Surface-enhanced Raman scattering of water adsorbed on silver electrodes

Temporal evolution of the Raman spectra of H₂O, D₂O and HDO during an oxidation-reduction cycle of a Ag electrode in aqueous 1 M KCl or KBr has been recorded with an optical multichannel analyzer. Surface enhanced Raman spectra of the adsorbed water are readily observable and are different from the Raman spectra of bulk water.     

Surface-enhanced Raman spectroscopic evidence of methanol oxidation on ruthenium electrodes

Electrooxidation of methanol on Ru surfaces was investigated using in situ surface-enhanced Raman spectroscopy. Although the cyclic voltammogram did not show a significant methanol oxidation current on Ru, a Raman band at approximately 1970-1992 cm(-1) was observed from 0.4 to 0.8 V in 0.1 M HClO(4) + 1 M methanol. By comparing with the C-O stretching band (nu(CO)) of carbon monoxide (CO) adsorbed on RuO(2)(110) in the ultrahigh vacuum and on oxidized Ru electrodes, the observed spectral feature is assigned to nu(CO) of adsorbed CO (CO(ads)) on RuO(2). The formation of CO(ads) suggests that methanol oxidation does occur on Ru at room temperature, which is in contrast to the perception that Ru is not active for the reaction. The lack of significant methanol oxidation current is attributed to the competing rapid surface oxidation, which forms inactive surface oxides and therefore inhibits the methanol oxidation.     

Surface-enhanced Raman study of organic sulfides adsorbed on silver

The surface-enhanced Raman scatterings of dimethyl sulfide, diethyl sulfide and dimethyl disulfide have been investigated in silver sol. The dimethyl disulfide molecule decomposes on silver to the corresponding mercaptide implying facile cleavage of its S---S bond. The C---S bond in dialkyl monosulfide appears not to cleave on silver. For diethyl sulfide, the C₂ conformation seems to be favorable on silver than other conformations.     

Self-assembly of 1,4-phenylene diisocyanide and terephthalic acid on Ni, Cu and Pt

This paper compares the adsorption behavior of 1,4-phenylene diisocyanide (PDI) and terephthalic acid (TA) on Ni, Cu and Pt surfaces. Following competitive adsorption from two-component equimolar solutions of PDI and TA, chemical analysis by XPS confirmed the preferential adsorption of PDI over TA on Ni and Cu. The ability to form "chemically sticky" surfaces on Ni, Cu and Pt surfaces by self-assembly into organized organic thin films (OOTFs) was also investigated. PM-IRRAS analysis revealed a tendency for PDI to bond in a terminal fashion through one isocyanide group, on both Ni and Cu. In contrast, PDI adsorbed in a flat configuration on Pt. Chemically sticky OOTFs have potential for utilization as coupling agents to achieve a high cross-link density and enhance stress transfer between the nanoclusters and the organic matrix molecules in metal-nanocluster-filled polymer matrix nanocomposites. The results of this work indicate that 1,4-phenylene diisocyanide is a suitable choice as a coupling agent for metal nanoclusters of Ni and Cu.     

Self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol adsorbed on silver nanoparticles: Surface-enhanced Raman scattering study

Self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol (1,4-BDT) adsorbed on silver nanoparticles were investigated experimentally with surface-enhanced Raman scattering (SERS) and theoretically with density functional theory (DFT) and finite difference time domain (FDTD) method. The absorption spectroscopy of 1,4-BDT in silver sol at different time intervals was measured, which give the indirect evidence of self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol (1,4-BDT) adsorbed on silver nanoparticles. To obtain the direct evidence of self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol (1,4-BDT) adsorbed on silver nanoparticles, the SERS of 1,4-BDT were measured experimentally and investigated theoretically. The appearances of S–S stretching band (revealing the formation of multilayers of 1,4-BDT), and strongly enhanced S–C stretching, C–C ring stretching vibrational modes clearly show self-assembled dynamics of 1,4-BDT.     

