Subscribe to RSS
DOI: 10.1055/s-0035-1545911
Supercritical Fluid Chromatography – Theoretical Background and Applications on Natural Products
Publication History
received 01 October 2014
revised 03 February 2015
accepted 04 March 2015
Publication Date:
23 April 2015 (online)
Abstract
The use of supercritical fluid chromatography for natural product analysis as well as underlying theoretical mechanisms and instrumental requirements are summarized in this review. A short introduction focusing on the historical development of this interesting separation technique is followed by remarks on the current instrumental design, also describing possible detection modes and useable stationary phases. The overview on relevant applications is grouped based on their basic intention, may it be (semi)preparative or purely analytical. They indicate that supercritical fluid chromatography is still primarily considered for the analysis of nonpolar analytes like carotenoids, fatty acids, or terpenes. The low polarity of supercritical carbon dioxide, which is used with modifiers almost exclusively as a mobile phase today, combined with high efficiency and fast separations might explain the popularity of supercritical fluid chromatography for the analysis of these compounds. Yet, it has been shown that more polar natural products (e.g., xanthones, flavonoids, alkaloids) are separable too, with the same (if not superior) selectivity and reproducibility than established approaches like HPLC or GC.
-
References
- 1 Saito M. History of supercritical fluid chromatography: instrumental development. J Biosci Bioeng 2013; 115: 590-599
- 2 De Klerck K, Mangelings D, Vander Heyden Y. Supercritical fluid chromatography for the enantioseparation of pharmaceuticals. J Pharmaceut Biomed 2012; 69: 77-92
- 3 Sandra P, Pereira A, Dunkle M, Brunelli C, David F. Green chromatography (Part 2): The role of GC and SFC. LCGC Europe 2010; 23: 396-405
- 4 Taylor LT. Packed column supercritical fluid chromatography of hydrophilic analytes via water-rich modifiers. J Chromatogr A 2012; 1250: 196-204
- 5 Farrell WP, Aurigemma CM, Masters-Moore DF. Advances in high throughput supercritical fluid chromatography. J Liq Chromatogr Relat Techno 2009; 32: 1689-1710
- 6 Bamba T. Application of supercritical fluid chromatography to the analysis of hydrophobic metabolites. J Sep Sci 2008; 31: 1274-1278
- 7 Wang RQ, Ong TT, Ng SQ, Tang W. Recent advances in pharmaceutical separations with supercritical fluid chromatography using chiral stationary phases. TrAC 2012; 37: 83-100
- 8 Klesper E, Corwin AH, Turner DA. High pressure gas chromatography above critical temperatures. J Org Chem 1962; 27: 700-701
- 9 Sie ST, Van Beersum W, Rjinders GWA. High-pressure gas-chromatography and chromatography with supercritical fluids. 1. The effect of pressure on partition coefficients in gas-liquid chromatography with carbon dioxide as carrier gas. Sep Sci 1966; 1: 459-490
- 10 Jentoft RE, Gouw TH. Pressure-programmed supercritical fluid chromatography of wide molecular weight range mixtures. J Chromatogr Sci 1970; 8: 138-142
- 11 Hartmann W, Klesper E. Preparative supercritical fluid chromatography of styrene oligomers. J Polym Lett Ed 1977; 15: 713-719
- 12 Randall LG, Wahrhaftig AL. Dense gas chromatograph/mass spectrometer interface. Anal Chem 1978; 50: 1703-1705
- 13 Novotny M, Springston SR, Peaden PA, Fjelsted JC, Lee ML. Capillary supercritical fluid chromatography. Anal Chem 1981; 53: 407A-414A
