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PEST MANAGEMENT SCIENCE · 2020 ·Vol. 76 ·期 12 ·4210-4221 · IF 3.75

Acute and chronic toxicity of deltamethrin, permethrin, and dihaloacetylated heterocyclic pyrethroids in mice

Qiuyan Zhu,Yang Yang,Zhiting Lao,Yingying Zhong,Kun Zhang,Suqing Zhao

BACKGROUND Pyrethroids, a class of insecticides, that act on the nervous system of insects. Frequent consumption of foods with pyrethroid residues increase the risk of developmental and neurological diseases in humans. Assessing the toxicity of novel synthetic pyrethroids to mammals is also critical to the development of agrochemicals. RESULTS Using mice as models, the acute and chronic toxicity of deltamethrin, permethrin, dihaloacetylated pyrethroids to mammals was researched by gavage administration. Acute toxicity assessment displayed that the median lethal dose (LD 50 ) of deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids DCA-O, DCA-01, and DCA-11 tested were greater than 500 mg/kg of weight. Furthermore, chronic toxicity assessment demonstrated that deltamethrin, permethrin caused epidermal damage near the genitals, while dihaloacetylated heterocyclic pyrethroids DCA-O, DCA-01, and DCA-11 showed no relevant symptoms. However, both the acute and chronic toxicity assessment suggested that pyrethroids exposure induced mice loss weight. Additionally, the elevated plus maze (EPM) test showed that pyrethroids caused anxiety-like behaviors and no motor defects in Kunming mice. Beside, during the sucrose preference test (SPT), 60-day pyrethroids exposure increased excitatory behaviors in mice. However, the neurochemical studies displayed that pyrethroids exposure increased the total amount of glutamate (Gln), glutamine (Glu) and γ -aminobutyric acid (GABA) in the mice's blood. CONCLUSION Pyrethroids exposure induced weight loss in mice, although the acute oral toxicity of deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids DCA-O, DCA-01, and DCA-11 was low. However, regarding chronic toxicity, deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids DCA-O, DCA-01, and DCA-11 induced anxiety-like behaviors, excitatory behaviors, Gln-Glu-GABA circulatory dysfunction in blood. Particularly, deltamethrin, though permethrin also had reproductive toxicity. © 2020 Society of Chemical Industry

研究领域: 毒理学 · 神经科学 · 农业化学
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2016 ·Vol. 17 ·期 4 ·493 · IF 3.257

Bacterial Expression and Kinetic Analysis of Carboxylesterase 001D from Helicoverpa armigera

Yongqiang Li,Jianwei Liu,Mei Lu,Zhiqing Ma,Chongling Cai,Yonghong Wang,Xing Zhang

Carboxylesterasesare an important class of detoxification enzymes involved in insecticide resistance in insects. A subgroup ofHelicoverpa armigeraesterases, known as Clade 001, was implicated in organophosphate and pyrethroid insecticide resistance due to their overabundance in resistant strains. In this work, a novel carboxylesterasegene001DofH. armigerafrom China was cloned, which has an open reading frame of 1665 nucleotides encoding 554 amino acid residues. We used a series of fusion proteins to successfully express carboxylesterase 001D inEscherichia coli. Three different fusion proteins were generated and tested. The enzyme kinetic assay towards 1-naphthyl acetate showed all three purified fusion proteins are active with aKcat between 0.35 and 2.29 s−1, and aKm between 7.61 and 19.72 μM. The HPLC assay showed all three purified fusion proteins had low but measurable hydrolase activity towardsβ-cypermethrin and fenvalerate insecticides (specific activities ranging from 0.13 to 0.67 μM·min−1·(μM−1·protein)). The enzyme was stable up to 40 °C and at pH 6.0–11.0. The results imply that carboxylesterase 001D is involved in detoxification, and this moderate insecticide hydrolysis may suggest that overexpression of the gene to enhance insecticide sequestration is necessary to allow carboxylesterases to confer resistance to these insecticides inH. armigera.Keywords:Helicoverpaarmigera;carboxylesterase;pyrethroid;heterologous expression

研究领域: 昆虫学 · 分子生物学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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SCIENCE OF THE TOTAL ENVIRONMENT · 2020 · IF 6.551

Photodegradation kinetics, mechanism and aquatic toxicity of deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids

