Synthesis of isoquinoline derivatives using ROM-RCM of cyclobutene-yne

Isoquinoline derivatives were synthesized from cyclobutenylmethylamine derivatives having an alkyne moiety in a tether using a second-generation ruthenium carbene complex under ethylene gas in good yields.     

Critical concentration for colloidal crystallization determined with microliter centrifuged suspensions

We report an elegant method using centrifugal sedimentation for determining the critical particle concentration for colloidal crystallization. A small amount of a dilute suspension of monodispersed particles stored in a flat capillary cell was centrifuged to temporarily generate a nonequilibrium gradient of the particle concentration including a crystalline-noncrystalline phase boundary in the cell. In the recovering process after the centrifugation, the particle concentration of the crystalline phase at the boundary was found to always have the equilibrium value, although the global concentration distribution evolved with time. The critical concentration was determined based on spatially resolved spectrometry. The present method requires only one batch of a suspension of the order of microliters and is applicable up to high concentration regions near the closest packing without the effect of the particle aggregation.     

Spectroscopic and excited-state properties of tri-9-anthrylborane II: Electroabsorption and electrofluorescence spectra

Electroabsorption and electrofluorescence spectroscopies were conducted for tri-9-anthrylborane (TAB) doped in poly(methyl methacrylate) films (1.0 mol %) to reveal the spectroscopic and excited-state properties of the compound. TAB showed three distinct absorption bands: bands I [(19 - 25) x 10(3) cm(-1)], II [(25-31) x 10(3) cm(-1)], and III (>31 x 10(3) cm(-1)). The electroabsorption spectrum demonstrated that the electronic transitions in bands I and III accompanied electric dipole moment changes (Deltamu), while the change in the molecular polarizability contributed mainly to electroabsorption band II. Because of the similarities of the electroabsorption spectrum of band II with that of anthracene itself, band II was assigned to the electronic transition to the locally excited (LE) state of the anthryl group. On the other hand, bands I and III were best described by the electronic transitions to the excited charge-transfer (CT) states. The study demonstrated furthermore that the Deltamu value of TAB accompanied by the lowest-energy electronic transition was as large as 7.8 D, which agreed very well with that determined by the solvent dependences of the absorption and fluorescence maximum energies of TAB (approximately 8.0 D, ref 1): Deltamu = 7.8-8.0 D. The results proved explicitly that the excited state of TAB was localized primarily on the p orbital of the boron atom. Despite the dipole moment change (Deltamu = 7.8-8.0 D) for the lowest-energy electronic transition (band I), the electrofluorescence of TAB accompanied the change in the molecular polarizability. The spectroscopic and excited-state properties of TAB including the curious behavior of the electrofluorescence spectrum as mentioned above were discussed on the basis of theoretical considerations.     

Effect of phosphatidylserine content on the partition coefficients of diazepam and flurazepam between phosphatidylcholine-phosphatidylserine bilayer of small unilamellar vesicles and water studied by second derivative spectrophotometry

The affinity of the psychotropic benzodiazepine drugs diazepam (DZ) and flurazepam (FZ) to phosphatidylserine (PS) was examined since PS is abundantly contained in brain membranes. The effect of PS content on the partition coefficients (K(p)s) of these drugs between phosphatidylcholine (PC)-PS bilayer membranes of small unilamellar vesicles (SUV) and water was measured using second derivative spectrophotometry. The second derivative spectra of DZ and FZ measured in the solutions containing various amounts of PC-PS SUV clearly showed derivative isosbestic points and a distinct derivative intensity change depending on the amount of the SUV added. The derivative intensity differences (AD) of the drugs before and after addition of the SUV suspension were measured at a specific wavelength. Using the AD values, the Kp values were calculated and obtained with relative standard deviation of below 10%. The Kp values of both drugs increased according to the PS content in the PS-PC bilayer membranes of the SUV proving that both have higher affinity to the PC-PS bilayer membranes than to PC membranes. The effect was much larger for FZ, i.e., the Kp value of FZ at 30 mol% PS content increased to about five times the value for the PC SUV. This can be explained by the fact that at the experimental pH of 7.4, 80% of FZ molecules are in a cationic form (pKa=8.1), so that these molecules are highly accessible to the negatively charged PS molecules. The results support the rapid and high distribution of DZ and FZ in the central nervous system after their administration.     

Corner sharing tetrahedral network in Co(3)(HAT)[N(CN)(2)](6)(OH(2))(2) (HAT = 1,4,5,8,9,12-hexaazatriphenylene)

We report a trinuclear Co(II) complex containing bridging dicyanamides and a tris-chelated HAT, which possesses approximately 37% void space. The magnetic exchange pathways appear in the structure as a corner sharing tetrahedral network. The compound crystallizes in the monoclinic space group P2(1)/c [a = 13.655(3) A, b = 15.189(3) A, c = 22.367(4) A, beta = 114.100(2) degrees, V = 4234.5(14) A(3), Z = 4, R(F(o)) = 0.0823]. The magnetic data were fit to an S = 3/2 model for systems dominated by zero-field splitting effects with g = 2.01 and D = 38.9 cm(-1).     

Transient film profile of thin liquid film flow on a stretching surface

In this paper we have studied a non-planar thin liquid film flow on a planar stretching surface. The stretching surface is assumed to stretch impulsively from rest and the effect of inertia of the liquid is considered. Equations describing the laminar flow on the stretching surface are solved analytically. It is observed that faster stretching causes quicker thinning of the film on the stretching surface. Velocity distribution in the liquid film and the transient film profile as functions of time are obtained.     

Near-Field Evaluation of a Quantum Size Effect in Self-Aligned GaN Whiskers Fabricated Using Photochemical Etching

We fabricated nanoscale GaN whiskers using photochemical etching. The fabricated GaN whiskers were conjugated and aligned perpendicular to the incident light polarization used for photochemical etching in a self-assembling manner. Their far-field photoluminescence spectra exhibited a blue-shifted photoluminescence peak at 3.60eV. Near-field photoluminescence spectra of individual GaN whiskers were obtained, for the first time. The evaluation of the near-field spectra identified several peaks from individual whiskers, corresponding to a diameter range of 5–10 nm, and revealed a stepwise change in the diameter along the axis of individual whisker.     

X-ray studies on layer structure and bistability in ferroelectric liquid crystals

X-ray diffraction measurements of thin chiral smectic C (S_c*) liquid crystals between solid plates coated with rubbed polymer film were performed under an electric field. A variety of local layer structures which depend upon the boundary conditions could be observed, including bookshelf and chevron, and some distorted structures. Moreover, the method of layer deformation could be seen in a stepwise induced field, and seven deformation types could be detected. The relation between a bistability effect and the type of layer deformation was clarified and four deformation types were found favourable to bistability. A vertical layer structure at the boundary, like the bookshelf structure, was necessary to produce bistability. A high pretilt film seemed to have a smectic layer reform a tilted structure even under an induced field and it was difficult to produce bistability with the high pretilt one.