Highly Cooperative Tetrametallic Ruthenium-mu-Oxo-mu-Hydroxo Catalyst for the Alcohol Oxidation Reaction

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy(3))(CO)RuH](4)(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was synthesized in two steps from the monomeric complex (PCy(3))(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C(6)H(4)CH(2)OH (rho = -0.45) and p-X-C(6)H(4)CH(OH)CH(3) (rho = +0.22) (X = OMe, CH(3), H, Cl, CF(3)). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH(3)] (K(0.5) = 0.34 M; Hill coefficient, n = 4.2+/-0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols.     

Material removal and surface damage in EDM of Ti3SiC2 ceramic

Material removal and surface damage of Ti₃SiC₂ ceramic during electrical discharge machining (EDM) were investigated. Melting and decomposition were found to be the main material removal mechanisms during the machining process. Material removal rate was enhanced acceleratively with increasing discharge current, i_e, working voltage, u_i, but increased deceleratively with pulse duration, t_e. Microcracks in the surface and loose grains in the subsurface resulted from thermal shock were confirmed, and the surface damage in Ti₃SiC₂ ceramic led to a degradation of both strength and reliability.     

Synthesis of nonsharp distillation sequences via genetic programming

This paper addresses the application of Genetic Programming (GP) to the synthesis of multicomponent product nonsharp distillation sequences. Combined with the domain knowledge of chemical engineering, some evolutionary factors are improved, and a set of special encoding method and solving strategy is proposed to deal with this kind of problem. The system structural variable is optimized by GP and the continuous variable is optimized by the simulated annealing algorithm simultaneously. Because GP has an automatic searching function, the optimal solution can be found including distillation, splitting, blending and bypassing operations automatically without any superstructures of nonsharp distillation sequences. Three illustrative examples are presented to demonstrate the effective computational strategies.     

钢纤维聚合物混凝土抗压本构关系

钢纤维聚合物混凝土是由聚合物混凝土基体和钢纤维共同组成的纤维增强复合材料，它的力学行为不仅依赖于聚合物混凝土基体的行为，而且与钢纤维的掺量、分散特征以及钢纤维的几何尺寸有关，本文将基于损伤力学原理研究在不同纤维掺量下的钢纤维聚合物混凝土的全程压力-应变曲线及其本构模型。     

Electrochemical determination of estradiol using a poly(l-serine) film-modified electrode

A thin film of poly(l-serine) was prepared via electropolymerization for the determination of trace levels of estradiol. In pH 5.0 phosphate buffer, l-serine was oxidized during the cyclic potential sweeps between −0.60 and 2.0 V, forming a thin film at the electrode surface. The electrochemical behavior of estradiol was investigated. The oxidation peak potential of estradiol shifts negatively at the poly(l-serine) film-coated glassy carbon electrode (GCE) compared with that at the bare GCE. Otherwise, the oxidation peak current greatly increases at the poly(l-serine) film-modified GCE. These phenomena suggest that the poly(l-serine) film exhibits catalytic activity towards the electrochemical oxidation of estradiol. Based on this, a sensitive, rapid and simple electrochemical method was proposed for the determination of estradiol. The limit of detection is evaluated to be 2.0 × 10⁻⁸ mol L⁻¹. Finally, this method was successfully used to determine estradiol in blood serum.     

Application of ultrasonic waves in activation of microcrystalline cellulose

In this work, microcrystalline cellulose (MCC) was activated with ultrasonic waves. The influences of ultrasonic treatment on the changes of supramolecular structures and morphology structure were studied by WAXS and SEM. The accessibility of the MCC was characterized by water retention value (WRV) and specific surficial area. The influence of ultrasonic treatment on the reactivity of MCC was investigated through the reaction of MCC being oxidized into 2,3‐diadehyde cellulose (DAC) by periodate sodium. The mechanism of the reactivity change of ultrasonically treated MCC was examined. The results showed that the degree of crystallinity of MCC decreased and the degree of polymerization showed little change after treatment with ultrasonic waves. The morphologial variation of the treated MCC was significant when compared with the untreated MCC, which contribute to the improvement of accessibility. The aldehyde content of DAC prepared from ultrasonically treated MCC was improved from 64.19 to 85.00%, indicating that the regioselective oxidation reactivity of MCC was significantly improved. The aldehyde content was found to first increase with time of ultrasonic treatment to a point, and then decrease as time progressed. In addition, the aldehyde content was found to increase with an increase in ultrasonic power. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone) grafted sodium alginate hydrogel beads for the controlled release of indomethacin

Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 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     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008