Flow injection assays for NADH and ethanol using photosensitized rose bengal and luminol-copper (II) chemiluminescence system.

The online photoreaction of the rose bengal photosensitized luminol-copper (II) chemiluminescence (CL) system was used for the determination of ß-nicotinamide adenine dinucleotide (NADH) and ethanol (EtOH) in pharmaceutical formulations combined with a flow injection technique. NADH can significantly enhance the CL emission of the reaction. For EtOH, alcohol dehydrogenase in soluble form was utilized in the presence of nicotinamide adenine dinucleotide resulting in NADH production. The limit of detection (3σ blank, 𝑛 = 3) of 4.0 × 10-8 and 2.17 × 10-5  M, and linear range 1.3 × 10-7 to 2.5 × 10-5  M (R2  = 0.9998, n = 6) and 0.11-2.17 × 10-3  M (R2  = 0.9996, n = 6) were obtained for NADH and EtOH respectively. The injection rate was 100 h-1 with a relative standard deviation (n = 3) of 1.5-4.8% in the range studied for both analytes. The procedure was satisfactorily applied to pharmaceutical formulations with recoveries in the range 91.6 ± 3.0% to 110 ± 2.0% for NADH and 88 ± 3.0% to 95.4 ± 4.0% for EtOH. The results obtained were very consistent and did not differ considerably from the reported approaches at a 95% confidence limit. The possible mechanism of the CL reaction is also explained briefly.

Determination of thiram residues in fresh water using flow injection diperiodatonickelate(IV)-quinine chemiluminescence detection.

This study developed a simple flow injection (FI) method based on diperiodatonickelate(IV)-sulfuric acid reaction using chemiluminescence (CL) detection for the determination of thiram (THI) fungicide in fresh water using quinine as the sensitizer. The possible mechanism of the CL reaction was described using UV-Vis. absorption and CL spectra. Experimental variables were optimized by applying a univariate approach, and a linear calibration curve was obtained in the range of 1.0 × 10-3 -2.0 mg L-1 (R2 = 0.9994, n = 9) with a limit of detection of 5.0 × 10-4  mg L-1 (S/N = 3) and an injection throughput of 200 h-1 . This approach was successfully applied to determine THI in fresh water by using solid-phase extraction and achieved a good recovery rate of 94%-110% with a relative standard deviation of 1.9%-3.7% (n = 4). The results obtained were compared with the reported FI-CL and high-performance liquid chromatography-ultraviolet methods, and the three methods did not differ significantly at the 95% confidence limit.

A Flow Injection Chemiluminescence Method for the Determination of Retinol in Pharmaceutical Formulations by Using Luminol-Diperiodatoargentate(III) Reaction.

In this paper, a chemiluminescence (CL) method is proposed for retinol determination by combining flow injection (FI) methodology. The CL reaction is based on the oxidation of luminol by diperiodatoargentate(III) (DPA) in the presence of retinol. Under the optimum conditions, the relative CL intensity was linear to the concentration of retinol over the range 5.0×10-3-14 mg L-1 (y=347.26x+2.5944, R2=0.9999, n=8) with limit of detection (LOD) of 1.5×10-3 mg L-1 (S/N=3) and limit of quantification (LOQ) of 5.0×10-3 mg L-1 (S/N=10). The relative standard deviation (RSD) was from 1.04-3.4% over the range studied and injection throughputs of 150 h-1. The method was satisfactorily applied to retinol in pharmaceutical formulation samples. The samples were saponified and extracted with liquid-liquid extraction using ether as an extractant. The possible CL mechanism is supported by CL and UV-visible spectrophotometric studies.

Flow-injection determination of manganese (II) using surfactant enhanced diperiodatonickelate (IV)-rhodamine 6G chemiluminescence.

