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Liquid crystal polymer networks (LCNs) are stimuli-responsive materials that can be programmed to realize spatial variation in mechanical response and undergo shape transformation. Herein, we report a process to introduce chemical specificity to the stimuli response of LCNs by integrating enzymes as molecular triggers. Specifically, the enzyme urease was immobilized in LCN films via acyl fluoride conjugation chemistry. Activity assays and confocal fluorescence imaging confirmed retention of urease activity after immobilization as well as widespread distribution of enzyme on the film. The addition of urea triggered a response in the LCN whereby newly generated ammonia reacted with free acyl fluorides to form benzamide moieties. These moieties were capable of dimerizing through the formation of supramolecular hydrogen bonds, which was reflected in a 4-fold increase in Young's modulus. Through dynamic mechanical analysis and calorimetry, we further confirmed that the degree of hydrogen bonding in the LCNs could be judiciously designed to fine-tune the mechanical properties and glass transition temperature. These findings demonstrate the untapped potential of biochemical mechanisms as molecular triggers in LCNs and open the door to the use of nucleophilic chemistries in modulating the mechanical properties of LCNs.

We use both lyotropic liquid crystals composed of prolate micelles and thermotropic liquid crystals made of rod-like molecules to uniformly disperse and unidirectionally align relatively large gold nanorods and other complex-shaped nanoparticles at high concentrations. We show that some of these ensuing self-assembled orientationally ordered soft matter systems exhibit polarization-dependent plasmonic properties with strongly pronounced molar extinction exceeding that previously achieved in self-assembled composites. The long-range unidirectional alignment of gold nanorods is mediated mainly by anisotropic surface anchoring interactions at the surfaces of gold nanoparticles. Polarization-sensitive absorption, scattering, and extinction are used to characterize orientations of nanorods and other nanoparticles. The experimentally measured unique optical properties of these composites, which stem from the collective plasmonic effect of the gold nanorods with long-range order in a liquid crystal matrix, are reproduced in computer simulations. A simple phenomenological model based on anisotropic surface interaction explains the alignment of gold nanorods dispersed in liquid crystals and the physical underpinnings behind our observations.

Cholesteric liquid crystals (CLCs) are selectively reflective optical materials, the color of which can be tuned via electrical, thermal, mechanical, or optical stimuli. In this work, we show that self-regulation of the transmission of a circularly polarized incident beam can occur upon phototuning of the selective reflection peak of a photosensitive CLC mixture towards the pump wavelength. The autonomous behavior occurs as the red-shifting selective reflection peak approaches the wavelength of the incident laser light. Once the red-edge of the CLC bandgap and incident laser wavelength overlap, the rate of tuning dramatically slows. The dwell time (i.e., duration of the overlap of stimulus wavelength with CLC bandgap) is shown to depend on the radiation wavelength, polarization, and intensity. Necessary conditions for substantial dwell time of the CLC reflection peak at the pump beam wavelength include irradiation with low intensity light (~1mW/cm²) and the utilization of circularly polarized light of the same handedness as the helical structure within the CLC. Monitoring the optical properties in both reflection and transmission geometries elucidates differences associated with attenuation of the light through the thickness of the CLC film.

A structured polymer was synthesized by surface initiated photopolymerization in the presence of a cholesteric liquid crystal (CLC). The templated helical polymer (traversing 2/3 the cell thickness) was backfilled with an opposite handedness, photoresponsive CLC mixture yielding a photo-induced, large contrast, hyper-reflective (R > 99%) CLC film.

The electrically‐directed, isothermal response of liquid crystal elastomers (LCEs) to an applied electric field is a compelling approach to realize spatially tailorable, sequence‐controllable, and high‐frequency deformation. The electromechanical response is facilitated by coating aligned LCEs with compliant electrodes. Upon application of an electric field, the electrodes attract and generate Maxwell stress. The directional difference in moduli for aligned LCEs produces directional deformation of the material and does not require mechanical bias or framing. Here, LCEs prepared from a newly reported thiol‐ene reaction are explored as DEAs with improved mechanical and dielectric properties. This report details that incorporating a difunctional liquid crystalline monomer composed of allyl ether functional groups reduces Young's modulus, increases the dielectric constant, and improves cyclic recovery compared to an analogous LCE prepared by thiol‐ene polymerization. Electrically‐induced, isothermal deformation of as much as 30% strain is reported. The facile chemistry and enhanced electromechanical response reported here may enable the functional integration of LCEs in applications such as robotics. [ABSTRACT FROM AUTHOR]

