Determination of organophosphate and carbamate pesticides in spiked samples of tap water and fruit juices by a biosensor with photothermal detection.

The determination of organophosphate (paraoxon, chlorpyrifos, diazinon) and carbamate (carbaryl, carbofuran) pesticides in spiked drinking water and fruit juices was carried out using a photothermal biosensor. The biosensor consists of a cartridge containing immobilised enzyme acetylcholinesterase (AChE) placed in a flow-injection analysis (FIA) manifold and a photothermal detector based on thermal lens spectrometry. With this approach, 0.2 ng/ml of paraoxon can be detected in less than 15 min. Limits of detection for other organophosphate (chlorpyrifos, diazinon) and carbamate (carbaryl, carbofuran) pesticides varied, depending on their antiacetylcholinesterase (AntiAChE) toxicity, from 1 ng/ml to 4 microg/ml. The biosensor was used for the direct detection of pesticides in spiked tap water and fruit juices without any pretreatment steps. In these cases, the LOD3sigma of 1.5, 2.8 and 4 ng/ml paraoxon in tap water, orange juice and apple juice were obtained, respectively.     

Sensitive determination of synephrine by flow-injection chemiluminescence.

It was found that light emission produced by the oxidation of luminol by potassium ferricyanide in basic medium was enhanced by synephrine, an anti-obesity drug. The optimum conditions for this chemiluminescent reaction were studied in detail in a flow injection system and employed in a new, simple and rapid method for the determination of synephrine. A mechanism for this reaction is proposed, based on the chemiluminescence reaction spectra. In the optimum conditions, CL intensity is proportional to concentration of synephrine in the 0.008-1 microg/mL range. The limit of detection is 1.6 ng/mL for synephrine (3sigma), and the relative standard deviation (n = 11) is 2.6% for 0.5 microg/mL synephrine. The method was applied to the determination of synephrine in herbal products, citrus fruit and biological fluids. The recoveries were satisfactory (90-102%). The results given by the proposed method are in good agreement with those given by HPLC-UV.     

A flow-injection chemiluminescence method for the determination of human serum albumin, using the reaction of fluorescein-human serum albumin-sodium hypochlorite by the enhancement effect of the cationic surfactant cetyltrimethylammonium bromide.

The interaction between surfactant and fluorescein was studied, using a fluorescence spectroscopy and flow-injection (FI) chemiluminescence (CL) method. It was found that the cationic surfactant cetyltrimethylammonium bromide (CTAB) could cause the structural transformation of fluorescein from the quinone to the spirolactone form, and greatly enhance the CL intensity of the fluorescein-human serum albumin (HSA) complex. Based on this finding, a rapid and sensitive FI-CL method was developed for the determination of HSA. Under the optimum conditions, the proposed method has a linear range of 0.05-24.0 microg/mL, with a detection limit of 0.03 microg/mL for HSA (3sigma). The relative standard deviation (RSD) of 1.2 microg/mL HSA (n = 8) is 0.8%. The method was applied to the determination of protein content in urine samples, with satisfactory results. Density functional theory was used to study the mechanism of surfactant-enhanced CL intensity of the fluorescein-HSA complex.     

Potential of the luminol reaction in the sensitive detection of pesticide residues by flow injection analysis.

This study presents the first analytical application of the luminol chemiluminescence (CL) reaction for the sensitive detection of carbamate residues. Some experiments have been carried out to check the influence of the presence of traces of a N-methylcarbamate (carbaryl) on the CL emission produced from the oxidation of luminol using different oxidants, showing a significant enhancing effect on the CL emission when the oxidation of luminol is produced by potassium permanganate in alkaline medium, this enhancement being proportional to the carbaryl concentration. This fact has permitted the establishment of a sensitive chemiluminescence flow-injection (CL-FIA) method for the direct determination of carbaryl. The optimization of instrumental and chemical variables influencing the CL response has been carried out by applying experimental designs. Under the optimal conditions, the CL intensity was linear for a carbaryl concentration over the range 5-100 ng/mL with a detection limit of 4.9 ng/mL. This luminol-KMnO4-based FIA-CL system in basic medium shows an easy, fast and cheap alternative detection mode for the analysis of carbaryl residues in environmental water samples.     

