Plutonium(III) oxidation under α-irradiation in nitric acid solutions

Plutonium(III) oxidation under high energy α-irradiation in nitric acid solutions has been studied relative to concentrations of both nitric acid (0.12–2.9 mol/l) and plutonium (1.4–10 mmol/l) using spectrophotometric techniques. Curium-244 has been used as the basic alpha-irradiation source. It has been stated that in solutions with nitric acid concentrations lower than 0.5 mol/l plutonium(III) does not oxidize completely. In the course of the process the formation of a plutonium(IV) peroxide complex is observed. Increase in the nitric acid concentration results in that in both the rate and degree of plutonium(III) oxidation. When c_{HNO 3} is higher than 0.5 mol/l the peroxide complex does not form and the process assumes an autocatalytic character. It has also been shown that plutonium(III) oxidation kinetics is significantly affected by nitrous acid, one of the nitrate ion radiolysis products. To describe plutonium chemical transformations under irradiation in nitric acid solutions, a kinetic scheme is proposed. The calculations have been carried out on a BESM-6 computer; a satisfactory agreement between the calculated and experimental data has been obtained.     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (Φ/Φ) in the cyclotetrasiloxanes Φ_mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of Φ_mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from Φ_mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes Φ_mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings ΦD₃, Φ₂D₂, Φ₃D, and Φ₄. The reactivity of the siloxane links rises in the sequence ～ (CH₃)₂Si-O-Si(CH₃)₂ ～<～ (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ ～<(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) ～. Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.     

Influence of the method of synthesis on the composition and structure of copper(II) complexes with galactaric acid

The influence of the conditions and the method of synthesis on the composition of copper(II) complexes with galactaric acid (H₂Gala) has been studied. In aqueous and water-DMSO solutions, 1 : 1 complexes are formed. Depending on the procedure and conditions of the synthesis, CuGala · 4H₂O, Cu(HGala)₂ · 4H₂O, and (CuOH)₂Gala · 2H₂O compounds have been obtained. The structure of the coordination environment of the metal ion has been identified by IR spectroscopy.     

Quantum-Chemical Study of Methyl Phenyl Sulfide

Steric and electronic structure of the methyl phenyl sulfide molecule was studied by nonempirical quantum-chemical methods. The calculations were performed by the B3LYP and MP2 procedures with account taken of electronic correlation using extended 6-311++G(3d,p) basis sets. The use of a balanced method and basis set allowed us to avoid discrepancy between the experimental and calculated data reported by other authors. The results confirmed coplanar orientation of the CÄSÄC fragment and the benzene ring, which follows from most experimental studies.     

Chlorin e6-liposome interaction. Investigation by the methods of fluorescence spectroscopy and inductive resonance energy transfer

On the basis of spectral fluorescence and polarization measurements and results obtained on the luminescence quenching of the membrane fluorescent probe 1,6-diphenyl-1,3,5-hexatriene (DPH) by incorporated chlorin e6 (chl e6) molecules, it is shown that the interaction of the water-soluble pigment with smaller unilamellar lipid vesicles occurs by a mechanism of partition between the aqueous and lipid phases (partition coefficient Kp = 6.7 x 10(3) and provides rigid fixing of chl e6 monomers at the boundary between the polar and non-polar parts of the lipid membrane. In terms of inductive resonance electronic excitation energy transfer between DPH and chl e6 (R0 = 36.2 A), we have analysed data on DPH fluorescence quenching under different conditions of chl e6 localization in the lipid bilayer and have concluded that the incorporation of the pigment molecules into the vesicles from the aqueous phase occurs mainly into the external monolayer.     

Determination de O et N dans les metaux alcalins et de O dans d'autres metaux par methode d'activation γ avec separation chimique des isotopes de courtes periodes

Résumé On a étudié une méthode de séparation rapide des isotopes de courte période¹⁵O et¹³N dans les métaux alcalins et¹⁵O dans d'autres métaux pour déterminer l'oxygène et le carbone par activation γ à l'aide d'un microtron.     

Highly accurate evaluation of atomic three-electron integrals of lowest orders

Calculations of three-electron atomic systems in Hylleraas coordinates require integrals involving all the interparticle distances r(ij), which have usually been evaluated by introducing series expansions. For integrals with the smallest powers of r(ij) these expansions do not converge at a satisfactory rate, leading some investigators to introduce convergence-acceleration procedures. This paper recommends the alternative of evaluating these integrals in closed form and presents stable explicit formulas for so doing. Some of the formulas are more compact versions of those in the literature; others have not been previously reported. It is also shown that finite-difference methods can be used with advantage to obtain additional low-order integrals. Sample integral values have been provided for test purposes.     

X-ray and IR spectroscopic studies of specific intermolecular interactions inN′-substituted isonicotinohydrazides

_N-Thenylidene- andN-(o-nitrobenzylidene)hydrazides of isonicotinic acid have been studied by X-ray structural analysis and IR spectroscopy. In the crystalline state, these molecules are linked through intermolecular N—H ... Np_y hydrogen bonds. Carbonyl groups are not involved in intermolecular hydrogen bonds. However, it was found that the C=O group participates in an attractive interaction with the sulfur atom of the thiophene group. The energy of this interaction is comparable with the energies of intermolecular C=O ... H—N hydrogen bonds in amides.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 896–900, April, 1996.