SCIENCE OF THE TOTAL ENVIRONMENT
·
2020
·
IF 6.551
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.
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Analytical Methods
·
2020
·Vol. 13
·期 5
·672-684
·
IF 2.596
Xiao-Chun Ma,Zong-Qin Ma,Meng-Xin Zhao,Ying-Hui Wang,Yuan Peng,Xin Guo,Fang-Huan Wang,Zhe Meng,Hao-Bo Zheng
A novel magnetic molybdenum disulfide@graphene (Fe3O4/MoS2@G) nanocomposite with amphiphilic properties was prepared via a co-mixing solvothermal method. To demonstrate the feasibility of Fe3O4/MoS2@G as a sorbent during sample preparation, it was employed for the magnetic solid phase extraction (MSPE) of ten pyrethroids, three triazoles and two acaricide pyridaben and picoxystrobin in an emulsified aqueous solution. Dichloromethane was used as the extractant to form an emulsified aqueous solution. Subsequently, the Fe3O4/MoS2@G sorbent with amphiphilic properties was used to retrieve 15 wide polarity insecticides from dichloromethane via MSPE. The proposed method has the advantage of being applicable to different polar pesticides, strengthening the capacity of enrichment and purification of target analytes. The π–π interaction between the hydrophilic and hydrophobic moieties of Fe3O4/MoS2@G and the aromatic rings of target analytes were responsible for the efficient sorption. Thus, a reliable, convenient, and efficient method for the analysis of 15 insecticides with wide polarity in wolfberry samples was established by coupling Fe3O4/MoS2@G nanocomposite MSPE with gas chromatography-mass spectrometry (GC-MS) analysis. The obtained linearity of this method was in the range from 1 to 5000 ng mL−1 for 15 analytes, with determination coefficients (R2) ≥0.9907. The limit of detection (LOD) for 15 insecticides was in the range from 0.1 to 5.0 ng g−1. The recoveries of 15 insecticides from spiked wolfberry samples were in the range from 71.41% to 110.53%, and RSD was less than 14.8%.
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PEST MANAGEMENT SCIENCE
·
2020
·Vol. 76
·期 12
·4210-4221
·
IF 3.75
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
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ARCHIVES OF INSECT BIOCHEMISTRY AND PHYSIOLOGY
·
2021
·Vol. 108
·期 2
·e21835
·
IF 1.698
Mao-Ye Li,Yun Wang,Xiao Lei,Chuan-Tao Xu,Dong-Dong Wang,Su Liu,Shi-Guang Li
The green peach aphid, Myzus persicae (Sulzer), is a serious agricultural pest with a worldwide distribution. Catalase (CAT), which is encoded by the catalase ( Cat ) gene, is an extremely important antioxidant enzyme that plays a pivotal role in protecting cells against the toxic effects of hydrogen peroxide. The Cat gene has not been characterized in M. persicae ; therefore, this study describes the identification of the Cat ( MpCat ) gene from M. persicae . MpCat contains an open reading frame of 1515 bp and encodes a MpCAT protein consisting of 504 amino-acid residues. MpCAT possesses features typical of other insect catalases, including 7 conserved amino acids involved in binding heme and 15 involved in binding nicotinamide adenine dinucleotide phosphate. Phylogenetic analysis showed that MpCAT was closely related to orthologs from other aphid species. MpCat consisted of nine exons and eight introns, and the number and insertion sites of introns are consistent with those of Cat genes from Acyrthosiphon pisum (Harris) and Aphis gossypii Glover. The mRNA transcripts of MpCat were detected at all tested developmental stages, with the highest mRNA level in alate adults. The expression of MpCat was significantly upregulated when M. persicae was exposed to low and high temperatures, ultraviolet radiation, Beauveria bassiana , and permethrin. The transcription of MpCat and the activity of catalase were suppressed by RNA interference, and knockdown of MpCat significantly reduced the survival rate in M. persicae under heat stress. The results provide valuable information for further study on the physiological functions of MpCat . Research Highlights A catalase gene ( MpCat ) was characterized in Myzus persicae . Transcription of MpCat was responsive to various environmental stresses. Knockdown of MpCat increased mortality in M. persicae under heat stress.
