Implications of the solvent effect in quantitative capillary gas chromatography of minor constituents in mixtures—a study using deuterium labeled and unlabeled benzofluoranthenes

Perdeuterated benzofluoranthenes have slightly shorter retention times than their equivalent unlabeled forms in a DB-5 capillary column. Under column overload conditions, perdeuterated benzofluoranthenes in moderate multifold excesses, which might be encountered in their use as internal standards and carriers for quantitative analysis, are seen to exhibit both normal and reverse solvent effects on their close eluting congeners. In some cases the effects may be used to advantage by knowledgeable analysts, but for the ignorant and unwary the effects can lead to serious errors in identification and quantification.     

An analytical solution of a newly proposed peak broadening equation and extension of polydispersities to higher molecular weight averages in size exclusion chromatography (SEC)

Summary Herein is reported an analytical solution to the peak broadening or peak dispersion/flattening equation based on the recently proposed Instrumental Spreading Shape Function and its application to correction for imperfect resolution (inadequate peak separation and/or excessive peak broadening) for higher molecular weight averages. The relationship of these higher MW averages with the familiar Weight Average and number average molecular weights is also discussed. Criteria for perfect resolution are specified and a true molecular weight calibration curve is accordingly defined.     

Band broadening evaluation by back-and-forth capillary electrophoresis

The purpose of this study is to develop a method for precise evaluation of band broadening in capillary electrophoresis. A capillary electrophoresis system with on-column twin detectors is constructed. Back-and-forth electrophoresis permits zones to make a round trip between the twin detectors placed at distant positions on the capillary. The system is capable of eliminating extra-column effects and discriminating between reversible and irreversible band-broadening mechanisms.     

胰岛素反相制备色谱的方法开发

以胰岛素反相制备色谱方法的开发和优化为目标,通过考察色谱保留参数、峰展宽及样品流出曲线的浓度分布等色谱参数,对流动相梯度、色谱填料、载样量等色谱条件进行了优化,并建立了胰岛素制备色谱峰参数的描述方法。结果表明,所建立的方法可快速筛选出最适于胰岛素分离的色谱条件(包括流动相梯度及分离填料),即流动相中的强洗脱溶剂(有机相)需采取缓梯度窄区间的变化条件,筛选出的分离填料需具备峰向两侧展宽且展宽程度较小、样品最高浓度居中分布的特点。将方法用于实际胰岛素粗品的纯化制备,获得了杂质去除效果好、胰岛素纯度高的产品。该法为胰岛素反相色谱纯化制备方法的快速建立提供了指导,具有较强的实用价值,同时为发展大分子化合物的制备色谱方法提供了参考。     

On the statistical independence of various column contributions to band broadening. Part 1: Second moment contributions from statistically independent,longitudinal diffusion in both phases

The total length-based second moment contribution from longitudinal sample diffusion in both phases on a column, σD , is derived by adding individual partial differential contributions to a partial differential equation accounting for the longitudinal diffusion processes only. Although each diffusion-dispersed sample part is equilibrated between two phases, the resulting σ,D (= 2D _mt _m + 2D _st _s) can be interpreted as the sum of two independent contributions in accordance with the variance addition rule. (D _m and D _s are the mean diffusion coefficients and t _mand t _s the mean residence times of the sample in the mobile and stationary phases, respectively.) The same σD expression is derived from the random walk model of Giddings by treating the diffusional process in each phase as statistically independent of the other processes. Under these conditions the broadening contribution from longitudinal diffusion in the mobile phase is shown to be independent of the velocity profile.     

Measurements and calculations of H2-broadening and shift parameters of water vapour transitions of the ν1 + ν2 + ν3 band

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm^?1 and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.     

Semi-gas kinetics model for performance modeling of flowing chemical oxygen-iodine lasers (COIL)

The gas pressure in a laser cavity of flowing chemical oxygen-iodine laser (COIL)is about 133.31333 Pa[1]. In this pressure range, effects of homogeneous and inhomo-geneous broadening competing with each other on the performances of a COIL are no-ticeable. Generally, a rate equation (RE) model is adopted to the performance modeling of a supersonic COIL, such as in refs. [1—4]. This model assumes the spectral line pro-file is homogeneously broadened. Homogeneous broadening assumption sim…     

An intermediate distribution between Gaussian and Cauchy distributions

In this paper, we construct an intermediate distribution linking the Gaussian and the Cauchy distribution. We provide the probability density function and the corresponding characteristic function of the intermediate distribution. Because many kinds of distributions have no moment, we introduce weighted moments. Specifically, we consider weighted moments under two types of weighted functions: the cut-off function and the exponential function. Through these two types of weighted functions, we can obtain weighted moments for almost all distributions. We consider an application of the probability density function of the intermediate distribution on the spectral line broadening in laser theory. Moreover, we utilize the intermediate distribution to the problem of the stock market return in quantitative finance.     

A multispectrum analysis of the ν2 band of HCN: Part II. Theoretical calculations of self-broadening, self-induced shifts, and their temperature dependences

A semiclassical theory based upon the Robert-Bonamy formalism has been developed to explain the experimental measurements of self-broadening, self-induced pressure shift coefficients in the ν₁,ν₂, 2ν₂ bands of H¹²C¹⁴N and the 2ν₁ band of H¹³C¹⁴N, as well as the temperature dependences of these parameters with special emphasis on the ν₂ band. Our calculations include only electrostatic interactions and neglect the vibrational dependence of the isotropic part of the intermolecular potential, which probably has a weak contribution to the HCN self-shifts for the bands investigated in this study. The agreement between theory and measurements is good in the cases of self-broadening coefficients and their variation with temperature, as well as the self-shift coefficients determined at room temperature. However, the observed temperature dependence of self-shift coefficients in the ν₂ band is different from that derived theoretically.     

Research on speckle noise of laser Doppler velocimeter for the vehicle self-contained navigation

A novel multipoint layer-type laser Doppler velocimeter (MLLDV) is designed to measure the velocity of a vehicle for the self-contained navigation system. In order to investigate the speckle's influence on the Doppler spectrum, formulas of time-lagged covariance and speckle broadening were derived for our MLLDV. Simulations and experiments are made for detailed analysis. The results show that the time-lagged covariance of photocurrent is directly proportional to the incident angle, and is inversely proportional to the elevation fluctuation of the ground together with the velocity of the vehicle. Speckle broadening is a function of the vehicle's velocity, the 1/e² Gaussian spot radius and the phase correlation length of the ground. For our MLLDV, Doppler frequency and Doppler broadening are both directly proportional to the velocity of the vehicle. Besides, the ratio between Doppler broadening and the corresponding Doppler frequency is about 0.72% when the speed of the vehicle varies from 0 to 9.6 m/s.