Silver Nanoparticles and Nanorings for Surface-Enhanced Raman Scattering

Silver (Ag) nanoparticles (NPs) and Ag nanorings (NRs) have been fabricated. Due to the inherent features of Ag NPs and Ag NRs, strong electromagnetic (EM) near-field distributions were expected, and hence surface-enhanced Raman scattering (SERS) activity was demonstrated. Size and interparticle gaps distribution of Ag NPs were estimated to be 48.14?±?10.14 nm and 14.11?±?5.24 nm respectively along with estimated coverage density of?~?4?×?10¹⁰ cm^?2. On the other hand, Ag NRs were found to consist of Ag clusters and of various shapes and sizes, instead of a perfect ring structure. High-resolution FESEM revealed that the individual constituent clusters were different from each other, particularly in terms of size and shape in addition to the cases how such clusters were connected to form the edge of the NR. However, the coverage density of Ag NRs was estimated to be?~?5.6?×?10⁶ cm^?2. Based on the scenarios, it was speculated that the local EM near-field distribution would excel and thus led to enhanced SERS signals. SERS enhancement of R6G was estimated as high as 2.18?×?10⁴ and 2.78?×?10⁴ at 610 cm^?1 (C???C ring bending mode in phenyl rings) for Ag NPs and Ag NRs respectively. FDTD analysis was carried out to elucidate the EM near-field distributions.

Graphical abstract

Ag NPs and Ag NRs from an ultrathin layer of Ag on ZnO/Glass (middle pane) confirming high EF of R6G adsorbed on Ag NRs (right pane) and Ag NPs (left pane) supported by corresponding EM near-field distributions.

     

Detection of Melamine in Feed Using Liquid-Liquid Extraction Treatment Combined with Surface-Enhanced Raman Scattering Spectroscopy

A rapid, selective, and sensitive method to determine the melamine content in animal feeds was developed using surface-enhanced Raman scattering spectroscopy on aggregated 55 nm Au nanoparticles with liquid–liquid extraction sample preparation. Butyl alcohol was used as the initial extraction solvent, and liquid–liquid extraction was performed twice using HCl (pH 3–4) and 6∶1 (v/v) n-butyl alcohol/ethyl acetate. The intensity of the matrix-based peak at 731 cm⁻¹ was set at 100 as a basis for the feeds, and the peak at 707 cm⁻¹ was the characteristic peak of melamine used in the calculations. Sufficient linearity was obtained in the range 2–10 µg·g⁻¹ (R² = 0.991). Limits of detection and quantification in the feeds were 0.5 and 2 µg·g⁻¹, respectively. The recovery rates were 82.5–90.2% with coefficients of variation below 4.02%. This new protocol could be easily developed for the routine monitoring of on-site feed quality and market surveillance.     

Interface-Induced Ag Monolayer Film for Surface-Enhanced Raman Scattering Detection of Water-Insoluble Enrofloxacin

Water-insoluble molecules usually show poor surface-enhanced Raman scattering (SERS) signals, because they are hardly adsorbed on the surface of most commonly used SERS substrates, such as aqueous Ag or Au colloids. In this work, a highly sensitive and reproducible Ag monolayer film (Ag MLF) SERS substrate prepared by self-assembly of Ag nanoparticles (Ag NPs) on water/oil interface can realize the trace SERS detection of water-insoluble enrofloxacin. The positively charged phase transfer catalyst can transfer the negatively charged Ag nanoparticles in aqueous solution to the water/oil interface. At the same time, the water-insoluble enrofloxacin can also be attracted to the interface because of its lipophilic group. The type/volume of the oil phase and phase transfer catalyst and the vortex mixing time were all optimized to maximize the SERS effect of Ag MLF. Results showed that trace water-insoluble enrofloxacin can be identified by Ag MLF and its detection sensitivity was significantly improved. The proposed novel Ag MLF can be further applied to detect other water-insoluble molecules in SERS.

