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With the advent of direct laser writing using two-photon polymerization, the generation of high-resolution three-dimensional microstructures has increased dramatically. However, the development of stimuli-responsive photoresists to create four-dimensional (4D) microstructures remains a challenge. Herein, we present a supramolecular cholesteric liquid crystalline photonic photoresist for the fabrication of 4D photonic microactuators, such as pillars, flowers, and butterflies, with submicron resolution. These micron-sized features display structural color and shape changes triggered by a variation of humidity or temperature. These findings serve as a roadmap for the design and creation of high-resolution 4D photonic microactuators.

The development of light-responsive materials has captured scientific attention and advanced the development of wirelessly driven terrestrial soft robots. Marine organisms trigger inspiration to expand the paradigm of untethered soft robotics into aqueous environments. However, this expansion toward aquatic soft robots is hampered by the slow response of most light-driven polymers to low light intensities and by the lack of controlled multishape deformations. Herein, we present a surface-anchored artificial aquatic coral polyp composed of a magnetically driven stem and a light-driven gripper. Through magnetically driven motion, the polyp induces stirring and attracts suspended targets. The light-responsive gripper is sensitive to low light intensities and has programmable states and rapid and highly controlled actuation, allowing the polyp to capture or release targets on demand. The artificial polyp demonstrates that assemblies of stimuli-responsive materials in water utilizing coordinated motion can perform tasks not possible for single-component devices., Competing Interests: The authors declare no competing interest., (Copyright © 2020 the Author(s). Published by PNAS.)

Remotely addressable actuators are of great interest in fields like microrobotics and smart textiles because of their simplicity, integrity, flexibility, and lightweight. However, most of the existing actuator systems are composed of complex assemblies and/or offer a low response rate. Here, the actuation performance of a light-driven, highly oriented film based on ultra-high molecular weight polyethylene (UHMW-PE), containing a photo-responsive additive, 2-(2 H -benzotriazol-2-yl)-4,6-ditertpentylphenol (BZT), is reported. The material exhibits a fast (<1 s) and reversible photo-induced thermal response upon exposure to UV light, which results in an exceptionally high actuation stress (∼70 MPa) at a low strain (<0.1%). The proposed actuation mechanism originates from light absorption by BZT and energy transfer into heat, in combination with the intrinsic high stiffness (∼80 GPa) and a negative thermal expansion (NTE) of the oriented polymer films. This unique set of properties of this actuator, in particular the very high specific actuation stress, compared to existing organic and inorganic actuators, and the remote optical actuation, promises impact in fields related to soft robotics, composites, medical devices, optics, prosthetics, and smart textiles.

Liquid crystalline elastomers (LCEs) and liquid crystalline networks (LCNs) are classes of polymers very suitable for fabricating advanced functional materials. Two main pathways to obtain LCEs and LCNs have gained the most attention in the literature, namely the two-step crosslinking of LC side-chain polymers and the photoinitiated free-radical polymerisation of acrylate LC monomers. These liquid crystal polymers have demonstrated remarkable properties resulting from their anisotropic shapes, being used in soft robotics, responsive surfaces and as photonic materials. In this review, we will show that LCs with cyclic ethers as polymerisable groups can be an attractive alternative to the aforementioned reactive acrylate mesogens. These epoxide and oxetane based reactive mesogens could offer a number of advantages over their acrylate-based counterparts, including oxygen insensitivity, reduced polymerisation shrinkage, improved alignment, lower processing viscosity and potentially extended resistivity. In this review, we summarise the research on these materials from the past 30 years and offer a glimpse into the potential of these cyclic ether mesogens.

Narrowly dispersed, 10 micron-sized, liquid crystalline elastomer polymer actuators were first prepared via thiol-ene dispersion polymerization and then embedded and stretched in a polyvinyl alcohol film, followed by photopolymerization of the residual acrylate groups. Prolate micro spheroids in which the mesogens are aligned parallel to the long axis were obtained and showed reversible thermally driven actuation owing to nematic to isotropic transition of the liquid crystal molecules. The particles were also compressed to form disk-shaped oblate microactuators in which the mesogens are aligned perpendicular to the short axis, demonstrating that the reported method is a versatile method to fabricate liquid crystal elastomer microactuators with programmable properties.

