Surface‐enhanced Raman scattering of 4‐aminobenzenethiol on silver: confirmation of the origin of b2‐type bands

In order to resolve the dispute on the origin of the b₂‐type bands in the surface‐enhanced Raman scattering (SERS) of 4‐aminobenzenethiol (4‐ABT), we have measured its SERS spectra under a variety of conditions, including variable temperature and rotation, electrochemistry, and pH, as well as in the presence of a reducing agent. For comparison, the SERS spectra of 4‐nitrobenzenethiol (4‐NBT) and methyl orange (MO), a prototype azo compound, were also measured. First, we found that 4‐ABT on Ag is not subjected to photoreaction, although 4‐NBT is highly photoreactive on a silver surface. In the electrochemical environment, b₂‐type bands of 4‐ABT lost their intensity at very negative potentials, but the intensity recovered immediately upon raising the potential. In addition, b₂‐type bands were observed under rotation even after lowering the potential. The disappearance and reappearance of the b₂‐type bands could also be observed by bringing the sample of 4‐ABT on Ag into contact consecutively with a borohydride solution and water. This is because the surface potential of Ag is lowered by contact with a borohydride solution. Besides, we found that not only the normal Raman but also the SERS spectral features of 4‐ABT are hardly affected by pH variation, while the spectral features of MO are greatly affected, especially in the region of the NN stretching vibration, suggesting that the possibility of a photoconversion of 4‐ABT to an azo compound is low. Altogether, the b₂‐type bands were attributed to 4‐ABT, appearing in conjunction with the chemical enhancement mechanism in SERS. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanostructured gold surfaces as reproducible substrates for surface‐enhanced Raman spectroscopy

Raman spectroscopy is a common tool for the qualitative and quantitative chemical analysis of molecules. Although the unique identification of molecules is possible via their vibrational lines, high concentrations (mmol/l) are needed for their nonresonant excitation owing to their low scattering cross section. The intensity of the Raman spectra is amplified by the use of the surface‐enhanced Raman scattering (SERS) technique. While the use of silver sols results only in a limited reproducibility of the Raman line intensities, lithographically designed, nanostructured gold surfaces used as SERS‐active substrates should, in principle, combine the high sensitivity with better reproducibility. For this purpose, we have produced gratings of gold dots on Si(001) surfaces by means of electron beam lithography. Qualitative and quantitative investigations of crystal violet (CV) performed using nanostructured surfaces give high reproducibility and enhancement of the Raman lines. The substrates are reusable after cleaning; all results presented could be obtained from a single SERS substrate. For the experiments very low laser powers were used. Copyright © 2006 John Wiley & Sons, Ltd.     

Theoretical investigation on surface‐enhanced Raman evidence for conformation transition of dimercaptoazobenzene adsorbed on gold nanoclusters

Probing and controlling the configurations and mechanical motions of the azobenzenes adsorbed on the metal substrates are preliminary for their applicability in various functional devices. In this work, we presented a detailed investigation of Raman properties of the dimercaptoazobenzene (DMAB) bound to gold nanoclusters using density functional calculations. It is demonstrated that the spectral features of the trans conformation of DMAB are quite different from the cis conformation, and the Raman intensities of the trans‐DMAB are much larger. Magnitude of chemical enhancement for the adsorbed trans‐DMAB is found to be close to or less than that for the adsorbed cis‐DMAB for the molecule–cluster complexes. This change trend can be, to a large extent, governed by the energy difference between the highest occupied energy level of the molecule and the lowest unoccupied energy level of the gold. Moreover, it is further demonstrated that differences in Raman intensities of the two conformations can be amplified for the cluster–molecular–cluster junctions, and thus chemical enhancement is much larger for the trans conformation than the cis conformation, possibly facilitating the experimental identification of the trans/cis DMAB. Copyright © 2012 John Wiley & Sons, Ltd.     

