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JOURNAL OF NANOPARTICLE RESEARCH · 2019 ·Vol. 21 ·期 7 ·1-14 · IF 2.009

A plasmonic and SERS dual-mode iodide ions detecting probe based on the etching of Ag-coated tetrapod gold nanostars

Chen Xiao-Hong,Zhu Jian,Li Jian-Jun,Zhao Jun-Wu

In this paper, we report plasmonic spectra and surface-enhanced Raman scattering (SERS) dual-mode iodide ions (I − ) detecting probe based on Ag-coated tetrapod Au nanostars (Au@Ag tetrapod nanostars). This probe depends on the fact that I − can etch the silver layer of Au@Ag tetrapod nanostars in the presence of Cu 2+ , which leads to the red shift of in-plane localized surface plasmon resonance (LSPR) peak and decrease of SERS intensity. Indeed, our regular morphologies of Au@Ag tetrapod nanostars provide a uniform response space for the plasmonic spectral probe. The red shift caused by both the silver layer etching and gold tips exposing make the in-plane LSPR peak more sensitive to the changes of I − concentration, which results in an extremely wide linear range of 0.5–280 μM. Meanwhile, when the four Au tips are not fully coated by silver layer but still exposed to outsides, the strong SERS enhancement effect from Ag coating and tip effect together leads to the lower limit of detection (LOD) of 26 nM. Furthermore, this proposed method exhibits a good selectivity for I − over other ions and is well applied in dried kelp and drinking water. The proposed plasmonic spectrum and SERS dual-mode probe based on the Ag-coated tetrapod gold nanostars exhibits extremely wide linear range and relatively low LOD

CAS / MDL: 50-81-7 1310-73-2
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SENSORS AND ACTUATORS B-CHEMICAL · 2017 · IF 5.401

A SERS substrate of mesoporous g-C3N4 embedded with in situ grown gold nanoparticles for sensitive detection of 6-thioguanine

Ya-Ning Wang,Ying Zhang,Wen-Shu Zhang,Zhang-Run Xu

A novel surface-enhanced Raman scattering substrate was developed through in situ growing gold nanoparticles inside the mesoporous graphitic carbon nitride with a large surface area. The mesoporous structure afforded support for loading more gold nanoparticles, defined the nanoparticle diameter and ensured uniform distribution of the nanoparticles. Crystal violet used as a Raman probe was detected by SERS based on the hybrids with an enhancement factor of 5.0 × 10 5 , and the relative standard deviation of the peak intensity (at 1174 cm −1 and 1618 cm −1 ) were 6.2% and 6.1% (n = 30) for solid samples, and 5.1% and 5.0% (n = 11) for liquid samples. The high SERS activity was attributed to abundant hot spots formed by high-density gold nanoparticles and chemical enhancement from mpg-C 3 N 4 , and the good reproducibility was due to controlled size and uniform distribution of the gold nanoparticles. An antineoplastic drug, 6-thioguanine was detected with a wide linear range from 0.60 μM to 48 μM and a low detection limit of 0.24 μM. The mesoporous g-C 3 N 4 embedded with gold nanoparticles significantly improved the SERS sensitivity and reproducibility for 6-thioguanine detection, and it holds promising potential in noninvasive and ultrasensitive drug monitoring.

CAS / MDL: 7631-86-9 154-42-7
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 2 ·1-11 · IF 5.3

A flexible semiconductor SERS substrate by in situ growth of tightly aligned TiO2 for in situ detection of antibiotic residues

Li Kaiwei,Jiang Han,Wang Liying,Wang Rui,Zhang Xuewei,Yang Libin,Jiang Xin,Song Wei,Zhao Bing

Semiconductor materials have become a competitive candidate for surface-enhanced Raman scattering (SERS) substrate. However, powdered semiconductors are difficult to execute a fast in situ detection for trace analytes. Here, we developed a new flexible semiconductor SERS substrate by in situ densely growing anatase TiO 2 nanoparticles on the surface of cotton fabric through a filtration-hydrothermal method, in which TiO 2 exhibits excellent controllability in size and distribution by regulating the ratio of water to alcohol in synthesis and the number of filtration-hydrothermal repetitive cycle. Cotton fabric/TiO 2 (Cot/TiO 2 ) substrate exhibits a high SERS activity and excellent spectral repeatability. The developed substrate has an ultra-high stability that can withstand long-term preservation; it can even resist the corrosions of strong acid and alkali, as well as high temperature up to 100 °C and low temperature down to − 20 °C. The flexible substrate can be used to carry out a rapid in situ detection for quinolone antibiotic (enrofloxacin and enoxacin) residues on the fish body surface by using a simple swabbing method, with high quantitative detection potential (up to an order of magnitude of 10 −7  M), and even for the simultaneous detection of both drug residues. The flexible substrate also exhibits an excellent recyclability up to 6 recycles in the actual SERS detection. Graphical Abstract

