Nano-Micro Core-Shell Fibers for Efficient Pest Trapping.

Insect sex pheromones as an alternative to chemical pesticides hold promising prospects in pest control. However, their burst release and duration need to be optimized. Herein, pheromone-loaded core-shell fibers composed of degradable polycaprolactone and polyhydroxybutyrate were prepared by coaxial electrospinning. The results showed that this core-shell fiber had good hydrophobic performance and thermal stability, and the light transmittance in the ultraviolet band was only below 40%, which provided protection to pheromones. The core-shell structure alleviated the burst release of pheromone in the fiber and extended the release time to about 133 days. In the field, the pheromone-loaded core-shell fibers showed the same continuous and efficient trapping of Spodoptera litura as the commercial carriers. More importantly, the electrospun fibers combined with biomaterials had a degradability unmatched by commercial carriers. The structure design strategy provides ideas for the innovative design of pheromone carriers and is a potential tool for the management of agricultural pests.

Preparation of Thifluzamide Polylactic Acid Glycolic Acid Copolymer Microspheres and Its Effect on the Growth of Cucumber Seedlings.

The polylactic acid-glycolic acid copolymer (PLGA) has been proven to be applicable in medicine, but there is limited research on its application and safety in the agricultural field. In this paper, thifluzamide PLGA microspheres were prepared via phacoemulsification and solvent volatilization, using the PLGA copolymer as the carrier and thifluzamide as the active component. It was found that the microspheres had good slow-release performance and fungicidal activity against Rhizoctonia solani. A comparative study was conducted to show the effect of thifluzamide PLGA microspheres on cucumber seedlings. Physiological and biochemical indexes of cucumber seedlings, including dry weight, root length, chlorophyll, protein, flavonoids, and total phenol content, indicated that the negative effect of thifluzamide on plant growth could be mitigated when it was wrapped in PLGA microspheres. This work explores the feasibility of PLGA as carriers in fungicide applications.

Effects of Methoxyfenozide-Loaded Fluorescent Mesoporous Silica Nanoparticles on Plutella xylostella (L.) (Lepidoptera: Plutellidae) Mortality and Detoxification Enzyme Levels Activities.

The diamond back moth, Plutella xylostella, causes severe damage at all crop stages, beside its rising resistance to all insecticides. The objective of this study was to look for a new control strategy such as application of insecticide-loaded carbon dot-embedded fluorescent mesoporous silica nanoparticles (FL-SiO2 NPs). Two different-sized methoxyfenozide-loaded nanoparticles (Me@FL-SiO2 NPs-70 nm, Me@FL-SiO2 NPs-150 nm) were prepared, with loading content 15% and 16%. Methoxyfenozide was released constantly from Me@FL-SiO2 NPs only at specific optimum pH 7.5. The release of methoxyfenozide from Me@FL-SiO2 NPs was not observed other than this optimum pH, and therefore, we checked and controlled a single release condition to look out for the different particle sizes of insecticide-loaded NPs. This pH-responsive release pattern can find potential application in sustainable plant protection. Moreover, the lethal concentration of the LC50 value was 24 mg/L for methoxyfenozide (TC), 14 mg/L for Me@FL-SiO2 NPs-70 nm, and 15 mg/L for Me@FL-SiO2 NPs-150 nm after 72 h exposure, respectively. After calculating the LC50, the results predicted that Me@FL-SiO2 NPs-70 nm and Me@FL-SiO2 NPs-150 nm exhibited better insecticidal activity against P. xylostella than methoxyfenozide under the same concentrations of active ingredient applied. Moreover, the activities of detoxification enzymes of P. xylostella were suppressed by treatment with insecticide-loaded NPs, which showed that NPs could also be involved in reduction of enzymes. Furthermore, the entering of FL-SiO2 NPs into the midgut of P. xylostella was confirmed by confocal laser scanning microscope (CLSM). For comparison, P. xylostella under treatment with water as control was also observed under CLSM. The control exhibited no fluorescent signal, while the larvae treated with FL-SiO2 NPs showed strong fluorescence under a laser excitation wavelength of 448 nm. The reduced enzyme activities as well as higher cuticular penetration in insects indicate that the nano-based delivery system of insecticide could be potentially applied in insecticide resistance management.

