The ring transformations of 1,2,3,4-diepoxybutane (2,2′-bioxirane) catalysed by various aluminosilicates

The transformations of a molecule containing two adjacent epoxide rings, 2,2-bioxirane that is, were studied over various acidic aluminosilicates (HZSM-5, HY-FAU, AlMCM-41), for the first time, In the 373–473 K temperature range, in a pulse reactor, a ring-opening–ring-enlargment reaction producing furan only occured over the zeolites and it was the predominant reaction on AlMCM-41 as well. The driving force of this transformation route is water formation via elimination from 2,2-bioxirane. Suprising is the lack of the mono- or dialdehyde, the would-be products of the cleavage of the sterically more hindered C–O bonds – an acid-catalysed reaction typical for alkyl-substituted oxiranes.     

Preparation of rechargeable lithium batteries with poly(methyl methacrylate) based gel polymer electrolyte by <Emphasis Type="Italic">in situ</Emphasis>γ-ray irradiation-induced polymerization

An admixture of commercial liquid electrolyte (LB302, 1 M solution of LiPF₆ in 1:1 EC/DEC) and methyl methacrylate (MMA) was enclosed in CR2032 cells. The assembled cells were then -ray-irradiated using configurations of half cells and full cells. Through this in situ irradiation polymerization process, we obtained rechargeable lithium ion cells with poly(methyl methacrylate) (PMMA) based gel polymer electrolytes (GPE). Galvanostatic cycling, AC impedance spectroscopy, and cyclic voltammetry were employed to investigate the electrochemical properties of the cells and the gel polymer electrolyte. This PMMA-based gel polymer electrolyte was found to exhibit a high ionic conductivity (at least 10^–3 S cm^–1) at room temperature. Due to a significant increase in the charge transfer resistance between the GPE and the cathode, the cell impedance of a PMMA-based lithium ion cell is greater than that of a liquid-electrolyte-based cell. The discharge capacity of a LiNi_0.8Co_0.2O₂/GPE/graphite is approximately 145 mAh g^–1 for the first cycle and decreases to123 mAh g^–1 after 20 cycles. In addition, a large initial cell impedance (LICI) was observed in the irradiated positive half cell. In this paper, we propose a possible mechanism related to the detachment of the PMMA layer from the lithium electrode. This detachment of the PMMA layer from the lithium electrode has not been explicitly discussed previously.     

Calcium binding mode of {gamma}-carboxyglutamic acids in conantokins

Conantokin-T (con-T) and conantokin-G (con-G) are two highlyhomologous peptide toxins found in Conus venom. The former isa 21-residue peptide with four -carboxyglutamic acid (Gla) residues(at positions 3, 4, 10 and 14), while the latter is a 17-residuepeptide with five -carboxyglutamic acid residues (at positions3, 4, 7, 10 and 14). Despite the apparent similarity in numberand relative positions of the -carboxyglutamic acid residues,¹¹³Cd-NMR studies indicated a distinct metal binding behaviorfor con-G and con-T. There appears to be four binding sitesin con-G in contrast to one metal binding site in con-T. Toelucidate the mode of calcium binding by the -carboxyglutamicacid residues in these conantokins, we designed various analogouspeptides with their -carboxyglutamic acid replaced by otheramino acid residues. ¹¹³Cd-NMR experiments on conantokin analoguesreveal that the major difference in the number of metal bindingsites between con-G and con-T is due to the residue at position7. We also performed molecular simulations to calculate therelative binding free energies of several potential bindingsites. Based on our theoretical and experimental results, wepropose a `four-site' binding model for conantokin-G and a `single-site'binding model for conantokin-T.     

Oxygen and chlorine evolution on RuO2 + TiO2 + CeO2 + Nb2O5 mixed oxide electrodes

A systematic investigation was conducted on the mechanism and electrocatalytic properties of O₂ and Cl₂ evolution on mixed oxide electrodes of nominal composition: Ti/[Ru_(0.3)Ti_(0.6)Ce_(0.1−x)]O₂[Nb₂O₅]_(x) (0 ≤ x ≤ 0.1). For the oxygen evolution, a 30 mV Tafel slope is obtained in the presence of CeO₂, while in its absence a 40 mV coefficient is observed. The intrinsic electrocatalytic activity is mainly due to electronic factors, as result of the synergism between Ru and Ce oxides. For chlorine evolution, the Tafel slope (30 mV) is independent on oxide composition. The best global electrocatalytic activity for ClER was observed in the absence of Nb₂O₅ additive. Variation of the voltammetric charge throughout the experiments confirms high CeO₂ content compositions are fragile, due mainly to the porosity caused by CeO₂ presence. On the other hand, Nb₂O₅ addition decreases considerably this instability.     

