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1.
J Sep Sci ; 44(8): 1652-1661, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33527734

RESUMO

This paper reports a simple method for the preparation of suitable graphene quantum dots after surface passivation, to be used for the determination of carbaryl in juice samples. A comparison of synthetic conditions for the preparation of graphene quantum dots following the top-down approach is described. In the one-step route selected, evaluation of diverse reaction time for cutting and modulating the oxidizing sites in the broken pieces of the initial graphene layer is conducted with a mixture of concentrated acids. Exploring the passivation effect on the purified graphene quantum dots, we demonstrated the suitability of the selected graphene quantum dots for practical application in the detection of carbaryl using fluorometric detection. Higher sensitivity was achieved after 8 min of contact, in which graphene quantum dots promotes the degradation of carbaryl into naphthol, being the latter responsible for the analytical signal. The detection and quantification limits were 0.36 and 1.21 µg/L, respectively, being the response linear up to 26 µg/L with excellent precision (better than 3.2% at the limit of detection). The recovery of the analyte from commercial juice samples (91.4-96.7%) testifies to the applicability of the proposal for the analytical problem selected.


Assuntos
Carbaril/análise , Sucos de Frutas e Vegetais/análise , Grafite/química , Pontos Quânticos/química , Tamanho da Partícula , Propriedades de Superfície
2.
J Environ Sci Health B ; 56(3): 222-234, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33417510

RESUMO

Surface-enhanced Raman scattering (SERS) is a promising technique for rapid detection of pesticide residues. However, conventional SERS substrates require extraction processes which are time consuming and they also lack selectivity, stability and reproducibility. Herein, we present a multifunctional stable zero-valent iron based core-shell substrate. It combines magnetic separation, selective adsorption by molecular imprinting technique and sensitive detection of carbaryl by SERS. The core-shell substrate was successfully prepared by immobilizing silver on the surface of zero-valent iron microspheres. Subsequent molecular imprinting on the bimetallic magnetic silver microspheres ensured selective removal and detection. The substrate exhibited magnetization saturation of 8.89 emu/g providing efficient analyte separation. It showed high sensitivity and selectivity toward carbaryl detection to nanomolar concentration level. Linear regression models for peaks at Raman shift 1599 cm-1 and 2233 cm-1 demonstrated a good linear fit with R2=0.9738 and R2=0.8952 respectively. The composite was successfully applied on spiked water samples resulting in average recovery rate of 89%. The findings of this study demonstrate great substrate potential for application in separation and detection of trace quantities of chemical contaminants for environment safety and protection.


Assuntos
Carbaril/análise , Nanopartículas Metálicas/química , Resíduos de Praguicidas/análise , Análise Espectral Raman/métodos , Poluentes Químicos da Água/análise , Adsorção , Ferro/química , Fenômenos Magnéticos , Microesferas , Impressão Molecular/métodos , Oxirredução , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Prata/química
3.
Sensors (Basel) ; 20(5)2020 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-32164236

RESUMO

Accurate analysis of pesticide residue in real samples is essential for food safety and environmental protection. However, a traditional electrochemical sensor based on single-signal output is easily affected by background noise, environmental conditions, electrode diversity, and a complex matrix of samples, leading to extremely low accuracy. Hence, in this paper, a ratiometric strategy based on dual-signal output was adopted to build inner correction for sensing of widely-used carbaryl (CBL) for the first time. By comparison, Nile blue A (NB) was selected as reference probe, due to its well-defined peak, few effects on the target peak of CBL, and excellent stability. The effects of a derivatization method, technique mode, and pH were also investigated. Then the performance of the proposed ratiometric sensor was assessed in terms of three aspects including the elimination of system noise, electrode deviation and matrix effect. Compared with traditional single-signal sensor, the ratiometric sensor showed a much better linear correlation coefficient (r > 0.99), reproducibility (RSD < 10%), and limit of detection (LOD = 1.0 µM). The results indicated the introduction of proper reference probe could ensure the interdependence of target and reference signal on the same sensing environment, thus inner correction was fulfilled, which provided a promising tool for accurate analysis.


