Negative effect of [bmim][PF6] on the catalytic activity of alcohol dehydrogenase: mechanism and prevention

BACKGROUND: [bmim][PF₆] is a hydrophobic ionic liquid which could be considered as an environmentally friendly solvent for biocatalysis. In pure [bmim][PF₆], however, alcohol dehydrogenase from yeast (YADH) has no catalytic activity. The aim of the present work was (1) to quantitatively study the negative effect of [bmim][PF₆] on the catalytic activity of YADH and the related mechanism and (2) to made an attempt to lessen the negative effect of [bmim][PF₆] on YADH by microemulsifying [bmim][PF₆]. RESULTS: The activity of YADH in the homogeneous solution formed by H₂O, CH₃CH₂OH and [bmim][PF₆] decreased rapidly with the increase of the molar fraction of [bmim][PF₆]. The inhibitory effect of [bmim][PF₆] on YADH was probably caused by the competition of the imidazole group of [bmim][PF₆] with the coenzyme NAD⁺ for the binding sites on YADH. In a water‐in‐[bmim][PF₆] microemulsion, YADH was catalytically active due to the formation of the interfacial membrane of the nonionic surfactant TritonX‐100, which separated YADH from [bmim][PF₆] and avoided the direct inactivation of [bmim][PF₆] on YADH. Under optimal conditions, the activity of YADH was as high as 51 µmol L^?1 min^?1. CONCLUSION: [bmim][PF₆] was an inhibitor of YADH and its negative effect on YADH could be lessened by its microemulsification. Copyright © 2008 Society of Chemical Industry     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Epoxidation of high trans‐1,4‐polyisoprene and its properties

A new organic‐solvent‐free water‐phase suspension method was used to synthesize partially epoxidized high trans‐1,4‐polyisoprene (TPI) to improve its properties, including oil resistance and wet‐skid resistance. The epoxidation was conducted in an aqueous peracetic acid solution and on the TPI granules prepared by a bulk precipitation method with supported titanium catalyst. The effects of the synthesis conditions, including reaction temperature, reaction time, and pH value, on the epoxy content were investigated. Epoxidized trans‐1,4‐polyisoprene (ETPI) with epoxy contents between 10 and 80% were obtained within 4 h. Both the amorphous and crystalline regions of TPI were epoxidized. The crystallization properties decreased with increasing epoxy content. ETPIs possessed lower mechanical properties than TPI but could be enhanced by vulcanization. The oil resistance and wet‐skid resistance were significantly improved after epoxidation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a novel proton‐exchange membrane for fuel cells operating at high temperatures and low humidities

The synthesis of a p‐toluidine/formaldehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and ¹³C‐NMR spectra were used to characterize the PTF. Wide‐angle X‐ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90–100°C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

Accelerated wear testing with a microfabricated surface to evaluate the lubrication ability of biomolecules on polyethylene

Wear of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and wear‐particle‐induced osteolysis and bone resorption are the major factors causing the failure of total joint replacements. It is feasible to improve the lubrication and reduce the wear of artificial joints. We need further understanding of the lubrication mechanism of the synovial fluid. The objective of this study is to evaluate the lubricating ability of three major components in the synovial fluid: albumin, globulin, and phospholipids. An accelerated wear testing procedure in which UHMWPE is rubbed against a microfabricated surface with controlled asperities has been developed to evaluate the lubrication behavior. An analysis of the wear particle dimensions and wear amount of the tests has provided insights for comparing their lubrication performance. It is concluded that the presence of biomolecules at the articulating interface may reduce friction. A higher concentration of a biological lubricant leads to a decrease in the wear particle width. In addition, in combination with the wear results and mechanical analysis, the roles of individual biomolecules contributing to friction and wear at the articulating interface are discussed. These results can help us to identify the role of the biomolecules in the boundary lubrication of artificial joints, and further development of lubricating additives for artificial joints may be feasible. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Water bamboo husk reinforced poly(lactic acid) green composites

The water bamboo husk is one of major agricultural wastes in Taiwan. In this study, the powder obtained from the water bamboo husk was added to poly(lactic acid) (PLA) to form novel reinforced biodegradable composites. Morphologies, mechanical properties, and heat resistance of these water bamboo powder reinforced composites were investigated. The results indicate that the char yields were increased as plant powder was incorporated to PLA. In addition, the mechanical properties were also enhanced due to the addition of powders. The increments of storage moduli of PLA were about 50–200%. Moreover, the increments of loss moduli of PLA were about 70–200%. On the other hand, the T_g of PLA was slightly decreased by the addition of powder, and this may improve the brittle characteristics of PLA. Furthermore, this type of reinforced PLA would be more environmental friendly than the artificial additive‐reinforced one. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

New approach to enhance adhesions between carbon nanotube emitters and substrate by the combination of electrophoresis and successive electroplating

Complementary electroplating combined with electrophoresis enhanced the field emission characteristics of emitters by improving the adhesions between CNT emitters and substrate. The emitting current of the CNT emitters prepared by our combined method increased nine times higher than that of CNT emitters prepared by electrophoresis only, since electroplating improved the adhesion of CNT emitters. During the life-time measurement for 10 h, the emitting current of CNT emitters fabricated by electrophoresis only was drastically decreased to 13% of the initial current, while that prepared by the combination of electrophoresis and successive electroplating decreased to 64% of the initial current. We suggest that our method is a promising approach for the efficient fabrication of reliable CNT emitters.     

Hydrothermal Synthesis of Magnesium Aluminate Platelets

Magnesium aluminate (MgAl₂O₄) platelets were first synthesized by hydrothermal treatment of γ-AlO(OH) in a magnesium nitrate aqueous solution at 400°C. The platelets are 100–200 nm in width and 25 nm in thickness. The influence of temperature, the anions of the magnesium salt, the amount of magnesium salt, and precursor pH on the formation of such structure was investigated. The experimental results indicated that the anions of the magnesium salt and precursor pH could have a significant influence on the growth of MgAl₂O₄. MgAl₂O₄ formation followed the in situ transformation mechanism, which was the reason why the MgAl₂O₄ crystallites had a platelet morphology.     

Effects of tube rupture modeling and the parameters on the analysis of multiple steam generator tube rupture event progression in APR1400

A multiple steam generator tube rupture (MSGTR) event in APR1400 has been investigated using the best estimate thermal hydraulic system code, MARS1.4. The effects of the parameters such as the number of ruptured tubes, rupture location, affected steam generator on the analysis of the MSGTR event in APR1400 are examined. In particular, tube rupture modeling methods, single tube modeling (STM) and double tube modeling (DTM), are compared. The APR1400 is found to have the capability of allowing more than 30 min to operators for the MSGTR event of five tubes. The effects of rupture location on the MSSV lift time is not significant in the case of STM, but the MSSV lift time for tube-top rupture is found to be 25.3% larger than that for rupture at the hot-leg side tube sheet in the case of DTM. The MSSV lift time for the cases that both steam generators are affected (4C5x, 4C23x) are found to be larger than that of the single steam generator cases (4A5x, 4B5x) due to a bifurcation of the primary leak flow. The discharge coefficient of Cd is found to affect the MSSV lift time only for a smaller value of 0.5. It is found that the most dominant parameter governing the MSSV lift time is the leak flow rate. Whether any modeling method is used, it gives the similar MSSV lift time if the leak flow rate is close, except in the case where both steam generators are affected. Therefore, the system performance and the MSSV lift time of the APR1400 are strongly dependent on the break flow model used in the best estimate system code.