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VIBRATIONAL SPECTROSCOPY · 2022 · IF 2.382

SERS detection of negatively charged molecules by interface-induced self-assembly of PDDA modified Ag nanoparticles

Yuanjie Teng,Zhenni Wang,Weihao Huang,Yuanbin She

Some noble metal colloids with negative charges were mostly used as surface-enhanced Raman scattering (SERS) substrates, that the Raman signals of negatively charged molecules are hard to be detected because of the electrostatic repulsion among them and the negatively charged metal nanoparticles . Herein, Ag nanoparticles (Ag NPs) with positive charges and its Ag nanofilm were prepared by poly dimethyl diallyl ammonium chloride (PDDA) to realize the SERS detection of negatively charged molecules directly. The zeta potential and its particle sizes were characterized to select the optimum condition of PDDA. In addition, the morphology of positive Ag NPs and Ag nanofilm was characterized by UV–Vis spectroscopy and transmission electron microscopy . The SERS effect of negatively charged thiamphenicol on positively charged Ag nanofilm was significantly enhanced at the optimum condition and its sensitivity was significantly improved compared with normal Ag nanofilm. The proposed novel positively charged Ag nanofilm can be further applied to detect other negatively charged molecules by SERS.

研究领域: 分析化学 · 纳米科学 · 光谱学
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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

研究领域: 材料科学 · 分析化学 · 环境科学
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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Gold nanoparticle decorated electrospun nanofibers: A 3D reproducible and sensitive SERS substrate

Zhicheng Liu,Zhaodong Yan,Lu Jia,Ping Song,Linyu Mei,Lu Bai,Yaqing Liu

The design and fabrication of three-dimensional (3D) nanostructures with fascinating SERS performance have drawn much attention in the field of materials science and nanotechnology. In this work, 3D poly (acrylic acid) (PAA)/poly (vinyl alcohol) (PVA) nanofibrous membrane was used as templates for the electrostatic assembly of gold nanoparticles. The PAA/PVA electrospun nanofibers were crosslinked using a simple thermal treatment, which would prevent the nanofibers from dissolution in the nanoparticle solution. It was found that the gold nanoparticles were uniformly immobilized on the nanofibers, causing high reproducibility of this SERS substrate. The nanocomposite membrane also showed high sensibility for the detection of trace amount of analytes such as 4-aminothiophenol and Rhodamine 6G.

研究领域: 材料科学 · 纳米技术
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Materials Today Communications · 2023 · IF 3.8

Bi5O7Br-nanotube@Au-nanoparticle core-shell assembly for high signal-to-noise ratio SERS detection of adenine

Ran Feng,Jiazhi Meng,Hualei Yuan,Xu Zhang,Chunlang Gao,Chaogang Ban,Yizhong Guo,Kaiwen Wang

Cancers, Down’s syndrome, Alzheimer’s and other diseases of gene mutation always occur with anomalous changes of DNA nucleic acid base. Therefore, the development of highly sensitive and reproducible nucleic acid sensors that based upon surface enhanced Raman scattering (SERS) is of immense interest for clinical medical analysis and diagnosis. Herein, a rationally designed core-shell assembly of Au nanoparticle wrapped with Au doped Bi 5 O 7 Br nanotube with eliminated fluorescent background and notable chemical enhancement effect was exploited and served as a SERS sensor for detection of adenine. Especially, we found the fluorescent background was remarkably suppressed in Raman spectra by introducing Au element into Bi 5 O 7 Br. The sensor exhibited a maximum SERS enhancement factor of up to 5.45 × 10 7 and a detection limit as low as 10 −11 M after constructing Au nanoparticle/Au atom doped Bi 5 O 7 Br heterojunction . More importantly, good reproducibility and long term stability under work condition were achieved. To gain in-depth understanding into chemical mechanism (CM) of the Raman signal enhancement, density functional calculations (DFTs) were combined with atom-specific model derived via aberration corrected transmission electron microscope (AC-TEM) to demonstrate the enhanced charge transfer (CT) and substrate-adsorbate adsorption. The doping and coupling strategy holds the potential to fabricate high signal-to-noise ratio SERS sensors for other molecule detection.