Assuntos
Carbaril/análise , Eletroquímica/métodos , Análise de Alimentos/métodos , Verduras , Água/química , Técnicas Biossensoriais , Brassica , Calibragem , Cromatografia Líquida de Alta Pressão , Eletrodos , Concentração de Íons de Hidrogênio , Limite de Detecção , Modelos Lineares , Solanum lycopersicum , Oxazinas/análise , Reprodutibilidade dos Testes , Processamento de Sinais Assistido por Computador
4.
J Sci Food Agric ; 100(6): 2468-2472, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-31965575

RESUMO

BACKGROUND: In recent years there has been a concern about the presence of pesticides in honey because residues of DDT and carbaryl were found in honey samples. Traditional techniques, such as chromatography, reach the required limits of detection (LOD) but are not suitable for in situ implementation in the honey-packaging industry due to their high cost and the need for highly qualified staff for routine operation. Biosensors offer simplicity, low cost, and easy handling for analytical purposes in food applications. RESULTS: Piezoelectric immunosensors based on high fundamental frequency quartz crystal microbalance (HFF-QCM) have been developed for the detection of carbaryl and DDT in honey. Biorecognition was based on competitive immunoassays in the conjugate-coated format, using monoclonal antibodies as specific immunoreagents. The assay LODs attained by the HFF-QCM immunosensors were 0.05 µg L-1 for carbaryl and 0.24 µg L-1 for DDT, reaching a similar level of detectability to that of the usual reference techniques. The practical LODs in honey samples were 8 µg kg-1 for carbaryl and 24 µg kg-1 for DDT. The immunosensors' analytical performance allow the detection of these pesticides in honey at EU regulatory levels with good accuracy (recovery percentages ranging from 94% to 130% within the working range of each pesticide standard curve) and precision (coefficients of variation in the 9-36% range). CONCLUSION: The proposed immunosensor is a promising analytical tool that could be implemented for quality control in the honey packaging industry, to simplify and to reduce the cost of the routine pesticide analysis in this appreciated natural food. © 2020 Society of Chemical Industry.


Assuntos
Carbaril/análise , DDT/análise , Mel/análise , Anticorpos Monoclonais , Técnicas Biossensoriais , Contaminação de Alimentos/análise , Imunoensaio/métodos , Inseticidas/análise , Resíduos de Praguicidas/análise , Técnicas de Microbalança de Cristal de Quartzo/métodos , Sensibilidade e Especificidade
5.
J Environ Sci Health B ; 55(10): 929-939, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32715921

RESUMO

The aim of this study is to investigate the synergetic effect of ozonation on ultraviolet irradiation on the degradation of carbaryl (CBL) (1-naphthyl-N-methylcarbamate) in aqueous solutions (40 mg L-1). The degradation of CBL and the intermediates formed during ozonation were determined by gas chromatography-mass spectrometer. The change in formaldehyde, dissolved oxygen, pH, and total acidity were determined as a function of ozonation time. It was found that the dissolved oxygen and total acidity were increased with the increasing ozonation time but the pH was decreased with the increasing ozonation time. The aliphatic acids formed during ozonation were followed by ion chromatography as a function of ozonation time. It was found that the effect of ozonation is highly effective on the degradation of CBL. The complete degradation of CBL has occurred at 75-second ozonation time. As a consequence of the obtained results the possible degradation pathway was proposed. The results confirmed that ozonation is an effective method for the degradation of CBL.


