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Voltammetry as a Tool to Monitor the Aggregation Behavior of a Zwitterionic Ferrocene Surfactant

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Langmuir. American Chemical Society (ACS). 2021, 37(14), pp. 4183-4191. ISSN 0743-7463. eISSN 1520-5827. Available under: doi: 10.1021/acs.langmuir.1c00049

Zusammenfassung

Amphiphiles are unique in their ability to self-assemble in aqueous solution into aggregates. The control of the self-organization of amphiphiles and the live monitoring of the ensuing structure changes by analytical methods are key challenges in this field. One way to gain control and to trigger the self-assembly/disassembly of amphiphiles is to introduce a redox-active constituent to the amphiphile structure, as is the case with metallosurfactants. In this work, we report a cyclic and square-wave voltammetric study on the multi-stimuli-responsive amphiphile 1-(Z)-heptenyl-1′-dimethylammoniummethyl-(3-sulfopropyl)ferrocene (1). We observe separate waves/peaks for molecules of 1 present as the monomer in its electrode-immobilized, its freely diffusing form, and its aggregated form. This allows for a direct monitoring of how the underlying equilibria depend on the concentration and time. Isothermal titration calorimetry indicates that aggregation is entropically and enthalpically favored. Our findings thus illustrate the utility of voltammetric methods for investigating self-assembly processes of redox-active amphiphiles and their redox switchability.

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ISO 690BITTER, Stefan, Markus SCHILLING, Jan P. BRAHM, Sebastian POLARZ, Rainer F. WINTER, 2021. Voltammetry as a Tool to Monitor the Aggregation Behavior of a Zwitterionic Ferrocene Surfactant. In: Langmuir. American Chemical Society (ACS). 2021, 37(14), pp. 4183-4191. ISSN 0743-7463. eISSN 1520-5827. Available under: doi: 10.1021/acs.langmuir.1c00049
BibTex
@article{Bitter2021Volta-53759,
  year={2021},
  doi={10.1021/acs.langmuir.1c00049},
  title={Voltammetry as a Tool to Monitor the Aggregation Behavior of a Zwitterionic Ferrocene Surfactant},
  number={14},
  volume={37},
  issn={0743-7463},
  journal={Langmuir},
  pages={4183--4191},
  author={Bitter, Stefan and Schilling, Markus and Brahm, Jan P. and Polarz, Sebastian and Winter, Rainer F.}
}
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