Supalax Srijaranai

Determination of six pyrethroid insecticides in fruit juice samples using dispersive liquid–liquid microextraction combined with high performance liquid chromatography

Dispersive liquid-liquid microextraction (DLLME) coupled to high performance liquid chromatography (HPLC) with UV detection was applied for the determination of six pyrethroids (tetramethrin, fenpropathrin, cypermethrin, deltamethrin, fenvalerate and permethrin) in various fruit juices including apple, red grape, orange, kiwi, passion fruit, pomegranate and guava juice. Six pyrethroids were separated within 30 min using a Waters Atlantis T3 column under an isocratic elution of acetonitrile-water (72:28). The parameters affecting extraction efficiency of the DLLME method such as type of disperser and extraction solvent, volume of disperser and extraction solvent and centrifugation time were investigated. Under the optimum conditions, 5.00 mL of sample solution, 300 μL of chloroform as extraction solvent and 1.25 mL of methanol as dispersive solvent gave high enrichment factor in the range of 62-84. Good linearity was obtained from 2 to 1,500 μg/L (r(2)>0.995). The mean recoveries of the pyrethroids evaluated by fortification of real samples were in the range of 84-94%. The limits of detection ranging from 2 to 5 μg/L are sufficient to analyze pyrethroid residues at the maximum residue limits (MRLs) established by the European Union (EU) in fruit juices. The proposed method can be applied to direct determination of pyrethroid residues in fruit juices.

Enhanced chromatographic selectivity for Na+ ions on a calixarene-bonded silica phase

Abstract Functional esters of calixarenes, which are phenolic metacyclophanes annulated by a single methylene bridge, are immobilised onto silica particles for use in the separation of alkali metal ions by high performance liquid chromatography with conductivity detection. The immobilisation of tetrameric and hexameric calixarene ethyl esters was carried out using the triethoxy silane derivatives of p-allylcalix[n]arene ethyl esters. At an injected concentration of 10−2M, optimum selectivity for Na ions was achieved using a mobile phase of 30% MeOH/H2O with the calix[4]arene ester stationary phase. A mixture of four alkali metal chlorides is shown on injection to give a clear separation of Na+ from the other unresolved ions, the retention order being Na+ » K+ > Cs+ > Li+ = to.

Vortex-assisted low density solvent based demulsified dispersive liquid-liquid microextraction and high-performance liquid chromatography for the determination of organophosphorus pesticides in water samples.

A simple, rapid, effective and eco-friendly preconcentration method, vortex-assisted low density solvent based solvent demulsified dispersive liquid-liquid microextraction (VLDS-SD-DLLME), followed by high performance liquid chromatography-diode array detector (HPLC-DAD) analysis, has been developed for the first time for the determination of four organophosphorus pesticides (OPPs) (e.g., azinphos-methyl, parathion-methyl, fenitrothion and diazinon) in environmental water samples. In this preconcentration procedure, an emulsion was obtained after the mixture of extraction solvent (1-dodecanol) and dispersive solvent (acetonitrile, ACN) was injected rapidly into 10 mL of the sample solution. The vortex agitator aided the dispersion of the extraction solvent into the sample solution. After the formation of an emulsion, the demulsifier (ACN) was added, resulting in the rapid separation of the mixture into two phases without centrifugation. Under optimal conditions, the proposed method provided high extraction efficiency (90-99%), good linearity range (0.5-500 ng mL(-1)), low limits of detection (0.25-1 ng mL(-1)) and good repeatability and recoveries were obtained.

Vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction with solidification of floating organic droplet combined with HPLC for the determination of neonicotinoid pesticides.

A microextraction procedure based on vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction with solidification of floating organic droplet (VSLLME-SFO) for preconcentration of neonicotinoid pesticides, including acetamiprid, clotianidin, nitenpyram, imidacloprid, and thiamethoxam, has been developed. In VSLLME-SFO process, the addition of surfactant (as an emulsifier), could be enhance the mass-transfer from the aqueous solution into the extraction solvent. The extraction solvent could be dispersed into the aqueous by vortex process. Other experimental parameters affected the extraction efficiency, including the kind and concentration of salt, concentration and volume of HCl, kind and concentration of surfactant and its volume, kind and volume of extraction solvent, vortex time and the centrifugation extraction time, were also optimized. The optimum extraction conditions of VSLLME-SFO were 10.00 mL of sample, 0.3% (w/v) Na2SO4, 50 µL of 0.050 mol L(-1) SDS, 1.0 mol L(-1) HCl (400 µL), 150 µL of octanol, vortex time 1 min and centrifugation time 10 min. The sediment phase was analyzed by subjecting it to HPLC using a mobile phase of 25% acetonitrile in water, at a flow rate of 1.0 mL min(-1), and photodiode array detection at 254 nm. Under the optimum extraction conditions, high enrichment factors (20-100 fold) and low limit of detection (0.1-0.5 μg L(-1)) could be obtained. This method provided high sensitivity, low toxic organic solvents used, and simplicity of the extraction processes. The proposed method was successfully applied in the analysis of neonicotinoids in fruit juice and water samples.

