Supercritical Fluid Chromatography for the Analysis of Natural Products

  • Joe P. Foley
  • Jeffrey A. Crow
Part of the Recent Advances in Phytochemistry book series (RAPT, volume 25)


As with many branches of science, advances in the field of natural products research have always depended largely on the analytical methods available. The separation, identification, structure elucidation, and quantitation of components in phytochemical samples are all essential steps to the study of natural products chemistry. As a result, many of the advances in this field parallel the improvement of analytical methodologies.


Supercritical Fluid Polar Compound Packed Column Supercritical Carbon Dioxide Supercritical Fluid Extraction 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    ETTRE, L.S. 1980. Evolution of liquid chromatography: A historical perspective. In: High Performance Liquid Chromatography: Advances and Perspectives. (C. Horváth, ed.), Academic Press, New York, pp 1–74.Google Scholar
  2. 2.
    CHESTER, T.L., PINKSTON, J.D. 1990. Supercritical fluid chromatography. Anal. Chem. 62: 394R–402R.PubMedCrossRefGoogle Scholar
  3. 3.
    CLEMENT, R.E., ONUSKA, F.I., EICEMAN, G.A., HILL, H.H. Jr. 1988. Gas chromatography. Anal. Chem. 60: 283R–284R.CrossRefGoogle Scholar
  4. 4.
    CLEMENT, R.E., ONUSKA, F.I., EICEMAN, G.A., HILL, H.H. Jr.. 1986. Gas chromatography. Anal. Chem. 58: 325R–326R.CrossRefGoogle Scholar
  5. 5.
    SMITH, ROGER M. 1988. Supercritical Fluid Chromatography. Royal Society of Chemistry, London, 238pp.Google Scholar
  6. 6.
    LEE, M. L., MARKIDES, K. E., eds. 1990. Analytical Supercritical Fluid Chromatography and Extraction. Chromatography Conferences, Inc., 577 pp.Google Scholar
  7. 7.
    CHARPENTIER, B.A, SEVENANTS, M.R., eds. 1988. Supercritical Fluid Extraction and Chromatography: Techniques and Applications. ACS Symp. Ser. 366, American Chemical Society, Washington, DC, 253 pp.Google Scholar
  8. 8.
    YANG, F.J., ed. 1989. Microbore Column Chromatography: A Unified Approach to Chromatography. Chromatographic Science, Vol. 45. Marcel Dekker, New York, 405 pp.Google Scholar
  9. 9.
    SCHOENMAKERS, P.J., VERHOEVEN, F.C.C.J.G. 1987. Super-critical fluid chromatography—prospects and problems. Trends Anal. Chem. 6: 10–17.CrossRefGoogle Scholar
  10. 10.
    CHESTER, T.L. 1989. Practice and applications of supercritical fluid chromatography in the analysis of industrial samples. Chromatogr. Sci. Microbore Column Chromatogr. 45: 369–397.Google Scholar
  11. 11.
    KLESPER, E.G. 1988. Supercritical-fluid chromatography (SFC), Nachr. Chem. Tech. Lab. Spec. Issue 36: 93–100.Google Scholar
  12. 12.
    KLESPER, E., CORWIN, A.H., TURNER, D.A. 1962. High pressure gas chromatography above critical temperatures. J. Org. Chem. 27: 700–706.CrossRefGoogle Scholar
  13. 13.
    FIELDS, S.M., GROLIMUND, K. 1989. Evaluation of supercritical sulfur hexafluoride as a mobile phase for polar and non-polar compounds. J. Chromatogr. 472: 197–208.CrossRefGoogle Scholar
  14. 14.
    LAUER, H.H., MCMANIGILL, D., BOARD, R.D. 1983. Mobile phase transfer properties of liquified gases in near critical and supercritical fluid chromatography. Anal. Chem. 55: 1370–1375.CrossRefGoogle Scholar
  15. 15.
    ASHRAF-KHORASSANI, M., TAYLOR, L.T., ZIMMERMAN, P. 1990. Nitrous oxide versus carbon dioxide for supercritical fluid extraction and chromatography of amines. Anal. Chem. 62: 1177–1180.CrossRefGoogle Scholar
  16. 16.
    SCHWARTZ, H.E., BROWNLEE, R.G. 1986. Hydrocarbon group-type separations using supercritical fluid chromatography with sulfur hexafluoride as a mobile phase. J. Chromatogr. 353: 77–93.CrossRefGoogle Scholar
  17. 17.