研究领域: 生物医学工程 · 分子生物学 · 分析化学
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

Advancing Protein Detection and Analysis Based on Ag/Au PHCN for Enhanced SERS Sensitivity and Specificity in Biomolecular Diagnostics

Jing Wu,Ying Zhang,Jiuchuan Wang,Zhuangzhuang Ling,Xuanhua Yan,Xiaoming Lyu,Jinghuai Fang,Mingfei Cheng,Min Zhao,Tao Ban,Yu Liu,Yang Li

In the realm of disease diagnostics, particularly for conditions such as proteinuria and hemoglobinuria, the quest for a method that combines accurate, label-free detection of protein compositions and their conformational changes remains a formidable challenge. In this study, we introduce an innovative Ag/Au plasmonic hybrid coupling nanoarray (Ag/Au PHCN) architecture marked by sub-10 nm interparticle gaps. These nanoarrays, leveraging plasmonic hybrid coupling and synergistic enhancement mechanisms, create a plethora of uniform surface-enhanced Raman spectroscopy (SERS) hotspots. The Ag/Au PHCN substrates demonstrated unparalleled sensitivity in the unmarked detection of hemoglobin (HGB), bovine serum albumin (BSA), and cytochrome C (Cyt.C) in bodily fluids, incorporating the advantages of high sensitivity, high reproducibility, durability, recyclability, and biocompatibility. Notably, the detection limits for BSA and HGB are unprecedented at 0.5 and 5 ng/mL, respectively. This achievement sets a new benchmark for label-free protein detection using two-dimensional nanostructures. Crucially, the Ag/Au PHCNs possess the novel capability to discern protein conformational changes post denaturation, underscoring their potential in probing protein functionalities. Most importantly, these nanoarrays can differentiate between normal and proteinuria-affected urine samples and monitor protein content variations over time, heralding a new era in clinical diagnostics with particular relevance to proteinuria and hemoglobinuria detection.

CAS / MDL: 989-38-8
研究领域: 生物医学 · 纳米技术 · 诊断学
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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

Highly sensitive and reproducible SERS substrates based on a novel 3D waffle-like PMMA-CsPbBr3-Au ternary film

XianWei Wang,Yue Zhai,Yuanhui Chen,Wei Zhang,Pei Liang,Qiangqiang Zhu,Hong Zhang,Juan Kang,Le Wang

s The development of a highly sensitive and reliable surface-enhanced Raman scattering (SERS) substrate is crucial for overcoming the limitations in its practical applications. Herein, a novel 3D waffle-like SERS substrate with high activity is constructed for detecting trace amounts of myricetin in complex analytes extracted from green tea. The substrate is achieved through a layered ternary film structure, where ordered poly (methyl methacrylate) opal photonic crystals (PMMA OPCs) serving as a 3D hot spots template and enhancing the performance of CsPbBr 3 film that facilitates efficient charge transport, and an Au film covered over the CsPbBr 3 film modulating the vibronic coupling and providing plasmonic hot spots. The PMMA-CsPbBr 3 -Au substrate exhibits a low detection limit of 10 −10 M with an 8.9 × 10 7 enhancement factor, signal repeatability and stability for R6G molecules. Furthermore, the SERS detection of myricetin content in Longjing green tea from different years is carried out, and the results show a good linear positive correlation with storage years (R 2 =98.2 %), demonstrating the potential application of 3D substrate for sensitive and reproducible SERS.

研究领域: 材料科学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2021 · IF 7.46

Dual functional molecule aided background-free SERS sensor for intracellular pH dynamic monitoring based on foldable DNA transition

Ying Zhang,Qian Liu,Mengting Liu,Xueni Zhang,Xiaoya Li,Lihui Dai,Meng Meng,Dingbin Liu,Yongmei Yin,Rimo Xi

The microenvironment of lysosomes plays an important role in various functions within cells. Abnormal pH changes in lysosomes account for multiple diseases including tumors. Acid-responsive nanomaterials with reconfigurable structures and properties have garnered significant interests. Owing to the potential in biosensing, controlled release and nanomachinery, DNA based pH-responsiveness has been widely pursued. Herein, we designed an AuNPs-i-motifs based SERS probe to monitor the pH dynamics of lysosomal maturation in different cells. Taking advantages of biocompatibility and structural flexibility of DNA, unique optical and plasmonic properties of gold nanoparticles , excellent stability and enhanced sensitivity of background-free Raman reporter, the designed SERS probe could indicate the pH variation dynamically in lysosomes. What is more valuable is that 4-mercaptobenzonitrile is not only used as a Raman reporter to provide sensitive Raman signal for pH sensing, but also used as a sealing agent allowing for controllable aggregation, to improve the stability and accuracy of the sensor. With this versatile design, the sensor was prepared simply and feasibly and a tedious trial was avoided. It provides a feasible tool for understanding the relationship of lysosomal pH with fundamental cellular functions and mechanism of diseases.

