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Development of Electrophoretic Methods for Simultaneous Determination of Enantiomeric Ratio and Composition of Diastereomeric Salt Mixtures

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Abstract

Obtaining enantiomeric pure compounds is—among other techniques—possible in a resolvation experiment via diastereomeric salt formation, excellently exemplified by a modified Pope–Peachy method performed in supercritical carbon dioxide as solvent. The salt precipitation is followed by supercritical fluid extraction (SFE) to separate the diastereomeric salts and the unreacted enantiomers. To evaluate the extraction efficiency, conversion and enantioselectivity achieved, it is essential to determine the enantiomer excess and the residual resolving agent content in extracts and raffinates. Carefully chosen experimental parameters enable the simultaneous determination of certain anions and cations in capillary electrophoresis in a single run, which has not been reported for diastereomeric mixtures so far. In this paper, a partially validated chiral selective cyclodextrin enabled capillary electrophoresis method is presented for the characterization of cis-permethrinic acid samples resolved with (R)-1-phenylethylamine prepared by the SFE-based resolvation technique. To evaluate the efficiency of the resolvation, a cyclodextrin enabled chiral separation method was developed applying permethylated-β-cyclodextrin as chiral selector. The theoretical possibility of the widespread application of the developed method (with minor adjustments) is justified for other selectands and selectors. The developed methods can be thereby applied for the fast and reliable control of resolvation experiments.

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References

  1. Department of Health and Human Service of USA Food and Drug Administration’s (1992) Policy Statement for the Development of New Stereoisomeric Drugs. Fed Regist 57:102

  2. Zadra C, Marucchini C, Zazzerini A (2002) Behavior of metalaxyl and its pure R-enantiomer in sunflower plants (Helianthus annus). J Agric Food Chem 50:5373–5377

    Article  CAS  Google Scholar 

  3. Kozma D (ed) (2001) CRC handbook of optical resolutions via diastereomeric salt. CRC Press, London

    Google Scholar 

  4. Fogassy E, Acs M, Szili T, Simandi B, Sawinsky J (1994) Molecular chiral recognition in supercritical solvents. Tetrahedron Lett 35:257–260

    Article  CAS  Google Scholar 

  5. Simandi B, Keszei S, Fogassy E, Kemeny S, Sawinsky J (1998) Separation of enantiomers by supercritical fluid extraction. J Supercrit Fluids 13:331–336

    Article  CAS  Google Scholar 

  6. Szekely E, Gy Bansaghi, Thorey P, Molnar P, Madarasz J, Vida L, Simandi B (2010) Environmentally benign chiral resolution of trans-1-2-cyclohexanediol by two-step supercritical fluid extraction. Ind Eng Chem Res 49:9349–9354

    Article  CAS  Google Scholar 

  7. Schurig V, Juza M (2014) Analytical separation of enantiomers by gas chromatography on chiral stationary phases. Adv Chromatogr 52:117–168

    Article  CAS  Google Scholar 

  8. Kalikova K, Slechtova T, Vozka J, Tesarova E (2014) Supercritical fluid chromatography as a tool for enantioselective separation; a review. Anal Chim Acta 821:1–33

    Article  CAS  Google Scholar 

  9. Aboul-Enein HY, Ali I (2003) Chiral Separations By Liquid Chromatography and Related Technologies. Chromatographic Science Series, vol 90. Marcel Dekker, New York

    Book  Google Scholar 

  10. Chankvetadze B (1997) Capillary electrophoresis in chiral analysis. Wiley, New York

    Google Scholar 

  11. Kuban P, Kuban P, Kuban V (2002) Simultaneous determination of inorganic and organic anions, alkali, alkaline earth and transition metal cations by capillary electrophoresis with contactless conductometric detection. Electrophoresis 23:3725–3734

    Article  CAS  Google Scholar 

  12. Gy Bansaghi, Lorincz L, Szilagyi IM, Madarasz J, Szekely E (2014) Crystallizations and resolution of cis-permethrinic acid with carbon dioxide antisolvent. Chem Eng Technol 37:1417–1421

    Article  Google Scholar 

  13. Varga D (2014) Bansaghi Gy, Perez JAM, Miskolczi S, Hegedus L, Simandi B, Szekely E. Chiral resolution of racemic cyclopropanecarboxylic acids in supercritical carbon dioxide Chem Eng Technol 37:1885–1890

    CAS  Google Scholar 

  14. Gy Bansaghi, Szekely E, Mendez Sevillano D, Juvancz Z, Simandi B (2012) Diastereomer salt formation of ibuprofen in supercritical carbon dioxide. J Supercrit Fluids 69:113–116

    Article  Google Scholar 

  15. Gan J, Lee S, Werner I (2005) Isomer selectivity in aquatic toxicity and biodegradation of bifenthrin and permethrin. Environ Toxicol Chem 24:1861–1866

