Microdetermination of chlorine and bromine in some organic compounds by ion-selective electrodes

Summary The solid state ion-selective chloride and bromide electrodes are used for the microdetermination of chlorine and bromine in organic compounds. After combustion in an oxygen-filled flask, potentiometric titration with silver nitrate at pH 5–7 in presence of 50% dioxan is carried out. Results accurate to ±0.3% absolute are obtained with some partially and highly halogenated compounds.

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Mikrobestimmung von Chlor und Brom in einigen organischen Verbindungen mit Hilfe von ionenselektiven Elektroden

Zusammenfassung Chlorid- und bromidselektive Festkörperelektroden wurden zur Chlor- und Brombestimmung in teilweise bzw. hochhalogenierten organischen Verbindungen benutzt. Nach Verbrennung im Sauerstoffkolben erfolgt eine potentiometrische Titration mit Silbernitrat bei pH 5–7 in Gegenwart von 50% Dioxan. Die erhaltenen Ergebnisse sind auf ±0,3 % genau.

     

Synergism in the solvent extraction of samarium by thenoyltrifluoroacetone and triphenyl or trioctyl phosphine oxide mixture

Synergistic extraction of samarium with TTA(HA) and TPPO or TOPO (B) mixtures were investigated. The extracted complex was proved to have the general formula SmA₃ · 2B. A graphical determination for the formation constants of these complexes gave the values 3.9 × 10¹³ and 8.2 × 10¹⁰ for SmA₃ · 2TOPO and SmA₃ · 2TPPO in benzene, respectively.     

Studies on indian medicinal plants-XLIV: Solanoforthine,a new steroidal alkaloid from solanum seaforthianum. a note on the mass spectrum of solanocapsine

The structure of solanoforthine, m.p. 208–10°, [α]_D- 26.6°, a new steroidal alkaloid isolated from Solanum seaforthianum Andr., has been established as 3β-amino-22,26-epimino-16α,23-epoxy-22αH,25βH-cholest- 5- en -23β - ol 3, based on chemical and spectroscopic evidence and by its reduction to solanocapsine 2, another steroidal alkaloid encountered in the same species. The mass spectra of2 and 3 are discussed.     

Enantioselective synthesis of functionalized γ-butyrolactones

Sharpless asymmetric dihydroxylation and aminohydroxylation of (E)-dimethyl-2-alkylidene glutarates 2 were shown to afford enantio-enriched or enantiopure highly functionalized γ-butyrolactones 3 and 7.     

Single nanocrystal arrays on patterned poly(ethylene glycol) copolymer microstructures using selective wetting and drying

Single nanocrystal arrays were fabricated on sub-microwells of poly(ethylene glycol) (PEG) copolymer using selective wetting on the hydrophilic regions of the exposed substrate surface and subsequent drying. Templates were produced by molding a thin film of a PEG-based random copolymer on hydrophilic substrates such as glass or silicon dioxide. The polymeric microstructures provide a topographical barrier around the well, which makes it possible to create nanocrystal arrays with controlled geometrical features. The size of the nanocrystal was found to decrease with decreasing well size and also decrease with decreasing topological height. A simple empirical equation was derived to predict the size of the crystal as a function of the pattern size and height, which is in good agreement with the experimental data.     

Comparison of analytical techniques to quantify malondialdehyde in milk powders

Several analytical methods were compared to quantify malondialdehyde (MDA) in milk powders. Modified thiobarbituric acid (TBA) methods, using either visible spectrophotometry (direct absorbance reading or after third derivative transformation of the spectrum) or HPLC, required derivatisation at elevated temperature, which appeared to catalyse artefactual MDA formation and thus overestimate the MDA content. In contrast to the TBA derivatisation method, the measurement of MDA as the dinitrophenylhydrazone derivative by HPLC or as the phenylhydrazone product by GC-MS with a deuterated internal standard resulted in lower estimates in the ranges of 2-17- and 3-30-fold, respectively; apparently due to the milder derivatisation conditions. The estimates of MDA determined by both HPLC-UV and GC-MS techniques result in lower values which are similar in magnitude even though the GC-MS technique is more sensitive.     

Umbellactal, a novel diterpenoid from the Formosan soft coral Xenia umbellata

Umbellactal, isolated from the soft coral Xenia umbellata, is an unprecedented diterpenoid. The structure of umbellactal was established by extensive analysis of spectroscopic data.     

Microdetermination of the fluoride ion using an amplification reaction

Summary A new simple, rapid and accurate amplification micro method for fluoride determination is described. It is based on the reaction between the sparingly soluble calcium iodate and the fluoride ion. After adding isopropyl alcohol to the solution, so that its final concentration is 65%, and filtering, an equivalent amount of the iodate is obtained. The latter is titrated iodometrically resulting in a six-fold amplification of the titre. The method is reproducible over a range from 0.4–8 mg fluoride ion. The mean recovery is 99.69%, after applying a correction factor due to potassium iodate solubility.

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Zusammenfassung Ein Multiplikationsverfahren zur Mikrobestimmung von Fluorid wurde beschrieben. Es beruht auf der Umsetzung zwischen dem schlecht löslichen Calciumjodat und Fluorid. Nach Zusatz von i-Propylalkohol, bis die Lösung 65% davon enthält, wird filtriert. Die äquivalente Jodatmenge wird jodometrisch titriert. Zwischen 0,4 und 8 mg Fluorid sind die Ergebnisse reproduzierbar. Bei Anwendung eines Korrekturfaktors wegen der Löslichkeit von Kaliumjodat wurden 99,69% Fluorid wieder gefunden.

     

The unusual cyclic products from tetra- and penta-peptides of α-methylalanine

Tetra- and pentapeptides of α-methylalanine give with PCl₅, SOCl₂ etc. intermediates which, with or without loss of amino adds, lead to bi- and tricyclic products containing imidazole and piperazine rings through different routes.     

X=Y=ZH Systems as potential 1,3-dipoles. Part 58: Cycloaddition route to chiral conformationally constrained (R)-pro-(S)-pro peptidomimetics

Imines of (1S,9S)-t-butyl-9-amino-octahydro-6,10-dioxo-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate undergo thermal (toluene, 110°C) or LiBr-DBU catalysed (MeCN, room temperature) regio- and stereo-specific cycloaddition to a range of chiral dipolarophiles giving enantiopure spiro-cycloadducts in excellent yield. The reactions proceed via intermediate NH azomethine ylides and litho azomethine ylides, respectively and results in the multiplication of chiral centres from 2 (one of which is lost in the process) to 5.