Redox-Responsive Nanopesticides Based on Natural Polymers for Environmentally Safe Delivery of Pesticides with Enhanced Foliar Dispersion and Washout Resistance.

Based on the modified cross-linking of the degradable natural polymers chitosan oligosaccharides (COS) and gelatin (GEL) via introduction of a functional bridge 3,3'-dithiodipropionic acid, this study constructed an environmentally responsive dinotefuran (DNF) delivery system (DNF@COS-SS-GEL). The introduction of the disulfide bond (-S-S-) endowed DNF@COS-SS-GEL with redox-responsive properties, allowing for the rapid release of pesticides when stimulated by glutathione (GSH) in the simulated insect. Compared with commercial DNF suspension concentrate (DNF-SC), DNF@COS-SS-GEL showed superior wet spreading and retention performance on cabbage leaves with a reduced contact angle (57°) at 180 s and 4-fold increased retention capacity after rainfall washout. Nanoencapsulation effectively improved the UV-photostability with only a 31.4% decomposition rate of DNF@COS-SS-GEL at 96 h. The small scale and large specific surface area resulted in excellent uptake and transportation properties in plants as well as higher bioactivity against Plutella xylostella larvae. This study will help promote sustainable agricultural development by reducing environmental pollution through improved pesticide utilization.

Compositional Optimization for Miticidal Activity, Ecotoxicity, and Phytotoxicity of Rosmarinus officinalis Essential Oils as Biorational Pesticides.

Recognizing the challenges in using botanicals as sustainable pest control agents due to compositional variation, this study addresses the limitations of traditional component-based approaches such as Hewlett and Plackett or Wadley's models. Based on the assumption of noninteractivity among constituents, these models often fail to predict outcomes accurately due to dynamic intermolecular interactions. We introduce a whole mixture-based approach, employing a combination of experimental design and polynomial modeling. This technique accurately predicts miticidal activity on Tetranychus urticae, ecotoxicity on Daphnia magna, and phytotoxic activities on Phaseolus vulgaris of Rosemarinus officinalis essential oils with varying composition. The RMSE values from the polynomial model are 66.9 and 5.0 for miticidal activity and ecotoxicity, respectively, while they are much higher in component-based models, up to 1097.7 and 41.3, respectively. Additionally, we utilize multiobjective optimization algorithms to identify the optimal supplementary blending of oils and compounds. This strategy aims to maximize miticidal effectiveness while minimizing ecotoxicity and phytotoxicity. Our approach for predicting multicomponent mixture effects is likely to bridge the knowledge gap between research and commercialization.

Molecular interaction mechanisms on (-)-epigallocatechin-3-gallate improving activities of inhibited acetylcholinesterase by selected organophosphorus pesticides in vitro & vivo.

(-)-Epigallocatechin-3-gallate (EGCG) is reported to have benefits for the treatment of Alzheimer's disease by binding with acetylcholinesterase (AChE) to enhance the cholinergic neurotransmission. Organophosphorus pesticides (OPs) inhibited AChE and damaged the nervous system. This study investigated the combined effects of EGCG and OPs on AChE activities in vitro & vivo. The results indicated that EGCG significantly reversed the inhibition of AChE caused by OPs. In vitro, EGCG reactived AChE in three group tubes incubated for 110 min, and in vivo, it increased the relative activities of AChE from less than 20% to over 70% in brain and vertebral of zebrafish during the exposure of 34 h. The study also proposed the molecular interaction mechanisms through the reactive kinetics and computational analyses of density functional theory, molecular docking, and dynamic modeling. These analyses suggested that EGCG occupied the key residues, preventing OPs from binding to the catalytic center of AChE, and interfering with the initial affinity of OPs to the central active site. Hydrogen bonding, conjugation, and steric interactions were identified as playing important roles in the molecular interactions. The work suggests that EGCG antagonized the inhibitions of OPs on AChE activities and potentially offered the neuroprotection against the induced damage.

Encapsulated Thuja plicata essential oil into biopolymer matrix as a potential pesticide against Phytophthora root pathogens.