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Analytical Methods · 2024 · IF 2.7

A novel SERS-lateral flow assay (LFA) tray for monitoring of miR-155-5p during pyroptosis in breast cancer cells

Xiaoxia Lu,Wenlong Lu,Dong Hua

In the study, a novel surface-enhanced Raman scattering (SERS)-lateral flow assay (LFA) tray for the real-time detection of pyroptosis-associated miR-155-5p in breast cancer cells was established and validated. The SERS probe modified with monoclonal antibodies and functionalized HP1@5-FAM was first synthesized. When miR-155-5p was present, HP1@5-FAM on the SERS probe specifically recognized target miRNAs and hybridized with them, resulting in HP2 on the T line only capturing some SERS probes that were not bound to miR-155-5p. The T line appeared as a light orange band or there was no color change, and the corresponding Raman detection result showed a weak or insignificant Raman signal. The SERS probe showed high selectivity, satisfactory stability, and excellent reproducibility, and the limit of detection (LOD) for miR-155-5p was 7.26 aM. Finally, the proposed SERS-LFA tray was applied to detect miR-155-5p in MBA-MD-468 cells that underwent varying degrees of pyroptosis, and the detection results of SERS were consistent with those of the conventional real-time quantitative reverse transcription polymerase chain reaction (qRT-PCR) assay. The study demonstrated that the SERS-LFA tray was a convenient and ultrasensitive method for miR-155-5p real-time detection, which could provide more detailed information for pyroptosis and be of potential value in guiding the treatment of breast cancer.

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RSC Advances · 2017 ·Vol. 7 ·期 58 ·36201-36207 · IF 3.108

Aim and shoot: molecule-imprinting polymer coated MoO3 for selective SERS detection and photocatalytic destruction of low-level organic contaminants

Lingzhi Wang,Yin Xu,Xianjun Tan,Sen Tapas,Jinlong Zhang

A sensitive and selective SERS sensor with easy and excellent recyclability is highly demanded because of its great potential application in complex detection environments. Here, using methylene blue (MB) as a model target, a semiconductor-based SERS substrate composed of a MoO3 nanorod core and a uniform molecule-imprinting polymethacrylic acid shell (MIP) with a thickness of 4 nm was designed and fabricated (MoO3@MIP) to achieve selective detection. The key to the successful coating of the ultrathin uniform MIP shell lies in the pretreatment of a MoO3 core with nitric acid, providing sufficient surficial hydroxyls for the anchoring of a polymer precursor. The molecule-imprinted voids for MB were formed simply via light irradiation as a result of photocatalytic degradation by a MoO3 semiconductor. This core–shell MIP composite shows a high SERS selectivity towards low-level MB in a mixed MB/CV solution. The enhanced factor (EF) is high, at 1.6 × 104. More importantly, the selective detection allows the further photocatalytic recycling of MoO3@MIP in an “aim-and-shoot” way, which well preserves the detection selectivity and sensitivity towards MB at least for 4 cycles. Based on decreased sensitivity with the increasing shell thickness (10–24 nm), a MIP-gating charge transfer mechanism is proposed to demonstrate the high EF instead of the molecule-enrichment effect. This “aim-and-shoot” strategy is expected to push forward the prosperous application of selective SERS for trace detection in versatile environments.

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FOOD CHEMISTRY · 2017 · IF 4.529

Investigation of degradation and penetration behaviors of dimethoate on and in spinach leaves using in situ SERS and LC-MS

Ruyan Hou,Mengmeng Tong,Wanjun Gao,Lei Wang,Tianxi Yang,Lili He

To investigate the degradation and penetration behaviors of the organophosphate insecticide dimethoate applied on spinach leaves, in situ SERS and LC-MS methods were used to detect dimethoate residue on&in spinach leaves picked on different days after treatment (DAT). The SERS and LC-MS methods determined that the dimethoate degradation rate followed first-order kinetics, with a half-life of 3.56 or 4.13   days, depending on the respective method. The correlation coefficient of quantification value of these two methods was 0.9562. With the SERS method, we detected most of the penetrated dimethoate in the depth of 60–110   μm. With the LC-MS method, we detected dimethoate up to 0.17   ng in leaves and that the dimethoate on:in ratio of spinach leaves ranged from 562.25 on 0 DAT to 5.23 on 14 DAT. The combination of these two methods facilitated a better understanding of the behavior and biological fate of pesticides in a complex biological system.

