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Adv Mater. 2017 Nov;29(43). doi: 10.1002/adma.201703495. Epub 2017 Oct 10.

Stimulated Transitions of Directed Nonequilibrium Self-Assemblies.

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Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52056, Aachen, Germany.
DWI Leibniz Institute for Interactive Materials and Center for Chemical Polymer Technology (CPT), Forckenbeckstr. 50, D-52074, Aachen, Germany.
Department of Chemistry and Chemical Biology, Physical Chemistry I, TU Dortmund University, Otto-Hahn Str. 6, D-44227, Dortmund, Germany.
Institut Laue-Langevin ILL, DS/LSS, 71 Avenue des Martyrs, F-38000, Grenoble, France.
School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, UK.


Near-equilibrium stimulus-responsive polymers have been used extensively to introduce morphological variations in dependence of adaptable conditions. Far-less-well studied are triggered transformations at constant conditions. These require the involvement of metastable states, which are either able to approach the equilibrium state after deviation from metastability or can be frozen on returning from nonequilibrium to equilibrium. Such functional nonequilibrium macromolecular systems hold great promise for on-demand transformations, which result in substantial changes in their material properties, as seen for triggered gelations. Herein, a diblock copolymer system consisting of a hydrophilic block and a block that is responsive to both pressure and temperature, is introduced. This species demonstrates various micellar transformations upon leaving equilibrium/nonequilibrium states, which are triggered by a temperature deflection or a temporary application of hydrostatic pressure.


gels; hydrostatic pressure; micelles; rheology; small angle neutron scattering

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