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JOURNAL OF HAZARDOUS MATERIALS · 2025 · IF 11.3

Rapid and on-site detection of carbaryl in complex matrices using cellulose-based organogel sensor with assist of machine learning

Shuai Liu,Lili Yao,Jianpeng Chen,Kaiying Hu,Shengjie Gao,Ling Yan,Yu Mao,Baolei Dong,Lei Zheng

Rapid and on-site monitoring of carbaryl residues in complex matrix is important for ensuring environmental and food safety, but it also presents significant challenges. We have developed a cellulose organogel sensor, which, with the aid of smartphones and portable imaging devices, enables accurate and quantitative detection of carbaryl. Specifically, p -aminobenzoic acid was covalently immobilized onto the cellulose. The cellulose organogel sensor was fabricated using a solvent-induced strategy, which exhibits good stability. The naphthol produced by the hydrolysis of carbaryl could react with p -aminobenzoic acid through an azo coupling reaction, generating a red product, thereby enabling the visual detection of carbaryl. The cellulose organogel features a dense and porous internal network structure, which effectively excludes interfering substances from the sample matrix and absorbs carbaryl into the organogel. The cellulose organogel sensor demonstrates excellent resistance to matrix interference from complex samples. The organogel sensor can directly detect carbaryl in extracts from river water, rice, cabbage, and soybean oil samples without additional separation or enrichment steps. We used the You Only Look Once (YOLO) algorithm to analyze the organogel images captured by the smartphone, effectively reducing interference and improving the sensor's detection accuracy. The organogel sensor achieves a detection limit of 0.19 mg kg –1 for carbaryl, with recoveries higher than 85.2 % in the samples. The entire detection process including sample pretreatment takes less than 40 min. This study presents a new and reliable solution for the on-site, accurate detection of carbaryl in complex samples by combining organogel sensors with machine learning.

研究领域: 分析化学 · 环境监测 · 食品安全 · 生物传感 · 材料科学 · 农业化学 · 计算生物学
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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Multifunctional nanoenzyme lateral flow immunoassay strip for rapid and ultrasensitive detection of carbofuran in vegetables

Shengxi Zhai,Haowei Dong,Haifang Wang,Jingcheng Huang,Donghan Li,Zhengtao Li,Zhaopeng Li,Peisen Li,Pengwei Zhang,Mingxin Zhao,Xia Sun,Yemin Guo

A lateral flow immunoassay strip (LFIAS) is one of the most frequently rapid test technologies for carbofuran (CAR). Nevertheless, the LFIAS has a poor quantitative capability and low sensitivity. And, it also requires often complex sample handling steps, making testing time longer. In this study, Fe 3 O 4 nanoparticles were successively modified with MIL-100(Fe)-based metal-organic framework (MOF) and chloroplatinic acid hexahydrate to obtain a core-shell complex of Fe 3 O 4 -MOF-Pt. The complex had a peroxidase-mimicking activity catalytic function that enabled signal amplification and sensitivity enhancement. Upon coupling with carbofuran monoclonal antibody (CAR-mAb), the magnetic separation properties of the probe enabled target-specific enrichment. The LFIAS based on Fe 3 O 4 -MOF-Pt nanocomposites could detect CAR in the range of 0.25–50 ng mL −1 with a limit of detection (LOD) of 0.15 ng mL −1 , enabling colorimetric and catalytic analysis. In addition, the method showed high specificity and stability for detecting CAR in various vegetables, and recovery rates of the spiked samples were 91.40%−102.40%. In conclusion, this study provided one-stop detection of “target enrichment-visual inspection”. While lowering the LOD, it reduced the detection time and improved the detection efficiency. The multifunctional Fe 3 O 4 -MOF-Pt nanocomposite provides an idea for the construction of novel multifunctional probes to improve the detection performance of conventional LFIAS.

