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1.
Regul Toxicol Pharmacol ; 148: 105595, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38453128

RESUMO

Several New Approach Methodologies (NAMs) for hazard assessment of skin sensitisers have been formally validated. However, data regarding their applicability on certain product classes are limited. The purpose of this project was to provide initial evidence on the applicability domain of GARD™skin and GARD™potency for the product class of agrochemical formulations. For this proof of concept, 30 liquid and 12 solid agrochemical formulations were tested in GARDskin for hazard predictions. Formulations predicted as sensitisers were further evaluated in the GARDpotency assay to determine GHS skin sensitisation category. The selected formulations were of product types, efficacy groups and sensitisation hazard classes representative of the industry's products. The performance of GARDskin was estimated by comparing results to existing in vivo animal data. The overall accuracy, sensitivity, and specificity were 76.2% (32/42), 85.0% (17/20), and 68.2% (15/22), respectively, with the predictivity for liquid formulations being slightly higher compared to the solid formulations. GARDpotency correctly subcategorized 14 out of the 17 correctly predicted sensitisers. Lack of concordance was justifiable by compositional or borderline response analysis. In conclusion, GARDskin and GARDpotency showed satisfactory performance in this initial proof-of-concept study, which supports consideration of agrochemical formulations being within the applicability domain of the test methods.


Assuntos
Agroquímicos , Dermatite Alérgica de Contato , Animais , Agroquímicos/química , Irritantes/farmacologia , Pele , Bioensaio , Estudo de Prova de Conceito , Alternativas aos Testes com Animais
2.
J Nanobiotechnology ; 22(1): 91, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38443975

RESUMO

The primary factors that restrict agricultural productivity and jeopardize human and food safety are heavy metals (HMs), including arsenic, cadmium, lead, and aluminum, which adversely impact crop yields and quality. Plants, in their adaptability, proactively engage in a multitude of intricate processes to counteract the impacts of HM toxicity. These processes orchestrate profound transformations at biomolecular levels, showing the plant's ability to adapt and thrive in adversity. In the past few decades, HM stress tolerance in crops has been successfully addressed through a combination of traditional breeding techniques, cutting-edge genetic engineering methods, and the strategic implementation of marker-dependent breeding approaches. Given the remarkable progress achieved in this domain, it has become imperative to adopt integrated methods that mitigate potential risks and impacts arising from environmental contamination on yields, which is crucial as we endeavor to forge ahead with the establishment of enduring agricultural systems. In this manner, nanotechnology has emerged as a viable field in agricultural sciences. The potential applications are extensive, encompassing the regulation of environmental stressors like toxic metals, improving the efficiency of nutrient consumption and alleviating climate change effects. Integrating nanotechnology and nanomaterials in agrochemicals has successfully mitigated the drawbacks associated with traditional agrochemicals, including challenges like organic solvent pollution, susceptibility to photolysis, and restricted bioavailability. Numerous studies clearly show the immense potential of nanomaterials and nanofertilizers in tackling the acute crisis of HM toxicity in crop production. This review seeks to delve into using NPs as agrochemicals to effectively mitigate HM toxicity and enhance crop resilience, thereby fostering an environmentally friendly and economically viable approach toward sustainable agricultural advancement in the foreseeable future.


Assuntos
Arsênio , Produção Agrícola , Humanos , Agricultura , Agroquímicos/toxicidade , Alumínio
3.
Malar J ; 23(1): 69, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38443984

