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Microbial consortia are a promising alternative to monocultures of genetically modified microorganisms for complex biotransformations. We developed a versatile consortium-based strategy for the direct conversion of lignocellulose to short-chain fatty acids, which included the funneling of the lignocellulosic carbohydrates to lactate as a central intermediate in engineered food chains. A spatial niche enabled in situ cellulolytic enzyme production by an aerobic fungus next to facultative anaerobic lactic acid bacteria and the product-forming anaerobes. Clostridium tyrobutyricum , Veillonella criceti , or Megasphaera elsdenii were integrated into the lactate platform to produce 196 kilograms of butyric acid per metric ton of beechwood. The lactate platform demonstrates the benefits of mixed cultures, such as their modularity and their ability to convert complex substrates into valuable biochemicals., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Vivid colours found in living organisms are often the result of scattering from hierarchical nanostructures, where the interplay between order and disorder in their packing defines visual appearance. In the case of Flavobacterium IR1, the complex arrangement of the cells in polycrystalline three-dimensional lattices is found to be a distinctive fingerprint of colony organization. By combining analytical analysis of the angle-resolved scattering response of in vivo bacterial colonies with numerical modelling, we show that we can assess the inter-cell distance and cell diameter with a resolution below 10 nm, far better than what can be achieved with conventional electron microscopy, suffering from preparation artefacts. Retrieving the role of disorder at different length scales from the salient features in the scattering response enables a precise understanding of the structural organization of the bacteria.

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., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 ( A BET = 46-64 m 2 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 SnO 2 -based CO sensors. This is attributed to the high gas accessibility of the very thin porous film.

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., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A novel mediatorless photo-bioelectrochemical sensor operated with a biofilm of the cyanobacterium Synechocyst i s PCC6803 wt . for herbicide detection with long term stability (>20 days) was successfully developed and tested. Photoanodic current generation was obtained in the absence of artificial mediators. The inhibitory effect on photocurrent of three commonly used herbicides (i.e., atrazine, diuron, and paraquat) was used as a means of measuring their concentrations in aqueous solution. The injection of atrazine and diuron into the algal medium caused an immediate photocurrent drop due to the inhibition of photosynthetic electron transport. The detected concentrations were suitable for environmental analysis, as revealed by a comparison with the freshwater quality benchmarks set by the Environmental Protection Agency of the United States (US EPA). In contrast, paraquat caused an initial increase (~2 h) of the photocurrent effect of about 200%, as this compound can act as a redox mediator between the cells and the anode. A relatively long-term stability of the biosensor was demonstrated, by keeping anodes colonized with cyanobacterial biofilm in the dark at 4 °C. After 22 days of storage, the performance in terms of the photocurrent was comparable with the freshly prepared biosensor. This result was confirmed by the measurement of chlorophyll content, which demonstrated preservation of the cyanobacterial biofilm. The capacity of this biosensor to recover after a cold season or other prolonged environmental stresses could be a key advantage in field applications, such as in water bodies and agriculture. This study is a step forward in the biotechnological development and implementation of storable mediatorless electrochemical biosensors for herbicide detection., Competing Interests: The authors declare no conflict of interest

