Cellulose nanocrystals (CNCs), known for more than 50 years, have attracted attention because of their unique properties such as high specific strength and modulus, high surface area, and fascinating optical properties. Just recently, however, their potential in supramolecular templating was identified by making use of their self-assembly behavior in aqueous dispersions in the presence of compatible precursors. The combination of the mesoporosity, photonic properties, and chiral nematic order of the materials, which are available as freestanding films, has led to a significant number of interesting and promising discoveries towards new functional materials. This Review summarizes the use of cellulose derivatives, especially CNCs, as novel templates and gives an overview of the recent developments toward new functional materials.
Cellulose nanocrystals (CNCs) are obtained from the sulfuric acid-catalyzed hydrolysis of bulk cellulose. The nanocrystals have diameters of ~5-15 nm and lengths of ~100-300 nm (depending on the cellulose source and hydrolysis conditions). This lightweight material has mostly been investigated to reinforce composites and polymers because it has remarkable strength that rivals carbon nanotubes. But CNCs have an additional, less explored property: they organize into a chiral nematic (historically referred to as cholesteric) liquid crystal in water. When dried into a thin solid film, the CNCs retain the helicoidal chiral nematic order and assemble into a layered structure where the CNCs have aligned orientation within each layer, and their orientation rotates through the stack with a characteristic pitch (repeating distance). The cholesteric ordering can act as a 1-D photonic structure, selectively reflecting circularly polarized light that has a wavelength nearly matching the pitch. During CNC self-assembly, it is possible to add sol-gel precursors, such as Si(OMe)4, that undergo hydrolysis and condensation as the solvent evaporates, leading to a chiral nematic silica/CNC composite material. Calcination of the material in air destroys the cellulose template, leaving a high surface area mesoporous silica film that has pore diameters of ~3-10 nm. Importantly, the silica is brilliantly iridescent because the pores in its interior replicate the chiral nematic structure. These films may be useful as optical filters, reflectors, and membranes. In this Account, we describe our recent research into mesoporous films with chiral nematic order. Taking advantage of the chiral nematic order and nanoscale of the CNC templates, new functional materials can be prepared. For example, heating the silica/CNC composites under an inert atmosphere followed by removal of the silica leaves highly ordered, mesoporous carbon films that can be used as supercapacitor electrodes. The composition of the mesoporous films can be varied by using assorted organosilica precursors. After removal of the cellulose by acid-catalyzed hydrolysis, highly porous, iridescent organosilica films are obtained. These materials are flexible and offer the ability to tune the chemical and mechanical properties through variation of the organic spacer. Chiral nematic mesoporous silica and organosilica materials, obtainable as centimeter-scale freestanding films, are interesting hosts for nanomaterials. When noble metal nanoparticles are incorporated into the pores, they show strong circular dichroism signals associated with their surface plasmon resonances that arise from dipolar coupling of the particles within the chiral nematic host. Fluorescent conjugated polymers show induced circular dichroism spectra when encapsulated in the chiral nematic host. The porosity, film structure, and optical properties of these materials could enable their use in sensors. We describe the development of chiral nematic mesoporous silica and organosilica, demonstrate different avenues...
Anion-π interactions, intuitively repulsive forces, turned from controversial to a well-established non-covalent interaction over the past quarter of a century. Within this time frame the question "Anion-π interactions. Do they exist?" could be answered and even more importantly its functional relevance was proven. The present feature article summarizes the experimental findings of anion-π studies in the gas phase, solution and in the solid state and highlights the application of anion-π interactions in anion recognition, sensing and transport as well as in catalysis. Moreover, the biochemical relevance of this weak intermolecular force is comprehensively reviewed.
Cellulose-based materials have been and continue to be exceptionally important for humankind. Considering the bioavailability and societal relevance of cellulose, turning this renewable resource into an active material is a vital step towards sustainability. Herein we report a new form of cellulose-derived material that combines tunable photonic properties with a unique mesoporous structure resulting from a new supramolecular cotemplating method. A composite of cellulose nanocrystals and a urea-formaldehyde resin organizes into a chiral nematic assembly, which yields a chiral nematic mesoporous continuum of desulfated cellulose nanocrystals after alkaline treatment. The mesoporous photonic cellulose (MPC) films undergo rapid and reversible changes in color upon swelling, and can be used for pressure sensing. These new active mesoporous cellulosic materials have potential applications in biosensing, optics, functional membranes, chiral separation, and tissue engineering.
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