Chemiluminescence (CL) of the rhodamine 6-G-diperiodatonickelate (IV) (Rh6-G-Ni(IV) complex) in the presence of Brij-35 was examined in an alkaline medium and implemented using flow-injection analysis to analyze Mn(II) in natural waters. Brij-35 was identified as the surfactant of choice that enhanced CL intensity by about 62% of the reaction. The calibration curves were linear in the range 1.7 × 10-3 - 0.2 (0.9990, n = 7) and 8.0 × 10-4 - 0.1 µg ml-1 (0.9990, n = 7) with limits of detection (LODs) (S:N = 3) of 5.0 × 10-4 and 2.4 × 10-4 µg ml-1 without and with using an in-line 8-hydroxyquinoline (8-HQ) resin mini-column, respectively. The sample throughput and relative standard deviation were 200 h-1 and 1.7-2.2% in the range studied respectively. Mn(II) concentrations in certified reference materials and natural water samples was successfully determined. A brief discussion about the possible CL reaction mechanism is also given. In addition, analysis of V(III), Cr(III) and Fe(II) was also performed without and with using an in-line 8-HQ column and selective elution of each metal ion was achieved by adjusting the pH of the sample carrier stream with aqueous HCl solution.

Surfactant enhanced flow injection chemiluminescence method for vitamin D3 determination in pharmaceutical formulations.

A flow injection based chemiluminescence process has been reported for vitamin D3 determination without using especial chemiluminescence reagent. Vitamin D3 shows enhancement on the CL intensity of diperiodatocuprate(III) with surfactant (Triton X-100) solution. The calibration curve was found to be linear over the concentration range 0.01-40 mg/L (R2 = 0.9997, n = 8) tested. A limit of detection (S/N = 3), limit of quantification (S/N = 10) and sample injection throughput of 2.5 × 10-3, 8.3 × 10-3 mg/L and 150 h-1 respectively were obtained. Various experimental variables were tested to get most suitable response, e.g., the concentrations of reagents, and their flow rates, sample injection volume and photomultiplier tube voltage. The effect of potential interferences was also examined. Vitamin D3 determination was successfully carried out in pharmaceutical formulations. The recoveries from the formulations were obtained in the range of 96 ±â€¯4-108 ±â€¯2%. The reaction mechanism discussion for diperiodatocuprate(III) complex-Triton X-100-vitamin D3 was also included.

Fate, distribution, and bioconcentration of pesticides impact on the organic farms of Cameron Highlands, Malaysia.

Occurrence and distribution of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), and pyrethroid pesticides (PYRs) residues in the leafy vegetables were analyzed together with the soil samples using gas chromatography-electron capture detector. Edible tissues of vegetables showed detectable residues of these compounds indicating the influence of the conventional farms and nearby organic farms. In the vegetables, the OCPs concentrations were recorded as nd-133.3 ng/g, OPPs as nd-200 ng/g, and PYRs as nd-33.3 ng/g. In the soil, the OCPs concentrations were recorded as nd-30.6 ng/g, OPPs as nd-26.6 ng/g, and for PYRs as nd-6.7 ng/g. Bioconcentration factor (BCF) was higher for the OPPs (0.3) than the OCPs and PYRs (1.1). The OCPs concentration in the vegetables decreased in the following order: spinach > celery > broccoli > cauliflower > cabbage > lettuce > mustard. For OPPs, the concentration decreased in the following order: cauliflower > spinach > celery > cabbage > broccoli > lettuce > mustard and for PYRs as spinach > celery > lettuce > cabbage > broccoli. Principal component analysis indicates that the sources of these pesticides are not the same, and the pesticide application on the vegetables depends on the type of crop. There is a significant positive correlation between OPPs and the soil (r = 0.65) as compared to OCPs and PYRs (r = 0.1) as the vegetables accumulated OPPs more efficiently than OCPs and PYRs.

Flow Injection-Chemiluminescence Method for Determination of Hyoscine Butylbromide Using Silver(III) as Oxidizing Agent.

