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1.
Theriogenology ; 218: 183-192, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38330862

RESUMO

Previously studied classes of pesticides, including organochlorines, organophosphates and pyrethroids disturb the mechanism that causes bovine myometrial contractions. Hence, the aim of this study was to investigate the effects of carbaryl and thiram, which are representative carbamate pesticides commonly used in global agriculture, on the motor and secretory functions of bovine cervixes. Additionally, the impacts of these pesticides on intra- and intercellular signaling in vitro were estimated. In this study, cervical cells or strips were obtained from cows at days 18-20 of the estrous cycle and were treated with carbaryl or thiram. Neither carbamate (10 or 100 ng/ml) exerted cytotoxic effects. Carbaryl increased the level of mRNA (at a dose of 0.1 ng/ml) and protein (at both doses, 1 and 10 ng/ml) expression for the oxytocin receptor (OXTR), while thiram (at 0.1 and 10 ng/ml or 0.1-10 ng/ml, respectively) caused the opposite effects. Moreover, the level of the second messenger inositol-trisphosphate (IP3) was decreased by carbaryl (10 ng/ml) but increased by thiram (10 ng/ml). Only thiram decreased prostaglandin-endoperoxide synthase 2 (PTGS2; 0.1 ng/ml) and aldo-keto reductase family 1, member B1 (AKR1B1; 0.1 ng/ml), and prostaglandin E synthase 2 (PTGES2; 0.1-10 ng/ml) mRNA expression, while thiram (0.1-10 ng/ml) and carbaryl (0.1 and 10 ng/ml) both decreased the release of PGF2α. Carbaryl (10 ng/ml) and thiram (10 ng/ml) also decreased the level of a gap junction protein (GAP). Moreover, carbaryl (10 ng/ml) decreased the level of myosin light chain kinase (MLCK). However, the strength of cervical contractions was increased by thiram (1 and 10 ng/ml) but decreased by carbaryl (1 and 10 ng/ml). Carbaryl increased the receptivity of cervical cells to oxytocin (OXT), but inhibited further transduction (IP3) of this signal. Hence, direct inhibition of cervical strip contraction may occur. In contrast, thiram mostly decreased the receptivity of cervical cells to OXT, while it stimulated the contraction of cervical strips. Moreover, compared to carbaryl, thiram more greatly affected the synthesis and release of prostaglandins. These results suggest that carbaryl and thiram disturb OXT signaling, PG secretion and cervical contraction in vitro.


Assuntos
Carbaril , Praguicidas , Feminino , Bovinos , Animais , Carbamatos/farmacologia , Tiram , Colo do Útero/metabolismo , Ocitocina/metabolismo , RNA Mensageiro/genética
2.
Food Chem ; 431: 137127, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-37573744

RESUMO

On-site multi-pesticide residues detection is particularly urgent and challenging. Here, we fabricated an enzyme-free ratiometric fluorescent detection system in combination with a hinge-like dual-channel 3D microfluidic paper analytical device (3D µPAD) for simultaneous visual detection of carbaryl and glyphosate. Blue-emission 1-naphthol (Em. 470 nm) was hydrolyzed from carbaryl, while yellow-emission 2,3-diaminophenazine (Em. 570 nm) was produced with the aid of Cu2+ for glyphosate sensing. Inner-filter effect between 1-naphthol or 2,3-diaminophenazine and green-emission carbon dots (Em. 510 nm) realized two ratiometric fluorescent detection systems. Remarkable color variation of green-blue for carbaryl (50.00-1100 µΜ) and yellow-green for glyphosate (5.00-600 µΜ) were observed on a dual-channel 3D µPAD without crosstalk. Their detection limits were 1.11 and 0.63 µΜ, respectively. The strategy realized simultaneous visual detection of carbaryl and glyphosate in food/herbal with excellent accuracy (spiked recoveries, 91.00-107.2%), high precision (RSD ≤ 8.43%), and superior selectivity.


Assuntos
Carbaril , Pontos Quânticos , Corantes Fluorescentes/química , Microfluídica , Pontos Quânticos/química , Carbono/química , Limite de Detecção
3.
Appl Environ Microbiol ; 89(10): e0080223, 2023 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-37800922

