FT-Raman and SERS spectra of rivanol in silver sol

FT-Raman of solid rivanol (2-ethoxy-6,9-diaminoacridinium lactate C(15)H(16)N(3)O-C(3)H(5)O(3) . H(2)O) and surface-enhanced Raman scattering (SERS) on silver surface of rivanol solution at pH 5.5 have been obtained and compared. The assignment of vibrational modes has been made for the monocation specie of rivanol. SERS spectrum shows a physisorption of rivanol on the silver surface.     

Influence of laser illumination during an oxidation-reduction cycle on the surface structure of silver: Implications for the mechanism of SERS

The structural changes produced by oxidation and reduction of a silver surface in 1 M CKl with and without illumination were examined by scanning electron microscopy. Laser illumination (632.8 nm) during the oxidation-reduction cycle (ORC) produces a surface covered with a high density of sub-μm sized particles. The silver particles are the result of the photolytic reduction of the silver chloride made possible by the presence of the applied electric field within the silver chloride layer which prevents the recombination of the photoelectrons and holes. As the maximum anodization voltage of the ORC is increase to +100 mV vs. SCE, the number of photolytically produced silver particles increases. As the maximum anodization voltage is increased from +100 mV to +200 mV, the individual particle size increases from ≈200 nm to ≈800 nm. The intensity of Raman scattering from water adsorbed on the silver surface was maximized by a laser illuminated ORC with a maximum anodization voltage of +100 mV.Since recent theoretical studies indicate an optimum particle size of r≈50 nm for maximizing the electromagnetic component of the enhancement, the present results indicate that either the individual silver particles contain small scale (≈50 nm) roughness features or the electromagnetic factors are not the sole contributors to the enhancement.     

Surface enhanced Raman spectra (SERS) of pyridine and dye-1555 adsorbed on silver bromide colloids

SERS from pyridine and dye-1555 molecules adsorbed on silver bromide colloids were detected for the first time. The influences of ferricyanide, thiosulfate, hydrogen peroxide and excess bromide ions on SERS of pyridine on AgBr colloids are studied.     

Vibrational spectra of isomeric pyridinic carboxylic acids in solid state and in solution and their SERS studies in silver sol

Raman spectroscopic studies of three isomeric pyridinic carboxylic acids, viz. picolinic, nicotinic and iso-nicotinic acid in solid state, in aqueous solution and in silver hydrosol, in the frequency range 900–1750 cm⁻¹, have been made. Assignments of the observed bands have been proposed in relation to the molecular forms present in solid state and in solution. Different degrees of intensity enhancements of the Raman bands in surface-enhanced Raman scattering (SERS) have been observed in all the three isomeric molecules. In iso-nicotinic acid, the intensity enhancement has been found to be minimum. Comparisons of Raman spectra in aqueous solution with those due to SERS in silver sol indicate that picolinic and nicotinic acid adsorb perpendicularly to the sol surface whereas in iso-nicotinic acid it occurs via donation of a π-electron of the aromatic ring, i.e. the plane of the ring lies parallel to the surface of the sol.     

Visualization of aerosol particles generated by near infrared nano- and femtosecond laser ablation

The expansion of aerosols generated by near infrared (NIR) nanosecond (ns) and femtosecond (fs) laser ablation (LA) of metals at atmospheric pressures was explored by laser-induced scattering. In order to achieve adequate temporal and spatial resolution a pulsed laser source was utilized for illuminating a 0.5 mm-wide cross section of the expanding aerosol. It could, for instance, be shown that NIR-ns-LA under quiescent argon atmosphere provokes the formation of a dense aerosol confined within a radially propagating vortex ring. The expansion dynamics achieved under these conditions were found to be fairly slow whereas the degree of aerosol dispersion for NIR-ns-LA using helium drastically increased due to its lower viscosity. As a consequence, the maximum diameter of expansion differed by a factor of approximately four. The trajectories of aerosol particles generated by NIR-ns-LA using argon could, furthermore, be simulated on the basis of computational fluid dynamics (CFD). For this purpose, a model inspired by the thermal character of NIR-ns-LA taking into account a sudden temperature build-up of 10,000 K at the position of the laser focus was implemented.     

Effect of laser illumination oxidation-reduction cycles upon surface-enhanced Raman scaterring from silver electrodes

The intensity of surface-enhanced Raman scattering (SERS) from thiocyanate and chloride adsorbed on silver electrodes is shown to depend critically on whether the electrode is illuminated during the oxidation-reduction cycle used to pretreat the electrode. The value and magnitude of the photoeffect is dependent upon the type of surface vibrational mode, the adsorbate and the wavelength of the radiation during the ORC. The effects are attributed to the production of SERS active clusters of Ag atoms by photoreduction of the Ag(I) phase films during the ORC.     

