Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 1.466
Filtrar
1.
J Chromatogr A ; 1627: 461387, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823095

RESUMO

A simple and efficient magnetic solid-phase extraction (MSPE) method was established with magnetic covalent organic framework (COF) as adsorbent to enrich organophosphorus pesticides from fatty milk samples, followed by the sensitive determination via LC-MS/MS. The key parameters influencing the MSPE efficiency were comprehensively investigated to afford an optimized procedure. All the target analytes could be captured directly by magnetic COF from milk without protein precipitation, making the pretreatment rapid and convenient. Systematic method validation demonstrated its satisfactory linearity, recoveries (80.0-105 %), and precision (RSDs <12.3 %). The method limits of quantification were 0.2-0.5 µg L-1. A comparison experiment to the reported solid-phase extraction fully verified the present MSPE more rapid, accurate, and environment-friendly. Furthermore, FT-IR and XPS analysis were performed to reveal the adsorption mechanisms of magnetic COF to organophosphorus pesticides, which could offer guidance on the rational design of COF adsorbent for various target analytes.


Assuntos
Fenômenos Magnéticos , Estruturas Metalorgânicas/química , Leite/química , Compostos Organofosforados/análise , Praguicidas/análise , Extração em Fase Sólida/métodos , Acetonitrilos/análise , Adsorção , Animais , Limite de Detecção , Espectroscopia Fotoeletrônica , Padrões de Referência , Reprodutibilidade dos Testes , Solventes/química , Espectroscopia de Infravermelho com Transformada de Fourier
2.
J Chromatogr A ; 1627: 461390, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823096

RESUMO

A dispersive solid phase extraction method was combined with deep eutectic solvent-based solidification of floating organic drop-dispersive liquid-liquid microextraction and used for the extraction/preconcentration of some organophosphorus pesticides residues from edible oil samples. The extracted analytes were quantified with gas chromatography-nitrogen phosphorous detector. In this procedure, the sample lipids are saponified with a sodium hydroxide solution and then the analytes are adsorbed onto a primary secondary amine sorbent. After that the analytes are desorbed with acetone as an elution/dispersive solvent and mixed with choline chloride: 3,3-dimethyl butyric acid deep eutectic solvent and the mixture is rapidly dispersed into deionized water. Then, the obtained cloudy solution is centrifuged and placed into an ice bath. The extraction solvent is solidified on the top of the solution. Finally, it is removed and dissolved in acetonitrile, and 1 µL of the solution is injected into the separation system. Validation of the method showed that limits of detection and quantification were in the ranges of 0.06-0.24 and 0.20-0.56 ng mL-1, respectively. Enrichment factors and extraction recoveries of the analytes ranged from 170-192 and 68-77%, respectively. The method had an acceptable precision with relative standard deviations less than ≤9.2% for intra- (n=6) and inter-day (n=6) precisions at four concentrations (3, 10, 50, and 250 ng mL-1, each analyte). Finally the method was used for determination of the analytes in five edible oil samples.


Assuntos
Microextração em Fase Líquida/métodos , Compostos Organofosforados/análise , Praguicidas/análise , Óleos Vegetais/química , Extração em Fase Sólida/métodos , Solventes/química , Acetonitrilos/química , Reprodutibilidade dos Testes , Hidróxido de Sódio/química , Soluções , Sonicação , Fatores de Tempo
3.
Food Chem ; 331: 127352, 2020 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-32652343

RESUMO

The influence of some additives, including metal ions, antioxidants, enzyme inhibitors and organic solvents, on the storage stability of four organophosphorus pesticides in cucumber samples were investigated. It was found that metal ions, including Al3+, Fe3+, and Co2+, increased the stability of dichlorvos, malathion, and chlorpyrifos. Conversely, Al3+, Fe3+, Fe2+, and Co2+ caused catalytic degradation of diazinon. With the addition of organic solvents (CH2Cl2, CHCl3, CCl4, CH3OH and CH3COCH3), remaining of diazinon residues was higher (16-54%) after storage for seven days. CCl4 was associated with the highest retention of malathion, diazinon, and chlorpyrifos (33%, 48% and 44%, respectively) in samples. SDS also stabilized the pesticides since residues were, again, higher (13-38%) after seven days storage. Furthermore, addition of Al3+ and Fe3+ decreased peroxidase (POD) activity and inhibited degradation of dichlorvos and malathion. After 14 days, lyophilization increased the pesticide residues remaining by 36%, 29%, and 58% for diazinon, malathion and chlorpyrifos, respectively. Overall, the stability of these pesticides during storage is impacted by water content and addition of exogenous substances. This could ensure higher quality of pesticide residue data in samples.