Qiuyan Zhu,Yang Yang,Zhiting Lao,Yingying Zhong,Kun Zhang,Suqing Zhao

Photochemical methods attracted much research interests for their high-efficiency and low secondary pollution. Decomposition of synthetic pyrethroids , the fourth major group of insecticides in use worldwide, was also of great significance due to their possible environmental risks. The photodegradation of deltamethrin , permethrin and dihaloacetylated heterocyclic pyrethroids in methanol/acetone = 9/1 (by volume) by a 400 W mercury lamp was examined. The t 1/2 of tested pyrethroids was less than 25 min, except for cis -permethrin with a t 1/2 of up to 50 min. The trans -isomer of permethrin and compound DCA-01 with a smaller t 1/2 might be more susceptible to degradation than their cis -isomer. Besides, the photodegradation of pyrethroids was divided into twelve pathways including isomerization , ester hydrolysis, ester bond cleavage, C O bond cleavage, 3,3-dimethylacrylate formation, double bond break, C1-C3 bond cleavage in cyclopropyl, reductive dehalogenation, decarboxylation , nucleophilic reagents attack on lone pair electrons on oxygen atoms in the phenyl ether, cyano hydrolysis, and halogenated hydrocarbon hydrolysis. The ECOSAR program displayed that pyrethroids and most of their photodegradation products were toxic to fish, daphnid, green algae . Particularly, some photodegradation products were more harmful to aquatic organisms than their parents.

CAS / MDL: 52645-53-1
研究领域: 环境科学 · 毒理学 · 化学
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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

Hydrophobic deep eutectic solvent-based ferrofluid for the multi-residue analysis of pyrethroid insecticides in agricultural products: Facile pretreatment and MS-friendly detection

Yuxin Liu,Chenjie Ma,Mantang Chen,Jufang Hao,Wei Liu,Jingjing Yu

Pyrethroid insecticides (PYs) overuse poses ecological and health risks, leading to tightened restrictions on maximum residue limits (MRLs) by regulatory bodies like the European Union and China's National Food Safety Standards. It is important to develop multi-residue analytical methods for PYs residues. In present work, oleic acid-coated Fe 3 O 4 nanoparticles (Fe 3 O 4 -OA) were dispersed in hydrophobic deep eutectic solvents (HDES) to prepare ferrofluids (FFs), with the HDES synthesized from coumarin and thymol at a 1:2 molar ratio. And the HDES-FF was subsequently utilized as a vortex-assisted liquid-phase microextraction sorbent for the enrichment of 16 PYs, combined with GC–MS/MS analysis. HDES-FF could effectively enrich PYs within merely 3.5 min according to π-π stacking interactions and hydrophobic effects, while Fe 3 O 4 -OA nanoparticles were responsible for magnetic separation. It could successfully solve the problem of separation difficulty after liquid-liquid microextraction based on DES. Simultaneously, thermogravimetric analysis confirmed that the HDES could decompose at injection port of GC–MS/MS instrument, and mass spectrometry signals of the decomposed HDES could not be collected by adjusting the solvent delay time. Thus, it could effectively protect the ion source from contamination, making DES compatible with GC–MS methods. The detection limit (LOD) of the proposed method is 0.41–7.91 ng/mL, with the recoveries of 83.33–106.02 %. The intra-day and inter-day relative standard deviations (RSDs) are less than 4.20 % and 6.94 %, respectively. The method successfully detected 16 PYs in various real fruit and vegetable samples.

研究领域: 食品安全检测 · 农药残留分析 · 食品化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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AQUACULTURE · 2024 · IF 3.9

Cultured shrimp Penaeus vanmamei from eastern China accumulates PAHs and PYRs through different pathways: Water and food sources matter

Juan-ying Li,Yuxiao Tong,Qi Gong,Yaxiong Tian,Yanhao Yang,Luting Wen,Hongjie Chen,Qian Wang