Mixed micelle-cloud point extraction for the analysis of penicillin residues in bovine milk by high performance liquid chromatography

A mixed micelle-cloud point extraction (MM-CPE) has been developed for the analysis of penicillin antibiotics (ampicillin, penicillin G, oxacillin, and cloxacillin) in milk samples using Triton X-114 (TX-114) and cethyl trimethylammonium bromide (CTAB) as the mixed micellar extractant. The parameters affecting the MM-CPE that were investigated including solution pH, CTAB concentration, TX-114 concentration, electrolyte salt, equilibration temperature and incubation time. The optimum MM-CPE conditions were: 10 mmol L(-1) phosphate buffer pH 8, 0.06% (w/v) CTAB, 1.5% (w/v) TX-114, and 7% (w/v) Na(2)SO(4), and 5 min equilibration at 40 degrees C. The separation of penicillins was achieved within 8 min under the HPLC conditions: a Vydac C(18) column, isocratic elution of 5 mmol L(-1) phosphate buffer (pH 6.6) and methanol (55:45, v/v), and a flow rate of 1 mL min(-1), with photodiode array detection at 215 and 244 nm. Under the selected condition, the proposed method gave linear calibrations in the range 0.002-10 microg mL(-1) with correlation coefficients greater than 0.999. Limits of detection (LOD) were 2-3 ng mL(-1), and 15-40-fold enhancement compared to that without preconcentration. Good reproducibility was achieved with relative standard deviation <5% for peak area and <3% for retention time. High accuracy, with recoveries higher than 80%, was obtained. The proposed mixed micelle-CPE-HPLC method has shown to be of high potential for the analysis of penicillin residues in milk with LOD comparable to the established maximum residue limits (4-30 ng mL(-1)).

Micellar electrokinetic chromatography with amperometric detection and off-line solid-phase extraction for analysis of carbamate insecticides.

Six selected primary carbamate insecticides, methomyl, carbaryl, carbofuran, propoxur, isoprocarb, and promecarb, were hydrolyzed in alkaline solution, resulting in electroactive derivatives detectable at a platinum (Pt) electrode poised at +0.8 V vs Ag/AgCl (3 M NaCl). The Pt electrode was inserted into a small electrochemical cell and positioned close to the capillary outlet as an end-column detector to detect the carbamate derivatives after electrophoretic separation. Based on their predicted pK(a) values and aqueous solubilities, micellar electrokinetic chromatography (MEKC) was optimized for baseline separation of the derivatives using 20 mM borate, pH 10.2 containing 20 mM sodium dodecyl sulfate as a running buffer. When combined with solid-phase extraction (SPE) on octadecyl silica, a preconcentration factor of 100-fold achieved detection to 0.5 microM methomyl and to 0.01 microM for the remaining five pesticides, significantly below the level regulated by government agencies of most countries. The SPE-MEKC method when applied to the separation and analysis of spiked river water and soil samples, yielded results with excellent reproducibility, recovery and selectivity.

Determination of organophosphorus pesticides using dispersive liquid-liquid microextraction combined with reversed electrode polarity stacking mode-micellar electrokinetic chromatography.

