Porphyrin Photoabsorption and Fluorescence Variation with Adsorptive Loading on Gold Nanoparticles

Abstract

Here, we report the photophysical structure–property relationship of porphyrins adsorbed on gold nanoparticles. The number of porphyrin–alkanethiolate adsorbates per particle was adjusted by a post-synthetic thiol/thiolate exchange reaction on 1-dodecanethiolate–protected gold nanoparticles. Even with a low loading level of adsorbates (<10% of all thiolate sites on gold nanoparticles), the shoulder absorption at the Soret band was intensified, indicating the formation of aggregates of porphyrin adsorbates on the nanoparticles. Steady-state fluorescence quantum yields could be adjusted by the bulkiness of substituents at the meso-positions of the porphyrin or the methylene linker chain length, regardless of the porphyrin loading level and the nanoparticle diameter.

Singlet Oxygen Generation Driven by Sulfide Ligand Exchange on Porphyrin–Gold Nanoparticle Conjugates

“…We have previously shown that a gold nanoparticle (AuNP) efficiently quenches the excited state of porphyrin when they are covalently linked to form a conjugate [16][17][18]. In the porphyrin-AuNP conjugates [16], 1 O 2 generation was almost quenched (singlet oxygen generation quantum yield, Φ ∆ = 0.01−0.08) from corresponding unbound porphyrin (Φ ∆ = 0.70 for meso-tetraphenyl porphyrin (TPP) [19], at a partial pressure of oxygen pO 2 = 0.21 atm).…”