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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

pH/redox dual responsive from natural polymer-based nanoparticles for on-demand delivery of pesticides

Ming Zhao,Peiquan Li,Hongjun Zhou,Li Hao,Huayao Chen,Xinhua Zhou

With the increase in global food demand and the destruction of environment, the development of sustainable agriculture has become increasingly more important. Stimuli-responsive controlled-release agrochemicals enhance the bioavailability of active ingredients and reduce the frequency of use and environmental pollution. Herein, 3,3′-dithiodipropionic acid was used as a functional bridge to covalently link the degradable natural polymer zein and chitosan oligosaccharides (CS) to prepare a water-dispersed environmentally friendly pesticide carrier. Subsequently, via hydrophobic and hydrogen bonding interactions photo-decomposable avermectin (AVM) was encapsulated forming a stimuli-responsive intelligent nanopesticide delivery system (AVM@CS-SS-Zein) was developed by encapsulating in the carrier. AVM was released slowly from AVM@CS-SS-Zein particles in a neutral condition and was released rapidly under stimulation of glutathione and alkalinity in simulated insects. The photostability of AVM@CS-SS-Zein was improved by 6-fold compared with that of AVM and the nanoparticles had good adherence to the leaves, slowly releasing AVM and avoiding the light decomposition of active ingredients. When the pests ingest the leaves containing AVM@CS-SS-Zein, the rapid disintegration of the nanoparticles in vivo leads to a good insecticidal effect and the control rate of AVM@CS-SS-Zein on Plutella xylostella was higher than that of AVM. After 120 h of UV irradiation, the pest mortality rate of AVM@CS-SS-Zein was 46.7% while that of AVM and AVM emulsifiable concentrate was only 13.3% and 20.0%, respectively. Therefore, this pH/redox dual stimuli-responsive nanopesticide formulation achieves target control of pests and provides an efficient nanoplatform for green agriculture.

研究领域: 农业科学 · 材料科学 · 环境科学
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Halloysite Nanotube-Based Pesticide Formulations with Enhanced Rain Erosion Resistance, Foliar Adhesion, and Insecticidal Effect

Linhong Chen,Jiawei Huang,Jie Chen,Qingxing Shi,Ting Chen,Guojun Qi,Mingxian Liu

The incorporation of green and sustainable nanomaterials in pesticide formation is an effective method to lower the use of conventional pesticides without adverse effects on productivity. Here pesticide Pickering emulsions stabilized by halloysite nanotubes (HNTs) were developed for low cost, less environmental pollution, low toxic effects, and better emulsion stability. HNTs were added to chlorantraniliprole (CAP) emulsions, and good stability was exhibited due to the adsorption and aggregation of HNTs at the interface of CAP oil droplets, forming a three-dimensional network structure that prevented the emulsion from aggregation. In addition, Spodoptera frugiperda was used as a pest model and corn was used as a plant model to explore the washout resistance, insecticidal effect, and biological safety of HNTs–CAP emulsion. After spraying emulsion on corn leaves and washing for 10 min, the HNTs–CAP emulsion (5 wt % HNTs) pesticide residue rate was 2.7 times that of pristine CAP emulsion. When the HNT dispersion concentration was 2 wt %, the larva mortality was 83%, which was 1.5 times that of the CAP emulsion group. These results demonstrated that HNTs–CAP emulsion showed good foliar adhesion, rainfall resistance, and insecticidal effect. The tubular clay-based nanopesticide formulations show potential applications in the control of crop pests with modern agriculture technology.

CAS / MDL: 1330-20-7
研究领域: 农业科学 · 环境科学 · 材料科学
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JOURNAL OF ASIA-PACIFIC ENTOMOLOGY · 2024 · IF 1.1

Mode of action underlying toxicity of Camptothecin to Spodoptera frugiperda (Lepidoptera) larvae

Jun-li Lv,Wen-qing Lai,Lei Pang,Xiao-ying Zhang,Kai-yi Zheng,Qiang Zhang,Zhan-peng Lu,Zhi-sheng Wang,Fasihul Lisan,Xue-yang Wang,Lu-feng Hu,Ming-jie Deng

