Biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) microcapsules for controlled release of trifluralin with improved photostability and herbicidal activity.

Microencapsulation of pesticide is a promising technology to reduce the negative environmental impact and benefit the sustainable development. Trifluralin, commonly used as a selective pre-emergence herbicide, is vulnerably subject to loss by volatilization and decomposition by sunlight when applied to the surface of soils. In the present study, trifluralin has been encapsulated using biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (PHB) polymers as carriers to develop controlled release formulations. PHB trifluralin microcapsules were obtained using a convenient solvent evaporation method. The influences of preparation parameters on the size and its distribution of the microcapsules were discussed. The particle size decreased from 4.44 µm to 2.50 µm as the shearing speeds increased from 4000 r/min to 12,000 r/min, and the value decreased from 3.64 µm to 3.23 µm as the mass fraction of emulsifier polyvinyl alcohol increased from 0.5% to 2.0%. The loading content (LC) as well as the encapsulation efficiency (EE) of trifluralin microcapsules are multiple factors dependent. Orthogonal table L9(34) was designed and range analysis was used to suggest the optimal preparation parameters. When performed under the optimized conditions, the corresponding LC and EE were 16.50% and 90.65%, respectively. The release of trifluralin from PHB microcapsules showed slow and sustained patterns, which could be easily achieved by modifying the preparation parameters including shearing speed and concentration of emulsifier. Compared to conventional trifluralin formulation of emulsifiable concentrate, trifluralin microcapsules exhibited significantly improved photostability and herbicidal activity against target weed barnyardgrass. These results demonstrated that microencapsulation with PHB could dramaticlly improve the effective utilization rate and decrease the dosage of such agricultural chemicals.

Fluorophore-free luminescent double-shelled hollow mesoporous silica nanoparticles as pesticide delivery vehicles.

Recently, mesoporous silica nanoparticles (MSNs) have become popular nanomaterials in smart delivery systems. Although research progress in the application of MSNs as pesticide carriers has been achieved, multifunctional MSNs endowed with bright luminescent centers facilitating the tracking of MSNs in biological systems and versatile structural properties possessing a high drug loading capacity and regulable release are still highly desirable. In the present work, we reported a fluorophore-free method to endow MSNs with stable fluorescence and a double-shelled hollow structure; they were prepared by a selective-etching strategy and subsequent annealing treatment. The strong and stable luminescence is found to originate from the carbon dots generated from the calcination. Their well-defined morphological structure was confirmed by SEM and TEM imaging. These versatile silica nanoparticles served as a novel delivery system for the pesticide pyraclostrobin with a loading content of 28.5%. The pyraclostrobin-loaded nanoparticles showed an initial burst, followed by subsequent sustained release behavior. The fungicidal activity of pyraclostrobin-loaded silica nanoparticles against the fungus Phomopsis asparagi (Sacc.) as well as their visual observation in the mycelium was explored. Furthermore, the effect of pyraclostrobin-loaded nanoparticles on the morphology and ultrastructure of the mycelium was investigated by SEM and TEM observations. This research seeks to develop a novel nanocarrier platform for the potential application of pesticides in sustainable plant protection.

Effect of adhesion force on the height pesticide droplets bounce on impaction with cabbage leaf surfaces.

The relationship between adhesion force and the height drops containing difenoconazole-loaded mesoporous silica nanoparticles (DF-MSNs)/Tween 80 bounce on cabbage leaf surfaces was investigated as a function of Tween 80 concentration. The adhesion force of a pesticide droplet on cabbage leaf surfaces was assessed using a high-sensitivity microelectromechanical balance system and the impact behavior was recorded with a high-speed camera. The height droplets bounced decreased with increasing adhesion force, with a negative correlation between the height of the bouncing drops and adhesion force. Although droplets containing ≥0.06% Tween 80 adhered to the cabbage leaves, the retraction height was still observed to decrease as the adhesion force increased. The experimental results indicate that for cabbage leaf surfaces, the adhesion force has a significant effect on the height drops bounce. The results provide new insights into how researchers can screen for formulations for hydrophobic target crops and how to increase spray adhesion to difficult-to-wet crop leaf surfaces.

Influence of the surface limiting elasticity modulus on the impact behavior of droplets of difenoconazole-loaded mesoporous silica nanoparticles with associated SDS.

