SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
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2026
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IF 4.8
Yuxuan Xin,Zixiao Yang,Rubing Liu,Yinan Gai,Wei Wang,Yongchao Lai
A dynamic ratiometric in-tube SPME-SERS platform was built for thiram detection. • Forced convection shortened adsorption equilibrium from ∼90 min to ∼300 s. • SCN − internal standard enabled ratiometric correction with RSD < 10%. • Direct analysis of environmental water achieved recoveries of 90.9%–108.5%. Surface-enhanced Raman spectroscopy (SERS) is a powerful tool for pesticide detection but is hindered in field applications by slow analyte mass transport and quantitative irreproducibility. Herein, we report an in-tube solid-phase microextraction-SERS (in-tube SPME-SERS) strategy that simultaneously overcomes these bottlenecks. A silver-nanoplate-decorated copper wire was synthesized via galvanic replacement, functionalized with thiocyanate (SCN − ) as a covalently bonded internal standard (IS), and assembled into a fused-silica capillary. Hydrodynamic flow compresses the diffusion boundary layer, accelerating the extraction equilibrium from ∼90 min (static mode) to ∼300 s. The SCN − internal standard (2136 cm −1 ) enables ratiometric correction ( I 1380 /I 2136 ) for thiram quantification, effectively compensating for substrate heterogeneity and instrumental drift. Mechanistic studies reveal a competitive adsorption process where thiram partially displaces SCN − , ensuring precise analyte-IS co-localization. This method exhibits excellent analytical performance for thiram, including a wide linear range (20–1000 nM), a low limit of detection (33.8 nM), and high reproducibility (RSD < 10%). Furthermore, direct analysis of surface and groundwater samples without pretreatment yields satisfactory recoveries (90.9%–108.5%). With robust 28-day stability, this ratiometric in-tube SPME-SERS platform provides a reliable, kit-based solution for on-site environmental monitoring. Download: Download high-res image (105KB) Download: Download full-size image
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JOURNAL OF PHYSICS D-APPLIED PHYSICS
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2025
·
IF 3.2
Hexing Ren,Yaxin Wang,Jiahong Wen,Fan Zhang,Chengxuan Tang,Xiqiang Zhong,Yongjun Zhang,Yuxia Wang,Renxian Gao,Kun Zhang,Fengyi Zhang,Rufei Cui,Xiaoyu Zhao
Nanosphere lithography enables tunable fabrication of Si nanoarrays (hexagons, stages, cones) on Si (100) by precisely controlling etching time. Specifically, the nanostage arrays, with their high surface area due to neck regions, can absorb more Ag nanoparticles (AgNPs), leading to superior SERS performance through the formation of hotspots. In addition, COMSOL simulations confirm plasmon coupling inter-particle, particle-film, and inter-structure. The linear detection of Thiram (0.05–50 ppm) remains stable within 120 days, meeting practical requirements for pesticide detection and showing potential for food safety applications.
研究领域:
分析化学
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食品安全
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纳米技术
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FOOD CHEMISTRY
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2025
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IF 9.8
Yunhai Chen,Xuecheng Zhu,Huilin Liu,Baoguo Sun
A dual-emission ratiometric sensing platform was developed for sensitive and selective detection of thiram, a toxic dithiocarbamate fungicide, by integrating fluorescence and room temperature phosphorescence (RTP) signals. The system employs boron-doped silane-functionalized carbon dots (RhB-CDs@SiO 2 @BA) with Rhodamine B (RhB) to establish Förster resonance energy transfer (FRET)-mediated dual emission at 440/570 nm (fluorescence) and 490/590 nm (phosphorescence). The Cu 2+ -thiram complex selectively quenched both signals via inner filter effect (IFE), enabling precise quantification of thiram within a linear range of 0.1–120 μM and achieving a detection limit of 0.056 μM. The sensor exhibited excellent selectivity for thiram in the presence of common pesticides and ions, while maintaining robust stability under thermal, UV, and long-term storage conditions. Validated in real food samples (pears, cabbages), the method exhibited recoveries of 85.72 %–121.27 % and the detection was achieved in less than 15 min. This work enabled rapid and efficient monitoring of thiram residues.