A new formulation that gradually released encapsulated Thuja plicata essential oil (TPEO) as an active component from a biopolymer matrix within a given period was obtained. Antimicrobial activity was determined in in-vitro tests where pure TPEO successfully inhibited the development of different Phytophthora species. The TPEO essential oil was encapsulated into the biopolymer matrix and an oil-in-water emulsion was formed. FTIR spectra analysis confirmed the formation of electrostatic interaction between these polymers, and hydrogen interactions between active components of TPEO and polymer chains. The stability of the emulsions was confirmed by zeta potential measurements, with a value of about 30 mV, even after 14 days of aging. UV-Vis spectra analysis revealed that >60 % of TPEO remained in the emulsion after 14 days of exposure to ambient conditions, whereas pure TPEO evaporated faster, and around 20 % remained after 6 days. Encapsulated TPEO almost completely inhibited the growth of Phytophthora species during the ten-day day's exposition being statistically significantly improved compared to fungicide treatment. It was demonstrated that the emulsion exhibited a prolonged antimicrobial effect and successfully suppressed the growth of Phytophthora species, and can be considered as a means of protection in forests and crops.

Superhydrophobic Metal-Organic Framework-Based Composite Featuring Removal of Hydrophobic Drugs and Pesticides and Antibacterial Activities.

The widespread use and contamination of natural sources by new-generation drugs and pesticides have enhanced concern about environmental pollution. Understanding the above importance, we developed a superhydrophobic metal-organic framework (MOF) (SHMOF': [Zr6O4(OH)4(BDC-NH-CO-R)2.4(BDC-NH2)0.6(CF3COO)6]·2.5H2O·4DMF) for ecological remediation via adsorption-based separation of hydrophobic drugs (flurbiprofen) and pesticides (fluazinam). The newly developed SHMOF' has a high adsorption capacity toward flurbiprofen and fluazinam, i.e., 435 and 575 mg/g, respectively. The adsorption equilibrium time of the MOF is very short (15 and 10 min for flurbiprofen and fluazinam, respectively). The outstanding superhydrophobic nature of the MOF was employed to separate flurbiprofen and fluazinam from highly alkaline and acidic media and environmental water samples. The SHMOF' has excellent selectivity toward the adsorption-based separation of flurbiprofen and fluazinam in the coexistence of common analytes. Again, we developed a polypropylene (PP) fabric-based composite of SHMOF' (SHMOF'@PP) to separate the hydrophobic targeted analytes by using a zero-energy-consuming filtration-based separation method, which made this separation process cost-efficient and user-friendly. Moreover, Ag nanoparticles were doped to the superhydrophobic composite. The Ag-doped reusable SHMOF'@PP@Ag composite exhibited excellent bacterial antiadhesion and antibacterial properties toward Staphylococcus aureus bacteria.

Efficacy of selected pesticides on Citrus Brown Mite, Eutetranychus orientalis (Acari: Tetranychidae) and the side effects on three predatory mites under citrus orchard conditions.

The present study has been conducted to evaluate the effect of two sprays of seven pesticides at recommended dose on citrus brown mite, Eutetranychus orientalis and the side effects on their predatory mites, Euseius scutalis, Amblyseius swirskii, Phytoseiulus persimilis (Acari: Phytoseiidae) under field conditions at 2022 & 2023 seasons. The obtained results show that, all tested pesticides achieved high reduction % of E. orientalis ranged between (82.1-90.0%) and (81.6-87.1%) after the 1st and 2nd sprays of 2022 season, where it ranged between (84.9- 88.7%) and ( 79.7- 88.7%) after 1st and 2nd sprays of 2023 season. Abamectin recorded the highest reduction % against the citrus brown mite, whereas Congest pesticide recorded the lowest reduction % after the two sprays along 2022 & 2023 seasons. As for the side effects of tested pesticides on associated predatory mites, all pesticides were safely for E. scutalis numbers recording decrease % between (18.4-28.6%) and (16.2 -26.1%) after the 1st and 2nd spray at 2022 season , where it ranged between (15.3- 29.1%) and (19.6-32.0%) after the 1st and 2nd sprays of 2023 season. On contrary, imidacloprid was unsafely for E. scutalis numbers recording the highest mean decrease % after 1st and 2nd sprays during the two seasons. Also, all tested pesticides were safely for A. swirskii numbers, after the 1st and 2nd sprays of the two seasons recording decrease (from 10.9 to 28.1%) & (24.4 to 31.4%) for the 2022 season, and (19-38.9%) & (18.7-39.4%) at 2023 season. On contrary, imidacloprid was unsafely for A. swirskii numbers recorded the highest decrease % after 1st and 2nd sprays during the two seasons. As for, Ph. Persimilis numbers, all tested pesticides were safely, where it recorded low decrease % ranged between (17-33.8%) & (20.4-34.8%) after the 1st and 2nd sprays of 2022 season, and (24.3-39%) & (20.2-28.9%) after the 1st and 2nd sprays of 2023 season. On the other side, imidacloprid was unsafely for Ph. persimilis numbers recording the highest decrease % after the 1st and 2nd sprays during the two seasons. The present study proved that all tested pesticides were high effective against E. orientalis and appeared to be safely and selective for associated predatory mites except imidacloprid which was very harmful for all tested predatory mites, and it could be concluded that the tested pesticides, Fenpyroximate, Hexythiazox , Congest , Spirodiclofen, Abamectin, and Chlorfenapyr could be used in the Integrated Pest Management (IPM) programs for E. orientalis at citrus orchards.

