Achintya Singha — Page 2

arXiv2006

pH Dependent surface enhanced Raman study of Phe + Ag Complex and DFT calculations for spectral analysis

Surface enhanced Raman spectra of Phenylalanine (Phe) in Ag colloidal solution have been recorded for Phe solutions of different pH. Spectral line-shape analyses of the enhanced modes, at 1005, 1380 and 1582 cm-1, between pH 4.5 and 10.5, have been carried out. The variation of spectral line-width with pH reveals two possible mechanisms in solution: (i) the fluctuation of pH in microscopic volume in an overall uniform pH solution and/or (ii) the motional narrowing caused by the intermolecular ionic interaction. We suggest that different charge states of the reference molecule are responsible for the observed bond softening with decrease in pH. The observed Raman shift and the Raman activity of the vibrational modes with maximum enhancement have been explained by carrying out DFT calculations.

cond-mat.mtrl-sci↗

arXiv2005

Comparison of metal-amino acid interaction in Phe-Ag and Tyr-Ag complexes by spectroscopic measurements

In this article, we have compared the metal-amino acid interactions in Tyr-Ag and Phe-Ag complexes through pH dependent SERS measurements. By analyzing the variation in relative intensities of SERS bands with the pH of the amino acid solution, we have obtained the orientation and conformation of the amino acid molecules on the Ag surface. The results obtained from our experimental studies are supported by the the energy minimized strucutres and the observed charge distributions in different terminals of the molecules. This, in a way, shows that SERS measurements not only exhibit the interaction of the amino acid molecules with Ag clusters but also demonstrate their orientation around it. We have addressed a long standing query on whether the amine group is directly attached with Ag surface along with the carboxylate group and $π$-electrons in these systems. In addition, pH dependent optical absorption and transmission electron microscopy measurements have been performed to understand the required conditions for the appearance of the SERS spectra in the light of the aggregation of metal particles and the number of hot sites in the sol. Our results confirm that the formation of hot sites in the sol plays a direct role to form a stable Ag-ligand complex. Furthermore, the interaction kinetics of metal-amino acid complexes have been analyzed via both Raman and absorption measurements.

physics.bio-ph↗