Scalable Photochromic Film for Solar Heat and Daylight Management.

The adaptive control of sunlight through photochromic smart windows could have a huge impact on the energy efficiency and daylight comfort in buildings. However, the fabrication of inorganic nanoparticle and polymer composite photochromic films with a high contrast ratio and high transparency/low haze remains a challenge. Here, a solution method is presented for the in situ growth of copper-doped tungsten trioxide nanoparticles in polymethyl methacrylate, which allows a low-cost preparation of photochromic films with a high luminous transparency (luminous transmittance Tlum = 91%) and scalability (30 × 350 cm2 ). High modulation of visible light (ΔTlum = 73%) and solar heat (modulation of solar transmittance ΔTsol = 73%, modulation of solar heat gain coefficient ΔSHGC = 0.5) of the film improves the indoor daylight comfort and energy efficiency. Simulation results show that low-e windows with the photochromic film applied can greatly enhance the energy efficiency and daylight comfort. This photochromic film presents an attractive strategy for achieving more energy-efficient buildings and carbon neutrality to combat global climate change.

Multicolor photonic patterns through an intensity-controlled single photopolymerization step.

The UV intensity during photopolymerization allows control over the structural color of a cholesteric liquid crystal (CLC) polymer photonic coating in a single step. Simultaneously, the glass transition temperature (Tg) of the polymer can be tuned by the applied UV intensity. Most likely the low intensity photopolymerization increases the inhibition time, leading to in situ formation of polymer fragments through oxygen inhibition. The formation of polymer fragments changes the matrix during the inhibition time, which results in a color change before the polymer network is formed. Additionally, these fragments inside the network act as a plasticizer, effectively lowering the Tg. This method can be combined with temperature responsive properties based on shape memory to fabricate photonic coatings with multiple, responsive colored patterns. The presented work allows for new functionalities in responsive photonic polymers as multiple colors and response temperatures can be incorporated in a single polymerization step.

One-Pot Synthesis of Melt-Processable Supramolecular Soft Actuators.

The application of reprocessable and reprogrammable soft actuators is limited by the synthetic strategies, 3D-shaping capabilities, and small deformations. In this work, melt-processable supramolecular soft actuators based on segmented copolymers containing thiourethane and liquid crystal segments have been prepared via sequential thiol addition reactions in a one-pot approach using commercially available building blocks. The actuators demonstrated immediate, reversible response and weightlifting capabilities with large deformations up to 32 %. Through exploiting the supramolecular cross-links, the material could be recycled and reprogrammed into 3D actuators and welded into an actuator assembly with different deformation modes. Our work offers a one-pot synthesis and straightforward melt-processable approach to prepare supramolecular soft actuators with large deformations that can be reprocessed and reprogrammed into arbitrary 3D shapes.

Anisotropic Iridescence and Polarization Patterns in a Direct Ink Written Chiral Photonic Polymer.

The iridescence of structural color and its polarization characteristics originate from the nanoscale organization of materials. A major challenge in materials science is generating the bright, lustrous hues seen in nature through nanoscale engineering, while simultaneously controlling interaction of the material with different light polarizations. In this work, a suitable chiral nematic liquid crystal elastomer ink is synthesized for direct ink writing, which self-assembles into a chiral photonic structure. Tuning the writing direction and speed leads to the programmed formation of a slanted photonic axis, which exhibits atypical iridescence and polarization selectivity. After crosslinking, a freely programmable, chiroptical photonic polymer material is obtained. The strongly perspective-dependent appearance of the material can function as specialized anticounterfeit markers, as optical elements in decorative iridescent coatings, or, as demonstrated here, in optically based signaling features.

Polymer Stabilized Cholesteric Liquid Crystal Siloxane for Temperature-Responsive Photonic Coatings.