Both vertebrates and invertebrates commonly exploit photonic structures adjacent to their photoreceptors for visual benefits. For example, use of a reflecting structure (tapetum) behind the retina increases photon capture, enhancing vision in dim light [1-5]. Colored filters positioned lateral or distal to a photoreceptive unit may also be used to tune spectral sensitivity by selective transmission of wavelengths not absorbed or scattered by the filters [6-8]. Here we describe a new category of biological optical filter that acts simultaneously as both a transmissive spectral filter and narrowband reflector. Discovered in the larval eyes of only one family of mantis shrimp (stomatopod) crustaceans (Nannosquillidae), each crystalline structure bisects the photoreceptive rhabdom into two tiers and contains an ordered array of membrane-bound vesicles with sub-wavelength diameters of 153 ± 5 nm. Axial illumination of the intrarhabdomal structural reflector (ISR) in vivo produces a narrow band of yellow reflectance (mean peak reflectivity, 572 ± 18 nm). The ISR is similar to several synthetic devices, such as bandgap filters, laser mirrors, and (in particular) fiber Bragg gratings used in optical sensors for a wide range of industries. To our knowledge, the stomatopod larval ISR is the first example of a naturally occurring analog to these human-made devices. Considering what is known about these animals' visual ecology, we propose that these reflecting filters may help improve the detection of pelagic bioluminescence in shallow water at night. VIDEO ABSTRACT., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Many potential applications of monolayer transition metal dichalcogenides (TMDs) require both high photoluminescence (PL) yield and high electrical mobilities. However, the PL yield of as prepared TMD monolayers is low and believed to be limited by defect sites and uncontrolled doping. This has led to a large effort to develop chemical passivation methods to improve PL and mobilities. The most successful of these treatments is based on the nonoxidizing organic "superacid" bis(trifluoromethane)sulfonimide (TFSI) which has been shown to yield bright monolayers of molybdenum disulfide (MoS 2 ) and tungsten disulfide (WS 2 ) but with trap-limited PL dynamics and no significant improvements in field effect mobilities. Here, using steady-state and time-resolved PL microscopy we demonstrate that treatment of WS 2 monolayers with oleic acid (OA) can greatly enhance the PL yield, resulting in bright neutral exciton emission comparable to TFSI treated monolayers. At high excitation densities, the OA treatment allows for bright trion emission, which has not been demonstrated with previous chemical treatments. We show that unlike the TFSI treatment, the OA yields PL dynamics that are largely trap free. In addition, field effect transistors show an increase in mobilities with the OA treatment. These results suggest that OA serves to passivate defect sites in the WS 2 monolayers in a manner akin to the passivation of colloidal quantum dots with OA ligands. Our results open up a new pathway to passivate and tune defects in monolayer TMDs using simple "wet" chemistry techniques, allowing for trap-free electronic properties and bright neutral exciton and trion emission.

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.

Reaching the full potential of X-ray nanotomography, in particular for biological samples, is limited by many factors, of which one of the most serious is radiation damage. Although sample deformation caused by radiation damage can be partly mitigated by cryogenic protection, it is still present in these conditions and, as we exemplify here using a specimen extracted from scales of the Cyphochilus beetle, it will pose a limit to the achievable imaging resolution. We demonstrate a generalized tomographic model, which optimally follows the sample morphological changes and attempts to recover the original sample structure close to the ideal, damage-free reconstruction. Whereas our demonstration was performed using ptychographic X-ray tomography, the method can be adopted for any tomographic imaging modality. Our application demonstrates improved reconstruction quality of radiation-sensitive samples, which will be of increasing relevance with the higher brightness of 4th generation synchrotron sources.

Plasmonic metasurfaces are a promising route for flat panel display applications due to their full color gamut and high spatial resolution. However, this plasmonic coloration cannot be readily tuned and requires expensive lithographic techniques. Here, we present scalable electrically driven color-changing metasurfaces constructed using a bottom-up solution process that controls the crucial plasmonic gaps and fills them with an active medium. Electrochromic nanoparticles are coated onto a metallic mirror, providing the smallest-area active plasmonic pixels to date. These nanopixels show strong scattering colors and are electrically tunable across >100-nm wavelength ranges. Their bistable behavior (with persistence times exceeding hundreds of seconds) and ultralow energy consumption (9 fJ per pixel) offer vivid, uniform, nonfading color that can be tuned at high refresh rates (>50 Hz) and optical contrast (>50%). These dynamics scale from the single nanoparticle level to multicentimeter scale films in subwavelength thickness devices, which are a hundredfold thinner than current displays.

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.

Hierarchical, structurally colored materials offer a wide variety of visual effects that cannot be achieved with standard pigments or dyes. However, their fabrication requires simultaneous control over multiple length-scales. Here we introduce a robust strategy for the fabrication of hierarchical photonic pigments via the confined self-assembly of bottlebrush block copolymers within emulsified microdroplets. The bottlebrush block copolymer self-assembles into highly ordered concentric lamellae, giving rise to a near perfect photonic multilayer in the solid state, with reflectivity up to 100%. The reflected color can be readily tuned across the whole visible spectrum by either altering the molecular weight or by blending the bottlebrush block copolymers. Furthermore, the developed photonic pigments are responsive, with a selective and reversible color change observed upon swelling in different solvents. Our system is particularly suited for the scalable production of photonic pigments, arising from their rapid self-assembly mechanism and size-independent color.

