Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination

The use of catalytic metal carbene methodology with diazoacetates for the construction in high yield of polyether macrocycles having ring sizes greater than 25 has been achieved by preventing access to gamma-C-H positions for intramolecular insertion. Cyclopropanation is the exclusive outcome of reactions performed with dirhodium(II) catalysts, and product yields of greater than 70% are obtained without resorting to high dilution with solvents. With copper(I) catalysts having multiple sites for polyether coordination, intramolecular oxonium ylide formation occurs at the terminal oxygen, followed by [2,3]-sigmatropic rearrangement of the pendant allyl group, in competition with cyclopropanation. Sodium ion coordination with the reactant diazo compound inhibits oxonium ylide formation in copper-catalyzed reactions. The composite results are consistent with copper serving as a template for the substrate as well as the site in the ether complex for diazo decomposition and subsequent metal carbene reactions.     

Anion transfer at a micro-water/1,2-dichloroethane interface facilitated by beta-octafluoro-meso-octamethylcalix[4]pyrrole

The facilitated transfer of four hydrophilic anions, i.e., Cl-, Br-, NO2-, and CH3CO2-, at the micro-water/1,2-dichloroethane interface supported at the tip of a micropipet has been observed successfully using beta-octafluoro-meso-octamethylcalix[4]pyrrole 2 as the receptor. We have also shown for the first time that the dynamics of this process can be studied by micropipet voltammetry. The standard kinetic rate constants (kdegrees) for facilitated anion transfer at such an interface were determined to be (2.11 +/- 0.90) x 10(-2) and (0.75 +/- 0.50) x 10(-2) cm/s in the case of Cl- and CH3CO2-, respectively. These values are much smaller than those associated with the facilitated transfer of analogous alkali metal ions. This difference is thought to reflect a number of underlying factors, including the higher hydration of anions as compared to similar sized cations. Studies such as these are expected to be useful in understanding the mechanism of anion transport at soft interfaces and for the design of yet-improved anion receptors and carriers.     

Systematic study of the transfer of amino acids across the water/l,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Failitated ion transfer reactions of 20 amino acids with dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, lle, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (β°), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively. The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization. Moreover, the association constants and the standard rate constants for different amino acids showed good correlations with their hydrophobicity (π), except Gly and Met, which inferred that the selectivity of such heterogeneous complex reaction for different amino acids with DB18C6, was not only affected by discrimination in binding these ions to the crown ether macro-cycle, but also significantly modified by the ion transfer Gibbs energy which was closely related to the structure of the transferred ions, protonated amino acids.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

A facile interfacial reaction route to prepare magnetic hollow spheres with tunable shell thickness

Magnetic Fe3O4 hollow spheres were successfully synthesized with a water in oil in water (W/O/W) emulsion. During the facile procedure, no high pressure, high temperature, or other complex reaction conditions were required. Transmission electric microscope (TEM) images showed that all the hollow structural products have a good spherical morphology with an average diameter of 160 nm. The average size and the size distribution were further determined with dynamic light scattering (DLS), which reveals that the hollow nanospheres have a narrow size distribution. The average size from DLS was about 180 nm, which approximated that from TEM data. X-ray diffraction (XRD) demonstrates that the products were all Fe3O4 phase without any impurity. By increasing or decreasing the dosage of precipitate and precipitant sources, we controlled the shell thickness successfully in the tens of nanometers range. The formation mechanism of those hollow magnetic nanospheres was discussed by using the "reverse micelle transport" mechanism.     

Progressive refinement for robust image registration

A new image registration algorithm with robust cost function and progressive refinement estimation is developed on the basis of direct method (DM). The robustness lies in M-estimation to avert larger local noise and outliers.     

Giant dielectric permittivity observed in Li and Ti doped NiO

A giant low-frequency dielectric constant ( epsilon 0 approximately 10(5)) near room temperature was observed in Li,Ti co-doped NiO ceramics. Unlike currently best-known high epsilon 0 ferroelectric-related materials, the doped oxide is a nonperovskite, lead-free, and nonferroelectric material. It is suggested that the giant dielectric constant response of the doped NiO could be enhanced by a grain boundary-layer mechanism as found in boundary-layer capacitors. In addition, there is about a one-hundred-fold drop in the dielectric constant at low temperature. This anomaly is attributed to a thermally excited relaxation process rather than a thermally driven phase transition, as for that yielding ferroelectrics.     

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

In this work, the influence of Lu₂O₃ doped on the dielectric and electrical properties of CaCu₃Ti₄O₁₂ was reported. Lu₂O₃-doped CCTO was prepared by a conventional solid state technique using CuO, TiO₂, and CaCO₃ as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 10² Hz–10⁷ Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu₂O₃ resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu₂O₃ resulted in decreasing nonlinear coefficients.     

基于SOM算法和免疫神经网络的飞机燃油系统故障诊断

针对传统的飞机燃油系统故障诊断方法如硬件冗余方法和系统模型检测方法存在的飞机重量限制和难以建立精确数学模型的问题,设计了一种基于SOM算法和BP神经网络的故障诊断模型;首先,建立了系统故障诊断模型并对诊断原理进行了描述,然后,对故障征兆数据进行预处理,即先采用SOM算法进行连续属性离散化处理,再通过粗糙集互信息方法进行属性降维,以减少数据量和提高诊断效率;最后,建立了基于BP神经网络的故障诊断模型,为了进一步提高故障诊断精度,在采用免疫优化算法对BP神经网络故障诊断模型中的各参数即权值和阈值等进行优化的基础上,进一步采用BP反向传播算法进行参数调整,从而得到最终的故障诊断模型。通过飞机燃油系统故障诊断实例仿真实验证明了文中方法能较为精确地实现故障诊断,且与其它方法相比,具有较高的诊断精度和诊断效率,具有较大的优越性。     

基于强化学习和蚁群算法的WSN节点故障诊断

为了克服现有的WSN节点故障诊断方法所具有的难以实现在线诊断和诊断精度仍然不够高的缺点,设计了一种基于Sarsa算法和改进蚁群算法的WSN节点在线故障诊断方法。首先,建立了监测区域的网络模型和WSN节点故障诊断模型,然后,采用主成分分析法对节点故障样本数据进行降维,从而提高诊断效率,将样本数据作为层次,将故障诊断类作为各层节点建立层次树,采用改进的Sarsa算法求取各层节点的Q值,并将其用于初始化蚁群算法中路径的信息素,最后,提出了一种改进的蚁群算法求取从第一层出发的蚁群到各层节点之间的路径,将各层中信息素最大的节点作为最终的故障诊断类别。在Matlab环境下进行仿真实验,结果证明文中方法能有效实现WSN节点故障诊断,且与其它方法相比,具有故障诊断精确度高且能在线故障的优点,是一种有效的节点故障诊断方法。