Temperature-responsive photonic coatings are appealing for a variety of applications, including smart windows. However, the fabrication of such reflective polymer coatings remains a challenge. In this work, we report the development of a temperature-responsive, infrared-reflective coating consisting of a polymer-stabilized cholesteric liquid crystal siloxane, applied by a simple bar coating method. First, a side-chain liquid crystal oligosiloxane containing acrylate, chiral and mesogenic moieties was successfully synthesized via multiple steps, including preparing precursors, hydrosilylation, deprotection, and esterification reactions. Products of all the steps were fully characterized revealing a chain extension during the deprotection step. Subsequently, the photonic coating was fabricated by bar-coating the cholesteric liquid crystal oligomer on glass, using a mediator liquid crystalline molecule. After the UV-curing and removal of the mediator, a transparent IR reflective polymer-stabilized cholesteric liquid crystal coating was obtained. Notably, this fully cured, partially crosslinked transparent polymer coating retained temperature responsiveness due to the presence of non-reactive liquid-crystal oligosiloxanes. Upon increasing the temperature from room temperature, the polymer-stabilized cholesteric liquid crystal coating showed a continuous blue-shift of the reflection band from 1400 nm to 800 nm, and the shift was fully reversible.

Unravelling humidity-gated, temperature responsive bilayer actuators.

By spraying liquid crystal mixtures onto stretched polyamide 6 (PA6) substrates, dual-responsive heat/humidity bilayer actuators are generated. The oriented PA6 guides the self-organization of the liquid crystal monomers into well-aligned, anisotropic liquid crystal networks. The bilayer responds to changes in the environmental relative humidity, resulting in bending of the actuator with the liquid crystal network inside the curvature. In contrast, in conditions of constant high humidity (80%RH), increasing the temperature triggers the liquid crystal network coating to bend the bilayer in the opposing direction. The dual-responsivity to changes in environmental humidity and temperature is examined in detail and discussed theoretically to elucidate the humidity-gated, temperature responsive properties revealing guidelines for fabricating anisotropic bilayer actuators.

Dual Light and Temperature Responsive Micrometer-Sized Structural Color Actuators.

Externally induced color- and shape-changes in micrometer-sized objects are of great interest in novel application fields such as optofluidics and microrobotics. In this work, light and temperature responsive micrometer-sized structural color actuators based on cholesteric liquid-crystalline (CLC) polymer particles are presented. The particles are synthesized by suspension polymerization using a reactive CLC monomer mixture having a light responsive azobenzene dye. The particles exhibit anisotropic spot-like and arc-like reflective colored domains ranging from red to blue. Electron microscopy reveals a multidirectional asymmetric arrangement of the cholesteric layers in the particles and numerical simulations elucidate the anisotropic optical properties. Upon light exposure, the particles show reversible asymmetric shape deformations combined with structural color changes. When the temperature is increased above the liquid crystal-isotropic phase transition temperature of the particles, the deformation is followed by a reduction or disappearance of the reflection. Such dual light and temperature responsive structural color actuators are interesting for a variety of micrometer-sized devices.

Transparent, High-Thermal-Conductivity Ultradrawn Polyethylene/Graphene Nanocomposite Films.

Transparent, ultradrawn, ultrahigh molecular weight polyethylene (UHMWPE)/graphene nanocomposite films with a high thermal conductivity are successfully fabricated by solution-casting and solid-state drawing. It is found that the low optical transmittance (<75%) of the ultradrawn UHMWPE/graphene composite films is drastically improved (>90%) by adding 2-(2H-benzontriazol-2-yl)-4,6-ditertpentylphenol (BZT) as a second additive. This high transmission is interpreted in terms of a reduced void content in the composite films and the improved dispersion of graphene both of which decrease light scattering. The high thermal conductivity is attributed to the π-π interaction between BZT and graphene. In addition, a high specific thermal conductivity of ≈75 W m-1 K-1 ρ-1 of the ultradrawn UHMWPE/graphene/BZT composite films is obtained, which is higher than most metals and polymer nanocomposite. These transparent films are potentially excellent candidates for thermal management in various applications due to a combination of low density, ease of processing, and high thermal conductivity.

Discrete π-Stacks from Self-Assembled Perylenediimide Analogues.

The formation of well-defined finite-sized aggregates represents an attractive goal in supramolecular chemistry. In particular, construction of discrete π-stacked dye assemblies remains a challenge. Reported here is the design and synthesis of a novel type of discrete π-stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss-cross PEP-PBP dimers in solution and (PBP-PEP)-(PEP-PBP) tetramers in the solid state are well elucidated using single-crystal X-ray diffraction, dynamic light scattering, and diffusion-ordered NMR spectroscopy. Extensive π-π stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow-tailed alkyl substituents are responsible for the selective formation of discrete dimer and tetramer stacks. Our results reveal a new approach to preparing discrete π stacks that are appealing for making assemblies with well-defined optoelectronic properties.