Flow-injection with enhanced chemiluminescence detection of ofloxacin in human plasma.

A simple, rapid and sensitive method for the determination of ofloxacin in plasma has been developed based on flow-injection analysis with enhanced chemiluminescence (CL) detection. This method employs the CL reaction of cerium(IV) and sulphite sensitized by a Tb(III)-ofloxacin complex. Plasma samples were deproteinized with acetonitrile before analysis. Under optimal conditions, the method allowed the quantitative analysis of ofloxacin in plasma over the range of 22.5-900 ng/mL with a detection limit of 7.5 ng/mL (3sigma). The intra-day and inter-day precision was < 3.0% (n = 11) and < 7.0% (n = 3), respectively. The method was a convenient tool, rapid (20 s/analysis) and well suited for pharmacokinetics studies in which thousands of samples must be analysed daily. It was applied to pharmacokinetics studies of ofloxacin.     

Reverse micelle-based chemiluminescence system for quinine sulphate.

A new chemiluminescence (CL) method is proposed for the determination of quinine sulphate, which is based on the dichloromethane solvent extraction of the ion-pair complex of tetrachloroaurate (III) with quinine sulphate, and luminol CL detection in a reversed micellar medium formed by the cation surfactant cetyltrimethylammonium bromide in a dichloromethane-cyclohexane (3:7, v/v)-water (0.35 mol/L Na2CO3 buffer solution, pH 11.5). The ion-pair complex of tetrachloroaurate (III) with quinine sulphate produced an analytical CL signal when it entered the reversed micellar water pool. In optimum conditions, CL intensities are proportional to the concentrations of the studied drug over the range 0.015-10 microg/mL, with a detection limit of 1.5 ng/mL. The relative standard deviation (RSD) is 1.38% for 2.5 microg/mL quinine sulphate (n=11). The method has been applied to the determination of the studied drug in biological fluids, with satisfactory results.     

Development of a sensitive and rapid nucleic acid assay with tetraphenyl porphyrinatoiron chloride by a resonance light scattering technique.

Based on the interaction between nucleic acids and tetraphenyl porphyrinatoiron chloride (FeTPPCl), a novel method for the determination of nucleic acids at the nanogram level has been developed. Under the optimum conditions, the weak resonance light scattering (RLS) intensity of FeTPPCl was greatly enhanced by nucleic acids and the enhanced RLS intensity was proportional to the concentration of nucleic acids in the range 0.02-2.8 microg/mL for calf thymus DNA, 0.05-3.3 microg/mL for fish sperm DNA and 0.07-4.5 microg/mL for yeast RNA. The detection limits (3sigma) were 2.9 ng/mL for calf thymus DNA, 3.9 ng/mL for fish sperm DNA and 5.2 ng/mL for yeast RNA. Almost no interference could be observed from proteins, nucleosides and most of the metal ions. The proposed method showed good reliability, sensitivity, rapidity and reproducibility when applied to the determination of nucleic acids in synthetic and biochemical samples. The time savings make this method suitable for large routine analyses.     

Flow injection analysis of riboflavin with chemiluminescence detection using a N-halo compounds-luminol system.

A chemiluminescent method for the determination of riboflavin is described. The method is based on the chemiluminescence (CL) generated during the oxidation of luminol by N-bromosuccinimide (NBS) and N-chlorosuccinimide (NCS) in alkaline medium. It was found that riboflavin could greatly enhance this CL intensity when present in the luminol solution. Based on this observation, a new flow-injection CL method for the determination of riboflavin is proposed in this paper. The detection limits were 7.5 ng/mL and 3.5 ng/mL of riboflavin for the NBS- and NCS-luminol CL systems, respectively. The relative CL intensity was linear, with riboflavin concentration in the range 19-600 ng/mL and 600-2000 ng/mL for the NBS-luminol CL system, and 12-200 ng/mL and 200-2000 ng/mL for the NCS-luminol CL system. The results obtained for the assay of pharmaceutical preparations compared well with those obtained by the official method and demonstrated good accuracy and precision.     

