Vibrational and surface-enhanced Raman spectra of 1,6-diphenyl-1,3,5-hexatriene

The vibrational spectra and surface-enhanced Raman scattering (SERS) of 1,6-diphenyl-1,3,5-hexatriene (DPH) are discussed. The fundamental vibrational frequencies, overtones, and combinations observed in the infrared and Raman spectra of DPH are reported. The interpretation of the observed vibrational spectra was supported by a complete geometry optimization, followed by vibrational frequency and intensity computations for the cis- and trans- isomers of the DPH using density functional theory at the B3LYP/6-31G(d,p) level of theory. Because the molecule is photo-chemically active on Ag metal surfaces, the best SERS results for silver islands were obtained at low temperature and low energy density of the exciting laser line. DPH SERS on Au films was obtained at room temperature.     

Single-molecule detection using surface-enhanced resonance Raman scattering and Langmuir-Blodgett monolayers

The Langmuir-Blodgett (LB) technique has been used to obtain spatially resolved surface-enhanced resonance Raman scattering (SERRS) spectra of single dye molecules dispersed in the matrix of a fatty acid. The experimental results presented here mimic the original electrochemical surface-enhanced Raman scattering (SERS) work where the background bulk water did not interfere with the detection of the SERS signal of molecules adsorbed onto the rough silver electrode. LB monolayers of the dye in fatty acid have been fabricated on silver island films with a concentration, in average, of one probe molecule per micrometer square. The properties of single-molecule spectroscopy were investigated using micro-Raman including mapping and global images. Blinking of the SERRS signal was also observed.     

Surface-enhanced vibrational microspectroscopy of fulvic acid micelles

Micro-Raman spectroscopy, infrared absorption microspectroscopy, and AFM images of nano- or microsized micelles formed by fulvic acid (FA) solutions, prepared at different pHs, and cast on glass slides or gold island films, are reported. FA films cast on gold islands are characterized by surface-enhanced infrared absorption (SEIRA), surface-enhanced infrared reflection absorption, and surface-enhanced Raman scattering (SERS). Based on spectral evidence, it is expected that the chemisorption of FA on gold island films takes place through thiol groups, which become more active as pH increases. The SEIRA spectra of these films show increased peak intensity, as well as improved band resolution. Microspectroscopy SERS studies show that, at pH 5, FA form small aggregates on gold surfaces. At pH 8, FA tends to expand due to electrostatic repulsion, giving rise to a fractal surface composed of different domains. SERS studies of these domains reveal that the most polar molecules are located on the external faces. At pH 11, fractal conformations are even more pronounced and give rise to radial patterned structures. At this pH, the position of fulvic acid molecules in the fractal micelles is the same as observed at pH 8. In this way, SERS can be viewed as a powerful tool for the analysis of the composition, apparent contribution of the surface functional groups of FA films, and the FA building blocks (i.e., catechol, gallic, salicylic, or ftalic acids) in the structures of these materials.     

Surface-enhanced resonance Raman scattering of Langmuir-Blodgett monolayers of copper phthalocyanine-tetrasulphonate by island films

A copper phthalocyanine-tetrasulphonate (CuTsPc) layer is formed by adsorption of anions onto a cationic lipid monolayer. Then the films of CuTsPc were transferred to a glass substrate coated with evaporated gold islands. The surface-enhanced resonance Raman spectrum was investigated. All the Raman lines were assigned. The intensities of the Raman lines from CuTsPc films one, three, five,seven, nine and 11 layers thick were measured. We have chosen some typical Raman vibrational lines, such as those at 1538, 1499, 1451, 1339 and 957 cm^-1, to try to find the law of intensity reduction using our experiments.     