3D Helix Engineering in Chiral Photonic Materials.

Engineering the helical structure of chiral photonic materials in three dimensions remains a challenge. 3D helix engineered photonic materials are fabricated by local stratification in a photopolymerizable chiral nematic liquid crystal. The obtained chiral photonic materials reflect both handedness of circular polarized light and show super-reflectivity. Simulations match the experimentally observed photonic properties and reveal a distorted helical structure. 3D engineered polymer films can be made that reflect both left- and right handed circular and linear polarized light dependent and exhibit a changing color contrast upon altering the polarization of incident light. Hence, these 3D engineered photonic materials are of interest for new and emerging applications ranging from anti-counterfeit labels and data encryption to aesthetics and super-reflective films.

Optical Patterns on Drawn Polyethylene by Direct Laser Writing.

Optical patterns are produced on the surface of drawn linear polyethylene containing 2-(2H-benzotriazol-2-yl)-4,6-ditertpentylphenol (BZT), a photothermal dye, by direct laser writing. The photothermal dye absorbs the UV light and dissipates heat in the polyethylene film. This heat locally results in the melting, shrinking, and recrystallization of PE and the loss of the fibrillar crystalline morphology which is typical for these materials. By using this writing method, an optical image can be obtained by controlling the local UV irradiation dose with a pulsed UV laser. The optical image is visible with the naked eye but also between crossed polarizers giving an overt and covert authentication verification that might be interesting for anti-counterfeit applications.

Environmentally responsive photonic polymers.

Stimulus-responsive photonic polymer materials that change their reflection colour as function of environmental stimuli such as temperature, humidity and light, are attractive for various applications (e.g. sensors, smart windows and communication). Polymers provide low density, tunable and patternable materials. This feature article focusses on various autonomously responding photonic polymer materials such as hydrogels, block copolymers and liquid crystals and discusses their potential industrial implementation.

Tetrazine- trans-Cyclooctene Chemistry Applied to Fabricate Self-Assembled Fluorescent and Radioactive Nanoparticles for in Vivo Dual Mode Imaging.

Multimodal imaging agents combine two or more imaging modalities into one probe. Self-assembling fluorescent nanoparticles are a promising class of modular multimodal imaging probes as they can allow easy blending of imaging and targeting modalities. Our group recently developed a class of self-assembling and intrinsically fluorescent small molecule-based nanoparticles (SMNPs) with excellent optical properties. In this article, we describe the efficient radiolabeling of these SMNPs via a two-step bioconjugation strategy involving the inverse-electron-demand Diels-Alder ligation between a tetrazine (Tz)-tagged radiolabel and a trans-cyclooctene (TCO)-tagged fluorescent small molecule building block of the SMNPs. Studies in mice revealed that the SMNPs are well tolerated and could be monitored by both radioactivity and fluorescence, thereby demonstrating the potential of SMNPs in optical and dual-mode imaging in vivo. The work also testifies to the utility of the Tz-TCO conjugation chemistry for the labeling of self-assembled nanoparticles.

Butterfly proboscis-inspired tight rolling tapered soft actuators.

Liquid crystalline networks have been fashioned into thin films with tapered thicknesses, revealing the possibility of rolling up extremely tightly when triggered thermally or with light. Compared to the often limited bending shown previously in liquid crystal network actuators, these tapered films curl up several hundreds of degrees. Finite element results of simulated functionally graded thin films with tapered thicknesses corroborate well with experimental work.

Re- and Preconfigurable Multistable Visible Light Responsive Surface Topographies.

Light responsive materials that are able to change their shape are becoming increasingly important. However, preconfigurable bistable or even multi-stable visible light responsive coatings have not been reported yet. Such materials will require less energy to actuate and will have a longer lifetime. Here, it is shown that fluorinated azobenzenes can be used to create rewritable and pre-configurable responsive surfaces that show multi-stable topographies. These surface structures can be formed and removed by using low intensity green and blue light, respectively. Multistable preconfigured surface topographies can also be created in the absence of a mask. The method allows for full control over the surface structures as the topographical changes are directly linked to the molecular isomerization processes. Preliminary studies reveal that these light responsive materials are suitable as adaptive biological surfaces.