Enhanced Fungicidal Efficacy by Co-Delivery of Azoxystrobin and Diniconazole with Cauliflower-Like Metal-Organic Frameworks NH2-Al-MIL-101.

Long-term use of a single fungicide increases the resistance risk and causes adverse effects on natural ecosystems. Controlled release formulations of dual fungicides with different modes of action can afford a new dimension for addressing the current issues. Based on adjustable aperture and superhigh surface area, metal-organic frameworks (MOFs) are ideal candidates as pesticide release carriers. This study used Al3+ as the metal node and 2-aminoterephthalic acid as the organic chain to prepare aluminum-based metal-organic framework material (NH2-Al-MIL-101) with "cauliflower-like" structure and high surface area of 2359.0 m2/g. Fungicides of azoxystrobin (AZOX) and diniconazole (Dini) were simultaneously encapsulated into NH2-Al-MIL-101 with the loading content of 6.71% and 29.72%, respectively. Dual fungicide delivery system of AZOX@Dini@NH2-Al-MIL-101 demonstrated sustained and pH responsive release profiles. When the maximum cumulative release rate of AZOX and Dini both reached about 90%, the release time was 46 and 136 h, respectively. Furthermore, EC50 values as well as the percentage of inhibition revealed that AZOX@Dini@NH2-Al-MIL-101 had enhanced germicidal efficacy against rice sheath blight (Rhizoctonia solani), evidenced by the synergistic ratio of 1.83. The present study demonstrates a potential application prospect in sustainable plant protection through co-delivery fungicides with MOFs as a platform.

Effective and Sustained Control of Soil-Borne Plant Diseases by Biodegradable Polyhydroxybutyrate Mulch Films Embedded with Fungicide of Prothioconazole.

Soil-borne diseases and plant rhizosphere nematode have caused many crop yield losses. Increased environmental awareness is leading to more restrictions on the use of certain fumigants and root irrigation methods due to their impact on human health and soil system. Therefore, it is necessary to find alternative treatments to maintain crop economic yields and environmental sustainability. In the present work, biodegradable antifungal mulches were prepared by blending poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (PHB) with fungicide of prothioconazole (PRO), which were used for effective and sustained control of soil-borne plant diseases. To reveal the application prospect of the PHB/PRO composite films in the management of soilborne plant diseases, some physical and biological properties were evaluated. The proper mulch film of PHB/PRO was assessed based on its mechanical and optical properties, while water solubility and the film micromorphology was further characterized. The release patterns of composite films under different pH levels were investigated. Moreover, the in vitro antifungal bioassay and pot experiment showed satisfactory bioactivity of the PHB/PRO films against Sclerotium rolfsii Sacc., a soil-borne disease in peanut fields. This study demonstrated that the biodegradable mulch films containing PRO fungicide are capable of inhibiting soil-borne plant pathogenic fungi effectively, and this facile but powerful strategy may find wide applicability in sustainable plant and horticulture protection.

Sulfonate-Functionalized Mesoporous Silica Nanoparticles as Carriers for Controlled Herbicide Diquat Dibromide Release through Electrostatic Interaction.

