Self-assembly of polymeric supramolecules is a powerful tool for producing functional materials that combine several properties and may respond to external conditions. We illustrate the concept using a comb-shaped architecture. Examples include the hexagonal self-organization of conjugated conducting polymers and the polarized luminance in solid-state films of rodlike polymers obtained by removing the hydrogen-bonded side chains from the aligned thermotropic smectic phase. Hierarchically structured materials obtained by applying different self-organization and recognition principles and directed assembly form a basis for tunable nanoporous materials, smart membranes, preparation of nano-objects, and anisotropic properties, such as proton conductivity.

There is an emerging quest for lightweight materials with excellent mechanical properties and economic production, while still being sustainable and functionalizable. They could form the basis of the future bioeconomy for energy and material efficiency. Cellulose has long been recognized as an abundant polymer. Modified celluloses were, in fact, among the first polymers used in technical applications; however, they were later replaced by petroleum‐based synthetic polymers. Currently, there is a resurgence of interest to utilize renewable resources, where cellulose is foreseen to make again a major impact, this time in the development of advanced materials. This is because of its availability and properties, as well as economic and sustainable production. Among cellulose‐based structures, cellulose nanofibrils and nanocrystals display nanoscale lateral dimensions and lengths ranging from nanometers to micrometers. Their excellent mechanical properties are, in part, due to their crystalline assembly via hydrogen bonds. Owing to their abundant surface hydroxyl groups, they can be easily modified with nanoparticles, (bio)polymers, inorganics, or nanocarbons to form functional fibers, films, bulk matter, and porous aerogels and foams. Here, some of the recent progress in the development of advanced materials within this rapidly growing field is reviewed.

Recently it was shown that enzymatic and mechanical processing of macroscopic cellulose fibers lead to disintegration of long and entangled native cellulose I nanofibers in order to form mechanically strong aqueous gels (Pääkkö et al., Biomacromolecules, 2007, 8, 1934). Here we demonstrate that (1) such aqueous nanofibrillar gels are unexpectedly robust to allow formation of highly porous aerogels by direct water removal by freeze-drying, (2) they are flexible, unlike most aerogels that suffer from brittleness, and (3) they allow flexible hierarchically porous templates for functionalities, e.g. for electrical conductivity. No crosslinking, solvent exchange nor supercritical drying are required to suppress the collapse during the aerogel preparation, unlike in typical aerogel preparations. The aerogels show a high porosity of ∼98% and a very low density of ca. 0.02 g cm⁻³. The flexibility of the aerogels manifests as a particularly high compressive strain of ca. 70%. In addition, the structure of the aerogels can be tuned from nanofibrillar to sheet-like skeletons with hierarchical micro- and nanoscale morphology and porosity by modifying the freeze-drying conditions. The porous flexible aerogel scaffold opens new possibilities for templating organic and inorganic matter for various functionalities. This is demonstrated here by dipping the aerogels in an electrically conducting polyaniline–surfactant solution which after rinsing off the unbound conducting polymer and drying leads to electrically conducting flexible aerogels with relatively high conductivity of around 1 × 10⁻² S cm⁻¹. More generally, we foresee a wide variety of functional applications for highly porous flexible biomatter aerogels, such as for selective delivery/separation, tissue-engineering, nanocomposites upon impregnation by polymers, and other medical and pharmaceutical applications.