ENVIRONMENTAL POLLUTION
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2021
·
IF 8.071
Xiuping He,Junhui Chen,Xiaotong Li,Jiuming Wang,Ming Xin,Xia Sun,Wei Cao,Baodong Wang
The occurrence, spatiotemporal variations, influence factors and environmental risks of eight common neonicotinoids (NEOs), fipronil , and three fipronil metabolites (fipronil and its metabolites are collectively referred to as FIPs) in different seasons from the estuary to the inner area of Jiaozhou Bay, China were comprehensively investigated. First- and second-generation NEOs were found to be the predominant pesticides in this area. The average contents of ∑NEOs and ∑FIPs from the estuary to the inner bay decreased from 12.99 ng/L to 0.82 ng/L and from 1.10 ng/L to 0.17 ng/L, respectively. NEO and FIP concentrations were higher in summer and autumn. High ∑NEO content is distributed in main inflow rivers, such as Dagu River and Licun River, which are influenced by pesticide application . NEO concentrations in all rivers were high upstream and low downstream because of the influence of heavy rainfall and seawater dilution in summer. NEO concentrations were high along the coast and low at the mouth and center of Jiaozhou Bay in summer and autumn and evenly distributed in winter and spring. Temperature has a great influence on most NEOs and FIPs owing to its effect on their degradation. Nitrogen-containing nutrients have an important influence on the distribution of fipronil and acetamiprid, which may be due to the activity of nitrogen-containing functional groups in their structure. Only Licun River, Dagu River and Haibo river sewage treatment plant in summer posed a certain risk of chronic toxicity for NEOs using the new threshold established by the species sensitive distribution (SSD) method for Chinese native aquatic lives. These findings should arouse people's attention.
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MICROCHEMICAL JOURNAL
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2020
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IF 3.594
Cong Wang,Yao Lin,Yichao Wang,Ting-Fu Jiang,Zhihua Lv
A novel and sensitive dispersive liquid–liquid micro-extraction (DLLME) combined with 19 F quantitative nuclear magnetic resonance spectroscopy (qNMR) method was developed and validated for determination of fipronil and its metabolites in chicken egg. The qNMR analysis was carried out under the optimum experimental conditions including deuterated DMSO as solvent, calibrated 4′-Bromo-2′-fluoro acetanilide as internal standard, d 1 (relaxation delay) = 1 s, and NS (number of scan) = 1024. The analytes were extracted in a mixed emulsion system of extraction solvent (chloroform) and dispersing solvent (acetonitrile). A demulsifier (acetonitrile) was added to break up the emulsion. Then, the lower layer (chloroform) was collected and analyzed by qNMR. Important parameters affecting the extraction efficiency of DLLME were investigated in detail. Although the pretreatment time is relatively long, we have obtained satisfactory experimental results. The newly established method has a good linear relationship, the linear correlation coefficient r is between 0.9972 and 0.9995, the minimum detection limit is 0.025 μg mL −1 , and the extraction reproducibility is good (RSD ≤ 3.67%, n = 6). The optimized new method was applied to the analysis of fipronil and its metabolites in chicken egg. The recoveries of spiked samples were between 97.49% and 103.0%, and satisfactory experimental results were obtained. The obtained results show that the establishment of this method provides an excellent alternative for the detection of fipronil and its metabolites in chicken egg.
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Analytical Methods
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2020
·Vol. 12
·期 46
·5581-5590
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IF 2.596
Xin Pan,Zhangjun Wang,Chao Chen,Hui Li,Xianxin Li,Quanfeng Zhang,Xiufen Wang,Yanan Zhang
Neonicotinoid and fipronil insecticides have been consumed worldwide, particularly in China. There is growing interest in the environmental research community about the occurrence, sources, and risks of neonicotinoids and fipronil. A new method based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and disc solid phase extraction (SPE) techniques were developed for the determination of neonicotinoids and fipronil in seawater in this research. The effects of the styrene divinyl benzene-reverse phase sulfonated (SDB-RPS) membrane-based solid phase extraction optimization process and the HPLC separation parameters on the detection results of the target compounds were studied. Under the optimized conditions, the detection limit of this method for 12 target compounds ranged from 0.05 ng L−1 to 0.50 ng L−1 and absolute recovery was achieved from 58.9–106.5%. The results proved that this method can effectively detect neonicotinoid and fipronil pesticides in seawater. At the same time, dinotefuran, nitenpyram, thiamethoxam, imidacloprid, thiacloprid, fipronil and its metabolites were found in seawater samples from the Yangtze River Estuary and the adjacent sea area. Among them, the total concentration of neonicotinoid insecticides ranged from ND-12.45 ng L−1 and the average total concentration was 3.5 ng L−1; the total concentration of fipronil and its metabolites ranged from ND-2.45 ng L−1, and the average total concentration was 0.79 ng L−1. The results showed that there was contamination of neonicotinoids and fipronil in the Yangtze River Estuary and its adjacent area.
