Nanoparticle Size Influences the Self-Assembly of Gold Nanorods Using Flexible Streptavidin–Biotin Linkages

The self-assembly of colloidal nanocrystals remains of robust interest due to its potential in creating hierarchical nanomaterials that have advanced function. For gold nanocrystals, junctions between nanoparticles yield large enhancements in local electric fields under resonant illumination, which is suitable for surface-enhanced spectroscopies for molecular sensors. Gold nanorods can provide such plasmonic fields at near-infrared wavelengths of light for longitudinal excitation. Through the use of careful concentration and stoichiometric control, a method is reported herein for selective biotinylation of the ends of gold nanorods for simple, consistent, and high-yielding self-assembly upon addition of the biotin-binding protein streptavidin. This method was applied to four different sized nanorods of similar aspect ratio and analyzed through UV-vis spectroscopy for qualitative confirmation of self-assembly and transmission electron microscopy to determine the degree of self-assembly in end-linked nanorods. The yield of end-linked assemblies approaches 90% for the largest nanorods and approaches 0% for the smallest nanorods. The number of nanorods linked in one chain also increases with an increased nanoparticle size. The results support the notion that the lower ligand density at the ends of the larger nanorods yields preferential substitution reactions at those ends and hence preferential end-to-end assembly, while the smallest nanorods have a relatively uniform ligand density across their surfaces, leading to spatially random substitution reactions.