Assuntos
Cucumis sativus/química , Contaminação de Alimentos/análise , Armazenamento de Alimentos , Inseticidas/química , Compostos Organofosforados/química , Alumínio/química , Clorpirifos/análise , Clorpirifos/química , Diazinon/análise , Diazinon/química , Diclorvós/análise , Diclorvós/química , Aditivos Alimentares/química , Liofilização , Inseticidas/análise , Malation/análise , Malation/química , Compostos Organofosforados/análise , Oxirredutases/química , Peroxidases/química , Peroxidases/metabolismo , Resíduos de Praguicidas/análise , Resíduos de Praguicidas/química , Proteínas de Plantas/química , Proteínas de Plantas/metabolismo , Dodecilsulfato de Sódio/química , Água/química
4.
Chemosphere ; 256: 126895, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32460157

RESUMO

The appearance of an increased amount of organophosphate flame retardant (OPFRs) in natural water is related the treated effluents from wastewater treatment plants (WWTPs) and thus understanding the OPFRs concentration and reduction variation in WWTPs would provide valuable insight into OPFR management and reduction. In this study, we have analyzed OPFRs (10 kinds: tris(chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCPP), tris(1,3-dichloropropyl) phosphate (TDCP), tris(phenyl) phosphate (TPhP), tris(2-ethylhexyl) phosphate (TEHP), diphenylcresylphosphate (DCP), tris(methylphenyl) phosphate (TCP), tris(2-butoxyethyl) phosphate (TBEP), 2-ethylhexyl diphenyl phosphate (EHDP), and tris(butyl) phosphate (TBP)) in both water and sludge samples collected from different phases of a WWTP upgrading. The results show that TCPP and TCEP were mainly present in the aqueous phase, whereas TEHP dominated in the solid phase. The overall OPFR reduction efficiencies were above 40% through whole treatment processes by all the phases. More OPFRs reduction efficiency in primary sedimentation tanks was higher mainly because of bigger tank volume. The anaerobic zone in all cases could decrease OPFRs by over 13%. The removal of OPFRs in the oxic zone highly varied under the influence of the aeration pipe, water temperature, and aeration amount. Compared with chlorinated OPFRs, aryl and alkyl OPFRs were easier to reduce and less affected by the upgrading. Because OPFRs have been widely used in plastic materials such as pipes, WWTP upgrading - which usually requires more aeration and addition of reagents and instruments and the aim of which is normally to reduce more COD, N and P -- has introduced more OPFRs into the water within the WWTP.


Assuntos
Retardadores de Chama/análise , Compostos Organofosforados/análise , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias , Organofosfatos , Esgotos
5.
Food Chem ; 324: 126889, 2020 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-32353659

RESUMO

Pesticides have been extensively applied worldwide to protect crops from worms and insects; however, the continuous use of pesticides affects ecosystems, agricultural product safety, nontarget organisms, and human health. In this paper, we report a highly sensitive biosensor for the determination of pesticides based on tin sulfide (SnS2) and chitosan (CHIT) nanocomposites decorated with a unique British housefly acetylcholinesterase (AChE). The hydrothermally synthesized nano-SnS2 mixed with chitosan solution (CHIT-SnS2) was drop-casted onto a glassy carbon electrode (GCE). Subsequently, the British housefly AChE was immobilized on the CHIT/SnS2-coated GCE that was then employed for pesticide detection. The developed biosensor showed an ultra-high sensitivity and wide linear detection range from 0.02 nM to 20000 nM with a detection limit of 0.02 nM for the detection of chlorpyrifos as the model pesticide. Furthermore, the AChE/CHIT-SnS2/GCE exhibited acceptable storage stability, good reproducibility, and selectivity.


