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FOOD CHEMISTRY · 2023 · IF 8.8

High-throughput, highly sensitive and rapid SERS detection of Escherichia coli O157:H7 using aptamer-modified Au@macroporous silica magnetic photonic microsphere array

Xiu Wang,Wei Li,Shijie Dai,Menghua Dou,Saisai Jiao,Jing Yang,Weiwei Li,Ya Su,Qianjin Li,Jianlin Li

The aim of this research was to develop a simple, rapid, sensitive, high-throughput detection method for foodborne Escherichia coli (E. coli) O157:H7 based on the aptamer-modified gold nanoparticles@macroporous magnetic silica photonic microsphere (Au@MMSPM). Such Au@MMSPM array system for E. coli O157:H7 not only integrated sample pretreatment with rapid detection, but also showed highly enhanced effect to develop a highly sensitive SERS assay. The established SERS assay platform gave a wide linear detection range (10–10 6 CFU/mL) and low limit of detection (2.20 CFU/mL) for E. coli O157:H7. The whole analysis time including sample pretreatment and detection was 110 min. This SERS-based assay platform provided a new high-throughput, highly sensitive and fast detection technology for monitoring E. coli O157:H7 in real samples from the fields of food industry, medicine and environment.

CAS / MDL: 69-78-3 1317-61-9
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FOOD CHEMISTRY · 2023 · IF 8.8

Convenient self-assembled PDADMAC/PSS/Au@Ag NRs filter paper for swift SERS evaluate of non-systemic pesticides on fruit and vegetable surfaces

Zhiyang Chen,Yue Sun,Jiyong Shi,Wen Zhang,Xinai Zhang,Xiaowei Hang,Zhihua Li,Xiaobo Zou

The goal of food safety supervision is to directly identify the pesticide residues on the surface of fruits and vegetables. This study proposed to develop a facile, non-destructive, and sensitive method based on surface-enhanced Raman scattering (SERS) to detect non-systemic pesticides on the surface of fruits and vegetables. The composite material was prepared by loading CTAB guided Au@Ag NRs with positive charge onto filter paper which was modified with PDADMAC(+) and PSS(−) using electrostatic adsorption. Au@Ag NRs with bimetallic synergies were effectively adsorbed in the fiber grid to generate 3D SERS hotspots within a few microns of depth. The results showed that the 3D composite flexible substrate had a high SERS activity, great repeatability, and sensitivity when the method was utilized to detect 4-MBA, methyl-parathion, thiram and chlorpyrifos. Three kinds of non-systemic pesticides on the peel could be detected directly and quickly owing to the arbitrary bending of the substrate, demonstrating the efficiency of the SERS “paste-reading” method. The acquired findings demonstrated that PDADMAC/PSS/Au@Ag NRs composite filter paper had the potential to provide rapid feedback for in- situ analysis of pesticide residues on the surface of fruit and vegetable.

CAS / MDL: 16961-25-4 16940-66-2
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MICROCHIMICA ACTA · 2023 ·Vol. 191 ·期 1 ·1-10 · IF 5.7

Ultra-sensitive detection of tumor necrosis factor alpha based on silver-coated gold core shell and magnetically separated recognition of SERS aptamer sensors

Nie Qingling,Zhang Bohan,Li Rong,Yang Yixuan,Ren Junjie,Qiu Liting,Lu Yudong,Zhu Lanjin,Shen Huiying,Liu Yunzhen,You Ruiyun

