Chong Cao

Quaternized Chitosan-Capped Mesoporous Silica Nanoparticles as Nanocarriers for Controlled Pesticide Release

Nanotechnology-based pesticide formulations would ensure effective utilization of agricultural inputs. In the present work, mesoporous silica nanoparticles (MSNs) with particle diameters of ~110 nm and pore sizes of ~3.7 nm were synthesized via a liquid crystal templating mechanism. A water-soluble chitosan (CS) derivative (N-(2-hydroxyl)propyl-3-trimethyl ammonium CS chloride, HTCC) was successfully capped on the surface of pyraclostrobin-loaded MSNs. The physicochemical and structural analyses showed that the electrostatic interactions and hydrogen bonding were the major forces responsible for the formation of HTCC-capped MSNs. HTCC coating greatly improved the loading efficiency (LC) (to 40.3%) compared to using bare MSNs as a single encapsulant (26.7%). The microstructure of the nanoparticles was revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The pyraclostrobin-loaded nanoparticles showed an initial burst and subsequent sustained release behavior. HTCC-capped MSNs released faster than bare MSNs in the initial stage. Pyraclostrobin-loaded HTCC-capped MSNs with half doses of pyraclostrobin technical demonstrated almost the same fungicidal activity against Phomopsis asparagi (Sacc.), which obviously reduced the applied pesticide and enhanced the utilization efficiency. Therefore, HTCC-decorated MSNs demonstrated great potential as nanocarriers in agrochemical applications.

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 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.

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.

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.

Impact of Imidazolium Based Ionic Liquid Surfactant Additions on Dilational Rheology Properties of Different Protein Adsorption Layer

ABSTRACT The interfacial behavior of β-casein and BSA solutions have been investigated in the presence of imidazolium-based ionic liquid surfactant ([C14mim]Br) at the decane/water interface with the oscillating the drop and interfacial tension relaxation measurements. Both the electrostatic and the hydrophobic interaction between protein and [C14mim]Br played crucial roles as [C14mim]Br concentration increases. Furthermore, it was found that the dilational rheology parameters provided information of the adsorbed layers structure, and the dynamics properties of the adsorbed layers depend on the bulk [C14mim]Br concentration. Moreover, with the concentration of [C14mim]Br increasing, β-casein in the interfacial layer was subject to conformational changes where it gave space to [C14mim]Br molecules in the form of co-adsorb; for BSA/[C14mim]Br solutions, the globule protein BSA deformed and then co-adsorb with [C14mim]Br molecules at the decane/water interface. These results will contribute to elucidation of the influence of the surfactant on the different structure proteins and the wide applications of protein/surfactant systems in practice. GRAPHICAL ABSTRACT

Bounce Behavior and Regulation of Pesticide Solution Droplets on Rice Leaf Surfaces

Pesticide spray droplets can damage ecological environments and negatively affect biodiversity if they reach nontarget areas. Effective retention of pesticide droplets on plant surfaces is an important challenge. In this study, a high-speed camera was utilized to visualize the bounce behavior of droplets of different pesticide solutions on rice leaf surfaces. We explored the addition of surfactants (SAAs) to different pesticide solutions and altered a pesticide solution system to prevent or regulate droplet bounce behavior. Experimental results indicate that the addition of SAAs to a pesticide solution can inhibit the bouncing of droplets on rice leaf surfaces. Additionally, a water-in-oil (EO) emulsion not only can significantly inhibit droplet rebound on a superhydrophobic surface, but also can quickly and automatically spread pesticide droplets to maximize the wetting area. Therefore, this work effectively improves the utilization of pesticides and reduces environmental pollution.

Uptake and Distribution of Fenoxanil-Loaded Mesoporous Silica Nanoparticles in Rice Plants

Mesoporous silica nanoparticles (MSNs) can be used as carriers to deliver pesticides into plants, which is considered to be one method of improving the efficacy of pesticide usage in agricultural production. In the present work, MSNs with an average diameter of 258.1 nm were synthesized and loaded with Fenoxanil. The structure of the nanocarriers was observed by scanning electron microscopy. The loading content of Fenoxanil-loaded MSNs was investigated. After rice plants in a hydroponic system were treated with loaded MSNs, the concentrations of Fenoxanil in different samples were determined using high-performance liquid chromatography–tandem mass spectrometry. The results suggested that rice plants can absorb MSNs from water through their roots, and the dosage has almost no effect on the distribution of Fenoxanil in rice plants. The application of pesticide-loaded nanoparticles in a hydroponic system poses a low risk of Fenoxanil accumulation in rice.