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ANALYST · 2024 ·Vol. 149 ·期 15 ·3951-3960 · IF 3.6

Degradation and detection of organophosphorus pesticides based on peptides and MXene–peptide composite materials

Qiuying Wang,Ruiqing Jiu,Yunyao Wang,Zongda Li,Jianan Chen,Haochi Liu,Jifeng Liu,Jia Cao

Safety problems caused by organophosphorus pesticide (OP) residues are constantly occurring, so the development of new methods for the degradation and detection of OPs is of great scientific significance. In the present study, β-sheet peptides and β-hairpin peptides for catalyzing the hydrolysis of OPs were designed and synthesized. The peptide sequences with the highest hydrolytic activity (EHSGGVTVDPPLTVEHSAG) were screened by investigating the effect of the location of the active sites of the peptide and the peptide's structure on the degradation of OPs. In addition, the relationship between the peptides’ conformation and hydrolytic activity was further analyzed based on density functional theory calculations. The noncovalent interactions of the peptides with the OPs and the electrostatic potential on the molecular surface and molecular docking properties were also investigated. It was found that peptides with approximate active amino acids consisting of the catalytic triad and with the hairpin structure had enhanced hydrolytic activity toward the hydrolysis of OPs. To develop an electrochemical sensor technique to detect OPs, the conductive MXene (Ti3C2) material was first immobilized with a caffeic acid monolayer via enediol–metal complex chemistry and then bound with the β-hairpin peptide (EHSGGVTVDPPLTVEHSAG) via carboxy–amine condensation chemistry between the –COOH of caffeic acid and the –NH2 of the peptide to prepare a MXene–peptide composite. Then, the prepared composite was modified on the surface of a glassy carbon electrode to construct an electrochemical sensor for the detection of OPs. The developed technique could be used to monitor OPs within 15 min with a two orders of linear working range and with a detection limit of 0.15 μM. Meanwhile, the sensor showed good reliability for the detection of OPs in real vegetables.

CAS / MDL: 331-39-5 6066-82-6
研究领域: 生物化学 · 材料科学 · 分析化学
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FOOD CHEMISTRY · 2024 · IF 8.5

pH-responsive dual-emission carbon dots for the ratiometric detection of organophosphorus pesticides in Brassica chinensis and Hg2+ in water

Huifang Wu,Qiqi Wang,Miaochen Dong,Xinyue Liu,Yanfeng Tang

Accurate and rapid monitoring of organophosphorus pesticides (OPs) residues is crucial for regulating food safety. Herein, dual-emission carbon dots (de-CDs) were fabricated for the ratiometric detection of OPs and Hg 2+ . The de-CDs exhibited two emission peaks at 678 and 485 nm when excited with visible light. Interestingly, the fluorescence at 678 nm was significantly quenched by Hg 2+ mainly because of the static quenching effect, whereas that at 485 nm exhibited a slight change. More significantly, the quenched fluorescence of the de-CDs recovered remarkably after introducing omethoate , diazinon and malathion . Accordingly, the ratiometric detection of the three OPs and Hg 2+ was achieved with high selectivity and robust performance. In addition, the OPs residues assay in Brassica chinensis was successfully performed with satisfactory results. This study not only provides an attractive tool for the simple and rapid assay of OPs but also offers new insights into the fabrication of multi-functional carbon dots .

研究领域: 食品科学 · 环境科学 · 分析化学
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 6 ·1-12 · IF 5.3

Multifunctional 2D hemin-bridged MOF for the efficient removal and dual-mode detection of organophosphorus pesticides

Shen Hao,Tang Yan,Ma Hongmei

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g −1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H 2 O 2 -directed transformation of 3,3′,5,5′-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing. Graphical Abstract

研究领域: 环境科学 · 分析化学 · 生物医学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Multifunctional Fe-doped carbon dots and metal-organic frameworks nanoreactor for cascade degradation and detection of organophosphorus pesticides

