Zhao Kefei, Xu Guangchun, Wang Leng, Wu Tianyue, Zhang Xingyu, Zhang Chenhui, Zhao Yuhang, Li Zilu, Gao Yuxia, Du Fengpei
Department of Applied Chemistry, College of Science, China Agricultural University, Beijing 100193, P.R. China.
Institute of Plant Protection, Jiangsu Academy of Agricultural Sciences, Nanjing 210014, P.R. China.
ACS Appl Mater Interfaces. 2023 Aug 2;15(30):37093-37106. doi: 10.1021/acsami.3c07530. Epub 2023 Jul 24.
Various strategies have been developed to improve the applicability of hydrophobic pesticides for better effectiveness in agriculture. However, existing formulations of hydrophobic pesticides still suffer from complicated processing, abused organic solvents, indispensable surfactants, or inescapable ecotoxicity, which strictly limit their applications. Herein, a dynamic covalent bond tailored pesticide (fipronil) amphiphile is constructed to address the above issues, which accomplishes the nanodispersion, full wetting, and precise delivery without organic solvents, surfactants, and materials simultaneously. By introducing a hydrophilic ligand on the hydrophobic fipronil through an imine bond, the cleavable fipronil amphiphile (FPP) exhibits superior water solubility and can even self-assemble into micelles at higher concentrations, which can be directly applied in powder form without organic solvents. Attributed to the suitable hydrophilic/hydrophobic ratio, FPP achieves full wetting and effective deposition on superhydrophobic rice leaves without surfactants. Moreover, benefiting from the unique dynamic nature of the imine bond, FPP maintains good storage stability while sensitively releasing back to fipronil under the humidity and pH trigger, consequently implementing the precise delivery for nontarget and target without materials. To our knowledge, this dynamic covalent bond tailored amphiphile strategy is the first idea that simultaneously takes the dispersibility, wettability, and responsiveness of hydrophobic pesticides into account, providing a possibility to control the entire journey of field application and even promising to be incorporated into the synthesis process, thus paving the way for modern sustainable agriculture.
人们已经开发出各种策略来提高疏水性农药的适用性,以在农业中获得更好的效果。然而,现有的疏水性农药制剂仍然存在加工复杂、有机溶剂滥用、离不开表面活性剂或不可避免的生态毒性等问题,这严格限制了它们的应用。在此,构建了一种动态共价键定制的农药(氟虫腈)两亲物来解决上述问题,它无需有机溶剂、表面活性剂和材料即可实现纳米分散、完全润湿和精确递送。通过亚胺键在疏水性氟虫腈上引入亲水性配体,可裂解的氟虫腈两亲物(FPP)表现出优异的水溶性,甚至在较高浓度下能自组装成胶束,无需有机溶剂即可直接以粉末形式应用。由于具有合适的亲水/疏水比,FPP在没有表面活性剂的情况下能在超疏水水稻叶片上实现完全润湿和有效沉积。此外,受益于亚胺键独特的动态性质,FPP在湿度和pH触发下能在保持良好储存稳定性的同时灵敏地释放回氟虫腈,从而在没有材料的情况下实现对非靶标和靶标的精确递送。据我们所知,这种动态共价键定制两亲物策略是首个同时兼顾疏水性农药的分散性、润湿性和响应性的理念,为控制田间应用的整个过程提供了可能,甚至有望纳入合成过程,从而为现代可持续农业铺平道路。