Upconversion nanoparticle-decorated gold nanoshells for near-infrared induced heating and thermometry

The present work involves the design of a multifunctional system based on gold nanoshells (AuNSs) decorated with lanthanide-based upconversion nanoparticles (UCNPs) intended as an optical heater and a temperature probe at the nanoscale. The synthesis of NaGdF₄ UCNPs doped with ions Yb³⁺:Er³⁺ was performed via thermal decomposition of lanthanide fluoride precursors at high temperatures (>300 °C) in the presence of a coordinating ligand (oleic acid). UCNPs were synthesized at three different temperatures (310, 315 and 320 °C) and characterized in terms of morphological, structural and emission properties. In view of the intended biological applications, the surface of hydrophobic oleate-capped UCNPs was modified using a silica coating to achieve sufficient water dispersibility, through a modified Stöber process using a reverse micro-emulsion method. Monodisperse NaGdF₄:Yb³⁺:Er³⁺ upconversion nanocrystals (∼25 nm dia.) were obtained in cubic (at 310, 315 °C) and hexagonal (at 320 °C) phases. The UCNPs in the hexagonal phase were shown to be more suitable as temperature sensors, due to their lower red-to-green emission ratios and higher thermal sensitivities. The emission spectrum of NaGdF₄:Yb³⁺:Er³⁺ (oleate- or silica-coated) UCNPs was recorded at different temperatures in the vicinity of the physiological range (20-70 °C) and presented suitable properties for application as temperature sensors, such as excellent linearity (r² > 0.99) and sensitivity (>3 × 10^-3 K^-1). The heating capacity of AuNSs@UCNPs was verified by monitoring the Er³⁺ emission, showing their potential for application as a hyperthermia agent controlled using a nanothermometer function.