从自模式曲线分辨到渐进类因子分析法

本文对自模式曲线分辨法的发展作了简要回顾，其中特别对近来来迅速发展的一类用于色谱波谱联用仪产生的二维分析数据的渐进类分析法作了详尽的讨论。这些新化学计量学方法的涌现，对复杂的未知分析体系的定性定量分析，将带来深刻的变化。     

Hepatobiliary excretion and brain distribution of caffeine in rats using microdialysis

To investigate the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine, this study uses a method based on microdialysis technique and liquid chromatography that allows continuous and concurrent in vivo monitoring of extracellular caffeine in the blood, brain and bile of anesthetized rats following the administration of caffeine (3 or 10 mg/kg, i.v.) through the femoral vein. Dialysates of the blood, brain and bile were directly injected onto the liquid chromatographic system and no further clean-up procedures were required. The study design consisted of two groups of six rats in parallel: the rats of the control group received caffeine (3 or 10 mg/kg, i.v.) alone and those of the cyclosporine treated-group were injected cyclosporine (10 mg/kg, i.v.) 10 min prior to caffeine administration (3 or 10 mg/kg, i.v.). The decline of caffeine in the blood, brain striatum and bile suggested that caffeine had rapid exchange and equilibration between the peripheral compartment and the central nervous system. In addition, the results indicated that caffeine underwent hepatobiliary excretion and was distributed into brain. When cyclosporine was co-administered, the pharmacokinetic parameters were not significantly altered. The results of this study reveal that the pharmacokinetic mechanism of hepatobiliary excretion and brain distribution of caffeine might not relate to P-glycoprotein.     

Study of reaction processes by in-line near-infrared spectroscopy in combination with multivariate curve resolution: Esterification of myristic acid with isopropanol

The acid-catalysed esterification of myristic acid with isopropanol was studied by using near-infrared spectroscopy (NIR) in combination with soft-modeling curve resolution (MCR) methodology with a view to establishing the effect of experimental variables on the reaction kinetics. The reaction was conducted at temperatures above the boiling point of the alcohol, with continuous addition of an isopropanol/water mixture to the reactor. Spectral and concentration profiles were determined by applying soft-modeling curve resolution methodology to a column-wise augmented data matrix containing the spectra for the pure components. MCR profiles were compared with reference values and found to depart from then by less than 3% as %RSE for concentrations and to exhibit correlation above 0.999 for spectra.The reaction kinetics as estimated from the concentration profiles was found to be pseudo-first-order. Also, the pseudo-first-order rate constant was found to depend on the flow-rate of the isopropanol/water mixture and its water content; although the constant decreased with increase in the proportion of water, a content of ca. 15% could be used without important retarding effects on the kinetics. The proposed NIR-MCR method allows the rate constant and the influence of the initial water content to be determined with a view to minimizing consumption of the raw materials and optimizing the experimental conditions.     

Monte—Carlo model of the diffusion-limited reaction kinetics in microheterogeneous media. Comparison with the experimental plots of the forward and backward electron phototransfer kinetics on the pore diameter in silica gel

The kinetics of the diffusion-limited decay reaction A + B B was simulated by the Monte—Carlo method on a two-dimensional square lattice with defects presented by randomly distributed sites. The cases were considered where [B] [A] at the random initial distribution (quenching reaction) and [B] = [A] with the initial distribution of the A and B particles on neighboring sites (geminate recombination). The kinetic curves were approximated by the simplest analytical equation [A]/[A]₀ = (1 – )exp[–(kt)^1–h ] + (where k and are constants). The plots of the heterogeneity parameter (h) and time-averaged first-order rate constant vs. concentration of defects (p) or B particles (in the case of quenching) were obtained and compared with similar correlations obtained earlier by the experimental study of the kinetics of forward (quenching reaction) and backward (geminate recombination) electron phototransfer on the surface of different porous silica gels. The experimental plots of h vs. silica gel porosity are in satisfactory agreement with the plots of h vs. p in the model space, if the fraction of volume inaccessible for reactants, calculated from the free silica gel volume, is chosen as the p parameter for silica gel.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1536–1541, August, 2004.     

