Surface geometry of tryptophan adsorbed on gold colloidal nanoparticles

Two distinct surface-enhanced Raman (SER) spectra of tryptophan depending on the surface adsorption geometry were obtained by using colloidal gold nanoparticles reduced by borohydride and citrate ions. According to the vibrational assignments based on OFT simulations, the SER spectra of tryptamine and 3-indolepropionic acid, and the pH dependence of tryptophan SER spectrum, we found that some indole ring vibrations are very sensitive to the surface adsorption geometry of the molecules. With citrate-reduced gold colloids, tryptophan and related molecules mainly adsorb via the protonated amine group while maintaining a perpendicular geometry of the indole ring to the surface. However, a flat geometry of the indole ring to the surface is preferred on the borohydride-reduced gold colloids where the surface adsorption occurs mainly through the indole ring it electrons. By comparing our results with previous reports on the SER spectra of byptophan on various silver and gold surfaces, we propose a general adsorption model of tryptophan on metal nanosurfaces. (C) 2015 Elsevier B.V. All rights reserved.