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Thiram
CHEMOSPHERE · 2021 · IF 7.086

Layered filter paper-silver nanoparticle-ZIF-8 composite for efficient multi-mode enrichment and sensitive SERS detection of thiram

Fugang Xu,Wenjuan Shang,Mengren Xuan,Guangran Ma,Zixiang Ben

A SERS substrate FP/Ag/ZIF-8 composed of filter paper (FP), silver nanoparticles (AgNPs) and zeolitic imidazolate framework (ZIF-8) film arranged in a layered structure was developed for sensitive detection of pesticide thiram in various samples. Roles of these components in analyte adsorption and Raman signal enhancement were studied using a pesticide intermediate 4-Aminothiophenol (4-ATP) as the probe. The substrate showed high adsorption and optimized SERS response with thick metal organic framework (MOF) coating (125 nm), which is different from previous reported plasmonic particle-MOF composite substrate, where thinnest MOF coating produced the strongest SERS signal. Detection limit for 4-ATP improved 1000-fold on FP/Ag/ZIF-8 (3 pM) compared with that on FP/Ag (3 nM). Importantly, the FP/Ag/ZIF-8 with porous and flexible property can efficiently capture pesticide thiram in different real samples using soaking, filtration or swabbing operation. The subsequent SERS detection of thiram showed advantages of low detection limit (soaking, LOD: 0.04 nM in lake water), fast detection (filtration, within 1 min in peach juice) and suitable for curve surface analysis (swabbing, LOD: 0.1 ng/cm 2 on apple peel), respectively. The substrate also displayed good reproducibility, high stability and size-selective response for thiram detection. Such a layered plasmonic particle/MOF hybrid may hold great promise for toxicant analysis in environment and food.

研究领域: 分析化学 · 环境科学 · 食品安全
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2026 · IF 4.8

Multi-channel colorimetric detection of thiram in food and water samples via activated dual enzyme-like activities of Cu2+

Zijia Jin,Yao Li,Zhenhui Yue,Feng Zhao,Zhen Lei

Thiram (Thr) residues pose potential risks to ecological environment and human health. Herein, a simple multi-channel colorimetric assay for Thr detection was proposed. Cu 2+ served as the colorimetric probe, and coordinated with Thr, forming Cu 2+ -Thr complex with satisfactory oxidase (OXD)-like and laccase (LAC)-like activity. The catalytic kinetics of Cu 2+ -Thr complex well fitted Michaelis-Menten model. Leveraging Thr activated OXD and LAC-like activities of Cu 2+ , colorimetric assays for Thr detection were developed. The detection range and limit of detection of this method were comparable to those methods involving nanomaterials. By integrating smartphone with test papers and test swabs, two portable sensing platforms were developed to achieve on-site detection of Thr. The concentrations of Thr in food and water samples were successfully determined via multiple channels with satisfactory recoveries and relative standard deviation. The simple and low-cost multi-channel colorimetric sensing platforms showed potential for food safety analysis and environmental monitoring.

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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Facile Synthesis of Ultrasmooth Au Nanospheres into Macroscopic 3D Supercrystals for Machine-Learning-Driven Analysis of Thiram in Soil

Mingyuan Dong,Fangfang Ding,Yanan Jin,Chi Li,Xiang Lin,Shuang Lin

Self-assembly of nanocrystals into a macroscopic 3D superlattice has emerged as a promising nanostructure due to its collective optical and electrical properties. In this work, a macroscale supercrystal was constructed under constant temperature and humidity with an ultrasmooth Au nanosphere (NS) as a building block synthesized by a facile route. In particular, a reproducible and facile strategy was developed to fabricate highly spherical Au NSs with nanoscale size tenability. Importantly, this method does not require a syringe pump and breaks the limitation of instrumentation for the synthesis of Au NS, significantly contributing to the promotion and popularization of Au NSs. Meanwhile, an operable and cost-effective droplet slow evaporation self-assembly approach was applied to form a homogeneous 3D superlattice array against coffee rings with an enhancement factor as high as 1.37 × 108 verified by FDTD simulation results. Furthermore, integrating a convolutional neural network (CNN) model with the ultrasensitive 3D superlattice SERS platform, the precise and wide-range concentration prediction of the pesticide thiram in soil was successfully demonstrated, breaking the limitation of high-concentration saturation in the conventional concentration–intensity fitting curve. Consequently, this innovative Au NS 3D supercrystal facilitates the fabrication of novel nanoassemblies with ideal plasmonic functions for extensive applications in the fields of food safety, environment, medicine, and biology.

