Multi-Stimuli-Responsive, Topology-Regulated, and Lignin-Based Nano/Microcapsules from Pickering Emulsion Templates for Bidirectional Delivery of Pesticides.

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 Botrytis disease, enabling the intelligent release of Pyr. The in vivo 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.

Near-infrared-responsive CuS@Cu-MOF nanocomposite with high foliar retention and extended persistence for controlling strawberry anthracnose.

Strawberry anthracnose (Colletotrichum gloeosporioides) exhibits a high pathogenicity, capable of directly infecting leaves through natural openings, resulting in devastating impacts on strawberries. Here, nanocomposite (CuS@Cu-MOF) was prepared with a high photothermal conversion efficiency of 35.3% and a strong response to near-infrared light (NIR) by locally growing CuS nanoparticles on the surface of a copper-based metal-organic framework (Cu-MOF) through in situ sulfurization. The porosity of Cu-MOF facilitated efficient encapsulation of the pesticide difenoconazole within CuS@Cu-MOF (DIF/CuS@Cu-MOF), achieving a loading potential of 19.18 ± 1.07%. Under NIR light irradiation, DIF/CuS@Cu-MOF showed an explosive release of DIF, which was 2.7 times higher than that under dark conditions. DIF/CuS@Cu-MOF exhibited a 43.9% increase in efficacy against C. gloeosporioides compared to difenoconazole microemulsion (DIF ME), demonstrating prolonged effectiveness. The EC50 values for DIF and DIF/CuS@Cu-MOF were 0.219 and 0.189 µg/mL, respectively. Confocal laser scanning microscopy demonstrated that the fluorescently labeled CuS@Cu-MOF acted as a penetrative carrier for the uptake of hyphae. Furthermore, DIF/CuS@Cu-MOF exhibited more substantial resistance to rainwater wash-off than DIF ME, with retention levels on the surfaces of cucumber leaves (hydrophilicity) and peanut leaves (hydrophobicity) increasing by 36.5-fold and 9.4-fold, respectively. These findings underscore the potential of nanocomposite to enhance pesticide utilization efficiency and leaf retention.

Bidirectional Uptake, Transfer, and Transport of Dextran-Based Nanoparticles in Plants for Multidimensional Enhancement of Pesticide Utilization.

The development of effective multifunctional nano-delivery approaches for pesticide absorption remains a challenge. Here, a dextran-based pesticide delivery system (MBD) is constructed to deliver tebuconazole for multidimensionally enhancing its effective utilization on tomato plants. Spherical MBD nanoparticles are obtained through two-step esterification of dextran, followed by tebuconazole loading using the Michael addition reaction. Confocal laser scanning microscopy shows that fluorescein isothiocyanate-labeled MBD nanoparticles can be bidirectionally transported in tomato plants and a modified quick, easy, cheap, effective, rugged, and safe-HPLC approach demonstrates the capacity to carry tebuconazole to plant tissues after 24 h of root uptake and foliar spray, respectively. Additionally, MBD nanoparticles could increase the retention of tebuconazole on tomato leaves by up to nearly 2.1 times compared with the tebuconazole technical material by measuring the tebuconazole content retained on the leaves. In vitro antifungal and pot experiments show that MBD nanoparticles improve the inhibitory effect of tebuconazole against botrytis cinerea by 58.4% and the protection against tomato gray molds by 74.9% compared with commercial suspensions. Furthermore, the MBD nanoparticles do not affect the healthy growth of tomato plants. These results underline the potential for the delivery system to provide a strategy for multidimensional enhancement of pesticide efficacy.

Lignin-based non-crosslinked nanocarriers: A promising delivery system of pesticide for development of sustainable agriculture.

Lignin sulfonate (LS), a waste material from the paper pulping, was modified with benzoic anhydride to obtain benzoylated lignin sulfonates of adjustable hydrophilicity (BLS). When BLS was combined with difenoconazole (Di), a broad-spectrum fungicide, lignin-based, non-crosslinked nanoparticles were obtained either by solvent exchange or solvent evaporation. When a mass ratio of 1:5 LS: benzoic anhydride was used, the Di release from Di@BLS5 after 1248 h was ca. 74 %, while a commercial difenoconazole microemulsion (Di ME) reached 100 % already after 96 h, proving the sustained release from the lignin nanocarriers. The formulation of Di in lignin-based nanocarriers also improved the UV stability and the foliar retention of Di compared to the commercial formulation of the fungicide. Bioactivity assay showed that Di@BLS5 exhibited high activities and duration against strawberry anthracnose (Colletotrichum gloeosporioides). Overall, the construction of fungicide delivery nano-platform using BLS via a simple non-crosslinked approach is a novel and promising way to develop new formulations for nanopesticide and the development of sustainable agriculture.

Acetalated dextran microparticles for the smart delivery of pyraclostrobin to control Sclerotinia diseases.

