Synthesis and properties of sulfonated poly(arylene ether)s containing azole groups

Random and multiblock sulfonated poly(arylene ether sulfone)s (SPEs) containing various azole groups such as oxadiazole and triazole were synthesized and characterized for fuel cell application. Successful preparation of SPE membranes depended on the structure of azole groups, which affected solubility of precursors and the resulting SPEs. Although oxadiazole groups were incorporated into hydrophobic component, they were found to be hydrophilic to give higher proton conductivity. Introduction of oxadiazole groups into random SPE gave comparable proton conductivity to that of Nafion NRE at >60% relative humidity at 80 °C. Block copolymer structure further increased the proton diffusion coefficient without increasing ion exchange capacity. Hydrolytic and oxidative stability of the SPE membranes was affected by both hydrophilic and hydrophobic components. Oxadiazole groups gave negative impact on hydrolytic and mechanical stability to the SPE membranes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Predicting the proton conductivity of perfluorosulfonic acid membrane via combining statistical thermodynamics and molecular dynamics simulation

The electrochemical properties of a perfluorosulfonic acid (PFSA) membrane are estimated using a combination of molecular dynamics simulation and statistical thermodynamic model. We obtain all parameters in an ionic conductivity model from an atomistic simulation and remove all adjusted model parameters. From a microscopic point of view, the hydrated PFSA membrane shows micro‐phase segregation which separated into hydrophilic and hydrophobic phases. Our present work originates with this phenomenon and we treat this phase segregation as if it is a continuous phase for each of which the proton (H⁺) is transported inside the PFSA membrane/solvent (water and alcohols) mixture. The chemical potential for a given system is estimated using a molecular simulation technique to predict the van der Waals interaction energy between the polymer and solvent. In addition, the self diffusion coefficients are calculated from the molecular dynamics simulation. We study various polymer/solvent compositions to understand the concentration dependence of self diffusion coefficient. Our self diffusion coefficients and also the predicted final ionic conductivity agree well with previously reported experimental data. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1455–1463, 2011     

Multiresidue analysis of pesticides with hydrolyzable functionality in cooked vegetables by liquid chromatography tandem mass spectrometry

It would be preferable for pesticide residues substituted by hydrolyzable functionality to be analyzed after cooking because their structures are apt to degrade during boiling and/or heating. A liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method for the quantitative determination of 44 pesticide residues with hydrolyzable functional group in five typical vegetable widely consumed in Republic of Korea is described. The sample clean‐up was carried out according to the method of Food Code No. 83 established by the Korea Food and Drug Administration (KFDA). Zorbox XDB‐C₁₈ column was selected for the analysis because of the best peak separation. The LC mobile phase consisted of water and 5 mm methanolic ammonium formate, which resulted in a peak shape with good symmetry at each run. Tandem mass spectroscopic (MS/MS) experiments were performed in ESI positive mode and the multiple reaction monitoring modes. A conventional matrix effect was modified to more comprehensive form 100γ_ij (%). A high matrix effect (相似文献   

Optical and Electrical Properties of Ferroelectric SBN Thin Films Prepared by Sol-Gel Process

Strontium barium niobate thin films were prepared by sol-gel method on various substrates using an improved process, two-step heating process. The two-step heating process applies an additive heat-treatment before crystallization for enhancement of the densification and the nucleation of films. Also, highly c-axis oriented SBN thin films with various compositions were obtained on MgO(100) and Pt(100)/MgO(100) substrates. Their optical and electrical properties such as optical propagation loss, refractive index, P-E hysteresis, and dielectric constant, were characterized as a function of the film composition.     

Effects of low hydrocarbons on the solid oxide fuel cell anode

In this work, the effects of ethylene on the solid oxide fuel cell (SOFC) anode were investigated both for an SOFC single cell and an SOFC stack. Two fuels were used to observe the effects that low hydrocarbons (over C1-hydrocarbons) in the reformate gas stream have on the SOFC anode. Methane or ethylene was supplied to the electrolyte-supported SOFC anode. Using ethylene as a fuel, catastrophic degradation of SOFC performance was observed due to ethylene-induced carbon deposition onto the SOFC anode. Thus, a new methodology, termed “post-reforming,” is introduced for the removal of low hydrocarbons (over C1-hydrocarbons) from the reformate gas stream. The CGO-Ru catalyst was selected as the post-reforming catalyst because of its high selectivity for removing low hydrocarbons (over C1-hydrocarbons) and for its long-term stability. The diesel reformer and post-reformer were continuously operated for ∼250 h in coupled-operation mode. The reforming performance was not degraded, and low hydrocarbons (over C1-hydrocarbons) in the diesel reformate were completely removed.     

Toll-like receptor 9-mediated inhibition of apoptosis occurs through suppression of FoxO3a activity and induction of FLIP expression

Synthetic oligodeoxynucleotides (ODN) with a CpG-motif are recognized by Toll-like receptor 9 (TLR9) and pleiotropic immune responses are elicited. Stimulation of macrophages with TLR9 agonist prevented apoptosis induced by serum deprivation through increased expression of FLICE-like inhibitory protein (FLIP). CpG ODN-mediated anti-apoptosis depended on the TLR9-Akt-FoxO3a signaling pathway. Inhibition of TLR9 by small interfering (si) RNA or an inhibitor suppressed CpG ODN-mediated anti-apoptosis. Analysis of signaling pathways revealed that the anti-apoptotic effect of CpG ODN required phosphorylation of FoxO3a and its translocation from the nucleus to the cytosol. Overexpression of FoxO3a increased apoptosis induced by serum deprivation and CpG ODN blocked these effects through FLIP expression. In contrast, siRNA knock-down of FoxO3a decreased apoptosis by serum deprivation. In addition, Akt activation was involved in CpG ODN-induced phosphorylation of FoxO3a, expression of FLIP, and anti-apoptosis. Taken together, these results demonstrate the involvement of Akt-FoxO3a in TLR9-mediated anti-apoptosis and indicate that FoxO3a is a distinct regulator for FLIP expression.     

Convective heat transfer to CO2 at a supercritical pressure flowing vertically upward in tubes and an annular channel

The Super-Critical Water-Cooled Reactor (SCWR) has been chosen by the Generation IV International Forum as one of the candidates for the next generation nuclear reactors. Heat transfer to water from a fuel assembly may deteriorate at certain supercritical pressure flow conditions and its estimation at degraded conditions as well as in normal conditions is very important to the design of a safe and reliable reactor core. Extensive experiments on a heat transfer to a vertically upward flowing CO₂ at a supercritical pressure in tubes and an annular channel have been performed. The geometries of the test sections include tubes of an internal diameter (ID) of 4.4 and 9.0 mm and an annular channel (8 × 10 mm). The heat transfer coefficient (HTC) and Nusselt numbers were derived from the inner wall temperature converted by using the outer wall temperature measured by adhesive K-type thermocouples and a direct (tube) or indirect (annular channel) electric heating power. From the test results, a correlation, which covers both a deteriorated and a normal heat transfer regime, was developed. The developed correlation takes different forms in each interval divided by the value of parameter Bu. The parameter Bu (referred to as Bu hereafter), a function of the Grashof number, the Reynolds number and the Prandtl number, was introduced since it is known to be a controlling factor for the occurrence of a heat transfer deterioration due to a buoyancy effect. The developed correlation predicted the HTCs for water and HCFC-22 fairly well.