Quantitative applications of the resolution of enantiomers by capillary electrophoresis
Abstract
The separation and quantitation of enantiomers are important applications of capillary electrophoresis. Other chapters cover the background to the separation selectivities that can be obtained in free solution capillary electrophoresis (FSCE) and micellar electrokinetic capillary chromatography (MECC) using a variety of chiral selectors such as cyclodextrins (CDs), bile salts and crown ethers. This chapter covers the validation and quantitative application of chiral CE methods. Table 24.1 covers the majority of quantitative applications with selected details of selectivity modes, performance and application. The validation criteria applied to chiral CE methods are similar to those employed when assessing HPLC (high performance liquid chromatography) methods. Standard criteria assessed include linearity, repeatability, reproducibility, precision and accuracy. HPLC and CE may be employed in tandem to confirm accuracy. The majority of quantitative reports have focused on the analysis of chiral pharmaceuticals and agrochemicals. Application areas include enantiomeric purity testing of single enantiomer compounds, reaction rate monitoring, stability testing and enantiomeric separation of drugs in clinical samples.
Keywords
Capillary Electrophoresis Crown Ether Capillary Zone Electrophoresis Chiral Selector Chiral SeparationPreview
Unable to display preview. Download preview PDF.
References
- 1.Altria, K.D.; Goodall, D.M.; Rogan, M.M. (1994) Quantitative applications and validation of the resolution of enantiomers by capillary electrophoresis. Electrophoresis 15, 824–827.CrossRefGoogle Scholar
- 2.Williams, R.C.; Edwards, J.F.; Ainsworth, C.R. (1994) Analysis of diastereoisomeric impurities in chiral pharmaceutical compounds by capillary electrophoresis. Chromatographia 38, 441–445.CrossRefGoogle Scholar
- 3.Peterson, T.E.; Trowbridge, D. (1992) Quantitation of l-epinephrine and determination of the d-/l-epinephrine enantiomer ratio in a pharmaceutical formulaion by capillary electrophoresis. J. Chromatogr. 603, 298–301.CrossRefGoogle Scholar
- 4.Dethy, J.M.; De Broux, S.; Lesne, M.; Longstreth, J.; Gilbert, P. (1994) Stereoselective determination of verapmil and norverapmil by capillary electrophoresis. J. Chromatogr. 654, 121–127.CrossRefGoogle Scholar
- 5.Gareil, P.; Gramond, J.P.; Guyon, F. (1993) Separation and determination of warfarin enantiomers in human plasma samples by capillary zone electrophoresis using a methylated (β-cyclodextrin-containing electrolyte. J. Chromatogr. 615, 317–325.CrossRefGoogle Scholar
- 6.Altria, K.D.; Harden, R.C.; Hart, M.; Hevizi, J.; Hailey, P.A.; Makwana, J.; Portsmouth, M.J. (1993) An inter-company cross-validation exercise on capillary electrophoresis. 1. Chiral analysis of clenbuterol. J. Chromatogr. 641, 147–153.CrossRefGoogle Scholar
- 7.Guttman, A.; Cooke, N. (1994) Practical aspects in chiral separation of pharmaceuticals by capillary electrophoresis II. Quantitative separation of naproxen enantiomers. J. Chromatogr. 685, 155–159.CrossRefGoogle Scholar
- 8.Abushoffa, A.M.; Clark, B.J. (1995) Resolution of the enantiomers of oxamniquine by capillary electrophoresis and high-performance liquid chromatography with cyclodextrins and heparin as chiral selectors. J. Chromatogr. 700, 51–58.CrossRefGoogle Scholar
- 9.Altria, K.D.; Walsh, A.R.; Smith, N.W. (1993) Validation of a capillary electrophoresis method for the enantiomeric purity testing of fluparoxan. J. Chromatogr. 645, 193–196.CrossRefGoogle Scholar
- 10.Rickard, E.C.; Bopp, R.J. (1994) Optimization of a capillary electrophoresis method to determine chiral purity of a drug. J. Chromatogr. 680, 609–621.CrossRefGoogle Scholar
- 11.Noroski, J.E.; Mayo, D.J.; Moran, M. (1995) Determination of the enantiomer of a cholesterol-lowering drug by cyclodextrin-modified micellar electrokinetic chromatography. J. Pharm. Biomed. Anal. 13, 52–54.Google Scholar
- 12.Rogan, M.M.; Goodall, D.M.; Altria, K.D. (1994) Enantiomeric separation of salbutamol and related impurities using capillary electrophoresis. Electrophoresis 15, 808–817.CrossRefGoogle Scholar
- 13a.Nielen, M.W.F. (1993) (Enantio-) separation of phenoxy acid herbicides using capillary zone electrophoresis. J. Chromatogr. 637, 81–90.CrossRefGoogle Scholar