Well-Adhering, Easily Producible Photonic Reflective Coatings for Plastic Substrates.

The development of well-adhering, easily producible photonic reflective coatings is still a challenge. Here, an easy-to-produce, industrial viable process is reported that uses a primer layer of the so-called type II photoinitiator to obtain an excellent adhesion between a plastic substrate and one-dimensional (1D) photonic liquid crystalline coatings. Furthermore, a good alignment of the reactive cholesteric liquid crystal mixture is obtained using a bar-coating process, without alignment layers or surfactants. After photopolymerization, cross-hatch tape tests show a good adhesion of the photonic coating having a reflection band of 50% transmission with almost no scattering. Additionally, we demonstrate the ability to create well-adhering ∼100% reflective coatings by coating double layers and the ability to create single-layered cholesteric broadband reflectors using solely a reactivity gradient created by the primer layer. Our new interfacial method gives new opportunities to use reflecting 1D photonic coatings in industrial processes and applications and allows the bonding of almost any polymer to a plastic substrate.

A full color photonic polymer, rewritable with a liquid crystal ink.

A printable and rewritable photonic polymer coating has been fabricated from a cholesteric liquid crystal. Full color images can be patterned in polymer coatings by using a liquid crystal ink. The printed patterns can be erased and rewritten multiple times, making these coatings interesting as rewritable papers.

Synthesis and Self-Assembly of Bay-Substituted Perylene Diimide Gemini-Type Surfactants as Off-On Fluorescent Probes for Lipid Bilayers.

Interest in bay-substituted perylene-3,4:9,10-tetracarboxylic diimides (PDIs) for solution-based applications is growing due to their improved solubility and altered optical and electronic properties compared to unsubstituted PDIs. Synthetic routes to 1,12-bay-substituted PDIs have been very demanding due to issues with steric hindrance and poor regioselectivity. Here we report a simple one-step regioselective and high yielding synthesis of a 1,12-dihydroxylated PDI derivative that can subsequently be alkylated in a straightforward fashion to produce nonplanar 1,12-dialkoxy PDIs. These PDIs show a large Stokes shift, which is specifically useful for bioimaging applications. A particular cationic PDI gemini-type surfactant has been developed that forms nonfluorescent self-assembled particles in water ("off state"), which exerts a high fluorescence upon incorporation into lipophilic bilayers ("on state"). Therefore, this probe is appealing as a highly sensitive fluorescent labelling marker with a low background signal for imaging artificial and cellular membranes.

Light-responsive polymers for microfluidic applications.

While the microfluidic device itself may be small, often the equipment required to control fluidics in the chip unit is large e.g. pumps, valves and mixing units, which can severely limit practical use and functional scalability. In addition, components associated with fluidic control of the device, more specifically the valves and pumps, contribute significantly to the overall unit cost. Here we sketch the problem of a gap between high end accurate, but expensive sensor platforms, versus less accurate, but widely employable hand-held low-cost devices. Recent research has shown that the integration of light-responsive materials within microfluidic devices can provide the function of expensive fluidic components, and potentially enable sophisticated measurements to be made using much less expensive equipment. An overview of the most recent developments will be presented for valves, mixers, transport and sample handling inside microfluidic devices.

Full Color Camouflage in a Printable Photonic Blue-Colored Polymer.

A blue reflective photonic polymer coating which can be patterned in full color, from blue to red, by printing with an aqueous calcium nitrate solution has been fabricated. Color change in the cholesteric liquid-crystalline polymer network over the entire visible spectrum is obtained by the use of nonreactive mesogen. The pattern in the coating is hidden in the blue color dry state and appears upon exposure to water or by exhaling breath onto it due to different degrees of swelling of the polymer network. The degree of swelling depends on the printed amount of calcium which acts as a cross-linker. The printed full color pattern can also be hidden simply by using a circular polarizer. The responsive full color camouflage polymers are interesting for various applications ranging from responsive house and automobile decors to anticounterfeit labels and data encryption.