lα-hydroxy previtamin D3, and its selective formation from 1-keto previtamin D3

An efficient method for the preparation of crystalline α-hydroxy previtamin D₃ is described. Also the stereoselective reduction of 1-keto previtamin $\text{9}$ is discussed; it was observed that with aluminum hydride $\text{7}$ is the most abundant product. This stands in contrast with previously reported LiAlH₄ and NaBH₄ mediated reductions.     

Globin chain separation by SDS polyacrylamide gel electrophoresis. Simple screening method for elongated hemoglobin chains

A simple method for the separation of hemoglobin chains from hemolysate or globin, by sodium dodecyl sulfate polyacrylamide gel electrophoresis, is described. The alpha, beta, and gamma chains can be clearly separated from each other. The alpha chain has the highest mobility, the beta chain has a slower mobility than the gamma chain, while the delta chain has about the same mobility as the beta chain. Hemoglobins with elongated chains can easily be detected by this method. Tak-beta, elongated by 11 residues, moves much more slowly than betaA but is much faster than alpha Constant Spring which is elongated by 31 residues. Screening of several individuals with slow-moving hemoglobins using this method led to the finding of a case with Hb Tak-beta thalassemia and other carriers of Hb Tak.     

EPR-untersuchungen an carbonsäureestern—III: Thiooxalsäureester-radikalanionen

Polarographic and cyclovoltammetric investigation of the thiooxalates 1–6 shows that they are reversibly reduced to the corresponding radical anions. Accordingly, EPR spectra are obtained after in-situ electroreduction. Taking also the electronic spectra into consideration, conclusions about the spin density distribution can be drawn. It is shown thatp^π is higher at the oxygen atoms of oxoesters than at the sulfur atoms of the corresponding thiono esters.     

Die IR-Spektren der Phasen ABTe3O8 (A = Fe,In, Sc; B = Nb,Ta) und UTe3O9

I.R. Spectra of the Phases A B Te₃O₈ (A = Fe, In, Sc; B = Nb, Ta) and UTe₃O₉ The infrared spectra of the title compounds have been recorded and discussed in comparison to formerly investigated M^IVTe₃O₈ phases. The spectrum of UTe₃O₉ (synthetic cliffordite) confirms the presence of uranyl groups and the structural relation of this compound to the fluorite.     

On the photochemical conversion of an alpha, beta-unsaturated gamma, delta-epoxy ketone: 3-oxo-6-alpha, 7-alpha-oxide-17-beta-acetoxy-Delta-androstane

The α,β-unsaturated γ,δ-epoxyketone 7 is isomerized almost exclusively to the δ-diketone 9 both upon irradiation in the n → π* absorption band with light of wavelengths above 310 nm (in anhydrous dioxane or benzene solutions) and upon triplet sensitization using acetophenone in benzene. The reaction may be formulated by the cleavage of the C_γ? O oxide bond and the shift of the δ-hydrogen to the γ-position, and thus bears a formal “double bond homology” to the photochemical α,β-epoxyketone rearrangement. Excitation in the π → π* absorption band of 7 with light of wavelength 253,7 nm (in anhydrous dioxane solution) leads to the formation of product 10 as well as to the triplet rearrangement to 9 . With this result a novel partial synthesis of O-acetyl-B-nortestosterone has been accomplished, which has the advantages of fewer steps and higher product yield ( 7 → 10 : ～30% yield) than previously published syntheses. On the basis of the presently available experiments, the mechanism of the transformation 7 → 10 , which constitutes one of the still few examples of enone photoreactions induced selectively from the π,π* excited singlet, remains unknown.     

Isolation and cleanup of organophosphorus insecticides and their oxones from animal tissues

Summary A simple isolation and cleanup procedure for the determination of organophosphorus insecticides and their oxones in animal tissues has been developed. This procedure unites partly extraction of organophosphorus pesticides and their oxones with cleanup by column chromatography. Most polar coextracts remain on the column and in its further processing the eluate does not tend to form emulsion. The process has been studied on model mixtures of ³²P- and ¹⁴C-labelled pesticides with tissues as well as after application of pesticides to white rats. The average recovery of the method is 90.5%, with a standard deviation of ±5.1%.

