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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Insertable and reusable SERS sensors for rapid on-site quality control of fish and meat products

Binbin Zhou,Weihui Ou,Chenghao Zhao,Junda Shen,Guobin Zhang,Xianghu Tang,Zhiqin Deng,Guangyu Zhu,Yang Yang Li,Jian Lu

Surface-enhanced Raman spectrometry (SERS) is one of the most important on-site testing tools. However, it remains a great challenge for the SERS to achieve on-site safety evaluation for fish and meat products, due to their extremely complicated compositions of wide-ranging chemicals, the potential existence of unknown micro-organisms, and the difficulty to directly acquire spectra information from inside the product. Here, we report a convenient strategy for mass fabrication of a novel type of SERS sensors through electrochemical nanoetching of commercial Ag needles. The thus obtained SERS sensor features rich surface nanostructures of ultrahigh SERS sensitivity, making them highly compatible with low-cost portable Raman spectrometers to realize on-site detection. These sensors can be inserted into the products to read out the depth-profile information, e.g., from purine, proteins, and lipids. Unlike the conventional insertable SERS sensors that are coated with foreign plasmonic nanoparticles, the novel sensor possesses nano-carved plasmonic surface structures that are highly resistant to aggregation and materials loss, enabling much improved durability well suited for depth-profiling applications. Interestingly, these sensors can be repetitively regenerated by acid rinsing while maintain high enhancement effect. Instant detection of fish or meat spoilage at early stage is realized in a few minutes using the novel sensors reported here, demonstrating an attractive means for on-site food quality control in a rapid, low-cost, and convenient manner.

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SENSORS AND ACTUATORS B-CHEMICAL · 2019 · IF 6.393

Selective determination of dinitolmide and toltrazuril by surface-enhanced raman spectroscopy (SERS) using AgNPs as substrate

Di Shao,Shuyun Bi,Rui Zhao,Xiaoyue Sun,Xu Li,Jingfu Yu

Two sensitive surface-enhanced Raman spectroscopy (SERS) analytical methods for dinitolmide and toltrazuril were developed by silver nanoparticles (AgNPs). The dinitolmide and toltrazuril were determined in 0.0565 mol L −1 and 0.0847 mol L −1 NaOH solutions respectively. The enhancement factors (EF) were 1.76 × 10 5 for dinitolmide and 1.27 × 10 5 for toltrazuril. Under optimum conditions, the methods had good linear relationship in the concentration ranges of 0.30–33.30 nmol L −1 for dinitolmide ( I SERS  = 1522.52 c  + 27,890.46, c :nmol L −1 , R 2  = 0.998) and 0.30–66.70 nmol L −1 for toltrazuril ( I SERS  = 1334.29 c  + 46,347.83, c :nmol L −1 , R 2  = 0.999). The limits of detection (LOD) (S/N = 3) were 0.915 nmol L −1 for dinitolmide and 1.03 nmol L −1 for toltrazuril. The effects of interferences on the determinations of dinitolmide and toltrazuril were studied. These SERS methods were successfully used to measure the content of dinitolmide and toltrazuril in the duck and chicken samples. The relative standard deviation (RSD) for the detection of dinitolmide and toltrazuril samples could reach 1.45 % ( n  = 5). The recoveries were 95.67%–105.39% ( n  = 5) and 94.79%–99.44% ( n  = 5) for dinitolmide and toltrazuril system respectively.

CAS / MDL: 69004-03-1
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Food Analytical Methods · 2019 ·Vol. 12 ·期 5 ·1086-1091 · IF 2.413

Simultaneous Detection of Listeria monocytogenes and Salmonella typhimurium by a SERS-Based Lateral Flow Immunochromatographic Assay

Wu Zhengzong

Foodborne diseases arise from Listeria monocytogenes ( L. monocytogenes ) and Salmonella typhimurium ( S. typhimurium ) are global public health problems, influencing both developing and developed countries. Therefore, their rapid and accurate detection is of much concern in food safety and point-of-care diagnostics. In this study, a surface-enhanced Raman scattering (SERS)-based lateral flow assay (LFA) for simultaneous detection of them was developed. Under optimal conditions, the proposed assay showed good linear responses in the ranges of 10 2 –10 7 cfu/mL and 10 2 –10 7 cfu/mL with limits of detection of 75 cfu/mL and 75 cfu/mL, respectively, for L. monocytogenes and S. typhimurium , respectively. The practicality of the LFA in real food sample (milk) was also validated. Overall, the proposed assay is promising and has a good chance to be employed for multiple pathogen detection in food products.

