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Featured Discoveries

Mechanically Strong yet Metabolizable Supramolecular Plastics

A strong, glassy supramolecular polymer has been shown to prevent the formation of marine microplastics by slowly dissolving in salt water into metabolizable compounds. Cheng et al. show that salt bridging between sodium hexametaphosphate or sulfated polysaccharides and guanidinium sulfates expels sodium sulfate to create a cross-linked network that is stable until the electrolytes are added back. The dried material is a moldable and recyclable thermoplastic that can be water stabilized with hydrophobic coatings.

Mechanically Robust, Readily Repairable Polymers via Tailored Noncovalent Cross-linking

The very long molecules found in synthetic polymers, and their tendency to entangle and partially crystallize, impart many of the polymers' useful properties. However, these same characteristics also mean that chain dynamics are slow, which impedes potential self-healing. Yanagisawa et al. developed a family of ether-thiourea linear polymers that form hydrogen-bonded networks and still manage to stay amorphous. The polymers are stiff, showing the strength of the hydrogen bonding; however, because these bonds can easily reform, the polymer is also able to self-heal when compressed.

Solvent-Free Autocatalytic Supramolecular Polymerization

Solvent-free chemical manufacturing is one of the awaited technologies for addressing an emergent issue of environmental pollution. Here, we report solvent-free autocatalytic supramolecular polymerization (SF-ASP), which provides an inhibition-free template-assisted catalytic organic transformation that takes great advantage of the fact that the product (template) undergoes a termination-free nucleation–elongation assembly (living supramolecular polymerization) under solvent-free conditions. SF-ASP allows for reductive cyclotetramerization of hydrogen-bonding phthalonitriles into the corresponding phthalocyanines in exceptionally high yields (>80%). SF-ASP requires the growing polymer to form hexagonally packed crystalline fibres, which possibly preorganize the phthalonitriles at their cross-sectional edges for their efficient transformation. With metal oleates, SF-ASP produces single-crystalline fibres of metallophthalocyanines again in exceptionally high yields, which grow in both directions without terminal coupling until the phthalonitrile precursors are completely consumed. By taking advantage of this living nature of polymerization, multistep SF-ASP without/with metal oleates allows for the precision synthesis of multi-block supramolecular copolymers.

Ultrafast Water Permeation through Nanochannels with a Densely Fluorous Interior Surface

Ultrafast water permeation in aquaporins is promoted by their hydrophobic interior surface. Polytetrafluoroethylene has a dense fluorine surface, leading to its strong water repellence. We report a series of fluorous oligoamide nanorings with interior diameters ranging from 0.9 to 1.9 nanometers. These nanorings undergo supramolecular polymerization in phospholipid bilayer membranes to form fluorous nanochannels, the interior walls of which are densely covered with fluorine atoms. The nanochannel with the smallest diameter exhibits a water permeation flux that is two orders of magnitude greater than those of aquaporins and carbon nanotubes. The proposed nanochannel exhibits negligible chloride ion (Cl–) permeability caused by a powerful electrostatic barrier provided by the electrostatically negative fluorous interior surface. Thus, this nanochannel is expected to show nearly perfect salt reflectance for desalination.

Image Credit: Bart van Overbeeke