To address global challenges such as population growth and climate change, introduction of new technologies and innovations in agriculture are paramount. Polymer-based formulations of agrochemicals have received much attention in recent years, and there is strong motivation to develop agrochemicals that are not harmful to the environment. Proteinoid polymers are produced by thermal step-growth polymerization of natural and unnatural amino acids. Under suitable gentle conditions, the proteinoid polymers may self-assemble to form nano-sized hollow proteinoid nanoparticles (NPs) of a relatively narrow size distribution. Agrochemical molecules may be encapsulated within these hollow proteinoid NPs, integrated in the crude proteinoid shell, or bound covalently/physically to the NP surface. In the present manuscript we prepared and characterized four model proteinoid polymers and NPs: P(KEf), P(KF), P(EWH-PLLA) and P(KWH-PLLA), where Ef denotes the unnatural herbicidal amino acid glufosinate. The NPs were fluorescently labeled and loaded with agrochemicals such as the plant hormone auxin. In addition, the NP surface was hydrophobized by covalent conjugation of dodecyl aldehyde via its surface primary amine groups. Following treatment of the plants with the different fluorescent-labeled NPs, fluorescent microscopic techniques enabled to localize the NPs and observe the accumulation in the plant's vascular system. Next, using genetically modified plants, which express fluorescent protein and are responsive to the level of auxin, we demonstrated the possibility to deliver encapsulated agrochemicals into cells. We also illustrated that the proteinoid NPs are non-toxic to human umbilical vein endothelial cells, and apart from P(KEf) also to lettuce plants.

Quinestrol (QUN), a synthetic estrogen used as an oral contraceptive or emergency contraceptive component, has been shown to be an endocrine-disrupting chemical. To assess the environmental risk of QUN, batch equilibration experiments were conducted to investigate the adsorption-desorption of QUN in five contrasting soils from different areas of China. The leaching properties were also calculated based on the adsorption and degradation data from our previous study with the same soils. The Freundlich and Langmuir models were applied to the sorption-desorption data to examine the affinity towards QUN of the soils, which had varying physical and chemical properties. The Kf and Kfdes values of QUN in the tested soils ranged from 3.72 to 20.47 mg1-n Ln kg-1 and from 1.26 to 7.8 mg1-n Ln kg-1, respectively, and Qm ranged from 28.25 to 126.58 mg/kg. The desorption data showed that hysteresis occurred. The Kf and Kfdes values of QUN were positively correlated with the soil total organic carbon (OC) and cation exchange capacity (CEC), and it may be due to the content of TOC and CEC exhibited a positive correlation. A low mobility potential of QUN in soils was predicted and verified the adsorption results by the groundwater ubiquity score (GUS) and retardation factor (Rf).

Grey mold disease results from Botrytis cinerea, a classical "high-risk" plant pathogenic fungus in meaning of resistance development to fungicides, and its management depends largely on the frequent applications of fungicides. The evolution of resistance to benzimidazole chemicals during 2008 and 2016 was monitored continuously in strawberry greenhouses located in Zhejiang province. Results showed that extensive applications of the mixture of carbendazim and diethofencarb caused the rapid spread of Ben MR subpopulation. The withdraw of this mixture lead to the sharply decrease of Ben MR and re-dominance of Ben HR isolates of B. cinerea with the E198A mutation in β-tubulin gene. The LAMP primers, based on the E198A point mutation, were designed to detect the E198A genotype specifically. HNB (Hydroxynaphthol blue), a metalion indicator, acted as a visual LAMP reaction indicator that turned the violet colored into a sky-blue color. The detection limit of concentration of DNA was 100 × 10-2 ng/μL and this LAMP assay could be applied to detect the E198A genotype with 100% accuracy in strawberry greenhouses of three Province and was more rapid and easier to operate. In summary, we establish a simple and sensitive on-field LAMP assay which can be adopted to determine within 1.5 h whether the benzimidazoles or the mixture of a benzimidazole fungicide and diethofencarb is suitable for management of B. cinerea.