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FOOD CHEMISTRY
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2021
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IF 7.514
Xu Jing,Jing Wu,Huihui Wang,Luyao Guo,Xiaojiao Zheng,Xiaowen Wang,Shuo Wang
A novel deep eutectic solvent-based extraction and sulfur-doped carbon quantum dots (S-CQDs) serving as fluorescence probes to detect pirimicarb in cereals were established. The deep eutectic solvent was synthesized using choline chloride and butanediol, achieving direct and efficient extraction of pirimicarb residue in the cereals. The fluorescence quenching of S-CQDs was caused by the electrostatic interaction between the negatively charged S-CQDs and positively charged thiocholine, which was the hydrolysate of acetylthiocholine. The fluorescence of S-CQDs was enhanced as the activity of acetylcholinesterase (AChE) was inhibited by pirimicarb, achieving the detection of pirimicarb in the cereal samples. The limit of detection (LOD) was 0.006 μg mL −1 . The recovery ranged from 96.6% to 108.2%. This extraction and detection method of pirimicarb based on an environmentally friendly DES and S-CQD fluorescent sensor maintains good stability and convenience, offering a promising strategy for extracting and testing harmful substances in food samples.
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MICROCHIMICA ACTA
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2021
·Vol. 188
·期 11
·1-9
·
IF 5.833
Chen Shuqin,Huang Mengna,Huang Mianli,Feng Liang
A strategy based on CsPbBr 3 quantum dots (QDs) is described for the determination of ziram pesticide. A facile and inert gas-free method was used for the synthesis of CsPbBr 3 QDs. The obtained CsPbBr 3 QDs displayed turn-off fluorescence behavior for ziram. The fluorescence intensity of the CsPbBr 3 QDs ( E x / E m = 365/516 nm) was inversely proportional to the concentration of ziram (0.10 to 50.0 ppm) with a detection limit of 0.086 ppm. Notably, satisfactory recoveries (100 ± 0.25 to 107 ± 5.72%) were obtained in spiked fruit samples, which demonstrated that this method is capable of detecting ziram in real samples. In addition, the mechanism for the detection of ziram was investigated in detail. According to the results, this mechanism can be tentatively explained by fluorescence quenching originating from the increased surface defects and the structural changes of the CsPbBr 3 QDs. The detection ability of this strategy shows promising applicability in food safety. Graphical abstract
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FOOD CHEMISTRY
·
2019
·
IF 5.399
Jing Zhao,Zhaorui Meng,Zexin Zhao,Longshan Zhao
A green and highly efficient ultrasound-assisted deep eutectic solvent extraction combined with functionalized magnetic multi-walled carbon nanotubes solid-phase extraction method for determination of seven pesticide residues in food products was developed. Various types of deep eutectic solvents (DESs) were screened for high extraction efficiencies and DES composing of proline and propylene glycol at 1:3 M ratio was selected as it exhibited highest yields. Extraction conditions were statistically optimized through response surface methodology using a Box-Behnken design. The established method was linear, precise, and accurate over the range of 0.1–50 μg mL −1 . Limit of detection and limit of quantification were in the range of 0.02–0.05 μg mL −1 and 0.05–0.10 μg mL −1 , respectively. The mean recoveries for pesticides ranged from 76.09 to 97.96% with relative standard deviation of 0.13–10.05%. The proposed method was successfully applied to analysis of the pesticides in real samples, which is a potentially promising technique for food matrix.