研究领域: 生物传感 · 纳米医学 · 细胞生物学
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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Recyclable SERS monitoring of food quality based on the shrubby morphology of titania oxide-triggered electromagnetic “hotspots”

Likun Han,Huan Liu,Jinjie Zhang,Jun Zhou,Tao Jiang

Constructing of plasmonic substrate with the capability of detecting nutritional food quality will soon be emerged as the frontier research directions with broad prospects in surface-enhanced Raman scattering (SERS) technology ascribed to an improvement of living standards. Herein, a novel TiO 2 framework with a shrubby morphology was successfully constructed on carbon cloth (CC) matrix to trigger significantly enhanced electromagnetic “hotspots” after dense Ag network with numerous sharp corners and edges was formed by a photo-induced reduction. Particularly, the structure-dependent optical performance was investigated for these as-prepared CC/TiO 2 /Ag hybrid substrates, screening out an optimal one with an enhancement factor of 6.38 × 10 7 . Regarding a prominent photocatalytic efficiency ascribed to the high electron-hole separation efficiency assisted by the CC matrix and Ag decoration, a recyclable SERS-based monitoring of quercetin (QR) was achieved in teas, demonstrating recovery values distributed from 88.9 % to 106.4 %. The strategy proposed here opened a new way to create high-density “hotspots” for multifunctional SERS substrates, which might play a crucial role in food quality monitoring applications.

CAS / MDL: 548-62-9 5593-70-4
研究领域: 材料科学 · 纳米技术 · 食品科学 · 分析化学
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 8 ·1-8 · IF 5.479

RETRACTED ARTICLE: A SERS-based lateral flow assay for the stroke biomarker S100-β

Wang Ying,Hou Yajun,Li Hanxia,Yang Mingfeng,Zhao Peng,Sun Baoliang

A surface-enhanced Raman scattering (SERS)-based lateral flow assay (LFA) is described for the quantitative analysis of the proteinic stroke biomarker S100-β that has to be detected at very low concentration levels. The Raman reporter 5,5′-dithiobis-2-nitrobenzoic acid (DTNB) on gold nanoparticles (GNPs) was employed as the SERS tags. They are shown to perform much better than bare GNPs in LF strips. The S100-β protein can be detected by this method with very low detection limits by monitoring the intensity of the characteristic Raman peak of the S100-β protein-conjugated GNPs at 1332 cm −1 . Under optimized conditions, the assay works in the 1 pg·mL −1 to 40 ng·mL −1  S100-β concentration range, and the detection limit is as low as 0.14 pg·mL −1 . This is lower by a factor of 3 compared to colorimetric or fluorimetric methods. Schematic illustration of the configuration (A) and the principle of the SERS-based lateral flow assay for quantification of S100-β (B).

研究领域: 生物医学工程 · 分析化学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Development of Fe3O4/DEX/PDA@Au(Raman reporters)@Au-MPBA nanocomposites based multi-hotspot SERS probe for ultrasensitive, reliable, and quantitative detection of glucose in sweat

Lun Han,Xu Wang,Bin Yu,Xiaoyuan Qin,Baocheng Liu,Xu Han,Huifen Yuan,Bin Yu,Zhiqi Zhao

Glucose is a key biomarker of diabetes, and effective glucose monitoring methods are crucial to the prevention and management of diabetes. Therefore, in this paper, Fe 3 O 4 /DEX/PDA@Au (Raman reporters) @Au nanocomposites were synthetized that with DTNB (5,5′-dithiobis(2-nitrobenzoic)), MMTA (2-mercapto-4-methyl-5-thiazole acetic acid), MBA (4-mercaptobenzoic acid) and 4-Mpy(4-Mercaptopyridine) were used separately as Raman reporters. Fe 3 O 4 and PDA (Polymerized dopamine) could supply more high surface area of active sites and high SERS (Surface-Enhanced Raman Scattering) substrate, which has high stability and reproducibility. Dextran coating is an effective way to prepare biocompatible materials TEM, XRD, TG and VSM were used to analyze the size, morphology and magnetic properties of the nanocomposites. Fe 3 O 4 /DEX/PDA@Au(Raman reporters)@Au that integrates a multi-hotspot structure and magnetic separation techniques were studied the enhancement effect of Raman spectra, and glucose solutions with different concentrations were tested. Furthermore, the optimal Fe 3 O 4 /DEX/PDA@Au(Raman reporters)@Au nanocomposites were supplied as SERS substrates for detection of glucose accurately and quickly in sweat. SERS signal intensity is linearly correlated with glucose concentration within the measurement range of 5 × 10 -3 to 10 mM, and the minimum detectable concentration is 5 µM. The Fe 3 O 4 /DEX/PDA@Au(Raman reporters)@Au nanocomposites exhibit high reliability, specificity and repeatability of the strategy were then verified by practical detection of sweat.

