Reversible Temperature Sensing using Blue-Winged Grasshopper Coloracris azureus Wings.

Thermochromic materials have been widely investigated due to their relevance in technological applications, including anti-counterfeiting materials, fashion accessories, displays, and temperature sensors. While many organisms exhibit color changes, few studies have explored the potential of the responsive natural materials for temperature sensing, especially given the often limited and irreversible nature of these changes in live specimens. Here, it is shown that the hindwings of the blue-winged grasshopper Coloracris azureus can act as a reversible, power-free bio-thermometer, transitioning from blue to purple/red in a 30-100°C temperature range. Using microspectrophotometry, light microscopy and Raman microscopy, it is found that the blue color of the wings originates from pigmentary coloration, based on a complex of astaxanthin and proteins. The thermochromic shift from blue to red, induced by a temperature increase, is attributed to a denaturation of this carotenoprotein complex, upon which astaxanthin is released. This process is reversible upon a subsequent temperature decrease. The color changes are both swift and consistent upon temperature change, making the grasshopper's wings suitable as direct visual sensors on thermally dynamic, curved surfaces. The potential possibilities of sustainable, power-free temperature sensors or microthermometers based on biomaterials are demonstrated.

Thin film structural color is widespread in slime molds (Myxomycetes, Amoebozoa).

Brilliant colors in nature arise from the interference of light with periodic nanostructures resulting in structural color. While such biological photonic structures have long attracted interest in insects and plants, they are little known in other groups of organisms. Unexpected in the kingdom of Amoebozoa, which assembles unicellular organisms, structural colors were observed in myxomycetes, an evolutionary group of amoebae forming macroscopic, fungal-like structures. Previous work related the sparkling appearance of Diachea leucopodia to thin film interference. Using optical and ultrastructural characterization, we here investigated the occurrence of structural color across 22 species representing two major evolutionary clades of myxomycetes including 14 genera. All investigated species showed thin film interference at the peridium, producing colors with hues distributed throughout the visible range that were altered by pigmentary absorption. A white reflective layer of densely packed calcium-rich shells is observed in a compound peridium in Metatrichia vesparium, whose formation and function are still unknown. These results raise interesting questions on the biological relevance of thin film structural colors in myxomycetes, suggesting they may be a by-product of their reproductive cycle.

Anoplophora graafi longhorn beetle coloration is due to disordered diamond-like packed spheres.

While artificial photonic materials are typically highly ordered, photonic structures in many species of birds and insects do not possess a long-range order. Studying their order-disorder interplay sheds light on the origin of the photonic band gap. Here, we investigated the scale morphology of the Anoplophora graafi longhorn beetle. Combining small-angle X-ray scattering and slice-and-view FIB-SEM tomography with molecular dynamics and optical simulations, we characterised the chitin sphere assemblies within blue and green A. graafi scales. The low volume fraction of spheres and the number of their nearest neighbours are incompatible with any known close-packed sphere morphology. A short-range diamond lattice with long-range disorder best describes the sphere assembly, which will inspire the development of new colloid-based photonic materials.

Robust Full-Spectral Color Tuning of Photonic Colloids.

Creation of color through photonic morphologies manufactured by molecular self-assembly is a promising approach, but the complexity and lack of robustness of the fabrication processes have limited their technical exploitation. Here, it is shown that photonic spheres with full-color tuning across the entire visible spectrum can be readily and reliably achieved by the emulsification of solutions containing a block copolymer (BCP) and two swelling additives. Solvent diffusion out of the emulsion droplets gives rise to 20-150 µm-sized spheres with an onion-like lamellar morphology. Controlling the lamellar thickness by differential swelling with the two additives enables color tuning of the Bragg interference-based reflection band across the entire visible spectrum. By studying five different systems, a set of important principles for manufacturing photonic colloids is established. Two swelling additives are required, one of which must exhibit strong interactions with one of the BCP blocks. The additives should be chosen to enhance the dielectric contrast, and the formation kinetics of the spheres must be sufficiently slow to enable the emergence of the photonic morphology. The proposed approach is versatile and robust and allows the scalable production of photonic pigments with possible future applications in inks for cosmetics and arts, coatings, and displays.

Structural color from pigment-loaded nanostructures.

