Silica chemical modifications

The most widely used columns contain a chemically modified silica stationary phase, with the chemical modification determining the polarity of the column. A... 

Iodine is a less suitable reagent for use on moderately polar phases and RP materials. The chemical modification of the silica gel that such layers have undergone makes them considerably more lipophilic, so that the contrast between substance-coated chromatogram zone and substance-free background is not very strong. The same applies to polyamide layers. 

August 21-26, 1994 edited by Y. izumi, H.Arai and M. Iwamoto Volume 93 Characterization and Chemical Modification of the Silica Surface... 

Reversed-phase PLC precoated plates are based on silica gel matrices with chemical modifications in such a manner that the accessible polar, hydrophilic silanol groups at the silica gel surface are replaced by nonpolar, hydrophobic alkyl chains via silicon-carbon bonds. For preparative purposes, up to now only PLC precoated RP plates with C-18 modification are available. This abbreviation is often also designated as RP-18, meaning that an octadecyl alkyl chain is chemically bonded to the silica gel surface. 

Sample adsorption to the silica wall is a problem in HPCE, one that is highly undesirable. As we mentioned earlier, adsorption can be minimized by proper buffer selection, additives, or chemical modification of the surface. The selection of pH is one of the simplest separation parameters to manipulate and is critical to the success of all electrophoretic separations. The pH of the media will determine the charge of the sample and the charge of the silica surface. At low values of pH, the capillary wall is protonated, the EOF... 

In gc there is only one phase (the stationary liquid or solid phase) that is available for interaction with the sample molecules. Because the mobile phase is a gas, all sample vapours are soluble in it in all proportions. In hplc both the stationary phase and the mobile phase can interact selectively with the sample. Interactions such as complexation or hydrogen bonding that are absent in the gc mobile phase may occur in the hplc mobile phase. The variety of these selective interactions can also be increased by suitable chemical modification of the silica surface, hence hplc is a more versatile technique than gc, and can often achieve more difficult separations. 

Chromatographic use of monolithic silica columns has been attracting considerable attention because they can potentially provide higher overall performance than particle-packed columns based on the variable external porosity and through-pore size/skeleton size ratios. These subjects have been recently reviewed with particular interests in fundamental properties, applications, or chemical modifications (Tanaka et al., 2001 Siouffi, 2003 Cabrera, 2004 Eeltink et al., 2004 Rieux et al., 2005). Commercially available monolithic silica columns at this time include conventional size columns (4.6 mm i.d., 1-10 cm), capillary columns (50-200 pm i.d., 15-30 cm), and preparative scale columns (25 mm i.d., 10 cm). 

In a sense each monolithic column is unique, or produced as a product of a separate batch, because the columns are prepared one by one by a process including monolith formation, column fabrication, and chemical modification. Reproducibility of Chro-molith columns has been examined, and found to be similar to particle-packed-silica-based columns of different batches (Kele and Guiochon, 2002). Surface coverage of a Chromolith reversed-phase (RP) column appears to be nearly maximum, but greater silanol effects were found for basic compounds and ionized amines in buffered and nonbuffered mobile phases than advanced particle-packed columns prepared from high purity silica (McCalley, 2002). Small differences were observed between monolithic silica columns derived from TMOS and those from silane mixtures for planarity in solute structure as well as polar interactions (Kobayashi et al., 2004). 

Brandhuber, D., Peterlik, H. and Husing, N. (2005) Simultaneous drying and chemical modification of hierarchically organized silica monoliths with organofunctional silanes. Journal of Materials Chemistry, 15, 3896-3902. 

Interestingly, in HPLC the stationary phase and the mobile-phase is able to interact with the sample selectively. Besides, such interactions as hydrogen bonding or complexation which are absolutely not possible in the GC-mobile phase may be accomplished with much ease in the HPLC-mobile phase. Furthermore, the spectrum of these selective interactions may also be enhanced by an appropriate chemical modification of the silica surface the stationary phase. Therefore, HPLC is regarded as a more versatile technique than GC and capable of achieving more difficult separations. 

In this synthetic strategy, the macrocyclic antibiotic is covalently bonded to the silica matrix in two steps (1) chemical modification of the selector via reaction between suitable groups of the antibiotic and proper groups of the spacer, reacting also as a di- or trialkoxysilane (2) immobilization of the functionalized selector on unmodified silica particles. 

The influence of chemical modification of silica surfaces by treatment with trimethylsilyl chloride was studied also by A. V. Kiselev and collaborators (221), Babkin et al. (222), and Babkin and Kiselev (223). They reported that no change occurred in (CHglaSiCl-treated Aerosil even after storing for months underwater (221). Lowen and Broge (224) investigated the influence on the heat of wetting and methyl red adsorption. 

In general, the silanization of hydroxyl-terminated substrates such as silica or glass is an effective method which is used quite often for chemical modification of the substrate surface for immobilization of biomolecules. The main focus for silanization procedures is once again the examination of the self-organizing silane-monolayers. The properties of the monolayer depend on the chemical structure of the silanization reagent, the density of silanol-groups which are available on the surface and the physical surface structure on a nano-scale level. 

Covalent immobilization methods of NAs to a silica surface require its chemical modification. Functionally inert surface silanols (Si - OH) need to be transformed into reactive species to which the NAs can be attached irreversibly. To date, the main method for the attachment of biological moieties to silica surfaces has involved substrate reaction with organofunctional silanes of the general structure (RO)3Si(CH2)X, followed by the covalent attachment of the biological molecule to the newly introduced fimctional group on the surface [31,32]. Examples of organofimctional silanes used this way include (3-glycidoxypropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane,... 

It is generally accepted that the only important polar adsoiption sites on the silica surface are the silanol functions, i.e., hydroxyl groups, that are attached to silicon atoms (2). They can interact with the sample molecules by hydrogen bonding and various physical observations ctAi be used to prove this statement. Complete dehydration of silica by beating, i.e., removal of all surface hydroxyl groups, yields a hydrophobia silica which no longer shows adsorption for unsaturated and polar molecules and is no more wetted by water (15). Chemical modification of the surface hydroxyls such as used in the preparation of chemically bonded phases also eliminates the selective adsorption properties of the silica. ... 

Vansant EF, Van der Woort P, Vrancken KC (eds) (1995) Characterization and chemical modification of the silica surface. Elsevier, New York... 

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