Xuejuan Ma,Qi Ou,Jiajia Yuan,Jiaojiao Yang,Shuxia Xu,Xinfeng Zhang

Organophosphorus pesticides (OPs) are the most widely used pesticides, hence it is crucial to effectively prevent and control OPs residues for agricultural product safety and ecological development. In this work, the nanoreactor consisting of Fe-doped carbon dots (Fe-CDs) and metal-organic framework (MOF-808) were developed for selective degradation as well as sensitive detection of paraoxon and parathion. MOF-808 was selected as the host and used to rapidly degrade paraoxon due to its excellent organophosphorus hydrolase activity. Fe-CDs were severed as guest molecules not only for photocatalytic degradation of parathion, but also for sensing to detect OPs. Through host–guest interaction, Fe-CDs/MOF-808 and Fe-CDs@MOF-808 were synthesized for cascade degradation and detection of paraoxon and parathion, respectively. Paraoxon and parathion were detoxified by catalytic hydrolysis and photocatalytic degradation by Fe-CDs/MOF-808 and Fe-CDs@MOF-808, respectively. Meanwhile, the fluorescence of the nanocomposites was quenched by the internal filtering effect with 4-nitrophenol (4-NP), the degradation product of OPs. Fe-CDs/MOF-808 has a wide linear range for detection of paraoxon from 0.001 to 360 μM, with a limit of detection (LOD) as low as 0.3 nM. Fe-CDs@MOF-808 exhibited a linear range of 0.01–100 μM for parathion, with an LOD about 3.3 nM. The reliability of the nanoreactor was verified by testing the recovery rate of OPs spiked water sample. Meanwhile, the nanoreactors were applied for degradation and detection of OPs in pakchoi. The OPs in pakchoi can be fully degraded within 5 min, and the analytical results are consistent with those by standard method (HPLC). Therefore, the proposed nanoreactor provides a feasible alternative for effective degradation and timely detection of OPs during agricultural production.

研究领域: 农业科学 · 环境科学 · 分析化学
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Journal of Environmental Chemical Engineering · 2025 · IF 7.2

Hierarchically porous Cu-MOF fiber membrane enables instantaneous and continuous removal of organophosphorus pesticides in water

Yaqing Zhao,Kang Qin,Yaqing Zhou,Wei Liu,Zhixian Gao,Yuan Peng

Organophosphorus pesticides, commonly used in agricultural practices, remain as residues in food and the environment, presenting a significant risk to human health. The removal of these pesticides is essential to protect both human health and the environment. This study presents an in-situ synthesis technique that combines Cu-MOF (ZZU-282) with electrospinning technology to create a novel cross-linked MOF fiber membrane (cross-linked Cu-MOF-PAN FM, with PAN representing Polyacrylonitrile). The coexistence of micro/meso/macropores within the cross-linked Cu-MOF-PAN FM reduces mass transfer resistance and improves its pesticide removal capacity. The half-life for chlorpyrifos removal by the cross-linked Cu-MOF-PAN FM is about 18 s. The Langmuir model estimates the theoretical maximum removal capacity for chlorpyrifos at 208.3 mg g –1 . Additionally, the removal performance of organophosphorus pesticides is tested in simulated water samples, with results showing that over 70 % of six mixed organophosphorus pesticides are removed within 10 min using the proposed FM. The cross-linked Cu-MOF-PAN FM demonstrates superior efficiency in both rapid and sustained removal of organophosphorus pesticides from water, offering promising potential for environmental applications and pollutant removal. Moreover, the cross-linking process enhances the membrane’s resistance to organic solvents. This in-situ growth and cross-linking method offers a promising approach for fabricating MOF fiber membrane composites.

研究领域: 环境科学 · 材料科学
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FOOD CHEMISTRY · 2015 · IF 3.391

A sensitive fluorescent sensor for selective determination of dichlorvos based on the recovered fluorescence of carbon dots-Cu(II) system

Juying Hou,Guangjuan Dong,Zhengbin Tian,Jiutian Lu,Qianqian Wang,Shiyun Ai,Minglin Wang

In this paper, a simple and sensitive fluorescent sensor for dichlorvos was first constructed based on carbon dots-Cu(II) system. These carbon dots were obtained by simple hydrothermal reaction of feather. The fluorescence of these carbon dots can be selectively quenched by Cu 2+ ion. When acetylcholinesterase and acetylthiocholine were introduced into the system, thiocholine came into being, which can react with Cu 2+ ion and restore the fluorescence of the system. The reaction mechanism between Cu 2+ ion and thiocholine was confirmed by X-ray photoelectron spectroscopy. As one kind of acetylcholinesterase inhibitor, organophosphorus pesticides can be detected based on this sensing system. As an example of organophosphorus pesticides, dichlorvos was detected with a linear range of 6.0   ×   10 −9 –6.0   ×   10 −8   M. This sensing system has been successfully used for the analysis of cabbage and fruit juice samples.