Assuntos
Acetilcolinesterase/metabolismo , Técnicas Biossensoriais/métodos , Quitosana/química , Moscas Domésticas/enzimologia , Compostos Organofosforados/análise , Sulfetos/química , Compostos de Estanho/química , Acetilcolinesterase/química , Animais , Carbono/química , Clorpirifos/análise , Técnicas Eletroquímicas , Eletrodos , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Limite de Detecção , Nanocompostos/química , Praguicidas/análise , Reprodutibilidade dos Testes
6.
PLoS One ; 15(4): e0231981, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32348360

RESUMO

An acetylcholinesterase biosensor modified with graphene and transition metal carbides was prepared to detect organophosphorus pesticides. Cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy were used to characterize the electrochemical catalysis of the biosensor: acetylcholinesterase/chitosan-transition metal carbides/graphene/glassy carbon electrode. With the joint modification of graphene and transition metal carbides, the biosensor has a good performance in detecting dichlorvos with a linear relationship from 11.31 µM to 22.6 nM and the limit of detection was 14.45 nM. Under the premise of parameter optimization, the biosensor showed a good catalytic performance for acetylcholine. Compared to the biosensors without modification, it expressed a better catalytic performance due to the excellent electrical properties, biocompatibility and high specific surface area of graphene, transition metal carbides. Finally, the biosensor exhibits good stability, which can be stored at room temperature for one month without significant performance degradation, and has practical potential for sample testing.


Assuntos
Acetilcolinesterase/metabolismo , Técnicas Biossensoriais/métodos , Grafite/química , Nanocompostos/química , Compostos Organofosforados/análise , Praguicidas/análise , Técnicas Eletroquímicas , Eletrodos , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Limite de Detecção , Reprodutibilidade dos Testes , Titânio/química , Elementos de Transição/química
7.
Bull Environ Contam Toxicol ; 104(6): 792-798, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32335690

RESUMO

In this study, the photodegradation of organophosphorus (OPs) pesticides in the honey medium was evaluated under sunlight irradiation. Some of the 22 samples collected at different sites contained OPs pesticides (Methyl parathion, Coumaphos and Fenitrothion) with an average of 8 ng/g. Moreover, three samples were found with pesticide residue levels exceeding the maximum residue limits (MRL ≥ 50 ng/g) imposed by the standard water (WHO). Gas chromatography (GC) combined with a tritium electron capture detector system was used for the analysis of OPs pesticides in honey. Total degradation of the Methyl parathion was obtained in less than 60 min of irradiation. Moreover, the elimination of the other OPs found in the samples was also effective with a rate of 85% for Coumaphos and Fenitrothion after 50 min of sunlight irradiation. The kinetics of the photodegradation reaction of all OPs pesticides studied followed a pseudo-first order model.


Assuntos
Contaminação de Alimentos/análise , Contaminação de Alimentos/prevenção & controle , Mel/análise , Compostos Organofosforados/análise , Praguicidas/análise , Luz Solar , Argélia , Cromatografia Gasosa , Mel/efeitos da radiação , Mel/normas , Cinética , Resíduos de Praguicidas/análise , Fotólise
8.
Sci Total Environ ; 726: 138526, 2020 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-32304943

RESUMO

Tris(1,3-dichloro-2-propyl) phosphate (TDCPP), a widely used organophosphorus flame retardant, has been frequently detected in the environment including indoor dust. Long-term exposure to TDCPP-containing dust may adversely affect human skin, however, little is known about its potential cytotoxicity. In this study, human skin keratinocytes (HaCaT) were employed to study TDCPP-induced cytotoxicity and associated mechanisms. The effects of TDCPP on cell morphology, viability, apoptosis, and cycle, and the mRNA levels of apoptosis (Bcl-2, Bax and Caspase-3) and cell cycle (cyclin D1, CDK2, CDK4 and CDK6) regulatory genes were investigated. The results showed that TDCPP caused a concentration-dependent decrease in cell viability after exposing to TDCPP ≥100 µg/mL for 48 h, with a median lethal concentration of 163 µg/mL (LC50). In addition, TDCPP induced cell apoptosis and arrested cell cycle in the G0/G1 phase at 16 and 160 µg/mL by enhancing Bax and Caspase-3 expression besides inhibiting cyclin D1, CDK2, CDK6 and Bcl-2 expression. Our results showed that TDCPP-induced toxicity in HaCaT cells was probably through cell apoptosis and cell cycle arrest. This study provides information on the toxicity of TDCPP to human skin cells, which may help to reduce its toxicity to human skin.