    ONG, C.P., LEE, H.K., LI, S.F.Y. 1990. Chlorodifluoromethane as the mobile phase in supercritical fluid chromatography of selected phenols. Anal. Chem. 62: 1389–1391.CrossRefGoogle Scholar
  18. 18.
    YONKER, C.R., MCMINN, D.G., WRIGHT, B.W., SMITH, R.D. 1987. Effect of temperature and modifier concentration on retention in supercritical fluid chromatography. J. Chromatogr. 388: 19–29.CrossRefGoogle Scholar
  19. 19.
    LOCHMULLER, C.H., MINK, L.P. 1989. Adsorption isotherms on silica for methanol and 1-hexanol modifiers from supercritical fluid chromatography. J. Chromatogr. 471: 357–366.CrossRefGoogle Scholar
  20. 20.
    GEISER, F.O., YOCKLOVICH, S.G., LURCOTT, S.M., GUTHRIE, J.W., LEVY, E.J. 1988. Water as a stationary phase modifier in packed-column supercritical fluid chromatography. J. Chromatogr. 459: 173–181.CrossRefGoogle Scholar
  21. 21.
    GIDDINGS, J.C., MEYERS, M.N., KING, J.W. 1968. Dense gas chromatography at pressures to 2000 atm. Science. 4: 276–283.Google Scholar
  22. 22.
    BERGER, T.A., DEYE, J.F., ANDERSON, A.G. 1990. Nile Red as a solvatochromic dye for measuring solvent strength in normal liquids and mixtures of normal liquids with supercritical and near critical fluids. Anal. Chem. 62: 615–622.CrossRefGoogle Scholar
  23. 23.
    Buyer’s guide issue. 1990. LC-GC: The Magazine of Separation Science. 8: 567–674.Google Scholar
  24. 24.
    Labguide issue. 1990. Anal. Chem. 62: 1G–268G.Google Scholar
  25. 25.
    SCHWARTZ, H.E., BARTHEL, P.J., MORING, S.E., LAUER, H.H. 1987. Packed vs. capillary columns for supercritical fluid chromatography: theoretical considerations. LC-GC: The Magazine of Separation Science. 5: 490–497.Google Scholar
  26. 26.
    PAYNE, K.M., TARBET, B.J., BRADSHAW, J.S., MARKIDES, K.E., LEE, M.L. 1990. Simultaneous deactivation and coating of porous silica particles for microcolumn supercritical fluid chromatography. Anal. Chem. 62: 1379–1384.CrossRefGoogle Scholar
  27. 27.
    TAYLOR, L.T., CHANG, H.K. 1990. Packed column development in supercritical fluid chromatography. J. Chromatogr. Sci. 28: 357–366.Google Scholar
  28. 28.
    SCHOENMAKERS, P.J. 1988. Supercritical fluid chromatography: open columns vs packed columns. HRC&CC, J. High Resolut. Chromatogr. Chromatogr. Commun. 11: 278–282.CrossRefGoogle Scholar
  29. 29.
    WHEELER, J.R., MCNALLY, M.E. 1987. Comparison of packed column and capillary column supercritical fluid chromatography and high-performance liquid chromatography using representative herbicides and pesticides as typical moderate polarity and molecular weight range molecules. J. Chromatogr. 410: 343–353.PubMedCrossRefGoogle Scholar
  30. 30.
    TAYLOR, L.T., CALVEY, E.M. 1989. Supercritical fluid chromatography with infrared spectrometric detection. Chem. Rev. 89: 321–330.CrossRefGoogle Scholar
  31. 31.
    GREEN, S., BERTSCH, W. 1988. Simple restrictors for capillary column supercritical fluid chromatography. HRC&CC, J. High Resolut. Chromatogr. Chromatogr. Commun. 11: 414–415.CrossRefGoogle Scholar
  32. 32.
    RAYNOR, M.W., BARTLE, K.D., DAVIES, I.L. 1988. Preparation of robust tapered restrictors for capillary SFC. HRC&CC, J. High Resolut. Chromatogr. Chromatogr. Commun. 11: 289–291.CrossRefGoogle Scholar
  33. 33.
    BERGER, T.A. 1989. Modeling linear and tapered restrictors in capillary supercritical fluid chromatography. Anal. Chem. 61: 356–361.CrossRefGoogle Scholar
  34. 34.
    SNYDER, L.R., KIRKLAND, J.J. 1979. Introduction to Modern Liquid Chromatography. Wiley, New York.Google Scholar
  35. 35.