Environmental stimuli-responsive pesticide release is desirable for enhanced efficiency and reduced side effects. In most cases, the loading and release of pesticides mainly depends on hydrophobic interactions and hydrogen bonding. Electrostatic interaction is less investigated as a weapon for achieving high loading content and controlled pesticide release. In this work, negative-charge decorated mesoporous silica nanoparticles (MSNs) were facilely fabricated by introducing sulfonate groups onto MSNs through a post-grafting method. Sulfonate-functionalized MSNs (MSN-SO3) were synthesized by conversion of epoxy group into sulfonate group using a bisulfite ion as a ring opening reagent. Diquat dibromide (DQ), one of the globally used quaternary ammonium herbicides, was efficiently loaded into these negatively charged MSN-SO3 nanoparticles. The loading content was increased to 12.73% compared to those using bare MSNs as carriers (5.31%). The release of DQ from DQ@MSN-SO3 nanoparticles was pH and ionic strength responsive, which was chiefly governed by the electrostatic interactions. Moreover, DQ@MSN-SO3 nanoparticles exhibited good herbicidal activity for the control of Datura stramonium L., and the bioactivity was affected by the ionic strength of the release medium. The strategy of cargo loading and release dependent on the electrostatic interactions could be generally used for charge-carrying pesticides using carriers possessing opposite charges to mitigate the potential negative impacts on the environment.

Wetting Behavior and Maximum Retention of Aqueous Surfactant Solutions on Tea Leaves.

In this research, the maximum retention and wetting behavior of surfactant solutions (N-200, N-300, Tween-80, Morwet EFW, DTAB, SDS) on the surfaces of tea leaves was investigated based on surface free energy, surface tension, the contact angle, adhesion work, and adhesion force. The results showed that the contact angles of all surfactant solutions were kept constant with low adsorption at the tea leaf-liquid interfaces below 0.005%. With an increase in concentration, the contact angle of Tween-80 decreased sharply because the adsorption of molecules at the solid-liquid interfaces (ΓSL') was several times greater than that at the liquid-air interfaces (ΓLV). Adhesion work decreased sharply and then reached a minimum at the critical micelle concentration (CMC), but then increased until reaching a constant. Moreover, a high adhesion force did not indicate better wettability, as it does with rose petals and peanut leaves. For tea leaf surfaces, an increase in the contact angle brought about an increase in the adhesion force. In addition, the maximum retention for Morwet EFW is at different concentrations compared to N-200, N-300, Tween-80, DTAB, and SDS, where the maximum retention of Morwet EFW on tea leaves was 6.05 mg/cm2 at 0.005%.According to the mechanisms of wetting behavior on plant surfaces, a recipe for pesticide formulation can be adjusted with better wettability to reduce loss, improve utilization efficiency, and alleviate adverse effects on the environment.

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.

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.

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.

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.

Determination of Propionylbrassinolide and Its Impurities by High-Performance Liquid Chromatography with Evaporative Light Scattering Detection.

The discovery of brassinolide in 1979, a milestone in brassinosteroids research, has sparked great interest of brassinolide analogs (BLs) in agricultural applications. Among these BLs, propionylbrassinolide has captured considerable attention because it shows plant growth regulating activity with an excellent durability. Two impurities of propionylbrassinolide were isolated and purified by semi-preparative high-performance liquid chromatography (HPLC), and the chemical structures were confirmed. For simultaneous separation and determination of propionylbrassinolide and impurities, an efficient analytical method based on HPLC with evaporative light scattering detector (HPLC-ELSD) was developed. The optimized analysis was performed on a C18 reversed phase column (250 mm × 4.60 mm, 5 µm) with isocratic elution of acetonitrile and water (90:10, v/v) as the mobile phase. The drift tube temperature of the ELSD system was set to 50 °C and the auxiliary gas pressure was 150 kPa. The regression equations demonstrated a good linear relationship (R² = 0.9989-0.9999) within the test ranges. The limits of detection (LODs) and quantification (LOQs) for propionylbrassinolide, impurity 1 and 2 were 1.3, 1.2, 1,3 and 4.3, 4.0, 4.2 mg/L, respectively. The fully validated HPLC-ELSD method was readily applied to quantify the active ingredient and impurities in propionylbrassinolide technical concentrate. Moreover, the optimized separation conditions with ELSD have been successfully transferred to mass spectrometry (MS) detector for LC-MS determination.

