Synthesis of vinyl-terminated Au nanoprisms and nanooctahedra mediated by 3-butenoic acid: direct Au@pNIPAM fabrication with improved SERS capabilities.

Here we describe the first seedless synthesis of vinyl-terminated Au nanotriangular prisms (AuNTPs) and nanooctahedra (AuNOC) in aqueous media. This synthesis is performed by chemical reduction of chloroauric acid (HAuCl4) with 3-butenoic acid (3BA) in the presence of benzyldimethylammonium chloride (BDAC). The principal novelties of the presented method are the use of a mixture of 3BA and BDAC, the synthesis of gold prisms and octahedra with controllable size, and the presence of terminal double bonds on the metal surface. Initially this method produces a mixture of triangular gold nanoprisms and octahedra; however, both morphologies are successfully separated by surfactant micelle induced depletion interaction, reaching percentages up to ∼90%. Moreover, the alkene moieties present on the gold surface are exploited for the fabrication of hybrid core@shell particles. Gold octahedra and triangular prisms are easily encapsulated by free radical polymerization of N-isopropylacrylamide (NIPAM). Finally, in order to obtain a gold core with the most number of tips, AuNTP@pNIPAM microgels were subjected to gold core overgrowth, thus resulting in star-shaped nanoparticles (AuSTs@pNIPAM). We use 4-amino-benzenethiol as the model analyte for SERS investigations. As expected, gold cores with tips and high curvature sites produced the highest plasmonic responses.