Blue and near-ultraviolet structural colours have often been reported in understorey plants living in deep shade. While this intense blue coloration is very catchy to the eye of a human observer, there are cases in which structural colours can be hidden either by the scattered light interacting with pigments or because they are found in unexpected positions in the plants. Here, we show that the fronds of Microsorum thailandicum produce structural coloration on both the adaxial and abaxial epidermal surface. While cellulose helicoidal structures are responsible for this coloration in both epidermal layers, the reflected colours are consistently different: an intense blue reflection is found in the adaxial epidermis while red-shifted and less intense colours are observed in the abaxial epidermis, possibly suggesting photo-adaptation of the plant to the light environment. By comparing the optical properties of the fern with its anatomy we computed the theoretical reflection accounting for the presence of disorder in the cellulose helicoidal architecture., Competing Interests: We declare we have no competing interests.

The scattering strength of a random medium relies on the geometry and spatial distribution of its components as well as on their refractive index. Anisotropy can, therefore, play a major role in the optimization of the scattering efficiency in both biological and synthetic materials. In this study, we show that, by exploiting the coherent backscattering phenomenon, it is possible to characterize the optical anisotropy in Cyphochilus beetle scales without the need to change their orientation or their thickness. For this reason, such a static and easily accessible experimental approach is particularly suitable for the study of biological specimens. Moreover, estimation of the anisotropy in Cyphochilus beetle scales might provide inspiration for improving the scattering strength of artificial white materials., Competing Interests: We declare we have no competing interests.

Hydroxypropyl-cellulose (HPC), a derivative of naturally abundant cellulose, can self-assemble into helical nanostructures that lead to striking colouration from Bragg reflections. The helical periodicity is very sensitive to pressure, rendering HPC a responsive photonic material. Recent advances in elucidating these HPC mechano-chromic properties have so-far delivered few real-world applications, which require both up-scaling fabrication and digital translation of their colour changes. Here we present roll-to-roll manufactured metre-scale HPC laminates using continuous coating and encapsulation. We quantify the pressure response of the encapsulated HPC using optical analyses of the pressure-induced hue change as perceived by the human eye and digital imaging. Finally, we show the ability to capture real-time pressure distributions and temporal evolution of a human foot-print on our HPC laminates. This is the first demonstration of a large area and cost-effective method for fabricating HPC stimuli-responsive photonic films, which can generate pressure maps that can be read out with standard cameras.

Aqueous colloidal suspensions, both man-made and natural, are part of our everyday life. The applicability of colloidal suspensions, however, is limited by the range of conditions over which they are stable. Here we report a novel type of highly monodisperse raspberry-like colloids, which are prepared in a single-step synthesis that relies on simultaneous dispersion and emulsion polymerisation. The resulting raspberry colloids behave almost like hard spheres. In aqueous solutions, such prepared raspberries show unexpected stability against aggregation over large variations of added salt concentrations without addition of stabilisers. We present simple Derjaguin-Landau-Verwey-Overbeek (DLVO) calculations performed on raspberry-like and smooth colloids showing that this stability results from our raspberries' unique morphology, which extends our understanding of colloidal stability against salting. Further, the raspberries' stability facilitates the formation of superspheres and thin films in which the raspberry colloids self-assemble into hexagonally close-packed photonic crystals with exquisite reproducibility.

The petals of Eschscholzia californica (California poppy) are robust, pliable and typically coloured intensely orange or yellow owing to the presence of carotenoid pigments; they are also highly reflective at certain angles, producing a silky effect. To understand the mechanisms behind colour enhancement and reflectivity in California poppy, which represents a model species among early-divergent eudicots, we explored the development, ultrastructure, pigment composition and optical properties of the petals using light microscopy and electron microscopy combined with both spectrophotometry and goniometry. The elongated petal epidermal cells each possess a densely thickened prism-like ridge that is composed primarily of cell wall. The surface ridges strongly focus incident light onto the pigments, which are located in plastids at the cell base. Our results indicate that this highly unusual, deeply ridged surface structure not only enhances the deep colour response in this desert species, but also results in strongly angle-dependent 'silky' reflectivity that is anisotropic and mostly directional., (© 2018 The Authors. New Phytologist © 2018 New Phytologist Trust.)

