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.     

Synthesis of Benzazepine Analogues of Noscapine

The synthesis of benzazepine analogues of the opium alkaloid noscapine ( 1 ) is described. The benzazepines 2 and 3 were prepared starting from nornarceine ethyl ester ( 4 ; readily available from 1 ) in several steps. X-Ray analysis of compound 2 revealed that it is not a diastereosisomer mixture but a racemate of the threo-form and thus has the same configuration as 1 .     

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.     

Investigation of the conditions for feeding filamentary silicon crystals,growing in a reactor with hot walls

An estimate of the factors which influence the rate of growth of filamentary silicon crystals in a standard chloride system using a quartz reactor with hot walls is given. It is shown that a diffusion form of crystallization is observed under the conditions investigated.Voronezh State Technical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 22–26, October, 1995.     

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.     

Analytical torisionL-tensor formulas for anharmonic force constant transformation

New analytical formulas for the torsionL-tensor are reported, which are used in molecular normal mode analysis calculations for the nonlinear transformation of the force constants from internal coordinates to normal coordinates. The proposed formalism exhibits a relative simplicity as compared to previous reported results. Sample calculations for methanol and hydrazine are presented.     

An infinite family of simply connected flag-transitive tilde geometries

We consider tilde-geometries (orT-geometries), which are geometries belonging to diagrams of the following shape: Here the rightmost edge stands for the famous triple cover of the classical generalized quadrangle related to the group Sp₄(2). The automorphism group of the cover is the nonsplit extension 3·Sp₄(2) – 3 ·S ₆. Five examples of flag-transitiveT-geometries were known. These are rank 3 geometries related to the groupsM ₂₄ (the Mathieu group),He (the Held group) and and 3⁷·Sp₆(2) (a nonsplit extension); a rank 4 geometry related to the Conway groupCo ₁ and a rank 5 geometry related to the Fischer-Griess Monster groupF ₁. In the present paper we construct an infinite family of flag-transitiveT-geometries and prove that all the new geometries are simply connected. The automorphism group of the rankn geometry in the family is a nonsplit extension of a 3-group by the symplectic group Sp_2n (2). The rank of the 3-group is equal to the number of 2-dimensional subspaces in ann-dimensional vector space over GF(2).