Assuntos
Carbaril/análise , Inseticidas/análise , Ozônio/química , Fotólise , Raios Ultravioleta , Cromatografia Gasosa-Espectrometria de Massas
6.
Anal Biochem ; 572: 9-15, 2019 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-30831096

RESUMO

Immunoassays provide a high-throughput method for monitoring pesticides in foods and the environment. Due to easy generation and capable of being manipulated, chicken single-chain variable fragment (scFv) is attractive in the development of immunoassays for pesticides. Two scFvs (X1 and X2) against the insecticide carbaryl were generated from a chicken immunized with hapten C1 conjugated to keyhole limpet hemocyanin and fused with alkaline phosphatase (AP) to develop a rapid one-step enzyme-linked immunosorbent assay for this pesticide. X2-AP showed higher binding affinity to carbaryl than X1-AP. The X2-AP-based ELISA had a half-maximum signal inhibition concentration of 15 ng mL-1 and a limit of detection of 1.6 ng mL-1. This assay showed negligible cross-reactivity with other carbamate pesticides (<0.1%) and low cross-reactivity with 1-naphthol (5%). The average recoveries of carbaryl spiked in soil, apple and pear samples by the one-step assay ranged from 90% to 114% and agreed well with those of high-performance liquid chromatography. The chicken scFv-based assay showed promise as a high-throughput screening tool for carbaryl in environmental and food matrices.


Assuntos
Carbaril/análise , Imunoensaio/métodos , Inseticidas/análise , Anticorpos de Cadeia Única/imunologia , Fosfatase Alcalina/química , Fosfatase Alcalina/metabolismo , Animais , Carbaril/imunologia , Galinhas , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Inseticidas/imunologia , Limite de Detecção , Pyrus/química , Pyrus/metabolismo , Anticorpos de Cadeia Única/química , Solo/química
7.
Appl Microbiol Biotechnol ; 103(7): 3205-3213, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30770965

RESUMO

Transcriptional regulatory proteins (TRPs)-based whole-cell biosensors are promising owing to their specificity and sensitivity, but their applications are currently limited. Herein, TRPs were adapted for the extracellular detection of a disease biomarker, uric acid, and a typical pesticide residue, carbaryl. A mutant regulatory protein that specifically recognizes carbaryl as its non-natural effector and activates transcription upon carbaryl binding was developed by engineering the regulatory protein TtgR from Pseudomonas putida. The TtgR mutant responsive to carbaryl and a regulatory protein responsive to uric acid were used for in vitro detection, based on their allosteric binding of operator DNA and inducer molecules. Based on the quantitative polymerase chain reactions (qPCRs) output, the minimum detectable concentration was between 1 nM-1 µM and 1-10 nM for uric acid and carbaryl, respectively. Our results demonstrated that engineering the effector specificity of regulatory proteins is a potential technique for generating molecular recognition elements for not only in vivo but also in vitro applications.


Assuntos
Proteínas de Bactérias/genética , Biomarcadores/análise , Resíduos de Praguicidas/análise , Proteínas Repressoras/genética , Proteínas de Bactérias/isolamento & purificação , Sítios de Ligação , Carbaril/análise , Mutação , Reação em Cadeia da Polimerase , Pseudomonas putida/genética , Fatores de Transcrição/genética , Ácido Úrico/análise
8.
J Sci Food Agric ; 99(9): 4383-4390, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30851058

RESUMO

BACKGROUND: The variable domain of camelid heavy-chain antibodies (VHH) is increasingly being adapted to detect small molecules in various matrices. The insecticide carbaryl is widely used in agriculture while its residues have posed a threat to food safety and human health. RESULTS: VHHs specific for carbaryl were generated from an alpaca immunized with the hapten CBR1 coupled to keyhole limpet hemocyanin. An enzyme-linked immunosorbent assay (ELISA) based on the VHH C1 and the coating antigen CBR2-BSA was developed for the detection of carbaryl in cereals. This assay, using an optimized assay buffer (pH 6.5) containing 10% methanol and 0.8% NaCl, has a half-maximum signal inhibition concentration of 5.4 ng mL-1 and a limit of detection (LOD) of 0.3 ng mL-1 for carbaryl, and shows low cross reactivity (≤0.8%) with other tested carbamates. The LOD of carbaryl using the VHH-based ELISA was 36 ng g-1 in rice and maize and 72 ng g-1 in wheat. Recoveries of carbaryl in spiked rice, maize and wheat samples were in the range of 81-106%, 96-106% and 83-113%, respectively. Relative standard deviations of repeatability and intra-laboratory reproducibility were in the range of 0.8-9.2% and 2.9-9.7%, respectively. CONCLUSION: The VHH-based ELISA was highly effective in detecting carbaryl in cereal samples after simple sample extraction and dilution. © 2019 Society of Chemical Industry.