Assuntos
Retardadores de Chama , Apoptose , Poeira , Humanos , Queratinócitos/química , Organofosfatos , Compostos Organofosforados/análise
9.
Food Chem ; 320: 126683, 2020 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-32229401

RESUMO

Here, we demonstrate use of acetylcholinesterase (AChE)-responsive polyoxometalate (POM)/surfactant supramolecular spheres to build a liquid crystal (LC)-based sensing platform for detection of organophosphorus pesticides. The self-assembled spheres are composed of hybrid materials of a POM, sodium dodecatungstophosphate (PW12), and a surfactant, myristoylcholine (Myr). It displays dark appearance when the aqueous solution is in contact with LCs supported on the octadecyltrichlorosilane-treated glass deposited with the supramolecular spheres, suggesting perpendicular orientation of LCs at the aqueous/LC interface. In contrast, LCs show bright appearance when the surface-deposited supramolecular spheres are enzymatically hydrolyzed by AChE, corresponding to planar orientation of LCs at the aqueous/LC interface. Detection of organophosphates are successfully achieved as they are potent inhibitors of AChE. The detection limit of the sensing platform reached 0.9 ng/mL for dimethoate. This method can avoid disturbance of external interference with excellent specificity and sensitivity, which makes it very promise in detection of organophosphorus pesticides.


Assuntos
Acetilcolinesterase/metabolismo , Análise de Alimentos/métodos , Cristais Líquidos/química , Praguicidas/análise , Análise de Alimentos/instrumentação , Hidrólise , Lagos/análise , Limite de Detecção , Compostos Organofosforados/análise , Silanos/química , Tensoativos/química , Compostos de Tungstênio/química , Água/química , Poluentes Químicos da Água/análise
10.
Food Chem ; 321: 126678, 2020 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-32240916

RESUMO

A simple analytical method was developed and validated, as per SANTE 2017 guidelines, for simultaneous determination of 10 organophosphorus residues in curry leaf using gas chromatography with flame photometric detection, and confirmed using gas chromatography-mass spectrometry. Samples were extracted with ethyl acetate and cleaned up with primary secondary amine and graphitized carbon black. Average recoveries were in the range 80-108% with the RSD of less than 8%. The effects of different household cleaning techniques to reduce the concentration of pesticide residues in curry leaf were evaluated and found to remove 2-65% of residues. The method was applied to analyse sample to fresh curry leaf samples, and analysis of potential health risks estimated the residues did not pose a direct hazard. This method could be useful for routine analysis of organophosphorus residue for monitoring purposes.


Assuntos
Descontaminação , Compostos Organofosforados/análise , Rutaceae/química , Cromatografia Gasosa-Espectrometria de Massas , Resíduos de Praguicidas/análise , Fotometria/métodos , Folhas de Planta/química , Medição de Risco
11.
J Chromatogr A ; 1620: 461020, 2020 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-32173024

RESUMO

In this study, for the first time, stainless steel meshes coated with poly(ethylene glycol) and carbon nanotubes (PEG-CNT) by sol-gel technique were used as the adsorbent for solid-phase extraction. The coated stainless steel is loaded onto a cartridge and used to isolate and extract organophosphorus pesticides (OPPs) from water and fruit juice samples. Effective extraction parameters such as sample volume, desorption solvent, and desorption solvent volume were studied and investigated. Under optimal conditions, the linearity of the method was obtained in the range of 0.03 to 80 ng mL-1 and also the limits of detection (LODs) of the method were ranged from 0.01 to 0.03 ng mL-1. The repeatability of the method was evaluated at three concentration levels (0.1, 1, and 50 ng mL-1), and the relative standard deviation (RSD%) of the method was obtained in the range of 3.8 to 4.8%. Finally, the proposed method was used to analysis of OPPs in real water and fruit juice samples, with relative recovery in the range of 94.3 to 99.8%.