A novel chemiluminescence method for the determination of orciprenaline based on ferricyanide-rhodamine 6G.

A novel flow injection chemiluminescence method for the determination of orciprenaline was developed. The method is based on the chemiluminescence (CL) reaction of orciprenaline with potassium ferricyanide in sodium hydroxide medium, sensitized by the fluorescent dye rhodamine 6G. The proposed procedure allows quantitation of orciprenaline in the concentration range 0.01-1.2 microg/mL, with a detection limit of 7.2 x 10(-3) microg/mL. The relative standard deviation (RSD) is 2.7% for 0.1 microg/mL orciprenaline (n = 9). The sampling frequency was calculated at approximately 120/h. The method was successfully applied to the determination of orciprenaline in pharmaceutical preparations. A brief discussion on the possible CL reaction mechanism is presented.     

Flow injection chemiluminescence determination of dihydralazine sulphate based on permanganate oxidation sensitized by rhodamine B.

A novel flow injection chemiluminescence (CL) method for the determination of dihydralazine sulphate (DHZS) is described. The method is based on the CL produced during the oxidation of DHZS by acidic permanganate solution in the presence of rhodamine B. Rhodamine B is suggested as a fluorescing compound for the energy-transferred excitation. The CL emission allows quantitation of DHZS concentration in the range 5-800 ng/mL, with a detection limit of 1.9 ng/mL (3sigma). The experimental conditions for the CL reaction are optimized and the possible reaction mechanism is discussed. The method has been applied to the determination of DHZS in pharmaceutical preparations and compares well with the high performance liquid chromatography (HPLC) method.     

An assay for inorganic mercury(II) based on its post-catalytic enhancement effect on the potassium permanganate-luminol system.

A strong chemiluminescence (CL) response is observed when potassium permanganate solution is injected into basic luminol solution. When the CL reaction terminates, subsequent injection of Hg2+ solution into the reaction mixture results in a new CL reaction. Based on the post-catalytic enhancement effect of Hg2+ on the potassium permanganate-luminol system in basic media, a fast and simple CL-coupled flow injection analysis for the determination of Hg2+ was developed. In optimum conditions, CL intensity is proportional to Hg2+ concentration over the range 1.0 x 10(-8)-1.0 x 10(-5) g/mL, with a detection limit of 2.0 x 10(-9) g/mL. The relative standard deviation (RSD) is 3.6% for 1.0 x 10(-7) g/mL Hg2+ (n = 11). After pretreatment with sulphydryl cotton fibre, environmental water samples were analysed by the proposed method for total mercury determination with satisfactory results. The results were in good agreement with those given by hydride generation-cold vapour atomic absorption spectrometry (HG-CVAAS).     

Flow-injection chemiluminescence determination of catecholamines based on their enhancing effects on the luminol-potassium periodate system.

A rapid and sensitive chemiluminescence (CL) method using flow injection analysis is described for the determination of four catecholamines, dopamine, adrenaline, isoprenaline and noradrenaline, based on their greatly enhancing effects on the CL reaction of luminol-potassium periodate in basic solutions. The optimized chemical conditions for the chemiluminescence reaction were 1.0 x 10(-4) mol/L luminol and 1.0 x 10(-5) mol/L potassium periodate in 0.2 mol/L sodium hydroxide (NaOH). Under the optimized conditions, the calibration graphs relating the CL signal intensity (peak height) to the concentration of the analytes were curvilinear and they were suitable for determining dopamine, adrenaline, isoprenaline, and noradrenaline in the range 0.1-10 ng/mL, 0.1-100 ng/mL, 1-100 ng/mL and 5-50 ng/mL, respectively, with the relative standard deviations of 0.8-1.7%. The detection limits of the method are 0.02 ng/mL for dopamine, 0.01 ng/mL for adrenaline, 0.1 ng/mL for isoprenaline and 2.0 ng/mL for noradrenaline. The sampling frequency was calculated to be about 60/h. The selectivity of the method was good, because a series of common ions or excipients, such as K(+), Ba(2+), CO(3)(2-), NO(3)(-), SO(4)(2-), PO(4)(3-), sodium citrate, sodium bisulphite, oxidate dopamine, starch, lactose, carbamide and gelatin, could not produce interference when their concentrations were 1000-fold than those of dopamine. The present method was successfully applied to the determination of the four catecholamines in pharmaceutical injections.     