The relation between the surface limiting elasticity modulus, ε0, of difenoconazole-loaded mesoporous silica nanoparticle (DF-MSN) formulations with associated SDS and the height of the first returning droplet impacting on cabbage and rice leaf surfaces was investigated. The surface dilational rheology properties were determined by means of surface tension relaxation. The impact of a droplet on the leaf surface was recorded with a high-speed camera. The surface limiting elasticity modulus, ε0, shows differences with different SDS concentrations. A positive correlation between droplet first rebound height and the surface limiting elasticity modulus, ε0, is observed. The pesticide droplet impact on the target leaf surface is a rather complex phenomenon, so the focus of this article is to establish a relationship between the surface limiting elasticity modulus, ε0, and droplet first rebound height. These findings introduce a chemical way to affect the impact behavior of pesticide droplets on target crop leaf surfaces, which may be of particular importance for pesticide spraying and crop protection, especially for hydrophobic and superhydrophobic target crops.

Potential dermal and inhalation exposure to imidacloprid and risk assessment among applicators during treatment in cotton field in China.

Quantifying operator exposure to pesticides is a key component of the decision-making procedure for risk assessment. China is the largest cotton-planting country in the world. Dense cotton planting patterns and pesticide overuse potentially place Chinese cotton farmers at high levels of exposure risk. Using whole-body dosimetry during backpack spraying application in cotton filed, the present study monitored potential dermal and inhalation exposure to the insecticide imidacloprid. For forward spraying (when the operators walked forward), the total potential dermal and inhalation exposure was 2059mg/kg of active ingredient (ai), corresponding to 0.21% of the applied quantity of the insecticide. However, the total exposure of backward walking (188mg/kg of ai) was approximately 11 times lower than that of forward walking. The upper body parts (head, chest, back and arms) were the most exposed. The potential inhalation exposure contributed to <0.1% of the total exposure. The exposure risk to imidacloprid inherent in these agricultural procedures was evaluated by margin of exposure values and was found to be safe under the present cotton treatment scenarios. In general, similar body exposure and distribution between Allura Red and imidacloprid verify Allura Red's feasibility as an environmentally friendly pesticide surrogate for exposure assessment.

Effect of surfactant concentration on the evaporation of droplets on cotton (Gossypium hirsutum L.) leaves.

The evaporation kinetics of pesticide droplets deposited on a leaf surface can affect their application efficiency. Evaporation of droplets on the hydrophobic leaves has received considerable attention, but little is known about hydrophilic leaf surfaces. In this study, the effect of surfactant concentration on the evaporation of droplets deposited on cotton leaves was investigated. The evaporation time is roughly decreased for concentrations ranging from 0% to 0.01% and increased from 0.01% to 0.10%. Contrary to the widely held belief that pesticide retention on target crops can rapidly be formed only with surfactant concentrations exceeding the CMC (critical micelle concentration), this study demonstrates that, on hydrophilic cotton leaves, fast evaporation of the droplet at surfactant concentrations of 0.01% (CMC) can reduce the volume quickly, lower the loss point and enhance pesticide retention. In addition, the evolution of droplet volume, height and contact angle on the cotton leaf surface were measured to confirm this conclusion. The result presented herein can be used to guide the use of surfactants and pesticides in agriculture.

Synthesis and Characterization of Stimuli-Responsive Poly(2-dimethylamino-ethylmethacrylate)-Grafted Chitosan Microcapsule for Controlled Pyraclostrobin Release.

Controllable pesticide release in response to environmental stimuli is highly desirable for better efficacy and fewer adverse effects. Combining the merits of natural and synthetic polymers, pH and temperature dual-responsive chitosan copolymer (CS-g-PDMAEMA) was facilely prepared through free radical graft copolymerization with 2-(dimethylamino) ethyl 2-methacrylate (DMAEMA) as the vinyl monomer. An emulsion chemical cross-linking method was used to expediently fabricate pyraclostrobin microcapsules in situ entrapping the pesticide. The loading content and encapsulation efficiency were 18.79% and 64.51%, respectively. The pyraclostrobin-loaded microcapsules showed pH-and thermo responsive release. Microcapsulation can address the inherent limitation of pyraclostrobin that is photo unstable and highly toxic on aquatic organisms. Compared to free pyraclostrobin, microcapsulation could dramatically improve its photostability under ultraviolet light irradiation. Lower acute toxicity against zebra fish on the first day and gradually similar toxicity over time with that of pyraclostrobin technical concentrate were in accordance with the release profiles of pyraclostrobin microcapsules. This stimuli-responsive pesticide delivery system may find promising application potential in sustainable plant protection.

Translocation, distribution and degradation of prochloraz-loaded mesoporous silica nanoparticles in cucumber plants.