- 14 Smith RM. Supercritical fluids in separation science–the dreams, the reality and the future. J Chromatogr A 1999; 856: 83-114
- 15 Gere DR, Board R, McManigill D. Supercritical fluid chromatography with small particle diameter packed columns. Anal Chem 1982; 54: 736-740
- 16 Lesellier E. Retention mechanisms in super/subcritical fluid chromatography on packed columns. J Chromatogr A 2009; 1216: 1881-1890
- 17 Poole CF. Stationary phases for packed-column supercritical fluid chromatography. J Chromatogr A 2012; 1250: 157-171
- 18 Lesellier E. Overview of the retention in subcritical fluid chromatography with varied polarity stationary phases. J Sep Sci 2008; 31: 1238-1251
- 19 Brunelli C, Gorecki T, Zhao Y, Sandra P. Corona-charged aerosol detection in supercritical fluid chromatography for pharmaceutical analysis. Anal Chem 2007; 79: 2472-2482
- 20 Vanthuyne N, Roussel C. Chiroptical detectors for the study of unusual phenomena in chiral chromatography. Top Curr Chem 2013; 340: 107-151
- 21 Lesellier E, Valarche A, West C, Dreux M. Effects of selected parameters on the response of the evaporative light scattering detector in supercritical fluid chromatography. J Chromatogr A 2012; 1250: 220-226
- 22 Li F, Hsieh Y. Supercritical fluid chromatography-mass spectrometry for chemical analysis. J Sep Sci 2008; 31: 1231-1237
- 23 Gurdale K, Lesellier E, Tschapla A. Study of dead volume measurement in packed subcritical fluid chromatography with ODS columns and carbon dioxide-modifier mobile phases. J Chromatogr A 2000; 866: 241-251
- 24 Berger TA, Deye JF. Role of aditives in packed column supercritical fluid chromatography: supression of solute ionization. J Chromatogr A 1991; 547: 377-392
- 25 Medina I. Determination of diffusion coefficients for supercritical fluids. J Chromatogr A 2012; 1250: 124-140
- 26 Turner C, King JW, Mathiasson L. Supercritical fluid extraction and chromatography for fat-soluble vitamin analysis. J Chromatogr A 2001; 936: 215-217
- 27 Senorans FJ, Ibanez E. Analysis of fatty acids in foods by supercritical fluid chromatography. Anal Chim Acta 2002; 465: 131-144
- 28 Fornari T, Vicente G, Vazquez E, Garcia-Risco MR, Reglero G. Isolation of essential oil from different plants and herbs by supercritical fluid extraction. J Chromatogr A 2012; 1250: 34-48
- 29 Sovova H. Modeling the supercritical fluid extraction of essential oils from plant materials. J Chromatogr A 2012; 1250: 27-33
- 30 Herrero M, Mendiola JA, Cifuentes A, Ibanez E. Supercritical fluid extraction: recent advances and applications. J Chromatogr A 2010; 1217: 2495-2511
- 31 Zhannan Y, Shiqiong L, Quancai P, Chao Z, Zhengwen Y. GC-MS analysis of the essential oil of coral ginger (Zingiber corallinum Hance) rhizome obtained by supercritical fluid extraction and steam distillation extraction. Chromatographia 2009; 69: 785-790
- 32 Kotnik P, Skerget M, Knez J. Supercritical fluid extraction of chamomile flower heads: comparison with conventional extraction, kinetics and scale-up. J Supercrit Fluids 2007; 43: 192-198
- 33 Aleksovski SA, Sonova H. Supercritical CO2 extraction of Salvia officinalis L. J Supercrit Fluids 2007; 40: 239-245
- 34 Gouveia L, Nobre BP, Marcelo FM, Mrejen S, Cardoso MT, Palavra AF, Mendes RL. Functional food oil coloured by pigments extracted from microalgae with supercritical CO2 . Food Chem 2007; 101: 717-723
- 35 Salimi A, Fatemi S, Zakizadeh Nei Nei H, Safaralie A. Mathematical modeling of supercritical extraction of valerenic acid from Valeriana officinalis L. Chem Eng Technol 2008; 31: 1470-1480