An optical time-temperature steam sensor is presented based on the loss of structural color in a supramolecularly cross-linked cholesteric liquid crystal photonic coating. A gradual decrease in the selective reflection band is observed upon exposure to temperatures above 105 °C related to the cholesteric to isotropic transition temperature. The linear polymers with carboxylic acid side chains provide physical cross-linking through hydrogen bonding that allows a time-temperature-dependent order loss through the dynamic equilibrium between supramolecular dimer and free monomer states. Steam is accelerating the color loss, and autoclave experiments show that the photonic supramolecular polymer is applicable as a steam sterilization sensor for medical applications.

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.

Arbitrary shape (re)programming is appealing for fabricating untethered shape-morphing photo-actuators with intricate configurations and features. We present re-programmable light-responsive thermoplastic actuators with arbitrary initial shapes through spray-coating of polyethylene terephthalate (PET) with an azobenzene-doped light-responsive liquid crystal network (LCN). The initial geometry of the actuator is controlled by thermally shaping and fixing the thermoplastic PET, allowing arbitrary shapes, including origami-like folds and left- and right-handed helicity within a single sample. The thermally fixed geometries can be reversibly actuated through light exposure, with fast, reversible area-specific actuation such as winding, unwinding and unfolding. By shape re-programming, the same sample can be re-designed and light-actuated again. The strategy presented here demonstrates easy fabrication of mechanically robust, recyclable, photo-responsive actuators with highly tuneable geometries and actuation modes., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

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.

Mobile organisms with ability for locomotion and transportation, such as humans and other animals, utilize orchestrated actuation to perform actions. Mimicking these functionalities in synthetic, light-responsive untethered soft-bodied devices remains a challenge. Inspired by multitasking and mobile biological systems, an untethered soft transporter robot with controlled multidirectional locomotion with the ability of picking up, transporting, and delivering cargo driven entirely by blue light is created. The soft robot design is an ensemble of light-responsive liquid crystalline polymers that can harness motion either collectively or individually to obtain a high degree of motion control for the execution of advanced tasks in a dry environment. Through orchestrated motion of the device's "legs", single displacement strides, which exceed 4 mm and can be taken in any direction, allow for locomotion around objects. Untethered cargo transportation is demonstrated by a pickup and release mechanism using the device's "arms". This strategy demonstrates the constructive harnessing of orchestrated motion in assemblies of established actuators, performing complex functions, mimicking constructive behavior seen in nature., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2019 Eindhoven University of Technology. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The production of liquid crystalline (LC) polymer particles with a narrow size distribution on a large scale remains a challenge. Here, we report the preparation of monodisperse, cross-linked liquid crystalline particles via precipitation polymerization. This versatile and scalable method yields polymer particles with a smectic liquid crystal order. Although the LC monomers are randomly dissolved in solution, the oligomers self-align and LC order is induced. For the polymerization, a smectic LC monomer mixture consisting of cross-linkers and benzoic acid hydrogen-bonded dimers is used. The average diameter of the particles increases at higher polymerization temperatures and in better solvents, whereas the monomer and initiator concentration have only minor impact on the particle size. After deprotonating of the benzoic acid groups, the particles show rapid absorption of a common cationic dye, methylene blue. The methylene blue in the particles can be subsequently released with the addition of Ca 2+ , while monovalent ions fail to trigger the release. These results reveal that precipitation polymerization is an attractive method to prepare functional LC polymer particles of a narrow size distribution and on a large scale., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

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., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A triangular shaped liquid crystal network is shown to undergo a continual, rocking chair-like oscillatory chaotic motion upon exposure to a surface of constant temperature. With the addition of an azobenzene chromophore, dual response is achieved, extending the actuation freedom towards a film that shows rocking and rolling motion.

A new principle is developed to fabricate temperature-responsive, multicolor photonic coatings that are capable of switching color. The coating is composed of a non-cross-linked liquid crystal siloxane-based elastomer that is interpenetrated through an acrylate-based liquid crystal network. Discrete temperature changes induce phase separation and mixing between the siloxane and the acrylate polymers and change the reflective colors correspondingly. The temperature-responsive color change of the coatings can be programmed by the processing conditions and coating formulation, which allows for the fabrication of photopatterned multicolor images. The photonic ink can be coated on flexible poly(ethylene terephthalate) films using roll-to-roll flexographic printing, making these temperature-responsive, multicolor-changing polymers appealing for applications such as responsive color decors, optical sensors, and anticounterfeit labels.