Is the Biopesticide from Tea Tree Oil an Effective and Low-Risk Alternative to Chemical Pesticides? A Critical Review.

The use of chemical pesticides in agriculture contributes to soil, water and air pollution, biodiversity loss, and injury to non-target species. The European Commission has already established a Harmonized Risk Indicator to quantify the progress in reducing the risks linked to pesticides. Therefore, there is an increasing need to promote biopesticides, or so-called low-risk pesticides (LRP). Tea tree oil (TTO) is known for its antiseptic, antimicrobial, antiviral, antifungal, and anti-inflammatory properties. TTO has been extensively studied in pest management as well as in the pharmaceutical and cosmetic industry; there are already products based on its active substances on the market. This review focuses on the overall evaluation of TTO in terms of effectiveness and safety as a biopesticide for the first time. The collected data can be an added value for further evaluation of TTO in terms of the authorization extension as a fungicide in 2026.

Fabrication of zein-coated brush-like silica nanocarriers for high foliage deposition and responsive release of pesticide.

Responsive release systems have received extensive attention to enhance pesticide utilization efficiency and reduce environmental pollution. In this study, pH/GSH dual responsive release system based on brush-like silica (bSiO2) carriers was constructed to enhance the utilization of pesticides. The bSiO2 carriers present core-shell structure, length of 550 nm, diameter of 350 nm and shell thickness of 100 nm. The carrier had a high pesticide loading (20.0 %, w/w) for dinotefuran (Din). After loading Din, zein was covalently linked with cysteine-bridge to seal the loaded pesticides (namely Din@bSiO2@Zein). The Din@bSiO2@Zein exhibited superior foliar affinity, retention and photostability, and retention rate still remain above 95 % with 220 min UV irradiation. Din@bSiO2@Zein displayed pH/GSH responsive release and the cumulative release within 92 h was up to 81 % under pH=9/CGSH=6 mM, mimicking the microenvironment of lepidopteran. The Din@bSiO2@Zein possessed good control efficacy against Plutella xylostella. Appreciably, Din@bSiO2@Zein could be transported bi-directionally to various regions of tobacco plants within 24 h, which had potential to promote pesticide efficacy. This work offers a strategy to minimize the pesticide dosage and encourage sustainable agricultural development.

Recent Advances and Outlook of Benzopyran Derivatives in the Discovery of Agricultural Chemicals.

Scaffold structures, new mechanisms of action, and targets present enormous challenges in the discovery of novel pesticides. The discovery of new scaffolds is the basis for the continuous development of modern agrochemicals. Identification of a good scaffold such as triazole, carbamate, methoxy acrylate, pyrazolamide, pyrido-pyrimidinone mesoionic, and bisamide often leads to the development of a new series of pesticides. In addition, pesticides with the same target, including the inhibitors of succinate dehydrogenase (SDH), oxysterol-binding-protein, and p-hydroxyphenyl pyruvate dioxygenase (HPPD), may have the same or similar scaffold structure. Recent years have witnessed significant progress in the discovery of new pesticides using natural products as scaffolds or bridges. In recent years, there have been increasing reports on the application of natural benzopyran compounds in the discovery of new pesticides, especially osthole and coumarin. A systematic and comprehensive review of benzopyran active compounds in the discovery of new agricultural chemicals is helpful to promote the discussion and development of benzopyran active compounds. Therefore, this work systematically reviewed the research and application of benzopyran derivatives in the discovery of agricultural chemicals, summarized the antiviral, herbicidal, antibacterial, fungicidal, insecticidal, nematicidal and acaricidal activities of benzopyran active compounds, and discussed the structural-activity relationship and mechanism of action. In addition, some active fragments were recommended to further optimize the chemical structure of benzopyran active compounds based on reference information.