RESUMO

BACKGROUND: There are several indications that pesticides used in agriculture contribute to the emergence and spread of resistance of mosquitoes to vector control insecticides. However, the impact of such an indirect selection pressure has rarely been quantified and the molecular mechanisms involved are still poorly characterized. In this context, experimental selection with different agrochemical mixtures was conducted in Anopheles gambiae. The multi-generational impact of agrochemicals on insecticide resistance was evaluated by phenotypic and molecular approaches. METHODS: Mosquito larvae were selected for 30 generations with three different agrochemical mixtures containing (i) insecticides, (ii) non-insecticides compounds, and (iii) both insecticide and non-insecticide compounds. Every five generations, the resistance of adults to deltamethrin and bendiocarb was monitored using bioassays. The frequencies of the kdr (L995F) and ace1 (G119S) target-site mutations were monitored every 10 generations. RNAseq was performed on all lines at generation 30 in order to identify gene transcription level variations and polymorphisms associated with each selection regime. RESULTS: Larval selection with agrochemical mixtures did not affect bendiocarb resistance and did not select for ace1 mutation. Contrastingly, an increased deltamethrin resistance was observed in the three selected lines. Such increased resistance was not majorly associated with the presence of kdr L995F mutation in selected lines. RNA-seq identified 63 candidate resistance genes over-transcribed in at least one selected line. These include genes coding for detoxification enzymes or cuticular proteins previously associated with insecticide resistance, and other genes potentially associated with chemical stress response. Combining an allele frequency filtering with a Bayesian FST-based genome scan allowed to identify genes under selection across multiple genomic loci, supporting a multigenic adaptive response to agrochemical mixtures. CONCLUSION: This study supports the role of agrochemical contaminants as a significant larval selection pressure favouring insecticide resistance in malaria vectors. Such selection pressures likely impact kdr mutations and detoxification enzymes, but also more generalist mechanisms such as cuticle resistance, which could potentially lead to cross-tolerance to unrelated insecticide compounds. Such indirect effect of global landscape pollution on mosquito resistance to public health insecticides deserves further attention since it can affect the nature and dynamics of resistance alleles circulating in malaria vectors and impact the efficacy of control vector strategies.


Assuntos
Anopheles , Poluentes Ambientais , Inseticidas , Malária , Nitrilas , Fenilcarbamatos , Piretrinas , Animais , Anopheles/genética , Agroquímicos , Inseticidas/farmacologia , Teorema de Bayes , Resistência a Inseticidas/genética , Mosquitos Vetores/genética , Perfilação da Expressão Gênica
4.
GM Crops Food ; 15(1): 32-39, 2024 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-38375857

RESUMO

Innovation is of fundamental importance for improving food production, as well as sustainability food production. Since 1960, food production has benefited from innovations in plant breeding technologies, fertilizer, chemicals and equipment. These innovations have dramatically increased food production, while the amount of land used has minimally increased. However, future food production increases are jeopardized from widening knowledge gaps between rural food producers and large urban food consuming populations. Over time, that gap has fueled disinformation. The development of disinformation business models contributes to urban consumers receiving inaccurate information about the importance of inputs essential to food production, resulting in political pressures being applied that are targeted at reductions in the use of many food production inputs. The use of chemicals are a frequent target of disinformation campaigns. This article examines how the lack of government clarity about the safe use of chemicals contributes to a lack of public information.


Assuntos
Agricultura , Agroquímicos , Humanos , Agricultura/métodos , População Rural , População Urbana , Tecnologia
5.
Environ Monit Assess ; 196(2): 156, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38227120

RESUMO

In recent times, public concerns over the potential accumulation of heavy metals in agricultural soils and crops due to the excessive use of agrochemicals are increasing. This study was conducted in the Abuakwa North Municipality of Eastern Region, Ghana, to assess the status of heavy metals in cocoa soils and beans. Cocoa farms aged between 10 and 20 years and have received agrochemicals for at least 5 years were selected, and their adjacent forests were used as controls. Soil samples and cocoa pods were collected randomly and processed for laboratory analysis. The study discovered that across the sampling sites, heavy metal concentrations in soil were below permissible limits. However, contamination factor and geo-accumulation index results revealed that Tontro cocoa farms were considerably contaminated and moderately polluted respectively with Cu, probably due to long-term fungicide application. The concentrations of Fe (39.3-47.1 mg kg-1) and Zn (54.8-70.0 mg kg-1) in the cocoa beans across the communities were below the FAO/WHO's safe limit of 99.4 mg kg-1 and 73.0 mg kg-1 respectively. Lead (0.03-0.06 mg kg-1) and Cd (0.12-0.20 mg kg-1) concentrations were below the EU's maximum allowable level and Codex Alimentarius Commission's limit of 1.0 mg kg-1 respectively. However, bean Cu content in the Tontro farm (51.5 mg kg-1) was slightly above the EU's recommended maximum limit of 50.0 mg kg-1, possibly due to the continuous application of copper-based fungicides. The study showed that, overall, agrochemicals used for cocoa farming in Abuakwa North Municipality of Ghana did not cause serious harm to the soils and beans, since the mean metal concentrations were not alarming and guarantee public health safety.