研究领域:
分析化学
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材料科学
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环境科学
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传感器
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纳米技术
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FOOD CHEMISTRY
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2026
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IF 9.8
Yunling Shao,Miao Wang,Jianpeng Zhang,Yongxin She,Zhen Cao,Guohua Zhang,Fen Jin,Jing Wang,A.M. Abd El-Aty
In this study, we constructed a peptide‑copper (peptide-Cu) mimetic enzyme for thiram detection. The enzyme mimics peroxidase-like activity (POD), which allows it to catalyze the oxidation of o -phenylenediamine (OPD) substrates in the presence of hydrogen peroxide (H₂O₂). Thiram can prevent the catalytic activity of peptide-Cu mimetic enzymes by surface blocking, inhibiting chromogenic substrate oxidation and facilitating the rapid detection of thiram. The inhibitory mechanism was elucidated through molecular dynamics (MD) simulations and density functional theory (DFT) calculations, revealing that thiram synergistically reduces the catalytic activity of the peptide-Cu mimetic enzyme by disrupting its structural stability and electronic properties. Thiram exhibited good linearity in the concentration range from 0.01 to 5 μg/mL, with a lowest limit of detection (LOD) of 0.048 μg/mL, and showed a good recovery range from 79.71% to 108.13% in real samples. This approach, based on peptide-metal complexes, offers a straightforward and affordable method for pesticide monitoring.
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FOOD CHEMISTRY
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2026
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IF 9.8
Weishen Zhou,Songrui Li,Hetong Wang,Huifeng Zhang,Qiong Jia
Thiram residue has drawn widespread attention due to its severe threat to the agricultural safety. Herein, a ratiometric fluorescence probe was designed for thiram detection based on glutathione capped zinc nanoclusters (GSH-ZnNCs) and o -phenylenediamine (OPD). OPD was oxidized by Ag + to produce 2, 3-diaminophenazine (DAP), and the fluorescence of GSH-ZnNCs was quenched by DAP through fluorescence resonance energy transfer (FRET) effect. When exposed to thiram, Ag + led to the cleavage of S S bond in thiram to form Ag + -dimethyl thiocarbamate complex, inhibiting the oxidation of OPD. Accordingly, specific thiram detection was constructed with GSH-ZnNCs. The ratiometric fluorescence value of lg( I 574 / I 442 ) decreased linearly with increasing thiram concentration, and the limit of detection 0.116 μM was achieved. Moreover, the convenient sensing of thiram was achieved by combining with a smartphone. Both the fluorescence and portable sensing strategies were applied to real food sample analysis, showing potential in thiram sensing in agricultural areas.
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MICROCHIMICA ACTA
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2020
·Vol. 187
·期 3
·1-8
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IF 6.232
Mei He,Shu Huawei,Lv Mengyu,Liu Wei,Wang Xuedong
Phenyl-modified graphitic carbon nitride nanosheets (Ph- g -C 3 N 4 NSs) were synthesized by a thermal copolymerization and ultrasonic exfoliation method. The Ph- g -C 3 N 4 NSs are used as a fluorescent assay for determination of thiram. The results of X-ray photoelectron spectroscopy, 13 C solid-state nuclear magnetic resonance and Fourier transform infrared spectra confirm that phenyl group is integrated into the heptazine network of g -C 3 N 4 . Compared to the g -C 3 N 4 NSs, the Ph- g -C 3 N 4 NSs show bigger stokes shift about 185 nm and higher fluorescence intensity. The fluorescence of Ph- g -C 3 N 4 NSs is quenched by Cu 2+ via the photo-induced electron transfer mechanism, which then recovers in the presence of thiram. The fluorescence restoring of Ph- g -C 3 N 4 NSs is correlated with the concentration of thiram. Under the optimized conditions, the fluorescent intensity of g -C 3 N 4 NSs at excitation/emission wavelengths of 310/455 nm give a linear range of 33.0–670 nM with detection limit of 9.90 nM. While fluorescent assay based on the Ph- g -C 3 N 4 NSs show the linear range of 6.70–1300 nM at excitation/emission wavelengths of 310/495 nm with detection limit of 2.01 nM.
Schematic representation of fluorescent “on-off-on” assay based on phenyl-modified graphitic carbon nitride nanosheets (Ph- g -C 3 N 4 NSs) for determination of thiram.
