Structural Color from Cellulose Nanocrystals or Chitin Nanocrystals: Self-Assembly, Optics, and Applications.

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.

Angle-resolved optical spectroscopy of photonic cellulose nanocrystal films reveals the influence of additives on the mechanism of kinetic arrest.

Cellulose nanocrystals (CNCs) are rod-like nanoparticles whose chiral self-assembly into photonic films has been promoted as a sustainable source of colouration. Upon drying, an aqueous CNC suspension passes through two regimes: first, a liquid phase, where the CNCs self-organise into a cholesteric liquid crystal, followed by a kinetically-arrested phase, where the helicoidal structure compresses upon loss of solvent, resulting in a solid film with vibrant structural colour. The transition between these two regimes plays an important role in the visual appearance of photonic CNC films, but details on when and how kinetic arrest occurs have remained elusive. In this work, we combine angle-resolved optical spectroscopy of photonic films (approx. 100 vol% CNC) with a model for compressed helicoidal structures to retrieve the suspension conditions during kinetic arrest (approx. 10 vol% CNC). This analysis indicates a shift in the mechanism of kinetic arrest from a glass transition at lower ionic strength to gelation at higher ionic strength, explaining the trends in domain size and film colour. In contrast, neutral additives (glucose, poly(ethylene glycol)) appear to primarily reduce the compression upon drying without affecting cholesteric behaviour, as supported by a general analytical model. These findings deepen our understanding of CNC co-assembly with various commonly-used additives, enabling better control over the production of multifunctional structurally coloured materials.

Large-scale fabrication of structurally coloured cellulose nanocrystal films and effect pigments.

Cellulose nanocrystals are renewable plant-based colloidal particles capable of forming photonic films by solvent-evaporation-driven self-assembly. So far, the cellulose nanocrystal self-assembly process has been studied only at a small scale, neglecting the limitations and challenges posed by the continuous deposition processes that are required to exploit this sustainable material in an industrial context. Here, we addressed these limitations by using roll-to-roll deposition to produce large-area photonic films, which required optimization of the formulation of the cellulose nanocrystal suspension and the deposition and drying conditions. Furthermore, we showed how metre-long structurally coloured films can be processed into effect pigments and glitters that are dispersible, even in water-based formulations. These promising effect pigments are an industrially relevant cellulose-based alternative to current products that are either micro-polluting (for example, non-biodegradable microplastic glitters) or based on carcinogenic, unsustainable or unethically sourced compounds (for example, titania or mica).

Electrohydrodynamic convection instabilities observed in suspensions of cellulose nanocrystals.

Cellulose nanocrystals are slender, negatively charged nanoparticles that spontaneously form a cholesteric liquid crystal in aqueous suspension above a critical concentration. When they are suspended in apolar solvents such as toluene using surfactants, the application of an AC electric field leads to the reorientation and then distortion of the cholesteric order until the cholesteric structure completely unwinds into a nematic-like order, typically above 0.4-0.6 kV/cm at 1kHz. In this work, we show that at much higher electric fields (≥ 4.6 kV/cm at 1 kHz) the sample develops a periodic pattern that varies with the field amplitude. We ascribed this pattern to electrohydrodynamic convection instabilities. These instabilities usually present complex regimes varying with the field, the voltage, the frequency and the geometry. However, the typical geometry where these instabilities were most documented across the literature differs from the geometry used in this work. This work concludes with possible future experimental investigations to clarify the exact regime of instability responsible for these observations. Supplementary Information: The online version contains supplementary material available at 10.1007/s10570-023-05391-6.

Modeling the cholesteric pitch of apolar cellulose nanocrystal suspensions using a chiral hard-bundle model.

