Substoichiometric determination of heavy rare earths by isotopic dilution analysis

A substoichiometric method for the determination of heavy rare earths (holmium, thulium) has been developed. After the addition of a substoichiometric amount of EDTA to the test sample of rare earth labelled with its radioactive isotopes, the negatively charged complex formed was separated by passage through a column of Dowex 50 x 8. Interfering metals can be removed by preliminary cupferron and diethylammonium diethyldithiocarbamate extraction. Concentrations of rare earth down to 4 x 10(-7)g 5 ml have been determined.     

Preparation and stereoselectivity of 1,3-dipolar cycloaddition ofD-glucose-derived nitrones to N-arylmaleimides

Summary Nitrones2 derived fromD-glucose oxime and benzaldehydes without employing any protection of hydroxyl group were isolated in pure state. The 1,3-dipolar cycloaddition of2 to N-arylmaleimides gave predominantly theanti isoxazolidines3 and was rationalized byZ/E isomerization of N-glycosylnitrones2. The structure and steric configuration of the products have been assigned on the basis of¹H- and¹³C-NMR spectroscopy. AM1 calculations of the nitrones and MM2 calculations of the adducts were performed.

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Darstellung und Stereoselektivität der 1,3-dipolaren Cycloaddition vonD-Glucose-abgeleiteten Nitronen an N-Arylmaleimiden

Zusammenfassung Die Nitrone2 wurden ausD-Glucoseoxim und Benzaldehyden ohne Schutz von Hydroxylgruppen in reinem Zustand erhalten. Die 1,3-dipolare Cycloaddition von2 an N-Arylmaleimiden ergab bevorzugt dieanti-Isoxazolidine3; dies wurde über eineZ/E-Isomerisierung der N-Glycosylnitrone2 rationalisiert. Struktur und Stereochemie wurden auf Basis von¹H- und¹³C-NMR-Spektroskopie ermittelt. Außerdem wurden AM1-Berechnungen an den Nitronen und MM2-Rechnungen an den Addukten ausgeführt.

     

Structure and Thermodynamics of NaF-AlF(3) Melts with Addition of CaF(2) and MgF(2)

The NaF-AlF(3) system with additions of CaF(2) and MgF(2) has been studied with Raman and vapor pressure measurements for 3 >/= CR (NaF/AlF(3) molar ratio) >/= 1 and up to 50 mol % additive. The results show that the binary melt can be described using the two equilibria AlF(6)(3)(-) = AlF(6)(2)(-) + F(-) and AlF(5)(2)(-) = AlF(4)(-) + F(-) with equilibrium constants 0.25 and 0.05, respectively, at 1293 K. Both reactions have positive reaction enthalpies. The first equilibrium is strongly shifted to the right resulting in a melt mixture with very low AlF(6)(3)(-) concentrations even at the Na(3)AlF(6) composition. Evidence for nonideal mixing of anions was found. For the ternaries, models based on Raman data are presented and compared with vapor pressure measurements. Good agreement is observed when association between the additives, CaF(2) or MgF(2), with the AlF(5)(2)(-) ions in the melt was considered. This association could be experimentally observed through a band broadening and a slight shift in the AlF(5)(2)(-) band frequency. Our vapor pressures and Raman data both indicate that MgF(2) clearly acts as an acid when added to NaF-AlF(3) melts of any composition. When CaF(2) is added, a slight decrease of vapor pressure occurs. Raman data indicate a decrease of AlF(4)(-) concentration, corresponding to a dissociation of CaF(2) with liberation of F(-) ions. All these results are, however, very much dependent on the initial melt composition. These data are explained in terms of acid-base, dilution, and association reactions of the solute with the solvent.     

Einige bestrahlungsexperimente mit 2, 1-Benzisothiazolen

Some Irradiation Experiments with 2, 1-Benzisothiazoles 2, 1-Benzisothiazole ( 1 ) on irradiation with a mercury high-pressure lamp in benzene/diethylamine yields, after acetylation, 2-acetylamino-benzaldehyde ( 3 ; Scheme 1). Similarly, irradiation of 3-chloro-2, 1-benzisothiazole ( 2 ) in benzene/diethylamine leads to a mixture of 3-dimethylamino-2, 1-benzisothiazole ( 6a ) and N, N-diethyl-thioanthranilamide ( 7a ; Scheme 2). Benzisothiazole 6a , on irradiation, is not transformed into 7a . On the other hand, when 2 is irradiated in methanol a mixture of 3-methoxy-2, 1-benzisothiazole ( 4a ) and methyl anthranilate ( 5a ; Scheme 2) is obtained. In this case, 4a on irradiation in methanol or ethanol also yields 5a . No exchange of the methoxy group in 4a is observed when the irradiation is performed in ethanolic solution. Thus, 2, 1-benzisothiazoles 1 , 2 and 4a react photochemically by N,S-bond cleavage and hydrogen-atom abstraction from the solvent (Scheme 3). 3-Chloro-2, 1-benzisothiazole ( 2 ) shows a second photoreaction, i.e. nucleophilic exchange of the chloro substituent by methanol or diethyl amine. The latter reaction can also be observed thermally, e.g. in boiling methanol in the presence of methoxide ions.     

