Key Laboratory of Biology of Crop Pathogens and Insects of Zhejiang Province, Ministry of Agriculture Key Lab of Molecular Biology of Crop Pathogens and Insects, Zhejiang University, Hangzhou 310058, P. R. China.
Sustainable Polymer Chemistry, Department of Molecules and Materials, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, Universiteit Twente, PO Box 217, 7500 AE Enschede, The Netherlands.
ACS Nano. 2024 Apr 9;18(14):10031-10044. doi: 10.1021/acsnano.3c11621. Epub 2024 Mar 28.
The increasing demand for improving pesticide utilization efficiency has prompted the development of sustainable, targeted, and stimuli-responsive delivery systems. Herein, a multi-stimuli-responsive nano/microcapsule bidirectional delivery system loaded with pyraclostrobin (Pyr) is prepared through interfacial cross-linking from a lignin-based Pickering emulsion template. During this process, methacrylated alkali lignin nanoparticles (LNPs) are utilized as stabilizers for the tunable oil-water (O/W) Pickering emulsion. Subsequently, a thiol-ene radical reaction occurs with the acid-labile cross-linkers at the oil-water interface, leading to the formation of lignin nano/microcapsules (LNCs) with various topological shapes. Through the investigation of the polymerization process and the structure of LNC, it was found that the amphiphilicity-driven diffusion and distribution of cyclohexanone impact the topology of LNC. The obtained Pyr@LNC exhibits high encapsulation efficiency, tunable size, and excellent UV shielding to Pyr. Additionally, the flexible topology of the Pyr@LNC shell enhances the retention and adhesion of the foliar surface. Furthermore, Pyr@LNC exhibits pH/laccase-responsive targeting against disease, enabling the intelligent release of Pyr. The fungicidal activity shows that efficacy of Pyr@LNC is 53% ± 2% at 14 days postspraying, whereas the effectiveness of Pyr suspension concentrate is only 29% ± 4%, and the acute toxicity of Pyr@LNC to zebrafish is reduced by more than 9-fold compared with that of Pyr technical. Moreover, confocal laser scanning microscopy shows that the LNCs can be bidirectionally translocated in plants. Therefore, the topology-regulated bidirectional delivery system LNC has great practical potential for sustainable agriculture.
提高农药利用率的需求不断增长，促使人们开发出可持续、靶向和刺激响应型的递药系统。在此，通过从基于木质素的 Pickering 乳液模板进行界面交联，制备了一种载有吡唑醚菌酯（Pyr）的多刺激响应性纳米/微胶囊双向递药系统。在此过程中，将甲基丙烯酰化碱木质素纳米颗粒（LNPs）用作可调油/水（O/W）Pickering 乳液的稳定剂。随后，在油水界面处，酸不稳定交联剂与巯基-烯自由基反应，导致形成具有各种拓扑形状的木质素纳米/微胶囊（LNCs）。通过对聚合过程和 LNC 结构的研究，发现环己酮的两亲性驱动扩散和分布影响 LNC 的拓扑结构。所得到的 Pyr@LNC 表现出高包封效率、可调尺寸和对 Pyr 的优异紫外屏蔽性能。此外，Pyr@LNC 壳的灵活拓扑结构增强了叶面的保留和附着力。此外，Pyr@LNC 表现出对疾病的 pH/漆酶响应靶向性，能够智能释放 Pyr。杀菌活性表明，Pyr@LNC 在施药后 14 天的防治效果为 53%±2%，而 Pyr 悬浮剂的防治效果仅为 29%±4%，并且 Pyr@LNC 对斑马鱼的急性毒性比 Pyr 技术降低了 9 倍以上。此外，共聚焦激光扫描显微镜显示，LNC 可以在植物中双向迁移。因此，拓扑调控的双向递药系统 LNC 在可持续农业中具有巨大的实际潜力。