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., (© 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Most studies of structural color in nature concern periodic arrays, which through the interference of light create color. The "color" white however relies on the multiple scattering of light within a randomly structured medium, which randomizes the direction and phase of incident light. Opaque white materials therefore must be much thicker than periodic structures. It is known that flying insects create "white" in extremely thin layers. This raises the question, whether evolution has optimized the wing scale morphology for white reflection at a minimum material use. This hypothesis is difficult to prove, since this requires the detailed knowledge of the scattering morphology combined with a suitable theoretical model. Here, a cryoptychographic X-ray tomography method is employed to obtain a full 3D structural dataset of the network morphology within a white beetle wing scale. By digitally manipulating this 3D representation, this study demonstrates that this morphology indeed provides the highest white retroreflection at the minimum use of material, and hence weight for the organism. Changing any of the network parameters (within the parameter space accessible by biological materials) either increases the weight, increases the thickness, or reduces reflectivity, providing clear evidence for the evolutionary optimization of this morphology., (© 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Block copolymer micelles (BCMs) are self-assembled nanoparticles in solution with a collapsed core and a brush-like stabilizing corona typically in the size range of tens of nanometers. Despite being widely studied in various fields of science and technology, their ability to form structural colors at visible wavelength has not received attention, mainly due to the stringent length requirements of photonic lattices. Here, we describe the precision assembly of BCMs with superstretched corona, yet with narrow size distribution to qualify as building blocks for tunable and reversible micellar photonic fluids (MPFs) and micellar photonic crystals (MPCs). The BCMs form free-flowing MPFs with an average interparticle distance of 150-300 nm as defined by electrosteric repulsion arising from the highly charged and stretched corona. Under quiescent conditions, millimeter-sized MPCs with classical FCC lattice grow within the photonic fluid-medium upon refinement of the positional order of the BCMs. We discuss the generic properties of MPCs with special emphasis on surprisingly narrow reflected wavelengths with full width at half-maximum (fwhm) as small as 1 nm. We expect this concept to open a generic and facile way for self-assembled tunable micellar photonic structures.

The understanding of the interaction between light and complex, random structures is the key for designing and tailoring the optical appearance and performance of many materials that surround us, ranging from everyday consumer products, such as those for personal care, paints, and paper, to light diffusers used in the LED-lamps and solar cells. Here, it is demonstrated that the light transport in membranes of pure cellulose nanofibrils (CNFs) can be controlled to achieve bright whiteness in structures only a few micrometers thick. This is in contrast to other materials, such as paper, which require hundreds of micrometers to achieve a comparable appearance. The diffusion of light in the CNF membranes is shown to become anomalous by tuning the porosity and morphological features. Considering also their strong mechanical properties and biocompatibility, such white coatings are proposed as a new application for cellulose nanofibrils., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite a huge variety of methodologies having been proposed to produce photonic structures by self-assembly, the lack of an effective fabrication approach has hindered their practical uses. These approaches are typically limited by the poor control in both optical and mechanical properties. Here we report photonic thermosetting polymeric resins obtained through brush block copolymer (BBCP) self-assembly. We demonstrate that the control of the interplay between order and disorder in the obtained photonic structure offers a powerful tool box for designing the optical appearance of the polymer resins in terms of reflected wavelength and scattering properties. The obtained materials exhibit excellent mechanical properties with hardness up to 172 MPa and Young's modulus over 2.9 GPa, indicating great potential for practical uses as photonic coatings on a variety of surfaces., Competing Interests: The authors declare no competing financial interest.

Naturally occurring photonic structures are responsible for the bright and vivid coloration in a large variety of living organisms. Despite efforts to understand their biological functions, development, and complex optical response, little is known of the underlying genes involved in the development of these nanostructures in any domain of life. Here, we used Flavobacterium colonies as a model system to demonstrate that genes responsible for gliding motility, cell shape, the stringent response, and tRNA modification contribute to the optical appearance of the colony. By structural and optical analysis, we obtained a detailed correlation of how genetic modifications alter structural color in bacterial colonies. Understanding of genotype and phenotype relations in this system opens the way to genetic engineering of on-demand living optical materials, for use as paints and living sensors., Competing Interests: The authors declare no conflict of interest.