Adsorption of 4,4′‐thiobisbenzenethiol on silver surfaces: surface‐enhanced Raman scattering study

Adsorption of 4,4′‐thiobisbenzenethiol (4,4′‐TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface‐enhanced Raman scattering (SERS) for the first time, which indicates that 4,4′‐TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H‐atoms of the S H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4′‐TBBT in the two systems. It is inferred from the SERS signal that the two aromatic rings in 4,4′‐TBBT molecule are parallel to the colloidal silver surface as seen from the disappearance of ν_{C H} band (3054 cm⁻¹), which is a vibrational mode to be used to determine the orientation of a molecule on metals according to the surface selection rule, while on the roughened silver electrode surface they are tilted to the surface as seen from the enhanced signal of ν_{C H}. The orientation of the C‐S bond is tilted with respect to the silver surface in both cases as inferred from the strong enhancement of the ν_{C S}. SERS spectra of 4,4′‐TBBT on the roughened silver electrode with different applied potentials reveal that the enhancement of 4,4′‐TBBT on the roughened silver electrode surface may be related to the chemical mechanism (CM). More importantly, the adsorption of 4,4′‐TBBT on the silver electrode is expected to be useful to covalently adsorb metal nanoparticles through the free S H bond to form two‐ or three‐ dimensional nanostructures. Copyright © 2007 John Wiley & Sons, Ltd.     

Nanostructured thin films as surface‐enhanced Raman scattering substrates

Nanoporous thin films with silver nanoparticles were synthesized with a bottom–up approach, and its potential as effective surface‐enhanced Raman scattering (SERS) substrates was demonstrated. The use of mesoporous titania films as substrates allowed to control the growth of nanoparticles on the film surface. Atomic force microscopy measurements, Ultraviolet‐visible and X‐ray diffraction analysis confirmed the photoreduction of Ag⁺ to Ag⁰ with the formation of nanoparticles with crystallite dimensions of 32 to 36 nm. The new substrates allowed the detection of two analytes (rhodamine B isothiocyanate and cytochrome c), present in solutions at very low concentrations, highlighting their potential in SERS sensing. Reproducibility, homogeneity, enhancement factor of the substrate, consistency of results and detection limits were also assessed. Copyright © 2012 John Wiley & Sons, Ltd.     

Nanostructures and nanostructured substrates for surface—enhanced Raman scattering (SERS)

We review the performance of various nanoscaled structures needed to support the propagation of the surface plasmons responsible for surface‐enhanced Raman scattering (SERS), and assess the potential for the optimisation of the compromise between enhancement and reproducibility that they provide, and hence their utility for relevant applications. We divide these nanostructures into those comprising structured arrays of discrete nanoparticles in two or three dimensions, and those comprising structured or regularly patterned surfaces in two or three dimensions. The most promising in terms of this compromise are those that involve the tethering of functionalised metal nanoparticles to surfaces. They are not only reproducible, but the functionalisation provides a measure of selectivity to relevant target analytes that the majority of SERS applications require. Copyright © 2008 John Wiley & Sons, Ltd.     

Single‐molecule detection of thionine on aggregated gold nanoparticles by surface enhanced Raman scattering

We report observations of single‐molecule detection of thionine and its dynamic interactions on aggregated gold nanoparticle clusters using surface enhanced Raman scattering (SERS). Spectral intensities were found to be independent of the size of Au nanoparticles studied (from 17 to 80 nm) at thionine concentration below 10⁻¹² M or at single‐molecule concentration levels. Raman line separations and, in particular, spectral fluctuations and blinking were also observed, suggesting temporal changes in single molecular motion and/or arrangements of thionine on Au nanoparticle surfaces. In contrast, by using dispersed Au nanoparticles, only ensemble SERS spectra could be observed at relatively high concentrations (> 10⁻⁸ M thionine), and spectral intensities varied with the size of Au nanoparticles. Copyright © 2007 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering spectroscopy via gold nanostars

