COF-SiO2@Fe3O4 Composite for Magnetic Solid-Phase Extraction of Pyrethroid Pesticides in Vegetables.

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.

Pyrethroid residues in Indonesian river Citarum: A simple analytical method applied for an ecological and human health risk assessment.

Pyrethroid residues in the Citarum River, Indonesia, was first investigated based on their occurrences, water assimilative capacity, and risk assessment. In this paper, first, a relatively simple and efficient method was built and validated for analysis of seven pyrethroids in a river water matrix: bifenthrin, fenpropathrin, permethrin, ß-cyfluthrin, cypermethrin, fenvalerate, and deltamethrin. Next, the validated method was used to analyze pyrethroids in the Citarum River. Three pyrethroids, ß-cyfluthrin, cypermethrin, and deltamethrin, were detected in some sampling points with concentration up to 0.01 mg/L. Water assimilative capacity evaluation shows that ß-cyfluthrin and deltamethrin pollution exceed the Citarum river water capacity. However, due to hydrophobicity properties of pyrethroids, removal through binding to sediments are expected. Ecotoxicity risk assessment shows that ß-cyfluthrin, cypermethrin and deltamethrin pose risks to the aquatic organisms in the Citarum River and its tributaries through bioaccumulation in food chain. Based on bioconcentration factors of the detected pyrethroids, ß-cyfluthrin poses the highest adverse effect to humans while cypermethrin is the safest. Human risk assessment based on hazard index suggests that acute non-carcinogenic risk associated to consuming fish from the study location polluted with ß-cyfluthrin, cypermethrin and deltamethrin is unlikely. However, hazard quotient shows that chronic non-carcinogenic risk associated to consuming fish from the study location polluted with ß-cyfluthrin is likely. However, since the risk assessment was performed separately for each pyrethroid, further assessment on the impact of mixture pyrethroid to aquatic organisms and humans should be performed to explore the real impact of pyrethroids to the river system.

The role of pyrethroid derivatives in autophagy and apoptosis crosstalk signaling and potential risk for malignancies.

Pyrethroids and its derivatives widespread and uncontrolled continuous use has influenced multiple deleterious effects resulting in as a potential risk factor causing damage to the organ systems. Allethrin and prallethrin are extensively used yet their influences on human primary cells are very limited or under reported. The potential mechanisms by which allethrin and prallethrin modulates human primary cells, especially the molecular mechanisms or interconnectivity of autophagy-apoptosis, their clinical relevance in human subjects or patients are not well defined. In this current study, we've furnished the evidence that both allethrin and prallethrin user samples significantly induced Ccl2 mRNA expression, increased amount of reactive oxygen intermediate, inhibited membrane bound enzymes and altered membrane fluidity. Pyrethroid derivative users had induced levels of lipid peroxidation and induced binding activities of transcription factors(tfs) like CEBP-ß and NF-AT. Pyrethroid derivatives induced autophagy, elicited intracellular Ca2+ concentration, calcineurin and regulated proapoptotic genes, DAPK1, Bim. Our current study presumably comprises the initial investigation of a very new mechanism of pyrethroid derivatives-moderated programed cell death in various cell sets or types, like human primary cells where-in this is a late event, is documented. Hence, current research-study might be significant in the various pyrethroid derivatives-allied hematological-related cancers and immunosuppressant or auto-immune disorders. In the foremost instance, we present data stating that pyrethroid derivatives induces multiple cell signaling cascades, like CEBP-ß, NF-AT, ERK and MAPK having a role in autophagy thereby; synchronously effectively impact on the apoptosis, therefore causing hematological tumors and toxic or immune related disorders.

TcGLIP GDSL Lipase Substrate Specificity Co-determines the Pyrethrin Composition in Tanacetum cinerariifolium.

