A photoresponsive nanoporous polymer film has been produced from the templated self-assembly of a columnar liquid crystal containing azo units. A liquid crystalline complex of polymerizable azobenzoic acid and a tris-benzimidazolyl benzene template molecule was cross-linked via thiol-ene radical copolymerization with dodecanedithiol. Subsequent removal of the template yielded nanoporous polymer films with pores of approximately 1 nm in diameter. Both trans–cis and cis–trans photoisomerizations of azobenzoic acid took place in the porous films. At room temperature, the cis isomer was sufficiently long-lived to establish a difference in dye absorption kinetics of the two isomers. The cationic dye rhodamine 6G was bound to both isomers, but the rate of binding to films enriched in the cis isomer was 8 times faster.

We report on the self‐assembly in water of a set of bis‐urea amphiphiles. A range of techniques, including dynamic light scattering, Cryo‐TEM, SAXS, and MS are used to study the effect of structural variation on the morphology of the assemblies. The length, dispersity, and end‐group of the ethylene glycol hydrophilic part of the molecule, as well as of the alkyl chain length are varied to tailor the morphology towards soluble wormlike micelles. Slight modification on molecular structures gave a large difference in self‐assembly behavior in water, giving guidelines for the design of rodlike supramolecular fibers with novel functionalities, such as strain‐stiffening and bioactivity.

Two synthetic supramolecular hydrogels, formed from bis-urea amphiphiles containing lactobionic acid (LBA) and maltobionic acid (MBA) bioactive ligands, are applied as cell culture matrices in vitro. Their fibrillary and dynamic nature mimics essential features of the extracellular matrix (ECM). The carbohydrate amphiphiles self-assemble into long supramolecular fibers in water, and hydrogels are formed by physical entanglement of fibers through bundling. Gels of both amphiphiles exhibit good self-healing behavior, but remarkably different stiffnesses. They display excellent bioactive properties in hepatic cell cultures. Both carbohydrate ligands used are proposed to bind to asialoglycoprotein receptors (ASGPRs) in hepatic cells, thus inducing spheroid formation when seeding hepatic HepG2 cells on both supramolecular hydrogels. Ligand nature, ligand density, and hydrogel stiffness influence cell migration and spheroid size and number. The results illustrate the potential of self-assembled, carbohydrate-functionalized hydrogels as matrices for liver tissue engineering.

New materials developed in the last years promise to contribute significantly to the preparation of membranes with improved performance in water filtration. Specifically, the use of dynamic‐responsive systems provides reversibility of the membrane properties. In this work, a reversible photo‐switchable membrane based on templated liquid crystals is presented. Crosslinking of a columnar network, formed by the self‐assembly of a discotic supramolecular complex with a photo‐responsive moiety, results in a switchable filtration membrane. The azo groups in the membrane undergo a photoinduced trans‐cis isomerization by irradiation with 365 nm light and relax back to the cis isomer with a lifetime of 5.7 h or within a few minutes by irradiation at 455 nm. The membranes have a light‐induced reversible change in the water permeability and molecular weight cut off of poly (ethylene glycol). The effective pore size of the trans isomer (1.2 nm) increases to 1.4 nm for the cis isomer. Rejection of the organic dye Rhodamine B is reversibly switched between 50 and 85% by alternating irradiation at 365 nm and 455 nm. The reversible and specific switching demonstrates the potential of this system for light‐controlled separation in nanoporous membranes.

The design of photo-responsive supramolecular hydrogels based on coumarin dimerization and de-dimerization is described. The photo-responsive coumarin unit is chemically incorporated into an oligo(ethylene glycol) (OEG) bis-urea amphiphile that is capable of co-assembling with non-functionalized OEG amphiphile, to form supramolecular fibers. UV light with two different wavelengths (365 nm and 254 nm) is employed to induce a photo-reversible dimerization and de-dimerization process of coumarin units, respectively. The co-assembled solutions could be photo-crosslinked to induce a sol-to-gel transition through dimerization of coumarin with 365 nm UV light, and de-dimerization occurs with 254 nm UV light, to provide a weaker gel. In this system, the mechanical strength of supramolecular hydrogels can be tuned using the irradiation time, providing precise control of gelation in a supramolecular hydrogelator.