A highly sensitive tumor necrosis factor α (TNF-α) detection method based on a surface-enhanced Raman scattering (SERS) magnetic patch sensor is reported. Magnetic beads (MNPs) and core shells were used as the capture matrix and signaling probe, respectively. For this purpose, antibodies were immobilized on the surface of magnetic beads, and then Au@4-MBN@Ag core–shell structures coupled with aptamers and TNF-α antigen were added sequentially to form a sandwich immune complex. Quantitative analysis was performed by monitoring changes in the characteristic SERS signal intensity of the Raman reporter molecule 4-MBN. The results showed that the limit of detection (LOD) of the proposed method was 4.37 × 10 −15 mg·mL −1 with good linearity ( R 2 = 0.9918) over the concentration range 10 −12 to 10 −5 mg·mL −1 . Excellent assay accuracy was also demonstrated, with recoveries in the range 102% to 114%. Since all reactions occur in solution and are separated by magnetic adsorption of magnetic beads, this SERS-based immunoassay technique solves the kinetic problems of limited diffusion and difficult separation on solid substrates. The method is therefore expected to be a good clinical tool for the diagnosis of the inflammatory biomarker THF-α and in vivo inflammation screening. Graphical Abstract

CAS / MDL: 919-30-2
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VIBRATIONAL SPECTROSCOPY · 2023 · IF 2.5

Synthesis of recyclable SERS platform based on magnetic Fe3O4/mTiO2/Ag composites for photodegradation and identification of organic pollutants in different water samples

Xiaojun Wen,Jumei Li

In this study, we coatedmagnetic Fe 3 O 4 nanospheres with a crystalline mesoporous TiO 2 (mTiO 2 ) layer with photocatalytic activity, followed by the deposition of Ag nanoparticles as an outer layer through in-situ reduction of AgNO 3 to obtain multifunctional Fe 3 O 4 /mTiO 2 /Ag core-shell-shell structured composites. By adjusting the amount of AgNO 3 , we were able to precisely control the size and coverage of the Ag nanoparticles. To evaluate the surface-enhanced Raman spectroscopy (SERS) activity of the Fe 3 O 4 /mTiO 2 /Ag composites, we employed 4-mercaptobenzoic acid (4-MBA) as a model Raman reporter. The limit of detection (LOD) of 4-MBA was down to 10 −10 M. Moreover, for practical applications, we successfully detected methylene blue (MB) in different water samples, such as tap water and industrial wastewater, and both of systems presented an ultralow LOD of 10 −9 M. Notably, a strong linear relationship (R 2 ≥ 0.95) between the SERS intensities and the logarithmic concentration of MB was observed, highlighting the excellent quantitative sensing capabilities of these substrates. The Fe 3 O 4 /mTiO 2 /Ag composites also exhibited remarkable signal reproducibility and exceptional stability during storage. Additionally, these composites demonstrated promising photocatalytic property. In five consecutive cycles, we were able to efficiently detect MB by utilizing the composites' photocatalytic removal ability under UV irradiation , which was facilitated by simple magnetic separation. These findings hold significant importance for environmental safety and pollutant removal applications.

CAS / MDL: 1074-36-8 5593-70-4
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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

Paper-based 3D SERS immunoassay array based on self-assembly of AuNBPs@Ag nanorods for ultrasensitive and highly stable detection of α-fetoprotein

Kunfeng Xue,Bingyong Lin,Qiukai Tang,Yuanyuan Yao,Yueliang Wang,Lifen Chen,Zuguang Li,Yanbo Zeng,Lei Li,Longhua Guo

Establishing a simple, sensitive, and accurate α-fetoprotein (AFP) detection methods is of great significance for the early diagnosis of hepatocellular carcinoma (HCC). Surface-enhanced Raman spectroscopy (SERS) has been identified as one of the most promising techniques for clinical monitoring. However, accurate detection of AFP is still challenging due to the poor stability of SERS substrate and the low abundance of AFP in the early stages of HCC. Herein, we developed an ultrasensitive and highly stable paper-based 3D SERS immunoassay array for AFP detection, combining the superior advantages of self-assembled AuNBPs@Ag nanorods, filter paper, and sandwich immunoassay. In the immunoassay array, 4-mercaptobenzoic acid (4-MBA) linked to the secondary antibody was employed as the Raman reporter, while the array modified with antibodies was used to capture AFP. The SERS immunoassay array sensor exhibited a wide linear range (3 pg mL −1 to 10 µg mL −1 ), low detection limit (0.086 pg mL −1 ), good specificity, and high signal reproducibility (RSD < 5 %). Meanwhile, the sensor is further used for accurate detection of trace AFP in serum, which paves an avenue for the fabrication of SERS substrates with high stability and provides a new outlook for their application in the early diagnosis of cancer.

