Shun He

Preparation and characterization of 1-naphthylacetic acid?silica conjugated nanospheres for enhancement of controlled-release performance

Chemical pesticides have been widely used to increase the yield and quality of agricultural products as they are efficient, effective, and easy to apply. However, the rapid degradation and low utilization ratio of conventional pesticides has led to environmental pollution and resource waste. Nano-sized controlled-release formulations (CRFs) can provide better penetration through the plant cuticle and deliver the active ingredients efficiently to the targeted tissue. In this paper we reported novel conjugated nanospheres derived from 1-naphthylacetic acid (NNA), 3-aminopropyltriethoxysilane (APTES) and tetraethyl orthosilicate and their application as a controlled-release plant growth regulator. The NNA and APTES conjugate was prepared through a covalent cross-linking reaction and subsequent hydrolyzation and polycondensation to synthesize NNA-silica nanospheres. The release data indicated that the release of NNA was by non-Fickian transport and increased as particle size decreased. It was also found that the acidity-alkalinity was enhanced and as the temperature increased, the release of the active ingredient was faster. The nanoconjugate displayed a better efficacy in promoting root formation than NNA technical. The present study provides a novel synthesis route for CRFs comprising a pesticide, with long-duration sustained-release performance and good environmental compatibility. This method may be extended to other pesticides that possess a carboxyl group.

Preparation and characterization of double-shelled avermectin microcapsules based on copolymer matrix of silica–glutaraldehyde–chitosan

Controlled release formulation (CRF) of pesticides is highly desirable for attaining the most effective utilization of the pesticide as well as reducing environmental pollution. Due to the selective permeation and protection properties of the semi-permeable membrane, pesticide microcapsules have been widely used. In this work, we developed a novel two-step method for synthesizing highly stable silica-glutaraldehyde-chitosan composite avermectin microcapsules. The silica shell was formed through the hydrolysis and polycondensation of tetraethyl orthosilicate (TEOS) at the oil droplet-water interface by using TEOS as the silica precursor and hexadecyl trimethyl ammonium chloride as a surfactant. Then the silica shell was modified with 3-aminopropyltriethoxysilane. Chitosan nanospheres were prepared by adjusting the pH value of the solution and then cross-linking with modified silica at the surface of the silica shell in the presence of glutaraldehyde to form double-shelled avermectin microcapsules. The results showed that the resulting microcapsules had a remarkable loading ability for avermectin (about 40% w/w) and can protect avermectin against photo- and thermal degradation effectively. Compared to single-shelled microcapsules, the double-shelled ones had better controlled release properties under all conditions. The present study provides a novel CRF comprising a pesticide which is light-sensitive or high temperature-sensitive, and a method for preparing the improved pesticide formulation so that the pesticide release rate and release period could be adjusted.

Preparation and Characterization of Novel Functionalized Prochloraz Microcapsules Using Silica–Alginate–Elements as Controlled Release Carrier Materials

Controlled release formulation of pesticides is an effective approach to achieve the desirable purpose of increasing the utilization of pesticides and reducing the environmental residuals. In this work, a novel functionalized microcapsule using silica cross-linked with alginate, and some beneficial elements to crops, was prepared. The microcapsules were structurally characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The results showed that the microcapsules had a high loading efficiency of prochloraz (about 30% w/w) and could effectively protect prochloraz against degradation under UV irradiation and alkaline conditions, showed sustainable release for at least 60 days, and also likely increased disease resistance due to the element on the surface. Given the advantages of the microcapsules, this delivery system may be extended to other photosensitive or pH-sensitive pesticides in the future.

Synthesis and characterization of gibberellin-chitosan conjugate for controlled-release applications.

Controlled release formulations (CRFs) are promising in improving the efficiency of pesticide and minimizing the spreading of hazardous residues in environment. By coupling with the pesticide covalently, chitosan can be used as a carrier material for the vulnerable ingredient. For the first time, gibberellic acid (GA3), one of plant growth regulators, was attached to chitosan (CS) to form a GA3-CS conjugate via the formation of an amide bound using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide. The novel conjugate was structurally characterized by fourier transform infrared spectroscopy, ultraviolet spectrophotometer, and thermal gravimetric analysis. Effects of pH, temperature, and UV irradiation on the release of this conjugate were investigated. The results showed that the new conjugate had a remarkable modification degree for CS (more than 60%, w/w) and the optimal coupling conditions were defined as: the molar ratio of GA3:EDC/NHS:CS was 1:1.2:1.2, at pH 6.0 for 24 h. The release data showed the novel conjugate protected GA3 against photo- and thermal-degradation effectively and the concentration of GA3 in GA3-CS kept unchangeable about 60 d in different pH conditions. Compared with GA3 technical, the conjugate had better water solubility and stability and have potential applications. The present study also provides a novel preparation method of CRFs comprising a pesticide with long duration, sustained-release performance and good environmental compatibility. This method may be extended to other pesticides that possess a carboxyl group.

A rapid liquid chromatography method for determination of glufosinate residue in maize after derivatisation

A rapid liquid chromatographic method for glufosinate analysis in maize samples after derivatisation has been developed. The labelled glufosinate was separated on a Kromasil C(18) column (250mm×4.6mm, 5μm) and UV detection was applied at 360nm. The optimisation of derivatisation conditions and the influence of different ion-pair reagents on the separation were discussed. The method linearity correlation coefficient was 0.9998 in concentrations ranging from 0.1 to 20mgL(-1). The level of quantification was set to 0.02mgkg(-1), and reached pesticide EU-MRLs for glufosinate in the maize samples. The proposed method was applied to the quantitative determination of glufosinate in samples with recoveries of 98.0-100.5% and RSDs of 2.13-4.13%.

