On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe2+ /H2 O2 ) and Fenton-like (Mn+ /H2 O2 ; Mn+  = Fe3+ , Co2+ , Cu2+ , Mn2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe2+ /H2 O2  â‰« H2 O2  â‰« Cu2+ /H2 O2  > Mn+ /H2 O2 (Mn+  = Fe3+ , Co2+ , Mn2+ ) ~ Mn+ (Mn+  = Fe2+ , Fe3+ , Co2+ , Cu2+ , Mn2 ). The superior capability of Fe2+ /H2 O2 in causing the degradation of sildenafil indicates that Fe2+ efficiently decomposes H2 O2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H2 O2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, ie, Fe3+ , Co2+ , Cu2+ , and Mn2+ . A unique oxidation by-product was detected in the reaction between Fe2+ /H2 O2 with sildenafil, and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shows to be a convenient platform to promptly monitor on-surface oxidation reactions.

Simple sol-gel process to obtain silica-coated anatase particles with enhanced TiO2-SiO2 interfacial area.

In this study we prepared silica-titania composites with a low SiO2:TiO2 molar ratio. These materials were prepared using a simple sol-gel route in which a hydrothermal treatment was used to obtain mesoporous anatase particles. Pure titania was also synthetized for comparison purposes. These materials were examined by scanning and transmission electron microscopy (SEM and TEM, respectively), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and nitrogen sorption tests. A thin silica coating was formed on the anatase particles. It was observed that the presence of this coating led to samples with an enhanced thermal stability. Indeed, the composites prepared in this work showed an anatase structure and a high specific surface area (SSA), even after their calcination at 800°C. Thus, we believe that the synthetized material present an outstanding SiO2-TiO2 interfacial area associated with a high amount of anatase particles which could improve its photoactive properties.