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1.
Article in English | MEDLINE | ID: mdl-34655891

ABSTRACT

In this study, we have demonstrated a separation of positional isomers of some derivatives of alkoxyphenylcarbamic acid. These compounds belong to drugs with local anesthetics activity. The low volatility compounds were analysed by a Thin Layer Chromatography (TLC) and Ion Mobility Spectrometry (IMS) using diode laser desorption for sample introduction to IMS. This combined approach allowed the identification of compounds. Also, we have carried out IMS studies of all compounds and determined their ion mobilities The ion mobilities were increasing with the geometry change from position ortho to para of alkoxy chain, which is in agreement with their different collision cross section (CCS).


Subject(s)
Chromatography, Thin Layer/methods , Ion Mobility Spectrometry/methods , Phenylcarbamates/analysis , Phenylcarbamates/chemistry , Isomerism
2.
Nat Commun ; 12(1): 132, 2021 01 08.
Article in English | MEDLINE | ID: mdl-33420104

ABSTRACT

The use of pesticides to reduce mosquito vector populations is a cornerstone of global malaria control efforts, but the biological impact of most pesticides on human populations, including pregnant women and infants, is not known. Some pesticides, including carbamates, have been shown to perturb the human immune system. We measure the systemic absorption and immunologic effects of bendiocarb, a commonly used carbamate pesticide, following household spraying in a cohort of pregnant Ugandan women and their infants. We find that bendiocarb is present at high levels in maternal, umbilical cord, and infant plasma of individuals exposed during pregnancy, indicating that it is systemically absorbed and trans-placentally transferred to the fetus. Moreover, bendiocarb exposure is associated with numerous changes in fetal immune cell homeostasis and function, including a dose-dependent decrease in regulatory CD4 T cells, increased cytokine production, and inhibition of antigen-driven proliferation. Additionally, prenatal bendiocarb exposure is associated with higher post-vaccination measles titers at one year of age, suggesting that its impact on functional immunity may persist for many months after birth. These data indicate that in utero bendiocarb exposure has multiple previously unrecognized biological effects on the fetal immune system.


Subject(s)
Environmental Pollutants/adverse effects , Fetus/immunology , Maternal Exposure/adverse effects , Measles/blood , Pesticides/adverse effects , Adult , Antibodies, Viral/blood , Child, Preschool , Clinical Trials, Phase III as Topic , Female , Fetal Blood/chemistry , Follow-Up Studies , Humans , Immune System/drug effects , Immunogenicity, Vaccine , Immunoglobulin G/blood , Infant , Infant, Newborn , Malaria/prevention & control , Maternal-Fetal Exchange/immunology , Measles/immunology , Measles/prevention & control , Measles Vaccine/administration & dosage , Measles Vaccine/immunology , Mosquito Control/methods , Pesticides/analysis , Phenylcarbamates/adverse effects , Phenylcarbamates/analysis , Pregnancy , Randomized Controlled Trials as Topic
3.
J Pharm Biomed Anal ; 185: 113244, 2020 Jun 05.
Article in English | MEDLINE | ID: mdl-32193041

ABSTRACT

Currently, controllable linker cleavage at the target site will facilitate the clinical treatment of cancer. Dual-functional prodrugs in combination of carbohydrate as targeting group and pH-sensitive cleavable linker are desired in clinical development. Here, a qualified structure of N-phenylcarbamate-d-gluconhydroximo-1,5-lactam was employed and proved to be a potential candidate prodrug in the drug design. To proof this concept, the possible mechanism of Beckmann rearrangement and the degraded products were confirmed by HPLC and LC-MS under the acid condition mimic lysosome. Hence, the strategy of d-gluconhydroximo-1,5-lactam as a prodrug carrier fabricated with interested drugs will provide a great potential approach for chemotherapy.


