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Food Additives and Contaminants Part A-Chemistry Analysis Control Exposure & Risk Assessment · 2019 · IF 2.17

Dissipation, residues and risk assessment of oxine-copper and pyraclostrobin in citrus

Xiangwu Liu,Ya Yang,Ya Chen,Qingtao Zhang,Ping Lu,Deyu Hu

An efficient, sensitive, simple and fast method for the simultaneous determination of oxine-copper and pyraclostrobin in citrus fruit was developed and validated. The method uses ethylene diamine tetra-acetic acid as a competitive ligand to convert oxine-copper to soluble 8-hydroxyquinoline for analysis by QuEChERS and LC-MS/MS. Linear relationships were determined with correlation coefficients ranging from 0.9904 to 0.9998. The limits of detection for the analytes were 0.012–0.8 μg kg−1, and the limits of quantitation were 0.04–2.6 μg kg−1 in citrus. The average recoveries were 79.1–114.9% with relative standard deviations of less than 7.4%. The analyses of dissipation indicated that the half-lives of oxine-copper and pyraclostrobin were 1.94–3.67 and 1.79–2.48 days and the terminal residues were <0.08–8.99 and <0.02–1.90 mg kg−1, respectively. The risk quotients of oxine-copper and pyraclostrobin were 0.026–0.199 and 0.003–0.022, respectively. This risk assessment provides a reference for the safe and reasonable use of oxine-copper and pyraclostrobin and may help to establish maximum residue limits for these pesticides in China.

研究领域: 农业科学 · 食品科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Foods · 2022 ·Vol. 11 ·期 5 ·669 · IF 5.561

Dissipation and Residues of Pyraclostrobin in Rosa roxburghii and Soil under Field Conditions

Lei Han,Qiong Wu,Xiaomao Wu

Rosa roxburghiihas been widely planted in China. Powdery mildew is the most serious disease ofR. roxburghiicultivation. Pyraclostrobin was widely used as a novel fungicide to control powdery mildew ofR. roxburghii. To assess the safety of pyraclostrobin for use onR. roxburghiifruits, its residue rapid analysis as well as an investigation on its dissipation behaviors and terminal residues inR. roxburghiiand soil under field conditions were carried out. The QuEChERS method was simplified using LC–MS/MS detection and combined with liquid–liquid extraction purification to allow determination of pyraclostrobin levels inR. roxburghiifruits and the soil. The fortified recoveries at 0.1~5.0 mg/kg were 93.48~102.48%, with the relative standard deviation of 0.64~3.21%. The limit of detection of the analytical method was 0.16 and 0.15 µg/kg forR. roxburghiifruit and soil, respectively. The effects of different spray equipment and formulations on the persistence of pyraclostrobin inR.roxburghiiwere as follows: gaston gasoline piggyback agricultural sprayer (5.38 d) > manual agricultural backpack sprayer (3.37 d) > knapsack multi-function electric sprayer (2.91 d), suspension concentrate (SC) (6.78 d) > wettable powder (WP) (5.64 d) > water dispersible granule (WG) (4.69 d). The degradation of pyraclostrobin followed the first-order kinetics and its half-lives inR.roxburghiiand soil were 6.20~7.79 days and 3.86~5.95 days, respectively. The terminal residues of pyraclostrobin inR.roxburghiiand soil were 0.169~1.236 mg/kg and 0.105~3.153 mg/kg, respectively. This study provides data for the establishment of the maximum residue limit (MRL) as well as the safe and rational use of pyraclostrobin inR.roxburghiiproduction.Keywords:pyraclostrobin;Rosa roxburghii;soil;dissipation;residue

CAS / MDL: 1343-88-0
研究领域: 植物保护 · 环境科学
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ENVIRONMENTAL POLLUTION · 2023 · IF 8.9

Modification of sedimentation and bioaccumulation behavior as an efficient strategy to modulate the toxicity of pyraclostrobin to zebrafish (Danio rerio)

Aiping Wang,Yue Sun,Zhengyi Sun,Xiao Liu,Xin Yu,Ke Li,Xianxia Zhang,Yue Xu,Wei Mu,Beixing Li

