Micellar proportion: a parameter to compare the hydrophobicity of the pseudostationary phases or that of the analytes in micellar electrokinetic chromatography.
Micellar proportion, t(prop,mic) = t(mic)/t(m), a quantity expressing how much time is spent by the analyte in the micellar phase related to its whole migration time (t(m)) has been introduced by utilizing the micellar phase residence time (t(mic)). The t(prop,mic) values have been determined for analytes of different chemical structures (alkyl benzene and alkyl phenone homologous series, alcohols, strongly hydrophobic peptides) studied by micellar elektrokinetic chromatography (MEKC) using various cationic and anionic pseudostationary phases. A good linear correlation was obtained between t(prop,mic) and the calculated hydrophobicity (CLOGP) of the analytes for all pseudostationary phases (CLOGP = A.logt(prop,mic) + B). Considering a given pseudostationary phase, t(prop,mic) as a relative quantity is a suitable parameter to characterize and compare experimentally the behavior of the various analytes in MEKC. Applying a set of probe molecules with known hydrophobicity, the CLOGP(50) value (showing the value of hydrophobicity of a virtual molecule spending exactly 50% of its migration time in the pseudostationary phase) has been calculated for each pseudostationary phase applied here. This experimentally determinable numerical value (characterizing the pseudostationary phase) can be utilized to compare the hydrophobicity and hence retention ability of the pseudostationary phases. The t(prop,mic) value was found to be applicable to compare the methylene selectivity of the different pseudostationary phases as well: logt(prop,mic) = A.Z + B, where Z is the number of carbon atoms of the alkyl chain in the alkyl benzene homologous series.
Dobos
Zsófia
Z
Peptide Biochemistry Research Group of Hungarian Academy of Sciences and Semmelweis University, Semmelweis University Budapest, Department of Medical Chemistry, Molecular Biology and Pathobiochemistry.|Cooperative Research Center, Semmelweis University, Budapest, Hungary.
Kiss
Éva
É
Eötvös Loránd University, Department of Colloid Chemistry.
Hallgas
Balázs
B
Peptide Biochemistry Research Group of Hungarian Academy of Sciences and Semmelweis University, Semmelweis University Budapest, Department of Medical Chemistry, Molecular Biology and Pathobiochemistry.|Cooperative Research Center, Semmelweis University, Budapest, Hungary.
Kéri
György
G
Peptide Biochemistry Research Group of Hungarian Academy of Sciences and Semmelweis University, Semmelweis University Budapest, Department of Medical Chemistry, Molecular Biology and Pathobiochemistry.
Idei
Miklós
M
Peptide Biochemistry Research Group of Hungarian Academy of Sciences and Semmelweis University, Semmelweis University Budapest, Department of Medical Chemistry, Molecular Biology and Pathobiochemistry.
D020374:Chromatography, Micellar Electrokinetic Capillary / Q000295:instrumentation / Q000379:methods*; D057927:Hydrophobic and Hydrophilic Interactions; D008433:Mathematics; D008823:Micelles; D009842:Oligopeptides / Q000302:isolation & purification*
D008823:Micelles; D009842:Oligopeptides
Terabe, S., Otsuka, K., Ichikawa, K., Tsuchiyo, A., Ando, T., Anal. Chem. 1984, 56, 111-113.
Muijselaar, P. G., Otsuka, K., Terabe, S., J. Chromatogr. A 1997, 780, 41-61.
Trone, M. D., Mack, J. P., Godell, H. P., Khaled, M. G., J. Chromatogr. A 2000, 888, 229-240.
Terabe, S., Otsuka, K., Ando, T., Anal. Chem. 1985, 57, 834-841.
Vindevogel, J., Sandra, P., Introduction to Micellar Electrokinetic Chromatography, Hüthig Buch Verlag, Heidelberg 1992, pp.  13-69.
Abraham, M. H., Gola, J. M. R., Kumarshing, R., Cometto-Muniz, J. E., Cain, W. S., J. Chromatogr. B 2000, 745, 103-115.
Muijselaar, P. G., J. Chromatogr. A 1997, 780, 117-127.
Roses, M., Rafols, C., Bosch, E., Martinez, A. M., Abraham, M. H., J. Chromatogr. A 1999, 845, 217-226.
Molero-Monfort, M., Martin-Biosca, Y., Sagrado, S., Villanueve-Camanas, R. M., Medina-Hernández, M. J., J. Chromatogr. A 2000, 870, 1-11.
Nishi, H., Tsumagari, N., Kakimoto, T., Terabe, S., J. Chromatogr. 1989, 477, 359-363.
Cole, R. C., Sepaniak, M. J., Hinze, W. L., J. High Resolut. Chromatogr. 1990, 13, 579-582.
Roda, A., Hoffmann, A., Mysels, K. J., J. Biol. Chem. 1983, 258, 6362-6366.
Lindman, B., Wennerstrom, H., Topics Curr. Chem. 1980, 87, 1-7.