Diverse forms of nanoscale architecture generate structural colour and perform signalling functions within and between species. Structural colour is the result of the interference of light from approximately regular periodic structures; some structural disorder is, however, inevitable in biological organisms. Is this disorder functional and subject to evolutionary selection, or is it simply an unavoidable outcome of biological developmental processes? Here we show that disordered nanostructures enable flowers to produce visual signals that are salient to bees. These disordered nanostructures (identified in most major lineages of angiosperms) have distinct anatomies but convergent optical properties; they all produce angle-dependent scattered light, predominantly at short wavelengths (ultraviolet and blue). We manufactured artificial flowers with nanoscale structures that possessed tailored levels of disorder in order to investigate how foraging bumblebees respond to this optical effect. We conclude that floral nanostructures have evolved, on multiple independent occasions, an effective degree of relative spatial disorder that generates a photonic signature that is highly salient to insect pollinators.

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., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Subwavelength metal-dielectric plasmonic metasurfaces enable light management beyond the diffraction limit. However, a cost-effective and reliable fabrication method for such structures remains a major challenge hindering their full exploitation. Here, we propose a simple yet powerful manufacturing route for plasmonic metasurfaces based on a bottom-up approach. The fabricated metasurfaces consist of a dense distribution of randomly oriented nanoscale scatterers composed of aluminum (Al) nanohole-disk pairs, which exhibit angle-independent scattering that is tunable across the entire visible spectrum. The macroscopic response of the metasurfaces is controlled via the properties of an isolated Al nanohole-disk pair at the nanoscale. In addition, the optical field confinement at the scatterers and their random distribution of sizes result in a strongly enhanced Raman signal that enables broadly tunable excitation using a single substrate. This unique combination of a reliable and lithography-free methodology with the use of aluminum permits the exploitation of the full potential of random plasmonic metasurfaces for diagnostics and coloration., Competing Interests: The authors declare no conflict of interest.

Structural colours in living organisms have been observed and analysed in a large number of species, however the study of how the micro- and nano-scopic natural structures responsible of such colourations develop has been largely ignored. Understanding the interplay between chemical composition, structural morphology on multiple length scales, and mechanical constraints requires a range of investigation tools able to capture the different aspects of natural hierarchical architectures. Here, we report a developmental study of the most widespread strategy for structural colouration in nature: the cuticular multilayer. In particular, we focus on the exoskeletal growth of the dock leaf beetle Gastrophysa viridula, capturing all aspects of its formation: the macroscopic growth is tracked via synchrotron microtomography, while the submicron features are revealed by electron microscopy and light spectroscopy combined with numerical modelling. In particular, we observe that the two main factors driving the formation of the colour-producing multilayers are the polymerization of melanin during the ecdysis and the change in the layer spacing during the sclerotisation of the cuticle. Our understanding of the exoskeleton formation provides a unique insight into the different processes involved during metamorphosis.

Cellulose is the most abundant biopolymer on Earth. Cellulose fibers, such as the one extracted form cotton or woodpulp, have been used by humankind for hundreds of years to make textiles and paper. Here we show how, by engineering light-matter interaction, we can optimize light scattering using exclusively cellulose nanocrystals. The produced material is sustainable, biocompatible, and when compared to ordinary microfiber-based paper, it shows enhanced scattering strength (×4), yielding a transport mean free path as low as 3.5 μm in the visible light range. The experimental results are in a good agreement with the theoretical predictions obtained with a diffusive model for light propagation.