The combination of enzymes and chemically responsive smart materials presents considerable opportunities in anti‐fouling, sensing or medicine. Among stimuli‐responsive polymers, liquid crystal elastomers (LCEs) have emerged as a leading actuator platform due to their inherent programmability, realizing large shape transformations upon exposure to stimuli. Herein, three different hydrolytic enzymes are immobilized into acid‐responsive LCEs, which impart the LCEs with sensitivity to three distinctive classes of biomolecules: lipids, carbohydrates, and peptides. Dye‐doped biocatalytic LCEs readily switch their color and shape upon exposure to the appropriate substrate. Twisted nematic patterning and direct ink writing are used to showcase the versatility of shape changes the enzyme‐containing LCEs may undergo. Multiplexed responsiveness is also demonstrated using a connected array of 3D printed disks, each containing a different enzyme, highlighting the excellent chemical selectivity of the LCEs. This work presents a novel platform of versatile bioresponsive color‐switchable actuators that may have application in a wide range of fields. [ABSTRACT FROM AUTHOR]

Electrochromic devices have seen widespread adoption in the automotive and aerospace industries and are increasingly considered for applications in the built environment, such as smart windows. Here, a distinctive approach is reported to realizing electrochromism in solid, polymeric materials. The optical elements are based on liquid crystalline elastomers (LCEs) that retain the cholesteric phase (CLCEs). By integrating flexible, optically transparent, and conductive electrodes the CLCEs are actuated as dielectric elastomer actuators. Application of an electric field causes a significant change in the reflection wavelength of fully solid CLCE. The electromechanical response (Maxwell stresses) is reversible. Both uniaxial and biaxial prestrain are shown to enhance and differentiate the stimuli‐response in the photonic device. [ABSTRACT FROM AUTHOR]

Liquid crystal elastomers (LCE) are an emerging class of material actuators. LCE undergo macroscopic dimensional changes when subjected to a stimulus. The large stimuli‐response of LCE is associated with thermotropic disruption of order. Historically, comparatively high temperatures are required to disrupt orientation in LCE to achieve meaningful work output. Here, we introduce an approach to prepare LCE via thiol‐Michael/thiol–ene reactions that actuate at or below ambient temperature. Alignment was imparted to the LCE by mechanical alignment and 3D printing. The LCE materials detailed here achieve strains of 40 % with a maximum deformation rate of 6.5 % °C−1. The functional utility of the tunability of the thermotropic response of these materials is illustrated in reconfiguration triggered via body heat and sequential actuation of a multi‐material element. [ABSTRACT FROM AUTHOR]

The development of deployable biosensors that monitor the cumulative dose of toxic pesticides is essential to enable monitoring of soil and water exposure in populated areas. Liquid crystal elastomers (LCEs) offer unique potential as cumulative dose biosensors due to their ability to store chemical information within the polymer network that can later be decoded in the form of quantifiable shape changes. Here, we present an LCE-based biosensor for the detection of the organophosphorus pesticide malathion through the immobilization of the hydrolytic enzyme pig liver esterase (PLE). Exposure to malathion was detected via shape change of the LCE from a flat ribbon to a helical structure. Quantification of the helical pitch provided a label free readout that correlated directly with the cumulative dose of malathion and enabled detection of successive doses independent of dosage timing or dilution. The cumulative dose was chemically encoded in the LCE and could be decoded by hydration, even after successive drying and rehydration steps. Importantly, the signal from the LCE was largely insensitive to sensing conditions and to interference from various chemicals. The combined results illustrate the utility of biocatalytic LCEs for monitoring harmful pollutants while allowing continuous and cumulative dose sensing in real-world conditions. [Display omitted] • LCE-based biosensor for malathion detection using pig liver esterase. • Label-free shape-change readout by measuring the ribbon helical pitch. • Malathion cumulative dose is chemically encoded in LCE. • Output can be rapidly encoded/decoded by drying/hydration of LCE. [ABSTRACT FROM AUTHOR]

Electrical reconfiguration of the cholesteric liquid crystal phase is subject to extensive prior research. Here, a distinctive composition that allows the typically singular selective reflection to be split into two distinct and tunable selective reflections with an electric field is reported. The distinctive electro‐optic phenomena (reflection notch splitting) are shown to be composition dependent and enabled by the introduction of appreciable amounts of side chain liquid crystalline mesogens. Functional opportunities enabled by the distinguished control of the two reflection elements are demonstrated, including spectrally variant polarization filters. [ABSTRACT FROM AUTHOR]

