Second-harmonic-generation microscope using eight-segment polarization-mode converter to observe three-dimensional molecular orientation

We developed a compact polarization-mode converter for microscopy to control three-dimensional polarization at the focus. The converter consisted of two homogeneously aligned liquid-crystal spatial light modulators with eight independently controllable electrodes (segments), and a quarter-waveplate. The converter converted a linearly polarized beam to three polarization modes: two orthogonal linear polarizations and a pseudo-radial polarization. We applied the converter to second-harmonic-generation microscopy and demonstrated the detection of three-dimensional molecular orientation.     

Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to CdII and Hydrogen Sulfide Imaging in Living Cells

Non‐coordinative interactions between a metal ion and the aromatic ring of a fluorophore can act as a versatile sensing mechanism for the detection of metal ions with a large emission change of fluorophores. We report the design of fluorescent probes based on arene–metal‐ion interactions and their biological applications. This study found that various probes having different fluorophores and metal binding units displayed significant emission redshift upon complexation with metal ions, such as Ag^I, Cd^II, Hg^II, and Pb^II. X‐ray crystallography of the complexes confirmed that the metal ions were held in close proximity to the fluorophore to form an arene–metal‐ion interaction. Electronic structure calculations based on TDDFT offered a theoretical basis for the sensing mechanism, thus showing that metal ions electrostatically modulate the energy levels of the molecular orbitals of the fluorophore. A fluorescent probe was successfully applied to the ratiometric detection of the uptake of Cd^II ions and hydrogen sulfide (H₂S) in living cells. These results highlight the utility of interactions between arene groups and metal ions in biological analyses.     

Monte carlo simulations for blue-phase structure in liquid crystals

Blue-phase liquid crystals form three-dimensional structures in a self-organizing manner and are similar to living tissue structures such as the teeth of mice and collagen tissues. This study presents numerical results regarding the conditions under which blue-phase liquid crystals occur. The Monte Carlo simulations are performed by employing an improved Lennard–Jones potential that considers anisotropy and chirality. The conditions for the formation of the blue phase, which vary with respect to the chirality, are examined first. The relationship between the anisotropic parameters and the chiral parameter for the formation of the blue phase is discussed. Identical blue-phase structures are obtained, even when the cell size and molecular number are varied drastically. This discussion is useful for considering the scale-up problem, which is almost always a difficult issue for molecular-scale simulations.     

Simple Synthesis of a Heterocyclophane Exhibiting Anti-c-Met Activity by Acting as a Hatch Blocking Access to the Active Site**

A simple approach to the synthesis of heterocyclophane consisting of two 4,4’-bithiazoles has been developed in mild conditions. The heterocyclophane with two short chains was conveniently prepared by Hantzsch thiazoles synthesis using the reaction of 3-tert-butoxycarbonyl-3-azapentanethiocarboxamide with 1,4-dibromobutane-2,3-dione in methanol under reflux for only 15 min. Amino groups at the linkers of this heterocyclophane can be functionalized to give acylated and carbamate derivatives. Their properties as protein kinase inhibitors were investigated, and one of the heterocyclophanes exhibited specific anti-activity for c-mesenchymal epithelial transition factor (IC₅₀=603 nm ), among seven types of protein kinases investigated. The computational site identification by ligand competitive saturation method was used to determine why the one heterocyclophane exhibited strong anti-activity for c-mesenchymal epithelial transition factor.     

Reaction of o-oxazolinylphenyllithium with carbon monoxide. Carbonylative cyclization via an aroyllithium intermediate

The carbonylation of a phenyllithium containing an oxazoline group at the ortho position, followed by quenching with water, afforded a tricyclic compound, 3,3-dimethyl-2,3-dihydrooxazolo[2, 3-a]isoindol-5(9bH)-one, in 91% yield. This reaction proceeded via an intramolecular cyclization of the aroyllithium species, to give the tricyclic dienolate. Treatment of the tricyclic dienolate with electrophiles, such as alkyl halides, aldehydes, ketones, and epoxides gave the substituted oxazolo[2,3-a]isoindolinones in good yield.     

Synthesis of novel liquid crystals having the perfluoropyrrolidino group

Novel liquid crystals which have the perfluoropyrrolidino group, a heterocyclic perfluoroalkyl group, and which show smectic phases have been synthesized with perfluoro-(2-pyrrolidinopropionyl fluoride) as one of the starting materials. Analogues with a polymerizable functional group also have been prepared and polymerized to give side chain liquid crystal polymers.     

Electro-optic properties of liquid crystal phase gratings and their simulation using a homogeneous alignment model

Electro-optic properties of liquid crystal phase gratings (LCPGs), regarding groove depth, temperature and a cell gap, have been studied. The off response times are proportional to the square of the groove depth. The transmitted light colour depends on temperature. When there is a gap between the grating and the opposite substrate, their transmittance-voltage curve has a maximum and a minimum. The authors have also simulated the LCPG properties using a homogeneous alignment model. The simulating results coincide with experimental results; therefore the simulation method is considered useful to predict LCPG properties.