Abstract
The use of amino acid-based polymeric surfactants (a.k.a. molecular micelles) in chiral micellar electrokinetic chromatography (CMEKC) has been shown to be a successful separation mode for capillary electrophoresis (CE). In this mode, chiral compounds can be enantioseparated with high efficiency, high chiral selectivity, and versatility. This chapter describes the state-of-the art studies published in the past 5 years in CMEKC using polymeric surfactants. Recent trends in the compatibility of chiral polymeric surfactants with mass spectrometric (MS) detection suggest that this type of chiral selector may be the most promising ones for chiral CE-MS applications. The synthesis of new anionic and cationic MS-compatible polymeric surfactants and their utility in CMEKC and CMEKC-MS are demonstrated. Examples of how to run a typical CMEKC-MS experiment using univariate and multivariate optimization of CMEKC and MS parameters are discussed.
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References
Gassmann E, Kuo JE, Zare RN (1985) Electrokinetic separation of chiral compounds. Science 230:813–814
Fanali S (1989) Separation of optical isomers by capillary zone electrophoresis based on host-guest complexation with cyclodextrins. J Chromatogr A 474:441–446
Nielen MWF (1993) Chiral separation of basic drugs using cyclodextrin-modified capillary zone electrophoresis. Anal Chem 65:885–893
Zhu W, Vigh G (2001) Separation selectivity patterns in the capillary electrophoretic separation of anionic enantiomers by octakis-6-sulfato–γ-cyclodextrin. Electrophoresis 22:1394–1398
Terabe S, Shibata M, Miyashita Y (1989) Chiral separation by electronkinetic chromatography while bile salt micelles. J Chromatogr A 480:403–411
Nishi H, Fukuyama T, Terabe S (1991) Chiral separation by cyclodextrin-modified micellar electrokinetic chromatography. J Chromatogr A 553:503–516
Wang J, Warner IM (1994) Chiral separations using micellar electrokinetic capillary chromatography and a polymerized chiral micelle. Anal Chem 66:3773–3776
Guttman A, Paulus A, Cohen AS, Grinberg N, Karger BL (1988) Use of complexing agents for selective separation in high-performance capillary electrophoresis: chiral resolution via cyclodextrins incorporated within polyacrylamide gel columns. J Chromatogr A 448:41–53
Dowling VA, Charles JAM, Nwakpuda E, McGown LB (2004) A reversible gel for chiral separations. Anal Chem 76:4558–4563
De BT, Bijma R, Ensing K (1999) Modeling of conditions for the enantiomeric separation of beta 2-adrenergic sympathicomimetics by capillary electrophoresis using cyclodextrins as chiral selectors in a polyethylene glycol gel. J Pharm Biomed Anal 19:529–537
Lin JM, Nakagama T, Uchiyama K, Hobo T (1996) Molecularly imprinted polymer as chiral selector for enantioseparation of amino acids by capillary gel electrophoresis. Chromatographia 43:585–591
Glukhovskiy P, Vigh G (1999) Analytical- and preparative-scale isoelectric focusing separation of enantiomers. Anal Chem 71:3814–3820
Spanik I, Lim P, Vigh G (2002) Use of full-column imaging capillary isoelectric focusing for the rapid determination of the operating conditions in the preparative-scale continuous free-flow isoelectric focusing separation of enantiomers. J Chromatogr A 960:241–246
Hoffmann P, Wagner H, Weber G, Lanz M, Caslavska J, Thormann W (1999) Separation and purification of methadone enantiomers by continuous- and interval-flow electrophoresis. Anal Chem 71:1840–1850
Kaniansky D, Šimuničova E, Ölvecká E, Ferancová A (1999) Separations of enantiomers by preparative capillary isotachophoresis. Electrophoresis 20:2786–2793
Snopek J, Jelínek I, Smolková-Keulemansová E (1988) Use of cyclodextrins in isotachophoresis: IV. The influence of cyclodextrins on the chiral resolution of ephedrine alkaloid enantiomers. J Chromatogr A 438:211–218
Mayer S, Schurig V (1992) Enantiomer separation by electrochromatography on capillaries coated with chirasil-dex. J High Res Chromatogr 15:129–131
Otsuka K, Mikami C, Terabe S (2000) Enantiomer separations by capillary electrochromatography using chiral stationary phases. J Chromatogr A 887:457–463