Dextran has emerged as a promising biopolymer carrier for controlled release formulations of pesticides. In this study, pH-sensitive acetalated dextran microparticles (Pyr@Ac-Dex) are prepared to encapsulate and control the release of pyraclostrobin (Pyr). In vitro fungicidal activity experiments showed that the prepared Pyr@Ac-Dex particles show comparable fungicidal ability against S. sclerotiorum compared to that of Pyr technical. In a 10-day pot experiment, the control efficacy of the Pyr@Ac-Dex treatment against S. sclerotiorum (77.1%) is significantly higher than that of Pyr emulsifiable concentrate (Pyr EC) treatment (42.4%). Photodegradation experiments show that compared to Pyr technical, Pyr@Ac-Dex doubles the half-life of Pyr in water. Acute toxicity experiments show that Pyr@Ac-Dex significantly reduced the acute exposure toxicity of Pyr to zebrafish. This study provides an environmentally friendly, feasible, and sustainable strategy for plant disease management.

A Light-Triggered pH-Responsive Metal-Organic Framework for Smart Delivery of Fungicide to Control Sclerotinia Diseases of Oilseed Rape.

Using a simple one-pot method, we developed a prochloraz (Pro) and pH-jump reagent-loaded zeolitic imidazolate framework-8 (PD@ZIF-8) composite for the smart control of Sclerotinia disease. The pH-jump reagent can induce the acidic degradation of ZIF-8 using UV light to realize the controlled release of Pro. Thus, the physical properties of PD@ZIF-8, such as its release, formulation stability, and adhesion, were investigated in detail. The results showed that the quantity of Pro released by PD@ZIF-8 under UV light irradiation (365 nm) was 63.4 ± 3.5%, whereas under dark conditions, it was only 13.7 ± 0.8%. In vitro activity indicated that the EC50 of PD@ZIF-8 under UV light irradiation was 0.122 ± 0.02 µg/mL, which was not significantly different from that of Pro (0.107 ± 0.01 µg/mL). Pot experiments showed that the efficacy of PD@ZIF-8 under light irradiation was 51.2 ± 5.7% for a fungal infection at 14 days post-spraying, whereas the effectiveness of prochloraz emulsion in water was only 9.3 ± 3.3%. Furthermore, fluorescence tracking of ZIF-8 and biosafety experiments showed that ZIF-8 could be absorbed by plant leaves and transported to various parts of oilseed rape in a short period of time and that PD@ZIF-8 was relatively safe for plants and HepG2 cells. These results highlight the potential of the composite to provide efficient and smart delivery of fungicides into plants for protection against diseases and provide an idea for developing sustainable agriculture.

A temperature-responsive release cellulose-based microcapsule loaded with chlorpyrifos for sustainable pest control.

Controlled pesticide release in response to environmental stimuli by encapsulating pesticide in carrier is a feasible approach to improve the effective utilization rate. Here, a temperature-responsive release microcapsule loaded with chlorpyrifos (CPF@CM) was prepared from n-hexadecane-in-water emulsions via interfacial polymerization. The microcapsule was consisted of nanofibrillated cellulose (NFC) as the shell wall material and isophorone diisocyanate (IPDI) as the crosslinker. The prepared CPF@CM had pesticide-loading efficiency (33.1 wt%) and favorable adhesion on the surface of cucumber and peanut foliage compared with conventional formulation. Additionally, CPF@CM could protect chlorpyrifos against photodegradation effectively. The in vitro release test showed that microcapsule had adjustable controlled-release characteristics with the change in temperature based on phase transition of the n-hexadecane core. Bioassay studies showed that control efficacy of CPF@CM microcapsule against P. xylostella was positively correlated with temperature because of temperature-induced changes in release rate. The acute toxicity of CPF@CM to zebrafish was reduced more than 5-fold compared with that of CPF technical. These results indicated that the microcapsule release system has great potential in the development of an effective and environmentally friendly pesticide formulation.

3D, eco-friendly metal-organic frameworks@carbon nanotube aerogels composite materials for removal of pesticides in water.

To alleviate the secondary risks of using metal-organic frameworks (MOFs) nanoparticles as adsorbent, a novel method of loading two MOFs (ZIF-8 or UiO66-NH2) on the carbon nanotube aerogels (MPCA) by in situ nucleation and growth of MOFs nanoparticles onto carbon nanotubes were developed. The prepared MOFs@MPCA aerogels were well characterized via SEM, TEM, EDS, FT-IR, XRD and XPS to reveal the microstructure and formation mechanism of MOF@MPCA. Besides, the hydrophilia, mechanical property and thermostability of MOF@MPCA were investigated. The results showed that MOF@MPCA had good hydrophilia, compression resilience and thermostability. The study on the ability to adsorb herbicides (chipton and alachlor) showed that the adsorption capacity of MOF@MPCA was stronger compared with single MOFs nanoparticles, which indicated that there was a synergistic effect between MOFs and MPCA. The equilibrium adsorption capacity of chipton adsorbed by UiO66-NH2@MPCA was 227.3 mg/g, and can be expediently reused for 5 cycles without a significant decrease in adsorption performance. Moreover, the results of biosafety experiments showed that MPCA can reduce the risk of MOFs nanoparticles leakage into the environment and accumulation in organisms. This work can provide a new research idea, which has potential applications to remove pollutants effectively and safely from the environment.