Synthesis and X-ray crystal structures of six [TeL4][MF6] salts, where L is ethylene- or trimethylene-thiourea, and M is Si, Ge or Sn. Five Te(II) complexes with a novel type of structure linked together by unusual N–HF hydrogen bonds

The complexes [Te(etu)₄][SiF₆] (1), [Te(etu)₄][SiF₆] · H₂O (2), [Te(trtu)₄][SiF₆] (3), [Te(etu)₄][GeF₆] · H₂O (4), [Te(trtu)₄][GeF₆] (5) and [Te(etu)₄][SnF₆] (6) (etu = ethylenethiourea, trtu = trimethylenethiourea) have been prepared and their crystal structures determined by X-ray crystallographic methods. The crystals of 1, 3 and 5 are tetragonal; space groups P4cc (No. 103) with Z = 4 for 1, P4nc (No. 104) with Z = 2 for 3, and I4 (No. 79) with Z = 2 for 5. The crystals of 2, 4 and 6 are orthorhombic, space group Pccn (No. 56) with Z = 8 for 2 and 4 and Z = 4 for 6; those of 2 and 4 being isomorphous. The cations contain square planar or slightly distorted square planar TeS₄ coordination groups. In 1, 3 and 5 the Te atoms are located on fourfold rotation axes; the cations have fourfold rotational symmetry and the four thiourea ligands extend to the same side of the TeS₄ plane. These are the first examples of [TeL₄]²⁺ conformers of this type. In 2 and 4 the Te atoms lie on general positions; the cations are distorted versions of those in 1, and also in these the four ligands extend to the same side of the TeS₄ plane. In 6 the Te atoms are located on twofold rotation axes, the conformation of the cations corresponds to the point group C₂ with two neighbouring ligands extending to one side of the coordination plane and the remaining two to the opposite side. In 1–5 each of the four ligands forms a N–HF bond to the same F atom in the counter ion. The crystals of 1–5 are red, and those of 6 are yellow. The red colour is attributed to interactions of Te and S lone electron pairs caused by ligand TeS₄/TeSC tilt angles markedly different from 90°.     

Photoelectron spectroscopy on thin films of extended zinc porphyrazines

Photoemission measurements were performed on a series of stepwise benzoannelated zinc porphyrazine molecules in thin films. The electronic structure of tert-butyl-substituted zinc tetraazaporphyrin, phthalocyanine, and naphthalocyanine is investigated using mainly EUV synchrotron radiation. A detailed analysis of the zinc satellites in the spectra of the valence region is performed in an attempt to infer the effect of ligand size extension on the metal-ligand interactions. No differences in the character of the bond between zinc and ligand were detected as a function of ligand size. The results are compared with those for the respective metal-free and copper-containing molecules.     

The cycloaddition way to novel deoxy disaccharide analogs

A novel heterocycloaddition merges 2-thiono-3-ketolactones with carbohydrate glycals to afford materials which resemble disaccharides with an O-glycosidic linkage at the anomeric center and a thioether linking both C-2 and C-2′, thus creating a third heterocyclic ring. Upon desulfurization, these novel cycloadducts afford materials which are models for 2-deoxydisaccharides. Studies with two keto lactones and seven glycals are described.     

On the exceptional zeros of cross-products of derivatives of spherical Bessel functions

The lowest zeros of the cross-products of derivatives of spherical Bessel functions are not obtainable from a McMahon-type formula. This paper derives an analytical approximation for these lowest, exceptional, zeros, through to 4th order in a parameter specifying the thinness of the corresponding concentric spherical region.

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Zusammenfassung Die kleinsten Nullstellen der Kreuzprodukte der Ableitungen von spherischen Bessel-funktionen können nicht durch eine Formel von McMahon Typ erhalten werden. Durch eine Entwicklung bis zu vierter Ordnung in einem Parameter proportional zur Dicke des zugeordneten spherischen Gebietes berechnen wir eine analytische Näherung für diese kleinsten, außergewöhnlichen, Nullstellen.