Natural pesticides pyrethrins biosynthesized by Tanacetum cinrerariifolium are biodegradable and safer insecticides for pest insect control. TcGLIP, a GDSL lipase underpinning the ester bond formation in pyrethrins, exhibits high stereo-specificity for acyl-CoA and alcohol substrates. However, it is unknown how the enzyme recognizes the other structural features of the substrates and whether such specificity affects the product amount and composition in T. cinrerariifolium. We report here that the cysteamine moiety in (1R,3R)-chrysanthemoyl CoA and the conjugated diene moiety in (S)-pyrethrolone play key roles in the interactions with TcGLIP. CoA released from chrysanthemoyl CoA in the pyrethrin-forming reaction reduces the substrate affinity for TcGLIP by feedback inhibition. (S)-Pyrethrolone shows the highest catalytic efficiency for TcGLIP, followed by (S)-cinerolone and (S)-jasmololone, contributing, at least in part, to determine the pyrethrin compositions in T. cinerariifolium.

Green photosensitisers for the degradation of selected pesticides of high risk in most susceptible food: A safer approach.

Pesticides are the leading defence against pests, but their unsafe use reciprocates the pesticide residues in highly susceptible food and is becoming a serious risk for human health. In this study, mint extract and riboflavin were tested as photosensitisers in combination with light irradiation of different frequencies, employed for various time intervals to improve the photo-degradation of deltamethrin (DM) and lambda cyhalothrin (λ-CHT) in cauliflower. Different source of light was studied, either in ultraviolet range (UV-C, 254 nm or UV-A, 320-380 nm) or sunlight simulator (> 380-800 nm). The degradation of the pesticides varied depending on the type of photosensitiser and light source. Photo-degradation of the DM and λ-CHT was enhanced by applying the mint extracts and riboflavin and a more significant degradation was achieved with UV-C than with either UV-A or sunlight, reaching a maximum decrement of the concentration by 67-76%. The light treatments did not significantly affect the in-vitro antioxidant activity of the natural antioxidants in cauliflower. A calculated dietary risk assessment revealed that obvious dietary health hazards of DM and λ-CHT pesticides when sprayed on cauliflower for pest control. The use of green chemical photosensitisers (mint extract and riboflavin) in combination with UV light irradiation represents a novel, sustainable, and safe approach to pesticide reduction in produce.

Investigation of pesticides on honey bee carbonic anhydrase inhibition.

Carbonic anhydrase (CA, EC 4.2.1.1) plays crucial physiological roles in many different organisms, such as in pH regulation, ion transport, and metabolic processes. CA was isolated from the European bee Apis mellifera (AmCA) spermatheca and inhibitory effects of pesticides belonging to various classes, such as carbamates, thiophosphates, and pyrethroids, were investigated herein. The inhibitory effects of methomyl, oxamyl, deltamethrin, cypermethrin, dichlorodiphenyltrichloroethane (DDT) and diazinon on AmCA were analysed. These pesticides showed effective in vitro inhibition of the enzyme, at sub-micromolar levels. The IC50 values for these pesticides ranged between of 0.0023 and 0.0385 µM. The CA inhibition mechanism with these compounds is unknown at the moment, but most of them contain ester functionalities which may be hydrolysed by the enzyme with the formation of intermediates that can either react with amino acid residues or bid to the zinc ion from the active site.

Eco-friendly Water-Based λ-Cyhalothrin Polydopamine Microcapsule Suspension with High Adhesion on Leaf for Reducing Pesticides Loss.

Recently, innovations of nano/microcarrier formulations have been focused on improving application efficiencies and retention time. In this study, a water-based 2.5% λ-cyhalothrin (LC) microcapsule suspension (CS) was developed by orthogonal test with biodegradable and adhesive polydopamine (PDA) microcapsules (MCs) as carriers. The obtained LC-PDA CS had good suspension properties, flow behavior, storage stability, and rheological properties. LC-PDA CS had higher retention, wettability, and decreased rainwater washing out on the leaves than commercial CS. LC-PDA CS displayed higher insecticidal activity against Lipaphis erysimi compared to commercial CS. LC-PDA CS reduced the toxicity of LC to the aquatic organism Danio rerio compared to LC. The above results demonstrated that LC-PDA CS would be eco-friendly water-based pesticides carrier system for prolonging the retention time on target leaf and reducing toxicity to aquatic organisms.