Subject(s)
Drug Carriers/analysis , Gluconates/analysis , Lactams/analysis , Phenylcarbamates/analysis , Prodrugs/analysis , Antineoplastic Agents/administration & dosage , Chromatography, High Pressure Liquid/methods , Drug Carriers/chemistry , Drug Compounding/methods , Drug Design , Gluconates/chemistry , Humans , Hydrogen-Ion Concentration , Hydrolysis , Lactams/chemistry , Mass Spectrometry/methods , Neoplasms/drug therapy , Phenylcarbamates/chemistry , Prodrugs/chemistry , Proof of Concept Study
4.
Anal Chim Acta ; 1103: 84-96, 2020 Mar 22.
Article in English | MEDLINE | ID: mdl-32081192

ABSTRACT

We report herein the design of a novel electrochemical sensing strategy for sensitive detection of pesticide based on graphitic carbon nitride (g-C3N4)/graphene oxide(GO) nanocomposite covalently bound to a ferrocene containing dendrimer(Fc-TED). The g-C3N4 with sufficient N atoms for providing lone pairs of electrons to an electron acceptor so as to enhance the adsorption towards organic molecules. The Fc-TED dendrimers with the native redox signaling center (Fe3+/Fe2+) can increase the electron transition of g-C3N4 from valence to conduction band. While GO can accelerate the electron transfer from g-C3N4 surface and Fc-TED to glassy carbon electrode(GCE), which would amplify the electrochemical signal of g-C3N4/GO/Fc-TED/GCE sensor and then improve the sensing performance. It is found that the fabricated electrode demonstrated an admirable electrochemical sensing performance towards metolcarb in terms of low detection limit (8.3 nM), wide concentration range (0.045-213 µM) and rapid response time (2s). The proposed sensor can selectively detect the metolcarb and easily discriminated metolcarb from the possible interfering species. The practical applicability of the sensor was successfully evaluated in real vegetable sample and achieved satisfactory recoveries with good precision and accuracy.


Subject(s)
Dendrimers/chemistry , Electrochemical Techniques/methods , Ferrous Compounds/chemistry , Metallocenes/chemistry , Nanocomposites/chemistry , Pesticide Residues/analysis , Phenylcarbamates/analysis , Biosensing Techniques/methods , Electrochemical Techniques/instrumentation , Electrodes , Food Contamination/analysis , Graphite/chemistry , Limit of Detection , Nitrogen Compounds/chemistry , Oxidation-Reduction , Pesticide Residues/chemistry , Phenylcarbamates/chemistry , Spinacia oleracea/chemistry
5.
Electrophoresis ; 40(12-13): 1648-1655, 2019 07.
Article in English | MEDLINE | ID: mdl-30924161

ABSTRACT

A strategy on amperometric detection for CZE of phenol carbamates as model analytes with a facile in-line thermal hydrolysis was presented, in which a thermal hydrolysis, subsequent CZE separation and final column-end amperometric detection were accomplished in an intact capillary. Key parameters of hydrolysis dynamics of carbamates and electrochemical detection of the hydrolysates were studied, as well as electrophoretic conditions. Under the optimal conditions, the capillary was utilized as chambers for in situ hydrolysis, CZE separation, and electrochemical detection. The successive separation of hydrolysates of five carbamates (propoxur, carbofuran, 3-OH-carbofuran, carbaryl and bendiocarb) were achieved within 17 min. Applied to vegetable samples, the recoveries of carbamates fortified at 0.02 and 0.05 mg/kg were ranging in 88-107.2 and 86.3-107.3%, respectively. The success in the implementation of such a scheme resulted in a simple instrument as compared with those current analytical methods with post-column derivization or pre-column hydrolysis, or online enrichment in chip, respectively. This protocol might possess a potential utility for the sensitive amperometric detection of phenol carbamates.


Subject(s)
Electrophoresis, Capillary/methods , Pesticide Residues/analysis , Phenylcarbamates/analysis , Electrophoresis, Capillary/instrumentation , Equipment Design , Hot Temperature , Hydrolysis , Limit of Detection , Linear Models , Pesticide Residues/chemistry , Pesticide Residues/isolation & purification , Phenylcarbamates/chemistry , Phenylcarbamates/isolation & purification , Reproducibility of Results , Vegetables/chemistry
6.
Ecotoxicol Environ Saf ; 165: 459-466, 2018 Dec 15.
Article in English | MEDLINE | ID: mdl-30218969

ABSTRACT

A sensitive and fast ultrasound-assisted dispersive liquid-liquid microextraction procedure combined with ion mobility spectrometry has been developed for the simultaneous extraction and determination of bendiocarb and azinphos-ethyl. Experimental parameters affecting the analytical performance of the method were optimized: type and volume of extraction solvent (chloroform, 150 µL), pH (9.0), type and volume of buffer (ammonium buffer pH = 9.0, 4.5 mL) and extraction time (3.0 min). Under optimum conditions, the linearity was found to be in the range of 2-40 and 6-100 ng/mL and the limits of detection (LOD) were 1.04 and 1.31 ng/mL for bendiocarb and azinphos-ethyl, respectively. The method was successfully validated for the analysis of bendiocarb and azinphos-ethyl in different samples such as waters, soil, food and beverage samples.


