Linearization of column responses by correlation chromatography. Separation improvement and reduction of undesired adsorption effects

Summary Experiments and simulations prove that correlation chromatography can greatly reduce the disadvantage of a non-linear response of the chromatographic column. A factor that has been accepted as being an important source of error in correlation or multiplex chromatography, has been shown not to be. Separations affected, improve dramatically when correlation chromatography is used, and a substantial amount of correlation noise only arises when there is a large difference in separation between a conventional chromatogram and a correlogram.A model has been developed for simulating these nonlinearities. It is shown that, especially for correlation chromatography, the simulation results match the practical measurements very well.     

Recent developments in the chemistry of stable doubly bonded germanium compounds

During the last 10 years, several compounds of the type Ge=X (X = C, Ge, N, P, S) have been isolated as monomers. The stabilization of such derivatives, which are generally highly polymerizable, was achieved by using very bulky groups both on the germanium atom and on the heteroelement X. Conjugation (particularly in a few germenes and germaimines) and intramolecular or intermolecular coordination with oxygen or nitrogen, also contributes, in some cases, to the stabilization. The X-ray analyses of such compounds show a significant bond shortening of the double bond (8–10%) relative to the corresponding single bond and a planar or nearly planar germanium. These doubly bonded germanium derivatives are usually thermally stable but must be handled in an inert atmosphere because of their high sensitivity to oxygen and moisture; they are extremely reactive, much more than the corresponding carbon analogues. Nearly quantitative additions on the double bond have been observed with electrophiles and nucleophiles, and various types of cycloadditions also occur. Except in one case, a germylene behavior has not been observed, proving that such compounds retain their structural integrity in solution.     

The lead tetraacetate oxidation of bisacylhydrazones of α-diketones: A scope re-assesment

Oxidation of the title compounds yields, besides the reported isoimides 3 and/or the amides 4 , also the imides 5 . The observed product dichotomy is considered as the result of an intramolecular nucleophilic attack on the aroyl group, of the pressumed zwitterionic intermediate 2 , by O or N present in the ambident N-aroylimine site of 2 . The results of AM1 calculations agree with the product studies and both permit the formulation of a set of rules correlating structure and selectivity.     

A semi-analytical numerical method for time-dependent radiative transfer problems in slab geometry with coherent isotropic scattering

We describe a semi-analytical numerical method for coherent isotropic scattering time-dependent radiative transfer problems in slab geometry. This numerical method is based on a combination of two classes of numerical methods: the spectral methods and the Laplace transform (LTS_N) methods applied to the radiative transfer equation in the discrete ordinates (S_N) formulation. The basic idea is to use the essence of the spectral methods and expand the intensity of radiation in a truncated series of Laguerre polynomials in the time variable and then solve recursively the resulting set of “time-independent” S_N problems by using the LTS_N method. We show some numerical experiments for a typical model problem.     

Forecasting call frequency at a financial services call centre

A forecasting model is developed for the number of daily applications for loans at a financial services telephone call centre. The purpose of the forecasts and the associated prediction intervals is to provide effective staffing policies within the call centre. The model building process is constrained by the availability of only 2 years and 7 months of data. The distinctive feature of the data is that demand is driven in the main by advertising. The analysis given focuses on applications stimulated by press advertising. Unlike previous analyses of broadly similar data, where ARIMA models were used, a model with a dynamic level, multiplicative calendar effects and a multiplicative advertising response is developed and shown to be effective.     

Surface grating formation and erasing on a-Se films

Surface relief formation at holographic recording on amorphous selenium films was demonstrated and investigated. The presence of this optical phase modulation component is essential for ensuring significant, stable and erasable optical recording in a-Se films at 290–320 K temperatures, where conventional photodarkening was known as insignificant and unstable. Photocrystallization can only be observed in super-exposed a-Se films at the given experimental conditions of hologram recording. Erasing behavior of surface relief gratings under heat treatment was also investigated in order to reveal further details of the mechanism. Photoinduced structural transformations within the amorphous phase, connected to local ordering under the condition of light-induced fluidity, are proposed as an explanation for the relief formation and erasing. The observed reversible optical recording process may be useful for the various optoelectronic applications of photoconductive a-Se layers. Received: 12 June 2000 / Accepted: 6 June 2001 / Published online: 30 August 2001