Inhibition mechanism of Rhizoctonia solani by pectin-coated iron metal-organic framework nanoparticles and evidence of an induced defense response in rice.

Nanocrop protectants have attracted much attention as sustainable platforms for controlling pests and diseases and improving crop nutrition. Here, we reported the fungicidal activity and disease inhibition potential of pectin-coated metal-iron organic framework nanoparticles (Fe-MOF-PT NPs) against rice stripe blight (RSB). An in vitro bacterial inhibition assay showed that Fe-MOF-PT NPs (80 mg/L) significantly inhibited mycelial growth and nucleus formation. The Fe-MOF-PT NPs adsorbed to the surface of mycelia and induced toxicity by disrupting cell membranes, mitochondria, and DNA. The results of a nontargeted metabolomics analysis showed that the metabolites of amino acids and their metabolites, heterocyclic compounds, fatty acids, and nucleotides and their metabolites were significantly downregulated after treatment with 80 mg/L NPs. The difference in metabolite abundance between the CK and Fe-MOF-PT NPs (80 mg/L) treatment groups was mainly related to nucleotide metabolism, pyrimidine metabolism, purine metabolism, fatty acid metabolism, and amino acid metabolism. The results of the greenhouse experiment showed that Fe-MOF-PT NPs improved rice resistance to R. solani by inhibiting mycelial invasion, enhancing antioxidant enzyme activities, activating the jasmonic acid signaling pathway, and enhancing photosynthesis. These findings indicate the great potential of Fe-MOF-PT NPs as a new RSB disease management strategy and provide new insights into plant fungal disease management.

Pectin-Coated Iron-Based Metal-Organic Framework Nanoparticles for Enhanced Foliar Adhesion and Targeted Delivery of Fungicides.

Conventional agrochemicals are underutilized due to their large particle sizes, poor foliar retention rates, and difficult translocation in plants, and the development of functional nanodelivery carriers with high adhesion to the plant body surface and efficient uptake and translocation in plants remains challenging. In this study, a nanodelivery system based on a pectin-encapsulated iron-based MOF (TF@Fe-MOF-PT NPs) was constructed to enhance the utilization of thifluzamide (TF) in rice plants by taking advantage of the pectin affinity for plant cell walls. The prepared TF@Fe-MOF-PT NPs exhibited an average particle size of 126.55 nm, a loading capacity of 27.41%, and excellent dual-stimulus responses to reactive oxygen species and pectinase. Foliar washing experiments showed that the TF@Fe-MOF-PT NPs were efficiently adhered to the surfaces of rice leaves and stems. Confocal laser scanning microscopy showed that fluorescently labeled TF@Fe-MOF-PT NPs were bidirectionally delivered through vascular bundles in rice plants. The in vitro bactericidal activity of the TF@Fe-MOF-PT NPs showed better inhibitory activity than that of a TF suspension (TF SC), with an EC50 of 0.021 mg/L. A greenhouse test showed that the TF@Fe-MOF-PT NPs were more effective than TF SC at 7 and 14 d, with control effects of 85.88 and 78.59%, respectively. It also reduced the inhibition of seed stem length and root length by TF SC and promoted seedling growth. These results demonstrated that TF@Fe-MOF-PT NPs can be used as a pesticide nanodelivery system for efficient delivery and intelligent release in plants and applied for sustainable control of pests and diseases.

Effect of Brucea javanica Oil on the Toxicity of ß-Cypermethrin Emulsifiable Concentrate Formulation.