Flow-injection resonance light scattering detection of proteins at the nanogram level.

A resonance light scattering (RLS) detection method for protein was developed, using a flow-injection system based on the enhancement of RLS signals from Biebrich scarlet (BS) by protein. The enhanced RLS intensities at 286.0 nm, in acidic aqueous medium, were proportional to the protein concentration over the range 0.005-18 microg/mL and 0.008-16 microg/mL for human serum albumin (HSA) and bovine serum albumin (BSA), respectively, with corresponding limits of detection (3sigma) of 5.00 ng/mL for HSA, and 7.80 ng/mL for BSA. The method was successfully applied to the quantification of total proteins in human serum samples.     

Determination of thyroxine in pharmaceuticals using flow injection with luminol chemiluminescence inhibition detection.

A simple flow injection method is reported for the determination of thyroxine, based on its inhibition effect on luminol-iron(II) chemiluminescence in alkaline medium in the presence of molecular oxygen. The detection limits (2s) for d- and l-thyroxine are 0.08 and 0.1 mg/L, respectively, with a sample throughput of 100/h. The calibration data for d- and l-thyroxine over the range 0.2-1.0 mg/L gives correlation coefficients (r(2)) of 0.9915 and 0.984 with relative standard deviations (RSD; n = 4) in the range 1.2-2.8%. The effects of some organic compounds was studied on luminol-iron(II) CL system for thyroxine determination. The method was applied to pharmaceutical thyroxine tablets and the results obtained (in the range 50.5 +/- 2.0-51.6 +/- 1.2 microg l-thyroxine/tablet) were in reasonable agreement with the value quoted.     

Ultrasensitive assay of clindamycin in medicine and bio-fluids with chemiluminescence detection.

A simple chemiluminescence (CL) method using flow injection has been developed for the determination of clindamycin, based on the inhibitory effect of clindamycin on the CL generated from the luminol-K(3)Fe(CN)(6) system in alkaline medium. It was found that the decrement of CL intensity was linear with the logarithm of clindamycin concentration over the range 0.7-1000 ng/mL. The detection limit was 0.2 ng/mL with a relative standard deviation (RSD) of <5.0% (n = 7). At a flow rate of 3.0 mL/min, a complete analytical process could be performed within 0.5 min, including sampling and washing. The proposed procedure was applied successfully to the determination of clindamycin in pharmaceutical preparations and human urine without pretreatment.     

Determination of propylthiouracil and methylthiouracil in human serum using high-performance liquid chromatography with chemiluminescence detection

Based on the sensitizing effect of formaldehyde on the chemiluminescence (CL) reaction of propylthiouracil (PTU) and methylthiouracil (MTU) with acidic potassium permanganate and the combination technique of high-performance liquid chromatography (HPLC), a sensitive, selective and simple post-column CL detection method for determining PTU and MTU is described. The optimal conditions for the CL detection and HPLC separation were carried out. The linear ranges were 0.1-20 microg mL(-1) for MTU and 0.1-10 microg mL(-1) for PTU, the detection limits were 0.03 microg mL(-1) for PTU, 0.03 microg mL(-1) for MTU and the quantification limits were 0.1 microg mL(-1) for PTU, 0.1 microg mL(-1) for MTU. The method has been satisfactorily applied for the determination of MTU and PTU in human serum samples.     

