Emamectin benzoate nanogel suspension constructed from poly(vinyl alcohol)-valine derivatives and lignosulfonate enhanced insecticidal efficacy.

To reduce the negative impact of nanopesticide carriers of on the environment, a greener nanodelivery system is necessary. Nanogels are nontoxic and degradable carriers, however, the potential of nanogels for delivering pesticides has not been proven. In this study, poly(vinyl alcohol)-valine, an ecofriendly polymer, was synthesized and used to fabricate emamectin benzoate nanogel suspension (EB NS). The nanoformulation showed favorable stability at low temperature, high temperature or one year storage, and in water with different hardnesses. The retention of the EB NS solution on leaves was higher than that of an EB emulsifiable concentrate (EC) by approximately 9% at a concentration of 10 mg L-1. The half-life of EB nanogels under Ultra Violet irradiation was prolonged by 3.3-fold. Moreover, the bioactivity of the EB NS against Plutella xylostella was higher than that of the EB EC. These advantages resulted in a relatively long duration of pest control. The response of nanogels to laccase, a digestive enzyme in the digestive tract of lepidopteran pests, enables pesticide release on demand. Nanogels have the advantages of being ecofriendly carriers, exhibiting higher utilization, and prolonged pest control periods, and they have a brilliant future in pesticide delivery.

Using a reactive emulsifier to construct simple and convenient nanocapsules loaded with lambda-cyhalothrin to achieve efficient foliar delivery and insecticidal synergies.

Nanocapsules are a promising controlled release formulation for foliar pest control. However, the complicated process and high cost limit widespread use in agriculture, so a simpler and more convenient preparation system is urgently needed. Meanwhile, under complex field conditions, the advantageous mechanism of the nanosize effect and sustained release have no quantitative and detailed study. In this study, a reactive emulsifier (OP-10) is used to participate in the interfacial polymerization of the nanoemulsion, and polymer nanocapsules loaded with lambda-cyhalothrin (NCS@LC) are quickly and easily prepared to study the efficacy and synergistic mechanism of foliar pest control. As a result, the nanocapsule is about 150 nm with a stable core-shell structure. The nanoscale state increases the distribution and adhesion of the particles on the leaf surface, which increases the contact efficiency of pesticides under the different physiological stages and behavioral activities of the target organism. The shell structure provides sustained release characteristics and increases the UV resistance by about 2.5 times for pesticides. Compared with microcapsules loaded with lambda-cyhalothrin (CS@LC), NCS@LC not only shows rapid and synergistic insecticidal efficacy but also provides sustained insecticidal efficacy. The mortality of NCS is 3.4 times that of the nanosized emulsion in water (NEW) at the lowest concentration (0.5 mg L-1), and the control efficacy remained 77.3% after 7 days. Compared with NEW, NCS@LC provides excellent field efficacy, while LC50 for zebrafish is only 0.68 times without increasing the aquatic toxicity risk.

Self-Assembled Degradable Nanogels Provide Foliar Affinity and Pinning for Pesticide Delivery by Flexibility and Adhesiveness Adjustment.

At present, it is highly important to develop a simple and compatible nano delivery system for pesticides for foliar application, which can improve their insecticidal efficacy and resistance to adverse climates while reducing the environmental risks. Polyethylene glycol and 4,4-methylenediphenyl diisocyanate are used as hydrophilic soft and hydrophobic hard segments, respectively, for polymer self-assembly and polyurethane gelation in a nanoreactor. The nanocarrier synthesis and the pesticide loading are realized by a one-step integration procedure and suited well for hydrophobic active compounds. Modifying the molecular structure of the soft segment can adjust the flexibility of the nanocarriers and result in viscosity and deformation characteristics. After foliar spray application, the foliar flattening state of the nanogels increases the foliar protection area by 2.21 times and improves both pesticide exposure area and target contact efficiency. Concurrently, the flexibility and viscosity of the nanogels increase the washing resistance and the retention rate of the pesticide by approximately 80 times under continuous washing. The encapsulation of the nanogels reduces the foliar ultraviolet (UV) degradation and aquatic pesticide exposure, which increase the security of λ-cyhalothrine by 9.33 times. Moreover, the degradability of nanogels is beneficial for pesticide exposure and reducing pollution. This system has simple preparation, good properties, and environmental friendliness, making the nanocarriers promising for delivering pesticides.

Ecotoxicological effects of pyraclostrobin on tilapia (Oreochromis niloticus) via various exposure routes.