    FJELDSTED, J.C., JACKSON, W.P., PEADEN, P.A., Lee, M.L. 1983. Density programming in capillary supercritical fluid chromatography. J. Chromatogr. Sci. 21: 222–225.Google Scholar
  36. 36.
    LATER, D.W., CAMPBELL, E.R., RICHTER, B.E. 1988. Synchronized temperature/density programming in capillary SFC. HRC&CC, J. High Resolut. Chromatogr. Chromatogr. Commun. 11:65–69.CrossRefGoogle Scholar
  37. 37.
    SCHWARTZ, H.E., BROWNLEE, R.G., BODUSZYNSKI, M.M., SU, F. 1987. Simulated distillation of high boiling petroleum fractions by capillary supercritical fluid chromatography and vacuum thermal gravimetric analysis. Anal. Chem. 59: 1393–1401.CrossRefGoogle Scholar
  38. 38.
    GORNER, T., PERRUT, M. 1989. Separation of unsaturated fatty acid methyl esters by supercritical fluid chromatography on a silica column. LC-GC: The Magazine of Separation Science. 7: 502–507.Google Scholar
  39. 39.
    NOMURA, A., YAMADA, J., TSUNODA, K., SAKAKI, K., YOKOCHI, T. 1989. Supercritical fluid chromatographic determination of fatty acids and their esters on an ODS-silica gel column. Anal. Chem. 61:2076–2078.CrossRefGoogle Scholar
  40. 40.
    HOLZER, G.U., KELLY, P.J., JONES, WJ. 1988. Analysis of lipids from a hydrothermal vent methanogen and associated vent sediment by supercritical fluid chromatography. J. Microbiol. Methods. 8: 161–173.CrossRefGoogle Scholar
  41. 41.
    CHESTER, T.L., INNIS, D.P. 1986. Separation of oligo- and polysaccharides by capillary supercritical fluid chromatography. HRC &CC, J. High Resolut. Chromatogr. Chromatogr. Commun. 9: 209–212.CrossRefGoogle Scholar
  42. 42.
    KUEI, J., HER, G.R., REINHOLD, V.N. 1988. Supercritical fluid chromatography of glycosphingolipids. Anal. Biochem. 172: 228–234.PubMedCrossRefGoogle Scholar
  43. 43.
    HERBRETEAU, B., LAFOSSE, M., MORIN-ALLORY, L., DREUX, M. 1990. Analysis of sugars by supercritical fluid chromatography using polar packed columns and light-scattering detection. J. Chromatogr. 505: 299–305.CrossRefGoogle Scholar
  44. 44.
    RAYNOR, M.W., KITHINJI, J.P., BARKER, I.K., BARTLE, K.D., WILSON, I.D. 1988. Supercritical fluid chromatography of ecdysteroids. J. Chromatogr. 436:497–502.CrossRefGoogle Scholar
  45. 45.
    MORGAN, E.D., MURPHY, S.J., GAMES, D.E., MYLCHREEST, I.C. 1988. Analysis of ecdysteroids by supercritical-fluid chromatography. J. Chromatogr. 441: 165–169.CrossRefGoogle Scholar
  46. 46.
    RAYNOR, M.W., KITHINJI, J.P., BARTLE, K.D., GAMES, D.E., MYLCHREEST, I.C., LAFONT, R., MORGAN, E.D., WILSON, I.D. 1989. Packed column supercritical fluid chromatography and linked supercritical fluid chromatography-mass spectrometry for the analysis of phytoecdysteroids from Silene nutans and Silene otites. J.Chromatogr. 467: 292–298.CrossRefGoogle Scholar
  47. 47.
    SHAH, S., ASHRAF-KHORASSANI, M., TAYLOR, L.T. 1989. Normal-phase liquid and supercritical fluid chromatographic separations of steroids with Fourier-transform infrared spectrometric detection. Chromatographia. 27: 441–448.CrossRefGoogle Scholar
  48. 48.
    DAVID, P.A., NOVOTNY, M. 1989. Analysis of steroids by capillary supercritical fluid chromatography with phosphorus-selective detection. J. Chromatogr. 461: 111–120.PubMedCrossRefGoogle Scholar
  49. 49.
    HOLZER, G., ZALKOW, L.H., ASIBAL, C.F. 1987. Capillary supercritical fluid chromatography of pyrrolizidine alkaloids. J. Chromatogr. 400: 317–322.PubMedCrossRefGoogle Scholar
  50. 50.
