Search

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.

Funder: Chinese Scholarship Council : Cambridge Scholarship, Funder: Croucher Foundation : Cambridge International Scholarship, Hydroxypropyl cellulose (HPC) is a widely commercialized cellulose derivative. While it is typically used as a binder or stabilizer for foods and pharmaceuticals, it can also form a cholesteric liquid crystal in aqueous solution. Moreover, at high HPC concentrations this lyotropic and thermotropic mesophase is known to reflect structural color. However, it remains a challenge to retain this vibrant coloration into the solid state. Here, by combining the emulsification of a HPC mesophase with drying at elevated temperature, we produce solid microparticles that can reflect color across the visible spectrum, from blue to green and red. This method provides a facile and scalable pathway to fabricate structurally colored, edible pigments, which can displace existing synthetic additives used in a wide range of foods and cosmetics.

Funder: Emil Aaltosen Säätiö; Id: http://dx.doi.org/10.13039/501100004756, To unlock the widespread use of block copolymers as photonic pigments, there is an urgent need to consider their environmental impact (cf. microplastic pollution). Here we show how an inverse photonic glass architecture can enable the use of biocompatible bottlebrush block copolymers (BBCPs), which otherwise lack the refractive index contrast needed for a strong photonic response. A library of photonic pigments is produced from poly(norbornene‐graft‐polycaprolactone)‐block‐poly(norbornene‐graft‐polyethylene glycol), with the color tuned via either the BBCP molecular weight or the processing temperature upon microparticle fabrication. The structure–optic relationship between the 3D porous morphology of the microparticles and their complex optical response is revealed by both an analytical scattering model and 3D finite‐difference time domain (FDTD) simulations. Combined, this allows for strategies to enhance the color purity to be proposed and realized with our biocompatible BBCP system.

Block copolymer self-assembly has proven to be an effective route for the fabrication of photonic films and, more recently, photonic pigments. However, despite extensive research on this topic over the past two decades, the palette of monomers and polymers employed to produce such structurally colored materials has remained surprisingly limited. In this perspective, we summarize the commonly used block copolymer systems in the literature (considering both linear and brush architectures) and rationalize their use from the point of view of both their historical development and physicochemical constraints. Finally, the current challenges facing the field are discussed and promising new areas of research are highlighted to inspire the community to pursue new directions., The European Research Council [ERC-2014-STG H2020 639088; ERC-2017-POC 790518] The Biotechnology and Biological Science Research Council [BBSRC David Phillips Fellowship BB/K014617/1; BB/V00364X/1] The Engineering and Physical Sciences Research Council [EPSRC EP/N016920/1; EP/R511675/1] The Royal Society [IE160420] CSC Cambridge Scholarship Croucher Cambridge International Scholarship.

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, we demonstrate 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 dry solid-state films. By exploiting the interplay between order and disorder, a robust and simple methodology towards the preparation of polarization and angular independent color was developed, which constitutes an important step towards the development of real-world photonic colorants., This work is funded by EPSRC grant EP/R511675/1 to B.F.-P., S.V.; by EPSRC grant EP/L016087/1 to C.A.W.; by BBSRC David Phillips fellowship BB/K014617/1 to G.J., S.V.; by EU’s Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant agreement No. 722842 (ITN Plant-inspired Materials and Surfaces – PlaMatSu) to G.T.K., S.V.; by Swiss National Science Foundation #165176 to R.V.; by Croucher Cambridge International Scholarship to C.L.C.C.; by ERC grant ERC 2014 STG H2020 639088 to M.M.B., G.J., S.V.; by ERC grant ERC 2017 POC 790518 to R.M.P., S.V.

Rational design of molecular acceptors for non-fullerene organic solar cells remains challenging. Here we show that the introduction of two simple methyl groups on a bithiophene-bridged perylene diimide dimer leads to two molecular acceptors with distinctly different properties and solar cell performance. This work contributes towards understanding the structure–performance relationship of high-performance molecular acceptors.