In vitro monitoring of nanogram levels of puerarin in human urine using flow injection chemiluminescence

A rapid and sensitive chemiluminescence (CL) determination of puerarin with the flow injection technique was presented. It was found that puerarin could enhance the CL generated from luminol-KIO(4) system significantly. The increment of CL intensity was linear over the concentration of puerarin ranging from 0.3 to 100.0 ng mL(-1) (r(2)=0.9963), offering a detection limit as low as 0.1 ng mL(-1) (3 sigma). 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 5.0%. The experimental results demonstrated that the excretive amounts of puerarin reached its maximum in 3 h after taking 250 mL green drink containing 275 mg puerarin, and the puerarin excretive ratio during 24 h was 9.70% in the body of volunteers.     

Flow injection determination of benzhexol based on its sensitizing effect on the chemiluminescent reaction of Ce(IV)–sulfite

In this paper, a novel chemiluminescent (CL) method for the determination of benzhexol has been developed by combining the flow injection technique and its sensitizing effect on the weak CL reaction between sulfite and acidic cerium(IV). A mechanism for the CL reaction has been proposed on the basis of CL spectra. Under the optimized conditions, the proposed method allows the measurement of benzhexol hydrochloride over the range 0.1–10 μg/mL with a correlation coefficient of 0.9992 (n = 8), a detection limit of 0.02 μg/mL (3σ), and a relative standard deviation for 2.0 μg/mL benzhexol (n = 11) of 1.65%. The utility of this method was demonstrated by determining benzhexol hydrochloride in tablets. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of erythromycin in rat plasma with capillary electrophoresis-electrochemiluminescence detection of tris(2,2'-bipyridyl) ruthenium(II)

A fast and sensitive approach for determination of erythromycin in rat plasma was described. The method used capillary electrophoresis coupled with end-column electrochemiluminescence (ECL) detection of Ru(bpy)(3)(2+). The separation column used had an inner diameter of 75 microm. The running buffer was 15 mmol/L sodium phosphate (pH=7.5). The solution in the detection cell was 50 mmol/L sodium phosphate (pH=8.0) and 5 mmol/L Ru(bpy)(3)(2+). ECL intensity varied linearly with erythromycin concentration from 1.0 ng/mL to 10 microg/mL. The detection limit (S/N=3) was 0.35 ng/mL. The relative standard deviations, of ECL intensity and migration time for eight consecutive injections of 1.0 microg/mL erythromycin (n=8), were 1.3% and 1.8%, respectively. The method was successfully applied to erythromycin determination in rat plasma. The recovery ranged from 92.5 to 97.5%.     

Quantification of fat-soluble vitamins in human breast milk by liquid chromatography-tandem mass spectrometry

Sensitive quantification method for fat-soluble vitamins in human breast milk by liquid chromatography-tandem mass spectrometry was developed. Vitamins A, D and E were extracted from 10.0 mL of breast milk after saponifying by basic condition. Vitamin K derivatives were extracted from 3.0 mL of breast milk after lipase treatment. The corresponding stable isotope-labeled compounds were used as internal standards. For the determination of vitamin D compounds, derivatization with a Cookson-type reagent was performed. All fat-soluble vitamins were determined by liquid chromatography-tandem mass spectrometry in the positive ion mode. The detection limits of all analytes were 1-250 pg per 50 microL. The recoveries of fat-soluble vitamins were 91-105%. Inter-assay CV values of each vitamin were 1.9-11.9%. The mean concentrations of retinol, vitamin D3, 25-hydroxyvitamin D3, alpha-tocopherol, phylloquinone and menaquinone-4 were 0.455 microg/mL, 0.088 ng/mL, 0.081 ng/mL, 5.087 microg/mL, 3.771 ng/mL, and 1.795 ng/mL, respectively (n=82). This method makes possible to determine fat-soluble vitamins with a wide range of polarities in human breast milk. The assay may be useful for large-scale studies.