Surface-enhanced Raman spectroscopic detection of Bacillus subtilis spores using gold nanoparticle based substrates

The detection of bacterial spores requires the capability of highly sensitive and biocompatible probes. This report describes the findings of an investigation of surface-enhanced Raman spectroscopic (SERS) detection of Bacillus subtilis spores using gold-nanoparticle (Au NP) based substrates as the spectroscopic probe. The SERS substrates are shown to be highly sensitive for the detection of B. subtilis spores, which release calcium dipicolinate (CaDPA) as a biomarker. The SERS bands of CaDPA released from the spores by extraction using nitric acid provide the diagnostic signal for the detection, exhibiting a limit of detection (LOD) of 1.5×10(9) spores L(-1) (or 2.5×10(-14) M). The LOD for the Au NP based substrates is quite comparable with that reported for Ag nanoparticle based substrates for the detection of spores, though the surface adsorption equilibrium constant is found to be smaller by a factor of 1-2 orders of magnitude than the Ag nanoparticle based substrates. The results have also revealed the viability of SERS detection of CaDPA released from the spores under ambient conditions without extraction using any reagents, showing a significant reduction of the diagnostic peak width for the detection. These findings have demonstrated the viability of Au NP based SERS substrates for direct use with high resolution and sensitivity as a biocompatible probe for the detection of bacterial spores.     

Infrared and Raman spectroscopic study of 1,2-benzenedithiol adsorbed on silver

Adsorption of 1,2-benzenedithiol (1,2-BDT) on a silver surface has been investigated by surface-enhanced Raman (SER) and reflection-absorption infrared (RAI) spectroscopy. The molecule was adsorbed on silver very favorably by forming two Ag---S bonds after deprotonation. From the RAI spectral pattern, the benzene ring of adsorbed 1,2-BDT was presumed to be tilted by ca. 38° from the surface normal. This RAI information was used to test the validity of various proposed SER selection rules. Being frequently quoted in the literature, the presence or absence of the benzene ring CH stretching vibration in the SER spectrum seemed, in fact, to be a very useful indicator in judging the perpendicular or parallel orientation of the benzene ring with respect to the surface. However, the so-called in-plane/out-of-plane dichotomy as well as the more elaborate symmetry-based electromagnetic selection rule was found not to work in the present system.     

Simultaneous Raman spectroscopic and differential double-layer capacitance measurements of pyridine adsorbed on roughened silver electrodes

It is shown that differential double-layer capacitance data can be obtained simultaneously with the recording of the Raman spectra of adsorbates at a roughened silver microelectrode. The use of such data to provide information about the structure of the silver electrode/aqueous KCl (0.1 M)/pyridine (0.1 M) interface is demonstrated.     

A comparison of surface-enhanced infrared and surface-enhanced Raman spectra of pyrazine adsorbed on polycrystalline gold electrodes

The adsorption of pyrazine at a polycrystalline Au film electrode has been investigated using in situ surface-enhanced infrared absorption spectroscopy (SEIRAS), chronocoulometry, and ac impedance. Combining the SEIRA data and the thermodynamic data (the surface charge density of the electrode and the relative Gibbs surface excess of pyrazine), pyrazine was found to adsorb on the surface with a vertical end-on configuration via one N atom. The SEIRA spectra were compared with published surface-enhanced Raman (SER) spectra of pyrazine in order to clarify the reason for the breakdown of the Raman selection rule in the SER spectra. The activation of originally Raman-forbidden modes in the SER spectra is well explained by a photo-driven charge-transfer mechanism. The charge-transfer is deduced to be from filled metal states near the Fermi level to the first and second excited states of pyrazine. It is emphasized that the comparative SEIRA and SER studies are important for a better understanding of the electrochemical interface.     