Cellulose nanocrystals (CNCs) are naturally sourced elongated nanocolloids that form cholesteric phases in water and apolar solvents. It is well accepted that CNCs are made of bundles of crystalline microfibrils clustered side-by-side, and there is growing evidence that each individual microfibril is twisted. Yet, the origin of the chiral interactions between CNCs remains unclear. In this work, CNCs are described with a simple model of chiral hard splinters, enabling the prediction of the pitch using density functional theory and Monte Carlo simulations. The predicted pitch P compares well with experimental observations in cotton-based CNC dispersions in apolar solvents using surfactants but also with qualitative trends caused by fractionation or tip sonication in aqueous suspensions. These results suggest that the bundle shape induces an entropy-driven chiral interaction between CNCs, which is the missing link in explaining how chirality is transferred from the molecular scale of cellulose chains to the cholesteric order.

Small-Angle Neutron Scattering Reveals the Structural Details of Thermosensitive Polymer-Grafted Cellulose Nanocrystal Suspensions.

Thanks to the use of small-angle neutron scattering (SANS), a detailed structural description of thermosensitive polymer-grafted cellulose nanocrystals (CNCs) was obtained and the behavior of aqueous suspensions of these derivatized biosourced particles upon temperature increase was revealed. Although literature data show that the surface grafting of thermosensitive polymers drastically enhances the colloidal properties of CNCs, direct space microscopic investigation techniques fail in providing sufficient structural information on these objects. In the case of CNCs decorated with temperature-sensitive polyetheramines following a peptide coupling reaction, a qualitative and quantitative analysis of SANS spectra shows that CNCs are homogeneously covered by a shell comprising polymer chains in a Gaussian conformation with a thickness equal to their radius of gyration in solution, thus revealing a mushroom regime. An increase of the temperature above the lower critical solution temperature (LCST) of the polyetheramine results in the formation of finite size bundles whose aggregation number depends on the particle concentration and suspension temperature deviation from the LCST. SANS analysis further reveals local changes at the CNC surface corresponding to a release of water molecules and a related denser polymer shell conformation. Noticeably, data show a full reversibility at all length scales when a sample was cooled down to below the LCST after being heated above it. Overall, the results obtained by SANS allow an in-depth structural investigation of derivatized CNCs, which is of high interest for the design of functional materials comprising these biosourced colloids.

Controlling the Self-Assembly Behavior of Aqueous Chitin Nanocrystal Suspensions.

As with many other biosourced colloids, chitin nanocrystals (ChNCs) can form liquid crystalline phases with chiral nematic ordering. In this work, we demonstrate that it is possible to finely tune the liquid crystalline behavior of aqueous ChNC suspensions finely. Such control was made possible by carefully studying how the hydrolysis conditions and suspension treatments affect the colloidal and self-assembly properties of ChNCs. Specifically, we systematically investigated the effects of duration and acidity of chitin hydrolysis required to extract ChNCs, as well as the effects of the tip sonication energy input, degree of acetylation, pH and ionic strength. Finally, we show that by controlled water evaporation, it is possible to retain and control the helicoidal ordering in dry films, leading to a hierarchical architecture analogous to that found in nature, e.g. in crab shells. We believe that this work serves as a comprehensive insight into ChNC preparation and handling which is required to unlock the full potential of this material in both a scientific and industrial context.

Bioinspired Photonic Materials from Cellulose: Fabrication, Optical Analysis, and Applications.