The use of agrochemicals in vegetable production could influence the selection for insecticide resistance in malaria vectors. Unfortunately, there is a dearth of information on the potential contribution of agrochemicals to insecticide resistance in Anopheles mosquitoes breeding on vegetable farms in southern Benin. A Knowledge, Attitudes and Practices study was conducted with 75 vegetable farmers from Houeyiho and Seme to determine the main agrochemicals used in vegetable production, and the concentration and frequency of application, among other details. Mosquitoes and breeding water were sampled from the farms for analysis. Bioassays were conducted on mosquitoes, while breeding water was screened for heavy metal and pesticide residue contamination. Lambda-cyhalothrin was the main insecticide (97.5%) used by farmers, and Anopheles coluzzii was the main mosquito identified. This mosquito species was resistant (30-63% mortality rate) to λ-cyhalothrin. It was also observed that 16.7% of the examined breeding sites were contaminated with λ-cyhalothrin residues. Furthermore, copper contamination detected in mosquito breeding sites showed a positive correlation (r = 0.81; P = 0.0017) with mosquito resistance to λ-cyhalothrin. The presence of copper in λ-cyhalothrin-free breeding sites, where mosquitoes have developed resistance to λ-cyhalothrin, suggests the involvement of copper in the insecticide resistance of malaria vectors; this, however, needs further investigation.

QYR301, 1,3-Dimethyl-1H-pyrazole-4-carboxylic acid 4-[2-chloro-3-(3,5-dimethyl-pyrazol-1-ylmethyl)-4-methanesulfonyl-benzoyl]-2,5-dimethyl-2H-pyrazol-3-yl ester, is a novel HPPD-inhibiting herbicide and was evaluated to provide a reference for post-emergence (POST) application under greenhouse and field conditions. The crop safety (180 and 360 g active ingredient (a.i.) ha-1 treatments) experiment revealed that wheat, paddy, garlic and corn were the only four crops without injury at both examined herbicide rates. The weed control efficacy (60 and 120 g a.i. ha-1) experiment showed that QYR301 exhibited high efficacy against many weeds, especially weeds infesting paddy fields. Furthermore, it is interesting that both susceptible and multiple herbicide resistant Echinochloa crus-galli (L.) Beauv. and Echinochloa phyllopogon (Stapf) Koss, two notorious weed species in paddy field, remained susceptible to QYR301. Further crop tolerance results indicated that 20 tested paddy hybrids displayed different levels of tolerance to QYR301, with the japonica paddy hybrids having more tolerance than indica paddy hybrids under greenhouse conditions. Results obtained from field experiments showed that QYR301 POST at 135 to 180 g a.i. ha-1 was recommended to provide satisfactory full-season control of E. crus-galli and Leptochloa chinensis (L.) Nees and to maximize rice yields. These findings indicate that QYR301 possesses great potential for the management of weeds in paddy fields.

Fusarium stalk rot (FSR) caused by Fusarium graminearum (FG) significantly affects the productivity of maize grain crops. Application of agrochemicals to control the disease is harmful to environment. In this regard, use of biocontrol agent (BCA) is an alternative to agrochemicals. Although Trichoderma species are known as BCA, the selection of host-pathogen specific Trichoderma is essential for the successful field application. Hence, we screened a total of 100 Trichoderma isolates against FG, selected Trichoderma harzianum (CCTCC-RW0024) for greenhouse experiments and studied its effect on changes of maize rhizosphere microbiome and biocontrol of FSR. The strain CCTCC-RW0024 displayed high antagonistic activity (96.30%), disease reduction (86.66%), biocontrol-related enzyme and gene expression. The root colonization of the strain was confirmed by eGFP tagging and qRT-PCR analysis. Pyrosequencing revealed that exogenous inoculation of the strain in maize rhizosphere increased the plant growth promoting acidobacteria (18.4%), decreased 66% of FG, and also increased the plant growth. In addition, metabolites of this strain could interact with pathogenicity related transcriptional cofactor FgSWi6, thereby contributing to its inhibition. It is concluded that T. harzianum strain CCTCC-RW0024 is a potential BCA against FSR.