RESUMO

In a previous study, the novel gene cluster cehGHI was found to be involved in salicylate degradation through the CoA-mediated pathway in Rhizobium sp. strain X9 (Mol Microbiol 116:783-793, 2021). In this study, an IclR family transcriptional regulator CehR4 was identified. In contrast to other regulators involved in salicylate degradation, cehR4 forms one operon with the gentisyl-CoA thioesterase gene cehI, while cehG and cehH (encoding salicylyl-CoA ligase and salicylyl-CoA hydroxylase, respectively) form another operon. cehGH and cehIR4 are divergently transcribed, and their promoters overlap. The results of the electrophoretic mobility shift assay and DNase I footprinting showed that CehR4 binds to the 42-bp motif between genes cehH and cehI, thus regulating transcription of cehGH and cehIR4. The repeat sequences IR1 (5'-TTTATATAAA-3') and IR2 (5'-AATATAGAAA-3') in the motif are key sites for CehR4 binding. The arrangement of cehGH and cehIR4 and the conserved binding motif of CehR4 were also found in other bacterial genera. The results disclose the regulatory mechanism of salicylate degradation through the CoA pathway and expand knowledge about the systems controlled by IclR family transcriptional regulators.IMPORTANCEThe long-term residue of aromatic compounds in the environment has brought great threat to the environment and human health. Microbial degradation plays an important role in the elimination of aromatic compounds in the environment. Salicylate is a common intermediate metabolite in the degradation of various aromatic compounds. Recently, Rhizobium sp. strain X9, capable of degrading the pesticide carbaryl, was isolated from carbaryl-contaminated soil. Salicylate is the intermediate metabolite that appeared during the degradation of carbaryl, and a novel salicylate degradation pathway and the involved gene cluster cehGHIR4 have been identified. This study identified and characterized the IclR transcription regulator CehR4 that represses transcription of cehGHIR4 gene cluster. Additionally, the genetic arrangements of cehGH and cehIR4 and the binding sites of CehR4 were also found in other bacterial genera. This study provides insights into the biodegradation of salicylate and provides an application in the bioremediation of aromatic compound-contaminated environments.


Assuntos
Rhizobium , Salicilatos , Humanos , Salicilatos/metabolismo , Carbaril , Proteínas de Bactérias/metabolismo , Família Multigênica , Rhizobium/genética , Rhizobium/metabolismo , Regulação Bacteriana da Expressão Gênica
4.
Environ Res ; 238(Pt 2): 117193, 2023 12 01.
Artigo em Inglês | MEDLINE | ID: mdl-37758116

RESUMO

Carbaryl and carbofuran are the carbamate pesticides which have been widely used worldwide to control insects in crops and house. If the pesticides entered in to the food products and drinking water, they could cause serious health effects in humans. Therefore, the development of a rapid, simple, sensitive and selective analytical device for on-site detection of carbamates is crucial to evaluate food and environmental samples. Recently, semiconducting single-walled carbon nanotube-based field effect transistors (s-SWCNT/FETs) have shown several advantages such as high carrier mobility, good on/off ratio, quasi ballistic electron transport, label-free detection and real-time response. Herein, cobalt ferrite (CFO) nanoparticles decorated s-SWCNTs have been prepared and used to bridge the source and drain electrodes. As-prepared CFO/s-SWCNT/FET had been used for the non-enzymatic detection of carbaryl and carbofuran. When used as a sensing platform, the CFO/s-SWCNT hybrid film exhibited high sensitivity, and selectivity with a wide linear range of detection from 10 to 100 fMand the lowest limit of detections for carbaryl (0.11 fM) and carbofuran (0.07 fM) were estimated. This sensor was also used to detect carbaryl in tomato and cabbage samples, which confirmed its practical acceptance. Such performance may be attributed to the oxidation of carbamates by potent catalytic activity of CFO, which led to the changes in the charge transfer reaction on the s-SWCNTs/FET conduction channel. This work presents a novel CFO/s-SWCNT based sensing system which could be used to quantify pesticide residues in food samples.


Assuntos
Carbofurano , Nanotubos de Carbono , Praguicidas , Humanos , Carbaril , Nanotubos de Carbono/química , Carbamatos
5.
Ecotoxicol Environ Saf ; 263: 115353, 2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37586199

RESUMO

UDP-glucuronosyltransferases (UGTs) could transform various exogenous and endogenous compounds, which help detoxification of pesticides in insects. To investigate the role of UGTs in the detoxification metabolism of insecticides in Chironomus kiiensis, CkUGT302M1, CkUGT302N1, CkUGT308N1 and CkUGT36J1 genes were identified with 1449-1599 bp encoding 482-532 amino acids. Four UGT genes shared 40.86∼53.36% identity with other homologous insect species, and expressed in all developmental stages, notably in the larval and adult stages. Expression of CkUGTs was higher in the gastric caecum, midgut and head. Moreover, CkUGTs expression and activity were significantly increased in C. kiiensis larvae in exposure to sublethal concentrations of carbaryl, deltamethrin and phoxim, respectively. To further explore the functions of UGT genes, the CkUGT308N1 was effectively silenced in 4th instar C. kiiensis larvae by RNA interference, which resulted in the mortality of dsCkUGT308N1 treated larvae increased by 71.43%, 111.11% and 62.50% under sublethal doses of carbaryl, deltamethrin and phoxim at the 24-h time point, respectively. The study revealed that the CkUGT308N1 gene in C. kiiensis could contribute to the metabolism of pesticides and provide a scientific basis for evaluating the water pollution of pesticides.


