• L-arginine;
  • Raman spectroscopy;
  • zeta potential (ξ);
  • surface enhanced Raman scattering (SERS);
  • extended Hückel theory (EHT)

Raman 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. ξ 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. Copyright © 2013 John Wiley & Sons, Ltd.