Subject(s)
Azinphosmethyl/analogs & derivatives , Beverages/analysis , Environmental Monitoring/methods , Food/standards , Ion Mobility Spectrometry , Liquid Phase Microextraction/methods , Phenylcarbamates/analysis , Soil/chemistry , Ultrasonics , Water/analysis , Azinphosmethyl/analysis , Environmental Pollutants/analysis , Food Analysis/methods , Limit of Detection , Solvents/chemistry
7.
Pest Manag Sci ; 72(11): 2099-2109, 2016 Nov.
Article in English | MEDLINE | ID: mdl-27299476

ABSTRACT

BACKGROUND: The objective was to refine the standard regulatory exposure scenario used in plant protection product authorisations by developing a more realistic landscape-related GIS-based exposure assessment for terrestrial non-target arthropods. We quantified the proportion of adjacent off-target area in agricultural landscapes potentially exposed to insecticide drift from applications of the active substance fenoxycarb. High-resolution imagery, landscape classification and subsequent stepwise analysis of a whole landscape using drift and interception functions were applied to selected areas in representative fruit-producing regions in Germany. RESULTS: Even under worst-case assumptions regarding treated area, use rate and drift, less than 12% of the non-agricultural habitat area would potentially be exposed to fenoxycarb drift above regulatory acceptable concentrations. Additionally, if the filtering effect of tall vegetation were taken into account, this number would decrease to 6.6%. Further refinements to landscape elements and application conditions indicate that less than 5% of the habitat area might be exposed above regulatory acceptable concentrations, meaning that 95% of the non-agricultural habitat area will be unimpacted (i.e. no unacceptable effects) and can serve as refuge for recolonisation. CONCLUSION: Approaches and tools are proposed for standardisable and transparent refinements in regulatory risk assessments on the landscape level. © 2016 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Subject(s)
Environmental Exposure , Environmental Monitoring/methods , Environmental Pollutants/analysis , Insecticides/analysis , Phenylcarbamates/analysis , Agriculture , Germany , Risk Assessment/methods
8.
Food Chem ; 201: 153-9, 2016 Jun 15.
Article in English | MEDLINE | ID: mdl-26868560

ABSTRACT

The effects of various washing procedures, including stagnant, running, and stagnant and running tap water, and the use of washing solutions and additives, namely NaCl (1% and 2%), vinegar (2%, 5%, and 10%), detergent (0.5% and 1%), and charcoal (1% and 2%), on the reduction rate of diethofencarb were estimated in field-incurred crown daisy, a model of leafy vegetables, grown under greenhouses located in 3 different areas (Gwangju, Naju, and Muan). The original Quick, Easy, Cheap, Effective, Rugged, and Safe "QuEChERS" method was modified for extraction and liquid chromatography-tandem mass spectrometry (LC/MS/MS) was used for analysis. The recovery of diethofencarb in unwashed and washed samples was satisfactory and ranged between 84.28% and 115.32% with relative standard deviations (RSDs) of <6%. The residual levels decreased following washing with stagnant, running, and stagnant+running tap water (i.e., decline in levels increased from 65.08% to 85.02%, 69.99 to 86.79, and 74.75 to 88.96, respectively). The percentage of decline increased and ranged from 77.46% to 91.19% following washing with various solutions. Application of 1% detergent was found to be the most effective washing method for reducing the residues in crown daisy. Additionally, washing with stagnant and running tap water or even stagnant water for 5 min might reduce the residue levels substantially, making the prepared food safe for human consumption.