Quinoline Derivatives in Discovery and Development of Pesticides.

Finding highly active molecular scaffold structures is always the key research content of new pesticide discovery. In the research and development of new pesticides, the discovery of new agricultural molecular scaffold structures and new targets still faces great challenges. In recent years, quinoline derivatives have developed rapidly in the discovery of new agriculturally active molecules, especially in the discovery of fungicides. The unique quinoline scaffold has many advantages in the discovery of new pesticides and can provide innovative and feasible solutions for the discovery of new pesticides. Therefore, we reviewed the use of quinoline derivatives and their analogues as molecular scaffolds in the discovery of new pesticides since 2000. We systematically summarized the agricultural biological activity of quinoline compounds and discussed the structure-activity relationship (SAR), physiological and biochemical properties, and mechanism of action of the active compounds, hoping to provide ideas and inspiration for the discovery of new pesticides.

Adhesion Peptide-Functionalized Biobased Microgels for Controlled Delivery of Pesticides.

Widespread use of plant protection agents in agriculture is a major cause of pollution. Apart from active ingredients, the environmental impact of auxiliary synthetic polymers should be minimized if they are highly persistent. An alternative to synthetic polymers is the use of natural polysaccharides, which are abundant and biodegradable. In this study, we explore pectin microgels functionalized with anchor peptides (P-MAPs) to be used as an alternative biobased pesticide delivery system. Using copper as the active ingredient, P-MAPs effectively prevented infection of grapevine plants with downy mildew under semi-field conditions on par with commercial copper pesticides. By using anchor peptides, the microgels tightly bind to the leaf surface, exhibiting excellent rain fastness and prolonged fungicidal activity. Finally, P-MAPs are shown to be easily degradable by enzymes found in nature, demonstrating their negligible long-term impact on the environment.

A Smart Pesticide-Controlled Release Platform with Dual Stimuli-Responsive Functions for Enhanced Treatment of Plant Black Shank.

Realizing controllable input of botanical pesticides is conducive to improving pesticide utilization, reducing pesticide residues, and avoiding environmental pollution but is extremely challenging. Herein, we constructed a smart pesticide-controlled release platform (namely, SCRP) for enhanced treatment of tobacco black shank based on encapsulating honokiol (HON) with mesoporous hollow structured silica nanospheres covered with pectin and chitosan oligosaccharide (COS). The SCRP has a loading capacity of 12.64% for HON and could effectively protect HON from photolysis. Owing to the pH- and pectinase-sensitive property of the pectin, the SCRP could smartly release HON in response to a low pH or a rich pectinase environment in the black shank-affected area. Consequently, the SCRP effectively inhibits the infection of P. nicotianae on tobacco with a controlled rate for tobacco black shank of up to 87.50%, which is mainly due to the SCRP's capability in accumulating ROS, changing cell membrane permeability, and affecting energy metabolism. In addition, SCRP is biocompatible, and the COS layer enables SCRP to show a significant growth-promoting effect on tobacco. These results indicate that the development of a stimuli-responsive controlled pesticide release system for plant disease control is of great potential and value for practical agriculture production.

Multi-Stimuli-Responsive, Topology-Regulated, and Lignin-Based Nano/Microcapsules from Pickering Emulsion Templates for Bidirectional Delivery of Pesticides.