Assuntos
Chironomidae , Inseticidas , Animais , Chironomidae/genética , Inseticidas/toxicidade , Carbaril/toxicidade , Larva/genética , Difosfato de Uridina/farmacologia
6.
Colloids Surf B Biointerfaces ; 230: 113508, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37562121

RESUMO

Stimuli-responsive nanocarriers are being widely applied in the development of new strategies for the diagnosis and treatment of diseases. An inherent difficulty in general drug therapy is the lack of precision with respect to a specific pathological site, which can lead to toxicity, excessive drug consumption, or premature degradation. In this work, the controlled drug delivery is achieved by using magnetite nanoparticles coated with mesoporous silica with core-shell structure (MMS) and grafted with the thermoresponsive polymer poly [N-isopropylacrylamide-co-3-(trimethoxysilyl)propyl methacrylate] (MMS-P). The efficiency of MMS-P as a temperature-controlled drug delivery system was evaluated by in vitro release experiments using ibuprofen (IBU) in various mammalian cell models. Further, the effects of IBU as a photoprotectant in cells exposed to photodynamic therapy (PDT) in a carbaryl-induced neurodegenerative model were evaluated. The results showed that MMS-P nanocarriers do not exhibit cytotoxicity in HepG2 cells at high doses such as 7600 µg mL-1. Pre-incubation of MMS-P charged with IBU showed no effect on the PDT in N2A cells; however, it produced a further decrease in the viability of HepG2 cells, leading to a reduction to PDT resistance. On the other hand, a cytoprotective effect against carbaryl toxicity in N2A cells was observed in IBU administrated by MMS-P, which confirms the effective intracellular IBU uptake by means of MMS-P. These results encourage the potential application of MMS-P as a drug delivery system and confirm the effect of IBU as a cytoprotective agent in a neurodegenerative model.


Assuntos
Ibuprofeno , Nanopartículas , Ibuprofeno/química , Carbaril , Sistemas de Liberação de Medicamentos , Polímeros/química , Fenômenos Magnéticos , Dióxido de Silício/química , Nanopartículas/química
7.
Ecotoxicol Environ Saf ; 263: 115293, 2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37517307

RESUMO

Dietary restriction (DR) and dietary deprivation (DD) have been shown to be significantly beneficial in terms of lifespan gains and stress alleviation in invertebrate and vertebrate species. Such beneficial effects, however, have yet to be clearly assessed in the presence of chemical stressors. We conducted a comparative evaluation of the toxicity of carbaryl in Eisenia fetida individuals subjected to a full diet (FD), DR and DD. For 14 days, groups of ten worms subjected to FD received 5 g oatmeal, those subjected to DR received 2.5 g oatmeal, and those subjected to DD received 0 g oatmeal weekly. We evaluated concentrations of 0, 7, 14 and 28 mg carbaryl.kg-1 soil and measured effects on survival, reproduction, biomass and biomarkers (Catalase- CAT and acetylcholine esterase- AChE). Carbaryl caused a total inhibition of reproduction in all the treatments. For each diet level, the 14-day LC50 s were higher than 28 mg.kg-1, but the 14-day LC20 s for the earthworms subjected to FD, DR, and DD were 11.24, 20.51 and > 28 mg.kg-1, respectively. This showed that the toxicity of carbaryl consistently decreased with the reduction in nutrients. Carbaryl caused a significant weight loss in the worms subjected to FD in the 7 mg.kg-1 treatment (P = 0.0065). Such weight loss was not found in any of the other treatments and diets. Both CAT and AChE were significantly inhibited in the two highest treatments (P = 0.0071 and P = 0.0073, respectively). Interestingly, the earthworms subjected to DD showed relatively lower biomarker inhibition, indicating a greater tolerance to oxidative and neurotoxic stresses in these starved earthworms. For all endpoints investigated, aside from reproduction, the starved earthworms fared better under carbaryl toxicity than those given the other diets. Overall, a positive correlation was observed between the amount of food and chemical toxicity as mortality rates, AChE and CAT inhibition increased with the increased amount of nutrients given to the worms. These results show that, in the presence of a chemical stressor, the beneficial effects of DR and DD were variably manifest for select lifecycle parameters and biomarker responses, further suggesting dietary reduction as a non-genetic intervention that could help extend lifespan and alleviate stress even under a chemical insult.