Classification of wheat varieties: use of two-dimensional gel electrophoresis for varieties that can not be classified by matrix assisted laser desorpiton/ionization-time of flight-mass spectrometry and an artificial neural network

Analyzing a gliadin extract by matrix assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS) combined with an artificial neural network (ANN) is a suitable method for identification of wheat varieties. However, the ANN can not distinguish between all different wheat varieties. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) was applied to three pairs of wheat varieties, which can not be classified correctly by ANN. By 2-D PAGE the varieties in the three pairs can be discriminated and these six wheat varieties can be separated from each other, which could not be separated by MALDI-TOF-MS and NN.     

An Efficient Straightforward Synthesis of Benz[a]azulene

Benz[a]azulene ( 1 ) is synthesized in five steps (cf. Scheme 2) starting from commercially available 2-iodobenzyl alcohol ( 4 ) and tropylium tetrafluoroborate in an overall yield of 44%. The key step (cf. also Scheme 1) is the intramolecular Heck reaction of the 8-phenylsulfonyl-substituted heptafulvene 7 , which leads in nearly quantitative yield directly to 10-(phenylsulfonyl)benz[a]azulene ( 8 ). The desulfonylation of 8 can be accomplished by Julia's method with Na₂S₂O₄/NaHCO₃ in DMF/H₂O at 85–90°, thus leading to pure 1 in 78% yield. The phenylation of 8 with PhLi or PhCul at ?78° in THF occurs regioselectively at C(9). Dehydrogenation of the formed dihydroazulenes with o-chloroanil in toluene at room temperature gives 9-phenyl-10-(phenylsulfonyl)-benz[a]azulene ( 9 ) in 70% yield (cf. Scheme 3), which, again, can be desulfonylated with Na₂S₂O₄/NaHCO₃ in DMF/H₂O in good yields. The addition of PhLi to 1 in THF occurs at temperatures ? ?25°. Ionic dehydrogenation (1. Ph₃C⁺BF/MeCN; 2. Et₃N) of the dihydro forms leads to 3 , as the main product, and its positional isomers.     

Isentropic partial molal compressibilities of alcohols in propylene carbonate at 25°C

The isentropic coefficients of compressibility of the homologous series of alcohols and diols R _n CH₂OH (n=2–6), CH₃CHOHR _n (n=1–5), 1,2-propanediol, 1,3- 1,4- and 2,3-butanediol, 1,5-pentanediol, and 1,7-heptanediol dissolved in propylene carbonate have been measured at 25°C. Isentropic partial molal compressibilities and group partial molal compressibilities at infinite dilution have been evaluated. The isentropic partial molal compressibilities of these alcohols and diols have been compared with the corresponding values in water. This comparison shows that the values in propylene carbonate are higher than in water by a factor of 10 due to an increased compressibility of the solvation sheath around nonpolar groups in PC.     

Photobleaching of radiation induced trapped electrons in neutral and alkaline glasses. Hydrogen atom formation

Photomobilization of trapped electrons in 7 M NaClO₄- and 9 M NaOH-glass gives rise to trapped hydrogen atoms. This is probably due to the reaction e^?_m + H₂O → H + OH^?. Experiments with an electron scavenger indicate that electrons are not precursors to radiolytically produced hydrogen atoms. It seems that the mobile electrons produced during photobleaching are not slowed down to thermal energy before they react to produce hydrogen atoms, since the yield of the latter species is strongly dependent on the wavelength of the bleaching light.     

Isotherme und thermisch stimulierte Depolarisation in Polyäthylen

Zusammenfassung An verschiedenen Modifikationen eines Polyäthylens niederer Dichte wurden thermisch stimulierte Ströme (TSC) und isotherme Depolarisationsströme gemessen. Die thermisch stimulierten Ströme zeigen Maxima im Bereich der ß- und -Relaxationen der molekularen Beweglichkeit des Materials und weitgehende Übereinstimmung mit mechanischen und dielektrischen Verlustfaktormessungen. Die Zeitabhängigkeit isothermer Depolarisationsströme folgt im untersuchten Temperaturbereich 80 bis 320 K einem Potenzgesetzjt ^–n mitn ¨ 1. Die gesamten Depolarisationserscheinungen sind auf die Relaxation in die Polyäthylenkette eingebauter Dipole zurückzuführen und die Ergebnisse können mit Hilfe des Fröhlich-Modells der Dipolorientierung durch ein kontinuierliches Relaxationszeitspektrum beschrieben werden. Die Messung thermisch stimulierter Ströme erweist sich als einfaches Hilfsmittel das Spektrum der molekularen Beweglichkeit abzutasten.Die diesem Vortrag zugrunde liegenden Arbeiten werden mit Mitteln des Bundesministers für Forschung und Technologie im Rahmen des Technologieprogramms gefördert. Die Verantwortung für den Inhalt liegt jedoch allein bei den Autoren.