Assuntos
Compostos Organofosforados/isolamento & purificação , Praguicidas/isolamento & purificação , Transição de Fase , Extração em Fase Sólida/métodos , Aço Inoxidável/análise , Adsorção , Limite de Detecção , Nanotubos de Carbono/química , Compostos Organofosforados/análise , Praguicidas/análise , Polietilenoglicóis/química , Solventes/química , Poluentes Químicos da Água/análise
12.
J Anal Toxicol ; 44(4): 391-401, 2020 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-32103269

RESUMO

A recently proposed model for the incorporation of xenobiotics of forensic interest into the human skeleton suggests nerve agent metabolites may incorporate into bone at relatively elevated concentrations based on their unique chemical properties. To test the hypothesis that nerve agent metabolites interact with bone, methods for the extraction, isolation and semi-quantitative detection of nerve agent metabolites (MPA, EMPA, IMPA, iBuMPA, CMPA and PMPA, corresponding to the nerve agents VX, Russian VX, sarin, cyclosarin and soman, respectively) from osseous tissue were developed using liquid chromatography-mass spectrometry with both quadrupole time-of-flight and triple quadrupole (QqQ) instruments. The optimized methods were validated on the QqQ instrument. Despite high ion suppression, the achieved limits of detection (5-20 pg/g for four analytes; 350 pg/g for the fifth analyte) were lower than many of those published for the same analytes in other biomatrices, including serum and urine. These methods were tested on the skeletal remains of minipigs exposed to the chemical weapon VX in vivo. The VX metabolite was detected in multiple minipig bone samples; to the authors' knowledge, this is the first time in vivo nerve agent exposure has been detected from bone. Further, detected concentrations and diaphyseal-to-epiphyseal area count ratios reflect animal exposure history. Although the results are limited, they are promising, indicating that nerve agent metabolites may interact with bone as a pharmacokinetic compartment and can be extracted from bone postmortem. Additional studies, assessing the effects of different agents, exposure pathways and taphonomic variables, are needed; however, these results suggest the method may be used with human bone to detect use of chemical weapons from postmortem biomatrices even well after a suspected attack. More general implications for both nerve agent toxicology and skeletal toxicology are also discussed.


Assuntos
Osso e Ossos/química , Agentes Neurotóxicos/análise , Animais , Substâncias para a Guerra Química/análise , Cromatografia Líquida , Humanos , Limite de Detecção , Compostos Organofosforados/análise , Compostos Organotiofosforados/análise , Sarina/análise , Soman/análise , Suínos
13.
Mol Biotechnol ; 62(5): 280-288, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32108285

RESUMO

Biosensors based on microbial cells have been developed to monitor environmental pollutants. These biosensors serve as inexpensive and convenient alternatives to the conventional lab based instrumental analysis of environmental pollutants. Small monomeric naturally occurring fluorescent proteins (fp) can be exploited by converting them as small biosensing devices for biomedical and environmental applications. Moreover, they can withstand exposure to denaturants, high temperature, and a wide pH range variation. The current study employs newly identified novel fluorescent protein HriGFP from Hydnophora rigida to detect environmental contaminants like heavy metals and organo-phosphorous (pesticide) compounds such as methyl parathion. The HriGFP was initially tested or its expression in bacterial systems (Gram positive and Gram negative) and later on for its biosensing capability in E coli (BL21DE3) for detection of heavy metals and methyl parathion was evaluated. Our results indicated the discrete and stable expression of HriGFP and a profound fluorescent quenching were observed in the presence of heavy metals (Hg, Cu, As) and methyl parathion. Structural analysis revealed heavy metal ions binding to HriGFP via amino acid residues. In-silico-analysis further revealed strong interaction via hydrogen bonds between methyl parathion phosphate oxygen atoms and the amino group of Arg119 of HriGFP. This study implies that HriGFP can act as a biosensor for detecting harmful carcinogenic pesticide like methyl parathion in water resources in the vicinity of heavily pesticide impregnated agricultural lands and heavy metal contaminated water bodies around industrial areas.