Assuntos
Carbaril/análise , Ensaio de Imunoadsorção Enzimática/métodos , Inseticidas/análise , Triticum/química , Zea mays/química , Animais , Camelídeos Americanos , Grão Comestível/química , Contaminação de Alimentos/análise , Cadeias Pesadas de Imunoglobulinas/análise , Cadeias Pesadas de Imunoglobulinas/imunologia , Limite de Detecção , Anticorpos de Cadeia Única/análise , Anticorpos de Cadeia Única/imunologia
9.
J Environ Sci Health B ; 53(7): 469-475, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29624471

RESUMO

Chlorpyrifos (O, O-diethyl O-3,5,6-trichloropyridin-2-yl phosphorothioate) and carbaryl (1-naphthyl methylcarbamate) are often applied concurrently as insecticides in food production. The aim of this study was to research their migration behavior in a real environment. We researched the leaching of both pesticides by setting up field lysimeters on a farm with the typical soil used in fruit production today. In order to analyze the variables involved in this process, we performed complementary adsorption studies, we performed complementary adsorption studies using batches and undisturbed soil laboratory columns for both compounds. The results for pesticide transport through the lysimeters showed that less than 1% of chlorpyrifos was recovered in the leachates, while almost 17% was recovered for carbaryl. Having completed the experiment in undisturbed laboratory columns, soil analysis showed that chlorpyrifos mainly remained in the first 5 cm, while carbaryl moved down to the lower sections. These results can be explained in view of the sorption coefficient values (KD) obtained in horizons A and B for chlorpyrifos (393 and 184 L kg-1) and carbaryl (3.1 and 4.2 L kg-1), respectively. By integrating the results obtained in the different approaches, we were able to characterize the percolation modes of these pesticides in the soil matrix, thus contributing to the sustainable use of resources.


Assuntos
Carbaril/análise , Clorpirifos/análise , Poluentes do Solo/análise , Solo/química , Adsorção , Carbaril/química , Clorpirifos/química , Inseticidas/análise , Inseticidas/química , Poluentes do Solo/química
10.
J Environ Sci Health B ; 53(3): 161-170, 2018 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-29206083

RESUMO

Water quality assessment was conducted on the Ruiru River, a tributary of an important tropical river system in Kenya, to determine baseline river conditions for studies on the aquatic fate of N-methyl carbamate (NMC) pesticides. Measurements were taken at the end of the long rainy season in early June 2013. Concentrations of copper (0.21-1.51 ppm), nitrates (2.28-4.89 ppm) and phosphates (0.01-0.50 ppm) were detected at higher values than in uncontaminated waters, and attributed to surface runoff from agricultural activity in the surrounding area. Concentrations of dissolved oxygen (8-10 ppm), ammonia (0.02-0.22 ppm) and phenols (0.19-0.83 ppm) were found to lie within normal ranges. The Ruiru River was found to be slightly basic (pH 7.08-7.70) with a temperature of 17.8-21.2°C. The half-life values for hydrolysis of three NMC pesticides (carbofuran, carbaryl and propoxur) used in the area were measured under laboratory conditions, revealing that rates of decay were influenced by the electronic nature of the NMCs. The hydrolysis half-lives at pH 9 and 18°C decreased in the order carbofuran (57.8 h) > propoxur (38.5 h) > carbaryl (19.3 h). In general, a decrease in the electron density of the NMC aromatic ring increases the acidity of the N-bound proton removed in the rate-limiting step of the hydrolysis mechanism. Our results are consistent with this prediction, and the most electron-poor NMC (carbaryl) hydrolyzed fastest, while the most electron-rich NMC (carbofuran) hydrolyzed slowest. Results from this study should provide baseline data for future studies on NMC pesticide chemical fate in the Ruiru River and similar tropical water systems.