    BALSEVICH, J., HOGGE, L.R., BERRY, A.J., GAMES, D.E., MYLCHREEST, I.C. 1988. Analysis of indole alkaloids from leaves of Catharanthus roseus by means of supercritical fluid chroma-tography/mass spectrometry. J. Nat. Prod. 51: 1173–1177.CrossRefGoogle Scholar
  51. 51.
    JANICOT, J.L., CAUDE, M., ROSSET, R. 1988. Separation of opium alkaloids by carbon dioxide sub- and supercritical fluid chromatography with packed columns. Application to the quantitative analysis of poppy straw extracts. J. Chromatogr. 437: 351–364.PubMedCrossRefGoogle Scholar
  52. 52.
    MORIN, P., CAUDE, M., RICHARD, H., ROSSET, R. 1987. Supercritical fluid chromatography — Fourier transform infrared spectrometry coupling applied to polycyclic aromatic and sesquiterpene hydrocarbons analysis. Analysis. 15:117–127.Google Scholar
  53. 53.
    MORIN, P., PICHARD, H., RICHARD, H., CAUDE, M., ROSSET, R. 1989. Supercritical fluid chromatography of sesquiterpene hydrocarbons on silica packed columns with on-line Fourier-transform infrared detection. J. Chromatogr. 464: 125–137.CrossRefGoogle Scholar
  54. 54.
    CROW, J.A., FOLEY, J.P. 1990. Optimization of separations in supercritical fluid chromatography using a modified simplex algorithm and short capillary columns. Anal. Chem. 62: 378–386.CrossRefGoogle Scholar
  55. 55.
    CALVEY, E.M., TAYLOR, L.T., PALMER, J.K. 1988. Supercritical fluid chromatography with Fourier-transform infrared detection of peracetylated aldononitrile derivatives and by-products from monosaccharides. HRC&CC, J. High Resolut. Chromatogr. Chromatogr. Commun. 11: 739–741.CrossRefGoogle Scholar
  56. 56.
    BERRY, A.J., GAMES, D.E., PERKINS, J.R. 1986. Supercritical fluid chromatographic and supercritical fluid chromatographic-mass spectrometry studies of some polar compounds. J. Chromatogr. 363: 147–158.CrossRefGoogle Scholar
  57. 57.
    LATER, D.W., RICHTER, B.E., KNOWLES, D.E., ANDERSEN, M.R. 1986. Analysis of various classes of drugs by capillary supercritical fluid chromatography. J. Chromatogr. Sci. 24: 249–153.PubMedGoogle Scholar
  58. 58.
    ROACH, J.A.G., SPHON, J.A., EASTERLING, J.A., CALVEY, E.M. 1989. Capillary supercritical fluid Chromatography/negative ion chemical ionization mass spectrometry of trichothecenes. Biomed. Environ. Mass Spectrom. 18: 64–70.CrossRefGoogle Scholar
  59. 59.
    YAMAUCHI, Y., SAITO, M. 1990. Fractionation of lemon-peel oil by semi-preparative supercritical fluid chromatography. J. Chromatogr. 505: 237–246.CrossRefGoogle Scholar
  60. 60.
    DEMING, S.N., MORGAN, S.L. 1973. Simplex optimization of variables in analytical chemistry. Anal. Chem. 45: A278–A283.Google Scholar
  61. 61.
    BERRIDGE, J.C., MORRISSEY, E.G. 1984. Automated optimization of reversed-phase high-performance liquid chromatography separations: an improved method using the sequential simplex procedure. J. Chromatogr. 316: 69–79.CrossRefGoogle Scholar
  62. 62.
    BERRIDGE, J.C. 1982. Unattended optimization of reversed-phase high-performance liquid chromatographic separations using the modified simplex algorithm. J. Chromatogr. 244: 1–14.CrossRefGoogle Scholar
  63. 63.
    BALCONI, M.L., SIGON, F. 1989. Simplex optimization of high-performance liquid chromatographic separations. J. Chromatogr. 485: 3–14.CrossRefGoogle Scholar
  64. 64.
    DOSE, E.V. 1987. Off-line optimization of gas chromatographic temperature programs. Anal. Chem. 59: 2420–2423.CrossRefGoogle Scholar
  65. 65.
    MORGAN, S.L., DEMING, S.N. 1975. Optimization strategies for the development of gas-liquid chromatographic methods. J. Chromatogr. 112:267–285.CrossRefGoogle Scholar
  66. 66.
    MORGAN, S.L., JACQUES, C.A. 1978. Response surface evaluation and optimization in GC. J. Chromatogr. Sci. 16: 500–504.Google Scholar
  67. 67.