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Isolierung und Reinigung von Organophosphorinsecticiden und ihren Oxonen aus tierischen Gewehen

Zusammenfassung Ein einfaches Isolations- und Reinigungsverfahren wurde ausgearbeitet. Die Extraktion der Insecticide aus einer Homogenatsäule, die aus Kieselgel und Tiergewebe besteht, umfaßt zum Teil auch die Reinigung der Extrakte, da die polaren Verbindungen an die Säule gebunden bleiben. Der Mittelwert der Ausbeute des Verfahrens wurde im Modellversuch mit ¹⁴C- und ³²P-markierten Insecticiden zu 90,5% festgestellt. Die Standardabweichung beträgt ± 5,1%.

     

Étude thermodynamique de la complexation des lanthanides trivalents avec l'acide hydroxyethyl-ethylenediaminetriacetique et d'autres acides aminoacetiques: III. Détermination des Constantes de Formation des Complexes Mixtes par Titrage Potentiométrique

A thermodyrmmic study of the complex formation of trivaient lanthanides with hydroxyethylethyienediaminetriacetic acid and other aminoacetic acids. Part III. The determination of the formation constants of mixed complexes by potentiometric titration.The partial stability constants of the mixed and 1:2 complexes Ln—HEDTA—L (where Ln = La, Ce,... and L = glycine, IMDA, NTA, HEDTA and EDTA) have been determined by potentiometric titration at 25°C and at a constant ionic strength of 1 (KCl). The changes in stability of the complexes studied (1:1, 1:2, mixed, protonated and unprotonated) vs. atomic number of the lanthanide are discussed. The changes observed in the trends of the partial and overall stability constants across the lanthanide series are attributed to the decrease in the number of water molecules in the 1:1 LnHEDTA ·xH₂O from x = 3 for light lanthanides to x = 2 for heavy ones. However, in this 1:1 complex, HEDTA seems to be a hexadeutate ligand in the La—Sm range of the series and a pentadentate ligand in the Gd—Lu range. Significant differences have been found between the complexes containing four nitrogen atoms, i.e. L = HEDTA, EDTA, and those with three nitrogen atoms i.e. L = glycine, IMDA, NTA.     

Solvent extraction for cleaning phosphoric acid in fertilizer production

Phosphorites of sedimentary origin utilized in manufacturing of fertilizer contain uranium, thorium and products of their radioactive decay, as well as health-endangering compounds of cadmium, arsenic and fluorides. Some of them may transit into the phosphoric acid, when breaking down the phosphorites with sulphuric, acid, and then into the fertilizer. The purpose of the phosphoric acid cleaning is its decontamination from uranium and thorium as well as the removal of toxic cadmium. The above task can be achieved by solvent extraction. The paper presents the results of the extraction of uranium and cadmium from phosphoric acid using polyalkyl phosphasene and trioctyl amine, respectively. The extraction kinetics, equilibrium distribution of uranium and cadmium within the phases, the effect of extractant concentrations and temperature of the process is also discussed. The technological schemes for cleaning phosphoric acid from uranium and cadmium are given.     

Recovery of thick shear bands in atactic polystyrene

The DSC thermograms of the shear band material cut out by a diamond saw to include some undeformed material revealed two T_g's clearly separated by about 10°C. The first T_g was at the same temperature as the T_g of the undeformed material. The second T_g, which was at a higher temperature than the first T_g, appeared shortly after the shear strain recovery during the heating of the shear band material in the DSC. When the shear strain in the shear band was partially reversed by mechanical means before taking the DSC thermogram, the ΔT between the two T_g's decreased and when the shear strain was mechanically reversed to almost zero, the second T_g disappeared. The stored energy of shear band material was found to be similar to that of the bulk compressed material for large strains. Dimensional recovery during heating of specimens with thick and fine bands was similar, both taking place above T_g.     

Lifetime measurements of two-photon excited vibronic levels in the low pressure limit: naphthalene

Single vibronic lifetimes of two-photon excited states are measured in the low pressure limit for naphthalene. The two-photon spectrum, besides yielding new states in S₁, is also free of the interference from the neighborhood of the S₂, known from one-photon experiments, and hence unperturbed lifetimes can be measured to higher excess energies. The overall pattern of lifetimes with excess energy including both one-photon and two-photon states shows that the vibronic structure is subordinate to an overall monotonic decrease, much as found earlier for β-naphthylamine. This indicates, at least for naphthalene, that radiationless processes into triplets are dominated by Franck—Condon factors and not by vibronic inductions and promoting modes.