Assuntos
Cacau , Fungicidas Industriais , Metais Pesados , Solo , Cobre , Gana , Monitoramento Ambiental , Produtos Agrícolas , Agroquímicos
6.
Environ Sci Pollut Res Int ; 31(8): 12371-12386, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38228952

RESUMO

In the modern fast-paced lifestyle, time-efficient and nutritionally rich foods like corn and oat have gained popularity for their amino acids and antioxidant contents. The increasing demand for these cereals necessitates higher production which leads to dependency on agrochemicals, which can pose health risks through residual present in the plant products. To first report the phytotoxicity for corn and oat, our study employs QSAR, quantitative Read-Across and quantitative RASAR (q-RASAR). All developed QSAR and q-RASAR models were equally robust (R2 = 0.680-0.762, Q2Loo = 0.593-0.693, Q2F1 = 0.680-0.860) and find their superiority in either oat or corn model, respectively, based on MAE criteria. AD and PRI had been performed which confirm the reliability and predictability of the models. The mechanistic interpretation reveals that the symmetrical arrangement of electronegative atoms and polar groups directly influences the toxicity of compounds. The final phytotoxicity and prioritization are performed by the consensus approach which results into selection of 15 most toxic compounds for both species.


Assuntos
Relação Quantitativa Estrutura-Atividade , Zea mays , Avena , Agroquímicos/toxicidade , Consenso , Reprodutibilidade dos Testes , Medição de Risco
7.
Arch Microbiol ; 206(2): 65, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-38227026

RESUMO

Tea, a highly aromatic and globally consumed beverage, is derived from the aqueous infusion of dried leaves of Camellia sinensis (L.) O. Kuntze. Northeast India, encompassing an expansive geographical area between 24° and 27° N latitude and 88° and 95° E longitude, is a significant tea-producing region covering approximately 312,210 hectares. Despite its prominence, this region faces persistent challenges owing to a conducive climate that harbors the prevalence of pests, fungal pathogens, and weeds, necessitating agrochemicals. Helopeltis theivora, Oligonychus coffeae, and Biston suppressaria are prominent among the tea pests in this region. Concurrently, tea plants encounter fungal infections such as blister blight, brown root rot, and Fusarium dieback. The growing demand for safer tea production and the need to reduce pesticide and fertilizer usage has spurred interest in exploring biological control methods. This review focuses on Actinomycetia, which potentially safeguards plants from diseases and pest infestations by producing many bioactive substances. Actinomycetia, which resides in the tea rhizosphere and internal plant tissues, can produce antagonistic secondary metabolites and extracellular enzymes while promoting plant growth. Harnessing the biocontrol potential of Actinomycetia offers a promising solution to enhance tea production, while minimizing reliance on harmful agrochemicals, contributing to a more environmentally conscious and economically viable tea cultivation system.


Assuntos
Actinobacteria , Camellia sinensis , Agroquímicos , Clima , Chá
8.
Chemosphere ; 350: 141089, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38163465

RESUMO

The European honey bee, Apis mellifera, serves as the principle managed pollinator species globally. In recent decades, honey bee populations have been facing serious health threats from combined biotic and abiotic stressors, including diseases, limited nutrition, and agrochemical exposure. Understanding the molecular mechanisms underlying xenobiotic adaptation of A. mellifera is critical, considering its extensive exposure to phytochemicals and agrochemicals present in the environment. In this study, we conducted a comprehensive structural and functional characterization of AmGSTD1, a delta class glutathione S-transferase (GST), to unravel its roles in agrochemical detoxification and antioxidative stress responses. We determined the 3-dimensional (3D) structure of a honey bee GST using protein crystallography for the first time, providing new insights into its molecular structure. Our investigations revealed that AmGSTD1 metabolizes model substrates, including 1-chloro-2,4-dinitrobenzene (CDNB), p-nitrophenyl acetate (PNA), phenylethyl isothiocyanate (PEITC), propyl isothiocyanate (PITC), and the oxidation byproduct 4-hydroxynonenal (HNE). Moreover, we discovered that AmGSTD1 exhibits binding affinity with the fluorophore 8-Anilinonaphthalene-1-sulfonic acid (ANS), which can be inhibited with various herbicides, fungicides, insecticides, and their metabolites. These findings highlight the potential contribution of AmGSTD1 in safeguarding honey bee health against various agrochemicals, while also mitigating oxidative stress resulting from exposure to these substances.