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PEST MANAGEMENT SCIENCE
·
2019
·Vol. 76
·期 2
·636-644
·
IF 3.255
Qiuyan Zhu,Yang Yang,Zhiting Lao,Yingying Zhong,Bingjie Zhang,Xiping Cui,Paul O'Neill,David Hong,Kun Zhang,Suqing Zhao
BACKGROUND The use of safe and effective insecticides against mosquito-borne stocks is still one of the most effective ways to rapidly interrupt the spread of diseases such as malaria, dengue etc., but many insects are resistant to most insecticides and most of the traditional pyrethroids (like permethrin, deltamethrin etc.) contain phenoxy groups so it is easy to form dibenzofuran, a pollutant, after photodegradation. It is therefore necessary to synthesize novel pyrethroids which have better mosquito-killing activity, poor resistance to mosquitoes, and no dibenzofuran formation during photodegradation. RESULTS A series of novel dihaloacetylated heterocyclic pyrethroids were synthesized to enhance antimosquito activity. Bioassays based on the guidelines of the Chinese Center for Disease Control and Prevention (CDC) indicate that the synthesized compounds DCA-O (LC 50 = 2.95 ± 0.05 μg L −1 ), DCA-01 (LC 50 = 5.83 ± 0.36 μg L −1 ) and DCA-11 (LC 50 = 5.79 ± 1.51 μg L −1 ) exhibit high insecticidal activities and sensitivity against Aedes albopictus while deltamethrin and permethrin produced moderate levels of resistance. Moreover, the analysis of the photodegradation implies that the novel compounds synthesized by substituting a phenoxy group with a heterocyclic ring do not form dibenzofuran, a pollutant. Lastly, the cytotoxicity data of pyrethroids on human dopaminergic neuroblastoma SH-SY5Y cells confirm that the synthesized compounds have low toxicity for the cells. CONCLUSION Novel dihaloacetylated heterocyclic pyrethroids, made by simple synthesis steps, have better antimosquito activity, lower drug resistance, are less polluting to the environment and show low toxicity to human nerve cells. This also provides an effective idea for the synthesis of pyrethroids. Novel dihaloacetylated heterocyclic pyrethroids have better antimosquito activity, lower drug resistance, are less polluting to the environment, ahow low toxicity to human nerve cells and simple synthesis steps. © 2019 Society of Chemical Industry
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FOOD CHEMISTRY
·
2018
·
IF 4.946
Fang Liu,Xiaoling Yang,Xiaoling Wu,Xuefei Xi,Haixiang Gao,Sanbing Zhang,Wenfeng Zhou,Runhua Lu
A novel dispersive magnetic solid phase microextraction method based on ionic liquid-coated and cyclodextrin-functionalized magnetic core dendrimer nanocomposites has been developed for the determination of pyrethroids in juice samples. The different generation magnetic core dendrimer nanocomposites were successfully synthesized and the nanocomposites possess both the selective retention of guest dendrimer and cyclodextrin molecules and high adsorption capacities of ionic liquids. The extraction efficiencies of different generation magnetic core dendrimer nanocomposites were compared, and the type of nanocomposite with the highest recovery was obtained. Under the optimized experimental conditions, the method showed good linearity in the range of 3.5–500 μg L −1 . The LODs and LOQs were in the ranges of 0.36–1.3 μg L −1 and 1.2–4.3 μg L −1 , respectively. The method also showed acceptable accuracies ranging from 98.2% to 99.4%. The proposed method was demonstrated to broaden the potential applications of dendrimer for the detection of pyrethroid residues in various juice samples.
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FOOD CHEMISTRY
·
2018
·
IF 4.946
Peipei Zhou,Kai Chen,Man Gao,Jingang Qu,Zhanen Zhang,Randy A. Dahlgren,Yanyan Li,Wei Liu,Hong Huang,Xuedong Wang
Conventional magnetic effervescent tablet has many drawbacks, such as not practicable for field processing, rapid moisture absorption, and poor tablet storage characteristics. Herein, we developed a novel magnetic effervescent tablet containing ionic liquid microextraction (MET-ILM) for determination of pyrethroids in dairy milk. It contains only Na 2 CO 3 as an alkali source (no acidic source) in the Fe 3 O 4 magnetic tablet; the CO 2 -forming reaction is initiated in the acidic solution containing the analytes, and thus the prepared tablet can be stored for long time periods without deterioration. The combined action of extractant and sorbent vastly increase the extraction efficiency. The optimized procedure consisted of an effervescent tablet, 2:1 HCl:Na 2 CO 3 , and 60 μL [C 6 MIM]PF 6 as extraction solvent. The LODs for five pyrethroids were 0.024–0.075 μg kg −1 with recoveries of 78.3–101.8%. The RSDs were <4.8% and <6.3% for intra- and inter-day precisions. Overall, the method is very feasible for use in the field.