Resonance Raman evidence of immobilization of laccase on self-assembled monolayers of thiols on Ag and Au surfaces

Resonance Raman (RR) and surface-enhanced Raman scattering (SERS) spectroscopy have been used to study immobilization of laccase on self-assembled monolayers (SAMs) of thiols containing carboxylic and amino groups, deposited on silver and gold electrodes. A new, indirect way of monitoring laccase bound to the thiol-coated Ag and Au surfaces is presented. It was demonstrated that by recording the resonance Raman spectra of the colored product of the oxidation of syringaldazine (4-hydroxy-3,5-dimethoxybenzaldehydeazine) by laccase in the presence of molecular oxygen, one may easily confirm binding as well as enzymatic activity of laccase immobilized on the SAMs modified silver and gold surfaces.     

Surface-enhanced spectra on D-gluconic acid coated silver nanoparticles

Coated silver (Ag) colloids synthesized with D-glucose permit the observation of surface-enhanced fluorescence (SEF) and surface-enhanced resonance Raman scattering (SERRS) of the rhodamine B (RhB) molecule. The organic coating formed during the synthesis of the Ag nanostructures was identified by its surface-enhanced Raman scattering (SERS) spectrum as D-gluconic acid. The RhB molecule is used to exemplify the distance dependence of SEF and SERRS on the coated Ag nanostructures. The fluorescence enhancement factor for RhB on D-gluconic acid coated silver nanoparticles was determined experimentally and estimated using a simple model. Further support for the plasmon enhancement is obtained from the fact that the measured fluorescence lifetime of RhB on the silver coated with D-gluconic acid is shorter than that found on a glass surface. A very modest enhancement factor is obtained, as expected for very short distance between RhB and the metal surface. Given the very thin metal-fluorophore separation, estimated from the size of the D-gluconic acid, the energy transfer or fluorescence quenching is still efficient and the SEF enhancement is just overcoming the energy transfer. Therefore, both SEF and SERRS are observed. Notably, the aggregation of coated nanoparticles also increases the enhancement factor for SEF.     

Surface-enhanced vibrational spectroscopy of adsorbates on microemulsion synthesized gold nanoparticles

Very small (<10 nm) monodisperse gold nanoparticles (AuNPs) coated with a monolayer of decanethiol were prepared and their surface-enhanced infrared absorption (SEIRA) spectra were measured in the transmission mode. The AuNPs were prepared by the borohydride reduction of HAuCl(4) inside reverse micelles that were made by adding water to a hexane solution of sodium bis(2-ethylhexyl)sulfosuccinate (AOT). The gold nanoparticles were then stabilized by the addition of decanethiol. Subsequent addition of p-nitrothiophenol both facilitated the removal of excess AOT and showed that the gold surface was completely covered by the decanethiol. SEIRA spectra of decanethiol on gold particles prepared in AOT microemulsions were about twelve times more intense than corresponding layers on gold produced by electroless deposition and gave a significantly less noisy spectrum compared to the corresponding surface-enhanced Raman spectrum. The surface-enhanced Raman scattering (SERS) spectra of the same samples showed that the most intense spectrum was obtained from gold nanoparticles with a mean diameter of 2.5 nm. This result is in contrast to previous statements that SERS spectra could only be obtained from particles larger than 10 nm.     

Optical probes for biological applications based on surface-enhanced Raman scattering from indocyanine green on gold nanoparticles

We report surface-enhanced Raman scattering (SERS) studies on indocyanine green (ICG) on colloidal silver and gold and demonstrate a novel optical probe for applications in living cells. In addition to its own detection by the characteristic ICG SERS signatures, the ICG gold nanoprobe delivers spatially localized chemical information from its biological environment by employing SERS in the local optical fields of the gold nanoparticles. The probe offers the potential to increase the spectral specificity and selectivity of current chemical characterization approaches of living cells and biomaterials based on vibrational information.     