Pyraclostrobin is a widely used and highly efficient fungicide that also has high toxicity to aquatic organisms, especially fish. Although some research has reported the toxic effects of pyraclostrobin on fish, the main toxic pathways of pyraclostrobin in fish remain unclear. The present study has integrated histopathological, biochemical and hematological techniques to reveal the main toxic pathways and mechanisms of pyraclostrobin under different exposure routes. Our results indicated that pyraclostrobin entered fish mainly through the gills. The highest accumulation of pyraclostrobin was observed in the gills and heart compared with accumulation in other tissues and gill tissue showed the most severe damage. Hypoxia symptoms (water jacking, tummy turning and cartwheel formation) in fish were observed throughout the experiment. Taken together, our results suggested that the gills are important target organs. The high pyraclostrobin toxicity to gills might be associated with oxidative damage to the gills, inducing alterations in ventilation frequency, oxygen-carrying substances in blood and disorders of energy metabolism. Our research facilitates a better understanding of the toxic mechanisms of pyraclostrobin in fish, which can promote the ecotoxicological research of agrochemicals on aquatic organisms.

Achieving Win-Win Ecotoxicological Safety and Fungicidal Activity of Pyraclostrobin-Loaded Polyurea Microcapsules by Selecting Proper Polyamines.

The fungicide pyraclostrobin is highly toxic to aquatic organisms. Microencapsulation is an effective way to reduce the exposure of pyraclostrobin to aquatic organisms but it also reduces the contact probability between the fungicide and plant pathogens. Hence, winning a balance between the toxicity and bioactivity of pyraclostrobin is very necessary. In this study, triethylenetetramine (TETA), ethylenediamine (EDA), hexamethylenediamine (HAD), and isophoronediamine (IPDA) were selected as cross-linkers to prepare the pyraclostrobin-loaded polyurea microcapsules (PU-MCs) by interfacial polymerization. TETA formed the shells with the highest degree of cross-linking, the slowest release profile, and the best protection against ultraviolet (UV). In terms of MCs fabricated by diamines, higher leaking, weaker UV resistance of the shells was observed with increasing carbon skeleton. TETA-MCs showed the highest safety to zebrafish (LC50 of 10.086 mg/L), whereas EDA-MCs, HAD-MCs, and IPDA-MCs were 5.342, 3.967, and 0.767 mg/L, respectively. TETA-MCs had the best long-term disease management, while the control efficacies of other MCs were higher at the early stage of disease development. Overall, a balance between the aquatic toxicities and fungicidal activities of pyraclostrobin-loaded PU-MCs could be reached through a simple selection of polyamines in the fabrication.

Lignin-Modified Electronegative Epoxy Resin Nanocarriers Effectively Deliver Pesticides against Plant Root-Knot Nematodes (Meloidogyne incognita).

It is highly desirable to fabricate a pesticide delivery system with excellent permeability to reduce the damage caused by root-knot nematodes in the soil. In this work, a novel electronegative pesticide nanocarrier was established by bonding anionic lignosulfonate with epoxy resin nanocarriers, which were loaded with abamectin (Aba). The results demonstrated that nanoparticles were negatively charged (-38.4 mV) spheres with an average size of 150 nm, and the encapsulation efficiency of nanocarriers for Aba was 93.4%. Polymer nanocarriers could prevent premature release of Aba and protect active ingredients from microbiological degradation. The adsorption strength of the soil to Aba loaded in nanocarriers was reduced by 6 to 10 times, so nanonematicides have remarkable soil mobility. Meanwhile, nanoparticles could easily penetrate the roots and nematodes. The application test confirmed that the control effect of this nanopesticide was 26-40% higher than that of the other agrochemicals. In consideration of its superior bioactivity and utilization rate, this pesticide delivery system has promising potential to control root-knot nematodes and improve the pesticide's utilization efficiency.

Tunable thermal, mechanical, and controlled-release properties of epoxy phenolic novolac resin microcapsules mediated by diamine crosslinkers.

Diverse shell structures can endow microcapsules (MCs) with a variety of properties. In this study, four kinds of MCs encapsulated with epoxy phenolic novolac resin (EPN) were obtained using diamines as crosslinkers. The FTIR and CLSM confirmed that the EPN-shell was successfully synthesized. SEM results suggested that all four of the MCs possessed smooth and imporous surfaces, and they displayed uniform size distribution, with the average size ranging from 11.2 to 14.8 µm. Specifically, the MCs synthesized with the crosslinkers of hexamethylene diamine (HAD) and isophorone diamine (IPDA) were more stable and could maintain their spherical shapes in a dry environment, while those synthesized with ethylene diamine (EDA) and triethylene tetramine (TETA) exhibited poorer thermal stabilities and faster release profiles. Lipophilic diamines can form thicker shell thickness, and have smaller d-space values and higher Young's modulus values. Therefore, the lipophilicity of the diamine agents is the key factor that influences the specific properties of the MCs. The hybrid approach was validated as a flexible strategy to meet diverse requirements. The present study can provide a comprehensive understanding of diamine crosslinkers in the synthesis of EPN-MCs, and such MCs can be extended to a wide range of fields because of their broad tunable performance.

