twins in Mo-doped TiSi 2 thin films with the C54 structure

The defect structures in orthorhombic C54 crystallites in thin films of Mo-doped TiSi 2 produced by co-sputtering have been investigated by transmission electron microscopy. Almost all C54 crystallites contain a twin boundary parallel to (101), dividing a crystallite into two regions, each of which also contains many thin twins with the habit plane parallel to (001), which is inclined by about 45° from (101). Both of the two regions divided by the twin boundary parallel to (101) tend to have facets on (001) as well as thin twins with the habit plane parallel to (001). As a result, C54 crystallites exhibit a characteristic shape just like an oak leaf. While twins with the (001) habit plane have been observed in C54 crystallites in both binary and Mo-doped TiSi 2 thin films, those with the (101) habit plane are present only in Mo-doped TiSi 2 thin films. The twinning elements for (101) twins are determined to be K 1 = (101), , K 2 = (001) and m2 = [100]. The origin of (101) twins in Mo-doped TiSi 2 is discussed in terms of the change in the c / a axial ratio upon alloying TiSi 2 with Mo.     

Stereochemical Dichotomy in Two Competing Cascade Processes: Total Syntheses of Both Enantiomers of Spiroxin A

The first total synthesis of the marine antibiotic spiroxin A has been achieved for both enantiomeric forms. The discovery of two competing cascade processes triggered by two orthogonal stimuli, photo‐irradiation or acid/base treatment, enabled the divergent conversion of a single chiral, nonracemic bis‐quinone into both enantiomers of an advanced intermediate en route to both (?)‐ and (+)‐spiroxin A. The mechanism of the enantiodivergence is discussed.     

Development of ultrahigh-precision coherent control and its applications

Coherent control is based on optical manipulation of the amplitudes and phases of wave functions. It is expected to be a key technique to develop novel quantum technologies such as bond-selective chemistry and quantum computing, and to better understand the quantum worldview founded on wave-particle duality. We have developed high-precision coherent control by imprinting optical amplitudes and phases of ultrashort laser pulses on the quantum amplitudes and phases of molecular wave functions. The history and perspective of coherent control and our recent achievements are described.     

Controlled synthesis of amphiphilic block copolymers with pendant glucose residues by living cationic polymerization

Amphiphilic block copolymers of vinyl ethers (VEs) of the type —[CH₂CH(OCH₂CH₂OR)]_m—[CH₂CH(OiBu)]_n—were synthesized by living cationic polymerization, where R is a D-glucose residue, and m and n are the degrees of polymerization (m = 20–50; n = 11–89). To obtain them, sequential living block copolymerization of isobutyl vinyl ether (IBVE) and the vinyl ether carrying 1,2:5,6-diisopropylidene-D -glucose residue was conducted by using the HCl adduct of IBVE, CH₃CH(OiBu)Cl, as initiator in conjunction with zinc iodide. These precursor block copolymers had a narrow molecular weight distribution (M̄_w/M̄_n ∼ 1.1) and a controlled composition. Treatment of them with a trifluoroacetic acid/water mixture led to the target amphiphiles. The solubility of the amphiphilic block copolymers in various solvents depended strongly on composition or the m/n ratio. Their solvent-cast thin films were observed, under a transmission electron microscope, to exhibit various microphase-separated surface morphologies such as spheres, cylinders, and lamellae, depending on composition. © 1997 John Wiley & Sons, Inc.     

Enhancement of electroluminescence intensity in poly(3-alkylthiophene) with different alkyl side-chain length by doping of fluorescent dye

Electroluminescent diodes utilizing poly(3-alkylthiophene) (PAT) containing fluorescent dyes have been fabricated and their unique enhancement of emission characteristics have been studied. Remarkable enhancement of the electroluminescence efficiency has been observed for diodes with PAT doped with oxadiazole derivative (2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; PBD) and perylene derivative (N,N′ - Bis(2,5 - di - tert - butylphenyl) - 3,4,9,10 - perylenedi- carboximide; BPPC). The mechanism of emission enhancement by doping of PBD into PAT has been discussed with different alkyl side-chain lengths. © 1997 John Wiley & Sons, Ltd.     

Synthetic Study of (−)‐Norzoanthamine: Construction of the ABC Ring Moiety

Throw your hat in the ring : A highly diastereoselective synthesis of the ABC rings of (?)‐norzoanthamine has been achieved starting from the (?)‐Hajos–Parrish ketone (see scheme). Three asymmetric quaternary carbon centers on the C ring were constructed by a 1,4‐addition, and an intramolecular Diels–Alder reaction provided a trans‐decalin scaffold on the AB rings.