Experimental
conditions favoring the tryptophan tight binding to
the surface of citrate-reduced gold nanoparticles (Cit-AuNPs) were
explored. For this, the adsorption of three molecular compounds, free
amino acid (Trp), tripeptide NH2-Gly-Trp-Gly-CONH2, and lanreotide, a synthetic cyclic somatostatin analogue, on large-size
(∼70 nm) Cit-AuNPs was analyzed. UV–visible absorption,
transmission electron microscopy, and surface-enhanced Raman scattering
(SERS) were jointly used in the present investigation. At low pH (∼3.5),
when the repulsive electrostatic interactions between gold particles
are sufficiently reduced, both peptides can induce strong NP aggregation,
leading particularly to substantial changes in the characteristic
tryptophan Raman markers, as well as to the appearance of strong SERS
markers at 1228 and 1113 cm–1. In contrast, upon
increasing the pH toward a neutral value, the mentioned Trp Raman
markers tend to adopt a spectral shape comparable to that observed
in solution (bulk). In free amino acids, the SERS effect could not
be observed within a large pH interval, except at low pH upon increasing
the ionic strength. The reported data would be of benefit for following
the adsorption processes that should be further considered in preparing
Au-peptide nanodevices for therapeutic applications.