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JOURNAL OF MOLECULAR STRUCTURE
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2019
·
IF 2.12
Lianqing Chen,Zhongda Wu,Yanting Du,Yufeng Huang,Shiwei Jin
In order to find a new type of fluorescent insecticides, a series of phenylpyrazole Schiff base derivatives have been synthesized by a facile one-pot solvothermal method based on the amino group of fipronil addition-elimination condensation reaction with the corresponding benzaldehyde derivatives in high yields, which were fully characterized by 1 H NMR, IR, MS and elemental analysis . Crystal structure determination indicated that 1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-5-(4-fluoro-benzylidene-amino)-4-(trifluoromethylsulfinyl)-1 H -pyrazole-3-carbonitrile ( 7 ) crystallized into zigzag chains by π···π packing interactions between phenyl rings of neighbouring molecules. The investigation for insecticidal bioactivities of these pesticides against 3rd instar larvae of Plutella xylostella exhibited better activities than that of fipronil, which can be elucidated by enhanced calcium ions' coordination abilities with C N double bonds and chloride ions , extended conjugated parent structure, steric hindrance of the stereoscopic structure and electronegativity of substituted groups. The electronic absorption, fluorescent and electrochemical properties of phenylpyrazole Schiff base derivatives have been systematically investigated for the first time, which all emitted blue-green light in both solution and solid state at room temperature . The relationships between extended conjugated moieties of parent structure, positions of substituent group and the kinds of substitutes at 4-position on the phenyl ring and photophysical properties have been discussed, which was confirmed by electrochemical analysis . The alteration of absorption and emission wavelengths can be rationalized by substitutes' electronegativity and Substituents’ Hammett constants. The fluorescent quantum yields of phenylpyrazole Schiff base insecticides were almost 4 times that of Fipronil, which laid a foundation for their natural degradation and fluorescence detection of pesticide residues . This approach proposes a unique insight to provide a great number of novel phenylpyrazole Schiff base fluorescent insecticides by a general green method.
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
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2018
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IF 3.412
Bo Zhang,Lei Zhang,Lujue He,Xiaodong Yang,Yali Shi,Shaowei Liao,Shan Yang,Jiagao Cheng,Tianrui Ren
Fipronil is an efficient phenylpyrazole insecticide that acts on insect γ-aminobutyric acid (GABA) receptors (GABARs) and has low toxicity to mammals but high toxicity to nontarget organisms such as fish. To develop novel efficient low-toxicity insecticides, it is necessary to determine the detailed toxic mechanism at the molecular target level. In this work, methods including affinity chromatography, fluorescent-labeled binding assays, and molecular modeling were integrated to explore the binding of fipronil to GABARs in fish (Aristichthys nobilis) and insects (Musca domestica). Affinity chromatography revealed that fipronil acts on two different subunits of GABARs in fish and M. domestica. Moreover, fluorescence assays revealed that fipronil exhibits similar affinity to the two GABARs. The Kd and Bmax of fipronil binding to the A. nobilis GABAR were 346 ± 6 nmol/L and 40.6 ± 3.5 pmol/mg of protein, respectively. And the Kd and Bmax of fipronil binding to the GABAR in M. domestica brain were 109 ± 9 nM and 21.3 ± 2.5 pmol/mg of protein, respectively. In addition, similar fipronil binding positions but different binding modes were observed in docking studies with Brachydanio rerio var. and M. domestica GABARs. These findings indicated similar interactions of fipronil with fish and insects, leading to high toxicity. The different binding features of fipronil between the two species might be helpful for the design and development of highly selective insecticides with low toxicity to fish.
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JOURNAL OF SEPARATION SCIENCE
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2018
·Vol. 42
·期 4
·888-896
·
IF 2.415
Tianfu Wei,Gongke Li,Zhuomin Zhang
Covalently cross-linked microporous polymers are a new class of highly cross-linked porous network materials with large surface area and potential superiority in sample pretreatment. In this work, a covalently cross-linked microporous polymer was well designed and synthesized by condensation of acylhydrazines in terephthalic dihydrazide with aldehyde groups in 1,3,5-benzenetricarboxaldehyde. The adsorption mechanism was explored and discussed based on π-π stacking interaction and steric effect. Then, a covalently cross-linked microporous polymer was employed as the adsorbent of online micro-solid-phase extraction coupled with high-performance liquid chromatography for the enrichment and analysis of trace pesticide residues in citrus fruits. The method was successfully applied to the online analysis of sugar orange and Huangdigan samples with the detection limits of 0.10–0.30 μg/kg. It was satisfactory that chlorpifos and triazophos in real sugar orange and Huangdigan samples could be actually found and quantified at concentrations of 0.20 and 0.51 mg/kg, respectively. The recoveries of sugar orange and Huangdigan samples were in the range of 70.0–103 and 74.0–119% with relative standard deviations of 0.4–9.7 and 0.5–9.2% ( n = 3), respectively. The proposed method was accurate, reliable, and convenient for the online simultaneous analysis of trace pesticide residues in citrus fruits.
