First observation of a smectic A-cholesteric phase transition in a thermotropic liquid crystal consisting of a rigid-rod helical polysilane

A smectic A-cholesteric phase transition for a rigid-rod helical polymer, poly[n-decyl-(S)-2-methylbutylsilane] (PD2MBS), with a narrow molecular weight distribution, has been observed for the first time. Polarizing optical microscopy showed that the fan-shaped texture of the smectic A phase turned into the characteristic planar texture of the cholesteric phase upon heating. The positive CD band, which corresponds to the reflection band of the cholesteric phase, gradually decreased in intensity within a range 30°C below the transition temperature on cooling, while the peak maximum shifted towards shorter wavelengths. It was concluded that the system has a very wide temperature region over which the cholesteric-smectic A phase transition occurs and in which the cholesteric pitch varies with temperature.     

Instrumental Requirements for Non-Invasive Blood Glucose Measurement Using NIR Spectroscopy

The magnitude of spectral change in blood glucose measurements with diffuse reflectance spectroscopy is investigated. Spectral change is estimated by simulation of light propagation in skin tissue and measurements of absorbance spectra of aqueous glucose solution. Required sensitivity of spectrophotometers for monitoring change in the blood glucose concentration as small as 10 mg/dL has been obtained using the estimated change in the absorbance spectrum and mean pathlength of light in tissue.     

Relative position of four subspaces in a Hilbert space

We study the relative position of several subspaces in a separable infinite-dimensional Hilbert space. In finite-dimensional case, Gelfand and Ponomarev gave a complete classification of indecomposable systems of four subspaces. We construct exotic examples of indecomposable systems of four subspaces in infinite-dimensional Hilbert spaces. We extend their Coxeter functors and defect using Fredholm index. The relative position of subspaces has close connections with strongly irreducible operators and transitive lattices. There exists a relation between the defect and the Jones index in a type II₁ factor setting.     

Bistable Optical Devices Using Laser Diodes Coupled to Interference Filters

A bistable optical device was demonstrated by using the longitudinal mode hopping of the laser diode and the narrow transmission spectrum of an interference filter. The device is capable of converting changes in the wavelength of the laser diode into changes in intensity by transmitting it through the filter. Exclusive OR operation was observed with the use of triple signal outputs. In addition, an optical switch-off phenomenon was confirmed by directly injecting a pulse 500 ps wide into an external dye laser.     

Trapping Nanostructures on Surfaces through Weak Interactions

The assembly of imidazole‐functionalized phenanthroline‐strapped zinc porphyrins (ZnPorphen) with alkyl or polyethylene glycol (PEG) side chains was studied in solution and by AFM after casting on highly oriented pyrolytic graphite (HOPG) or mica. The nature of the solvent and its evaporation time influenced the morphology of the objects observed. On HOPG, short rods of about 100 nm were observed after fast evaporation of solutions of the alkyl derivatives in CHCl₃, THF, or pyridine, whereas islands of aligned rows of longer wires were obtained from methylcyclohexane (MCH). Slow evaporation of MCH led to a three‐dimensional assembly. The PEG porphyrin assembled into short wires on HOPG or fibers on mica after slow evaporation of solutions in THF. This study shows the role of surface–molecule interactions in the interfacial assembly of ZnPorphen derivatives and contributes to understanding the parameters that control their noncovalent assembly into molecular wires on a surface.     

Enantioselective synthesis of chelidonine, a B/C-cis-11-hydroxyhexahydrobenzo[c]phenanthridine alkaloid

Both enantiomers of chelidonine, a B/C-cis-11-hydroxyhexahydrobenzo[c]phenanthridine alkaloid, were synthesized by manipulation of the B/C-dehydro ring juncture of benzo[c]phenanthridine skeleton using Sharpless asymmetric dihydroxylation and stereospecific catalytic hydrogenation after introduction of oxygen functions on the C ring as key reaction steps for the construction of stereogenic centers.     

The reaction process of firefly bioluminescence triggered by photolysis of caged-ATP

The reaction process of firefly bioluminescence was studied by photolyzing caged-ATP to adenosine triphosphate (ATP) within 100 ms. The intensity of luminescence increases markedly to reach a maximum within 1 s, maintains almost the same intensity up to 5 s and then decays monotonically. The rise γ(1) and decay γ(2) rate constants were determined to be about 5 s(-1) and 1 × 10(-2) s(-1), respectively, so as to phenomenologically fit the time course. A second luminescence peak appears after around 350 s. The dependence of the rate constants on the concentrations of reactants and a viscous reagent revealed that two kinds of reaction contribute the observed time course: (1) an intrinsic reaction by ATP photolyzed from caged-ATP that is already trapped in luciferase; and (2) a diffusion-controlled reaction by free ATP in the buffer solution outside luciferase. Numerical analysis based on reaction kinetics related γ(1) and γ(2) to the rate constants of a three-step reaction model, and accurately described the effects of concentration of reactants and a viscous reagent on the time courses of bioluminescence. Thus, it has been clearly concluded that the binding mode of caged-ATP at the catalytic center of luciferase is very different from that of ATP.     

Complete C-labeling pattern of yessotoxin a marine ladder-frame polyether

Biosynthesis of a marine ladder-frame polyether yessotoxin (YTX) produced by the dinofalgellate Protoceratium reticulatum was investigated. The ¹³C-labeling experiments indicated that the carbons in YTX were derived from acetates, a methyl of methionine and glycolate, and six-membered ring tetrads (rings A-D and H-K) were constructed from repetition of C3 units (m-m-c), which consisted of a methyl of acetate and acetate.     

Differential Effects of Cold Exposure on Gene Expression Profiles in White Versus Brown Adipose Tissue

The thermogenic function of brown adipose tissue (BAT) is known to be markedly elevated when animals are exposed to the cold, and intensive studies have been carried out to understand the molecular basis enabling effective thermogenesis in cold-exposed animals. In this study, we used microarray analysis to examine the effects of cold exposure of animals on their gene expression profiles in white adipose tissue (WAT), which seems to function as a counterpart tissue of BAT. The results indicate that the effects of cold exposure on the gene expression profiles of WAT were much more moderate than the effects on those of BAT. Possible reasons for the different responses of BAT and WAT to cold exposure are discussed.     

Domino Pd-catalyzed Heck cyclization and bismuth-catalyzed hydroamination: formal synthesis of elacomine and isoelacomine

The formal synthesis of hemiterpene spirooxindole alkaloids elacomine (1) and isoelacomine (2) is described. Heck reaction of protected iodoanilines with 5,6-dihydro-2H-pyran-2-one or six-membered unsaturated lactams was investigated. The coupling product was readily converted to a carbamoyl chloride with an incorporated diene unit. The spiro(pyrrolidine-3,3'-oxindole) skeleton, which corresponds to the carbon skeleton of 1 and 2, was efficiently constructed from this intermediate by using a domino palladium-catalyzed Heck reaction and bismuth-catalyzed hydroamination. An isolated byproduct of the reaction could also be converted to the spirooxindole skeleton.