Liquid Crystalline Networks Research Articles

Liquid Crystal-Induced Myoblast Alignment.

The ability to control cell alignment represents a fundamental requirement toward the production of tissue in vitro but also to create biohybrid materials presenting the functional properties of human organs. However, cell cultures on standard commercial supports do not provide a selective control on the cell organization morphology, and different techniques, such as the use of patterned or stimulated substrates, are developed to induce cellular alignment. In this work, a new approach toward in vitro muscular tissue morphogenesis is presented exploiting liquid crystalline networks. By using smooth polymeric films with planar homogeneous alignment, a certain degree of cellular order is observed in myoblast cultures with direction of higher cell alignment corresponding to the nematic director. The molecular organization inside the polymer determines such effects since no cell organization is observed using homeotropic or isotropic samples. These findings represent the first example of cellular alignment induced by the interaction with a nematic polymeric scaffold, setting the stage for new applications of liquid crystal polymers as active matter to control tissue growth.

Butterfly proboscis-inspired tight rolling tapered soft actuators.

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

Printable photonic polymer coating based on a monodomain blue phase liquid crystal network

In this paper, a printable photonic polymer coating was fabricated from a monodomain liquid crystalline blue phase network.

A self-sustained soft actuator able to rock and roll.

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.

Light-induced mechanical response in crosslinked liquid-crystalline polymers with photoswitchable glass transition temperatures

Energy conversion of light into mechanical work is of fundamental interest in applications. In particular, diligent molecular design on nanoscale, in order to achieve efficient photomechanical effects on macroscopic scale, has become one of the most interesting study topics. Here, by incorporating a “photomelting” azobenzene monomer crosslinked into liquid crystalline (LC) networks, we generate photoresponsive polymer films that exhibit reversible photoswitchable glass transition temperatures (Tg) at room temperature (~20 °C) and photomechanical actuations under the stimulus of UV/visible light. The trans-to-cis isomerization of azo chromophores results in a change in Tg of the crosslinked LC polymers. The Tg of the polymer network is higher than room temperature in the trans-form and lower than room temperature in the cis-form. We demonstrate the photoswitchable Tg contribute to the photomechanical bending and a new mechanism for photomechanical bending that attributes the process to an inhomogeneous change in Tg of the film is proposed.

Curing Reaction and Dielectric Properties of Rigid and Elastic Liquid Crystal Epoxy Networks Modified with Nanofillers

The aim of the paper is to compare the progress of the curing reaction and the dielectric properties of liquid crystalline epoxy networks of different elasticity and to investigate how modification with nanofillers influences their properties. The study focuses on a liquid crystalline epoxy monomer with four aromatic rings in the mesogen, cross-linked with 4,4′-diaminodiphenylmethane (DDM) and pimelic acid (PA) to produce rigid and elastic polymer networks. The obtained results are compared to networks modified with nanofillers (diphenyl aluminum phosphate nanorods). The curing process is monitored in situ with broadband dielectric spectroscopy, which is a good tool to view the progress of the reaction. Two stages with different reaction dynamics are observed in the studied cases. Dielectric properties of the products cured with two chosen agents show significant differences in the obtained parameters (activation energy, glass transition, and fragility index) as well as in the dynamics of the α and β relaxations. Although the curing agent is the main factor determining the properties of the product, the nanofiller additive also modifies the values of specific parameters that characterize both the process of the reaction and the properties of the final composites. Particularly, adding the nanofiller raises the glass transition temperature in both the cases. The obtained results are in good agreement with the earlier calorimetric study.

Motion control in free-standing shape-memory actuators

In this work, free-standing shape-memory thermally triggered actuators are developed by laminating ‘thiol-epoxy’-based glassy thermoset (GT) and stretched liquid-crystalline network (LCN) films. A sequential curing process was used to obtain GTs with tailored thermomechanical properties and network relaxation dynamics, and also to assemble the final actuator. The actuation extent, rate and time were studied by varying the GT and the heating rate in thermo-actuation with an experimental approach. The results demonstrate that it is possible to tailor the actuation rate and time by designing GT materials with a glass transition temperature close to that of the liquid-crystalline-to-isotropic phase transition of the LCN, thus making it possible to couple the two processes. Such coupling is also possible in rapid heating processes even when the glass transition temperature of the GT is clearly lower than the isotropization temperature of the LCN, depending on the network relaxation dynamics of the GT and the presence of thermal gradients within the actuators. Interestingly, varying the GT network relaxation dynamics does not affect the actuation extent. As predicted by the analytical model developed in our previous work, the modulus of the GT layer is mainly responsible for the actuation extent. Finally, to demonstrate the enhanced control of the actuation, specifically designed actuators were assembled in a three-dimensional actuating device able to make complex motions (including ‘S-type’ bending). This approach makes it possible to engineer advanced functional materials for application in self-adaptable structures and soft robotics.