     

Plasmonic Interaction Between Silver Nano-Cubes and a Silver Ground Plane Studied by Surface-Enhanced Raman Scattering

The plasmonic interaction between silver nano-cubes and a silver ground plane with and without a dielectric spacer is studied for surface-enhanced Raman scattering (SERS) for rhodamine 6G (R6G) molecules absorbed onto the silver nano-cubes. Experimental results show that the composite substrates made from silver nano-cubes and the silver ground plane produce a stronger SERS signal than by the cubes alone, due to the plasmonic interaction between the cubes and the film. Numerical simulation is used to verify the plasmonic enhancement of the composite substrate and is consistent with the experimental results. The lowest concentration of R6G molecules which can be detected with the composite substrate is about 10⁻¹¹ M with our setup.     

Effect of Interparticle Field Enhancement in Self-Assembled Silver Aggregates on Surface-Enhanced Raman Scattering

The presence of so-called hot spots, regions with strongly enhanced electromagnetic field, is a critical property of a substrate enabling detection of surface-enhanced Raman scattering (SERS) signals at high enhancement levels. In this work, the effect of interparticle field enhancement on SERS signals was investigated comparing SERS spectra of ethylenediaminetetraacetic-disodium salt in the chemically produced colloids with isolated and aggregated silver nanoparticles using 473 and 532-nm wavelength excitation. The presence of aggregates in the colloidal solution resulted in SERS spectra that were insensitive to wavelength excitation and much richer in structural information and of higher resolution than the corresponding SERS spectra for the colloid with isolated nanoparticles. The experimental SERS spectra were found to be consistent with the finite-difference time-domain simulation results that explored the electromagnetic response of the isolated and aggregated nanoparticles. These results provide more evidence to suggest that the aggregate formation offers favorable electromagnetic properties increasing sensitivity of Raman spectroscopy.     

Surface-Enhanced Raman Scattering on Silver Sinusoidal Nanograting: Impact of Interactions of Grating-Coupled Surface Plasmon Polaritons

Plasmonics - In this study, we reported a silver sinusoidal nanograting used in microchannels, forming H2O/Ag/NOA/SiO2 heterostructure and studied the impact of interactions of grating-coupled...     

Ag-Cu Nanoparticles Encaptured by Graphene with Magnetron Sputtering and CVD for Surface-Enhanced Raman Scattering

An efficient surface-enhanced Raman scattering (SERS) substrate has been developed based on Ag-Cu nanoparticle-decorated graphene. The Ag-Cu-graphene (Ag-Cu@G) hybrid structure was prepared by magnetron sputtering for Ag and Cu film and chemical vapor deposition (CVD) for graphene, which avoided defects produced by graphene transferring process. The hybrid materials were confirmed by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. With R6G as analyst molecule, the enhancement factor (EF) of the order of 10⁶ for Ag-Cu@G sample was obtained. Meanwhile, the substrates had stable enhanced SERS signals after 78-day exposure in air, which could be explained by the fact that the graphene is efficient at maintaining chemical and optical stability. The formation of graphene can contribute a stabilization and fluorescence quenching effect. Moreover, the electromagnetic distribution based on AFM images was simulated by finite difference time domain (FDTD) method.     

One-Step Synthesis of Gold Nanoparticles Using Liquid Crystal Molecules for Surface-Enhanced Raman Scattering Detection

Plasmonics - Gold nanoparticles have received widespread attention as surface-enhanced Raman scattering (SERS) detection active substrates. In this work, we used the nematic liquid crystal molecule...     

A Simple and Sensitive Resonance Scattering Spectral Assay for Detection of Melamine Using Aptamer-Modified Nanosilver Probe

Nanosilver of 10-nm size was prepared by the NaBH₄–sodium citrate procedure, and it was modified by a single-strand DNA (ssDNA) aptamer to fabricate an AgssDNA probe for melamine. The probe was stabile at pH 7.0 Na₂HPO₄–NaH₂PO₄ buffer solutions and in the presence of 25.0 mmol/L NaCl. Upon the addition of melamine, it interacted with the probe to aggregate big clusters, which led to the resonance scattering (RS) intensity at 470 nm increasing greatly. Under the selected conditions, the increased RS intensity (ΔI _470 nm) is linear to melamine concentration in the range of 6.31–378.4 μg/L, with a regression equation of DI_{470 nm} = 1.124c + 10.8 \Delta {I_{{47}0{\rm{ nm}}}} = {1}.{124}c + { 10}.{8} and a detection limit of 3.1 μg/L. The aptamer-modified nanosilver RS assay has been applied for the determination of melamine in milk, with satisfactory results.     