Diperiodatoargentate(III) (DPA)/silver(III) complex, [Ag(HIO6)2]5-, in sulfuric acid medium has been used to determine hyoscine butylbromide (HBB) by flow injection (FI) coupled with chemiluminescence (CL) detector. A linear standard curve between the CL intensity and concentration range from 0.005 to 20 mg L-1 was obtained. The determination coefficient (R2), limit of detection (3s × blank), relative standard deviation (RSD) for 0.5 mg L-1 HBB and analytical throughput were 0.9992 (n = 8), 5 × 10-4 mg L-1, 1.5% (n = 10) and 160 injections h-1, respectively. The developed method was applied for the determination of HBB in pharmaceutical formulations with recoveries from 92 ± 4 to 108 ± 3%. For comparison, a spectrophotometric method was used and the results obtained by both methods were in good agreement at a 95% confidence level. The effect of key chemical and physical variables (reagent concentration, flow rate, sample volume, PMT voltage) and interfering species (pharmaceutical excipients and inorganic ions) on the determination of HBB was examined. The possible CL mechanism of HBB on silver(III) complex in sulfuric acid medium was also discussed in brief.

Flow-Injection Determination of Thiabendazole Fungicide in Water Samples Using a Diperiodatocuprate(III)-Sulfuric Acid-Chemiluminescence System.

Chemiluminescence (CL) with a flow-injection method is reported for the determination of thiabendazole (TBZ) fungicide based on its enhancement effect on diperiodatocuprate(III) (DPC)-sulfuric acid-CL system. The calibration graph was linear in the concentration range of 1 - 2000 µg L(-1) (R(2) = 0.9999, n = 8) with a limit of detection (S/N = 3) of 0.3 µg L(-1). The injection throughput was 160 h(-1) with relative standard deviations (RSD, n = 4) of 1.1 - 2.9% in the concentration range studied. The experimental variables e.g., reagents concentrations, flow rates, sample volume, and PMT voltage were optimized, and the potential interferences were investigated individually. The method was successfully applied to the determination of TBZ in water samples showing good agreement and recovery in the range of 92 ± 2.2 - 108 ± 3% (n = 3) using dispersive liquid-liquid micro-extraction (DLLME). The possible CL reaction mechanism for DPC-sulfuric acid-TBZ is also discussed.

Determination of manganese- and manganese-containing fungicides with lucigenin-Tween-20-enhanced chemiluminescence detection.

A flow-injection (FI) method is reported for the determination of Mn(II), maneb and mancozeb fungicides based on the catalytic effect of Mn(II) on the oxidation of lucigenin and dissolved oxygen in a basic solution. The Tween-20 surfactant has been reported for first time to enhance lucigenin chemiluminescence (CL) intensity in the presence of Mn(II) (53%) and maneb and mancozeb (89%). The calibration graphs were linear in the concentration range of 0.001-1.5 mg L(-1) (R(2) = 0.9982 (n = 11) with a limit of detection (S/N = 3) of 0.1 µg L(-1) for Mn(II) and 0.01-3.0 mg L(-1) [R(2) = 0.9989 and R(2) = 0.9992 (n = 6)] with a limit of detection (S/N =3) of 1.0 µg L(-1) for maneb and mancozeb respectively. Injection throughputs of 90 and 120 h(-1) for Mn(II) and maneb and mancozeb respectively, and relative standard deviations of 1.0-3.4% were obtained in the concentration range studied. The experimental variables, e.g., reagents concentrations, flow rates, sample volume, and photomultiplier tube voltage, were optimized and potential interferences were investigated. The analysis of Mn(II) in river water reference materials (SLRS-4 and SLRS-5) showed good agreement with the certified values incorporating an on-line 8-hydroxyquinoline chelating column in the manifold for removing interfering metal ions. Recoveries for maneb and mancozeb were in the range of 92 ± 5 to 104 ± 3% and 91 ± 2 to 100 ± 4% (n = 3) respectively. The effect of 30 other pesticides (fungicides, herbicides and insecticides) was also examined in the lucigenin-Tween-20 CL system.

Vitamin A determination in milk samples based on the luminol-periodate chemiluminescence system.

A simple and rapid flow injection (FI) method for the determination of retinyl acetate is reported based on its enhancing effect on the luminol-periodate chemiluminescence (CL) system in an alkaline medium. The detection limit (3s×blank) was 8.0×10⁻8 mol L⁻¹, with an injection throughput of 90 h⁻¹. The method allows linear increase of CL intensity over the retinyl acetate concentration range of 1.0-100×10⁻7 mol L⁻¹ (R²=0.9996) with relative standard deviations of 2.4% (n=10) for 5.0×10⁻7 mol L⁻¹. The key chemical and physical variables (reagent concentrations, flow rates, sample volume, and photomultiplier tube (PMT) voltage) were optimized and potential interferences were investigated. The method was successfully applied to human milk, fresh cow's milk and infant milk-based formulas and the results were in good agreement with the previously reported HPLC method. A brief discussion on the possible CL reaction mechanism is also presented.