The increasing demand for improving pesticide utilization efficiency has prompted the development of sustainable, targeted, and stimuli-responsive delivery systems. Herein, a multi-stimuli-responsive nano/microcapsule bidirectional delivery system loaded with pyraclostrobin (Pyr) is prepared through interfacial cross-linking from a lignin-based Pickering emulsion template. During this process, methacrylated alkali lignin nanoparticles (LNPs) are utilized as stabilizers for the tunable oil-water (O/W) Pickering emulsion. Subsequently, a thiol-ene radical reaction occurs with the acid-labile cross-linkers at the oil-water interface, leading to the formation of lignin nano/microcapsules (LNCs) with various topological shapes. Through the investigation of the polymerization process and the structure of LNC, it was found that the amphiphilicity-driven diffusion and distribution of cyclohexanone impact the topology of LNC. The obtained Pyr@LNC exhibits high encapsulation efficiency, tunable size, and excellent UV shielding to Pyr. Additionally, the flexible topology of the Pyr@LNC shell enhances the retention and adhesion of the foliar surface. Furthermore, Pyr@LNC exhibits pH/laccase-responsive targeting against Botrytis disease, enabling the intelligent release of Pyr. The in vivo fungicidal activity shows that efficacy of Pyr@LNC is 53% ± 2% at 14 days postspraying, whereas the effectiveness of Pyr suspension concentrate is only 29% ± 4%, and the acute toxicity of Pyr@LNC to zebrafish is reduced by more than 9-fold compared with that of Pyr technical. Moreover, confocal laser scanning microscopy shows that the LNCs can be bidirectionally translocated in plants. Therefore, the topology-regulated bidirectional delivery system LNC has great practical potential for sustainable agriculture.

Design, Synthesis, and Biological Activities of Novel Coumarin Derivatives as Pesticide Candidates.

Food security is an important issue in the 21st century; preventing and controlling crop diseases and pests are the key to solve this problem. The creation of new pesticides based on natural products is an important and effective method. Herein, coumarins were selected as parent structures, and a series of their derivatives were designed, synthesized, and evaluated for their antiviral activities, fungicidal activities, and insecticidal activities. We found that coumarin derivatives exhibited good to excellent antiviral activities against tobacco mosaic virus (TMV). The antiviral activities of I-1, I-2a, I-4b, II-2c, II-2g, II-3, and II-3b are better than that of ribavirin at 500 µg/mL. Molecular docking research showed that these compounds had a strong interaction with TMV CP. These compounds also showed broad-spectrum fungicidal activities against 14 plant pathogenic fungi. The EC50 values of I-1, I-2a, I-3c, and II-2d are in the range of 1.56-8.65 µg/mL against Rhizoctonia cerealis, Physalospora piricola, Sclerotinia sclerotiorum, and Pyricularia grisea. Most of the compounds also displayed good insecticidal activities against Mythimna separata. Pesticide-likeness analysis showed that these compounds are following pesticide-likeness and have the potential to be developed as pesticide candidates. The present work lays a foundation for the discovery of novel pesticide lead compounds based on coumarin derivatives.

5-Aminolevulinic acid treatment mitigates pesticide stress in bean seedlings by regulating stress-related gene expression and retrotransposon movements.

Overdoses of pesticides lead to a decrease in the yield and quality of plants, such as beans. The unconscious use of deltamethrin, one of the synthetic insecticides, increases the amount of reactive oxygen species (ROS) by causing oxidative stress in plants. In this case, plants tolerate stress by activating the antioxidant defense mechanism and many genes. 5-Aminolevulinic acid (ALA) improves tolerance to stress by acting exogenously in low doses. There are many gene families that are effective in the regulation of this mechanism. In addition, one of the response mechanisms at the molecular level against environmental stressors in plants is retrotransposon movement. In this study, the expression levels of superoxide dismutase (SOD), ascorbate peroxidase (APX), catalase (CAT), glutathione reductase (GR), and stress-associated protein (SAP) genes were determined by Q-PCR in deltamethrin (0.5 ppm) and various doses (20, 40, and 80 mg/l) of ALA-treated bean seedlings. In addition, one of the response mechanisms at the molecular level against environmental stressors in plants is retrotransposon movement. It was determined that deltamethrin increased the expression of SOD (1.8-fold), GPX (1.4-fold), CAT (2.7-fold), and SAP (2.5-fold) genes, while 20 and 40 mg/l ALA gradually increased the expression of these genes at levels close to control, but 80 mg/l ALA increased the expression of these genes almost to the same level as deltamethrin (2.1-fold, 1.4-fold, 2.6-fold, and 2.6-fold in SOD, GPX, CAT, and SAP genes, respectively). In addition, retrotransposon-microsatellite amplified polymorphism (REMAP) was performed to determine the polymorphism caused by retrotransposon movements. While deltamethrin treatment has caused a decrease in genomic template stability (GTS) (27%), ALA treatments have prevented this decline. At doses of 20, 40, and 80 mg/L of ALA treatments, the GTS ratios were determined to be 96.8%, 74.6%, and 58.7%, respectively. Collectively, these findings demonstrated that ALA has the utility of alleviating pesticide stress effects on beans.

