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.     

End unit effect on the Tg of differentiated series of perfluoro-poly (oxymethylene-co-oxyethylene) oligomers

Twelve series of linear oligomers of four different degrees of polymerization (x_n = 8.77−41.55), having a common perfluorinated random copolymeric chain as molecular body and two equal foreign end units of one of the types listed in Table 1, have been synthesized by derivatization of base samples of one of them having a diolic---CH₂OH functionality. The glass transition temperature T_g of all the series was measured and thus examined as a function of x_n. A clear end unit effect is observed, dominantly determined in every series by chemical nature and structure of the end units, quantitatively expressed at any x_n by different positive or negative T_g deviations from the common asymptotic T_g∞ value. The results are also discussed in terms of copolymer end effect and of relation between T_g and end copolymeric composition.     

Application of differential electrolytic potentiometry for detection in flow injection analysis

The applicability of differential electrolytic potentiometry as a detection system in flow injection analysis is investigated. A computer-controlled injector which delivers precise volumes of sample solutions in a reproducible manner was developed. Conditions such as current density employed, the concentrations of the solutions used and the flow rate were optimized. Chloride in water was determined by means of this system. The relation between chloride concentration and the measured signal was found to be Nernstian for solutions of concentrations above 6 μg ml⁻¹ chloride. For solutions below this concentration, the relation is linear.     

Improved spacer design and cost reduction in an electrodialysis system

In electrodialysis using thin membranes and spacers, the compactness of the membrane cell-pairs leads to a small potential drop, and hence to energy saving. The spacer design itself has a great effect on the cost of the plants, since spacers act as turbulence promoters. A careful design, to increase the mass transfer coefficients, can reduce the membrane surface area required for a given application. Limiting current measurements, cell-pair resistance and pressure losses are presented for several thin spacers, for different flow-velocity values and feed water concentrations. It was possible to find an advantageous geometry of the separating mesh leading to substantial savings on investment and operation costs.     

Studies of the compositions of Pd(II) hydrolysis products

The characterization of the clusters formed on alkaline hydrolysis of [PdCl₄]^2– was performed using¹⁷O,²³Na,³⁵Cl,¹³³Cs NMR and UV spectroscopy. The chemical composition of the clusters was found to be [Pd(OH)₂] _n ·nNaCl. No mononuclear oxo- or hydroxocomplexes were detected. The spatial structure of the clusters is stabilized by alkali metal cations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 675–679, April, 1993.     

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.