甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化

在碱性甘油电氧化反应中,利用电化学傅里叶变换衰减全反射谱红外光谱法,研究了薄膜流动池中滴注硼酸镍催化剂负载量对玻碳电极性能的影响.连续操作的径向流动池包括一个位于内反射元件上方50μm的钻孔电极,可实现红外光谱分析.这是在确定条件下对电催化剂进行简便和可重复筛选的一个适合的方法,同时还提供了对复杂反应(如甘油氧化)产物选择性的检测.通过对泵送电解液进行更耗时的定量高效液相色谱分析,结果表明,衰减全反射红外光谱法可快速鉴定产物.在层流条件下,水中使用0.1 M甘油和1 M KOH,流速为5μL min-1时,甘油转化率较高.转化率和选择性取决于催化剂的负载量,负载量又决定了催化剂层的厚度和粗糙度.由于在更粗糙的膜中停留时间更长有利于再吸附和C-C键断裂,因此当负载量最高达210μg cm-2时,甘油转化率为73％且甲酸选择性接近80％.当最低负载量为13μg cm-2时,甘油转化率达到63％,甲酸选择性降至60％,相应地,C2物种(如乙醇酸盐)选择性较高,为8％.因此,只有催化剂负载量较低时才能形成几微米厚度范围内的薄膜,此时才适合进行优质催化剂的筛选.     

Total Synthesis of Pulvomycin D

A synthetic route to the pulvomycin class of natural products is presented, which culminated in the first synthesis of a pulvomycin, pulvomycin D. Key elements of the strategy include a pivotal aldol reaction which led to bond formation between the C24-C40 and the C8-C23 fragment. The remaining C1-C7 fragment was attached by a Yamaguchi esterification completing the assembly of the 40 carbon atoms within the main skeleton. Ring closure to the 22-membered lactone ring was achieved in the final stages of the synthesis by a Heck reaction. The completion of the synthesis required the removal of six silyl protecting groups in combination with olefin formation at C26-C27 by a Peterson elimination.     

X-ray diffraction effects from 2H crystals undergoing transformation to the 4H structure by the shear mechanism

The 2H or ABAB… structure may be transformed to the 4H or ABCB… structure if deformation faults occur in a non-random manner. The theory of X-ray diffraction from one-dimensionally disordered crystals undergoing the 2H → 4H structural transformation by the deformation mechanism is developed. For this it is necessary to consider that the faults are not distributed entirely at random but tend to occur in such a manner as to statistically create a 4H structure. The X-ray diffraction effects are predicted.     

Crystallization and grain growth characteristics of yttria-stabilized zirconia thin films grown by pulsed laser deposition

Knowledge about the crystallization and grain growth characteristics of metal oxide thin films is essential for effective microstructural engineering by thermal post-annealing and the integration to Si-based miniaturized electroceramic devices. Finite size and interface effects may cause fundamentally different behavior compared to three dimensional macroscopic systems. This work presents a comprehensive investigation of the crystallization kinetics and microstructural evolution upon thermal post-annealing of amorphous 200 nm and 1.2 μm thin films of 8 mol% yttria-stabilized zirconia grown by pulsed laser deposition (PLD) using ex- and in-situ X-ray diffraction, Raman spectroscopy, and electron microscopy techniques. The layers exhibit a remarkably low crystallization temperature of 200-250 °C while exposure to energetic electrons induces the formation of randomly dispersed ~ 20 nm sized crystallites already at ambient temperature. The isothermal amorphous to crystalline phase transformation kinetics can be described quantitatively by the Johnson-Mehl-Avrami-Kolmogorov model. They reveal characteristics of a three dimensional growth under cation bulk diffusion control with heterogeneous nucleation that changes from continuous to instantaneous initial seeding at temperatures above 300 °C. Large (> 100 nm) equiaxed grains are formed rapidly without a stabilization of transient nanocrystals during the thermally induced phase transformation. A stagnation of normal grain growth resulting in a logarithmic normal size distribution is observed once the average grain dimensions approach the film thickness. The results on the crystallization and grain growth of the PLD-grown YSZ films are evaluated with regards to the fabrication of YSZ solid electrolyte membranes for Si-supported micro solid oxide fuel cells and gas sensors.     

Substrate-target distance dependence of structural and optical properties in case of Pb(Zr,Ti)O3 films obtained by pulsed laser deposition

The paper presents the influence of pulsed laser deposition (PLD) parameters on the structural and optical properties of PZT thin films grown on platinum substrate. X-ray diffraction (XRD), spectroscopic ellipsometry (SE) and X-ray photoelectron spectroscopy (XPS) are used to determine the thin film properties. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) are employed to get additional information. By changing the distance between target and substrate, different crystalline orientations of PZT are obtained. The thin film thickness and its roughness, as well as the refractive index are also influenced by the chosen distance.     

Deformations of duality-symmetric theories

We prove that a sum of free non-covariant duality-symmetric actions does not allow consistent, continuous and local self-interactions that deform the gauge transformations. For instance, non-abelian deformations are not allowed, even in 4 dimensions where Yang–Mills type interactions of 1-forms are allowed in the non-manifestly duality-symmetric formulation. This suggests that non-abelian duality should require to leave the standard formalism of perturbative local field theories. The analyticity of self-interactions for a single duality-symmetric gauge field in four dimensions is also analyzed.     

Chaotic dynamics of driven flux drops: a superconducting "dripping faucet"

When a current is applied to a type-I superconducting strip containing a narrow channel across its width, magnetic flux spots nucleate at the edge and are then driven along the channel by the current. These flux "drops" are reminiscent of water drops dripping from a faucet, a model system for studying low-dimensional chaos. We use a novel high-bandwidth Hall probe to detect in real time the motion of individual flux spots moving along the channel. Analyzing the time series consisting of the intervals between successive flux drops, we find distinct regions of chaotic behavior characterized by positive Lyapunov exponents, indicating that there is a close analogy between the dynamics of the superconducting and water drop systems.     

Gauge Model Based on Group G×SU（2）

We present a model of gauge theory based on the symmetry group G×SU（2） where G is the gravitational gauge group and SU（2） is the internal group of symmetry. We employ the spacetime of four-dimensional Minkowski, endowed with spherical coordinates, and describe the gauge fields by gauge potentials. The corresponding strength field tensors are calculated and the field equations are written. A solution of these equations is obtained for the case that the gauge potentials have a particular form potentials induces a metric of Schwarzschild type on with spherical symmetry. The solution for the gravitational the gravitational gauge group space.     

Blocks adjustment—reduction of bias and variance of detrended fluctuation analysis using Monte Carlo simulation

The length of minimal and maximal blocks equally distant on log-log scale versus fluctuation function considerably influences bias and variance of DFA. Through a number of extensive Monte Carlo simulations and different fractional Brownian motion/fractional Gaussian noise generators, we found the pair of minimal and maximal blocks that minimizes the sum of mean-squared error of estimated Hurst exponents for the series of length . Sensitivity of DFA to sort-range correlations was examined using ARFIMA(p,d,q) generator. Due to the bias of the estimator for anti-persistent processes, we narrowed down the range of Hurst exponent to      

Homogenization heat treatment and segregation analysis of equiaxed CMSX-4 superalloy for gas turbine components

Journal of Thermal Analysis and Calorimetry - Two new zinc(II) coordination compounds have been synthesized by the reaction of diazine-ring containing Schiff bases di(2-pyridyl) ketone...