Assuntos
Fungicidas Industriais , Inseticidas , Abelhas , Animais , Agroquímicos/toxicidade , Glutationa Transferase/metabolismo , Inseticidas/metabolismo , Estrutura Molecular
9.
Sci Rep ; 14(1): 1836, 2024 01 22.
Artigo em Inglês | MEDLINE | ID: mdl-38246913

RESUMO

The production of oil palm (Elaeis guineensis) in Southeast Asia is vital to the economies of Indonesia and Malaysia. Both fertilisers and pesticides used in palm production can contain elevated concentrations of Trace Elements (TEs) which may accumulate in soils and leaf tissues of plants. We hypothesised that leaves from oil palms may be deficient in essential elements, while containing elevated concentrations of non-essential TEs commonly found in agrichemicals. Samples of plant materials (leaves and fruitlets) were collected from active and former plantations in Sumatra, Indonesia, and analysed for essential and non-essential elements. Indonesian palm oil samples were sourced in New Zealand and their elemental concentrations determined. Leaf materials from both active and abandoned production sites were deficient in N, K, S and Mo, while leaf materials from abandoned sites were deficient in P. These deficiencies may have been a contributing factor to the abandonment of production at these sites. Concentrations of non-essential elements were below or comparable to average plant concentrations and no evidence of contamination was found in plant tissues. Palm oil contained low concentrations of TEs, which did not pose any toxicity risks. However, Na and Al were present in concentrations of 1198 and 159 mg kg-1 respectively, which were higher than have been previously reported. Tropical oil palm production could benefit from the determination of bioaccumulation factors for fertiliser contaminants in E. guineensis, to limit the transfer of contaminants to plants and products if increased fertiliser applications were used to correct nutrient deficiencies.


Assuntos
Arecaceae , Oligoelementos , Fertilizantes , Óleo de Palmeira , Agroquímicos , Bioacumulação
10.
11.
Mutagenesis ; 39(2): 146-155, 2024 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-38183270

RESUMO

The two-test in vitro battery for genotoxicity testing (Ames and micronucleus) has in the majority of cases replaced the three-test battery (as two-test plus mammalian cell gene mutation assay) for the routine testing of chemicals, pharmaceuticals, cosmetics, and agrochemical metabolites originating from food and feed as well as from water treatment. The guidance for testing agrochemical groundwater metabolites, however, still relies on the three-test battery. Data collated in this study from 18 plant protection and related materials highlights the disparity between the often negative Ames and in vitro chromosome aberration data and frequently positive in vitro mammalian cell gene mutation assays. Sixteen of the 18 collated materials with complete datasets were Ames negative, and overall had negative outcomes in in vitro chromosome damage tests (weight of evidence from multiple tests). Mammalian cell gene mutation assays (HPRT and/or mouse lymphoma assay (MLA)) were positive in at least one test for every material with this data. Where both MLA and HPRT tests were performed on the same material, the HPRT seemed to give fewer positive responses. In vivo follow-up tests included combinations of comet assays, unscheduled DNA synthesis, and transgenic rodent gene mutation assays, all gave negative outcomes. The inclusion of mammalian cell gene mutation assays in a three-test battery for groundwater metabolites is therefore not justified and leads to unnecessary in vivo follow-up testing.


Assuntos
Hipoxantina Fosforribosiltransferase , Linfoma , Camundongos , Animais , Testes de Mutagenicidade , Ensaio Cometa , Roedores , Agroquímicos , Testes para Micronúcleos , Dano ao DNA
12.
Pest Manag Sci ; 80(3): 1300-1313, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37903719

