Statistical calculations of tracer and intrinsic diffusion coefficients in concentrated alloys and estimates of microscopic parameters of diffusion from experimental data

The earlier-developed statistical theory of diffusion in concentrated alloys based on the master equation approach is generalized to treat tracer diffusion in binary alloys. The theory developed is used to describe concentration dependencies of both tracer and intrinsic diffusion coefficients and to estimate microscopic parameters of diffusion in alloys CuNi, CuZn and AgCd for which necessary experimental data are available. We show that all main features of strong and peculiar concentration dependencies of diffusion coefficients observed in these alloys are naturally explained by the theory. Signs and scales of interatomic interactions important for diffusion in these alloys are found to strongly depend on the ratio of atomic sizes of alloy components, and types of these dependencies agree with simple physical considerations. We also discuss physical reasons for sharp concentration dependencies of diffusion coefficients characteristic of real alloys.     

Computing Lagrangian statistics from tracer observations and a model output

A stable method of low computational cost is suggested for estimating Lagrangian trajectories by combining observations of a continuously distributed conservative tracer and a circulation model output (background velocity field). A theoretical error analysis for a homogeneous flow is provided while for a more sophisticated synthetic flow the error is evaluated numerically. The reduction in error compared to the background varies in the range 1–34% depending on the flow structure. Finally, the method is applied for estimating the absolute and relative dispersion in a gyre perturbed by periodic or stochastic fluctuations.     

Biased Diffusion in a One-Dimensional Adsorbed Monolayer

We study the dynamics of a probe particle, which performs biased diffusive motion in a one-dimensional adsorbed monolayer composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of a mean-field-type approach, based on the decoupling of the third-order correlation functions into the product of pairwise correlations, we determine analytically the density profiles of the monolayer particles, as seen from the stationary moving probe, and calculate the terminal velocity V _pr, mobility _pr and the self-diffusion coefficient D _pr of the probe. Our analytical results are confirmed by Monte Carlo simulations.     

The Sensitivity of Tracer Concentration to Nonuniform Permeability and Porosity

Concentration of tracer at a producing well is a function of time and of the flow field that transports the tracer from one well to another. Small localized changes in the permeability and porosity fields result in small changes in the observed concentration history. Calculation of the effect of changes in the petrophysical parameter fields on observed concentration is an integral part of most approaches to solving the inverse problem, i.e. calculation of permeability and porosity fields that are consistent with observed tracer concentrations. This paper does not address the inverse problem directly, only the forward problem, but the results are presented as semi-analytic formulas which are intended to provide physical insight into the limitations of the inverse procedure. In particular, for a simple example of dipole flow between two wells in a nearly homogeneous infinite 2D porous medium, the width of the region of significant influence is shown to scale as d where is the dispersivity and d is half the interwell distance. Also, for fixed injection and production rates the influence on concentration of variation in porosity and in log-permeability are shown to be similar in magnitude.     

Theoretical aspects of C metabolic flux analysis with sole quantification of carbon dioxide labeling

The potential of using sole respirometric CO2 labeling measurement for 13C metabolic flux analysis was investigated by metabolic simulations. For this purpose a model was created, considering all CO2 forming and consuming reactions in the central catabolic and anabolic pathways. To facilitate the interpretation of the simulation results, the underlying metabolic network was parameterized by physiologically meaningful flux parameters such as flux partitioning ratios at metabolic branch points and reaction reversibilities. For real case flux scenarios of the industrial amino acid producer Corynebacterium glutamicum and different commercially available (13)C-labeled tracer substrates, observability and output sensitivity towards key flux parameters was investigated. Metabolic net fluxes in the central metabolism, involving, e.g. glycolysis, pentose phosphate pathway, tricarboxylic acid cycle, anaplerotic carboxylation, and glyoxylate pathway were found to be determinable by the respirometric approach using a combination of [1-13C] and [6-13C] glucose in two parallel studies. The reversibilities of bidirectional reactions influence the isotopic labeling of CO2 only to a negligible degree. On one hand, they therefore cannot be determined. On the other hand, their precise values are not required for the quantification of net fluxes. Computer-aided optimal experimental design was carried out to predict the quality of the information from the respirometric tracer experiments and identify suitable tracer substrates. A combination of [1-13C] and [6-13C] glucose in two parallel studies was found to yield a similar quality of information as compared to an approach with mass spectrometric labeling analysis of secreted products. The quality of information can be further increased by additional studies with [1,2-13C2] or [1,6-13C2] glucose. Respirometric tracer studies with sole labeling analysis of CO2 are therefore promising for 13C metabolic flux analysis.     

