We present the preparation and characterization of methylene blue-containing silica-coated magnetic particles. The entrapment of methylene blue (MB), a photodynamic therapy drug under study in our group, in the silica matrix took place during the growth of a silica layer over a magnetic core composed of magnetite nanoparticles. The resulting material was characterized by transmission electron microscopy (TEM), light scattering, and X-ray diffraction. It is composed of approximately 30 nm silica spheres containing magnetic particles of 11 +/- 2 nm and methylene blue entrapped in the silica matrix. The immobilized drug can generate singlet oxygen, which was detected by its characteristic phosphorescence decay curve in the near-infrared and by a chemical method using 1,3-diphenylisobenzofuran to trap singlet oxygen. The lifetime of singlet oxygen was determined to be 52 micros (in acetonitrile) and 3 micros (in water), with both values being in good agreement with those in the literature. The release of singlet oxygen (etaDelta) was affected by the encapsulation of MB in the silica matrix, which caused a reduction to 6% of the quantum yield of MB free in solution. The magnetization curve confirmed the superparamagnetic behavior with a reduced saturation magnetization in respect to uncoated magnetic nanoparticles, which is consistent with the presence of a diamagnetic component over the magnetite surface. The result is a single particle platform that combines therapy (photosensitizer) and diagnostic (MRI contrast agent) possibilities at the same time, as well as drug targeting.
The present study is focused on developing a nanoparticle carrier for the photosensitizer protoporphyrin IX for use in photodynamic therapy. The entrapment of protoporphyrin IX (Pp IX) in silica spheres was achieved by modification of Pp IX molecules with an organosilane reagent. The immobilized drug preserved its optical properties and the capacity to generate singlet oxygen, which was detected by a direct method from its characteristic phosphorescence decay curve at near-infrared and by a chemical method using 1,3-diphenylisobenzofuran to trap singlet oxygen. The lifetime of singlet oxygen when a suspension of Pp IX-loaded particles in acetonitrile was excited at 532 nm was determined as 52 micros, which is in good agreement with the value determined for methylene blue in acetonitrile solution under the same conditions. The Pp IX-loaded silica particles have an efficiency of singlet oxygen generation (eta Delta) higher than the quantum yield of free porphyrins. This high efficiency of singlet oxygen generation was attributed to changes on the monomer-dimer equilibrium after photosentisizer immobilization.
Copper catalysts are very promising, affordable alternatives for noble metals in CO oxidation; however, the nature of the active species remains unclear and differs throughout previous reports. Here, we report the preparation of 8 nm copper nanoparticles (Cu NPs), with high metallic content, directly deposited onto the surface of silica nanopowders by magnetron sputtering deposition. The as-prepared Cu/SiO2 contains 85% Cu0 and 15% Cu2+ and was enriched in the Cu0 phase by H2 soft pretreatment (96% Cu0 and 4% Cu2+) or further oxidized after treatment with O2 (33% Cu0 and 67% Cu2+). These catalysts were studied in the catalytic oxidation of CO under dry and humid conditions. Higher activity was observed for the sample previously reduced with H2, suggesting that the presence of Cu-metal species enhances CO oxidation performance. Inversely, a poorer performance was observed for the sample previously oxidized with O2. The presence of water vapor caused only a small increase in the temperature require for the reaction to reach 100% conversion. Under dry conditions, the Cu NP catalyst was able to maintain full conversion for up to 45 h at 350 °C, but it deactivated with time on stream in the presence of water vapor.
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