CAS / MDL: 64-17-5 57-50-1
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JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH PART B-PESTICIDES FOOD CONTAMINANTS AND AGRICULTURAL WASTES · 2019 · IF 1.463

Raman and SERS spectra of thiamethoxam and the Ag3–thiamethoxam complex: an experimental and theoretical investigation

Yu Gao,Meng-Lei Xu,Jinfeng Xiong

The insecticide thiamethoxam (TMX) is one of the most important neonicotinoid pesticides. The chromatographic methods currently employed to detect TMX require multiple operational steps. This study proposes a simple method that detects TMX via surface-enhanced Raman scattering (SERS) spectroscopy with Ag nanoparticles (NPs) as the SERS active substrate. Density functional theory (DFT) was used to calculate the structures and vibrational modes of the Ag– and Ag3–TMX complexes at the B3LYP/6-311++G(d,p)(C,H,N)/LanL2DZ(Ag) level of theory. The results reveal that the atoms in the thiazole ring all lie in the same plane, while the six-membered ring is perpendicular to the thiazole ring. Data from both Ultraviolet-visible and Raman spectroscopy indicated that TMX bonds to Ag through its nitro group, vertically. A weak intramolecular (N22–O23…H26) hydrogen bonding and Ag–O bands shift N–O symmetrical vibration to down to lower wavenumber. This was supported by the appearance of a strong 866 cm−1 band in the SERS spectrum assigned to the N–O symmetrical vibration coupled with the N–N stretching vibrational mode of different excitation wavelength. Notably, a good linear relationship was observed in the TMX concentration range 1.0 × 10−6–1.0 × 10−4 mol·L−1 (R2 = 0.9667). SERS is an extremely simple and rapid technique that requires little sample for analysis.

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JOURNAL OF RAMAN SPECTROSCOPY · 2019 ·Vol. 50 ·期 7 ·926-935 · IF 2.809

Preparation of a high-performance magnetic molecularly imprinted sensor for SERS detection of cyfluthrin in river

Yan Wang,Hongji Li,Xiaonan Wang,Zirun Wang,Mingchao Wang,Yue Li,Qingwei Wang

A novel magnetic molecularly imprinted sensor (Fe 3 O 4 /GO/Ag-MIPs) was successfully synthesized. Combining with the technique of surface-enhanced Raman scattering (SERS), it could be applied to detect cyfluthrin (LC). Herein, GO and Ag particles were anchored on the surface of the Fe 3 O 4 @SiO 2 to obtain the composite (Fe 3 O 4 /GO/Ag), which was prepared as a SERS substrate. Then, the Fe 3 O 4 /GO/Ag-MIPs (FGA-MIPs) prepared by precipitation polymerization was evaluated as the SERS imprinted sensor for selective detection of LC from aqueous medium. The morphology and structural properties of FGA-MIPs were characterized by a series of modern analysis measurements. The results proved that FGA-MIPs possessed wonderful magnetic separation, sensitive SERS detection, and selectivity. Under optimal conditions, it exhibited a good linear relationship ( R 2 = 0.9926) between the Raman shift (at 1,004 cm −1 ) and the concentration of LC among 10 −3 –10 −8 mol/L, and the limit of detection was 10 −8 mol/L. Meanwhile, the selective experiment indicated that this material owned specific selectivity to the template molecules. Thus, the result of this experiment demonstrated that the FGA-MIPs was a highly sensitive and selective sensor material in the field of LC detection, and it provided a new approach to other residual pyrethroid detection in the environment water.

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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Stable, Flexible, and High-Performance SERS Chip Enabled by a Ternary Film-Packaged Plasmonic Nanoparticle Array

Kaiqiang Wang,Da-Wen Sun,Hongbin Pu,Qingyi Wei,Lunjie Huang

The high sensitivity and long-term storage stability of a plasmonic substrate are vital for practical applications of the surface-enhanced Raman scattering (SERS) technique in real-world analysis. In this study, a rationally designed, ternary film-packaged, silver-coated gold-nanoparticle (Au@Ag NP) plasmonic array was fabricated and applied as a stable and high-performance SERS chip for highly sensitive sensing of thiabendazole (TBZ) residues in fruit juices. The ternary films played different roles in the plasmonic chip: a newborn poly(methyl methacrylate) (PMMA) film serving as a template for fixing the self-assembled closely packed monolayer Au@Ag NP array that provided an intensive hot spot, a fluorescent quantitative polymerase chain reaction adhesive film (qPCR film) acting as a carrier to retrieve the Au@Ag/PMMA film that was used to improve the robustness of the plasmonic array, and a polyethylene terephthalate (PET) film covered over the Au@Ag/PMMA/qPCR film performing as a barrier to improve the stability of the chip. The Au@Ag/PMMA/qPCR-PET film chip showed high sensitivity with an enhancement factor of 3.14 × 106, long-term storage stability without changing SERS signals for more than 2 months at room temperatures, and a low limit of detection for sensing TBZ in pear juice (21 ppb), orange juice (43 ppb), and grape juice (69 ppb). In addition, the procedure for fabricating the Au@Ag/PMMA/qPCR-PET film SERS chip was easy to handle, offering a new strategy to develop flexible and wearable sensors for on-site monitoring of chemical contaminants with a portable Raman spectrometer in the future.

