Novel Gas-assisted Three-liquid-phase Extraction System for Simultaneous Separation and Concentration of Anthraquinones in Herbal Extract

doi:10.1016/j.cjche.2014.06.029

Abstract

Abstract: Gas-assisted three-liquid-phase extraction (GATE), which has the advantages of both three-liquid-phase extraction and solvent sublation, is a novel separation technique for separation and concentration of two organic compounds into different phases in one step. This highly effective and economically applicable method has been developed for separating emodin and rhein from herbal extract. In a GATE system composed of butyl acetate/ PEG4000/ammoniumsulfate aqueous solution, influence of various parameters including gas flow rate, flotation time, salt concentration, initial volumeof PEG and butyl acetatewas investigated. Within 50 min of 30 ml·min^-1 nitrogen flow, removal ratio of emodin and rhein from aqueous phase could be over 99% and 97%, respectively. Mass fraction of emodin in the BA phase and rhein in the PEG phase could reach 97% and 95%, respectively. It is demonstrated that gas bubbling is effective for partitioning of emodin and rhein into butyl acetate and PEG phase respectively, and dispersed PEG and butyl acetate could be captured from the aqueous solution. Experimental results showthat GATE could be an effective and economical technology for concentration and separation of co-existed products in medicinal plants.

Key words: Three-liquid-phase extraction, Gas-assisted solvent extraction, Separation, Anthraquinones

摘要： Gas-assisted three-liquid-phase extraction (GATE), which has the advantages of both three-liquid-phase extraction and solvent sublation, is a novel separation technique for separation and concentration of two organic compounds into different phases in one step. This highly effective and economically applicable method has been developed for separating emodin and rhein from herbal extract. In a GATE system composed of butyl acetate/ PEG4000/ammoniumsulfate aqueous solution, influence of various parameters including gas flow rate, flotation time, salt concentration, initial volumeof PEG and butyl acetatewas investigated. Within 50 min of 30 ml·min^-1 nitrogen flow, removal ratio of emodin and rhein from aqueous phase could be over 99% and 97%, respectively. Mass fraction of emodin in the BA phase and rhein in the PEG phase could reach 97% and 95%, respectively. It is demonstrated that gas bubbling is effective for partitioning of emodin and rhein into butyl acetate and PEG phase respectively, and dispersed PEG and butyl acetate could be captured from the aqueous solution. Experimental results showthat GATE could be an effective and economical technology for concentration and separation of co-existed products in medicinal plants.

关键词: Three-liquid-phase extraction, Gas-assisted solvent extraction, Separation, Anthraquinones

Xingfu Yang, Xiangfeng Liang, Liangrong Yang, Feng Pan, Fuli Deng, Huizhou Liu. Novel Gas-assisted Three-liquid-phase Extraction System for Simultaneous Separation and Concentration of Anthraquinones in Herbal Extract[J]. , 2014, 22(9): 968-973.