Co-exposure risks of pesticides residues and bacterial contamination in fresh fruits and vegetables under smallholder horticultural production systems in Tanzania.

This study was carried out to investigate the risks of simultaneous exposure to pesticide residues and bacteria contaminants in locally produced fresh vegetables and vegetables in Tanzania. A total of 613 samples were analyzed for pesticide residues, out of which 250 were also analyzed for bacterial contamination. Overall, 47.5% had pesticide residues, 74.2% exceeded Maximum Residue Levels (MRLs). Organophosphorus (95.2%), organochlorines (24.0%), pyrethroids (17.3%), and carbamates (9.2%) residues dominated. MRL values were mostly exceeded in tomatoes, onions, watermelons, cucumbers, Chinese cabbage, and sweet paper. Tetramethrin (0.0329-1.3733 mg/kg), pirimiphos-methyl (0.0003-1.4093 mg/kg), permethrin (0.0009-2.4537 mg/kg), endosulfan (beta) (0.0008-2.3416 mg/kg), carbaryl (0.0215-1.5068 mg/kg), profenofos (0.0176-2.1377 mg/kg), chlorpyrifos (0.0004-1.2549 mg/kg) and dieldrin (0.0011-0.5271 mg/kg) exceeded MRLs. The prevalence of bacteria contamination was high (63.2%). Enterobacter (55.6%) Pseudomonas aeruginosa (32.4%), E. coli (28.2%), Citrobacter (26.8%), Klebsiella oxytoca (14.8%), and Salmonella (7.7%) were isolated. Furthermore, 46.4% tested positive for both pesticide residues and bacterial contaminants. Vegetables from farms (60.7%) contained more dual contaminants than market-based vegetables (41.8%). This may have resulted from excessive pesticide use and unhygienic handling of fresh fruits and vegetables at production level. Binary logistic regression showed that fresh fruits and vegetables with pesticide residues were 2.231 times more likely to have bacteria contaminants (OR: 2.231; 95% CI: 0.501, 8.802). The contamination levels of pesticide residues and bacterial contaminants could be perceived as a serious problem as most fresh fruits and vegetables recorded values of pesticide residues far above the MRLs with pathogenic bacteria isolated in higher proportions. MRLs was higher in most vegetables consumed raw or semi-cooked such as watermelons, carrots, cucumber, tomatoes, onion and sweet paper. There is an urgent need to develop pesticide monitoring and surveillance systems at farmer level, educating farmers and promoting the use of greener pesticides to mitigate the health effects of pesticides and bacterial contaminants.

Four cypermethrin isomers induced stereoselective metabolism in H295R cells.

Cypermethrin (CP) is widely used for controlling agricultural and indoor vermin. Previous studies have reported the stereoselective difference of CP in biological activities. However, little is known about their potential mechanisms between metabolic phenotypes and endocrine-disrupting effects. Herein, nuclear magnetic resonance (NMR)-based metabolomics combining metabolite identification and pathway analysis were applied to evaluate the stereoselective metabolic cdisorders induced by CP isomers in human adrenocortical carcinoma cells (H295R) culture medium. Then, gene expression levels related to disturbed metabolic pathways were assessed to verify according to metabolic phenotypes. Metabolomics profiles showed that [(S)-cyano(3-phenoxyphenyl)methyl](1R,3R)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate [(1R,3R,αS)-CP] induced the most significant changes in metabolic phenotypes than did the other stereoisomers. There are 10 differential metabolites (isoleucine, valine, leucine, ethanol, alanine, acetate, aspartate, arginine, lactate, and glucose) as well as two significantly disturbed pathways, including "pyruvate metabolism" and "alanine, aspartate, and glutamate metabolism," that were confirmed in H295R cells culture medium of (1R,3R,αS)-CP compared with other stereoisomers. Polymerase chain reaction (PCR) array also confirmed the results of metabolomics. Our results can help to understand the potential mechanisms between the isomer selectivity in metabolic phenotypes and endocrine-disrupting effects. Data provided here not only lend authenticity to the cautions issued by the scientists and researchers but also offer a solution for the balance between environment and political regulations.

