Understanding and shaping adsorption orientations of molecular compounds on nano‐structured metallic surfaces is an important issue across many areas of contemporary research including the design of nano‐structured surfaces and catalytic processes. Here, we used surface‐enhanced Raman spectroscopy to study these orientations on nano‐structured silver surfaces using dicarboxylic acids (maleic acid and fumaric acid) as model substances. Results revealed a clear pH dependence of the observed adsorption geometries of dicarboxylic acids correlating well with the dissociation states of the two acidic groups. Our data demonstrate the potential of the technique and contribute to an improved understanding of adsorption orientations of molecules at the interface between nano‐structured metal surfaces and a liquid phase. Copyright © 2012 John Wiley & Sons, Ltd.

Silver colloids were produced for surface-enhanced Raman scattering (SERS) experiments using hydroxylamine hydrochloride as the reduction agent. The roles of hydroxylamine hydrochloride and bulk solution pH values in the formation of functional groups on the surface of silver colloids and in determining the dimensions of silver colloids were examined using Raman, Fourier transform infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, atomic force microscopy (AFM), and zeta-size measurements. The spectrum of hydroxylamine hydrochloride reduced silver colloids was compared with the spectrum of sodium borohydride reduced colloids. The effect of colloid solution pH on SERS results was demonstrated using analyte molecules with biological significance, such as ribonucleic acid, egg albumin, L-alpha-phosphatidylcholine, and glucose. In general, it was shown that at high pH values the SERS effect was more pronounced due to the surface functional groups and colloid dimensions, and sharp, high spectral intensity values were obtained. At low pH values, protonation and rapid aggregation of colloids occurred and the surface chemistry was different. Depending on the analyte, bands were shifted, broadened, and/or the enhancement effect was reduced. Using Pseudomonas aeruginosa PAO1 and Streptococcus mutans it was also shown that by changing the solution bulk pH value, it was possible to enhance the response from different molecular groups in the bacteria and obtain different spectra from the same bacteria strain and the process was reversible. It was concluded that it is possible to produce site- or molecule-specific metal colloids and to tune the SERS effect to certain functional groups of analytes by means of the pH of colloidal suspension.