The Effects of a Varied Gold Shell Thickness on Iron Oxide Nanoparticle Cores in Magnetic Manipulation, T1 and T2 MRI Contrasting, and Magnetic Hyperthermia.

Fe3O4-Au core-shell magnetic-plasmonic nanoparticles are expected to combine both magnetic and light responsivity into a single nanosystem, facilitating combined optical and magnetic-based nanotheranostic (therapeutic and diagnostic) applications, for example, photothermal therapy in conjunction with magnetic resonance imaging (MRI) imaging. To date, the effects of a plasmonic gold shell on an iron oxide nanoparticle core in magnetic-based applications remains largely unexplored. For this study, we quantified the efficacy of magnetic iron oxide cores with various gold shell thicknesses in a number of popular magnetic-based nanotheranostic applications; these included magnetic sorting and targeting (quantifying magnetic manipulability and magnetophoresis), MRI contrasting (quantifying benchtop nuclear magnetic resonance (NMR)-based T1 and T2 relaxivity), and magnetic hyperthermia therapy (quantifying alternating magnetic-field heating). We observed a general decrease in magnetic response and efficacy with an increase of the gold shell thickness, and herein we discuss possible reasons for this reduction. The magnetophoresis speed of iron oxide nanoparticles coated with the thickest gold shell tested here (ca. 42 nm) was only ca. 1% of the non-coated bare magnetic nanoparticle, demonstrating reduced magnetic manipulability. The T1 relaxivity, r1, of the thick gold-shelled magnetic particle was ca. 22% of the purely magnetic counterpart, whereas the T2 relaxivity, r2, was 42%, indicating a reduced MRI contrasting. Lastly, the magnetic hyperthermia heating efficiency (intrinsic loss power parameter) was reduced to ca. 14% for the thickest gold shell. For all applications, the efficiency decayed exponentially with increased gold shell thickness; therefore, if the primary application of the nanostructure is magnetic-based, this work suggests that it is preferable to use a thinner gold shell or higher levels of stimuli to compensate for losses associated with the addition of the gold shell. Moreover, as thinner gold shells have better magnetic properties, have previously demonstrated superior optical properties, and are more economical than thick gold shells, it can be said that "less is more".

Spectral drifts in surface textured Fe3O4-Au, core-shell nanoparticles enhance spectra-selective photothermal heating and scatter imaging.

We report a significant spectral drift (up to 110 nm) between optical scattering and extinction in magnetite-gold (Fe3O4-Au) core-shell nanostructures. The drift was observed experimentally using single-particle broadband dark-field scattering microspectroscopy and solution extinction experiments. Infrared thermography demonstrates an enhanced photothermal activity of these nanoparticles at extinction wavelengths that are far drifted from the wavelengths that produce the best results for imaging via scattering. For example, a relatively smooth gold shell leads to 19% more photothermal activity at 532 nm compared to 690 nm whereas a rough-texture, popcorn type morphology gold shell with three times higher drift, is 170% more efficient at 532 nm. We suggest that the enhanced photothermal response results directly from a reduced competition between absorption and scattering as a consequence of the spectral drift. This spectral drift can be advantageous in multimodal theranostics where therapy and imaging are performed independently at different wavelengths.