Enhancing the performance of traditional pesticide formulations by improving their leaf surface wetting capabilities is a crucial approach for maximizing the pesticide efficiency. This study develops an emulsifiable concentrate (EC) of 4.5% ß-cypermethrin containing Brucea javanica oil (BJO). The incorporation of BJO aims to improve the leaf-wetting properties of the EC formulation and enhance its insecticidal effectiveness. The droplet size and emulsion characteristics of ß-CYP EC emulsion with varying concentrations of the emulsifier were evaluated, and changes after incorporating BJO were assessed to develop the optimal formulation. A comprehensive comparison was conducted among commercial 4.5% ß-cypermethrin EC (ß-CYP EC-1), 4.5% ß-cypermethrin EC with BJO (ß-CYP EC-2), and 4.5% ß-cypermethrin EC without BJO (ß-CYP EC-3). This comparison encompassed various factors including storage stability, insecticidal activity, cytotoxicity, and wetting performance on cabbage leaves. The results indicated that the ideal emulsifier concentration was 15% emulsifier 0201B. ß-CYP EC-2 demonstrated superior wetting properties on cabbage leaves (the wetting performance of ß-CYP EC-2 emulsion on cabbage leaves is 2.60 times that of the ß-CYP EC-1 emulsion), heightened insecticidal activity against the third larvae of Plutella xylostella [diamondback moth (DBM)] [the insecticidal activity of the ß-CYP EC-2 emulsion against the third larvae of DBM is 1.93 times that of the ß-CYP EC-1 emulsion (12 h)], and more obvious inhibitory effects on the proliferation of DBM embryo cells than the other tested formulations. These findings have significant implications for advancing pest control strategies and promoting sustainable and effective agricultural practices.

Chitosan-based nanopesticides enhanced anti-fungal activity against strawberry anthracnose as "sugar-coated bombs".

A chitosan-based nanoparticle was prepared using chitosan (CS) and O-carboxymethyl chitosan (O-CMCS). Our study revealed that chitosan/O-carboxymethyl chitosan/tebuconazole nanoparticles (CS/O-CMCS/TBA NPs) exhibited superior antifungal activity, foliar adhesion, and microbial target adhesion performance compared to commercial suspension concentrate (SC). The antifungal activity of CS/O-CMCS/TBA NPs against C. gloeosporioides, with a 3.13-fold increase in efficacy over TBA (SC). We also found that low concentrations of CS/O-CMCS NPs promoted the growth of C. gloeosporioides and enhanced the fungal catabolism of chitosan. Overall, the CS/O-CMCS/TBA NPs were found to possess the remarkable capability to selectively aggregate around pathogenic microorganisms and CS/O-CMCS NPs can enhance the fungal catabolism of chitosan. CS/O-CMCS/TBA NPs, as a "sugar-coated bomb", was a promising asset for effective plant disease management and pesticide utilization through the affinity of chitosan-based nanoparticles and C. gloeosporioides, enabling targeted delivery and targeted release of their encapsulated active ingredient, which was important for the development and application of biocompatible chitosan-based nanopesticides.

Green synthesis of a chlorfenapyr chitosan nanopesticide for maize root application: Reducing environmental pollution and risks to nontarget organisms.

Chlorfenapyr (CHL) is a pyrrole insecticide with a novel structure that is used to control resistant pests. However, its weak systemic activity limits its application to crop roots. Herein, a novel CHL formulation with improved effective utilization rates and suitability for root application is developed to avoid or reduce contamination caused by pesticide spraying. Accordingly, we prepared CHL@CS/CMCS nanoparticle (NP) suspensions with a particle size of approximately 100 nm using chitosan (CS) and carboxymethyl chitosan (CMCS). These suspensions exhibited better thermal stability, adhesion, permeability and systemic activity than a CHL suspension concentrate (CHL-SC). The nanoformulation deposition rate on maize leaves after spraying was 12.28 mg/kg, significantly higher than that of CHL-SC. The nanosuspension was effectively absorbed and transported by roots after irrigation and was suitable for root application. The efficacy was 89.46-92.36 % against Spodoptera frugiperda at 7 d, 7.5-17.5 times higher than that of CHL-SC. Furthermore, the CHL@CS/CMCS nanosuspension was safer for earthworms. These results suggest that chitosan-based nanoformulations improve the efficacy, utilization efficiency and active period of CHL control, providing a new approach for CHL application, reducing pollutant dispersal and the environmental impacts of pesticide application and facilitating sustainable agricultural production.

Enhanced Insecticidal Activity of Chlorfenapyr against Spodoptera frugiperda by Reshaping the Intestinal Microbial Community and Interfering with the Metabolism of Iron-Based Metal-Organic Frameworks.

