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ANALYTICA CHIMICA ACTA · 2022 · IF 6.911

An ultra sensitive and rapid SERS detection method based on vortex aggregation enhancement effect for anti-infective drug residues detection in water

Xinqi Zheng,Pengran Guo,Yue Zhang,Jingwei Xu,Jian Sun,Yongqian Lei

The environmental pollution and human health risks caused by anti-infective residual drugs in the environment have attracted much attention. More convenient and effective detection methods to achieve the rapid and high sensitivity detection for such pollutants are required. In this work, a novel surface-enhanced Raman scattering (SERS) strategy based on vortex aggregation of AgNPs was proposed for the detection of anti-infective drugs in environmental water. The method enhanced the Raman signal of the targets by 2–7.4 times. The mechanism of aggregation enhancement effect under the low-frequency oscillation procedure which significantly enhanced the SERS signal of targets molecular on the aggregated AgNPs was revealed by UV–vis and ICP-MS methods. Three drugs of cefazolin sodium, pefloxacin , and chloroquine phosphate were determined. The detect limits were 3.97 × 10 −9  mol/L, 2.42 × 10 −10  mol/L, and 7.34 × 10 −9  mol/L for cefazolin sodium, pefloxacin, and chloroquine phosphate, respectively. The quantitative relationships were obtained in a wide linear range of 4–5 orders as well as good accuracy and stability with the recoveries of 84.0%–97.1% and the relative standard deviations (RSDs) less than 4.6% for spiked in actual water samples. This method also had excellent repeatability and stability, which have potential application for rapid detection of trace pollutants in water environment.

CAS / MDL: 50-63-5 149676-40-4
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Journal of Materials Research and Technology-JMR&T · 2022 · IF 6.267

A study on a hybrid SERS substrates based on arrayed gold nanoparticle/graphene/copper cone cavities fabricated by a conical tip indentation

Jingran Zhang,Siwei Lu,Guangfeng Shi,Wenkun Xie,Yanquan Geng,Zuobin Wang

The pesticide residues with low concentration are important to detect in food safety. Although a lot of methods, such as spectrophotometry, colorimetry and liquid chromatography, are used to detect pesticide residues, they often suffer from low efficiency and long detection time. Here, a hybrid Surface Enhanced Raman Scattering (SERS) substrate, namely, Au nanoparticle/copper-based graphene/arrayed cone cavities (Au@GR@Cu cone cavities), is fabricated for pesticide residues detection through sputtering Au nanoparticle and generating periodical cone cavity structures on the copper-based graphene surface. By actively controlling the interspace between adjacent cone cavities, both surface topographies and the number of graphene layers on the SERS substrate could be modulated, creating an effective control on the functional performance of the SERS substrate. Both sensitivity and reliability of the hybrid SERS substrate were evaluated by Raman Spectroscopy detection. The experimental results indicated that both 10 −9  mol/L malachite green and 10 −7  mol/L paraquat could be detected, respectively. Moreover, the detected Raman intensity of malachite green only dropped by 11.89% in a month and 29.8% in two months, respectively. The hotspot distribution was also characterized by 2-dimensional Raman mapping. The research finding is expected to provide a new insight in development of innovative SERS substrates.

CAS / MDL: 569-64-2
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Chemosensors · 2022 ·Vol. 10 ·期 10 ·423 · IF 4.229

Flexible and Transparent SERS Substrates Composed of Au@Ag Nanorod Arrays for In Situ Detection of Pesticide Residues on Fruit and Vegetables

Chao Liu,Shenhao Wang,Xuan Dong,Qing Huang

Due to the increasing importance of food quality/safety control, there is an imminent need to develop efficient methods for the rapid detection of pesticide residues in agricultural products. Herein, we proposed a simple and rapid detection approach to the in situ detection of residual pesticides on fruit/vegetable using surface-enhanced Raman spectroscopy (SERS). Flexible and transparent SERS substrates were fabricated by transferring Au@Ag core-shell nanorods (Au@Ag NRs) arrays to silicone membranes, with the single-layer Au@Ag NRs arrays prepared by the liquid–liquid interface self-assembly method. The as-prepared SERS sensor showed excellent SERS activity and repeatability, and it could be readily pasted onto the surface of fruit and vegetables for residual pesticide detection. For the inspection of thiram in contaminated strawberries, apples, and mushrooms, the limit of detection (LOD) could reach 2 ng/cm2with high measurement recovery and reproducibility. In general, this work provides an effective way for the preparation and application of flexible and transparent SERS substrates in food-safety control.Keywords:surface-enhanced Raman spectroscopy (SERS);Au@Ag nanorods;flexible substrates;rapid detection;pesticide detection

