Customizable ligand exchange on the surface of gold nanotriangles enables their application in LSPR-based sensing

Nanomaterials made of noble metals have been actively utilized in sensorics and bioanalytics. Nanoparticles of anisotropic shapes are promising for increasing sensitivity due to the generated hotspots of electron density. Such structures can be effectively manufactured by a relatively accessible colloidal synthesis. However, the shape control requires the attachment of a surfactant on specific crystal facets during their growth. Commonly used cetrimonium halides form a closely packed bilayer, lowering the surface accessibility for subsequent (bio)functionalization steps. While there are numerous studies on functionalizing gold nanospheres, novel materials, such as nanotriangles (AuNTs), often require thorough studies to adapt the existing procedures. This is mainly caused by the incomplete characterization of initial nanoparticle colloids in empirically developed protocols. Herein, we report a rational approach utilizing the surface area of AuNTs as a function of both their dimensions and concentration, determined with an express UV-VIS analysis. We demonstrate its efficiency for the exchange of cetyltrimethylammonium chloride (CTAC) with polystyrene sulfonate (PSS) and with biocompatible citrate using direct and indirect methods, respectively. Fourier-transform infrared spectroscopy unequivocally proves the ligand exchange. Such functionalization allows evaluating the bulk refractive index sensitivity of AuNTs as a measure of their potential in LSPR-based sensing.