Subject(s)
Chrysanthemum/chemistry , Fungicides, Industrial/analysis , Pesticide Residues/analysis , Phenylcarbamates/analysis , Chromatography, Liquid/methods , Plant Leaves/chemistry , Tandem Mass Spectrometry/methods , Vegetables/chemistry
9.
Talanta ; 142: 124-30, 2015 Sep 01.
Article in English | MEDLINE | ID: mdl-26003701

ABSTRACT

A new on-line SPE-HPLC method using fused-core columns for on-line solid phase extraction and large volume sample injection for increasing the sensitivity of detection was developed for the determination of insecticides fenoxycarb and cis-, trans-permethrin in surface waters. The separation was carried out on fused-core column Phenyl-Hexyl (100×4.6 mm), particle size 2.7 µm with mobile phase acetonitrile:water in gradient mode at flow rate 1.0 mL min(-1), column temperature 45°C. Large volume sample injection (1500 µL) to the extraction dimension using short precolumn Ascentis Express RP C-18 (5×4.6 mm); fused-core particle size 2.7 µm allowed effective sample preconcentration and efficient ballast sample matrix removal. The washing mobile phase consisting of a mixture of acetonitrile:water; 30:70, (v/v) was pumped at flow rate of 0.5 mL min(-1) through the extraction precolumn to the waste. Time of the valve switch for transferring the preconcentrated sample zone from the extraction to the separation column was set at 3rd min. Elution of preconcentrated insecticides from the extraction precolumn and separation on the analytical column was performed in gradient mode. Linear gradient elution started from 40% of acetonitrile at time of valve switch from SPE column (3rd min) to 95% of acetonitrile at 7th min. Synthetic dye sudan I was chosen as an internal standard. UV detection at wavelength 225 nm was used and the method reached the limits of detection (LOD) at ng mL(-1) levels for both insecticides. The method showing on-line sample pretreatment and preconcentration with highly sensitive determination of insecticides was applied for monitoring of fenoxycarb and both permethrin isomers in different surface water samples in Czech Republic. The time of whole analysis including on-line extraction, interferences removal, chromatography separation and system equilibration was less than 8 min.


Subject(s)
Insecticides/analysis , Permethrin/analysis , Phenylcarbamates/analysis , Water Pollutants, Chemical/analysis , Chromatography, High Pressure Liquid , Czech Republic , Environmental Monitoring , Lakes/analysis , Online Systems , Rivers/chemistry , Solid Phase Extraction
10.
Biosens Bioelectron ; 64: 247-54, 2015 Feb 15.
Article in English | MEDLINE | ID: mdl-25240126

ABSTRACT

In this work, we presented a three-dimensional (3D) molecularly imprinted electrochemical sensor (MIECS) with novel strategy for ultrasensitive and specific quantification of metolcarb based on prussian blue (PB) mediated amplification combined with signal enhancement of ordered mesoporous carbon. The molecularly imprinted polymers were synthesized by electrochemically induced redox polymerization of para aminobenzoic acid (p-ABA) in the presence of template metolcarb. Ordered mesoporous carbon material (CMK-3) was introduced to enhance the electrochemical response by improving the structure of the modified electrodes and facilitating charge transfer processes of PB which was used as an inherent electrochemical active probe. The modification process for the working electrodes of the MIECS was characterized by scanning electron microscope (SEM) and cyclic voltammetry (CV), and several important parameters controlling the performance of the MIECS were investigated and optimized in detail. The MIECS with 3D structure had the advantages of ease of preparation, high porous surface structure, speedy response, ultrasensitivity, selectivity, reliable stability, good reproducibility and repeatability. Under the optimal conditions, the MIECS offered an excellent current response for metolcarb in the linear response range of 5.0 × 10(-10)-1.0 × 10(-4) mol L(-1) and the limit of detection (LOD) was calculated to be 9.3 × 10 (-11)mol L(-1) (S/N = 3). The proposed MIECS has been successfully applied for the determination of metolcarb in real samples with satisfactory recoveries. Furthermore, the construction route of this ultrasensitive 3D MIECS may provide a guideline for the determination of non-electroactive analytes in environmental control and food safety.


