Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands

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

Biphenyl-based liquid crystals for elevated temperature processing with polymers

<div><p>Due to the limited thermal stability of current commercially available liquid crystals (LCs), the incorporation into polymer composites through standard processing techniques, such as melt coextrusion, has been hindered. Motivated by this dilemma, a series of smectic B liquid crystalline structures based on the 4,4ʹ-alkyl substituted biphenyl moiety were synthesised through conventional methodologies and probed for their thermal stability and LC properties. Degradation temperatures were found to increase with increasing aliphatic chain length – up to 295 °C for C16 substituted structures, which is well above the processing temperatures of commercial polymers. Additionally, all compounds were found to be liquid crystalline in nature with crystal-to-smectic B transition temperatures ranging from 49.8 °C to 91.4 °C. Thermal stability, phase separation, and compatibility of LC/polystyrene composites were also examined. Less than 10% of 15A15 LC by weight in polystyrene exhibited good polymer miscibility, while phase separation occurred at loads higher than 15% by weight. We foresee the use of these LCs in applications that require elevated processing conditions to produce materials with enhanced mechanical or gas barrier properties.</p></div

Intermolecular G‑Quadruplex Induces Hyaluronic Acid–DNA Superpolymers Causing Cancer Cell Swelling, Blebbing, and Death

Over the past decade, nanomedicine has gained considerable attraction through its relevance, for example, in “smart” delivery, thus creating platforms for novel treatments. Here, we report a natural polymer–DNA conjugate that undergoes self-assembly in a K⁺-dependent fashion to form a G-quadruplex (GQ) and generate superpolymeric structures. We derivatized a thiolated conjugate of the naturally occurring glycosaminoglycan polymer hyaluronic acid (HASH) with short G-rich DNA (HASH–DNA) that can form an intermolecular noncanonical GQ structure. Gel mobility shift assay and circular dichroism measurements confirmed HASH conjugation to DNA and K⁺-dependent GQ formation, respectively. Transmission electron microscopy and scanning electron microscopy results indicated that the addition of K⁺ to the HASH–DNA conjugate led to the formation of micron-range structures, whereas control samples remained unordered and as a nebulous globular form. Confocal microscopy of a fluorescently labeled form of the superpolymer verified increased cellular uptake. The HASH–DNA conjugates showed toxicity in HeLa cells, whereas a scrambled DNA (Mut) conjugate HASH–Mut showed no cytotoxicity, presumably because of nonformation of the superpolymeric structure. To understand the mechanism of cell death and if the superpolymeric structure is responsible for it, we monitored the cell size and observed an average of 23% increase in size compared to 4.5% in control cells at 4.5 h. We believe that cellular stress is generated presumably by the intracellular assembly of this large superpolymeric nanostructure causing cell blebbing with no exit option. This approach provides a new strategy of cellular delivery of a targeted naturally occurring polymer and a novel way to induce superpolymeric structure formation that acts as a therapeutic

Detecting, Visualizing, and Measuring Gold Nanoparticle Chirality Using Helical Pitch Measurements in Nematic Liquid Crystal Phases

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

Wide temperature-range, multi-component, optically isotropic antiferroelectric bent-core liquid crystal mixtures for display applications

<p>We present studies on 21 multi-component mixtures consisting of bent-core liquid crystals to obtain room temperature switching between optically isotropic and birefringent states. Four of the mixtures show a significant enhancement over our previous results that were obtained either only at elevated temperatures, or did not show switching at room temperatures with appreciable contrast or speed. Although the switching of the new mixtures still requires high fields and shows only speeds at ~100 ms, the results appear already useful for specific applications, such as transparent displays, that do not require video-rate switching and fast refresh rates of the content.</p

Liquid Crystal Elastomer Microspheres as Three-Dimensional Cell Scaffolds Supporting the Attachment and Proliferation of Myoblasts

We report that liquid crystal elastomers (LCEs), often portrayed as artificial muscles, serve as scaffolds for skeletal muscle cell. A simultaneous microemulsion photopolymerization and cross-linking results in nematic LCE microspheres 10–30 μm in diameter that when conjoined form a LCE construct that serves as the first proof-of-concept for responsive LCE muscle cell scaffolds. Confocal microscopy experiments clearly established that LCEs with a globular, porous morphology permit both attachment and proliferation of C2C12 myoblasts, while the nonporous elastomer morphology, prepared in the absence of a microemulsion, does not. In addition, cytotoxicity and proliferation assays confirm that the liquid crystal elastomer materials are biocompatible promoting cellular proliferation without any inherent cytotoxicity

Controlling the Structure and Morphology of Organic Nanofilaments Using External Stimuli

In our continuing pursuit to generate, understand, and control the morphology of organic nanofilaments formed by molecules with a bent molecular shape, we here report on two bent-core molecules specifically designed to permit a phase or morphology change upon exposure to an applied electric field or irradiation with UV light. To trigger a response to an applied electric field, conformationally rigid chiral (S,S)-2,3-difluorooctyloxy side chains were introduced, and to cause a response to UV light, an azobenzene core was incorporated into one of the arms of the rigid bent core. The phase behavior as well as structure and morphology of the formed phases and nanofilaments were analyzed using differential scanning calorimetry, cross-polarized optical microscopy, circular dichroism spectropolarimetry, scanning and transmission electron microscopy, UV–vis spectrophotometry, as well as X-ray diffraction experiments. Both bent-core molecules were characterized by the coexistence of two nanoscale morphologies, specifically helical nanofilaments (HNFs) and layered nanocylinders, prior to exposure to an external stimulus and independent of the cooling rate from the isotropic liquid. The application of an electric field triggers the disappearance of crystalline nanofilaments and instead leads to the formation of a tilted smectic liquid crystal phase for the material featuring chiral difluorinated side chains, whereas irradiation with UV light results in the disappearance of the nanocylinders and the sole formation of HNFs for the azobenzene-containing material. Combined results of this experimental study reveal that in addition to controlling the rate of cooling, applied electric fields and UV irradiation can be used to expand the toolkit for structural and morphological control of suitably designed bent-core molecule-based structures at the nanoscale