Assuntos
Oligoquetos , Poluentes do Solo , Animais , Carbaril/toxicidade , Acetilcolinesterase , Catalase , Dieta , Biomarcadores , Poluentes do Solo/farmacologia , Solo
8.
Environ Pollut ; 335: 122265, 2023 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-37517641

RESUMO

The simultaneous determination of carbaryl and its metabolite 1-naphthol is essential for risk assessment of pesticide exposure in agricultural and environmental samples. Herein, several bispecific nanobodies (BsNbs) with different lengths of hydrophilic linkers and junction sites were prepared and characterized for the simultaneous recognition of carbaryl and its metabolite 1-naphthol. It was found that the affinity of BsNbs to the analytes could be regulated by controlling linker length and linking terminal. Additionally, molecular simulation revealed that linker lengths affected the conformation of BsNbs, leading to alteration in sensitivity. The BsNb with G4S linker, named G4S-C-N-VHH, showing good thermal stability and sensitivity was used to develop a bispecific indirect competitive enzyme-linked immunosorbent assay (Bic-ELISA). The assay demonstrated a limit of detection of 0.8 ng/mL for carbaryl and 0.4 ng/mL for 1-naphthol in buffer system. Good recoveries from soil and rice samples were obtained, ranging from 80.0% to 112.7% (carbaryl) and 76.5%-110.8% (1-naphthol), respectively. Taken together, this study firstly provided a BsNb with high sensitivity and efficiency against environmental pesticide and its metabolite, and firstly used molecular dynamics simulation to explore the influence of linker on recognition. The results are valuable for the application of immunoassay with high efficiency in the fields of environment and agriculture.


Assuntos
Inseticidas , Oryza , Carbaril/análise , Inseticidas/análise , Solo , Ensaio de Imunoadsorção Enzimática/métodos
9.
J Chromatogr A ; 1705: 464210, 2023 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-37451198

RESUMO

The residue of carbaryl in food is a threat to human health. In this study, activated soybean shell biochar (A-SBC) was used as a carrier, methacrylic acid (MAA) was used as a functional monomer, and carbaryl was used as a template molecule to synthesize the activated biochar surface molecularly imprinted polymer (A-SBC@MIP). The synthesized A-SBC@MIP was characterized by SEM, FT-IR, XRD and XPS techniques, and then applied as adsorbent for carbaryl removal. The adsorption capacity of A-SBC@MIP for carbaryl was 8.6 mg‧g-1 and the imprinting factor was 1.49 at the optimum ionic strength and pH. The kinetic and isothermal data indicated that it had fast mass transfer rate and high binding capacity(Qmax=47.9 mg‧g-1). A-SBC@MIP showed good regenerative properties and the adsorption of carbaryl was excellent in its structural analogues. A solid-phase extraction (SPE) column composed of A-SBC@MIP was developed for the detection of rice and corn under optimized conditions, with recoveries of 93-101% for the spiked carbaryl. The limit of detection (LOD) of the method was 3.6 µg‧kg-1 with good linearity (R2=0.994) in the range of 0.01-5.00 mg‧L-1. The results show that the developed MIPs-SPE can enrich carbaryl from food samples as a specific and cost-effective method.


Assuntos
Impressão Molecular , Oryza , Humanos , Carbaril , Polímeros Molecularmente Impressos , Impressão Molecular/métodos , Zea mays , Polímeros/química , Adsorção , Espectroscopia de Infravermelho com Transformada de Fourier , Extração em Fase Sólida/métodos
10.
Environ Monit Assess ; 195(8): 988, 2023 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-37490187

RESUMO

Pesticide use has increased in the Lake Tana sub-basin due to increased agricultural activity, potentially endangering nontargeted organisms. To assess its potential impact on fish health and fish-consuming human populations, pesticide concentrations in the fillet and liver tissue of three fish species, namely Labeobarbus megastoma, Labeobarbus tsanensis, and Oreochromis niloticus, were investigated in Lake Tana. Fish samples were taken from the lake near the rivers of Ribb and Gumara, which flow through agricultural areas where considerable amounts of pesticides have been applied. A total of 96 fish samples were collected. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) revealed the presence of ten pesticides. Pyrimethanil was frequently detected in 96% of liver and 65% of fillet samples at a median concentration of 33.9 µg kg-1 and 19.7 µg kg-1, respectively. The highest concentration of pyrimethanil was found in L. megastoma (1850.0 µg kg-1). Labeobarbus megastoma also had the highest concentration of oxamyl (507.0 µg kg-1) and flazasulfuron (60.1 µg kg-1) detected in the liver tissue. The highest concentration of carbaryl (56.5 µg kg-1) was found in the liver tissue of O. niloticus. Fish tissue samples from the two study sites contained pyrimethanil, oxamyl, carbaryl, and flazasulfuron. Only pyrimethanil showed a statistically significant difference between the two sites and the species L. megastoma and L. tsanensis. The amounts of pesticides found in the fish species pose no direct risk to the health of fish consumer human population. However, the results show that the lake ecosystem needs immediate attention and regular monitoring of the rising pesticide usage in the lake watershed.