Liquid crystal elastomers (LCEs) are anisotropic polymeric materials. When subjected to an applied stress, liquid crystalline (LC) mesogens within the elastomeric polymer network (re)orient to the loading direction. The (re)orientation during deformation results in nonlinear stress‐strain dependence (referred to as soft elasticity). Here, we uniquely explore mechanotropic phase transitions in elastomers with appreciable mesogenic content and compare these responses to LCEs in the polydomain orientation. The isotropic (amorphous) elastomers undergo significant directional orientation upon loading, evident in strong birefringence and x‐ray diffraction. Functionally, the mechanotropic displacement of the elastomers to load is also nonlinear. However, unlike the analogous polydomain LCE compositions examined here, the isotropic elastomers rapidly recover after deformation. The mechanotropic orientation of the mesogens in these materials increase the toughness of these thiol‐ene photopolymers by nearly 1300 % relative to a chemically similar elastomer prepared from wholly isotropic precursors. [ABSTRACT FROM AUTHOR]

ABSTRACT: Polymerization of crosslinkable liquid crystal monomers in chiral liquid crystalline media stabilizes the phase and enables distinct electro‐optic properties relative to small‐molecule analogs. Particularly interesting are cases where the polymerization forms a crosslinked polymer network that maintains a “structural” chirality. Recent reports have employed this methodology to realize a diverse set of electro‐optic responses in polymer stabilized cholesteric liquid crystals (PSCLCs) including reflection bandwidth broadening, reflection wavelength tuning, and dynamic scattering modes. It has been proposed that the mechanism at the root of these electro‐optic responses is an ion‐mediated, electromechanical deformation of the stabilizing and structurally chiral polymer network. In an effort to better understand the nature of these deformations, here we have characterized the electro‐optic response of PSCLCs with different polymer concentrations and crosslink densities. The dynamic response of PSCLCs to electric fields exhibits a time‐dependent behavior reminiscent of the creep of polymeric materials to mechanical deformations. The electro‐optic response can be described as the superposition of two contributions: the fast deformation of a relatively soft component of the polymer network (1–2 s) and the slower (10–20 s) deformation of a harder component. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 1087–1093 [ABSTRACT FROM AUTHOR]

ABSTRACT: Liquid crystals are widely employed as stimuli‐responsive materials. Liquid crystallinity can be retained in polymeric form. Photoinduced mechanical effects in liquid crystalline polymer networks and elastomers have been a topic of considerable recent research. This review details the historical underpinnings and recent advances in the synthesis and the corresponding photomechanical response of these materials. In nearly all cases, the conversion of light into mechanical work has employed azobenzene as either a guest additive or covalently attached to the network. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 695–705 [ABSTRACT FROM AUTHOR]

Photoinduced isothermal and order-increasing phase transitions can be observed in guest-host liquid crystal mixtures containing naphthopyran derivatives. The changes are attributed to the different geometry and a less energetically favorable interaction with the liquid crystal molecules for the ground state naphthopyran species with respect to the photoproduct. In this study, we have investigated the thermal relaxation of the naphthopyran photoproduct back to the initial species as a function of temperature and excitation conditions. It was found that the thermal relaxation is typically first-order and its characteristic rate has a temperature dependence that is different in the anisotropic and isotropic states of the mesogenic solvents. In particular, the activation energy for thermal relaxation is larger in the ordered phases of mesogenic solvents relative to their isotropic phase. The findings suggests that the naphthopyran relaxation is hindered by the organization of the host environment. These results will be useful to build a more complete understanding of the mutual guest-host interactions in naphthopyran-containing guest-host LC systems. [ABSTRACT FROM AUTHOR]

All-optical deformation and recovery of complex topographical features is demonstrated within elastic sheets composed of main-chain type azobenzene-functionalized liquid crystalline elastomers (azo-LCEs). The azo-LCEs are synthesized via an orthogonal, two-step reaction between commercially available LC monomers and n-butylamine. By employing surface alignment, the local orientation of the nematic director is spatially complex ('blueprinted'). Exposing the blueprinted LCE films to light as an actinic stimulus generates a photomechanical response which yields reversible shape changes between 2D and 3D shapes. The deformation of azo-LCEs strongly depends on the azobenzene concentration as well as the network structure (i.e., crosslink density). Blueprinting complex director profiles within azo-LCEs yield reconfigurable elastic sheets that can be addressed both remotely and selectively which may have benefit in a variety of applications in aerospace, medicine, and optics. [ABSTRACT FROM AUTHOR]

