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MICROCHIMICA ACTA · 2023 ·Vol. 190 ·期 5 ·1-10 · IF 5.7

Cucurbit[8]uril-mediated SERS plasmonic nanostructures with sub-nanometer gap for the identification and determination of estrogens

Teng Yuanjie,Li Xin,Chen Yingxin,Xu Pei,Pan Zaifa,Shao Kang,Sun Nan

The SERS intensity of analytes is primarily influenced by the density and distribution of hotspots, which are often difficult to manipulate or regulate. In this study, cucurbit[8]uril (CB[8]), a kind of rigid macrocyclic molecule, was introduced to achieve ~ 1-nm nanogap between gold nanoparticles to increase the density of SERS hotspots. Three kinds of estrogens (estrone (E1), bisphenol A (BPA), and hexestrol (DES)) which are molecules with weak SERS signals were targeted in the hotspots by CB[8] to further improve the sensitivity and selectivity of SERS. It was demonstrated that CB[8] can link gold nanoparticles together through carbonyl groups. In addition, the host–guest interaction of CB[8] and estrogens was proved from the nuclear magnetic resonance hydrogen and infrared spectra. In the presence of CB[8], the SERS intensities of E1, BPA, and DES were increased to 19-fold, 74-fold, and 4-fold, respectively, and the LOD is 3.75 µM, 1.19 µM, and 8.26 µM, respectively. Furthermore, the proposed SERS method was applied to actual milk sample analysis with recoveries of E1 (85.0 ~ 112.8%), BPA (83.0 ~ 103.7%), and DES (62.6 ~ 132.0%). It is expected that the proposed signal enlarging strategy can be applied to  other analytes after further development. Graphical Abstract

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Chemosensors · 2023 ·Vol. 11 ·期 4 ·232 · IF 4.2

Rapid Fabrication of Homogeneous Submicron Silver Particles via a Microfluidic Chip and Use as a SERS Detection Substrate

Junjie Chen,Suyang Li,Fuqi Yao,Wanbing Xu,Yunfeng Li,Qiang Chen,Pei Liang

Silver particles have been widely used in SERS detection as an enhancement substrate. The large-scale synthesis of Ag particles with controllable size and shape is still a challenge. We demonstrate a high-throughput method for the preparation of monodisperse submicron silver particles using S-shaped microfluidic chips. Submicron silver particles were prepared by a simplified reduction method. By adjusting the concentration of the reducing agent ascorbic acid and the stabilizer PVP, the particle size and morphology could be controlled, obtaining a size distribution of 1–1.2 μm for flower-like silver particles and a size distribution of 0.5–0.7 μm for quasi-spherical silver particles. This microfluidic system can be used to fabricate submicron silver particles on a large scale, continuously and stably, with a production efficiency of around 1.73 mg/min. The synthesized submicron silver particles could realize ultra-sensitive SERS detection, and the lowest concentration of rhodamine 6G (R6G) that could be detected was 10−9M.Keywords:submicron silver particles;microfluidic chip;SERS detection

CAS / MDL: 50-81-7 7761-88-8
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RSC Advances · 2023 ·Vol. 13 ·期 15 ·10135-10143 · IF 3.9

An accuracy improved ratiometric SERS sensor for rhodamine 6G in chili powder using a metal–organic framework support

Yangjie Chen,Juan Hao,Zhihang Yin,Qinghui Wang,Youting Zhou,Lingpu Jia,Huiming Li,Wenlong Liao,Kunping Liu

Internal standard molecule 4-mercaptobenzoic acid (4-MBA) embedded Au core-Ag shell nanorods (Au-MBA@Ag NRs) were prepared by a seed-mediated growth method, then loaded on octahedral MIL-88B-NH2 to obtain a novel ratiometric SERS substrate of Au-MBA@Ag NRs/PSS/MIL-88B-NH2 (AMAPM) for detecting rhodamine 6G (R6G) in chili powder. The porous structure and excellent adsorption ability of MIL-88B-NH2, allowed for increased loading of Au-MBA@Ag NRs, thereby shortening the distance between adsorbed R6G and the “hot spot” resulting from local surface plasmon resonance (LSPR) of Au-MBA@Ag NRs. Based on the SERS characteristic peak ratio of R6G to 4-MBA, the ratiometric SERS substrate displayed improved accuracy and excellent performance for R6G detection, with a wide linear range of 5–320 nM and a low detection limit of 2.29 nM as well as fine stability, reproducibility and specificity. The proposed ratiometric SERS substrate offered a simple, fast and sensitive sensing strategy for R6G detection in chili powder, which demonstrated potential applications in food safety and the analysis of trace analytes in complex matrices.