Fruit and vegetable crops that are not consumed immediately, unlike other agricultural products, require economic and time investments until they reach the final consumers. Synthetic agrochemicals are used to maintain and prolong the storage life of crops and avoid losses caused by phytopathogenic microorganisms. However, the excessive use of synthetic agrochemicals creates health problems and contributes to environmental pollution. To avoid these problems, less toxic and environment-friendly alternatives are sought. One of these alternatives is the application of biopesticides. However, few biopesticides are currently used. In this study, the biopesticide activity of Bursera morelensis and Lippia graveolens essential oils was evaluated. Their antifungal activity has been verified in an in vitro model, and chemical composition has been determined using gas chromatography-mass spectrometry. Their antifungal activity was corroborated in vitro, and their activity as biopesticides was subsequently evaluated in a plant model. In addition, the persistence of these essential oils on the surface of the plant model was determined. Results suggest that both essential oils are promising candidates for producing biopesticides. This is the first study showing that B. morelensis and L. graveolens essential oils work by inhibiting mycelial growth and spore germination and are environment-friendly biopesticides.

Nanocarrier systems for the encapsulation of agrochemicals can contribute to sustainable agriculture, but few nanosystems have been developed for plant growth regulators (PGRs). The present study evaluated the effects of seed priming using alginate/chitosan (nanoALG/CS) and chitosan/tripolyphosphate (nanoCS/TPP) containing GA3 on the growth and productivity of Solanum lycopersicum cultivated under field conditions. The results demonstrated that nanocarrier systems could improve fruit production, with the productivity increasing almost 4-fold using nanoALG/CS-GA3. This pioneering study demonstrates the potential of nanocarrier systems with PGRs for applications in agriculture.

Agriculture plays a crucial role in safeguarding food security, more so as the world population increases gradually. A productive agricultural system is supported by seed, soil, fertiliser and good management practices. Food productivity directly correlates to the generation of solid wastes and utilization of agrochemicals, both of which negatively impact the environment. The rice and paddy industry significantly adds to the growing menace of waste management. In low and middle-income countries, rice husk (RH) is an underutilized agro-waste discarded in landfills or burned in-situ. RH holds enormous potential in the development of value-added nanomaterials for agricultural applications. In this study, a simple and inexpensive sol-gel method is described to extract mesoporous silica nanoparticles (MSNs) from UKMRC8 RH using the bottom-up approach. RHs treated with hydrochloric acid were calcinated to obtain rice husk ash (RHA) with high silica purity (> 98% wt), as determined by the X-ray fluorescence analysis (XRF). Calcination at 650 °C for four hours in a box furnace yielded RHA that was devoid of metal impurities and organic matter. The X-ray diffraction pattern showed a broad peak at 2θ≈20-22 °C and was free from any other sharp peaks, indicating the amorphous property of the RHA. Scanning electron micrographs (SEM) showed clusters of spherically shaped uniform aggregates of silica nanoparticles (NPs) while transmission electron microscopy analysis indicated an average particle size of < 20 nm. Besides Energy Dispersive X-Ray which validated the chemical constituent of the silica NPs, the Fourier transform infrared (FT-IR) spectra showed peaks at 796.4 cm-1 and 1052 cm-1 corresponding to O-Si-O symmetric stretching vibration and O-Si-O asymmetric stretching, respectively. The Brunauer-Emmet-Teller (BET) analysis indicated an average pore size = 8.5 nm while the specific surface area and the pore volume were 300.2015 m2/g and 0.659078 cm3/g, respectively. In conclusion, agrowaste-derived MSN was synthesized using a simple and economical sol-gel method without the addition of surfactant reagents for controlled formation at the structural level. Owing to the MSNs' excellent physical properties, the method established herein, could be used singly (without any modifications) for the functionalization of a myriad of agrochemicals.