Subject(s)
Carbon/chemistry , Conductometry/instrumentation , Electrodes , Ferrocyanides/chemistry , Molecular Imprinting/methods , Phenylcarbamates/analysis , Equipment Design , Equipment Failure Analysis , Pesticides/analysis , Phenylcarbamates/chemistry , Porosity , Reproducibility of Results , Sensitivity and Specificity
11.
Anal Bioanal Chem ; 406(14): 3451-8, 2014 May.
Article in English | MEDLINE | ID: mdl-24756818

ABSTRACT

A rapid and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for determination of Meserine ((-)-meptazinol phenylcarbamate), a novel potent inhibitor of acetylcholinesterase (AChE), was developed, validated, and applied to a pharmacokinetic study in mice brain. The lower limit of quantification (LLOQ) was 1 ng mL(-1) and the linear range was 1-1,000 ng mL(-1). The analyte was eluted on a Zorbax SB-Aq column (2.1 × 100 mm, 3.5 µm) with the mobile phase composed of methanol and water (70:30, v/v, aqueous phase contained 10 mM ammonium formate and 0.3% formic acid) using isocratic elution, and monitored by positive electrospray ionization in multiple reaction monitoring (MRM) mode. The flow rate was 0.25 mL min(-1). The injection volume was 5 µL and total run time was 4 min. The relative standard deviation (RSD) of intraday and interday variation was 2.49-7.81 and 3.01-7.67%, respectively. All analytes were stable after 4 h at room temperature and 6 h in autosampler. The extraction recoveries of Meserine in brain homogenate were over 90%. The main brain pharmacokinetic parameters obtained after intranasal administration were T max = 0.05 h, C max = 462.0 ± 39.7 ng g(-1), T 1/2 = 0.4 h, and AUC(0-∞) = 283.1 ± 9.1 ng h g(-1). Moreover, Meserine was distributed rapidly and widely into brain, heart, liver, spleen, lung, and kidney tissue. The method is validated and could be applied to the pharmacokinetic and tissue distribution study of Meserine in mice.


Subject(s)
Alzheimer Disease/metabolism , Brain/drug effects , Chromatography, Liquid , Meptazinol/analogs & derivatives , Phenylcarbamates/analysis , Phenylcarbamates/pharmacokinetics , Tandem Mass Spectrometry , Animals , Area Under Curve , Brain/metabolism , Calibration , Chemistry, Pharmaceutical/methods , Female , Formates/chemistry , Male , Meptazinol/analysis , Meptazinol/pharmacokinetics , Mice , Phenylcarbamates/chemistry , Quality Control , Reproducibility of Results , Spectrometry, Mass, Electrospray Ionization , Temperature , Tissue Distribution
12.
Biomed Chromatogr ; 28(11): 1431-90, 2014 Nov.
Article in English | MEDLINE | ID: mdl-24515838

ABSTRACT

Alzheimer's disease (AD) is a neurological disorder and is the most frequent type of dementia among elderly people. Donepezil, rivastigmine, galantamine, tacrine and memantine are the US Food and Drug Administration approved oral drugs used in the treatment of AD. Quantitation of these drugs in various biological matrices and monitoring them in long-term treatment is essential to titer the dose of these drugs and ensure patient compliance. This review provides a comprehensive account of various HPLC and LC-MS/MS assays, which have been successfully employed to measure the drug levels in various biological matrices arising from preclinical and clinical studies. In addition, this review collates various considerations such as internal standard selection, extraction schemes, matrix effect, selectivity evaluation and optimization of mass spectrometric conditions to enable the development of sound bioanalytical methods for quantitation of Alzheimer's drugs. Overall LC-MS/MS methods have proven to be the choice of bioanalytical method for the quantification of Alzheimer's drugs in both preclinical and clinical studies. In conclusion, important features of LC-MS/MS methodology for Alzheimer's drugs include shortened analysis time, increased throughput, selectivity and lower cost of analysis.


Subject(s)
Alzheimer Disease/drug therapy , Cholinesterase Inhibitors/analysis , Chromatography, High Pressure Liquid/methods , Neuroprotective Agents/analysis , Nootropic Agents/analysis , Tandem Mass Spectrometry/methods , Cholinesterase Inhibitors/therapeutic use , Donepezil , Galantamine/analysis , Galantamine/therapeutic use , Humans , Indans/analysis , Indans/therapeutic use , Neuroprotective Agents/therapeutic use , Nootropic Agents/therapeutic use , Phenylcarbamates/analysis , Phenylcarbamates/therapeutic use , Piperidines/analysis , Piperidines/therapeutic use , Rivastigmine
13.
Anal Sci ; 29(11): 1061-6, 2013.
Article in English | MEDLINE | ID: mdl-24212732

ABSTRACT

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.