RESUMO

BACKGROUD: Pseudomonas syringae pv. actinidiae (Psa), P. syringae pv. tomato (Pst) and P. savastanoi pv. savastanoi (Psav) are bacterial plant pathogens with worldwide impact that are mainly managed by the preventive application of cupric salts. These are dangerous for ecosystems and have favoured the selection of resistant strains, so they are candidates to be replaced in the next few years. Thus, there is an urgent need to find efficient and bio-based solutions to mitigate these bacterial plant diseases. Nanotechnology could represent an innovative way to control plant diseases, providing alternative solutions to the agrochemicals traditionally employed, thanks to the formulation of the so-called third-generation and nanotechnology-based agrochemicals. RESULTS: In this work, a novel nanostructured formulation (NPF) composed of cellulose nanocrystals (CNC) as carrier, high amylose starch (HAS) as excipient, and chitosan (CH) and gallic acid (GA) as antimicrobials, was tested at 2% in vitro and in vivo with respect to the three different Pseudomonas plant pathogens. In vitro agar assays demonstrated that the NPF inhibited ≤80% Psa, Pst and Psav. Moreover, the NPF did not decrease biofilm synthesis and it did not influence bacterial cells flocculation and adhesion. On plants, the NPF displayed complete biocompatibility and boosted the transcript levels of the major systemic acquired resistance responsive genes in kiwifruit and olive plants. CONCLUSION: This works provides novel and valuable information regarding the several modes-of-action of the novel NPF, which could potentially be useful to mitigate Psa, Pst and Psav infections even in organic agriculture. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Assuntos
Quitosana , Olea , Pseudomonas syringae , Olea/microbiologia , Ecossistema , Antibacterianos , Agroquímicos , Doenças das Plantas/microbiologia
13.
Environ Sci Pollut Res Int ; 31(1): 1368-1381, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38036908

RESUMO

We present the results of an in situ study of a set of blood parameters in adult marsh frogs (Pelophylax ridibundus (Pallas 1771) from populations inhabiting the largest system of rice fields in Bulgaria, the Tsalapitsa rice fields (TRF), under chronic stress conditions. This study was conducted in spring 2022 to assess the health status of TRF frogs compared to that of frogs occupying a reference site (RS). Furthermore, this study also compared the results obtained for the TRF population with those obtained in a study conducted at the exact same location with P. ridibundus individuals in 2013 (Zhelev et al. 2018). This comparison highlights the potential effects of persistent use of agrochemicals (pesticides and fertilizers) on the marsh frogs of later generations. Our results suggest that the general health of marsh frogs in the polluted site (PS) in southern Bulgaria has severely deteriorated. Frogs of both sexes were anemic with weakened immune systems compared to those living in the RS. The long-term use of agrochemicals in the PS affected males to a greater extent than it did females. Statistically significant hypochromia was observed in males, combined with general leukopenia, neutrophilia, lymphopenia, monocytosis, eosinophilia, and higher neutrophil/lymphocyte (N/L) ratios.


Assuntos
Oryza , Praguicidas , Masculino , Feminino , Animais , Humanos , Áreas Alagadas , Agroquímicos , Ranidae
14.
Small ; 20(7): e2304588, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37840413

RESUMO

Current practices for delivering agrochemicals are inefficient, with only a fraction reaching the intended targets in plants. The surfaces of nanocarriers are functionalized with sucrose, enabling rapid and efficient foliar delivery into the plant phloem, a vascular tissue that transports sugars, signaling molecules, and agrochemicals through the whole plant. The chemical affinity of sucrose molecules to sugar membrane transporters on the phloem cells enhances the uptake of sucrose-coated quantum dots (sucQD) and biocompatible carbon dots with ß-cyclodextrin molecular baskets (suc-ß-CD) that can carry a wide range of agrochemicals. The QD and CD fluorescence emission properties allowed detection and monitoring of rapid translocation (<40 min) in the vasculature of wheat leaves by confocal and epifluorescence microscopy. The suc-ß-CDs more than doubled the delivery of chemical cargoes into the leaf vascular tissue. Inductively coupled plasma mass spectrometry (ICP-MS) analysis showed that the fraction of sucQDs loaded into the phloem and transported to roots is over 6.8 times higher than unmodified QDs. The sucrose coating of nanoparticles approach enables unprecedented targeted delivery to roots with ≈70% of phloem-loaded nanoparticles delivered to roots. The use of plant biorecognition molecules mediated delivery provides an efficient approach for guiding nanocarriers containing agrochemicals to the plant vasculature and whole plants.