The behavior of pesticide particles or droplets might significantly influence their environmental risks. However, studies on the risk of different pesticide formulations in aqueous environments have rarely been reported. In this study, we prepared three types of pyraclostrobin formulations to evaluate their behavior in the aqueous environment and toxicological risks to zebrafish. The results showed that pyraclostrobin emulsifiable concentrate (EC) sank faster in water with increasing hydrophilicity and density of the solvent. The particles also sank faster with increasing particle size and particle density for suspension concentrate (SC) and microcapsules (MCs). Diverse behavior in water results in different temporal and spatial distributions of the active ingredient. EC-EGDA, SC-5 μm, CS-Large and EC-MO sink or float over time, therefore reducing the effective dose suspended in water. Lower toxicological risks of the pesticides were also observed by reducing the enrichment of pyraclostrobin in zebrafish. In addition to the direct toxicity of the active ingredient, the type of pesticide formulations and their specific compositions might also influence the integrated toxicity. The environmental behavior of pesticide formulations should also be considered for their systematic assessment of environmental risks to ensure the scientific application of pesticides in different scenarios.

CAS / MDL: 11138-66-2 124-09-4
研究领域: 环境科学 · 毒理学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Green synthesized lignin nanoparticles for the sustainable delivery of pyraclostrobin to control strawberry diseases caused by Botrytis cinerea

Jun Liu,Xin Wang,Jinzhe Chang,Pengrui Du,Jian Wu,Ruiquan Hou,Shiqi Zhu,Pengpeng Liu,Xiaoran Miao,Peiwen Zhang,Zhixiang Zhang

Lignin, renowned for its renewable, biocompatible, and environmentally benign characteristics, holds immense potential as a sustainable feedstock for agrochemical formulations. In this study, raw dealkaline lignin (DAL) underwent a purification process involving two sequential solvent extractions . Subsequently, an enzyme-responsive nanodelivery system (Pyr@DAL-NPs), was fabricated through the solvent self-assembly method, with pyraclostrobin (Pyr) loaded into lignin nanoparticles . The Pyr@DAL-NPs shown an average particle size of 250.4 nm, demonstrating a remarkable loading capacity of up to 54.70 % and an encapsulation efficiency of 86.15 %. Notably, in the presence of cellulase and pectinase at a concentration of 2 mg/mL, the release of Pyr from the Pyr@DAL-NPs reached 92.66 % within 120 h. Furthermore, the photostability of Pyr@DAL-NPs was significantly improved, revealing a 2.92-fold enhancement compared to the commercially available fungicide suspension (Pyr SC). Bioassay results exhibited that the Pyr@DAL-NPs revealed superior fungicidal activity against Botrytis cinerea over Pyr SC, with an EC 50 value of 0.951 mg/L. Additionally, biosafety assessments indicated that the Pyr@DAL-NPs effectively declined the acute toxicity of Pyr towards zebrafish and posed no negative effects on the healthy growth of strawberry plants. In conclusion, this study presents a viable and promising strategy for developing environmentally friendly controlled-release systems for pesticides, offering the unique properties of lignin.

CAS / MDL: 81-88-9
研究领域: 植物病理学 · 农药科学 · 材料科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

A sustainable and smart fungicide release platform through cocrystal nanocapsules for improved utilization rate and environmental safety

Haibin Qu,Songgu Wu,Junbo Gong

Pesticides have always been restricted by environmental factors and utilization rate. Smart delivery systems are important to modify pesticides and improve utilization rate, but the economic and environmental risks of the carriers limit their practical applications. Here, responsive release nanocapsules were constructed with metal-phenolic networks and pyraclostrobin - thiophanate-methyl (PYR-TM) cocrystal core to modify the poor physicochemical properties and safety of pesticides. PYR-TM was prepared by sustainable mechanochemical method and deposited by metal-phenolic networks in water, producing the PYR-TM@TA-Cu nanocapsules. The crystal structure and DFT calculations proved that TM improved the photostability of PYR by 75.7-fold through competitive energy absorption of photon and molecular conformation modulation. With a loading capacity up to 91.2%, PYR-TM@TA-Cu exhibited pH-responsive release behavior triggered by acidic conditions, which showed that 43.6%, 51.4%, 62.4% and 81.6% of encapsulated PYR were released at pH 7.9, 6.2, 5.3, and 4.0, respectively. Additionally, PYR-TM@TA-Cu exhibited favorable fungicidal activity ( EC 50  = 0.123 mg/L) in controlling Botrytis cinerea . The greenhouse control efficiency of fungal infection was enhanced from12.0% to 70.7% by PYR-TM@TA-Cu after 7 days spraying. The coating of metal-phenolic network improved the washing persistence of the pesticides from 51.26% to 79.88%, the security for zebrafish by 42-fold, and decreased the leaching potential of the pesticides. Meanwhile,   PYR-TM@TA-Cu showed no phytotoxicity on the growth of corn and cucumber plants. Overall, this study provides insight into efficient and sustainable agricultural production with the construction of an eco-friendly nanocapsules platform by cocrystal engineering strategy.