Flow Injection Photosensitized Chemiluminescence of Luminol with Cu(II)-Rose Bengal: Mechanistic Approach and Vitamin A and C Determination.

Rose Bengal photosensitized flow injection chemiluminescence method is reported using luminol-Cu(II) for the determination of vitamins A and C in pharmaceutical formulations. The reaction is based on the enhancement effect of analyte in the production of anion radicals of Rose Bengal (RB (•-)) which rapidly interact with dissolved oxygen and generate superoxide anions radicals (O2 (•-)) and hydrogen peroxide (H2O2). Highly reactive hydroxyl radicals ( (•) OH) were produced via dismutation of H2O2 by catalyst (Cu(2+)). The generated superoxide anions radicals and hydroxyl radicals thus oxidize luminol in alkaline medium to generate strong chemiluminescence. The limit of detection (3s of the blank, n = 6) of vitamins A and C and RB was found to be 0.008, 0.005, and 0.05 µg mL(-1), respectively. The sample throughput of 70 h(-1) for vitamins A and C and 30 h(-1) for RB was found. Calibration curve was linear in the range of 0.05-15, 0.01-20, and 0.1-50 µg mL(-1) for vitamins A and C and RB, respectively, with relative standard deviations (RSDs; n = 3) in the range 1.6-3.6%. The method was successfully applied to pharmaceutical formulations and the results obtained were in good agreement with the labeled values.

Determination of thiram and aminocarb pesticides in natural water samples using flow injection with tris(2,2'-bipyridyl)ruthenium(II)-diperiodatoargentate(III) chemiluminescence detection.

A simple and sensitive flow-injection (FI) method is reported for the determination of thiram and aminocarb pesticides in natural water samples based on the strong enhancing effects of these pesticides on the tris(2,2'-bipyridyl)ruthenium(II)-diperiodatoargentate(III) (Ru(bipy)3(2+)-DPA) chemiluminescence (CL) system. Under the optimum experimental conditions, the CL intensity was linear over the range of 1.0 - 1000 and 1.0 - 10000 ng mL(-1) (R(2) = 0.9998 (n = 7) and 0.9994 (n = 11)) for thiram and aminocarb, respectively, with relative standard deviations (RSDs; n = 3) in the range 1.0 - 2.6%. The limits of detection (S/N = 3) were 0.1 ng mL(-1) for both pesticides with injection throughputs of 150 h(-1). The key chemical and physical variables (reagent concentrations, flow rates, sample volume, PMT voltage) were optimized and potential interferences investigated. The method was successfully applied to natural water samples and the results obtained were not significantly different (95% confidence interval) from results obtained by the previously reported FI-CL and HPLC methods. Thiram could be determined in the presence of aminocarb using Triton X-100. The possible CL reaction mechanism is also discussed briefly.

Determination of nitrate and nitrite in freshwaters using flow-injection with luminol chemiluminescence detection.

A simple and sensitive flow-injection (FI) method for the determination of nitrate and nitrite in natural waters, based on luminol chemiluminescence (CL) detection, is reported. Nitrate was reduced online to nitrite via a copperized cadmium (Cu-Cd) column and then reacted with acidic hydrogen peroxide to form peroxynitrous acid. CL emission was observed from the oxidation of luminol in an alkaline medium in the presence of the peroxynitrite anion. The limits of detection (S:N = 3) were 0.02 and 0.01 µg N/L, with sample throughputs of 40 and 90 /h for nitrate and nitrite, respectively. Calibration graphs were linear over the range 0.02-50 and 0.01-50 µg N/L [R2 = 0.9984 (n = 8) and R2 = 0.9965 (n = 7)] for nitrate and nitrite, respectively, with relative standard deviations (RSDs; n = 3) in the range 1.8-4.6%. The key chemical and physical variables (reagent concentrations, buffer pH, flow rates, sample volume, Cu-Cd reductor column length) were optimized and potential interferences investigated. The effect of cations [Ca(II), Mg(II), Co(II), Fe(II) and Cu(II)] was masked online with EDTA. Common anions (PO4(3-) , SO4(2-) and HCO3-) did not interfere at their maximum admissible concentrations in freshwaters. The effect of salinity on the luminol CL reaction with and without nitrate and nitrite (2 and 0.5 µg N/L, respectively) was also investigated. The method was successfully applied to freshwaters and the results obtained were in good agreement with those obtained by an automated segmented flow analyser reference method.