Silver nanowire layer-by-layer films as substrates for surface-enhanced Raman scattering

In this paper, the fabrication of highly stable, surface-enhanced Raman scattering (SERS) active dendrimer/silver nanowire layer-by-layer (LBL) films is reported. Ag nanowires, approximately 100 nm in diameter, were produced in solution and transferred, using the LBL technique, onto a single fifth-generation DAB-Am dendrimer layer on a glass substrate. The Ag nanowires, and the resulting LBL films were characterized using UV-visible surface plasmon absorbance, while the LBL films were further characterized by atomic force microscopy measurements and surface-enhanced Raman and resonance Raman scattering of several analytes. The dendrimer was found to effectively immobilize the Ag nanowires with increased control over spacing and aggregation of the particles. These films are shown to be excellent substrates for SERS/SERRS measurements, demonstrating significant enhancement, and trace detection capability. Several trial analytes were tested using a variety of excitation energies, and results confirmed effective enhancement of Raman signals throughout the visible range (442-785 nm) with different molecules. Analytes were deposited onto the enhancing Ag nanowire LBL films surface using both casting and Langmuir-Blodgett monolayer transferring techniques.     

Surface-enhanced Raman scattering on uniform transition-metal films: toward a versatile adsorbate vibrational strategy for solid-nonvacuum interfaces?

Procedures are outlined for the electrodeposition of ultrathin films of Pt-group transition metals onto gold that provide intense surface-enhanced Raman scattering (SERS) for adsorbates bound to the overlayers yet (unlike earlier reports) are sufficiently "pinhole-free" to avoid significant spectral and chemical interferences from the underlying substrate. Constant-current electrodeposition of Pd, Rh, Pt, and Ir from perchloric acid and/or phosphate electrolytes yields essentially layer-by-layer growth, so that near-ideal pinhole-free electrochemical and spectral characteristics are achieved for film thickness of ～2 monolayers or more. The desired film uniformity is diagnosed from the voltammetric oxide formation-removal behavior and, especially, from the absence of the characteristic C-O stretching (ν(CO)) SERS band at 2110-2120 cm(-)(1) due to CO binding to Au surface sites. Carbon monoxide is also employed as a surface environment-sensitive adsorbate to probe the electrochemical SERS characteristics as a function of the transition-metal film thickness. The Raman enhancement was observed to decrease by 2-fold every 10-20 ? or so, exhibiting a "spacer distance" dependence that is weaker than (but functionally similar to) recently reported organic insulator films. The practical value of the present films for obtaining rich vibrational spectra for diverse adsorbates on transition metals is pointed out and briefly illustrated for benzonitrile on a Pt film electrode. The more general promise of this overlayer film SERS strategy as a versatile vibrational technique for characterizing other types of chemically important surface materials is also noted.     

Silver-island films as substrates for enhanced Raman scattering: effect of deposition rate on intensity.

The relationship between surface-enhanced resonance Raman scattering (SERRS) intensity and the rate of deposition during silver-island film preparation was examined, using zinc tetraphenylporphine (ZnTPP) as the adsorbate. The effect of the deposition rate on the optical properties of the films at specific wavelengths was also analyzed. The data show that the film extinction (the term extinction is used rather than absorption because the spectra have not been corrected for reflection or scattering losses) increases exponentially at 514 and 458 nm as the deposition rate is decreased. SERRS intensities also increase exponentially at these two excitation wavelengths with a decrease in the deposition rate. The optical density is linearly related to the SERRS intensity, and maximal enhancement is observed for films with the greatest extinction at these excitation wavelengths. In contrast, neither the extinction at 406 nm nor the SERRS scattering intensities resulting from excitation at this wavelength differ substantially. The surface-enhanced Raman scattering (SERS) intensity and the electronic spectra of 4,4'-bipyridine (BP) adsorbed onto silver films as a function deposition rate were also examined. The behavior of the nonresonantly enhanced BP is comparable to that of the resonantly enhanced ZnTPP samples. The effects of the surface morphology, as determined from transmission electron micrographs of the films at various deposition rates, on the corresponding electronic spectra and SERS/SERRS spectra are described.     

