Da-xia Zhang

Phoxim Microcapsules Prepared with Polyurea and Urea–Formaldehyde Resins Differ in Photostability and Insecticidal Activity

The application of pesticide microcapsules (MCs) in agriculture is becoming more and more popular. In this study, the effects of different wall materials on the stomach toxicity, contact toxicity, length of efficacy, and photolysis characteristics of pesticide microcapsules were investigated. The results showed that microencapsulation reduced the stomach and contact toxicities of phoxim and prolonged the efficacy of this light-sensitive chemical in the greenhouse test. Neither of the degradation curves for microencapsulated phoxim under ultraviolet light fit a first-order model, although the emulsifiable concentrate (EC) degradation curve fit it well. The phoxim-loaded polyurea microcapsules (PUA-MCs) showed significantly increased UV-resistance ability, stomach toxicity, and contact toxicity compared with the phoxim-loaded urea-formaldehyde microcapsules (UF-MCs). These experiments indicated that it is crucial to select the appropriate wall materials for pesticide microcapsules on the basis of application sites and physicochemical properties of pesticide active ingredients.

Integrating uniform design and response surface methodology to optimize thiacloprid suspension

A model 25% suspension concentrate (SC) of thiacloprid was adopted to evaluate an integrative approach of uniform design and response surface methodology. Tersperse2700, PE1601, xanthan gum and veegum were the four experimental factors, and the aqueous separation ratio and viscosity were the two dependent variables. Linear and quadratic polynomial models of stepwise regression and partial least squares were adopted to test the fit of the experimental data. Verification tests revealed satisfactory agreement between the experimental and predicted data. The measured values for the aqueous separation ratio and viscosity were 3.45% and 278.8 mPa·s, respectively, and the relative errors of the predicted values were 9.57% and 2.65%, respectively (prepared under the proposed conditions). Comprehensive benefits could also be obtained by appropriately adjusting the amount of certain adjuvants based on practical requirements. Integrating uniform design and response surface methodology is an effective strategy for optimizing SC formulas.

Effects of trans ‐2‐hexenal on reproduction, growth and behaviour and efficacy against the pinewood nematode, Bursaphelenchus xylophilus

BACKGROUND Bursaphelenchus xylophilus is a serious quarantined pest that causes severe damage and major economic losses to pine forests. Because of the adverse effects of some traditional nematicides on humans and the environment, the search for new plant toxicants against these nematodes has intensified. Nematicidal activity of trans-2-hexenal, which is a six-carbon aldehyde present in many plants, was tested against the nematode. RESULTS trans-2-Hexenal showed significant efficacy against B. xylophilus in a dose range of 349.5-699 g m-3 by fumigation of pinewood logs. Additionally, it had significant nematicidal activity against different life stages of B. xylophilus in an in vitro test, with second-stage larvae (L2s) being the most sensitive, with an LC50 value of 9.87 µg mL-1 at 48 h. Egg hatch was also significantly inhibited. Further studies revealed that trans-2-hexenal inhibited the reproductive activity of B. xylophilus, with negative effects on reproduction rate and egg numbers. Moreover, trans-2-hexenal reduced the body length of B. xylophilus. Respiratory rate and thrashing behaviour of B. xylophilus also decreased following treatment with this compound. CONCLUSION trans-2-Hexenal had significant nematicidal activity against B. xylophilus, providing a basis for elucidation of the mode of action of trans-2-hexenal against plant-parasitic nematodes in future studies.

Thiacloprid suspension formula optimization by a response surface methodology

A model thiacloprid 25% suspension concentrate was prepared using Tersperse2700 (X1), AE1601 (X2), xanthan gum (X3) and Veegum (X4). A response surface methodology (RSM) was used to evaluate the influences of four experimental factors on the aqueous separation ratio (R1), centrifugal sedimentation ratio (R2) and viscosity (R3). The results show that the main factors influencing the three responses were X3, X4 and X2 followed by X1; moreover, several interactions were also significant. Multiple-response optimization was performed based on a desirability function, considering the minimum R1, R2, and R3 as well as the financial cost. The integrated optimum conditions were X3 = 0.24%, X4 = 1.33%, X2 = 0.50%, and X1 = 2.90% (mass fraction). A verification experiment demonstrated that the optimized formula R1, R2, and R3 were 1.69%, 2.63% and 257.74 mPa s with the average relative predicted value errors 7.69%, 4.18% and −1.41%, respectively. The response surface methodology is an effective approach for optimizing the suspension concentrate formula with comprehensive advantages.

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.

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.

Easily Tunable Membrane Thickness of Microcapsules by Using a Coordination Assembly on the Liquid-Liquid Interface

A model solvent, 1,3,5-trimethylbenzene, was encapsulated using coordination assembly between metal ions and tannic acid to reveal the deposition of coordination complexes on the liquid-liquid interface. The deposition was confirmed by zeta potential, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. Scanning electron microscopy and transmission electron microscopy were integrated to characterize the microcapsules (MCs). According to atomic force microscopy height analysis, membrane thickness of the MCs increased linearly with sequential deposition. For MCs prepared using the Fe3+-TA system, the average membrane thicknesses of MCs prepared with 2, 4, 6, and 8 deposition cycles were determined as 31.3 ± 4.6, 92.4 ± 15.0, 175.4 ± 22.1, and 254.8 ± 24.0 nm, respectively. Dissolution test showed that the release profiles of all the four tested MCs followed Higuchi kinetics. Membrane thicknesses of MCs prepared using the Ca2+-TA system were much smaller. We can easily tune the membrane thickness of the MCs by adjusting metal ions or deposition cycles according to the application requirements. The convenient tunability of the membrane thickness can enable an extensive use of this coordination assembly strategy in a broad range of applications.

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.

Causation Analysis and Improvement Strategy for Reduced Pendimethalin Herbicidal Activity in the Field after Encapsulation in Polyurea

To reduce the amount of organic solvents in pendimethalin emulsifiable concentrate (EC), small-size microcapsules (S-MCs) and large-size microcapsules (L-MCs) were prepared with polyurea as a wall material. Petri-dish bioassays were carried out to investigate the bioactivity of formulations and the influence of both organic matter and moisture. The relationships between degradation and the biological activity of three pendimethalin formulations in the soil were investigated, and field experiments were executed to verify the laboratory results. The laboratory tests showed the following: (1) the bioactivity of EC and S-MCs was similar and greater than that of L-MCs; (2) organic matter could reduce the bioactivity of MCs and EC, and the impact of organic matter on L-MCs was greater; (3) increased soil moisture content had no significant effect on the bioactivity of EC but slightly reduced that of the MCs; and (4) the L-MCs showed significantly more prolonged residual and effective persistence in the soil than did EC and S-MCs. However, the field experiments indicated that the herbicidal efficacies of L-MCs at the early and late stages were both lower than those of EC. Comprehensive analysis of the results indicated that the main reason that the herbicidal efficacy of L-MCs was lower than that of EC in the field was that L-MCs missed the optimal herbicidal periods due to the slow-release characteristics of L-MCs. The S-MCs had both similar release rates and herbicidal efficacy in the field as EC. Therefore, to develop a good pesticide formulation, the occurrence and damage characteristic of pests must be considered.