Synthesis and characterization of new aromatic polyimides containing well‐defined conjugation units

A series of aromatic polyimides composed of well‐defined conjugation units were synthesized form 5,5′‐bis(4‐aminophenyl)‐2,2′‐bifuryl (PFDA) and 2,2′‐bis(furyl) benzidine (FurylBZ) with various dianhydrides. The synthesized polyimides emit blue to green light with a quantum yield of 7.3–14.9%, depending on the polymer backbone. In particular, PFDA‐based polymers exhibit extremely narrow photo‐luminescence. The structure, thermal stability, refractive index and dielectric properties of the polymer films were also determined.     

The role of the WO x ad-component to Pt and PtRu catalysts in the electrochemical CH3OH oxidation reaction

High surface area carbon-supported platinum-based catalysts, Pt/C, PtWO _x /C, PtRu/C and PtRuWO _x /C, were prepared via a chemical reduction route using single metal precursor salts. The catalyst particles were found to be in the nanoscale range, and the addition of Ru clearly decreased the particle size. The Ru was found to be partially incorporated into the face centered cubic lattice of Pt and to form a single Ru catalyst component. X-ray diffraction and X-ray photon spectroscopy did not provide evidence for electronic interactions between WO _x and Pt as well as WO _x and Ru. However, the addition of tungsten to the PtRuWO _x /C catalyst resulted in a high degree of catalyst particle agglomeration. Both Ru containing catalysts showed significantly higher activities for the CH₃OH oxidation reaction in terms of Pt + Ru mass as well as electroactive Pt + Ru surface area than the Pt/C and PtWO _x /C catalysts. The addition of tungsten appeared to mainly result in some ‘physical’ modification of the catalytically active Pt and Ru surface components such as differences in electroactive surface area rather than promotion of the CH₃OH oxidation reaction via a true catalytic mechanism.     

Ligand-binding domain of farnesoid X receptor (FXR) had the highest sensitivity and activity among FXR variants in a fluorescence-based assay

The farnesoid X receptor (FXR, NR1H4) has been recognized as an attractive therapeutic target because it is a nuclear hormone receptor that controls the expression level of cholesterol-7α-hydroxylase, which in turn regulates bile acid production and cholesterol excretion. To compare receptor activity between each domain and the full-length protein, human FXR cDNA was cloned from a human liver cDNA library. Three human FXR cDNA, designated FXR₂₀, FXR₃₃, and FXR₅₃ cDNA, were subcloned and ligated into a pET28a expression vector. Each protein was expressed in Escherichia coli (BL21) and purified by nickel-nitrilotriacetic acid column chromatography. Approximately 5 mg of FXR₃₃ (1–182 amino acids deleted from FXR, 37 kDa) and 2 mg of FXR₅₃ (the full-length protein of FXR, 59 kDa) was purified from 1 L of Luria-Bertani culture, achieving at least 90% purity. The coactivator recruitment assay for FXR activation was carried out with the three variants of the FXR protein by using dissociation-enhanced lanthanide fluoroimmunoassay-europium-N¹-labeled anti-His antibody. From an optimized assay, a saturated hyperbolic fluorescence signal curve was produced when 250 nM of FXR₃₃ and 100 nM of steroid receptor coactivator-1 peptide, a coactivator of FXR consisting of 26 amino acids, were used with a concentration dependence on chenodeoxycholic acid (from 0 to 200 μM). The ligand-binding domain of FXR (FXR₃₃) was the most suitable protein for studying the activation of FXR with a fluorescence-based assay, because it showed better structural stability than either the full length of FXR (FXR₅₃) or the DNA-binding domain of FXR (FXR₂₀).     