Polysaccharides are a class of biopolymers that are widely exploited in living organisms for a diversity of applications, ranging from structural reinforcement to energy storage. Among the numerous types of polysaccharides found in the natural world, cellulose is the most abundant and widespread, as it is found in virtually all plants. Cellulose is typically organized into nanoscale crystalline fibrils within the cell wall to give structural integrity to plant tissue. However, in several species, such fibrils are organized into helicoidal nanostructures with a periodicity comparable to visible light (i.e., in the range 250-450 nm), resulting in structural coloration. As such, when taking bioinspiration as a design principle, it is clear that helicoidal cellulose architectures are a promising approach to developing sustainable photonic materials. Different forms of cellulose-derived materials have been shown to produce structural color by exploiting self-assembly processes. For example, crystalline nanoparticles of cellulose can be extracted from natural sources, such as cotton or wood, by strong acid hydrolysis. Such "cellulose nanocrystals" (CNCs) have been shown to form colloidal suspensions in water that can spontaneously self-organize into a cholesteric liquid crystal phase, mimicking the natural helicoidal architecture. Upon drying, this nanoscale ordering can be retained into the solid state, enabling the specific reflection of visible light. Using this approach, colors from across the entire visible spectrum can be produced, alongside striking visual effects such as iridescence or a metallic shine. Similarly, polymeric cellulose derivatives can also organize into a cholesteric liquid crystal. In particular, edible hydroxypropyl cellulose (HPC) is known to produce colorful mesophases at high concentrations in water (ca. 60-70 wt %). This solution state behavior allows for interesting visual effects such as mechanochromism (enabling its use in low-cost colorimetric pressure or strain sensors), while trapping the structure into the solid state enables the production of structurally colored films, particles and 3D printed objects. In this article, we summarize the state-of-the-art for CNC and HPC-based photonic materials, encompassing the underlying self-assembly processes, strategies to design their photonic response, and current approaches to translate this burgeoning green technology toward commercial application in a wide range of sectors, from packaging to cosmetics and food. This overview is supported by a summary of the analytical techniques required to characterize these photonic materials and approaches to model their optical response. Finally, we present several unresolved scientific questions and outstanding technical challenges that the wider community should seek to address to develop these sustainable photonic materials.

Cellulose photonic pigments.

When pursuing sustainable approaches to fabricate photonic structures, nature can be used as a source of inspiration for both the nanoarchitecture and the constituent materials. Although several biomaterials have been promised as suitable candidates for photonic materials and pigments, their fabrication processes have been limited to the small to medium-scale production of films. Here, by employing a substrate-free process, structurally coloured microparticles are produced via the confined self-assembly of a cholesteric cellulose nanocrystal (CNC) suspension within emulsified microdroplets. Upon drying, the droplets undergo multiple buckling events, which allow for greater contraction of the nanostructure than predicted for a spherical geometry. This buckling, combined with a solvent or thermal post-treatment, enables the production of dispersions of vibrant red, green, and blue cellulose photonic pigments. The hierarchical structure of these pigments enables the deposition of coatings with angular independent colour, offering a consistent visual appearance across a wide range of viewing angles.

Chiral self-assembly of cellulose nanocrystals is driven by crystallite bundles.

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.

Revealing the Structural Coloration of Self-Assembled Chitin Nanocrystal Films.

The structural coloration of arthropods often arises from helicoidal structures made primarily of chitin. Although it is possible to achieve analogous helicoidal architectures by exploiting the self-assembly of chitin nanocrystals (ChNCs), to date no evidence of structural coloration has been reported from such structures. Previous studies are identified to have been constrained by both the experimental inability to access sub-micrometer helicoidal pitches and the intrinsically low birefringence of crystalline chitin. To expand the range of accessible pitches, here, ChNCs are isolated from two phylogenetically distinct sources of α-chitin, namely fungi and shrimp, while to increase the birefringence, an in situ alkaline treatment is performed, increasing the intensity of the reflected color by nearly two orders of magnitude. By combining this treatment with precise control over ChNC suspension formulation, structurally colored chitin-based films are demonstrated with reflection tunable from blue to near infrared.

Effect of thermal treatments on chiral nematic cellulose nanocrystal films.

The ability to manipulate the optical appearance of materials is essential in virtually all products and areas of technology. Structurally coloured chiral nematic cellulose nanocrystal (CNC) films proved to be an excellent platform to design optical appearance, as their response can be moulded by organising them in hierarchical architectures. Here, we study how thermal treatments influence the optical appearance of structurally coloured CNC films. We demonstrate that the CNCs helicoidal architecture and the chiral optical response can be maintained up to 250 °C after base treatment and cross-linking with glutaraldehyde, while, alternatively, an exposure to vacuum allows for the helicoidal arrangement to be further preserved up to 900 °C, thus producing aromatic chiral carbon. The ability to retain the helicoidal arrangement, and thus the visual appearance, in CNC films up to 250 °C is highly desirable for high temperature colour-based industrial applications and for passive colorimetric heat sensors. Similarly, the production of chiral carbon provides a new type of conductive carbon for electrochemical applications.