    BARTU, V., WICAR, S., SCHERPENZEEL, G.J., LECLERCQ, P.A. 1986. Optimization of temperature programming in gas chromatography with respect to separation time: I. temperature program optimization fundamentals. J. Chromatogr. 370: 219–234.CrossRefGoogle Scholar
  68. 68.
    SCHOENMAKERS, P.J. 1986. Optimization of Chromatographic Selectivity. Elsevier, Amsterdam.Google Scholar
  69. 69.
    BERRIDGE, J.C. 1985. Techniques for the Automated Optimization of HPLC Separations. Wiley, Chichester.Google Scholar
  70. 70.
    JURS, P.C. 1986. Computer Software Applications in Chemistry. Wiley, New York.Google Scholar
  71. 71.
    DEMING, S.N., PARKER, L.R. JR. 1978. A review of simplex optimization in analytical chemistry. CRC Crit Rev. Anal. Chem., September: 187–202.Google Scholar
  72. 72.
    SHAVERS, C.L., PARSONS, M.L., DEMING, S.N. 1979. Simplex optimization of chemical systems. J. Chem. Ed. 56: 307–309.CrossRefGoogle Scholar
  73. 73.
    WATSON, M.W., CARR, P.W. 1979. Simplex algorithm for the optimization of gradient elution high-performance liquid chromatography. Anal. Chem. 51: 1835–1842.CrossRefGoogle Scholar
  74. 74.
    IMANISHI, N., FUKUZATO, R., FURUTA, S., IKAWA, N. 1989. Supercritical fluid extraction of fish oil with carbon dioxide. R&D, Res. Dev. (Kobe Steel Ltd.). 39: 29–32.Google Scholar
  75. 75.
    CHOI, K.J., NAKHOST, Z., KRUKONIS, V.J., KAREL, M. 1987. Supercritical fluid extraction and characterization of lipids from algae Scenedesmus obliquas. Food Biotechnol. (N.Y.) 1: 263–281.CrossRefGoogle Scholar
  76. 76.
    NDIOMU, D.P., SIMPSON, C.F. 1988. Some applications of supercritical fluid extraction. Anal. Chim. Acta 213: 237–243.CrossRefGoogle Scholar
  77. 77.
    SUGIYAMA, K., SAITO, M. 1988. Simple microscale supercritical fluid extraction system and its application to gas chromatography-mass spectrometry of lemon peel oil. J. Chromatogr. 442: 121–131.CrossRefGoogle Scholar
  78. 78.
    MCDONALD, E.C., HOWARD, J., BENNETT, B. 1983. Chemicals from forest products by supercritical fluid extraction. Fluid Phase Equilib. 10: 337–44.CrossRefGoogle Scholar
  79. 79.
    SCHAEFFER, S.T., ZALKOW, L.H., TEJA, A.S. 1989. Supercritical fluid isolation of monocrotaline from Crotalaria spectabilis using ion-exchange resins. Ind. Eng. Chem. Res. 28: 1017–1020.CrossRefGoogle Scholar
  80. 80.
    MIYACHI, H., MANABE, A., TOKUMORI, T., SUMIDA, Y., YOSHIDA, T., NISHIBE, S., AGATA, I., NOMURA, T., OKUDA, T. 1987. Application of supercritical fluid extraction to components of crude drugs and plants. II. Extraction of coumarins, lignans and prenylflavonoids. Yakugaku Zasshi. 107: 435–439.PubMedGoogle Scholar
  81. 81.
    TEMELLI, F., CHEN, C.S., Braddock, R.J. 1988. Supercritical fluid extraction in citrus oil processing. Food Technol. (Chicago) 42: 145–150.Google Scholar
  82. 82.
    HAWTHORNE, S.B., MILLER, D.J., KRIEGER, M.S. 1988. Rapid extraction and analysis of organic compounds from solid samples using coupled supercritical fluid extraction/gas chromatography. Fresenius’ Z. Anal. Chem. 330: 211–215.CrossRefGoogle Scholar
  83. 83.
    HAWTHORNE, S.B., MILLER, D.J., KRIEGER, M.S. 1988. Analysis of flavor and fragrance compounds using supercritical fluid extraction coupled with gas chromatography. Anal. Chem. 60: 472–477.PubMedCrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1991

Authors and Affiliations

  • Joe P. Foley
    • 1
  • Jeffrey A. Crow
    • 1
  1. 1.Department of ChemistryLouisiana State UniversityBaton RougeUSA

Personalised recommendations