Intensive conventional farm management, characterized by high agrochemicals input, could alter the composition of microbial communities with potential negative effects on both functional traits and the ecosystem services provided. In this study, we investigated the gut microbial composition of a high ecological relevance carabid Pseudoophonus rufipes, sampled in two fields subjected to conventional and organic management practices. Carabids' gut microbiota was analyzed via qPCR and NGS. Profound differences between the microbial composition of organic and conventional samples were detected: the abundance of Tenericutes and Proteobacteria was significant higher in organic and conventional samples, respectively. Spiroplasmataceae and Bifidobacteriaceae families were significantly more abundant in samples from organic management, while Enterococcaceae, Morganellaceae and Yersiniaceae were more abundant in samples from conventional management. The diverse gut microbial composition of insects between the two management systems is related to the pressure of environmental stressors and it may representing an important bioindication of ecological functions and services provided by a carabid species.

Humans alter the environment at unprecedented rates through habitat destruction, nutrient pollution and the application of agrochemicals. This has recently been proposed to act as a potentially significant driver of pathogen-carrying mosquito species (disease vectors) that pose a health risk to humans and livestock. Here, we use a unique set of locations along a large geographical gradient to show that landscapes disturbed by a variety of anthropogenic stressors are consistently associated with vector-dominated mosquito communities for a wide range of human and livestock infections. This strongly suggests that human alterations to the environment promote the presence and abundance of disease vectors across large spatial extents. As such, it warrants further studies aimed at unravelling mechanisms underlying vector prevalence in mosquito communities, and opens up new opportunities for preventative action and predictive modelling of vector borne disease risks in relation to degradation of natural ecosystems.

As compared to organic farming system, conventional farming system relies on higher inputs of synthetic agrochemicals, which may reduce the abundance, diversity, and beneficial effects of plant endophytic fungal communities. This study compares the diversity and abundance of culturable endophytic fungal communities associated with four plant species -corn, tomato, pepper, and watermelon grown in separate organic and conventional fields. In all, 740 fungal isolates were identified, of which 550 were from the organic fields and 190 from the conventional ones. These fungal isolates were grouped into eight orders and 22 species, with the two most abundant species being Trichoderma sp. and Pichia guilliermondi. The fungal species diversity and abundance were both significantly higher in the organic than in the conventional fields. All the isolated endophytic fungi improved tomato plants' shoot growth and biomass significantly, as compared with the water control. Six fungal isolates also exhibited activity that enhanced tomato fruit yields. These results suggest that these endophytic fungi might be a considerable boost to sustainable agricultural production, while also reducing the agricultural application of chemicals and thus benefiting the environment and human health.

Sleep plays an essential role in both neural and energetic homeostasis of animals. Honey bees (Apis mellifera) manifest the sleep state as a reduction in muscle tone and antennal movements, which is susceptible to physical or chemical disturbances. This social insect is one of the most important pollinators in agricultural ecosystems, being exposed to a great variety of agrochemicals, which might affect its sleep behaviour. The intake of glyphosate (GLY), the herbicide most widely used worldwide, impairs learning, gustatory responsiveness and navigation in honey bees. In general, these cognitive abilities are linked with the amount and quality of sleep. Furthermore, it has been reported that animals exposed to sleep disturbances show impairments in both metabolism and memory consolidation. Consequently, we assessed the sleep pattern of bees fed with a sugar solution containing GLY (0, 25, 50 and 100 ng) by quantifying their antennal activity during the scotophase. We found that the ingestion of 50 ng of GLY decreased both antennal activity and sleep bout frequency. This sleep deepening after GLY intake could be explained as a consequence of the regenerative function of sleep and the metabolic stress induced by the herbicide.

