RESUMO
The synthesis and characterization of bare silica (4 nm in diameter) nanoparticle-attached meso-tetra(N-methyl-4-pyridyl)porphine (SiO(2)-TMPyP, 6 nm in diameter) are described for pH-controllable photosensitization. Distinguished from organosilanes, SiO(2) nanoparticles were functionalized as a potential quencher of triplet TMPyP and/or singlet oxygen ((1)O(2)) at alkaline pH, thereby turning off sensitizer photoactivity. In weak acidic solutions, TMPyP was released from SiO(2) surface for efficient production of (1)O(2). By monitoring (1)O(2) luminescence at 1270 nm, quantum yields of (1)O(2) production were found to be pH-dependent, dropping from ~ 0.45 in a pH range of 3-6 to 0.08 at pH 8-9, which is consistent with pH-dependent adsorption behavior of TMPyP on SiO(2) surface. These features make bare SiO(2)-attached cationic porphyrin a promising candidate for use in PDT for cancer treatment in which efficient (1)O(2) production at acidic pH and sensitizer deactivation at physiological pH are desirable. The enhanced therapeutic selectivity was confirmed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) tests and trypan blue exclusion tests of cell viability in breast cancer cell lines. Bimolecular quenching rate constants of (1)O(2) by free TMPyP, SiO(2) and SiO(2)-TMPyP nanoparticles were also determined.