Color can originate from wavelength-dependence in the absorption of pigments or the scattering of nanostructures. While synthetic colors are dominated by the former, vivid structural colors found in nature have inspired much research on the latter. However, many of the most vibrant colors in nature involve the interactions of structure and pigment. Here, we demonstrate that pigment can be exploited to efficiently create bright structural color at wavelengths outside its absorption band. We created pigment-enhanced Bragg reflectors by sequentially spin-coating layers of poly-vinyl alcohol (PVA) and polystyrene (PS) loaded with ß-carotene (BC). With only 10 double layers, we achieved a peak reflectance over 0.8 at 550 nm and normal incidence. A pigment-free multilayer made of the same materials would require 25 double layers to achieve the same reflectance. Further, pigment loading suppressed the Bragg reflector's characteristic iridescence. Using numerical simulations, we further show that similar pigment loadings could significantly expand the gamut of non-iridescent colors addressable by photonic glasses.

Pachyrhynchus Weevils Use 3D Photonic Crystals with Varying Degrees of Order to Create Diverse and Brilliant Displays.

The brilliant appearance of Easter Egg weevils, genus Pachyrhynchus (Coleoptera, Curculionidae), originates from complex dielectric nanostructures within their elytral scales and elytra. Previous work, investigating singular members of the Pachyrhynchus showed the presence of either quasi-ordered or ordered 3D photonic crystals based on the single diamond ( Fd3¯m ) symmetry in their scales. However, little is known about the diversity of the structural coloration mechanisms within the family. Here, the optical properties within Pachyrhynchus are investigated by systematically identifying their spectral and structural characteristics. Four principal traits that vary their appearance are identified and the evolutionary history of these traits to identify ecological trends are reconstructed. The results indicate that the coloration mechanisms across the Easter Egg weevils are diverse and highly plastic across closely related species with features appearing at multiple independent times across their phylogeny. This work lays a foundation for a better understanding of the various forms of quasi-ordered and ordered diamond photonic crystal within arthropods.

Heterolytic Bond Cleavage in a Scissile Triarylmethane Mechanophore.

Covalent mechanophores display the cleavage of a weak covalent bond when a sufficiently high mechanical force is applied. Three different covalent bond breaking mechanisms have been documented thus far, including concerted, homolytic, and heterolytic scission. Motifs that display heterolytic cleavage typically separate according to non-scissile reaction pathways that afford zwitterions. Here, we report a new mechanochromic triarylmethane mechanophore, which dissociates according to a scissile heterolytic pathway and displays a pronounced mechanochromic response. The mechanophore was equipped with two styrenylic handles that allowed its incorporation as a cross-linker into poly(N,N-dimethylacrylamide) and poly(methyl acrylate-co-2-hydroxyethyl acrylate) networks. These materials are originally colorless, but compression or tensile deformation renders the materials colored. By combining tensile testing and in situ transmittance measurements, we show that this effect is related to scissile cleavage leading to colored triarylmethane carbocations.

Enhancing the Refractive Index of Polymers with a Plant-Based Pigment.

Polymers are essential components of many nanostructured materials. However, the refractive indices of common polymers fall in a relatively narrow range between 1.4 and 1.6. Here, it is demonstrated that loading commercially-available polymers with large concentrations of a plant-based pigment can effectively enhance their refractive index. For polystyrene (PS) loaded with 67 w/w% ß-carotene (BC), a peak value of 2.2 near the absorption edge at 531 nm is achieved, while maintaining values above 1.75 across longer wavelengths of the visible spectrum. Despite high pigment loadings, this blend maintains the thermoforming ability of PS, and BC remains molecularly dispersed. Similar results are demonstrated for the plant-derived polymer ethyl cellulose (EC). Since the refractive index enhancement is intimately connected to the introduction of strong absorption, it is best suited to applications where light travels short distances through the material, such as reflectors and nanophotonic systems. Enhanced reflectance from films is experimentally demonstrated, as large as sevenfold for EC at selected wavelengths. Theoretical calculations highlight that this simple strategy can significantly increase light scattering by nanoparticles and enhance the performance of Bragg reflectors.

Photonic Particles Made by the Confined Self-Assembly of a Supramolecular Comb-Like Block Copolymer.