Paramagnetic behaviour of silver nanoparticles generated by decomposition of silver oxalate

Silver oxalate Ag₂C₂O₄, was already proposed for soldering applications, due to the formation when it is decomposed by a heat treatment, of highly sinterable silver nanoparticles. When slowly decomposed at low temperature (125 °C), the oxalate leads however to silver nanoparticles isolated from each other. As soon as these nanoparticles are formed, the magnetic susceptibility at room temperature increases from −3.14 10⁻⁷ emu.Oe⁻¹.g⁻¹ (silver oxalate) up to −1.92 10⁻⁷ emu.Oe⁻¹.g⁻¹ (metallic silver). At the end of the oxalate decomposition, the conventional diamagnetic behaviour of bulk silver, is observed from room temperature to 80 K. A diamagnetic-paramagnetic transition is however revealed below 80 K leading at 2 K, to silver nanoparticles with a positive magnetic susceptibility. This original behaviour, compared to the one of bulk silver, can be ascribed to the nanometric size of the metallic particles.     

pH dependent SERS and solvation studies of tyrosine adsorbed on silver colloidal nano particles combined with DFT calculations

The surface enhanced Raman spectra of tyrosine in colloidal Ag solution have been recorded over a range of pH. A line shape analysis of the bands at 1359, 1505 and 1577 cm⁻¹ was performed between pH 3.5 and 8.5. The variation of spectral linewidth (FWHM) of the band at 1359 cm⁻¹ with pH is explained in terms of two mechanisms in solution: (i) the fluctuation of the pH of a microscopic volume in a solution with an overall uniform pH and/or (ii) the role of changing viscosity and solvation at different pH values due to the intermolecular ionic interactions between different charged states of the tyrosine molecule. The blue shift in three bands with increasing pH has been explained in terms of charge transfer between the different charged states of tyrosine and metal ions upon chemisorption. The experimental spectra are compared with ab initio/DFT calculations of vibrational wavenumbers, bond geometries, binding energy and charge distributions obtained by means of Hartree–Fock (HF) analysis, the nonlocal density functional method (BLYP) and the hybrid functional method (B3LYP). Two basis sets, CEP-31G and lanl2DZ, were used for all calculations.     

Theoretical study on the absorption spectra of pseudoisocyanine bromide (PIC-Br) molecular J-aggregates

The linear dichroic absorption spectrum of pseudoisocyanine bromide (PIC-Br) molecular J-aggregates is theoretically analyzed by using the dynamical coherent potential approximation and numerical calculations. The absorption spectra with the electric field polarization parallel and perpendicular to the one-dimensional axis of the oriented J-aggregates are well explained in terms of Davydov components. Above the one-phonon continuum in the dispersion curve of the exciton–phonon system, splitting off of an exciton polaron band is observed. This exciton polaron state is assigned to the largest peak in the case of the latter polarization. The absorption intensity differences between the lowest peak and the 2nd peak observed in two polarization conditions are simply explained by the character of relevant states.     

Surface-enhanced Raman scattering of 1-butanethiol in silver sol

The surface-enhanced Raman scattering (SERS) of 1-butanethiol was investigated in a silver sol. The molecule was found to be chemisorbed dissociatively on the silver surface by rupture of its SH bond. It is concluded that conformers of 1-butanethiol adsorbed selectively on the silver surface, the trans conformer around the C (1)C (2) axes being more likely adsorbed when the bulk concentration of the molecule is enough for the full monolayer coverage. The vibrational assignment of the molecule in liquid phase has also been refined by using the SERS data.     

Adsorption mechanisms of sulfathiazole on gold,silver and copper surfaces studied by SERS

Surface-enhanced Raman scattering (SERS) of sulfathiazole was studied in gold, silver and copper colloids as well as on a gold plate. SERS spectra of sulfathiazole in gold and silver colloids indicated chemisorption of molecules on the metal nanoparticles through the amide nitrogen, with the phenyl moiety orthogonally placed and the thiazole ring almost parallel positioned towards the metal surface. Although selectively enhanced phenyl bands pointed to a very similar position of the sulfathiazole molecules on the copper colloid, a chemical bonding was not implied. Unlike adsorption mechanisms and position of the molecules on the colloid metal surfaces, a sideway adsorption of sulfathiazole on the gold plate was proposed. Hereby, both, the amide nitrogen and the thiazole nitrogen were considered responsible for approaching of sulfathiazole to the gold enhancing surface.     

