Design, synthesis, insecticidal activities and translocation of amino acid-tralopyril conjugates as vectorizing agrochemicals.

BACKGROUND: Conjugating amino acid moieties to active ingredients has been recognized as an effective method for improving the precise targeting of the active form to the specific site. Based on the vectorization strategy, a series of amino acid-tralopyril conjugates were designed and synthesized as novel proinsecticide candidates, with the potential capability of root uptake and translocation to the foliage of crops. RESULTS: Bioassay results showed excellent insecticidal activities of some conjugates, in particular, the conjugates 6b, 6e, and 7e, against the diamondback moth (Plutella xylostella), with equivalent insecticidal activity to chlorfenapyr (CFP). Importantly, conjugate 6e exhibited significantly higher in vivo insecticidal activity against P. xylostella than CFP. Furthermore, the systemic test experiments with Brassica chinensis demonstrated that conjugates 6e and 7e could be transported to the leaves, in contrast to CFP, which remained in the root. CONCLUSION: This study demonstrated the feasibility of amino acid fragment conjugation as a vectorization strategy for transporting non-systemic insecticides into the leaves of B. chinensis while maintaining in vivo insecticidal activity. The findings also provide insights for subsequent mechanism studies on the uptake and transport of amino acid-insecticide conjugates in plants. © 2023 Society of Chemical Industry.

An amino acid transporter-like protein (OsATL15) facilitates the systematic distribution of thiamethoxam in rice for controlling the brown planthopper.

Characterization and genetic engineering of plant transporters involved in the pesticide uptake and translocation facilitate pesticide relocation to the tissue where the pests feed, thus improving the bioavailability of the agrichemicals. We aimed to identify thiamethoxam (THX) transporters in rice and modify their expression for better brown planthopper (BPH) control with less pesticide application. A yeast library expressing 1385 rice transporters was screened, leading to the identification of an amino acid transporter-like (ATL) gene, namely OsATL15, which facilitates THX uptake in both yeast cells and rice seedlings. In contrast to a decrease in THX content in osatl15 knockout mutants, ectopic expression of OsATL15 under the control of the CaMV 35S promoter or a vascular-bundle-specific promoter gdcsPpro significantly increased THX accumulation in rice plants, thus further enhancing the THX efficacy against BPH. OsATL15 was localized in rice cell membrane and abundant in the root transverse sections, vascular bundles of leaf blade, and stem longitudinal sections, but not in hull and brown rice at filling stages. Our study shows that OsATL15 plays an essential role in THX uptake and its systemic distribution in rice. OsATL15 could be valuable in achieving precise pest control by biotechnology approaches.

Development of Multifunctional Avermectin Poly(succinimide) Nanoparticles to Improve Bioactivity and Transportation in Rice.

Avermectin (AVM) as a nonsystemic pesticide possesses a low effective utilization rate. Studies of the multifunctional pesticide delivery system for improving biological activity are developing prosperously. In this study, multifunctional avermectin/polysuccinimide with glycine methyl ester nanoparticles (AVM-PGA) were prepared by the self-assembly process. The AVM loading capacity was up to 23.7%. After 24 h of UV irradiation, there was still about 70% of AVM remaining in PGA42 nanocarriers, as opposed to less than 5% of the free-form AVM. The rising ambient pH promoted the release of AVM using an in vitro releasing test, revealing a favorable pH-responsively controlled-release property. The mortality rate of Plutella xylostella with 2.5 µg/mL of AVM content of AVM-PGA42 was 96.3% after 48 h, while that of free AVM was only 51.5%. In addition, the AVM could be detected in stems and all leaves treated with AVM-PGA42 nanoparticles, whereas rare AVM was detected only in treated leaves for the free-form AVM, which achieved the transportation of nanocarriers carrying AVM in rice for the first time. Furthermore, the PGA nanoparticles performed a good growth promoting effect on rice. These results show that the AVM-PGA42 nanopesticides have a great potential application prospect to control the pest and improve the drug utilization efficiency on agriculture.

The physicochemical properties of a room-temperature liquidus binary ionic liquid mixture of [HNMP][CH3SO3]/[Bmim]Cl and its application for fructose conversion to 5-hydroxymethylfurfural.

Via heating first and then cooling, binary ionic liquid (IL) mixture of N-methyl-2-pyrrolidonium methylsulfonate ([HNMP][CH3SO3]) and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) could form a liquid at room temperature. The glass-transition temperature (T g) characterized by DSC depends on its composition with T g being as low as -63 °C. The physicochemical properties of the binary IL mixtures also vary with the composition. With the increase of the mole fraction of [Bmim]Cl, the hydrogen-bond accepting ability (ß) of the binary IL mixture increases, but the hydrogen-bond donating ability (α) deceases. In this binary IL mixture, fructose could be effectively converted into 5-hydroxymethylfurfural (HMF) at room temperature. The HMF yields at a given time are found to be well correlated with the physicochemical properties of the binary mixture, especially the α and ß values. Under specified conditions, the present IL mixture as medium for fructose dehydration into HMF is comparable to the medium formed by ILs and alcohol, where the alcohols have negative effect on the HMF formation.