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Supramolecular Chromaticity and Thermoresponsive Hydrogels: A Self-Assembly Study on Maleamic Acid-Based Amphiphiles

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Intelligent Hydrogels

Part of the book series: Progress in Colloid and Polymer Science ((PROGCOLLOID,volume 140))

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Abstract

A new class of homologous low molecular weight amphiphiles based on maleamic acid was synthesized and investigated in terms of its self-assembly behavior in bulk and in solution. The unexpected yellow color as bulk material and in organic solvents was revealed by means of spectroscopic and theoretical investigations to originate from intermolecular π-π interactions yielding supramolecular chromophores. It was found that the length of the alkyl chain of the amphiphiles and the resulting hydrophilic/lipophilic balance dictates the aggregation mode in bulk. One special compound exhibiting an n-tetradecyl chain was found to form stable thermoreversible supramolecular hydrogels in aqueous sodium hydroxide solutions. The corresponding hydrogels feature a rare cellular bilayer-based morphology and can be transferred into viscoelastic solutions upon heating and vice versa.

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Notes

  1. 1.

    Only molecule peak (m∙+) and peaks with relative intensities ≥ 10 % are listed in the corresponding characterization datasets for compounds 1–6.

  2. 2.

    The multiplicity of this signal cannot be determined as it is covered by the signal of DMSO. However, the presence of this peak can be proven by HH-COSY NMR experiments. This is also the case for compounds2–6.

  3. 3.

    5 has been favored over 6 that features the longest alkyl chain because the former shows higher solubilities in organic media.

  4. 4.

    The hydrogel samples prepared from 5 in aq. NaOH sol. can be stored under ambient conditions for more than a year without any recognizable decomposition.

  5. 5.

    It has to be noted that solutions of 5 in aq. NaOH sol. at elevated temperatures as well as hydrogels of 5 (where in both cases 5 is transformed in situ into the corresponding sodium carboxylate 5Na) do not show any color. In contrast, a comparable sample of 1 in aq. NaOH sol. (1Na) exhibits a pale yellow color. We explain this by a strong difference of the HLB that leads to different favored aggregation modes of the corresponding sodium carboxylates 1Na and 5Na (π-π vs. van der Waals interactions).

  6. 6.

    The onset of the melting peak of the μDSC traces is in good agreement with macroscopically observed gel melting at ca. 35–36 °C (“falling steel ball method”, ca. 1 °C min−1).

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Acknowledgement

Financial support by the German Research Foundation (DFG) in the frame of Priority Programme SPP 1259 “Intelligente Hydrogele” is gratefully acknowledged. Computational studies were carried out in the frame of Research Training Group GRK 1640 “Photophysics of Synthetic and Biological Multichromophoric Systems”. We thank M. Bieligmeyer, M. Schieder, C. Stelling, N. Al Nakeeb, S. Ganzleben and J. Failner for their support during synthesis and characterization of the compounds. B. Gossler is acknowledged for the cryo-SEM investigations. We are indebted to Dr. M. Drechsler for conducting the cryo-TEM experiments and Dr. M. Krekhova for the ff-TEM examinations. We thank B. Brunner (Prof. A. Jess, Chemical Engineering) for carrying out the elemental analysis.

Author information

Authors and Affiliations

  1. Macromolecular Chemistry I, Bayreuth Institute for Macromolecular Research (BIMF), Bayreuth Center for Colloids and Interfaces (BZKG), University of Bayreuth, Universitätsstrasse 30, 95440, Bayreuth, Germany

    Andreas Bernet, Marina Behr & Hans-Werner Schmidt

  2. Theoretical Physics IV, University of Bayreuth, Universitätsstrasse 30, 95440, Bayreuth, Germany

    Rodrigo Q. Albuquerque

  3. Institute of Chemistry of São Carlos, University of São Paulo (USP), Av. Trab. São-carlense 400, 13560-970, São Carlos, SP, Brazil

    Rodrigo Q. Albuquerque

  4. Inorganic Chemistry III, University of Bayreuth, Universitätsstrasse 30, 95440, Bayreuth, Germany

    Marko Schmidt & Jürgen Senker

Authors
  1. Andreas Bernet
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  2. Marina Behr
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  3. Rodrigo Q. Albuquerque
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  4. Marko Schmidt
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  5. Jürgen Senker
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  6. Hans-Werner Schmidt
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Corresponding author

Correspondence to Andreas Bernet .

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Editors and Affiliations

  1. Fakultät Bio- und Chemieingenieurwesen Thermodynamik, Technische Universität Dortmund, Dortmund, Germany

    Gabriele Sadowski

  2. RWTH Aachen LS für Physikalische Chemie II, Aachen, Germany

    Walter Richtering

Electronic Supplementary Material

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BERNET HW SCHMIDT et al suppl information.doc

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Bernet, A., Behr, M., Albuquerque, R.Q., Schmidt, M., Senker, J., Schmidt, HW. (2013). Supramolecular Chromaticity and Thermoresponsive Hydrogels: A Self-Assembly Study on Maleamic Acid-Based Amphiphiles. In: Sadowski, G., Richtering, W. (eds) Intelligent Hydrogels. Progress in Colloid and Polymer Science, vol 140. Springer, Cham. https://doi.org/10.1007/978-3-319-01683-2_1

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