Electrochemical properties of sulfur adsorbed on gold electrodes

The electrochemical properties of sulfur adsorbed on gold electrodes were studied in 10^?5M solutions of S^2? in 1 M NaOH. In general, ∵_S is less than a monolayer. At E=0.05 V only, a monolayer will be formed after long times. The sulfur layer is stable in the potential range between ?0.6 and +0.4 V. At lower potentials, sulfur can be desorbed cathodically (charge Q_red), but at higher potentials, where layers of gold oxide are formed, the sulfur is oxidized anodically (charge Q_ox). From the ratio Q_red·6/Q_ox=γ, the electrosorption valency γ=?2 is obtained. This means, that the sulfide ions are almost completely discharged during adsorption. The same layer can be formed by adsorption from polysulfide solutions, which can be explained by a break of the sulfur bond and adsorption of single sulfur atoms. The double layer capacity decreases during adsorption of sulfur indicating the formation of an insulating sulfur layer with a dielectric constant of about 2. The anodic adsorption of sulfide ions is limited by diffusion only. For longer polarisation times, the coverage is independent of time, i.e. place exchange reactions between Au and S can be excluded. The cathodic desorption as well as the anodic oxidation of the adsorbed sulfur are potential dependent charge transfer processes, as can be concluded from potentiodynamic measurements with various sweep rates.     

Surface-enhanced Raman scattering from crystal violet adsorbed on a silver electrode

SERS from crystal violet (CV) on a Ag electrode was investigated under preresonance and resonance conditions. The excitation profile of the chemisorbed species is like that of dissolved molecules but intensities are ≈ 1000 times larger. The Raman enhancement is ≈ 10⁸ and exhibits a specific potential dependence even in the absence of adsorption-desorption process. At potentials where reduction of CV occurs leuco crystal violet was detected.     

Surface-enhanced Raman studies of bradykinin using colloidal gold

In this paper, bradykinin (BK), an endogenous peptide hormone, which is involved in a number of physiological and pathophysiological processes was deposited onto the colloidal Au nanoparticles. The surface-enhanced Raman spectroscopy (SERS) was used to determine the adsorption mode of BK under different environmental conditions, including: excitation wavelengths (514.5 nm and 785.0 nm), pH of aqueous sol solutions (from pH = 3 to pH = 11), and size of the colloidal nanoparticles (10, 20, and 50 nm). The metal surface plasmon of the colloidal suspended Au nanoparticles was examined by ultraviolet-visible (UV–vis) spectroscopy. The results showed that the C-terminal part of BK plays a crucial role in the adsorption process onto the colloidal suspended Au particles. The Phe^5/8 and Arg⁹ residues of BK mainly participate in the interactions with the colloidal Au nanoparticles. At acidic pH of the solution (pH = 3), the BK COO⁻ terminal group through the both oxygen atoms strongly binds to the Au nanoparticles. The Phe⁵/Phe⁸ rings adopt tilted orientation with respect to the colloidal Au nanoparticles with diameters of 10 and 20 nm. As the particle size increases to 50 nm, the flat orientation of the Phe ring(s) with respect to the Au nanoparticles is observed.     

Surface-enhanced Raman spectra of quinoxaline adsorbed at a silver electrode

Surface-enhanced Raman scattering from quinoxaline adsorbed at a Ag electrode was observed. The SER spectrum exhibited remarkable a concentration and potential dependence, and indicated of two types of adsorbed species. They were assigned as flat and end-on species on the electrode.     

Sodium dodecyl sulfate adsorbed monolayers on gold electrodes

Self-assembled aggregates of amphiphilic surfactant molecules formed on solid surfaces are similar to biological membranes. To understand the formation mechanism of these aggregates, we have studied the formation of self-organized monolayers from low-concentration sodium dodecyl sulfate (SDS) aqueous solutions (concentration below the critical micelle concentration) on gold surfaces. The study has been carried out by using simultaneously quartz crystal microbalance (QCM) and open circuit potential measurements in situ. We have developed a model which explains the variation of the QCM frequency and open circuit potential following SDS additions to water. The dominant growth mechanism during the major part of film formation was demonstrated to be surface diffusion of surfactant molecules.     