Larvae of Colorado potato beetle (Leptinotarsa decemlineata Say) resistant to double-stranded RNA (dsRNA) remain susceptible to small-molecule pesticides.

BACKGROUND: Implementation of resistance management tools is crucial for the continued efficacy of insect control technologies. An important aspect of insect resistance management (IRM) is the combined or sequential use of different modes-of-action to reduce selection pressure and delay evolution of resistance. This is especially important for insect pests with established ability to develop resistance to insecticides, such as the Colorado potato beetle (Leptinotarsa decemlineata, CPB). A new class of insecticides, based on double-stranded RNA (dsRNA) activating the gene silencing RNA-interference (RNAi) pathway, are currently under review for regulatory approval and commercial use in the USA against CPB. However, there is no information available on the potential for cross-resistance between RNAi insecticides and other classes of insecticides used against CPB. Herein, we aim to fill this knowledge gap by capitalizing on the availability of a CPB strain highly resistant to dsRNAs and test its susceptibility to diverse small-molecule insecticide classes compared to reference dsRNA-susceptible CPB strains. RESULTS: Differences in activity were observed among the four insecticides tested, with abamectin demonstrating highest activity against all three strains of CPB. However, no differences were observed among the dsRNA-resistant and susceptible CPB strains for any of the tested compounds. Overall, these results demonstrate lack of cross-resistance to commonly used chemical insecticides in the dsRNA-resistant strain of CPB. CONCLUSION: These data support the use of these different insecticide classes along with RNAi-based insecticides as part of an effective insect resistance management framework aimed at delaying resistance in CPB. © 2023 Society of Chemical Industry.

Control of sweet potato whitefly (Bemisia tabaci) using entomopathogenic fungi under optimal and suboptimal relative humidity conditions.

BACKGROUND: Sweet potato whitefly (Bemisia tabaci) is one of the most destructive pests to an extensive range of crops and vegetables. Pesticide-dependent management programs have led to severe health problems, including pesticide poisoning and cancer in human beings, as well as pesticide resistance in insect pests. Entomopathogenic fungi (EPF) are considered safe and highly effective against many pests. Therefore, identifying the pathogenicity and virulence of EPFs against Bemisia tabaci is a valuable addition to the management of their infestations. In this study, we investigated the efficacy of conidia suspensions of Aschersonia aleyrodis, Isaria fumosorosea, Beauveria bassiana, and Akanthomyces muscarius (= Lecanicillium muscarium) against nymphal stages of Bemisia tabaci in cucumber seedlings under both optimal and suboptimal conditions. RESULTS: All of the EPFs demonstrated significant ovicidal effects, with the highest cumulative mortalities observed in Aschersonia aleyrodis (96.46%) and I. fumosorosea-treated (94.60%) seedlings against host eggs and crawlers. Similarly, in the L4-instars experiment, Aschersonia aleyrodis and I. fumosorosea were the most efficient, resulting in cumulative mortalities of 94.82% and 94.75%, respectively. However, Bemisia tabaci cumulative mortalities on seedlings treated with Akanthomyces muscarius (78.36%) and Beauveria bassiana (85.90%) were also significantly different from untreated seedlings (7.10%). Under suboptimal relative humidity (RH) conditions (≤ 45% RH), Aschersonia aleyrodis exhibited greater tolerance to harsh conditions, causing a significantly higher infection rate in L1-L2 nymphs (~92%) compared to the approximately 32% infected young nymphs observed in I. fumosorosea-treated seedlings. CONCLUSION: All the selected EPF were more effective against the young nymphal instars. Our results also highlight the efficacy of Aschersonia aleyrodis under suboptimal conditions. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Non-target estrogenic screening of 60 pesticides, six plant protection products, and tomato, grape, and wine samples by planar chromatography combined with the planar yeast estrogen screen bioassay.