Liquid crystals are the basis of a pervasive technology of the modern era. Yet, as the display market becomes commoditized, researchers in industry, government and academia are increasingly examining liquid crystalline materials in a variety of polymeric forms and discovering their fascinating and useful properties. In this Review, we detail the historical development of liquid crystalline polymeric materials, with emphasis on the thermally and photogenerated macroscale mechanical responses - such as bending, twisting and buckling - and on local-feature development (primarily related to topographical control). Within this framework, we elucidate the benefits of liquid crystallinity and contrast them with other stimuli-induced mechanical responses reported for other materials. We end with an outlook of existing challenges and near-term application opportunities. [ABSTRACT FROM AUTHOR]

A different generation of polymer-dispersed liquid crystals (PDLCs) based on a liquid crystalline polymer host is reported wherein the fluid behavior of the reactive mesogenic monomer is an enabler to concentration windows (liquid crystal polymer/liquid crystal) (and subsequent morphologies) not previously explored. These liquid crystal (LC) polymer/LC composites, LCPDLCs, exhibit excellent optical and electro-optical properties with negligible scattering losses in both the ON and OFF states. These systems thus have application in systems where fast phase modulation of optical signal instead of amplitude control is needed. Polarized optical microscopy and high resolution scanning electron microscopy confirm a bicontinuous morphology composed of aligned LC polymer coexisting with a phase separated LC fluid. Operating voltages, switching times, and spectra of LCPDLCs compare favourably to conventional PDLC films. The LCPDLCs exhibit a low switching voltage (4-5 V/µm), symmetric and submillisecond (200 µs) on/off response times, and high transmission in both the as formed and switched state in a phase modulation geometry. [ABSTRACT FROM AUTHOR]

On the other hand: Azoarene compounds with axially chiral binaphthyl units of the same and opposite chiral configurations were doped into achiral liquid crystals (LCs). They were found to efficiently induce self‐organized helical superstructures, which could be reversibly tuned by light irradiation using trans–cis photoisomerization to change the handedness of the helix (see scheme) in LC hosts. [ABSTRACT FROM AUTHOR]

Circularly polarized light was previously employed to stimulate the reversible and reconfigurable writing of scattering states in cholesteric liquid crystal (CLC) cells constructed with a photosensitive layer. Such dynamic photodriven responses have utility in remotely triggering changes in optical constructs responsive to optical stimulus and applications where complex spatial patterning is required. Writing of scattering regions required the handedness of incoming radiation to match the handedness of the CLC and the reflection bandwidth of the CLC to envelop the wavelength of the incoming radiation. In this paper, the mechanism of transforming the CLC into a light scattering state via the influence of light on the photosensitive alignment layer is detailed. Specifically, the effects of: (i) the polarization state of light on the photosensitive alignment layer; (ii) the exposure time; and (iii) the incidence angle of radiation on domain formation are reported. The photogenerated light-scattering domains are shown to be similar in appearance between crossed polarizers to a defect structure that occurs at a CLC/air interface (i.e., a free CLC surface). This observation provides strong indication that exposure of the photosensitive alignment layer to the circularly polarized light of appropriate wavelength and handedness generates an out-of-plane orientation leading to a periodic distortion of the original planar structure. [ABSTRACT FROM AUTHOR]

Prior examinations have reported that polymer stabilisation of azobenzene-based cholesteric liquid crystal (CLC) mixtures can reduce the time necessary for complete colour restoration in the dark from three days to as few as five minutes. This work extends upon these prior examinations by exploring and elucidating the role of crosslinker concentration and monomer polarity on the colour restoration of a representative CLC mixture composed of a high HTP bis(azo) binapthanyl chiral dopant (QL76) mixed into the cyanobiphenyl nematic liquid crystal host MDA-00-1444. The impact of these variables was unexpectedly convoluted. In all the formulations examined here, polymer stabilisation dramatically reduces the time for complete colour restoration of the starting reflection notch. In mixtures based on nonpolar liquid crystal monomers, increasing the crosslinker concentration reduces the time necessary for complete colour restoration. However, the dependence on crosslinker concentration reverses in mixtures composed from polar liquid crystal monomers in which increasing the crosslinker concentration serves to increase the time necessary for complete colour restoration. [ABSTRACT FROM AUTHOR]