The fabrication of self-assembled cellulose nanocrystal (CNC) films of tunable photonic and mechanical properties using a facile, green approach is demonstrated. The combination of tunable flexibility and iridescence can dramatically expand CNC coating and film barrier capabilities for paints and coating applications, sustainable consumer packaging products, as well as effective templates for photonic and optoelectronic materials and structures., (© 2016 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Biopolymer-based composites enable to combine different functionalities using renewable materials and cost-effective routes. Here we fabricate novel thermoresponsive photonic films combining cellulose nanocrystals (CNCs) with a polydiolcitrate elastomer exhibiting shape memory properties, known as hydroxyl-dominant poly(dodecanediol-co-citrate) (PDDC-HD). Iridescent films of CNCs are first made by evaporation-induced self-assembly, then embedded in the PDDC-HD prepolymer, and finally cured to obtain a cross-linked composite with shape memory properties. The fabricated samples are characterized by polarized optical microscopy, scanning electron microscopy, and thermomechanical cycling. The obtained hybrid material combines both intense structural coloration and shape memory effect. The association of stiff cellulose nanocrystals and soft polydiolcitrate elastomer enhances the overall mechanical properties (increased modulus and reduced brittleness). This hybrid nanocomposite takes advantage of two promising materials and expands their possibilities to cover a wide range of potential applications as multiresponsive devices and sensors. As they perform from room to body temperatures, they could be also good candidates for biomedical applications.

The butterfly genus Hypolimnas features iridescent blue colouration in some areas of its dorsal wings. Here, we analyse the mechanisms responsible for such colouration on the dorsal wings of Hypolimnas salmacis and experimentally demonstrate that the lower thin lamina in the white cover scales causes the blue iridescence. This outcome contradicts other studies reporting that the radiant blue in Hypolimnas butterflies is caused by complex ridge-lamellar architectures in the upper lamina of the cover scales. Our comprehensive optical study supported by numerical calculation however shows that scale stacking primarily induces the observed colour appearance of Hypolimnas salmacis.

The bright and intense blue-green coloration of the fruits of Margaritaria nobilis (Phyllanthaceae) was investigated using polarization-resolved spectroscopy and transmission electron microscopy. Optical measurements of freshly collected fruits revealed a strong circularly polarized reflection of the fruit that originates from a cellulose helicoidal cell wall structure in the pericarp cells. Hyperspectral microscopy was used to capture the iridescent effect at the single-cell level., (© 2016 The Authors.)

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.

The ability to control and modulate the interaction of light with matter is crucial to achieve desired optical properties including reflection, transmission, and selective polarization. Photonic materials rely upon precise control over the composition and morphology to establish periodic interactions with light on the wavelength and sub-wavelength length scales. Supramolecular assembly provides a natural solution allowing the encoding of a desired 3D architecture into the chemical building blocks and assembly conditions. The compatibility with solution processing and low-overhead manufacturing is a significant advantage over more complex approaches such as lithography or colloidal assembly. Here we review recent advances on photonic architectures derived from block copolymers and highlight the influence and complexity of processing pathways. Notable examples that have emerged from this unique synthesis platform include Bragg reflectors, antireflective coatings, and chiral metamaterials. We further predict expanded photonic capabilities and limits of these approaches in light of future developments of the field.

The marine world is incredibly rich in brilliant and intense colours. Photonic structures are found in many different species and provide extremely complex optical responses that cannot be achieved solely by pigments. In this study we examine the cuticular structure of the red alga Chondrus crispus (Irish Moss) using anatomical and optical approaches. We experimentally measure the optical response of the multilayer structure in the cuticle. Using finite-difference time-domain modelling, we demonstrate conclusively for the first time that the dimensions and organisation of lamellae are responsible for the blue structural colouration on the surface of the fronds. Comparison of material along the apical-basal axis of the frond demonstrates that structural colour is confined to the tips of the thalli and show definitively that a lack of structural colour elsewhere corresponds with a reduction in the number of lamellae and the regularity of their ordering. Moreover, by studying the optical response for different hydration conditions, we demonstrate that the cuticular structure is highly porous and that the presence of water plays a critical role in its ability to act as a structural light reflector.

Polymer self-assembly of a 3D continuous gyroid morphology was replicated into a network consisting of hollow gold struts. This was achieved by first replicating a gyroid structured film into nickel. The Ni network was employed as an electrode for electrochemical Au deposition, followed by the removal of Ni. The resulting hollow network of plasmonic gold exhibited a substantial optical transmission enhancement by a factor of nearly 3, compared to a network of full Au struts. The overall transmission across the hollow wave-guide morphology depends sensitively on the wall-thickness of the hollow struts down to 1 nm. The dramatic transmission increase arises from an interplay of three mechanisms: (1) the additional number of modes propagating through the wave-guide structure, (2) the increased efficiency of light in-coupling, and (3) a reduction of dissipation by decreasing the Au-volume experienced in plasmon mode propagation.

