Design and synthesis of zero–zero-birefringence polymers in a quaternary copolymerization system

We designed and synthesized quaternary copolymers of methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate (TFEMA), benzyl methacrylate (BzMA), and 3,3,5-trimethylcyclohexyl methacrylate (TMCHMA) and we investigated their birefringence, thermal properties, and other optical properties. When the copolymer composition was MMA/TFEMA/BzMA/TMCHMA = 50:38:8:4, 40:30:7:23, or 30:21:7:42 (wt%), a zero–zero-birefringence polymer that exhibited neither orientational nor photoelastic birefringence was obtained. We demonstrated that such zero–zero-birefringence polymers with a variety of compositions could be successfully prepared in the quaternary system by using the same compensation method as applied in ternary random copolymerization. We also demonstrated that the glass-transition temperature (T_g) and refractive index (n_D) of these copolymers could be controlled with high accuracy while retaining their zero–zero-birefringence property. We can therefore predict the type of birefringence, the T_g, and the n_D of a particular copolymer before polymerization. Zero–zero-birefringence polymers with the most appropriate characteristics can then be synthesized selectively by quaternary copolymerization.     

Preparation of bismuth nanowire encased in quartz template for Hall measurements using focused ion beam processing

ABSTRACT: Forming electrodes on opposite sides of an individual bismuth nanowire was attempted to prepare for Hall measurements. Although a 1-mm-long bismuth nanowire which is completely covered with a quartz template has been successfully fabricated to prevent oxidation, it is very difficult to attach Hall electrodes on the opposite sides of the nanowire due to the quartz covering. One side of the cylindrical quartz template was removed by polishing without exposure of the nanowire to the atmosphere; the thickness between the polished template surface and the nanowire was estimated to be several micrometers. Focused ion beam processing was successfully employed to expose both surfaces of the nanowire under high vacuum by removing part of the quartz template. A carbon thin film was then deposited in situ on the wire surface to fabricate an electrical contact on the bismuth nanowire sample. Furthermore, the energy dispersive X-ray analysis was performed to the area processed by focused ion beam, and the bismuth component of the nanowire was successfully detected. It was confirmed that the focused ion beam processing was applicable to attach electrodes to bismuth nanowire for Hall measurement.     

Synthesis and optical properties of the [2.2]paracyclophane-containing π-conjugated polymer with a diacetylene unit

Summary Novel through-spaceπ-conjugated polymer based on poly(p-henyleneethynylene)/poly(p-phenylenebutadiynylene) hybrids containing a [2.2]paracyclophane unit in the main chain was synthesized by copper-catalyzed alkyne coupling reaction. The structure of the polymer was supported by ¹H NMR and IR spectra. The obtained polymer was soluble in common organic solvents such as THF, CH₂C1₂, CHC1₃ and toluene. The number-average of molecular weight of the polymer was estimated to be 63000 by GPC. The polymer emitted a bluish green light in solution and in the solid state. Received:24 September 2002/Revised version: 19 November 2002/Accepted: 19 November 2002 Correspondence to Yoshiki Chujo     

Synthesis and properties of conjugated copolymers having a tricarbonyl(arene)chromium and thiophene units in the main chain

Summary Palladium-catalyzed polymerization of η ⁶-(1,4-diethynylbenzene)tricarbonyl chromium (1) with 3-alkyl-2,5-dibromothiophene (2a-c) was carried out to give the corresponding alternating conjugated copolymers (5a-c) in good yields. The structures of the polymers were supported by ¹H NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical and electrical properties were investigated in detail. Received: 18 March 2002 /Accepted: 1 April 2002     

N-Alkylation of chitin and some characteristics of the novel derivatives

Summary Introduction of simple alkyl groups at the C-2 nitrogen of chitin and some properties of the resulting N-alkyl-chitins have been examined. Chitosan was fully deacetylated and treated with three kinds of aldehydes, formaldehyde, acetaldehyde, and pentanal. The Schiff bases of chitosan, whose extents of substitution were dependent on the amount of aldehydes, were reduced with sodium cyanoborohydride to N-alkylated chitosans. The N-alkyl-chitosans were then transformed into the corresponding N-alkyl-chitins by acetylation with acetic anhydride followed by transesterification to remove partly formed O-acetyl groups. The resulting N-methyl-, ethyl-, and pentyl-chitins were amorphous and showed improved affinity for organic solvents. Received: 13 December 2001/Revised version: 11 January 2002/Accepted: 17 January 2002     