Camptothecin (CPT) is derived from Camptotheca acuminate and its main action is the inhibition of the DNA topoisomerase I (Top I) complex. Therefore, CPT and its derivatives are always used as antitumor and antimicrobial agents and also have some insecticidal effects. However, the mode of action underlying the toxicity of CPT to the virulence of pests is still not fully understood. In this study, the effects of CPT on Spodoptera frugiperda ( S. frugiperda ) were determined by performing toxicity assessments, metabolomics, and mechanism analysis. The results showed that CPT increased the efficiency of inhibition of larval weight in a dose and time-dependent manner. In addition, the metabolomics of 5th-instar larval hemolymph was determined by UPLC-MS/MS and 1 H NMR analysis. UPLC-MS/MS analysis showed that the energy metabolic pathway was more important than the amino acid pathway for the resistance of S. frugiperda to CPT. Furthermore, metabolites involved in the energy metabolic pathway were analyzed using 1 H NMR, and fumarate and pyruvate were identified as interesting metabolites. Bioassays confirmed that they play a key role in enhancing the resistance of S. frugiperda larvae to CPT. Finally, the underlying mechanisms were found to be related to the restorative effects of the two metabolites on metabolic pathways associated with the TCA cycle. In a word, CPT is a potential biological insecticide that exhibits a strong toxicological effect against S. frugiperda by inhibiting the TCA cycle, which provides theoretical support for applying CPT in the control of pests.

CAS / MDL: 56180-94-0
研究领域: 昆虫学 · 药理学 · 代谢组学 · 毒理学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2017 · IF 3.154

Fabrication of Novel Avermectin Nanoemulsion Using a Polyurethane Emulsifier with Cleavable Disulfide Bonds

Wenxun Guan,Wenxiang Zhang,Liming Tang,Yan Wang,Haixin Cui

In this study, a polyurethane emulsifer with various functional groups was prepared from isophorone diisocyanate, avermectin, 2,2-dimethylol propionic acid, and bis(2-hydroxyethyl) disulfide. The chemical structure of the polymer was confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, and element analysis. The polymer exhibited adequate emulsification ability for avermectin after neutralization with triethylamine. A satisfaying nanoemulsion was obtained, in which avermectin was encapsulated in nanoparticles with 50 wt % drug loading, low organic solvent content, and high stability under dilution and centrifuging treatment in addition to low surface tension, high affinity to crop leaf, and improved avermectin photostability. The resulting nanoparticles showed degradability in the presence of dl-dithiothreitol or inside the insect as a result of the disulfide bonds, promoting the release of avermectin. As a result, the avermectin nanoparticles showed higher insecticidal ability compared to both the avermectin nanoparticles without a disulfide group and the avermectin emulsifiable concentrate.

研究领域: 纳米技术 · 药学 · 农药化学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Degradable ZIF-8/silica carriers with accropode-like structure for enhanced foliar affinity and responsive pesticide delivery

Menghui Wan,Yuting Zhang,Tao Hong,Junyan Cui,Yanbao Zhao,Zhihua Wang

The development of novel intelligent pesticide formulations for enhanced foliage deposition and efficient utilization remains a challenge. Accropode stones are general employed to attenuate the impact of waves. Herein, we constructed novel accropode-like carriers based on zeolitic imidazolate framework-8 (ZIF-8) and silica (SiO 2 ) for pesticide delivery with enhanced foliar affinity. Firstly, β-cyclodextrin-doped ZIF-8 (β-CD/ZIF-8) carrier was prepared by a one-pot method. Subsequently, a selective occupation strategy was applied to achieve facet-specific growth of mesoporous SiO 2 on β-CD/ZIF-8 (β-CD/ZIF-8@S). The β-CD/ZIF-8@S nanocarriers exhibited regular structure with sixteen facets. The accropode-like structure would achieve effective foliage retention and resistance to rainwater washout by the reduction of carrier bouncing and rolling on foliage. The β-CD/ZIF-8@S presented a high loading efficacy for imidacloprid (IMI) (24.43 %) and good biocompatibility. After loading IMI, tannic acid (TA) was utilized to block the loaded pesticide (IMI@β-CD/ZIF-8@ST). The IMI@β-CD/ZIF-8@ST exhibited dual responsive release behavior and could be effectively transported in both directions in various parts of tobacco plants. The photostability of IMI@β-CD/ZIF-8@ST was 5-times that of IMI solution. Moreover, the insecticidal efficacy against Plutella xylostella of IMI@β-CD/ZIF-8@ST was 80 % after 120 h of UV irradiation, while that of IMI and IMI water dispersible granule was only 23.33 % and 26.67 %, respectively. This work provides new insights into enhancing the foliage retention and efficiency utilization of pesticide.

