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MICROCHEMICAL JOURNAL · 2022 · IF 5.304

Gold nanoparticles and nitrogen-doped carbon dots based fluorescent nanosensor for ultrasensitive detection of thiram in hawthorn

Lizhu Fu,Yujiao Hou,Haipeng Guo,Chang Liu,Ying Li,Boyu Jia,Lidong Zhou,Weijun Kong

Development of highly efficient and sensitive methods for trace detection of pesticides in foods is in great need. In this study, a signal “on–off-on” fluorescent nanosensor was proposed based on gold nanoparticles (AuNPs) and biomass derived nitrogen-doped carbon dots (N-CDs) for accurate qualitation and quantitation of thiram in hawthorn. The water-soluble orange peel-derived N-CDs were obtained through a facile one-step microwave-assisted synthesis strategy. The fluorescence of biomass N-CDs could be effectively quenched by AuNPs through inner filter effect (IFE), and recovered when AuNPs were aggregated. In the presence of thiram, N-CDs specially bound with AuNPs through Au-S bonds, causing the aggregation of AuNPs with a visible color change from red to blue, accompanying with the release of N-CDs and a recovery of fluorescence. The restored fluorescence intensity was relevant with the added amount of thiram in a concentration-dependent manner for reliable quantitation. Under the optimized conditions, the newly-developed fluorescent nanosensor exhibited high selectivity for thiram out of other six interfering pesticides, as well as excellent sensitivity with an ultralow detection limit of 4.7 ng/mL and a wide detection range of 10–200 ng/mL. The practical application of the established nanosensor in the spiked hawthorn samples confirmed satisfactory recoveries of 102.22–107.57% with relative standard deviations (RSDs) lower than 5%. The results indicated the feasibility, practicality and wide application prospect of the proposed fluorescent nanosensor for thiram in foods and other commodities.

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

Bimetallic metal–organic frameworks-based ratiometric fluorescence sensor for the quantitative detection of thiram in fruits samples

Fuxiang Wang,Zuopeng Li,Hongping Jia,Chang-qing Miao,Runhua Lu,Sanbing Zhang,Zhiqiang Zhang

The identification of residual thiram (Tr) in foods is vital in view of its harmful effects on human health. Herein, a ratiometric fluorescence sensor ( I 435 / I 590 ) based on rhodamine B/NH 2 -MIL-53(Al 0.75 Fe 0.25 ) was constructed for the detection of Tr. Interestingly, the probe RhB/NH 2 -MIL-53(Bim) assisted by Cu 2+ could rapidly and sensitively recognize Tr with a low detection limit of 0.11 μg/mL in 10 min. The fluorescence sensing mechanism was investigated using fluorescence spectra, UV–Vis absorption spectra, the fluorescence lifetime and quantum yield. The results showed that the excellent sensing performance was attributed to fluorescence resonance energy transfer, electrostatic interaction, and photoinduced electron transfer. In addition, the practical application of this platform showed acceptable relative recoveries for Tr (84.03–107.81 %), and precisions were also achieved (relative standard deviation ≤ 8.69 %, n = 3). These results show that the presented herein can be applied to monitor the Tr content in real fruit samples.

CAS / MDL: 10312-55-7
研究领域: 分析化学 · 食品科学 · 材料科学
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Analytical Methods · 2023 ·Vol. 15 ·期 35 ·4533-4540 · IF 3.1

Silver decahedral nanoparticles with uniform and adjustable sizes for surface-enhanced Raman scattering-based thiram residue detection

Hongda Sun,Yu Tian,Jinping Wei,Wenli Wei,Zhichao Zhang,Shuang Han,Wenxin Niu

Surface-enhanced Raman scattering (SERS) has been widely used as a sensitive molecular spectroscopy technology in food safety detection. Precise morphology control of plasmonic nanoparticles for high sensitivity and high uniformity SERS substrates remains challenging. Herein, silver decahedral nanoparticles (AgDeNPs) with uniform and adjustable sizes were synthesized by a photochemical seed-mediated method and utilized as SERS substrates for pesticide residue detection. The SERS sensitivity was demonstrated by using 4-mercaptobenzoic acid (4-MBA) as a typical model molecule, and the limit of detection (LOD) reached 1.0 × 10−13 M. The pesticide residue detection of thiram in aqueous solution and on fruit peels was successfully realized; the LODs were 1.0 × 10−11 M and 0.96 ng cm−2, respectively, and SERS repeatability was also proved. Overall, size-tunable AgDeNPs show attractive SERS performances and are expected to hold potential application in sensitive food and environmental safety detection.