Spodoptera frugiperda (S. frugiperda) is an invasive pest that threatens global crop production and food security and poses a serious threat to maize production worldwide. Metal-organic framework (MOF) nanocarriers have great potential for agricultural pest control applications. The present study successfully prepared the chemical cross-linking of iron-based metal-organic framework nanoparticles (MIL-101(Fe)-NH2 NPs) with sodium lignosulfonate (SL) as a pH/laccase double stimuli-responsive pesticide release system. The average particle size of the prepared chlorfenapyr (CF)-loaded nanoparticles (CF@MIL-101-SL NPs) was 161.54 nm, and the loading efficiency was 44.52%. Bioactivity assays showed that CF@MIL-101-SL NPs increased the toxicity of CF to S. frugiperda and caused the rupture of the peritrophic membrane and enlargement of the midgut. Data from 16S rRNA gene sequencing showed that CF@MIL-101-SL treatment reduced the resistance of S. frugiperda to pesticides and pathogens and affected nutrient and energy availability by remodeling the intestinal microbiota of S. frugiperda. The dysregulated microbial community interacted with the broken peritrophic membrane, which exacerbated damage to the host. Nontargeted metabolomic results showed that ABC transporters may be a potential mechanism for the enhanced toxicity of CF@MIL-101-SL to S. frugiperda. In summary, the present study provides effective strategies for toxicological studies of nanopesticides against insects.

Nano-pesticide carrier O-Carboxymethyl chitosan is indigestible in Apis cerana cerana and affects intestinal flora.

O-Carboxymethyl chitosan nanoparticles (O-CMC-NPs), which are organic pesticide carriers, have excellent application potential. Exploring the effects of O-CMC-NPs on non-target organisms, such as Apis cerana cerana, is critical for their effective application; however, such studies are limited. This study investigated the stress response of A. cerana Fabricius after O-CMC-NPs ingestion. The administration of high O-CMC-NP concentrations enhanced the activities of antioxidant and detoxifying enzymes in A. cerana, with the activity of glutathione-S-transferase increasing by 54.43 %-64.33 % after one day. The transit of O-CMC-NPs into the A. cerana midgut resulted in their deposition and adherence to the intestinal wall, as they cluster and precipitate in acidic conditions. The population of Gillianella bacteria in the middle intestine was remarkably reduced after 6 d of administration of high O-CMC-NP concentrations. Contrastingly, the abundance of Bifidobacteria and Lactobacillus in the rectum significantly increased. These results indicate that the intake of high concentrations of O-CMC-NPs causes a stress response in A. cerana and affects the relative abundance of crucial intestinal flora, which may pose a potential risk to the colony. This implies that even nanomaterials with favorable biocompatibility should be applied reasonably within a specific range to avoid adverse effects on the environment and non-target organisms in the context of large-scale research and promotion of nanomaterials.

pH-responsive λ-cyhalothrin nanopesticides for effective pest control and reduced toxicity to Harmonia axyridis.

In this study, pH-responsive LC@O-CMCS/PU nanoparticles were prepared by encapsulating λ-cyhalothrin (LC) with O-carboxymethyl chitosan (O-CMCS) to form LC/O-CMCS and then covering it with polyurethane (PU). Characterization and performance test results demonstrate that LC@O-CMCS/PU had good alkaline release properties and pesticide loading performance. Compared to commercial formulations containing large amounts of emulsifiers (e.g., emulsifiable concentrate, EC), LC@O-CMCS/PU showed better leaf-surface adhesion. On the dried pesticide-applied surfaces, the acute contact toxicity of LC@O-CMCS/PU to Harmonia axyridis (H. axyridis) was nearly 20 times lower than that of LC EC. Due to the slow-releasing property of LC@O-CMCS/PU, only 16.38 % of LC was released at 48 h in dew and effectively reduced the toxicity of dew. On the pesticide-applied leaves with dew, exposure to the LC (EC) caused 86.66 % mortality of H. axyridis larvae significantly higher than the LC@O-CMCS/PU, which was only 16.66 % lethality. Additionally, quantitative analysis demonstrated 11.33 mg/kg of λ-cyhalothrin in the dew on LC@O-CMCS/PU lower than LC (EC) with 4.54 mg/kg. In summary, LC@O-CMCS/PU effectively improves the safety of λ-cyhalothrin to H. axyridis and has great potential to be used in pest control combining natural enemies and chemical pesticides.

Eco-friendly O-carboxymethyl chitosan base chlorfenapyr nanopesticide for effective pest control and reduced toxicity to honey bees.

