By controlling the interaction of biological building blocks at the nanoscale, natural photonic nanostructures have been optimized to produce intense coloration. Inspired by such biological nanostructures, the possibility to design the visual appearance of a material by guiding the hierarchical self‐assembly of its constituent components, ideally using natural materials, is an attractive route for rationally designed, sustainable manufacturing. Within the large variety of biological building blocks, cellulose nanocrystals are one of the most promising biosourced materials, primarily for their abundance, biocompatibility, and ability to readily organize into photonic structures. Here, the mechanisms underlying the formation of iridescent, vividly colored materials from colloidal liquid crystal suspensions of cellulose nanocrystals are reviewed and recent advances in structural control over the hierarchical assembly process are reported as a toolbox for the design of sophisticated optical materials.

Widespread concerns over the impact of human activity on the environment have resulted in a desire to replace artificial functional materials with naturally derived alternatives. As such, polysaccharides are drawing increasing attention due to offering a renewable, biodegradable, and biocompatible feedstock for functional nanomaterials. In particular, nanocrystals of cellulose and chitin have emerged as versatile and sustainable building blocks for diverse applications, ranging from mechanical reinforcement to structural coloration. Much of this interest arises from the tendency of these colloidally stable nanoparticles to self-organize in water into a lyotropic cholesteric liquid crystal, which can be readily manipulated in terms of its periodicity, structure, and geometry. Importantly, this helicoidal ordering can be retained into the solid-state, offering an accessible route to complex nanostructured films, coatings, and particles. In this review, the process of forming iridescent, structurally colored films from suspensions of cellulose nanocrystals (CNCs) is summarized and the mechanisms underlying the chemical and physical phenomena at each stage in the process explored. Analogy is then drawn with chitin nanocrystals (ChNCs), allowing for key differences to be critically assessed and strategies toward structural coloration to be presented. Importantly, the progress toward translating this technology from academia to industry is summarized, with unresolved scientific and technical questions put forward as challenges to the community.

Complex hierarchical architectures are ubiquitous in nature. By designing and controlling the interaction between elementary building blocks, nature is able to optimize a large variety of materials with multiple functionalities. Such control is, however, extremely challenging in man-made materials, due to the difficulties in controlling their interaction at different length scales simultaneously. Here, hierarchical cholesteric architectures are obtained by the self-assembly of cellulose nanocrystals within shrinking, micron-sized aqueous droplets. This confined, spherical geometry drastically affects the colloidal self-assembly process, resulting in concentric ordering within the droplet, as confirmed by simulation. This provides a quantitative tool to study the interactions of cellulose nanocrystals beyond what has been achieved in a planar geometry. Our developed methodology allows us to fabricate truly hierarchical solid-state architectures from the nanometer to the macroscopic scale using a renewable and sustainable biopolymer.

Microencapsulation is a fundamental concept behind a wide range of daily applications ranging from paints, adhesives, and pesticides to targeted drug delivery, transport of vaccines, and self-healing concretes. The beauty of microfluidics to generate microcapsules arises from the capability of fabricating monodisperse and micrometer-scale droplets, which can lead to microcapsules/particles with fine-tuned control over size, shape, and hierarchical structure, as well as high reproducibility, efficient material usage, and high-throughput manipulation. The introduction of supramolecular chemistry, such as host–guest interactions, endows the resultant microcapsules with stimuli-responsiveness and self-adjusting capabilities, and facilitates hierarchical microstructures with tunable stability and porosity, leading to the maturity of current microencapsulation industry. Supramolecular architectures and materials have attracted immense attention over the past decade, as they open the possibility to obtain a large variety of aesthetically pleasing structures, with myriad applications in biomedicine, energy, sensing, catalysis, and biomimicry, on account of the inherent reversible and adaptive nature of supramolecular interactions. As a subset of supramolecular interactions, host–guest molecular recognition involves the formation of inclusion complexes between two or more moieties, with specific three-dimensional structures and spatial arrangements, in a highly controllable and cooperative manner. Such highly selective, strong yet dynamic interactions could be exploited as an alternative methodology for programmable and controllable engineering of supramolecular architectures and materials, exploiting reversible interactions between complementary components. Through the engineering of molecular structures, assemblies can be readily functionalized based on host–guest interactions, with desirable physicochemical characteristics. In this Account, we summarize the current state of development in the field of monodisperse supramolecular microcapsules, fabricated through the integration of traditional microfluidic techniques and interfacial host–guest chemistry, specifically cucurbit[n]uril (CB[n])-mediated host–guest interactions. Three different strategies, colloidal particle-driven assembly, interfacial condensation-driven assembly and electrostatic interaction-driven assembly, are classified and discussed in detail, presenting the methodology involved in each microcapsule formation process. We highlight the state-of-the-art in design and control over structural complexity with desirable functionality, as well as promising applications, such as cargo delivery stemming from the assembled microcapsules. On account of its dynamic nature, the CB[n]-mediated host–guest complexation has demonstrated efficient response toward various external stimuli such as UV light, pH change, redox chemistry, and competitive guests. Herein, we also demonstrate different microcapsule modalities, which are engineered with CB[n] host–guest chemistry and also can be disrupted with the aid of external stimuli, for triggered release of payloads. In addition to the overview of recent achievements and current limitations of these microcapsules, we finally summarize several perspectives on tunable cargo loading and triggered release, directions, and challenges for this technology, as well as possible strategies for further improvement, which will lead to substainitial progress of host–guest chemistry in supramolecular architectures and materials.

The transfer of chirality across length-scales is an intriguing and universal natural phenomenon. However, connecting the properties of individual building blocks to the emergent features of their resulting large-scale structure remains a challenge. In this work, we investigate the origins of mesophase chirality in cellulose nanocrystal suspensions, whose self-assembly into chiral photonic films has attracted significant interest. By correlating the ensemble behaviour in suspensions and films with a quantitative morphological analysis of the individual nanoparticles, we reveal an inverse relationship between the cholesteric pitch and the abundance of laterally-bound composite particles. These ‘bundles’ thus act as colloidal chiral dopants, analogous to those used in molecular liquid crystals, providing the missing link in the hierarchical transfer of chirality from the molecular to the colloidal scale.