The application of nanotechnology in pesticide loading can improve the uptake and transportation behavior in plants, which helps to increase the utilization efficiency of pesticides. In this work, prochloraz-loading mesoporous silica nanoparticles were prepared to study the translocation, distribution and degradation of the target pesticide in cucumber plants. Fluorescein isothiocyanate labeled nanoparticles were used to track the distribution of the carriers in plants. Four hours after the treatment on the leaves, the nanoparticles could be found in the leaves, stem, petioles and roots. Fourteen days later the concentration levels of prochloraz and its metabolite were measured in different parts of cucumber using high performance liquid chromatography tandem mass spectrometry. Compared to the conventional suspension concentrate, prochloraz-loaded mesoporous silica nanoparticles had almost the same fungicidal activity, and they tend to be absorbed by cucumber plants with a better deposition performance. The final residue levels of prochloraz in cucumbers were lower than the maximum residue levels, which indicated the low risk of p-MSN application on the plant.

Positive-Charge Functionalized Mesoporous Silica Nanoparticles as Nanocarriers for Controlled 2,4-Dichlorophenoxy Acetic Acid Sodium Salt Release.

Because of its relatively high water solubility and mobility, 2,4-dichlorophenoxy acetic acid (2,4-D) has a high leaching potential threatening the surface water and groundwater. Controlled release formulations of 2,4-D could alleviate the adverse effects on the environment. In the present study, positive-charge functionalized mesoporous silica nanoparticles (MSNs) were facilely synthesized by incorporating trimethylammonium (TA) groups onto MSNs via a postgrafting method. 2,4-D sodium salt, the anionic form of 2,4-D, was effectively loaded into these positively charged MSN-TA nanoparticles. The loading content can be greatly improved to 21.7% compared to using bare MSNs as a single encapsulant (1.5%). Pesticide loading and release patterns were pH, ionic strength and temperature responsive, which were mainly dominated by the electrostatic interactions. Soil column experiments clearly demonstrated that MSN-TA can decrease the soil leaching of 2, 4-D sodium salt. Moreover, this novel nanoformulation showed good bioactivity on target plant without adverse effects on the growth of nontarget plant. This strategy based on electrostatic interactions could be widely applied to charge carrying agrochemicals using carriers bearing opposite charges to alleviate the potential adverse effects on the environment.

Evaporation kinetics of surfactant solution droplets on rice (Oryza sativa) leaves.

The dynamics of evaporating sessile droplets on hydrophilic or hydrophobic surfaces is widely studied, and many models for these processes have been developed based on experimental evidence. However, few research has been explored on the evaporation of sessile droplets of surfactant or pesticide solutions on target crop leaves. Thus, in this paper the impact of surfactant concentrations on contact angle, contact diameter, droplet height, and evolution of the droplets' evaporative volume on rice leaf surfaces have been investigated. The results indicate that the evaporation kinetics of surfactant droplets on rice leaves were influenced by both the surfactant concentrations and the hydrophobicity of rice leaf surfaces. When the surfactant concentration is lower than the surfactant CMC (critical micelle concentration), the droplet evaporation time is much longer than that of the high surfactant concentration. This is due to the longer existence time of a narrow wedge region under the lower surfactant concentration, and such narrow wedge region further restricts the droplet evaporation. Besides, our experimental data are shown to roughly collapse onto theoretical curves based on the model presented by Popov. This study could supply theoretical data on the evaporation of the adjuvant or pesticide droplets for practical applications in agriculture.

Synthesis of Pyrimethanil-Loaded Mesoporous Silica Nanoparticles and Its Distribution and Dissipation in Cucumber Plants.

Mesoporous silica nanoparticles are used as pesticide carries in plants, which has been considered as a novel method to reduce the indiscriminate use of conventional pesticides. In the present work, mesoporous silica nanoparticles with particle diameters of 200-300 nm were synthesized in order to obtain pyrimethanil-loaded nanoparticles. The microstructure of the nanoparticles was observed by scanning electron microscopy. The loading content of pyrimethanil-loaded nanoparticles was investigated. After treatment on cucumber leaves, the concentrations of pyrimethanil were determined in different parts of cucumber over a period of 48 days using high performance liquid chromatography tandem mass spectrometry. It was shown that the pyrimethanil-loaded mesoporous silica nanoparticles might be more conducive to acropetal, rather than basipetal, uptake, and the dosage had almost no effect on the distribution and dissipation rate in cucumber plants. The application of the pesticide-loaded nanoparticles in leaves had a low risk of pyrimethanil accumulating in the edible part of the plant.