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ANALYST
·
2018
·Vol. 143
·期 12
·2883-2888
·
IF 3.864
Hui Ouyang,Wenwen Wang,Qi Shu,Zhifeng Fu
A novel immunochromatographic assay (ICA) using a dual-readout signal probe was developed for multiplexed detection of pesticide residues by adopting methyl parathion and fenpropathrin as model analytes. Luminol-reduced Au nanoparticles (LRAuNPs) were synthesized and utilized in the proposed ICA platform as a colorimetric/chemiluminescent (CL) dual-readout probe. The methyl parathion antibody and fenpropathrin antibody were tagged with the prepared LRAuNPs to conduct spatially-resolved multiplexed detection. After the occurrence of two immunoreactions on the test strip, the probes were captured by the immobilized antigens on the two test zones. The red color resulting from the accumulation of captured LRAuNPs was adopted as the visual and semi-quantitative readout. For the sensitive quantitative detection of the analytes, the CL signals caused by the luminophore in the LRAuNPs were collected after triggering the luminol-H2O2 CL reaction. Under the optimal conditions, the detection limits for methyl parathion and fenpropathrin were 0.17 ng mL−1 and 0.10 ng mL−1 (S/N = 3), respectively. The whole procedure for ICA was completed within 15 min. The present ICA protocol was successfully applied for detection of pesticide residues in spiked traditional Chinese medicine samples. This dual-readout ICA platform showed merits such as low cost, time efficiency, easy operation and high sensitivity. Its application potential has been demonstrated in the rapid screening and field detection of multiple pesticide residues.
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MICROCHIMICA ACTA
·
2018
·Vol. 185
·期 12
·1-7
·
IF 5.705
Pang Yachao,Zang Xiaohuan,Wang Mengting,Chang Qingyun,Zhang Shuaihua,Wang Chun,Wang Zhi
A fibrous magnetic boron nitride nanocomposite was synthesized and is shown to be a viable adsorbent for the magnetic solid phase extraction of pesticides prior to their quantitation by gas chromatography with electron capture detection. The optimum conditions were obtained by both single factor optimization and response surface analysis (Box-Behnken design). Under the optimized conditions, the response to the ten pesticides (dicofol, α-endosulfan, p,p’ -DDE, nitrofen, β -endosulfan, p,p’ -DDD, p,p’ -DDT, bifenthrin, permethrin and fenvalerate) is linear in the 0.03–40 ng·mL −1 concentration range with the coefficients of determination ranging from 0.9970 to 0.9992. The relative standard deviations at concentration levels of 0.5 ng·mL −1 , 20 ng·mL −1 and 40 ng·mL −1 were below 8.7%. The recoveries of the analytes from spiked tea water and tea beverage samples varied between 84.5% and 122%, with relative standard deviations ranging from 4.8 to 12%. The limits of detection are between 0.01 and 0.05 ng·mL −1 . The adsorbent can be reused over 50 times without significant loss of extraction efficiency.
A novel fibrous-shape magnetic boron nitride nanocomposite (Fe 3 O 4 @ f -BN) was used as the adsorbent for the magnetic solid phase extraction (MSPE) of ten pesticides from tea water and tea beverage samples prior to their determination by gas chromatography (GC).