Surface-enhanced Raman spectroscopic studies of coactivator-associated arginine methyltransferase 1

We report, for the first time, the surface-enhanced Raman spectra of an important enzyme, coactivator-associated arginine methyltransferase 1 (CARM1), involved in various biological activities such as tumor suppressor function and stem cell differentiation. We have employed surface-enhanced Raman scattering (SERS) to obtain insight into the structural details of CARM1 by adsorbing it to silver (Ag) nanoparticles. The enzyme retains its activity even after its adsorption onto Ag nanoparticles. We observe strong SERS modes arising from amide vibrations and aromatic ring amino acids. The SERS spectra revealed amide I bands at 1637 cm(-1) and 1666 cm(-1), which arise as a result of the alpha helix of the protein and the polypeptide backbone vibration of a random coil, respectively. In order to confirm the amide vibrations, we have performed SERS on deuterated CARM1, which exhibits a clear red shift in amide band positions. The SERS spectra may provide useful information, which could be harnessed to study the functional interactions of CARM1 with small molecule modulators.     

Raman spectroscopic investigation of silver electrodes

Raman spectroscopy has been applied to the study of the reduction of carbon dioxide and of formate and carbonate ions at a silver electrode. Raman spectra of adsorbed intermediate species, which are as yet only partially identified, have been detected and show marked variations with electrode potential. These spectral variations are clearly correlated with the voltammetric features for carbonate solutions and suggest that these reduction products complicate most measurements on silver electrodes in the cathodic region. The interpretation of the previously reported spectra due to adsorbed pyridine at silver electrodes has been reconsidered; interactions with surface carboxy species may be significant.     

Raman spectra of carbon monoxide adsorbed on silver electrodes

Weak Raman spectra of carbon monoxide on silver electrode surfaces exhibit frequency and intensity variations with changing potential. The frequency-potential dependence is rationalized in terms of electron-transfer to the antibonding π^* state of electrosorbed CO.     

Voltammetric and surface-enhanced resonance Raman spectroscopic characterization of cytochrome C adsorbed on a 4-mercaptopyridine monolayer on silver electrodes

To combine voltammetric techniques with surface-enhanced resonance Raman scattering (SERRS), cytochrome c (cyt c) was immobilized on a roughened silver electrode chemically modified with a self-assembled monolayer (SAM) of 4-mercaptopyridine (PySH). All measurements were performed on the same electrode in a homemade spectroelectrochemical cell suitable for such applications. Cyt c on a PySH-SAM shows a quasi-reversible, monoelectronic, adsorption-controlled CV response with a formal reduction potential of -0.061 V (vs SCE), which is comparable to the values found for native cyt c adsorbed on different SAMs. SERRS spectra proved that cyt c adsorbed on a PySH monolayer is present in the native conformer (the B1 state). Voltammetric and SERRS experiments at high ionic strength revealed that the interaction between the SAM and the protein is electrostatic in nature. In conclusion, PySH was found to be suitable for adsorption of cyt c at SERRS-active silver surfaces. In comparison with other SAMs, PySH requires less time (10 min vs 12-18 h) to form a long-time durable and reproducible coating on the roughened electrode surface.     

Surface-enhanced Raman spectroscopy study on the structure changes of 4-mercaptopyridine adsorbed on silver substrates and silver colloids

Surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine (4-mpy) adsorbed on HNO3 etched silver foil, chemically deposited silver films (silver mirror) and silver colloids were measured. The SERS study has revealed that 4-mpy was adsorbed onto the three kinds of silver surfaces by a sulfur-silver bond with the plane of pyridine ring being normal to the silver substrates. The structure of 4-mpy adsorbed on the silver surfaces depends largely on the pH values of environment. When the pH values of the environment are changed, the structure of 4-mpy adsorbed on silver surfaces can easily be altered through a protonation or deprotonation reaction occurring on the N atom of the pyridine ring, and the modified structure shows unique characters on the SERS spectrum. Owing to the remarkable enhancement ability of SERS technique and characteristic spectrum of different species, a monolayer of 4-mpy assembled on a silver mirror holds potential as a H+ sensor for highly sensitive detection of the proton concentration in an aqueous solution.