Assuntos
Ciclídeos , Praguicidas , Animais , Humanos , Etiópia , Carbaril , Cromatografia Líquida , Ecossistema , Lagos , Espectrometria de Massas em Tandem , Monitoramento Ambiental
11.
Environ Sci Pollut Res Int ; 30(30): 75281-75299, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37213015

RESUMO

In the aim to determine neurotoxicity, new methods are being validated, including tests and test batteries comprising in vitro and in vivo approaches. Alternative test models such as the zebrafish (Danio rerio) embryo have received increasing attention, with minor modifications of the fish embryo toxicity test (FET; OECD TG 236) as a tool to assess behavioral endpoints related to neurotoxicity during early developmental stages. The spontaneous tail movement assay, also known as coiling assay, assesses the development of random movement into complex behavioral patterns and has proven sensitive to acetylcholine esterase inhibitors at sublethal concentrations. The present study explored the sensitivity of the assay to neurotoxicants with other modes of action (MoAs). Here, five compounds with diverse MoAs were tested at sublethal concentrations: acrylamide, carbaryl, hexachlorophene, ibuprofen, and rotenone. While carbaryl, hexachlorophene, and rotenone consistently induced severe behavioral alterations by ~ 30 h post fertilization (hpf), acrylamide and ibuprofen expressed time- and/or concentration-dependent effects. At 37-38 hpf, additional observations revealed behavioral changes during dark phases with a strict concentration-dependency. The study documented the applicability of the coiling assay to MoA-dependent behavioral alterations at sublethal concentrations, underlining its potential as a component of a neurotoxicity test battery.


Assuntos
Síndromes Neurotóxicas , Poluentes Químicos da Água , Animais , Peixe-Zebra , Rotenona , Carbaril , Hexaclorofeno , Ibuprofeno/toxicidade , Acrilamidas , Embrião não Mamífero
12.
Pest Manag Sci ; 79(10): 3451-3458, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37132399

RESUMO

BACKGROUND: Historically, integrated mite management in Washington apple orchards has focused on conservation of the predatory mite Galendromus occidentalis (Nesbitt) to reduce secondary pest mite pressure. However, pesticide use has changed to include more selective products, coinciding with a shift in the predatory mite community composition to include a new major predator, Amblydromella caudiglans (Schuster). There is evidence that A. caudiglans is more pesticide sensitive than G. occidentalis. Therefore, updates to pesticide selectivity recommendations are needed to conserve this 'new' key predator. Using bioassays, we examined the lethal (female mortality) and sublethal effects (fecundity, egg hatch, larval survival) of 4 fungicides and 11 insecticides on A. caudiglans, to determine whether existing conservation recommendations can be applied to this predatory mite. Susceptibility was compared with prior research on G. occidentalis. RESULTS: Mancozeb was the least selective fungicide tested on A. caudiglans; it caused high acute toxicity and sublethal effects. Carbaryl was the least selective insecticide and caused 100% mortality. Captan was the most selective fungicide. Chlorantraniliprole and cyantraniliprole were the most selective insecticides and therefore least likely to disrupt biological control by A. caudiglans. Non-target effects on A. caudiglans and G. occidentalis were similar, but A. caudiglans experienced higher mortality to some broad-spectrum insecticides. CONCLUSIONS: All the products tested had some non-target effects on A. caudiglans. However, A. caudiglans sensitivity to most tested pesticides was similar to that of G. occidentalis. In general, existing spray recommendations for conserving G. occidentalis can be adjusted slightly and applied to A. caudiglans conservation. © 2023 Society of Chemical Industry. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.


Assuntos
Fungicidas Industriais , Inseticidas , Ácaros , Praguicidas , Humanos , Animais , Feminino , Praguicidas/farmacologia , Inseticidas/farmacologia , Fungicidas Industriais/farmacologia , Carbaril/farmacologia
13.
Protein Expr Purif ; 210: 106310, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37211150

RESUMO

Escherichia coli has been widely employed as a host for heterologous protein expression. However, due to certain limitations, alternative hosts like Pseudomonas, Lactococcus and Bacillus are being explored. Pseudomonas bharatica CSV86T, a novel soil isolate, preferentially degrades wide range of aromatics over simple carbon sources like glucose and glycerol. Strain also possesses advantageous eco-physiological traits, making it an ideal host for engineering xenobiotic degradation pathways, which necessitates the development of heterologous expression systems. Based on the efficient growth, short lag-phase and rapid metabolism of naphthalene, Pnah and Psal promoters (regulated by NahR) were selected for expression. Pnah was found to be strong and leaky as compared to Psal, using 1-naphthol 2-hydroxylase (1NH, ∼66 kDa) as reporter gene in strain CSV86T. The Carbaryl hydrolase (CH, ∼72 kDa) from Pseudomonas sp. C5pp was expressed under Pnah in strain CSV86T and could successfully be translocated to the periplasm due to the presence of the Tmd + Sp sequence. The recombinant CH was purified from the periplasmic fraction and the kinetic characteristics were found to be similar to the native protein from strain C5pp. These results potentiate the suitability of P. bharatica CSV86T as a desirable host, while Pnah and the Tmd + Sp can be employed for overexpression and periplasmic localisation, respectively. Such tools find application in heterologous protein expression and metabolic engineering applications.


