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BACKGROUND Chemical control is the most used and effective method to control Diaphorina citri, the vector of the phloem-limited bacteria associated with citrus huanglongbing (HLB) disease. The objectives of this study were to determine the effectiveness of flupyradifurone applied via dripping irrigation systems on D. citri. Bioassays were conducted using leaves harvested on various dates post treatment, and insecticide residue in leaf tissue was quantified. RESULTS The drip application of flupyradifurone on citrus trees provided high-level and long-term control against D. citri adult, and the median lethal concentration (LC50 ) for ingestion of flupyradifurone in D. citri was 22.22 mg kg-1 (fresh leaf). Flupyradifurone residue was detected in leaf tissue within 3 days after treatment. The measured level of flupyradifurone peaked on day 40 day after application, and then showed a steady decline in subsequent days for all three applied dosages. The amounts of flupyradifurone in upper, middle, and lower leaves were similar, and trends in the change in concentration of flupyradifurone were consistent. CONCLUSIONS The results demonstrate that flupyradifurone can be a valuable new tool for D. citri management programs, and drip-applied flupyradifurone provides an extended period of control efficacy. This paper could provide a reference to reduce the dependence on foliar-applied insecticides, with associated benefits for non-target exposure to workers and pollinators. © 2021 Society of Chemical Industry.

In a previous study, we showed that two glycosyl-pesticide conjugates with a β-d-glucoside moiety, N-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl)-sulfinyl]-1H-pyrazol-5-yl}-2-aminoethyl-β-d-glucopyranoside (GOF) and N-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl) sulfinyl]-1H-pyrazol-5-yl}-1-(2-triazolethyl-β-d-glucopyranoside)-1H-1,2,3-triazole-4-methanamine (GOTF), can move in the phloem and be hydrolyzed by β-glucosidase at different rates. Simulations were carried out to investigate differences in the hydrolysis process in GOF, GOTF and p-nitrophenyl β-d-glucopyranoside (pNPG). A new series of glycosyl-O-fipronil conjugates was then designed and synthesized based on the simulation results. The phloem mobilities of the new conjugates were examined using a Ricinus model, and their hydrolysis efficiencies based on β-glucosidase were determined.New glycosyl-O-fipronil conjugates GOE2-6 were designed and synthesized. To reduce steric hindrance, the conjugating site of the glycone moiety was moved to the 4'-sulfonyl group on the pyrrole ring. As a result, the hydrolysis efficiencies of the new conjugates were significantly improved, with GOE4 having the highest hydrolysis efficiency. All five conjugates could be transported in Ricinus phloem sap, consistent with previously studied glycosyl-O-fipronil conjugates. The insecticidal activities of the conjugates were tested against Plutella xylostella.A strategy for the development of new phloem-mobile pesticides was proposed: linking a glycosyl group to the existing pesticide structure with a linear alkyl connection approximately four carbons in length. The resultant conjugates feature not only good phloem mobility, but also potential high bioactivity due to the efficient release of active pesticide components under the action of glucosidase. © 2022 Society of Chemical Industry.

Fruit acidity determines the organoleptic quality and nutritive value of most fruits. In litchi, although the organic acid composition of pulps is known, the molecular mechanisms and genes underlying variation in fruit acidity remain elusive. Herein, developing pulps of two contrasting litchi varieties, Huaizhi (HZ, low-acidity) and Boye_No.8 (B8, high-acidity), were subjected to metabolomics and transcriptomics, and the dynamic metabolome and transcriptional changes were determined. Measurements revealed that the dominant acidity-related organic acid in litchi pulps is malate, followed in low levels by citrate and tartrate. Variation in litchi pulps’ acidity is mainly associated with significant differences in malate and citrate metabolisms during fruit development. Malic acid content decreased by 91.43% and 72.28% during fruit ripening in HZ and B8, respectively. The content of citric acid increased significantly in B8, while in HZ it was reduced considerably. Differentially accumulated metabolites and differentially expressed genes analyses unveiled fumarate, succinate, 2-oxoglutarate, GABA (γ-aminobutyric acid), phosphoenolpyruvate, and citrate metabolisms as the key driving pathways of litchi fruits’ acidity variation. The drastic malate and citrate degradation in HZ was linked to higher induction of fumarate and GABA biosynthesis, respectively. Thirty candidate genes, including three key genes (LITCHI026501.m2, fumarase; LITCHI020148.m5, glutamate decarboxylase; and LITCHI003343.m3, glutamate dehydrogenase), were identified for functional studies toward genetic modulation of litchi fruit acidity. Our findings provide insights into the molecular basis of acidity variation in litchi and provide valuable resources for fruit quality improvement.

The catalytic ozonation-based advanced oxidation process (AOP) is applied to remove nondegradable chemical oxygen demand (COD), while the application in industry is limited by the economics and activity of catalysts. In this study, we demonstrate that by taking atrazine (ATZ) as a model pollutant, the removal rates of catalytic ozonation were negatively correlated with the interlayer water content of metal-modified montmorillonite (M

Background Endogenous plant β-glucosidases can be utilized to hydrolyze pro-pesticides and release the bioactive pesticide. Two related glucose-fipronil conjugates with different linkers structure, N-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl) sulfinyl]-1H-pyrazol-5-yl}-1-(2-triazolethyl-β-d-glucopyranoside)-1H-1,2,3-triazole-4-methanamine (GOTF) and N-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl) phenyl]-4-[(trifluoromethyl)-sulfinyl]-1H-pyrazol-5-yl}-2-aminoethyl-β-d-glucopyranoside (GOF), were deglucolysated by β-glucosidase both in vitro and in vivo at different rates. Here, the basis for these differences was investigated by revealing the kinetics of the reaction and by modeling molecular docking between enzyme and substrate. Results Results from kinetic study showed that the reaction rate was the main reason for the poorer rate of GOF hydrolysis with respect to GOTF. Modeling of substrate docking indicated that the spacer arm of glucose-fipronil conjugates affects the strength of non-covalent bonds within the active site and the position of fipronil within the pocket. Four glucose-fipronil conjugates and four corresponding aglycones were synthesized, and the hydrolysis data confirmed that the increased tether length between the bulky aglycone and glycone would lead to faster hydrolysis rate. The bioassay results indicated that most glucose-fipronil conjugates displayed moderate to excellent insecticidal activities in vivo against Plutella xylostella larvae. Conclusion This study provides a potential strategy to optimize the substrate structure to enhance hydrolytic specificity in order to design appropriate phloem mobile pro-pesticides. © 2018 Society of Chemical Industry.

Background Conjugating amino acid and glucose fragments with existing pesticide structures has been shown to be an effective way to introduce phloem mobility into non-phloem mobile species. However, the resulting derivatives always suffer from lower bioactivity compared with their parent compound. To solve this problem, we designed and synthesised a series of ester-capped amino-acid-conjugated chlorantraniliproles. Results The systemic test showed that all conjugates exhibited excellent phloem mobility and xylem mobility in a Ricinus communis model. In particular, compounds 7b, 8b and 8c were able to accumulate in phloem tissues in the form of their hydrolysis products, and the concentrations in phloem sap can reach 3 times the concentration in the incubation medium. Although their insecticidal activity (LC50 ) against the beet armyworm (Spodoptera exigua) in vitro was weaker than that of chlorantraniliprole, compounds 7b, 8b and 8c showed similar insecticidal activity in vivo against beet armyworm compared with the parent compound. Conclusions This work provides a potential strategy to obtain pesticide derivatives that possess both improved uptake and improved mobility in crops while retaining the in vivo insecticidal effect of the parent compound. © 2017 Society of Chemical Industry.