Stereoselective Syntheses of all the Possible Stereoisomers of Coronafacic Acid

An efficient and stereoselective syntheses of all the possible stereoisomers of coronafacic acid (CFA) has been developed. The stereochemistries of C3a and C7a were controlled in a diastereoselective Diels-Alder type cycloaddition using a chiral auxiliary. CFA and 6-epi-CFA were synthesized by hydrogenation of a common intermediate. During the synthesis of 6-epi-CFA, we established that its cis-fused configuration is important for the introduction of C4-C5 double bond by dehydration. This report is the first practical synthesis of both 6-epi-CFA, and its enantiomer.     

Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity

Dodecavanadate, [V₁₂O₃₂]^4? (V12), possesses a 4.4 Å cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br₂ was inserted into V12, inducing the inversion of one of the VO₅ square pyramids to form [V₁₂O₃₂(Br₂)]^4? (V12(Br2)). The inserted Br₂ molecule was polarized and showed a peak at 185 cm^?1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br₂ molecule. Compound V12(Br2) also reacted with propane, n‐butane, and n‐pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3‐bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2‐,3‐dibromobutane and 2,3‐dibromopenane. The unique inorganic cavity traps Br₂ leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br₂ shows selective functionalization of alkanes.     

Phospholipid Polymer Hydrogel Matrices with Dually Immobilized Cytokines for Accelerating Secretion of the Extracellular Matrix by Encapsulated Cells

Construction of 3D tissues by various types of cells with specific characteristics is an important and fundamental technology in tissue reconstruction medicine and animal‐free diagnosis system. To do so, an excellent extracellular matrix (ECM) is needed for encapsulation of cells and maintaining cell activity. Spontaneously forming hydrogel matrix is used by complexation between two water‐soluble polymers, 2‐methacryloyloxyethyl phosphorylcholine polymer bearing phenylboronic acid groups and poly(vinyl alcohol). Two cytokines for cell proliferation are immobilized in the hydrogel matrix to control the activities of the encapsulated cells. The cytokine‐immobilized hydrogel matrix can encapsulate both L929 fibroblasts and normal human dermal fibroblasts under mild condition. The physical properties of the hydrogel matrix can follow the proliferation process of the encapsulated cells. The encapsulated cells secrete ECM in the polymer hydrogel networks upon 3D culturing for 7 days. Consequently, the tissue‐mimicking ECM hybrid hydrogels are fabricated successfully.     

O2/n2-separation by polymer-bound cobalt complexes

Facilitated or complexation-mediated transport of oxygen in the solid membrane containing a fixed carrier was described, by using the polymer-bound cobalt Schiff's base chelate (CoS) and cobaltporphyrin (CoP). α³ β-Substituted cobaltporphyrin derivatives were synthesized: The oxygen-binding reaction to cobalt was affected by the cavity structure on porphyrin, i.e., unbulky amido-substituted groups such as acetylamido- and acrylamido-substituents enhanced oxygen-binding and -dissociation rate constant or provided an oxygen-binding pathway. Oxygen transport through the membranes of these polymer-bound CoP derivatives was selectively augmented due to the rapid and reversible oxygen-binding. Diffusion constants via the fixed CoPs correlated to the characteristics of oxygen-binding reaction.     

Three-dimensional visualization of columnar vortices in rotating Rayleigh–Bénard convection

Journal of Visualization -  To enrich the three-dimensional experimental details of vortex structures in rotating Rayleigh–Bénard convection, we established a technique...     

New fabrication approach to develop a high birefringence photo-crosslinked film based on a sulfur-containing liquid crystalline molecule with large temperature dependence of birefringence

ABSTRACT

We present a new fabrication approach to achieve a high birefringence film by means of photopolymerization based on an alkylthio-containing rod-like liquid crystalline molecule exhibiting large temperature dependence of birefringence. We designed a new reactive mesogen having alkylthio linkages (BPM–S). It was found that BPM–S had a larger increment of birefringence with decreasing temperature, relative to commercially available alkoxy analog LC242. This result could be thought to be due to enhanced intermolecular attractive interaction for an alkylthio mesogen implied by the proximity of laterally neighboring molecules and cybotactic nematic tendency based on wide-angle X-ray measurement. The uniaxially-aligned photo-polymerized film for BPM–S showed higher birefringence than that for LC 242.