Supercritical fluid chromatography separation of chiral pesticides: Unique capabilities to study cyhalothrin and metalaxyl as examples.

Evaluation of chiral pesticides remains a frequently neglected matter in routine food control laboratories. This fact is due to the existence of many residue definitions but also due to the lack of robust instrumental methods for the evaluation of these isomeric compounds. However, supercritical fluid chromatography coupled to mass spectrometry (SFC-ESI-MS/MS) has been demonstrated to perform fast and highly efficient separations without the need to change the mobile phase employed in multiresidue pesticide analyses. Regarding chiral stationary phase columns, the polysaccharide-based ones clearly demonstrate the best separation technology. Two polysaccharide-based columns were tested in this study, and the robustness of their combination with SFC was verified. The enantiomers of lambda-cyhalothrin and metalaxyl were studied precisely due to their markedly distinct toxicity and enantioselectivity. Furthermore, the acute reference dose for gamma-cyhalothrin is half in comparison with its enantiomer (0.0025 and 0.005 mg/kg respectively), which is present in the lambda-cyhalothin residue definition. These enantiomers were analyzed in terms of linearity, reproducibility, and matrix effects in four representative matrices (tomato, orange, leek, and cayenne). Additionally, field tests under greenhouse conditions for these compounds were performed. The results obtained after different sample collections revealed a similar degradation in lambda-cyhalothrin enantiomers (R, S, S, and S, R, R) but not in the case of metalaxyl-M (mefenoxam) where the degradation in tomato was 2 to 6 times less in comparison with its S-enantiomer.

Wastewater-based epidemiology approach to assess population exposure to pesticides: a review of a pesticide pharmacokinetic dataset.

Wastewater-based epidemiology is an innovative approach to estimate a population's intentional and unintentional consumption of chemicals based on biomarker assays found in wastewater. This method can provide real-time objective information on the xenobiotics to which a population is directly or indirectly exposed. This approach has already been used to assess the population exposure to four classes of pesticides: organochlorines (chlordecone), triazines, organophosphates, and pyrethroids. This review aims to obtain the data (excretion rates) and characteristics (pesticide and metabolites stability, including in-sewer one) for other pesticides to broaden the scope of this new method. Excretion rates and stability descriptions for 14 pesticides, namely 2,4-D, aldrin, carbaryl, chlorobenzilate, dieldrin, diquat, ethion, glufosinate, glyphosate, folpet, malathion, parathion, penconazole, and tebuconazole, will be discussed in a practical framework.

Utilization of gum polysaccharide of Araucaria heterophylla and Azadirachta indica for encapsulation of cyfluthrin loaded super paramagnetic iron oxide nanoparticles for mosquito larvicidal activity.

Surface engineering of super paramagnetic iron oxide nanoparticles (SPIONs) favor the tagging of any molecule or compound onto it, encapsulating them with a biopolymer make them biocompatible and favor slow release of loaded molecules. Recovery of SPIONs is easier as they obey to external magnetic field. In this study, SPIONS were used for mosquito larvicidal activity after surface engineered with oleic acid to favor the tagging of Cyfluthrin (mosquito larvicidal agent), it was then encapsulated with gum polysaccharide derived from Azadirachta indica and Araucaria heterophylla. Every stage of coreshell formation was microscopically and spectroscopically characterized. The coreshell SPIONs produced using Azadirachta indica and Araucaria heterophylla gum derived polysaccharide encapsulation were found to be the size around 80 nm. Thus, prepared coreshell SPIONs was subjected for mosquito larvicidal activity against Culex sp. The coreshell SPIONs was efficiently killing the mosquito larva and its impact was studied by percentage mortality studies.

Modelling peak exposure of pesticides in terrestrial and aquatic ecosystems: importance of dissolved organic carbon and vertical particle movement in soil.