Ultrasonic spray pyrolysis of nano crystalline spinel LiMn2O4 showing good cycling performance in the 3 V range

Spherical lithium manganese oxide spinel was synthesized by an ultrasonic spray pyrolysis method, and has been characterized using X-ray diffraction, scanning electron microscopy, transimission electron microscopy and electrochemical cycling at 3 V regions. The LiMn₂O₄ powders were composed of about 10 nm-sized primary particles. The delivered discharge capacity of the synthesized nano-material was 125 mAh g⁻¹ between 2.4 and 3.5 V and its retention was about 96% upon 50 cycling. From the high resolution transmission electron microscopic study, it was found that structural transition of the parent material did not occur even after the 50th electrochemical cycling on the 3 V region. It seems that the reversible structural change is possible for nanocrystalline LiMn₂O₄ as observed by the X-ray diffraction and transition electron microscopic observations.     

Characteristics of selective adsorption using D-phenylalanine imprinted terpolymer beads

A D-Phenylalanine (Phe) imprinted terpolymer, Polyacrylonitrile-Poly(acrylic acid)-Poly(acryl amide) (Poly(AN-AA-AAm)) bead was prepared by the wet-phase inversion method. Acrylamide (AAm) and acrylic acid (AA) were used as the functional monomer and acrylonitrile (AN) was used as a physical cross linker. The characteristics of selective adsorption by the D-Phe imprinted terpolymer beads were investigated at high concentrations of Phe racemate solution, 1 g Phe/L, and 10 g Phe/L. The adsorption selectivity of the D-Phe imprinted terpolymer beads prepared by anin-situ implanting method reached 0.82 and 0.8 at 1.0 g and 10 g Phe/L racemate solution, respectively, and almost all of the adsorbed D-Phe and about 43% of the adsorbed L-Phe were desorbed by 4% acetic acid. The uptake capacities of the terpolymer beads were maintained for several repeated batches.     

Migration of Intergranular Liquid Films and Formation of Core-Shell Grains in Sintered TiC–Ni Bonded to WC–Ni

When TiC–20 wt% Ni powder mixtures are sintered at 1400°C, relatively large TiC grains possibly containing some Ni form with near-equilibrium shapes. When these specimens are heat-treated again at 1400°C in contact with sintered WC–20 wt% Ni pieces, the liquid films between the TiC grains in the contact region migrate against their increasing curvatures, forming (Ti,W)C solid solution behind them. These migrating liquid films reverse their directions on further heat-treatment. As in other alloys, this liquid film migration must be driven by the coherency strain energy produced by W diffusion at the surface of the dissolving TiC grains. Shells of (Ti,W)C solid solution also form around the cores of TiC grains near the contact region, and this process is probably driven by both coherency strain energy and free energy of mixing. At some contact regions, (Ti,W)C precipitates nucleate and grow, probably driven mainly by the free energy of mixing. In powder mixtures, the formation of core-shell grains is expected to be driven by the coherency strain energy, the free energy of mixing, and the capillary effect.     

Preparation and characterization of syndiotactic polystyrene/ethylene‐propylene copolymer blends

The reactive compatibilization of syndiotactic polystyrene (sPS)/oxazoline‐styrene copolymer (RPS)/maleic anhydride grafted ethylene‐propylene copolymer (EPR‐MA) blends is investigated in this study. First, the miscibility of sPS/RPS blends is examined by thermal analysis. The cold crystallization peak (T_cc) moved toward higher temperature with increased PRS, and, concerning enthalpy relaxation behaviors, only a single enthalpy relation peak was found in all aged samples. These results indicate that the sPS/RPS blend is miscible along the various compositions and RPS can be used in the reactive compatibilization of sPS/RPS/EPR‐MA blends. The reactive compatibilized sPS/RPS/EPR‐MA blends showed finer morphology than sPS/EPR‐MA physical blends and higher storage modulus (G') and complex viscosity (η*) when RPS contents were increased. Moreover, the impact strength of sPS/RPS/EPR‐MA increased significantly compared to sPS/EPR‐MA blend, and SEM micrographs after impact testing show that the sPS/RPS/EPR‐MA blend has better adhesion between the sPS matrix and the dispersed EPR‐MA phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2084–2091, 2002     