The magnitude of the color changes induced by heating chiral templated polymer structures formed in spatially heterogeneous cells is examined. The large blue and subsequent red tuning of the selective reflection wavelength, caused by deswelling/reswelling of the network at the transition temperatures, is affected by the network crosslink density, heating/cooling rates, and architecture of the cell. The system is stable to multiple heat/cool cycles and shows large scale coloration changes at heating rates up to 10°C/min. At higher heating rates, a distortion of the selective reflection notch shape occurs during tuning. The magnitude of the color change is not affected by rate. At both high and low crosslink density, no tuning is observed. A window of network elasticity and responsiveness is needed to enable the anisotropic contraction/expansion processes to be observed macroscopically. Finally, the magnitude of tuning relative to the cell thickness and spatial heterogeneity across the thickness direction is explored. In thin cells, the tuning range was substantially diminished. [ABSTRACT FROM AUTHOR]

Abstract: A study of nanoporous polymer gratings, with controllable nanostructured porosity, as a function of grating performance, photopolymerization kinetics and morphology is presented. Modifying the standard holographic polymer dispersed liquid crystal (H-PDLC) system, by including a non-reactive solvent, results in a layered, nanoporous morphology and produces reflective optical elements with excellent optical performance of broadband reflection. The addition of the non-reactive solvent in the pre-polymer mixture results in a morphology typified by void/polymer layer-by-layer structures if sufficient optical energy is used during the holographic writing process. The duration and intensity of optical exposure necessary to form well-aligned nanoporous structures can only be obtained in the modified system by (a) illumination under longer time of holographic interference patterning (30min) or (b) illumination under very short time of holographic interference patterning (30s) and followed by post-curing using homogeneous optical exposure for 60min. Comparatively, a typical H-PDLC is formed in less than 1min. To further understand the differences in the formation of these two analogous materials, the temporal dynamics of the photoinitiation and polymerization (propagation) kinetics were examined. It is shown herein that the writing exposure gives a cross-linked polymer network that is denser in the bright regions. With 60% (or even 45%) acrylate conversion, almost no free monomer would be left after the writing. Continued exposure serves primarily to add cross-links. This has the tendency to collapse the network, especially the less dense portions, which in effect get glued down to the more dense parts. To the extent that the solvent increases the mobility of the polymer network, this process will be aided. Equally important, the size of the periodic nanopores can be varied from 10 to 50nm by controlling either the LC concentration in the pre-polymer mixture or by controlling the time of the homogeneous post-cure. [Copyright &y& Elsevier]

Fundamental control of the polymerization behaviour of polymer-dispersed liquid crystals (PDLCs) is critical to the formation of high-performance devices by polymer-induced phase separation (PIPS). Previous PDLC research has shown that monomer functionality and additives such as surfactants or reactive diluents can impart significant changes to the electro-optical behaviour of a system, especially in acrylate-based materials. The influence of monomer functionality and additives on the polymerization kinetics and LC phase separation were examined in the formation of acrylate-based PDLCs. Real-time infrared (RTIR) spectroscopy was utilized to simultaneously monitor polymerization rate, double bond conversion and LC phase separation. In the formation of PDLCs by PIPS, increasing acrylate monomer functionality reduces the polymerization rate, overall double bond conversion and the extent of LC phase separation. Interestingly, the additives octanoic acid and N-vinylpyrrolidone (NVP) increase the polymerization rate but suppress LC phase separation. During PDLC formation, both octanoic acid and NVP enhance the solubility of the LC in the growing polymer matrix, reducing the rate of liquid-gel demixing and decreasing nematic fraction in PDLCs. As a non-reactive component, octanoic acid increases the polymerization rate by plasticizing the crosslinked polymerization. NVP, a reactive diluent added to decrease viscosity, increases polymerization rate through favourable copolymerization with acrylate monomer. [ABSTRACT FROM AUTHOR]

