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Multi-stimuli responsive nanomaterials assembled from spiropyran-containing peptoids.

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Summary

Amphiphilic peptoids with spiropyran groups form tunable nanostructures. Light and heat control assembly, crystallinity, and catalytic activity, mimicking carbonic anhydrase enzymes.

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Area of Science:

  • Supramolecular chemistry
  • Materials science
  • Biomimetic catalysis

Background:

  • Stimuli-responsive materials are crucial for tunable functionalities.
  • Controlling supramolecular assembly morphology and crystallinity is key.
  • Spiropyran (SP) photoisomerization offers a route to stimuli-responsive systems.

Purpose of the Study:

  • To develop stimuli-responsive peptoid assemblies with tunable morphology and crystallinity.
  • To investigate the role of spiropyran isomerization in assembly formation.
  • To explore the application of these assemblies in mimicking enzyme catalysis.

Main Methods:

  • Synthesis of amphiphilic peptoids incorporating a multifunctional spiropyran (SP) group.
  • Characterization of self-assembled nanostructures (2D nanosheets, 1D nanotubes) using light and heat stimuli.
  • Computational analysis using periodic density functional theory (DFT) to study SP/merocyanine (MC) energetics.
  • Evaluation of catalytic activity in mimicking carbonic anhydrase (CA) enzymes.

Main Results:

  • Amphiphilic peptoids self-assembled into light- and heat-responsive 2D nanosheets and 1D nanotubes.
  • Spiropyran (SP) isomerization to merocyanine (MC) was confirmed as the mechanism for assembly control.
  • DFT calculations showed MC dimers have more favorable packing energetics than SP dimers, correlating with higher assembly crystallinity.
  • Catalytic activity, mimicking carbonic anhydrase, was tuned by controlling the assembly crystallinity.

Conclusions:

  • Light and heat stimuli can effectively control the self-assembly of spiropyran-functionalized peptoids.
  • The isomerization of spiropyran to merocyanine influences the packing and crystallinity of the assemblies.
  • Tunable supramolecular assemblies offer a platform for developing responsive catalytic systems.