References

[1] Q. Huang, G. Lu, H. Shen,M. Chung, C. Ong, Anti-cancer properties of anthraquinones from rhubarb, Med. Res. Rev. 27 (2007) 609-630.
[2] S. Agarwal, S.S. Singh, S. Verma, S. Kumar, Antifungal activity of anthraquinone derivatives from Rheum emodi, J. Ethnopharmacol. 72 (2000) 43-46.
[3] B. Onegi, C. Kraft, I. Köhler, M. Freund, K. Jenett-Siems, K. Siems, G. Beyer, M.F. Melzig, U. Bienzle, E. Eich, Antiplasmodial activity of naphthoquinones and one anthraquinone from Stereospermum kunthianum, Phytochemistry 60 (2002) 39-44.
[4] D.O. Andersen, N.D.Weber, S.G. Wood, B.G. Hughes, B.K. Murray, J.A. North, In vitro virucidal activity of selected anthraquinones and anthraquinone derivatives, Antiviral Res. 16 (1991) 185-196.
[5] D.L. Barnard, J.H. Huffman, J.L.B. Morris, S.G. Wood, B.G. Hughes, R.W. Sidwell, Evaluation of the antiviral activity of anthraquinones, anthrones and anthraquinone derivatives against human cytomegalovirus, Antiviral Res. 17 (1992) 63-77.
[6] R. Liu, A. Li, A. Sun, Preparative isolation and purification of hydroxyanthraquinones and cinnamic acid from the Chinese medicinal herb Rheum officinale Baill. by highspeed counter-current chromatography, J. Chromatogr. A 1052 (2004) 217-221.
[7] Y. Xie, Y. Liang, H.W. Chen, T.Y. Zhang, Y. Ito, Preparative isolation and purification of anthraquinones from Cassia seed by high-speed countercurrent chromatography, J. Liq. Chromatogr. Relat. Technol. 30 (2007) 1475-1488.
[8] S. Genovese, F. Tammaro, L. Menghini, G. Carlucci, F. Epifano, M. Locatelli, Comparison of three different extractionmethods and HPLC determination of the anthraquinones aloe-emodine, emodine, rheine, chrysophanol and physcione in the bark of Rhamnus alpinus L. (Rhamnaceae), Phytochem. Anal. 21 (2010) 261-267.
[9] Y.X. Gong, S.P. Li, Y.T.Wang, P. Li, F.Q. Yang, Simultaneous determination of anthraquinones in Rhubarb by pressurized liquid extraction and capillary zone electrophoresis, Electrophoresis 26 (2005) 1778-1782.
[10] Z.J. Tan, F.F. Li, J.M. Xing, Separation and purification of aloe anthraquinones using PEG/Salt aqueous two-phase system, Sep. Sci. Technol. 46 (2011) 1503-1510.
[11] M. Locatelli, F. Tammaro, L.Menghini, G. Carlucci, F. Epifano, S. Genovese, Anthraquinone profile and chemical fingerprint of Rhamnus saxatilis L. from Italy, Phytochem. Lett. 2 (2009) 223-226.
[12] M. Mojski, I. Gluch, Characteristics and applications of three-phase extraction systems, J. Anal. Chem. 51 (1996) 329-342.
[13] H. Liu, C. Guo, J. Yu, J. Xing, Z. Chang, Y. Guan, Principle and Applications of Microemulsion Phase Extraction, Science Press, Beijing, 2005.
[14] L.H. Silva,W. Loh, Polymer induced multiphase generation in water/organic solvent mixtures. Strategies towards the design of triphasic and tetraphasic liquid systems, Chem. Commun. 1 (1998) 787-788.
[15] L. Liu, Y. Dong, Z. Xiu, Three-liquid-phase extraction of diosgenin and steroidal saponins from fermentation of Dioscorea zingibernsis CH Wright, Process Biochem. 45 (2010) 752-756.
[16] S. Shen, Z. Chang, J. Liu, X. Sun, X. Hu, H. Liu, Separation of glycyrrhizic acid and liquiritin from Glycyrrhiza uralensis Fisch extract by three-liquid-phase extraction systems, Sep. Purif. Technol. 53 (2007) 216-223.
[17] J. Chen, H. Liu, B.Wang, Z. An, Q. Liu, Study on the three-phase extraction of penicillin G with a single-step method, Proceedings of the International Solvent Extraction Conference, Johannesburg, South Africa, 2002.
[18] S. Shen, Z. Chang, X. Sun, X. Hu, H. Liu, Application of block copolymer in threeliquid-phase extraction system, Tsinghua Sci. Techol. 11 (2006) 248-251.
[19] P. Yu, K. Huang, H. Liu, Two and three-phase separation of phenol and onitrophenol: correlation between phase behavior and partitioning behavior, Colloids Surf. A 403 (2012) 15-24.