CAS / MDL: 7778-80-5
研究领域: 纳米材料科学 · 食品安全 · 环境科学 · 机器学习应用
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FOOD CHEMISTRY · 2025 · IF 9.8

Smartphone-assisted portable swabs for thiram specific analysis based on target-regulated CuWO4 nanozyme activity combined with sample pretreatment

Jia Wu,Huimei Liang,Shulan Zeng,Shulin Zhao,Fanggui Ye

Pesticide residues pose significant risks to consumer health. Therefore, it is essential to develop convenient and practical detection methods. Nanozyme colorimetric sensing is widely used for pesticide detection. However, improving its sensitivity and selectivity remains a major challenge. In this study, a smartphone-assisted portable test swab fabricated using CuWO 4 as the extractant, combined with solid-phase extraction (SPE), was designed for the colorimetric detection of thiram (THR). Based on the specific binding between the Cu sites in CuWO 4 and THR, interference was eliminated after the SPE to improve selectivity. Moreover, the sensitivity improved after SPE enrichment. Additionally, THR enhanced the peroxidase-like activity of CuWO 4 , whereas tungsten as a co-catalyst further boosted the nanozyme activity, thereby improving the detection sensitivity (limit of detection: 19 nM). The experimental results demonstrate that this method exhibits high stability and good selectivity, with recoveries in real samples ranging from 90.8 % to 112.4 %.

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 · 2025 · IF 4.6

Highly SERS active composite of silver nanospheres-decorated Ag nanostar/ZIF-8 for determination of diquat and thiram residues

Wei Zhang,Kuang Luo,Wenjie Chen,Min Chen,Ning Cai,Jumei Li

In surface-enhanced Raman scattering (SERS) measurements, the creation of “hot spots” and the effective concentration of analytes in these areas are crucial for enhancing detection sensitivity. In this work, a novel composite with highly SERS activity, Ag nanospheres decorated Ag nanostar/ZIF-8 composite (Ag NS/ZIF-8/Ag) was achieved via first coating the Ag nanostars with the metal-organic framework ZIF-8, known for its strong molecular adsorption capabilities, followed by the electrostatic self-assembly of Ag nanospheres. The composites produce numerous hotspots due to the abundant plasmonic nanogaps, including the interstitial space between the Ag nanostar and Ag nanospheres, as well as internanogaps between neighboring Ag nanospheres, resulting in outstanding SERS performance. It was successfully applied for the quantitative and simultaneous detection of diquat and thiram in fruit juice, achieving detection limits of 5.0 × 10 −8  mol/L and 1 × 10 −8  mol/L, respectively, with recovery rates ranging from 86.6 % to 118.4 %. Notably, under UV light exposure, the composite was able to degrade pesticides efficiently within 80 min. Additionally, its reusability was demonstrated by sustaining strong SERS activity over five continuous detection cycles. These results emphasize the capability of Ag NS/ZIF-8/Ag composites for sensitive pesticide detection via SERS.

研究领域: 分析化学 · 纳米技术 · 表面科学 · 环境监测 · 材料科学
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Journal of Materials Chemistry B · 2025 · IF 5.7

Smartphone-integrated colorimetric and fluorometric sensor based on copper-doped carbon dots for visual and rapid detection of thiram

Tingting Lei,Yating Xu,Yuanyu Tang,Siyi Tan,Jiafu Xiao,Shaojing Zhao,Minhuan Lan

Achieving highly selective visual detection of thiram is essential for ensuring food safety and environmental protection. Here, we developed a smartphone-integrated colorimetric and fluorometric dual-mode sensor based on copper-doped carbon dots (Cu-CDs). The Cu-CDs were synthesized via hydrothermal treatment of L-tryptophan and CuCl2·2H2O. These Cu-CDs exhibited two fluorescence emission peaks at 350 nm and 450 nm, with a fluorescence quantum yield of 20.8%. Cu2+ on the surface of the Cu-CDs could selectively bind to thiram to form a Cu2+-thiram complex, which quenched the fluorescence at 450 nm of Cu-CDs via the inner filter effect and dynamic quenching effect. In contrast, the fluorescence at 350 nm was changed slightly. The color of the solution was changed from colorless to yellow. These changes allowed for a fluorometric and colorimetric dual-mode optical response. The proposed sensor possessed high sensitivity and selectivity and demonstrated reliable performance in real water samples. Its integration with a smartphone further enabled convenient, on-site detection. This work presented a robust and cost-effective strategy for monitoring thiram in applications related to food safety and environmental protection.

