Silica monolithic supports

Despite the fact that the first silica monolithic supports have been already reported in the late 1970s, the first uniform porous silica rods used for reversed-phase chromatography... 

In this study, chromatographic experiments were 10 times faster with the monolithic column and results were equivalent to those obtained with the silica-based columns. This approach could be further optimized with faster gradient since flow rate should be increased by a factor 3 or 7 compared to conventional Cig supports [61, 62] and gradient time reduced by the same factor [63] to fully exploit the potential of monolithic supports. 

Another recent trend focused on supports in the shape of monolithic columns having the goal to benefit from the high permeability and the improved mass transfer characteristics of such structures. With this goal in mind, Lubda and Lindner [75] prepared enantioselective silica monolith columns with tert-butylcarbamoylquinine surface modification. A commercial sol-gel-derived Chromolith Performance Si (100 X 4.6 mm ID) monolith (1.9 tim macropore diameter, 12.5 nm mesopore... 

Enantiomer separation of various compounds such as barbituric acids, benzoin, MTH-proline, glutethimide, a-methyl-oc-phenyl-succinimide, y-phenyl-y-butyrolac-tone, methyl-mandelate, l-(2-naphthyl)ethanol, mecoprop methyl, diclofop methyl and fenoxaprop methyl by pressure supported CEC on a permethyl-P-cyclodextrin modified stationary phase was described by Wistuba and Schurig [42-44]. Three different separation beds were used (i) permethyl-P-cyclodextrin was covalently attached via a thioether to silica (Chira-Dex-silica) [42], permethyl-P-cyclodextrin was linked to a dimethylpolysiloxane and thermally immobilized (ii) on silica (Chirasil-Dex-silica) [43] or (iii) on a silica monolith (Chirasil-Dex-monolith) [44], respectively. 

The preparation of polymeric monoliths is relatively simple compared with those of the silica rods. A polymerization mixture consisting of monomer, cross-linker, initiator, and porogenic solvent is introduced into a sealed tube. The reaction can be temperature or redox initiated and in the case of transparent molds UV light can also be used to trigger the polymerization. At the end of the reaction the seals are removed and the tubes are attached to a pump, which flushes solvent through the monolith to remove the porogens and the unreacted components. The obtained monolith can be radial or axial compressed to prevent the formation of voids and further functionalized for different chromatographic modes. The majority of current monolithic supports... 

Ceramem membranes (CeraMem, USA) produces honeycomb-shaped monolithic supports of cordierite, the channels of which are coated with zirconia, silica, y-alumina or a-alumina separation layers. 

Irrespective of the reaction conditions used (/. e. ultrasound, microwave, changing reaction times, temperature and solvents), the maximum turnover number (TON) that was achieved was 75. In principle, second generation Grubbs-type initiators immobilized on non-porous silica should behave similar to those immobilized on monolithic supports[16]. In fact, catalysts immobilized onto monolithic supports give similar maximum TONs (< 65) in the absence of any chain transfer agent (CTA). Ruthenium measurements by means of ICP-OES revealed quantitative retention of the original amount of ruthenium at the support within experimental error ( 5%), thus otfering access to metal free products. 

Ammonia selectivity of platinum and platinum-nickel catalysts for NOx reduction varies with the nature of the supporting oxide. Silica, alumina, and silica-alumina supports on monolithic substrates were studied using synthetic automotive exhaust mixtures at 427°-593°C. The findings are explained by a mechanism whereby the reaction of nitric oxide with adsorbed ammonia is in competition with ammonia desorption. The ease of this desorption is affected by the chemistry of the support. Ammonia decomposition is not an important reaction on these catalysts when water vapor is present. 

Porous inorganic materials, in general, and porous silica in particular, are very popular supports widely used in chromatography. Therefore, development of silica monoliths followed closely to that of the organic polymers. Detailed accounts of these materials have also been published several times. Separations using these monolithic separation media have also been treated theoretically. ... 

The stationary phase in IMAC consists of an immobilized chelating ligand that is complexed with a metal ion. The chelating ligand is attached covalently to a support and used to entrap metal ions via coordinate binding. Agarose was the first support utilized in IMAC, but supports based on other materials, such as silica, are also now common [72,73]. Recent reports have further described the development of supports for IMAC based on cryogels, silica monoliths, and polymethacrylate monoliths [74-76]. 

Monolithic supports instead of columns packed with silica particles... 

The raw materials needed to supply about ten million new automobiles a year do not impose a difficult problem except in the case of the noble metals. Present technology indicates that each car may need up to ten pounds of pellets, two pounds of monoliths, or two pounds of metal alloys. The refractory oxide support materials are usually a mixture of silica, alumina, magnesia, lithium oxide, and zirconium oxide. Fifty thousand tons of such materials a year do not raise serious problems (47). The base metal oxides requirement per car may be 0.1 to 1 lb per car, or up to five thousand tons a year. The current U.S. annual consumption of copper, manganese, and chromium is above a million tons per year, and the consumption of nickel and tungsten above a hundred thousand tons per year. The only important metals used at the low rate of five thousand tons per year are cobalt, vanadium, and the rare earths. 

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