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.     

Solution of large‐scale weighted least‐squares problems

A sequence of least‐squares problems of the form min_y∥G^1/2(A^T y?h)∥₂, where G is an n×n positive‐definite diagonal weight matrix, and A an m×n (m?n) sparse matrix with some dense columns; has many applications in linear programming, electrical networks, elliptic boundary value problems, and structural analysis. We suggest low‐rank correction preconditioners for such problems, and a mixed solver (a combination of a direct solver and an iterative solver). The numerical results show that our technique for selecting the low‐rank correction matrix is very effective. Copyright © 2002 John Wiley & Sons, Ltd.     

Coupled intervals in the discrete calculus of variations: necessity and sufficiency

In this work we study nonnegativity and positivity of a discrete quadratic functional with separately varying endpoints. We introduce a notion of an interval coupled with 0, and hence, extend the notion of conjugate interval to 0 from the case of fixed to variable endpoint(s). We show that the nonnegativity of the discrete quadratic functional is equivalent to each of the following conditions: The nonexistence of intervals coupled with 0, the existence of a solution to Riccati matrix equation and its boundary conditions. Natural strengthening of each of these conditions yields a characterization of the positivity of the discrete quadratic functional. Since the quadratic functional under consideration could be a second variation of a discrete calculus of variations problem with varying endpoints, we apply our results to obtain necessary and sufficient optimality conditions for such problems. This paper generalizes our recent work in [R. Hilscher, V. Zeidan, Comput. Math. Appl., to appear], where the right endpoint is fixed.     

Quadratic Functionals with General Boundary Conditions

The purpose of this paper is to give the Reid ``Roundabout Theorem' for quadratic functionals with general boundary conditions. In particular, we describe the so-called coupled point and regularity condition introduced in [16] in terms of Riccati equation solutions. Accepted 27 February 1996     

Writhing instabilities of twisted rods: from infinite to finite length

We use three different approaches to describe the static spatial configurations of a twisted rod as well as its stability during rigid loading experiments. The first approach considers the rod as infinite in length and predicts an instability causing a jump to self-contact at a certain point of the experiment. Semi-finite corrections, taken into account as a second approach, reveal some possible experiments in which the configuration of a very long rod will be stable through out. Finally, in a third approach, we consider a rod of real finite length and we show that another type of instability may occur, leading to possible hysteresis behavior. As we go from infinite to finite length, we compare the different information given by the three approaches on the possible equilibrium configurations of the rod and their stability. These finite size effects studied here in a 1D elasticity problem could help us guess what are the stability features of other more complicated (2D elastic shells for example) problems for which only the infinite length approach is understood.     

Viscosity solutions of fully nonlinear parabolic systems

In this paper, we discuss the viscosity solutions of the weakly coupled systems of fully nonlinear second-order degenerate parabolic equations and their Cauchy-Dirichlet problem. We prove the existence, uniqueness and continuity of viscosity solution by combining Perron's method with the technique of coupled solutions. The results here generalize those in Proc. London Math. Soc. 63 (1991) 212-240 and Comm. Partial Differential Equations 16 (1991) 1095-1128.     

Lifetime analysis of quasibound states in coupled quantum wells

A simple time-dependent model is presented to investigate lifetimes of the quasibound states in coupled quantum wells (CQWs). The transfer matrix approach is employed to discretize the conduction-band profile of the heterostructure and form a dispersion equation whose zeros correspond to the complex eigenenergies. Both the bound and quasibound states are extracted numerically in the complex plane by Newton's method. The lower and higher well subbands are found to have negative and positive energy shift, respectively, as following the no level crossing theorem. Besides, the decay rate of the quasibound state is approximately proportional to the absolute energy shift. The quasibound states, which have larger energy shift, have shorter lifetime and decay more quickly. Furthermore, the differences in lifetime between the quasibound states in CQWs can be easily realized as all the wave functions are specially adjusted to form the relative probability density distributions.     

Signal averaging in gas chromatography

Ensemble or signal averaging, and the use of the technique for the solution of some unique problems with minimum sample handling, have previously been reported. The capability of the technique has been evaluated with microbore gas chromatography for the fast handling of a large number of analyses: ca 20–30 replicate injections are easily attainable in a reasonable analysis time. The implementation of the signal averaging technique with other concentration techniques for improving detection limits is also demonstrated.