Enhancing pesticide selectivity is one of the important strategies to improve pesticide utilization and protect non-target organisms. Herein, a pH-controlled release carrier was prepared to enhance insecticidal activity and reduce toxicity to bees by polysaccharide materials O-carboxymethyl chitosan (O-CMCS) and crosslinker­sodium tripolyphosphate (TPP). Chlorfenapyr (CF) was encapsulated through crosslinking and self-assembled to form a stable nanopesticide (CF@O-CMCS) with a loading ratio of 5.27 %. CF@O-CMCS had excellent pH release dependency. In 36 h, only 26.39 % of the CF in the CF@O-CMCS was released at pH 5.0, whereas 95.28 % was released at pH 10.0. Treated for 48 h with 2.5 mg.ai/L, CF@O-CMCS was 73.33 % more effective at controlling Spodoptera frugiperda larvae than CF SC (Suspension), which was only 40.00 % effective. The lethal concentration 50 % (LC50) of 11.41 mg/L in CF@O-CMCS was four times lower than that of 2.71 mg/L in CF SC at 96 h, making it safer for worker bees. Additionally, CF@O-CMCS treated the gut of worker bees had considerably lower contents of chlorfenapyr and tralopyril (1.13 and 0.59 mg/kg) than CF SC (3.22 and 1.91 mg/kg) group. In consideration of its eco-friendly, enhanced bioactivity, and low toxicity to worker bees, CF@O-CMCS will have a broad application prospect in sustainable agriculture.

Rotenone encapsulated in pH-responsive alginate-based microspheres reduces toxicity to zebrafish.

Rotenone is a botanical pesticide and has long been used for control of insect pests and also as a natural piscicide for management of fish populations in many countries. Field application for pest control, however, often encounters the movement of rotenone into surface water due to spray drift or surface runoff after rainfall, which could potentially result in water pollution and unexpected death of fishes. To minimize its effect on freshwater and the problem of fish dying, one solution was to encapsulate rotenone in specific microspheres, limiting its release and reducing its toxicity since rotenone can be quickly degraded under sunlight. In this study, pH-responsive alginate-based microspheres were synthesized to encapsulating rotenone, which were designated as rotenone beads. The rotenone beads, along with alginate beads (devoid of rotenone) were characterized and evaluated for their responses to pH and effects on zebrafish. Results showed that the microspheres had high loading efficiency (4.41%, w/w) for rotenone, and rotenone beads well responded to solution pH levels. The cumulative release rates of rotenone from the beads were 27.91%, 42.72%, and 90.24% at pH 5.5, 7.0, and 9.0, respectively. Under acidic conditions, the rotenone release rate was lower due to hydrogen bonding. On the contrary, rotenone became more quickly released at the high pH due to intermolecular repulsion. The toxicity of rotenone beads to zebrafish and fish embryos at a pH of 5.5 was reduced by 2- and 4-fold than chemical rotenone. Since pH levels in most freshwater lakes, ponds, and streams vary from 6 to 8, rotenone release from the beads in such freshwater could be limited. Thus, the synthesized rotenone beads could be relatively safely used for pest control with limited effects on freshwater fishers.

Effect of bifenthrin application at different maturity stages on its dissipation and residues in kumquat (Citrus japonica) and dietary intake risk assessment.

Bifenthrin is a pyrethroid pesticide widely used on kumquats, but the residues in the peel and pulp after bifenthrin application at different maturity stages of kumquats have not been evaluated. This study developed a simple and rapid high-performance liquid chromatography (HPLC) method for the quantitative analysis of bifenthrin residues in whole fruit, kumquat peel, kumquat pulp, and soil. The results showed that regardless of whether bifenthrin was applied one or three times during the near-mature period, the half-lives of the fruit peel and fruit pulp were longer than those in the immature period. Kumquat fruit residues decreased with time at both maturity levels. The residues of bifenthrin in near-mature fruit exceeded the MRL in Guangxi and Fujian 14 days after the three applications of bifenthrin, suggesting that this issue should be focused on in kumquat production and supervision. However, for bifenthrin application in either the near-mature or the immature fruit period, the calculated risks for chronic dietary intake of kumquat were well below 100%. The data demonstrate that the chronic dietary intake risk of bifenthrin through kumquat consumption is low and within acceptable limits. These results provide a reference and risk assessment data for the safe and rational use of bifenthrin insecticides.