Determination of Inorganic Cations and Anions in Chitooligosaccharides by Ion Chromatography with Conductivity Detection.

Chitooligosaccharides (COSs) are a promising drug candidate and food ingredient because they are innately biocompatible, non-toxic, and non-allergenic to living tissues. Therefore, the impurities in COSs must be clearly elucidated and precisely determined. As for COSs, most analytical methods focus on the determination of the average degrees of polymerization (DPs) and deacetylation (DD), as well as separation and analysis of the single COSs with different DPs. However, little is known about the concentrations of inorganic cations and anions in COSs. In the present study, an efficient and sensitive ion chromatography coupled with conductivity detection (IC-CD) for the determination of inorganic cations Na⁺, NH4⁺, K⁺, Mg2+, Ca2+, and chloride, acetate and lactate anions was developed. Detection limits were 0.01-0.05 µM for cations and 0.5-0.6 µM for anions. The linear range was 0.001-0.8 mM. The optimized analysis was carried out on IonPac CS12A and IonPac AS12A analytical column for cations and anions, respectively, using isocratic elution with 20 mM methanesulfonic acid and 4 mM sodium hydroxide aqueous solution as the mobile phase at a 1.0 mL/min flow rate. Quality parameters, including precision and accuracy, were fully validated and found to be satisfactory. The fully validated IC-CD method was readily applied for the quantification of various cations and anions in commercial COS technical concentrate.

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.

Enhanced Germicidal Efficacy by Co-Delivery of Validamycin and Hexaconazole with Methoxy Poly(ethylene glycol)-Poly(lactide-co-glycolide) Nanoparticles.

Co-delivery system has been proposed in pharmaceutical field aim to synergistic treatments. The combination formulation is also important in traditional pesticides formulations based on the low pest resistance risk and wide fungicidal spectrum. However, co-delivery nanoparticles (NPs) tend to be more environmentally friendly for the sustained-release behaviour and none of toxic organic solvents or dusts. Hence, we constructed co-delivery NPs which could delivery two kinds of pesticides, which function was similar with pesticides combination formulation. The co-delivery NPs of validamycin and hexaconazole were prepared with the amphiphilic copolymer methoxy poly(ethylene glycol)- poly(lactide-co-glycolide) (mPEG-PLGA) used an improved double emulsion method. The chemical structure of mPEG-PLGA copolymer was confirmed using fourier transform infrared spectroscopy (FT-IR), and nuclear magnetic resonance spectroscopy (NMR). The co-delivery NPs all exhibited good size distribution and held sustained-release property. Germicidal efficacy of the co-delivery NPs against Rhizoctonia cerealis was also studied. The germicidal efficacy of co-delivery NPs against Rhizoctonia cerealis was better than that of traditional pesticides formulation. In addition, co-delivery NPs showed a lasting impact against Rhizoctonia cerealis.

Size-Dependent Effect of Prochloraz-Loaded mPEG-PLGA Micro- and Nanoparticles.

As a controlled release formulation, polymer-based pesticide particle, provide an effective approach to achieve the target crop sites of increasing the pesticide utilization and reducing side effects. The particle size impacts on the dispersibility, pesticide loading content, control effect, etc. It is essential to investigate size-dependent effect. Hence, size-dependent effect of polymer-based pesticide particle was studied systematically in this paper. The biodegradable mPEG-PLGA copolymer with suitable molecular weight (45 KDa) was selected as carrier. Prochloraz-loaded mPEG-PLGA particles with different sizes (190.7 nm, 708.8 nm and 3980.0 nm) were constructed by emulsion/solvent evaporation method based on the same carrier. With the constant mass ratio of copolymer/prochloraz, as the particle size became large, the prochloraz loading content increased, and prochloraz released speed decreased. All prochloraz-loaded particles showed a sustained-release process and sustained impact against the Fusarium graminearum. Among the prochloraz-loaded mPEG-PLGA particles, the 190.7 nm particles exhibited the best germicidal efficacy in two weeks. Hence, the smaller size particles hold a better control efficacy in short time.