Assuntos
Carbamatos/análise , Praguicidas/análise , Poluentes Químicos da Água/análise , Qualidade da Água , Carbamatos/química , Carbaril/análise , Carbaril/química , Carbofurano/análise , Carbofurano/química , Meia-Vida , Hidrólise , Quênia , Propoxur/análise , Propoxur/química , Chuva , Rios/química , Estações do Ano , Relação Estrutura-Atividade , Clima Tropical
11.
Bull Environ Contam Toxicol ; 98(5): 656-661, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28289805

RESUMO

Organochlorines and carbamates are common pesticides predominantly employed in agriculture. Large amounts of pesticides make their way into rivers and marine habitats. They accumulate in aquatic organisms through different exposure routes and gradually move up the food chain. Since contaminant bioaccumulation in animals is affected by several factors, this work harnessed several different approaches to explore the persistence of lindane, a long banned organochlorine pesticide, and carbaryl, a newer generation pesticide, in common sole (Solea solea), a major commercial species in Adriatic fisheries. Lindane was not only more accumulated than carbaryl in sole liver, but it was also detected in greater amount in muscle tissue, the edible part (lindane, 7 ± 4 ng/g; carbaryl, <0.004 ng/g w/w). Additional assays documented a greater accumulation of lindane in adults compared with juveniles and in specimens caught offshore than in those collected close to the coast. The present findings demonstrate the different accumulation dynamics of the two pesticides to confirm the benefits derived from the replacement of organochlorine pesticides with carbamate compounds.


Assuntos
Carbaril/farmacocinética , Linguados/metabolismo , Hexaclorocicloexano/farmacocinética , Praguicidas/farmacocinética , Poluentes Químicos da Água/farmacocinética , Animais , Carbaril/análise , Pesqueiros , Cadeia Alimentar , Hexaclorocicloexano/análise , Hidrocarbonetos Clorados/análise , Hidrocarbonetos Clorados/farmacocinética , Fígado/efeitos dos fármacos , Fígado/metabolismo , Músculo Esquelético/efeitos dos fármacos , Músculo Esquelético/metabolismo , Praguicidas/análise , Rios/química , Alimentos Marinhos/análise , Poluentes Químicos da Água/análise
12.
Toxicol Ind Health ; 32(6): 1135-42, 2016 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-25342670

RESUMO

Cucumbers grown in two different greenhouses were exposed to mancozeb and carbaryl at different times. The effects of 10-day preharvest period, water and detergent washing, peeling, predetermined storage period at 4°C (refrigeration), and fermentation on the reduction of residue levels in the plant tissues were investigated. Mancozeb and carbaryl residues in cucumbers were determined by gas chromatography-electron capture detection. Results showed that residue levels in samples, which were collected after 10 days following the pesticide application, were significantly lower than the samples collected after 2 h subsequent to the pesticide application. The culinary applications were effective in reducing the residue levels of the pesticides in cucumbers. As a result, non-fermentative pickling in sodium chloride and acetic acid was the most effective way to reduce the mancozeb and carbaryl residues of the cucumbers.


Assuntos
Carbaril/análise , Cucumis sativus/química , Maneb/análise , Resíduos de Praguicidas/análise , Zineb/análise , Fermentação , Análise de Alimentos , Contaminação de Alimentos/análise , Armazenamento de Alimentos , Frutas/química
13.
Bull Environ Contam Toxicol ; 96(4): 423-31, 2016 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-26754544

RESUMO

Surface water sampling in 2007-2010 measured the occurrence of carbamates and metalaxyl during base flow conditions and wet weather events in southern Ontario surface waters. Carbaryl, metalaxyl and pirimicarb were the most frequently detected compounds. In 2008 these three compounds were detected in over 50 % of the samples. Overall mean concentrations of carbaryl and metalaxyl over the course of the study (2007-2010) were 15 and 18 ng/L, respectively. Elevated concentrations of carbaryl (~100 to ~950 ng/L) appeared associated with wet weather (high flow) events, while highest concentrations of metalaxyl (~20-1330 ng/L) were correlated with base flow conditions. We attributed these observations as the result of runoff of carbaryl from the watershed during rain events, while metalaxyl contamination may have resulted primarily from spray drift.


