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Stereoselective interaction of ketoprofen enantiomers with β-cyclodextrin: ground state binding and photochemistry

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Abstract

The chiral recognition ability of β-cyclodextrin (β-CyD) vs. S- and R-ketoprofen (KP) enantiomers has been studied by circular dichroism (CD), isothermal titration calorimetry (ITC) and NMR. The association constants of the 1 ∶ 1 complexes obtained from CD and ITC titration experiments resulted to be the same for both enantiomers within the experimental uncertainty. Well differentiated CD spectra were determined for the diastereomeric complexes. Their structure was assessed by molecular mechanics and molecular dynamics calculations combined with quantum mechanical calculation of the induced rotational strengths in the low energy KP:β-CyD associates, upon comparison of the calculated quantities with the corresponding experimental CD. The inclusion geometry is similar for both enantiomers with the aromatic carbonyl inserted in the CyD cavity, the monosubstituted ring close to the primary CyD rim and the carboxylate group exposed to the solvent close to the secondary rim. NMR spectra fully confirmed the geometry of the diastereomeric complexes. Tiny structural differences were sensibly probed by CD and confirmed by 2D ROESY spectra. Photoproduct studies with UV absorption and MS detection as well as nanosecond laser flash photolysis evidenced lack of chiral discrimination in the photodecarboxylation of KP within the cavity and formation of a photoaddition product to β-CyD by secondary photochemistry of 3-ethylbenzophenone.

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Authors and Affiliations

  1. Istituto per la Sintesi Organica e la Fotoreattività, Consiglio Nazionale delle Ricerche, via Piero Gobetti 101, I-40129, Bologna, Italy

    Giancarlo Marconi, Ilse Manet, Francesco Manoli & Sandra Monti

  2. Dipartimento di Chimica Organica «A. Mangini», Università di Bologna, Viale Risorgimento 4, I-40126, Bologna, Italy

    Elisabetta Mezzina

  3. Dipartimento di Scienze e Tecnologie Agro-ambientali, Università di Bologna, Via Fanin 40, I-40127, Bologna, Italy

    Barbara Zambelli

  4. CERM (Center for Magnetic Resonance), University of Florence, Via Luigi Sacconi 6, I-50019, Sesto Fiorentino, Italy

    Barbara Zambelli

Authors
  1. Giancarlo Marconi
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  2. Elisabetta Mezzina
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  3. Ilse Manet
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  4. Francesco Manoli
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  5. Barbara Zambelli
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  6. Sandra Monti
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Marconi, G., Mezzina, E., Manet, I. et al. Stereoselective interaction of ketoprofen enantiomers with β-cyclodextrin: ground state binding and photochemistry. Photochem Photobiol Sci 10, 48–59 (2011). https://doi.org/10.1039/c0pp00262c

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  • DOI: https://doi.org/10.1039/c0pp00262c

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