Maximizing crop yields relies on the use of agrochemicals to control insect pests. One of the most widely used classes of insecticides are neonicotinoids that interfere with signalling of the neurotransmitter acetylcholine, but these can also disrupt crop-pollination services provided by bees. Here, we analysed whether chronic low dose long-term exposure to the neonicotinoid thiamethoxam alters gene expression and alternative splicing in brains of Africanized honey bees, Apis mellifera, as adaptation to altered neuronal signalling. We find differentially regulated genes that show concentration-dependent responses to thiamethoxam, but no changes in alternative splicing. Most differentially expressed genes have no annotated function but encode short Open Reading Frames, a characteristic feature of anti-microbial peptides. As this suggested that immune responses may be compromised by thiamethoxam exposure, we tested the impact of thiamethoxam on bee immunity by injecting bacteria. We show that intrinsically sub-lethal thiamethoxam exposure makes bees more vulnerable to normally non-pathogenic bacteria. Our findings imply a synergistic mechanism for the observed bee population declines that concern agriculturists, conservation ecologists and the public.

Screening agrochemicals and pharmaceuticals for potential liver toxicity is required for regulatory approval and is an expensive and time-consuming process. The identification and utilization of early exposure gene signatures and robust predictive models in regulatory toxicity testing has the potential to reduce time and costs substantially. In this study, comparative supervised machine learning approaches were applied to the rat liver TG-GATEs dataset to develop feature selection and predictive testing. We identified ten gene biomarkers using three different feature selection methods that predicted liver necrosis with high specificity and selectivity in an independent validation dataset from the Microarray Quality Control (MAQC)-II study. Nine of the ten genes that were selected with the supervised methods are involved in metabolism and detoxification (Car3, Crat, Cyp39a1, Dcd, Lbp, Scly, Slc23a1, and Tkfc) and transcriptional regulation (Ablim3). Several of these genes are also implicated in liver carcinogenesis, including Crat, Car3 and Slc23a1. Our biomarker gene signature provides high statistical accuracy and a manageable number of genes to study as indicators to potentially accelerate toxicity testing based on their ability to induce liver necrosis and, eventually, liver cancer.

The entomopathogenic fungus Beauveria bassiana is a widely used biopesticide that is considered as an effective alternative to classical agrochemicals. B. bassiana is thought to be safe for pollinators although little is known about its side-effects on pollinators' behaviour and cognition. Here, we focused on honey bees and used the proboscis extension response (PER) protocol to assess whether B. bassiana affects individual sucrose responsiveness, non-associative and associative olfactory learning and memory. Fungus-treated bees displayed an enhanced sucrose responsiveness, which could not be explained by metabolic alterations. Strikingly, exposed bees were twice as inconsistent as controls in response to sucrose, showing PER to lower but not to higher sucrose concentrations. Exposed bees habituated less to sucrose and had a better acquisition performance in the conditioning phase than controls. Further, neither mid- nor long-term memory were affected by the fungus. As sucrose responsiveness is the main determinant of division of foraging labour, these changes might unsettle the numerical ratio between the sub-castes of foragers leading to suboptimal foraging. Although the use of biocontrol strategies should be preferred over chemical pesticides, careful assessment of their side-effects is crucial before claiming that they are safe for pollinators.