Assuntos
Alanina/análogos & derivados , Carbamatos/análise , Carbaril/análise , Água Doce/química , Praguicidas/análise , Pirimidinas/análise , Poluentes Químicos da Água/análise , Alanina/análise , Monitoramento Ambiental , Água Doce/análise , Ontário , Chuva
14.
Guang Pu Xue Yu Guang Pu Fen Xi ; 36(2): 541-4, 2016 Feb.
Artigo em Zh | MEDLINE | ID: mdl-27209765

RESUMO

Determination of carbaryl in rice by using Fourier transform far-infrared (FT- Far-IR) and terahertz time-domain spectroscopy (THz-TDS) combined with chemometrics was studied and the spectral characteristics of carbaryl in terahertz region was investigated. Samples were prepared by mixing carbaryl at different amounts with rice powder, and then a 13 mm diameter, and about 1 mm thick pellet with polyethylene (PE) as matrix was compressed under the pressure of 5-7 tons. Terahertz time domain spectra of the pellets were measured at 0.5~1.5 THz, and the absorption spectra at 1.6. 3 THz were acquired with Fourier transform far-IR spectroscopy. The method of sample preparation is so simple that it does not need separation and enrichment. The absorption peaks in the frequency range of 1.8-6.3 THz have been found at 3.2 and 5.2 THz by Far-IR. There are several weak absorption peaks in the range of 0.5-1.5 THz by THz-TDS. These two kinds of characteristic absorption spectra were randomly divided into calibration set and prediction set by leave-N-out cross-validation, respectively. Finally, the partial least squares regression (PLSR) method was used to establish two quantitative analysis models. The root mean square error (RMSECV), the root mean square errors of prediction (RMSEP) and the correlation coefficient of the prediction are used as a basis for the model of performance evaluation. For the R,, a higher value is better; for the RMSEC and RMSEP, lower is better. The obtained results demonstrated that the predictive accuracy of. the two models with PLSR method were satisfactory. For the FT-Far-IR model, the correlation between actual and predicted values of prediction samples (Rv) was 0.99. The root mean square error of prediction set (RMSEP) was 0.008 6, and for calibration set (RMSECV) was 0.007 7. For the THz-TDS model, R. was 0. 98, RMSEP was 0.004 4, and RMSECV was 0.002 5. Results proved that the technology of FT-Far-IR and THz- TDS can be a feasible tool for quantitative determination of carbaryl in rice. This paper provides a new method for the quantitative determination pesticide in other grain samples.


Assuntos
Carbaril/análise , Oryza/química , Espectroscopia de Infravermelho com Transformada de Fourier , Espectroscopia Terahertz , Calibragem , Análise dos Mínimos Quadrados
15.
Bioprocess Biosyst Eng ; 37(10): 1929-34, 2014 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-24770986

RESUMO

In this study, an acetylcholinesterase (AChE) biosensor with superior accuracy and sensitivity was successfully developed based on interdigitated array microelectrodes (IAMs). IAMs have a series of parallel microband electrodes with alternating microbands connected together. Chitosan was used as the enzyme immobilization material, and AChE was used as the model enzyme for carbaryl detection to fabricate AChE biosensor. Electrochemical impedance spectroscopy was used in conjunction with the fabricated biosensor to detect pesticide residues. Based on the inhibition of pesticides on the AChE activity, using carbaryl as model compounds, the biosensor exhibited a wide range, low detection limit, and high stability. Moreover, the biosensor can also be used as a new promising tool for pesticide residue analysis.