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

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., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An easy approach to pattern angular-independent, multicolor reflective coatings based on cholesteric liquid-crystalline (CLC) particles is presented. CLC particles are fabricated by emulsification, which is a scalable, cost-effective, and environmentally friendly synthesis process. The photonic particles can be easily dispersed in a binder to produce reflective coatings. Furthermore, a simple strategy to remove the photonic cross-communication between the particles has been developed. By incorporating a reactive blue/green absorbing dye into the network structure of the CLC particles the cross-communication is absorbed by the dye, leading to well-defined structural colors. Moreover, we demonstrate the possibility of producing patterned multicolor images by controlled swelling of the particles by the binder.

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.

Spiropyran is used as a photochromic dye to create colored patterns in highly drawn ultrahigh molecular weight polyethylene (UHMW PE) films. The dye is incorporated in highly crystalline, drawn UHMW PE tapes and fibers and isomerizes to its merocyanine state upon UV light irradiation, resulting in a color change from transparent to purple. The isomerization from merocyanine to spiropyran to erase the color can be simply induced by using heat or a green LED light. The combination of the use of a mask and the reversibility of the isomerization results in colored patterns that can be written, erased, and rewritten using UV light and heat or green LED light., Competing Interests: The authors declare no competing financial interest.

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.

The production of patterned photonic films on a large scale remains a challenge. Here, we report on a new class of photonic materials that are based on oxetane liquid crystals (LCs). Patterned reflective coatings can be produced from these materials on flexible substrates by using flexographic printing. This industrially relevant process allows for upscaling in future applications. Furthermore, the oxetane LCs used do not require an inert atmosphere for photopolymerization, unlike previously described acrylate systems. We show that the flexographic printing process results in excellent alignment, and that the patterns produced display a high resolution. Additionally, we demonstrate that free-standing photonic reflecting foils can also be produced from these materials. Our new oxetane-based patterned iridescent colored materials have potential application for both esthetic purposes as well as anticounterfeit labels.

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.

Beyond their colorful appearances and versatile geometries, flowers can self-shape-morph by adapting to environmental changes. Such responses are often regulated by a delicate interplay between different stimuli such as temperature, light, and humidity, giving rise to the beauty and complexity of the plant kingdom. Nature inspires scientists to realize artificial systems that mimic their natural counterparts in function, flexibility, and adaptation. Yet, many of the artificial systems demonstrated to date fail to mimic the adaptive functions, due to the lack of multi-responsivity and sophisticated control over deformation directionality. Herein, a new class of liquid-crystal-network (LCN) photoactuators whose response is controlled by delicate interplay between light and humidity is presented. Using a novel deformation mechanism in LCNs, humidity-gated photoactuation, an artificial nocturnal flower is devised that is closed under daylight conditions when the humidity level is low and/or the light level is high, while it opens in the dark when the humidity level is high. The humidity-gated photoactuators can be fueled with lower light intensities than conventional photothermal LCN actuators. This, combined with facile control over the speed, geometry, and directionality of movements, renders the "nocturnal actuator" promising for smart and adaptive bioinspired microrobotics., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

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., (© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

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.

The original version of this Article contained errors in Figs. 1a, 2a, 3a, and 4b, in which the units on the scale bars incorrectly read 'µm' rather than the correct 'nm.' This has been corrected in both the PDF and HTML versions of the Article.

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.

Stimuli-responsive liquid crystal elastomers with molecular orientation coupled to rubber-like elasticity show a great potential as elements in soft robotics, sensing, and transport systems. The orientational order defines their mechanical response to external stimuli, such as thermally activated muscle-like contraction. Here we demonstrate a dynamic thermal control of the surface topography of an elastomer prepared as a coating with a pattern of in-plane molecular orientation. The inscribed pattern determines whether the coating develops elevations, depressions, or in-plane deformations when the temperature changes. The deterministic dependence of the out-of-plane dynamic profile on the in-plane orientation is explained by activation forces. These forces are caused by stretching-contraction of the polymer networks and by spatially varying molecular orientation. The activation force concept brings the responsive liquid crystal elastomers into the domain of active matter. The demonstrated relationship can be used to design coatings with functionalities that mimic biological tissues such as skin.

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.