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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

Flexible silver ring SERS substrate array fabrication by vortex evaporation method and its application for high sensitive detection of sulfonamides residues in water

Xinqi Zheng,Zixi Huang,Pengran Guo,Wanzhu Zhou,Peishan Wu,Yanpin Zhao,Jingwei Xu,Jian Sun,Yongqian Lei

Flexible surface-enhanced Raman scattering (SERS) substrates have driven much attention in Raman detection of environmental pollutants due to their unique advantage of sensitivity, low-cost and fast sampling. However, it is still a high challenge for fabricating flexible SERS substrate with high reproducibility and sensitivity. In this study, we developed a novel silver nanoparticle assembly method based on vortex evaporation method to batch assemble multiple silver ring (SR) SERS substrate array on a parafilm. The flexible SR SERS substrates were uniformly covered with active silver nano-islands, which significantly improved the Raman signal intensity of the targets by 126 folds and showed 5 times Raman enhancement compared with the common SERS substrate by direct evaporation method, and also represented the unique bending response properties of flexible substrate. The Raman detection for sulfonamide residues in water with SR SERS substrate represented high sensitivity, which limits of detection for Sulfapyridine and Sulfacloropyridazine were 9.46 and 9.3 × 10 −8 mol/L, respectively. The quantitative relationships were obtained in wide linear range of 4 orders with good accuracy and stability. The flexible SR SERS substrate array can be large-scale prepared with good repeatability, stability, and low-cost, which has promising applications for trace contaminants detection in water environment.

CAS / MDL: 80-32-0 144-83-2
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Advanced Materials Interfaces · 2021 ·Vol. 8 ·期 12 ·2100412 · IF 6.147

From Dilute to Multiple Layers: Bottom-Up Self-Assembly of Rough Gold Nanorods as SERS Platform for Quantitative Detection of Thiram in Soil

Xinxin Li,Xiang Lin,Shuang Lin,Shijie Zhou,Guoqiang Fang,Haiyan Zhao,Li Wang,Shulin Cong

The nanoparticle density (PD) of the substrates is crucial for surface-enhanced Raman scattering (SERS) performance. Here, bottom-up SERS substrates based on rough gold nanorods (R-Au NRs) with different PD are fabricated and their SERS property are investigated. In particular, R-Au NRs are deposited on the Si wafer from sparse to dense through electrostatic interaction and from monolayer to multiple layers by interface self-assembly technique. It is found that the SERS intensity increases dramatically with increasing PD and remains almost unchanged when the PD increases to 241.22 counts µm −2 , and the limited penetration depth of laser is the reason for the intensity saturation. Additionally, similar results are observed in the smooth Au NRs substrates, re-confirming the PD-dependent SERS performance. Importantly, the SERS activity of R-Au NRs substrates is higher than smooth Au NRs substrates in each PD, indicating that R-Au NRs can produce stronger electromagnetic field enhancement, which is supported by the theoretical simulation results. Finally, it is demonstrated that the optimal SERS substrates can be effectively utilized for the quantitative measurement of thiram in soil. Briefly, the PD of substrates has a great impact on SERS activity, which offers an idea for the design of highly efficient SERS substrates.