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Journal of Materials Chemistry C · 2019 ·Vol. 7 ·期 33 ·10179-10186 · IF 6.641

Tunable 3D light trapping architectures based on self-assembled SnSe2 nanoplate arrays for ultrasensitive SERS detection

Weiwei Li,Lei Xiong,Nianci Li,Shuo Pang,Guoliang Xu,Chenghan Yi,Zhixun Wang,Guoqiang Gu,Kaiwei Li,Weimin Li,Lei Wei,Guangyuan Li,Chunlei Yang,Ming Chen

Adopting semiconductor materials with light-trapping architectures as the surface-enhanced Raman spectroscopy (SERS)-active substrates has received increasing attention, in which the multiple reflection and scattering of electromagnetic waves can improve the enhancement factor. However, the fabrication of these semiconductor SERS-active substrates commonly requires complicated processes, and these methods normally result in non-uniform and isolated particles/flakes, which have fundamental difficulties in meeting the practical needs in high performance and reliable SERS substrates. Herein, we demonstrate that SnSe2 nanoplate arrays (NPAs) via self-assembled growth can serve as uniform, highly sensitive and reliable SERS substrates. The cavity formed by the SnSe2 NPAs can trap light efficiently (∼96%) and thus improve the enhancement factor. Benefiting from the synergistic effect of the charge-transfer process and enhanced light trapping, the resulting SERS substrates based on pure SnSe2 NPAs show an ultralow detection limit (1 × 10−12 M), a high enhancement factor (6.33 × 106) and excellent uniformity (relative standard deviations down to 7.7%), demonstrating one of the highest sensitivities amongst the reported semiconductor SERS substrates. Furthermore, the effects of different SnSe2 structural configurations (planar vs. cavity), the height and tilt angle of the SnSe2 NPAs on the performance of SERS detection are systematically investigated. It is discovered that the SERS performance is strongly dependent on both the light-trapping ability and the absorption loss. We believe that our results not only provide an effective strategy to obtain tunable, uniform and high performance SERS substrates, but also lead to further understanding of designing 3D light trapping architectures.

CAS / MDL: 989-38-8
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Micro & Nano Letters · 2018 ·Vol. 13 ·期 6 ·868-871 · IF 0.841

Facile method for detecting C23H25ClN2 in fish using Au nanoparticle films as SERS substrates on glass

Yan-meng Li,Li-wei Wang,Ruo-ping Li,Jun-he Han,Ming-ju Huang

Malachite green (C 23 H 25 ClN 2 ) is an illegal fungicide of aquatic products due to its potential carcinogenic, teratogenic, and mutagenic effects. It is typically challenging to detect C 23 H 25 ClN 2 in fish with conventional techniques. The study reported a simple and rapid method for detecting C 23 H 25 ClN 2 on fish surface with surface-enhanced Raman scattering (SERS). Using the seed growth method with trometamol as the modifier, 110 nm in-diameter gold nanoparticles on thin glass as SERS substrate were prepared, which exhibited high SERS activity, reproducibility, stability, and flexibility in SERS measurement. The fish samples required no pretreatment and the entire measurement took <5 min. Quantitative analyses were also conducted. Excellent linear relationships ( R 2 = 0.9397–0.9977) were obtained between the concentrations and the peak intensities of C 23 H 25 ClN 2 at some characteristic peaks with a wide concentrations range (0.5–10 μM). The detection limit can reach 0.5 μM. This method provided an easy and fast way to detect C 23 H 25 ClN 2 on fish surface for food safety.

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Journal of Materials Chemistry B · 2018 ·Vol. 6 ·期 19 ·3030-3039 · IF 4.776

A gold nanoflower-based traceable drug delivery system for intracellular SERS imaging-guided targeted chemo-phototherapy

Chunyuan Song,Yanxia Dou,Lihui Yuwen,Youzhi Sun,Chen Dong,Fang Li,Yanjun Yang,Lianhui Wang