Anisotropic metallic nanoparticles (NPs) have unique optical properties, which lend them to applications such as surface‐enhanced Raman scattering (SERS) spectroscopy. Star‐shaped gold (Au) NPs were prepared in aqueous solutions by the seed‐mediated growth method and tested for Raman enhancement using 2‐mercaptopyridine (2‐MPy) and crystal violet (CV) probing molecules. For both molecules, the SERS activity of the nanostars was notably stronger than that of the spherical Au NPs of similar size. The Raman enhancement factors (EFs) for 2‐MPy on Au nanostars and nanorods are comparable and estimated as greater than 5 orders of magnitude. However, the enhancement for CV on nanostars was significantly higher than for nanorods, in particular at CV concentrations of 100 nM or lower. This article is a US Government work and is in the public domain in the USA. Published in 2008 by John Wiley & Sons, Ltd.     

Deep‐UV surface‐enhanced Raman scattering

The presented work demonstrates, to the best of our knowledge, for the first time the capability of an aluminium surface to act as an SERS‐active substrate for deep‐UV excitation wavelengths. Copyright © 2007 John Wiley & Sons, Ltd.     

Adsorption study of 4‐MBA on TiO2 nanoparticles by surface‐enhanced Raman spectroscopy

In this paper, the adsorption of 4‐mercaptobenzoic acid (4‐MBA) on TiO₂ nanoparticles was studied mostly by surface‐enhanced Raman spectroscopy (SERS) and UV‐vis spectroscopy, at different pH values as well as under different temperatures and concentrations. The results show that the 4‐MBA molecules are bonded to the TiO₂ surface both through the sulfur atoms and COO⁻ groups at neutral or alkaline pH, but only through the sulfur atom at acidic pH. Furthermore, the 4‐MBA molecules possess high adsorptive stability on TiO₂ at a comparatively high temperature (150 °C). Concentration‐dependent SERS experiments show that the saturation concentration for 4‐MBA adsorbed on TiO₂ is about 10⁻³ M in natural case (pH = 6). Copyright © 2009 John Wiley & Sons, Ltd.     

Biocompatible gold/silver nanostars for surface‐enhanced Raman scattering

Raman‐enhancing properties of chitosan (CS)‐coated gold/silver nanostars (Au/AgNSs) were demonstrated by using them as a surface‐enhanced Raman scattering (SERS) probe. Based on the energy‐dispersive X‐ray spectroscopy element distribution maps and highly enhanced SERS spectra, we suggest that the incorporation of silver into the NS tips leads to a stronger SERS behavior. The SERS spectra of the proteins adsorbed on the NS surface greatly differ from their respective Raman spectra in both the band positions and relative intensities, indicating that the protein molecules penetrate through the CS coating layer and interact closely with the NS surface. Raman and SERS spectra of Chlamydia trachomatis protease/proteasomelike activity factor are reported for the first time, demonstrating the potential of these NSs for the development of a diagnosis method for Chlamydia based on SERS. The results showed a good SERS performance of the Au/AgNSs and their potential for SERS detection of biomolecules. Copyright © 2016 John Wiley & Sons, Ltd.     

New insights on surface‐enhanced Raman scattering based on controlled aggregation and spectroscopic studies,DFT calculations and symmetry analysis for 3,6‐bi‐2‐pyridyl‐1,2,4,5‐tetrazine adsorbed onto citrate‐stabilized gold nanoparticles

A systematic study on the surface‐enhanced Raman scattering (SERS) for 3,6‐bi‐2‐pyridyl‐1,2,4,5‐tetrazine (bptz) adsorbed onto citrate‐modified gold nanoparticles (cit‐AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit‐AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge‐transfer (CT) effects. The most strongly enhanced vibrations belong to a₁ and b₂ representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright © 2010 John Wiley & Sons, Ltd.     

