Ferroelectric liquid crystalline phase transition of (S)-hexakis(4-(4'-(6-methyl)octyloxy)biphenoxy) cyclotriphosphazene

(S)-Hexakis(4-(4'-(6-methyl)octyloxy)biphenoxy)cyclotriphosphazene (SMOCP) was synthesized in a search for new ferroelectric liquid crystalline compounds. We found an enantiotropic ferroelectric smectic C* phase between 419 and 441 K in SMOCP by using polarizing microscopy and DSC measurements. The spontaneous polarization was estimated to be -130.5 μCm^-2 at 437.6 K, several times larger than that of DOBAMBC ((S)-2-methylbutyl 4-(4'-decyloxybenzylidene)aminocinnamate.     

A novel type secoiridoid glucoside,hydrangenoside a from Hydrangea macrophylla

Hydrangenoside A, isolated along with its three congeners from Hydrangea macrophylla, was proved to have a novel type of structure which is thought to be biosynthesized through an aldol-type condensation of secologanin with a unit formed by the shikimate-malonate route followed by decarboxylation.     

Finite difference simulation of nonlinear waves generated by ships of arbitrary three-dimensional configuration

A modified marker-and-cell method is developed in order to simulate nonlinear wave making in the near-field of ships of arbitrary three-dimensional (3D) configuration advancing steadily in deep water. The 3D Navier-Stokes equations are solved by a finite difference scheme under proper boundary conditions. Efforts are particularly focused on the treatment of the boundary conditions on the body surface and free surface which have complicated 3D configurations. An orthogonal cell system with more than 70,000 cells is used for the computation of the waves and flow field of ships. The agreement of computational results with experiment is good, and it promises effectiveness for engineering purposes.     

Nickel-catalyzed arylcyanation of alkynes

A nickel catalyst coordinated by trimethylphosphine is found to effect the addition reaction of Ar-CN bonds in aromatic nitriles across alkynes to give rise to various beta-arylalkenenitriles.     

Nickel-catalyzed intermolecular [3 + 2 + 2] cocyclization of ethyl cyclopropylideneacetate and alkynes

The [3 + 2 + 2] cocyclization of ethyl cyclopropylideneacetate (1a) and terminal alkynes (2) proceeded smoothly in the presence of 10 mol % "Ni(PPh3)2", which was prepared in situ from Ni(cod)2 and PPh3. The high reactivity of 1a, which was induced by the introduction of an electron-withdrawing group, is very important for the progress of this reaction. The cycloheptadiene derivatives were synthesized in highly selective manner in good yields.     

Probes for narcotic receptor-mediated phenomena. 33. Construction of a strained trans-5,6-ring system by displacement of a nitro-activated aromatic fluorine. synthesis of the penultimate oxide-bridged phenylmorphans

The synthesis of the ortho- and para-e isomers in the oxide-bridged 5-phenylmorphan series of rigid tetracyclic compounds was accomplished via rac-5-(2-fluoro-5-nitrophenyl)-2-methyl-2-azabicyclo[3.3.1]nonan-9beta-ol ((+/-)-10), an intermediate containing an aromatic nitro-activated fluorine atom. The fluorine atom was used as the leaving group for the formation of the strained tetracyclic trans-fused 5,6-ring system in rac-(1alpha,4aalpha,9aalpha)-1,3,4,9a-tetrahydro-2-methyl-6-nitro-2H-1,4a-propanobenzofuro[2,3-c]pyridine ((+/-)-11), although preference for cis ring fusion during the formation of tricyclic tetra- and hexahydrodibenzofurans has been well-documented. Single-crystal X-ray crystallographic study of the desired para-e isomer ((+/-)-2), as well as of two intermediates in its synthesis, provided assurance of the correct structures. The e-isomers are among the last of the 12 oxide-bridged 5-phenylmorphans to be synthesized. We envisioned the syntheses of these rigid, tetracyclic compounds in order to determine the three-dimensional pattern of a ligand that would enable interaction with opioid receptors as agonists or antagonists.     

Tissue velocity imaging of coronary artery by rotating-type intravascular ultrasound

Intravascular ultrasound (IVUS) provides not only the dimensions of coronary artery but the information of tissue components. In catheterization laboratory, soft and hard plaques are classified by visual inspection of echo intensity. So-called soft plaque contains lipid core or thrombus and it is believed to be more vulnerable than a hard plaque. However, it is not simple to analyze the echo signals quantitatively. When we look at a reflection signal, the intensity is affected by the distance of the object, the medium between transducer and objects and the fluctuation caused by rotation of IVUS probe. The time of flight is also affected by the sound speed of the medium and Doppler shift caused by tissue motion but usually those can be neglected. Thus, the analysis of RF signal in time domain can be more quantitative than intensity of RF signal. In the present study, a novel imaging technique called "intravascular tissue velocity imaging" was developed for searching a vulnerable plaque. Radio-frequency (RF) signal from a clinically used IVUS apparatus was digitized at 500 MSa/s and stored in a workstation. First, non-uniform rotation was corrected by maximizing the correlation coefficient of circumferential RF signal distribution in two consecutive frames. Then, the correlation and displacement were calculated by analyzing the radial difference of RF signal. Tissue velocity was determined by the displacement and the frame rate. The correlation image of normal and atherosclerotic coronary arteries clearly showed the internal and external borders of arterial wall. Soft plaque with low echo area in the intima showed high velocity while the calcified lesion showed the very low tissue velocity. This technique provides important information on tissue character of coronary artery.