Abstract: The morphology and corresponding performance of holographic polymer dispersed liquid crystals (HPDLCs) based on thiol–ene polymer are dependent on a number of factors including the gel point conversion of the polymer, polymerization kinetics, and extent of liquid crystal (LC) phase separation. Previous research of HPDLC reflection gratings made from thiol–allyl ether polymer indicates that increasing polymerization rate in systems with moderate gel point conversion can improve diffraction efficiency (DE). This work examines HPDLC reflection gratings that contain the ene monomer triallyl isocyanurate (TATATO). In HPDLCs, thiol–TATATO polymerization is two times faster than the thiol–ene polymerization of triallyl ether. By substituting TATATO for triallyl ether, the LC droplet size within HPDLC reflection gratings decreases from 100nm to 25nm. The dramatic reduction in LC droplet size for thiol–TATATO HPDLCs increases baseline transmission from 55% in thiol–triallyl ether HPDLCs to 90% at 450nm. Unfortunately, the DE of thiol–TATATO HPDLCs is only approximately 10% due to poorly defined lamellae in the grating morphology. As determined with real-time IR (RTIR) spectroscopy, thiol–TATATO HPDLCs have significantly faster LC demixing kinetics in comparison to thiol–allyl ether HPDLCs. During holographic photopolymerization, the increased rate of LC demixing causes formation of LC droplets throughout the grating. The low DE of thiol–TATATO HPDLCs can be improved by mixing TATATO and allyl ether monomer. The morphology of ternary thiol–ene HPDLC formulations containing TATATO and allyl ether has a well-defined grating structure due to increased LC solubility in the system, an average LC droplet size of 50nm, and baseline transmission of nearly 85% at 450nm. [Copyright &y& Elsevier]

Abstract: Holographic polymer dispersed liquid crystals (HPDLCs) are targeted for application in a wide range of devices as dynamically switchable transmission or reflection diffraction gratings tunable through the visible spectra. The inclusion of N-vinyl pyrrolidinone (NVP) has been shown to reduce liquid crystal (LC) droplet size in HPDLC gratings and subsequently improve HPDLC performance. In this work, the influence of NVP on HPDLC polymer/LC morphology is examined and correlated to the influence of NVP on HPDLC photopolymerization kinetics and LC phase separation. As in other photopolymer systems, NVP significantly increases the rate of polymerization in HPDLC photopolymerization. In all the HPDLC formulations studied, NVP is completely incorporated into the polymer network while less than half of acrylate double bonds react. Furthermore, as the highly cross-linked polymer network forms, the small mono-vinyl NVP appears to react preferentially with acrylate double bonds, facilitating additional conversion of pendant double bonds otherwise trapped in the polymer network. NVP also induces a delay in the onset of reaction diffusion termination and extends the range of conversions for which reaction diffusion is observed. Interestingly, NVP also impacts polymer/LC morphology by delaying LC phase separation to higher double bond conversions. Together, the influence of NVP on the polymerization kinetics and LC phase separation alters HPDLC morphology by limiting LC droplet size, consequently resulting in improved HPDLC performance. [Copyright &y& Elsevier]

We have previously reported that the application of a DC field can adjust the position and/or bandwidth of the selective reflection notch in polymer-stabilized cholesteric liquid crystals (PSCLCs). The proposed mechanism of these electro-optic (EO) response is ion-facilitated electromechanical deformation of the polymer stabilizing network. Accordingly, the concentration of ions trapped within the polymer network should considerably influence the EO response of PSCLC. Our prior studies have indicated that photoinitiators can increase ion density in PSCLC by an order of magnitude. Here, we isolate the contribution of ionic impurities associated with liquid crystal monomers (LCMs) by utilizing initiator-less polymerization. PSCLCs prepared with LCM with low ion concentration show bandwidth broadening of the reflection band whereas PSCLCs prepared with LCM with high ion concentration exhibit a red shifting tuning of the reflection band. The extent of the tuning or bandwidth broadening of the CLC reflection band depends on the concentration of LCMs and the chirality of the LCM. [ABSTRACT FROM AUTHOR]