Approaches that enable the preparation of robust polymeric photonic particles are of interest for the development of nonfading and highly reflective pigments for applications such as paints and display technologies. Here, the preparation of photonic particles that display structural color in both, aqueous suspension and the dry solid state is reported. This is achieved by exploiting the confined self-assembly of a supramolecular comb-like block copolymer (BCP) that microphase separates into a well-ordered lamellar morphology with dimensions that promote a photonic bandgap in the visible range. The comb-like BCP is formed by robust ionic interactions between poly(styrene-b-4-vinyl-pyridine) (PS-b-P4VP) BCP and dodecylbenzene sulfonic acid (DBSA), which selectively interacts with P4VP blocks. The components are combined in chloroform, and an aqueous emulsion is prepared. Evaporation of the organic solvent leads to the formation of solid microparticles with an onion-like 3D morphology. These photonic pigments display brilliant colors with reflectance spectra featuring pronounced optical bandgaps across the entire visible wavelength range with a peak reflectivity of 80-90%.

Genetic manipulation of structural color in bacterial colonies.

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.

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers.

Copper complexes have shown great versatility and a wide application range across the natural and life sciences, with a particular promise as organic light-emitting diodes. In this work, four novel heteroleptic Cu(I) complexes were designed in order to allow their integration in advanced materials such as metallopolymers. We herein present the synthesis and the electrochemical and photophysical characterisation of these Cu(I) complexes, in combination with ab initio calculations. The complexes present a bright cyan emission (λem ~ 505 nm) in their solid state, both as powder and as blends in a polymer matrix. The successful synthesis of metallopolymers embedding two of the novel complexes is shown. These copolymers were also found to be luminescent and their photophysical properties were compared to those of their polymer blends. The chemical nature of the polymer backbone contributes significantly to the photoluminescence quantum yield, paving a route for the strategic design of novel luminescent Cu(I)-based polymeric materials.

Designing refractive index fluids using the Kramers-Kronig relations.

For a number of optical applications, it is advantageous to precisely tune the refractive index of a liquid. Here, we harness a well-established concept in optics for this purpose. The Kramers-Kronig relation provides a physical connection between the spectral variation of the (real) refractive index and the absorption coefficient. In particular, a sharp spectral variation of the absorption coefficient gives rise to either an enhancement or reduction of the refractive index in the spectral vicinity of this variation. By using bright commodity dyes that fulfil this absorption requirement, we demonstrate the use of the Kramers-Kronig relation to predictively obtain refractive index values in water solutions that are otherwise only attained with toxic specialised liquids.

Diffusive structural colour in Hoplia argentea.

Nature's nanostructures can bring about vivid and iridescent colours seen in many insects, notably in beetles and butterflies. While the intense structural colours can be advantageous for display purposes, they may also be appealing to predators and therefore constitute an evolutionary disadvantage. Animals often employ absorption and scattering in order to reduce the directionality of the reflected light and thereby enhance their camouflage. Here, we investigated the monkey beetle Hoplia argentea using microspectrophotometry, electron microscopy, fluorimetry and optical modelling. We show that the dull green dorsal colour comes from the nanostructured scales on the elytra. The nanostructure consists of a multi-layered photonic structure covered by a filamentous layer. The filamentous layer acts as a spatial diffuser of the specular reflection from the multilayer and suppresses the iridescence. This combination leads to a colour-stable and angle-independent green reflection that probably enhances the camouflage of the beetles in their natural habitat.

Humidity-dependent colour change in the green forester moth, Adscita statices.

The colours of insects serve important visual functions in aiding mate recognition, camouflage and warning. The display of insects is usually static, as cuticle coloration does not (or hardly) change during the lifespan of a mature imago form. Here, we describe a case of humidity-dependent, brilliant coloration in the green forester moth, Adscita statices. We show, by employing spectroscopic and ultrastructural methods, that the moth's colour results from the interference of incident light with an unusual hydrophilic melanized-chitin multilayer present in the wing scales. Humidity changes in the environment affect the multilayer properties, causing a significant shift of the green-peaking reflectance in the dry state to a rusty colour when damp, resulting in the strong colour change between day and dusk or dawn.

When Black and White make Green: the Surprising Interplay of Structure and Pigments.

The natural world is teeming with color, which originates either from the wavelength-dependent absorp- tion of light by pigments or from scattering from nanoscale structures, or both. While the latter ' structural color ' has been a topic of intense study in recent years, the most vibrant colors in nature involve contributions from both structure and pigment. The study of structure-pigment interactions in biological systems is currently in its infancy and could inspire more technological applications, such as sustainable, toxin-free pigments and more efficient light harvesting.

A Literal Elytral Rainbow: Tunable Structural Colors Using Single Diamond Biophotonic Crystals in Pachyrrhynchus congestus Weevils.