- 36 Zarena AS, Udaya Sankar K. Supercritical carbon dioxide extraction of xanthones with antioxidant activity from Garcinia mangostana. Characterization by HPLC/LC-ESI-MS. J Supercrit Fluids 2009; 49: 330-337
- 37 Montanes F, Fornari T, Olano A, Ibanez E. Isolation of prebiotic carbohydrates by supercritical fluid extraction. Scaling-up and economical feasibility. J Chromatogr A 2012; 1250: 92-98
- 38 Arnaiz E, Bernal J, Martin MT, Nozal MJ, Bernal JL, Toribio L. Supercritical fluid extraction of free amino acids from broccoli leaves. J Chromatogr A 2012; 1250: 49-53
- 39 Mangelings D, Vander Heyden Y. Chiral separations in sub- and supercritical fluid chromatography. J Sep Sci 2008; 31: 1252-1273
- 40 Miller L. Preparative enantioseparations using supercritical fluid chromatography. J Chromatogr A 2012; 1250: 250-255
- 41 Santos C, Fabing I, Saffon N, Ballereau S, Génisson Y. Rapid access to jaspine B and its enantiomer. Tetrahedron 2013; 69: 7227-7233
- 42 Zhao Y, McCauley J, Pang X, Kang L, Yu H, Zhang J, Xiong C, Chen R, Ma B. Analytical and semipreparative separation of 25 (R/S)-spirostanol saponin diastereomers using supercritical fluid chromatography. J Sep Sci 2013; 36: 3270-3276
- 43 Li S, Lambros T, Wang Z, Goodnow R, Ho CT. Efficient and scalable method in isolation of polymethoxyflavones from orange peel extract by supercritical fluid chromatography. J Chromatogr B 2007; 846: 291-297
- 44 Alkio M, Gonzalez C, Jäntti M, Aaltonen O. Purification of polyunsaturated fatty acid esters from tuna oil with supercritical fluid chromatography. J Am Oil Chem Soc 2000; 77: 315-321
- 45 Pettinello G, Bertucco A, Pallado P, Stassi A. Production of EPA enriched mixtures by supercritical fluid chromatography: from laboratory scale to the pilot plant. J Supercrit Fluids 2000; 19: 51-60
- 46 Taylor SL, King JW. Optimization of the extraction and fractionation of corn bran oil using analytical supercritical fluid instrumentation. J Chrom Sci 2000; 38: 91-94
- 47 Han NM, May CY, Ngan MA, Hock CC, Hashim MA. Isolation of palm tocols using supercritical fluid chromatography. J Chrom Sci 2004; 42: 536-539
- 48 Ramirez P, Garcia-Risco MR, Santoyo S, Senorans FJ, Ibanez E, Reglero G. Isolation of functional ingredients from rosemary by preparative-supercritical fluid chromatography (Prep-SFC). J Pharmaceut Biomed 2006; 41: 1606-1613
- 49 Vicente G, Garcia-Risco MR, Fornari T, Reglero G. Isolation of carnosic acid from rosemary extracts using semi-preparative supercritical fluid chromatography. J Chromatogr A 2013; 1286: 208-215
- 50 Garcia-Risco MR, Vicente G, Reglero G, Fornari T. Fractionation of thyme (Thymus vulgaris L.) by supercritical fluid extraction and chromatography. J Supercrit Fluids 2011; 55: 949-954
- 51 Ashraf-Khorassani M, Taylor LT, Martin MT. Supercritical fluid extraction of kava lactones from kava root and their separation via supercritical fluid chromatography. Chromatographia 1999; 50: 287-292
- 52 Schmitz HH, Artz WE, Poor CL, Dietz JM, Erdmann JW. High-performance liquid chromatography and capillary supercritical-fluid chromatography separation of vegetable carotenoids and carotenoid isomers. J Chromatogr A 1989; 479: 261-268
- 53 Aubert MC, Lee CR, Krstulocic AM, Lesellier E, Pechard MR, Tchapla A. Separation of trans/cis- alpha- and beta-carotenes by supercritical fluid chromatography. I. Effects of temperature, pressure and organic modifiers on retention of carotenes. J Chromatogr 1991; 557: 47-58
