Chromatographic analysis of plant sterols in foods and vegetable oils.

This paper reviews recently published chromatographic methods for the analysis of plant sterols in various sample matrices with emphasis on vegetable oils. An overview of structural complexities and biological/nutritional aspects including hypocholesterolemic activities of phytosterols is provided in the Section 1. The principal themes of the review highlight the development and application of chromatographic techniques for the isolation, purification, separation and detection of the title compounds. Pertinent gas chromatographic and high-performance liquid chromatographic methods from the literature are tabulated to illustrate common trends and methodological variability. The review also covers specific analyses of natural/synthetic standard mixtures to shed light on potential applicability in plant sample assays. Examples of combined chromatographic techniques linked in tandem for the analysis of complex samples are included. Elution characteristics of sterol components are discussed in the context of analyte substituent effects, structural factors and stationary/mobile phase considerations.

[1]  M. Hupé,et al.  Analysis of sterols: a novel approach for detecting juices of pineapple, passionfruit, orange and grapefruit in compounded beverages , 1998 .

[2]  G. Fuller,et al.  Isopentenoids in plants : biochemistry and function , 1984 .

[3]  A. C. Bello.  Rapid Isolation Of The Sterol Fraction In Edible OilsUsing A Silica Cartridge , 1992 .

[4]  O. D. Blas,et al.  Determination of sterols by capillary column gas chromatography. Differentiation among different types of olive oil: Virgin, refined, and solvent-extracted , 1996 .

[5]  R. Evershed,et al.  Strategy for the analysis of steryl esters from plant and animal tissues. , 1987, Journal of chromatography.

[6]  J. King,et al.  Concentration of phytosterols for analysis by supercritical fluid extraction , 1999 .

[7]  Børge Holen,et al.  Rapid separation of free sterols by reversed-phase high performance liquid chromatography , 1985 .

[8]  T. A. Beek,et al.  Rapid analysis of apolar low molecular weight constituents in wood using high pressure liquid chromatography with evaporative light scattering detection , 2000 .

[9]  H. Indyk.  Simultaneous liquid chromatographic determination of cholesterol, phytosterols and tocopherols in foods. , 1990, The Analyst.

[10]  V. Andreev,et al.  Gas chromatographic determination of sterols in fat-soluble concentrates obtained from plant materials , 1990 .

[11]  R. Evershed,et al.  delta 13C analyses of vegetable oil fatty acid components, determined by gas chromatography--combustion--isotope ratio mass spectrometry, after saponification or regiospecific hydrolysis. , 1998, Journal of chromatography. A.

[12]  T. Bach,et al.  Evidence for a mevalonate shunt in a tracheophyte , 1985, Proceedings of the Royal Society of London. Series B. Biological Sciences.

[13]  T. Itoh,et al.  Sterol composition of 19 vegetable oils , 1973, Journal of the American Oil Chemists' Society.

[14]  M. Yalpani.  New Technologies For Health Foods and Nutraceuticals , 2002 .

[15]  Endalkachew Sahle-Demessie,et al.  Thermal gradient fractionation of glyceride mixtures under supercritical fluid conditions , 1997 .

[16]  N. Frega,et al.  High resolution gas chromatographic determination of diterpenic alcohols and sterols in coffee lipids , 1995 .

[17]  E. Parish,et al.  Analysis of Sterols and Other Biologically Significant Steroids , 1989 .

[18]  J. King,et al.  Supercritical carbon dioxide extraction of cedarwood oil: a study of extraction parameters and oil characteristics , 2000 .

[19]  E. Heftmann,et al.  A Comparison of Triterpenoids with Steroids as Membrane Components , 1981 .

[20]  R. L. Obendorf,et al.  Changes in sterols and fatty acids of buckwheat endosperm and embryo during seed development , 1992 .

[21]  R. Moreau,et al.  Analysis of major classes of plant lipids by high-performance liquid chromatography with flame ionization detection. , 1990 .