Kinetics of Ordering and Deformation in Photosensitive Azobenzene LC Networks.

Azobenzene-containing polymer networks are unique compounds that are able to change their shape in response to light, which makes them prospective materials for photocontrollable nano-templates, sensors, microrobots, artificial muscles, etc. In present work, we study the kinetics of light-induced ordering and deformation in two-component polymer networks containing optically inert liquid crystalline (LC) mesogens and azobenzene chromophores. By this, we generalize our previous theory [J. Phys. Chem. Lett. 2017, 8, 1094–1098] devoted to the kinetics of photoizomerization in one-component azo-polymers without mesogenic inclusions. The kinetic equations of photoisomerization are used, taking into account the angular selectivity of the photoisomerization with respect to the polarization direction of the light E. After multiple trans-cis-trans photoisomerization cycles, the azobenzenes are reoriented preferably perpendicular to the vector E. This changes the ordering of the mesogens due to the orientational LC interactions between the components. The light-induced reordering is accompanied by network deformation. Time evolution of ordering and deformation is found as a function of the intensity of light and structural parameters of the LC azo-networks, which define the viscosity, the strength of the LC interactions between the components, the volume fraction of the azobenzene moieties, and the angular distribution of azobenzenes in polymer chains. Established structure-property relationships are in agreement with a number of experimental data.

Structured Optical Materials Controlled by Light

AbstractMaterials whose optical response is determined by their structure are of much interest both for their fundamental properties and applications. Examples range from simple gratings to photonic crystals. Obtaining control over the optical properties is of crucial importance in this context, and it is often attempted by electro‐optical effect or by using magnetic fields. In this paper, the use of light is introduced to switch and tune the optical response of a structured material, exploiting a physical deformation induced by light itself. In this new strategy, light drives an elastic reshaping, which leads hence to a change in the optical response. This is made possible by using liquid crystalline networks structured by direct laser writing. As a proof of concept, a grating structure with sub‐millisecond time response is demonstrated for optical beam steering, exploiting an optically induced reversible shape change. Experimental observations are combined with finite‐element modeling in order to understand the actuation process dynamics, and to obtain information on how to tune the time and the power response of this technology. This optical beam steerer opens up full optical control of light in a broad range of structured optical materials.

Interfacial liquid crystalline mesophase domain on carbon nanofillers in aromatic thermosetting copolyester matrix

ABSTRACTThis work presents the formation process and thermophysical characteristics of preferentially oriented interfacial liquid crystalline (LC) mesophase domain emerging around graphene nanoplatelet (GNP) particles within an amorphous aromatic thermosetting copolyester (ATSP) matrix. Acetoxy‐ and carboxylic acid‐capped matched oligomers of ATSP interact with oxygen‐bearing functional groups on the GNPs during the thermal polymerization process which tethers the nanofillers to the crosslinked polymer backbone. Upon curing, a nematic phase LC network develops at the nanoparticle and matrix interface via the crystalline carbonaceous structure induced local ordering effects. The LC region exhibits a thermally reversible phase transition characteristic; attains an isotropic morphology through a heating cycle and reverses to the nematic form following a subsequent cooling cycle. Solid‐state nuclear magnetic resonance spectroscopy analysis reveals the presence of a robust interfacial attachment between the GNPs and ATSP backbone. The strong covalent conjugation induces a marked upshift in the glass transition temperature (Tg) in the ATSP‐GNP nanocomposites. Introduction of an LC interlayer region surrounding the nanofillers facilitated by a strong interfacial attachment mechanism could help to optimize the performance of polymer nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46584.