研究领域:
材料科学
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分析化学
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环境科学
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Small
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2024
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IF 13
Tao Yang,Jianping Zhou,Yongkang Wang,Ben Fan,Jing Qiao,Lixiang Chen,Xiaoyu Wang,Lingxiang Guo,Hong Yang,Quan Li
Surface-enhanced Raman scattering (SERS) is widely used in all kinds of detection due to its ultrahigh sensitivity and selectivity. Micromotors, when used as SERS sensors, or the so-called “hotspots on the fly”, can combine both controlled mobility and SERS sensing capacity, and are ideal for versatile in situ detection. In this work, mobile SERS sensors are successfully fabricated by growing gold nanospikes onto magnetic microsphere surfaces. These mobile micromotors can act as normal SERS sensors, characterized by the trace detection of thiram, a highly toxic fungicide. The detection limit can reach 0.1 n M , as good as most other noble metal deposited substrates. With significant magnetic gradient forces, separation of pathogenic bacteria from bulk solution is achieved once these magnetic micromotors bind with bacterial cells. Manipulated propulsion of micromotors, on the other hand, enables them to approach and contact pathogenic bacterial cells on command and further acquire Raman spectra under a controlled degree of contact, a capability never seen with passive sensors. The robotic SERS sensors have demonstrated unique sensing characteristics with controlled manipulations along with discriminative detection between bacterial species.
研究领域:
分析化学
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纳米技术
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生物医学工程
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环境科学
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ANALYST
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2024
·
IF 3.6
Yimeng Shi,Yan Zhu,Jiaojiao Sun,Huancai Yin,Jian Yin
Nowadays, trace detection of thiram is in urgent demand due to its widespread application in agriculture and significant harmful effects on public health. In this work, a three-dimensional (3D) sea cucumber-like flexible porous surface-enhanced Raman scattering (SERS) substrate composed of a poly(vinylidene fluoride) (PVDF) membrane, ZnO nanorods, gold films, and Ag nanoparticles (Ag/Au/ZnO/P) has been established for the highly sensitive detection of thiram. The substrate takes advantage of the 3D morphology of the Ag/Au/ZnO system on a flexible porous PVDF membrane to produce abundant plasmonic hot spots. Meanwhile, the employment of an AgNPs/Au shell system combined the benefits of both gold and silver metals, thus guaranteeing stable and sensitive detection. With 4-mercaptobenzoic acid (4-MBA) as a probe molecule, the Ag/Au/ZnO/P substrate exhibited excellent linear detection in the range of 10−11–10−5 M, with a correlation coefficient (R2) of 0.99 and an enhancement cofactor of 7.09 × 107. The substrate exhibited excellent uniformity with a related standard deviation (RSD) value of 3.82% and demonstrated high stability during a 15 d-storage test. In addition, the substrate could detect thiram in an aqueous solution at concentrations as low as 10−10 M with excellent selectivity. Meanwhile, thiram on the surface of apple peel could be easily detected by the Ag/Au/ZnO/P substrate with the “paste-and-peel” method in less than 10 s, and the detection limit could be as low as 0.48 ng cm−2. Overall, the remarkable performance of the Ag/Au/ZnO/P SERS substrate demonstrated its great potential for the environmental monitoring of thiram.
研究领域:
分析化学
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环境科学
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材料科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2026
·
IF 9.6
Bing Yang,Jiacheng Ding,Yandong Che,Xu Wang,Lingru Kong,Tõnu Pullerits,Peng Song,Yanqiu Yang
Surface-enhanced Raman scattering (SERS) has emerged as a powerful technique for the rapid and sensitive detection of pesticide residues, particularly targeted pesticides of concern in food safety. However, hotspot intensification strategies in hydrogel-based SERS substrates that rely on solvent-exchange-induced shrinkage often suffer from concomitant analyte loss, thereby limiting detection reliability. Herein, an interface-engineered Ag-PAM-GO hydrogel was developed by integrating graphene oxide (GO) into a polyacrylamide (PAM) network to simultaneously achieve structural regulation and interfacial interactions. The incorporation of GO tailors the pore architecture and promotes coordination-driven Ag + enrichment together with confined in situ nanoparticle growth, enabling the uniform generation of plasmonic hotspots. Meanwhile, solvent-exchange-induced volumetric shrinkage effectively increases hotspot density, leading to an enhanced electromagnetic (EM) effect. Focusing on thiram, a widely used dithiocarbamate fungicide, the proposed substrate