Photonic crystals built by time in ancient Roman glass.

Ancient glass objects typically show distinctive effects of deterioration as a result of environmentally induced physicochemical transformations of their surface over time. Iridescence is one of the distinctive signatures of aging that is most commonly found on excavated glass. In this work, we present an ancient glass fragment that exhibits structural color through surface weathering resulting in iridescent patinas caused by silica reprecipitation in nanoscale lamellae. This archaeological artifact reveals an unusual hierarchically assembled photonic crystal with extremely ordered nanoscale domains, high spectral selectivity, and reflectivity (~90%), that collectively behaves like a gold mirror. Optical characterization paired with nanoscale elemental analysis further underscores the high quality of this structure providing a window into this sophisticated natural photonic crystal assembled by time.

Co-modulation of structural and pigmentary coloration in Lyropteryx apollonia butterfly.

Nature produces some of the most striking optical effects through the combination of structural and chemical principles to give rise to a wide range of colors. However, creating non-spectral colors that extend beyond the color spectrum is a challenging task, as it requires meeting the requirements of both structural and pigmentary coloration. In this study, we investigate the magenta non-spectral color found in the scales of the ventral spots of the Lyropteryx apollonia butterfly. By employing correlated optical and electron microscopy, as well as pigment extraction techniques, we reveal how this color arises from the co-modulation of pigmentary and structural coloration. Specifically, the angle-dependent blue coloration results from the interference of visible light with chitin-based nanostructures, while the diffused red coloration is generated by an ommochrome pigment. The ability to produce such highly conspicuous non-spectral colors provides insights for the development of hierarchical structures with precise control over their optical response. These structures can be used to create hierarchically-arranged systems with a broadened color palette.

Generation of Complex Tunable Multispectral Signatures with Reconfigurable Protein-Based, Plasmonic-Photonic Crystal Hybrid Nanostructures.

Structurally colored materials, which rely on the interaction between visible light and nanostructures, produce brilliant color displays through fine control of light interference, diffraction, scattering, or absorption. Rationally combining different color-selective functions into a single form offers a powerful strategy to create programmable optical functions which are otherwise difficult, if not impossible to obtain. By leveraging structural protein templates, specifically silk fibroin, nanostructured materials that combine plasmonic and photonic crystal paradigms are shown here. This confluence of function enables directional, tunable, and multiple co-located optical responses derived from the interplay between surface plasmon resonance and photonic bandgap effects. Several demonstrations are shown with programmable coloration at varying viewing sides, angle, and by solvent infiltration, opening avenues for smart displays and multi-mode information encoding applications.

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.

Bombyx mori Silk Fibroin Regeneration in Solution of Lanthanide Ions: A Systematic Investigation.

Silk Fibroin (SF) obtained from Bombyx mori is a very attractive biopolymer that can be useful for many technological applications, from optoelectronics and photonics to biomedicine. It can be processed from aqueous solutions to obtain many scaffolds. SF dissolution is possible only with the mediation of chaotropic salts that disrupt the secondary structure of the protein. As a consequence, recovered materials have disordered structures. In a previous paper, it was shown that, by modifying the standard Ajisawa's method by using a lanthanide salt, CeCl3, as the chaotropic agent, it is possible to regenerate SF as a fibrous material with a very ordered structure, similar to that of the pristine fiber, and doped with Ce+3 ions. Since SF exhibits a moderate fluorescence which can be enhanced by the incorporation of organic molecules, ions and nanoparticles, the possibility of doping it with lanthanide ions could be an appealing approach for the development of new photonic systems. Here, a systematic investigation of the behavior of degummed SF in the presence of all lanthanide ions, Ln+3, is reported. It has been found that all lanthanide chlorides are chaotropic salts for solubilizing SF. Ln+3 ions at the beginning and the end of the series (La+3, Pr+3, Er+3, Tm+3, Yb+3, Lu+3) favor the reprecipitation of fibrous SF as already found for Ce+3. In most cases, the obtained fiber preserves the morphological and structural features of the pristine SF. With the exception of SF treated with La+3, Tm+3, and Lu+3, for all the fibers re-precipitated a concentration of Ln+3 between 0.2 and 0.4% at was measured, comparable to that measured for Ce+3-doped SF.

Rebirth in a COVID hospital: a point of view.