Zheng J, Norton D, Shamsi SA (2006) Fabrication of internally tapered capillaries for capillary electrochromatography electrospray ionization mass spectrometry. Anal Chem 78:1323–1330
Shamsi SA (2001) Micellar electrokinetic chromatography-mass spectrometry using a polymerized chiral surfactant. Anal Chem 73:5103–5108
Akbay C, Rizvi SAA, Shamsi SA (2005) Simultaneous enantioseparation and tandem UV-MS detection of eight beta-blockers in micellar electrokinetic chromatography using a chiral molecular micelle. Anal Chem 77:1672–1683
Rizvi SAA, Zheng J, Apkarian RP, Dublin SN, Shamsi SA (2006) Polymeric sulfated amino acid surfactants: a class of versatile chiral selectors for micellar electrokinetic chromatography (MEKC) and MEKC-MS. Anal Chem 79:879–898
Rizvi SAA, Shamsi SA (2006) Synthesis, characterization, and application of chiral ionic liquids and their polymers in micellar electrokinetic chromatography. Anal Chem 78:7061–7069
Hou J, Zheng J, Rizvi SAA, Shamsi SA (2007) Simultaneous chiral separation and determination of ephedrine alkaloids by MEKC-ESI-MS using polymeric surfactant I: method development. Electrophoresis 28:1352–1363
Hou J, Zheng J, Shamsi SA (2007) Separation and determination of warfarin enantiomers in human plasma using a novel polymeric surfactant for micellar electrokinetic chromatography-mass spectrometry. J Chromatogr A 1159:208–216
Hou J, Zheng J, Shamsi SA (2007) Simultaneous chiral separation of ephedrine alkaloids by MEKC-ESI-MS using polymeric surfactant II: application in dietary supplements. Electrophoresis 28:1426–1434
He J, Shamsi SA (2009) Multivariate approach for the enantioselective analysis in micellar electrokinetic chromatography-mass spectrometry: I. Simultaneous optimization of binaphthyl derivatives in negative ion mode. J Chromatogr A 1216:845–856
He J, Shamsi SA (2009) Multivariate approach for the enantioselective analysis in MEKC-MS: II. Optimization of 1,1′-binaphthyl-2,2′-diamine in positive ion mode. J Sep Sci 32:1916–1926
He J, Shamsi SA (2011) Chiral micellar electrokinetic chromatography-atmospheric pressure photoionization of benzoin derivatives using mixed molecular micelles. Electrophoresis 32:1164–1175
Wang B, He J, Shamsi SA (2010) A high-throughput multivariate optimization for the simultaneous enantioseparation and detection of barbiturates in micellar electrokinetic chromatography-mass spectrometry. J Chromatogr Sci 48:572–583
Terabe S, Otsuka K, Ichikawa K, Tsuchiya A, Ando T (1984) Electrokinetic separations with micellar solutions and open-tubular capillaries. Anal Chem 56:111–113
Palmer CP, Terabe S (1997) Micelle polymers as pseudostationary phases in MEKC: chromatographic performance and chemical selectivity. Anal Chem 69:1852–1860
Akbay C, Gill NL, Agbaria RA, Warner IM (2003) Copolymerized polymeric surfactants: characterization and application in micellar electrokinetic chromatography. Electrophoresis 24:4209–4220
Akbay C, Shamsi SA (2004) Polymeric sulfated surfactants with varied hydrocarbon tail: I. Synthesis, characterization, and application in micellar electrokinetic chromatography. Electrophoresis 25:622–634
Ahuja ES, Foley JP (1995) Influence of dodecyl sulfate counterion on efficiency, selectivity, retention, elution range, and resolution in micellar electrokinetic chromatography. Anal Chem 67:2315–2324
Terabe S, Otsuka K, Ando T (1985) Electrokinetic chromatography with micellar solution and open-tubular capillary. Anal Chem 57:834–841
Chankvetadze B (2007) Enantioseparations by using capillary electrophoretic techniques: the story of 20 and a few more years. J Chromatogr A 1168:45–70
Wren SAC, Rowe RC (1992) Theoretical aspects of chiral separation in capillary electrophoresis: I. Initial evaluation of a model. J Chromatogr A 603:235–241
Palmer CP, Khaled MY, McNair HM (1992) A monomolecular pseudostationary phase for micellar electrokinetic capillary chromatography. J High Res Chromatogr 15:756–762
Palmer CP, McNair HM (1992) Novel pseudostationary phase for micellar electrokinetic capillary chromatography. J Microcolumn Sep 4:509–514
Shamsi SA, Macossay J, Warner IM (1997) Improved chiral separations using a polymerized dipeptide anionic chiral surfactant in electrokinetic chromatography: separations of basic, acidic, and neutral racemates. Anal Chem 69:2980–2987