CAS / MDL: 57-09-0 989-38-8
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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

One-Step, On-Site Chemical Printing of a 3D Plasmon-Coupled Silver Nanocoral Substrate toward SERS-Based POCT

Xuefei Zhao,Yueliang Wang,Yuanyuan Yao,Lifen Chen,Bingyong Lin,Wenhan Zheng,Yanbo Zeng,Lei Li,Yuanbin She,Longhua Guo

Surface-enhanced Raman scattering (SERS) with the advantages of high sensitivity, nondestructive analysis, and a unique fingerprint effect shows great potential in point-of-care testing (POCT). However, SERS faces challenges in rapidly constructing a substrate with high repeatability, homogeneity, and sensitivity, which are the key factors that restrict its practical applications. In this study, we propose a one-step chemical printing strategy for synthesizing a three-dimensional (3D) plasmon-coupled silver nanocoral (AgNC) substrate (only need about 5 min) without any pretreatments and complex instruments. The galvanic replacement between AgNO3 and Cu sheets will provide both Ag0 for the formation of silver nanostructures and Cu2+ for the polymerization of fish sperm DNA (FSDNA). The protection of AgNCs is facilitated by the crosslinked FSDNA, which can improve the stability of the substrate and promote the control of its coral-like morphology. The obtained substrate displays excellent capacity of signal enhancement due to the 3D plasmon coupling both between nanocoral tentacles and between nanocorals and Cu sheets as well. Therefore, the AgNC substrates display high activity (enhancement factor = 1.96 × 108) and uniformity (RSD < 6%). Food colorants have been widely used in various foods to improve their color, but the inevitable toxicity of colorants seriously threatens food safety. Therefore, the proposed AgNC substrates were used to directly quantify three kinds of weak-affinity food colorant molecules including Brilliant Blue, Allura Red, and Sunset Yellow assisted by the capture by cysteamine hydrochloride (CA), showing the detection limits (S/N = 3) of 0.053, 0.087, and 0.089 ppm, respectively. The SERS method has been further applied in the detection of the three kinds of food colorants in both complex food samples and urine with recoveries of 91–119%. The satisfactory detection results suggest that the facile preparation strategy of AgNC substrates will be widely used in SERS-based POCT to promote the development of food safety and on-site healthcare.

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FOOD CHEMISTRY · 2023 · IF 8.8

Flexible SERS sensor using AuNTs-assembled PDMS film coupled chemometric algorithms for rapid detection of chloramphenicol in food

Huanhuan Li,Wenhui Geng,Zihan Zheng,Suleiman A. Haruna,Quansheng Chen

The misuse of chloramphenicol (CAP) has led to the development of drug-resistant strains that pose significant threats to public health. Here, we propose a universal flexible surface-enhanced Raman spectroscopy (SERS) sensor utilizing gold nanotriangles (AuNTs) and polydimethylsiloxane (PDMS) film for rapid detection of CAP in food samples. Initially, AuNTs@PDMS with unique optical and plasmonic properties were used to collect spectra of CAP. Afterward, four chemometric algorithms were executed and compared. Accordingly, random frog-partial least squares (RF-PLS) exhibited optimum results with correlation coefficient of prediction (Rp = 0.9802) and the lowest root-mean-square error of prediction (RMSEP = 0.348 µg/mL). Furthermore, the sensor's efficacy to detect CAP in milk samples was confirmed, and the findings were compatible with the conventional HPLC approach ( P  > 0.05). Therefore, the proposed flexible SERS sensor could effectively be used to monitor milk quality and safety.

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TALANTA · 2023 · IF 6.1

Size-controllable colloidal Ag nano-aggregates with long-time SERS detection window for on-line high-throughput detection

Jianxia Cheng,Zhiyang Zhang,Longfei Zhang,Jiaqi Miao,Yan Chen,Rongfang Zhao,Meichun Liu,Lingxin Chen,Xiaoyan Wang

Making metal nanoparticle aggregates is a common way to improve surface-enhanced Raman scattering (SERS) enhancement via the formation of hot spots between nanoparticles . Here, we propose a “freeze-thaw-ultrasonication” method to obtain stable colloidal Ag nano-aggregates (AgNAs) with controllable sizes, which can remain stable for a few days. Compared with other method using aggregation reagents (e.g., organic molecules and salt), this method can maintain metal surface charges and adsorption affinity, which ensures the excellent SERS stability and sensitivity. The SERS detection window during the experiment can reach more than 25 min, which makes it a prerequisite for accurate SERS detection during a long-time range. Combining the obtained stable AgNAs with microfluidic devices, we established a sequential SERS on-line continuous detection method for the high-throughput detection of multiplex samples. The UV-Fenton degradation process of methylene blue (MB) is continuously on-line monitored through this platform, which is more sensitive than the UV–Vis Spectrum. Moreover, we have realized the sensitive and accurate detection of 5-nitro-8-hydroxyquinoline (5-NQ) with antibacterial and anticancer activities based on chloride-functionalized silver , which paved a way for SERS high-throughput analysis in bioanalysis and other fields.