A rapid and sensitive method using two preconcentration techniques, dispersive liquid-liquid microextraction (DLLME) followed by reversed electrode polarity stacking mode (REPSM) was developed for the analysis of five organophosphorus pesticides (OPPs) by micellar electrokinetic chromatography (MEKC). Parameters that affect the efficiency of the extraction in DLLME and preconcentration by REPSM, such as the kind and volume of the extraction and disperser solvents, salt addition, sample matrix and injection time were investigated and optimized. Under the optimum conditions, the enrichment factors were obtained in the range from 477 to 635. The linearity of the method for parathion, azinphos and fenitrithion was in the range of 20-1000 ng mL(-1), and for malathion and diazinon in the range of 50-1000 ng mL(-1), with correlation coefficients (r(2)) ranging from 0.9931 to 0.9992. The limits of detecton (LODs) at a signal-to-noice ratio of 3 ranged from 3 to 15 ng mL(-1). The relative recoveries of five OPPs from water samples at spiking levels of 20 and 200 ng mL(-1) for parathion, azinphos and fenitrithion, and 50 and 500 ng mL(-1) for malathion and diazinon, were 69.5-103%. The proposed method provided high enrichment factors, good precision and accuracy with a short analysis time.

Vortex-assisted low density solvent liquid-liquid microextraction and salt-induced demulsification coupled to high performance liquid chromatography for the determination of five organophosphorus pesticide residues in fruits.

A simple and rapid microextraction method, vortex-assisted low density solvent liquid-liquid microextraction and salt-induced demulsification (VLLME-SID) coupled to high performance liquid chromatography (HPLC) was developed for the determination of organophosphorus pesticide (OPP) residues in fruits. The studied OPPs were azinphos-methyl, parathion-methyl, fenitrothion, diazinon and chlorpyrifos. For VLLME-SID, a mixture of low density solvents (1-dodecanol and hexane) was used as the extraction solvent under vortex agitation for enhancing dispersion. After complete dispersion, the emulsion was formed and the OPPs were extracted into extraction solvent droplets. Then, the emulsion was quickly broken up into two clear phases after the addition of AlCl3 as a demulsifier. Centrifugation was not required in this procedure. Under the optimal conditions, high enrichment factors (180-282), low limit of detections (LODs) (0.05-1 ng mL(-1)) and good precision (RSD≤7% for retention time and peak area) were obtained. The proposed method was successfully applied to the analysis of OPP residues in fruit samples (watermelon, grape, and cantaloupe). The LODs for samples were in the range 0.0006-0.0015 mg kg(-1) which are below the established EU-MRLs (0.01-0.3 mg kg(-1)). Good recoveries were also obtained (80-104%).

Room temperature imidazolium ionic liquid: A solvent for extraction of carbamates prior to liquid chromatographic analysis

A simple and rapid method for preconcentration of carbamate insecticides, including methomyl, propoxur, carbofuran, carbaryl, isoprocarb, methiocarb and promecarb, has been developed. It was based on a liquid-liquid microextraction using a [C(4)MIM][PF(6)] room temperature ionic liquid as an extraction solvent prior to analysis by high performance liquid chromatography with UV detection. Experimental parameters affecting the extraction performance, such as the volumes of sample, extractant and dissolving solvent, and extraction time, were studied. Under the selected conditions, the enrichment factors in the range between 10 and 25 could be achieved with the limit of detection in the range of 2-40 μg L(-1), and with the relative standard deviations of lower than 0.6 and 10.2% for retention time and peak area, respectively. The proposed method offers advantages in reduction of the exposure danger to toxic solvents used in the conventional liquid-liquid extraction, simplicity of the extraction processes, rapidity, and sensitivity enhancement. The method was demonstrated to apply to the analysis of fruit and natural surface water samples.

A New Approach for Removing Anionic Organic Dyes from Wastewater Based on Electrostatically Driven Assembly

A conceptually new approach for an efficient removal of anionic organic dyes from wastewater using layered double hydroxides (LDHs) through their formation is presented. Acid yellow 25 (AY25) was used as anionic organic dye model molecules. As a result of the electrostatic induction, the removal mechanism involved a concurrent incorporation of AY25 molecules into the interlayer of LDHs during their structural arrangement, where Mg(2+) and Al(3+) ions were utilized to construct the base of LDHs in an alkaline solution. It was found that the molar stoichiometry of all precursors was a key factor affecting the removal efficiency. Within 5 min removal time, this method still maintained high removal efficiency of over 97% and provided a removal capacity of ∼186 mg g(-1), comparable to that of other LDH-based methods. Also, almost complete dye recovery was simply achieved by anionic exchange with common anions (Cl(-), NO3(-), and CO3(2-)). Additionally, the present technique is straightforward, cost-effective, and environmentally friendly since it avoids the synthesis step of sorbents, thus significantly saving time, chemicals, and energy. Hence, this strategy not only exhibits the alternative exploitation of LDHs, but also provides new insights into the removal of contaminants from wastewater.