CAS / MDL: 50-81-7 112-02-7 57-09-0
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ANALYST · 2022 ·Vol. 147 ·期 24 ·5670-5679 · IF 5.227

Floating Ag-NPs@Cu-NW bundles fabricated on copper mesh for highly sensitive SERS detection of uric acid in pretreatment-free urine

Ziyan Song,Siyu Chen,Qiushi He,Hu Liang,Guangyao Huang,Pan Li,Zongyao Hao,Liangbao Yang

The rapid and sensitive detection of ultra-trace marker molecules from biological samples is of great significance for the wide application of surface-enhanced Raman spectroscopy (SERS) methods in clinical diagnosis and disease monitoring. However, the cumbersome biological sample processing procedures and the poor enrichment of target analytes in hot spots hinder the practical applications of SERS methods. In this paper, we synthesized a novel floating SERS substrate by a simple one-step oxidation process, annealing and in situ chemical etching to form Ag-NPs@Cu-NW bundles on copper mesh (CM). In particular, under spontaneous bottom-up capillary action, the pressure difference at different nanogaps drives uric acid molecules to actively enter hot spots, so that the Ag-NPs@Cu-NW bundle nanostructure with the advantages of a light weight CM is capable of preventing the common coffee-ring effect and enhancing the spatial enrichment of analytes. Therefore, this SERS substrate realizes highly sensitive detection of uric acid at a level of 50 nM in pretreatment-free urine. Currently, this portable, flexible, simple, fast and cost-effective SERS substrate has great potential for early screening and clinical diagnosis of diseases in different biofluids.

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MICROCHIMICA ACTA · 2022 ·Vol. 189 ·期 5 ·1-9 · IF 6.408

SERS determination of dopamine using metal–organic frameworks decorated with Ag/Au noble metal nanoparticle composite after azo derivatization with p-aminothiophenol

Zhu Anni,Wang Tiansheng,Jiang Yuning,Hu Sen,Tang Wanxin,Liu Xinling,Guo Xiaoyu,Ying Ye,Wu Yiping,Wen Ying,Yang Haifeng

A specific surface-enhanced Raman scattering (SERS) assay for dopamine (DA) based on an azo derivatization reaction is proposed for the first time by preparation of p-aminothiophenol (PATP)-modified composite SERS substrate, composed of metal–organic framework (MIL-101) decorated with Au and Ag nanoparticles. As the result, the SERS method for detection of the azo reaction between PATP and DA exhibits superior sensitivity, selectivity, and stability. A reasonable linearity in the range 10 −6 to 10 −10  mol∙L −1 is achieved, and the limit of detection is 1.2 × 10 −12  mol∙L −1 . The reactive SERS assay is free from interference in complex physiological fluid. The feasibility of the proposed SERS method for the detection of DA levels in fetal bovine serum (FBS) samples and human serum samples is validated by HPLC–MS methods, displaying promising application potential in early disease diagnosis. Graphical abstract

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Journal of Environmental Chemical Engineering · 2022 · IF 7.968

Facile construction of silver nanocubes/graphene oxide composites for highly sensitive SERS detection of multiple organic contaminants by a portable Raman spectrometer

Jiafeng He,Xian Li,Jumei Li

Here, we demonstrate a reliable surface-enhanced Raman scattering (SERS) substrate composed of graphene oxide (GO) nanosheets and Ag nanocubes for sensitive detection of varied organic contaminants , malachite green, methylene blue and crystal violet by a portable Raman spectrometer with the limits of detection (LODs) of 10 −9 , 10 −10 and 10 −9 M, respectively, owing to a synergistic SERS enhancement arising from electromagnetic field effect of Ag nanocubes and chemical enhancement of GO sheets. The SERS substrates also present highly uniform signal over substrates and low relative standard deviations of 6.53 %, 6.16 % and 6.70 %, respectively are obtained on each sample, which is attribute to the extremely uniform size of Ag nanocubes as well as the consistent distribution of Ag nanocubes on GO sheets. Moreover, the SERS substrate is capable of label-free detection of more complex organic pesticides such as tetramethylthiuram disulfide and diquat dibromide with the LOD of 10 −8 M, which is below the safety levels regulated by United States Environmental Protection Agency. Consequently, the Ag nanocubes/GO composites are promising as efficient SERS platforms for reliable and highly sensitive monitoring of food safety and environmental pollution .