In the present work, an existing vegetation/air/litter/soil model (SoilPlusVeg) was modified to improve organic chemical fate description in terrestrial/aquatic ecosystems accounting for horizontal and vertical particulate organic carbon (POC) transport in soil. The model was applied to simulate the fate of three pesticides (terbuthylazine, chlorpyrifos and etofenprox), characterized by increasing hydrophobicity (log KOW from about 3 to 7), in the soil compartment and more specifically, their movement towards surface and groundwater through infiltration and runoff processes. The aim was to evaluate the role of dissolved organic carbon (DOC) and POC in the soil in influencing the peak exposure of pesticides in terrestrial/aquatic ecosystems. Simulation results showed that while terbuthylazine and chlorpyrifos dominated the free water phase (CW-FREE) of soil, etofenprox was mainly present in soil porewater as POC associated chemical. This resulted in an increase of this highly hydrophobic chemical movement towards groundwater and surface water, up to a factor of 40. The present work highlighted the importance of DOC and POC as an enhancer of mobility in the water of poor or very little mobile chemicals. Further studies are necessary to evaluate the bioavailability change with time and parameterize this process in multimedia fate models.

Magnetic Solid-Phase Extraction of Pyrethroid Pesticides from Environmental Water Samples Using Deep Eutectic Solvent-type Surfactant Modified Magnetic Zeolitic Imidazolate Framework-8.

A simple, sensitive and effective magnetic solid-phase extraction (MSPE) technique was developed for the extraction of pyrethroid pesticides from environmental water samples, followed by gas chromatography tandem triple quadrupole mass spectrometry determination. An adsorbent of magnetic zeolitic imidazolate framework-8@deep eutectic solvent (M-ZIF-8@DES) was prepared using deep eutectic solvent coated on the surface of M-ZIF-8. The features of M-ZIF-8@DES were confirmed by material characterizations, and the results indicated that M-ZIF-8@DES has a good magnetism (61.3 emu g-1), a decent surface area (96.83 m2 g-1) and pore volume (0.292 mL g-1). Single factor experiments were carried out to investigate the effect of different conditions on the performance of MSPE. Under the optimal conditions, the developed method performs good linearity (R2 ≥ 0.9916) in the concentration range of 1-500 µg L-1. The limits of detection were in the range of 0.05-0.21 µg L-1 (signal/noise = 3/1). The intraday relative standard deviation (RSD) and interday RSD were less than 9.40%. Finally, the proposed technique was applied for the determination of pyrethroid pesticides in environmental water samples. This work shows the potential of DES-modified metal-organic frameworks for different sample pretreatment techniques.

Efficient biodegradation of 3-phenoxybenzoic acid and pyrethroid pesticides by the novel strain Klebsiella pneumoniae BPBA052.

A novel Klebsiella pneumoniae strain (BPBA052) capable of degrading 3-phenoxybenzoic acid (3-PBA) was isolated from soybean rhizosphere soil. The strain was obtained by screening after enrichment, isolation, and purification using 3-PBA as the sole carbon and energy source. It could degrade 96.37% of 3-PBA (100 mg/L) within 72 h, and its growth and 3-PBA degradation followed kinetics models of logistic growth (XBPBA052 = 0.0883 × e0.0947t / [1 - 0.0792 × (1 - 0.0883 × e0.0947t)]; µm = 0.0947 h-1, X0 = 0.0883, and Xm = 1.1145) and first-order degradation (CBPBA052 = 101.8194 × e-0.0403t, k = 0.0403, t1/2 = 17.22 h), respectively. Based on Box-Behnken response surface analysis, the optimal temperature, pH, and 3-PBA concentration for K. pneumoniae BPBA052 were 35.01 °C, 7.77, and 150 mg/L, respectively. Moreover, pyrethroid pesticides (PPs) (such as ß-cypermethrin, permethrin, bifenthrin, deltamethrin, and fenvalerate) and 3-PBA metabolites (including phenol, catechol, and protocatechuate) were efficiently utilized by BPBA052. We propose a novel microbial metabolic pathway for 3-PBA, based on metabolite identification; enzyme-degrading activity; and cloning of the phenol hydroxylase, catechol 1,2-dioxygenase, and protocatechuate 3,4-dioxygenase genes. This study provides a fundamental platform for further studies to reveal the mechanism of biodegradation of 3-BPA and show K. pneumoniae BPBA052 as a potential microbial resource for bioremediation of environments polluted with 3-PBA or PPs.

