Twist-grain-boundary structure in the B4 phase of a bent-core molecular system identified by second harmonic generation circular dichroism measurement

Second harmonic generation circular dichroism (SHG CD) measurements are performed on the B4 phase of a bent-core molecular system. Numerical analysis of SHG CD incorporating magnetic-dipole as well as electric-dipole interaction shows that the B4 phase is in a twist-grain-boundary structure with the helical axis along the bent direction of the molecules. The result is extremely important in the sense that achiral molecules are spontaneously optically resolved, i.e., deracemization, the chiral domains of which give rise to huge chiral nonlinear optical effect.     

Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts

The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH(3)OH) promoted by the conventional solid acids (H-mordenite, beta-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and gamma-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH(3)OH in the reaction of 2-aminoethanol with methanol (amine/CH(3)OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 degrees C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P(2)O(5)/SiO(2) and Cs/SiO(2), respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO(2). The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.     

Observation of electrostatically released DNA from gold electrodes with controlled threshold voltages

DNA oligo-nucleotides, localized at Au metal electrodes in aqueous solution, are found to be released when applying a negative bias voltage to the electrode. The release was confirmed by monitoring the intensity of the fluorescence of cyanine dyes (Cy3) linked to the 5' end of the DNA. The threshold voltage of the release changes depending on the kind of linker added to the DNA 3'-terminal. The amount of released DNA depends on the duration of the voltage pulse. Using this technique, we can retain DNA at Au electrodes or Au needles, and release the desired amount of DNA at a precise location in a target. The results suggest that DNA injection into living cells is possible with this method.     

Diastereoselective photochromism of a bisbenzothienylethene governed by steric as well as electronic interactions

Introduction of an asymmetric center to C-2 of one of the benzothiophene rings of bisbenzothienylperfluorocyclopentene results in a highly diastereoselective photochromic system. The stereogenic center bears a hydrogen atom, a methyl group, and a methoxymethoxy group. The steric as well as the electronic repulsions gave an 87-88% diastereomer excess in various solvents at room temperature with 80-85% conversion to the colored form. The enantioselective synthesis was also carried out. Upon photoirradiation in hexane, a change in optical rotation at 820 nm, where neither the open form nor the colored form absorbs light, was observed repeatedly.     

Validity of retinal oxygen saturation analysis: Hyperspectral imaging in visible wavelength with fundus camera and liquid crystal wavelength tunable filter

The purpose of this paper was to investigate the feasibility of a newly developed hyperspectral fundus imaging camera with a liquid crystal tunable filter. The intensities of different wavelengths of light transmitted through an artery, vein, and the area surrounding these vessels and reflected out were measured, and the differential spectral absorptions were analyzed. Measurements were made from 16 normal eyes and from two artificial capillaries. The ratios of absorption (ROA) of arteries to veins from 500 to 580 nm (range 1) and from 600 to 720 nm (range 2) were calculated. For all eyes, the ROA_range1 was larger than ROA_range2. The ROA obtained from the artificial capillary filled with blood saturated with oxygen or nitrogen was similar to that of simulated data of oxy- and deoxyhemoglobin extinction rate. Most ROAs of human eyes were lower than those of the simulated data and the artificial capillaries. Oxygen saturation analysis by hyperspectral fundus imaging of retinal vessels were qualitatively in agreement with thein vitro analysis or simulated values. However, further improvements are necessary to evaluate the oxygen saturation quantitatively in the retinal blood vessels.     

Intramolecular conjugate addition of γ- and δ-trichloroacetimidoyloxy-α,β-unsaturated esters in an acyclic system

An intramolecular conjugate addition of γ- and δ-trichloroacetimidoyloxy-α,β-unsaturated esters, a new way to construct 1,2-amino or 1,3-amino alcohol moieties in an acyclic system, is described. Very concise synthesis of d-vancosamine and 3-epi-d-vancosamine derivatives was also achieved utilizing this methodology.     

On generalized poly-Bernoulli numbers and related L-functions

Different two generalizations of the Dirichlet L-functions which are based on the construction of Arakawa–Kaneko?s zeta function are treated. Further special values at non-positive integers of such functions are evaluated and generalized poly-Bernoulli numbers are introduced via those values.     

Ullmann CO coupling of sterically hindered secondary alcohols using excess amount of strongly coordinating monodentate ligands

A new effective copper catalyzed CO coupling reaction using excess amount of strongly coordinating monodentate ligands was successfully developed. Among the DMAP-type monodentate ligands, 4-pyrrolidinopyridine afforded the best results. The developed reaction is widely applicable for the synthesis of various hindered or acyclic secondary alkyl-aryl ethers. In this study, a novel and remarkable acceleration of the coupling reaction using excess amount of monodentate ligands was discovered.