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FOOD RESEARCH INTERNATIONAL · 2022 · IF 7.425

Preparation of AgNPs self-assembled solid-phase substrate via seed-mediated growth for rapid identification of different bacterial spores based on SERS

Yaodi Zhu,Weijia Liu,Shijie Liu,Miaoyun Li,Lijun Zhao,Lina Xu,Na Wang,Gaiming Zhao,Qiuying Yu

In this study, we developed a novel and sensitive AgNPs self-assembled solid-phase (AgNPs-SASP) SERS substrate platform using seed-mediated and liquid interface self-assembly methods and applied the platform for the detection of three bacterial spores. Multivariate statistical analysis (HCA and LDA) were employed for identification and categorization of the obtained data. The results illustrated that AgNPs-SASP exhibited high reproducibility and Raman enhancement effect (1.43 × 10 4 ). The Raman shift bands of the three bacterial spores ranged from 400 to 1800 cm −1 demonstrating the difference in reigon and intensity. And the intensities of their Ca 2+ -DPA Raman bands are significantly different. HCA results revealed that the spectra for the three bacterial spores were statistically different while LDA completely differentiated the spectra for the three bacterial spores with 100 % sensitivity and specificity. Overall, the novel SERS platform based on AgNPs-SASP provides an effective tool for food safety risk control and detection.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2022 · IF 6.371

Multifunctional self-assembled gold nanorod monolayer/Ti3C2Tx nanocomposites based on interfacial electrostatic for highly sensitive SERS detection of organic dyes and adenine

Peng Fei Wu,Xiao Yang Fan,Hong Yan Xi,Niu Pan,Zi qian Shi,Ting Ting You,Yu Kun Gao,Peng Gang Yin

Gold nanorods (Au NRs)/Ti 3 C 2 T x composites were prepared by self-assembly method as surface enhanced Raman scattering (SERS) substrates. Due to strong electrostatic interaction , Au NRs are evenly arranged on the surface of Ti 3 C 2 T x nanosheets , forming rich SERS hotspots. Au NRs/Ti 3 C 2 T x have high sensitivity and good reproducibility for the determination of organic dyes such as rhodamine 6G, crystal violet and malachite green. The detection limits were 1 × 10 −13 , 1 × 10 −13 and 1 × 10 −12 M, respectively. The relative standard deviations of samples in 40 areas were 4.57 %, 2.79 % and 3.47 %, respectively. The synthesized SERS substrate is sensitive to adenine. For adenine molecules in the range of 1 × 10 −5 –1 × 10 −9 M, SERS results show that the peak intensity is linear with adenine molecular concentration, and the detection limit can be as low as 1 × 10 −9 M. In addition, adenine in aqueous solution has good anti-interference ability to other nucleic acids with similar structure, such as guanine, cytosine and thymine. Therefore, Au NRs/Ti 3 C 2 T x are expected to become a potential substrate for unmarked, rapid and sensitive SERS detection of adenine in the field of bioanalysis.

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Polymers · 2021 ·Vol. 13 ·期 19 ·3270 · IF 4.329

Layer-by-Layer Assembly of Polystyrene/Ag for a Highly Reproducible SERS Substrate and Its Use for the Detection of Food Contaminants

Sihan Zhang,Zhihua Xu,Jiaqi Guo,Haiying Wang,Yibo Ma,Xianming Kong,Hongtao Fan,Qian Yu

Polystyrene (PS) spheres were prepared through an emulsifier-free emulsion polymerization method, in which the reaction time, ionic strength, concentrations of copolymer were studied in detail. The resulting PS microspheres and Ag nanoparticles were used to construct a surface enhanced Raman scattering (SERS) substrate by a layer-by-layer assembly method. A relatively uniform distribution of PS/Ag in the films was obtained, and the multilayer substrate presented excellent SERS reproducibility and a tunable enhancement effect. The SERS substrate was used for detecting harmful pesticides (malachite green and dimetridazole) in food samples, with a limit of detection as low as 3.5 ppb. The obtained plasmonic composite has a promising future in the field of SERS sensing.Keywords:polystyrene;self-assembly;Ag nanoparticle;layer by layer;SERS;reproducibility

CAS / MDL: 1074-36-8 26062-79-3
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ANALYTICAL CHEMISTRY · 2021 · IF 6.986

Oil-Free Gold Nanobipyramid@Ag Microgels as a Functional SERS Substrate for Direct Detection of Small Molecules in a Complex Sample Matrix

Bingyong Lin,Yueliang Wang,Yuanyuan Yao,Lifen Chen,Yanbo Zeng,Lei Li,Zhenyu Lin,Longhua Guo