[22]  L. Conte,et al.  Chemical composition of tobacco seeds (Nicotiana tabacum L.) , 1991 .

[23]  R. Evershed,et al.  Detection of Vegetable Oil Adulteration Using Gas Chromatography Combustion/Isotope Ratio Mass Spectrometry , 1995 .

[24]  C. Bloch,et al.  Sterol synthesis in vitro in freshly isolated blood mononuclear leukocytes from familial hypercholesterolemic patients treated with probucol. , 1985, Biochimica et biophysica acta.

[25]  M. Novotny,et al.  Steroid profiles determined by capillary electrochromatography, laser-induced fluorescence detection and electrospray-mass spectrometry. , 2000, Journal of chromatography. A.

[26]  M. Gordon,et al.  Use of lipolysis in the isolation of sterol esters , 1996 .

[27]  E. Heftmann,et al.  High-performance liquid chromatography of triterpenoids , 1981 .

[28]  K. M. Phillips,et al.  Phytosterol content of experimental diets differing in fatty acid composition , 1999 .

[29]  G. Lercker,et al.  La frazione lipidica del caffè. 2: Su alcuni parametri di qualificazione , 1996 .

[30]  K. Grob,et al.  Evaluation of olive oils through the fatty alcohols, the sterols and their esters by coupled LC-GC , 1990 .

[31]  Taro Matsumoto,et al.  Sterol compositions of seeds and mature plants of family cucurbitaceae , 1986 .

[32]  N. Frega,et al.  Direct gas chromatographic analysis of the unsaponifiable fraction of different oils with a polar capillary column , 1992 .

[33]  E. Lorbeer,et al.  Determination of tocopherols and sterols in vegetable oils by solid-phase extraction and subsequent capillary gas chromatographic analysis. , 1999, Journal of chromatography. A.

[34]  A. Hiermann,et al.  Dünnschicht-, Säulen- und Hochleistung-Flussigkeitschromatographischer Auftrennung pflanzlicher Sterole an alkylsilylierten Kieselgelen , 1986 .

[35]  W. O. McReynolds,et al.  Characterization of Some Liquid Phases , 1970 .

[36]  G. Lercker,et al.  Analisi degli insaponificabili mediante GLC , 1985 .

[37]  G. Lercker.  Short capillary columns in the analysis of lipids , 1983 .

[38]  E. Lorbeer,et al.  Determination of free and esterified sterols in potential new oil seed crops by coupled on‐line liquid chromatography‐gas‐chromatography , 1999 .

[39]  W. Nes,et al.  Structural Elucidation of Sterols by Reversed-Phase Liquid Chromatography: I. Assignment of Retention Coefficients to Various Groups , 1982 .

[40]  Naomi Nakamura,et al.  Sterols of Cajanus cajan and three other leguminosae seeds , 1992 .

[41]  S. Zellmer,et al.  Individual variation of human plantar stratum corneum lipids, determined by automated multiple development of high-performance thin-layer chromatography plates. , 1997, Journal of chromatography. B, Biomedical sciences and applications.

[42]  P. J. V. Niekerk,et al.  The estimation of the composition of edible oil mixtures , 1985 .

[43]  K. White,et al.  Validated method for quantitation and identification of 4,4-desmethylsterols and triterpene diols in plant oils by thin-layer chromatography-high resolution gas chromatography-mass spectrometry. , 1997, Journal of AOAC International.

[44]  R. Evershed,et al.  Purity assessments of major vegetable oils based on δ13C values of individual fatty acids , 1998 .

[45]  S. Kadota,et al.  Effective separation of sterol C-24 epimers , 1989 .

[46]  P. Ghosh,et al.  Triterpene alcohols and 3-oxo steroids of nine Leguminosae seeds , 1994 .

[47]  M. Law,et al.  Plant sterol and stanol margarines and health , 2000, BMJ : British Medical Journal.

[48]  R. Heupel,et al.  Biosynthesis of ergosta-6(7),8(14),22(23)-trien-3β-ol by Gibberella fujikuroi: its importance to Ergosterol's metabolic pathway , 1985 .