The brilliant colors of many insects arise from the interference of incident light with complex nanostructured biomaterials that are present in their cuticle. Here, the rainbow-colored spots on the elytra of a snout weevil, Pachyrrhynchus congestus pavonius (Coleoptera: Curculionidae), are investigated using synchrotron small-angle X-ray scattering, scanning electron microscopy, microspectrophotometry, and photonic bandgap modeling. It is shown that the iridescent scales present in the rainbow-hued spots are due to a 3D photonic crystal network of chitin in air with a single diamond (Fd-3m) symmetry. In many insects, different orientations of photonic crystal domains are used to create various hues. In this weevil, however, both the chitin volume fractions as well as the lattice parameters of the biologically self-assembled single diamond nanostructure are varied to achieve the remarkable tuning of the structural colors across the visible light spectrum on a scale-by-scale basis. Uncovering the precise mechanism of color tuning employed by this weevil has important implications for further structural and developmental research on biophotonic nanostructures and may provide fresh impetus for bioinspired and biomimetic multifunctional applications, as synthesis of photonic crystals at visible length scales is currently challenging.

Controlling Self-Assembly in Gyroid Terpolymer Films By Solvent Vapor Annealing.

The efficacy with which solvent vapor annealing (SVA) can control block copolymer self-assembly has so far been demonstrated primarily for the simplest class of copolymer, the linear diblock copolymer. Adding a third distinct block-thereby creating a triblock terpolymer-not only provides convenient access to complex continuous network morphologies, particularly the gyroid phases, but also opens up a route toward the fabrication of novel nanoscale devices such as optical metamaterials. Such applications, however, require the generation of well-ordered 3D continuous networks, which in turn requires a detailed understanding of the SVA process in terpolymer network morphologies. Here, in situ grazing-incidence small-angle X-ray scattering (GISAXS) is employed to study the self-assembly of a gyroid-forming triblock terpolymer during SVA, revealing the effects of several key SVA parameters on the morphology, lateral order, and, in particular, its preservation in the dried film. The robustness of the terpolymer gyroid morphology is a key requirement for successful SVA, allowing the exploration of annealing parameters which may enable the generation of films with long-range order, e.g., for optical metamaterial applications.

Ultrastructure and optics of the prism-like petal epidermal cells of Eschscholzia californica (California poppy).

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.

Magnificent magpie colours by feathers with layers of hollow melanosomes.

The blue secondary and purple-to-green tail feathers of magpies are structurally coloured owing to stacks of hollow, air-containing melanosomes embedded in the keratin matrix of the barbules. We investigated the spectral and spatial reflection characteristics of the feathers by applying (micro)spectrophotometry and imaging scatterometry. To interpret the spectral data, we performed optical modelling, applying the finite-difference time domain (FDTD) method as well as an effective media approach, treating the melanosome stacks as multi-layers with effective refractive indices dependent on the component media. The differently coloured magpie feathers are realised by adjusting the melanosome size, with the diameter of the melanosomes as well as their hollowness being the most sensitive parameters that influence the appearance of the feathers.

Longwing (Heliconius) butterflies combine a restricted set of pigmentary and structural coloration mechanisms.

BACKGROUND: Longwing butterflies, Heliconius sp., also called heliconians, are striking examples of diversity and mimicry in butterflies. Heliconians feature strongly colored patterns on their wings, arising from wing scales colored by pigments and/or nanostructures, which serve as an aposematic signal. RESULTS: Here, we investigate the coloration mechanisms among several species of Heliconius by applying scanning electron microscopy, (micro)spectrophotometry, and imaging scatterometry. We identify seven kinds of colored scales within Heliconius whose coloration is derived from pigments, nanostructures or both. In yellow-, orange- and red-colored wing patches, both cover and ground scales contain wavelength-selective absorbing pigments, 3-OH-kynurenine, xanthommatin and/or dihydroxanthommatin. In blue wing patches, the cover scales are blue either due to interference of light in the thin-film lower lamina (e.g., H. doris) or in the multilayered lamellae in the scale ridges (so-called ridge reflectors, e.g., H. sara and H. erato); the underlying ground scales are black. In the white wing patches, both cover and ground scales are blue due to their thin-film lower lamina, but because they are stacked upon each other and at the wing substrate, a faint bluish to white color results. Lastly, green wing patches (H. doris) have cover scales with blue-reflecting thin films and short-wavelength absorbing 3-OH-kynurenine, together causing a green color. CONCLUSIONS: The pigmentary and structural traits are discussed in relation to their phylogenetic distribution and the evolution of vision in this highly interesting clade of butterflies.