CAS / MDL: 1317-61-9
研究领域: 分析化学 · 纳米技术 · 环境科学 · 食品安全
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JOURNAL OF SEPARATION SCIENCE · 2020 ·Vol. 43 ·期 8 ·1514-1522 · IF 2.878

Fe3O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and β-cyclodextrin for magnetic solid-phase extraction of carbaryl and carbofuran

Qiong Ma,Xiaolan Liu,Yingying Zhang,Ling Chen,Xueping Dang,Youhong Ai,Huaixia Chen

In this study, porous sandwich structure Fe 3 O 4 nanoparticles coated by polyhedral oligomeric silsesquioxanes and β-cyclodextrin were prepared by surface polymerization and were used as the magnetic solid phase extraction adsorbent for the extraction and determination of carbaryl and carbofuran. The Fe 3 O 4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and β-cyclodextrin were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, and scanning electron microscopy. After optimizing the extraction conditions, a method that combined magnetic solid phase extraction with high-performance liquid chromatography was developed for the determination of carbaryl and carbofuran in apple. The method exhibited a good linearity in the range of 2–400 μg/kg for carbaryl and carbofuran ( R 2 = 0.9995), respectively. The limits of detection were 0.5 μg/kg of carbaryl and 0.7 μg/kg for carbofuran in apple, respectively. Extraction recoveries ranged from 94.2 to 103.1% with the preconcentration factor of 300 and the relative standard deviations were less than 5.9%. These results indicated that the method combined magnetic solid phase extraction with high-performance liquid chromatography and was promising for the determination of carbaryl and carbofuran at trace amounts.

CAS / MDL: 111689-03-3
研究领域: 分析化学 · 纳米技术 · 环境科学 · 食品科学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2013 · IF 2.906

Dispersive Microextraction Based on “Magnetic Water” Coupled to Gas Chromatography/Mass Spectrometry for the Fast Determination of Organophosphorus Pesticides in Cold-Pressed Vegetable Oils

Qin Zhao,Qian Lu,Qiong-Wei Yu,Yu-Qi Feng

This article presents a novel application of dispersive microextraction based on “magnetic water” (m-water) for the purification of organophosphorus pesticides (methamidophos, omethoate, monocrotophos) from cold-pressed vegetable oils. In the present study, a trace amount of water (extractant) was adsorbed on bare Fe3O4 by hydrophilic interaction to form m-water. Rapid extraction can be achieved while the m-water is dispersed in the sample solution with the aid of a vigorous vortex. After extraction, the analyte-adsorbed m-water can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for pesticide analysis was established by coupling with gas chromatography/mass spectrometry (GC/MS). The linearity range of the proposed method was 2–100 ng/g with satisfactory correlation coefficients (R) of 0.9997–0.9998, and the limits of quantification (LOQ) for the target compounds were in the range of 0.70–1.27 ng/g. In addition, the reproducibility was obtained by evaluating the intra- and interday precisions with relative standard deviations (RSDs) less than 7.2% and 6.5%, respectively. Finally, the established “magnetic water” microextraction method was successfully applied for the determination of pesticide residues in several kinds of cold-pressed vegetable oils.

CAS / MDL: 50-70-4
研究领域: 分析化学 · 环境科学 · 食品科学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Smartphone-based colorimetric paper chip sensor using single-atom nanozyme for the detection of carbofuran pesticide residues in vegetables

Lifan Zhang,Ziyue Lang,Bozhi Lu,Tinglan Yang,Xinyi Zhang,Muxue Wang,Xiaomei Zhang,Hongmei Cao,Daixin Ye

Carbofuran (CBF), which exhibit high toxicity, persistent residues, ease of accumulation, and resistance to degradation, pose serious threats to human health and harm the ecological environment. Therefore, there is an urgent need to develop a rapid and accurate method for detecting CBF. In this work, a low-cost, portable, and easy-to-use paper chip biosensor was developed, integrating smartphones for the detection of CBF pesticide residues. This biosensor facilitates rapid on-site testing, meeting the needs for immediate analysis. CBF has the ability to inhibit acetylcholinesterase (AChE) activity. In the presence of AChE, acetylthiocholine (ATCh) is hydrolyzed to produce thiocholine (TCh). TCh, in turn, can inhibit the catalytic activity of Ni-N-C single-atom nanozymes (SAzyme) synthesized using Ni(OH) 2 nanochip as a metal precursor, which possess high peroxidase activity. Consequently, the concentration of CBF can be determined by observing the resultant color changes. The results showed that this sensor had a good linear response in the range of CBF concentration from 10 to 500 ng/mL, and the LOD was as low as 8.79 ng/mL. In testing three actual samples—Chinese cabbage, cabbage, and lettuce—the recoveries ranged from 81.09% to 125.27%. This demonstrated that the proposed smartphone-based colorimetric paper chip sensor, utilizing Ni-N-C SAzyme, offers an immediate, convenient, and rapid new strategy for detecting CBF.