Ionic liquid-crystalline network polymers formed by sulfonic acid-containing polysiloxanes and pyridinium compounds

Self-assembly of both ionic aggregates and mesogens in one polymer system represents the capability integrating intermolecular interactions and functions of materials. A series of ionic liquid-crystalline network polymers (ILCNs) containing cholesterol derivatives, siloxane backbone and ionic pyridinium sulfonic groups are synthesized, and the characterization, self-assembly behavior, and possible applications are discussed. The ILCNs are made from sulfonic acid-containing precursor polymers synthesized by use of cholest-5-en-3-ol-(3β)-4-(allyloxy)benzoate, 4-(allyloxy)benzenesulfonic acid and poly(methylhydro)siloxane. The ILCNs show a cubic mesophase and a smectic A (SmA) mesophase. The SmA layers develop saddle splay curvature and adopt the shape of infinite minimal surfaces, therefore self-assembly of bicontinuous cubic phases takes place due to ionic electrostatic attraction and asymmetry derived from the chiral cholesterol elements. Large ionic conductivity and remarkable thermal stability of the ILCNs provide promising opportunities for ion transport devices because they provides facilitated ion-transport pathways including smectic ordering and three-dimensional interconnected ionic channels.

Photomechanical effects in liquid crystalline polymer networks and elastomers

ABSTRACTLiquid 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

Phase behavior of main-chain liquid crystalline polymer networks synthesized by alkyne-azide cycloaddition chemistry.

Liquid crystalline polymer networks (LCNs) couple polymer chain organization to molecular ordering, the switching of which has been shown to impart stimuli-responsive properties, including actuation and one-way shape memory, to the networks. While LCNs have long been proposed as artificial muscles, recent reports have also suggested potential as dynamic biomaterial substrates. In contrast to many existing LCNs synthesized using hydrophobic spacers, this work investigates networks synthesized using more hydrophilic spacers to promote interaction with water. A challenge with such materials is liquid crystalline phases could be disrupted in hydrated networks. This work thus investigates the impact of polyether spacers and mesogen composition on the phase behavior of LCNs. Main-chain LCNs were synthesized using alkyne-azide cycloaddition ("click" chemistry), where two different mesogens (5yH and 5yMe) and a non-LC monomer (5yTe) were coupled with one of two different polyether spacers, poly(ethylene glycol) and poly(propylene glycol), and a crosslinker. The chemistry led to high gel fraction materials, the workup of which resulted in networks that displayed no difference in cellular toxicity due to leachable components compared to tissue culture plastic control. Calorimetric analysis, dynamic mechanical analysis, and X-ray scattering revealed the LC microstructure and temperature-responsive properties of the networks. The use of low molecular weight polyether spacers was found to prevent their crystallization within the LC network, and adjusting mesogen composition to enhance its LC phase stability allowed the use of spacers with larger molecular weights and pendant groups. Hydrated networks were found to rearrange their structure compared to dry networks, while maintaining their LC phases. Like other crosslinked LC materials, the networks display shape changes (actuation) that are tied to changes in LC ordering. The result is a new synthetic approach for polydomain networks that form stable LC phases that are tailorable using polyether spacers and may enable future application as hydrated, stimuli-responsive materials.

Tissue Engineering: Liquid Crystalline Networks toward Regenerative Medicine and Tissue Repair (Small 46/2017)

Tissue Engineering: Liquid Crystalline Networks toward Regenerative Medicine and Tissue Repair (Small 46/2017)

Aliphatic flexible spacer length controls photomechanical response in compact, ordered liquid crystalline polymer networks

The aliphatic spacer length connected to the rigid mesogenic cores is shown to control the structural organization and mechanical actuation in response to light-stimulus in azobenzene-functionalized liquid crystalline polymers networks. The spacer lengths in the mesogenic host (non-photochromic) and in the photo-active azobenzene-functionalized cross linker are parametrically varied to create monodomain liquid crystalline samples. A suite of thermomechanical, photomechanical and structural characterization is used to characterize the binary co-polymers. The photomechanical responses are compared by calculating a figure-of-merit – Photocompliance (Cp). This parameter, Cp, which characterizes the incremental strain generated in response to unit intensity of irradiation (W/cm2), is found to correlate strongly with the Sxray order parameter and the D-spacings. We show that compact (smaller D) and higher ordering of the mesogens that result in copolymers with longer flexible spacers manifest greater photomechanical activity.

Liquid Crystalline Networks toward Regenerative Medicine and Tissue Repair.