Surface properties for poly(perfluoroalkylethyl methacrylate)/poly(n-alkyl methacrylate)s mixtures

A poly(perfluoroalkylethyl methacrylate) and a series of poly(n-alkyl methacrylate)s such as poly(methyl methacrylate), poly(ethyl methacrylate), and poly(n-butyl methacrylate) were prepared and used to investigate the surface properties of polymer mixtures containing a fluorinated homopolymer and a nonfluorinated homopolymer and the effect of the side-chain length of poly(n-alkyl methacrylate) on the surface free energy for the polymer mixtures. Contact angles were measured for the surfaces of polymer mixtures by varying the concentration of poly(perfluoroalkylethyl methacrylate). From the contact angle data, it can be inferred that most of the poly(perfluoroalkylethyl methacrylate) added to poly(n-alkyl methacrylate)s is located in the outermost layer of polymer-mixture surface. Surface free energies for the outermost surfaces of polymer mixtures were calculated from the contact angle data using Owen and Wendt's equation. The decrease in the surface free energy for the polymer mixture with the poly(perfluoroalkylethyl methacrylate) addition is more pronounced as the side-chain length of poly(n-alkyl methacrylate) decreases. Due to the steric effect of the side chain of poly(n-alkyl methacrylate), the arrangement of the perfluoroalkylethyl group of poly(perfluoroalkylethyl methacrylate) to the air side is considerably hindered. The ESCA analysis of atomic compositions of the surface for the polymer mixture verified that poly(perfluoroalkylethyl methacrylate) is preferentially arranged and concentrates at the polymer mixture–air interface. The results of functional group compositions obtained by ESCA showed that the functional group composition of  CF₃ for the outermost layer has a more important effect on the surface free energy than that of  CF₂ and confirmed the hindrance of the arrangement of perfluoroalkylethyl group to the air side by the side chain of poly(n-alkyl methacrylate). © 1994 John Wiley & Sons, Inc.     

Transferring information from one experiment to another

This paper presents a rational method (based on Bayes' Theorem) for transferring information on parameter values from one experiment to another, in situations where the mathematical models for the two experiments share some parameters in common. The uncertainty in the estimates of the parameters, which reflects the experimental error in the initial experiment, is properly transferred as well. The use of the method is demonstrated by applying it to a fairly complicated system, typical in chemical reaction engineering, in which the kinetic parameters in a model for the hydrogenolysis of butane reaction were estimated using data obtained from a bench-scale, integral packed-bed reactor. These parameter estimates were then transferred to a model for a fluidized bed reactor in which the same chemical reaction occurred. Using the fluidized bed data they were updated and two additional parameters in the fluidized bed model were also estimated. This procedure allows a more realistic estimate of the uncertainty in all parameter values in the model for the fluidized bed reactor.     

The effct of asymmetries of die exit geometry on extrudate swell and melt fracture

Experimental investigations were performed to see how the die exit geometry and the extrusion velocity influence on extrudate swell and melt fracture for several polymer melts [low-density polyethylene, styrene-butadiene rubber (SBR) and SBR/HAF (carbon black) compound]. Four different types of die exit geometry were considered; 0° (symmetric. usual capillary die), and 30°, 45° and 60° (asymmetric dies) were chosen for the die exit angle. Extrudate diameters were measured without draw-down under isothermal condition. Polymer melts were extruded into an oil that has the same density and temperature as those of the extrudate. Extrudate swells from dies with different diameters were correlated with volumetric flow rates. It was observed that the extrudate swell increases with increasing volumetric flow rate and exhibits through a minimum value at about 45° die exit angle. As to the fracture phenomena, it was observed that the critical shear for the onset of melt fracture increases with the increasing die exit angle up to 45°. However, for 60° die exit angle, the onset of melt fracture is again similar to that of 0° exit angle.