研究领域: 农业科学 · 环境科学 · 材料科学
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

Nanoencapsulation-based fabrication of eco-friendly pH-responsive pyraclostrobin formulations with enhanced photostability and adhesion to leaves

Yingjian Ma,Linjie Li,Rui Zhao,Zhe Sun,Yinmin Wang,Meng Yu,Shouhe Pan,Xinyu Guo,Yong Xu,Hongmei Wang,Ping Wang,Xuemin Wu

The development of pesticide-loaded nanocapsules responding to environmental stimuli holds great promise for sustainable disease control and may help to reduce pesticide usage while making it more efficient. Herein, pH-responsive nanocapsules containing pyraclostrobin (Pyr) were constructed by the rapid interfacial assembly of tannic acid (TA), ethylene oxide-propylene oxide block copolymer , and Cu 2+ ions using a fine reversed-phase emulsion as a template. Under acidic conditions similar to those caused by Rhizoctonia solani infestation, these nanocapsules released Pyr to achieve its intelligent delivery and, hence, efficient R. solani control. Nanoencapsulation significantly increased the photostability of Pyr, and the half-life increased by 10 times compared with the Pyr-technical (Pyr-TC). In addition, the introduction of TA enhanced its spreading performance and rainfall resistance in crops, and contact angle drops to 2.2° ± 0.1° in 100 s. Its toxicity to non-target organisms ( Daphnia magna and humans) was reduced. The fabricated nanocapsules exhibited a high antifungal activity superior to that of commercially available agents and exerted no significant adverse effects on crop growth and soil microbial communities . Thus, our work highlights the potential of nanoencapsulation for the intelligent delivery of fungicides to target crops, thus providing an effective strategy for improving the efficiency of pesticide usage and promoting sustainable pesticide development.

CAS / MDL: 10031-43-3
研究领域: 农业科学 · 环境科学 · 材料科学
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CARBOHYDRATE POLYMERS · 2022 · IF 10.723

Acetalated dextran microparticles for the smart delivery of pyraclostrobin to control Sclerotinia diseases

Zhengang Xie,Wenlong Liang,Qiuyu Xiong,Yanyan Zhao,Jingli Cheng,Xianbin Li,Jinhao Zhao

Dextran has emerged as a promising biopolymer carrier for controlled release formulations of pesticides. In this study, pH-sensitive acetalated dextran microparticles (Pyr@Ac-Dex) are prepared to encapsulate and control the release of pyraclostrobin (Pyr). In vitro fungicidal activity experiments showed that the prepared Pyr@Ac-Dex particles show comparable fungicidal ability against S. sclerotiorum compared to that of Pyr technical. In a 10-day pot experiment, the control efficacy of the Pyr@Ac-Dex treatment against S. sclerotiorum (77.1%) is significantly higher than that of Pyr emulsifiable concentrate (Pyr EC) treatment (42.4%). Photodegradation experiments show that compared to Pyr technical, Pyr@Ac-Dex doubles the half-life of Pyr in water. Acute toxicity experiments show that Pyr@Ac-Dex significantly reduced the acute exposure toxicity of Pyr to zebrafish. This study provides an environmentally friendly, feasible, and sustainable strategy for plant disease management.

