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Inclusion complexes of cationic xanthene dyes in cucurbit[7]uril

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Abstract

Improvements in optical properties of organic xanthene fluorophores through molecular encapsulation in cucurbit[7]uril (CB7) should enable better molecular probes and devices to be designed. Although the interactions of several dyes with CB7 have been studied, the data have often been incomplete. Uniformly applied ensemble spectroscopic studies are presented herein, including 1H NMR, UV–Vis, and fluorescence titration experiments of aqueous CB7 complexes with the monocationic xanthene dyes rhodamine 6G (Rh6G, 1), rhodamine B (RhB, 2), rhodamine B benzyl ester (RhBBE, 3), pyronin B (PyB, 4) and pyronin Y (PyY, 5). All of these cationic xanthene dyes formed 1:1 complexes with cucurbit[7]uril as evidenced by NMR data and Job’s plots of fluorescence changes upon addition of CB7. Non-linear regression analysis of the fluorescence titration curves gave precise Ka’s for RhB, RhBBE and PyB between 1.1 × 105 M−1 and 9.1 × 106 M−1. The fluorescence emission intensity of Rh6G was lowered 0.8-fold in the presence of CB7 while the other dyes examined showed an increase between 1.3 and 4.7-fold. NMR titration experiments from 0 to 2.0 equivalents of CB7 per equivalent of xanthene gave in only some cases very clear evidence of inclusion complexation. Non-specific adsorption of these xanthene dyes onto borosilicate glass was very pronounced and could be inhibited by dye inclusion into CB7.

Graphical Abstract

Pyronin B-Cucurbit[7]uril complex

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Acknowledgements

Support through NSF (DMR-0805233) and from the University of Oklahoma and Oklahoma State Regents for Higher Education is appreciated. JLM acknowledges the DOEd for a GAANN Fellowship. KY, JAIH, KAW acknowledge support through the Undergraduate Research Program.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Oklahoma, 620 Parrington Oval, Norman, OK, 73019, USA

    Ronald L. Halterman, Jason L. Moore, Krystle A. Yakshe, Julie A. I. Halterman & Kevin A. Woodson

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  1. Ronald L. Halterman
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  2. Jason L. Moore
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  3. Krystle A. Yakshe
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Correspondence to Ronald L. Halterman.

Electronic supplementary material

Below is the link to the electronic supplementary material. General experimental procedures and NMR spectral data for RhBBE 3. UV/Vis absorption spectra, fluorescent emission spectra, Job’s plots, titration curves of changes in fluorescence with added CB7 and non-linear regression analysis to give Ka’s, NMR titration spectra of xanthenes 1–5 in presence of varying amounts of CB7. Absorption and emission spectra of PyY (5)–CB7 mixtures after storage in borosilicate, polypropylene or polystyrene containers.

Supplementary material 1 (DOC 8825 kb)

Non-linear regression analysis of Rh6G-CB7 titration curve (JPEG 74 kb)

Non-linear regression analysis of Rh6G benzyl ester-CB7 titration curve (JPEG 115 kb)

Non-linear regression analysis of pyronin B-CB7 titration curve (JPEG 70 kb)

Non-linear regression analysis of initial pyronin Y-CB7 titration curve (JPEG 81 kb)

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Halterman, R.L., Moore, J.L., Yakshe, K.A. et al. Inclusion complexes of cationic xanthene dyes in cucurbit[7]uril. J Incl Phenom Macrocycl Chem 66, 231–241 (2010). https://doi.org/10.1007/s10847-009-9615-9

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