Nanoparticle Surface-Enhanced Raman Scattering of Bacteriorhodopsin Stabilized by Amphipol A8-35

Surface-enhanced Raman spectroscopy (SERS) has developed dramatically since its discovery in the 1970s, because of its power as an analytical tool for selective sensing of molecules adsorbed onto noble metal nanoparticles (NPs) and nanostructures, including at the single-molecule (SM) level. Despite the high importance of membrane proteins (MPs), SERS application to MPs has not really been studied, due to the great handling difficulties resulting from the amphiphilic nature of MPs. The ability of amphipols (APols) to trap MPs and keep them soluble, stable, and functional opens up onto highly interesting applications for SERS studies, possibly at the SM level. This seems to be feasible since single APol-trapped MPs can fit into gaps between noble metal NPs, or in other gap-containing SERS substrates, whereby the enhancement of Raman scattering signal may be sufficient for SM sensitivity. The goal of the present study is to give a proof of concept of SERS with APol-stabilized MPs, using bacteriorhodopsin (BR) as a model. BR trapped by APol A8-35 remains functional even after partial drying at a low humidity. A dried mixture of silver Lee–Meisel colloid NPs and BR/A8-35 complexes give rise to SERS with an average enhancement factor in excess of 10². SERS spectra resemble non-SERS spectra of a dried sample of BR/APol complexes.     

Direct Observation of Single DNA Structural Alterations at Low Forces with Surface-Enhanced Raman Scattering

DNA experiences numerous mechanical events, necessitating single-molecule force spectroscopy techniques to provide insight into DNA mechanics as a whole system. Inherent Brownian motion limits current force spectroscopy methods from observing possible bond level structural changes. We combine optical trapping and surface-enhanced Raman scattering to establish a direct relationship between DNA’s extension and structure in the low force, entropic regime. A DNA molecule is trapped close to a surface-enhanced Raman scattering substrate to facilitate a detectable Raman signal. DNA Raman modes shift in response to applied force, indicating phosphodiester mechanical alterations. Molecular dynamic simulations confirm the local structural alterations and the Raman sensitive band identified experimentally. The combined Raman and force spectroscopy technique, to our knowledge, is a novel methodology that can be generalized to all single-molecule studies.     

Three-Dimensional Analysis of Scattering Field Interactions and Surface Plasmon Resonance in Coupled Silver Nanospheres

Scattering field interactions and surface plasmon resonance (SPR) in coupled silver nanospheres are simulated by using the finite-element method, which includes the influences of near-field enhancements of electric field by the particle sizes, separation distances, propagation directions, as well as the polarizations of the incident wave. The proposed structures exhibit a red- and blue-shifted that can be tuned by varying the particle sizes and the separation distances, respectively. Implications for surface-enhance Raman scattering and nano-optics are discussed in three-dimensional models. The evolution of SPR and nano-photonic device with the structural variations can be designed in a controlled manner.     

表面增强拉曼光谱在DNA检测中的应用

随着光学技术的发展,表面增强拉曼光谱(SERS)作为一种新兴的技术被逐渐应用于生物医学领域。SERS波谱作为一种振动波谱,能够反应被测物质的内部信息,具有指纹识别特征;具备高灵敏度、高效能的特点,且能实现复合样本的同时测定;带标记的SERS技术能进一步提高SERS检测的特异性。目前SERS技术已被广泛用于体内外DNA、蛋白分子的检测,为生物分子的分析检测提供了一种崭新、高效的手段。     

A Rapid Surface-Enhanced Raman Scattering Method for the Determination of Trace Hg2+ Using Rhodamine 6G-Aggregated Nanosilver as Probe

In pH 6.0 Na₂HPO₄-NaH₂PO₄ buffer solution and in the presence of cetyltrimethyl ammonium bromide, nanosilver particles were aggregated to a stable suspension. Therein, rhodamine 6G (Rh6G) exhibited three strong surface-enhanced Raman scattering (SERS) peaks at 613, 1,363, and 1,510 cm^?1, and their SERS intensities were enhanced when the concentration of Rh6G increased. In the presence of Hg²⁺, the SERS intensity decreased greatly owing to formation of stable Rh6G-HgBr ₄ ^2? ternary association complex molecules as well as its particles. In the optimal condition, the decreased SERS intensity at 613 cm^?1 responds linearly with the concentration of Hg²⁺ over 25–2,000 nmol/L. Thus, a new sensitive SERS method has been proposed for the determination of trace Hg²⁺ in the water sample, with satisfactory results.     