CAS / MDL: 7722-84-1 16940-66-2
研究领域: 食品安全检测 · 纳米技术 · 分析化学
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FOOD CHEMISTRY · 2026 · IF 10.4

Controllable synthesis of uniform chitosan hydrogel-based SERS substrates for rapid detection of thiram on various fruit surfaces

Jiechen Xu,Lei Ding,Jie Ao,Zilun Qiao,Qingchun Yin,Gaohao Tan,Long Wu,Shouxiang Jiang,Sihang Zhang

Rapid, ultrasensitive, and nondestructive detection of pesticide residues on fruit surfaces remains a significant challenge. Herein, we developed a series of flexible silver nanoparticles@chitosan hydrogel (AgNPs@CSHG) SERS substrates by a controllable in-situ growth strategy, creating uniformly distributed SERS hot spots through electrostatic interactions between silver ions and the hydroxyl/amino groups in chitosan molecules. Hydrophilic CSHG exhibits excellent adsorption and permeability properties, enabling effective enrichment of probe molecules within hotspot regions to further improve detection sensitivity. The optimal AgNPs-45@CSHG SERS substrate achieves a remarkable detection sensitivity of 10 −8  M and exceptional reproducibility (RSD = 8.14%) for 4-mercaptobenzoic acid (4-MBA). Importantly, the flexible and robust AgNPs@CSHG SERS substrates realize rapid, simple and nondestructive thiram detection at a concentration as low as 10 −7  M on fruit peel by a simple stick-and-read method. The flexible, ultrasensitive and nondestructive AgNPs@CSHG SERS substrate presents significant potential for applications in food safety monitoring.

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DYES AND PIGMENTS · 2026 · IF 3.9

A Broad-pH photozyme platform based on Mn, N co-doped carbon dots for colorimetric detection of thiram

Yating Xu,Tingting Lei,Chen Wang,Shaojing Zhao,Cheng Li,Minhuan Lan

Thiram, a widely used dithiocarbamate pesticide, can threaten ecological systems and human health through residual contamination. Here, manganese and nitrogen co-doped carbon dots (Mn, N-CDs) were harnessed as a photo-driven oxidase-like nanozyme to build a visual colorimetric assay for thiram. Under light irradiation, Mn, N-CDs can generate singlet oxygen ( 1 O 2 ) and superoxide (O 2 − ·) and maintain good photozyme activity over a broad pH range. The Mn, N-CDs/3,3′,5,5′-tetramethylbenzidine (TMB) mixture produces a blue oxidized product under illumination; after introducing thiram, the oxidation of TMB is suppressed because thiram consumes 1 O 2 and O 2 − ·, thereby producing a thiram concentration-dependent color-fading signal. Notably, extending the irradiation time enhances the analytical sensitivity by allowing the chromogenic reaction to approach a more stable readout. The proposed method can be coupled with smartphone-based RGB quantification to enable portable digital readout under natural light. In addition, satisfactory recoveries and repeatability were obtained in diverse real water samples. The proposed approach thus offers a feasible strategy for developing broad-pH-applicable, facile, and on-site colorimetric sensing for pesticide monitoring.

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Analytical Methods · 2025 · IF 2.6

Ni/Ag bimetallic nanoparticle-engineered Ti3C2Tx MXene composite as a SERS substrate for trace detection of thiram pesticide

Jinping Tang,Yuhai Wang,Chunxu Wang,Ziwei Yu,Jin Wang

Surface-enhanced Raman scattering (SERS) has emerged as a powerful analytical tool for trace molecular detection, enabling identification of target analytes through their characteristic vibrational fingerprints. Its high sensitivity, selectivity, and non-destructive detection capabilities make it extremely valuable in fields such as biological detection, food safety, and environmental detection. Currently, metal carbonitride (MXene) as an emerging two-dimensional material has become a hot topic in the field of SERS. In this work, by combining the advantages of bimetallic nanoparticles and MXene nanosheets, Ni/Ag nanoparticles with different proportions were modified on monolayer MXene nanosheets through chemical reduction and transmetallation reactions for the rapid detection of thiram. The evaluation of the SERS performance of the MXene–Ni/Ag composite substrate for the Raman reporter molecule mercaptobenzoic acid (MBA) demonstrates a high SERS performance factor (SPF) of 8.2 × 106, and a low detection limit of 10−10 M. Also, for the detection of the pesticide thiram, the substrate exhibits high sensitivity and reliable quantitative analysis capabilities, retaining detectable spectral features even at concentrations down to 10−9 M. Meanwhile, the substrate also exhibits a low relative standard deviation (RSD) value in reproducibility and maintains good stability over a certain period. Ni/Ag bimetallic nanoparticles provide high SERS activity, while MXene nanosheets effectively concentrate target molecules through their strong adsorption capacity. These results indicate that MXene–Ni/Ag composite substrates can serve as a highly effective SERS platform for sensitive and reliable environmental monitoring.