Khaledi, M. G., Bumgarner, J. G., Hadjmohammadi, M., J. Chromatogr. A 1998, 802, 35-47.
Fuquet, E., Rafols, C., Bosch, E., Abraham, M. H., Roses, M., J. Chromatogr. A 2002, 942, 237-248.
Poole, C. F., Poole, S. K., Abraham, M. H., J. Chromatogr. A. 1998, 798, 207.
Garcia, M. A., Diez-Masa, J. C., Marina, M. L., J. Chromatogr. A. 1996, 742, 251-256.
Yang, S., Bumgarner, J. F., Kruk, L. F. R., Khaledi, M. G., J. Chromatogr. A. 1996, 721, 323-335.
Herbert, B. J., Dorsey, J. G., Anal. Chem. 1995, 67, 744-749.
Valkó, K., Slegel, P., J. Chromatogr. 1993, 631, 49-61.
Overton, E., Z. Phys. Chem. (Leipzig) 1897, 22, 189-195.
Meyer, H., Arch. Exp. Pathol. Pharmacol. 1951, 42, 774-780.
Hansch, C., Fujita, T., J. Am. Chem. Soc. 1964, 86, 1616-1625.
Leo, A. J., Hansch, C., Elkins, D., Chem. Rew. 1971, 7, 525-616.
Meylan, W. M., Howard, P. H., J. Pharm. Sci. 1995, 84, 83-88.
Takács-Novák, K., Acta Pharm. Hung. 1998, 68, 39-48.
Leo, A., Chem. Rev. 1993, 93, 1281-1295.
Brauman, T., J. Chromatogr. 1986, 373, 191-197.
Kaliszan, R., Quantitative Structure-Activity Chromatographic Relationships, Wiley, New York 1987, pp.  232-252.
Valkó, K., Bevan, C., Reynolds, D., Anal. Chem. 1997, 69, 2022-2029.
Davis, A. M., Teague, A. M., Angew. Chem. Int. Ed. 1999, 38, 736-749.
Muijselaar, P. G., Claessens, H. A., Cramer, C. A., Anal. Chem. 1994, 66, 635-644.
Taft, R. W., Abboud, J. M., Kamlet, M. J., Abraham, M. H., J. Solut. Chem. 1985, 14, 153.
Carr, P. W., Microchem. J. 1993, 48, 4.
Abraham, M. H., Chem. Soc. Rev. 1993, 22, 73.
Sándi, Á., Szepesy, L., J. Chromatogr. A 1998, 818, 1-18.
Sándi, Á., Szepesy, L., J. Chromatogr. A 1998, 818, 19-30.
Engelhardt, H., Jungheim, M., Chromatographia 1990, 29, 59-66.
Engelhardt, H., Löw, H., Jungheim, M., J. Chromatogr. 1991, 544, 371-379.
Kimata, K., Iwaguchi, K., Onisiki, S., Jinno, K., Eksteen, R., Hosoya, K., Araki, M., Tanaka, N., J. Chromatogr. Sci. 1989, 27, 721-728.
Jandera, P., J. Chromatogr. 1986, 352, 91-110.
Claessens, H. A., de Haan, J. W., van de Ven, L. J. M., de Bruyn, P. C., Cramers, C. A., J. Chromatogr. 1988, 436, 345-365.
Szepesy, L., J. Chromatogr. A. 2002, 960, 69-83.
Idei, M., Kiss, Ü., Kéri, G, Electrophoresis 1996, 17, 762-766.
Idei, M., Kiss, Ü., Hollósy, F., Tamás, B., Örfi, L., Seprödi, J., Mészáros, Gy., Kéri, Gy, J. Liq. Chromatogr. Rel. Technol. 2001, 24, 303-315.
Eur. Patent Bull. Section 02.05.97 (Eur. Publ. No. 0770091) Int. Publ. No WO/95/31474.
Idei, M., Seprödi, J., Gyorffy, E., Hollósy, F., Vadász, Zs., Mészáros, Gy., Teplán, I., Kéri, G., Anal. Chim. Acta 1998, 372, 273-279.
Idei, M., Gyorffy, E., Kiss, Ü., Örfi, L., Seprödi, J., Tamás, B., Hollósy, F., Mészáros, Gy., Kåri, G., Electrophoresis 1999, 20, 1561-1567.
Hansch, C., Leo, A., Substituent Constants for Correlation Analysis in Chemistry and Biology, Wiley, New York 1979.
Idei, M., Hollósy, F., Kiss, Ü., Tamás, B., Örfi, L., Seprödi, J., Mészáros, G., Kéri, G., 25. Int. Symp. On High Performance Liquid Phase Separations, Maastricht, 2001, p.  123.
Yang, S., Khaledi, M. G., Anal. Chem. 1995, 67, 499-508.
Karger, B. L., Snyder, L. R., Horváth, C., An Introduction to Separation Science, Wiley and Sons, New York 1973, p.  55.