Stabilizing the Localized Surface Plasmon Resonance (LSPR) of Citrate-Synthesized Metal Nanoparticles in Organic Solvents

Gold-silver nanoshells (GS-NSs) are hollow spherical nanoparticles with an alloyed Ag-Au shell. GS-NSs exhibit a tunable localized surface plasmon resonance (LSPR) in the visible to near-IR wavelengths as a function of composition and shell thickness and offer greater stability across pH ranges compared to other metal nanoparticles. These properties make GS-NSs promising materials for diagnostics, photothermal therapy, and photocatalysis. However, current research has explored GS-NSs only in aqueous systems, since they immediately aggregate in other solvents, limiting their utility. This paper provides an in-depth study of the choice and effect of non-thiol ligands on the stability and phase-transfer of GS-NSs from aqueous to non-aqueous solvents, such as ethylene glycol, tetrahydrofuran, dichloromethane, and toluene. Ligand exchange for functionalization of GS-NSs was performed with Triton X-100 (TX100), sodium stearate (NaSt), polyvinylpyrrolidone (PVP), and hydroxypropyl cellulose (HPC), prior to phase-transfer. The nanoparticles were phase-transferred to the non-aqueous solvents, and the stability of the colloids in the various solvents before and after functionalization was recorded with UV-visible spectroscopy, dynamic light scattering (DLS), zeta potential (ζ), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The study was also extended to include silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) to evaluate broad-range applicability. Among the ligands studied, HPC functionalization demonstrated the widest range of phase-transfer stability across 21 days for all three particle systems studied. UV-vis spectroscopy demonstrated sustained LSPR integrity after HPC functionalization in EG, THF, and DCM. SEM, TEM, and hydrodynamic size measurements by DLS further confirmed no aggregation in EG, THF, and DCM but suggested possible twinning or clustering in the solution. Overall, this work successfully identified non-toxic alternatives to expand the LSPR stability of citrate-synthesized metal nanoparticles in organic solvents.