Acceleration of the redox kinetics of VO2+/VO2 + and V3+/V2+ couples on carbon paper

The redox kinetics of VO²⁺/VO₂ ⁺ and V³⁺/V²⁺ couples on a carbon paper (CP, HCP030 N, Shanghai Hesen, Ltd., China) electrode were investigated in terms of their standard rate constant (k ₀) and reaction mechanism. The values determined for k ₀ for VO²⁺ ?? VO₂ ⁺ and V³⁺ ?? V²⁺ using the CP electrode are 1.0 × 10^?3 and 1.1 × 10^?3 cm s^?1, respectively. The value of k ₀ increases by one or two order(s) of magnitude compared with values obtained using electrodes composed of pyrolytic graphite and glassy carbon. The acceleration of the redox kinetics of vanadium ions is a result of the large surface area of the CP electrode. An inner-sphere mechanism for the reaction on the surface of the electrode is proposed. The kinetic features of vanadium redox reactions on the CP electrode reveal that CP is suitable for use as the electrodes in vanadium redox-flow batteries.     

Aqueous solution properties of disulfide-linked fluorinated gemini and cleaved monomeric thiol surfactants

We prepared a fluorinated gemini surfactant containing a disulfide bond in its spacer chain, [C?F??(CH?)?N(CH?)?CH?CH?SSCH?CH?N(CH?)?(CH?)?C?F??]2Cl, and its analogue with a hexamethylene spacer. Monomeric thiol surfactant, [C?F??(CH?)?N(CH?)?CH?CH?SH]Cl, was readily produced by the cleavage of the gemini surfactant using dithiothreitol in water. The critical micelle concentration was determined using surface tension, conductivity, and fluorescence probe methods. The critical micelle concentration of the monomeric surfactant was significantly larger than that of the gemini surfactant. The surface tension of aqueous solution for the cleaved monomeric thiol surfactant returned gradually to the original value through the formation of the disulfide bond via air oxidation.     

Structural chirality of cholesteric liquid crystal produces atropisomerism: Chiroptical polyisocyanides from achiral monomer in cholesteric liquid crystal matrix

1-Naphthyl isocyanide was polymerized with Ni(II) catalyst in a cholesteric matrix at the liquid crystal (LC) temperature range. The resultant polymers showed optical activity. In this reaction, the structural chirality of cholesteric LC effectively functions to impart one-handed helicity on the corresponding polymers as an optically active atropisomer.     

Preparation of pectin‐inorganic composite material as accumulative material of metal ions

Pectin is one of the biopolymers in the cell walls of all plant tissues, but the pectin‐containing materials have been discarded as industrial waste in food‐processing factories. We prepared a water‐insoluble pectin‐inorganic composite material by mixing pectin and a silane coupling reagent, bis(3‐trimethoxysilylpropyl)amine. The mechanical strength of the pectin‐inorganic composite material was higher than that of the pectin material without the addition of an inorganic component. In addition, the thermal stability of the composite material increased with the addition of the inorganic component. Furthermore, when the pectin‐inorganic composite materials were incubated in an aqueous solution of Cu(II), Zn(II), or In(III), these composite materials effectively accumulated not only the heavy metal ions, but also rare‐earth metal ions. Additionally, based on the infrared (IR) measurements, the metal ion accumulative mechanism into the composite material is described. As a result, the IR spectra suggested an electrostatic interaction between the metal ion and carboxy group in the pectin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42056.     

Anhydrous proton conductor consisting of pectin–inorganic composite material

An organic–inorganic proton conductive composite material consisting of a biopolymer was prepared by mixing the pectin, tetraethyl titanate, and imidazole. Although the pectin material without the composite dissolved in water, the pectin–inorganic composite material did not show water solubility. In addition, in the composite material, the pectin and imidazole formed an acid–base structure by an electrostatic interaction, and as a result, these composite materials showed a thermal stability at intermediate temperatures (100–200°C). Furthermore, these composite materials indicated the proton conductivity of 5.6 × 10^?4 S cm^?1 at 180°C under anhydrous conditions. The activation energy of the proton conduction under anhydrous conditions was 0.32–0.22 eV and these values were one order of magnitude higher than that of the typical humidified perfluorinated membrane, such as Nafion^®. The organic–inorganic composite material consisting of a biocomponent may have the potential to be utilized as a novel proton conductor under anhydrous conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42433.     

Mechanisms Underlying Decreased Hepatic Triacylglycerol and Cholesterol by Dietary Bitter Melon Extract in the Rat

In these studies, we focused on finding the mechanism(s) underlying the bitter melon (Momordica charantia L.) methanol fraction (MF)-dependent reduction in the concentration of hepatic triacylglycerol (TAG) and cholesterol in the rat. Rats were fed diets containing low (5 %) fat for 2 weeks (experiment 1), or low (5 %) and high (15 %) fat for a longer period of 8 weeks (experiment 2). MF was supplemented at 1 % level in both experiments. After feeding, rats were sacrificed, and their livers were prepared as slices and hepatocytes, followed by incubation with [1(2)-¹⁴C] acetate or [1-¹⁴C] oleic acid (18:1 n-6). Under these conditions, we found that rats fed diets containing MF, as compared to those without MF, showed: (1) no adverse effects on food intake and growth, (2) a decreased hepatic TAG and total cholesterol, irrespective of the difference in dietary fat level or feeding period, and (3) a decreased incorporation of [1(2)-¹⁴C] acetate and [1-¹⁴C] oleic acid into TAG of liver slices and hepatocytes. MF-supplemented rats also showed no altered incorporation of labeled acetate into cholesterol and cholesterol ester, an increased fecal excretion of neutral steroids, but not of acidic steroids, and an enhanced mRNA abundance of carnitine palmitoylacyltransferase I, which is the rate-limiting enzyme for fatty acid oxidation. These results suggest that dietary MF decreases hepatic TAG synthesis while enhancing fatty acid oxidation, thereby reducing the concentration of hepatic TAG. The liver cholesterol-lowering effect of MF, however, is probably mediated through an increased fecal excretion of neutral steroids, without an effect on cholesterogenesis.     