The communication reports the use of liquid crystalline networks (LCNs) for engineering tissue cultures with human cells. Their ability as cell scaffolds for different cell lines is demonstrated. Preliminary assessments of the material biocompatibility are performed on human dermal fibroblasts and murine muscle cells (C2C12), demonstrating that coatings or other treatments are not needed to use the acrylate-based materials as support. Moreover, it is found that adherent C2C12 cells undergo differentiation, forming multinucleated myotubes, which show the typical elongated shape, and contain bundles of stress fibers. Once biocompatibility is demonstrated, the same LCN films are used as a substrate for culturing human induced pluripotent stem cell-derived cardiomyocites (hiPSC-CMs) proving that LCNs are capable to develop adult-like dimensions and a more mature cell function in a short period of culture in respect to standard supports. The demonstrated biocompatibility together with the extraordinary features of LCNs opens to preparation of complex cell scaffolds, both patterned and stimulated, for dynamic cell culturing. The ability of these materials to improve cell maturation and differentiation will be developed toward engineered heart and skeletal muscular tissues exploring regenerative medicine toward bioartificial muscles for injured sites replacement.

Thermally-triggered free-standing shape-memory actuators

This investigation presents a new approach to obtain free-standing thermally-triggered “two-way” shape-memory actuators by realizing multilayer structures constituted by glassy thermoset (GT) films anchored to a previously programmed liquid-crystalline network (LCN) film. The GT is obtained via dual-curing of off-stoichiometric “thiol-epoxy” mixtures, thus enabling the development of complex actuator configurations thanks to the easy processing in the intermediate stage, and a compact and resistant design due to the strong adhesion between the layers obtained upon the final curing stage of the GT. A model based on the classical multilayered beam theory to predict the maximum deflection of a “beam-like” design is proposed and its reliability is verified by experimental investigation of actuators with different configurations and LCN stretching levels. The results show the capability of these actuators to bend and unbend under various consecutive heating–cooling procedures in a controlled way. The maximum deflection can be modulated through the configuration and the LCN stretching level, showing an excellent fitting with the model predictions. The model is able to predict high actuation levels (angles of curvature≈180°) and the bidirectional shape-memory behavior of the device as a function of the thickness, configuration of the layers, and the LCN stretching level. This approach enables the design of free-standing two-way actuators covering a range of bending actuation from 27 to 98% of the theoretical maximum deflection.

Synthesis and Characterization of Liquid-Crystalline Networks: Toward Autonomous Shape-Memory Actuation

In this paper, epoxy-based shape-memory liquid-crystalline lightly cross-linked networks (LCN) are synthesized and characterized with a view to the future development of two-way autonomous shape-memory actuators by coupling the LCN with an external epoxy-matrix. Carboxylic acids of different aliphatic chain lengths are used as curing agents for a rigid-rod epoxy-based mesogen. Thermal and liquid-crystalline (LC) properties of the LCN are investigated through calorimetric and X-ray diffraction analysis on unstretched and stretched samples. Structural and thermomechanical properties are studied by means of tensile and dynamic-mechanical analyses and the shape-memory capabilities are analyzed in terms of actuation strain and stress under partially- and fully constrained thermomechanical procedures. The results have shown the possibility to obtain LCN with isotropization temperatures above 100 °C, controlled degree of liquid crystallinity, and high actuation stress and strain by simply varying the aliphatic c...

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation.

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.

Functional liquid-crystalline polymers and supramolecular liquid crystals

The design and functions of liquid-crystalline (LC) polymers with classifying them into conventional-, supramolecular-, dendritic- and network-type LC polymers are described. LC polymers show new functions as new devices in the field of energy and environment by incorporating mesogenic moieties exhibiting photonic, electronic and ionic functions. Supramolecular LC polymers show dynamic and unique properties because the mesogenic moieties are built with non-covalent interactions. Dendritic-type LC polymers exhibit liquid crystallinity by nanosegregation of aromatic and aliphatic moieties. Dendritic fork-like mesogens have also been prepared. A variety of nonmesogeic functional building blocks including fullerene, π-conjugated moieties, catenane, rotaxane and others can be incorporated into LC phases by attaching these dendritic moieties. LC networks are constructed in situ polymerization of polymerizable nematic or nanostructured liquid crystals. The specific characteristics of the LC networks have generated new research trends to develop well-defined polymers that exhibit optical, transport and separation properties. In these materials, through suitable design of LC monomers, the preservation of smectic, columnar and bicontinuous cubic phases has been successfully used for the development of membranes with one-dimensional, two-dimensional and three-dimensional nanostructures. The design and functions of various liquid-crystalline (LC) polymers including main-chain, side-chain and network LC polymers as well as dendritic structures are described. These polymeric LC materials can be applied for electro-, ion-, photo-active materials as well as mechanically tough materials. The introduction of supramolecular design has also generated a new category of functional LC materials.