D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Color Zone Map in Peripheral Vision at Various Illuminance Levels

We measured the entire region of mesopic and photopic vision to determine the color zone covering the visual field with unique red, yellow, green, and blue hue components. Eight kinds of test stimuli in the natural color system (NCS) color notation system were used. These stimuli were presented at horizontal and vertical meridians, and at meridians inclined at 45° angles. The illuminance level was set at six levels: 0.01 lx-1000 lx. The evaluation method measured chromatic, white, and black components as well as the hue component of the stimuli. Results show that the color zone of the retina extended further into the periphery with increasing illuminance; the response of opponent colors y-b was shown to be greater than that of the opponent colors r-g.     

One step synthesis of 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals in an ionic liquid

Investigation of one step synthesis of 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals has been carried out using versatile aldehydes, tri- or di-fluoroacetaldehyde ethyl hemiacetal in the presence of diethylaminotrimethylsilane (DEATMS) in an ionic liquid, and it was demonstrated that this route enabled us to successfully construct 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals with the high level selectivity of geometric isomers.     

Introduction of several trifluoromethyl groups onto the activated aromatic materials with CF3TMS-CuI-KF system

Trifluoromethylation onto the tetrafluorophthalonitrile and tetrafluoroisophthalonitrile has been carried out using CF₃TMS-CuI-KF system, and it was demonstrated that these trifluoromethylation enabled us to successfully construct di- and/or tri-trifluoromethylated benzonitriles via the decyanotrifluoromethylation.     

Highly regio- and stereocontrolled SN2′ reactions of gem-difluorinated vinyloxiranes with monoalkylcopper reagents

Reaction of gem-difluorinated vinyloxiranes with RCu(X)Li allowed us to introduce the R group regioselectively at the fluorine-attached terminal carbon atom in an S_N2′ manner to afford (E)-allylic alcohols exclusively, while homoallylic alcohols with anti stereochemical relationship were found to be obtained selectively from higher-ordered cuprates derived from CuCl and RMgBr in a ratio of 1:3.     

Spectrofluorimetric assay for acyl CoA-cholesterol acyltransferase

A sensitive assay for acyl CoA-cholesterol acyltransferase (EC 2.3.1.26) in rat liver microsomal and mitochondrial preparations is described. The lowered cholesterol concentration in the enzyme reaction with oleoyl CoA is determined spectrofluorimetrically by using the cholesterol oxidase/peroxidase/p-hydroxyphenylpropionic acid system. The assay requires as little as 20 μg of protein in the enzyme preparation.