Electrochemical conversion of carbon dioxide to methane in aqueous NaHCO3 solution at less than 273 K

The electrochemical reduction of CO₂ on a Cu electrode was investigated in aqueous NaHCO₃ solution, at low temperature. A divided H-type cell was employed, the catholyte was 0.65 mol dm⁻³ NaHCO₃ aqueous solution and the anolyte was 1.1 mol dm⁻³ KHCO₃ aqueous solution. The temperature during the electrolysis of CO₂ was decreased stepwise to 271 K. Methane and formic acid were obtained as the main products. The maximum Faradaic efficiency of methane was 46% at −2.0 V and 271 K. The efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was significantly depressed with decreasing temperature. Based on the results of this work, the proposed electrochemical method appears to be a viable means for removing CO₂ from the atmosphere and converting it into more valuable chemicals. The synthesis of methane by the electrochemical method might be of practical interest for fuel production and the storage of solar energy.     

Grafted stock synthesis of ABS at the ultimate high ratio of polybutadiene to poly(styrene‐co‐acrylonitrile)

This study describes the emulsion grafting of styrene and acrylonitrile onto 60–70% polybutadiene (PB), in the presence or absence of tert‐dodecanetiol as a chain transfer reagent with a radical initiator, and the properties of the obtained grafted stock. There was no significant difference in terms of effect of the initiation mode on the grafting efficiency resulting from the high grafting reactivity of PB. However, the grafted stock with 70% PB prepared in the presence of tert‐dodecanetiol and the adequate selection of an initiation system gave a homogeneous dispersion of the PB particles into poly(styrene‐co‐acrylonitrile) (SAN) matrix. The initiation system involves tert‐butyl peroxylaurate, tert‐butyl peroxyacetate, and tert‐butyl peroxyisopropylcarbonate coupled with ferrous sulfate. The efficient coverage of the SAN grafted layer around 70% PB particles was observed by TEM to eventually give excellent impact resistance, high surface gloss, and good thermal resistance. The absence of tert‐dodecanetiol resulted in a toughness reduction of ABS. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3462–3470, 2001     

Power characteristics of unsteadily forward–reverse rotating impellers in an unbaffled aerated agitated vessel

Power characteristics of an unbaffled aerated agitated vessel with unsteadily forward‐reverse rotating impellers, ie a new type of gas–liquid agitator named ‘AJITER’, treating viscous Newtonian liquids were studied experimentally. Measurements were first made on the agitation torque, ie the torque on the drive shaft on which forward–reverse rotating impellers with four delta‐type blades were attached, and the data obtained were analyzed by fitting them to an equation consisting of two terms with respect to the resistance of the fluid, one due to viscous drag and the other due to added moment of inertia. The effects of operating conditions and physical properties of liquids on the drag and added moment of inertia coefficients were then evaluated, and empirical relationships which estimate values of these coefficients, useful to predict the unsteady behavior and magnitude of agitation torque, were presented. Furthermore, equations were developed for estimating the average and maximum power consumptions as a function of the drag and added moment of inertia coefficients. Prediction of respective power levels in AJITER by these equations was also discussed. © 2001 Society of Chemical Industry     

Matrix influence on the piezoelectric properties of piezoelectric ceramic/polymer composite exhibiting particle alignment

This study was addressed to the influence of an electric field strength applied at fabrication process and matrix properties, such as the dielectric constant and the Young's modulus, on “pseudo‐1‐3 piezoelectric ceramic/polymer composite” in order to further enhance the piezoelectricity of that. The pseudo‐1‐3 piezoelectric ceramic/polymer composite consists of linearly ordered piezoelectric ceramic particles in polymer material. Silicone gel, silicone rubber, urethane rubber, and poly‐methyl‐methacrylate, which exhibit different dielectric constants and Young's modulus, were used as matrices to evaluate the matrix influence. The piezoelectricity of the pseudo‐1‐3 piezoelectric ceramic/polymer composite was evaluated using the piezoelectric strain constant d₃₃. The d₃₃ is one of the indices of the piezoelectric properties for piezoelectric materials. As a result, it was confirmed that d₃₃ of the pseudo‐1‐3 piezoelectric ceramic/polymer composite increased with the increase of the electric filed strength applied at fabrication process, though, it reached a constant value at a certain strength value. Further it was confirmed that dielectric constant of the matrix had a small influence on d₃₃ of the pseudo‐1‐3 piezoelectric ceramic/polymer composite, however, in case of matrix of lower Young's modulus, d₃₃ was increase. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41817.