研究领域: 环境科学 · 分析化学 · 生物传感器 · 食品安全 · 农药检测
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CHEMOSPHERE · 2020 · IF 5.778

Carbofuran induces increased anxiety-like behaviors in female zebrafish (Danio rerio) through disturbing dopaminergic/norepinephrinergic system

Shuang Liu,Miao Yu,Xincen Xie,Yiran Ru,Shaoguo Ru

Carbofuran , a carbamate pesticide , is widely used in developing countries to manage insect pests. Studies have found that carbofuran posed potential risks for the neurotransmitter systems of non-target species, we speculated that these disruptive effects on the neurotransmitter systems could trigger anxiety-like behaviors. In this study, female zebrafish were exposed to environmental levels (5, 50, and 500 μg/L) of carbofuran for 48 h to evaluate the effects of carbofuran on anxiety-like behaviors. Results showed that zebrafish exhibited more anxiety-like behaviors which proved by the observed higher bottom trend and more erratic movements in the novel tank after carbofuran treatment. In order to elucidate the underlying molecular mechanisms of carbofuran-induced anxiety-promoting effects, we measured the levels of neurotransmitters, precursors, and major metabolites, along with the level of gene expression and the enzyme activities involved in neurotransmitter synthesis and metabolism. The results demonstrated that acute carbofuran exposure stimulated the mRNA expression and enzyme activity of tyrosine hydroxylase, which sequentially induced the increased levels of dopamine and norepinephrine . Tyrosine hydroxylase inhibitor relieved the anxiety-related changes induced by carbofuran, confirming the overactive tyrosine hydroxylase-mediated accumulation of dopamine and norepinephrine in the brain was one of the main reasons for carbofuran-induced anxiety-like behaviors in the female zebrafish. Overall, our study indicated the environmental health risks of carbamate pesticide in inducing neurobehavioral disorders and provided novel insights into the investigation of the relevant underlying mechanisms.

CAS / MDL: 658-48-0 620-30-4
研究领域: 环境毒理学 · 神经科学 · 水生毒理学
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LUMINESCENCE · 2021 ·Vol. 37 ·期 2 ·348-356 · IF 2.464

Fluorescence detection of carbofuran in aqueous extracts based on dual-emission SiO2@Y2O3:(Eu3+,Tb3+)@MIP core-shell structural nanoparticles

Shilin Shen,Zerong Long,Yi Lu,Jia Chen

A novel double-windows fluorescence sensor for carbofuran (CF) detection was successfully developed based on rare-earth Eu,Tb-doped Y 2 O 3 @SiO 2 -based molecularly imprinted nanoparticles (MINs) with a multilayer core-shell structure. The recognition process of the MINs for CF was fairly fast and needed only ~8 min to reach a dynamic equilibrium. Interestingly, one fluorescence attenuation window was found with an increase in CF concentration ( Q ) from 0.1 to 10 μg ml −1 and with a limit of detection (LOD) of 0.04 μg ml −1 at 544 nm belonging to the Tb 3+ emission, as well as another fluorescence enhanced window within the CF concentration range 10–100 μg ml −1 (LOD = 4 μg ml −1 ) at 617 nm of Eu 3+ emission in the dispersed rare-earth-doped MIN colloidal aqueous solution. Luminescence resonance energy transfer from CF to Eu 3+ and an inner filter effect of CF towards Tb 3+ , as well from the two independent detection windows were clearly observed simultaneously. The competition experiment displayed hardly any marked interference during detection of CF following addition of its analogues (carbaryl, isoprocarb, aldicarb, methomyl, and etofenprox). Moreover, the MINs could also be applied to accurately detect CF in rhubarb and wolfberry samples with recoveries of 85.7–92.2%. This sensing system has high specific recognition and a wide detection range for CF and provides new opportunities for pesticide detection.