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JOURNAL OF THE BRAZILIAN CHEMICAL SOCIETY
·
2013
·Vol. 24
·期 6
·1034-1040
·
IF 1.283
Yu Chen,Zhang Sanbing,Zhang Jiaheng,Li Songqing,Zhou Wenfeng,Gao Haixiang,Lu Runhua
An in situ ionic liquid dispersive liquid-liquid microextraction (IL-DLLME) method was developed as a new approach for the detection of four pyrethroid pesticides in environmental water samples. The method is fast, simple, accurate and environmentally friendly. The hydrophobic ionic liquid, [C8MIM]-NTf2, formed by the water-soluble ionic liquid [C8MIM]Cl and the ion exchange reagent LiNTf2 was used as the extraction solvent. The experimental parameters affecting the extraction efficiency, including the amount of the IL, the extraction and the centrifugation times and the salt concentration were investigated and optimized using an orthogonal array design (OAD). A suitable molar ratio of LiNTf2 to [C8MIM]Cl on the recoveries of analytes was determined after OAD optimization. The method showed a good linear response in the range of 0.5 to 500 µg L-1 with correlation coefficients (R²) above 0.9998. The relative standard deviation (RSD) varied from 0.6 to 1.9%. The enrichment factor, the limit of detection and recovery ranged from 134 to 153, 0.02 to 0.18 µg L-1 and 89.7 to 95.6%, respectively. For water samples, the RSD ranged from 0.02 to 2.34% and the recovery ranges from 91.4 to 99.9%.
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TALANTA
·
2016
·
IF 4.035
Xiaoling Yang,Panjie Zhang,Xiaobing Li,Lu Hu,Haixiang Gao,Sanbing Zhang,Wenfeng Zhou,Runhua Lu
In this research, an effervescence-assisted β-cyclodextrin/attapulgite composite (β-CD/ATP) for the in-syringe dispersive solid-phase extraction (EAIS-DSPE) of pyrethroids in environmental samples was developed for the first time. A syringe was used to conduct the extraction procedure and a small amount of β-CD/ATP was dispersed into the solution with the release of carbon dioxide when the effervescent tablet components dissolved in water. Then, the sorbent was recovered using a filter membrane , and the analytes were directly eluted using acetonitrile . In the process, the β-CD/ATP sorbent resulted in an excellent extraction efficiency compared to commercially available sorbents such as C 18 and HLB. Moreover, in the extraction procedure, both the β-cyclodextrin inclusion interactions (especially the hydrophobic effects) and the special structure of the ATP contributed to the efficient enrichment of pyrethroids in aqueous media. The amount of β-CD/ATP sorbent, the volume of desorption, the ratio of NaH 2 PO 4 /Na 2 CO 3 , the volume of the sample, and the pH were screened using a Plackett–Burman design. All factors affecting the procedure were optimized by applying a central composite design. Under the optimized conditions, a good repeatability (RSDs) ranging from 1.7 to 2.3, linearity (2.5–500 μg L −1 ), limits of detection (LODs) (0.15–1.03 μg L −1 ), and an acceptable recoveries (76.8–86.5%) were achieved. Finally, the proposed method was successfully applied for the determination of pyrethroids in environmental samples including river water, reservoir water and lake water.
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TALANTA
·
2017
·
IF 4.162
Shuaihua Zhang,Qian Yang,Xiumin Yang,Wenchang Wang,Zhi Li,Lihong Zhang,Chun Wang,Zhi Wang
A high-surface-area nanoporous carbon (NPC) has been successfully synthesized by using the metal-organic framework ZIF-90 as both the template and precursor together with furfuryl alcohol as a secondary carbon source. The prepared ZIF-90 templated NPC (ZIF-90-NPC) was then coated onto a stainless steel wire by a simple physical adhesion approach to prepare solid-phase microextraction (SPME) fiber. By coupling the ZIF-90-NPC coated fiber-based SPME with gas chromatography-microelectron capture detection (GC-μECD), the developed method gave a large enhancement factor (984-2869), low limit of detection (0.1–0.5 ng g −1 ) and good linearity (0.3–50 ng g −1 ) for the determination of some pyrethroid pesticides (bifenthrin, fenpropathrin , cyhalothrin , permethrin, cyfluthrin , flucythrinate, fenvalerate and deltamethrin) from different fruits and vegetables. The relative standard deviations (RSDs) for six replicate extractions of the pyrethroids by the ZIF-90-NPC coated fiber ranged from 4.3% to 8.0%. The recoveries of the spiked pyrethroids (5 ng g −1 and 20 ng g −1 ) from fruit and vegetable samples were in the range of 88.0–104.0% and 86.0–103.5% with the RSDs ranging from 4.8% to 12.9% and 5.0–10.8%, respectively. Besides, the ZIF-90-NPC coated fiber was stable enough for 100 extraction cycles without a significant loss of extraction efficiency. The method was successfully applied to the determination of the pyrethroids in fruit and vegetable samples.
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