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Investigation of gas chromatographic interaction mechanism on permethylated cyclodextrins by molecular modelling

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Summary

The capillary gas chromatographic retention behavior of α-pinene and tricyclene has been investigated on stationary phases of different polarities. On all but one of the columns employed, tricyclene eluted before α-pinene; only permethylated β-cyclodextrins dissolved in moderately polar polisiloxanes gave a reversed elution order. The intermolecular interactions which caused the unexpected retention behavior were investigated in detail, applying methods of computer simulation. To achieve this, we have developed a calculation algorithm on the basis of molecular mechanical optimizations and programmed it in a macro. This makes it possible to systematically investigate a given configuration space in which all the possible interactions can take place. It was shown that permethylated β-cyclodextrin as host molecule for both guest molecules offers an optimum cavity size. As a result the number of energetically favorable contacts between host and guest molecules as well as the strength of the interactions in this stationary phase were larger. As a consequence the elution order, normally only influenced by the vapor pressure of the compounds at a given temperature, was changed. Nonspecific interactions played an especially important role for these kinds of substances.

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Author notes

  1. R. Reinhardt

    Present address: Dr. Roth bio TEST, Heinrich-Rau-Str. 39, 04249, Leipzig, Germany

Authors and Affiliations

  1. Institut für Pharmakologie und Toxikologie, Universität Leipzig, Härtelstraße 16-18, 04107, Leipzig, Germany

    R. Reinhardt, M. Richter & P. P. Mager

  2. Fakultät für Chemie und Mineralogie, Institut für Analytische Chemie, Universität Leipzig, Linnéstraße 3-5, 04103, Leipzig, Germany

    P. Hennig & W. Engewald

Authors
  1. R. Reinhardt
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  2. M. Richter
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  3. P. P. Mager
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  4. P. Hennig
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  5. W. Engewald
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Reinhardt, R., Richter, M., Mager, P.P. et al. Investigation of gas chromatographic interaction mechanism on permethylated cyclodextrins by molecular modelling. Chromatographia 43, 187–194 (1996). https://doi.org/10.1007/BF02292949

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  • DOI: https://doi.org/10.1007/BF02292949

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