Controlled epitaxial growth of mesoporous silica/gold nanorod nanolollipops and nanodumb-bells

Abstract

In this work, we describe the controlled synthesis of novel heterogeneous nanostructures comprised of mesoporous silica-coated gold nanorods (MSGNRs) in the form of core–shell nanolollipops and nanodumb-bells, using a seed-mediated sol–gel method. Although MSGNR core–shell (θ-MSGNR) structures have been reported previously by us and others, we herein discuss the first ever fabrication of MSGNR nanolollipops (φ-MSGNR) and nanodumb-bells (β-MSGNR), achieved by simply controlling the aging time of gold nanorods (GNRs), the residual cetyltrimethylammonium bromide (CTAB) coating of GNRs, and the addition of dimethyl formamide during incubation, centrifugation, and sonication, respectively. Transmission electron microscopy revealed two bare GNR isoforms, with aspect ratios of approximately 4 and 6, while scanning electron microscopy was used to further elucidate the morphology of φ-MSGNR and β-MSGNR heterostructures. In agreement with the smaller dielectric constants afforded by incomplete silica encasement, spectroscopic studies of φ-MSGNR and β-MSGNR, surface plasmon resonance (SPR) bands revealed 20-40 nm blue shifts relative to the SPR of θ-MSGNR. On the basis of the attributes and applications of more conventional θ-MSGNRs, φ-MSGNRs and β-MSGNRs are anticipated to provide most of the utility of θ-MSGNRs, but with the additional functionalities that accompany their incorporation of both bare gold and mesoporous silica encased tips; with significant/unique implications for biomedical and catalytic applications.