New strategy for ready application of surface-enhanced resonance Raman scattering/surface-enhanced Raman scattering to chemical analysis of organic films on dielectric substrates

Dropping of appropriately concentrated AgNO3 and NaBH4 solutions, as well as laser-ablated Ag sols, onto organic molecules results in the formation of aggregated Ag nanoparticles that can induce surface-enhanced Raman scattering (SERS) for the molecules. The addition of flocculating agents such as alkali halides can further increase the Raman signals. We demonstrate in this work that Raman spectra can be obtained even for 0.01 monolayers of R6G on Si simply by spreading silver nanoparticles and/or fabricating Ag nanoparticles and nanoaggregates at the gaps and vacant sites of R6G molecules. The application prospect of the present methodology is extremely high, not only because of its simplicity but also because of the fact that the observation of vibrational spectra is one of the most incisive methods for understanding the chemical and physical phenomena on a variety of surfaces.     

Hole-enhanced Raman scattering

Stokes and anti-Stokes non-resonant hole-enhanced Raman scattering (HERS) spectra with high signal-to-noise ratio (S/N) are reported for the first time for aqueous phase R6G molecules adsorbed onto random nanoholes in thin gold films. Compared to conventional surface-enhanced Raman scattering from nanometric gold colloid particles, HERS exhibits higher strength gain, exceptional reproducibility, simple and reliable substrate preparation, and excellent mechanical stability. By correlating the hole density with Raman scattering gain, we determined optimum HERS gain for 50 nm diameter holes at approximately 100 holes/microm(2). Providing a Raman substrate with uniform "hot spots", we expect that HERS will make the quantitative Raman analysis of biological molecules possible.     

Deposition of the fractal-like gold particles onto electrospun polymethylmethacrylate fibrous mats and their application in surface-enhanced Raman scattering

The ultrafine polymethylmethacrylate fibers containing gold nanoparticles have been prepared by using the electrospinning technique. Then the continuously coarse gold films formed by fractal-like thorny gold particles were deposited on the organic eletrospun fiber surface by an electroless process. The morphology of coarse gold films was characterized by scanning electron and transmission electron microscopy. The results revealed that the morphology of the gold particles was affected not only by the amount of gold seeds embedded in the organic fibers but also by the amount of gold deposited on the fiber's surfaces. The surface-enhanced Raman scattering (SERS) effect of the fibrous mats coated with gold films was evaluated by using Rhodamine B as an adsorbate. The results indicated that this kind of fibrous mat exhibited high and reproducible SERS activity and could be developed as highly sensitive SERS substrate.     

Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon

This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.     

Broadband coherent anti-Stokes Raman spectroscopy characterization of polymer thin films

Broadband coherent anti-Stokes Raman spectroscopy (CARS) is demonstrated as an effective probe of polymer thin film materials. A simple modification to a 1 kHz broad bandwidth sum frequency generation (SFG) spectrometer permits acquisition of CARS spectra for polymer thin films less than 100 nm thick, a dimension relevant to organic electronic device applications. CARS spectra are compared to the conventional Raman spectra of polystyrene and the resonance-enhanced Raman spectra of poly(3-hexylthiophene). The CARS spectra obtained under these conditions consistently demonstrate enhanced signal-to-noise ratio compared to the spontaneous Raman scattering. The sensitivity of the CARS measurement is limited by the damage threshold of the samples. The dielectic properties of the substrate have a dramatic effect on the detected signal intensity. For ultrathin films, the strongest signals are obtained from fused silica surfaces. Similar to surface-enhanced Raman scattering (SERS), Au also gives a large signal, but contrary to SERS, no surface roughening is necessary.     