CAS / MDL: 7558-79-4 7558-80-7
研究领域: 分析化学 · 环境科学 · 生物化学
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Foods · 2021 ·Vol. 10 ·期 7 ·1616 · IF 4.35

ZrO2 Nanoparticles and Poly(diallyldimethylammonium chloride)-Doped Graphene Oxide Aerogel-Coated Stainless-Steel Mesh for the Effective Adsorption of Organophosphorus Pesticides

Xiudan Hou,Rong Ding,Shihai Yan,Haiyan Zhao,Qingli Yang,Wei Wu

A novel sorbent based on the ZrO2nanoparticles and poly(diallyldimethylammonium chloride)-modified graphene oxide aerogel-grafted stainless steel mesh (ZrO2/PDDA-GOA-SSM) was used for the extraction and detection of organophosphorus pesticides (OPPs). Firstly, the PDDA and GO composite was grafted onto the surface of SSM and then freeze-dried to obtain the aerogel, which efficiently reduced the accumulation of graphene nanosheets. It integrated the advanced properties of GOA with a thin coating and the three-dimensional structural geometry of SSM. The modification of ZrO2nanoparticles brought a selective adsorption for OPPs due to the combination of the phosphate group as a Lewis base and ZrO2nanoparticles with the Lewis acid site. The ZrO2/PDDA-GOA-SSM was packed into the solid-phase extraction (SPE) cartridge to extract OPPs. According to the investigation of different factors, the extraction recovery was mainly affected by the hydrophilic-hydrophobic properties of analytes. Effective extraction and elution parameters such as sample volume, sample pH, rate of sample loading, eluent, and eluent volume, were also investigated and discussed. Under the optimal conditions, the linearity of phoxim and fenitrothion was in the range of 1.0–200 μg L−1, and the linearity of temephos was in the range of 2.5–200 μg L−1. The limits of detection were ranged from 0.2 to 1.0 μg L−1. This established method was successfully applied to detect OPPs in two vegetables. There was no OPP detected in real samples, and results showed that the matrix effects were in the range of 46.5%–90.1%. This indicates that the ZrO2/PDDA-GOA-SSM-SPE-HPLC method could effectively extract and detect OPPs in vegetables.Keywords:graphene aerogel;ZrO2;solid-phase extraction;organophosphorus pesticides

研究领域: 材料科学 · 环境科学 · 分析化学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2013 · IF 2.906

Dissipation Behavior of Organophosphorus Pesticides during the Cabbage Pickling Process: Residue Changes with Salt and Vinegar Content of Pickling Solution

Yuele Lu,Zhonghua Yang,Luyao Shen,Zhenmin Liu,Zhiqiang Zhou,Jinling Diao

In this experiment, the behavior of 10 pesticides in three different cabbage pickling treatments has been studied. The brine used for pickling was made up with different salt and vinegar contents to determine the influence of different pickling solutions on pesticide dissipation and distribution. A modified QuECHERS and SPE method was established for the analysis of the pesticides in the cabbage and brine. It was found that different pesticides showed different dissipation patterns and finally represented dissimilar residue levels in the cabbage and brine. Statistical analysis was performed to compare the distinctions of these pesticides between each treatment and proved that salt content and pH value had certain influence on the dissipation and distribution of these pesticides during the pickling process. The data from this experiment would help to control pesticide residues in pickled cabbage and prevent potential risk to human health and environmental safety.

研究领域: 食品科学 · 环境科学
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Journal of Food Measurement and Characterization · 2024 · IF 2.9

Colorimetric detection of organophosphorus pesticides based on Nb2CTx MXene self-reducing PdPt nanozyme integrated with hydrogel and smartphone

Liao Diyan,Zhao Yong,Zhou Yi,Yi Yinhui,Weng Wenchuan,Zhu Gangbing

The extensive usage of organophosphate pesticides (OPs) has posed severe harm to human health and environmental system, but achieving highly effective and on-site detection is still a great challenge. In this work, a novel nanozyme Nb 2 CT x MXene/bimetallic PdPt (Nb 2 CT x @PdPt) was synthesized firstly through a simple self-reduction method, and the results show that the as-prepared Nb 2 CT x @PdPt nanozyme exhibits outstanding peroxidase-like activity. Interestingly, the nanozyme activity of Nb 2 CT x @PdPt is restrained remarkably in the presence of acetylcholine chloride and acetylcholinesterase while it can be restored through the addition of OPs (selecting glyphosate as a model). Based on this phenomenon, a sensitive colorimetric assay coupled with hydrogel and smartphone for OPs was then constructed. After optimizing various conditions, the designed sensing platform can achieve stable, rapid, and sensitive on-site detection for OPs, showing superior sensing performances: a wide linearity of 1.0 ng mL −1 –1.0 µg mL −1 and low detection limit of 0.419 ng mL −1 .