Nanoencapsulated deltamethrin as synergistic agent potentiates insecticide effect of indoxacarb through an unusual neuronal calcium-dependent mechanism.

The use of neurotoxic chemical insecticides has led to consequences against the environment, insect resistances and side-effects on non-target organisms. In this context, we developed a novel strategy to optimize insecticide efficacy while reducing doses. It is based on nanoencapsulation of a pyrethroid insecticide, deltamethrin, used as synergistic agent, combined with a non-encapsulated oxadiazine (indoxacarb). In this case, the synergistic agent is used to increase insecticide efficacy by activation of calcium-dependant intracellular signaling pathways involved in the regulation of the membrane target of insecticides. In contrast to permethrin (pyrethroid type I), we report that deltamethrin (pyrethroid type II) produces an increase in intracellular calcium concentration in insect neurons through the reverse Na/Ca exchanger. The resulting intracellular calcium rise rendered voltage-gated sodium channels more sensitive to lower concentration of the indoxacarb metabolite DCJW. Based on these findings, in vivo studies were performed on the cockroach Periplaneta americana and mortality rates were measured at 24 h, 48 h and 72 h after treatments. Comparative studies of the toxicity between indoxacarb alone and indoxacarb combined with deltamethrin or nanoencapsulated deltamethrin (LNC-deltamethrin), indicated that LNC-deltamethrin potentiated the effect of indoxacarb. We also demonstrated that nanoencapsulation protected deltamethrin from esterase-induced enzymatic degradation and led to optimize indoxacarb efficacy while reducing doses. Moreover, our results clearly showed the benefit of using LNC-deltamethrin rather than piperonyl butoxide and deltamethrin in combination commonly used in formulation. This innovative strategy offers promise for increasing insecticide efficacy while reducing both doses and side effects on non-target organisms.

Supercritical Fluid Chromatography and Gas Chromatography Coupled to Tandem Mass Spectrometry for the Analysis of Pyrethroids in Vegetable Matrices: A Comparative Study.

This study describes a comprehensive comparison between supercritical fluid chromatography (SFC) and gas chromatography (GC) coupled to mass spectrometry for the analysis of pyrethroids in vegetable matrices. The ionization process used was electrospray ionization (ESI) in SFC and electron ionization in GC. In general, liquid chromatography coupled to mass spectrometry with ESI sources provides poor results for pyrethroid detection, as described in previous literature. A total of 14 pyrethroids were selected, together with 6 representative matrices. The differences in chromatographic separation and ionization process were assessed. Similar results were obtained in terms of sensitivity (limits of quantification close to 2 µg/kg, injecting the same amount of sample), matrix effect, and linearity. A total of 17 real samples were analyzed by both systems, obtaining similar results. These data suggest that SFC offers a suitable alternative to GC in the analysis of pyrethroids and allows for their inclusion in a wider multiresidue method.

Exploring the Insecticidal Potential of Boldo (Peumus boldus) Essential Oil: Toxicity to Pests and Vectors and Non-target Impact on the Microcrustacean Daphnia magna.