SERS Study of Histamine by Using Silver Film over Nanosphere Structure

Optical properties of histamine and l-histidine have been analyzed by using surface-enhanced Raman scattering (SERS). A silver film over nanosphere (AgFON) structure with 120-nm-thick silver film on polystyrene nanospheres 1,000?nm in diameter is fabricated by nanosphere lithography to enhance the Raman signal excited at the laser wavelength of 532?nm. Normal Raman spectrum and the SERS spectrum of histamine and l-histidine were compared. Further, vibration modes of these molecules were calculated by using density functional method. In the SERS experiment, we were able to measure the Raman spectrum with a histamine concentration as less as 100?pM. This sensitivity is higher than that from high-performance liquid chromatography.     

高灵敏荧光探针用于肿瘤 Ramos 细胞的快速检测

本文以聚苯乙烯纳米微球为载体,基于适体特异性识别和 DNA 杂交原理,组装了一种 DNA-CdTe 量子点纳米线,制备了具有较高荧光强度的复合型荧光探针,并成功用于 Ramos 细胞的荧光成像。该探针可以用于特异性识别肿瘤细胞,在荧光成像中信号强灵敏度高,为肿瘤细胞的检测提供一种新方法。     

Application of AAO Matrix in Aligned Gold Nanorod Array Substrates for Surface-Enhanced Fluorescence and Raman Scattering

In this paper, we probed surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from probe molecule Rhodamine 6G (R6G) on self-standing Au nanorod array substrates made using a combination of anodization and potentiostatic electrodeposition. The initial substrates were embedded within a porous alumina template (AAO). By controlling the thickness of the AAO matrix, SEF and SERS were observed exhibiting an inverse relationship. SERS and SEF showed a non-linear response to the removal of AAO matrix due to an inhomogeneous plasmon activity across the nanorod which was supported by FDTD calculations. We showed that by optimizing the level of AAO thickness, we could obtain either maximized SERS, SEF or simultaneously observe both SERS and SEF together.     

Theoretical Simulation and Focused Ion Beam Fabrication of Gold Nanostructures for Surface-Enhanced Raman Scattering (SERS)

This paper describes the fabrication of gold nanopillar and nanorod arrays and theoretical calculations of electromagnetic fields (EMFs) around ordered arrangements of these nanostructures. The EMFs of both single nanopillars and dimers of nanopillars—having nanoscale gaps between the two adjacent nanopillars forming the dimers—are simulated in this work by employing the finite-difference time-domain method. In the case of simulations for dimers of nanopillars, the nanoscale gaps between the nanopillars are varied between 5 and 20 nm, and calculations of the electromagnetic fields in the vicinity of the nanopillars and in the gaps between the nanopillars were carried out. Fabrication of gold nanopillars in a controlled manner for forming SERS substrates involves focused ion beam (FIB) milling. The nanostructures were fabricated on gold-coated silica, mica, and quartz planar substrates as well as on gold-coated tips of four mode and multimode silica optical fibers.     

Biosensor for Rapid and Sensitive Detection of Influenza Virus

Influenza viruses continue to threaten human life, causing considerable damage socially and economically. To reduce influenza-related morbidity and mortality, there is an immediate requirement to develop efficient and effective tools to detect the virus. Several methods are currently employed for diagnosing influenza infections in humans, including viral culture, polymerase chain reaction (PCR), and immunoassay. In addition, biosensors are being developed to improve the limitations of the conventional methods. In this article, we review the current progress in investigative techniques, including the development of biosensors having high sensitivity and selectivity and shorter detection time.