Assessment of ethylene glycol diacetate as an alternative carrier for use in agrochemical emulsifiable concentrate formulation.

The conventional emulsifiable concentrate (EC) formulation contains a large amount of aromatic solvents, which causes adverse effects to both the environment and human health due to the toxicity of the solvents. Here, we developed a 2.5% lambda-cyhalothrin EC formulation with ethylene glycol diacetate (EGDA) as the solvent, and the developed formulation serves as an environmental-friendly alternative to overcome the adverse effects of aromatic solvents. The physicochemical characterizations, wettability properties, phytotoxicity and bioassays of the EGDA-EC formulation were systematically investigated and compared with that of the EC formulation with xylene as the solvent. The results showed that both EC formulations had excellent emulsion properties and storage stabilities. Additionally, the EGDA-EC formulation possessed a higher flash point (96 °C), indicating safer production, storage and transport. The retentions of the EGDA-EC sample on leaves were 1.22-1.46-fold higher than that of the xylene-EC sample, and the EGDA-EC also exhibited lower surface tensions and contact angles, which would benefit decreasing drift-off and improving utilization. Furthermore, the bioassays demonstrated that the EGDA-EC formulation had lower acute toxicity to aquatic organisms and higher control efficacy to target insects compared with the xylene-EC formulation. Therefore, EGDA is a promising carrier for oil-soluble agrochemicals to improve their application performance and reduce their adverse effects.

Two-stage controlled release system possesses excellent initial and long-term efficacy.

In this work, a series of polyurea-based lambda-cyhalothrin-loaded microcapsules (MCs) with three different size distributions (average diameters of 1.35 µm, MC-S; 5.13 µm, MC-M; and 21.48 µm, MC-L) were prepared and characterized. The results indicated that MCs with a smaller particle size distribution had a faster release rate and excellent initial efficacy against pests. MC-L had a remarkably slow incipient release rate, outstanding photostability and better later-stage efficacy than that of the other tested MCs. The results clarified that the diameter distribution of MCs is the key factor in determining the release property and bioactivity of the MC formulations. Subsequently, the binary mixture MC formulations of MC(+M), MC(S+L) and MC(M+L) were obtained by mixing MC-S, MC-M or MC-L at 1:1 to establish a two-stage release system utilized for foliar application situations. Greenhouse and field experiments showed that MC(S+L) provided an optimal efficacy, and its effective duration was much longer than that of the emulsifiable concentrate (EC) group. Therefore, the release system established in this study was simple and workable for regulating the initial and long-term efficacy by adjusting the particle size distribution; in addition, this system has potential applications in other fields such as drug delivery devices.

Porous epoxy phenolic novolac resin polymer microcapsules: Tunable release and bioactivity controlled by epoxy value.

Microcapsules (MCs) prepared with diverse wall material structures may exhibit different properties. In this study, MCs were fabricated with three kinds of epoxy phenolic novolac resins (EPNs), which possessed unique epoxy values as wall-forming materials by interfacial polymerization. The effects of the EPN types on the surface morphology, particle size distribution, encapsulation efficiency, thermal stability as well as release behavior and bioactivity of the MCs were investigated. In all three samples, the MCs had nearly spherical shapes with fine monodispersities and sizes in the range of 7-30 µm. Scanning electron microscopy (SEM) images showed that some small pores (ranging from 50 nm to 400 nm) appeared on the microcapsule surfaces and that the porosity decreased with an increasing of epoxy value. The X-ray diffractometer (XRD) analysis indicated that the cured EPN shells had larger degrees of crosslinking with higher epoxy values, leading to better thermal stabilities. Moreover, the release rate of the core material (pendimethalin) decreased with an increasing of epoxy value and thus resulted in a lower herbicidal control efficacy. The results of our research will enhance the potential application of EPNs as smart wall-forming materials to prepare porous MCs for controlled release.

Porous microcapsules with tunable pore sizes provide easily controllable release and bioactivity.

In this paper, porous microcapsules with tunable pore sizes were prepared using interfacial polymerization by employing a temperature-responsive cross-linking agent above its so-called cloud point temperature (Tscp). The influences of porosity on the surface morphology, release profile and biological activity of the microcapsules were investigated. The results showed that both pore size and pore density could be controlled by regulating either the amount of cross-linking agent or the ratio of core material to shell material. Furthermore, the porosity of the microcapsules determined their release properties and further regulated the bioactivity of the microcapsules. In addition, the mechanism of pore formation was confirmed by investigating the morphology of microcapsules below the Tscp. The microencapsulation methodology described here is convenient and versatile, which can be easily extended to encapsulate a broad range of lipophilic core materials.