On the structure formation of hydrophobed particles in the boundary layer of water and octane phases

Two-dimensional aggregation of the surface modified glass beads was carried out in the boundary layer of water and octane phases. The effect of particles' hydrophobicity was investigated on the structure of forming aggregates and the growth process. The structure of the aggregates and their growth were characterized by a density function which demonstrates the change of mean particle density as a function of aggregate size. The growth yielded fractal or nonfractal structures in the investigated systems. The fractal structure of the aggregates was observed to be dependent on restructuring processes controlled by the surface properties of the beads.The experimental results are compared with earlier findings for aggregation of hydrophobic beads in the boundary layer of water and air phases.On leave from Loránd Eötvös University, Budapest, Hungary     

Etude Experimentale et Modelisation des Equilibres Solide—Liquide du Systeme Binaire H2O—UO2(NO3)2

The binary system H₂O—UO₂(NO₃)₂ was studied by solubility measurements and constant heat flow thermal analysis. Temperature and composition of the eutectic transformation between ice and uranyl nitrate hexahydrate were accurately defined. A new hydrate with 24 molecules of water decomposes at –21°C according to the peritectoid reaction<UO₂(NO₃)₂·24H₂O> <UO₂(NO₃)₂·6H₂O> + 18<H₂O>The quasi-ideal model was applied to the solid—liquid equilibria, using the following reaction hypothesis:((UO ₂ ²⁺ )) + 2((NO ₃ ^– ))+ h((H₂O)) ((UO₂OH⁺aq)) + ((H₃O⁺aq + 2((NO ₃ ^– aq))A complete calculation of the binary system was carried out with a global ionic hydration number h equal to 9 in the aqueous solutions. It allowed to the melting enthalpies of uranyl nitrate hydrates.

This revised version was published online in November 2005 with corrections to the Cover Date.     

The Aggregation Kinetics of Colloidal Particles of Basic Yttrium Carbonate

Studyofthegrowthprocessofcolloidalparticlesofnonequilibriumandirreversibilityisanactiveareaofresearch.Therecognitionofcolloidalaggregatesasfractalobjectshasinspiredalargenumberofexperimentalandtheoreticalstudiesonthestructuralandkineticaspectsofaggregationprocesses"'.Morerecently,kineticsofhematiteaggregationbypolyacrylicacidhavebeenstudiedbyzhangandBume3.Theprimaryhematiteparticleswerequiteuniformandfairlyspherical.Inthispaper,wewillreportthesizeevolutionoffractalaggregatesofinitiallypolydis…     

一般增长曲线模型参数阵的BLU估计

考虑一般增长曲线模型：Ｙ＝Ｘ１ＢＸ２＋εＥ（Ｖｅｃ（ε））＝０Ｖ（Ｖｅｃ（ε））＝σ２ＶＩｎ（Ｖ０）本文对任一可估函数ＫＢＬ给出了它的ＢＬＵ估计（最佳线性无偏估计），并得到了方差σ２的一个无偏估计．     

Dynamic Properties of Two-Dimensional Polydisperse Granular Gases

We propose a two-dimensional model of polydisperse granular mixtures with a power-law size distribution in the presence of stochastic driving. A fractal dimension D is introduced as a measurement of the inhomogeneity of the size distribution of particles. We define the global and partial granular temperatures of the multi-component mixture. By direct simulation Monte Carlo, we investigate how the inhomogeneity of the size distribution influences the dynamic properties of the mixture, focusing on the granular temperature, dissipated energy, velocity distribution, spatial clusterization, and collision time. We get the following results: a single granular temperature does not characterize a multi-component mixture and each species attains its own "granular temperature"; The velocity deviation from Gaussian distribution becomes more and more pronounced and the partial density of the assembly is more inhomogeneous with the increasing value of the fractal dimension D; The global granular temperature decreases and average dissipated energy per particle increases as the value of D augments.     

基于光谱曲线形态的高光谱影像检索方法研究

随着传感器技术、数据通讯技术的飞速发展,利用各种机载和星载传感器,己经获取到各种不同的海量遥感影像数据。巨大的数据量带来了数据存储和管理的问题,如何实现从海量影像数据中检索出我们所需要的信息显得十分迫切。影像检索最早由Chang于1980年提出,是对传统信息检索的扩展。针对海量遥感影像高效检索的需求和高光谱遥感影像波段数目多的特点,分析了影像检索中的影像距离函数和相似性度量问题,基于经典的曲线简化Douglas-Peucke算法(简称DP算法)提取光谱曲线的形态特征,利用“提取特征”的思想,提出了基于DP算法的光谱曲线和影像检索(简称DPSR)方法,将光谱形态特征应用于影像检索当中。DPSR利用光谱曲线上的特征点,减小了计算量,实现了有效地匹配和检索,适合高光谱遥感影像的光谱检索。文章选择了OMISI高光谱数据的四种易混分地类进行了相似性度量的对比实验。通过与常规的分析方法光谱角匹配(SAM)、光谱信息散度(SID)的对比可以看到,DPSR在较少计算量的情况下能保持较高的计算精度,提供了一种新的影像光谱高效检索方法。此外,文章还提出了尚待进一步研究的问题。