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Ionic dye–surfactant nanoassemblies: interplay of electrostatics, hydrophobic effect, and π–π stacking

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Abstract

The interplay of several non-covalent interaction forces is used as key to supramolecular structures. Combining cationic alkyltrimethylammonium bromide surfactants and the divalent anionic azo dye Acid Red 26 (Ar26) as small building blocks in aqueous solution, electrostatic interactions of the oppositely charged building blocks in combination with hydrophobic effect and π–π interactions play a major role in aggregate formation. Static and dynamic light scattering and small-angle neutron scattering (SANS) revealed different sizes of aggregates in the range of 2 nm ≤ R H ≤ 420 nm depending on surfactant length, concentration and of dye to surfactant loading ratio. A strong relationship of assembly size with surfactant concentration has been found, where initial surfactant monomers and micelles influence the aggregate formation differently. The stability of dye–surfactant aggregates which also shows a dependency on surfactant tail length has been related to ζ-potential measurements. Small-angle neutron scattering elucidated that dye–surfactant aggregates possess cylindrical shapes with different aspect ratios. UV/Vis spectroscopy gave information on the dye–dye π–π stacking geometry and extent, while the thermodynamic parameters for micellization and dye–surfactant binding ΔH, ΔG, and ΔS as well as stoichiometry and binding constant obtained by isothermal titration calorimetry revealed insight into the interplay of interactions.

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Notes

  1. The weight of peak was found to be 15 % for the first peak and 85 % for the second peak.

  2. The weight of peak was found to be 16 % for the first peak and 84 % for the second peak.

  3. The weight of peak was found to be 65 % for the first peak and 35 % for the second peak.

  4. For aggregates with l = 0.7, dimensions of at least 153 nm in length and 4.7 nm in diameter were found whereas aggregates with l = 0.5 were at least 233 nm in length and 5.6 nm in diameter.

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Acknowledgments

This work is based upon experiments performed at D11 at Institit Laue Langevin, Grenoble France and at the KWS 2 instrument operated by JCNS at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany. We thank Ralf Schweins (ILL) and Henrich Frielinghaus (MLZ) for help with SANS experiments.

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Authors and Affiliations

  1. Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstr. 3, 91058, Erlangen, Germany

    Anne Kutz, Giacomo Mariani & Franziska Gröhn

  2. Institut Laue-Langevin, DS/LSS, 71 Avenue des Martyrs, 38000, Grenoble, France

    Giacomo Mariani

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  1. Anne Kutz
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  2. Giacomo Mariani
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Correspondence to Franziska Gröhn.

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Funding

This study was funded by the Interdisciplinary Center for Molecular Materials (ICMM, University Erlangen-Nürnberg). The authors gratefully acknowledge the financial support provided by Institit Laue Langevin, Grenoble France and by JCS to perform the neutron scattering measurements at ILL and at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany.

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The authors declare that they have no conflict of interest.

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Kutz, A., Mariani, G. & Gröhn, F. Ionic dye–surfactant nanoassemblies: interplay of electrostatics, hydrophobic effect, and π–π stacking. Colloid Polym Sci 294, 591–606 (2016). https://doi.org/10.1007/s00396-015-3814-2

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  • DOI: https://doi.org/10.1007/s00396-015-3814-2

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