Organic amine-functionalized silicas

Aminosilanes contain the catalyzing amine function in the organic chain. The reaction of aminosilanes with silica gel in dry conditions is therefore self-catalyzed. They show direct condensation, even in completely dry conditions. Upon addition of the aminosilane to the silica substrate, the amine group may form hydrogen bonds or proton transfer complexes with the surface silanols. This results in a very fast adsorption, followed by direct condensation. This reaction mechanism of APTS with silica gel in dry conditions, is displayed in figure 8.9. After liquid phase reaction, the filtered substrate is cured, in order to consolidate the modification layer. 

The electron rich amine function is a good acceptor for hydrogen bonds. On the other hand, the basic character of the amine causes proton transfer from acidic groups. Both types of interaction occur on the silica surface. Together with the siloxane bond formation, three types of hydroxyl-specific interaction of the aminosilane molecule with the silica surface may be described, for the modification in organic solvent. These are displayed in figure 9.23. 

The presence of surface OH groups or H2 O molecules can play a primary role in adsorption. For example, a microcalorimetric study of the adsorption of stearic acid, from heptane solution, on ferric oxide (Husbands et al., 1971) revealed that preadsorbed water enhanced adsorption of stearic acid. When adsorption takes place from a dry organic liquid, residual surface water may act as special agent. This was shown for the adsorption of a silane coupling agent (y-amino-propyl-triethoxysilane) on silica covered with water molecules for 6 < 1 (Trens and Denoyel, 1996). By the simultaneous determination of adsorption isotherms and the enthalpies of displacement (of heptane by various silanes) it was demonstrated that the amine function was able to displace some of the surface water and make it available for the hydrolysis of the silane into trisilanol, whereas the residual water was able to promote the formation of siloxane bonds between the trisilanol molecules and the surface. 

Inorganic-organic hybrid silica was prepared via co-condensation of tetraethoxy- or tetramethoxysilane (TEOS or TMOS) and aminoalkoxysilane with appropriate amounts of ethanol (or methanol), water, and ammonia. The amine functional groups in the silica were converted to N-diazeniumdiolate NO donors via exposure to high pressures of NO (5 atm) under basic conditions. Control over both the structure and concentration of the silane precursors (i.e., tetraalkoxy-and aminoalkoxysilanes) and specific synthetic conditions allowed for the preparation of NO donor silica particles of widely varying sizes (20-500 nm), NO payloads (50-1,780 nmol/mg), maximum amounts of NO released (10-5,500 ppb/mg), half-lives (0.1-12 h), and NO release durations (up to 30 h)... 

This technique is based on the same separation mechanisms as found in liquid chromatography (LC). In LC, the solubility and the functional group interaction of sample, sorbent, and solvent are optimized to effect separation. In SPE, these interactions are optimized to effect retention or elution. Polar stationary phases, such as silica gel, Florisil and alumina, retain compounds with polar functional group (e.g., phenols, humic acids, and amines). A nonpolar organic solvent (e.g. hexane, dichloromethane) is used to remove nonpolar inferences where the target analyte is a polar compound. Conversely, the same nonpolar solvent may be used to elute a nonpolar analyte, leaving polar inferences adsorbed on the column. 

The previous example took inspiration from earlier work of Lin et al.18 In their seminal work, Lin and coworkers functionalized the inner pores of MCM-41 with o-phthalic hemithioacetal moieties that are able to react with amines to produce a highly fluorescent isoindole derivative. In order to enhance selectivity in the sense we have discussed above, the solids were also hydrophobized with different groups such as propyl, phenyl, and pentafluorophenyl in a second step. Interestingly, some of these solids displayed a remarkably selective and differentiable response to dopamine versus the less lipophilic glucosamine. The authors also demonstrated that this selectivity was not observed when amorphous (nonporous) silica functionalized with the same organic groups was used, stressing the importance of the 3D... 

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