Chiral Incommensurate Helical Phase in a Smectic of Achiral Bent-Core Mesogens.

An achiral, bent-core mesogen forms several tilted smectic liquid crystal phases, including a nonpolar, achiral de Vries smectic A which transitions to a chiral, ferroelectric state in applied electric fields above a threshold. At lower temperature, a chiral, ferrielectric phase with a periodic, supermolecular modulation of the tilt azimuth, indicated by a Bragg peak in carbon-edge resonant soft x-ray scattering, is observed. The absence of a corresponding resonant umklapp peak identifies the superlayer structure as a twist-bend-like helix that is only weakly modulated by the smectic layering.

A supramolecular hydrogel prepared from a thymine-containing artificial nucleolipid: study of assembly and lyotropic mesophases.

An artificial nucleolipid containing thymine, a triazole-ring, and phosphatidylcholine (TTPC) moieties was prepared by copper catalyzed azide alkyne cycloaddition (CuAAC) under aqueous conditions. The resulting TTPC molecules assembled in situ into a fibrous aggregation. The study of the TTPC fiber assembly using XRD and NMR spectroscopy revealed that the formation of fibers was driven by the unique combination of the lipid and nucleobase moieties in the structure of TTPC. At a critical TTPC concentration, entanglement of the fibers resulted in the formation of a supramolecular hydrogel. Investigation of the lyotropic mesophases in the TTPC supramolecular hydrogel showed the presence of multiple phases including two liquid crystal phases (i.e., nematic and lamellar), which have a certain degree of structural order and are promising templates for constructing functional biomaterials.

Thermomechanical properties of monodomain nematic main-chain liquid crystal elastomers.

Two-stage thiol-acrylate Michael addition reactions have proven useful in programming main-chain liquid crystal elastomers (LCEs). However, the influence of excess acrylate concentration, which is critical to monodomain programming, has not previously been examined with respect to thermomechanical properties in these two-stage LCEs. Previous studies of thiol-acrylate LCEs have focused on polydomain LCEs and/or variation of thiol crosslinking monomers or linear thiol monomers. This study guides the design of monodomain LCE actuators using the two-stage methodology by varying the concentration of mesogenic acrylate monomers from 2 mol% to 45 mol% in stoichiometric excess of thiol. The findings demonstrate a technique to tailor the isotropic transition temperature by 44 °C using identical starting monomers. In contrast to expectations, low amounts of excess acrylate showed excellent fixity (90.4 ± 2.9%), while high amounts of excess acrylate did not hinder actuation strain (87.3 ± 2.3%). Tensile stress-strain properties were influenced by excess acrylate. Linear elastic behavior was observed parallel to the director with modulus increasing from 1.4 to 6.1 MPa. The soft elastic plateau was observed perpendicular to the director with initial modulus and threshold stresses increasing from 0.6 MPa to 2.6 MPa and 14 kPa to 208 kPa, respectively. Overall, this study examines the influence of excess acrylate on mechanical properties of LCE actuators.

New SmAPF Mesogens Designed for Analog Electrooptics Applications.

We have previously reported the first realization of an orthogonal ferroelectric bent-core SmAPF phase by directed design in mesogens with a single tricarbosilane-terminated alkoxy tail. Given the potentially useful electrooptic properties of this phase, including analog phase-only electrooptic index modulation with optical latching, we have been exploring its "structure space", searching for novel SmAPF mesogens. Here, we report two classes of these-the first designed to optimize the dynamic range of the index modulation in parallel-aligned cells by lowering the bend angle of the rigid core, and the second expanding the structure space of the phase by replacing the tricarbosilane-terminated alkyl tail with a polyfluorinated polyethylene glycol oligomer.

High strain actuation liquid crystal elastomers via modulation of mesophase structure.

Control of the mesophase in liquid crystalline elastomers (LCEs) is a critical aspect in harnessing their unique stimuli-responsive properties. Few studies have compared nematic and smectic main-chain LCEs in a direct way. Traditionally, it is believed that the mesogen core and synthetic route determines the phase behavior. In this study, we hypothesized that tuning the LC phases in main-chain LCE systems can be achieved by varying the spacer length while maintaining the same mesogen (RM257). By increasing the length of dithiol alkyl spacers containing two to eleven carbons along the spacer backbone (C2 to C11), we can modulate the mesophase from nematic to smectic, tailor the nematic to isotropic transition temperature between 90 and 140 °C, and increase the average work capacity from 128 to 262 kJ m-3. Phase nano-segregation resulting in the smectic C phase is achieved at room temperature for the C6, C9, and C11 spacers. In a shape switching system, this manifests in impressive actuation stroke of 700%. Upon heating from room temperature, these samples transition into the nematic and later, the isotropic phase. Furthermore, this segregation occurs along with polymer chain crystallinity, which increases the modulus of the networks by an order of magnitude; however, the crystallization rate is highly time dependent on the spacer length and can vary between 5 minutes for the C11 spacer and 24 hours for shorter spacers. This study presents several possibilities of a thiol-acrylate reaction in modulation of the thermomechanical and liquid-crystalline properties of LCEs and discusses their potential use for biomedical applications.

Fabrication of Liquid Crystalline Polyurethane Networks with a Pendant Azobenzene Group to Access Thermal/Photoresponsive Shape-Memory Effects.

Herein, we report a novel thermal/photoresponsive shape-memory polyurethane network with a pendant azobenzene group by utilizing its anisotropic-isotropic phase transitions and photoresponsive feature concurrently. To achieve this goal, the side-chain liquid crystalline polyurethane networks based on the pendant azobenzene group [SCLCPU(AZO)-Ns] were developed in a well-defined architecture. The smectic C nature of an LC phase in the polyurethane networks was confirmed by differential scanning calorimetry, polarized optical microscopy, and one-dimensional and two-dimensional wide-angle X-ray diffraction. The well-defined architecture-made SCLCPU(AZO)-N displays two distinct transition temperatures (Ttrans) (Tg and Tcl), with a difference of about 40 °C. Consequently, the excellent triple-shape-memory effect in this network was demonstrated by cyclic thermomechanical analysis. By making full use of the trans-cis photoisomerization of azobenzene, the reversible bending and unbending behaviors were realized under the light irradiation with wavelengths of 450 and 550 nm, respectively.

Mutually tangled colloidal knots and induced defect loops in nematic fields.

Colloidal dispersions in liquid crystals can serve as a soft-matter toolkit for the self-assembly of composite materials with pre-engineered properties and structures that are highly dependent on particle-induced topological defects. Here, we demonstrate that bulk and surface defects in nematic fluids can be patterned by tuning the topology of colloidal particles dispersed in them. In particular, by taking advantage of two-photon photopolymerization techniques to make knot-shaped microparticles, we show that the interplay of the topologies of the knotted particles, the nematic field and the induced defects leads to knotted, linked and other topologically non-trivial field configurations. These structures match theoretical predictions made on the basis of the minimization of the elastic free energy and satisfy topological constraints. Our approach may find uses in self-assembled topological superstructures of knotted particles linked by nematic fields, in topological scaffolds supporting the decoration of defect networks with nanoparticles, and in modelling other physical systems exhibiting topologically analogous phenomena.