Investigation of h complexes of 2-thienyl phenyl ketones by IR spectroscopy

The shifts of the stretching vibrations of the hydroxyl groups of phenol and pentachlorophenol during the formation of intermolecular hydrogen bonds with 2-thienyl phenyl ketones containing substituents in the benzene ring were measured. A correlation dependence between theD _OH values and ⁺ substituent constants was established.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 482–485, April, 1974.     

Kinetic modelling of the thermal oxidation of polyisoprene elastomers. Part 1: Unvulcanized unstabilized polyisoprene

The thermal oxidation of an unvulcanized, unstabilized polyisoprene rubber (IR) has been studied in the 40-140 °C temperature range. Ageing was monitored by FTIR determination of double bonds and carbonyl groups, mass uptake measurement, and weight average molar mass determination. A mechanistic scheme based on the standard scheme for radical chain oxidation, but taking into account the diversity of initiation processes and the existence of inter- and intramolecular radical additions to double bonds, was built. The kinetic model derived from this scheme is composed of seven differential equations to be solved in discrete thickness layers to take into account the kinetic control by oxygen diffusion. This system was numerically solved using a Matlab program dedicated to stiff systems of differential equations. The elementary rate constants and other kinetic parameters were then determined from experimental data, using an inverse approach. A set of physically reasonable parameter values was obtained, thus allowing us to envisage lifetime predictions at low temperature (long term). The results led to observations difficult to make from classical analytical studies, for instance the predominance of bimolecular hydroperoxide decomposition among other initiation modes or the competition between intermolecular hydrogen abstraction and intramolecular addition of peroxy radicals to double bonds.     

Colorimetric method for the determination of vanadium with tannic acid in water and oils

A new spectrophotometric method was developed to determine vanadium using tannic acid as a complexing reagent to form a coloured reaction product which can easily be extracted by 1-pentanol in the presence of cetylpyridinium. The developed method can successfully be applied to determine trace levels of 10 ng/ml of vanadium in natural waters without any preconcentration step. It can also determine less than 1 mg/kg of vanadium in edible oils and petroleum products.     

Electron impact mass spectrometry of the acetates of zinc,magnesium, cobalt and manganese

The electron impact mass spectra of the acetates of zinc, magnesium, cobalt and manganese have been investigated using a direct inlet probe. Volatile tetrahedral complexes are produced on heating, and ions of the form [M₄(OCOCH₃)₆O]^+˙ (M = Co and Mn) and [N₄(OCOCH₃)₅O]⁺ (N = Zn or Mg) are observed. A mixture of magnesium and cobalt acetates produces ions of the form [Mg_nCo_4–n(OCOCH₃)₆O]^+˙.     

Azo coupling and aminomethylation of 2,5-diphenylpyrrole and its derivatives

The azo coupling of 2,5-diphenylpyrrole with arenediazonium chlorides has given previously unknown 3-arylazopyrroles and 4-phenylazo-3-phenylhydrazono-3H-pyrrole. The methylation and reductive acetylation of the anylazo derivatives have led to N-methylarylazo and acetylamino derivatives of 2,5-diphenylpyrrole. 3-Amino-2, 5-diphenylpyrrole has been obtained by the reduction of 3-p-chlorophenylazo-2,5-diphenylpyrrole. The aminomethylation of 2,5-diphenylpyrrole and its derivatives with bis(dialkylamino)methanes had led to aminomethyl derivatives.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5. pp. 612–615, May, 1986.     

Research on the aromas. On the aroma of coffee. I

The analysis of a coffee concentrate is described: 202 constituents have been identified, 154 of which for the first time. Some of these compounds are new chemicals; their synthesis is described. Most identifications are based upon mass spectrometry combined in many cases with IR. spectrometry and comparison with reference compounds. MS. and IR. data are given in detail. The analysis shows that a large number of minor constituents is present, many of which could not be identified.     

Über den Nachweis und die Bestimmung des Schädlingsbekämpfungsmittels E 605 in der gerichtlichen Chemie

Zusammenfassung Es wird gezeigt, daß sich Insektizide auf der Basis der Ester der Thiophosphorsäure (E 605) aus biologischem Material mittels Wasser-dampfdestillation auf verhältnismäßig einfache Weise abscheiden lassen. Im Destillat erfolgt die Bestimmung nach Ausäthern und Lösen des Rückstandes in Äthanol durch Messen der Lichtabsorption im UV. Hierbei zeigt sich, daß die rechnerische Eliminierung der Störstoffe bei geringeren Konzentrationen der Ester leichter ist als bei hohen.Durch Messung der Lichtabsorption im IR läßt sich, genügende Konzentration vorausgesetzt, entscheiden, welcher Ester vorliegt.

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Summary It was shown that insecticides based on the ester of thiophosphoric acid (E 605) can be separated in relatively simple fashion from biological material by means of steam distillation. The distillate is shaken out with ether and the residue dissolved in ethanol and the determination is accomplished by measuring the absorption in ultraviolet light. It was found that the computational elimination of the interfering materials is easier at lower concentrations of the ester than when higher concentrations are present. By measuring the light absorption in infrared, it is possible to decide which ester is present, provided the concentration is high enough.

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Résumé On montre que les insecticides se séparent d'une manière relativement simple de l'élément biologique par un entraînement à la vapeur d'eau sur la base de l'ester de l'acide thiophosphorique (E 605). Le dosage s'effectue sur le distillat d'après l'épuisement à l'éther et la solubilité du résidu dans l'éthanol et la mesure de l'absorption lumineuse dans l'ultraviolet. On en déduit que l'élimination calculée de la substance gênante est plus facile pour les faibles concentrations de l'ester que pour les grandes. En mesurant l'absorption de la lumière dans l'infrarouge, on peut savoir de quel ester il s'agit pour des concentrations supposées suffisantes.

     

3'-nitrophenylpropyloxycarbonyl (NPPOC) protecting groups for high-fidelity automated 5' --> 3' photochemical DNA synthesis

[structure: see text]. The most powerful DNA microarrays would be prepared by photolithography with free 3'-ends that could be processed enzymatically. A photoremovable group that could be removed in quantitative yield would ensure high purity of the synthesized probes. We have developed new pyrimidine building blocks for 5' --> 3' DNA synthesis with high cycle yields using the NPPOC (3'-nitrophenylpropyloxycarbonyl) protecting group. These phosphoramidites were proved in automated photochemical DNA synthesis on a modified synthesizer.     

Preparation of alkyl-containing derivatives of chitosan and its oligomers in polymer-analogous reactions

It has been shown that the interaction of chitosan and oligochitosan with unsaturated acrylic esters via the nucleophilic addition mechanism and their condensation with heptadecyl isocyanate yield hydrophobic alkyl-containing derivatives of the above polymers. The method of modification of oligochitosan in reactions via end functional groups is developed.