研究领域: 农业科学 · 材料科学 · 农药化学 · 植物科学
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Royal Society Open Science · 2019 ·Vol. 6 ·期 7 · IF 2.515

Soy protein isolate-carboxymethyl cellulose conjugates with pH sensitivity for sustained avermectin release

Long Chen,Hongjun Zhou,Li Hao,Huayao Chen,Xinhua Zhou

Carboxymethyl cellulose (CMC) was grafted onto the surface of soy protein isolate (SPI) to obtain soy protein isolate-carboxymethyl cellulose conjugate (SPC). Avermectin (AVM) was hydrophobically encapsulated as a model drug to obtain SPC@AVM. The reaction between SPI and CMC was confirmed by infrared spectroscopy, thermal analysis and SDS-PAGE electrophoresis. The results of scanning electron microscopy showed that the average particle size of the drug-loaded microspheres was 129 nm and the shape of microspheres changed from block to spherical after the addition of AVM. After encapsulation of AVM, the absolute value of zeta potential was greater than 15 mV, which indicated better stability. Compared to AVM solution, SPC@AVM showed more wettability on the leaf surface and the contact angle on the leaves decreased from 71.64° to 57.33°. The maximum liquid holding capacity increased by 41.41%, from 8.85 to 12.52 mg cm−2, which effectively reduced leaf loss. SPC@AVM also prevented UV photolysis, wherein the half-life was extended from 18 to 68 min when exposed to UV light. Moreover, toxicity tests showed that the encapsulation of AVM was beneficial to retain the insecticidal effect of AVM in the presence of ultraviolet light. The release rate of AVM showed pH responsiveness and the release rate under neutral conditions was faster than acidic and alkaline conditions. Moreover, the process conformed to the Weibull model.

研究领域: 材料科学 · 药学 · 农业科学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2022 · IF 10.753

Mesoporous silica size, charge, and hydrophobicity affect the loading and releasing performance of lambda-cyhalothrin

Shuting Xiao,Ali Shoaib,Jiang Xu,Daohui Lin

Nanopesticides are attracting increasing attention as a promising technology in agriculture to improve insecticidal efficacy, decrease pesticides uses, and reduce potential environmental impacts. We synthesized mesoporous silica nanoparticles , i.e., Mobil Composition of Matter No.48 (MCM-48), with different sizes (63–130 nm), charges (−22 to 12 mV), and hydrophobicity (water contact angle 29–103°) to assess their loading amount and release of a typical poorly soluble halogenated pyrethroid (i.e., lambda-cyhalothrin particles, LCNS). The smallest MCM-48 displayed relatively higher loading amount of LCNS (~16%) compared to the larger MCM-48 nanoparticles, likely because of its higher pore volume (1.46 cm 3 g −1 ) and pore size (3.56 nm). LCNS loading amount was further improved to ~26% and ~36% after –NH 2 (positively charged) and –CH 3 (hydrophobic) functionalization, respectively, probably due to hydrogen bonding, electrostatic, and hydrophobic interactions with LCNS. Loading LCNS in MCM-48 nanoparticles also significantly improved its dispersion in water and ultraviolet (UV) light stability, with a 3–7 times longer half-life than that of free LCNS. Although the –NH 2 and –CH 3 modifications of MCM-48 slightly decreased the UV stability of LCNS, they significantly decreased the release efficiency of LCNS, possibly because of their stronger interactions with LCNS. In addition, the insecticidal effects of LCNS-loaded MCM-48 were more efficient and longer than those of free LCNS. The findings clarify the relationships between physicochemical properties and performance of mesoporous silica nanoparticles, and will inform the rational design of materials for controlled release of pesticides and sustainable control of pests.

CAS / MDL: 151-21-3 78-10-4
研究领域: 农业科学 · 纳米技术 · 环境科学
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CROP PROTECTION · 2021 · IF 2.571

Fabricated chlorantraniliprole loaded chitosan/alginate hydrogel rings effectively control Spodoptera frugiperda in maize ears

Liupeng Yang,Zixia Song,Chao Li,Suqing Huang,Dongmei Cheng,Zhixiang Zhang

Damage to the growing ears by Spodoptera frugiperda is a major economic burden, therefore, the development of a novel targeted treatment with safe, environmentally friendly, and effective is necessary to control the damage of S. frugiperda in maize ears. In this study, chitosan/sodium alginate hydrogel rings loaded with chlorantraniliprole (CLAP) were prepared by physical embedding and ionic cross-linking method. The CLAP-loaded hydrogel rings were evaluated for their morphology, loading efficiency, encapsulation efficiency, and release kinetics at different pH levels. The efficacy of the CLAP-loaded hydrogel rings and CLAP suspension were evaluated under field conditions for control of S. frugiperda in maize ears, and the distribution and dissipation of CLAP on maize ears were investigated. The results of the two-year trial showed that the insecticidal effects of the CLAP-loaded hydrogel rings treatment were significantly improved contrasted with the use of CLAP suspension, and increased the transfer efficiency of the pesticide from maize bracts to maize kernels. The terminal residues showed that it is safe to use CLAP suspension and CLAP-loaded hydrogel rings on maize ears. This study provides guidance for the use of pesticides to control pests in maize ears in rainfall-rich areas.

CAS / MDL: 7758-29-4
研究领域: 农业科学 · 害虫管理 · 环境科学 · 材料科学
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