[49]  D. Firestone,et al.  Official methods and recommended practices of the American Oil Chemists' Society , 1990 .

[50]  R. Norton.  Isolation and identification of steryl cinnamic acid derivatives from corn bran , 1994 .

[51]  T. Goodwin,et al.  Separation of C27, C28 and C29 sterols by reversed-phase high-performance liquid chromatography on small particles. , 1976, Journal of chromatography.

[52]  N. Andrikopoulos,et al.  Separation of the Main Neutral Lipids into Classes and Species by PR-HPLC and UV Detection , 1994 .

[53]  P. Dutta,et al.  Saturated Sterols (Stanols) in Unhydrogenated and Hydrogenated Edible Vegetable Oils and in Cereal Lipids , 1996 .

[54]  J. Nourooz-Zadeh,et al.  Isolation and quantitative determination of sterol oxides in plant-based foods: Soybean oil and wheat flour , 1992 .

[55]  W. Christie,et al.  Separation of lipid classes from plant tissues by high performance liquid chromatography on chemically bonded stationary phases , 1995 .

[56]  N. Frega,et al.  High-resolution gas chromatographic determination of alkanols in oils extracted from olives , 1993 .

[57]  V. Piironen,et al.  Factors affecting sample preparation in the gas chromatographic determination of plant sterols in whole wheat flour , 2000 .

[58]  G. Patterson,et al.  Separation of Epimeric Pairs of C-24 Alkylsterols by Reversed-Phase High Performance Liquid Chromatography of the Free Sterols at Subambient Temperature , 1991 .

[59]  Gerard J. Martin,et al.  Authentication of Mustard Oils by Combined Stable Isotope Analysis (SNIF-NMR and IRMS) , 1997 .

[60]  D. Schaufelberger,et al.  Rapid Analysis of Norgestimate and Its Potential Degradation Products by Capillary Electrochromatography , 1998 .

[61]  J. King,et al.  Enrichment of ferulate phytosterol esters from corn fiber oil using supercritical fluid extraction and chromatography , 2000 .

[62]  G. Guiochon,et al.  Comparison of Various Systems for the separation of Free Sterols by High Performance Liquid Chromatography , 1979 .

[63]  I. Warner,et al.  Capillary electrochromatography of cholesterol and its ester derivatives. , 2000, Analytical chemistry.

[64]  R. Evershed,et al.  Isolation and characterisation of intact steryl ferulates from seeds , 1988 .

[65]  Robert A. Moreau,et al.  Extraction and Quantitative Analysis of Oil from Commercial Corn Fiber , 1996 .

[66]  J. Ai.  Rapid Measurement of Free Phytosterols in Tobacco by Short-Column GC/MS/MS , 1997 .

[67]  P. Marěs,et al.  Simplified gas chromatographic method for the simultaneous determination of phytosterols and cholesterol. , 1991, Journal of chromatography.

[68]  T. L. Mounts,et al.  Effect of genetic modification on the content and composition of bioactive constituents in soybean oil , 1996 .

[69]  G. List,et al.  Effect of genetic modification on the distribution of minor constituents in canola oil , 1999 .

[70]  V. Piironen,et al.  Gas chromatographic determination of major sterols in edible oils and fats using solid-phase extraction in sample preparation , 1998 .

[71]  B. Nagel.  Standard methods for the analysis of oils, fats and derivatives. 7th Revised and enlarged edition. Oxford, London, Edinburgh, Boston, Palo Alto, Melbourne: Blackwell Scientific Publication, 1987. 347 pp. 55 Ł, ISBN 0‐632‐01586‐1 , 1988 .

[72]  Jan Hazebroek,et al.  Phytosterol accumulation in canola, sunflower, and soybean oils: Effects of genetics, planting location, and temperature , 2000 .

[73]  H. Mohamed,et al.  The use of sesame oil unsaponifiable matter as a natural antioxidant , 1998 .