Eastern China is an important area for aquaculture, but the aquaculture environment, as well as the aquatic product quality, are threatened by environmental pollutants such as polycyclic aromatic hydrocarbon (PAHs) and pyrethroid pesticides (PYRs). A three-month monitoring program for PAHs and PYRs throughout the whole culture processes of the shrimp Penaeus vanmamei was carried out. Specifically, concentrations of PAHs and PYRs ranged from 339 ± 19.5–631 ± 75.6 ng·L −1 and 65.3 ± 6.74–93.5 ± 10.8 ng·L −1 in water, 183 ± 33.8–369 ± 25.1 ng·g −1 dw and 441 ± 132–521 ± 62.8 ng·g −1 dw in sediments, while 416 ± 84.3–646 ± 19.7 and 483 ± 23.3–513 ± 22.1 ng·g −1 dw in suspended solids. Mean concentrations of PAHs and PYRs in the adult shrimp were 634 ± 82.3 ng·g −1 ww and 665 ± 58.1 ng·g −1 ww, respectively. A health threat would arise if men consume more than 28.8 g and women consume more than 24.4 g each day. PAHs in the aquaculture environment were generally from the influent water and rainfall, while PYRs were mainly introduced by feed. After entering the culture environment, PAHs primarily increased the water load, leading to more significant bioaccumulation of the shrimp from the water phase (72–95 %). For PYRs, the main sources were feed (44.4 %) and influent water (20.6 %), and they were accumulated in shrimp through feed assimilation directly (15.0 %–32.0 %). Additionally, feed waste containing PYRs increased the contamination burden of sediments and suspended solids, leading to bioaccumulation through assimilation (4.00 %–15.0 %) as well. Although the contribution of influent water to PYRs in the culture environment was lower than that of feed, the contribution of aqueous exposure to the enrichment of PYRs in the shrimp was higher (53.0 %–81.0 %) than that of food (feed, sediments, and suspended solid) intake (19.0 %–47.0 %). The hydrophobicity of PYRs led to an easier bioaccumulation from freely dissolved phase to biota. Therefore, it is important to pay attention to the water quality during the whole culture period, as well as feed quality, to ultimately improve the quality of aquaculture products. In summary, different pollutants in the aquaculture environment and products were from different sources and exposure pathways. Water quality monitoring and improvement are more efficient in decreasing PAHs in the shrimp, while PYRs reduction should be assisted with feed quality control.

研究领域: 环境科学 · 水产养殖学 · 生态毒理学
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2017 · IF 6.198

Relationships of Pyrethroid Exposure with Gonadotropin Levels and Pubertal Development in Chinese Boys

Xiaoqing Ye,Wuye Pan,Shilin Zhao,Yuehao Zhao,Yimin Zhu,Jing Liu,Weiping Liu

Although an acceleration of male pubertal development has been observed, precisely which endocrine-disrupting chemicals (EDCs) might contribute to the advancing onset of puberty in boys remains unclear. Here, pyrethroids, a class of widely used insecticides that have been considered as EDCs, are proposed as new environmental risk factors. In this study, 463 boys at the age of 9–16 years old were recruited in Hangzhou, Zhejiang, China. The common metabolites of pyrethroids, 3-phenoxybenzoic acid (3-PBA), and 4-fluoro-3-phenoxybenzoic acid (4-F-3-PBA), as well as gonadotropins, including luteinizing hormone (LH) and follicle-stimulating hormone (FSH), were analyzed in urine samples. Pubertal development was assessed based on Tanner stages and testicular volume (TV). A positive association between 3-PBA and gonadotropins was found (p < 0.001), in which a 10% increase in 3-PBA was associated with a 2.4% and 2.9% increase in LH and FSH, respectively. Higher urinary levels of 3-PBA in boys were associated with 275% and 280% increase in the risk of being genitalia stage 3 (G3) and G4, respectively (p < 0.05). There was a significant (132%) induction in odd of being TV 12–19 mL with increasing 3-PBA concentration compared to being in TV < 4 mL (p < 0.05). For the first time to our knowledge, this work reports on an association of increased pyrethroid exposure with elevated gonadotropins levels and earlier pubertal development in boys.

研究领域: 环境科学 · 内分泌学 · 公共卫生
✓ 已验证 DOI PubMed 高影响因子
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TALANTA · 2013 · IF 3.498

Ionic liquid-linked dual magnetic microextraction: A novel and facile procedure for the determination of pyrethroids in honey samples

