pH-dependent complex formation of amino acids with β-cyclodextrin and quaternary ammonium β-cyclodextrin

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Abstract

Stability constants for the complexes of anionic, neutral (zwitterionic) and protonated forms of l- and d-enantiomers of eight amino acids with β-cyclodextrin and the positively charged quaternary ammonium β-cyclodextrin (QA-β-CD, DS = 3.6 ± 0.3) have been determined by spectrophotometric and pH-potentiometric methods. The highest stability constants have been obtained for the aromatic amino acids phenylalanine, tyrosine and tryptophan. Except the dianion of tyrosine and QA-β-CD, values for the anions in the range of 80–120 have been found, the stability constants for the zwitterionic forms are much smaller and complex formation is negligible with the protonated species. In the case of the other amino acids the differences are less pronounced. The results are interpreted in terms of hydrogen bonding, steric effects and electrostatic interactions between the amino acid moiety and the rims of the cyclodextrins, in addition to the inclusion of the side chain, and are supported by 1H and 13C NMR investigations on the systems containing l-phenylalanine and l-tyrosine. The differences between the complex formation constants of the l- and d-enantiomers do not exceed the limits of experimental error in most cases.

Keywords

Amino acids Quaternary ammonium β-cyclodextrin Stability constants Ionization state Enantiomers 
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Notes

Acknowledgement

We are grateful to Cyclolab Ltd. for supplying the β-CD and QA-β-CD and to the Ministry of National Resources of Hungary (Ferenc Deák Fellowship) for the partial financial support.

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© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  1. 1.Institute of ChemistryLoránd Eötvös UniversityBudapestHungary
  2. 2.Department of PharmaceuticsSemmelweis UniversityBudapestHungary

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