Controlled Direct Growth of Polymer Shell on Upconversion Nanoparticle Surface via Visible Light Regulated Polymerization

Abstract

<p>Lanthanide-doped upconversion nanoparticles (UCNPs) have unique photoluminescent properties that are useful in many biomedical applications. Modification of UCNPs with a polymer layer can confer additional functionality such as biocompatibility, stability <i>in vivo</i>, or drug delivery capability. It is also important that the modification process can be controlled precisely and without having adverse effects on the UCNPs luminescence properties. Herein, a polymer shell was grafted directly from the surface of UCNPs (grafting from) via visible light (λ_max = 635 nm, 0.7 mW/cm²) regulated photoenergy/electron transfer-reversible addition fragmentation chain transfer polymerization (PET-RAFT). The polymerization kinetics, grafting density, and thickness of the surface-tethered polymer chains can be tuned precisely by adjusting the monomer and RAFT agent ratio or the light exposure time. This approach also permits temporal control of the polymerization process. That is, the polymerization process can be initiated, halted, or terminated by switching the light source on and off. By limiting the non-radiative decay caused by surface defects, as well as from vibrational deactivation from solvents, the polymer shell enhanced the upconversion luminescence of the silica-coated UCNPs. This investigation paves the way for the development of UCNPs with controlled properties for various application requirements.</p>