Plasmon-Resonant Nanoparticles and Nanostars with Magnetic Cores: Synthesis and Magnetomotive Imaging

Abstract

Plasmon-resonant gold nanostars (NSTs) with magnetic cores were synthesized by a multistep sequence from superparamagnetic Fe₃O₄ nanoparticles (NPs) and evaluated as optical contrast agents under magnetomotive (MM) imaging conditions. Core−shell Fe₃O₄@Au NPs were prepared in nonpolar organic solvents with nanometer control over shell thickness and with good epitaxy to the Fe₃O₄ surface. Anisotropic growth was performed in micellar solutions of cetyltrimethylammonium bromide (CTAB) under mildly reducing conditions, resulting in NSTs with physical features similar to those produced from colloidal gold seeds. NSTs could be produced below 100 nm from tip to tip, but seed size had a significant impact on growth habit, with larger seed particles producing submicrometer-sized “morning stars”. Both NSTs and aggregated core−shell NPs are responsive to in-plane magnetic field gradients and can provide enhanced near-infrared (NIR) contrast under MM conditions, but do so by different mechanisms. NSTs can modulate polarized NIR scattering with minimal translational motion, giving the appearance of a periodic but stationary “blinking”, whereas core−shell NP aggregates require lateral displacement for signal modulation. The polarization-sensitive MM imaging modality offers the dual advantage of enhanced signal quality and reduced background signal and can be applied toward the detection of magnetomotive NSTs in heterogeneous biological samples, as illustrated by their detection inside of granular cells such as macrophages.