CAS / MDL: 9048-71-9 9004-54-0
研究领域: 植物保护 · 农药科学 · 环境毒理学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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ACS Sustainable Chemistry & Engineering · 2023 · IF 8.4

Novel Biodegradable Composite Mulch Film Embedded with Temperature-Responsive Pesticide Microcapsules for Durable Control of Phytophthora Root Rot on Soybean

Zhengang Xie,Qiuyu Xiong,Yun Fang,Qi Zhang,Wenlong Liang,Jingli Cheng,Wenxuan Shang,Wei Zhao,Jinhao Zhao

Soil-borne diseases have caused substantial economic losses to agricultural production due to their rapid onset and few means of control. Here, pyraclostrobin (Pyr) microcapsules (Pyr@MCC) with temperature-responsive pesticide release capability were prepared using temperature-sensitive phase-change materials as capsule cores. Then, the Pyr@MCC was organically combined with poly(vinyl alcohol)-starch film (PVA/ST) to prepare a composite mulch film (PM/PVA/ST) with intelligent control of pesticide release rate according to external temperature change, which realized sustainable and efficient control of Phytophthora root rot (PRR) on soybean. Tensile tests showed that the PM/PVA/ST film exhibited good tensile deformation ability (134.9%) and high tensile stress (18.0 Mpa). The water vapor transmission rate test showed that the PM/PVA/ST film exhibited good barrier performance to H2O, CO2, and O2. The release test data proved that the PM/PVA/ST film could slowly release Pyr at lower temperatures (15 °C) and release Pyr rapidly at higher temperatures (35 °C), corresponding to the high temperature at which the Phytophthora root rot outbreak. In vitro antifungal and pot experiments showed that the PM/PVA/ST film had a good control efficiency on Fusarium spp. These results show that the functional pesticide microcapsules loaded onto the film have good application potential for controlling PRR on soybean. In general, this composite mulch film provided some innovative research ideas for optimizing the pesticide delivery pathway and thereby efficiently controlling soil-borne pests and diseases, reducing the frequency and amount of pesticide use and minimizing white pollution from traditional plastic mulch films.

CAS / MDL: 77-58-7
研究领域: 农业科学 · 植物病理学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2021 · IF 5.279

Achieving Win–Win Ecotoxicological Safety and Fungicidal Activity of Pyraclostrobin-Loaded Polyurea Microcapsules by Selecting Proper Polyamines

Haichao Cao,Da-xia Zhang,Shanggang Liu,Jian Luo,Tongfang Jing,Shouhe Pan,Feng Liu,Beixing Li,Wei Mu

The fungicide pyraclostrobin is highly toxic to aquatic organisms. Microencapsulation is an effective way to reduce the exposure of pyraclostrobin to aquatic organisms but it also reduces the contact probability between the fungicide and plant pathogens. Hence, winning a balance between the toxicity and bioactivity of pyraclostrobin is very necessary. In this study, triethylenetetramine (TETA), ethylenediamine (EDA), hexamethylenediamine (HAD), and isophoronediamine (IPDA) were selected as cross-linkers to prepare the pyraclostrobin-loaded polyurea microcapsules (PU-MCs) by interfacial polymerization. TETA formed the shells with the highest degree of cross-linking, the slowest release profile, and the best protection against ultraviolet (UV). In terms of MCs fabricated by diamines, higher leaking, weaker UV resistance of the shells was observed with increasing carbon skeleton. TETA-MCs showed the highest safety to zebrafish (LC50 of 10.086 mg/L), whereas EDA-MCs, HAD-MCs, and IPDA-MCs were 5.342, 3.967, and 0.767 mg/L, respectively. TETA-MCs had the best long-term disease management, while the control efficacies of other MCs were higher at the early stage of disease development. Overall, a balance between the aquatic toxicities and fungicidal activities of pyraclostrobin-loaded PU-MCs could be reached through a simple selection of polyamines in the fabrication.

研究领域: 环境科学 · 农业科学
✓ 已验证 DOI PubMed 高影响因子
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SCIENCE OF THE TOTAL ENVIRONMENT · 2022 · IF 10.753

The simple strategy to improve pesticide bioavailability and minimize environmental risk by effective and ecofriendly surfactants

Zhenping Bao,Yanling Wu,Ridan Song,Yuxia Gao,Songhao Zhang,Kefei Zhao,Tianyue Wu,Chenhui Zhang,Fengpei Du

