Mixtures of nematic liquid crystals (LCs) were produced by doping small quantities of gold nanoparticles coated with non-chiral hexane-(Au1), dodecane-(Au2) or chiral Naproxenfunctionalized dodecane thiolates (Au3, Au4). Circular dichroism (CD) spectroscopy confirmed the optical activity for both Naproxen-functionalized gold nanoclusters. The small CD measured for Au1 and Au2 as well as the weak CD above 400 nm measured for Au3 and Au4 is attributed to scattering artifacts of dense particles aggregating in solution. For all mixtures, characterization of the nanoparticle doped nematic phase by polarized optical microscopy revealed the formation of uniform stripe textures or patterns separated by areas of homeotropic alignment due to a spatial separation of particle-rich and particle-poor domains. Similar characteristic textures were also observed for mixtures of the chiral nematic phase produced by doping either only the Naproxenfunctionalized thiol 3b or Naproxen and additionally dodecane thiolate-protected gold nanoparticles Au2. On the basis of these findings, observed for the first time for alkane thiolatecapped gold nanoclusters doped into nematic LCs, two different scenarios are suggested. In the first scenario, the optically active gold nanoparticles Au3 and Au4 transfer chirality to the nonchiral nematic LC host. In the second scenario, all functionalized gold nanoclusters Au1-Au4 form topological defects resulting in chain-like particle aggregates, separated by areas of homeotropic alignment due to particles residing at the LC-glass interface.
We demonstrate that alkylthiol‐capped gold nanoclusters doped into nematic liquid crystals (N‐LCs) with positive dielectric anisotropy give rise to an unprecedented dual alignment mode and electro‐optical response, which has a potential impact on current liquid crystal (LC) display technologies and N‐LC optical‐biosensor design. By fine‐tuning experimental conditions (temperature, electric field, and alignment), N‐LCs doped with gold nanoclusters can be aligned and electrically reoriented either like N‐LCs with a positive dielectric anisotropy in a planar cell or, alternatively, as N‐LCs with a negative dielectric anisotropy in a homeotropic cell, both at lower threshold voltages than the pure N‐LC.
Induction, transmission, and manipulation of chirality in molecular systems are well known, widely applied concepts. However, our understanding of how chirality of nanoscale entities can be controlled, measured, and transmitted to the environment is considerably lacking behind. Future discoveries of dynamic assemblies engineered from chiral nanomaterials, with a specific focus on shape and size effects, require exact methods to assess transmission and amplification of nanoscale chirality through space. Here we present a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles to nanorods. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding liquid crystal–a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand decorated nanomaterials differing in shape and size as calculated from a suitable pseudoscalar chirality indicator.
Torsten (2019) 'Heliconical-layered nanocylinders (HLNCs) hierarchical self-assembly in a unique B4 phase liquid crystal morphology.', Materials horizons., 6 (5). 959968.
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Combinations of liquid crystals and materials with unique features as well as properties at the nanoscale are reviewed. Particular attention is paid to recent developments, i.e., since 2007, in areas ranging from liquid crystal-nanoparticle dispersions to nanomaterials forming liquid crystalline phases after surface modification with mesogenic or promesogenic moieties. Experimental and synthetic approaches are summarized, design strategies compared, and potential as well as existing applications discussed. Finally, a critical outlook into the future of this fascinating field of liquid crystal research is provided.
Liquid crystal nanoscience, a field exploring the mutually beneficial combination of the unique properties of nanoscale materials and fluid, yet ordered liquid crystalline phases, is increasingly focusing on semiconductor quantum dots. In one major research thrust, the anisotropic properties of the liquid crystal host are sought to facilitate the assembly of quantum dots into arrays, in another, both size-and shape-dependent optical and electronic properties of quantum dots are used to manipulate optical, electro-optical and alignment properties of liquid crystalline materials. This feature article reviews recent accomplishments and new insights in this fascinating area of soft matter nanocomposites including work from our laboratory on a series of CdSe and CdTe quantum dots as additives in nematic liquid crystal hosts.
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