研究领域: 分析化学 · 食品安全 · 环境监测 · 纳米生物技术 · 传感器开发
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FOOD CHEMISTRY · 2020 · IF 6.306

Bimetallic core shelled nanoparticles (Au@AgNPs) for rapid detection of thiram and dicyandiamide contaminants in liquid milk using SERS

Abid Hussain,Da-Wen Sun,Hongbin Pu

Existing methods for contaminants detection in liquid milk are complex, requires chemicals and time-consuming experimental procedure. In this study, SERS based on bimetallic core shelled nanoparticles was employed for simultaneous and fast detection of thiram and dicyandiamide (DCD) in the milk. Spectra ranging from 400 to 1700 cm −1 were selected to examine thiram (0.5, 1, 2, 5 and 10 ppm) and DCD (20, 40, 80,160 and 320 ppm), by employing 28 nm gold cores and silver-shell thickness of 8 nm. A strong peak at 1379 cm −1 was ascribed to thiram with LOD of 0.21 ppm and R 2 of 0.9896, whereas a band at 929 cm −1 was associated with DCD, delivering LOD of 14.88 ppm and R 2 of 0.9956. The proposed method could achieve results within 34 min and this ecofriendly method can be further employed for simultaneous and rapid screening of other accidental contaminants in milk.

研究领域: 分析化学 · 食品科学 · 环境科学
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FOOD CHEMISTRY · 2022 · IF 9.231

High-performance homogeneous carboxymethylcellulose-stabilized Au@Ag NRs-CMC surface-enhanced Raman scattering chip for thiram detection in fruits

Bingxue Hu,Da-Wen Sun,Hongbin Pu,Zhibin Huang

Cellulose material holds considerable promise for effective surface-enhanced Raman scattering (SERS) substrate construction due to its extensive availability, chemically modifying capacity, ease of manufacture, high flexibility and low optical activity. A large-area, high-sensitivity, stable and uniform Au@Ag nanorods (NRs)-CMC substrate was successfully developed via electrostatic repulsion by using negatively-charged core–shell Au@Ag NRs as SERS active plasmonic nanomaterial, combined with negatively-charged carboxymethylcellulose (CMC) hydrogel for nanoparticles stabilization, homodisperse and protection. The obtained Au@Ag NRs-CMC substrate showed excellent sensitivity for the detection of thiram residues in fruits containing low and abundant pigment interferents, such as apples and blueberries, with detection limits of 58 and 78 ppb, respectively. Additionally, it retained more than 80% SERS performance after storage for 9 months under ambient conditions, demonstrating its great potential in facilitating the commercialization of cellulose-based SERS technology for cost-effective detection of food contaminants with advantages of facile preparation procedure, uniformity, reproducibility and long-term stability.

研究领域: 材料科学 · 分析化学 · 食品安全 · 纳米技术
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FOOD CHEMISTRY · 2023 · IF 8.8

Inner filter effect-based upconversion nanosensor for rapid detection of thiram pesticides using upconversion nanoparticles and dithizone–cadmium complexes

Shuhua Li,Jizhong Wu,Shen Zhang,Tianhui Jiao,Jie Wei,Xiaomei Chen,Qingmin Chen,Quansheng Chen

Herein, we propose a method for detecting thiram based on the fluorescence inner filter effect using upconversion nanoparticles and dithizone–cadmium complexes (DZ-Cd 2+ ). The ultraviolet absorption of DZ-Cd 2+ was in the range of 480–600 nm under alkaline conditions, resulting in fluorescence quenching of the nanoparticles at 540 nm. Thiram had a stronger coordination effect with Cd 2+ than dithizone ; thus, more thiram–cadmium complex (T-Cd 2+ ) formed when thiram was added, leading to fluorescence recovery at 540 nm. The standard thiram curve was found to have a detection limit of 6.75 ng/mL in the linear range of 0.01–1000 µg/mL. In addition, high-performance liquid chromatography results for detecting thiram in apple samples revealed good application performance. The results demonstrate that the developed method has great potential to detect thiram residues in food.

研究领域: 分析化学 · 纳米技术 · 环境科学 · 食品安全
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ANALYST · 2023 ·Vol. 148 ·期 21 ·5435-5444 · IF 4.2

Ultrasensitive detection of thiram based on surface-enhanced Raman scattering via Au@Ag@Ag core/shell/shell bimetallic nanorods