Subject(s)
Coordination Complexes/chemistry , Flow Injection Analysis , Luminescent Measurements/methods , Pesticides/analysis , Phenylcarbamates/analysis , Thiram/analysis , Water Pollutants, Chemical/chemistry , Flow Injection Analysis/instrumentation , Luminescence , Luminescent Measurements/instrumentation , Molecular Structure , Solid Phase Extraction/instrumentation
14.
Food Chem Toxicol ; 60: 419-23, 2013 Oct.
Article in English | MEDLINE | ID: mdl-23941774

ABSTRACT

The aim of this study is to ascertain the in vitro bioavailablity of pesticides that regulate and inhibit the growth of insects--flufenoxuron, lufenuron, pyriproxyfen and fenoxycarb--in grapes grown under good agricultural practice (GAP), while respecting the pre-harvest intervals (PHI) for critical conditions (CAP), in the most unfavorable conditions. The bioavailability of wines obtained from grapes in each assay and in standard solutions is also studied in order to establish matrix-related differences. Human gastric digestion, intestinal digestion and absorption were imitated. Porcine pepsin, porcine pancreatin, bile salts and semipermeable cellulose dialysis tubing were used. The analysis of the residues of the insecticides studied was performed by extraction with the QuEChERS method, and determination was with HPLC-MS. In all cases it was observed that the pesticides can be ordered according to their dialyzation capacity: fenoxycarb>pyriproxyfen>lufenuron>flufenoxuron. The different matrices can also be ordered according to the matrix effect they impose on the dialysis: grape>wine>standards. The highest percentages of dialyzation for grape and wine matrices are achieved for fenoxycarb (3.27%) and pyriproxifen (2.04%) in wine.


Subject(s)
Food Contamination/analysis , Insecticides/analysis , Pesticide Residues/analysis , Wine/analysis , Animals , Benzamides/analysis , Biological Availability , Chemical Phenomena , Food Handling/methods , Humans , Phenylcarbamates/analysis , Phenylurea Compounds/analysis , Pyridines/analysis , Renal Dialysis , Reproducibility of Results , Swine , Vitis
15.
Methods Mol Biol ; 970: 81-111, 2013.
Article in English | MEDLINE | ID: mdl-23283772

ABSTRACT

This chapter summarizes the application of polysaccharide-based chiral stationary phases (CSPs) for separation of enantiomers in high-performance liquid chromatography (HPLC). Since this book contains dedicated chapters on enantioseparations using supercritical fluid chromatography (SFC), capillary electrochromatography (CEC), and simulated moving bed (SMB) chromatography, the application of polysaccharide-based materials in these modes of liquid phase separation techniques are touched just superficially. More emphasis is directed toward a discussion of the optimization of polysaccharide-based chiral selectors, their attachment onto the carrier, and the optimization of the support. The optimization of the separation of enantiomers based on various parameters such as mobile phase composition and temperature is also discussed.


Subject(s)
Chromatography, High Pressure Liquid/methods , Polysaccharides/analysis , Polysaccharides/chemistry , Capillary Electrochromatography , Chromatography, Supercritical Fluid , Phenylcarbamates/analysis , Phenylcarbamates/chemistry , Stereoisomerism
16.
J Chromatogr A ; 1247: 10-7, 2012 Jul 20.
Article in English | MEDLINE | ID: mdl-22682952

