THE PHOTOSENSITIZED OXIDATION OF SULPHIDES

Abstract— The rates of photosensitized oxidation of a number of sulphides were determined under standard conditions in 1, 1, 2,2-tetrachloroethane and in methanol. It was found that the ratio of the rates of reaction in the two solvents was not constant for different sulphides and that t -butyl sulphide does not react in methanol. It is inferred that the presence of an H atom in the α position is essential for reaction in polar solvents and an appropriate mechanism is suggested. The results indicate that reaction in chlorinated solvents may take place by a different mechanism which possibly involves H-abstraction by triplet sensitizer.     

Analysis of tea components by high-performance liquid chromatography and high-performance capillary electrophoresis

Tea is one of the most popular beverages in the world. The number of reports on the analysis of tea components, especially for catechins, has recently been increasing. We review the recent reports on the analysis of tea components using the analytical methods of high-performance liquid chromatography and high-performance capillary electrophoresis.     

Bindungsverhältnisse und Elektronenverteilung im Br 4 2− -Ion

The linear ions Br ₄ ^2– which has been discovered for the first time by Siepmann and Schnering [13] in W₆Br₁₆ have been studied theoretically using the free electron model for the valence electrons. Electronic structure, binding energy and charge distribution show that Br ₄ ^2– is a typical electron deficient compound stabilized by a 4c-6e bond.

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Herrn Prof. Dr. H. Dunken bin ich für sein stetes Interesse und die rege Anteilnahme an diesen Modellrechnungen zu großem Dank verpflichtet.     

Use of diode-array detectors for the simultaneous spectrophotometric determination of calcium and magnesium by flow injection

A method for the simultaneous flow injection spectrophotometric determination of calcium and magnesium with Arsenazo III based on the use of diode-array detector and merging zones is described. The method is applicable to the resolution of mixtures in which the chromogenic reagent has a high absorbance and its spectrum strongly overlaps those of its complexes. In resolving the mixtures, the excess reagent is considered as another component. Quantitation is based on the normal absorbance and first-derivative absorbance spectra. The method is applied to 0.2–1.5 μg ml^?1 Ca and 0.1–1.0 μg ml^?1 Mg. The analysis rate is 50 h^?1.     

Syntheses of a Cp'Re=S derivative and more complex products

The reaction of Cp'ReCl(2)S(3) (Cp' = Me(4)EtC(5)) with slightly less than 2 equiv of a phosphine reagent results in the formation of [Cp'Re(Cl)(2)(mu-S)](2), 2, which has been characterized by an X-ray diffraction study. Reactions of 2 with nucleophiles did not lead to monomeric derivatives of the type Cp'ReS(Cl)(2)(Nuc). The reaction of Cp'ReCl(2)(SC(2)H(4)S) with (Me(3)Si)(2)S resulted in the formation of three new products: Cp'ReS(SC(2)H(4)S), 4; Cp'Re(S(3))(SC(2)H(4)S), 5; and a tetranuclear derivative, [(Cp'Re)(2)(mu-S)(mu,eta(2)-SC(2)H(4)S)(mu,eta(1)-SC(2)H(4)S](2)Cl(2), 6. Complexes 4 and 6 have been characterized by X-ray diffraction studies. The electrochemical properties of the mononuclear Re=S derivative, 4, are compared with those of Re=O and Re=NR analogues.     

Automated carbohydrate synthesis to drive chemical glycomics

This feature article describes the development of the first automated solid-phase oligosaccharide synthesizer. A series of chemical challenges had to be addressed to accomplish this breakthrough and provide rapid access to oligosaccharides of biological significance. Accelerated synthesis of glycoconjugates promises to greatly impact the emerging field of glycobiology. Chemical glycomics uses synthetic carbohydrates and analogs to study their role in recognition, signal transduction pathways and other events of fundamental biomedical significance and shapes up to become the next major wave in biomedical research. The automated synthesis of a novel malaria vaccine candidate is discussed to illustrate the medical potential of chemical glycomics.     

Dimethylzinc-mediated addition of alkenylzirconocenes to alpha-keto and alpha-imino esters

[reaction: see text] Hydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivities.     

The effect of metal oxides on the oxidation of polybutadiene

Carboxy-terminated polybutadiene (CTPB) was oxidised as a coating on various metal oxides by heating in air on a thermobalance. The oxidation was found to be free from diffusion control and was catalysed by certain of the oxides. The catalysis was shown to be independent of semiconductor type and to be associated with those oxides for which the width of the forbidden zone between the valence and conduction bands (U) is less than 1.9 eV. In general, low values of U result in high catalytic activity. It is proposed that catalysis occurs by a redox mechanism, viz. RO₂H + p → RO₂^. + H⁺, RO₂H + e → RO^. + OH^?.     

Mikrobestimmung von Kohlenstoff und Wasserstoff, sowie von 14C, Tritium und Deuterium im Stickstoffstrom

Zusammenfassung Eine mikroanalytische Kohlenstoff-Wasserstoffbestimmung wird beschrieben, bei der die organische Substanz im Stickstoffstrom verbrannt und deren Crackprodukte mit Sauerstoff oxydiert werden. Halogene und Schwefel werden vom Verbrennungskatalysator (nach Körbl) absorbiert, während eventuell entstandene Stickoxide an einer Kupferschicht zur Reduktion gelangen. Die entstandenen Verbrennungsprodukte CO₂ und H₂O können gravimetrisch erfaßt oder bei radioaktiven Proben durch entsprechende Absorptionsmöglichkeiten in einem Flüssigkeits-Szintillationszähler zur Zählung gebracht werden.Stark quenchende einfache, sowie doppelt markierte Proben, die man auch durch Modifikationen des Zählgeräts nicht mehr genau auszählen kann, können mit gleich hoher Zählausbeute wie nichtquenchende erfaßt werden (75% für ¹⁴C und 30% für ³H), da keine störenden Fremdgase die Zählung beeinflussen.Deuterium wird durch Ausmessen der OD-Bande bei 2500 cm^–1 mit einem Infrarot-Spektrometer quantitativ bestimmt.

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Microanalytical determination of carbon and hydrogen, ¹⁴C, tritium and deuterium in a stream of nitrogen

A microanalytical method for the determination of carbon and hydrogen is described. The procedure involves the combustion of the organic substance in a stream of nitrogen and the oxidation of the decomposition products with oxygen. Halogens and sulphur are absorbed by the combustion catalyst (according to Körbl), whereas nitrogen oxides are reduced on a copper surface. The combustion products, CO₂ and H₂O are determined gravimetrically; in the case of radioactive samples they are appropriately absorbed and counted in a liquid scintillation counter. Strongly quenching singly and doubly labelled samples, which cannot be accurately counted even by modification of the counting device, give equally high radioactive yields (75% for ¹⁴C, 30% for ³H), since counting is not influenced by other gaseous impurities. Deuterium is quantitatively determined by measuring the intensity of the OD-signal at 2500 cm^–1 with an infrared spectrometer.

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Herrn Prof. Dr. H. Schmid bin ich für das wohlwollende Verständnis meinen Arbeiten gegenüber zu bestem Dank verpflichtet. Sämtliche Glas- und Quarzgeräte wurden in der Glasbläserei unserer Institute von Herrn B. Thueler angefertigt, wofür ich auch ihm an dieser Stelle danken möchte.