Validated HPAEC-PAD Method for the Determination of Fully Deacetylated Chitooligosaccharides.

An efficient and sensitive analytical method based on high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) was established for the simultaneous separation and determination of glucosamine (GlcN)1 and chitooligosaccharides (COS) ranging from (GlcN)2 to (GlcN)6 without prior derivatization. Detection limits were 0.003 to 0.016 mg/L (corresponding to 0.4-0.6 pmol), and the linear range was 0.2 to 10 mg/L. The optimized analysis was carried out on a CarboPac-PA100 analytical column (4 × 250 mm) using isocratic elution with 0.2 M aqueous sodium hydroxide-water mixture (10:90, v/v) as the mobile phase at a 0.4 mL/min flow rate. Regression equations revealed a good linear relationship (R² = 0.9979-0.9995, n = 7) within the test ranges. Quality parameters, including precision and accuracy, were fully validated and found to be satisfactory. The fully validated HPAEC-PAD method was readily applied for the quantification of (GlcN)1-6 in a commercial COS technical concentrate. The established method was also used to monitor the acid hydrolysis of a COS technical concentrate to ensure optimization of reaction conditions and minimization of (GlcN)1 degradation.

Assessment of potential dermal and inhalation exposure of workers to the insecticide imidacloprid using whole-body dosimetry in China.

In China, although improvements to the pesticide registration process have been made in last thirty years, no occupational exposure data are required to obtain a commercial license for a pesticide product. Consequently, notably little research has been conducted to establish an exposure assessment procedure in China. The present study monitored the potential dermal operator exposure from knapsack electric sprayer wheat field application of imidacloprid in Liaocheng City, Shandong Province and in Xinxiang City, Henan Province, China, using whole-body dosimetry. The potential inhalation exposure was determined using a personal air pump and XAD-2 sample tubes. The analytical method was developed and validated, including such performance parameters as limits of detection and quantification, linear range, recovery and precision. The total potential dermal and inhalation exposures were 14.20, 16.80, 15.39 and 20.78 mL/hr, respectively, for the four operators in Liaocheng and Xinxiang, corresponding to 0.02% to 0.03% of the applied volume of spray solution. In all trials, the lower part (thigh, lower leg) of the body was the most contaminated, accounting for approximately 76% to 88% of the total exposure. The inhalation exposure was less than 1% of the total exposure. Such factors as the application pattern, crop type, spray equipment, operator experience and climatic conditions have been used to explain the exposure distribution over the different parts of the body. As indicated by the calculated Margin of Exposure, the typical wheat treatment scenarios when a backpack sprayer was used are considered to be safe in terms of imidacloprid exposure.

Determination of abamectin residues in edible oils by high-performance liquid chromatography with fluorescence detection.

A rapid and simple HPLC-fluorescence detection method has been developed for the determination of abamectin residues in edible oil. Residues are extracted with acetonitrile and by vortexing and then directly derivatized with no need for a time-consuming cleanup step. Trifluoroacetic anhydride and N-methylimidazole were used as derivatizing agents of abamectin. Abamectin was detected and quantitated with fluorescence detection (excitation: 365 nm; emission: 475 nm), and methanol was used as the mobile phase. The LOD was 0.001 mg/kg and the LOQ was 0.003 mg/kg. The recoveries ranged from 86 to 100.4% with satisfactory precision (RSD < 10.1%). This method proved to be sensitive, environmentally friendly, time-saving, and efficient.

Parameterized hilbert-type integral inequalities in the whole plane.

By the use of the way of real analysis, we estimate the weight functions and give some new Hilbert-type integral inequalities in the whole plane with nonhomogeneous kernels and multiparameters. The constant factors related to the hypergeometric function and the beta function are proved to be the best possible. We also consider the equivalent forms, the reverses, and some particular cases in the homogeneous kernels.