CAS / MDL: 68-04-2
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FOOD AND AGRICULTURAL IMMUNOLOGY · 2022 · IF 3.268

Morphology-regulated core–shell Ag@Au NPs for rapid SERS detection of 1-amino-hydantoin (AHD) in crayfish

Peizhen Li,Xiuhua Xia,Jiannan Chen,Hang Yu,Yunfei Xie,Yahui Guo,Weirong Yao,He Qian,Yuliang Cheng

Gold-coated silver core–shell nanoparticles (Ag@Au NPs) have been widely used for SERS analysis due to plasmon resonance performances. However, it is a great challenge to fabricate Ag@Au core–shell structures with specified morphology. In this paper, the size and shape of Ag NPs (core) were precisely controlled by a seed-mediated approach, and then the gold shell was completely coated on under the strong reduction of ascorbic acid, resulting in Ag@Au NPs with highly regulated morphology. The obtained Ag@Au NPs achieved a similar or even better SERS enhancement factor (EF) (up to 5.7 × 107) compared to Ag NPs, but significantly higher stability. For the rapid SERS detection of nitrofurantoin metabolite AHD, a limit of detection (LOD) as low as 1 × 10−10 M and a wide linear range from 1 × 10−4 to 1 × 10−8 M were obtained. Furthermore, recoveries for crayfish samples were from 90.5% to 108%, indicating a good performance of the presented method in real sample detection.

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FOOD CHEMISTRY · 2022 · IF 9.231

Preparation of SERS substrate with 2D silver plate and nano silver sol for plasticizer detection in edible oil

Haonan Wang,Chuyi Wang,Jiali Huang,Yunzhen Liu,Yang Wu,Ruiyun You,Jian-Han Zhang,Yudong Lu,Huiying Shen

As a widely used industrial additive of plastic products, phthalate ester (PAE) plasticizers can easily migrate into food, threatening human health. In this work, we proposed a rapid, precise, and reliable method to detect PAE plasticizers in edible oils by using surface-enhanced Raman spectroscopy (SERS) technology. A two-dimensional (2D) silver plate synergizing with a nanosilver sol was prepared as a substrate for SERS to detect potassium hydrogen phthalate (PHP), a hydrolysate of a PAE plasticizer. Detection conditions, such as pH values, drying times, and hydrolysate interference, were optimized. The working curve was well fitted with a linear parameter R 2 of 0.9994, and the minimum detection limit was evaluated as 10 −9  mol/L. Furthermore, the detection accuracy was supported by five edible oil samples. Therefore, using SERS technology to detect PHP is expected to provide an avenue for PAE plasticizer detection in oils and fats, and it features promising potential applications in food safety.

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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 4 ·1-9 · IF 5.479

Rapid synthesis of a highly active and uniform 3-dimensional SERS substrate for on-spot sensing of dopamine

Lin Bingyong,Chen Jiaming,Kannan Palanisamy,Zeng Yanbo,Qiu Bin,Guo Longhua,Lin Zhenyu

A rapid method is described for the preparation of a highly uniform and sensitive SERS substrate by an improved ‘drop-and-dry’ method. Gold nanobipyramids (Au NBPs) were prepared inside the nanoholes (nanowalls) of anodic aluminum oxide (AAO) templates with a typically 5-μm nanohole depth. The SERS substrate can be prepared by this method within 40 s and on large scale. The SERS signals obtained with this Au NBPs-AAO substrate is stronger by four-orders of magnitude compared to conventional a silicon wafer substrate. The SERS signal for dopamine (DA; measured at 1311 cm −1 ) is found to be enhanced by a factor of 2.2 × 10 8 . The response to DA extends from 10 nM to 0.1 mM, and the limit of detection is 6.5 nM (at S/ N  = 3). The assay was applied to the determination of DA in spiked human serum. Schematic presentation of a highly active and uniform 3-dimensional substrate composed of gold nanobipyramids and anodic aluminum oxide (Au NBP/AAO). It was used for on-spot sensing of dopamine.