Azadirachtin inhibits the development and metabolism of the silk glands of Spodoptera frugiperda and affects spinning behavior.

BACKGROUND: Spodoptera frugiperda is a major agricultural pest, and the dispersal of its larvae by spinning silk is one of the causes of crop damage. At present, there are relatively few reports of pest control that affect larvae spinning silk. In this study, the effect of spinning behavior of the S. frugiperda larvae was investigated through a series of experiments. RESULTS: The 3rd instar larvae of S. frugiperda were exposed to azadirachtin, and the pathological changes in the silk glands of S. frugiperda and the differences in their metabolites were analyzed by scanning electron microscopy, histological sectioning, transmission electron microscopy and metabolomics. The results showed that azadirachtin could affect the silk gland of S. frugiperda. After 48 h of treatment with azadirachtin, the silk gland lumen of S. frugiperda appeared vacuolated. KEGG showed that 31 different metabolites were identified, of which 12 were upregulated and 19 were downregulated. These metabolites were enriched in 15 different metabolic pathways, which indicated that the silk gland of S. frugiperda was closely related to the formation of fatty acids and energy metabolism for the silk formation process. CONCLUSIONS: This study provides a preliminary report of the effect of azadirachtin on the spinning behavior of the S. frugiperda larvae. Metabolomic results indicated that histidine, glycine and leucine, which are related to serine protein synthesis, were down-regulated. Azadirachtin can damage the silk glands of S. frugiperda and thus affect spinning behavior. This provides the basis for the control of S. frugiperda by spinning silk. © 2022 Society of Chemical Industry.

Novel application of biodegradable chitosan in agriculture: Using green nanopesticides to control Solenopsis invicta.

Botanical pesticides are biological pesticides that are environment friendly. However, their instability and short persistence limit their application. In this study, pH sensitive chitosan based rotenone (Rot) nanoparticles (CS/CMCS/Rot-NPs) were prepared using chitosan and carboxymethyl chitosan to take advantage of the acidic nature of the red fire ant midgut. Chitosan based nanoparticles showed photoprotective and slow sustained release effects on Rot and significantly increased the insecticidal activity of Rot against red fire ants. The 24-96hLC50 of CS/CMCS/Rot-NPs against red fire ants was 3.28-6.84 fold that of Rot. The CS/CMCS/Rot-NPs significantly reduced the venom alkaloid content of red fire ants and their living environment and weakened their survival by increasing their survival cost in the ecological environment. Nanotechnology combined with botanical pesticides can be used as a novel, safe, effective, and ecofriendly method to control red fire ants.

Dissipation and Distribution of Prochloraz in Bananas and a Risk Assessment of Its Dietary Intake.

BACKGROUND: As a systematic fungicide, prochloraz is often used to control banana freckle disease, and it is significant to assess the safety and risk of prochloraz. METHODS: The dissipation kinetics and distribution of prochloraz in bananas were measured by high-performance liquid chromatography (HPLC). RESULTS: The results showed that the fortified recoveries in bananas were 83.01-99.12%, and the relative standard deviations (RSDs) were 2.45-7.84%. The half-life of prochloraz in banana peel (3.93-5.60 d) was significantly lower than it was in whole banana (8.25-10.80 d) and banana pulp (10.35-12.84 d). The terminal residue of prochloraz in banana fruits was below the maximum residue level (MRL, China) at pre-harvest intervals (PHI) of 21 d. Moreover, the residue of prochloraz in banana peel was always 1.06-7.71 times greater than it was in banana pulp. The dietary risk assessment results indicated that the prochloraz residue in bananas at PHI of 21 d was safe for representative populations. (4) Conclusions: We found that a 26.7% prochloraz emulsion oil in water (EW) diluted 1000-fold and sprayed three times under field conditions was safe and reliable, providing a reference for the safe application of prochloraz in bananas.

A pH- and redox-stimulated responsive hollow mesoporous silica for triggered delivery of fungicides to control downy mildew of Luffa cylindrica.