For non-target residue analysis of xenoestrogens in food, sophisticated chromatographic-mass spectrometric techniques lack in biological effect detection. Various in vitro assays providing sum values encounter problems when opposing signals are present in a complex sample. Due to physicochemical signal reduction, cytotoxic or antagonistic effect responses, the resulting sum value is falsified. Instead, the demonstrated non-target estrogenic screening with an integrated planar chromatographic separation differentiated opposing signals, detected and prioritized important estrogenic compounds, and directly assigned tentatively the responsible compounds. Sixty pesticides were investigated, ten of which showed estrogenic effects. Exemplarily, half-maximal effective concentrations and 17ß-estradiol equivalents were determined. Estrogenic pesticide responses were confirmed in six tested plant protection products. In food, such as tomato, grape, and wine, several compounds with an estrogenic effect were detected. It showed that rinsing with water was not sufficient to remove selected residues and illustrated that, though not usually performed for tomatoes, peeling would be more appropriate. Though not in the focus, reaction or breakdown products that are estrogenic were detected, underlining the great potential of non-target planar chromatographic bioassay screening for food safety and food control.

Compatibility of pesticides with the predatory mite Neoseiulus barkeri.

Multiple arthropod pests can affect the same crop in agricultural systems, requiring the integration of control methods. In the present study, the effects of residual exposure to four broad-spectrum insecticides/acaricides (azadiractin, abamectin, chlorfenapyr, and fenpyroximate) on immature (development and survival time) and adult females (longevity, fecundity, and fertility life table parameters) of the predatory mite Neoseiulus barkeri were evaluated. Additionally, the insecticides/acaricides were categorized according to their selectivity based on the classification proposed by the International Organization for Biological Control (IOBC) for assessing the susceptibility of arthropods in laboratory experiments. Method 004, proposed by the Insecticide Resistance Action Committee (IRAC), was adopted for the bioassays with predators exposed to insecticide-acaricide residues. Among the insecticides/acaricides studied, azadirachtin had minimal effects on immature and adult N. barkeri (all non-significant) and was considered harmless based on the classification of toxicity according to the standards/categories proposed by the IOBC. All other insecticides/acaricides affected immature and adult N. barkeri and were considered slightly harmful in terms of toxicity, according to the IOBC.

Combined in silico and in vitro approaches to identify P-glycoprotein-inhibiting pesticides.

The P-glycoprotein (P-gp) efflux pump plays a major role in xenobiotic detoxification. The inhibition of its activity by environmental contaminants remains however rather little characterised. The present study was designed to develop a combination of different approaches to identify P-gp inhibitors among a large number of pesticides using in silico and in vitro models. First, the prediction performance of four web tools was evaluated alone or in combination using a set of recently marketed drugs. The best combination of web tools-AdmetSAR2.0/PgpRules/pkCSM-was next used to predict P-gp activity inhibition by 762 pesticides. Among the 187 pesticides predicted to be P-gp inhibitors, 11 were tested in vitro for their ability to inhibit the efflux of reference substrates (rhodamine 123 and Hoechst 33342) in P-gp overexpressing MCF7R cells and to inhibit the efflux of the reference substrate rhodamine 123 in the Caco-2 cell monolayer. In MCF7R cell assays, ivermectin B1a, emamectin B1 benzoate, spinosad, dimethomorph and tralkoxydim inhibited P-gp activity; ivermectin B1a, emamectin B1 benzoate and spinosad were determined to be stronger inhibitors (half-maximal inhibitory concentration [IC50 ] of 3 ± 1, 5 ± 1 and 7 ± 1 µM, respectively) than dimethomorph and tralkoxydim (IC50 of 102 ± 7 and 88 ± 7 µM, respectively). Ivermectin B1a, emamectin B1 benzoate, spinosad and dimethomorph also inhibited P-gp activity in Caco-2 cell monolayer assays, with dimethomorph being a weaker P-gp inhibitor. These combined approaches could be used to identify P-gp inhibitors among food contaminants, but need to be optimised and adapted for high-throughput screening.