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Thermodynamics of the Dimer Formation of 2I,3I-O-(o-Xylylene)-per-O-Me-γ-cyclodextrin: Fluorescence, Molecular Mechanics and Molecular Dynamics

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Abstract

The thermodynamics of the dimer formation of 2I,3I-O-(o-xylylene)-per-O-Me-γ-cyclodextrin (XmγCD) in aqueous solution was studied by fluorescence techniques, Molecular Mechanics and Molecular Dynamics. Lifetime averages \( \left\langle \tau \right\rangle \), obtained from fluorescence decay profiles upon excitation of the xylylene appended group, were used as the property sensitive to the association process. The dimerization equilibrium constants (K D) were obtained from non-linear regression analysis of the plots of \( \left\langle \tau \right\rangle \) against [XmγCD] at several temperatures and they were compared with the values obtained for the counterparts Xmα- and XmβCDs. The van’t Hoff plot allows us to obtain the ΔH and ΔS showing that the dimerization process was also entropically disfavoured. Molecular Mechanics as well as Molecular Dynamics calculations in the presence of water were also employed to study the conformational behaviour of isolated XmγCDs, the possible structure of the dimers formed and the driving forces involved in such association processes. Results indicate that those conformations where Xy moiety does not block the cavity entrance are favoured. Dimers are preferably formed by head-to-head CD approaching. However, the formation of stable head-to-tail is not dismissed.

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Acknowledgments

This work was supported by the Spanish MEC (projects CTQ2006-15515C02-01/BQU, CTQ2007-61180/PPQ, CTQ2005-04710/BQU and CTQ2008-03149/BQU), the Junta de Andalucía (P06-FQM-01601), the Comunidad de Madrid (S-055/MAT/0227) and the Junta de Castilla-La Mancha (grant to M.J.G-A). FM and MJG-A acknowledge the assistance of M. L. Heijnen with the preparation of the manuscript and L. M. Frutos for his valuable co-operation in some calculations.

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  1. Dpto. Química Física, Universidad de Alcalá, 28871, Alcalá de Henares, Spain

    Maria José González-Álvarez & Francisco Mendicuti

  2. Instituto de Investigaciones Químicas, CSIC, 41092, Sevilla, Spain

    José Vicente & José Maria García Fernández

  3. Dpto. Química Orgánica, Facultad de Química, Universidad de Sevilla, 41012, Sevilla, Spain

    Carmen Ortiz Mellet

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  1. Maria José González-Álvarez
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González-Álvarez, M.J., Vicente, J., Mellet, C.O. et al. Thermodynamics of the Dimer Formation of 2I,3I-O-(o-Xylylene)-per-O-Me-γ-cyclodextrin: Fluorescence, Molecular Mechanics and Molecular Dynamics. J Fluoresc 19, 975–988 (2009). https://doi.org/10.1007/s10895-009-0497-4

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