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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Thermally Controlled Chiral Supramolecular Polymorphism in Water.

Zulema Fernández1, Yongsheng Li2, Daniel Martínez3

  • 1Organisch-Chemisches Institut, Universität Münster, Münster, Germany.

Angewandte Chemie (International Ed. in English)
|May 3, 2026
PubMed
Summary

Researchers developed a method for controlling chiral supramolecular polymorphism in water using temperature stimuli. This strategy allows for the creation of adaptive materials with tunable self-assembly properties.

Keywords:
LCSTchiralitysupramolecular polymerizationsupramolecular polymorphismπ‐conjugated systems

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Chiral Chemistry

Background:

  • Biological assemblies exhibit stimulus-responsive morphological changes.
  • Controlled polymorphic transitions in synthetic chiral supramolecular systems are not well understood.
  • Developing synthetic analogues that mimic biological adaptability is crucial.

Purpose of the Study:

  • To demonstrate controlled chiral supramolecular polymorphism in water.
  • To couple molecular design with external stimuli for tunable self-assembly.
  • To investigate temperature-responsive polymorphic transitions.

Main Methods:

  • Design and synthesis of an unsymmetrical oligo(phenyleneethynylene) derivative with specific functional groups (pyridine, amide, chiral side chains).
  • Investigation of self-assembly behavior in water across different temperature regimes.
  • Analysis of polymorphic transitions using stimuli such as temperature, co-solvents, and metal salts.

Main Results:

  • The designed molecule self-assembles into three distinct chiral supramolecular polymorphs (short cylinders, double helical fibers, planar aggregates) at different temperatures.
  • Polymorphic transitions are linked to temperature-dependent conformation and dehydration of glycol chains.
  • A transient double helical fiber polymorph can be stabilized at room temperature using chemical stimuli.

Conclusions:

  • LCST-coupled chirality is an effective strategy for regulating thermoresponsive supramolecular polymorphism.
  • The findings offer pathways for designing adaptive materials with controlled self-assembly.
  • This work advances the understanding of synthetic chiral supramolecular systems.