- 13b.Garrison, A.W.; Schmitt, P.; Kettrup, A. (1994) Separation of phenoxy acid herbicides and their enantiomers by high-performance capillary electrophoresis. J. Chromatogr. 688, 317–327.CrossRefGoogle Scholar
- 14.Nishi, H.; Nakumura, K.; Nakai, H.; Sato, T.; Terabe, S. (1995) Enantiomeric separation of trimetroquinol, denopamine, and timepidium by capillary electrophoresis and HPLC and the application of capillary electrophoresis to the optical purity testing of the drugs. Chromatographia 40, 638–644.CrossRefGoogle Scholar
- 15.Lurie, I.S. (1992) Micellar electokinetic capillary chromatography of the enantiomers of amphetamine, methamphetamine and their hydroxyphenethylamine precursors. J. Chromatogr. 605, 269–275.CrossRefGoogle Scholar
- 16.Okafo, G.N.; Rana, K.K.; Camilleri, P. (1994) Improved separation of diastereoisomers in capillary electrophoresis using a mixture of β-cyclodextrin and sodium taurocholate. Chromatographia 39, 627–630.CrossRefGoogle Scholar
- 17.Soini, H.; Riekkola, M-L.; Novotony, M.V. (1992) Chiral separations of basic drugs and quantitation of bupivacaine enantiomers in serum by capillary electrophoresis with modified cyclodextrin buffers. J. Chomatogr. 608, 265–274.CrossRefGoogle Scholar
- 18.Francotte, E.; Cherkaoul, S.; Faupel, M. (1993) Separation of the enantiomers of some racemic nonsteroidal aromatase inhibitors and barbiturates by capillary electrophoresis. Chirality 5, 516–526.CrossRefGoogle Scholar
- 19.Valko, I.E.; Billeiet, H.A.H.; Frank, J.; Luyben, K.Ch.A.M. (1994) Effect of degree of substitution of (2-hydroxy) propyl-(β-cyclodextrin on the enantioseparation of organic acids by capillary electrophoresis. J. Chromatogr. 678, 139–144.CrossRefGoogle Scholar
- 20.Rogan, M.M.; Altria, K.D.; Goodall, D.M. (1994) Plackett-Burman experimental design in chiral capillary electrophoresis. Chromatographia 38, 723–729.CrossRefGoogle Scholar
- 21.Altria, K.D. (1993) Essential peak area normalisation in capillary electrophoresis. Chromatographia 35, 177–182.CrossRefGoogle Scholar
- 22.Fanali, S.; Bocek, P. (1990) Enantiomeric resolution by using capillary zone electrophoresis: resolution of racemic trytophan and determinaiton of the enantiomer composition of commercial pharmaceutical epinephrine. Electrophoresis 11, 757–760.CrossRefGoogle Scholar
- 23.Nielen, M.W.F. (1993) Chiral separation of basic drugs using cyclodextrin-modified capillary zone electrophoresis. Anal. Chem. 65, 885–893.CrossRefGoogle Scholar
- 24.Altria, K.D.; Goodall, D.M.; Rogan, M.M. (1994) Quantitative applications and validation of the resolution of enantiomers by capillary electrophoresis. Electrophoresis 15, 824–827.CrossRefGoogle Scholar
- 25.Kuhn, R.; Stoecklin, F.; Erni, F. (1992) Chiral separations by host-guest complexation with cyclodextrins and crown ethers by capillary zone electrophoresis. Chromatographia 33, 32–36.CrossRefGoogle Scholar
- 26.Rogan, M.M.; Drake, C; Goodall, D.M.; Altria, K.D. (1993) Enantioselective enzymatic biotransformation of 2′-deoxy-3′-thiacytidine (BCH 189) monitored by capillary electrophoresis. Anal. Biochem. 208, 343–347.CrossRefGoogle Scholar
- 27.Sepaniak, M.J.; Cole, R.O.; Clark, B.K. (1992) Use of native and chemically modified cyclodextrins for the capillary electrophoretic separation of racemates. J. Liq. Chromatogr. 15, 1023–1040.CrossRefGoogle Scholar
- 28.Schmitt, T.; Engelhardt, H. (1995) Optimization of enantiomeric separations in capillary electrophoresis by reversal of the migration order and using different derivatized cyclodextrins. J. Chromatogr. 697, 561–570.CrossRefGoogle Scholar
- 29.Altria, K.D.; Kersey, M. (1995) Capillary electrophoresis and pharmaceutical analysis: a survey of the industrial application and their status of in the United States and United Kingdom. LC-GC 13, 40–46.Google Scholar
- 30a.Werner, A.; Nassauer, T.; Keichle, P.; Erni, F. (1994) Chiral separation by capillary zone elctrophoresis of an optically active drug and amino acids by host-guest complexation with cyclodextrins. J. Chromatogr. 666, 375–379.CrossRefGoogle Scholar
- 30b.Houben, R.J.H.; Gielen, H.; Van der Wal, S. (1993) Automated preseparation derivatization on a capillary electrophoresis instrument. J. Chromatogr. 634, 317–322.CrossRefGoogle Scholar
- 31.Quang, C; Khaledi, M.G. (1994) Chiral separations of acidic compounds by dextrin-mediated capillary zone electrophoresis. J. High Resolut. Chromatogr. Comm. 17, 609–612.CrossRefGoogle Scholar