Dzyaloshinsky-Moriya antisymmetric exchange coupling in cuprates: Oxygen effects

We reconsider the conventional Moriya approach to the Dzyaloshinsky-Moriya antisymmetric exchange coupling for a single Cu₁-O-Cu₂ bond in cuprates using a perturbation scheme that provides an optimal way to account for intra-atomic electron correlations, low-symmetry crystal field, and local spin-orbital contributions with a focus on the oxygen term. The Dzyaloshinsky vector and the corresponding weak ferromagnetic moment are shown to be a superposition of comparable and, sometimes, competing local Cu and O contributions. We predict the effect of oxygen staggered spin polarization in the antiferromagnetic edge-shared CuO₂ chains due to the uncompensated oxygen Dzyaloshinsky vectors. The polarization is perpendicular to both the main chain antiferromagnetic vector and the CuO₂ chain normal. The intermediate ¹⁷O NMR is shown to be an effective tool to inspect the effects of Dzyaloshinsky-Moriya coupling in an external magnetic field. In particular, we argue that the puzzling planar ¹⁷O Knight shift anomalies observed in the paramagnetic phase of the generic Dzyaloshinsky-Moriya antiferromagnetic cuprate La₂CuO₄ can be assigned to the effect of the field-induced staggered magnetization. Finally, we revisit the effects of symmetric spin anisotropy, in particular, those directly induced by the Dzyaloshinsky-Moriya coupling. The perturbation scheme generalizes the well-known Moriya approach and presents a basis for reliable quantitative estimates for the symmetric partner of the Dzyaloshinsky-Moriya coupling. In contrast to the conventional standpoint, the parameters of the effective two-ion spin anisotropy are shown to incorporate the contributions of a single-ion anisotropy for two-hole configurations at both Cu and O sites. The text was submitted by the author in English.     

Azines and Azoles: CXXII. New Regioselective Synthesis of 1-Substituted 6-Alkyluracils

Readily available 5-acyl-4-hydroxy-3,6-dihydro-2H-1,3-thiazine-2,6-diones with primary alkyl- and arylamines in mild conditions (boiling in propan-2-ol) to give Schiff bases. In more rigid conditions (boiling in DMF), the reaction is accompanied by COS liberation and provides 1-substituted 6-alkyluracils. This previously unknown reaction possesses a considerable synthetic potential and can be considered as a new, general, and regioselective synthetic approach to 1-substituted 6-alkyluracils.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 146–158.Original Russian Text Copyright © 2005 by Yuskovets, Moskvin, Mikhailov, Ivin.For communication CXXI, see [1].     

Dissolved oxygen removal from aqueous media by the chromatomembrane method

The possibilities of the new chromatomembrane method in the removal of oxygen dissolved in water are studied. The scheme of the water deoxygenation process is determined. The new reagent-free method allows production of water with oxygen content at the level of a few ppb.     

Determination of polonium in aqueous media using metal-containing membranes

A rapid method has been developed for the determination of polonium in water. The samples with a volume of 0.25 to 4.0 1 were filtered at a flow rate of 2 to 3 1 h^–1 on a membrane filter impregnated with silver. Optimum conditions are 0.1M hydrochloric acid in the presence of 0.01M ascorbic acid. After the filtration the membranes are flushed, dried and measured for -activity. The detection limit for a 41 sample with a membrane diameter of 35 mm is lower corresponding to 1.5×10^–3 Bq.1^–1. The method permits activity measurement with an -radiometer or -spectrometer with an error less than 30% at a confidence level of 0.95.     

Supertransferred hyperfine interaction in magnetic insulators (II)

The important mechanisms of supertransferred hyperfine (STHF) interactions in N–O–M chains are briefly discussed: (i) spin polarization ofns states in the N-ion due to the s-d exchange interaction,H _STHF ^sd ; (ii) contributions of spin-polarized states of the intervening O-ion,H _STHF ^II ; (iii) transfer of d-electrons of the M-ion to emptyns states in the N-ion,H _STHF ^III . The dependence ofH _STHF upon the N–O–M bond configuration, electronic structure, and orbital state of the M-ion is presented in a convenient form. The STHF interactions in the chains Sn⁴⁺–O^2––Fe³⁺, Cr³⁺ in compounds with slightly distorted Perovskite structure are considered. The STHF field in the chain Sn⁴⁺–O^2––Cr³⁺ is shown to change the sign within the range of angles near 170°. This conclusion is in line with published data on the isoelectronic chain Sn⁴⁺–O²–Mn⁴⁺ in the compounds Ca_1–x Sr _x MnO₃. The results obtained for the N–O–Fe³⁺ chain are rationalized by the predicted angular dependence ofH _STHF=+ cos + cos². Features of the STHF interactions in N–O–M chains with an M-ion in an orbital degenerate state are examplified by a preliminary analysis of N–O^2––V³⁺ chains in orthovanadites.     