Aligned silver nanorod arrays as substrates for surface-enhanced infrared absorption spectroscopy

Preferentially aligned silver nanorod arrays prepared by oblique angle vapor deposition were evaluated as substrates for surface-enhanced infrared absorption (SEIRA) spectroscopy. These nanorod arrays have an irregular surface lattice and are composed of tilted, cylindrically shaped nanorods that have an average length of 868 nm +/- 95 nm and an average diameter of 99 nm +/- 29 nm. The overall enhancement factor for chemisorbed organic films of para-nitrobenzoic acid (PNBA) deposited onto the Ag nanorod arrays analyzed by external reflection SEIRA was calculated to be 31 +/- 9 compared to infrared reflection-absorption spectroscopy (IRRAS) obtained from a 500 nm Ag film substrate. This enhancement is attributed to the unique optical properties of the nanorod arrays as well as the increased surface area provided by the nanorod substrate. SEIRA reflection-absorbance intensity was observed with both p- and s-polarized incident radiation with angles of incidence ranging from 25 degrees to 80 degrees . The largest intensity was achieved with p-polarization and incident angles larger than 75 degrees . Polarization-dependent ultraviolet/visible/near-infrared (UV/Vis/NIR) spectra of the nanorod arrays demonstrate that the red-shifted surface plasmon peaks of the elongated nanorods may be partially responsible for the observed SEIRA response. The SEIRA detection limit for the Ag nanorod arrays was estimated to be 0.08 ng/cm(2). Surface-enhanced Raman scattering (SERS) and SEIRA analysis of chemisorbed PNBA utilizing the same nanorod substrate is demonstrated.     

Plasmon-enhanced resonance Raman scattering and fluorescence in Langmuir-Blodgett monolayers

Localized surface plasmon resonances in silver and gold nanostructures are engaged to enhance the inelastic Raman scattering and the fluorescence of a phopholipid containing a sulforhodamine 101 acid chloride dye known as Texas Red. The most efficient coupling and enhancement are attained when the excitation laser line is in resonance with both the chromophore and the plasmon absorption of the nanostructure, the case of surface-enhanced resonance Raman scattering, allowing single-molecule detection. The tagged phospholipid was incorporated into a single fatty acid Langmuir monolayer at varying concentrations and transferred onto an evaporated Ag nanoparticle film. Surface-enhanced fluorescence is achieved using shell-isolated silica-coated gold nanoparticles, an emission enhancement named SHINEF.     

Overtones and combinations in single-molecule surface-enhanced resonance Raman scattering spectra

The observation of overtones and combinations in the SERRS spectra of single molecules dispersed in Langmuir-Blodgett monolayers is confirmed for a family of molecules. The detection of fundamentals, combinations, and overtones in single-molecule spectra of a series of perylenetetracarboxylic diimides (PTCD) is achieved with spatially resolved surface-enhanced resonance Raman scattering (SERRS). The Langmuir-Blodgett technique is used to create monomolecular thick films on metal islands containing on average one probed molecule within the field of view of the Raman microscope. The enhancement needed for single-molecule detection is achieved through the multiplicative effects of electromagnetic enhancement by metal nanostructures and resonance Raman enhancement by excitation into molecular electronic absorption bands. Overtone and combination progressions are well resolved in the average SERRS spectra of all three PTCD molecules.     

Multilayer enhanced gold film over nanostructure surface-enhanced Raman substrates

We have developed a novel class of gold multilayer, surface-enhanced Raman scattering (SERS) substrates that are capable of enhancing SERS signals by 15.3-fold over conventional gold film over nanostructure (GFON) SERS substrates, making them comparable in sensitivity to optimized silver film over nanostructure (SFON) substrates, while providing the long-term stability obtained from gold. They are fabricated by depositing 10 A thick silver oxide islands on conventional GFON substrates, followed by deposition of a second continuous gold layer. The silver oxide layer acts as a dielectric spacer between the two continuous gold films and produces significantly enhanced SERS signals, as compared to optimized single layer substrates of the same geometry or comparable substrates prepared by deposition of silver islands that are not oxidized. In addition to the enhanced sensitivity of these multilayer substrates, they also exhibit long SERS active shelf-lives (i.e., months), with no measurable degradation in SERS enhancement, and relative standard deviations in SERS enhancement of less than 5.2% across the substrate's surface.