Synthesis and properties of esters and amido esters of 1-(2-thienyl)-2,2,2-trichloroethylphosphorous acid

Conclusions The esterification of amido- and ester-amidophosphites with 1-(2-thienyl)-2,2,2-trichloroethanol gave the l-(2-thienyl)-2,2,2-trichloroethyl dialkyl- and 1-(2-thienyl)-2,2,2-trichloroethyl alkylamidophosphites, which easily add sulfur or are oxidized to the corresponding thiophosphates and phosphates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 182–187, January, 1981.     

Determination of four nitroimidazole residues in poultry meat by liquid chromatography-mass spectrometry

A multi-residue liquid chromatography-mass spectrometry (LC-MS) assay method is described for the determination of four nitroimidazoles in poultry muscle. The extraction procedure is based on liquid-liquid extraction with ethyl acetate followed by an evaporation step. A deuterated internal standard is used. The LC separation was made on a C18 bonded silica column with an aqueous formic acid (0.2%) solution-methanol-acetonitrile (81:13:6) mobile phase. Following electrospray ionization, the protonated molecular ion [M+H]+ is obtained for each compound. Monitoring several ions for each nitroimidazole provides the specificity required for confirmatory assay. Validation of the method was performed to estimate linearity, intra-day and inter-day repeatability, accuracy and detection limit. The present method is capable of identifying nitroimidazole residues in muscle at levels below 5 microg/kg.     

Untersuchung der Temperaturabhängigkeit derg ik -Tensoren von Polyäthyleneinkristallen

Zusammenfassung Es wurden die Kristallitgröße und die Änderungen der parakristallinen Gitterstörungen aus den Linienbreiten des Röntgenweitwinkeldiagramms von lösungskristallisiertem linearem Polyäthylen bei den Temperaturen 15°K, 73°K, 173°K und Zimmertemperatur bestimmt. Es wurde eine Zunahme der Gitterstörungen mit fallender Temperatur gefunden.

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Summary The crystallite size and the paracrystalline distortions in polyethylene single crystals were evaluated by the measurement of the linewidth in the X-ray wide angle diagram at four different temperatures (15°K, 73°K, 173°K and 297°K). An increase of the lattice distortions with decreasing temperature was found.

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Mit 3 Abbildungen

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Vorgetragen auf der Arbeitssitzung des Fachausschusses Physik der Hochpolymeren in der Frühjahrstagung 1970 des Regionalverbandes Hessen-Mittelrhein-Saar der Deutschen Physikalischen Gesellschaft in Darmstadt, 10.–13. März 1970.     

Die Schmelzdiagramme der Systeme CsN3/Zn(N3)2 und KN3/Zn(N3)2

The phase diagrams of the systems CsN₃/Zn(N₃)₂ and KN₃/Zn(N₃)₂ have been obtained employing the microscopic technique ofL. Kofler andA. Kofler. Within the system CsN₃/Zn(N₃)₂ three eutectics at 148°C, 142°C, and 210°C were found. Besides Cs₂Zn(N₃)₄, melting incongruently in the interval 153°C to 170°C, there exist two further compounds of the most probable composition Cs₃Zn₂(N₃)₇ and CsZn₂(N₃)₅, melting congruently at 170°C and 210°C, resp. In the system KN₃/Zn(N₃)₂ there exist two eutectics at 203°C and 172°C and two compounds, one of them, i.e. K₂Zn(N₃)₄, melting congruently at 206°C, the other one, with composition KZn₃(N₃)₇ or KZn₄(N₃)₉, melting incongruently at 210°C.

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Mit 8 Abbildungen

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Herrn Professor Dr.Heribert Grubitsch zum 70. Geburtstag gewidmet.     