- 54 Lesellier E, Tchapla A, Pechard MR, Lee CR, Krstulocic AM. Separation of trans/cis alpha- and beta-carotenes by supercritical fluid chromatography. II. Effect of type of octadecyl-bonded stationary phase on retention and selectivity of carotenes. J Chromatogr 1991; 557: 59-67
- 55 Lesellier E, Krstulocic AM, Tchapla A. Influence of the modifiers on the nature of the stationary phase and the separation of carotenes in sub-critical fluid chromatography. Chromatographia 1993; 36: 275-282
- 56 Matsubara A, Bamba T, Ishida H, Fukusaki E, Hirata K. Highly sensitive and accurate profiling of carotenoids by supercritical fluid chromatography coupled with mass spectrometry. J Sep Sci 2009; 32: 1459-1464
- 57 Matsubara A, Uchikata T, Shinohara M, Nishiumi S, Yoshida M, Fukusaki E, Bamba T. Highly sensitive and rapid profiling method for carotenoids and their epoxidized products using supercritical fluid chromatography coupled with electrospray ionzation-triple quadrupole mass spectrometry. J Biosci Bioeng 2012; 113: 782-787
- 58 Abrahamsson V, Rodriguez-Meizoso I, Turner C. Determination of carotenoids in microalgae using supercritical fluid extraction and chromatography. J Chromatogr A 2012; 1250: 63-68
- 59 Hannan RM, Hill HH. Analysis of lipids in aging seed using capillary supercritical fluid chromatography. J Chromatogr 1991; 547: 393-401
- 60 Yarita T, Nomura A, Abe K, Takeshita Y. Supercritical fluid chromatographic determination of tocopherols on an ODS-silica gel column. J Chromatogr A 1994; 679: 329-334
- 61 Saito M, Yamauchi Y, Inomata K, Kottkamp W. Enrichment of tocopherols in wheat germ by directly coupled supercritical fluid extraction with semi-preparative supercritical fluid chromatography. J Chrom Sci 1989; 27: 79-85
- 62 Gomez-Coronado DJM, Ibanez E, Ruperez FJ, Barbas C. Tocopherol measurement in edible products of vegetable origin. J Chromatogr A 2004; 1054: 227-233
- 63 Ibanez E, Palacios J, Reglero G. Analysis of tocopherols by on-line coupling supercritical fluid extraction – supercritical fluid chromatography. J Microcolumn Sep 1999; 11: 605-611
- 64 Braumann U, Händel H, Strohschein S, Spraul M, Krack G, Ecker R, Albert K. Separation and identification of vitamin A acetate isomers by supercritical fluid chromatography – 1H NMR coupling. J Chromatogr A 1997; 761: 336-340
- 65 Berger T, Berger B. Two minute separation of the cis- and trans-isomers of vitamin K1 without chlorinated solvents or acetonitrile. Chromatographia 2013; 76: 109-115
- 66 Berger T, Berger B. Chromatographic resolution of 7 of 8 stereoisomers of vitamin K1 on an amylose stationary phase using supercritical fluid chromatography. Chromatographia 2013; 76: 549-552
- 67 Han NM, May CY, Ngan MA, Hock CC, Hashim MA. Separation of coenzyme Q10 in palm oil by supercritical fluid chromatography. Am J App Sci 2006; 3: 1929-1932
- 68 Bernal JL, Martin MT, Toribio L. Supercritical fluid chromatography in food analysis. J Chromatogr A 2013; 1313: 24-36
- 69 Bamba T, Lee JW, Matsubara A, Fukusaki E. Metabolic profiling of lipids by supercritical fluid chromatography/mass spectrometry. J Chromatogr A 2012; 1250: 212-219
- 70 Lesellier E. Analysis of non-saponifiable lipids by super-/subcritical-fluid chromatography. J Chromatogr A 2001; 936: 201-214
- 71 Hirata Y, Sogabe I. Separation of fatty acid methyl esters by comprehensive two-dimensional supercritical fluid chromatography with packed columns and programming of sampling duration. Anal Bioanal Chem 2004; 378: 1999-2003