Determination of subnanomolar concentrations of vanadium in environmental water samples using flow injection with luminol chemiluminescence detection.

A flow injection chemiluminescence method is described for the determination of subnanomolar concentrations of vanadium in environmental water samples. The procedure is based on the oxidation of luminol in the presence of dissolved oxygen catalyzed by vanadium(IV). Vanadium(V) reduction and preconcentration of vanadium(IV) was carried out using in-line silver reductor and 8-hydroxyquinoline chelating columns at pH 3.15, respectively. The calibration graph for vanadium(IV) was linear in the concentration range of 0.025-10 µg/L with relative standard deviation in the range of 0.4-5.58%. The detection limit (3s blank) was 3.8 × 10(-3) µg/L without preconcentration; when the vanadium(IV) was preconcentrated with an 8-HQ column for 1 min (2.0 mL of sample loaded), the detection limit of 5.1 × 10(-4) µg/L was achieved. One analytical cycle can be completed in 2.0 min. The analysis of certified reference materials (CASS-4, NASS-5 and SLRS-4) by the proposed method showed good agreement with the certified values. The method was successfully applied to the determination of total dissolved vanadium in environmental water samples.

Flow injection methods for the determination of retinol and α-tocopherol using lucigenin-enhanced chemiluminescence.

Flow injection (FI) methods are reported to determine retinol and α-tocopherol based on its enhancement affect of lucigenin chemiluminescence (CL) in alkaline medium. Surfactants including Brij-35, Triton X-100, cetyltrimethyl ammonium bromide (CTAB) and sodium dodecyl sulfate have been reported for the first time to enhance lucigenin CL intensity in the presence of retinol and α-tocopherol. With Brij-35, the CL intensity was enhanced by 67% for retinol and 58% for α-tocopherol. CTAB was found to enhance the CL intensity by 16% for retinol whereas for α-tocopherol, the CL intensity was quenched up to 95%. Retinol could be determined specifically in the presence of α-tocopherol using CTAB. The calibration graphs were found to be linear up to 1.43 mg/L (R(2) = 0.9985, n = 8) with a detection limit (3s) of 1.43 × 10(-3) mg/L for retinol and 2.15 mg/L (R(2) = 0.9989; n = 8) with a detection limit (3s) of 4.31 × 10(-4) mg/L for α-tocopherol. An injection throughput of 120/h, and relative standard deviations of 0.9-2.8% (n = 4) were achieved in the concentration range studied. The influence of common ions, excipients in pharmaceutical formulations and related organic compounds on the determination of retinol and α-tocopherol individually was studied. The proposed methods were applied to determine retinol and α-tocopherol in pharmaceutical formulations and human blood serum. The results did not differ significantly from the CL method and HPLC reference method at 95% confidence level.

Determination of Nitrite and Nitrate in Freshwaters using Flow Injection Luminol Chemiluminescence Detection.

A flow injection method for determination of nitrite and nitrate in freshwaters is described based on luminol-hypochlorite chemiluminescence (CL) system. Nitrate is reduced on-line with a cadmium reduction column to nitrite and its inhibition effect on luminol CL emission was measured. The effects of chemical and physical parameters such as buffer pH and concentration, luminol, sodium hypochlorite and sulfuric acid concentrations, flow rate, and sample volume were investigated. The calibration graphs were linear over the range 0.1-50 µM (R2 = 0.9989 and 0.9984) for nitrite and nitrate respectively with a limit of detection (S/N = 3) of 4.0 × 10-8 M and a sample throughput of 120 samples per hour. The effect of foreign ions was studied and the method was successfully applied to the determination of nitrite and nitrate in water samples. The results obtained were in good agreement with those achieved by a spectrophotometric reference method at the 95% confidence level. Standard addition method was also applied to the freshwater samples and the recovery values were found in the range of 92-109% and 94-105% for nitrite and nitrate respectively.

