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Potential enthalpic energy of water in oils exploited to control supramolecular structure

Author

Listed:
  • Nathan J. Van Zee

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

  • Beatrice Adelizzi

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

  • Mathijs F. J. Mabesoone

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

  • Xiao Meng

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

  • Antonio Aloi

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology
    Eindhoven University of Technology)

  • R. Helen Zha

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

  • Martin Lutz

    (Bijvoet Center for Biomolecular Research, Utrecht University)

  • Ivo A. W. Filot

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology
    Eindhoven University of Technology)

  • Anja R. A. Palmans

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

  • E. W. Meijer

    (Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology)

Abstract

Water directs the self-assembly of both natural1,2 and synthetic3–9 molecules to form precise yet dynamic structures. Nevertheless, our molecular understanding of the role of water in such systems is incomplete, which represents a fundamental constraint in the development of supramolecular materials for use in biomaterials, nanoelectronics and catalysis 10 . In particular, despite the widespread use of alkanes as solvents in supramolecular chemistry11,12, the role of water in the formation of aggregates in oils is not clear, probably because water is only sparingly miscible in these solvents—typical alkanes contain less than 0.01 per cent water by weight at room temperature 13 . A notable and unused feature of this water is that it is essentially monomeric 14 . It has been determined previously 15 that the free energy cost of forming a cavity in alkanes that is large enough for a water molecule is only just compensated by its interaction with the interior of the cavity; this cost is therefore too high to accommodate clusters of water. As such, water molecules in alkanes possess potential enthalpic energy in the form of unrealized hydrogen bonds. Here we report that this energy is a thermodynamic driving force for water molecules to interact with co-dissolved hydrogen-bond-based aggregates in oils. By using a combination of spectroscopic, calorimetric, light-scattering and theoretical techniques, we demonstrate that this interaction can be exploited to modulate the structure of one-dimensional supramolecular polymers.

Suggested Citation

  • Nathan J. Van Zee & Beatrice Adelizzi & Mathijs F. J. Mabesoone & Xiao Meng & Antonio Aloi & R. Helen Zha & Martin Lutz & Ivo A. W. Filot & Anja R. A. Palmans & E. W. Meijer, 2018. "Potential enthalpic energy of water in oils exploited to control supramolecular structure," Nature, Nature, vol. 558(7708), pages 100-103, June.
  • Handle: RePEc:nat:nature:v:558:y:2018:i:7708:d:10.1038_s41586-018-0169-0
    DOI: 10.1038/s41586-018-0169-0
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    Cited by:

    1. Joseph F. Woods & Lucía Gallego & Pauline Pfister & Mounir Maaloum & Andreas Vargas Jentzsch & Michel Rickhaus, 2022. "Shape-assisted self-assembly," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    2. Shixin Fa & Tan-hao Shi & Suzu Akama & Keisuke Adachi & Keisuke Wada & Seigo Tanaka & Naoki Oyama & Kenichi Kato & Shunsuke Ohtani & Yuuya Nagata & Shigehisa Akine & Tomoki Ogoshi, 2022. "Real-time chirality transfer monitoring from statistically random to discrete homochiral nanotubes," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    3. Kuo Fu & Yanli Zhao & Guofeng Liu, 2024. "Pathway-directed recyclable chirality inversion of coordinated supramolecular polymers," Nature Communications, Nature, vol. 15(1), pages 1-13, December.

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