Assuntos
Antozoários/metabolismo , Técnicas Biossensoriais/métodos , Proteínas Luminescentes/genética , Proteínas Luminescentes/metabolismo , Animais , Antozoários/genética , Bacillus megaterium/genética , Bacillus megaterium/crescimento & desenvolvimento , Sítios de Ligação , Escherichia coli/genética , Escherichia coli/crescimento & desenvolvimento , Ligação de Hidrogênio , Proteínas Luminescentes/química , Metais Pesados/análise , Metais Pesados/química , Modelos Moleculares , Compostos Organofosforados/análise , Compostos Organofosforados/química
14.
Food Chem ; 307: 125534, 2020 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-31644980

RESUMO

There has been increasing recent concern about the agricultural use of organophosphorus pesticides. A rapid and sensitive fluorescence assay for the detection of three organophosphorus pesticides has therefore been developed using 6-carboxy-fluorescein labeling aptamer as the probe and functionalized magnetic nanoparticles as the separation carrier. The aptamer hybridized with complementary DNA conjugated on the surface of the magnetic nanoparticles to form a magnetic aptamer-complementary DNA complex. Upon introducing the target organophosphorus pesticide, the aptamer departed from the complementary DNA, resulting in the fluorescence signal. Under optimized conditions, the limits of detection (LODs, S/N = 3) for trichlorfon, glyphosate, and malathion were 72.20 ng L-1, 88.80 ng L-1, and 195.37 ng L-1, respectively. The method was applied for the detection of trichlorfon, glyphosate, and malathion in spiked lettuce and carrot samples. The recoveries were in the range of 79.4%-118.7%, which were in good agreement with those obtained by gas chromatography, and the relative standard deviations were also acceptable. The method therefore has high sensitivity, so provides a means for the detection of multiple organophosphorus pesticides.


Assuntos
Aptâmeros de Nucleotídeos/química , Nanopartículas , Compostos Organofosforados/análise , Praguicidas/análise , Espectrometria de Fluorescência , Cromatografia Gasosa , Daucus carota/química , Corantes Fluorescentes , Glicina/análogos & derivados , Glicina/análise , Alface/química , Limite de Detecção , Magnetismo , Malation/análise , Praguicidas/química , Triclorfon/análise
15.
Talanta ; 208: 120470, 2020 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-31816754

RESUMO

This study presents the development and validation of a new analytical method based on matrix solid-phase dispersion (MSPD), integrating sample extraction and clean-up in one single step, followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of 18 organophosphorus flame retardants and/or plasticizers (OPEs) in marine mussel (Mytilus edulis and Mytilus galloprovincialis) samples. Among these OPEs, 5 (tetraethyl 1,2-ethanediylbis(phosphonate), 6H-dibenzo[c,e] [1,2]oxaphosphinine 6-oxide, tris(2,3-dibromopropyl) phosphate, 2,2-propanediyldi-4,1-phenylene bis(phosphate) and resorcinol bis(diphenyl phosphate)) are considered here for the first time in marine samples. Different parameters affecting the MSPD (clean-up sorbent and elution solvent) were optimized to obtain a good compromise between analyte recoveries and extract clean-up. Also, particular attention was paid to tackle blank issues. The overall method was validated in terms of trueness, precision and detection and quantification limits. Percentages of recovery varied from 69% to 122% with relative standard deviations below 24%. Detection limits ranged from 0.06 to 5 ng g-1 and quantification limits from 0.19 to 17 ng g-1 dry weight. Finally, the method was applied to the analysis of 7 mussel samples collected in the coast of Galicia (Spain). 8 OPEs were detected in these samples at concentrations ranging from the LOQ to 291 ng g-1 dry weight.


Assuntos
Retardadores de Chama/análise , Contaminação de Alimentos/análise , Mytilus/química , Compostos Organofosforados/análise , Plastificantes/análise , Poluentes Químicos da Água/análise , Animais , Cromatografia Líquida , Extração em Fase Sólida , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas em Tandem
16.
Food Chem ; 309: 125755, 2020 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-31704075