Accurate and effective drug delivery in tumor cells significantly improves the curative effect with high drug delivery efficiency, low toxicity and side effects and has become an urgent demand for anticancer therapy. In this paper, a novel traceable and targeted drug delivery nanosystem (i.e. AuNF-nanocarriers) with high drug encapsulation and pH-controlled release was prepared based on gold nanoflowers (AuNFs) for efficient intracellular SERS imaging-guided chemo-phototherapy. SERS-active flower-like gold nanoparticles with large surface area were synthesized first and then modified with Raman and RGD molecules in sequence to prepare bright, traceable and targeted SERS tags of A549 human lung cancer cells. Furthermore, thiolated-PAA (PAA-SH) was synthesized and utilized for the first time to modify the SERS tags with a layer of negative charges for efficient pH-dependent loading and release of the anticancer drug doxorubicin. Based on the A549 human lung cancer cell model, the availability of the proposed AuNF-nanocarriers for efficient intracellular SERS imaging-guided chemo-phototherapy was studied and the results indicate that the AuNF-based drug delivery system exhibited attractive characteristics such as good stability, efficiency and pH-controlled drug loading and release, traceable and targeted delivery, as well as SERS imaging and chemo-phototherapy functions, and shows great potential for powerful SERS-imaging and as a theranostic candidate for precision nanomedicine that could achieve sensitive and accurate tumor detection and therapy.

CAS / MDL: 56390-09-1
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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

Fabrication of Ag@TiO2 electrospinning nanofibrous felts as SERS substrate for direct and sensitive bacterial detection

Yan Yang,Zhijie Zhang,Yali He,Zhihua Wang,Yanbao Zhao,Lei Sun

In order to develop a novel method for bacteria detection, Ag@TiO 2 electrospinning Nanofibrous felts have been fabricated by in situ decoration of size tunable Ag nanoparticles on anatase TiO 2 nanofibers. The morphologies and structures of the as-prepared Ag@TiO 2 electrospinning nanofibrous felts were characterized by techniques of scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The result show that Ag NPs were uniformly deposited on the surfaces of TiO 2 nanofibers, especially when the deposition time in Tollens’ reagent was 10 min. The free-standing composite nanofibrous felts processes superb performance of surface enhanced Raman scattering, which was demonstrated by small probe mecules of 4-mercaptobenzoic acid and 4-mercaptophenol, and the lowest detection limit was near to10 −9  mol/L. More importantly, the as-fabricated Ag@TiO 2 nanofibrous felts as SERS substrate can detect biomacromolecules such as bacteria of Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ) directly without previous bacteria-aptamer conjugation as the traditonal process. In addition, the composite nanofibrous felts also show outstanding antimicrobial activities against both Gram-negative of E. coli and Gram-positive of S. aureus , evaluated by method of absorption and microscopic observation. The results show that the bacteriostasis rate is reached to 99%, especially significant for E. coli . The free-standing, high porous, and flexible substrate of Ag@TiO 2 electrospun nanofibrous membranes have potential application in versatile fields such as microorganism sensors and water purifier.

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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

Highly selective determination of acid phosphatase in biological samples using a biomimetic recognition-based SERS sensor

Xiaoxu Li,Bingzhi Li,Junli Hong,Xuemin Zhou

In this paper, we introduce a synthetic biomimetic receptors-based surface enhanced Raman scattering (SERS) sensor for highly specific recognition and detection of acid phosphatase in complex biological samples. It depends on the establishment of molecular imprinted polymers (MIPs) which capture the target glycoprotein via biomimetic recognition, and SERS probes which bind to glycoproteins by boronate affinity. The MIPs layer was synthesized through self-polymerization of dopamine on the surface of glycoprotein-immobilized polymeric skeletons, which was prepared by choosing 4-vinylphenylboronic acid (VPBA) as functional monomers, pentaerythritol triacrylate (PETA) as crosslinker, ethyleneglycol (EG) and cyclohexanol as porogens. The accessible and stable recognition sites allowed the rebinding of the template and offered good reproducibility. The proposed biomimetic recognition-based SERS sensor showed superb performances for acid phosphatase detection with high sensitivity (LOD of 0.1 ng mL −1 ) and excellent selectivity.

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Nanoscale · 2018 ·Vol. 10 ·期 35 ·16895-16901 · IF 7.233

A flexible SERS-active film for studying the effect of non-metallic nanostructures on Raman enhancement

Guilin Wang,Ronghua Yi,Xueting Zhai,Renji Bian,Yongqian Gao,Dongyu Cai,Juqing Liu,Xiao Huang,Gang Lu,Hai Li,Wei Huang

Since the discovery of surface enhanced Raman scattering (SERS), the choice of SERS-active materials has been limited mainly to metals, especially gold and silver in the visible spectrum. Although non-metals can also be SERS-active by forming nanostructures or composite structures with SERS-active materials, the mechanism behind it is still unclear and there is no perfect technique to study it. In this work, by constructing a SERS structure on a flexible polydimethylsiloxane film, we provide a way to study the effect of non-metallic nanostructures on Raman enhancement by attaching the above film onto flat and nanostructured surfaces. It was found that a nanoporous silicon surface contributes to an additional, up to five times, Raman enhancement. The pore depth and pore size also influence the observed Raman enhancement. These findings will help us not only to understand the mechanism of SERS involving non-metallic nanostructures, but also to design more efficient SERS structures for various applications.

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