研究领域: 分析化学 · 纳米技术 · 环境科学 · 农药检测
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JOURNAL OF HAZARDOUS MATERIALS · 2022 · IF 14.224

Transgenerational effects of co-exposure to cadmium and carbofuran on zebrafish based on biochemical and transcriptomic analyses

Yanhua Wang,You Weng,Lu Lv,Dou Wang,Guiling Yang,Yuanxiang Jin,Qiang Wang

The combined toxicity of heavy metals and pesticides to aquatic organisms is still largely unexplored. In this study, we investigated the combined impacts of cadmium (Cd) and carbofuran (CAR) on female zebrafish (F0 generation) and their following F1 generation. Results showed that mixtures of Cd and CAR induced acute synergistic effects on both zebrafish adults of the F0 generation and embryos of the F1 generation. Combined exposure to Cd and CAR could obviously alter the hepatic VTG level of females, and the individual exposures increased the relative mRNA levels of vtg1 and vtg2 . Through maternal transmission, co-exposure of Cd and CAR caused toxicity to 4-day-old larvae of the F1 generation, evidenced by the significant changes in T4 and VTG levels, CYP450 activity, and the relative transcriptional levels of genes related to the hormone, oxidative stress , and apoptosis. These effects were also reflected by the global gene expression pattern to 7-day-old larvae of F1 generation using the transcriptomic analysis, and they could also affect energy metabolism. Our results provided a more comprehensive insight into the transgenerational toxic impacts of heavy metal and pesticide mixtures. These findings highlighted that it was highly necessary to consider transgenerational exposures in the ecological risk assessment of chemical mixtures.

研究领域: 环境毒理学 · 水生生物学 · 分子生物学 · 生态毒理学
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JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES · 2023 · IF 3

A retrospective screening method for carbamate toxicant exposure based on butyrylcholinesterase adducts in human plasma with ultra-high performance liquid chromatography–tandem mass spectrometry

Zhe Ren,Bo Chen,Deshen Liang,Dongxin Liu,Wu Lei,Shilei Liu

Carbamate pesticides are extensively used in agriculture for their inhibition to acetylcholinesterase and damages to the insects’ neural systems. Because of their toxicity, human poisoning incidents caused by carbamate pesticide exposure have occurred from time to time. What’s more, some lethally toxic carbamate toxicants known as carbamate nerve agents (CMNAs) have been supplemented in Schedule 1 of the Annex on Chemicals in the Chemical Weapons Convention (CWC) by Organisation of the Prohibition of Chemical Weapons (OPCW) from 2020. And some other carbamates, like physostigmine, have been used in clinical treatment as anticholinergic drugs and their misuse may also cause damages to the body. Similar to organophosphorus toxicants, carbamate toxicants would react with butyrylcholinesterase (BChE) in plasma when entering the human body, resulting in the BChE adducts, based on which the exposure of carbamate toxicants could be detected retrospectively. In this study, methylcarbamyl nonapeptide and dimethylcarbamyl nonapeptide from pepsin digestion of BChE adducts were identified with ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) in product ion scan mode. Carbofuran was chosen as the target to establish the detection method of carbamate toxicant exposure based on methylcarbamyl nonapeptide digested from methylcarbamyl BChE. Procainamide-gel affinity purification, pepsin digestion and UHPLC–MS/MS analysis in multiple reaction monitoring (MRM) mode were applied. Under the optimized conditions of sample preparation and UHPLC–MS/MS MRM analysis, the limits of detection (LODs) reached 10.0 ng/mL of plasma exposed to carbofuran with satisfactory specificity. The quantitation approach was established with d 3 -carbofuran-exposed plasma as the internal standard (IS) and the linearity range was 30.0–1.00 × 10 3 nmol/L (R 2  >0.998) with the accuracy of 95.6%–107% and precision of ≤9% relative standard deviation (RSD). The applicability was also evaluated by N,N-dimethyl-carbamates with the LODs of 30.0 nmol/L for pirimicarb-exposed plasma based on dimethylcarbamyl nonapeptide. Because most of carbamate toxicants has methylcarbamyl or dimethylcarbamyl groups, this approach could be applied on the retrospective screening of carbamate toxicant exposure including CMNAs, carbamate pesticides or carbamate drugs. This study could provide an effective means in the fields of CWC verification, toxicological mechanism investigation and down-selection of potential treatment options.

研究领域: 分析化学 · 毒理学 · 法医学 · 环境健康 · 临床化学
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