The extraordinary responsiveness and large diversity of self-assembled structures of liquid crystals are well documented and they have been extensively used in devices like displays. For long, this application route strongly influenced academic research, which frequently focused on the performance of liquid crystals in display-like geometries, typically between flat, rigid substrates of glass or similar solids. Today a new trend is clearly visible, where liquid crystals confined within curved, often soft and flexible, interfaces are in focus. Innovation in microfluidic technology has opened for high-throughput production of liquid crystal droplets or shells with exquisite monodispersity, and modern characterization methods allow detailed analysis of complex director arrangements. The introduction of electrospinning in liquid crystal research has enabled encapsulation in optically transparent polymeric cylinders with very small radius, allowing studies of confinement effects that were not easily accessible before. It also opened the prospect of functionalizing textile fibers with liquid crystals in the core, triggering activities that target wearable devices with true textile form factor for seamless integration in clothing. Together, these developments have brought issues center stage that might previously have been considered esoteric, like the interaction of topological defects on spherical surfaces, saddle-splay curvature-induced spontaneous chiral symmetry breaking, or the non-trivial shape changes of curved liquid crystal elastomers with non-uniform director fields that undergo a phase transition to an isotropic state. The new research thrusts are motivated equally by the intriguing soft matter physics showcased by liquid crystals in these unconventional geometries, and by the many novel application opportunities that arise when we can reproducibly manufacture these systems on a commercial scale. This review attempts to summarize the current understanding of liquid crystals in spherical and cylindrical geometry, the state of the art of producing such samples, as well as the perspectives for innovative applications that have been put forward.
Cholesteric liquid crystal elastomers (CLCEs) are soft and dynamic photonic elements that couple the circularly polarized structural color from the cholesteric helix to the viscoelasticity of rubbers: the reflection color is mechanically tunable (mechanochromic response) over a broad range. This requires uniform helix orientation, previously realized by long‐term centrifugation to ensure anisotropic deswelling, or using sacrificial substrates or external fields. The present paper presents a simple, reproducible, and scalable method to fabricate highly elastic, large‐area, millimeters thick CLCE sheets with intense uniform reflection color that is repeatably, rapidly, and continuously tunable across the full visible spectrum by stretching or compressing. A precursor solution is poured onto a substrate and allowed to polymerize into a 3D network during solvent evaporation. Pinning to the substrate prevents in‐plane shrinkage, thereby realizing anisotropic deswelling in an unprecedentedly simple manner. Quantitative stress–strain–reflection wavelength characterization reveals behavior in line with theoretical predictions: two linear regimes are identified for strains below and above the helix unwinding threshold, respectively. Up to a doubling of the sample length, the continuous color variation across the full visible spectrum repeatedly follows a volume conserving function of the strain, allowing the CLCE to be used as optical high‐resolution strain sensor.
Non-woven mats comprised of liquid crystal-functionalised fibres are coaxially electrospun to create soft gas sensors that function non-electronically, thus requiring no power supply, detecting organic vapours at room temperature. The fibres consist of a poly(vinylpyrrolidone) (PVP) sheath surrounding a core of nematic 4-cyano-4ʹpentylbiphenyl (5CB) liquid crystal. Several types of mats, containing uniformly cylindrical or irregular beaded fibres, in uniform or random orientations, are exposed to toluene vapour as a representative volatile organic compound. Between crossed polarisers all mats respond with a fast (response time on the order of a second or faster) reduction in brightness during gas exposure, and they return to the original state upon removal of the gas almost as quickly. With beaded fibres, the response of the mats is visible even without polarisers. We discuss how variations in fibre spinning conditions such as humidity level and the ratio of core-sheath fluid flow rates can be used to tune fibre morphology and thereby the response. Considering future development perspectives, we argue that fibres turned responsive through the incorporation of a liquid crystal core show promise as a new generation of sensors with textile form factor, ideal for wearable technology applications. ARTICLE HISTORY
Here we report on the modular synthesis and characterization of biodegradable, controlled porous, liquid crystal elastomers (LCE) and their use as three-dimensional cell culture scaffolds. The elastomers were prepared by cross-linking of star block-co-polymers with pendant cholesterol units resulting in the formation of smectic-A LCEs as determined by polarized optical microscopy, DSC, and X-ray diffraction. Scanning electron microscopy revealed the porosity of the as-prepared biocompatible LCEs, making them suitable as 3D cell culture scaffolds. Biodegradability studies in physiological buffers at varying pH show that these scaffolds are intact for about 11 weeks after which degradation sets in at an exponential rate. Initial results from cell culture studies indicate that these smectic LCEs are compatible with growth, survival, and expansion of cultured neuroblastomas and myoblasts when grown on the LCEs for extended time periods (about a month). These preliminary cell studies focused on characterizing the elastomer-based scaffolds' biocompatibility and the successful 3D incorporation as well as growth of cells in 60 to 150-μm thick elastomer sheets.
Chirality at the nanoscale, or more precisely, the chirality or chiroptical effects of chiral ligand-capped metal nanoparticles (NPs) is an intriguing and rapidly evolving field in nanomaterial research with promising applications in catalysis, metamaterials, and chiral sensing. The aim of this work was to seek out a system that not only allows the detection and understanding of NP chirality but also permits visualization of the extent of chirality transfer to a surrounding medium. The nematic liquid crystal phase is an ideal candidate, displaying characteristic defect texture changes upon doping with chiral additives. To test this, we synthesized chiral cholesterol-capped gold NPs and prepared well-dispersed mixtures in two nematic liquid crystal hosts. Induced circular dichroism spectropolarimetry and polarized light optical microscopy revealed that all three gold NPs induce chiral nematic phases, and that those synthesized in the presence of a chiral bias (disulfide) are more powerful chiral inducers than those where the NP was formed in the absence of a chiral bias (prepared by conjugation of a chiral silane to preformed NPs). Helical pitch data here visually show a clear dependence on the NP size and the number of chiral ligands bound to the NP surface, thereby supporting earlier experimental and theoretical data that smaller metal NPs made in the presence of a chiral bias are stronger chiral inducers.
Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.
Back Cover: Liquid crystal elastomers (LCE) for the use as three‐dimensional cell culture scaffolds are prepared by E. Hegmann and co‐workers by cross‐linking of star blockco‐polymers with pendant cholesterol units resulting in the formation of smectic‐A LCEs. http://doi.wiley.com/10.1002/mabi.201400325 these biodegradable materials prove to be compatible with growth, survival, and expansion of cultured neuroblastomas and myoblasts for extended time periods (about a month) and are also excellent candidates for testing on several other cell lines.
3D biodegradable and highly regular foamlike cell scaffolds based on biocompatible side-chain liquid crystal elastomers have been prepared. Scaffolds with a primary porosity characterized by spatially interlaced, interconnected microchannels or an additional secondary porosity featuring interconnected microchannel networks define the novel elastomeric scaffolds. The macroscale morphology of the dual porosity 3D scaffold resembles vascular networks observed in tissue. 3D elastomer foams show four times higher cell proliferation capability compared to conventional porous templated films and within the channels guide spontaneous cell alignment enabling the possibility of tissue construct fabrication toward more clinically complex environments.
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