Yuqiu Wang,Shuchang Liu,Yongjun Hu,Cuicui Fu,Weiqiang Chen

We developed a highly sensitive and stable SERS-active substrate of Au@Ag@Ag core/shell/shell nanorods, formed by encapsulating Au nanorods (Au NRs) into a bilayer silver shell with Raman reporter molecules (4-mercaptobenzoic acid (4-MBA) and thiram) in the shell–shell gap. The core/shell/shell nanostructures demonstrated a high SERS enhancement and easy assembly. The important role of the bilayer silver shell in boosting the SERS intensity and detection sensitivity was revealed by comparing the performances of the Au@Ag@4-MBA@Ag NRs, Au@Ag@4-MBA NRs, and Au@4-MBA NRs. The obtained Au@Ag@4-MBA@Ag NRs exhibited a significantly promoted SERS intensity, which could reach around 2.6 times and 240 times that of the Au@Ag@4-MBA NRs and Au@4-MBA NRs, where the enhancement factor was found to be strongly correlated with the shell thickness. The controllable plasma properties and SERS effect of the Au@Ag@4-MBA@Ag NRs could be optimized by adjusting the dose of silver nitrate. The SERS substrate comprising core/shell/shell nanorods was highly reproducible and stable (retaining 83% SERS intensity after one month). Moreover, the highly sensitive detection of the pesticide thiram with a detection limit as low as 1.74 × 10−9 M was achieved by taking advantage of the great SERS response of the core/shell/shell nanostructures, which was 1–2 orders of magnitude lower than for other SERS substrates. The developed SERS substrate could be readily extended to embed other target analytes into the core/shell/shell nanostructure for novel and sensitive detection. This study could enable fresh approaches toward next-generation ultrasensitive analyte detection.

研究领域: 分析化学 · 环境科学 · 材料科学
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FOOD CHEMISTRY · 2023 · IF 8.8

Au-Ag OHCs-based SERS sensor coupled with deep learning CNN algorithm to quantify thiram and pymetrozine in tea

Huanhuan Li,Xiaofeng Luo,Suleiman A. Haruna,Muhammad Zareef,Quansheng Chen,Zhen Ding,Yiyong Yan

Pesticide residue detection in food has become increasingly important. Herein, surface-enhanced Raman scattering (SERS) coupled with an intelligent algorithm was developed for the rapid and sensitive detection of pesticide residues in tea. By employing octahedral Cu 2 O templates, Au-Ag octahedral hollow cages (Au-Ag OHCs) were developed, which improved the surface plasma effect via rough edges and hollow inner structure, amplifying the Raman signals of pesticide molecules. Afterward, convolutional neural network (CNN), partial least squares (PLS), and extreme learning machine (ELM) algorithms were applied for the quantitative prediction of thiram and pymetrozine. CNN algorithms performed optimally for thiram and pymetrozine, with correlation values of 0.995 and 0.977 and detection limits (LOD) of 0.286 and 29 ppb, respectively. Accordingly, no significant difference ( P  greater than 0.05) was observed between the developed approach and HPLC in detecting tea samples. Hence, the proposed Au-Ag OHCs-based SERS technique could be utilized for quantifying thiram and pymetrozine in tea.

CAS / MDL: 50-81-7
研究领域: 分析化学 · 食品科学 · 机器学习
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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Recyclable Fe3O4@SiO2@PEI-DTC@Au-Ag nanocomposites as a SERS platform for sensitive detection of thiram on fruit surfaces

Tianna Wu,Shuo Yang,Wei Feng,Kaiyue Li,Yanru Li,Lili Wang,Rui Chen,Xiaodong Yang,Lulu Liu,Donglai Han

Equipped with surface-enhanced Raman scattering (SERS) effect and magnetic manipulation capacity, a new paradigm of recyclable SERS substrates based on Fe 3 O 4 nanoparticles (NPs) @SiO 2 @PEI-DTC adhesive layer @Au-Ag alloy quantum dots (QDs) were successfully prepared via engineering hydrothermal and seed deposition techniques. The SERS performance and uniformity of those substrates with different gold-silver (Au-Ag) weight ratios were evaluated by 4-aminothiophenol (4-ATP) molecules, revealing that the relative standard deviations (RSDs) of all substrates were less than 12 %, with the optimal SERS substrate achieving an enhancement factor (EF) of up to 1.39 × 10 5 . This phenomenon can be attributed to the magnetic core and plasmonic resonance properties of Au-Ag alloy QDs, which result in abundant interparticle hotspots in the Fe 3 O 4 @SiO 2 @PEI-DTC@Au-Ag (FSPAA) nanocomposites. Furthermore, the optimal FSPAA nanocomposite was employed as a SERS substrate for rapid non-destructive detection of thiram on fruit surfaces. The SERS signal intensity exhibited a robust manifesting a linear association with thiram concentration within the span of 1 × 10 −4 to 1 × 10 −9  M, and the minimal detectable concentration was 1.04 × 10 −10  M. The FSPAA core–shell nanocomposites exhibit high reusability and reliability and hold great promise for the practical applications in on-site assessment of food/environmental safety, as well as in spectroscopic identification of molecules adsorbed onto fruit surfaces.

CAS / MDL: 75-05-8 67-56-1 137-26-8
研究领域: 分析化学 · 食品安全 · 环境科学
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