ABSTRACT

A liquid-phase microextraction (LPME) methodology based on the use of porous polyvinylidene fluoride (PVDF) hollow fibres was developed for extracting seven pesticides from cucumbers. The seven pesticides include propoxur, carbofuran, atrazine, cyanatryn, metolachlor, prometryn and tebuconazole. The PVDF hollow fibre provides higher extraction efficiency due to its higher porosity and better solvent compatibility. A new desorption methodology was developed since some pesticides were absorbed by the wall pore of the PVDF. Ultra-high pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was used for pesticide analysis. In order to obtain high recoveries and enrichment factors of the analytes, several parameters such as method of sealing, acceptor phase (organic solvents), stirring speed, extraction time, salting out effect, desorption mode and time were optimized. A fast, simple method for closing fibre ends was practiced by using mechanical crimping. Pesticides were extracted from the sample to the organic solvent and then desorbed in a mixture of methanol:water (1:1 v/v) prior to chromatographic analysis. Limits of detection (LOD) for the multi-reaction-monitoring (MRM) mode of the method varies from 0.01 to 0.31 µg/kg with optimized sample preparation. Calibration curves are linear with R² ≥ 0.991. Enrichment factor of the hollow fibre LPME ranges from 100 to 147. Matrix effect has been considered and is in the range of 76-122%. The relative recoveries from cucumber samples are between 63% and 119% with the relative standard deviation (RSD, n=6) lower than 20%.


Subject(s)
Chromatography, High Pressure Liquid/methods , Cucumis sativus/chemistry , Liquid Phase Microextraction/methods , Pesticide Residues/analysis , Tandem Mass Spectrometry/methods , Acetamides/analysis , Acetamides/isolation & purification , Chloroform/chemistry , Limit of Detection , Linear Models , Pesticide Residues/isolation & purification , Phenylcarbamates/analysis , Phenylcarbamates/isolation & purification , Reproducibility of Results , Sodium Chloride/chemistry , Triazines/analysis , Triazines/isolation & purification , Triazoles/analysis , Triazoles/isolation & purification
17.
Electrophoresis ; 33(9-10): 1471-6, 2012 May.
Article in English | MEDLINE | ID: mdl-22648817

ABSTRACT

A capillary electrophoresis immunoassay (CEIA) was developed for the determination of trace metolcarb (MTMC) in food. The method was based on the competitive reactions between fluorescently labeled MTMC tracer and free MTMC with a limited amount of anti-MTMC antibody and the separation and determination by CE with LIF detector. A fluorescent reagent, FITC was labeled on MTMC to construct an immunofluorescent probe. CEIA experimental parameters such as the pH value and concentration of the running buffer and separation voltage as well as incubation time were systematically investigated. Under the optimized conditions, fluorescently labeled antigen and antibody bound could be well separated within 3 min using Na2B4O7/NaH2PO4 buffer (20:10 mmol/L, pH 9.0) for background electrolyte, 20 kV for the separation voltage, and 20°C for the column temperature. The linear range of the method was 0.25-50.0 µg/L with LOD 0.07 µg/L. The RSD for relative migration time and relative fluorescence intensity ratio were 2.90% (intraday) and 4.73% (intraday), respectively. The proposed method has been applied to determine the residue of MTMC in food samples with the satisfactory recovery.


Subject(s)
Electrophoresis, Capillary/methods , Food Analysis/methods , Immunoassay/methods , Pesticide Residues/analysis , Phenylcarbamates/analysis , Animals , Antibodies , Cucumis sativus/chemistry , Female , Hydrogen-Ion Concentration , Limit of Detection , Oryza/chemistry , Rabbits , Reproducibility of Results , Spectrometry, Fluorescence
18.
Environ Toxicol Chem ; 31(7): 1556-63, 2012 Jul.
Article in English | MEDLINE | ID: mdl-22505289

ABSTRACT

Although bats are reported as being threatened by pesticides, they are currently not considered in European Union pesticide risk assessments. The reason for that contradiction is probably related to the scarcity of information on bat activity in pesticide-treated fields and the pesticide residues on their food items. The authors recorded bat activity and measured pesticide residues on bat-specific food items following applications of two insecticides in an apple orchard. High activity levels of the common pipistrelle bat, a foraging habitat generalist, were detected. Airborne foragers and bats that take part of their food by gleaning arthropods from the vegetation were recorded frequently. The initial value and the decline of pesticide residues were found to depend on the arthropod type, their surface to volume ratio, their mobility, and the mode of action of the applied pesticide. The highest initial residue values were measured on foliage-dwelling arthropods. By following the toxicity-exposure ratio approaches of the current pesticide risk assessment, no acute dietary risk was found for all recorded bat species. However, a potential reproductive risk for bat species that include foliage-dwelling arthropods in their diet was indicated. The results emphasize the importance of adequately evaluating the risks of pesticides to bats, which, compared to other mammals, are potentially more sensitive due to their ecological traits.