Hyperspectral Imaging of Photonic Cellulose Nanocrystal Films: Structure of Local Defects and Implications for Self-Assembly Pathways.

Cellulose nanocrystals (CNCs) can spontaneously assemble into chiral nematic films capable of reflecting circularly polarized light in the visible range. As many other photonic materials obtained by bottom-up approaches, CNC films often display defects that greatly impact their visual appearance. Here, we study the optical response of defects in photonic CNC films, coupling optical microscopy with hyperspectral imaging, and we compare it to optical simulations of discontinuous cholesteric structures of increasing complexity. Cross-sectional SEM observations of the film structure guided the choice of simulation parameters and showed excellent agreement with experimental optical patterns. More importantly, it strongly suggests that the last fraction of CNCs to self-assemble, upon solvent evaporation, does not undergo the typical nucleation and growth pathway, but a spinodal decomposition, an alternative self-assembly pathway so far overlooked in cast films and that can have far-reaching consequences on choices of CNC sources and assembly conditions.

Retrieving the Coassembly Pathway of Composite Cellulose Nanocrystal Photonic Films from their Angular Optical Response.

Aqueous suspensions of cellulose nanocrystals (CNCs) are known to self-assemble into a chiral nematic liquid crystalline phase, leading to solid-state nanostructured colored films upon solvent evaporation, even in the presence of templating agents. The angular optical response of these structures, and therefore their visual appearance, are completely determined by the spatial arrangement of the CNCs when the drying suspension undergoes a transition from a flowing and liquid crystalline state to a kinetically arrested state. Here, it is demonstrated how the angular response of the final film allows for retrieval of key physical properties and the chemical composition of the suspension at the onset of the kinetic arrest, thus capturing a snapshot of the past. To illustrate this methodology, a dynamically evolving sol-gel coassembly process is investigated by adding various amounts of organosilica precursor, namely, 1,2-bis(trimethoxysilyl)ethane. The influence of organosilica condensation on the kinetic arrest can be tracked and thus explains the angular response of the resulting films. The a posteriori and in situ approach is general; it can be applied to a variety of additives in CNC-based films and it allows access to key rheological information of the suspension without using any dedicated rheological technique.

Cellulose Nanocrystal-Templated Tin Dioxide Thin Films for Gas Sensing.

Porous tin dioxide is an important low-cost semiconductor applied in electronics, gas sensors, and biosensors. Here, we present a versatile template-assisted synthesis of nanostructured tin dioxide thin films using cellulose nanocrystals (CNCs). We demonstrate that the structural features of CNC-templated tin dioxide films strongly depend on the precursor composition. The precursor properties were studied by using low-temperature nuclear magnetic resonance spectroscopy of tin tetrachloride in solution. We demonstrate that it is possible to optimize the precursor conditions to obtain homogeneous precursor mixtures and therefore highly porous thin films with pore dimensions in the range of 10-20 nm (ABET = 46-64 m2 g-1, measured on powder). Finally, by exploiting the high surface area of the material, we developed a resistive gas sensor based on CNC-templated tin dioxide. The sensor shows high sensitivity to carbon monoxide (CO) in ppm concentrations and low cross-sensitivity to humidity. Most importantly, the sensing kinetics are remarkably fast; both the response to the analyte gas and the signal decay after gas exposure occur within a few seconds, faster than in standard SnO2-based CO sensors. This is attributed to the high gas accessibility of the very thin porous film.

The angular optical response of cellulose nanocrystal films explained by the distortion of the arrested suspension upon drying.