研究领域: 环境科学 · 生物医学工程 · 分析化学
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INTERNATIONAL JOURNAL OF FOOD PROPERTIES · 2020 · IF 1.808

Pesticide residues in vegetables in four regions of Jilin Province

Di Hu,Mengmeng Jiang,Ting Ge,Xu Liu,Ziqi Li,Jinhong Liu,Ketong Zhu

A study of pesticide residues was investigated in vegetable samples to highlight the trend of drugs obtained from the Jilin Province, China. Total of 230 samples obtained from four regions over the period 2016–2017 were screened for 18 pesticides that were analyzed using gas chromatography with electron capture (GC-ECD). The results showed that 45 samples (19.6%) were positive including 17 samples (7.39%) exceeded the national maximum residue limit (MRL). Pesticides positive samples were detected in 32 leafy vegetables, 14 of which exceeded the MRLs (6.07%). There are 12 samples detected in celery that its detection rate was 5.22%, five of which exceeded the MRLs at the same time. In contrast, no pesticide residues were detected in beans or cauliflower. In the four types of pesticides, organophosphorus pesticides had the highest detection rate, which was 12.6% (29 samples). On the other hand, detectable residues of organochlorine pesticides were found, but it did not exceed the standard. Regional variations in pesticide occurrence were observed: fifteen, seven, and ten samples were positive from Ji’an, Siping City, and Tonghua City, respectively, six samples from the last city exceeded MRLs. There were 30 samples tested for pesticides at the farmers’ market and its detection rate was 13.04%, while only 15 samples contain pesticides that the samples (6.5%) purchased in the supermarket. The results indicated that high levels of the occurrence of pesticide residues in vegetables was an important source of exposure to pesticides. Therefore, we should pay attention to the consumers and their impact of pesticide residues on food and human health should be considered.

研究领域: 食品安全 · 环境科学 · 公共卫生
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MICROCHEMICAL JOURNAL · 2019 · IF 3.206

Fabrication of a novel azamacrocycle-based adsorbent for solid-phase extraction of organophosphorus pesticides in tea drinks

Li Gao,Longhui Liu,Yaming Sun,Wenjie Zhao,Lijun He

A novel azamacrocycle-based adsorbent for solid-phase extraction was synthesized by coupling a 26-membered aromatic-aliphatic-mixed azamacrocycle to 3-chloropropyltrimethoxylsilane-modified silica. The obtained material was characterized by elemental analysis and fourier transform-infrared spectroscopy. The adsorbent showed excellent performance for extracting organophosphorus pesticides (fenitrothion, parathion, fenthion and phoxim), which may be due to multiple interactions between the adsorbent and organophosphorus pesticides, including π–π, hydrophobic, dipole-dipole, charge-transfer, hydrogen-bonding and inclusion interactions. The main parameters that affected the extraction efficiency were investigated, including the amount of adsorbent, the volume and flow rate of the sample solution, the elution solvent and the ionic strength. This azamacrocycle-based extraction technique was further combined with high-performance liquid chromatography to measure trace organophosphorus pesticides in tea drinks. The method showed good linearity (5–500 ng/mL), low limit of detection (0.10 ng/mL), and high recoveries from spiked samples (90.4%–113.5%) were obtained with low relative standard deviation (0.6%–8.9%, n  = 3). The azamacrocycle-based adsorbent showed good extraction performance and offered a promising application in the extraction of organophosphorus pesticides from complicated tea drinks.

CAS / MDL: 2530-87-2 1477-55-0
研究领域: 分析化学 · 环境科学
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Food Analytical Methods · 2017 ·Vol. 11 ·期 1 ·270-281 · IF 2.038

Ionogel-Based Ionic Liquid Coating for Solid-Phase Microextraction of Organophosphorus Pesticides from Wine and Juice Samples

Pang Long,Yang Peijie,Pang Rong,Lu Xiaoling,Xiao Jingwen,Li Shunyi,Zhang Hongzhong,Zhao Jihong

In this work, a novel fiber coating was prepared by using a hybrid material of silica-based ionogels and ionic liquid 1-hexadecyl-3-methylimidazolium bis(trifuluoromethylsulfonyl)imide ([C 16 MIM][NTf 2 ]). Instead of chemical bonding to sol-gel matrix, high loadings of [C 16 MIM][NTf 2 ] was confined into the network of silica-based ionogels and thus, the extraction efficiency was significantly improved. The prepared fiber was used for solid-phase microextraction (SPME) of four organophosphorus pesticides (OPPs) from wine and juice samples prior to gas chromatography coupled with flame photometric detection. Under the optimized conditions, the proposed method results in good linearity ( R 2  > 0.9991), with low method detection limits (MDLs, S / N  = 3) and method quantification limits (MQLs, S / N  = 10) in the range of 0.57–4.13 and 1.89–13.76 ng L −1 , respectively. The precisions of the method were assessed with repeatability and reproducibility of RSD% ˂28 and ˂23%, respectively. The spiked recoveries of OPPs from wine and juice samples were in the range of 54 ± 5–118 ± 20 and 56 ± 14–109±12%, at two different concentration levels. The expanded uncertainties at 1 μg L −1 were below 20% for target OPPs in all selected samples.

CAS / MDL: 76-05-1 1185-55-3
研究领域: 分析化学 · 食品科学
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