Condensation of all-cis-tetraphenylcyclotetrasiloxanetetraol in ammonia: new method for preparation of ladder-like polyphenylsilsesquioxanes

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Trends in sorption preconcentration combined with noble metal determination.

Nowadays much attention is being paid to the determination of trace amounts of noble metals in geological, industrial, biological and environmental samples. The most promising techniques, such as inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS) are characterized by high sensitivity. However, the accurate determination of trace noble metals has been limited by numerous interferences generated from the presence of matrix elements. To decrease, or eliminate, these interferences, the sorption preconcentration of noble metals is often used prior to their instrumental detection. A great number of hyphenated methods of noble metal determination using sorption preconcentration have been developed. This review describes the basic types of available sorbents, preconcentration procedures and preparations of the sorbent to the subsequent determination of noble metals. The specific features of instrumental techniques and examples of ETAAS, FAAS, ICP-AES, ICP-MS determinations after the sorption preconcentration of noble metals are considered. The references cited here were selected mostly from the period 1996 - 2006.     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

Solid-phase reagent for molecular spectroscopic determination of heavy metal speciation in natural water

A solid-phase reagent based on 1-(4-adamantyl-2-thiasolylazo)-2-naphthol adsorbed onto silica gel was prepared for Co(II) recovery and preconcentration prior to its sorption-spectroscopic detection. The immobilized reagent was applied to the determination of free cobalt ions in natural water. The solid-phase reagent and chemiluminescent method coupled with membrane filtration, gel-permeation and ion-exchange chromatography were applied to the study of the speciation of iron and cobalt in water from the Dnieper reservoirs and lakes of Kyiv City; their predominant forms were complexes of Fe(III) and Co(II) with dissolved organic matter and fulvic acids play a main role in their complexation.     

Bestimmung von Ascorbinsäure auf Grund ihrer in einem Landolt-System ausgeübten reduzierenden Wirkung

Zusammenfassung Im Bromat-Jodid-Ascorbinsäure-System hängt die Zeit, die bis zur Jodausscheidung vergeht, von der Konzentration der Ascorbinsäure ab. Unter entsprechenden Versuchsbedingungen ist die Reaktionszeit proportional der Ascorbinsäurekonzentration. Danach kann die Ascorbinsäure sowohl mit Hilfe der Simultankomparationsmethode, als auch chronometrisch bestimmt werden. Die Genauigkeit ist ± 3% im Bereich von 5 bis 300g/5 ml. Die Grenzen der Bestimmung sind 1g bzw. 1000g Ascorbinsäure in 5 ml.

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Determination of ascorbic acid on the basis of its reducing action in a landolt system

Summary In the bromate-iodide-ascorbic acid system, the time that elapses until the iodine appears is dependent on the concentration of the ascorbic acid. Under appropriate experimental conditions, the reaction time is proportional to the ascorbic acid concentration. Accordingly, the ascorbic acid may be determined with the aid not only of the simultaneous comparison method but also chronometrically. The precision is ± 3% in the 5–300g/5 ml range. The limits of the determination are 1g and 1000g ascorbic acid in 5 ml respectively.

     

Die katalytischen Reaktionen bei der Spurenanalyse und die Untersuchung ihrer Mechanismen. II Untersuchung der Tiron—H2O2-Reaktion

Zusammenfassung Die Oxydation von Tiron durch H₂O₂ in basischem Milieu wird durch Kobalt stark katalysiert. Die katalysierten Vorgänge sind p_H-abhängig. Im p_H-Bereich 9 bis 11 entsteht ein rotes Oxydationsprodukt unbekannter Struktur; wahrscheinlich handelt es sich um ein o-Chinonderivat. Mit Hilfe der katalytischen Reaktion können 10^–4 g Kobalt/5 ml nachgewiesen werden. In diesem p_H-Bereiche stabilisiert Tiron H₂O₂ bei 100° C, bei 40° C jedoch katalysiert es — in Abhängigkeit von der Konzentration des Tirons — den Zerfall des H₂O₂. Der Effekt spielt im Mechanismus der katalysierten Reaktion wahrscheinlich eine Rolle, doch können die Zusammenhänge an Hand der bisher veröffentlichten Angaben nicht klar gedeutet werden. Der die Reaktion begleitende bzw. ihr folgende Nebenvorgang kann auf den katalytischen Zerfall des H₂O₂ · OOH-Komplexes zurückgeführt werden. Zwischen p_H 7 und 9 entsteht bei der katalysierten Reaktion Semichinon, über p_H 11 oxydiert Tiron das Semichinon unter Ringspaltung und Abspaltung von 1 Mol Sulfat zu Verbindungen, die Säurecharakter tragen.

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Summary The oxidation of Tiron by H₂O₂ in basic milieu is strongly catalyzed by cobalt. The catalyzed reactions are p_H-dependent. A red oxidation product of unknown structure results in the p_H range 9 to 11; probably it is ano-quinone product. As little as 10^–4 g cobalt/5ml can be detected by this catalytic action. In this p_H region, Tiron stabilizes H₂O₂ at 100° C, but at 45° C it catalyzes the decomposition of H₂O₂, in relation to the concentration of the Tiron. The effect probably plays a rôle in the mechanism of the catalyzed reaction, but the up to now published informations are not sufficient to clarify the relationships. The auxiliary process, accompanying or following the reaction, can be attributed to the catalytic decomposition of the H₂O₂-OOH^– complex. Semiquinone is produced by the catalytic reaction between p_H 7 and 9, above p_H 11, the Tiron oxidizes the semiquinone with opening of the ring and splitting off of 1 mol of sulfate yielding compounds which have an acidic character.