Assuntos
Plantas , Sacarose , Transporte Biológico , Plantas/metabolismo , Proteínas de Membrana Transportadoras/metabolismo , Agroquímicos , Folhas de Planta
15.
Int J Biol Macromol ; 257(Pt 2): 128730, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38081490

RESUMO

Some transporters play important roles in the uptake and acropetal xylem translocation of vectorized agrochemicals. However, it is poorly understood the basipetally phloem-loading functions of transporters toward vectorized agrochemicals. Here, L-Val-PCA (L-valine-phenazine-1-carboxylic acid conjugate) uptake was demonstrated carrier-mediated. RcAAP2, RcANT7, and RcLHT1 showed a similarly up-regulated expression pattern from 62 transporter coding genes in Ricinus at 1 h after L-Val or L-Val-PCA treatment. Subcellular localization revealed that fusion RcAAP2-eGFP, RcANT7-eGFP and RcLHT1-eGFP proteins were expressed in the plasma membrane of mesophyll and phloem cells. Yeast assays found that RcAAP2, RcANT7, and RcLHT1 facilitated L-Val-PCA uptake. To further demonstrate the phloem-loading functions, using vacuum infiltration strategy, an Agrobacterium-mediated RNA interference (RNAi) protocol was constructed in seedlings. HPLC detection indicated that L-Val-PCA phloem sap concentrations were significantly decreased 54.5 %, 27.6 %, and 41.6 % after silencing for 72 h and increased 48.3 %, 52.6 %, and 52.4 % after overexpression, respectively. In conclusion, the plasma membrane-located RcAAP2, RcANT7, and RcLHT1 can loaded L-Val-PCA into Ricinus sieve tubes for the phloem translocation, which may aid in the utilization of transporters and molecular design of phloem-mobile fungicides target root or vascular pathogens.


Assuntos
Ixodes , Ricinus , Animais , Ixodes/metabolismo , Valina/metabolismo , Floema/química , Sistemas de Transporte de Aminoácidos/genética , Agroquímicos/química , Fenazinas
16.
Regul Toxicol Pharmacol ; 146: 105543, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38081574

RESUMO

Multiple in vitro eye irritation methods have been developed and adopted as OECD health effects test guidelines. However, for predicting the ocular irritation/damage potential of agrochemical formulations there is an applicability domain knowledge gap for most of the methods. To overcome this gap, a retrospective evaluation of 192 agrochemical formulations with in vivo (OECD TG 405) and in vitro (OECD TG 437, 438, and/or 492) data was conducted to determine if the in vitro methods could accurately assign United Nations Globally Harmonized System for Classification and Labelling of Chemicals (GHS) eye irritation hazard classifications. In addition, for each formulation the eye irritation classification was derived from the classification of the contained hazardous ingredients and their respective concentration in the product using the GHS concentration threshold (CT) approach. The results herein suggest that the three in vitro methods and the GHS CT approach were highly predictive of formulations that would not require GHS classification for eye irritation. Given most agrochemical formulations fall into this category, methods that accurately identify non-classified agrochemical formulations could significantly reduce the use of animals for this endpoint.


Assuntos
Agroquímicos , Irritantes , Animais , Agroquímicos/toxicidade , Agroquímicos/química , Estudos Retrospectivos , Alternativas aos Testes com Animais , Olho
17.
Anal Bioanal Chem ; 416(5): 1127-1137, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38108844

RESUMO

Many agrochemicals are chiral molecules, and most of them are marketed as racemates or diastereomeric mixtures. Stereoisomers that are not the active enantiomer have little or no pesticidal activity and can exert serious toxic effects towards non-target organisms. Thus, investigating the possible exposure to different isomers of chiral pesticides is an urgent need. The present work was aimed at developing a new enantioselective high-performance liquid chromatography-mass spectrometry method for the simultaneous determination of nine chiral pesticides in urine. Two solid-phase extraction (SPE) procedures, based on different carbon-based sorbents (graphitized carbon black (GCB) and buckypaper (BP)), were developed and compared. By using GCB, all analytes were recovered with yields ranging from 60 to 97%, while BP allowed recoveries greater than 54% for all pesticides except those with acid characteristics. Baseline separation was achieved for the enantiomers of all target agrochemicals on a Lux Cellulose-2 column within 24 min under reversed-phase mode. The developed method was then validated according to the FDA guidelines for bioanalytical methods. Besides recovery, the other evaluated parameters were precision (7-15%), limits of detection (0.26-2.21 µg/L), lower limits of quantitation (0.43-3.68 µg/L), linear dynamic range, and sensitivity. Finally, the validated method was applied to verify the occurrence of the pesticide enantiomers in urine samples from occupationally exposed workers.


