Laser Photolysis of Dye-Sensitized Nanocapsules Occurs via a Photothermal Pathway

Light-addressable nanocapsules offer a powerful method for delivering spatiotemporally precise signals to cells. Thus far, the mechanism involved in the photolysis of nanocapsules has been opaque. This paper presents experimental evidence that rules out a photochemical pathway in favor of a photothermal mechanism in the far-red photolysis of dye-sensitized, lipid−vesicle based nanocapsules. Photolysis efficiency was unaffected by the presence of radical inhibitors, and mass spectrometry measurements confirmed that the photolytic process did not produce dye radicals. Measurements of dye quantum yield in the lipid membrane showed an inverse correlation between quantum yield of the dye and photolysis efficiency of the vesicle. The result is consistent with the notion that a decrease in quantum yield translates into more vibrational relaxation and thermal motion of the dye molecules in the membrane and thus more efficient photothermal disruption of the vesicle. Furthermore, we observed that the decrease in qu...