- 72 Okamoto D, Hirata Y. Development of supercritical fluid extraction coupled to comptehensive two-dimensional supercritical fluid chromatography (SFE-SFCxSFC). Anal Sci 2006; 22: 1437-1440
- 73 Lesellier E, Tchapla A. Separation of vegetable oil triglycerides in subcritical fluid chromatography with octadecyl packed columns and CO2/modifier mobile phases. Chromatographia 2000; 51: 688-694
- 74 Lee JW, Nagai T, Gotoh N, Fukusaki E, Bamba T. Profiling of regioisomeric triacylglycerols in edible oils by supercritical fluid chromatography/tandem mass spectrometry. J Chromatogr B 2014; 966: 193-199
- 75 Lee JW, Uchikata T, Matsubara A, Nakamura T, Fukusaki E, Bamba T. Application of supercritical fluid chromatography/mass spectrometry to lipid profiling in soybean. J Biosci Bioeng 2012; 113: 262-268
- 76 Sandra P, Medvedovici A, Zhao Y, David F. Characterization of triglycerides in vegetable oils by silver-ion packed-column supercritical fluid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization and coordination ion spray. J Chromatogr A 2002; 974: 231-241
- 77 Lesellier E, Latos A, Lopes de Oliveira A. Ultra high efficiency/low pressure supercritical fluid chromatography with superficially porous particles for triglyceride separation. J Chromatogr A 2014; 1327: 141-148
- 78 David PA, Novotny M. Analysis of steroids by capillary supercritical fluid chromatography with phosphorus-selective detection. J Chromatogr 1989; 461: 111-120
- 79 King JW. Applications of capillary supercritical fluid chromatography-supercritical fluid extraction to natural products. J Chrom Sci 1990; 28: 9-14
- 80 Huber W, Molero A, Pereyra C, Martinez de la Ossa E. Determination of cholesterol in milk fat by supercritical fluid chromatography. J Chromatogr A 1995; 715: 333-336
- 81 Baiocchi C, Giacosa D, Roggero MA, Marengo E. Analysis of steroids by capillary supercritical fluid chromatography with flame-ionization and electron-capture detectors. J Chrom Sci 1996; 34: 399-404
- 82 Tuomola M, Hakala M, Manninen M. Determination of androstenone in pig fat using packed column supercritical fluid chromatography-mass spectrometry. J Chromatogr B 1998; 719: 25-30
- 83 Hanson M. Aspects of retention behaviour of steroids in packed column supercritical fluid chromatography. Chromatographia 1995; 40: 58-68
- 84 Auerbach RH, Dost K, Davidson G. Characterization of varietat differences in essential oil components of Hops (Humulus lupulus) by SFC-FTIR spectroscopy. J AOAC Int 2000; 83: 621-626
- 85 Suto K, Ito Y, Sagara K, Itokawa H. Determination of magnolol and honokiol in Magnoliae Cortex using supercritical fluid chromatography on-line coupled with supercritical fluid extraction by on-column trapping. J Chromatogr A 1997; 786: 366-370
- 86 Kohler M, Haerdi W, Christen P, Veuthey JL. Determination of artemisinin and artemisinic acid by capillary and packed supercritical fluid chromatograppy. J High Resol Chromatogr 1997; 20: 62-66
- 87 Lesellier E, Destandau E, Grigoras C, Fougere L, Elfakir C. Fast separation of triterpenoids by supercritical fluid chromatography/evaporative light scattering detector. J Chromatogr A 2012; 1268: 157-165
- 88 Tavares MCH, Yariwake Vilegas JH, Lancas FM. Separation of underivatized triterpene acids by capillary supercritical fluid chromatography. Phytochem Anal 2001; 12: 134-137
- 89 Qiao X, An R, Hunag Y, Ji S, Li L, Tzeng YM, Guo DA, Ye M. Separation of 25R/S-ergostane triterpenoids in the medicinal mushroom Antrodia camphorata using analytical supercritical-fluid chromatography. J Chromatogr A 2014; 1358: 252-260