RESUMO

A simple, sensitive and environmentally-friendly method for determining organophosphorus and pyrethroid pesticides in vegetables was developed to better evaluate the risk of consuming them. The pesticides in vegetables were extracted, purified and concentrated by using the QuEChERS (quick, easy, cheap, effective, rugged and safe method) combined DLLME-SFO (dispersive liquid-liquid microextraction based on solidification of floating organic droplet) techniques. The key parameters were optimized through orthogonal array experimental design and statistical analysis. The linearity of the calibration curves was satisfied in matrix-matched standard solution with R2 ≥ 0.99. The limits of detection and limits of quantification were 0.3-1.5 and 0.9-4.7 µg/kg, respectively. The average recoveries of pesticides were 61.6-119.4% with relative standard deviations <16.1%. Furthermore, the method was applied successfully to analyse the pesticides in 15 pairs of organic and conventional vegetables. These results reflect the efficiency, reliability and robustness of the developed method.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas , Microextração em Fase Líquida/métodos , Compostos Organofosforados/análise , Praguicidas/análise , Piretrinas/análise , Verduras/química , Calibragem , Cromatografia Gasosa-Espectrometria de Massas/normas , Limite de Detecção , Compostos Organofosforados/isolamento & purificação , Compostos Organofosforados/normas , Praguicidas/isolamento & purificação , Praguicidas/normas , Piretrinas/isolamento & purificação , Piretrinas/normas , Reprodutibilidade dos Testes , Temperatura , Verduras/metabolismo
17.
Biosens Bioelectron ; 148: 111825, 2020 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-31677527

RESUMO

Acetylcholinesterase (AChE) has been widely applied on the enzyme inhibition-based detection of organophosphate pesticides (OPs). To improve the sensitivity of fluorometric OPs assay, great efforts were made to change the fluorometric probes or analytical strategies rather than improve the sensitivity of AChE towards OPs. In this work, AChE wild-type (WT) and mutants (E69Y and E69Y/F330L) from Drosophila were successfully displayed on the surface of yeast through a-agglutinin-mediated microbial surface display system. The location of AChE on yeast surface was confirmed by immunofluorescence analysis. Further, a fluorescence OPs detection method was developed by combining yeast surface-displayed AChE mutants and protein-directed electronegative fluorescent gold nanoclusters (Au NCs). Yeast surface-displayed AChE can catalyze the hydrolysis of acetylthiocholine to produce thiocholine. The electropositive thiocholine can not only bind with AuNCs by Au-S bond but also absorb Au NCs by the electrostatic interaction, leading to the aggregation of AuNCs and corresponding fluorescence quenching. When AChE was incubated with paraoxon, a typical model of OPs, the activity of AChE was inhibited and the thiocholine-induced aggregation of AuNCs was reduced. The fluorescence assay based on Au NCs and yest-AChE-E69Y/F330L exhibited the ultra-sensitivity for ultra-trace OPs and 2-6 orders of magnitude lower detection limit (3.3 × 10-14 M) than those of AChE-WT-based method and other reported methods. In addition, the proposed method showed excellent reliability for the real samples assay. This work would provide an alternative strategy for the improvement of bio-analysis at its source.


Assuntos
Acetilcolinesterase/genética , Técnicas Biossensoriais/métodos , Drosophila melanogaster/enzimologia , Compostos Organofosforados/análise , Praguicidas/análise , Saccharomyces cerevisiae/genética , Acetilcolinesterase/metabolismo , Animais , Drosophila melanogaster/genética , Drosophila melanogaster/metabolismo , Ouro/química , Limite de Detecção , Nanopartículas Metálicas/química , Nanopartículas Metálicas/ultraestrutura , Mutagênese Sítio-Dirigida , Mutação , Compostos Organofosforados/metabolismo , Praguicidas/metabolismo , Saccharomyces cerevisiae/metabolismo
18.
Molecules ; 24(24)2019 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-31817260

RESUMO

An in situ tracing study based on solid-phase microextraction (SPME) was conducted to investigate the uptake and elimination of organophosphorus pesticides in apples. A matrix-compatible polydimethylsiloxane/poly(styrene-co-divinylbenzene)/polydimethylsiloxane fiber was produced to meet the needs of in situ sampling. The fiber had high extraction ability, good sensitivity and accuracy with respect to the analytes in apple pulp, and could be used 85 times. Although the sampling rate was changing over time, quantification was still achieved by the sampling rate calibration method. Some factors that affect its applicability were studied. The limits of detection were 0.18 ng/g for diazinon and 0.20 ng/g for chlorpyrifos, rather lower than the maximum residue limits of the National Food Safety Standard of China (GB 2763-2016) and the European Commission (Reg.(EU) No 834/2013, 2018/686). The accuracy of in situ SPME quantification was verified by comparing with the results obtained by the traditional liquid-liquid extraction method. In this work, the in situ sampling method is developed using apples, diazinon, and chlorpyrifos as a model system; however, this method can be used for in vivo analysis of fruits and vegetables for nutrition and safety monitoring.