CAS / MDL: 919-30-2
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ACS Sustainable Chemistry & Engineering · 2020 · IF 7.632

Quantitative SERS-Based Detection and Elimination of Mixed Hazardous Additives in Food Mediated by the Intrinsic Raman Signal of TiO2 and Magnetic Enrichment

Yiran Tian,Hongmei Liu,Ying Chen,Chenjie Gu,Guodong Wei,Tao Jiang

Sophisticated surface-enhanced Raman scattering (SERS)-active nanocomposites with both self-correction and cleaning capabilities provide new perspectives for the quantitative detection and degradation of hazardous molecules. In this work, a multifunctional GO-coated Fe3O4@TiO2@AuAg SERS substrate was developed. Attributed to the magnetic core, a relatively uniform substrate was induced by an external magnetic field and a sensitive SERS-based detection of trace mixed additives in foods was facilitated by electromagnetic enhancement from the well-modified Au/Ag binary nanoparticles in conjunction with the molecular enrichment ability of the GO. Particularly, the intrinsic Raman signal at 149 cm–1 of TiO2 was fully exploited to act as an intrinsic internal standard for the improvement of the quantitative level of such detection. Additionally, the efficient green elimination of these target molecules within 60 min was enabled by the multifunctional TiO2 layer. It is expected that this novel SERS substrate with both quantitative analytical and photocatalytic capability may extend to a broad application for detecting analytes in complex systems.

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RSC Advances · 2019 ·Vol. 9 ·期 18 ·10314-10319 · IF 3.049

One-pot synthesis of hollow hydrangea Au nanoparticles as a dual catalyst with SERS activity for in situ monitoring of a reduction reaction

Yazhou Qin,Yuxiang Lu,Wufan Pan,Dongdong Yu,Jianguang Zhou

The controlled synthesis of metallic nanomaterials has attracted the interest of many researchers due to their shape-dependent physical and chemical properties. However, most of the synthesized nanocrystals cannot be combined with spectroscopy to measure the reaction kinetics, thus limiting their use in monitoring the catalytic reaction process to elucidate its mechanism. As a powerful analytical tool, surface-enhanced Raman spectroscopy (SERS) can be used to achieve in situ monitoring of catalytic reactions by developing bifunctional metal nanocrystals with both SERS and catalytic activities. Herein, we have developed a simple one-pot synthesis method for the large-scale and size-controllable preparation of highly rough hydrangea Au hollow nanoparticles. The growth mechanism of flower-like Au hollow nanostructures was also discussed. The hollow nanostructure with a 3D hierarchical flower shell combines the advantages of hollow nanostructure and hierarchical nanostructure, which possess high SERS activity and good catalytic activity simultaneously. Furthermore, the hydrangea Au hollow crystals were used as a bifunctional nanocatalyst for in situ monitoring of the reduction reaction of 4-nitrothiophenol to the 4-aminothiophenol.

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Photonics Research · 2020 ·Vol. 8 ·期 4 ·548-563 · IF 6.099

SERS study on the synergistic effects of electric field enhancement and charge transfer in an Ag2S quantum dots/plasmonic bowtie nanoantenna composite system

Bin Wang,Chen Zhao,Huanyu Lu,Tingting Zou,Subhash C. Singh,Zhi Yu,Chaonan Yao,Xin Zheng,Jun Xing,Yuting Zou,Cunzhu Tong,Weili Yu,Bo Zhao,Chunlei Guo

Localized surface plasmon resonance (LSPR) of nanostructures and the interfacial charge transfer (CT) of semiconductor materials play essential roles in the study of optical and photoelectronic properties. In this paper, a composite substrate of Ag2S quantum dots (QDs) coated plasmonic Au bowtie nanoantenna (BNA) arrays with a metal–insulator–metal (MIM) configuration was built to study the synergistic effect of LSPR and interfacial CT using surface-enhanced Raman scattering (SERS) in the near-infrared (NIR) region. The Au BNA array structure with a large enhancement of the localized electric field (E-field) strongly enhanced the Raman signal of adsorbed p-aminothiophenol (PATP) probe molecules. Meanwhile, the broad enhanced spectral region was achieved owing to the coupling of LSPR. The as-prepared Au BNA array structure facilitated enhancements of the excitation as well as the emission of Raman signal simultaneously, which was established by finite-difference time-domain simulation. Moreover, Ag2S semiconductor QDs were introduced into the BNA/PATP system to further enhance Raman signals, which benefited from the interfacial CT resonance in the BNA/Ag2S-QDs/PATP system. As a result, the Raman signals of PATP in the BNA/Ag2S-QDs/PATP system were strongly enhanced under 785 nm laser excitation due to the synergistic effect of E-field enhancement and interfacial CT. Furthermore, the SERS polarization dependence effects of the BNA/Ag2S-QDs/PATP system were also investigated. The SERS spectra indicated that the polarization dependence of the substrate increased with decreasing polarization angles (θpola) of excitation from p-polarized (θpola=90°) excitation to s-polarized (θpola=0°) excitation. This study provides a strategy using the synergistic effect of interfacial CT and E-field enhancement for SERS applications and provides a guidance for the development of SERS study on semiconductor QD-based plasmonic substrates, and can be further extended to other material-nanostructure systems for various optoelectronic and sensing applications.

