Multiple Fused Anthracenes as Helical Polycyclic Aromatic Hydrocarbon Motif for Chiroptical Performance Enhancement

Polycyclic aromatic hydrocarbons consisting of three fused anthracene units were designed as new π‐conjugated compounds having helical structures. These expanded helicenes were synthesized by Pt‐catalyzed cycloisomerization of the corresponding ethynyl‐substituted precursors. The nonplanar and helical structure was confirmed by X‐ray analysis and DFT calculations, and the barrier to helical inversion was estimated to be 34 kJ mol^?1. The enantiomers of the diphenyl derivative were successfully resolved by chiral HPLC. Enantiopure samples showed good chiroptical performance in the CD (|Δ?| 1380 L mol^?1 cm^?1) and CPL (|g_lum| 0.013) spectra, and these values were considerably large for simple organic molecules. The unique chiroptical properties are discussed on the basis of the molecular structure and the electronic state with the aid of time‐dependent DFT calculations.     

Ion chromatographic system with a novel switching suppression device

Ion chromatography (IC) has been a powerful tool for measuring ionic species in environmental samples such as tap, river and drain waters. Suppressor modules (membrane and disposable column types) have been used for reducing the background of a baseline. A new type of suppressor device, which has a suppressor resin and switching valve was developed. Fresh ionic resin is introduced into a groove for each analysis to perform the suppression of the working eluent. The eluent composition for obtaining higher sensitivity and better resolutions among ionic species and carbonate ion was also investigated. Although carbonate buffers are used for ion separation in general, the separation of carbonate ion from other ions was not achieved. A borate eluent resulted in good resolutions and higher sensitivity. A new column was also developed for obtaining higher column efficiency and resolution. The optimization of anion separation using a new IC system (IC-2001) that consists of a new suppressor device, an anion-exchange column (TSKgel SuperIC-Anion, 150x4.6 mm), an autosampler, a conductivity cell and a pump in a compact module is described.     

Vinyl-lambda 3-iodanes act as efficient sulfur atom acceptors: vinylic SN2-based strategy for conversion of tertiary thioamides to amides

Exposure of tertiary thioamides to (E)-1-hexenyl(phenyl)-lambda 3-iodane results in vinylic SN2 reaction to give the inverted (Z)-S-vinylthioimidonium salts, which under alkaline hydrolysis (Na2CO3 or K2CO3) selectively afford amides, while (Z)-S-vinyl thioesters are obtained in high yields via the hydrolysis under acidic conditions (HCl).     

Synthesis of large-pore phenylene-bridged mesoporous organosilica using triblock copolymer surfactant

Periodic mesoporous benzene-silicas with large pores of 6.0 to 7.4 nm in diameter are synthesized using triblock copolymer as a template. These mesoporous materials have a well-defined hexagonal rod morphology and high thermal stability up to 823 K in air.     

Face-selective addition to a cation-pi complex of a pyridinium salt: synthesis of chiral 1,4-dihydropyridines

Selective shielding of one side of the pyridinium face by way of intramolecular cation-pi complex formation enabled nucleophiles to attack only from the non-shielded side, and consequently, chiral 1,4-dihydropyridines were produced stereoselectively with up to 99% de. The structure of the cation-pi complex was elucidated by 1H NMR studies and X-ray analysis.     

Sulfuric acid-functionalized mesoporous benzene-silica with a molecular-scale periodicity in the walls

Novel sulfuric acid-functionalized mesoporous benzene-silicas with a molecular-scale periodicity in the walls were derived from the mesoporous benzene-silica possessing mercaptopropyl groups by the oxidative transformation of -SH into -SO3H.     

Evolution of lower-hybrid-driven current during the formation of an internal transport barrier

Evolution of the lower-hybrid(LH)-driven current profile was measured during the formation of an internal transport barrier (ITB) in a reversed magnetic shear discharge. As the ITB developed, the initially centrally peaked LH-driven current profile gradually turned hollow and was sometimes accompanied by an off-axis peak in the electron temperature profile. These observations indicate the concentration of LH power deposition to the ITB for this case as a result of nonlinear coupling between the LH waves and the target plasma.     

Off-resonant fifth-order response function for two-dimensional Raman spectroscopy of liquids CS2 and H2O

The off-resonant fifth-order response functions for two-dimensional (2D) Raman spectroscopy of molecular liquids CS2 and H2O are investigated by using molecular dynamics calculation. This spectroscopy, able to deal with a phase space dynamics, shows the existence of nodal lines in several polarization tensor elements [see L. Kaufman et al., Phys. Rev. Lett. 88, 207402 (2002) for experimental results]. The nodal property is found to arise from the dynamical couplings among rotational modes, not accounted for in a normal mode picture. The effects of anharmonicities and "mode coupling through polarizability" are also investigated by comparing the 2D Raman signal with a constant temperature velocity reassignment echo method.