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Spectroscopic characterization of the binding and isomerization cycle of Brooker’s merocyanine with α-, β-, and γ-cyclodextrins

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Abstract

Complexes of Brooker’s merocyanine dye with α-, β- and γ-cyclodextrin (CD) have been characterized to determine the relative strength and thermodynamics of binding, as well as the effect of binding on the protolytic-photochemical isomerization cycle of the dye. It was found that the dye binds most tightly to β-CD, with a binding equilibrium constant of 430 M−1, in agreement with previous results (Hamasaki et al. J. Incl. Phenom. Mol. Rec. Chem. 13, 349–359 (1992)), while α-CD and γ-CD complexes have a binding constant of approximately 110 M−1 and 70 M−1, respectively, determined using absorbance and fluorescence spectroscopy. The isomerization cycle for the dye in α- and γ-CD complexes was found to be the same as for the free dye. Complexation with β-CD, however, resulted in depressed trans-to-cis photoisomerization in acidic conditions followed by spontaneous cis-to-trans isomerization (with the addition of base). Thermodynamic results also indicated differences between α-CD (ΔS° = −48 J K−1) and β-CD (ΔS° =  +12 J K−1) complexes. There was no temperature dependence observed for the γ-CD complexes. These results can be justified in terms of the location of the dye molecule within the cyclodextrin cavity for each of the complexes.

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  1. School of Science, Penn State Erie, The Behrend College, 4205 College Dr., Erie, PA, 16563, USA

    Jennifer S. Holt, Anthony Campitella, Adam Rich & Jennifer L. Young

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  1. Jennifer S. Holt
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  2. Anthony Campitella
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Correspondence to Jennifer S. Holt.

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Holt, J.S., Campitella, A., Rich, A. et al. Spectroscopic characterization of the binding and isomerization cycle of Brooker’s merocyanine with α-, β-, and γ-cyclodextrins. J Incl Phenom Macrocycl Chem 61, 251–258 (2008). https://doi.org/10.1007/s10847-008-9415-7

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