Reduction of cytochrome c by halide-modified, laser-ablated silver colloids

Silver colloids of 20 nm mean particle diameter were prepared by laser ablation and modified by adsorption of iodide and bromide ions. Addition of cytochrome c to this colloid resulted in the reduction of the protein, which was monitored by surface-enhanced resonance Raman scattering and absorption spectroscopies. Colloidal metal films, prepared from the same Ag colloid, were employed to minimize contributions from aggregation. Effects of surface modification on the Ag plasmon resonance were studied in both colloidal suspensions and colloidal metal films. The conclusion was made that adsorption of I- and Br- results in charging of the Ag particle as a whole and a shift of its potential to more negative values. The donated charge is delocalized in a thin surface layer and does not significantly affect the plasmon resonance frequency of the particle.