Structural and phase characteristics of the diamond/matrix interfacial zone in high-resistant diamond composites

The structural-phase state of the contact zone and the factors that influence on the strength of diamond retention in the diamond carbide composites were determined. Composites were obtained by the new hybrid technology that eliminates the reheating of the metalized coating. The elaborated technology combines the thermal diffusion metallization of a diamond and the sintering by the scheme of self-dosed impregnation in a one-stage technological cycle. By the methods of electron microscopy, X-ray diffraction analysis, and Raman spectroscopy the structural and phase characteristics of the interphase boundary were investigated. The improvement of chemical and mechanical adhesion between the diamond and carbide matrix was obtained. It was shown that the specific productivity of the samples with a metalized diamond component is 39% higher than those without metallization.     

Electronic Structure of N-Bridged High-Valent Diiron-Oxo

Density functional theory (DFT) and an advanced ab initio technique based on density matrix renormalization group (DMRG-CASPT2) were employed to investigate a reactive N-bridged high-valent diiron-oxo species involved in H-abstraction reactions. We studied in detail two important doublet states, the ground state with two iron(IV) centers and a mixed valence Fe^V-Fe^IV excited state. We found that the latter state is low-lying. Furthermore, its electronic structure and spin density imply that it has significantly higher H-abstraction reactivity than the ground state. This low-lying excited state might be the reason behind the high oxidation reactivity of this diiron-oxo species towards methane.     

平面天线阵快速正交投影波束形成算法

针对大型平面天线阵列下样本数据含有期望信号时，正交投影（OP）波束形成算法不再适用的问题，提出一种新的基于阻塞矩阵的正交投影快速波束形成算法。该算法首先构造阻塞矩阵从样本信号中阻塞掉期望信号，再对阻塞后的样本信号进行施密特（GS）正交化得到重构后的干扰子空间，最后在此基础上实现正交投影波束形成。新算法适用于任意阵型的二维均匀平面阵，在小快拍数下能快速计算出自适应权重。仿真结果表明，无论是弱干扰信号还是强干扰信号，该算法都具有很好的抗干扰性能。     

Reagentless Bioluminescent Sensor for NADH

Abstract

A reagentless fiber optic biosensor specific for NADH, associated with flow injection analysis and based on bacterial bioluminescence is described. Only a buffer solution as flowing stream is required for the probe which works without supply of its coreactants (FMN and N-decyl-aldehyde). These are coentrapped in a poly(vinyl)alcohol (PVA) matrix which allows their internal release in the vicinity of the immobilized enzymes. Two PVA matrices differing by the reticulation process have been tested : first, by polymerization with glutaraldehyde and secondly, by a cyclic freezing-thawing process. The self-containment working time was estimated at 1 and 1.5 h of continuous measurements, respectively. NADH was determined using flow injection analysis. The sensor gave excellent reproducibility (RSD ≤ 3%) in the linear dynamic range 5 — 500 pmol with an average cycle-time of 2.5 min.     

Flash Vacuum Pyrolysis: Techniques and Reactions

Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation, and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave, and millimeterwave spectroscopies, gas‐phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution‐spray and falling‐solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism.     

Application of the transmission line matrix method for outdoor sound propagation modelling – Part 1: Model presentation and evaluation

The present paper deals with an original time-domain approach applied to outdoor sound propagation under meteorological effects. The transmission line matrix method, based on the Huygens’ principle, had already been validated over impedant grounds and complex topography. The presented formulation proposes to take into account meteorological effects (wind speed and temperature) through the relative sound speed. The necessary wavefront direction is determined through the calculation of the averaged intensity vector direction. A good agreement is found between simulations of both the transmission line matrix and parabolic equation methods. A relevant use of the method is shown in the framework of environmental acoustics and initial applications are proposed in Part 2.     

一种一致性排序标度方法

针对层次分析法判断矩阵一致性问题,提出了一种新的排序标度方法,证明了采用新方法形成的判断矩阵具有一致性,最后通过实例运用说明了此方法的可行性和有效性.     

Heavy-Atom Tunneling in Semibullvalenes: How Driving Force,Substituents, and Environment Influence the Tunneling Rates

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b .