2026-06-11 ノースウェスタン大学
＜関連情報＞
- https://news.northwestern.edu/stories/2026/06/cell-inspired-material-captures-energy-and-releases-it-on-demand
- https://www.cell.com/chem/abstract/S2451-9294(26)00141-5
発色団両親媒性分子のピマー超分子ポリマーにおける、蓄積および放出された電子によって媒介される動的な自己組織化 Dynamic self-assembly mediated by stored and released electrons in pimer supramolecular polymers of chromophore amphiphiles
Tyler J. Jaynes ∙ Luka Đorđević ∙ Hiroaki Sai ∙ … ∙ Steven Weigand ∙ J. Fraser Stoddart ∙ Samuel I. Stupp
Chem Published: May 27, 2026
DOI:https://doi.org/10.1016/j.chempr.2026.103075
Graphical abstract
The bigger picture
In the cell cytoskeleton, protein monomers polymerize and depolymerize dynamically through mechanisms powered by hydrolyzable chemical fuels such as ATP and GTP. Many critical functions are linked to this phenomenon related to cell mechanics, molecular transport, and cell division, among others. In this work, we describe a chemical system that is analogous in some respects to the dynamic cytoskeleton filaments since it exhibits reversible self-assembly of globular aggregates of monomers to supramolecular polymers. The system exhibits functions that are different from those in biological systems and takes advantage of useful energy storage and release as molecules assemble and disassemble under the action of various stimuli, such as light, chemical fuels, electricity, and X-rays. As the globules convert to supramolecular polymers, stabilized by π-π interactions and π-radical pimerization, the system stores electrons under anaerobic conditions that can be used on demand in chemical reactions, thus offering a model strategy for dark photosynthesis. Upon introduction of oxygen, the stored electrons within the supramolecular polymers are released to create reactive oxygen species that can be used in oxidation reactions of organic substrates. The system reversibly transitions between a yellow solution of globular aggregates and an electrically conductive black hydrogel that stores the electrons.
Highlights
- Supramolecular polymers store electrons when exposed to light, fuels, or X-rays
- π-π stacking and pimerization trigger a reversible supramolecular polymerization
- Conductive supramolecular polymers for dark photocatalysis and photopatterning
Summary
Reversible self-assembly of supramolecular polymers plays a critical role in living systems, exemplified by the cell cytoskeleton. Analogous synthetic systems could be functional in the spatiotemporal control of chemical reactions, design of active matter, and energy storage for use on demand. We report an energy-storing supramolecular system that reversibly converts from small aggregates of molecules to supramolecular polymers. The aminonaphthalimide chromophore amphiphile monomer is conjugated to a methyl viologen moiety that converts energy from visible light, chemical fuels, an electrochemical bias, or X-rays to store electrons and trigger the formation of a polymeric pimer, accompanied by conversion from a solution to a hydrogel. Supramolecular polymerization is synergistically triggered by π-π stacking and π-radical pimerization that stores electrons in the assembly. These electrons can be released, generating reactive oxygen species, which proceed to oxidize an organic substrate in the absence of visible light, thus providing a model system for dark photocatalysis.
