Greffage radiochimique de l'acrylonitrile dans la masse de films de PTFE

Acrylonitrole can be grafted in the bulk of PTFE films provided the monomer is allowed to diffuse into the grafted zones. For a given radiation dose, the amount of grafting is higher the lower the dose-rate. Even higher grafting efficiencies are reached under conditions of discontinuous irradiations, the reacting mixture being stored in the dark in a thermostat between successive irradiations. The grafting yield is higher the higher the storage temperature. The bulk grafting involves a progressive swelling of the grafted polyacrylonitrile branches by acrylonitrile monomer via a dipole-dipole association of the -CN groups of the monomer with the -CN groups in the polymer.     

A study of 1,2,3,4-tetrahydro-4-azafluorene-3,9-diones

Intramolecular cyclization of the diamides and N,N-dimethylamides of -[indan-1,3-dion-2-yl]benzylmalonic acids (I) has given 1-aryl-2-carbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3, 9-diones and 1-aryl-4-methyl-2-methylcarbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3,9-diones (II). The structure of compounds II was shown by chemical methods: bromination, xanthylation, and hydrolysis in alkaline and acid media, and also by a study of IR and UV spectra.     

Quantum scattering calculation of the O(1D)+HBr reaction

Three-dimensional time-dependent quantum wave packet calculation for the O((1)D)+HBr reaction has been carried out using an accurate ab initio global potential energy surface [K. A. Peterson, J. Chem. Phys. 113, 4598 (2000)]. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well.     

Natural (−)-7-methoxy-8-(β, γ-dihydroxyisopentyl)-coumarin

Chemistry of Natural Compounds - The roots ofPrangos ferulaceae (L.) Lindl. have yielded (?)-7-methoxy-8-(β, γ-dihydroxyisopentyl)-coumarin, composition C15H18O5, with mp 128°....     

Some hydrazides and hydrazones based on N-aminomorpholine and N-aminopiperidine

Some new hydrazides and hydrazones based on N-aminomorpholine and N-aminopiperidine have been synthesized and their antibacterial properties studied.     

Photobinding of ketoprofen in vitro and ex vivo

Ketoprofen (KP), a non-steroidal anti-inflammatory drug of the 2-aryl propionic class, has been shown to produce photoallergic side effects as well as cutaneous photosensitizing properties that induce other phototoxic effects. In the present study we investigated photobinding of ketoprofen to both human serum albumin (HSA), a model protein, and to ex vivo pig skin and its photodegradation. Results demonstrate that photoadduct formation and photodegradation progressively increased with irradiation time where they reach a maximum. Maximum photobinding to the viable layer of the epidermis was about 7-8% of the initial radiolabelled KP added, in the region of 15-30 min UV irradiation. These results were comparable to in vitro results that were seen with photobinding of KP to HSA; in this case, the quantity of covalently bound material was approximately 10% of the initial, after a maximum of 18 min irradiation. It was found by HPLC analysis that the KP decrease is accompanied by an increase of the corresponding photoproduct, decarboxylated ketoprofen (DKP). The yield of DKP reaches a maximum at around 15 min. DKP appears to play an important role in vitro and ex vivo, being the major photoproduct and responsible for the photobinding process. Using micro-autoradiographical techniques we investigated the penetration and distribution of ketoprofen in ex vivo pig skin in greater detail. It was apparent that percutaneous absorption was taking place and that most of the ketoprofen was predominately localised in fibroblasts in the papillary dermis. No other specific localisation within the skin architecture was identified. Although there were differences in the quantities of bound ketoprofen within the different layers of the skin, these levels did not appear to correlate with irradiation time.     

Reactions of (η6-Arene)tricarbonylchromium Complexes: Hydrogenation,Nitration, and Bromination

In this study, we explore the reactions of coordinated arenes, e.g., hydrogenation, nitration, and bromination, to prepare compounds which are not accessible from conventional organic synthesis. The reaction products formed from reactions with the coordinated and the uncoordinated arenes are compared. The polycyclic aromatic hydrocarbons (PAHs) employed for this study include phenanthrene, methyl- and acetyl-phenanthrene, and benz[a]anthracene (BA), The tricarbonylchromium group demonstrated various characteristics which influence the reactions in this work, such as an electronic effect to deactivate hydrogenation, a steric effect to exhibit, highly positional selective nitration, and a free radical mechanism to direct bromine to attack at the ring coordinated to tricarbonylchromium.     