Assuntos
Periplasma , Pseudomonas , Pseudomonas/genética , Periplasma/genética , Periplasma/metabolismo , Carbaril/metabolismo , Hidrolases/metabolismo , Proteínas Recombinantes/genética , Proteínas Recombinantes/metabolismo
14.
Spectrochim Acta A Mol Biomol Spectrosc ; 297: 122734, 2023 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-37080052

RESUMO

Conventional spectroscopic methods like IR, and Raman are not very effective at detecting low levels of pesticides or harmful chemicals in food matrices. A quick, highly accurate approach that can identify pesticides present in different food products at lower levels must be developed in order to address this problem and ensure food safety. In this study, a highly sensitive and uniform wafer-scale Au nanogap surface-enhanced Raman spectroscopy (SERS) substrate was used for the quantitative analysis of carbaryl pesticide levels in standard solution, mango juice, and milk samples using chemometrics. Carbaryl was detected up to 3 ppb concentration levels for all three group of samples. However, due to the higher sensitivity, uniformity, and enhancement factors of the SERS substrate used in this investigation, the limit of detection (LOD) values for the standard solution, mango juice, and milk were 0.37 ppb, 0.57 ppb, and 0.15 ppb at 1380 cm-1, 1380 cm-1, and 1364 cm-1 wavenumber ranges. In order to predict different carbaryl concentrations (1, 2, 3, 4, and 5 ppb), the variable importance in projection (VIP) method combined with partial least squares regression (PLSR) and attained the coefficient of determination (R2) values of 0.994, 0.989, and 0.978 along with minimum root mean square error (RMSE) values of 0.112, 0.190, and 0.278 ppb for the prediction datasets. Furthermore, PLS-DA was able to distinguish between pure and adulterated samples with the highest classification accuracy of 100 % for a standard solution, and mango juice and 94.4 % for milk samples. Considering this, we can conclude that the SERS Au Nanogap substrate can rapidly and effectively detect carbaryl pesticides quantitatively and qualitatively in mango juice and milk.


Assuntos
Praguicidas , Animais , Praguicidas/análise , Carbaril/análise , Leite/química , Análise Espectral Raman/métodos , Inocuidade dos Alimentos , Ouro/química
15.
Anal Chem ; 95(8): 4015-4023, 2023 02 28.
Artigo em Inglês | MEDLINE | ID: mdl-36802553

RESUMO

Specific and sensitive sensing of most pesticide residues relies on enzymes such as acetylcholinesterase and advanced materials, which need to be loaded on the surface of working electrodes, leading to instability, uneven surface, tedious process, and high cost. Meanwhile, employing certain potential or current in electrolyte solution could also modify the surface in situ and overcome these drawbacks. However, this method is only regarded as electrochemical activation widely applied in the pretreatment of electrodes. In this paper, by means of regulating the electrochemical technique and its parameters, we prepared a proper sensing interface and derivatized the carbaryl (a carbamate pesticide) hydrolyzed form (1-naphthol) to enhance sensing by 100 times within several minutes. After regulation I by chronopotentiometry with 0.2 mA for 20 s or chronoamperometry with 2 V for 10 s, abundant oxygen-containing groups form and the ordered carbon structure is destroyed. Sweeping from -0.5 to 0.9 V through cyclic voltammetry for only one segment, following regulation II, the composition of oxygen-containing groups changes and the disordered structure is alleviated. Finally, on the constructed sensing interface, test by regulation III through differential pulse voltammetry from 0.8 to -0.4 V, resulting in derivatization of 1-naphthol during 0.8-0 V, followed by electroreduction of the derivative at around -0.17 V. Compared with the electro-oxidation peak at 0.5 V in previous reports, it is essential to improve specificity, even toward several other carbamate pesticides with similar structures. Hence, the in situ electrochemical regulation strategy has demonstrated great potential for effective sensing of electroactive molecules.