Surface-enhanced Raman scattering (SERS) is a super-sensitive analysis technology based on the target molecular fingerprint information. The enhancement of local electromagnetic field of the SERS substrate would increase the target molecules’ Raman intensity which adsorb on the surface of nanoparticles. However, the existing adhesive macromolecules in the complex mixed sample would interfere with the adsorption of small target molecules, and it weakens the Raman intensity of target molecules. Microgels are one of the potential materials to suppress the interference of adhesive macromolecules and to avoid the complex pretreatments. However, most of the current microgel synthesis methods involve complex operations with precise instrumentation or the interference of oil and organic reagents. In this work, a simple and oil-free method was proposed to synthesize the gold nanobipyramid (Au NBP)@Ag@hyaluronic acid microgel via the condensation reaction of carboxyl and amino groups. As a proof-of-concept demonstration for small-molecule detection, the rhodamine 6G (R6G) molecules were allowed to enter inside the microgel through the meshes and adsorb on the surface of Au NBP@Ag nanoparticles within 30 min, while the macromolecule (bovine serum albumin in this case) was retained outside the microgel in the meantime. In addition, under the combined action of lightning rod effect of Au NBP and surface plasmon resonance effect of silver render the microgels with high SERS activity. The synthetic Au NBP@Ag@hyaluronic acid microgels were applied to detect 6-thioguanine in the human serum without any pretreatment process, and it showed a high signal enhancement and stable SERS signal, which can satisfy the requirement of clinical diagnosis. These results show that the proposed microgels have potential applications in the field of point-of-care testing.

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OPTICAL MATERIALS · 2021 · IF 3.08

The high active SERs substrate prepared by self assembling Ag nanoparticles on PPy@PEDOT:PSS film to detect the sodium formaldehyde sulfoxylate molecules

Xueqin Wang,Jinguo Jiang,Qingqing Zhang,Zhongchen Bai

The Ag/PPy@PEDOT:PSS film was used as a Surface-enhanced Raman scattering (SERs) substrate to directly detect the low concentration of sodium formaldehyde sulfoxylate (SFDS) molecules in solution. We prepared the PPy@PEDOT:PSS film by electrochemical potentiostatic (ECP) method and then directly grew Ag nanoparticles on its surface to prepare the SERs substrate of Ag/PPy@PEDOT:PSS film. The results showed that with the increase of depositional time of Ag nanoparticles, accordingly, the size and density of Ag nanoparticles could be increased on the film surface, and their SERs effect was also enhanced gradually; this SERs substrate could sensitively detect the SFDS molecules in aqueous solution. Moreover, the minimum detection limit was up to 1 ng/mL. This preparing and detecting method of SERs substrates provides a new way for the preparation of high sensitivity SERs substrate and for direct and rapid detection of low concentration of SFDS molecules in food and drug.

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SENSORS AND ACTUATORS B-CHEMICAL · 2021 · IF 7.46

Plasmonic Ag nanocube enhanced SERS biosensor for sensitive detection of oral cancer DNA based on nicking endonuclease signal amplification and heated electrode

Yan Liu,Shao-Hua Wu,Xing-Yuan Du,Jian-Jun Sun

Surface-enhanced Raman scattering (SERS) biosensing has attracted great attention due to its multiplexed capability, high sensitivity, and rapid readout. In this study, plasmonic Ag nanocube (AgNC) enhanced SERS biosensing platform was proposed by coupling nicking endonuclease-assisted target recycling signal amplification with heated electrode for sensitive detection of DNA species related to oral cancer. SERS tags were manufactured by signal DNA (sDNA) conjugating onto the surfaces of AgNCs, and 4-mercaptobenzoic acid (4-MBA) assembled on the surfaces of AgNC/sDNA as a Raman reporter. The sharp feature of edges and corners of AgNCs with high electromagnetic field provided SER hot spots with high quality, and stronger SERS signal could be achieved. In addition, the activity of nicking endonuclease Nt.BstNBI could be greatly enhanced by elevating the temperature of the surface of the heated Au electrode (HAuE) during Nt.BstNBI-assisted target recycling amplification process, resulting in dramatic amplification of target DNA detection. All of these contributed to the high sensitivity of the developed SERS biosensor. A limit of detection (LOD) of 3.1 fM (S/N = 3) could be obtained with an electrode temperature of 45 °C. This proposed SERS biosensor was anticipated to act as a promising biosensing platform for early clinical diagnosis of oral cancer.

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