Ternary mutual diffusion coefficients of KCl-LaCl3-water mixtures from taylor dispersion profiles

The Taylor dispersion (peak-broadening) method is used to measure ternary mutual diffusion coefficients at 25°C for fifteen different compositions of the system KCl–LaCl ₃ -water at ionic strengths from 0.02 to 0.24 mol-dm^–3. The diffusion coefficients are evaluated by least-squares analysis of the refractive index profiles across the dispersed solute peaks. Diffusing LaCl ₃ is found to cotransport significant amounts of KCl. Monte Carlo simulations are used to estimate the precision of ternary diffusion coefficients determined by the dispersion method. Tracer diffusion coefficients are also reported for La ³⁺ ions in aqueous KCl solutions and for K⁺ ions in aqueous LaCl ₃ solutions.     

A Synergistic Effect of Select Organotin Compounds and Ionic Surfactants on Liposome Membranes

Organometallic compounds and surfactants constitute a potential threat to the environment. For that reason we have embarked on a study of their joint action on membranes. Model lecithin liposome membranes were modified with the cationic surfactant trimethyldodecylammonium bromide or the anionic surfactant sodium dodecylsulfonate, and the effect of tripropyltin chloride on the process of calcium (Ca²⁺) and praseodymium (Pr³⁺) desorption from the liposome membrane was studied. Kinetic constants for the process of Ca²⁺ ion desorption from lecithin liposome membranes were determined using the radiotracer method. The percentage of Pr³⁺ ion desorption from liposome membranes was measured by the ¹H NMR method. Trimethyltin, triethyltin and tripropyltin alone caused increased Ca²⁺ and Pr³⁺ desorption from liposome membranes with increasing concentration of the compounds and alkyl chain length. For both the processes studied, a cationic surfactant brought about a lower effectiveness of tripropyltin and an anionic surfactant resulted in a higher effectiveness. The effect observed can be explained by changes in the surface charge of the membrane, induced by the surfactant modifiers and by the concomitant change in the partition coefficient of the organotin. The results obtained indicate a protective or harmful joint action of the surfactants used with tripropyltin on membranes. © 1997 John Wiley & Sons, Ltd.     

用太阳光谱测量空气中NO2浓度的方法研究

根据Noxon方法 ,利用NO2 在 430— 45 0nm范围内的吸收特性 ,测量空气中NO2 的浓度 .介绍了一种利用光学差分吸收原理 ,以太阳光为光源 ,二极管阵列为探测器 ,黄山光明顶上的太阳光谱为参考光谱测量大气中NO2 浓度的新光学方法 .     

Fluorescein labeling of estrogen for application of fluorescence polarization binding assays for antibody and receptor

The fluorescence polarization binding assay (FPBA) using fluorescein-labeled estrogen tracer is a homogeneous assay applicable to both estrogen antibody and estrogen receptor-binding assays. Two estrogen-ethylendiamine fluoresceinthiobamyl (E-EDF) tracers were synthesized; estrogen-6-EDF (E-6-F) derived from 6-ketoestradiol 6-(o-carboxymethyl) oxime and estrogen-17-EDF (E-17-F) was from 17β-estradiol 17-hemisuccinate. In both FPBAs using antibody and receptor, E-6-F tracer (Rf_365nm=0.58) showed a better binding response than E-17-F (Rf_365nm=0.70) indicating that the 17-position of estrogen seems to play an essential role as a binding site for antibody or receptor. In the optimized conditions of FPBA for E₂ using E-6-F tracer, antibody binding (K_d=9.4×10⁻⁹ M) is 50 times sensitive than receptor binding (K_d=4.6×10⁻⁸ M). Binding responses of estrogen and its related chemicals by FPBA indicate that antibody binding assay is able to screen the structural similarity of estrogen showing some response with methyltestosterone (K_i=2.1×10⁻⁵ M). On the other hand, the receptor assay is able to screen for estrogenic chemicals such as tamoxifen (K_i=4.5×10⁻⁹ M) and diethylstilbesterol (K_i=8.1×10⁻⁷ M). Therefore, E-6-F tracer is useful as a tracer for FPBA that is able to screen for chemicals structurally similar to estrogen using antibody, and that is able to screen for chemicals functionally similar to estrogen using receptor binding assay.