Living organisms can use minute structures to manipulate the reflection of light and display colours based on interference. There has been debate in recent literature over whether the diffractive optical effects produced by epoxy replicas of petals with folded cuticles persist and induce iridescence in the original flowers when the effects of petal pigment and illumination are taken into account. We explored the optical properties of the petal of Hibiscus trionum by macro-imaging, scanning and transmission electron microscopy, and visible and ultraviolet (UV) angle-resolved spectroscopy of the petal. The flower of Hibiscus trionum is visibly iridescent, and the iridescence can be captured photographically. The iridescence derives from a diffraction grating generated by folds of the cuticle. The iridescence of the petal can be quantitatively characterized by spectrometric measurements with several square-millimetres of sample area illuminated. The flower of Hibiscus trionum has the potential to interact with its pollinators (honeybees, other bees, butterflies and flies) through iridescent signals produced by its cuticular diffraction grating., (© 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.)

Whiteness arises from diffuse and broadband reflection of light typically achieved through optical scattering in randomly structured media. In contrast to structural colour due to coherent scattering, white appearance generally requires a relatively thick system comprising randomly positioned high refractive-index scattering centres. Here, we show that the exceptionally bright white appearance of Cyphochilus and Lepidiota stigma beetles arises from a remarkably optimised anisotropy of intra-scale chitin networks, which act as a dense scattering media. Using time-resolved measurements, we show that light propagating in the scales of the beetles undergoes pronounced multiple scattering that is associated with the lowest transport mean free path reported to date for low-refractive-index systems. Our light transport investigation unveil high level of optimisation that achieves high-brightness white in a thin low-mass-per-unit-area anisotropic disordered nanostructure.

Cellulose nanocrystals (CNCs) form chiral nematic phases in aqueous suspensions that can be preserved upon evaporation of water. The resulting films show an intense directional coloration determined by their microstructure. Here, microreflection experiments correlated with analysis of the helicoidal nanostructure of the films reveal that the iridescent colors and the ordering of the individual nematic layers are strongly dependent on the polydispersity of the size distribution of the CNCs. We show how this affects the self-assembly process, and hence multidomain color formation in such bioinspired structural films.

Disordered photonic materials can diffuse and localize light through random multiple scattering, offering opportunities to study mesoscopic phenomena, control light-matter interactions, and provide new strategies for photonic applications. Light transport in such media is governed by photonic modes characterized by resonances with finite spectral width and spatial extent. Considerable steps have been made recently towards control over the transport using wavefront shaping techniques. The selective engineering of individual modes, however, has been addressed only theoretically. Here, we experimentally demonstrate the possibility to engineer the confinement and the mutual interaction of modes in a two-dimensional disordered photonic structure. The strong light confinement is achieved at the fabrication stage by an optimization of the structure, and an accurate and local tuning of the mode resonance frequencies is achieved via post-fabrication processes. To show the versatility of our technique, we selectively control the detuning between overlapping localized modes and observe both frequency crossing and anti-crossing behaviours, thereby paving the way for the creation of open transmission channels in strongly scattering media.

The outer layers of a range of plant tissues, including flower petals, leaves and fruits, exhibit an intriguing variation of microscopic structures. Some of these structures include ordered periodic multilayers and diffraction gratings that give rise to interesting optical appearances. The colour arising from such structures is generally brighter than pigment-based colour. Here, we describe the main types of photonic structures found in plants and discuss the experimental approaches that can be used to analyse them. These experimental approaches allow identification of the physical mechanisms producing structural colours with a high degree of confidence.

The optical properties of metamaterials made by block copolymer self-assembly are tuned by structural and environmental variations. The plasma frequency red-shifts with increasing lattice constant and blue-shifts as the network filling fraction increases. Infiltration with dielectric liquids leads also to a red-shift of the plasma edge. A 300 nm-thick slab of gyroid-structured gold has a remarkable transmission of 20%., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)