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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Microcolumn Separations 3 (1991), S. 47-57 
    ISSN: 1040-7685
    Keywords: supercritical fluid chromatography ; modifiers ; formic acid ; mobile phase ; capillary columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A small percentage (0.3% w/w) of formic acid was added to supercritical carbon dioxide to increase mobile phase polarity and improve separation of polar solutes on three different commercially available capillary columns. Formic acid reduced retention and altered selectivity for several polar compounds. Thermodynamic studies revealed that the enthalpy of solvation was as much as 27 kcal mol-1 more negative when formic acid was added due to increased solute-solvent interactions. Entropy measurements show that formic acid modified mobile phase is more ordered than a pure carbon dioxide mobile phase, apparently as a result of modifier clustering around polar solutes. Van't Hoff plots for some very polar solutes showed a region of retrograde behavior at low temperatures and pressures, indicating an increase in modifier clustering. Comparisons between pure and modified mobile phases were also made by examining practical separations obtained with each, revealing differences in retention, selectivity and peak shape.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1040-7685
    Keywords: micellar electrokinetic capillary chromatography ; capillary electrophoresis ; micellar separations ; resolution ; mixed micelles ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of surfactant concentration on resolution in micellar electrokinetic capillary chromatography (MECC) was investigated using several phenylthiohydantoin (PTH) derivatized amino acids as test solutes. Two aqueous micellar systems were employed: sodium dodecyl sulfate (SDS) and a mixed micellar system consisting of SDS and polyoxyethylene(23)dodecanol (Brij® 35). In the SDS system, the tmc/to ratio (elution range) increased significantly with increasing surfactant concentration, making the determination of the optimal concentration, which is dependent on tmc/to, difficult. In contrast, in the Brij 35/SDS system the tmc/to ratio decreased only slightly with increasing concentration of Brij 35. Whereas the SDS and Brij 35/SDS systems are better suited for moderately hydrophobic and hydrophilic solutes, respectively, neither is well-suited for hydrophobic solutes without organic modifiers. The narrower elution range (lower tmc/to) observed for the Brij 35/SDS micellar system was compensated by several potentially important advantages over the pure SDS system, including significantly higher efficiencies (2-3 times) and lower operating currents. Differences in selectivity and retention mechanisms among solutes and surfactant systems are also discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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