Assuntos
Carbaril , Praguicidas , Acetilcolinesterase , Carbamatos , Praguicidas/análise , Eletrodos , Oxigênio , Técnicas Eletroquímicas/métodos
16.
Environ Pollut ; 322: 121165, 2023 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-36720337

RESUMO

Hyalella azteca are epibenthic amphipods that have developed resistance to pyrethroid and organophosphate insecticides due to single amino acid substitutions in the voltage-gated sodium channel and the acetylcholinesterase-1 gene, respectively. Aquatic systems are often contaminated with several different types of insecticides, therefore there is a possibility that H. azteca have also developed resistance to other classes of insecticides. The aims of the current study were to verify that pyrethroid- and organophosphate-resistant H. azteca have retained their resistance after being cultured in the absence of selective pressure for 5 years (Escondido Creek population) and 9 years (Mosher Slough population), to determine if these populations have cross-resistance to carbaryl (carbamate) and 4,4'-dichlorodiphenyltrichloroethane (DDT; organochlorine), and determine whether previous field exposure to fipronil (phenylpyrazole) and imidacloprid (neonicotinoid) caused resistance in cultured pyrethroid- and organophosphate-resistant H. azteca populations. Escondido Creek and Mosher Slough H. azteca populations both maintained high tolerances for bifenthrin due to L925I and I936F amino acid substitutions. Resistance was also found for chlorpyrifos in the Escondido Creek and Mosher Slough populations with lower genotype frequencies of the G119S substitution, indicating that additional factors may be responsible for organophosphate resistance in this study. Mosher Slough H. azteca were moderately resistant to DDT, and Escondido Creek and Mosher Slough H. azteca were moderately resistant to carbaryl, suggesting cross-resistance. No differences were observed in acute toxicity values across the three populations of H. azteca for fipronil and imidacloprid, and this is possibly due to the lack of exposure to toxic concentrations of these insecticides in the field and lack of similar modes of action to pyrethroids and organophosphates. Resistance is known to be associated with fitness costs that can place insecticide-resistant populations at risk for decline through decreased survival and reduced fecundity.


Assuntos
Anfípodes , Clorpirifos , Inseticidas , Piretrinas , Animais , Inseticidas/análise , Resistência a Inseticidas/genética , Carbaril , DDT , Acetilcolinesterase , Piretrinas/toxicidade , Clorpirifos/toxicidade
17.
Sci Total Environ ; 865: 161268, 2023 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-36592917

RESUMO

Carbaryl and fenitrothion are two insecticides sharing a common mode of action, the inhibition of the acetylcholinesterase (AChE) activity. Their use is now regulated or banned in different countries, and the environmental levels of both compounds in aquatic ecosystems have decreased to the range of pg/L to ng/L. As these concentrations are below the non-observed-adverse-effect-concentrations (NOAEC) for AChE inhibition reported for both compounds in aquatic organisms, there is a general agreement that the current levels of these two chemicals are safe for aquatic organisms. In this study we have exposed zebrafish, Japanese medaka and Daphnia magna to concentrations of carbaryl and fenitrothion under their NOAECs for 24-h, and the effects on heart rate (HR), basal locomotor activity (BLA), visual motor response (VMR), startle response (SR) and its habituation have been evaluated. Both pesticides increased the HR in the three selected model organisms, although the intensity of this effect was chemical-, concentration- and organism-dependent. The exposure to both pesticides also led to a decrease in BLA and an increase in VMR in all three species, although this effect was only significant in zebrafish larvae. For SR and its habituation, the response profile was more species- and concentration-specific. The results presented in this manuscript demonstrate that concentrations of carbaryl and fenitrothion well below their respective NOAECs induce tachycardia and the impairment of ecologically relevant behaviors in phylogenetically distinct aquatic model organisms, both vertebrates and invertebrates, emphasizing the need to include this range of concentrations in the environmental risk assessment.


Assuntos
Inseticidas , Praguicidas , Poluentes Químicos da Água , Animais , Carbaril/toxicidade , Fenitrotion/toxicidade , Peixe-Zebra , Inibidores da Colinesterase/toxicidade , Acetilcolinesterase , Frequência Cardíaca , Organismos Aquáticos , Ecossistema , Inseticidas/análise , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise
18.
Talanta ; 254: 124202, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36549139

RESUMO

Herein, we present a novel Origami 3D-µPAD for colorimetric carbaryl detection using a super-efficient catalyst, namely mesoporous silica-platinum nanoparticles coated with a molecularly imprinted polymer (MSN-PtNPs@MIP). Morphological and structural characterization reveals that coating MIP on the MSN-PtNPs surface significantly increases the selective area, leading to larger numbers of imprinting sites for improved sensitivity and selectivity in determining carbaryl. The as-prepared MSN-PtNPs@MIP was used for catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2. Carbaryl selectively binds to the cavities embedded on the MSN-PtNPs surface and subsequently inhibits TMB oxidation leading the color to change to light blue. The change of reaction color from dark blue to light blue depends on the concentration of carbaryl within the 3D-µPAD detection zone. This design integrates the advantages of highly efficient sample delivery through micro channels (top layer) and efficient partition/separation paths (bottom layer) of the cellulose substrate to achieve both improved detection sensitivity and selectivity. Assay on the Origami 3D-µPAD can determine carbaryl by ImageJ detection, over a dynamic range of 0.002-20.00 mg kg-1, with a very low limit of detection at 1.5 ng g-1. The developed 3D-µPAD exhibit high accuracy when applied to detect carbaryl in fruits, with satisfactory recoveries from 90.1% to 104.0% and relative differences from the reference HPLC values less than 5.0%. Furthermore, the fabricated Origami 3D-µPAD provides reliable durability and good reproducibility (3.19% RSD for fifteen devices).


