Surface Enhanced Raman Scattering Phenomenon Research Articles

Controllable preparation of Ti3C2Tx/Ag composite as SERS substrate for ultrasensitive detection of 4-nitrobenzenethiol

Currently, metal carbonitride (MXene) has been identified as a hot research topic in the research area of surface-enhanced Raman scattering (SERS). In this study, Ti3C2Tx/Ag composite was fabricated as SERS substrate with different Ag contents. The fabricated Ti3C2Tx/Ag composites show good SERS behavior by detecting 4-Nitrobenzenethiol (4-NBT) probe molecules. Through calculation, the SERS enhancement factor (EF) of the Ti3C2Tx/Ag substrate was as high as 4.15 × 106. It is worth noting that the detection limit of 4-NBT probe molecules can be achieved ultralow concentration of 10−11 M. In this system, electromagnetic enhancement mechanism and chemical enhancement mechanism have synergistic effects on SERS phenomenon. Meanwhile, the Ti3C2Tx/Ag composite substrate exhibited good SERS reproducibility. In addition, the SERS detection signal hardly changed after 6 months of natural standing, and the substrate showed good stability. This work suggests that the Ti3C2Tx/Ag substrate could be used as a sensitivity SERS sensor for practical application, and could be applied in the field of environmental monitoring.

Binding mechanism and SERS spectra of 5-fluorouracil on gold clusters.

The adsorption behaviour of the 5-fluorouracil (5FU) on small gold clusters Au N with N = 6, 8, 20 was evaluated by means of density functional theory using the PBE-D3 functional in combination with a mixed basis set, i.e. cc-pVDZ-PP for gold atoms and cc-pVTZ for non-metal elements. The binding energies between 5FU and gold clusters were determined in the range of 16-24 and 11-19kcal/mol in gas-phase and aqueous media, respectively. The corresponding Gibbs energies were found to be around -7 to -10kcal/mol in vacum and sigificantly reduced to -1 to -6kcal/mol in water solution, indicating that both the association and dissociation processes are likely spontaneous. An analysis on the charge density difference tends to confirm the existence of a charge transfer from the 5FU molecule to Au atoms. Analysis of the surface-enhanced Raman scattering (SERS) spectra of 5FU adsorbed on the Au surfaces shows that the stretching vibrations of N-H and C=O bonds play a major role in the SERS phenomenon. A mechanism for the drug releasing from the gold surfaces is also proposed. The process is triggered by either the low pH in cancerous tumors or the presence of cysteine residues in protein matrices.

Tailored FTO/Ag/ZIF-8 structure as SERS substrate for ultrasensitive detection

In this work, a series of F-doped SnO2/Ag/zeolite imidazole framework (FTO/Ag/ZIF-8) sandwich structure have been successfully fabricated via a magnetic sputtering method and serve as surface-enhanced Raman scattering (SERS) substrate. The magnetic sputtering time of Ag was adjusted to obtain the optimal SERS substrate. The commonly used 4-mercaptobenzoic acid (4-MBA) molecules was selected for the SERS experiment. When the sputtering time of Ag nanoparticles (NPs) was 120 s, the FTO/Ag/ZIF-8 substrate showed the maximum SERS performance. In the system, the electromagnetic mechanism (EM) and charge-transfer (CT) enhancement mechanism have synergistic effect on the SERS phenomenon. Ag NPs was used to generate electromagnetic hot spots, which was beneficial to the EM mechanism. ZIF-8 could adsorb and capture more 4-MBA probe molecules to the hotspots. At the same time, CT happened between Ag, ZIF-8, and 4-MBA probe molecules, which was attribute to the CM mechanism. The enhancement factor (EF) of the composite SERS substrate was as high as 7.67 × 106. The detection limit of the substrate can reach 10-9 M of 4-MBA probe molecules. Moreover, the SERS templates showed good stability, the SERS signals almost unchanged after naturally kept for 6 months. Besides, due to the high sensitivity and good stability of the substrates, this work might broaden the potential practical application of SERS.

Improved Surface-Enhanced Raman Scattering Properties of ZrO2 Nanoparticles by Zn Doping.

In this study, ZrO2 and Zn–ZrO2 nanoparticles (NPs) with a series of Zn ion doping amounts were synthesized by the sol-gel process and utilized as substrates for surface-enhanced Raman scattering (SERS). After absorbing the probing molecule 4–mercaptobenzoic acid, the SERS signal intensities of Zn–ZrO2 NPs were all greater than that of the pure ZrO2. The 1% Zn doping concentration ZrO2 NPs exhibited the highest SERS enhancement, with an enhancement factor (EF) value of up to 104. X-ray diffraction, X-ray photoelectron spectroscopy, Ultraviolet (UV) photoelectron spectrometer, UV–vis spectroscopy, Transmission Electron Microscope (TEM), and Raman spectroscopy were used to characterize the properties of Zn–ZrO2 NPs and explore the mechanisms behind the SERS phenomenon. The charge transfer (CT) process is considered to be responsible for the SERS performance of 4–MBA adsorbed on Zn–ZrO2. The results of this study demonstrate that an appropriate doping ratio of Zn ions can promote the charge transfer process between ZrO2 NPs and probe molecules and significantly improve the SERS properties of ZrO2 substrates.

