RESUMO
Nine hybrid silicas bearing the organic substituent groups methyl, octyl, octadecyl, vinyl, phenyl, mercaptopropyl, isocyanatopropyl, chloropropyl and glycidoxypropyl were synthesized by an acid-catalyzed, hydrolytic sol-gel process. The resulting solid materials were characterized by their absorbance and attenuated total reflection (ATR) IR and Raman spectra. The latter technique proved to be particularly useful in the identification of the organic moieties in the hybrid silicas. The effect of the presence of the organic groups on the silica networks was also investigated - there were increases observed in both the SiOSi bond angles and bond lengths. Moreover, deconvolution of the IR-active antisymmetric SiOSi stretching bands permitted detection of the four- and six-membered siloxane rings present in the silicas. There proved to be a greater number of four-membered rings on the surfaces of the particles. Both IR and Raman spectroscopy proved to be invaluable in the characterization of these hybrid materials.
Assuntos
Compostos de Organossilício/química , Dióxido de Silício/química , Modelos Moleculares , Compostos de Organossilício/síntese química , Transição de Fase , Espectroscopia de Infravermelho com Transformada de Fourier , Análise Espectral RamanRESUMO
Solid acid-base sensor materials were prepared by encapsulating three pH indicators (alizarin red, brilliant yellow, and acridine) within a silica matrix using a sol-gel approach through three different routes: (1) non-hydrolytic, (2) acid-catalyzed, and (3) base-catalyzed. Raman and Fourier transform infrared spectroscopies were used to evaluate the silica-indicator interactions. Because vibrational bands assigned to functional groups present in the indicator molecules were not detected, the main silica stretching mode νSi-O between approximately 1300 and 1000 cm(-1) was used to detect the presence of our indicators within the silica matrix. The large band centered at 1100 cm(-1) was deconvoluted into four components corresponding to the longitudinal optic and transversal optic modes of the silicon monoxide (SiO)4 and (SiO)6 siloxane rings. Using the component area of each mode, it was possible to calculate the percentage of each structure. Such percentages ranged from 49% to 70% (SiO)6 for the analyzed samples, within a confidence level of 95% (p = 0.05). (The confidence limits were 53-62%.) These results could be related to the pH indicator content, indicating that the quantity of the encapsulated molecule affects the (SiO)6 percentage values. In addition, a comparison with the radius of gyration obtained by small angle X-ray scattering was done. These results indicate that the analyte accesses the receptor elements through the passages between the siloxane rings but not through the siloxane rings themselves.