研究领域: 生物医学工程 · 分析化学
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 5 ·1-10 · IF 6.232

Fabrication of paper-based SERS substrates by spraying silver and gold nanoparticles for SERS determination of malachite green, methylene blue, and crystal violet in fish

Yang Guohai,Fang Xuejiao,Jia Qin,Gu Haixin,Li Yunpeng,Han Caiqin,Qu Lu-Lu

A disposable surface-enhanced Raman scattering (SERS) substrate was prepared by successively spraying silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) onto commercial filter paper using an inexpensive consumer sprayer. The strong surface enhancement of AgNPs and chemical stability of AuNPs can be advantageously combined. The substrate exhibited excellent SERS activity for malachite green (MG), methylene blue (MB), and crystal violet (CV) under 785-nm excitation, with limits of detection (LODs) of 4.3 × 10 −9 , 2.0 × 10 −8 , and 8.1 × 10 −8  M, respectively. The substrate exhibited long-term stability, and it can be stored under ambient conditions for 4 weeks with a relative standard deviation of less than 3% among peak intensities. The substrate also showed good reproducibility with a relative standard deviation of 7.1% among different substrate peak intensities. The substrates enable on-site determination of residual fishery drugs and distinguish MG, MB, and CV mixtures in spiked fish within 5 min, and the average recoveries in fish scales and fish meat were better 90.1% and 76.9%, respectively. The method exhibited rapidity, simplicity, and high sensitivity and is expected to be used for the screening of additives in food.

研究领域: 分析化学 · 食品安全 · 环境科学
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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

An in-situ method for SERS substrate preparation and optimization based on galvanic replacement reaction

Xing Zhong,Peng Liu,Jiaxing Wen,Yongfu Qiu,Min Zhang,Dong Xie,Shoushan Wang,Shilei Xie,Faliang Cheng

Background Various surface-enhanced Raman spectroscopy (SERS) substrate preparation methods have been reported, however, how to tune the “gap” between nanostructures to make more “hot spots” is still a barrier that restricts their application. The gap between nanostructures is usually fixed when the substrates are prepared. In other words, it is hard to tune interparticle distances for maximum electromagnetic coupling during substrate preparation process. Therefore, an in-situ substrate optimization method that could monitor the SERS signal intensity changes, i.e., to find the optimum gap width and particle size, during substrate preparation process is needed. Results A method based on the galvanic replacement reaction (GRR) is proposed for the in-situ gap width tuning between nanostructures as well as for the optimization of SERS substrates. Noble metal nanoparticles (NPs) form and grow on the sacrificial templates' surface while noble metal ions are reduced by sacrificial metal (oxides) in GRR. Along with the fresh and clean NPs’ surface generated, the gap between two noble metal NPs decreases with the growth of the NPs . To demonstrate this strategy, cuprous oxide/Ti (Cu 2 O/Ti) sacrificial templates were prepared, and then a GRR was carried out with HAuCl 4 . The real-time SERS detection during GRR show that the optimum reaction time (ORT) is 300 ± 30 s. Furthermore, SERS performance testing was conducted on the optimized substrate, revealing that the detection limit for crystal violet can reach 1.96 × 10 −11  M, confirming the feasibility of this method. Significance and novelty By monitoring the in-situ SERS signal of probes during GRR will obtain an “optimal state” of the SERS substrate with optimal gap width and particle size. The SERS substrate preparation and optimization strategy proposed in this article not only provides a simple, efficient, and low-cost method to fabricate surface-clean noble NPs but also paves the way for the in-situ optimization of NPs size and gap width between NPs which could achieve wider applications of SERS.

CAS / MDL: 548-62-9
研究领域: 材料科学 · 光谱学
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