Temperature-responsive luminescent solar concentrators (LSCs) have been fabricated in which the Förster resonance energy transfer (FRET) between a donor-acceptor pair in a liquid crystalline solvent can be tuned. At room temperatures, the perylene bisimide (PBI) acceptor is aggregated and FRET is inactive; while after heating to a temperature above the isotropic phase of the liquid crystal solvent, the acceptor PBI completely dissolves and FRET is activated. This unusual temperature control over FRET was used to design a color-tunable LSC. The device has been shown to be highly stable towards consecutive heating and cooling cycles, making it an appealing device for harvesting otherwise unused solar energy., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Microfluidic devices allow the manipulation of fluids down to the micrometer scale and are receiving a lot of attention for applications where low volumes and high throughputs are required. In these micro channels, laminar flow usually dominates, which requires long residence times of the fluids, limiting the flow speed and throughput. Here a switchable passive mixer has been developed to control mixing and to easily clean microchannels. The mixer is based on a photoresponsive spiropyran based hydrogel of which the dimensions can be tuned by changing the intensity of the light. The size-tunable gels have been used to fabricate a passive slanted groove mixer that can be switched off by light allowing to change mixing of microfluidics to non-mixed flows. These findings open new possibilities for multi-purpose microfluidic devices where mixers and valves can be tuned by light., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The thin-film directed self-assembly of molecular building blocks into oriented nanostructure arrays enables next-generation lithography at the sub-5 nm scale. Currently, the fabrication of inorganic arrays from molecular building blocks is restricted by the limited long-range order and orientation of the materials, as well as suitable methodologies for creating lithographic templates at sub-5 nm dimensions. In recent years, higher-order liquid crystals have emerged as functional thin films for organic electronics, nanoporous membranes, and templated synthesis, which provide opportunities for their use as lithographic templates. By choosing examples from these fields, recent progress toward the design of molecular building blocks is highlighted, with an emphasis on liquid crystals, to access sub-5 nm features, their directed self-assembly into oriented thin films, and, importantly, the fabrication of inorganic arrays. Finally, future challenges regarding sub-5 nm patterning with liquid crystals are discussed., (© 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on the fabrication of a rewritable and reprogrammable dual-photoresponsive liquid crystalline-based actuator containing an azomerocyanine dye that can be locally converted into the hydroxyazopyridinium form by acid treatment. Each dye absorbs at a different wavelength giving access to programmable actuators, the folding of which can be controlled by using different colors of light. The acidic patterning is reversible and allows the erasing and rewriting of patterns in the polymer film, giving access to reusable, adjustable soft actuators., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.

A photonic shape memory polymer film that shows large color response (∼155 nm) in a wide temperature range has been fabricated from a semi-interpenetrating network of a cholesteric polymer and poly(benzyl acrylate). The large color response is achieved by mechanical embossing of the photonic film above its broad glass transition temperature. The embossed film, as it recovers to its original shape on heating through the broad thermal transition, exhibits multiple structural colors ranging from blue to orange. The relaxation behavior of the embossed film can be fully described using a Kelvin-Voigt model, which reveals that the influence of temperature on the generation of colors is much stronger than that of time, thereby producing stable multiple colors.

Thermotropic smectic liquid crystalline polymers were used as a scaffold to create organic/inorganic hybrid layered nanomaterials. Different polymers were prepared by photopolymerizing blends of a hydrogen bonded carboxylic acid derivative and a 10 % cross-linker of variable length in their liquid crystalline phase. Nanopores with dimensions close to 1 nm were generated by breaking the hydrogen bonded dimers in a high pH solution. The pores were filled with positively charged silver (Ag) ions, resulting in a layered silver(I)-polymeric hybrid material. Subsequent exposure to a NaBH 4 reducing solution allowed for the formation of supported hybrid metal/organic films. In the bulk of the film the dimension of the Ag nanoparticles (NPs) was regulated with subnanometer precision by the cross-linker length. Ag nanoparticles with an average size of 0.9, 1.3, and 1.8 nm were produced inside the nanopores thanks to the combined effect of spatially confined reduction and stabilization of the nanoparticles by the polymer carboxylic groups. At the same time, strong Ag migration occurred in the surface region, resulting in the formation of a nanostructured metallic top layer composed of large (10-20 nm) NPs., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

While self-assembled molecular building blocks could lead to many next-generation functional organic nanomaterials, control over the thin-film morphologies to yield monolithic sub-5 nm patterns with 3D orientational control at macroscopic length scales remains a grand challenge. A series of photoresponsive hybrid oligo(dimethylsiloxane) liquid crystals that form periodic cylindrical nanostructures with periodicities between 3.8 and 5.1 nm is studied. The liquid crystals can be aligned in-plane by exposure to actinic linearly polarized light and out-of-plane by exposure to actinic unpolarized light. The photoalignment is most efficient when performed just under the clearing point of the liquid crystal, at which the cylindrical nanostructures are reoriented within minutes. These results allow the generation of highly ordered sub-5 nm patterns in thin films at macroscopic length scales, with control over the orientation in a noncontact fashion., (© 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A temperature-responsive near-infrared reflective coating was fabricated based on a side-chain liquid crystal siloxane polymer using a simple wired-bar method. The cholesteric liquid crystalline polymer film showed a blue shift of the reflection band of ∼1000 nm in the IR region upon heating. The temperature-responsive change of the reflection band was reversible. Compared to that of the same mixture system in an alignment cell, the coating showed a significantly faster response. This research demonstrates an easy way to prepare a temperature-responsive IR-reflective coating that shifts its reflection to a shorter wavelength upon heating. As IR radiation of shorter wavelengths is more strongly represented in sunlight than longer wavelengths, this coating could be used to selectively reduce heating of an indoor space when the temperature is high. This is promising for the future application of smart climate control., Competing Interests: The authors declare no competing financial interest.