Nanomaterials in agriculture represent one of the most innovative method for protecting crops, due to possibility of being applied as nanopesticides or nanocarriers for active ingredients. Furthermore, nanotechnology could be combined with the concept of circular economy through the opportunity of obtaining highly technological nanometric materials starting from agro-industrial wastes. The present research evaluated the possibility of synthesizing cellulose nanocrystals (CNCs) from olive pruning wastes through chemical bleaching, reusing them as sustainable tool to control the causal agent of the olive knot disease (Pseudomonas savastanoi pv. savastanoi). CNCs showed an interesting in vitro effect in inhibiting bacterial growth and bacterial biofilm formation, as well as the ability of reducing bacterial epiphytic survival in a comparable way to copper sulphate on leaf surfaces, when used at 1% w/v. CNCs were at the same time investigated for their interaction with olive tree seedlings, showing no negative effects on leaf development, and a promising root uptake, indicating that CNCs could be used also as nanocarriers for active ingredients. Obtained results highlight the innovative possibility of designing sustainable plant protection strategies capable of revalorise lignocellulosic wastes, meaning a simultaneous low environmental impact thanks to reduction of traditional agrochemicals input.

The discovery of novel bioactive compounds produced by microorganisms holds significant potential for the development of therapeutics and agrochemicals. In this study, we conducted genome mining to explore the biosynthetic potential of entomopathogenic bacteria belonging to the genera Xenorhabdus and Photorhabdus. By utilizing next-generation sequencing and bioinformatics tools, we identified novel biosynthetic gene clusters (BGCs) in the genomes of the bacteria, specifically plu00736 and plu00747. These clusters were identified as unidentified non-ribosomal peptide synthetase (NRPS) and unidentified type I polyketide synthase (T1PKS) clusters. These BGCs exhibited unique genetic architecture and encoded several putative enzymes and regulatory elements, suggesting its involvement in the synthesis of bioactive secondary metabolites. Furthermore, comparative genome analysis revealed that these BGCs were distinct from previously characterized gene clusters, indicating the potential for the production of novel compounds. Our findings highlighted the importance of genome mining as a powerful approach for the discovery of biosynthetic gene clusters and the identification of novel bioactive compounds. Further investigations involving expression studies and functional characterization of the identified BGCs will provide valuable insights into the biosynthesis and potential applications of these bioactive compounds.

Securing food supply for a growing population is a major challenge and heavily relies on the use of agrochemicals to maximize crop yield. It is increasingly recognized, that some neonicotinoid insecticides have a negative impact on non-target organisms, including important pollinators such as the European honeybee Apis mellifera. Toxicity of neonicotinoids may be enhanced through simultaneous exposure with additional pesticides, which could help explain, in part, the global decline of honeybee colonies. Here we examined whether exposure effects of the neonicotinoid thiamethoxam on bee viability are enhanced by the commonly used fungicide carbendazim and the herbicide glyphosate. We also analysed alternative splicing changes upon pesticide exposure in the honeybee. In particular, we examined transcripts of three genes: (i) the stress sensor gene X box binding protein-1 (Xbp1), (ii) the Down Syndrome Cell Adhesion Molecule (Dscam) gene and iii) the embryonic lethal/abnormal visual system (elav) gene, which are important for neuronal function. Our results showed that acute thiamethoxam exposure is not enhanced by carbendazim, nor glyphosate. Toxicity of the compounds did not trigger stress-induced, alternative splicing in the analysed mRNAs, thereby leaving dormant a cellular response pathway to these man-made environmental perturbations.

The Central Andes of Peru are a region of great concern regarding pesticide risk to the health of local communities. Therefore, we conducted an observational study to assess the level of pesticide contamination among Andean people. Analytical chemistry methods were used to measure the concentrations of 170 pesticide-related compounds in hair samples from 50 adult Andean subjects living in rural and urban areas. As part of the study, a questionnaire was administered to the subjects to collect information regarding factors that increase the risk of pesticide exposure. Our results indicate that Andean people are strongly exposed to agrochemicals, being contaminated with a wide array of pesticide-related compounds at high concentration levels. Multivariate analyses and geostatistical modeling identified sociodemographic factors associated with rurality and food origin that increase pesticide exposure risk. The present study represents the first comprehensive investigation of pesticide-related compounds detected in body samples collected from people living in the Central Andes of Peru. Our findings pinpoint an alarming environmental situation that threatens human health in the region and provide a rationale for improving public policies to protect local communities.