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1.
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. 相似文献
2.
《Journal of separation science》2018,41(6):1319-1337
The present review discusses the theory and application of van't Hoff analysis in chiral chromatography, with main focus on liquid chromatography. The topics considered include the physical meaning of van't Hoff equation's parameters, interpretation of thermodynamic data in terms of retention and enantioseparation mechanisms, abnormal behavior of van't Hoff plots, and best practices to avoid biased results. 相似文献
3.
本文在变量选择问题的基础上,提出了一种新的图示模型──减变残差图。并给出它的两种推广形式:均值平移异常值检验图和部分影响诊断图。通过它们不但可以容易地考察一个变量在模型中的作用和检验异常值,而且可以诊断样本点对模型和变量的影响大小。 相似文献
4.
Ranjana Yadav 《European Polymer Journal》2007,43(8):3531-3537
Models capable of predicting the maximum extent of conversion (p) of cardanol-based novolac-type phenolic resin, have been developed using response surface methodology to determine the optimum reaction conditions. Three-dimensional response surface and their contour plot were drawn. The maximum extent of conversion (98.93%) was predicted when the cardanol was condensed with formaldehyde (molar ratio 1:0.652) at 119.84 °C for a time period of 3 h with the catalyst (e.g., citric acid) concentration of 1.988% of total volume of cardanol and formaldehyde. The pH of the reaction mixture was maintained at 3.0. These predicted values for optimum process conditions were in good agreement with experimental data. 相似文献
5.
《Surface and interface analysis : SIA》2006,38(5):922-930
Enargite, a copper arsenic sulfide with the formula Cu3AsS4 is of environmental concern due to its potential to release toxic arsenic species. The oxidation and dissolution of enargite are governed by the composition and chemical state of the outermost surface layer. Qualitative and quantitative analysis of the enargite surface can be initially obtained on the basis of X‐ray photoelectron spectroscopy (XPS) binding energy and intensity data. However, a more precise determination of the chemical state of the principal elements of enargite (copper, arsenic and sulfur) in the altered surface layer and in the bulk of the mineral requires a combined analysis based on XPS photoelectron lines and the corresponding X‐ray excited Auger lines. On the basis of results obtained on natural and synthetic enargite samples and on standards of sulfides and oxides, the Auger parameter α′ of different compounds was calculated and the Wagner chemical state plots were drawn for arsenic, copper and sulfur. Arsenic in enargite is found to be in a chemical environment similar to that of arsenides or elemental arsenic, whereas copper in enargite is in a chemical state that corresponds to copper sulfide, Cu2S, for all samples irrespective of surface treatment (natural or freshly cleaved). Only sulfur changed from a chemical state similar to that of copper or iron sulfide in freshly cleaved samples to another state in natural enargite in the as‐received state. Thus, it is the sulfur atom at the surface of enargite that is most susceptible to changes in the enargite surface state and composition. A more detailed interpretation of this behavior, based on differences in the initial and final state effects, is proposed here. The concept of Auger parameter and chemical state plot, used here for the first time for investigating enargite, has proved to be a method to unambiguously assign the chemical state of the principal elements copper, arsenic and sulfur in these minerals. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
6.
原油三维荧光分析中猝灭现象辨析 总被引:5,自引:0,他引:5
研究了原油的三维荧光猝灭现象,指出浓度过高是原油产生荧光猝灭的主要原因,将会造成三维荧光等值线图畸变,致使定量分析数据失真,谱图特征变异,难以获取原油特征三维指纹图。提出了避免荧光猝灭的预试方法,并列出了不同类型原油的最佳测试浓度。 相似文献
7.
Heat divided by ligand concentration vs. heat, similar to the Scatchard plot, was introduced to obtain the equilibrium constant
(K) and the enthalpy of binding (DH) using isothermal titration calorimetry data. Values of K and DH obtained by this linear
pseudo-Scatchard plot for a system with a set of independent binding sites (such as binding fluoride ions on urease and monosaccharide
methyl a-D-mannopyranoside on concavalin A) were remarkably like that obtained from a normal fitting Wiseman method and other
our technical methods. On applying this graphical method to study the binding of copper ion on myelin basic protein (MBP),
a concave downward curve obtained was consistent with the positive cooperativity in the binding. A graphical fitting by simple
method for determination of thermodynamic parameters was also introduced. This method is general, without any assumption and
restriction made in previous method. This general method was applied to the product inhibition study of adenosine deaminase.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
8.
P. Baltazar V. H. Lara G. Córdoba R. Arroyo 《Journal of Sol-Gel Science and Technology》2006,37(2):129-133
Samples of TiO2 doped with 2 and 5 mol% of Cu2+ were prepared by the sol-gel process. Titanium(IV) isopropoxide and copper(II) nitrate were used as precursors. The samples
were prepared as monolithic shapes, dried at 80°C for 72 h and heat treated at various temperatures in the range 200–900°C
for 2 h. The structural transformation and texture of the samples were investigated by X-ray powder diffraction (XRD) and
nitrogen adsorption. Significant changes were observed during the crystallization process; on the one hand, the crystallization
profiles show that crystallization occurs uniformly and is practically insensitive to the dopant concentration, but when the
transformation at a given temperature is followed as a function of time, the rate of the amorphous-anatase transformation
is larger for the sample containing 2 mol% Cu2+. Electron spin resonance (ESR) results show that in this sample there is no segregation of Cu2+ ions. The sample containing 2 mol% of Cu2+ was selected for the kinetic studies and the temperatures selected were 300, 325, 350, 375 and 400°C, which were taken from
the amorphous to anatase crystallization profile. An activation energy of 137 ± 4 kJ/mol for the crystallization process was
estimated from the kinetic data. These results showed that the effect of the open structure present in the TiO2 amorphous phase provides the atomic mobility required for the crystallization. On the other hand, the differences in the
crystallization rate due to the amount of Cu2+ were explained by the segregation of copper ions to the surface of the samples. 相似文献
9.
Lichens are bioaccumulators of divalent metal ions and the interaction between the lichens and five heavy metals was studied. In order to have a better understanding of the metal-uptake process by the lichens, data from atomic absorption spectroscopy were used to calculate the apparent coordination constants of the lichen–metal ion interactions by means of the Langmuir elaboration and microcalorimetric measurements to obtain enthalpimetric information. The results showed a correlation between the Langmuir constants and enthalpimetric measurements. 相似文献
10.
A multi-element Saha–Boltzmann plot method is proposed for the determination of the temperature and the relative number density in laser-induced plasmas, assuming local thermodynamic equilibrium and stoichiometry conservation. The method has been applied to the characterization of a plasma generated with a Cu–Fe–Ni–Mn alloy, using a Nd:YAG laser in air at atmospheric pressure. Spectra of the local emissivity have been obtained by spatial deconvolution of the intensity spectra, obtained with spatial resolution. Saha–Boltzmann plots obtained from the emissivities of 58 spectral lines of Fe I, Fe II, Ni I, Ni II, Mn I and Mn II have been fitted to linear behavior with high correlation, which shows the validity of the equation proposed. Radial distributions of the temperature and number densities of neutral atoms and ions have been determined. The results obtained reinforce the initial considerations of local thermodynamic equilibrium and conservation of stoichiometry. The proposed equation can also be applied to only one ionization species (multi-element Boltzmann plot). Spatially-integrated measurements of the plasma emission have also been performed to show that, in this case, the application of the method to the line intensities provides the two different apparent temperatures for neutral atoms and ions. 相似文献