Sub-nanomolar detection of biogenic amines by SERS effect induced by hairy Janus silver nanoparticles

Surface enhanced Raman scattering (SERS) is largely used as a transduction method for analytes detection in liquid and vapor phase. In particular, SERS effect was promoted by a plethora of different metal and semiconducting nanoparticles (NPs) and silver and gold nanoparticles appear particularly suitable for this application. Nevertheless, silver nanoparticles intrinsic propensity to aggregate in large clusters reduces the possibility to use naked nanoparticles in SERS applications, for this reason they are usually functionalized with organic molecules. This approach inhibits the aggregation process but, on the other hand, reduces the surficial area of the NPs able to interact with the analyte molecules. In the present work, we propose a simple method to obtain surficial anisotropic Janus silver nanoparticles: octadecylamine was used to stabilize the nanoparticles and to promote the deposition of the silver nanoparticles on a solid substrate. The AgNPs/octadecylamine nanostructures showed the typical “hairy” Janus morphology and a strong SERS effect was observed when two biogenic amines, i. e. 2-phenylethylamine and tyramine, were fluxed on the solid film. SERS phenomenon was studied as a function both of the chemical structure of the fluxed amine and of the distance between the aromatic moiety and the nanoparticle allowing to propose the AgNPs/octadecylamine Janus nanoparticles as an active layer for the detection of phenylethylamine and tyramine in picomolar concentration.

Anisotropic surface enhanced Raman scattering in nanoparticle and nanowire arrays

Silver nanoparticles and nanowires self-aligned on pre-patterned rippled substrate are presented as active surface enhanced Raman scattering (SERS) substrates. The reported inter-particle gap of 5 nm and array periodicity of 35 nm are much lower than current lithographic limits. The observed anisotropy in SERS and surface plasmon resonance in such arrays is attributed to different plasmonic field enhancement along and across the chains of nanoparticles not due to shape anisotropy. For nanoparticle arrays higher SERS intensity is found along the particle chain, but for nanowire arrays higher SERS intensity is found for excitation across the wires. Higher intensity across nanowire arrays supports the argument that the SERS phenomenon is due to electromagnetic field enhancement (hot-junctions) caused by localized surface plasmon resonance across the nanowires having a 35 nm gap. The effect of inter-particle gap, ordering, and aspect ratio on field enhancement is demonstrated. Higher SERS intensity is observed in aligned elongated nanoparticles compared to aligned spherical, non-ordered nanoparticles, or aligned nanowires. Aligned silver nanowires enhance Raman scattering more strongly than aligned gold nanowires.

Label‐free detection of binary mixtures of proteins using surface‐enhanced Raman scattering

The surface‐enhanced Raman scattering (SERS) spectra of five binary mixtures of proteins were studied, including mixtures of apomyoglobin (apMb) and lysozyme, insulin and lysozyme, Mb and cytochrome c (cyt c), Mb and apoMb, and cyt c and human serum albumin. For mixtures in which both proteins did not contain chromophores, the variations in the intensities of SERS signals with changes in the relative concentration of the two proteins were largely proportional to the relative concentration of the protein mixtures. Similar results were obtained for mixtures in which both the proteins contained chromophores. However, for mixtures in which one protein contained chromophores and the other did not, the SERS intensities of the protein mixtures showed a bell‐shaped variation with changes in the compositions of the mixtures. The present study provides new insights into the application of SERS spectroscopy to label‐free detection in a binary of mixture of proteins. The complexities in both SERS phenomena and protein structures should be considered in the analysis of the SERS spectra of protein mixtures. By monitoring the heme band of a protein containing a heme and the NO3– band of a protein without a heme, the simultaneous detection of both proteins in a binary mixture may be possible. It has also been found that the larger the size of the protein, the smaller is the SERS intensity of that protein. Copyright © 2011 John Wiley & Sons, Ltd.

Optical Properties of Dye Molecules Adsorbed on Single Gold and Silver Nanoparticles

Despite the well-known relationship between the resonance Raman excitation profile and the absorption line shape, there is scant experimental evidence for effects in absorption or fluorescence spectroscopy related to the observations of surface-enhanced Raman scattering (SERS). On the other hand, numerous Raman studies have been done on the SERS phenomenon, where large enhancement factors have been determined. In this work, the absorption properties of molecules adsorbed on single gold and silver nanoparticles (monomers) have been investigated, with particular emphasis on an examination of the effect on the spectrum of the adsorbate. A number of the adsorbates studied are similar to those reported in SERS studies. The adsorbates can be divided into two classes according to the nature of the interaction with the adsorbent. Class I shows little change in the absorption spectrum. Class II shows a large reduction in absorption. The only examples of an increase in absorption arise from solvatochromic effects. ...