Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Boiling heat transfer characteristics of nanofluids in a flat heat pipe evaporator with micro-grooved heating surface

An experimental study was performed to understand the nucleate boiling heat transfer of water–CuO nanoparticles suspension (nanofluids) at different operating pressures and different nanoparticle mass concentrations. The experimental apparatus is a miniature flat heat pipe (MFHP) with micro-grooved heat transfer surface of its evaporator. The experimental results indicate that the operating pressure has great influence on the nucleate boiling characteristics in the MFHP evaporator. The heat transfer coefficient and the critical heat flux (CHF) of nanofluids increase greatly with decreasing pressure as compared with those of water. The heat transfer coefficient and the CHF of nanofluids can increase about 25% and 50%, respectively, at atmospheric pressure whereas about 100% and 150%, respectively, at the pressure of 7.4 kPa. Nanoparticle mass concentration also has significant influence on the boiling heat transfer and the CHF of nanofluids. The heat transfer coefficient and the CHF increase slowly with the increase of the nanoparticle mass concentration at low concentration conditions. However, when the nanoparticle mass concentration is over 1.0 wt%, the CHF enhancement is close to a constant number and the heat transfer coefficient deteriorates. There exists an optimum mass concentration for nanofluids which corresponds to the maximum heat transfer enhancement and this optimum mass concentration is 1.0 wt% at all test pressures. The experiment confirmed that the boiling heat transfer characteristics of the MFHP evaporator can evidently be strengthened by using water/CuO nanofluids.     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Automated method, based on micro-sequential injection, for the study of enzyme kinetics and inhibition.

A micro-reactor system with continual spectrophotometric detection has been operated in Sequential Injection lab-on-valve (SI-LOV) mode and applied to enzyme kinetics and inhibition studies, using acetylcholinesterase (AChE) and angiotensin-converting enzyme (ACE) as model systems. With the advantages of automation, real-time kinetic measurement, and thorough mixing, the SI-LOV micro-reactor system allows for the monitoring of initial reaction rates and determination of reactant concentrations in the reaction mixture, both of which are essential for the determination of kinetic constants for enzymes and inhibitors. Enzyme, substrate, and inhibitor are precisely metered by the syringe pump and delivered to a stirred micro-reactor, followed by a reference scan that establishes the baseline for the following reaction rate measurement. Michaelis constants (Km) for AChE and ACE were determined to be 0.16 mM and 0.30 mM, respectively, which are consistent with literature values. The type of inhibition (competitive, uncompetitive, or mixed), the dissociation constants for the inhibitors, and the inhibitor dose-response curves were also determined.     

Chiral separation of synthetic vicinal diol compounds by capillary zone electrophoresis with borate buffer and beta-cyclodextrin as buffer additive.

The investigation on capillary electrophoretic enantioseparation of six synthetic compounds containing vicinal diol groups has been undertaken to acquire the optimum conditions using native beta-cyclodextrin (beta-CD) as chiral selector and borate as a background electrolyte. The separation was carried out in an uncoated capillary (58.5 cm x 75 microm i.d., effective length 48.5 cm) and the effects of several important factors were investigated in detail. The results showed that beta-CD as a chiral selector exhibited good enantioselectivity and that the enantioseparation was greatly influenced by the structure of the diols, the borate concentration and the buffer pH. The optimum performance was obtained for the chiral vicinal diols under the conditions of 200 mM borate buffer of pH 9.8 containing 1.7% beta-CD at an applied voltage of 15 kV and a capillary temperature of 20 degrees C. Under the conditions, four diols were baseline separated with fast analysis time and the good theoretical plate numbers (above 10 x 10(4)) and favorable migration-time reproducibilities (RSDs below 3.0%) were obtained. The separation results were satisfactory.     

A highly sensitive and rapid assay for protein determination in human urine and penicillin using a Rayleigh light-scattering technique with benzeneazo-8-acetylamino-1-naphthol-3,6-disulfonic acid sodium salt.

A simple and sensitive method was conducted for the determination of trace amounts of proteins with benzeneazo-8-acetylamino-1-naphthol-3,6-disulfonic acid sodium salt (azophloxine, AP) using a Rayleigh light-scattering (RLS) technique. At pH 2.60 and in the presence of an emulsifier OP microemulsion, the RLS of AP can be greatly enhanced by proteins, owing to the interaction between AP and protein. The enhanced intensity is proportional to the concentration of proteins. Four proteins, including bovine serum albumin (BSA), human serum albumin (HSA), lysozyme (Lys) and gamma globulin (gamma-G) have been tested. For example, the linear range of BSA was 0 - 0.06 microg mL(-1) with detection limits of 2.38 ng mL(-1). The method was applied to the analysis of protein in human urine and penicillin samples with satisfactory results. The relative standard deviation was in all instances less than 4.0%, and the recovery was in the range of 97.5 - 104%.     

Effects of microstructure on the temperature dependence of relative initial permeability of NiCuZn ferrites

In the present work, ferrites with compositions of (Ni_0.27Zn_0.64Cu_x)Fe_1.98O₄ (x=0.1, 0.2) were prepared by conventional ceramic methods. The relationship between the microstructure and the temperature dependence of relative initial permeability was investigated. It was found that intergranular pores in the ferrites generate large demagnetizing fields, reducing the temperature dependence of the effective anisotropy field H_eff, and decreasing the temperature dependence of the relative initial permeability accordingly. However, intragranular pores pin the movement of domain walls. Compared with the permeability induced by domain wall motion, the permeability that resulted from the spin rotation is more sensitive to temperature. As a result, the relative initial permeability of ferrites becomes more sensitive to temperature with increasing micropores within grains.     

DIRICHLET BOUNDARY VALUE PROBLEMS FOR SECOND-ORDER QUASI-LINEAR DIFFERENTIAL EQUATIONS WITH CHANGING SIGN NONLINEARITIES

This paper is concerned with the existence of positive solutions of two-point Dirichlet singular and nonsingular boundary problems for second-order quasi-linear differential equations with changing sign nonlinearities.     

Synthesis and Structural Characterization of Adduct [La(NO_3)_3·4H_2O]·2(BQEB)

Differentkindsofopenchaincrownethershavebeensynthesizedasthemodelcompoundsofionophoresandtheirinteractionswithsodium,potassiumandrareearthionshavealsobeenstudiedl'z.PanshowedCe(III)yieldedalf1complexwithl,8-bis(8'-quinolyloxy)-3,6-dioxaandtheCe(IIl)ioncoordinatedbothtoetheroxygenandquinolinenitrogenatoms3.TUmInleridentifiedtwolanthanidenitratecomplexeshavingastoichiometryof3:2(3RE:2L)'.InordertostUdythefunctionsofbothquinolineandbenzenering,introducedintothepolyetherchain,a1inearpolyether…