Photoactivation of “snap-top” stoppers over the pore openings of mesoporous silica nanoparticles releases intact cargo molecules from the pores. The on-command release can be stimulated by either one UV photon or two coherent near-IR photons. Two-photon activation is particularly desirable for use in biological systems because it enables good tissue penetration and precise spatial control. Stoppers were assembled by first binding photolabile coumarin-based molecules to the nanoparticle surface. Then, after loading the particles with cargo, bulky β-cyclodextrin molecules were noncovalently associated with the substituted coumarin molecule, blocking the pores and preventing the cargo from escaping. One-photon excitation at 376 nm or two-photon excitation at 800 nm cleaves the bond holding the coumarin to the nanopore, releasing both the cyclodextrin cap and the cargo. The dynamics of both the cleavage of the cap and the cargo release was monitored using fluorescence spectroscopy. This system traps intact cargo molecules without the necessity of chemical modification, releases them with tissue penetrating near-IR light and have possible applications in photo-stimulated drug delivery.

Proton transfer caused by excitation of a photoacid attached to the surface of a mesoporous silica nanoparticle activates a nanovalve and causes release of trapped molecules. The protonation of an aniline- based stalk releases a noncovalently bound cyclodextrin molecule that blocked a pore. The results show that pH-responsive molecular delivery systems can be externally controlled using light.