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.

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.

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.

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.

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.

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.

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.

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.

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.

Photoresponsive Passive Micromixers Based on Spiropyran Size-Tunable Hydrogels.

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.

Temperature-Responsive Luminescent Solar Concentrators: Tuning Energy Transfer in a Liquid Crystalline Matrix.

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.

3D Orientational Control in Self-Assembled Thin Films with Sub-5 nm Features by Light.

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.

A Rewritable, Reprogrammable, Dual Light-Responsive Polymer Actuator.

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.

Regulating the modulus of a chiral liquid crystal polymer network by light.

We report a novel way to modulate the elastic modulus of azobenzene containing liquid crystal networks (LCNs) by exposure to light. The elastic modulus can cycle between different levels by controlling the illumination conditions. Exposing the polymer network to UV light near the trans absorption band of azobenzene gives a small reduction of the glass transition temperature thereby lowering the modulus. The addition of blue light addressing the cis absorption band surprisingly amplifies this effect. The continuous oscillatory effects of the trans-to-cis isomerization of the azobenzene overrule the overall net cis conversion. The influence on the chain dynamics of the network is demonstrated by dynamic mechanical thermal analysis which shows a large shift of the glass transition temperature and a modulus decrease by more than two orders of magnitude. The initial high modulus and the glassy state are recovered within a minute in the dark by switching off the light sources, despite the observation that azobenzene is still predominantly in its cis state. Based on these new findings, we are able to create a shape memory polymer LCN film at room temperature using light.

Model-driven optimization of multicomponent self-assembly processes.

Here, we report an engineering approach toward multicomponent self-assembly processes by developing a methodology to circumvent spurious, metastable assemblies. The formation of metastable aggregates often hampers self-assembly of molecular building blocks into the desired nanostructures. Strategies are explored to master the pathway complexity and avoid off-pathway aggregates by optimizing the rate of assembly along the correct pathway. We study as a model system the coassembly of two monomers, the R- and S-chiral enantiomers of a π-conjugated oligo(p-phenylene vinylene) derivative. Coassembly kinetics are analyzed by developing a kinetic model, which reveals the initial assembly of metastable structures buffering free monomers and thereby slows the formation of thermodynamically stable assemblies. These metastable assemblies exert greater influence on the thermodynamically favored self-assembly pathway if the ratio between both monomers approaches 1:1, in agreement with experimental results. Moreover, competition by metastable assemblies is highly temperature dependent and hampers the assembly of equilibrium nanostructures most effectively at intermediate temperatures. We demonstrate that the rate of the assembly process may be optimized by tuning the cooling rate. Finally, it is shown by simulation that increasing the driving force for assembly stepwise by changing the solvent composition may circumvent metastable pathways and thereby force the assembly process directly into the correct pathway.

Enhanced Amplified Spontaneous Emission in Perovskites Using a Flexible Cholesteric Liquid Crystal Reflector.

Organic-inorganic perovskites are highly promising solar cell materials with laboratory-based power conversion efficiencies already matching those of established thin film technologies. Their exceptional photovoltaic performance is in part attributed to the presence of efficient radiative recombination pathways, thereby opening up the possibility of efficient light-emitting devices. Here, we demonstrate optically pumped amplified spontaneous emission (ASE) at 780 nm from a 50 nm-thick film of CH3NH3PbI3 perovskite that is sandwiched within a cavity composed of a thin-film (∼7 µm) cholesteric liquid crystal (CLC) reflector and a metal back-reflector. The threshold fluence for ASE in the perovskite film is reduced by at least two orders of magnitude in the presence of the CLC reflector, which results in a factor of two reduction in threshold fluence compared to previous reports. We consider this to be due to improved coupling of the oblique and out-of-plane modes that are reflected into the bulk in addition to any contributions from cavity modes. Furthermore, we also demonstrate enhanced ASE on flexible reflectors and discuss how improvements in the quality factor and reflectivity of the CLC layers could lead to single-mode lasing using CLC reflectors. Our work opens up the possibility of fabricating widely wavelength-tunable "mirror-less" single-mode lasers on flexible substrates, which could find use in applications such as flexible displays and friend or foe identification.

Self-Assembled Fluorescent Nanoparticles from π-Conjugated Small Molecules: En Route to Biological Applications.

Since the development of supramolecular chemical biology, self-organised nano-architectures have been widely explored in a variety of biomedical applications. Functionalized synthetic molecules with the ability of non-covalent assembly in an aqueous environment are typically able to interact with biological systems and are therefore especially interesting for their use in theranostics. Nanostructures based on π-conjugated oligomers are particularly promising as theranostic platforms as they bear outstanding photophysical properties as well as drug loading capabilities. This Feature Article provides an overview on the recent advances in the self-assembly of intrinsically fluorescent nanoparticles from π-conjugated small molecules such as fluorene or perylene based chromophores for biomedical applications.

Humidity-responsive liquid crystalline polymer actuators with an asymmetry in the molecular trigger that bend, fold, and curl.

We show a versatile method for the preparation of a variety of humidity-responsive actuators based on a single sheet of a hydrogen-bonded, uniaxially aligned liquid crystal polymer network. In this approach, the asymmetry in the molecular trigger in the anisotropic polymer film plays a dominant role leading to programmed deformation events. The material is locally treated with a potassium hydroxide solution to create the asymmetry in the responsiveness toward humidity, which allows to prepare actuators that bend, fold, or curl.

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.

Patterned silver nanoparticles embedded in a nanoporous smectic liquid crystalline polymer network.

A nanoporous smectic liquid crystalline polymer network has been exploited to fabricate photo patternable organic-inorganic hybrid materials, wherein, the nanoporous channels control the diameter and orientational order of the silver nanoparticles.