Liquid crystals are traditionally classified as thermotropic, lyotropic or polymeric, based on the stimulus that governs the organization and order of the molecular system. The most widely known and applied class of liquid crystals are a subset of thermotropic liquid crystals known as calamitic, in which adding heat can result in phase transitions from or into the nematic, cholesteric and smectic mesophases. Photoresponsive liquid-crystal materials and mixtures can undergo isothermal phase transitions if light affects the order parameter of the system within a mesophase sufficiently. In nearly all previous examinations, light exposure of photoresponsive liquid-crystal materials and mixtures resulted in order-decreasing photo-induced isothermal phase transitions. Under specialized conditions, an increase in order with light exposure has been reported, despite the tendency of the photoresponsive liquid-crystal system to reduce order in the exposed state. A direct, photo-induced transition from the isotropic to the nematic phase has been observed in a mixture of spiropyran molecules and a nematic liquid crystal. Here we report a class of naphthopyran-based materials that exhibit photo-induced conformational changes in molecular structure capable of yielding order-increasing phase transitions. Appropriate functionalization of the naphthopyran molecules leads to an exceedingly large order parameter in the open form, which results in a clear to strongly absorbing dichroic state. The increase in order with light exposure has profound implications in optics, photonics, lasing and displays and will merit further consideration for applications in solar energy harvesting. The large, photo-induced dichroism exhibited by the material system has been long sought in ophthalmic applications such as photochromic and polarized variable transmission sunglasses. [ABSTRACT FROM AUTHOR]

A structured polymer was synthesized by surface initiated photopolymerization in the presence of a cholesteric liquid crystal (CLC). The templated helical polymer (traversing 2/3 the cell thickness) was backfilled with an opposite handedness, photoresponsive CLC mixture yielding a photo-induced, large contrast, hyper-reflective (R> 99%) CLC film. [ABSTRACT FROM AUTHOR]

Abstract: A light-responsive cholesteric liquid crystal (CLC) mixture is tuned with light and applied DC electric field. Interestingly, the reflection of the CLC is red shifted with UV light and blue shifted with applied DC electric fields. UV light exposure induces a red shift in the reflection of the CLC bandgap by as much as 800nm from the original spectral position. Spatial variations in pitch (and thus reflection color) are shown to blue shift with applied DC field regardless of the photohistory and restore the notch position or image upon removal of the field. The ability to tune the reflection of the CLC bandgap on demand to the red or blue with multiple stimuli is a never before demonstrated effect that could have potential utility in lasing, optical filtering, or data communication applications. [Copyright &y& Elsevier]

We report on the large wavelength range and light-initiated thermal tuning of the reflection of a liquid crystal (LC) formulation (S811/ZLI-2806) near a smectic (SmA) to cholesteric (CLC) phase transition enabled by the use of a high order parameter heat transfer dye (anthraquinone, AQ). Upon irradiation with a 647 nm Krypton ion (Kr+) laser line, absorption by AQ generates heat that is transferred to the surrounding LC host. In the S811/ZLI-2806 formulation examined here, the optically generated increase in temperature serves to transition the phase from SmA to CLC. As has been documented, the SmA→CLC transition is typified by a pitch contraction that blueshifts the position of the CLC reflection, in this case a shift from 2500 to 700 nm that can occur in less than 100 s. The tuning range and speed are dependent on the laser power and the amount of dye in the cell. [ABSTRACT FROM AUTHOR]

Keywords: 2-photon direct laser write; liquid crystal elastomers; photocationic polymerization In article number 1903761, Timothy J. White and co-workers employ two-photon polymerization to prepare hybrid micro-patterned actuators from liquid crystal elastomers. 2-photon direct laser write, liquid crystal elastomers, photocationic polymerization. [Extracted from the article]

Liquid crystal elastomers (LCEs) are soft materials that undergo large anisotropic shape change in response to stimuli. Rational organization of the local director field can impart spatial control of the strain profile, enabling stretch‐based deformation capable of nearly 20 J kg−1 of output force. LCEs are increasingly being considered in end‐use applications in robotics, therapeutics, and optics. Here, a new synthetic approach is introduced to prepare LCEs composed of main chain mesogens via the cationic photopolymerization of the epoxy liquid crystal monomer (LCM). This examination details the optical, mechanical, and thermal properties of epoxide‐based LCEs as a function of spacer length (3, 6, or 11 carbons). The oxygen insensitivity of the cationic photopolymerization of these monomers makes this approach particularly attractive for implementation with emerging additive manufacturing techniques. This contribution focuses on microstructuring LCEs via 2‐photon direct laser writing (2P‐DLW). A custom heated cell facilitated 2P‐DLW of the aligned LCE epoxy resin melts to fabricate diverse geometric arrays. Enabled by the orthogonality of the reaction chemistry, hybrid and microstructured material compositions are prepared via the encapsulation of LCE epoxy micropatterns with free‐radical polymerization of acrylate‐based LCEs. The distinct thermomechanical response of the hybridized and microstructured LCE composites enables local and spatially controlled actuation. [ABSTRACT FROM AUTHOR]