Preparation,and infrared and thermal properties of six adducts of tetrakis-(8-hydroxyquinolinato)thorium(IV)

Six adducts of the tctrakis(8-hydroxyquinolinato) complex of thorium(IV) with 8-hydroxyquinoline, pyridine, urea, dimethylsulphoxide, dimethylformamide and 1,10-phenanthroline were prepared and characterized, the infrared bands for the room-temperature forms are given and their particular thermal properties are reported. The thermal analyses were performed mostly in the presence of air, but in some cases an argon atmosphere was used for comparison. The adducts were lost from the principal complex at temperatures varying between 110 and 290°. Intermediate oxygenated complexes were formed in each case at about 400°. The thermal data suggest the standardization of a procedure for the formation of Th(C₉H₆NO)₄.

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Zusammenfassung Sechs Addukte des Tetrakis(8-hydroxyquinolinato)-Komplexes von Thorium(IV) mit 8-Hydroxyquinolin, Pyridin, Harnstoff, Dimethylsulphoxid, Dimethylformamid und 1,10-Phenanthrolin wurden dargestellt und charakterisiert. Infrarotbanden und spezielle thermische Eigenschaften der Raumtemperatur-Formen sind angegeben. Die thermischen Analysen wurden meist in Luft ausgeführt, in einigen Fällen zu Vergleichszwecken aber auch in Argonatmosphäre. Die Addukte wurden vom Komplex bei Temperaturen zwischen 110 und 290 °C abgegeben. Intermediäre oxydierte Komplexe wurden in jedem Fall bei etwa 400 °C gebildet. Die thermischen Daten ermöglichen die Standardisierung eines Verfahrens zur Darstellung von Th(C₉H₆NO)₄.

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-(8- ) (IV) 8- , , , - , 1,10-. - , . , , . 110–290°. 400° . Th(C₉H₆NO)₄.

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We are grateful to the Bangladesh University Grants Commission for a Fellowship Grant to AR.     

Plasma polymerization. V. A systematic investigation of the inductively coupled RF plasma polymerization of the isomeric tetrafluorobenzenes

A systematic investigation has been made of the composition, gross structural features, and rates of deposition of plasma polymer films produced from the excitation of inductively coupled RF plasmas in the isomeric tetrafluorobenzenes. ESCA data reveal that the dominant reaction involves rearrangement such that under a wide variety of experimental conditions the composition of the crosslinked products remains essentially the same as that of the starting material. Small differences in rates of deposition are observed for the different isomers, and theoretical SCF MO studies at the MNDO level provides a basis for discussion of the experimental data.     

Gas chromatographic determination of alkali metal O,O-diethyl phosphorodithioate present in trace amounts

Summary A gas Chromatographic determination of traces of alkali metal O,O-diethyl phosphorodithioates is described. The salts were converted into a volatile derivative by alkylation with diazomethane. The product was identified by gas chromatography-mass spectrometry. With aqueous samples a linear relationship of peak height to amount of salt was obtained in the range 0.04–1 ng and for urine samples a calibration curve was constructed. The detection limit (signal to noise ratio 4/1) was 40 pg of salt. The procedure was successfully used for monitoring phosalone absorption by occupationally exposed persons.

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Zusammenfassung Eine gaschromatographische Bestimmung von Spuren Alkalisalz des Diäthyldithiophosphorsäureesters wurde beschrieben. Die Salze wurden durch Alkylieren mit Diazomethan in ein flüchtiges Derivat übergeführt. Dessen Identifizierung erfolgte mittels eines gaschromatographisch-massenspektrometrischen Systems. In Wasserproben wurde ein lineares Verhältnis der Peakhöhen und der Salzmenge festgestellt und für Urinproben wurde eine Eichkurve ermittelt. Die Nachweisgrenze (Signal zu Rausch 41) wurde bei 40 pg Salz festgestellt. Die Methode wurde für die Kontrolle der Absorption von Phosalon bei beruflich exponierten Personen erfolgreich angewendet.

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Presented at the Fourth International Congress of Pesticide Chemistry (IUPAC), Zürich, July 24–28, 1978.