Low pesticide efficiency has caused serious environmental pollution and economic loss, which are closely related to each link in the targeted delivery of pesticides. However, the existing strategies for improving pesticide utilization rate are not comprehensive, and the regulation of foliar absorption and biological activity has been neglected. As surfactants are the most important agricultural synergists, the impact, wetting, adhesion, and leaf retention behaviors of pyraclostrobin (PYR) droplets containing the surfactant Triton X (TX) series on hydrophobic scallion leaf surfaces were studied. The results showed that TX-102 can sufficiently reduce the splash and roll of droplets when they impact inclined leaves, owing to its low dynamic surface tension. Moderate wetting ability and high adhesion also maximizes leaf retention of the TX-102-added PYR solution sprayed on scallion leaves. Furthermore, TX-102 improved the permeation and absorption of PYR in scallion leaves through the synergistic effects of opening the stomata and dissolving the waxy layer. The synergistic bioactivity of TX-102 against pathogenic fungi Alternaria porri and its safety to non-target organism zebrafish have also been demonstrated. Our study provides a more comprehensive theoretical rationale for screening adjuvants to improve the effectiveness and bioavailability of pesticides and reduce the risk of pesticides entering the environment.

研究领域: 农业科学 · 环境科学
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Photo-responsive supramolecular hydrogels to enhance pesticide bioavailability through multiple structural transformations

Hanghang Zhang,Yingxi Zhang,Manli Yu,Chong Cao,Pengyue Zhao,Qiliang Huang,Lidong Cao

An elaborate combination of molecular self-assembly strategies and structurally reversible hydrogels can provide a versatile toolbox to address the limitations of current pesticides. However, when hydrogels are deposited on target surfaces and transferred into non-target environments, the functionalization of hydrogels with regulatory switches to realize smart, responsive release of pesticides remains a significant challenge. Herein, a ternary mixture of C 18 -modified poly (acrylic acid), α-cyclodextrin, and 1-[ p -(phenyl-azo)benzyl]pyridinium bromide was used as an assembly building block to induce reversible phase transitions between pyraclostrobin (Pyr)-loaded gel (Gel@Pyr) and Pyr-loaded sol (Sol@Pyr) by repetitive irradiations of ultraviolet (UV) and visible light. This hydrogel system exhibited excellent stability, bioactivity, and biosafety. The protection of Gel@Pyr against UV irradiation was approximately 18 times that of NSC@Pyr, which can be attributed to the shielding effect of the supramolecular gel network. Owing to the superior affinity of Gel@Pyr for the micro/nanostructures of rice leaves, droplet rebounding was inhibited, resulting in a substantial increase surface deposition approximately 10-fold compared with that of Pyr nano-suspension concentrates. Moreover, water was employed as a trigger to initiate the in situ microencapsulation of Gel@Pyr to achieve a structural transformation, which considerably reduced the acute toxicity toward zebrafish, an aquatic organism. This study aims to pave the way for designing tailored supramolecular hydrogels with multifunctionality and sustainability for smart pesticide delivery.

研究领域: 材料科学 · 农业科学 · 环境科学
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COLLOID AND POLYMER SCIENCE · 2021 ·Vol. 300 ·期 1 ·1-10 · IF 1.931

Fabrication PDA-polyurea microcapsules with anti-photolysis and sustained-release performances via Pickering emulsion template

Jiang Binbin,Li Ranhong,He Xu,Chai Yunlong,Chai Yuxin,Wang Yan

In this study, the pyraclostrobin@polydopamine-polyurea microcapsules (Pyr@PNPMC) with anti-photolysis and sustained-release properties were prepared by interfacial polymerization based on O/W Pickering emulsion templates. The effects of water–oil ratio, stirring speed, temperature, and polydopamine nanoparticles (PDANPs) content on the preparation of microcapsules were systematically investigated. Under this condition, the encapsulation efficiency of microcapsules could reach up to 77.7%. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) images indicated that Pyr@PNPMC were prepared successfully, and the microcapsules were a regular sphere with a large number of PDANPs attached to the dense inner layer. According to the results of sustained-release and anti-photolysis experiments, the release rate of Pyr@PNPMC was slightly faster than that of the pyraclostrobin@polyurea microcapsules (Pyr@MC). Under UV light exposure for 7 h, Pyr@PNPMC still retains 83% of the active ingredient, while for Pyr@MC nearly 75% of the active ingredient had been lost.

研究领域: 材料科学 · 农药化学
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