Flow-injection determination of vanadium in seawater samples with acidic potassium permanganate chemiluminescence.

Chemiluminescence from the vanadium and potassium permanganate reaction was studied under acidic conditions to develop a sensitive method for vanadium determination using the formaldehyde enhancement effect. The method was successfully applied to the determination of vanadium in seawater. Experimental parameters were optimized, including acid concentration, potassium permanganate and formaldehyde concentration. A linear calibration graph was obtained in the concentration range of 2.0 x 10(-9)-5 x 10(-6) M with relative standard deviations (n = 4) in the range of 1.8-3.1%. The detection limit (3sigma blank) was 8.0 x 10(-10) mol L(-1) with a sample throughput of 100 h(-1). The effect of salinity and various interfering cations and anions were studied. The method was applied to determine total dissolved vanadium in seawater samples and certified reference materials after online reduction with amalgamated zinc column.

Determination of thiram in natural waters using flow-injection with cerium(IV)-quinine chemiluminescence system.

A simple and rapid flow-injection chemiluminescence method has been developed for the determination of dithiocarbamate fungicide thiram based on the chemiluminescence reaction of thiram with ceric sulfate and quinine in aqueous sulfuric acid. The present method allowed the determination of thiram in the concentration range of 7.5-2500 ng/mL and the detection limit (signal-to-noise ratio = 3) was 7.5 ng/mL with sample throughput of 120/h. The relative standard deviation was 2.5% for 10 replicate analyses of 500 ng/mL thiram. The effects of foreign species including various anions and cations present in water at environmentally relevant concentrations and some pesticides were also investigated. The proposed method was applied to determine thiram in spiked natural waters using octadecyl bonded phase silica (C(18)) cartridges for solid-phase extraction. The recoveries were in the range 99 +/- 1 to 104 +/- 1%.

Flow-injection determination of vitamin A in pharmaceutical formulations using Tris(2,2'-bipyridyl)Ru(II)-Ce(IV) chemiluminescence detection.

A flow injection method with chemiluminescence detection is reported for the determination of vitamin A. The method is based on the enhancement effect of vitamin A on chemiluminescence of tris(2,2'-bipyridyl)Ru(II)-Ce(IV) in acidic medium. The proposed procedure is used to quantitate vitamin A in the range 1.0-100 x 10(-6) mol/L with a correlation coefficient of 0.9991 (n = 9) and relative standard deviation in the range 1.2-2.3% (n = 4). The limit of detection (3 x blank) was 8.0 x 10(-8) mol/L( )with a sample throughput of 100/h. The effect of common excipients used in pharmaceutical formulations and some clinically important compounds was also studied. The method was applied to determine vitamin A in pharmaceutical formulations and the results obtained were in reasonable agreement with the amount quoted. The results were compared using spectrophotometric method and no significant difference was found between the results of the two methods at 95% confidence limit.

Photodegradation and flow-injection determination of dithiocarbamate fungicides in natural water with chemiluminescence detection.

A simple and rapid flow-injection method is reported for the determination of dithiocarbamate fungicides (maneb, nabam and thiram) based on chemiluminescence detection. The method involves the photodegradation of dithiocarbamate fungicides via UV light in an alkaline medium. Photoproducts are then reacted with luminol in the absence of an oxidant. Linear calibration graphs were obtained in the range 0.01 - 4.0 mg L(-1) for maneb and nabam and 0.05 - 1.0 mg L(-1) for thiram with relative standard deviations (n = 4) in the range 1.0 - 2.6%. The detection limits (S/N = 3) of maneb, nabam and thiram were 10, 8.0 and 5.0 ng mL(-1), respectively, with a sample throughput of 100 h(-1). The method was successfully applied to determine these dithiocarbamate fungicides in spiked natural water samples.