Artículo de publicación ISIRaman and surface enhanced Raman scattering (SERS) spectroscopies were used to study the pH effect (7 to 9) on the interaction of arginine (Arg) with colloidal Ag nanoparticles (AgNps). A new methodology was implemented in order to obtain reproducible SERS spectra in solution. The dependence of the Arg concentration on the stability of the AgNps is discussed. A pH increasing of the colloidal solution to the limits of the Arg pKa2 value induces a preferential and stable Arg–metal interaction. j potential measurements of the Arg–AgNps system at different pH conditions studied provide information about the Arg–AgNps interaction; the pH increasing favors the interaction. SERS spectra at pH 7 indicate that the molecule interacts with the Ag surface only through the guanidinium fragment. By increasing the pH to 9, the molecule adopts a new conformation on the surface; the metal–analyte interaction is verified through the guanidinium, carboxylate and the aliphatic moieties. In addition, theoretical calculations performed by using the extended Hückel method for a model of Arg interacting with an Ag surface support the observed SERS results
Artículo de publicación ISIThe Raman and surface enhanced Raman scattering (SERS) spectra of a black dyed silk sample (BDS) were registered. The spectral analysis was performed on the basis of Raman and SERS spectral data of isolated samples of Bombyx mori silk fibroin, its motif peptide component (GAGAGS) and the synthetic reactive black 5 dye (RB5). The macro FT-Raman spectrum of the silk sample is consistent with a silk II-Cp crystalline fraction of Bombyx mori silk fibroin; the SERS spectrum is highly consistent with conformational modifications of the fibroin due to the interactions with the Ag nanoparticles. The GAGAGS peptide sequence dominates the Raman spectrum of the silk. The SERS spectrum of the peptide suggests a random coil conformation imposed by the surface interaction; the serine residue in the new conformation is exposed to the surface. Quantum chemical calculations for a model of the GAGAGS–Ag surface predict a nearly extended conformation at the Ag surface. The Raman spectrum of the dye was analysed, and a complete band assignment was proposed; it was not possible to propose a preferential orientation or organization of the molecule on the metal surface. Quantum chemical calculations for a model of the dye interacting with a silver surface predict a rather coplanar orientation of the RB5 on the Ag metal surface. The Raman spectrum of the BDS sample is dominated by signals from the dye; the general spectral behaviour indicates that the dye mainly interacts with the silk through the sulphone (–SO2–) and sulphonate (–SO2–O–) groups. Besides the presence of dye signals, mainly ascribed to the sulphone and sulphonate bands, the SERS spectrum of the BDS sample also displays bands belonging to the amino acids alanine, glycine, serine and particularly tyrosine
Raman and surface-enhanced Raman scattering (SERS) spectra of the synthetic carboxy terminal peptide of human chorionic gonadatropin β-subunit free of carbohydrate moieties(P37) are reported. The spectral analysis is performed on the basis of our reported Raman spectrum and SERS data of oligopeptides displaying selected amino acids sequences MRKDV, ADEDRDA, and LGRGISL. SERS samples of P37 were prepared by coating the solid peptide with metal colloids on a quartz slide. This treatment makes possible to obtain high spectral batch to batch reproducibility. Amino acids components of P37 display net charges and hydrophobic characteristics, which are related to particular structural aspects of the adsorbate-substrate interaction. The spectroscopic results are supported by quantum chemical calculations performed by using extended Hückel theory method for a model of P37 interacting with an Ag surface. The P37-metal interaction is drove by positively charged fragments of selected amino acids,mainly threonine 109, lysine 122, and arginine in positions 114 and 133. Data here reported intend to contribute to the knowledge about the antigen-antibody interaction and to the drugs delivery research area
Pigments and fresco-related materials from the wall painting Historia de Concepción by Gregorio De La Fuente in Concepción, Chile were identified by Raman microscopy. The pigments were compared with those obtained from the artist's studio, and results allowed inference about subsequent interventions. Materials coming from processes such as salt efflorescence were also studied. The results contribute to the diagnosis of the current conservation state of the wall painting for its future restoration.
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