Development and validation of a high-performance liquid chromatography method for the determination of diacetyl in beer using 4-nitro-o-phenylenediamine as the derivatization reagent.

Diacetyl is a natural byproduct of fermentation and known to be an important flavor compound in many food products. Because of the potential undesirable effects of diacetyl on health safety and beer flavor, determination of its concentration in beer samples is essential and its analytical methods have attracted close attention recently. The aim of the present work is to develop and validate a novel high-performance liquid chromatography method for the quantification of diacetyl in beer based on the derivatization reaction of diacetyl with 4-nitro-o-phenylenediamine (NPDA). After the derivatization with NPDA in pH 3.0 at 45 °C for 20 min, diacetyl was separated on a kromasil C(18) column at room temperature in the form of the resulting 6-nitro-2,3-dimethylquinoxaline and detected by the ultraviolet detector at 257 nm. The results showed that the correlation coefficient for the method was 0.9992 in the range of 0.0050-10.0 mg L(-1) and the limit of detection was 0.0008 mg L(-1) at a signal-to-noise ratio of 3. The applicability of the proposed method was evaluated in the analysis of beer samples with the recovery range of 94.0-99.0% and relative standard deviation range of 1.20-3.10%. The concentration levels of diacetyl detected in beer samples from 12 brands ranged from 0.034 to 0.110 mg L(-1). The proposed method showed efficient chromatographic separation, excellent linearity, and good repeatability that can be applied to quantification of diacetyl in beer samples.

Determination of tobramycin in soil by HPLC with ultrasonic-assisted extraction and solid-phase extraction

Pharmaceuticals residues in the environment have become a growing scientific interest worldwide. In the light of the possible harmful effects of tobramycin, a rapid and sensitive analytical method for determination of tobramycin in soil was developed. The extraction and purification methods, derivatization conditions, and chromatographic conditions in the determination of tobramycin in soil have been fully investigated. Extraction was carried out by a combination of vortex mixer and ultrasonic oscillation using acetone/water as the extraction agent. The extract was concentrated to 1 mL and passed through the C(18) SPE cartridge rinsed with water (3 mL), methanol (3 mL). The derivatization procedure was followed by the reaction of tobramycin with 4-Chloro-3,5-dinitrobenzotrifluoride at 60°C for 10 min in pH 9.0 H(3)BO(3)-Na(2)B(4)O(7) medium. The labeled tobramycin was determined by high performance liquid chromatography at 245 nm. Separation was accomplished within 15 min in gradient elution mode with trifluoroacetic acid in mobile phase as ion-pair reagent. The correlation coefficient for the method was 0.9999 in concentrations ranging from 0.10 to 100.0 μg/g. The limit of detection was 0.02 μg/g for tobramycin in soil at a signal-to-noise ratio of 3. The calculated recoveries of the proposed method were from 78.0 to 91.0% and RSDs were 3.38-9.79% in the application to the quantitative determination of tobramycin in all types of soil. The method will help to establish adequate monitoring of tobramycin residue in soil and make the contribution to environmental behavior evaluation.

Determination and dynamics of kanamycin A residue in soil by HPLC with SPE and precolumn derivatization

As one of the aminoglycoside antibiotics, kanamycin has been widely used in human therapy and as an additive to promote growth and prevent disease in forage. The kanamycin residue may have potenital risks for organisms and the environment. Therefore, the monitoring of this drug may have dynamic importance. In this work, a novel method for determination and dynamic study of kanamycin A was developed through solid phase extraction and derivatization with 4-chloro-3,5-dinitrobenzotrifluoride before high-performance liquid chromatography analysis. The calculated recoveries were from 72.3 to 92.5%, with relative standard deviations from 2.99 to 6.94%. The detection limit of kanamycin A in soil was 0.006 mg kg−1 with a signal-to-noise ratio of 3. The dynamics in soil showed that the degradation of kanamycin A coincided with the equations C = 1.951e−0.0482 t for black soil and C = 1.807 e−0.0247 t for red soil and the half-lives were 14.38 and 28.06 d respectively. The degradation rate reached 95.19% in black soil after 63 days compared with 77.14% in red soil.

Evaluation of the efficacy of glyphosate plus urea phosphate in the greenhouse and the field

BACKGROUND Glyphosate is a non-selective, foliar-applied, systemic herbicide that kills weeds by inhibiting the synthesis of 5-enolpyruvylshikimate-3-phosphate synthase. Urea phosphate (UPP), made by the reaction of urea with phosphoric acid, was applied as an adjuvant for glyphosate in this study. Experiments in the greenhouse and the field were conducted to determine the effects of UPP by comparing the efficacies of glyphosate plus UPP, glyphosate plus 1-aminomethanamide dihydrogen tetraoxosulfate (AMADS) and Roundup. RESULTS The optimum concentration of UPP in glyphosate solution was 2.0% when UPP was used as an adjuvant. The ED50 values for glyphosate-UPP were 291.7 and 462.4 g AI ha(-1) in the greenhouse and the field respectively, while the values for Roundup were 448.2 and 519.6 g AI ha(-1). The ED50 values at 2 weeks after treatment (WAT) and 3 WAT were lowered when UPP was used as an adjuvant in the greenhouse and field study, and the glyphosate+UPP was absorbed over a 2 week period. UPP may increase the efficacy by causing severe cuticle disruption or accelerating the initial herbicide absorption. The result also showed that UPP could reduce the binding behaviour of Ca2+ to glyphosate. CONCLUSION The application of UPP as an adjuvant could increase the efficacy of glyphosate and make it possible to achieve effective control of weeds with glyphosate at lower dose. Moreover, UPP showed less causticity to spraying tools and presented less of a health hazard. Therefore, UPP is accepted as being a new, effective and environmentally benign adjuvant for glyphosate.