     

The Factorization of Queueing Equations and Their Interpretation

There are many queueing systems, including the M ^x /M ^y /c queue, the GI ^x /M/c queue and the M/D/c queue, in which the distribution of the queue length at certain epochs is determined by a Markov chain with the following structure. Except for a number of boundary states, all columns of the transition matrix are identical except for a shift which assures that there is always the same element occupying the main diagonal. This paper describes how one can find the equilibrium distribution for such Markov chains. Typically, this problem is solved by factorizing of a certain expression characterizing the repeated columns. In this paper, we show that this factorization has a probabilistic significance and we use this result to develop new approaches for finding the equilibrium distribution in question.     

A hydrogen-bonding receptor that binds cationic monosaccharides with high affinity in methanol

A dicarboxylate host (1) binds cationic monosaccharides such as D-glucosamine HCl (2), D-galactosamine-HCl (3), and D-mannosamine-HCl (4) with high affinity (K1 = 8.0 x 10(4)-2.0 x 10(5) M(-1)) in methanol. In circular dichroism (CD) spectroscopy a positive exciton-coupling band was observed near 290 nm; this indicates that the saccharides are recognized by multiple point interactions. Since the corresponding neutral monosaccharides are not significantly bound, one may conclude that complex formation is primarily due to the electrostatic interaction between NH3+ in the guest and one carboxylate in the host and secondarily due to hydrogen-bonding interactions of OH groups with the other carboxylate and/or nitrogen bases. Molar ratio plots and Job plots indicate that host 1 and cationic monosaccharide guests form CD-active, pseudo-cyclic 1:1 complexes at low guest concentration followed by the formation of CD-silent, acyclic 1:2 1-saccharide complexes at high guest concentration. The possible binding modes are discussed in detail on the basis of molecular mechanics calculations and chemical shift changes in 1H NMR spectra. The results of competition experiments with several cationic reference compounds bearing fewer OH groups than 2-4 are consistent with the proposed binding model. Thus, the present study is a rare example of saccharide recognition in a protic solvent, where in general, hydrogen-bonding interactions are rarely useful because of strong solvation energy. These are apparently the strongest saccharide complexes involving noncovalent interactions between host and guest. We believe that the findings are significant as a milestone toward development of new saccharide recognition systems ultimately useful in aqueous solution.     

Ascorbic acid reaction with disulphide compounds: effects and applications

A method was developed for estimation of concentrations of cystine based on the reaction of this oxidised amino acid with ascorbic acid and copper ion. The standard curve which was constructed was used as the basis for investigation of the effects which both cystine and glutathione disulphide, and some disulphide proteins, exerted on the amount of hydrogen peroxide formed in the reaction of ascorbic acid. The hydrogen peroxide product was lowered in the presence of the disulphide compounds. The disulphide compounds also lowered the amount of deoxyribose reacting material formed during the ascorbic acid oxidation. The reaction between ascorbic acid and copper and cystine was used to estimate the amount of the disulphide amino acid in acid digests of proteins.     

High-performance liquid chromatography of gentian violet, its demethylated metabolites, leucogentian violet and methylene blue with electrochemical detection

High-performance liquid chromatographic conditions are reported for the electrochemical detection (ED) of Gentian Violet, its demethylated metabolites, Leucogentian Violet and Methylene Blue. Gentian Violet, its demethylated metabolites and Leucogentian Violet were separated within 14 min on a cyano column eluted isocratically with methanol-buffer (60:40) as the mobile phase. ED responses for Gentian Violet, Leucogentian Violet and Methylene Blue were linear over the ranges 0.54-6.75, 0.50-25.2, and 5.7-285 ng, respectively. Under these conditions, the compounds were eluted in the following order: Leucogentian Violet, N"-2-tetra-methylparaosaniline chloride, N'-1-tetramethylpararosaniline chloride, pentamethylpararosaniline chloride and Gentian Violet. Methylene Blue and Gentian Violet had essentially the same retention time under these parameters. The detection limit for Gentian Violet, its demethylated metabolites and Leucogentian Violet was determined to be 0.1 pmol. A detection limit of 3 pmol was established for Methylene Blue. Detector response, elution, separation, linearity and sensitivity of detection are discussed.