Lyotropic liquid crystals and linear supramolecular polymers of end-functionalized oligosaccharides.

We synthesized permethylated maltoheptaose oligosaccharides, whose both ends, untrivially, have been functionalized with supramolecular binders 2-ureido-4[1H]-pyrimidinones (UPy) after single ring-opening of ß-cyclodextrin counterpart. In 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), they show lyotropic liquid crystallinity. In the dried state they allow linear saccharide-based supramolecular polymers by UPy-dimerization.

Hierarchical Supramolecular Cross-Linking of Polymers for Biomimetic Fracture Energy Dissipating Sacrificial Bonds and Defect Tolerance under Mechanical Loading.

Biological structural materials offer fascinating models how to synergistically increase the solid-state defect tolerance, toughness, and strength using nanocomposite structures by incorporating different levels of supramolecular sacrificial bonds to dissipate fracture energy. Inspired thereof, we show how to turn a commodity acrylate polymer, characteristically showing a brittle solid state fracture, to become defect tolerant manifesting noncatastrophic crack propagation by incorporation of different levels of fracture energy dissipating supramolecular interactions. Therein, poly(2-hydroxyethyl methacrylate) (pHEMA) is a feasible model polymer showing brittle solid state fracture in spite of a high maximum strain and clear yielding, where the weak hydroxyl group mediated hydrogen bonds do not suffice to dissipate fracture energy. We provide the next level stronger supramolecular interactions toward solid-state networks by postfunctionalizing a minor part of the HEMA repeat units using 2-ureido-4[1H]-pyrimidinone (UPy), capable of forming four strong parallel hydrogen bonds. Interestingly, such a polymer, denoted here as p(HEMA-co-UPyMA), shows toughening by suppressed catastrophic crack propagation, even if the strength and stiffness are synergistically increased. At the still higher hierarchical level, colloidal level cross-linking using oxidized carbon nanotubes with hydrogen bonding surface decorations, including UPy, COOH, and OH groups, leads to further increased stiffness and ultimate strength, still leading to suppressed catastrophic crack propagation. The findings suggest to incorporate a hierarchy of supramolecular groups of different interactions strengths upon pursuing toward biomimetic toughening.

Hydrogen bonding asymmetric star-shape derivative of bile acid leads to supramolecular fibrillar aggregates that wrap into micrometer spheres.

We report that star-shaped molecules with cholic acid cores asymmetrically grafted by low molecular weight polymers with hydrogen bonding end-groups undergo aggregation to nanofibers, which subsequently wrap into micrometer spherical aggregates with low density cores. Therein the facially amphiphilic cholic acid (CA) is functionalized by four flexible allyl glycidyl ether (AGE) side chains, which are terminated with hydrogen bonding 2-ureido-4[1H]pyrimidinone (UPy) end-groups as connected by hexyl spacers, denoted as CA(AGE6-C6H12-UPy)4. This wedge-shaped molecule is expected to allow the formation of a rich variety of solvent-dependent structures due to the complex interplay of interactions, enabled by its polar/nonpolar surface-active structure, the hydrophobicity of the CA in aqueous medium, and the possibility to control hydrogen bonding between UPy molecules by solvent selection. In DMSO, the surfactant-like CA(AGE6-C6H12-UPy)4 self-assembles into nanometer scale micelles, as expected due to its nonpolar CA apexes, solubilized AGE6-C6H12-UPy chains, and suppressed mutual hydrogen bonds between the UPys. Dialysis in water leads to nanofibers with lateral dimensions of 20-50 nm. This is explained by promoted aggregation as the hydrogen bonds between UPy molecules start to become activated, the reduced solvent dispersibility of the AGE-chains, and the hydrophobicity of CA. Finally, in pure water the nanofibers wrap into micrometer spheres having low density cores. In this case, strong complementary hydrogen bonds between UPy molecules of different molecules can form, thus promoting lateral interactions between the nanofibers, as allowed by the hydrophobic hexyl spacers. The wrapping is illustrated by transmission electron microscopy tomographic 3D reconstructions. More generally, we foresee hierarchically structured matter bridging the length scales from molecular to micrometer scale by sequentially triggering supramolecular interactions.