[20] X. He, K. Huang, P. Yu, C. Zhang, K. Xie, P. Li, J. Wang, Z. An, H. Liu, Liquid-liquid-liquid three phase extraction apparatus: operation strategy and influences on mass transfer efficiency, Chin. J. Chem. Eng. 20 (2012) 27-35.
[21] P. Yu, Z. Chang, Y. Ma, S. Wang, H. Cao, C. Hua, H. Liu, Separation of p-nitrophenol and o-nitrophenol with three-liquid-phase extraction system, Sep. Purif. Technol. 70 (2009) 199-206.
[22] S. Shen, Z. Chang, H. Liu, Three-liquid-phase extraction systems for separation of phenol and p-nitrophenol from wastewater, Sep. Purif. Technol. 49 (2006) 217-222.
[23] C. Zhang, K. Huang, P. Yu, H. Liu, Salting-out induced three-liquid-phase separation of Pt(IV), Pd(II) and Rh(Ⅲ) in system of S201-acetonitrile-NaCl-water, Sep. Purif. Technol. 80 (2011) 81-89.
[24] K. Xie, K. Huang, L. Xu, P. Yu, L. Yang, H. Liu, Three-liquid-phase extraction and separation of Ti(IV), Fe(Ⅲ), and Mg(II), Ind. Eng. Chem. Res. 50 (2011) 6362-6368.
[25] C. Zhang, K.Huang, P. Yu,H. Liu, Sugaring-out three-liquid-phase extraction and onestep separation of Pt(IV), Pd(II) and Rh(Ⅲ), Sep. Purif. Technol. 87 (2012) 127-134.
[26] P. Yu, K. Huang, C. Zhang, K. Xie, X. He, J. Zhao, F. Deng, H. Liu, Block copolymer micellization induced microphase mass transfer: partition of Pd(II), Pt(IV) and Rh(Ⅲ) in three-liquid-phase systems of S201-EOPO-Na2SO4-H₂O, J. Colloid Interface Sci. 362 (2011) 228-234.
[27] P. Yu, K. Huang, C. Zhang, K. Xie, X. He, H. Liu, One-step separation of platinum, palladium, and rhodium: a three-liquid-phase extraction approach, Ind. Eng. Chem. Res. 50 (2011) 9368-9376.
[28] P. Yu, K. Huang, H. Liu, K. Xie, Three-liquid-phase partition behaviors of Pt(IV), Pd(II) and Rh(Ⅲ): influences of phase-forming components, Sep. Purif. Technol. 88 (2012) 52-60.
[29] K. Xie, K. Huang, L. Yang, P. Yu, H. Liu, Three-liquid-phase extraction: a new approach for simultaneous enrichment and separation of Cr(Ⅲ) and Cr(VI), Ind. Eng. Chem. Res. 50 (2011) 12767-12773.
[30] K. Xie, K. Huang, L. Yang, H. Liu, Enhancing separation of titanium and iron by threeliquid-phase extraction with 1,10-phenanthroline as additive, J. Chem. Technol. Biotechnol. 87 (2012) 955-960.
[31] P. Yu, K. Huang, J. Zhao, C. Zhang, K. Xie, F. Deng, H. Liu, A novel separation technique: gas-assisted three-liquid-phase extraction for treatment of the phenolic wastewater, Sep. Purif. Technol. 75 (2010) 316-322.
[32] H. Liu, K.Wang, X. Chen, Z. Hu, Determination of rhein, baicalin and berberine in traditional Chinese medicinal preparations by capillary electrophoresis with twomarker technique, Biomed. Chromatogr. 18 (2004) 288-292.
[33] L. Liu, L. Fan, H. Chen, X. Chen, Z. Hu, Separation and determination of four active anthraquinones in Chinese herbal preparations by flow injection-capillary electrophoresis, Electrophoresis 26 (2005) 2999-3006.
[34] P. Bi, H. Dong, J. Dong, The recent progress of solvent sublation, J. Chromatogr. A 1217 (2010) 2716-2725.
[35] P.Å. Albertsson, Separation of particles and macromolecules by phase partition, Endeavour 1 (1977) 69-74.
[36] K. Ananthapadmanabhan, E. Goddard, Aqueous biphase formation in polyethylene oxide-inorganic salt systems, Langmuir 3 (1987) 25-31.
[37] P. Bi, H. Dong, Y. Yuan, Application of aqueous two-phase flotation in the separation and concentration of puerarin from Puerariae extract, Sep. Purif. Technol. 75 (2010) 402-406.
[38] H.O. Johansson, G. Karlstroem, F. Tjerneld, Experimental and theoretical study of phase separation in aqueous solutions of clouding polymers and carboxylic acids, Macromolecules 26 (1993) 4478-4483.
[39] J. Zhang, C. Bao, Y. Wang, W. Kong, F. Li, Separation and enrichment of the active constituents in Radix Et Rhizoma Rhei by solvent flotation, J. Anal. Sci. 3 (2009) 317-320 (in Chinese).