- 90 Agrawal H, Kaul N, Paradkar AR, Mahadik KR. Separation of bacoside A3 and bacopaside II, major triterpenoid saponins in Bacopa monnieri, by HPTLC and SFC. Application of SFC in implementation of uniform design for herbal drug standardization, with thermodynamic study. Acta Chrom 2006; 17: 125-150
- 91 Desmortreux C, Rothaupt M, West C, Lesellier E. Improved separation of furocoumarins of essential oils by supercritical fluid chromatography. J Chromatogr A 2009; 1216: 7088-7095
- 92 Bamba T, Fukusaki E, Kajiyama S, Ute K, Kitayama T, Kobayashi A. High-resolution analysis of polyprenols by supercritical fluid chromatography. J Chromatogr A 2001; 911: 113-117
- 93 Bamba T, Fukusaki E, Kajiyama S, Ute K, Kitayama T, Kobayashi A. The occurence of geometric polyprenol isomers in the rubber-producing plant, Eucommia ulmoides Oliver. Lipids 2001; 7: 727-732
- 94 Bamba T, Fukusaki E, Nakazawa Y, Sato H, Ute K, Kitayama T, Kobayashi A. Analysis of long-chain polyprenols using supercritical fluid chromatography and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. J Chromatogr A 2003; 995: 203-207
- 95 Wu C, Siems WF, Hill HH, Hannan RM. Analytical determination of nicotine in tobacco by supercritical fluid chromatography-ion mobility detection. J Chromatogr A 1998; 811: 157-161
- 96 Dost K, Davidson G. Development of a packed-column supercritical fluid chromatography/atmospheric pressure chemical-ionisation mass spectrometric technique for the analysis of atropine. J Biochem Biophys Methods 2000; 43: 125-134
- 97 Sato K, Sasaki SS, Goda Y, Yamada T, Nunomura O, Ishikawa K, Maitani T. Direct connection of supercritical fluid extraction and supercritical fluid chromatography as a rapid quantitative method for capsaicinoids in placentas of Capsicum . J Agric Food Chem 1999; 47: 4665-4668
- 98 Lanicot JL, Caude M, Rosset R. Separation of opium alkaloids by carbon dioxide sub- and supercritical fluid chromatography with packed columns. J Chromatogr 1988; 437: 351-364
- 99 Holzer G, Zalkow LH, Asibal CF. Capillary supercritical fluid chromatography of pyrrolizidine alkaloids. J Chromatogr 1987; 400: 317-322
- 100 Li S, Wang Z, Sang S, Huang MT, Ho CT. Identification of nobiletin metabolites in mouse urine. Mol Nutr Food Res 2006; 50: 291-299
- 101 Wang Z, Li S, Jonca M, Lambros T, Fergusson S, Goodnow R, Ho CT. Comparison of supercritical fluid chromatography and liquid chromatography for the separation of urinary metabolites of nobiletin with chiral and non-chiral stationary phases. Biomed Chromatogr 2006; 20: 1206-1215
- 102 West C, Lesellier E. Effects of mobile phase composition on retention and selectivity in achiral supercritical fluid chromatography. J Chromatogr A 2013; 1302: 152-162
- 103 Ganzera M. Supercritical fluid chromatography for the separation of isoflavones. J Pharmaceut Biomed 2015; 107: 364-369
- 104 Bernal JL, Nozal MJ, Toribio L, Serna ML, Borrull F, Marce RM, Pocurull E. Determination of phenolic compounds in water samples by online solid-phase extraction. Supercritical-fluid chromatography with diode-array detection. Chromatographia 1997; 46: 295-300
- 105 Ramsey ED, Minty B, Mccullagh MA, Games DE, Rees AT. Analysis of phenols in water at the ppb level using direct supercritical fluid extraction of aqueous samples combined online with supercritical fluid chromatography-mass spectrometry. Anal Commun 1997; 34: 3-6