    Article  Google Scholar 

  16. Nemeth K, Domonkos C, Sarnyai V, Szeman J, Jicsinszky L, Szente L, Visy J (2014) Cationic permethylated 6-monoamino-6-monodeoxy-β-cyclodextrin as chiral selector of dansylated amino acids in capillary electrophoresis. J Pharm Biomed Anal 99:16–21

    Article  CAS  Google Scholar 

  17. Pope WJ, Peachey SJ (1899) CVIII—The application of powerful optically active acids to the resolution of externally compensated basic substances. Resolution of tetrahydroquinaldine. J Chem Soc Trans 75:1066–1093

    Article  CAS  Google Scholar 

  18. Rawjee YY, Gy Vigh (1994) A Peak resolution model for the capillary electrophoretic sepatation of enantiomers of weak acids with hydroxypropyl β-cyclodextrin containing background electrolytes. Anal Chem 66:619–627

    Article  CAS  Google Scholar 

  19. Wren SA, Rowe RC (1993) Theoretical aspects of chiral separation in capillary electrophoresis: I. Initial evaluation of a model. J Chromatogr A 603:235–241

    Article  Google Scholar 

  20. ICH Harmonized Tripartite Guideline Q2 (R1) (2005) Validation of analytical procedures: text and methodology Q2 (R1). http://www.ich.org/fileadmin/Public_Web_Site/ICH_Products/Guidelines/Quality/Q2_R1/Step4/Q2_R1__Guideline.pdf

  21. Kuban P, Karlberg B (1998) Simultaneous determination of small cations and anions by capillary electrophoresis. Anal Chem 70:360–365

    Article  CAS  Google Scholar 

  22. Johns C, Yang W, Macka M, Haddad PR (2004) Simultaneous separation of anions and cations by capillary electrophoresis with high magnitude, reversed electroosmotic flow. J Chromatogr A 1005:217–222

    Article  Google Scholar 

  23. Kuban P, Gregus M, Pokojova E, Skrickova J, Foret F (2014) Double opposite end injection capillary electrophoresis with contactless conductometric detection for simultaneous determination of chloride, sodium and potassium in cystic fibrosis diagnosis. J Chromatogr A 1358:293–298

    Article  CAS  Google Scholar 

  24. Tabani H, Fakhari AR, Shahsavani A (2013) Simultaneous determination of acidic and basic drugs using dual hollow fibre electromembrane extraction combined with CE. Electrophoresis 34:269–276

    Article  CAS  Google Scholar 

  25. Evans CE, Stalcup AM (2003) Comprehensive strategy for chiral separations using sulfated cyclodextrins in capillary electrophoresis. Chirality 15:709–723

    Article  CAS  Google Scholar 

  26. De Boer T, De Zeeuw RA, De Jong GJ, Ensing K (2000) The use of charged cyclodextrins in capillary electrophoresis for chiral separations in pharmaceutical analysis. Electrophoresis 21:3220–3239

    Article  Google Scholar 

  27. Chankvetadze B (2009) Separation of enantiomers with charged chiral selectors in CE. Electrophoresis 30:S211–S221

    Article  Google Scholar 

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Acknowledgments

The continuous support and fruitful discussions with late prof. Béla Simándi are highly appreciated. We would like to thank the financial support of OTKA K72861 and OTKA K108979 grants and of the Gedeon Richter PhD scholarship (Gy.B.). The work of E. Sz. Was supported by the Bolyai Janos Research Fund. Technical assistance of D. Ujvarosi is appreciated in measurements.

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Authors and Affiliations

  1. CycloLab R&D. Ltd., Illatos ut 7, 1097, Budapest, Hungary

    Erzsebet Varga & Tamas Sohajda

  2. Rejto Sandor Faculty of Light Industry and Environmental Protection Engineering, Environmental Protection Engineering Institute, Obuda University, Doberdo ut 6, 1034, Budapest, Hungary

    Zoltan Juvancz & Rita Bodane Kendrovics

  3. Department of Chemical and Environmental Process Engineering, Budapest University of Technology and Economics, Műegyetem rkp 3, 1111, Budapest, Hungary

    Edit Szekely & Gyorgy Bansaghi

Authors
  1. Erzsebet Varga
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  2. Tamas Sohajda
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  3. Zoltan Juvancz
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  4. Rita Bodane Kendrovics
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  5. Edit Szekely
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  6. Gyorgy Bansaghi
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Corresponding author

Correspondence to Zoltan Juvancz.

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Published in the topical collection 20th International Symposium on Separation Sciences in Prague with guest editors Aleš Horna and Pavel Jandera.

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Varga, E., Sohajda, T., Juvancz, Z. et al. Development of Electrophoretic Methods for Simultaneous Determination of Enantiomeric Ratio and Composition of Diastereomeric Salt Mixtures. Chromatographia 78, 881–888 (2015). https://doi.org/10.1007/s10337-015-2923-x

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  • DOI: https://doi.org/10.1007/s10337-015-2923-x

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