BACKGROUND: Downy mildew, a devastating disease of cucurbitaceous crops caused by Pseudoperonospora cubensis. Although a variety of fungicides are used to control downy mildew, choosing an effective product can be challenging. Environmental stimulus-responsive pesticide delivery systems have great potential to improve the effectiveness of disease and pest control and reduce the impact on environmentally beneficial organisms. RESULTS: In this work, a disulfide bond (SS)-modified and chitosan oligosaccharide (COS)-capped hollow mesoporous silica (HMS) pesticide delivery system was synthesized using a hard template method for the control of downy mildew in cucurbit crops. The synthesized nanoparticles were loaded with dimethomorph (DMM), denoted as DMM@HMS-SS-COS, and the developmental toxicity of these nanoparticles to zebrafish embryos were evaluated. The results showed that the prepared DMM@HMS-SS-COS exhibited excellent dual response properties to pH and glutathione (GSH), with an encapsulation rate of up to 24.36%. DMM@HMS-SS-COS has good ultraviolet (UV) radiation stability and adhesion properties. Compared with dimethomorph suspension concentrate (SC), DMM@HMS-SS-COS was more effective against downy mildew for up to 21 days. Toxicity tests showed that DMM@HMS-SS-COS significantly reduced the effect of DMM on the hatching rate and survival rate of zebrafish embryos. CONCLUSIONS: This work not only demonstrates that DMM@HMS-SS-COS could be used as a nanodelivery system for intelligent control of downy mildew but also emphasizes the necessity of increasing the acute toxicity of nanoformulations to non-target organisms in environmental risk assessment. © 2022 Society of Chemical Industry.

Effects of sublethal azadirachtin on the immune response and midgut microbiome of Apis cerana cerana (Hymenoptera: Apidae).

As a wildly used plant-derived insecticide, azadirachtin (AZA) is commonly reported as harmless to a range of beneficial insects. However, with the research on the effect of AZA against pollinators in recent years, various negative physiological effects on other Apidae species have been demonstrated. Thus to explore the safety of azadirachtin to Apis cerana cerana, the different physiological effects of sublethal concentration of azadirachtin on worker bees A.c.cerana has been studied. With the exposure of 5 mg·L-1 and 10 mg·L-1 azadirachtin for 5 d, the relative expression of Apidaecin, Abaecin and Lysosome genes in workers has decreased significantly at 1, 2,3 and 5 d, and the mRNA levels of Defensin 2 and Hymenoptaecin were also significantly inhibited by 10 mg·L-1 azadirachtin at each check point. Besides, the activity of midgut antioxidant enzymes Superoxide Dismutase (SOD) and Catalase (CAT) which are the first line of defence in antioxidant systems was not affected by AZA, the activity of Peroxidase (POD) showed a fluctuating pattern at 24 h and 48 h, while the activity of polyphenol oxidase (PPO) has significantly inhibited by AZA. However, through 16sRNA analysis it was observed that 5 mg·L-1 AZA did not affect the midgut microbiome colony composition and relative abundance, as well as its main function. Therefore, to a certain extent, azadirachtin is safe for workers, but we should pay more attention to the sublethal effect of AZA that also detrimental to the healthy development of the honeybee colony.

Examination of acephate absorption, transport, and accumulation in maize after root irrigation for Spodoptera frugiperda control.

Since the invasion of the fall armyworm moth (Spodoptera frugiperda) in China in January 2019, damage to maize crops has gradually intensified, and chemical control has become the main control measure. This study aimed to examine methods of effective pest control while monitoring the environmental impact of pesticide use. The effectiveness of S. frugiperda pest control by foliar spraying and root irrigation of maize plants with acephate was determined, and the absorption, distribution, and dissipation of acephate and methamidophos by maize were studied. Field trials showed that acephate treatment at 6000 g a.i. ha-1 was the most effective for controlling S. frugiperda. Acephate and methamidophos were absorbed from the roots, transported upward, and concentrated in the leaves, particularly new leaves. The terminal residues of acephate and methamidophos in maize grains were below detectable levels at 60 days after treatment. The results demonstrate that acephate treatment via root irrigation can more effectively control the infestation of S. frugiperda in maize than acephate treatment via foliar spraying. The translocation and distribution of acephate and methamidophos by root irrigation were more uniform, and the holding efficiency was higher than those in foliar spraying, suggesting an extended period of control efficacy. This pest control method could be utilized to reduce pesticide residues while safely and efficiently controlling S. frugiperda infestation.

