Molecular design of flexible liquid crystal oligomers stabilising the chiral frustrated phases

ABSTRACT

Chirality induces structural frustration in liquid crystal systems, producing various kinds of chiral frustrated phases, for example, twist grain boundary (TGB) phases, blue phases (BPs) and dark conglomerate (DC) phases. Almost all molecules exhibiting these frustrated phases have a rigid shape. Especially, a bent–core unit is regarded as a key structure for BPs and DC phases. This paper describes that some flexible liquid crystal oligomers being far from a rigid bent–core molecule stabilise these phases. The LC oligomers have a supermolecular structure in which mesogenic units are connected via flexible spacers. By designing intermolecular interactions, they can exhibit various molecular packing structures in the liquid-crystalline phases as follows: chiral dimers inducing TGB phases, U-shaped and T-shaped oligomers stabilising BPs and achiral liquid crystal trimers exhibiting DC phases. I discuss how the designed liquid crystal oligomers produce the chiral frustrated phases.     

Electrochemical Motion Tracking of Microorganisms Using a Large-Scale-Integration-Based Amperometric Device

Motion tracking of microorganisms is useful to investigate the effects of chemical or physical stimulation on their biological functions. Herein, we describe a novel electrochemical imaging method for motion tracking of microorganisms using a large-scale integration (LSI)-based amperometric device. The device consists of 400 electrochemical sensors with a pitch of 250 μm. A convection flow caused by the motion of microorganisms supplies redox species to the sensors and increases their electrochemical responses. Thus, the flow is converted to electrochemical signals, enabling the electrochemical motion tracking of the microorganisms. As a proof of concept, capillary vibration was monitored. Finally, the method was applied to monitoring the motion of Daphnia magna. The motions of these microorganisms were clearly tracked based on the electrochemical oxidation of [Fe(CN)₆]⁴⁻ and reduction of O₂.     

Polymeric quasicrystal: mesoscopic quasicrystalline tiling in ABC star polymers

A mesoscopic tiling pattern with 12-fold symmetry has been observed in a three-component polymer system composed of polyisoprene, polystyrene, and poly(2-vinylpyridine) which forms a star-shaped terpolymer, and a polystyrene homopolymer blend. Transmission electron microscopy images reveal a nonperiodic tiling pattern covered with equilateral triangles and squares, their triangle/square number ratio of 2.3 (approximately equal to 4/sqrt[3]), and a microbeam x-ray diffraction pattern shows dodecagonal symmetry. The same kind of quasicrystalline structures have been found for metal alloys (approximately 0.5 nm), chalcogenides (approximately 2 nm), and liquid crystals (approximately 10 nm). The present result (approximately 50 nm) confirms the universal nature of dodecagonal quasicrystals over several hierarchical length scales.     

Evidence of subsurface oxygen vacancy ordering on reduced CeO2(111)

Surface and subsurface oxygen vacancies on the slightly reduced CeO(2)(111) surface have been studied by atomic resolution dynamic force microscopy at 80 K. Both types of defect are clearly identified by the comparison of the observed topographic features with the corresponding structures predicted from recent first-principles calculations. By combining two simultaneously acquired signals (the topography and the energy dissipated from the cantilever oscillation), we are able to unambiguously locate subsurface oxygen vacancies buried at the third surface atomic layer. We report evidence of local ordering of these subsurface defects that suggests the existence of a delicate balance between subtle interactions among adjacent subsurface oxygen vacancy structures.     

Mesoporous Zirconium Phenylenesiliconate‐phosphonate Hybrids with Ordered Lamellar Nanostructures

Novel ordered lamellar mesostructure pZrPS‐2 was hydrothermally prepared by using zirconium propoxide and 4‐(EtO)₂OPC₆H₄Si(OEt)₃ (pPPS‐E), which was hydrolyzed to organic building units substituted with both siliconate and phosphonate groups, in the presence of C_nTAB and TMAOH. The pZrPS‐2 materials were obtained at a Zr/PPS ratio of 2 or higher and the basal spacing was increased by using a longer‐chain surfactant (n=12–18). Removal of the occluded surfactants at 300 °C resulted in retention of the lamellar structure with negligible shrinkage of the interlayer distance. Nitrogen adsorption studies revealed the ordered mesoporous nature of pZrPS‐2 with a pore diameter of approximately 2 to 3 nm. The lamellar structure is assumed to be composed of layers that include zirconia‐based crystalline nanodomains and interlayer pillars mainly based on PPS units. Although lamellar structures with the same crystalline phase also formed when no surfactant was added or when the meta isomer of PPS was used, no mesoporous materials were obtained except pZrPS‐2. A possible schematic model to elucidate these results is also proposed.     

New Fluorescence Domain “Excited Multimer” Formed upon Photoexcitation of Continuously Stacked Diaroylmethanatoboron Difluoride Molecules with Fused π‐Orbitals in Crystals

The crystal‐packing structures of seven derivatives of diaroylmethanatoboron difluoride ( 1 a – gBF₂ ) are characterized by no overlap of the π‐conjugated main units of two adjacent molecules (type I), overlap of the benzene ring π‐orbitals of two adjacent molecules (type II), and overlap of the benzene and dihydrodioxaborinine rings π‐orbitals of adjacent molecules (type III). The crystal‐packing structures govern the fluorescence (FL) properties in the crystalline states. The FL domain that is present in type I crystals, in which intermolecular orbital interactions are absent, leads to excited monomer‐like FL properties. In the case of the type II crystals, the presence of intermolecular overlap of the benzene rings π‐orbitals generates new FL domains, referred to as “excited multimers”, which possess allowed S₀–S₁ electronic transitions and, as a result, similar FL lifetimes at longer wavelengths than the FL of the type I crystals. Finally, intermolecular overlap of the benzene and dihydrodioxaborinine ring π‐orbitals in the type III crystals leads to “excited multimer” domains with forbidden S₀–S₁ electronic transitions and longer FL lifetimes at similar wavelengths as that in type I crystals.