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APPLIED SURFACE SCIENCE · 2020 · IF 6.182

Recyclable label-free SERS-based immunoassay of PSA in human serum mediated by enhanced photocatalysis arising from Ag nanoparticles and external magnetic field

Yuanyuan Du,Hongmei Liu,Ying Chen,Yiran Tian,Xiaoling Zhang,Chenjie Gu,Tao Jiang,Jun Zhou

In the field of SERS-based immunoassay, the recyclable utilization of noble metal materials is essential for their practical application in clinical medicine. Herein, a kind of novel multifunctional Fe 3 O 4 @TiO 2 @Ag microparticles (MPs) was synthesized through a poly-step reaction, and then their feasibility for recyclable label-free SERS-based immunoassay of prostate specific antigen (PSA) was demonstrated. The photocatalytic efficiency of the Fe 3 O 4 @TiO 2 @Ag MPs was fully adjusted by tuning the thickness of the middle TiO 2 shell and the areal density of the outside Ag NPs. Particularly, the Fe 3 O 4 core played a critical role in further improving the photocatalytic activity under external magnetic field. Thereafter, the successfully photocatalytic degradation and recyclable detection of PSA in human serum was confirmed by the change of O 1s, N 1s, and C 1s signals in the XPS characterization and a limit of detection as low as 16.25 pg/mL was realized. Furthermore, the quantitative recyclable detection of PSA in clinical serum samples with prostate cancer was conducted, and the results are basically consistent with those of the traditional chemiluminescent immunoassay, showing small relative deviation less than or equal to 5.7%.

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ACS Sustainable Chemistry & Engineering · 2021 · IF 8.198

Construction of Reusable PMMA–Ag/g-C3N4/Ag Hybrid Substrates with Plasmonic-Enhanced Intrinsic Raman Signals for Quantitative SERS Detection and Green Degradation

Xiuting Li,Hongmei Liu,Ying Chen,Chenjie Gu,Guodong Wei,Jun Zhou,Tao Jiang

Pesticides and additives, extensively used in the raw agriculture samples and processed food, have attracted tremendous interests owing to their latent menace to the surroundings and human health. Herein, a rationally designed multifunctional polymethyl methacrylate-silver/graphite-like carbon nitride/silver (PMMA–Ag/g-C3N4/Ag) hybrid substrate with plasmonic-enhanced intrinsic Raman signals was exploited and served as a recyclable and quantitative surface-enhanced Raman scattering (SERS) sensor. Especially, the as-prepared flexible substrate with an electromagnetic enhancement factor of 1.64 × 106 could realize the sensitive monitoring and in-situ degradation of thiabendazole (TBZ) and carmine acid (CA) on apple or in applesauce with limits of detection as low as 2.29 × 10–6 and 6.76 × 10–5 mg/mL. Furthermore, heightened linear correlations with coefficients of 0.996 and 0.997 were accurately acquired using the film peak of PMMA as an internal standard. It was proved that the proposed sophisticated substrate may present attractive superior-in-practice multiplexed quantitative monitoring and facile decomposing of harmful molecules. The resulting recovery values distributed from 60.9 to 126% for the deeply processed foods that were decorated by 10–4 to 1 mg/mL CA together with TBZ.

CAS / MDL: 9002-98-6 7761-88-8
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