[74]  V. Piironen,et al.  Phytosterol content in seven oat cultivars grown at three locations in Sweden , 1999 .

[75]  M. Zlatanov.  Lipid composition of Bulgarian chokeberry, black currant and rose hip seed oils , 1999 .

[76]  V. Pretorius,et al.  Electro-osmosis: A new concept for high-speed liquid chromatography , 1974 .

[77]  C. Djerassi,et al.  Occurrence and seasonal variation of 19-norcholest-4-EN-3-one and 3β-monohydroxy sterols in the Californian gorgonian, Muricea californica , 1983, Steroids.

[78]  V. W. Trost.  Characterization of corn oil, soybean oil and sunflowerseed oil nonpolar material , 1989 .

[79]  N. Unklesbay,et al.  Plant sterols in soybean hulls. , 1990 .

[80]  G. Patterson,et al.  4α-methylvernosterol and other sterols from Vernonia anthelmintica seeds , 1992 .

[81]  G. P. Blanch,et al.  Rapid and simultaneous analysis of free sterols, tocopherols, and squalene in edible oils by coupled reversed-phase liquid chromatography-gas chromatography , 1998 .

[82]  L. Tsai,et al.  High performance liquid chromatography of oxygenated cholesterols and related compounds , 1981 .

[83]  L. Goad,et al.  Analysis of Sterols , 1997 .

[84]  R. Norton,et al.  Comparison of the chromatographic properties of sterols, select additional steroids and triterpenoids: gravity-flow column liquid chromatography, thin-layer chromatography, gas-liquid chromatography and high-performance liquid chromatography. , 1988, Journal of chromatography.

[85]  N. Frega,et al.  High resolution gas chromatographic method for determination of Robusta coffee in commercial blends , 1994 .

[86]  W. Nes.  A comparison of methods for the identification of sterols. , 1985, Methods in Enzymology.

[87]  E. Heftmann,et al.  Liquid column chromatography of free sterols , 1978 .

[88]  S. F. Herb,et al.  Pancreatic lipase hydrolysis of triglycerides by a semimicro technique , 1964 .

[89]  R. Nicolosi,et al.  Identification and quantitation of γ-oryzanol components and simultaneous assessment of tocols in rice bran oil , 1993 .

[90]  D. Firestone,et al.  Sterol and triterpene diol contents of vegetable oils by high-resolution capillary gas chromatography , 1999 .

[91]  E. B. Hoving.  Chromatographic methods in the analysis of cholesterol and related lipids. , 1995, Journal of chromatography. B, Biomedical applications.

[92]  J. Boatella,et al.  Analysis of olive and hazelnut oil mixtures by high-performance liquid chromatography-atmospheric pressure chemical ionisation mass spectrometry of triacylglycerols and gas-liquid chromatography of non-saponifiable compounds (tocopherols and sterols). , 2000, Journal of chromatography. A.

[93]  R. Heupel,et al.  Varietal similarities and differences in the polycyclic isopentenoid composition of sorghum , 1985 .

[94]  J. Sigoillot,et al.  Determination of sterol and triterpene alcohol acetates in natural products by reversed-phase liquid chromatography and gas chromatography-mass spectrometry. , 1985, Journal of chromatography.

[95]  R. Thompson,et al.  Determination of tocopherols and sterols by capillary gas chromatography , 1983 .

[96]  R. Heupel,et al.  Physiological requirement for biosynthesis of multiple 24 beta-methyl sterols in Gibberella fujikuroi. , 1986, Archives of biochemistry and biophysics.

[97]  A. Hautfenne.  Standard methods for the analysis of oils, fats and derivatives, 6th Edition. 1st Supplement: Part 5 (1982) Section III, Glycerines. Section IV, Alkaline soaps , 1982 .

[98]  R. Illman,et al.  Free sterols of citrus roots , 1985 .

[99]  R. E. Worthington,et al.  A method for the separation of seed oil steryl esters and free sterols: Application to peanut and corn oils , 1984 .