Every year Chile exports about 2000 tons of boldo folium (Peumus boldus), which is used around the world as a traditional herbal medicinal product (THMP), mostly to relieve gastrointestinal disorders. This biomass may be a resource for the agrochemical industry to manufacture botanical insecticides. In this regard, the insecticidal potential of boldo has been poorly investigated. In the present work, hydrodistillation of a commercial boldo folium gave 1.5% (w/w) of a yellowish essential oil (boldo essential oil, BEO) containing 1,8-cineole (20.7%), p-cymene (18.5%), limonene (9.1%), ascaridole (9.1%) and ß-phellandrene (6.4%) as the main constituents, as determined by gas chromatography-mass spectrometry (GC-MS). NMR analysis allowed us to determine that ascaridole was mainly represented by the cis-isomer. BEO was toxic to larvae of the filariasis vector Culex quinquefasciatus and adults of the housefly Musca domestica, showing LC50/LD50 values of 67.9 mg·L-1 and 98.5 µg·adult-1, respectively. On the other hand, lower insecticidal activity was observed against larvae of the moth pest Spodoptera littoralis (LD50 of 268.9 µg·larva-1). It is worth noting that, when tested at LC90 concentration, BEO was significantly less toxic to aquatic microcrustacean Daphnia magna than the conventional insecticide α-cypermethrin. Finally, in the attempt to explore the BEO mode of action, we tested it for acetylcholinesterase (AChE) inhibitory properties using the Ellman method, obtaining negligible effects (IC50 = 0.45 mg·mL-1). Taken together, these results gave new insights into the potential of BEO as a future ingredient of botanical insecticides.

Enantioselectivity in endocrine disrupting effects of four cypermethrin enantiomers based on in vitro models.

Cypermethrin (CP) is a kind of chiral pesticides that has been defined as endocrine disrupting chemical. The diversity in bioactivity, toxicity, metabolism, bioaccumulation, and degradation behaviors of CP enantiomers as well as the research deficiency had made the risk assessment of CP enantiomers very complicated. Herein, four CP enantiomers were separated as target chemicals to investigate their enantioselective endocrine disrupting effects. Firstly, dual-luciferase reporter gene assays were adopted to investigate their potential endocrine disrupting effects via various receptors. The expression levels of steroid hormones related genes and hormone secretion levels in H295R cell were measured to verify the results. Results from the reporter gene assay showed that 1R-cis-αS-CP (CP11) exhibited glucocorticoid receptor (GR), mineralocorticoid receptor (MR), and thyroid receptor (TR) antagonistic activity with the RIC20 values of 9.22 × 10-7, 3.33 × 10-7, and 4.47 × 10-7 M, respectively; 1R-trans-αS-CP (CP21) also showed androgen receptor (AR) agonist activity and estrogen receptor (ER) antagonistic activity with the REC20 and RIC20 values were 1.07 × 10-4 M and 4.78 × 10-6 M, respectively. Results of qRT-PCR and hormone measurement also showed that CP11 and CP21 could disturb the expression of steroid hormones related genes and hormone secretion accordingly. Results provided here can help to understand the enantioselective ecological and health risks of CP enantiomers comprehensively and provide constructive guidance for the safe use of chiral pesticides and the invention of green pesticides.

Assessment of ethylene glycol diacetate as an alternative carrier for use in agrochemical emulsifiable concentrate formulation.

The conventional emulsifiable concentrate (EC) formulation contains a large amount of aromatic solvents, which causes adverse effects to both the environment and human health due to the toxicity of the solvents. Here, we developed a 2.5% lambda-cyhalothrin EC formulation with ethylene glycol diacetate (EGDA) as the solvent, and the developed formulation serves as an environmental-friendly alternative to overcome the adverse effects of aromatic solvents. The physicochemical characterizations, wettability properties, phytotoxicity and bioassays of the EGDA-EC formulation were systematically investigated and compared with that of the EC formulation with xylene as the solvent. The results showed that both EC formulations had excellent emulsion properties and storage stabilities. Additionally, the EGDA-EC formulation possessed a higher flash point (96 °C), indicating safer production, storage and transport. The retentions of the EGDA-EC sample on leaves were 1.22-1.46-fold higher than that of the xylene-EC sample, and the EGDA-EC also exhibited lower surface tensions and contact angles, which would benefit decreasing drift-off and improving utilization. Furthermore, the bioassays demonstrated that the EGDA-EC formulation had lower acute toxicity to aquatic organisms and higher control efficacy to target insects compared with the xylene-EC formulation. Therefore, EGDA is a promising carrier for oil-soluble agrochemicals to improve their application performance and reduce their adverse effects.