Laminar and turbulent mass transfer simulations in a parallel plate reactor

Laminar and turbulent mass transfer in a parallel plate reactor at high Schmidt number obtained from numerical simulation is compared with literature data. In a first step, the fluid flow is determined numerically in the reactor by solving the Navier–Stokes equations. For turbulent flow, a low Reynolds number k— model is used to calculate the turbulent viscosity. Using the obtained flow field and turbulent viscosity, the current density distribution is calculated for different flow velocities by solving the equations describing the transport of multiple ions due to diffusion, convection and migration. For the laminar case, a very good agreement with literature data is obtained. For turbulent flow, different numerical models for turbulent mass transfer are proposed in the literature. A detailed study of the behaviour close to the wall of these different turbulence models is presented, together with a comparison of the calculated results with literature correlations. This allows identification of the benefits and disadvantages of each of the turbulence models for the numerical calculation of mass transfer at high Schmidt numbers in a parallel plate reactor.     

Molecular modelling of Staphylococcal {delta}-toxin ion channels by restrained molecular dynamics

-Toxin is a 26-residue channel-forming peptide from Staphylococcusaureus which forms an amphipathic -helix in a membrane environment.Channel formation in planar bilayers suggests that an averageof six -toxin helices self-assemble to form transbilayer pores.Molecular models for channels formed by -toxin and by a syntheticanalogue have been generated using a simulated annealing protocolapplied via restrained molecular dynamics. These models areanalysed in terms of the predicted geometric and energetic propertiesof the transbilayer pores. Pore radius calculations of the modelsdemonstrate that rings of channel-lining residues contributea series of constrictions along the pore. Electrostatic propertiesof the pores are determined both by pore-lining charged sidechains and by the aligned helix dipoles of the parallel helixbundle. Molecular dynamics simulations (100 ps) of -toxin modelscontaining intra-pore water were performed. Analysis of theresultant dynamics trajectories further supports the proposalthat alternative conformations of pore-constricting side chainsmay be responsible for the observed conductance heterogeneityof -toxin ion channels.     

Lω-空间的ωS-分离性

在Lω-空间中引入了Lω-分离性的概念,主要包括ωS-1、ωS0、次ωS0分离性,讨论了它们的一些基本的拓扑性质.给出了ωS-分离性的几个等价刻划,讨论了它们之间的关系.     

SAMPAVE沥青混合料级配设计研究

SAMPAVE(Stress Absorbing Mixtures Pavement)沥青混合料是一种新型的延缓和防止反射裂缝的应力吸收层材料,具有抗裂、防渗、粘结等特性.根据变i法对SAMPAVE混合料进行矿料组成设计,并与AC-5、美国规范、科氏公司推荐的级配范围进行比较.结果表明,对于变i法设计的SAMPAVE混合料,级配上限、级配下限确定的沥青用量在设计工程级配沥青用量的±0.3%范围内,满足生产控制的要求,且SAMPAVE混合料具有优良的耐高温、耐低温、抗变形、耐疲劳、抗水损害等路用性能.     

具有某种特性的向量优化问题的解的刻画

在有限维空间中,当目标函数凸下半连续时,向量优化问题一定有弱有效解,并且解集是紧的,但当目标函数非凸时,这不一定成立,文章讨论了把目标函数的凸性减弱之后,向量优化问题的解集是非空并且紧的,另外还得到一些等价的刻画。     

基于灰靶理论的城市应急供水方案评价研究

针对城市应急供水方案选择面临的多目标评价问题,从水量、水质、工程难度、工程投资等方面建立城市应急供水方案评价指标体系,运用灰靶理论,通过建立标准模式、灰靶变换、构建灰关联差异信息空间、计算灰关联系数和靶心系数,逐层次识别模式接近靶心度的程度,从而对方案进行评价及排序,最终选定方案6作为德阳市应急供水方案,为德阳市灾后重建城市供水提供了重要的科学依据.该方法适合处理信息不完全、少数据不确定性问题更简洁、高效、可行.