The facile synthesis of well‐aligned, main‐chain liquid crystalline elastomers that retain the cholesteric phase (CLCEs) is reported. The selective reflection inherent to this phase is thermally tuned more than 200 nm in these solid films, across the visible spectrum. The optical response is directly correlated to thermomechanical expansion of the CLCE film thickness. The bandwidth of the selective reflection of the CLCEs is increased to more than 200 nm by the incorporation of photosensitive chiral dopants that introduce heterogeneity in the pitch distribution. The mirror‐like reflection of this CLCE film is also thermochromic, shifting from the visible to infrared. Reminiscent of cephalopods, when combined with the mechanical deformation of voxelated nematic liquid crystal elastomer, the thermochromic response of the CLCE produces solid‐state elements with concurrent variation of specular and diffuse reflectance. These results demonstrate distinctive potential opportunities for liquid crystal elastomers to control light enabling new application in textiles, optics, and architecture. Nature employs concurrent shape and color change to control light and enable function. Concurrent shape and color change is realized in bilayer laminates of liquid crystal elastomers. The optical response is enabled by the facile synthesis of well‐aligned and main‐chain liquid crystalline elastomers retaining the cholesteric phase. Full‐spectrum thermochromism is observable in both narrow and broadband reflections in cholesteric liquid crystal elastomers. [ABSTRACT FROM AUTHOR]

The photoinduced topographical deformation of azobenzene‐functionalized liquid crystalline elastomers is reported by T.J. White and co‐workers on page 5819. The authors report on the use of UV light irradiation to transform originally flat sheets into topographical surfaces. The photoinduced shape transformation and relaxation is shown to strongly depend on the azobenzene concentration as well as the network structure. [ABSTRACT FROM AUTHOR]

The article discuses the demonstration of Snap through mechanisms in liquid crystalline elastomers (LCEs). It is reported that Liquid crystalline elastomers (LCEs) are stimuli responsive materials that are noted for their ability to generate large, complex deformations in response to a stimulus. It is further reported that snap through transitions in soft materials has been explored using gradients in crosslink density, light exposure, swelling, and pressure.

We report here a fast-photon-mode reversible handedness inversion of a self-organized helical superstructure (i.e., a cholesteric liquid crystal phase) using photoisomerizable chiral cyclic dopants. The two light-driven cyclic azobenzenophanes with axial chirality show photochemically reversible trans to cis isomerization in solution without undergoing thermal or photoinduced racemization. As chiral inducing agents, they exhibit good solubility, high helical twisting power, and a large change in helical twisting power due to photoisomerization in three commercially available, structurally different achiral liquid crystal hosts. Therefore, we were able to reversibly tune the reflection colors from blue to near-IR by light irradiation from the induced helical superstructure. More interestingly, the different switching states of the two chiral cyclic dopants were found to be able to induce a helical superstructure of opposite handedness. In order to unambiguously determine the helical switching, we employed a new method that allowed us to directly determine the handedness of the long-pitched self-organized cholesteric phase. [ABSTRACT FROM AUTHOR]

The article focuses on research into voxelated liquid crystal elastomers, which are soft materials capable of programmable shape change which can provide devices with multifunctionality. It states that the molecular order direction (MOD) is written into voxels and mentions that MOD controls the material's inherent mechanical response. It talks about how chemical or thermal stimuli can change flat sheets into three-dimensional objects through controlled stretching and bending.

Photoinduced order-increasing phase transitions can occur in dye-liquid crystal mixtures when the photoproduct of the excitation of the dye molecules is more compatible with the liquid crystalline medium than the initial dye species. A detailed investigation of the photoinduced changes of the phase behavior and optical properties of mixtures of liquid crystals with naphthopyran guests upon exposure to light at 365 nm is presented here. In these guest-host systems, the nematic-to-isotropic phase transition temperature is increased upon irradiation. We show that the nematic range can be extended up to 2.9 °C by illumination in 5CB (4−n-pentyl-4′-cyanobiphenyl) liquid crystal mixtures. The order parameter is significantly increased by illumination at all temperatures within the nematic range and the changes are larger at higher concentrations of the guests. In particular, the illuminated guest-host mixtures exhibit order parameters close to those of the neat liquid crystal host at the same temperature relative to the clearing point. An improved understanding of the photophysical processes taking place at the molecular level in these material systems can inform the design of photoresponsive materials and enhance their potential utility in optical or photonic devices. [ABSTRACT FROM AUTHOR]