[30] Hybrid Silver Nanocubes for Improved Plasmon-Enhanced Singlet Oxygen Production and Inactivatio

J. Am. Chem. Soc. 2019, 141 (1), pp 684–692.

Plasmonic nanoparticles can strongly interact with adjacent photosensitizer molecules, resulting in significant alteration of their singlet oxygen (1O2) production. In this work, we report the next generation of metal-enhanced 1O2 nanoplatforms exploiting the lightning rod effect, or plasmon hot spots, in anisotropic (non-spherical) metal nanoparticles. We describe the synthesis of Rose Bengal decorated silica-coated silver nanocubes (Ag@SiO2-RB NCs) with silica shell thicknesses ranging from 5 to 50 nm based on an optimized protocol yielding highly homogeneous Ag NCs. Steady-state and time-resolve 1O2 measurements demonstrate not only the silica shell thickness dependence on the metal-enhanced 1O2 production phenomenon, but also the superiority of this next generation of nanoplatforms. A maximum enhancement of 1O2 of approximately 12-fold is observed with a 10 nm silica-shell, which is amongst the largest 1O2 production metal enhancement factor ever reported for a colloidal suspension of nanoparticles. Finally, the Ag@SiO2-RB NCs were benchmarked against Ag@SiO2-RB nanospheres previously reported by our group, and the superior 1O2 production of Ag@SiO2-RB NCs resulted in improved antimicrobial activities in photodynamic inactivation experiments using both gram-positive and -negative bacteria model strains.