Selectivity changes towards steroids in packed column supercritical fluid chromatography (SFC) induced by temperature and pressure variation

Summary Pressure/temperature variation in SFC was shown to influence selectivity towards steroids. Major changes were observed for polar column packings compared to non-polar packings and variation of the amount of modifier showed that this is valid over the whole investigated range. The effect is underlined by a fall in resolution in the low density range (low pressure/high temperature) for polar stationary phases and appears to be significantly larger than for non-polar phases. Major selectivity shifts induced by variation of the physical properties of the mobile phase are considered to be due to the greater effect of polar modifiers on the nature of polar stationary phases than on non-polar phases.     

A priori tests of a stochastic mode reduction strategy

Several a priori tests of a systematic stochastic mode reduction procedure recently devised by the authors [Proc. Natl. Acad. Sci. 96 (1999) 14687; Commun. Pure Appl. Math. 54 (2001) 891] are developed here. In this procedure, reduced stochastic equations for a smaller collections of resolved variables are derived systematically for complex nonlinear systems with many degrees of freedom and a large collection of unresolved variables. While the above approach is mathematically rigorous in the limit when the ratio of correlation times between the resolved and the unresolved variables is arbitrary small, it is shown here on a systematic hierarchy of models that this ratio can be surprisingly big. Typically, the systematic reduced stochastic modeling yields quantitatively realistic dynamics for ratios as large as 1/2. The examples studied here vary from instructive stochastic triad models to prototype complex systems with many degrees of freedom utilizing the truncated Burgers–Hopf equations as a nonlinear heat bath. Systematic quantitative tests for the stochastic modeling procedure are developed here which involve the stationary distribution and the two-time correlations for the second and fourth moments including the resolved variables and the energy in the resolved variables. In an important illustrative example presented here, the nonlinear original system involves 102 degrees of freedom and the reduced stochastic model predicted by the theory for two resolved variables involves both nonlinear interaction and multiplicative noises. Even for large value of the correlation time ratio of the order of 1/2, the reduced stochastic model with two degrees of freedom captures the essentially nonlinear and non-Gaussian statistics of the original nonlinear systems with 102 modes extremely well. Furthermore, it is shown here that the standard regression fitting of the second-order correlations alone fails to reproduce the nonlinear stochastic dynamics in this example.     

初-边值问题驻波解的渐近稳定性

本文考虑一带有人工粘性的二维定常等熵无旋平面流方程组的初-边值问题. 在一定的假设下,我们证明其驻波解是渐近稳定的.     

Qualitative properties of stationary measures for three-dimensional Navier-Stokes equations

The paper is devoted to studying the distribution of stationary solutions for 3D Navier-Stokes equations perturbed by a random force. Under a non-degeneracy assumption, we show that the support of such a distribution coincides with the entire phase space, and its finite-dimensional projections are minorised by a measure possessing an almost surely positive smooth density with respect to the Lebesgue measure. Similar assertions are true for weak solutions of the Cauchy problem with a regular initial function. The results of this paper were announced in the short note [A. Shirikyan, Controllability of three-dimensional Navier-Stokes equations and applications, in: Sémin. Équ. Dériv. Partielles, 2005-2006, École Polytech., Palaiseau, 2006].     

光强一定时饱和光电流随入射光频率的变化关系辨析

对光电效应实验中饱和光电流随入射光频率变化关系的几种谬误进行了辨析，给出了光强一定时饱和光电流随入射光频率变化的正确规律并作了解释。     

Use of a long-spacer-side-chain liquid crystalline polysiloxane containing a crown ether as a stationary phase for capillary gas chromatography

A new kind of side chain liquid crystalline polysiloxane containing a crown ether with a longer spacer (PSC-11) has been prepared and coated on a fused silica capillary column. The main chroma-tographic characteristics including efficiency, polarity, and selectivity have been examined. The phase exhibits the retention properties of both liquid crystal and crown ether stationary phases and possesses higher efficiency and better selectivity than PSC-3, which has a shorter spacer between the main polysiloxane chain and liquid crystalline side chain.     

Bernoulli方程的演示设计

Bernoulli方程是流体力学的一个基本方程。本将介绍几种简单、有趣而又十分有效的Bernoulli方程演示设计。     

Preparation and evaluation of nickelmesogen for micropacked gas chromatography

The preparation and mesomorphic properties of a substituted bis(dithiolene)nickel complex derived from 4, 4'-dimethoxybenzil are reported. The phase transition temperatures were based on data obtained by polarized light microscopy and differential scanning calorimetry. The mesogenic phase existed over the temperature range from 77 to 175 degrees C. A novel micropacked column (1.5 or 3 m x 1 mm i.d.) prepared from the slurry of bis[1,2-bis(4-n-undecyloxyphenyl)ethane-1,2-dithiolene] nickel(II) (5%, w/w), coated on Chromosorb W was applied for the separation of dialkyl sulfides. The non-linearity (discontinuity) of Van't Hoff plots suggests that the liquid crystal property existed even in the coated phase. Factors affecting the retention and the sample selectivity on the prepared column were examined by using a flame photometric detector (FPD). The separation might be based on the mechanism of ligand exchange, shape selectivity and polarity interaction besides the vapor pressure. LOD for the determination of dialkyl sulfides was below 1 ng for most of the analytes.     

Host-guest complexation effect of 2,3,6-tri-O-methyl-β-cyclodextrin on a C60-porphyrin light-to-photocurrent conversion system

In a light-to-photocurrent conversion system based on a C₆₀-porphyrin bilayer prepared by electrostatic alternate adsorption, porphyrin units in a porphyrin polymer have been isolated by cyclodextrin utilizing the host-guest interaction. In this system, a high quantum yield was achieved by suppression of self-quenching of porphyrin units.