Studies on adsorption of 5-amino tetrazole on silver nanoparticles by SERS and DFT calculations

The surface-enhanced Raman scattering (SERS) studies of 5-amino tetrazole (5AT), a tetrazole derivative, in aqueous silver sol at pH approximately 9 and on deposited colloidal silver films were carried out and compared with the normal Raman spectrum of the molecule. The experimentally observed Raman bands along with their corresponding infrared bands were assigned based on the results of density functional theory (DFT) calculations. The significant changes evidenced between the SERS and the normal Raman spectra combined with the theoretical data obtained for Ag-5AT system demonstrated that the molecule is adsorbed on colloidal Ag particles through the lone pair of electrons of the nitrogen atom. The contribution of the chemical mechanism for the SERS enhancement was proved by the behavior of the electronic absorption spectrum of the Ag colloid upon addition of 5AT. This is further supported by the theoretical calculations that show that the favorable interaction of the frontier orbitals localized on Ag(+) and the negatively charged nitrogen from the tetrazole ring leads to the formation of the stable (up to 130 kJ mol(-1)) charge-transfer complex. The orientation of the adsorbed species with respect to the metal surface was also predicted by applying the "surface selection rule". In addition, the feasibility of the formation of the polymeric species has also been discussed.     

A Study of Relationship Between Universality in Fractal Colloids Aggregation and Time-dependent SERS

The relationship between the rule of time-dependent surface-enhanced Raman scattering (SERS) intensity of adsorbed pyridine in AgBr sol and silver bromide colloidal fractal aggregation is studied in this paper. The experimental results support the view of universality in colloidal aggregation and suggest that SERS may be a useful tool in the study of kinetics of colloidal aggregation.     

Surface enhanced Raman spectra of isomeric acetylpyridines adsorbed on silver sol

Raman spectra of 2-, 3- and 4-acetylpyridines (AP) are obtained in bulk phase, in aqueous solution and in the adsorbed state on colloidal silver particles. Addition of the acetylpyridines on the Ag-sol results in aggregation of the silver particles showing characteristic charge transfer (CT) bands. Significant surface enhancement of the Raman bands are observed. Both the estimated enhancement factor and the absorption maxima of the CT bands are in inverse parallel relationship with the electron density on the nitrogen atom as reflected by the Hammett σ values of the substituents. It is inferred that the charge transfer interactions between the adsorbates and the metal particles contribute to the enhancement mechanism. This is further substantiated by the concentration dependence of enhancement. A classical electromagnetic contribution is demonstrated by the Raman excitation frequency dependence of SERS. The results further show that the molecules are adsorbed on the metal surface through the nitrogen atom. Appearance of some out-of-plane modes in the SERS spectra suggests that the pyridyl ring planes are not perpendicular to the metal surface, but are tilted.     

在铜箔上电辅助制备纳米银及其SERS应用研究

在电化学工作站上以铜箔为工作电极,以硝酸银和PVP混合液作为前驱溶液,利用循环伏安法电辅助制备了纳米银,得到在铜箔上紧密均匀分布的纳米银颗粒聚集体作为SERS基底。通过X射线粉末衍射、X射线光电子能谱、扫描电子显微镜等表征手段,对铜箔上负载的银纳米颗粒进行了形貌和成分的表征,探讨了PVP及电辅助方法对纳米银形貌及基底SERS活性的影响。以4-巯基吡啶和罗丹明6G为探针溶液研究了制备基底的SERS活性,同时还对基底的均匀性进行了研究,结果表明所制备的SERS基底具有良好的性能。     

十二烷基三甲基溴化铵在聚苯乙烯胶乳粒子上的吸附

实验测得C~1~2TAB在PS胶乳粒子表面的吸附等温线呈L型的二阶段吸附特征,这表明初始的C~1~2TA^+离子是将其季铵正电性头基吸引在PS链的负电性硫酸根端基上,并将碳氢链通过疏水相互作用吸附在PS链上。结合光子相关谱测得胶乳粒子流体力学半径R~H的变化,表明第I阶段围绕着这些初始吸附位的聚集吸附,产生平均聚集数为4.0的松散小聚集体,此时对应的浓度c/cmc=0.32是文献通常所指的临界表面胶团浓度csmc。其后的进一步聚集吸附最终生成了附着在PS链端基处且平均聚集数为19.5的球形吸附胶团。这一饱和吸附的结果增加了胶乳粒子在水溶液中的分散稳定性。