研究领域: 分析化学 · 纳米材料 · 环境监测 · 传感器 · 农药检测
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Journal of Materials Research and Technology-JMR&T · 2021 · IF 5.039

In-situ preparation of Ferrero® chocolate-like Cu2O@Ag microsphere as SERS substrate for detection of thiram

Chengli Yao,Xinna Gao,Xuan Liu,Yuhua Shen,Anjian Xie

It is a challenging and valuable work to synthesize surface enhanced Raman scattering (SERS) substrate with low cost and high performance by simple methods, and use it to detect pesticide residues in food. Here, Ferrero® chocolate-like Cu 2 O@Ag microspheres (FRC-Cu 2 O@Ag) were fabricated by a facile in-situ redox reaction. Cu 2 O directly acted as templates and reducing agents to induce the nucleation and growth of Ag nanoparticles on the microspheres surfaces. The prepared semiconductor-noble metal hybrids of Cu 2 O@Ag were utilized as SERS substrates to detect 4-mercaptobenzoic acid (4-MBA) and thiram molecules. The distinguished SERS effect was achieved when target molecules absorbed on the FRC-Cu 2 O@Ag composite. The substrate presented excellent sensitivity and reproducibility for the detection of 4-MBA and thiram with the limit of 10 −10 and 10 −9  M, respectively. Due to combining both advantages of electromagnetic enhancement of Ag metals and chemical enhancement of Cu 2 O semiconductors, the obtained FRC-Cu 2 O@Ag microspheres provided a SERS platform to conveniently detect molecules with thiol groups. When it was applied to detect thiram residues on apple peel and the detection limit was 1.2 × 10 −7  M, low than maximal residue limit (MRL) of 7 × 10 −6  M in fruit prescribed by the U.S. Environmental Protection Agency (EPA).

研究领域: 食品科学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2019 · IF 6.393

On-site monitoring of thiram via aggregation-induced emission enhancement of gold nanoclusters based on electronic-eye platform

Xu Zhao,Deshuai Kong,Rui Jin,Hongxia Li,Xu Yan,Fangmeng Liu,Peng Sun,Yuan Gao,Geyu Lu

The rapid and on-site monitoring of thiram is of great significance because the residue of thiram in agriculture has caused great contamination in environment and food, as well as threaten to the human health. Herein, we constructed a fluorometric strategy for on-site monitoring thiram via the aggregation-induced emission enhancement (AIEE) effect of glutathione-capped gold nanoclusters (GSH-AuNCs). The dissociated Ag + ions can effectively enhance the fluorescent emission intensity of GSH-AuNCs at 570 nm owing to the AIEE phenomenon. Upon the addition of thiram, the fluorescence enhancement effect was weakened due to the strong coordinative interaction between Ag + and thiram. By monitoring the signal change, the thiram residues were quantitatively analyzed with the detection limit of 0.05 μg mL −1 . Notably, a home-made electronic-eye (E-eye) system, containing of a test-strip and a smartphone, was constructed as a portable platform to recognize and quantitatively analyze thiram in 10 min on the basis of captured fluorescence signals from a test strip with immobilized probe by direct photographing, which provides a direct quantitative tool to identify pesticide. Taking advantage of user-friendliness, portability and simplicity, the E-eye system are expected to fulfill the demand for quantitative on-site testing of pesticide especially in resource-limited areas.

CAS / MDL: 70-18-8 137-26-8
研究领域: 环境科学 · 分析化学
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 7 ·1-9 · IF 5.479

A 3D spongy flexible nanosheet array for on-site recyclable swabbing extraction and subsequent SERS analysis of thiram

Wang Ying,Yu Xiaofei,Chang Yuhong,Gao Cuiling,Chen Jing,Zhang Xiaoli,Zhan Jinhua

A sponge inspired three dimensional flexible aluminum foil based ZnO nanosheet array substrate is described for use in real-world surface enhanced Raman spectroscopic detection. Gold and silver nanoparticles were employed to form numerous hot spots on uniformly grown ZnO nanosheets on the substrate. This flexible spongy substrate can extract analytes (such as the fungicide thiram) from various complex sample surfaces by physical swabbing. Specifically, this substrate was applied to detect thiram on the surface of fruits and vegetables. Non-destructive recycling detection with a relative standard deviation of 6.1% was accomplished by monitoring the characteristic Raman peak at 1382 cm −1 . This modified substrate has a low detection limit (0.2 ng cm −2 of thiram for apple and tomato), outstanding uniformity (relative standard deviation = 8.9%) and thermal stability (relative standard deviation = 0.9%). Schematic representation of using a aluminum foil modified with ZnO nanosheets as a flexible and recyclable substrate for SERS analysis of pollutants. The substrate can be cleaned after use by UV irradiation.

CAS / MDL: 1193-02-8 5970-45-6
研究领域: 分析化学 · 环境科学
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Journal of Nanomaterials · 2021 · IF 2.986

Cost-Effective Tween 80-Capped Copper Nanoparticles for Ultrasensitive Colorimetric Detection of Thiram Pesticide in Environmental Water Samples

Nguyen Tuan Anh,Ngo Xuan Dinh,Hoang Van Tuan,Tran Hung Thuan,Le Minh Tung,Van Phan Le,Doan Quang Tri,Anh-Tuan Le

Thiram plays a critical role in protecting fruits and vegetables from damage by various crop diseases, but its residues significantly affect the environment, such as soil and water pollution, and becoming a serious threat to human health. Herein, Tween 80-capped copper nanoparticles (Tween 80-CuNPs) were developed as a convenient and low-cost colorimetric probe for selective detection of thiram pesticide. In the presence of thiram, the color of Tween 80-capped CuNPs changed from dark brown to olive green and colorless at high thiram concentrations. The Tween 80-capped CuNPs-based colorimetric probe exhibited good selectivity and high sensitivity (LOD about 0.17 μM) with a high linearity level in the calibration range of 0.5–25 μM of thiram concentrations. The thiram limit of detection (LOD) of proposed sensor is lower than the maximum residue limit (MRL) regulated by the governments of EU and Vietnam. Moreover, the proposed sensor was successfully applied to determine thiram in tap water with percentage recovery of 98-107% and high repeatability (). The obtained results indicated that Tween 80-capped CuNPs would become a cost-effective sensing platform for ultrahigh-sensitive thiram determination in the environmental water samples.

CAS / MDL: 137-26-8
研究领域: 环境科学 · 分析化学 · 纳米技术
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Combining thin-film microextraction and surface enhanced Raman spectroscopy to sensitively detect thiram based on 3D silver nanonetworks

Huan Zhang,Pei Zeng,Qi Guan,Xianzai Yan,Lili Yu,Guoping Wu,Yanping Hong,Chunrong Wang

By coupling thin-film microextraction (TFME) with surface enhanced Raman scattering (SERS), a facile method was developed for the determination of thiram in the complex matrix (orange juice or grape peel). The substrate of TFME was made by self-assembling silver sol on the silicon wafer to form a three-dimensional (3D) silver nanonetwork structure, without adding any template, which was used for TFME and SERS detection, respectively. The substrate exhibits high reproducibility with a relative standard deviation of about 7.32 % in spot and spot SERS intensity. The SERS signal intensity at a shift of 1384 cm −1 and the thiram concentration showed good linearity in the range of 0.01–5 µg/L and the linear correlation coefficient was 0.9912. The detection limit for thiram was found to be 0.01 µg/L. The TFME-SERS method was applied for the determination of thiram in fruit juice and the results were obtained very well. Therefore, this method is expected to play a role in the detection of trace pollutants.

研究领域: 分析化学 · 环境科学
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Analytical Methods · 2023 ·Vol. 15 ·期 36 ·4645-4655 · IF 3.1

Surface-enhanced Raman scattering of a gold core–silver shell-sponge substrate for detection of thiram and diquat

Chao Sun,Li Ye,Lizheng Wang,Zhiming Hu,Jianjun Ding

Aiming at the difficulty of traditional pesticide sampling, a low-cost and convenient flexible surface enhanced Raman scattering (SERS) gold core–silver shell-sponge (Au–Ag-sponge) substrate was synthesized by chemical reduction. The SERS substrate consisted of Au–AgNPs and a melamine sponge. The sponge had a rich open pore structure, which could well “capture” Au–AgNPs, generating a large number of “hot spots”. The SERS enhancement activity of the flexible substrate was characterized with rhodamine 6G (R6G) Raman probe molecules. The substrate showed good activity to 10−12 M rhodamine 6G with an enhancement factor (EF) of 7.72 × 106. Applying this substrate to the qualitative and quantitative detection of pesticide residues, the results showed that the Raman intensity was well related to the concentration of pesticide solution with the range of 0.1–10 mg L−1 of thiram and 1–10 mg L−1 of diquat. Furthermore, the substrate was analyzed by finite difference time domain (FDTD) simulation and the results were in good agreement with the experimental results. The reason for the difference in Raman signals of pesticide molecules on the same substrate was the different binding modes of Au–AgNPs on the sponge. Finally, we pointed out the advantages of flexible substrates in the field of pesticide residues, as well as future opportunities and challenges.

研究领域: 分析化学 · 环境科学 · 农业科学
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