Synthesis and Properties of Novel Poly(p-phenylenevinylene)s Containing a Tricarbonyl(arene)chromium Unit in the Main Chain

Summary Novel π-conjugated polymers based on poly(p-phenylenevinylene)s (PPVs) containing a tricarbonyl(arene)chromium unit in the main chain were synthesized by Horner-Wadsworth-Emmons olefination. The structures of the polymers were supported by ^lH NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical, and electrochemical properties were investigated in detail. Received: 18 November 2002/Revised version: 10 February 2003/ Accepted: 11 February 2003 Correspondence to Yoshiki Chujo     

Kinetically Stable Bicelles with Dilution Tolerance,Size Tunability,and Thermoresponsiveness for Drug Delivery Applications

Mixtures of a phospholipid (1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphatidylcholine, DPPC) and a sodium‐cholate‐derived surfactant (SC‐C₅) at room temperature formed phospholipid bilayer fragments that were edge‐stabilized by SC‐C₅: so‐called “bicelles”. Because the bilayer melting point of DPPC (41 °C) is above room temperature and because SC‐C₅ has an exceptionally low critical micelle concentration (<0.5 mm ), the bicelles are kinetically frozen at room temperature. Consequently, they exist even when the mixture is diluted to a concentration of 0.04 wt %. In addition, the lateral size of the bicelles can be fine‐tuned by altering the molar ratio of DPPC to SC‐C₅. On heating to ≈37 °C, the bicelles transformed into micelles composed of DPPC and SC‐C₅. By taking advantage of the dilution tolerance, size tunability, and thermoresponsiveness, we demonstrated in vitro drug delivery based on use of the bicelles as carriers, which suggests their potential utility in transdermal drug delivery.     

Molecular Dynamics Study of Atomic Structure and Diffusion Behavior in Amorphous Silicon Nitride Containing Boron

We have performed molecular dynamics simulations of amorphous Si₃N₄ containing boron (Si-B-N). We have examined short-range atomic arrangements and self-diffusion constants of amorphous Si-B-N systems with various boron contents. Our simulations show that boron atoms are threefold coordinated by nitrogen atoms and that nitrogen atoms are bonded to both silicon and boron atoms in the amorphous network of Si-B-N. Also, the self-diffusion constant of nitrogen in Si-B-N is much decreased compared with that in amorphous Si₃N₄. This suggests that boron is important in decreasing the mobility of atoms in amorphous Si-B-N, which may explain the improved thermal stability of amorphous Si-B-N relative to amorphous Si₃N₄ observed experimentally.     

Enantioselective addition Of diketene to aldehydes promoted by chiral schiff base—titanium alkoxide complex. Application to asymmetric synthesis of potential inhibitors of HMG coenzyme reductase

Highly enantioselective addition of diketene to aldehydes was achieved by using novel Schiff base—titanium alkoxide complexes. Up to 92% ee of 5-hydroxy-3-oxoesters was obtained. This procedure provides an efficient method for the asymmetric synthesis of potential inhibitors of HMG coenzyme reductase.     

EFFECTS OF OPERATIONAL CONDITIONS ON DRYING CHARACTERISTICS IN CLOSED SUPERHEATED STEAM DRYING

The effects of operational conditions on the drying performance in closed superheated steam drying were examined theoretically and experimentally. The vapor generated from the sample was circulated in the drying chamber. In the theoretical analysis, the replacement of air with vapor in drying chamber and the convective vapor transfer in sample were considered. At the start of drying, the drying chamber was filled with air. As the drying proceeded, the air was replaced with the vapor generated from sample. The calculated results explained the characteristics of experimental data. The pore diameter of sample had little effect on the drying characteristics. During the internal evaporation period, the evaporation occurred in the narrow zone, which moved from the surface to the bottom of sample. The convective vapor transfer in sample had a significant influence on the drying performance. The excess increments in temperature and velocity of drying gas hardly contributed to shortening the drying time.