Definition and detection of data-based uniqueness in evaluating bilinear (two-way) chemical measurements

Multivariate curve resolution methods, frequently used in analyzing bilinear data sets, result in ambiguous decomposition in general. Implementing the adequate constraints may lead to reduce the so-called rotational ambiguity drastically, and in the most favorable cases to the unique solution. However, in some special cases, non-negativity constraint as minimal information of the system is a sufficient condition to resolve profiles uniquely. Although, several studies on exploring the uniqueness of the bilinear non-negatively constrained multivariate curve resolution methods have been made in the literature, it has still remained a mysterious question. In 1995, Manne published his profile-based theorems giving the necessary and sufficient conditions of the unique resolution. In this study, a new term, i.e., data-based uniqueness is defined and investigated in details, and a general procedure is suggested for detection of uniquely recovered profile(s) on the basis of data set structure in the abstract space. Close inspection of Borgen plots of these data sets leads to realize the comprehensive information of local rank, and these argumentations furnish a basis for data-based uniqueness theorem. The reported phenomenon and its exploration is a new stage (it can be said fundament) in understanding and describing the bilinear (matrix-type) chemical data in general.     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.     

Numerical solutions of the shallow water equations with discontinuous bed topography

A simple scheme is developed for treatment of vertical bed topography in shallow water flows. The effect of the vertical step on flows is modelled with the shallow water equations including local energy loss terms. The bed elevation is denoted with z_b^‐ for the left and z_b⁺ for the right values at each grid point, hence exactly representing a discontinuity in the bed topography. The surface gradient method (SGM) is generalized to reconstruct water depths at cell interfaces involving a vertical step so that the fluxes at the cell interfaces can accurately be calculated with a Riemann solver. The scheme is verified by predicting a surge crossing a step, a tidal flow over a step and dam‐break flows on wet/dry beds. The results have shown good agreements compared with analytical solutions and available experimental data. The scheme is efficient, robust, and may be used for practical flow calculations. Copyright © 2002 John Wiley & Sons, Ltd.     

Numerical analysis of the spiral Couette flow of a rarefied gas between coaxial cylinders

An implicit quasi-monotone second-order accurate method is proposed for analyzing the spiral Couette flow of a rarefied gas between coaxial cylinders. The basic advantages of the method over the conventional method of stationry iterations are that the former is conservative with respect to the collision integral, has a simple software implementation for any types of boundary conditions, and applies to a wide range of Knudsen numbers.     

铁铝催化体系催化丙烯酸丁酯聚合

研究了Fe(acac)3-Al(i-Bu)3-8-羟基喹啉(acac=乙酰丙酮)催化体系催化丙烯酸丁酯(BA)聚合，考察了聚合规律，用凝胶渗透色谱研究了聚合物分子量和分子量分布．动力学研究表明聚合反应对单体浓度呈一级关系，表观活化能为13．9kJ／mol．     

可压稠密气固两相流动过程的模拟计算

基于稠密气体分子运动论和颗粒动理学,建立可压稠密气固两相流动模型。采用梯度模拟来考虑气相可压缩性对气相湍流的影响。模拟计算表明气固两相射流速度沿轴向和径向减小,颗粒浓度下降。气固两相射流具有高的颗粒温度,呈现强烈的气固两相湍流流动特性。     

从像上提取非旋转对称系统的传递函数制作解卷空间滤波器

本文提出从高分辨电子显微像中,利用光学、全息和部分相干等方法,提取传递函数,制作相位和振幅滤波器,实现解卷,提高高分辨电子显微像的分辨率.     

A numerical and experimental investigation of the interactions between a non‐uniform planar array of incompressible free jets

The interaction between multiple incompressible air jets has been studied numerically and experimentally. The numerical predictions have been first validated using experimental data for a single jet configuration. The spreading features of five unequal jets in the configuration of one larger central jet surrounded by four smaller equi‐distant jets, have been studied, for different lateral spacing ratios of 1.5, 2.0 and 2.5 and a central jet Reynolds number of 1.24×105 (corresponding to a Mach number of 0.16). Flow of five equal jets has also been simulated, for the sake of comparison. The jet interactions commence at an axial distance of about 3–4 diameters and complete by an axial distance of about 10 diameters for the lowest spacing ratio of 1.5. For larger spacing ratios, the length required for the start and completion of jet interaction increase. Peripheral jets bend more towards the central jet and merge at a smaller distance, when their sizes are smaller than that of the central jet. The entrainment ratio for multiple jets is higher than that for a single jet. Excellent agreement is observed between the experimental data and theoretical predictions for both mean flow field and turbulent quantities, at regions away from the jet inlet. The potential core length and initial jet development, however, are not predicted very accurately due to differences in the assumed and actual velocity profiles at the jet inlet. Copyright © 2004 John Wiley & Sons, Ltd.     

Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers

Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10^?3 mol L^?1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation‐binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4964–4975, 2004     

Heterochain model for simultaneous long‐chain branching and crosslinking. III. Multicomponent polymerization

The matrix formula developed in the context of heterochain theory, M?_w = M?_wp + WF ( I ? M )^?1 S , was applied to describe the molecular weight development during free‐radical multicomponent polymerization. All of the required probabilistic parameters are expressed in terms of the kinetic‐rate constants and the various concentrations associated with them. In free‐radical polymerization, the number of heterochain types, N, needs to be extrapolated to infinity, and such extrapolation is conducted with only three different N values. This matrix formula can be used as a benchmark test if other approximate approaches can give reasonable estimates of the weight‐average molecular weights. The moment equations with the average pseudo‐kinetic‐rate constants for branching and crosslinking reactions may provide poor estimates when the copolymer composition drift during polymerization is very significant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2801–2812, 2004