Hierarchically Structured Deformation-Sensing Mechanochromic Pigments.

Mechanochromic materials alter their color in response to mechanical force and are useful for both fundamental studies and practical applications. Several approaches are used to render polymers mechanochromic, but they generally suffer from limitations in sensing range, capacity to provide quantitative information, and their capability to enable broad and simple implementation. Here, is it reported that these problems can be overcome by combining photonic structures, which alter their reflection upon deformation, with covalent mechanophores, whose spectral properties change upon mechanically induced bond scission, in hierarchically structured mechanochromic pigments. This is achieved by synthesizing microspheres consisting of an elastic polymer with spiropyran-based cross-links and non-close-packed silica nanoparticles. A strain of less than 1% can be detected in a shift of the reflection band from the photonic structure, while the onset strain for the conversion of the spiropyran into fluorescent merocyanine ranges from 30% to 70%, creating a broad strain detection range. The two responses are tailorable and synergistic, permitting the activation strain for the mechanophore response to be tuned. The mechano-sensing photonic pigments are demonstrated to be readily incorporated into different polymeric materials of interest and quantitatively probe spatially heterogeneous deformations over a large strain range.

Photolithographic Fabrication of Mechanically Adaptive Devices.

Water-responsive polymers, which enable the design of objects whose mechanical properties or shape can be altered upon moderate swelling, are useful for a broad range of applications. However, the limited processing options of materials that exhibit useful switchable mechanical properties generally restricted their application to objects having a simple geometry. Here we show that this problem can be overcome by using a negative photoresist approach in which a linear hydrophilic polymer is converted into a highly transparent cross-linked polymer network. The photolithographic process allows the facile production of objects of complex shape and permits programming of the cross-link density, the extent of aqueous swelling, and thereby the stiffness and refractive index under physiological conditions over a wide range and with high spatial resolution. Our findings validate a straightforward route to fabricate mechanically adaptive devices for a variety of (biomedical) uses, notably optogenetic implants whose overall shape, mechanical contrast, and optical channels can all be defined by photolithography.

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%.

Structural Diversity with Varying Disorder Enables the Multicolored Display in the Longhorn Beetle Sulawesiella rafaelae.

Light control through layered photonic nanostructures enables the strikingly colored displays of many beetles, birds, and butterflies. To achieve different reflected colors, natural organisms mainly rely on refractive index variations or scaling of a fixed structure design, as opposed to varying the type of structure. Here, we describe the presence of distinct coloration mechanisms in the longhorn beetle Sulawesiella rafaelae, which exhibits turquoise, yellow-green, and orange colors, each with a variable iridescence. By optical and electron microscopy, we show that the colors originate from multilayered architectures in hair-like scales with varying amounts of structural disorder. Structural characterizations and optical modeling show that the disorder strongly influences the optical properties of the scales, allowing an independent adjustment of the optical response. Our results shed light on the interplay of disorder in multilayered photonic structures and their biological significance, and could potentially inspire new ecological research and the development of novel optical components.

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.

Thin-film structural coloration from simple fused scales in moths.

The metallic coloration of insects often originates from diverse nanostructures ranging from simple thin films to complex three-dimensional photonic crystals. In Lepidoptera, structural coloration is widely present and seems to be abundant in extant species. However, even some basal moths exhibit metallic coloration. Here, we have investigated the origin of the vivid metallic colours of the wing scales of the basal moth Micropterix aureatella by spectrophotometry and scanning electron microscopy. The metallic gold-, bronze- and purple-coloured scales share a similar anatomy formed of a fused lower and upper lamina resulting in a single thin film. The optical response of this thin-film scale can be attributed to thin-film interference of the incident light, resulting in the colour variations that correlate with film thickness. Subtle variations in the wing scale thickness result in large visible colour changes that give Micropterix moths their colourful wing patterns. This simple coloration mechanism could provide a hint to understand the evolution of structural coloration in Lepidoptera.