Transport properties of separating membranes MF-4SK during alkaline electrolysis of water

The transport properties of separating membranes MF-4SK are studied during electrolysis of H₂O in solutions of KOH. The effective diffusion coefficients of molecules of KOH and H₂O and the transfer coefficients of ions K⁺ and OH^? and molecules of H₂O are measured at KOH concentrations reaching 11 M, currents reaching 0.31 A cm^?2, at ambient temperature and at 80°C. In contact with a KOH solution in the concentration interval 0.1 to 11 M, the membranes that initially swelled in H₂O lose a considerable fraction of water that was present in them and the overall volume of clusters and solution-filled channels in them noticeably decreases. The coefficients of transfer by current of ions K⁺ out of anodic compartment into cathodic and the OH^? ions in the reverse direction, respectively, happen to be equal to about 0.6 and 0.4 at ambient temperature and 0.8 and 0.2 at 80°C. The coefficients of transfer of water molecules out of the anodic volume into the cathodic volume in the process of electrolysis happen to be in the limits 1.6–1.9 at ambient temperature and in the limits 2.2–2.8 at 80°C. The effective diffusion coefficients of molecules of KOH and H₂O at moderate concentrations of KOH (5.6 M) amount to ～2.6 × 10^?7 and 30 × 10^?7 cm²s^?1 at ambient temperature and ～4 × 10^?7 and 61 × 10^?7 cm²s^?1 at 80°C, respectively. At a high concentration of KOH (～10 M) these quantities substantially diminish.     

Membrane Methods of Substance Separation in Analytical Chemistry

A review of the membrane methods of substance separation used in analytical chemistry is presented. Membrane methods based on gas-diffusion separation and dialysis extraction, membrane filtration, membrane extraction, and chromatomembrane separation are considered. The possibility of combining membrane methods with modern methods of substance determination, such as flow-injection analysis, gas and liquid chromatography, capillary electrophoresis, mass spectrometry, and so on is discussed. The list of references consists of 200 items.     

Azoles and Azines: CXIX. Alkylation of 5,5'-(4-Nitrobenzylidene)bis(2-thiobarbituric) Acid and 5-(4-Nitrophenyl)-2,8-dithioxo-5,7,8,9-tetrahydro-2H-pyrano[2,3-d:6,5-d']dipyrimidine-4,6(1H,3H)-dione with Haloacetic Acids and Their Esters

5,5'-(4-Nitrobenzylidene)bis(2-thiobarbituric) acid and 5-(4-nitrophenyl)-2,8-dithioxo-5,7,8,9-tetrahydro-2H-pyrano[2,3-d:6,5-d']dipyrimidine-4,6(1H,3H)-dione, similar to unsubstituted 2-thiobarbituric acid, readily react with haloacetic acids and their esters to form regioselectively the S-alkylation products. The alternative routes fo 5,5'-(4-nitrobenzylidene)bis[(4-hydroxy-6-oxo-1,6-dihydropyrimidine-5,2-diyl)sulfanyl]diacetic acids, based on condensation of 4,6-dihydroxypyrimidin-2-ylthioacetic acid with carbonyl compounds followed by cyclodehydration to [(5-(4-nitrophenyl)-4,6-dioxo-3,5,6,7-tetrahydro-4H-pyrano[2,3-d:6,5-d']dipyrimidine-2,8-diyl)di(sulfanyl)]diacetic acid derivatives, are less efficient. Alkylation of 2-thiobarbituric acid with ethyl bromoacetate in ethanol in the presence of alkali yields 5-(2-oxo-2,5-dihydro-1,3-thiazol-4-yl)-2-thiobarbituric acid.