Photoacoustic Enhancement of Ferricyanide-Treated Silver Chalcogenide-Coated Gold Nanorods

Plasmonic gold nanorods (AuNRs) are often employed as photoacoustic (PA) contrast agents due to their ease of synthesis, functionalization, and biocompatibility. These materials can produce activatable signals in response to a change in optical absorbance intensity or absorbance wavelength. Here, we report a surprising finding: Ag2S/Se-coated AuNRs have a ∼40-fold PA enhancement upon addition of an oxidant but with no change in absorption spectra. We then study the mechanism underlying this enhancement. Electron micrographs and absorption spectra show good colloidal stability and retention of the core-shell structure after potassium hexacyanoferrate(III) (HCF) addition, ruling out aggregation and morphology-induced PA enhancement. X-ray diffraction data showed no changes, ruling out crystallographic phase changes upon HCF addition, thus leading to induced PA enhancement. Attenuated total reflectance-Fourier transform infrared spectroscopy and zeta potential analysis suggest that PA enhancement is driven by the irreversible displacement of hexadecyltrimethylammonium bromide with HCF. This is further confirmed using elemental mapping with energy-dispersive X-ray analysis. PA characterization after HCF addition showed a four-fold increase in the Grüneisen parameter (Γ), thus resulting in PA enhancement. The PA enhancement is not seen in uncoated AuNRs or spherical particles. Two possible mechanisms for PA enhancement are proposed: first, the photo-induced redox heating at the Ag2S/Se shell-HCF interface, resulting in an increase in temperature-dependent Γ, and second, an enhanced electrostriction response due to HCF adsorption on a layered plasmonic nanoparticle surface, resulting in a high thermal expansion coefficient (β) that is directly proportional to Γ.