Assuntos
Agroquímicos , Praguicidas , Humanos , Agroquímicos/análise , Estereoisomerismo , Fuligem , Espectrometria de Massas em Tandem/métodos , Praguicidas/análise , Extração em Fase Sólida/métodos , Cromatografia Líquida de Alta Pressão/métodos
18.
Plant Physiol Biochem ; 206: 108225, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38147708

RESUMO

The increased global food insecurity due to the growing population can be addressed with precision and sustainable agricultural practices. To tackle the issues regarding food insecurity, farmers used different agrochemicals that improved plant growth and protection. Among these agrochemicals, synthetic pesticides used for plant protection in the agricultural field have various disadvantages. Conventional applications of synthetic pesticides have drawbacks such as rapid degradation, poor solubility, and non-target effects, as well as increased pesticide runoff that pollutes the environment. Nanotechnology has evolved as a potential solution to increase agricultural productivity through the development of different nanoforms of agrochemicals such as nanopesticides, nano-fabricated fertilizers, nanocapsules, nanospheres, nanogels, nanofibers, nanomicelles, and nano-based growth promoters. Encapsulation of these pesticides inside the nanomaterials has provided good biocompatibility over conventional application by inhibiting the early degradation of active ingredients (AI), increasing the uptake and adhesion of pesticides, improving the stability, solubility, and permeability of the pesticides, and decreasing the environmental impacts due to the pesticide runoff. In this review, different nanoforms of encapsulated pesticides and their smart delivery systems; nanocarriers in RNA interference (RNAi) based pesticides; environmental fate, practical implications, management of nanopesticides; and future perspectives are discussed.


Assuntos
Nanoestruturas , Praguicidas , Agricultura , Agroquímicos/farmacologia , Nanotecnologia , Plantas
19.
Nat Microbiol ; 9(1): 29-34, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38151646

RESUMO

Widespread use of azole antifungals in agriculture has been linked to resistance in the pathogenic fungus Aspergillus fumigatus. We show that exposure of A. fumigatus to the agrochemical fungicide, ipflufenoquin, in vitro can select for strains that are resistant to olorofim, a first-in-class clinical antifungal with the same mechanism of action. Resistance is caused by non-synonymous mutations within the target of ipflufenoquin/olorofim activity, dihydroorotate dehydrogenase (DHODH), and these variants have no overt growth defects.


Assuntos
Aspergillus fumigatus , Fungicidas Industriais , Aspergillus fumigatus/genética , Fungicidas Industriais/farmacologia , Agroquímicos , Pirróis/farmacologia , Antifúngicos/farmacologia
20.
Chem Res Toxicol ; 37(1): 81-97, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-38118149

RESUMO

Toxicological assessments of newly developed agrochemical agents consider chemical modifications and their metabolic and biotransformation products. To carry out an in silico hazard assessment, understanding the type of chemical modification and its location on the original compound can greatly enhance the reliability of the evaluation. Here, we present and apply a method based on liquid chromatography-mass spectrometry (LC-MS) enhanced with infrared ion spectroscopy (IRIS) to better delineate the molecular structures of transformation products before in silico toxicology evaluation. IRIS facilitates the recording of IR spectra directly in the mass spectrometer for features selected by retention time and mass-to-charge ratio. By utilizing quantum-chemically predicted IR spectra for candidate molecular structures, one can either derive the actual structure or significantly reduce the number of (isomeric) candidate structures. This approach can assist in making informed decisions. We apply this method to a plant growth stimulant, digeraniol sinapoyl malate (DGSM), that is currently under development. Incubation of the compound in Caco-2 and HepaRG cell lines in multiwell plates and analysis by LC-MS reveals oxidation, glucuronidation, and sulfonation metabolic products, whose structures were elucidated by IRIS and used as input for an in silico toxicology assessment. The toxicity of isomeric metabolites predicted by in silico tools was also assessed, which revealed that assigning the right metabolite structure is an important step in the overall toxicity assessment of the agrochemical. We believe this identification approach can be advantageous when specific isomers are significantly more hazardous than others and can help better understand metabolic pathways.


Assuntos
Agroquímicos , Humanos , Reprodutibilidade dos Testes , Células CACO-2 , Espectrometria de Massas/métodos , Análise Espectral
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