Subject(s)
Chiroptera , Malus , Pesticide Residues/analysis , Animals , Arthropods , Diet , Environmental Exposure , European Union , Food Contamination/analysis , Insecticides/analysis , Phenylcarbamates/analysis , Risk Assessment
19.
Anal Chim Acta ; 724: 47-53, 2012 Apr 29.
Article in English | MEDLINE | ID: mdl-22483208

ABSTRACT

An in-syringe demulsified dispersive liquid-liquid microextraction (ISD-DLLME) technique was developed using low-density extraction solvents for the highly sensitive determination of the three trace fungicides (azoxystrobin, diethofencarb and pyrimethanil) in water samples by high performance liquid chromatography-mass spectrometry chromatography-diode array detector/electrospray ionisation mass spectrometry. In the proposed technique, a 5-mL syringe was used as an extraction, separation and preconcentration container. The emulsion was obtained after the mixture of toluene (extraction solvent) and methanol (dispersive solvent) was injected into the aqueous bulk of the syringe. The obtained emulsion cleared into two phases without centrifugation, when an aliquot of methanol was introduced as a demulsifier. The separated floating organic extraction solvent was impelled and collected into a pipette tip fitted to the tip of the syringe. Under the optimal conditions, the enrichment factors for azoxystrobin, diethofencarb and pyrimethanil were 239, 200, 195, respectively. The limits of detection, calculated as three times the signal-to-noise ratio (SN(-1)), were 0.026 µg L(-1) for azoxystrobin, 0.071 µg L(-1) for diethofencarb and 0.040 µg L(-1) for pyrimethanil. The repeatability study was carried out by extracting the spiked water samples at concentration levels of 0.02 µg mL(-1) for all the three fungicides. The relative standard deviations varied between 4.9 and 8.2% (n=5). The recoveries of all the three fungicides from tap, lake and rain water samples at spiking levels of 0.2, 1, 5 µg L(-1) were in the range of 90.0-105.0%, 86.0-114.0% and 88.6-110.0%, respectively. The proposed ISD-DLLME technique was demonstrated to be simple, practical and efficient for the determination of different kinds of fungicide residues in real water samples.


Subject(s)
Fungicides, Industrial/analysis , Liquid Phase Microextraction/methods , Pesticide Residues/analysis , Water Pollutants, Chemical/analysis , Chromatography, High Pressure Liquid , Emulsions , Environmental Monitoring , Limit of Detection , Mass Spectrometry , Methacrylates/analysis , Methanol/chemistry , Phenylcarbamates/analysis , Pyrimidines/analysis , Reproducibility of Results , Strobilurins , Toluene/chemistry
20.
J Chromatogr A ; 1234: 50-5, 2012 Apr 20.
Article in English | MEDLINE | ID: mdl-22349144

ABSTRACT

This article reports comparative high-performance liquid chromatographic separations of enantiomers with chiral stationary phases (CSPs) prepared by coating cellulose tris(4-chloro-3-methylphenylcarbamate) on totally porous and on core-shell type silica of comparable particle diameter. Several interesting observations were made: (1) the selectivity of separation was higher on core-shell type CSP compared to totally porous CSP at comparable content of chiral selector (polysaccharide derivative); (2) much flatter dependence of plate height on the mobile phase flow rate was observed for columns packet with CSP prepared with core-shell silica compared to the ones packed with CSPs prepared with totally porous particles; (3) at low mobile phase flow rates core-shell CSP provided lower resolving ability compared to a commercially available CSP having four times higher content of chiral selector along with higher retention of chiral analytes. However, at high flow rates core-shell type CSP performed similarly or better than the commercial column in regards of plate count (N) and peak resolution (R(s)) per column length and within a given total analysis time. The advantage of CSP prepared with core-shell silica is obvious from the viewpoint of plate numbers and resolution calculated per unit time (i.e. speed of analysis).


Subject(s)
Cellulose/analogs & derivatives , Chromatography, High Pressure Liquid/instrumentation , Chromatography, High Pressure Liquid/methods , Phenylcarbamates/analysis , Silicon Dioxide/chemistry , Benzene Derivatives/analysis , Benzene Derivatives/chemistry , Cellulose/analysis , Porosity , Stereoisomerism
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