Über einige Eigenschaften von Zinkphosphiten mit Berücksichtigung ihrer Wasserstoffbrückenbindung

Zinc phosphites ZnPHO₃·2.5 H₂O, Zn₂H₂P₃H₃O₉·H₂O, Zn₃H₄P₅H₅O₁₅·1.5 H₂O, ZnH₂H₂P₂H₂O₆ have been studied at higher temperatures and by X-rays and molecular spectroscopy. Hydrates ZnPHO₃·2.5 H₂O and Zn₂H₂P₃H₃O₉·H₂O, when heated, yield an anhydrous salt. Thermal decomposition of dihydrogen triorthophosphite and tetrahydrogen pentaorthophosphite leads, before oxidation of the anion, to a mixture of zinc phosphite ZnPHO₃ and dihydrogen diorthophosphite ZnH₂P₂H₂O₆ and then after loss of water of constitution dihydrogen diorthophosphite converts to zinc diphosphite ZnP₂H₂O₅. The results of the thermal decomposition study were confirmed by X-ray investigation. Anhydrous zinc dihydrogen triorthophosphite Zn₂H₂P₃H₃O₉ and zinc diphosphite ZnP₂H₂O₅ were hitherto unknown. Infrared spectra confirmed the existence of hydrogen bonding in all the phosphites studied and in the case of zinc phosphite ZnPHO₃·2.5 H₂O exhibited a symmetry decrease of the anion PHO₃ ^2– from the point group C_3v to C_s. In the crystal lattice of ZnPHO₃·2.5 H₂O hydrogen bonding by water molecules participates, with polyorthophosphites hydrogen bonding shares in the production of anions and in the case of their hydrates there is in addition hydrogen bonding by water molecules.

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Mit 3 Abbildungen     

Hydroxybromierung und Methoxybromierung von (Z)-Cycloocten

In addition totrans-2-bromocyclooctanol andtrans-1,2-dibromocyclooctane,cis-4-bromocyclooctanol,cis-1,4-dibromocyclooctane,trans-1,4-dibromocyclooctane, and (Z)-5-bromocyclooctene are obtained, when (Z)-cyclooctene is treated with N-bromosuccinimide in the presence of water. Similarly the methoxybromination of (Z)-cyclooctene gives transanular products.     

Interaction of dextran sulfates with positively and negatively charged silver bromide hydrosols

Summary The effects of dextran sulfates of different molecular weights and charge densities on the stability of positively and negatively charged silver bromide solsin statu nascendi have been studied by means of light scattering.The plots of scattering intensities of a positively charged sol against the concentration of the added dextran sulfates show one pronounced maximum, the position which is independent on the molecular weight of the polyelectrolyte used. The maximum shifts to lower polyion concentrations with dilution of the sol.The effect of polyanions on the stability of silver bromide sols of the same sign of charge were investigated as a function of molecular weight of the polymers, the sol concentration, the charge and the concentration of counterions, and the addition of methanol. Destabilization only occurred if sufficient amount of indifferent electrolyte was present in the system. However, the concentration of counterions necessary to produce a flocculation maximum was lower in the presence of the polyelectrolytes than in their absence. The results obtained were compared with the data on sols containing nonionic dextrans reported earlier.

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Zusammenfassung Der Einfluß der Dextransulfate von verschiedenen Molekulargewichten und Ladungsdichten auf die Stabilität der positiv und negativ geladenen Silberbromid-Solein statu nascendi wurden durch Lichtstreuung untersucht. Wenn die Intensitäten der Lichtstreuung eines positiv geladenen Silberbromid-Sols gegen die Konzentration der zugesetzten DextranSulfate aufgetragen werden, tritt ein ausgeprägtes Maximum auf, dessen Lage von dem Molekulargewicht des angewandten Polyelektrolyten unabhängig ist. Bei Verdünnung des Sols wird das Maximum zur niedrigeren Konzentration des Polyanions verschoben.Der Einfluß der Polyanionen auf die Stabilität der Silberbromid-Sole mit gleichem Ladungsvorzeichen wurde in Abhängigkeit von dem Molekulargewicht des zugesetzten Dextransulfats, der Solkonzentration, der Ladung und Konzentration der Gegenionen und dem Zusatz von Methylalkohol untersucht. Destabilisierung wird nur in Anwesenheit einer genügenden Menge von Neutralelektrolyten in den untersuchten Systemen beobachtet. Die Konzentration der Gegenionen, die ein Flockungsmaximum verursachen, ist immer niedriger als die kritische Koagulationsmenge derselben Ionen für das gleiche Sol in Abwesenheit von Makroionen. Die Resultate wurden mit den Wechselwirkungen der Silberbromid-Sole mit nichtionogenen Dextranen verglichen, und der Mechanismus der Flockung durch Polyelektrolyte wurde diskutiert.

