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Enantioseparation and chiral recognition of α-amino acids and their derivatives on (−)-18-crown-6-tetracarboxylic acid bonded silica by capillary electrochromatography

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Abstract

Capillary electrochromatography was employed for enantioseparation of α-amino acids and their derivatives. (−)-18-Crown-6-2,3,11,12-tetracarboxylic acid bonded on the silica was used as the chiral stationary phase and methanol/Tris-citric acid (20 mM, pH 3.0–4.5) (20:80, v/v) was used as mobile phase. The enantioseparation performance was discussed and structure-chiral separation relationship were tried to be explained. The enantiomeric resolution was increased when the pH of the mobile phase decreased or hydrogen of amino acid was substituted with halogen. The resolution of 4-bromophenylalanine was 2.37 at pH 4.5, however, this value was increased to 3.35 at pH 3.0. Bromo- or chloro-substituted phenylalanine tended to show higher resolution than fluoro-substituted one. For fluoro-substituted phenylalanine the resolution was increased in order of 4-, 3- and 2-substituted one. α-Methyltryptamine did not show reasonable separation. As the thermodynamic study is a useful tool to understand the chiral recognition, the temperature effect on the enantioseparation was studied and the thermodynamic parameters were calculated. The most important mechanism of chiral recognition for the analytes tested could be barrier effects based on the thermodynamic calculations. The coefficient of determination between hydrophobicity and separation factor was found to be 0.87, indicating favorable separation with higher hydrophobicity of amino acids.

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References

  • Abdalla, A.E., and O.S. Fakhreldin. 2011. Computational modeling of capillary electrophoretic behavior of primary amines using dual system of 18-crown-6 and β-cyclodextrin. Journal of Chromatography A 1218: 5344–5351.

    Article  Google Scholar 

  • Asnin, L., K. Sharma, and S.W. Park. 2011. Chromatographic retention and thermodynamics of adsorption of dipeptides on a chiral crown ether stationary phase. Journal of Separation Science 34: 3136–3144.

    Article  CAS  PubMed  Google Scholar 

  • Berkecz, R., A. Sztojkov-Ivanov, and I. Llisz. 2006. High-performance liquid chromatographic enantioseparation of β-amino acid stereoisomers on a (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid-based chiral stationary phase. Journal of Chromatography A 1125: 138–143.

    Article  CAS  PubMed  Google Scholar 

  • Berthod, A., L.H. Brian, and E.B. Thomas. 2004. Temperature and enantioseparation by macrocyclic glycopeptide chiral stationary phases. Journal of Chromatography A 1060: 205–214.

    Article  CAS  PubMed  Google Scholar 

  • Caslavska, J., and W. Thormann. 2011. Stereoselective determination of drugs and metabolites in body fluids, tissues and microsomal preparations by capillary electrophoresis. Journal of Chromatography A 1218: 588–601.

    Article  CAS  PubMed  Google Scholar 

  • Cho, S.I., J. Shim, M.S. Kim, Y.K. Kim, and D.S. Chung. 2004. On-line sample cleanup and chiral separation of gemifloxacin in a urinary solution using chiral crown ether as a chiral selector in microchip electrophoresis. Journal of Chromatography A 1055: 241–245.

    Article  CAS  PubMed  Google Scholar 

  • Despina, A. T., Raluca-Ioana Stefan-van Staden and Constantina, P., and Kapnissi-Christodoulou. 2013 Chiral selectors in CE: Recent developments and applications. Electrophoresis, 34: 178–204.

  • Hyun, M.H. 2006. Preparation and application of HPLC chiral stationary phases based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Journal of Separation Science 29: 750–761.

    Article  CAS  PubMed  Google Scholar 

  • Hyun, M.H., D.H. Kim, Y.J. Cho, and J.S. Jin. 2005. Preparation and evaluation of a doubly tethered chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Journal of Separation Science 28: 421–427.

    Article  CAS  PubMed  Google Scholar 

  • Lammerhofer. M. 2010. Chiral recognition by enantioselective liquid chromatography: Mechanisms and modern chiral stationary phases. Journal of Chromatography A 1217: 814–856.

  • Lee, A., H.J. Choi, K.B. Jin, and M.H. Hyun. 2011. Liquid chromatographic resolution of 1-aryl-1,2,3,4-tetrahydroisoquinolines on a chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Journal of Chromatography A 1218: 4071–4076.