achieves ultrasensitive detection with a limit of detection of 7.12 × 10 −4 mg/L, while maintaining excellent signal uniformity and reproducibility. Interfacial Lewis acid-base interactions and hydrogen bonding cooperatively drive the preferential retention and local enrichment of thiram molecules during solvent exchange. Density functional theory calculations further revealed pronounced charge-transfer (CT) characteristics, confirming the contribution of the CT mechanism, while the increased adsorption energy supported strengthened molecule−substrate interactions. Benefiting from the synergistic interplay between the EM and CT mechanisms, the developed platform enables the reliable detection of thiram residues in fruit juices as well as on curved fruit surfaces, providing an effective strategy for the rational design of high-performance flexible SERS substrates for selective thiram residue detection. Download: Download high-res image (172KB) Download: Download full-size image
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Analytical Methods
·
2026
·
IF 3
Nan Wang,Jing Wang,Hongfei Liu,Ruxi Huang,Jun Lu,Duo Lin
Pesticide residue contamination poses a significant threat to food safety and public health, necessitating the development of rapid and accurate on-site detection technologies. Herein, we report a flexible surface-enhanced Raman spectroscopy (SERS)-based tape fabricated through a three-phase liquid interface self-assembly approach, which integrates a paper-based substrate with uniformly deposited silver nanoparticles (AgNPs) and a commercially available adhesive tape. The developed platform demonstrates high sensitivity for two commonly used pesticides-thiram and thiabendazole (TBZ), with detection limits substantially lower than the national maximum residue limits (MRLs). The pre-immobilization of AgNPs on the paper matrix effectively addresses the nanoparticle detachment issue inherent to conventional tape-based methods. Using portable Raman spectrometers, the system features two operational modes: (1) a "paste-and-peel" mode for nondestructive sampling of pesticide residues from fruit/vegetable surfaces, and (2) a direct-drop mode for rapid analysis of liquid samples such as fruit juices. This work presents a reliable tool for on-site monitoring of agricultural product safety and demonstrates promising potential for food safety applications.
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Plasmonics
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2025
·
IF 4.3
Guo Jingtong,Ma Xiaodi,Song Wenjing,Yu Long
This study develops a novel, eco-friendly Surface Enhanced Raman Scattering (SERS) substrate, PDA-MMT/Au@Ag NPs, for ultrasensitive thiram (TRM) detection and pesticide screening. The substrate integrates polydopamine-functionalized montmorillonite (PDA-MMT) with Au@Ag core–shell nanoparticles synthesized via solvent-free photoreduction. MMT enriches analytes and prevents nanoparticle aggregation, while Au@Ag NPs generate high-density plasmonic hotspots. This dual synergy enables exceptional performance: a TRM detection limit of 1.34 × 10⁻⁹ M in solution (far below the FDA limit), with high uniformity (RSD = 9.54%) and stability (> 28 days). The substrate also demonstrates versatility for dyes (R6G, CV, NBA) and other pesticides. Optimization confirmed 30 min UV irradiation and a 1:10 MMT-to-Au@Ag volume ratio as ideal parameters. Characterization by TEM, XRD, XPS, and UV–vis validated the successful synthesis and core–shell structure. Compared to existing SERS platforms, this substrate offers superior sensitivity, reduced noble metal usage, and simpler, chemical-reductant-free fabrication, making it promising for on-site food safety and environmental monitoring.
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2017
·
IF 2.536
Jian Zhu,Mei-Jin Liu,Jian-Jun Li,Xin Li,Jun-Wu Zhao
The surface-enhanced Raman scattering (SERS) activity of multi-branched gold nanostars with fractal structure has been investigated for trace detection of pesticide thiram . Raman spectrum results show that the gold nanostars substrate can produce about 10 2 fold stronger signal than the thiram alone with the thiram concentration increase of 10 3 times and 1.4 fold stronger signal than the gold nanostars without fractal feature. In the detection procedure, the most prominent SERS peak at 1376 cm − 1 has been chosen to characterize and quantify the concentration of thiram. Experimental results indicate this Raman substrate based on fractal gold nanostars exhibits excellent selective probing performance for thiram with a detection limit as low as 10 − 10 M in solution and 0.24 ng/cm 2 in apple peels. Interference experiment results show that the effects from the interfering pesticides could be neglected in the detection procedure. Therefore, the gold nanostars as a SERS substrate have excellent sensitivity and selectivity.
研究领域:
分析化学
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纳米技术
·
环境科学
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