Measurement of the absolute Raman scattering cross section of the 1584‐cm−1 band of benzenethiol and the surface‐enhanced Raman scattering cross section enhancement factor for femtosecond laser‐nanostructured substrates

The absolute Raman scattering cross section (σ_RS) for the 1584‐cm⁻¹ band of benzenethiol at 897 nm (1.383 eV) has been measured to be 8.9 ± 1.8 × 10⁻³⁰ cm² using a 785‐nm pump laser. A temperature‐controlled, small‐cavity blackbody source was used to calibrate the signal output of the Raman spectrometer. We also measured the absolute surface‐enhanced Raman scattering cross section (σ_SERS) of benzenethiol adsorbed onto a silver‐coated, femtosecond laser‐nanostructured substrate. Using the measured values of 8.9 ± 1.8 × 10⁻³⁰ and 6.6 ± 1.3 × 10⁻²⁴ cm² for σ_RS and σ_SERS respectively, we calculate an average cross‐section enhancement factor (EF) of 0.8 ± 0.3 × 10⁶. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical elucidation of the origin of surface‐enhanced Raman spectra of PCB52 adsorbed on silver substrates

To better understand experimentally observed surface‐enhanced Raman Scattering (SERS) of polychlorinated biphenyls (PCBs) adsorbed on nanoscaled silver substrates, a systematic theoretical study was performed by carrying out density functional theory and time‐dependent density functional theory calculations. 2,2′,5,5′‐tetrachlorobiphenyl (PCB52) was chosen as a model molecule of PCBs, and Ag_n (n = 2, 4, 6, and 10) clusters were used to mimic active sites of substrates. Calculated normal Raman spectra of PCB52–Ag_n (n = 2, 4, 6, and 10) complexes are analogical in profile to that of isolated PCB52 with only slightly enhanced intensity. In contrast, the corresponding SERS spectra calculated at adopted incident light are strongly enhanced, and the calculated enhancement factors are 10⁴ ~ 10⁵. Thus, the experimentally observed SERS phenomenon of PCBs supported on Ag substrates should correspond to the SERS spectra rather than the normal Raman spectra. The dominant enhancement in Raman intensities origins from the charge transfer resonance enhancement between the molecule and clusters. Copyright © 2014 John Wiley & Sons, Ltd.     

Microwave monitoring of silver nanoparticle sintering for surface‐enhanced Raman scattering substrates

One of the most widely used methods for surface‐enhanced Raman scattering (SERS) employs silver or gold nanoparticles either in colloidal suspension or in the dry‐drop form. In such substrates the SERS amplification factors depend critically on the interparticle distances. Here, we report that microwave absorption as a function of temperature in dry‐drop substrates can be used as a probe to demarcate temperature regions for thermal annealing to produce SERS substrates with very high amplification factors. Copyright © 2011 John Wiley & Sons, Ltd.     

Ultrathin silver‐coated gold nanoparticles as suitable substrate for surface‐enhanced Raman scattering

Surface‐enhanced Raman scattering (SERS) is an extremely powerful tool for the analysis of the composition of bimetallic nanoparticle (BNP) surfaces because of the different adsorption schemes adopted by several molecules on different metals, such as Au and Ag. The preparation of BNPs normally implies a change in the plasmonic properties of the core metal. However, for technological applications it could be interesting to synthesize core–shell structures preserving these original plasmonic properties. In this work, we present a facile method for coating colloidal gold nanoparticles (NPs) in solution with a very thin shell of silver. The resulting bimetallic Au@Ag system maintains the optical properties of gold but shows the chemical surface affinity of silver. The effectiveness of the coating method, as well as the progressive silver enrichment of the outermost part of the Au NPs, has been monitored through the SERS spectra of several species (chloride, luteolin, thiophenol and lucigenin), which show different behaviors on gold and silver surfaces. A growth mechanism of the Ag shell is proposed on the basis of the spectroscopic and microscopic data consisting in the formation and deposit of Ag clusters on the Au NP surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering from polystyrene on gold clusters