CAS / MDL: 64-18-6
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ACS Applied Materials & Interfaces · 2017 · IF 7.504

Green in Situ Synthesis of Clean 3D Chestnutlike Ag/WO3–x Nanostructures for Highly Efficient, Recyclable and Sensitive SERS Sensing

Jian Huang,Dayan Ma,Feng Chen,Dongzhen Chen,Min Bai,Kewei Xu,Yongxi Zhao

Surface-enhanced Raman scattering (SERS) has proven to be an effective technique for identifying and providing fingerprint structural information on various analytes in low concentration. However, this analytical technique has been plagued by the ubiquitous presence of organic contaminants on roughened SERS substrate surfaces, which not only often result in poorer detection sensitivity but also significantly affect the reproducibility and accuracy of SERS analysis. Herein, we developed a clean, stable, and recyclable three-dimensional (3D) chestnutlike Ag/WO3–x (0 < x < 0.28) SERS substrate by simple hydrothermal reaction and subsequent green in situ decoration of silver nanoparticles. None of the organic additives were used in synthesis, which ensures the substrate surfaces are completely clean and free of interferences from impurities. The innovative design combines the SERS enhancement effect and self-cleaning property, making it a multifunctional and reusable SERS platform for highly sensitive SERS detection. Using malachite green as a model target, the as-prepared SERS substrates exhibited good reproducibility (relative standard deviation of 7.5%) and pushed the detection limit down to 0.29 pM. The enhancement factor was found to be as high as 1.4 × 107 based on the analysis of 4-aminothiophenol. The excellent regeneration performance indicated that the 3D biomimetic SERS substrates can be reused many times. In addition, the fabricated substrate was successfully employed for detecting thiram in water with a detection limit of 0.32 nM, and a good linear relationship was obtained between the logarithmic intensities and the logarithmic concentrations of thiram ranging from 1 nM to 1 μM. More importantly, the resultant SERS-active colloid can be used for accurate and reliable determination of thiram in real fruit peels. These results predict that the proposed SERS system have great potential toward rapid, reliable, and on-site analysis, especially for food safety and environmental supervision.

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2017 ·Vol. 19 ·期 33 ·22302-22308 · IF 4.123

Highly-dispersed TiO2 nanoparticles with abundant active sites induced by surfactants as a prominent substrate for SERS: charge transfer contribution

Libin Yang,Di Yin,Yu Shen,Ming Yang,Xiuling Li,Xiaoxia Han,Xin Jiang,Bing Zhao

In this study, highly-dispersed TiO2 nanoparticles (NPs) with abundant active sites were synthesized by a simple sol-hydrothermal method with the assistance of surfactant polyethylene glycol (PEG) which served as an effective SERS-active substrate for the first time. The observed considerable SERS enhancement of 4-mercaptobenzoic acid (4-MBA) probe molecules on TiO2 NPs is attributed to the contribution of the charge transfer mechanism from the substrate to the probe molecule. It is suggested that PEG can act as a protective agent in the reductive calcination of the surfactant-coated nanocrystallite and consequently brings about abundant surface oxygen vacancies for TiO2 NPs, which provide more effective sites for the adsorption of probe molecules and promote the charge transfer effect and its consequent SERS enhancement. Moreover, the prepared TiO2 NPs can serve as an effective substrate for highly sensitive detection of p-aminobenzoic acid (PABA). The detection limit of PABA is as low as 1 × 10−8 M, which is the highest sensitivity among the reported determination methods. And, it proves that the prepared TiO2 substrate with abundant active sites is characterized by high stability, which offers a unique long service lifetime for SERS detection without losing its activity.

CAS / MDL: 150-13-0
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RSC Advances · 2016 ·Vol. 6 ·期 83 ·79805-79810 · IF 3.289

Poly(dopamine) assisted in situ fabrication of silver nanoparticles/metal–organic framework hybrids as SERS substrates for folic acid detection

Zheng Juan Sun,Zhong Wei Jiang,Yuan Fang Li

In this contribution, a new in situ strategy for the preparation of AgNPs/MIL-101(Cr) hybrids as SERS substrates for folic acid detection was reported. In Tris–HCl buffer solution (pH = 8.5), poly(dopamine) (PDA) could be formed by self-polymerization of dopamine (DA), and was then effectively attached onto the surface of MIL-101(Cr) for further reduction of Ag+. By this strategy, AgNPs could be efficiently anchored on MIL-101(Cr) to form AgNPs/MIL-101(Cr) hybrids, which exhibited strong enrichment of folic acid (FA) due to electrostatic interaction, and the anchored AgNPs greatly enhanced the Raman signals of FA. Thus, the as-prepared hybrids have been used as excellent surface enhanced Raman scattering (SERS) substrates for the sensitive and selective detection of FA. Under the optimal experimental conditions, the SERS method shows good linearity in the range from 0.5 μM to 25 μM for FA with a correlation coefficient of 0.990, the detection limit was calculated to be 0.3 μM ± 0.02 μM. Moreover, it was successfully applied to detect FA in real samples with satisfactory results. These results demonstrated that the proposed SERS system has great practicability for chemical and biological assay applications, and the AgNPs/MIL-101(Cr) hybrids also offers potential for targeting cancer cells.

