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EPR, NMR, and Thermodynamic Evidences for Forced Nuclear Spin–Electron Spin Interactions in the Case of 1-Phenyl-2-Methylpropyl-1,1-Dimethyl-2-Nitroxide (TIPNO) Attached to Permethylated β-Cyclodextrin

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Abstract

In a recent paper (Bardelang et al. in J Org Chem 71:7657–7667, 2006), the deep inclusion of the TIPNO (1-phenyl-2-methylpropyl-1,1-dimethylethyl-2-nitroxide) free radical attached to a permethylated β-cyclodextrin (TRIMEB) into its cavity was questioned. In the present paper it is shown that the results of X-band and W-band electron paramagnetic resonance (EPR) and 1H nuclear magnetic resonance (NMR) studies of the TIPNO–TRIMEB in the presence of competitors of complexation (1-adamantanol, methyl orange and 1-adamantylamine) are consistent with a situation where the nitroxide is capping the small cavity entrance. The inclusion of the incoming guest was proven by 1H NMR, whereas no changes in EPR spectra were noticed whatever the competitors’ concentrations. These observations are rationalized in terms of an equilibrium between a nitroxide-capped cyclodextrin (weak complex) and a non-self included form, both species involving competitors’ inclusion without significant EPR spectral changes. These results not only confirm our preliminary findings, but also point out to the peculiar role of the cyclodextrin methoxy crown of the primary rim stabilizing the appended guest by means of weak interactions.

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Acknowledgments

P.T., H.K., J.P.F., S.C. B.D. A.R. and S.R.A.M. are grateful to cost P15 (grant: COST-STSM-P15-022268) for funding, the program ECONET (grant: 16321 WD) and the Conseil Re´gional Provence Alpes Côte, d’Azur, the Centre National de la Recherche Scientifique (CNRS), the Université de Provence and TROPHOS Company. K.M. and A.S. acknowledge support by the Deutschen Forschungsgemeinschaft (DFG) MO 132/19-2. E.G.B. and D.N.P. acknowledge support of the Russian Foundation for Basic Research RFBR (grant 08-04-0555), RFBR–DFG (09-03-91335) and Russian Federal Agency for Education (grant P1144).

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Authors and Affiliations

  1. International Tomography Center SBRAS, Institutskaya 3A, 630090, Novosibirsk, Russia

    Elena G. Bagryanskaya & Dmitriy Polovyanenko

  2. UMR 6517-CBRL CNRS, Aix-Marseille Université, case 521, Avenue Escadrille Normandie-Niemen, 13397, Marseille Cedex, France

    David Bardelang, Sandrine Chenesseau, Jean-Pierre Finet, Hakim Karoui, Sylvain R. A. Marque & Paul Tordo

  3. Cyclolab Ltd, PO Box 435, 1525, Budapest, Hungary

    Laszlo Jicsinszky

  4. Free University of Berlin, 14195, Berlin, Germany

    Klaus Möbius & Anton Savitsky

Authors
  1. Elena G. Bagryanskaya
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  2. David Bardelang
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  3. Sandrine Chenesseau
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  4. Jean-Pierre Finet
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  5. Laszlo Jicsinszky
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  6. Hakim Karoui
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  7. Sylvain R. A. Marque
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  8. Klaus Möbius
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  9. Dmitriy Polovyanenko
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  10. Anton Savitsky
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  11. Paul Tordo
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Corresponding authors

Correspondence to Elena G. Bagryanskaya or Sylvain R. A. Marque.

Additional information

Dr. J.-P. Finet deceased during the preparation of this paper.

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Bagryanskaya, E.G., Bardelang, D., Chenesseau, S. et al. EPR, NMR, and Thermodynamic Evidences for Forced Nuclear Spin–Electron Spin Interactions in the Case of 1-Phenyl-2-Methylpropyl-1,1-Dimethyl-2-Nitroxide (TIPNO) Attached to Permethylated β-Cyclodextrin. Appl Magn Reson 36, 181–194 (2009). https://doi.org/10.1007/s00723-009-0036-0

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  • DOI: https://doi.org/10.1007/s00723-009-0036-0

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