Assuntos
Acetilcolinesterase/metabolismo , Técnicas Biossensoriais , Carbaril/análise , Inibidores da Colinesterase/análise , Microeletrodos , Limite de Detecção , Espectrofotometria Ultravioleta
16.
Sensors (Basel) ; 14(9): 16434-53, 2014 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-25192313

RESUMO

A Love Wave (LW) immunosensor was developed for the detection of carbaryl pesticide. The experimental setup consisted on: a compact electronic characterization circuit based on phase and amplitude detection at constant frequency; an automated flow injection system; a thermal control unit; a custom-made flow-through cell; and Quartz /SiO2 LW sensors with a 40 µm wavelength and 120 MHz center frequency. The carbaryl detection was based on a competitive immunoassay format using LIB-CNH45 monoclonal antibody (MAb). Bovine Serum Albumin-CNH (BSA-CNH) carbaryl hapten-conjugate was covalently immobilized, via mercaptohexadecanoic acid self-assembled monolayer (SAM), onto the gold sensing area of the LW sensors. This immobilization allowed the reusability of the sensor for at least 70 assays without significant signal losses. The LW immunosensor showed a limit of detection (LOD) of 0.09 µg/L, a sensitivity of 0.31 µg/L and a linear working range of 0.14-1.63 µg/L. In comparison to other carbaryl immunosensors, the LW immunosensor achieved a high sensitivity and a low LOD. These features turn the LW immunosensor into a promising tool for applications that demand a high resolution, such as for the detection of pesticides in drinking water at European regulatory levels.


Assuntos
Acústica/instrumentação , Anticorpos Monoclonais/imunologia , Carbaril/análise , Imunoensaio/instrumentação , Sistemas Microeletromecânicos/instrumentação , Praguicidas/análise , Poluentes Químicos da Água/análise , Carbaril/imunologia , Desenho de Equipamento , Análise de Falha de Equipamento , Praguicidas/imunologia , Poluentes Químicos da Água/imunologia
17.
J Environ Sci Health B ; 49(10): 713-21, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-25065822

RESUMO

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10-700 ng mL(-1) and 10-500 ng mL(-1) with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL(-1) for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3-9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL(-1) of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL(-1).


Assuntos
Carbaril/análise , Carbofurano/análise , Criogéis , Monitoramento Ambiental/instrumentação , Grafite , Álcool de Polivinil , Poluentes Químicos da Água/análise , Absorção Fisico-Química , Adsorção , Monitoramento Ambiental/métodos , Ionização de Chama , Reprodutibilidade dos Testes
18.
Anal Methods ; 16(25): 4093-4103, 2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38855904

RESUMO

The performance of the QuEChERS method in this study, as indicated by a high percentage (>90%) of recovery observations falling within the range of 60-140% and a sample replicate deviation (% RSD) of <20%, for the routine analysis of isoprocarb and carbaryl pesticides, has been evaluated over a 14-month period for the export of Indonesian coffee. Following a seven-day observation of the stability of these pesticides in coffee extract, it was found that the added standard calibration solution remained stable and useable for seven days when stored at 4 °C and -20 °C. This validated method, with high sensitivity (a LOQ of 0.001 mg kg-1 for isoprocarb and carbaryl), has been employed to monitor residues in Indonesian coffee exports to comply with maximum residue limits (MRLs). The samples with higher contamination levels were predominantly from robusta coffee (57.76%), followed by arabica coffee (6.17%). The detection rates for residues decreased by more than 90% in the last two months of the method's application. In the observation of coffee processing, it was found that isoprocarb residues in contaminated samples could be transferred to the processed coffee (roasted and its infusion) to a limited extent, while residues from the carcinogenic carbaryl were not detected due to evaporation. Additionally, chronic dietary risk assessment showed that contaminated samples of robusta and arabica coffees should not be considered a significant public health concern (hazard index HI < 1). However, continuous monitoring of pesticide residues in Indonesian coffee is still recommended, not only to conform to the MRLs of importing countries but also to ensure food trade.