Cellulose nanocrystals (CNCs) are bio-sourced chiral nanorods that can form stable colloidal suspensions able to spontaneously assemble above a critical concentration into a cholesteric liquid crystal, with a cholesteric pitch usually in the micron range. When these suspensions are dried on a substrate, solid films with a pitch of the order of few hundreds of nanometers can be produced, leading to intense reflection in the visible range. However, the resulting cholesteric nanostructure is usually not homogeneous within a sample and comports important variations of the cholesteric domain orientation and pitch, which affect the photonic properties. In this work, we first propose a model accounting for the formation of the photonic structure from the vertical compression of the cholesteric suspension upon solvent evaporation, starting at the onset of the kinetic arrest of the drying suspension and ending when solvent evaporation is complete. From that assumption, various structural features of the films can be derived, such as the variation of the cholesteric pitch with the domain tilt, the orientation distribution density of the final cholesteric domains and the distortion of the helix from the unperturbed cholesteric case. The angular-resolved optical response of such films is then derived, including the iridescence and the generation of higher order reflection bands, and a simulation of the angular optical response is provided, including its tailoring under external magnetic fields. Second, we conducted an experimental investigation of CNC films covering a structural and optical analysis of the films. The macroscopic appearance of the films is discussed and complemented with angular-resolved optical spectroscopy, optical and electron microscopy, and our quantitative analysis shows an excellent agreement with the proposed model. This allows us to access the precise composition and the pitch of the suspension when it transited into a kinetically arrested phase directly from the optical analysis of the film. This work highlights the key role that the anisotropic compression of the kinetically arrested state plays in the formation of CNC films and is relevant to the broader case of structure formation in cast dispersions and colloidal self-assembly upon solvent evaporation.

Visual Appearance of Chiral Nematic Cellulose-Based Photonic Films: Angular and Polarization Independent Color Response with a Twist.

Hydroxypropyl cellulose (HPC) is a biocompatible cellulose derivative capable of self-assembling into a lyotropic chiral nematic phase in aqueous solution. This liquid crystalline phase reflects right-handed circular polarized light of a specific color as a function of the HPC weight fraction. Here, it is demonstrated that, by introducing a crosslinking agent, it is possible to drastically alter the visual appearance of the HPC mesophase in terms of the reflected color, the scattering distribution, and the polarization response, resulting in an exceptional matte appearance in solid-state films. By exploiting the interplay between order and disorder, a robust and simple methodology toward the preparation of polarization and angular independent color is developed, which constitutes an important step toward the development of real-world photonic colorants.

The Self-Assembly of Cellulose Nanocrystals: Hierarchical Design of Visual Appearance.

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.

Controlling the Photonic Properties of Cholesteric Cellulose Nanocrystal Films with Magnets.

The self-assembly of cellulose nanocrystals is a powerful method for the fabrication of biosourced photonic films with a chiral optical response. While various techniques have been exploited to tune the optical properties of such systems, the presence of external fields has yet to be reported to significantly modify their optical properties. In this work, by using small commercial magnets (≈ 0.5-1.2 T) the orientation of the cholesteric domains is enabled to tune in suspension as they assemble into films. A detailed analysis of these films shows an unprecedented control of their angular response. This simple and yet powerful technique unlocks new possibilities in designing the visual appearance of such iridescent films, ranging from metallic to pixelated or matt textures, paving the way for the development of truly sustainable photonic pigments in coatings, cosmetics, and security labeling.

Dynamically Controlled Iridescence of Cholesteric Cellulose Nanocrystal Suspensions Using Electric Fields.

Cellulose nanocrystal suspensions in apolar solvent spontaneously form iridescent liquid-crystalline phases but the control of their macroscopic order is usually poor. The use of electric fields can provide control on the cholesteric orientation and its periodicity, allowing macroscopic sample homogeneity and dynamical tuning of their iridescent hues, and is demonstrated here.