Lidong Cao

Protecting-Group-Free Total Synthesis of (±)-Subincanadine F

With chemoselective Dieckmann condensation as the key step, the protective-group-free total synthesis of (+/-)-subincanadine F was accomplished in 7 steps from the commercially available tryptamine in 33% overall yield.

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.

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.

Utilization of Chitosan-Lactide Copolymer Nanoparticles as Controlled Release Pesticide Carrier for Pyraclostrobin Against Colletotrichum gossypii Southw

Low effective availability of modern pesticides places heavy burdens on both the environment and costs to farmers. Nano-augmented delivery systems seem to be more promising to address the present challenge modern pesticides are facing. In this article, biodegradable chitosan-lactide copolymer (CPLA) was prepared and characterized as hydrophobic pesticide-pyraclostrobin carrier. Nano-precipitation method was used to fabricate pyraclostrobin-loaded nanoparticles. Loading content (LC), encapsulation efficiency (EE), size, and size distribution of the resulting nanoparticles were investigated. The size of pesticide-loaded nanoparticles can be adjusted between 77 to 128 nm by varying the feed mass ratio of copolymer to pyraclostrobin from 50/1 to 5/1. Compounds contained within nanoparticles was protected from light compared with the technical material. The pyraclostrobin-loaded nanoparticles showed an initial burst, subsequent sustained and pH-controlled release profile. Compared to 25% pyraclostrobin emulsifiable concentrate (EC), the nanoparticles demonstrated better fungicidal activity against Colletotrichum gossypii Southw under long incubation time, which further exhibited sustained release characteristic.

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.

Synthesis and Insecticidal Activity of Novel Camptothecin Derivatives Containing Analogs of Chrysanthemic Acid Moieties

Creating high-efficient and environment-friendly pesticides is very important to produce the pollution free agriculture food and maintain the balance of the survival environmental of the human being. According to reports, camptothecin (CPT) and its derivatives are now being explored as a class of botanical insecticide in agriculture due to its novel mode of action. In order to improve the insecticidal activity of CPT, ten novel camptothecin (1) and 10-hydroxycamptothecin (2) derivatives (1a, 1b, 1c, 1d, 1e; 2a, 2b, 2c, 2d, 2e) were designed and synthesized via esterification with analogs of chrysanthemic acid, which have outstanding insecticidal activity. The results showed that compound 2a exhibited potent antifeeding effect and the best contact toxicity among the target compounds against the third-instar larvae of beet armyworm, Spodoptera exigua Hubner. Compound 2a was also found to be the most effective cytotoxic compound to the tested insect cell lines, IOZCAS-Spex-II, which were established from the fat bodies of S. exigua. It was proposed that the 10-hydroxyl group in the camptothecin derivatives is a key factor for the antifeeding activity of a compound. The nature of the substituents was considered the major factor in determining the insecticidal activity of these compounds.

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.

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.

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.