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NEW JOURNAL OF CHEMISTRY · 2016 ·Vol. 41 ·期 4 ·1582-1590 · IF 3.277

Fabrication of Fe3O4@SiO2@Ag magnetic–plasmonic nanospindles as highly efficient SERS active substrates for label-free detection of pesticides

Qinye He,Aiwu Zhao,Lei Li,Henghui Sun,Dapeng Wang,Hongyan Guo,Mei Sun,Ping Chen

Fe3O4@SiO2@Ag magnetic–plasmonic nanospindles with efficient SERS performance and magnetic responsiveness have been successfully fabricated. Uniform and monodispersed Fe3O4@SiO2 nanospindles were prepared by a robust strategy through annealing the obtained β-FeOOH@SiO2 nanospindles in hydrogen atmospheres at 350 °C; the SiO2 shell could be regarded as an interlayer to maintain the morphology and offer a solid support for the further growth of Ag nanoparticles. Ag nanoparticles were introduced via in situ reduction of AgNO3, and the coverage rate of Ag nanoparticles anchored on Fe3O4@SiO2 was adjusted through regulating the AgNO3 concentration. Fe3O4@SiO2@Ag magnetic–plasmonic nanospindles can serve as highly efficient SERS active substrates with controllable magnetic aggregation due to steady enrichment of mass molecules in close proximity to abundant hot spots. Moreover, these nanospindles are used for label-free detection of thiram, and the detection limit is as low as 1 × 10−7 M (about 0.024 ppm), which is lower than the maximal residue limit of 7 ppm in fruits prescribed by the U.S. Environmental Protection Agency. Therefore, such magnetic–plasmonic nanospindles in the magnetic aggregation state may be potentially applied in rapid trace detection of residual pesticides or other specific analytes.

CAS / MDL: 1193-02-8 137-26-8
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Journal of Materials Chemistry A · 2013 ·Vol. 2 ·期 10 ·3648-3660 · IF 0

Versatile synthesis of high surface area multi-metallic nanosponges allowing control over nanostructure and alloying for catalysis and SERS detection

Shaochun Tang,Sascha Vongehr,Yongguang Wang,Juan Cui,Xiangyu Wang,Xiangkang Meng

We report a template- and surfactant-free synthesis of multi-metallic nanosponges with controllable composition, porosity, ligament and grain sizes, as well as control over alloying. The inexpensive approach is scalable to industrial production and produces not only sponges of various pure metals such as Ag, Au, Pd, Pt, Co, Ni, Cu, but also bi- and trimetallic alloys or non-alloys. The synthesis involves fast reduction of metal salts followed by a slow network assembly in ethanol–glycerol mixed solvents shaken in a temperature range of 25–90 °C. Freeze drying conserves the pores to ensure a high surface area. The involved growth mechanisms are discussed. Tri-metallic alloyed Ag34Au33Pd33 sponges with a specific surface area of 96 m2 g−1 exhibit the highest reported catalytic rate for the degradation of azo dyes and 4-nitrophenol reduction. They show higher catalytic activity and better long-term stability for formic acid electro-oxidation compared with Pd-based mono- and bimetallic nanostructures. The excellent catalytic performance is mainly attributed to the high porosity and large number of interfaces. Pressed into discs, the Ag sponges' sensitive SERS activity is highly reproducible over area.

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BIOSENSORS & BIOELECTRONICS · 2014 · IF 6.451

A “turn-off” SERS assay of heparin with high selectivity based on heparin–peptide complex and Raman labelled gold nanoparticles

Gan Qu,Guannan Zhang,Zitong Wu,Aiguo Shen,Jianbo Wang,Jiming Hu

Stable SERS response originating from gold nanoparticles (Au NPs) is demonstrated for the first time to be suitable for detection of heparin with high selectivity . Herein we report a novel “turn-off” SERS assay for heparin based on Raman labelled Au NPs and competitive bonding between heparin and two specialized peptides, such as RKGSGRRLVKC (11-peptide) and CALNN (5-peptide). By means of coordination interactions and other non-electrostatic forces, these 5-peptide capped Au NPs are induced to undergo controllable aggregation upon the additive of 11-peptide and heparin with a concentration range (0–2.4   U/mL), which correspondingly cause quantitative changes of SERS intensity of 4-MBA conjugated on Au NPs. The decreased Raman intensity obtained by subtracting two cases of additives which contain only 11-peptide and the mixture of 11-peptide and heparin, is proportional to the concentration of heparin over a range of 0.2–2.4   U/mL ( R 2 =0.99157), with a limit of detection (LOD) of 0.042   U/mL (S/N=3:1). Moreover, the proposed highly selective method has potential application for rapid, separation-free detection of heparin in human blood serum samples.

CAS / MDL: 9041-08-1
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