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PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY
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2015
·
IF 2.014
Baoyan Zhang,Zhiping Xu,Yixi Zhang,Xusheng Shao,Xiaoyong Xu,Jiaogao Cheng,Zhong Li
Fipronil is the first phenylpyrazole insecticide widely used in controlling pests, including pyrethroid, organophosphate and carbamate insecticides. It is generally accepted that fipronil elicits neurotoxicity via interactions with GABA and glutamate receptors, although alternative mechanisms have recently been proposed. This study evaluates the genotoxicity of fipronil and its likely mode of action in Drosophila S2 cells, as an in vitro model. Fipronil administrated the concentration- and time-dependent S2 cell proliferation. Intracellular biochemical assays showed that fipronil-induced S2 cell apoptosis coincided with a decrease in the mitochondrial membrane potential and an increase reactive oxygen species generation, a significant decrease of Bcl-2 and DIAP1, and a marked augmentation of Cyt c and caspase-3. Because caspase-3 is the major executioner caspase downstream of caspase-9 in Drosophila , enzyme activity assays were used to determine the activities of caspase-3 and caspase-9. Our results indicated that fipronil effectively induced apoptosis in Drosophila S2 cells through caspase-dependent mitochondrial pathways.
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CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Mengqi Wang,Jiayan Feng,Jiacheng Ding,Jinru Xiao,Dingbin Liu,Yang Lu,Yaqing Liu,Xia Gao
Multiple detection based on lateral flow immunoassay (LFA) holds significant research importance across various fields. Recently, the use of multi-color surface-enhanced Raman scattering (SERS) nanotags has enabled simultaneous detection of multiple targets within a single test line (T-line) in LFA , greatly enhancing detection efficiency, reliability, and application flexibility. However, challenges regarding signal overlap in the Raman-fingerprint region (400–1800 cm −1 ) and the difficulty in determining specific targets based on typical color analysis have persisted. In this study, we developed two types of nanoprobes that encode both color and Raman information to address these challenges in simultaneous multiple detection on a single T-line in SERS-LFA. The nanoprobes were encoded with distinguishable blue and red colors, respectively, enabling colorimetric study in multiplex LFA for qualitative analysis. Additionally, they were encoded with distinctive and non-overlapping Raman signals in the Raman-silent region (1800–2800 cm −1 ), ensuring accurate and sensitive detection by effectively avoiding interference from each other as well as background signals in the sample matrix. Using carbendazim (CBZ) and imidacloprid (IMI) as model targets, the color- and Raman-encoded SERS-LFA demonstrated promising potential for the simultaneous detection of CBZ and IMI in both standard and real samples, whether in a colorimetric or a SERS mode.
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Frontiers in Environmental Science
·
2024
·
IF 3.3
Ma Rong,Yu Shuangshuang,Li Yafang,Lin Yan,Ma Xiaodong
Background: With the growing use of nitrogen-containing pesticides in agriculture, their residues in the environment have raised significant public health concerns.Objective: This study aimed to develop a novel PPy-DBSA/IT-SPME coating to enhance the detection efficiency of polar nitrogen-containing pesticides in water matrices.Methods: The preparation conditions were optimized, including pyrrole concentration at 7.0 mol/L, DBSA concentration at 0.014 mol/L, oxidant concentration at 0.35 mol/L, and a coating cycle repeated 10 times. High-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was employed for detection.Results: The novel coating effectively adsorbed 19 different categories of polar nitrogen-containing pesticides, including sulfonylureas, triazolopyrimidines, diphenyl ether herbicides, benzoylurea insecticides, and phenylurea herbicides, with unadsorbed rates below 10%. The analytical method achieved an average recovery rate of 61.92% to 115.21%, with an RSD below 5.0%. Detection and quantification limits ranged from 0.012 to 0.524 μg/L and 0.127 to 5.243 μg/L, respectively.Conclusion: The developed method is green, efficient, simple, and cost-effective. It offers an environmentally friendly and user-friendly approach for the detection of polar nitrogen-containing pesticide residues, demonstrating good recovery and precision. This method holds potential for wide application in environmental monitoring and food safety.
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