Laser Ablation-Assisted Synthesis of Plasmonic Si@Au Core-Satellite Nanocomposites for Biomedical Applications

Owing to strong plasmonic absorption and excellent biocompatibility, gold nanostructures are among best candidates for photoacoustic bioimaging and photothermal therapy, but such applications require ultrapure Au-based nanoformulations of complex geometry (core-shells, nanorods) in order to shift the absorption band toward the region of relative tissue transparency (650-1000 nm). Here, we present a methodology for the fabrication of Si@Au core-satellite nanostructures, comprising of a Si core covered with small Au nanoparticles (NP), based on laser ablative synthesis of Si and Au NPs in water/ethanol solutions, followed by a chemical modification of the Si NPs by 3-aminopropyltrimethoxysilane (APTMS) and their subsequent decoration by the Au NPs. We show that the formed core-satellites have a red-shifted plasmonic absorption feature compared to that of pure Au NPs (520 nm), with the position of the peak depending on APTMS amount, water-ethanol solvent percentage and Si-Au volume ratio. As an example, even relatively small 40-nm core-satellites (34 nm Si core + 4 nm Au shell) provided a much red shifted peak centered around 610 nm and having a large tail over 700 nm. The generation of the plasmonic peak is confirmed by modeling of Si@Au core-shells of relevant parameters via Mie theory. Being relatively small and exempt of any toxic impurity due to ultraclean laser synthesis, the Si@Au core-satellites promise a major advancement of imaging and phototherapy modalities based on plasmonic properties of nanomaterials.