Photo-induced drug release at interfaces with arylazopyrazoles

Abstract

Smart responsive materials have spurred the progress in high-precision drug delivery. Enormous attention has been given to characterizing drug release in bulk aqueous solutions, however, aqueous–hydrophobic interfaces are vital components of biological systems which serve as the point of entry into cells. These interfaces are involved in many key biomolecular interactions, and while the potential for drug molecules to adsorb to these interfaces is recognized, their specific role in the context of drug release remains largely unexplored. We present a fundamental investigation on the release of encapsulated drugs at the air–water interface as a representative model to mimic the organic/aqueous interface of cells. Combining the advantages of light as an external stimulus and the superiority of arylazopyrazoles (AAP) over conventional azobenzene photoswitches, we report a micellar nanocarrier for the capture and release of the chemotherapeutic drug doxorubicin. Using a powerful combination of interface-sensitive techniques such as the Langmuir–Blodgett technique, surface tensiometry, and the interface-specific vibrational sum-frequency generation spectroscopy, we demonstrate the photoresponsive release of doxorubicin encapsulated in the micelles of AAP photosurfactants to the air–water interface. Complementary fluorescence measurements corroborate additional drug release in bulk aqueous solutions.