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RSC Advances · 2019 ·Vol. 9 ·期 6 ·2877-2884 · IF 3.049

Synthesis and evaluation of the SERS effect of Fe3O4–Ag Janus composite materials for separable, highly sensitive substrates

Yanlin Li,Sen Yang,Xuegang Lu,Wenyuan Duan,Toshihiro Moriga

Fe3O4–Ag Janus composites were synthesized using a two-step solvothermal method. The optimal growth process was determined by investigating the relationship between the particle morphologies and reaction time. Magnetic and Raman spectroscopic measurements showed that the as-synthesized Janus composites have both good magnetic response and significant surface-enhanced Raman scattering (SERS) effects, as well as reproducibility. The calculated Raman enhancement factor reached an unprecedented magnitude of 109 compared with the values of other Fe3O4–Ag compounds. Furthermore, the SERS effect was exhibited even at a concentration of probe molecules as low as 10−13 M. This demonstrates that the as-synthesized Fe3O4–Ag Janus composite particles have promise for application as separable, highly sensitive SERS substrates.

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APPLIED SURFACE SCIENCE · 2018 · IF 4.439

Silver nanocubes/graphene oxide hybrid film on a hydrophobic surface for effective molecule concentration and sensitive SERS detection

Chuhong Zhu,Xiaoye Hu,Xiujuan Wang

Surface-enhanced Raman scattering (SERS) is a promising analytical technique with molecular “fingerprint” characteristic and high sensitivity. To achieve high sensitivity, analytes should be located in or around the so-called SERS “hot spots” that are normally formed in sub-10 nm gaps between the neighboring plasmonic nanostructures. Ordinary SERS substrates generally show low sensitivity to the molecules that have weak affinity to noble-metal surfaces. Here, we fabricate an effective SERS system that can concentrate and adsorb organic pollutants in water for sensitive SERS detection. Such a SERS platform is composed of a thin film of Ag nanocubes/graphene oxide hybrid covered on a small Cu foil, and the Cu foil is placed on a hydrophobic teflon surface. The Ag nanocubes/graphene oxide hybrid film is synthesized by growth of graphene oxide on a Cu foil using electrophoresis and subsequent assembly of Ag nanocubes on the graphene oxide in ethanol via van der Waals interactions. Organic pollutant molecules can be concentrated on the hybrid film by adding a droplet of aqueous analyte solution on the hybrid film and evaporating. Due to the hydrophobic nature of teflon surface, the droplet will shrink onto the hybrid film and realize the concentration of analyte molecules on a SERS platform. There exists large delocalized π-electron system in the graphene oxide, so the Ag nanocubes/graphene oxide hybrid can effectively adsorb a large number of analyte molecules. As there are plenty of nano-sized gaps between the Ag nanocubes that are densely attached on the graphene oxide sheets, high density SERS hot spots can be formed in the gaps. As a result, the Ag nanocubes/graphene oxide hybrid has shown high SERS activity with an enhancement factor of 3.9 × 10 8 and good signal uniformity (relative standard deviation ∼12%). It is further demonstrated that the hybrid SERS substrates have exhibited high SERS sensitivity to organic pollutants such as 4-chlorobiphenyl and methyl parathion, showing promising applicability in many fields as diverse as chemical analysis, environmental monitoring, and food safety inspection.

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SENSORS AND ACTUATORS B-CHEMICAL · 2018 · IF 5.667

Highly reproducible and fast detection of 6-thioguanine in human serum using a droplet-based microfluidic SERS system

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

6-thioguanine is an anticancer drug with narrow safe dose range and intense toxic reactions, so it is urgently necessary to evaluate its clinical usage. Reproducibility and analysis speed are important factors to take into account when analyzing drug concentration in body fluids. In this work, we fabricated a droplet-based microfluidic chip for detecting 6-thioguanine in human serum by using the surface-enhanced Raman scattering (SERS) technique. The easily-prepared Au nanoparticles were used as SERS substrates, and reagent mixing and signal acquiring happened in droplets one by one. This assay device is endowed with the superiority in improving determination repeatability with coefficient of variation of no more than 5% (n = 25) and high speed of 10 s each assay. The SERS peak at 1295 cm −1 originated from N1-C6 stretching vibration mode of purine ring was selected for quantitating 6-thioguanine. The signals indicated a satisfied linear relationship with the concentrations of 6-thioguanine in the range of 0.010 μM to 10 μM, with a detection limit of 0.032 μM. The droplet-based microfluidic SERS system was successfully applied for credible and rapid analysis of 6-thioguanine in human serum, and is pretty promising for performing the therapeutic drug monitoring.

CAS / MDL: 70-18-8 154-42-7
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