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5 figures and 1 table

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Supported by the NSF Grant GP 42331 X.

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A part of the Ph.D. Thesis by David Lindsay.     

Reaction of mercury(II) and xylenol orange-I Effect of the buffering media

The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)).     

Crystal structure and magnetic structure of TbOOH

The monoclinic modification of terbium oxide hydroxide, TbOOH, was prepared using hydrothermal technique. The crystal structure was investigated by three-dimensional single-crystal X-ray analysis and was refined to a conventional R-value of 8.1%. The space group is $\text{P2}{}_1\text{m}$, No. 11, with a = 6.04 Å, b = 3.69 Å, c = 4.33 Å, and β = 109.0°. The terbium atom is seven coordinated with oxygen atoms, and the structure is not hydrogen bonded.The compound is antiferromagnetic with a Néel temperature of 10°K. Neutron diffraction powder patterns were measured at 300°K and 4.2°K. The magnetic super lattice reflections were indexed on the basis of a monoclinic unit cell with the dimensions a_M = 2a, b_M = b, c_M = c, and β_M = β, where a, b, c, and β are the dimensions of the chemical unit cell. The structure contains two independent magnetic atoms. A nonclinear antiferromagnetic arrangement of the spins describes the magnetic structure. The spin at one atom has an angle of 43° with the ac plane and the projection of the spin on the ac plane has an angle of 59° with the a axis. The spin on the other atom has an angle of ?43° with the ac plane, the projection having the same angle of 59° with the a axis.     

Semiempirical calculations on triplet and doublet states

Restricted open-shell SCF calculations are carried out on triplet states of electron systems and doublet states of some of their ions. The results are compared with the ones obtained by limited configuration interaction and by the use of Koopman's theorem. For some examples open-shell SCF wavefunctions are expanded into linear combinations of Slater determinants representing configurations built from closed-shell SCF orbitals. This allows a more detailed comparison of the different methods of calculation.

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Zusammenfassung Berechnungen nach der beschränkten SCF Methode für offene Schalen werden an Triplettzuständen von -Elektronensystemen und Dublettzuständen einiger ihrer Ionen ausgeführt. Die Resultate werden mit denjenigen verglichen, welche die beschränkte Konfigurationswechselwirkung und der Satz von Koopmans liefern. Die SCF Wellenfunktionen für offene Schalen werden, für gewisse Beispiele, in Linearkombinationen von Slater-Determinanten entwickelt, welche aus SCF Orbitalen für geschlossene Schalen aufgebaut sind und verschiedene Konfigurationen darstellen. Dies erlaubt einen eingehenderen Vergleich der verschiedenen Berechnungsmethoden.

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Résumé Des calculs selon la méthode SCF avec restriction pour les couches ouvertes sont effectués sur les états triplets de systèmes d'électrons et sur les états doublets de certains de leurs ions. Les résultats sont comparés à ceux obtenus par la méthode d'interáction de configurations limitée et par l'emploi du théorème de Koopmans. Pour certains exemples les fonctions SCF à couches ouvertes sont développées en combinaison linéaire de déterminants de Slater représentant des configurations bâties à partir d'orbitales S.C.F. de couches fermées. Cela permet une comparaison plus détaillée des différentes méthodes de calcul.

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Presented in parts at the Theoretical Chemistry Symposium in Vienna, March 1967.