New chiral dimers consisting of a rod-like and cholesterol mesogenic units are reported to form a chiral twist-bend nematic phase (NTB *) with heliconical structure. The compressibility of the NTB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the NTB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non-chiral compounds (ca. 10 nm).
Do the short helices exist in the nematic TB phase?Dimeric compounds forming twist-bend nematic, Ntb, phase show unusual optical texture related to the formation of arrays of focal conic defects. Some of the focal conics show submicron internal structure with 8 nm periodicity, which is very close to that found in the crystalline phase of the material, suggesting surface freezing.
The fabrication of molecular structures with a desired morphology, e.g., nanotubes, nanoribbons, nanosprings, and sponges, is essential for the advancement of nanotechnology. Unfortunately, realization of this objective is expensive and complicated. Here, we report that irradiating a film comprising azobenzene derivatives with UV light produces oriented arrays of helical nanofilaments via the photoisomerization-induced Weigert effect. As a result, structural colors are observed due to the extrinsic chiral reflection in the visible wavelength range, and the reflected color can be tuned by adjusting the molecular length of the azobenzene derivative. This simple fabrication method can be used for fabricating large, reversible, and patternable color reflectors, providing a new platform for interference-based structural coloration as it exists in nature, such as morpho butterflies, green-winged teal, and various beetles.
The achiral liquid crystalline materials showing two B4 (HN) phases have been found to exhibit strong gelation ability for various organic solvents with reversible sol-gel phase transition. The gel is formed by helical tubules, which build entangled 3D network, encapsulating the solvent. The equilibrium of left- and right-handed tubules is preserved in the gel, even if the chiral solvent is used.
A sequence of seven nematic phases has been observed in chiral mesogenic dimers, having odd number of carbon atoms in the spacer, thus a bent shape. The highest temperature phase is a chiral nematic (cholesteric) phase on heating or blue phases on cooling. The lowest temperature nematic phase expels the chiral twist and exhibits spontaneous bent-splay modulation. Fig. 1 General molecular structure of studied dimers.
A facile coprecipitation reaction between Ce(3+), Gd(3+), Tb(3+), and F(-) ions, in the presence of glycerine as a capping agent, led to the formation of ultrafine, nanocrystalline CeF3:Tb(3+) 5%, Gd(3+) 5% (LnF3). The as-prepared fluoride nanoparticles were successfully coated with an amine modified silica shell. Subsequently, the obtained LnF3@SiO2@NH2 nanostructures were conjugated with 4-ethoxybenzoic acid in order to prove the possibility of organic modification and obtain a new functional nanomaterial. All of the nanophosphors synthesized exhibited intense green luminescence under UV light irradiation. Based on TEM (transmission electron microscopy) measurements, the diameters of the cores (≈12 nm) and core/shell particles (≈50 nm) were determined. To evaluate the cytotoxic activity of the nanomaterials obtained, their effect on human erythrocytes was investigated. LnF3 nanoparticles were bound to the erythrocyte membrane, without inducing any cytotoxic effects. After coating with silica, the nanoparticles revealed significant cytotoxicity. However, further functionalization of the nanomaterial with -NH2 groups as well as conjugation with 4-ethoxybenzoic acid entailed a decrease in cytotoxicity of the core/shell nanoparticles.
The properties of liquid-crystalline (LC) hybrid systems made of inorganic nanoparticles grafted with photosensitive azo compounds are presented. For materials with a large density of azo ligands at the surface, the LC structure can be reversibly melted by UV light, and the return to the LC state does not require the absorption of visible light. For systems with a lower density of azo ligands, UV light causes shortening of the distance between metal sublayers in the lamellar phase. Interestingly, the azo derivatives attached to the nanoparticle surface show very different kinetics of cis/trans conformational change as compared to the free molecules. The cis form of free ligands in solution is stable for days, whereas the isomerization of molecules attached to the nanoparticle surface to the trans form takes only a few minutes. Apparently, owing to the crowded environment, azo ligands immobilized at a metal surface behave as they would in the condensed state.
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