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Résumé L'oxydation du Tiron par H₂O₂ en milieu basique est fortement catalysée par le cobalt. Les processus de catalyse dépendent du p_H. Dans le domaine de p_H de 9 à 11, il apparaît un produit d'oxydation rouge, de structure inconnue; il s'agit probablement d'un dérivé de l'o-quinone. La réaction catalytique permet de déceler 10^–4 g cobalt/5 ml. Dans ce domaine de p_H, à 100° C le Tiron stabilise l'eau oxygénée et à 45° C, suivant sa concentration, il catalyse la décomposition de l'eau oxygénée. L'effet joue probablement un rôle sur le mécanisme de la réaction catalysée; on ne peut pourtant pas interpréter clairement ces relations au moyen des indications publiées jusqu'ici. Le processus secondaire qui accompagne la réaction ou qui la suit, peut être ramené à la décomposition catalytique du complexe H₂O₂-OOH^–. Entre p_H 7 et 9, la réaction catalysée donne naissance à une semiquinone; au-dessus de p_H 11, le Tiron oxyde la semi-quinone avec ouverture du cycle et élimination d'une mole de sulfate ce qui donne ensuite des composés qui portent le caractère acide.

     

Synthesis,spectroscopic studies,and x-ray crystallographic analysis of the organotin carbohydrate: 1,2∶3,4-di-O-isopropylidene-6-O-triphenylstannylmethyl-α-D-galactopyranose

The title organotin carbohydrate, C₃₁H₃₆O₆Sn, has been synthesized and its molecular structure has been determined in solution and in the solid state. NMR, infrared, mass and X-ray crystallographic techniques were used. The chiral molecules crystallize in the monoclinic space group P2₁ withZ=2. The triphenyltin and carbohydrate moieties are linked by a trans methylene-oxygen-methylene arrangement. The pyranosyl ring adopts a twist-boat conformation and the isopropylidene rings adopt different (half-chair and envelope) forms. Solution and solid-state conformations are similar as only three ¹³C shift values are greater than 2ppm; the ¹¹⁹Sn value is 12 ppm.     

A simple procedure for the quantitative microdetermination of rhamnose

Summary A simple spectrophotometric procedure for microdetermination of rhamnose is described. It is based on breakdown of the sugar with sulphuric acid followed by treatment withp-hydroxydiphenyl. The coloured product is measured spectrophotometrically at 560 nm. A linear relationship exists between the amount of rhamnose (10-0g–) and the absorbance. The method is recommended for determination of rhamnose in samples containing rhamnose, different neutral sugars, amino-sugars, sugar alcohols, uronic acids, and muramic acid.

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Zusammenfassung Ein einfaches spektralphotometrisches Verfahren zur Mikrobestimmung von Rhamnose wurde beschrieben. Es beruht auf der Spaltung des Zuckers mit Schwefelsäure und nachfolgender Behandlung mit p-Hydroxydiphenyl. Das gefärbte Reaktionsprodukt wird spektralphotometrisch bei 560 nm gemessen. Die Extinktion steht mit der Rhamnosemenge in linearer Beziehung. Das Verfahren wird für die Rhamnosebestimmung in Proben empfohlen, die verschiedene Neutralzucker, Aminozucker, Zuckeralkohole, Uronsäuren und Muramsäure enthalten.

     

A simultaneous TG–DTA study of the thermal decomposition of 2-hydroxybenzoic acid, 2-carboxyphenyl ester (salsalate)

Simultaneous thermogravimetry–differential thermal analysis (TG–DTA) and gas and liquid chromatography with mass spectrometry detection have been used to study the kinetics and decomposition of 2-hydroxybenzoic acid, 2-carboxyphenyl ester, commercially known as salsalate. Samples of salsalate were heated in the TG–DTA apparatus in an inert atmosphere (100 ml min⁻¹ nitrogen) in the temperature range 30–500 °C. The data indicated that the decomposition of salsalate is a two-stage process. The first decomposition stage (150–250 °C) had a best fit with second-order kinetics with E_a=191–198 kJ/mol. The second decomposition stage (300–400 °C) is described as a zero-order process with E_a=72–80 kJ/mol. The products of the decomposition were investigated in two ways:

(a)Salsalate was heated in a gas chromatograph at various isothermal temperatures in the range 150–280 °C, and the exit gas stream analyzed by mass spectrometry (GC–MS). This approach suggested that salsalate decomposes with the formation of salicylic acid, phenol, phenyl salicylate, and cyclic oligomers of salicylic acid di- and tri-salicylides.

(b)One gram samples of salsalate were heated in a vessel under nitrogen to 150 °C, and the residues were analyzed by liquid chromatography–mass spectrometry (LC–MS). The major compound detected was a linear tetrameric salicylate ester.