Assuntos
Malus/química , Compostos Organofosforados/análise , Praguicidas/análise , Microextração em Fase Sólida/métodos , Calibragem , Clorpirifos/análise , Cromatografia Gasosa , Diazinon/análise , Temperatura
19.
Environ Sci Pollut Res Int ; 26(36): 36308-36321, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31713822

RESUMO

Glyphosate is a broad-spectrum, non-selective, post-emergence herbicide that controls weeds by inhibiting their ability to synthesize amino acids. It is characterized by high persistence and adsorption to soil, with its dissipation to be highly correlated to the climatic conditions. After its degradation in soil, aminomethylphosphonic acid (AMPA) is the sole and major metabolite produced, characterized also by high persistence and adsorption. Both substances have the potential to remain in soil rather than move to other environmental compartments. Considering the recent intense debate during the EU renewal of glyphosate along with its wide use, it is apparent that both glyphosate and AMPA require further attention and information on their occurrence and distribution in EU soils. The present study does constitute the first extended soil monitoring survey of glyphosate and AMPA with samples derived during the years 2013-2015, from the highest extent of the Greek territory. Specific attention was given to areas of high agricultural production as well as to urban areas, since glyphosate-containing products are also registered for non-professional uses. The positive samples represented the 36.7% for glyphosate and 44.9% for AMPA, while the detected residues fluctuated from 0.026 to 40.6 µg g-1 and from 0.01 to 2.5 µg g-1 for glyphosate and AMPA, respectively. Our findings can constitute a basis for the determination of the background concentration levels of glyphosate and its metabolite in the Greek territory. As such, apart from being the first study for glyphosate monitoring in Greece, the most significant highlights recognized in the present work are the following:The high levels of glyphosate and AMPA residues in urban areas that indicate possible misuse of pesticidesThe generally low detection in the main agricultural basins and particularly near water recipientsThe fact that a potential for misuse of herbicides cannot be excluded even in the case of agricultural areas (considering that the maximum detection was in an olive grove and exceeded the model-predicted concentrations by 13 times).


Assuntos
Glicina/análogos & derivados , Herbicidas/análise , Compostos Organofosforados/análise , Poluentes do Solo/análise , Solo/química , Adsorção , Agricultura , Monitoramento Ambiental , Glicina/análise , Grécia
20.
Artigo em Inglês | MEDLINE | ID: mdl-31731401

RESUMO

The occurrence of organic micropollutants (OMPs) in aqueous environments has potential effects on ecological safety and human health. Three kinds of OMPs (namely, pharmaceuticals, ultraviolet (UV) filters and organophosphate esters (OPEs)) in four drinking water source areas in Henan Province of China were analyzed, and their potential risks were evaluated. Among 48 target chemicals, 37 pollutants with total concentrations ranging from 403.0 to 1751.6 ng/L were detected in water, and 13 contaminants with total concentrations from 326.0 to 1465.4 ng/g (dry weight) were observed in sediment. The aqueous pollution levels in Jiangang Reservoir and Shahe Water Source Area were higher than that in Nanwan Reservoir and Baiguishan Reservoir, while the highest total amount of pollutants in sediment was found in Baiguishan Reservoir. Compared with pharmaceuticals and UV filters, OPEs presented higher concentrations in all investigated drinking water source areas. The highest observed concentration was triphenylphosphine oxide (TPPO, 865.2 ng/L) in water and tripentyl phosphate (TPeP, 1289.8 ng/g) in sediment. Moreover, the risk quotient (RQ) analysis implies that the determined aqueous contaminants exhibited high risks to algae and invertebrates, whereas moderate risk to fish was exhibited. The health risk assessment of aqueous OMPs by means of the hazard index (HI) indicates that the risks to adults and children were negligible. These observations are expected to provide useful information for the assessment of water quality in drinking water sources in Henan, China.


Assuntos
Água Potável/química , Poluentes Ambientais/análise , Organofosfatos/análise , Compostos Organofosforados/análise , Preparações Farmacêuticas/análise , Animais , Criança , China , Monitoramento Ambiental , Humanos , Medição de Risco , Poluentes Químicos da Água/análise
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA