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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Rapid detection of thiram on apple surfaces using a flexible and sticky SERS substrate coupled with chemometric methods

Sasa Peng,Zhilong Zhang,Jialin Guo,Tianchen Ma,Dongli Liu

In this paper, we developed a simple, rapid and sensitive method for detection of thiram on apple surfaces by surface enhance Raman spectroscopy (SERS) combined with chemometric methods. Ag NCs (Ag nanocubes) were firstly prepared by a sulfide-mediated polyol method. Then the flexible and adhesive Ag NCs@PDMS substrates were obtained by combining Ag NCs self-assembled films with PDMS films. Thiram residues on apple surfaces were transferred to the substrate using adhesion properties of Ag NCs@PDMS. And the SERS spectra were obtained by Raman microscopy and analyzed with chemometric methods. The results were analyzed by principal component analysis (PCA), for the limit of detection (LOD) of thriam on apple surfaces was 0.01 ppm. Principal component regression (PCR) and partial least squares regression (PLSR) were explored to develop quantitative models. Both models represented higher correlation coefficients (close to 1), but PLSR models exhibited better predictive performance, with the correlation coefficient was 0.99282 with a low root mean squared error of calibration (RMSEC = 0.438) and root mean squared error of validation (RMSECV = 0.597). The developed SERS method based on Ag NCs@PDMS substrate provide a simpler and more sensitive way to monitor thiram on apple surfaces.

研究领域: 分析化学 · 食品科学 · 农残检测
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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 46 ·期 15 ·7070-7077 · IF 3.925

Improved SERS performance of a silver triangular nanoparticle/TiO2 nanoarray heterostructure and its application for food additive detection

Zheng Lu,Wenxian Wei,Jingjing Yang,Qin Xu,Xiao-Ya Hu

A novel Ag triangle nanoparticles/TiO2 nanorod array (AgNTs/TNA) heterostructure was designed as a surface-enhanced Raman scattering (SERS) active substrate for the sensitive detection of Rhodamine 6G (R6G), Crystal Violet (CV), Malachite Green (MG) and Thiram in food samples. The heterostructure was constructed by simply stacking AgNTs and hydrothermally prepared rutile TNA together. On the surface of the heterostructure, the intensity of the Raman scattering intensity was about two times stronger compared with that on the AgNT substrate, using the R6G molecule as a probe. The AgNTs/TNA heterostructure could detect the SERS signal of R6G down to 10−10 M, showing excellent SERS performance. This platform has been successfully applied for the detection of CV and MG residues in crayfish. When irradiated with ultraviolet light, the SERS substrates can be cleaned and reused. This work demonstrated that the AgNTs/TNA metal–semiconductor heterostructure with high sensitivity, reproducibility and recyclability could provide an alternative reliable platform for food additive analysis.

CAS / MDL: 5593-70-4 9022-96-2
研究领域: 材料科学 · 分析化学 · 食品安全
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2026 ·Vol. 74 ·期 30 ·23935-23946 · IF 6.7

3D MOF Photonic Microspheres for Thiram SERS Fingerprint Detection

Li Ziqiang,Li Wei,Wang Ziyi,Chen Aiqin,Wang Yan,Lu Yuan,Muhammad Shan,Li Qianjin,Li Jianlin

The persistent migration of pesticides into aquatic ecosystems poses severe risks to environmental and public health. Monitoring pesticide residues along these migration pathways is therefore critical. Herein, we report the first application of a three-dimensional (3D) photonic microsphere surface-enhanced Raman spectroscopy (SERS) substrate (ZIF-8 PCMs-NH 2 @AuNPs) for the targeted adsorption and trace detection of the pesticide thiram. Synthesized via microfluidics, these hierarchically porous metal–organic framework microspheres overcome the poor reproducibility of conventional substrates by yielding highly uniform, stable “Raman hotspots” through surface-modified AuNPs. This structurally reproducible substrate achieved an enhancement factor of 8.4 × 10 7 . For thiram analysis, it demonstrated a broad linear range (0.05–10 μg/mL) and a low limit of detection (0.0137 μg/mL). Validated in real water samples, this platform provides a robust analytical tool for monitoring pesticide residues of the migration pathways (soil water–river water–tap water).

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2025 · IF 4.6

Paper-based SERS chips for the rapid detection of thiram

Wei Lin,Zesong Liu,Jingwen Zhang,Jinhua Xu,Fengfu Fu,Zhenyu Lin,Yiquan Chen,Yongqiang Dong

A simple one-pot method is developed to prepare positively charged aggregated silver nanoparticles (a-AgNPs). The obtained a-AgNPs show strong localized surface plasmon resonance (LSPR) absorption, whose wavelength can be easily tuned to match the commonly used lasers in surface enhanced Raman scattering (SERS). Furthermore, the obtained a-AgNPs can be easily fabricated into paper-based SERS chips by filtering against a negatively charged filter membrane. On the basis, a convenient SERS sensor has been developed for the detection of thiram using a 785 nm handheld Raman spectrometer.

CAS / MDL: 9002-98-6 7761-88-8
研究领域: 分析化学 · 环境科学 · 农业科学
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Small · 2026 · IF 11.8

Engineering a High-Affinity Monoclonal Antibody for Thiram Immunoassays and Protection

Linfang Lu,Kang Jiang,Na Li,Xiaoli Li,Lakshani Madushika,Sumei Ling,Shihua Wang

Thiram (TMTD), a widely used dithiocarbamate fungicide, provokes oxidative hepatotoxicity, yet practical strategies for its detection and immunoprotection remain scarce. Here we develop an antibody-enabled framework integrating detection, therapy, and prevention against TMTD. In the murine model, we characterized the dose-dependent hepatic injury induced by TMTD. Guided by rational C 3 /C 7 hapten design, we then generate a monoclonal antibody with high affinity. Building on this reagent, we create a portable immunodetection platform that couples Au nanoflowers with an Au/Ir@Zn/Cu-MOF probe, achieving an IC 50 of 0.246 µg/mL. To evaluate protective efficacy, we demonstrated that passive immunization conferred a clear time-dependent therapeutic benefit: mortality decreased from 37.5% in the TMTD-poisoned group to 0% with treatment at 15 or 30 min and to 12.5% with treatment at 60 min, while improving body weight, liver function, and oxidative-stress markers. Complementarily, active immunization with TMTD-BSA elicited high antibody titers and conferred complete survival with graded histopathological protection. Together, this work offers an integrated detection-to-protection strategy that effectively bridges immunodetection with immune protection against TMTD-induced toxicity.

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NANOTECHNOLOGY · 2021 ·Vol. 32 ·期 13 ·135301 · IF 3.874

Plasmonic structure with nanocavity cavities for SERS detection of pesticide thiram

Yongjun Zhang,Aonan Zhu,Yaxin Wang,Xiaolong Zhang

Excessive thiram residues in food have the potential to negatively impact human health. Hence, the development of a convenient and fast detection method is highly desirable. In this study, an efficient, repeatable, and sensitive surface-enhanced Raman scattering (SERS) active chip was manufactured via a low-cost colloidal lithography technique. The plasmonic structure was composed of a series of silver nanospheres and nanowires. Interestingly, this type structure creates a nanocavity space with a characteristic geometry generating a strong electromagnetic field coupling. The finite-different time-domain software was employed to simulate the electromagnetic field distribute on the nanocavity. Accordingly, SERS active chip that displays ultra-low concentration detection of thiram (10−11 M) was realized. Moreover, the excellent reproducibility of thiram (10−6 M) practical detection on an apple pericarp has great potential for application in food safety.

CAS / MDL: 137-26-8
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ACS Applied Nano Materials · 2019 · IF 0

Gold-Nanorod-Coated Capillaries for the SERS-Based Detection of Thiram

Yan Yu,Pan Zeng,Cheng Yang,Junyi Gong,Rongqing Liang,Qiongrong Ou,Shuyu Zhang

Surface-enhanced Raman scattering (SERS)-based capillary system is a promising route toward fast, real-time, and in-situ detection using a facile sampling process. Here, we demonstrate for the first time resonance-tunable SERS-active capillaries with high sensitivity, reproducibility, and stability. The strong signal consistency independent of measurement spots or storage time supports the long-term storage and signal tracking of analytes in practical use. The capillaries were successfully applied to the in-situ detection of pesticide residues, and the sampling process provides operation conveniency compared to conventional methods. These results indicate that our SERS-active capillaries have great potentials in fast in-situ detection for many practical applications.

研究领域: 分析化学 · 环境科学 · 食品安全
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SCIENCE OF THE TOTAL ENVIRONMENT · 2022 · IF 10.753

SERS detection of thiram using polyacrylamide hydrogel-enclosed gold nanoparticle aggregates

Kaiqiang Wang,Zilin Yue,Xiu Fang,Hong Lin,Lei Wang,Limin Cao,Jianxin Sui,Lei Ju

The development of sensitive and long-term signal-stable plasmonic substrates is vital to the in-field application of the surface-enhanced Raman spectroscopy (SERS) technique. The colloidal gold nanoparticles (AuNPs) system is commonly used in SERS detection, but it shows less signal stability and reproducibility due to the uncontrollable aggregation of nanoparticles by adding aggregating agents in SERS detection. In this study, we developed a new SERS detection platform based on polyacrylamide hydrogel-enclosed plasmonic gold nanoparticle aggregates (PAH-AuANs). In the system, the formation of PAH can rapidly stabilize the gold nanoparticle aggregates, avoiding the over-aggregation or precipitation of AuNPs. With the PAH concentration in the range of 6–10 % and AuNPs at the concentration of 0.2 nM, the resulting PAH-AuNAs platform exhibited both sensitive SERS activity and excellent SERS signal stability. The relative standard deviation of the 4-MBA probe SERS signal collected from the PAH-AuNAs platform was lower than 3 %. The limit of detection for the pesticide thiram was down to 0.38 μg/L with a handheld Raman spectrometer. Moreover, the procedure for preparing the PAH-AuNAs platform was easy to handle, offering a new strategy for in-field detection of environmental contaminants with a handheld Raman spectrometer in the future.

研究领域: 分析化学 · 环境科学 · 纳米技术
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2026 · IF 4.8

Gelatin‑silver nanocube composite hydrogel SERS substrate for sensitive detection of thiram

Rongmao Qiu,Yimin Zeng,Yiming Chen,Shuting Huang,Binghua Luo,Dechan Lu,Kui Huang

Surface-enhanced Raman scattering (SERS) is a powerful tool for rapid on-site detection of pesticide residues, but its performance heavily relies on the substrate. Herein, a gelatin‑silver nanocube (Ag NC) composite hydrogel SERS substrate was developed via mild EDC-NHS crosslinking coupled with low-temperature gelation. The three-dimensional porous hydrogel efficiently enriches target molecules, while the sharp edges of Ag NCs generate abundant electromagnetic hotspots. Using rhodamine 6G as a probe, the optimized substrate (20% gelatin, Ag NC/gelatin volume ratio 3:1) exhibited good uniformity, reproducibility, and stability. For thiram detection, a linear response was obtained from 10 −4 to 10 −7  M with a limit of detection (LOD) of 4.45 × 10 −8  M in standard solution. Practical applicability was demonstrated in orange juice, where thiram was detected down to 1.0 × 10 −6  M (LOD = 4.78 × 10 −7  M) with recoveries of 96.9–97.9%. This work provides a gelatin-based, stable and sensitive SERS platform for food safety monitoring.

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JOURNAL OF PHYSICS D-APPLIED PHYSICS · 2023 ·Vol. 56 ·期 5 ·055302 · IF 3.4

Ag@ZIF-67 nanocomposites for ultra-sensitive SERS detection to thiram molecules

Yangtao Yuan,Lei Gao,Yuanyuan Luo,Jiajia Mi,Zhenyu Cao,Man Wang,Jianping Shi,Guotao Duan

Surface-enhanced Raman scattering technique has become a powerful tool for detecting trace targets in the field of food-safety. However, it is a challenge to regulate the hot spots of the detection substrate and its interaction with target molecules for the enhancement of SERS activity. Herein, we reported the high performance SERS substrate based on Ag@ZIF-67 nanocomposite with sugar-coated haws like structure. It was found that the coverage of ZIF-67 particles on the surface of Ag nanowires can adjust the SERS ability of detection substrate. Compared with pure Ag nanowires, functionalized Ag nanowires exhibit outstanding SERS activity with good stability and uniformity. The detection limit of crystal violet and thiram can be as low as 10−10 M and 10−8 M, respectively. After 35 d, the SERS activity remains basically unchanged. Furthermore, it also has excellent SERS response to 5 \times 10−5 M thiram residues on the surface of vegetables. Such high SERS activity can be attributed to the enrichment and screening molecular effect of porous ZIF-67 nanoparticles, and the surface plasmon resonance effect of Ag nanowires. This work provides a simple strategy for the on-site detection of pesticide residues in the actual applications.

研究领域: 分析化学 · 食品安全 · 材料科学
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Food Bioscience · 2024 · IF 4.8

Lotus leaf-inspired biomimetic SERS substrate for detection of thiram on apple

Shunqian Zhuang,Jun Cheng,Songting Chen,Yuliang Li,Dazhi Ding,Zhilong Yu,Yunfei Xie

Lotus leaf is a super-hydrophobic material found in nature. Drawing inspiration from the micro-nano structure of lotus leaf surface, a hybrid surface-enhanced Raman spectroscopy (SERS) substrate owning both hydrophobic and hydrophilic properties was developed. The biomimetic part, which was fabricated by replicating the surface structure of lotus leaf using polydimethylsiloxane, exhibited a hydrophobic surface with a contact angle of 150.3°. Meanwhile, silver nanoparticles-coated filter paper was assembled on the top of the biomimetic part to render hydrophilic regions for SERS detection. Silver nanoparticles on the surface of filter paper owned a size of approximately 70–80 nm with an interval of about 5–10 nm. The hydrophobic/hydrophobic hybrid regions on the substrate significantly enhanced Raman signals of rhodamine 6g with mitigated coffee ring effects, showing a limit of detection low to 10 −10  M. Notably, the limit of detection of this technique for thiram on apple surface reached 0.5 ng/cm 2 , which was lower than the reported methods. The prepared substrate displayed exceptional uniformity and stability, with an RSD value of 7.21% calculated based upon 30 randomly selected Raman signals, and experienced a decrease in signal by only 29.7% after 30-d storage. This biomimetic substrate can be utilized for batch detection of pesticide residues on fresh produce with high sensitivity, thereby owning great potential for application as a rapid detection tool for food safety.

CAS / MDL: 78560-45-9 989-38-8
研究领域: 分析化学 · 食品安全 · 材料科学
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Journal of Food Measurement and Characterization · 2022 ·Vol. 16 ·期 2 ·1448-1458 · IF 3.006

Shell thickness-dependent Au@Ag nanorods aggregates for rapid detection of thiram

Pu Hongbin,Xu Fang,Wei Qingyi,Paliwal Jitendra,Sun Da-Wen

Plasmonic Au–Ag core–shell nanorods (Au@Ag NRs) have drawn great attention and are widely used in surface-enhanced Raman scattering (SERS) due to their distinctive local surface plasmon resonance peculiarities. To optimize the thickness of the Ag shell, the electromagnetic field distribution of Au@Ag NRs was firstly simulated using the Radiofrequency module of COMSOL. Then, Au@Ag NRs with different shell thicknesses were prepared by coating different amounts of silver nitrate, and the Raman signal of the molecule of 4-mercaptobenzoic acid was measured to evaluate the SERS activity of the prepared Au@Ag NRs. The experimental results showed that the Au@Ag NRs with the shell thickness of 7.51 nm performed the best SERS effect. Finally, the optimized Au@Ag NRs were used to detect thiram solution and a low limit of detection of 0.003 mg/L was achieved, indicating that the optimized Au@Ag NRs might be a promising substrate for pesticide residues detection.

研究领域: 纳米技术 · 分析化学 · 材料科学
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