Surface‐enhanced Raman scattering (SERS) constitutes a spectroscopic method of rapidly growing importance, and polystyrene is a widely used compound of great industrial importance. In this work, SERS data were obtained from polystyrene samples prepared by vapor deposition of gold and plasma‐induced polymerization of styrene gas. A thorough examination of this data is presented. The relationships between sample preparation parameters, gold‐cluster morphology, and SERS intensity were elucidated. Using Wilson's notation, vibrations were assigned to all bands between 250 and 1750 cm⁻¹ in the ordinary Raman and SERS spectra of polystyrene. The correct assignment of these bands would be a significant achievement because they have been controversial in the literature for ∼30 years. Our assignments were made by reviewing the literature and comparing the assignments found there to spectral data acquired during this study; they were confirmed using density functional theory (DFT) calculations performed on the styrene monomer. The orientation of polystyrene's phenyl ring, relative to the gold surface, was determined. It has been suggested that reactions involving silver catalyze polystyrene degradation during SERS, but we found that silver is not necessary for the degradation to occur. Copyright © 2009 John Wiley & Sons, Ltd.     

pH‐dependent surface‐enhanced Raman scattering observation of sulfanilamide on the silver surface

Monolayers of sulfanilamide on metallic surface can serve as an ideal model for understanding the interaction mechanism between the metal and the sulfanilamide molecule. In the present paper, the surface‐enhanced Raman scattering (SERS) technique was employed to obtain the SERS spectra of sulfanilamide monolayers formed on the silver surface under different pH values. Assignments of the spectra were carried out with the aid of density functional theory (DFT) calculations (BLYP/6‐311G). It can be found that the adsorption function of sulfanilamide on the silver surface was influenced by the pH value. The fully protonated sulfanilamide molecule adsorbed on the silver surface through N¹³H₂ group and the benzene ring anchored in a relatively perpendicular manner leading to N⁷H₂ and S¹⁰O₂ groups near the surface, while the completely deprotonated sulfanilamide molecule attached on the silver surface via N⁷H₂ and the benzene ring was perpendicular to, and the N¹³H₂ and S¹⁰O₂ groups were far from the silver surface. Copyright © 2009 John Wiley & Sons, Ltd.     

Improved surface‐enhanced Raman scattering properties of TiO2 nanoparticles by Zn dopant

In this paper, pure and Zn‐doped TiO₂ nanoparticles (NPs) with various content of Zn were prepared by a sol–hydrothermal method and were employed as active substrates for surface‐enhanced Raman scattering (SERS). On the 3% Zn‐doped TiO₂ substrate, 4‐mercaptobenzoic acid(4‐MBA) molecules exhibit a higher SERS intensity by a factor of 6, as compared with the native enhancement of 4‐MBA adsorbed on undoped TiO₂ NPs. Moreover, the higher SERS activity was still observed on the 3% Zn‐doped TiO₂ NPs at temperature even up to 125 °C. These results indicate that an appropriate amount of Zn doping can improve the SERS performances of TiO₂ SERS‐active substrates. The introduction of Zn dopant can enrich the surface states (defects) of TiO₂ and improve the separation efficiency of photo‐generated charge carriers (electrons and holes) in TiO₂, according to measurements of X‐ray diffraction, UV‐visible diffuse reflectance spectroscopy, and photoluminescence, which are responsible for the influence of Zn dopant on the improved SERS performances of TiO₂ NPs. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of Pb2+ on L‐glutathione monolayers on a silver surface investigated by surface‐enhanced Raman scattering spectroscopy

Surface‐enhanced Raman scattering (SERS) spectroscopy was applied to observe reduced L ‐glutathione [L‐Glut(R)] molecules self‐assembled on a silver surface and the effect of Pb²⁺ on them. The adsorption structure suggests that the mercapto group of the L‐Glut(R) molecule is covalently bonded to the silver surface along with the imine group, amino group and entire carboxyl group in a perpendicular orientation after self‐reorganization. Results of SERS experiment show that Pb²⁺ influences the structure of L‐glutathione monolayers as a result of the binding reaction possibly occurring between Pb²⁺ and the carboxyl and the amino groups. Copyright © 2009 John Wiley & Sons, Ltd.