Stationary phases, for

General structures of common stationary phases for gas chromatography. 

Proteias, amino acids bonded through peptide linkages to form macromolecular biopolymers, used as chiral stationary phases for hplc iaclude bovine and human semm albumin, a -acid glycoproteia, ovomucoid, avidin, and ceUobiohydrolase. The bovine semm albumin column is marketed under the name Resolvosil and can be obtained from Phenomenex. The human semm albumin column can be obtained from Alltech Associates, Advanced Separation Technologies, Inc., and J. T. Baker. The a -acid glycoproteia and ceUobiohydrolase can be obtained from Advanced Separation Technologies, Inc. or J. T. Baker, Inc. 

Diamide Chiral Separations. The first chiral stationary phase for gas chromatography was reported by GH-Av and co-workers in 1966 (113) and was based on A/-trifluoroacetyl (A/-TFA) L-isoleucine lauryl ester coated on an inert packing material. It was used to resolve the tritiuoroacetylated derivatives of amino acids. Related chiral selectors used by other workers included -dodecanoyl-L-valine-/-butylamide and... 

Gyclodextrins. As indicated previously, the native cyclodextrins, which are thermally stable, have been used extensively in Hquid chromatographic chiral separations, but their utihty in gc appHcations was hampered because their highly crystallinity and insolubiUty in most organic solvents made them difficult to formulate into a gc stationary phase. However, some functionali2ed cyclodextrins form viscous oils suitable for gc stationary-phase coatings and have been used either neat or diluted in a polysiloxane polymer as chiral stationary phases for gc (119). Some of the derivati2ed cyclodextrins which have been adapted to gc phases are 3-0-acetyl-2,6-di-0-pentyl, 3-0-butyryl-2,6-di-0-pentyl,... 

Several hundred types of Hquid phases are commercially available. These have been used individually or in combination with other Hquid phases, inorganic salts, acids, or bases. The selection of stationary phases for a particular appHcation is beyond the scope of this article, however, it is one of the most important chromatographic tasks. Stationary phase selection is discussed at length in books, journal articles, and catalogs from vendors. See General References for examples. 

Thermodynamic paths are necessary to evaluate the enthalpy (or internal energy) of the fluid phase and the internal energy of the stationary phase. For gas-phase processes at low and modest pressures, the enthalpy departure function for pressure changes can be ignored and a reference state for each pure component chosen to be ideal gas at temperature and a reference state for the stationarv phase (adsorbent plus adsorbate) chosen to be adsorbate-free solid at. Thus, for the gas phase we have... 

APPLICATION OF NANOTECHNOLOGY FOR PREPARATION OF STATIONARY PHASE FOR CHROMATOGRAPHY... 

New stationary phases for specific purposes in chromatographic separation are being continually proposed. Charge transfer adsorption chromatography makes use of a stationary phase which contains immobilised aromatic compounds and permits the separation of aromatic compounds by virtue of the ability to form charge transfer complexes (sometimes coloured) with the stationary phase. The separation is caused by the differences in stability of these complexes (Porath and Dahlgren-Caldwell J Chromatogr 133 180 1977). 

Scheme 2.5. Chiral Stationary Phases for HPLC Separation of Enantiomers...

The value of (q) takes into account the precise shape of the pool of stationary phase for a uniform liquid film as in a GC capillary column, q = 2/3. Diffusion in rod shaped and sphere shaped bodies (e.g., paper chromatography and LC) gives q=l/2 and 2/15, respectively [2]. 

In Figure 7, the resistance to mass transfer term (the (C) term from the Van Deemter curve fit) is plotted against the reciprocal of the diffusivity for both solutes. It is seen that the expected linear curves are realized and there is a small, but significant, intercept for both solutes. This shows that there is a small but, nevertheless, significant contribution from the resistance to mass transfer in the stationary phase for these two particular solvent/stationary phase/solute systems. Overall, however, all the results in Figures 5, 6 and 7 support the Van Deemter equation extremely well. 

The high thermal and chemical stability of fluorocarbons, combined with their very weak intermolecular interactions, makes them ideal stationary phases for the separation of a wide variety of organic compounds, including both hydrocarbons and fluorine-containing molecules Fluonnated stationary phases include per-fluoroalkanes, fluorocarbon surfactants, poly(chlorotrifluoroethylene), polyfper-fluoroalkyl) ethers, and other functionalized perfluoro compounds The applications of fluonnated compounds as stationary phases in gas-liquid chroma... 

FIGURE 1.4 Optical micrograph of macroporous chromatographic column materials, (a) Monosized particles of 20 tm. (b) Commercial column filling of 12-28 tm. [Reprinted from T. Ellingsen et al. (1990). Monosized stationary phases for chromatography.7. Chromawgr. 535,147-161 with kind permission from Elsevier Science-NL, Amsterdam, The Netherlands.]... 

In addition to the development of the powerful chiral additive, this study also demonstrated that the often tedious deconvolution process can be accelerated using HPLC separation. As a result, only 15 libraries had to be synthesized instead of 64 libraries that would be required for the full-scale deconvolution. A somewhat similar approach also involving HPLC fractionations has recently been demonstrated by Griffey for the deconvolution of libraries screened for biological activity [76]. Although demonstrated only for CE, the cyclic hexapeptides might also be useful selectors for the preparation of chiral stationary phases for HPLC. However, this would require the development of non-trivial additional chemistry to appropriately link the peptide to a porous solid support. 

In a series of papers published throughout the 1980s, Colin Poole and his co-workers investigated the solvation properties of a wide range of alkylammonium and, to a lesser extent, phosphonium salts. Parameters such as McReynolds phase constants were calculated by using the ionic liquids as stationary phases for gas chromatography and analysis of the retention of a variety of probe compounds. However, these analyses were found to be unsatisfactory and were abandoned in favour of an analysis that used Abraham s solvation parameter model [5]. 

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