Min Li,Jiaheng Zhang,Yubo Li,Bing Peng,Wenfeng Zhou,Haixiang Gao

A novel and facile microextraction technique, termed as ionic liquid-linked dual magnetic microextraction (IL-DMME), was developed for the determination of pyrethroids in honey samples. The distinct advantage of the proposed method is that high recoveries can be readily achieved through the combination of dispersive liquid–liquid microextraction (DLLME) and dispersive microsolid-phase extraction (D-μ-SPE) with the aid of synthetic ionic liquid and non-modified magnetic nanoparticles (MNPs), respectively. In the first DLLME step, [C 6 MIM]NTf 2 was used to extract the pyrethroids without the addition of any toxic dispersive solvent. In the following D-μ-SPE steps, non-modified MNPs were added to retrieve the ionic liquid. The effect of different variables on the extraction efficiency was studied simultaneously using the response surface methodology. The Plackett–Burman design was first employed to screen for the variables that significantly affected the extraction efficiency. Central composite design (CCD) was then introduced to optimize the significant factors using a polynomial fit. The optimal experimental conditions obtained from this statistical evaluation included: ionic liquid volume, 75   μL; S-BaFe quantity, 60   mg; sonication time, 4   min; vortex time, 100   s; desorption time, 150   s; and no addition of salt. Under the optimal conditions, good linearity in the range of 0.5   μg   L −1 –500   μg   L −1 , repeatability (RSD 1.1–3.8%), low LODs (0.03–0.05   μg   L −1 ) and good recovery (86.7–98.2%) were obtained. Finally, the developed method was evaluated for the extraction and determination of four pyrethroids in real honey samples.

研究领域: 分析化学 · 食品科学
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ANALYTICAL SCIENCES · 2018 ·Vol. 34 ·期 5 ·613-618 · IF 1.355

Direct Detection of Potential Pyrethroids in Yangtze River via an Imprinted Multilayer Phosphorescence Probe

Li CHEN,Xiaodong LV,Jiangdong DAI,Lin SUN,Pengwei HUO,Chunxiang LI,Yongsheng YAN

A novel tailored multilayer probe for monitoring potential pyrethroids in the Yangtze River was proposed. The room-temperature phosphorescence method was applied to realize a detection strategy that is superior to the fluorescence method. Efficient Mn-doped ZnS quantum dots with uniform size of 4.6 nm were firstly coated with a mesoporous silica to obtain a suitable intermediate transition layer, then an imprinted layer containing bifenthrin specific recognition sites was anchored. Characterizations verified the multilayer structure convincingly and the detection process relied on the electron transfer-induced fluorescence quenching mechanism. Optional detection time and standard detection curve were obtained within a concentration range from 5.0 to 50 μmol L−1. The stability was verified to be good after 12 replicates. Feasibility of the probe was proved by monitoring water samples from the Zhenjiang reach of the Yangtze River. The probe offers promise for direct bifenthrin detection in unknown environmental water with an accurate and stable phosphorescence analysis strategy.

研究领域: 环境科学 · 分析化学
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Foods · 2022 ·Vol. 12 ·期 1 ·8 · IF 5.561

Magnetic Composite Based on Carbon Nanotubes and Deep Eutectic Solvents: Preparation and Its Application for the Determination of Pyrethroids in Tea Drinks

Xiaodong Huang,Huifang Liu,Xiaomin Xu,Ge Chen,Lingyun Li,Yanguo Zhang,Guangyang Liu,Donghui Xu

In this study, a novel composite material prepared by using deep eutectic solvent (tetrabutylammonium chloride-dodecanol, DES5) functionalized magnetic MWCNTs−ZIF−8 (MM/ZIF−8@DES5) was employed as an adsorbent for the magnetic solid-phase extraction of six pyrethroids from tea drinks. The characterization results show that MM/ZIF−8@DES5possessed sufficient specific surface area and superparamagnetism, which could facilitate the rapid enrichment of pyrethroids from tea drink samples. The results of the optimization experiment indicated that DES5, which comprised tetrabutylammonium chloride and 1-dodecanol, was selected for the next experiment and that the adsorption properties of MM/ZIF−8@DES5were higher than those of MM/ZIF−8 and M-MWCNTs. The validation results show that the method has a wide linear range (0.5–400 μg L−1, R2≥ 0.9905), low LOD (0.08–0.33 μg L−1), and good precision (intra-day RSD ≤ 5.6%, inter-day RSD ≤ 8.6%). The method was successfully applied to the determination of pyrethroids in three tea drink samples.Keywords:magnetic solid-phase extraction;deep eutectic solvent;ZIF−8;pyrethroids;tea drinks

研究领域: 分析化学 · 环境科学
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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

Rational hapten design to produce high-quality antibodies against carbamate pesticides and development of immunochromatographic assays for simultaneous pesticide screening