BACKGROUND: Since COVID-19 was declared a pandemic, governments have taken actions to limit the transmission of the virus such as lockdown measures and reorganization of the local Health System. Quarantine measures have influenced pregnant women's daily lives. The aim of this study was to understand the impact of the changes imposed by COVID-19 emergency on the well-being of pregnant women and how the transformation of Schiavonia Hospital into a dedicated COVID hospital affected their pregnancy experience. METHODS: A cross-sectional survey was conducted. Pregnant women who gave birth in Schiavonia Hospital during the period May-September 2020 have been included. The assessment examined clinical characteristics, attitudes in relation to the pandemic and how it affected birth plans, perception of information received, and attitudes regards giving birth in a COVID hospital. RESULTS: One hundred four women responded to the survey, with an enrolment rate of 58%. About the influence of COVID-19 pandemic, 51% of respondents reported changing some aspect of their lifestyle. The identification of Schiavonia Hospital as COVID hospital did not modify the trust in the facility and in the obstetrics ward for the 90% of women, in fact for the 85.6% it was the planned Birth Center since the beginning of pregnancy. The communication was complete and exhaustive for 82.7% of the respondents. CONCLUSIONS: Despite the COVID hospital transformation, the women who came to give birth at Schiavonia Birth Center rated the healthcare assistance received at high level, evidencing high affection for the structure and the healthcare workers.

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.

Optomechanically Actuated Microcilia for Locally Reconfigurable Surfaces.

Artificial microcilia structures have shown potential to incorporate actuators in various applications such as microfluidic devices and biomimetic microrobots. Among the multiple possibilities to achieve cilia actuation, magnetic fields present an opportunity given their quick response and wireless operation, despite the difficulty in achieving localized actuation because of their continuous distribution. In this work, a high-aspect-ratio (>8), elastomeric, magnetically responsive microcilia array is presented that allows for wireless, localized actuation through the combined use of light and magnetic fields. The microcilia array can move in response to an external magnetic field and can be locally actuated by targeted illumination of specific areas. The periodic pattern of the microcilia also diffracts light with varying diffraction efficiency as a function of the applied magnetic field, showing potential for wirelessly controlled adaptive optical elements.

Large-Scale Patterning of Reactive Surfaces for Wearable and Environmentally Deployable Sensors.

Wearable interfaces are central to multiple healthcare and wellness strategies encompassing diet and nutrition, personalized health monitoring, and performance optimization. Specifically, the advent of flexible electronic formats coupled with microfluidic interfaces has resulted in sophisticated conformal devices for biofluid sampling and quantification. Here, a complementary approach is presented to wearable sensing by using a large-scale, conformal, distributed format that relies on the use of biomaterial-based inks to print and stabilize deterministic patterns of biochemical reporters with high resolution. Colorimetric devices can vary in size and a sensing T-shirt based on a colorimetric pattern is developed to illustrate the utility that such formats can add to the wearable interface space. Image analysis allows parameter variation to be tracked in real-time, yielding a map-like format of distributed biophysical response.

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.

Hierarchical Photonic Pigments via the Confined Self-Assembly of Bottlebrush Block Copolymers.

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.

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.

Unexpected stability of aqueous dispersions of raspberry-like colloids.

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.

Block Copolymer Micelles for Photonic Fluids and Crystals.

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 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.

Shape Memory Cellulose-Based Photonic Reflectors.

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.

Flexible Photonic Cellulose Nanocrystal Films.

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.

Hierarchical Self-Assembly of Cellulose Nanocrystals in a Confined Geometry.

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.

Severe and enduring anorexia nervosa (SEED-AN): a qualitative study of patients with 20+ years of anorexia nervosa.

Little is known about how patients with long-term eating disorders manage their clinical problems. We carried out a preliminary qualitative study (using Thematic Analysis) of patients with severe and enduring anorexia nervosa (SEED-AN) in which we undertook recorded interviews in eight participants whose conditions had lasted 20-40 years. We found 15 principle features in physical, psychological, social, family, occupational and treatment realms. Psychological and social realms were most affected. Severe physical problems were reported. They described feelings of unworthiness, frugality regarding money and obsessive time-keeping. Persisting with negligible social networks, participants described depression and hopelessness, while somehow achieving a sense of pride at their endurance and survival in spite of the eating disorder. They emphasized the importance of professional help in managing their care. The severe and enduring description, often reserved for people with psychotic illness, is appropriately applied to SEED-AN, which has major impacts in all realms.