Extracellular microenvironment is highly dynamic where spatiotemporal regulation of cell-instructive cues such as matrix topography tightly regulates cellular behavior. Recapitulating dynamic changes in stimuli-responsive materials has become an important strategy in regenerative medicine to generate biomaterials which closely mimic the natural microenvironment. Here, light responsive liquid crystal polymer networks are used for their adaptive and programmable nature to form hybrid surfaces presenting micrometer scale topographical cues and changes in nanoscale roughness at the same time to direct cell migration. This study shows that the cell speed and migration patterns are strongly dependent on the height of the (light-responsive) micrometer scale topographies and differences in surface nanoroughness. Furthermore, switching cell migration patterns upon in situ temporal changes in surface nanoroughness, points out the ability to dynamically control cell behavior on these surfaces. Finally, the possibility is shown to form photoswitchable topographies, appealing for future studies where topographies can be rendered reversible on demand., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Oligo(dimethylsiloxane)-based reactive mesogens were prepared and shown to form room-temperature smectic phases which were 'frozen-in' by photopolymerization. Homeotropically aligned, nanostructured thin films were obtained by spincoating, and micropatterning was demonstrated. These hybrid reactive mesogens are suitable for the preparation of aligned nanostructured polymer thin films with potential applications ranging from stimuli responsive coatings to nanoporous membranes.

The light-induced surface topography of a liquid crystal polymer coating is brought into a patterned oscillatory deformation. A dichroic photo-responsive azobenzene is co-aligned with the planar oriented nematic liquid crystal network molecules which makes the surface deformation sensitive to polarized UV light. Locally selective actuation is achieved in coatings with a complex alignment pattern. Dynamic oscillation, as controlled by the actuation and relaxation kinetics of the polymer, is obtained by a continuous change in the polarization of the UV source. The atypical deformation at the defect lines between the domains is of special interest. The amplitude and presence of the oscillation can be manipulated by changing the ratio between blue and UV light and by varying the ambient temperature of the coating.

The fate of small molecule nanoparticles (SMNPs) composed of self-assembling intrinsically fluorescent π-conjugated oligomers was studied in cells as a function of side-chain hydrophobicity. While the hydrophobic SMNPs remained intact upon cellular uptake, the more hydrophilic SMNPs disassembled and dispersed throughout the cytosol.

Perylene-3,4,9,10-tetracarboxylic acid diimides (PDIs) have recently gained considerable interest for water-based biosensing applications. PDIs have been studied intensively in the bulk state, but their physical properties in aqueous solution in interplay with side-chain polarity are, however, poorly understood. Therefore, three perylene diimide based derivatives were synthesized to study the relationship between side-chain polarity and their self-assembly characteristics in water. The polarity of the side chains was found to dictate the size and morphology of the formed aggregates. Side-chain polarity rendered the self-assembly and photophysical properties of the PDIs-both important for imminent water-based applications-and these were revealed to be especially responsive to changes in solvent composition.

An oligo(p-phenylene vinylene) (OPV) amphiphile has been synthesized with a positively charged head group on one end and a hydrophilic ethyleneglycol wedge on the other. In water, this bolaamphiphile forms vesicles consisting of a monolayer in which the OPV surfactants are organized in a helical head-to-tail fashion. Mass spectrometry analysis and reversed-phase high performance liquid chromatography (RP-HPLC) reveals that because of the presence of two double bonds in the OPV units, photo-induced [2+2] cycloaddition takes place resulting in polymerization of the surfactants. Performing RP-HPLC allowed the OPV dimer to be isolated in a sufficient amount to perform a variety of one- and two-dimensional NMR experiments. These experiments show a highly stereoselective photochemical cycloaddition process resulting in a regioselective head-to-tail dimerization with a stereoselective syn arrangement.