Assuntos
Nanopartículas Metálicas , Impressão Molecular , Carbaril , Polímeros Molecularmente Impressos , Dióxido de Silício/química , Polímeros/química , Platina , Nanopartículas Metálicas/química , Peróxido de Hidrogênio , Microfluídica , Reprodutibilidade dos Testes
19.
Environ Int ; 171: 107657, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36493610

RESUMO

BACKGROUND: Pesticide exposure has been associated with adverse health effects. We evaluated relationships between proximity to agricultural insecticide applications and insecticides in household dust, accounting for land use and wind direction. METHODS: We measured concentrations (ng/g) of nine insecticides in carpet-dust samples collected from 598 California homes. Using a geographic information system (GIS), we integrated the California Pesticide Use Reporting (CPUR) database to estimate agricultural use within residential buffers with radii of 0.5 to 4 km. We calculated the density of use (kg/km2) during 30-, 60-, 180-, and 365-day periods prior to dust collection and evaluated relationships between three density metrics (CPUR unit-based, agricultural land area adjusted, and average daily wind direction adjusted) and dust concentrations. We modeled natural-log transformed concentrations using Tobit regression for carbaryl, chlorpyrifos, cypermethrin, diazinon, and permethrin. Odds of detection were modeled with logistic regression for azinphos-methyl, cyfluthrin, malathion, and phosmet. We adjusted for season, year, occupation, and home/garden uses. RESULTS: Chlorpyrifos use within 1-4 km was associated with 1 to 2-times higher dust concentrations in both the 60- and 365-day periods. Carbaryl applications within 2-4 km of homes 60-days prior to dust collection were associated with 3 to 7-times higher concentrations and the 4 km trend was strongest using the wind-adjusted metric (p-trend = 0.04). For diazinon, there were 2-times higher concentrations for the 60-day metrics in the 2 km buffer and for the CPUR and wind-adjusted metrics within 4 km. Cyfluthrin, phosmet, and azinphos-methyl applications within 4 km in the prior 365-days were associated with 2-, 6-, and 3-fold higher odds of detection, respectively. CONCLUSIONS: Agricultural use of six of the nine insecticides within 4 km is an important determinant of indoor contamination. Our findings demonstrated that GIS-based metrics for quantifying potential exposure to fugitive emissions from agriculture should incorporate tailored distances and time periods and support wind-adjustment for some, but not all insecticides.


Assuntos
Clorpirifos , Inseticidas , Praguicidas , Fosmet , Inseticidas/análise , Diazinon , Azinfos-Metil , Exposição Ambiental/análise , Carbaril , Agricultura , Praguicidas/análise , Poeira/análise
20.
Pest Manag Sci ; 79(1): 464-473, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36209490

RESUMO

BACKGROUND: Fall armyworm (Spodoptera frugiperda) is one of the major invasive pests in China, and has been widely controlled by labor-intensive foliar sprays of agrochemicals in maize (Zea mays L.). RESULTS: Systemic bioassay showed that mixtures of chlorantraniliprole (Chlor) and carbaryl (Carb) had dramatically synergistic effect on toxicity to S. frugiperda. Particularly, a mixture of Chlor with Carb at a mass ratio of 2:1 (MCC) exhibited the highest toxicity to S. frugiperda. Therefore, seed treatment of Chlor mixed with Carb was studied as a simple, accurate, efficient and low-cost control technology. Our results showed that MCC treatment shortened the median lethal time and 90% lethal time to S. frugiperda compared to Chlor- and Carb-alone treatments. Meanwhile, smaller leaf consumption by S. frugiperda was recorded under MCC treatment compared to Chlor- and Carb-alone treatments. In field trial, maize-seed treatment with MCC showed efficacy up to 39 days post-emergence in preventing S. frugiperda foliar damage at a low infestation pressure. Moreover, chemical quantification by ultrahigh-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) showed that Chlor residues were more absorbed and concentrated in maize leaves of MCC treatment, compared to that of Chlor-alone treatment. CONCLUSION: These results suggested that seed treatment with MCC can be applied to increase the control efficacy and reduce the cost of Chlor-alone treatment for controlling S. frugiperda. The present study provided evidence of an enhanced translocation and accumulation of Chlor residues in maize leaves under MCC treatment, which likely contributed to a synergistic effect against S. frugiperda. © 2022 Society of Chemical Industry.


Assuntos
Carbaril , Zea mays , Carbaril/farmacologia , Cromatografia Líquida , Espectrometria de Massas em Tandem , Sementes
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