    Article  CAS  PubMed  Google Scholar 

  • Lee, W., J.Y. Jin, and C.S. Baek. 2005. Comparison of enantiomer separation on two chiral stationary phases derived from (+)-18-crown-6-2,3,11,12-tetracarboxylic acid of the same chiral selector. Microchemical Journal 80: 213–217.

    Article  CAS  Google Scholar 

  • Lili, -Z., Z. Lin, R.A. Reamer, M. Bing, and G. Zhinong. 2007. Stereoisomeric separation of pharmaceutical compounds using CE with a chiral crown ether. Electrophoresis 28: 2658–2666.

    Article  Google Scholar 

  • Llisz, I., A. Aranyi, Z. Pataj, and A. Peter. 2012. Enantiomeric separation of nonproteinogenic amino acids by high-performance liquid chromatography. Journal of Chromatography A 1269: 94–121.

    Article  Google Scholar 

  • Manolescu, C., M. Grinberg, C. Field, S. Ma, S. Shen, H. Lee, Y. Wang, A. Granger, Q. Chen, J. McCaffrey, D. Norwood, and N. Grinberg. 2008. Studies of the interactions of amino alcohols using high performance liquid chromatography with crown ether stationary phases. Journal of Liquid Chromatography & Related Technologies 31: 2219–2234.

    Article  CAS  Google Scholar 

  • Tak, K.M., E.J. Park, and M.H. Hyun. 2013. Liquid chromatographic resolution of racemic rasagiline and its analogues on a chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Journal of Separation Science 36: 3682–3687.

    Article  CAS  PubMed  Google Scholar 

  • Weng, W., Wang, Q. H., Yao, B. X., and Zeng, Q. L. 2004. Enantioseparation of amino acid derivatives on an immobilized network polymer derived from l-tartaric acid. Journal of Chromatography A 1042: 81–87.

  • Xiao, Y.G., and C.H. Peter. 2006. Enantiomeric separation of underivatized small amines in conventional and on-chip capillary electrophoresis with contactless conductivity detection. Electrophoresis 27: 4375–4382.

    Article  Google Scholar 

  • Zhang, C., X.H. Wei, Z. Chen, and A.M. Rustum. 2010. Separation of chiral primary amino compounds by forming a sandwiched complex in reversed-phase high performance liquid chromatography. Journal of Chromatography A 1217: 4965–4970.

    Article  CAS  PubMed  Google Scholar 

  • Zhang, D., F. Li, D.H. Kim, H.J. Choi, and M.H. Hyun. 2005. Resolution of β-blockers on a chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid: Unusual temperature effect. Journal of Chromatography A 1083: 89–95.

    Article  CAS  PubMed  Google Scholar 

  • Zhang, J., Du Yingxiang, Qi Zhang, Jiaquan Chen, Xu Guangfu, Yu. Tao, and Xiaoyi Hua. 2013. Investigation of the synergistic effect with amino acid-derived chiral ionic liquids as additives for enantiomeric separation in capillary electrophoresis. Journal of Chromatography A 1316: 119–126.

    Article  CAS  PubMed  Google Scholar 

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Acknowledgments

This work was supported by Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2009-0093815).

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Authors and Affiliations

  1. School of Lifescience, Inner Mongolia University for the Nationalities, Tongliao, China

    Enqi Wu

  2. College of Pharmacy, Chungnam National University, Daejeon, 305-764, Korea

    Kyung Tae Kim, Sreenivas Kalyan Adidi, Jong Woon Cho & Jong Seong Kang

  3. Daejeon Health Sciences College, Daejeon, 300-711, Korea

    Young Keun Lee

  4. College of Pharmacy, Chosun University, Gwangju, 501-759, Korea

    Wonjae Lee

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  1. Enqi Wu
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  2. Kyung Tae Kim
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  3. Sreenivas Kalyan Adidi
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  4. Young Keun Lee
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  5. Jong Woon Cho
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  6. Wonjae Lee
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  7. Jong Seong Kang
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Correspondence to Wonjae Lee or Jong Seong Kang.

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Wu, E., Kim, K.T., Adidi, S.K. et al. Enantioseparation and chiral recognition of α-amino acids and their derivatives on (−)-18-crown-6-tetracarboxylic acid bonded silica by capillary electrochromatography. Arch. Pharm. Res. 38, 1499–1505 (2015). https://doi.org/10.1007/s12272-014-0507-1

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  • DOI: https://doi.org/10.1007/s12272-014-0507-1

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