Zi-Jian Chen,Hui-Ling Wu,Zhi-Li Xiao,Hui-Jun Fu,Yu-Dong Shen,Lin Luo,Hong Wang,Hong-Tao Lei,Surat Hongsibsong,Zhen-Lin Xu

Carbamate pesticides (CPs) are the most used pesticides in agricultural production and pest control. In this study, carbofuran , isoprocarb and carbaryl were employed as models, and a general hapten strategy based on carbamate moiety recognition was proposed. Molecular modeling of the three-dimensional (3D) structure and surface electrostatic potential of the CPs indicated that the amide group formed by conjugation significantly influenced recognition by antibodies. The proposed strategy was used to obtain three sensitive and specific monoclonal antibodies (mAbs) with IC 50 values of 1.4 ng/mL, 8.4 ng/mL and 13.8 ng/mL for carbofuran, isoprocarb and carbaryl, respectively. Negligible cross-reactivity (%) with analogs was observed, except for fenobucarb (84.6%) for isoprocarb. The obtained antibodies were used to develop an immunochromatographic assay (ICA) to simultaneously and quantitatively detect the three CPs. A strip reader was used to determine the limits of quantitation (LOQs) as 0.05 ng/mL (carbofuran), 31.3 ng/mL (isoprocarb) and 31.3 ng/mL (carbaryl). The recoveries of cucumber and Chinese cabbage samples ranged from 76% to 111%, with CVs from 1.3% to 10.6%, indicating good potential for the rapid simultaneous detection of multiple pesticide residues in a large batch of samples.

研究领域: 农业科学 · 免疫学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

Ionic liquid-modified magnetic covalent organic framework for the extraction of four pyrethroids in traditional Chinese herbs

Sitian Gu,Wenli Zhu,Yufei Liu,Huixiao Duo,Qingli Yang,Xiudan Hou

Efficient enrichment of analytes and purification of matrices are crucial for the highly sensitive detection and monitoring of pesticides in traditional Chinese herbs. This work prepared magnetic ionic liquid-controlled covalent organic framework (IL-COF@Fe 3 O 4 ) as the sorbent via a simple in-situ precipitation polymerization and thiolene “click” strategy. The IL-COF@Fe 3 O 4 exhibited remarkable adsorption performance towards pyrethroids within 5 min. The adsorption of four pyrethroids on the surface of IL-COF@Fe 3 O 4 was according with Langmuir model and pseudo-second-order kinetic model. The adsorption energies were theoretically calculated, which were permethrin>cypermethrin>fenvalerate>bifenthrin. The modification of ILs improved extraction capacity mainly because of the interaction of imidazole and Cl or F and the pore size effect. This method was developed for the rapid extraction of four pyrethroids in Codonopsis pilosula and Angelica sinensis . The linear range was 0.05–200 μg L -1 . Matrix effects were ranging from -16.14% to 9.53%, indicating the strong matrix anti-interference ability of IL-COF@Fe 3 O 4 .

研究领域: 分析化学 · 环境科学
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JOURNAL OF CHROMATOGRAPHY A · 2020 · IF 4.049

Hydrophobic deep eutectic solvents based membrane emulsification-assisted liquid-phase microextraction method for determination of pyrethroids in tea beverages

Heng Qian,Qian Yang,Yuan Qu,Ziwei Ju,Wenfeng Zhou,Haixiang Gao

Deep eutectic solvents (DESs) were used as an extractant for the determination of pyrethroids  in environmental water and tea beverage samples. Three different acids were chosen as hydrogen bond donors for preparation of DESs, and decanoic acid was optimal because of its high recovery. Factors affecting relative recovery were optimized individually, including salt addition, surfactant addition, extraction temperature, DES amount, and sample volume etc. Under the optimized experimental conditions, the relative recovery of pyrethroids was from 89.3% to 97.7%, with relative standard deviation (RSD) values ranging from 1.75% to 2.73%. The linear correlation coefficient ranged from 0.9981 to 0.9992, and the linear range was between 1.9 and 500 μg/L. Based on a signal-to-noise ratio (S/N) of 3:1, the limit of detection (LOD) values were 0.56 to 1.24 μg/L. The enrichment factor ranged from 92 to 105. In conclusion, good extraction efficiency was achieved in tea beverage samples under the optimized conditions.

研究领域: 分析化学 · 环境科学
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