Fluorescent pH-sensing organic/inorganic hybrid mesoporous silica nanoparticles with tunable redox-responsive release capability.

We report on the fabrication of fluorescent pH-sensing organic/inorganic hybrid mesoporous silica nanoparticles (MSN) capable of tunable redox-responsive release of embedded guest molecules. The reversible addition-fragmentation chain transfer (RAFT) copolymerization of N-(acryloxy)succinimide (NAS), oligo(ethylene glycol) monomethyl ether methacrylate (OEGMA), and 1,8-naphthalimide-based pH-sensing monomer (NaphMA) at the surface of MSN led to fluorescent organic/inorganic hybrid MSN. The obtained hybrid MSN exhibits excellent water dispersibility and acts as sensitive fluorescent pH probes in the range pH 4-8 due to the presence of NaphMA moieties. After loading with rhodamine B (RhB) as a model drug molecule, P(NAS-co-OEGMA-co- NaphMA) brushes at the surface of hybrid MSN were cross-linked with cystamine to block nanopore entrances for the effective retention of guest molecules. Taking advantage of disulfide-containing cross-linkers, the release rate of RhB can be easily adjusted by adding varying concentrations of dithiothreitol (DTT), which can cleave the disulfide linkage to open blocked nanopores. The increase of DTT concentration from 0 to 20 mM led to 20-30 times enhancement of RhB release rate. The reported multifunctional hybrid MSN augurs well for applications in controlled-release nanocarriers, cell and tissue imaging, and clinical diagnosis.