Assuntos
Carbaril , Café , Resíduos de Praguicidas , Espectrometria de Massas em Tandem , Café/química , Resíduos de Praguicidas/análise , Indonésia , Carbaril/análise , Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massas em Tandem/métodos , Contaminação de Alimentos/análise , Limite de Detecção , Carbamatos/análise
19.
Food Chem ; 457: 140486, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39032478

RESUMO

A gold nanogap substrate was used to measure the thiram and carbaryl residues in various fruit juices using surface-enhanced Raman scattering (SERS). The gold nanogap substrates can detect carbaryl and thiram with limits of detection of 0.13 ppb (0.13 µgkg-1) and 0.22 ppb (0.22 µgkg-1). Raw SERS data were first preprocessed to reduce noise and undesirable effects and, were later used for model creation, implementing classification, and regression analysis techniques. The partial least-squares regression models achieved the highest prediction correlation coefficient (R2) of 0.99 and the lowest root mean square of prediction value below 0.62 ppb for both pesticide-infected juice samples. Furthermore, to differentiate between juice samples contaminated by both pesticides and control (pesticide-free), logistic-regression classification models were produced and achieved the highest classification accuracies of 100% and 99% for contaminated juice containing thiram and 100% accurate results for contaminated juice containing carbaryl. This indicates that the gold nanogap surface has significant potential for achieving high sensitivity in detecting trace contaminants in food samples.


Assuntos
Carbaril , Contaminação de Alimentos , Sucos de Frutas e Vegetais , Ouro , Resíduos de Praguicidas , Análise Espectral Raman , Tiram , Resíduos de Praguicidas/análise , Análise Espectral Raman/métodos , Carbaril/análise , Sucos de Frutas e Vegetais/análise , Tiram/análise , Contaminação de Alimentos/análise , Ouro/química , Quimiometria , Nanopartículas Metálicas/química , Limite de Detecção , Frutas/química
20.
J Environ Sci Health B ; 48(11): 893-905, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23998301

RESUMO

A simple and rapid online microchannel preconcentrator coupled with an amperometric detection for the analysis of carbofuran using polyethylene glycol coated onto magnetic particle (PEG-magnetic particles) sorbents was developed. This simple-to-prepare microchannel preconcentrator used an external magnet to retain the PEG-magnetic particle sorbents inside the microchannel. Under optimum conditions, the system provided two linear ranges, from 0.01 to 10.0 mg L(-1) and from 10.0 to 130.0 mg L(-1) with a limit of detection of 8.7 ± 0.1 µg L(-1). The microchannel preconcentrator provided very good stability; it can be used for up to 326 consecutive injections of 5.0 mg L(-1) carbofuran with a relative standard deviation of less than 3%. The developed system provided a good microchannel-to-microchannel and a good electrode-to-electrode reproducibility (n = 6, %RSD < 1). It also provided an excellent selectivity when it was tested with two other carbamate pesticides, carbaryl and methomyl, with a 43 and 256 times higher detection sensitivity for carbofuran, respectively. The developed system was successfully applied to detect carbofuran in surface water samples obtained near vegetable plantation areas. The concentrations of carbofuran in these samples were found to be in the range of non-detectable to 0.047 ± 0.001 mg L(-1). The developed system is easy to operate and easy to couple with other analytical instruments and it could be easily adapted for the analysis of other polar organic contaminants.


Assuntos
Carbofurano/análise , Monitoramento Ambiental/métodos , Sistemas On-Line/instrumentação , Praguicidas/análise , Poluentes Químicos da Água/análise , Carbaril/análise , Monitoramento Ambiental/instrumentação , Cromatografia Gasosa-Espectrometria de Massas , Fenômenos Magnéticos , Metomil/análise , Polietilenoglicóis/química , Sensibilidade e Especificidade
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