Rizvi SAA, Shamsi SA (2003) Polymeric alkenoxy amino acid surfactants: I. highly selective class of molecular micelles for chiral separation of beta-blockers. Electrophoresis 24:2514–2526
Billiot E, Macossay J, Thibodeaux S, Shamsi SA, Warner IM (1998) Chiral separations using dipeptide polymerized surfactants: effect of amino acid order. Anal Chem 70:1375–1381
Shamsi SA, Valle BC, Billiot F, Warner IM (2003) Polysodium N-undecanoyl-l-leucylvalinate: a versatile chiral selector for micellar electrokinetic chromatography. Anal Chem 75:379–387
Wang B, He J, Bianchi V, Shamsi SA (2009) Combined use of chiral ionic liquid and cyclodextrin for MEKC: Part I. Simultaneous enantioseparation of anionic profens. Electrophoresis 30:2812–2819
Wang B, He J, Bianchi V, Shamsi SA (2009) Combined use of chiral ionic liquid and CD for MEKC: Part II. Determination of binding constants. Electrophoresis 30:2820–2828
Valle BC, Morris KF, Fletcher KA, Fernand V, Sword DM, Eldridge S, Larive CK, Warner IM (2006) Understanding chiral molecular micellar separations using steady-state fluorescence anisotropy, capillary electrophoresis, and NMR. Langmuir 23:425–435
Luces CA, Warner IM (2010) Achiral and chiral separations using MEKC, polyelectrolyte multilayer coatings, and mixed mode separation techniques with molecular micelles. Electrophoresis 31:1036–1043
Rizvi SAA, Shamsi SA (2007) Polymeric alkenoxy amino acid surfactants: V. comparison of carboxylate and sulfate head group polymeric surfactants for enantioseparation in MEKC. Electrophoresis 28:1762–1778
Priego-Capote F, Ye L, Shakil S, Shamsi SA, Nilsson S (2008) Monoclonal behavior of molecularly imprinted polymer nanoparticles in capillary electrochromatography. Anal Chem 80:2881–2887
Shamsi SA (2002) Chiral capillary electrophoresis-mass spectrometry: modes and applications. Electrophoresis 23:4036–4051
Lamoree MH, Sprang AFH, Tjaden UR, van der Greef J (1996) Use of heptakis(2,6-di-O-methyl)-[beta]-cyclodextrin in on-line capillary zone electrophoresis-mass spectrometry for the chiral separation of ropivacaine. J Chromatogr A 742:235–242
Jäverfalk EM, Amini A, Westerlund D, Andrén PE (1998) Chiral separation of local anaesthetics by a capillary electrophoresis/partial filling technique coupled on-line to micro-electrospray mass spectrometry. J Mass Spectrom 33:183–186
Tanaka Y, Otsuka K, Terabe S (2000) Separation of enantiomers by capillary electrophoresis-mass spectrometry employing a partial filling technique with a chiral crown ether. J Chromatogr A 875:323–330
Schappler J, Guillarme D, Prat J, Veuthey J-L, Rudaz S (2007) Coupling CE with atmospheric pressure photoionization MS for pharmaceutical basic compounds: optimization of operating parameters. Electrophoresis 28:3078–3087
Williams AA, Fakayode SO, Huang X, Warner IM (2006) Use of multivariate analysis for optimization of separation parameters and prediction of migration time, resolution, and resolution per unit time in micellar electrokinetic chromatography. Electrophoresis 27:4127–4140
Ferreira SLC, Bruns RE, da Silva EGP, dos Santos WNL, Quintella CM, David JM, de Andrade JB, Breitkreitz MC, Jardim ICSF, Neto BB (2007) Statistical designs and response surface techniques for the optimization of chromatographic systems. J Chromatogr A 1158:2–14
Clarke HT, Gillespie HB, Weisshaus SZ (1933) The action of formaldehyde on amines and amino acids1. J Am Chem Soc 55:4571–4587
Acknowledgments
This work was supported by NIH grant (2R01-GM-062314) and, in part, by the American Chemical Society, Petroleum Research Foundation (Grant #PRF-47774-AC7).
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He, J., Shamsi, S.A. (2013). Application of Polymeric Surfactants in Chiral Micellar Electrokinetic Chromatography (CMEKC) and CMEKC Coupled to Mass Spectrometry. In: Scriba, G. (eds) Chiral Separations. Methods in Molecular Biology, vol 970. Humana Press, Totowa, NJ. https://doi.org/10.1007/978-1-62703-263-6_21
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DOI: https://doi.org/10.1007/978-1-62703-263-6_21
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