Floating chitosan-alginate microspheres loaded with chlorantraniliprole effectively control Chilo suppressalis (Walker) and Sesamia inferens (Walker) in rice fields.

Striped rice stem borer, Chilo suppressalis (Walker) and pink stem borer, Sesamia inferens (Walker) are two important pests, causing substantial yield loss in rice production. Application of conventional synthetic pesticides, such as suspension concentrates and water-dispersible granules, is a primary method for control of the two pests. Due to the flow of water in rice field, spray drift, and soil adsorption, applied such pesticides are often out of the target, resulting in low control efficacy, potential contamination of soil or surface water, and also threat to human health. Thus, there is an urgent need for developing environmentally friendly and highly targeted pesticide formulations to meet the challenges. The present study synthesized chlorantraniliprole loaded chitosan-alginate floating hydrogel microspheres (CCAM) through physical embedding, ionic crosslinking, and incorporation of citronellol as an oil phase. The morphology, particle size, entrapment efficiency, loading capacity, in vitro slow-release kinetics, and floating ability of the CCAM were tested in laboratory conditions. The CCAM and two commercial formulations (suspended and granulated) of chlorantraniliprole were respectively evaluated in two rice fields located in two provinces of China. The CCAM was able to float on the surface of rice field, gather around rice stems, and slowly release chlorantraniliprole, which resulted in significantly higher concentrations of chlorantraniliprole in rice stems and leaves for a prolonged time than suspended and granulated controls. The application of CCAM provided an on-target control of both striped stem borer and pink stem borer. Furthermore, CCAM application had very low residue of chlorantraniliprole in soils. As far as is known, this is the first report of chlorantraniliprole loaded on chitosan-alginate floating hydrogel microspheres for rice stem borer control. Our results indicate that the synthesized CCAM could potentially be used as a controlled-release product for effective control of the two rice pests, while reducing the residual chlorantraniliprole in the soil and avoiding pesticide drift.

Carboxylated ß-cyclodextrin anchored hollow mesoporous silica enhances insecticidal activity and reduces the toxicity of indoxacarb.

In this study, a pesticide controlled release system with dual response characteristics of pH and enzyme triggering was developed. Indoxacarb (IDC) was loaded into hollow mesoporous silica (HMS) nanoparticles, carboxylated ß-cyclodextrin (ß-CD) acted as a capping molecule to couple with the amino-functionalized HMS, and their well-defined morphological structures were confirmed by scanning electron microscopy and transmission electron microscopy. The results showed that the prepared IDC loaded HMS-CD had high loading efficiency (26.42%, w/w) and showed excellent dual response properties to pH and the α-amylase enzyme. IDC loaded HMS-CD nanoparticles showed better insecticidal activity against Spodoptera frugiperda than applying the same dose of IDC emulsifiable concentrate, and the toxicity of IDC loaded HMS-CD to zebrafish was reduced by more than 5-fold, indicating that insecticide delivery systems based on ß-CD-anchored HMS nanoparticles could potentially be applied for sustainable control of pests and reduce harm to non-target organisms and the environment.

Residue and dissipation of two formulations of emamectin benzoate in tender cowpea and old cowpea and a risk assessment of dietary intake.

The dissipation and residue levels of emamectin benzoate emulsifiable concentrate (EC) and microemulsion (ME) formulations in tender cowpeas and old cowpeas were investigated under field conditions. The decline curves of emamectin benzoate residues in cowpea corresponded to first-order kinetics. The dissipation rate of emamectin benzoate in tender cowpeas was faster than that in old cowpeas. The half-lives of the EC were 1.34-1.39 d and 1.74-2.31 d in tender cowpea and old cowpea, respectively. For the ME, the half-lives were 1.39-1.51 d and 2.08-2.67 d, respectively. The risk of adult intake of emamectin benzoate from cowpea is within the acceptable limits of the human body. Compared to tender cowpeas, the risk of eating old cowpeas is higher. Emamectin benzoate (EC) is recommended for cowpeas when the intention is to harvest tender cowpeas, while both formulations are acceptable for cowpeas when the intention is to harvest old cowpeas.