disinfectant in water samples obtained from five different swimming pools. Satisfying recovery values were also obtained.     

Molecularly imprinted on-line solid-phase extraction combined with flow-injection chemiluminescence for the determination of tetracycline

A molecularly imprinted polymer solid phase extraction (MISPE) method combined with flow-injection chemiluminescence (FI-CL) for the determination of residual tetracycline (TC) in fish samples is presented. The molecularly imprinted polymer (MIP) of TC was synthesized and particles of this MIP were packed into a polytetrafluoroethylene (PTFE) tube, which was connected into the sampling loop of an eight-way injection valve and served as the MISPE column for on-line selective adsorption of TC. The eluent (CH3CN : HNO3 (0.01 mol L(-1)) = 4 ratio 1, v ratio v) was used for extracting the adsorbed TC, which could be detected by its good enhancing effect on the CL reaction between Ce(iv) and rhodamine B. The CL intensity is linear to TC concentration in the range from 4 x 10(-9) to 4 x 10(-7) g mL(-1). The detection limit is 1 x 10(-9) g mL(-1) (3 sigma) and the relative standard deviation is 2.4% (n = 9). The conditions of preconcentration, extraction and CL reaction were carefully studied. The selectivity experiment shows that the selectivity and sensitivity of the CL method could be improved greatly when MIP was used as a recognition material in SPE. However, the MISPE column interacted indiscriminately with oxytetracycline (OTC) with a 49 +/- 2% binding. An intermediate differential pulsed elution (DPE) step using 3% acetic acid as eluent was employed to remove OTC and other interfering substances. The proposed MISPE-CL method has been applied successfully to the determination of TC in fish samples. At the same time, the binding characteristics of the polymer to tetracycline were evaluated by batch and dynamic methods.     

流动注射化学发光法快速测定尿液中左亚叶酸钙

在碱性介质中, 左亚叶酸钙对鲁米诺-K3Fe(CN)6体系有显著的增敏作用, 据此, 建立了一种简单、快速测定左亚叶酸钙的流动注射化学发光新方法. 在优化的实验条件下, 该法测定左亚叶酸钙的线性范围为5.0×10-8～1.0×10-5 g/mL; 检出限(3σ)为2.0×10-8 g/mL; 对浓度为1.0×10-6 g/mL的样品进行11次平行测定, 相对标准偏差为1.3%. 将此法用于尿液中左亚叶酸钙的测定, 同时进行回收率实验.     

流动注射-化学发光法测定富马酸依美斯汀

在酸性条件下,KMnO4与甲醛能够产生微弱的化学发光,而富马酸依美斯汀的存在能够大大增强该化学发光强度;结合流动注射技术,建立了测定富马酸依美斯汀的流动注射-化学发光新方法。该方法的线性范围分别为3.0×10-8～2.0×10-7g/mL,2.0×10-7～1.0×10-6g/mL和1.0×10-6～8.0×10-6g/mL。检出限为1.0×10-8g/mL,对2.0×10-6g/mL富马酸依美斯汀滴眼液平行测定11次,其相对标准偏差为1.3%。该方法已成功应用于滴眼液中富马酸依美斯汀的含量测定。     

Flow injection electrogenerated chemiluminescence determination of vanadium and its application to environmental water sample

A selective flow injection electrogenerated chemiluminescence(CL) method for the determination of vanadium is described in this paper. It was based on the chemiluminescence reaction of luminol with vanadium(II), which was on-line electrogenerated from vanadate using a flow-through carbon electrolytic cell. Under the optimal conditions, the CL intensity was linear to the concentration of vanadium in the range of 5.0x10(-10)-1.0x10(-7) gml(-1) with a detection limit of 2x10(-10) gml(-1) vanadium. The relative standard deviation was 4% for 5.0x10(-8) gml(-1) vanadium in 11 repeated measurements. The method has been successfully applied to the determination of vanadium in environmental water samples.