An experimental and theoretical study of the Cp2VO2CO: use of 13CO3(2-) for structure investigation of d1-metallocene complexes

EPR study has shown that the anticancer agent vanadocene dichloride (Cp2VCl2) interacts with carbonate contained in physiological solutions. Chelate complex Cp2VO2CO (|A(iso)(51V)| = 175.1 MHz, g(iso) = 1.9861) is the only paramagnetic species formed in the range about the physiological pH (5.5-11.0). The super-hyperfine coupling (|a(iso)(13C)| = 24.1 MHz) was evidenced at measurements using 13C labelled carbonate. The structure of carbonate complex was validated by comparison of observed and theoretical calculated HFC tensors (at the density functional level of theory).     

Oxidative reactivity of Cu-TESHHK- and its alanine analogues

Redox properties of Cu(II) complexes of the terminally blocked hexapeptide -TESHHK- and a series of its alanine substituted analogs: -TASHHK-, -TEAHHK-, -TESAHK-, -TESHAK-, were investigated in their reactions with hydrogen peroxide in solution and by cyclic voltammetry in a broad range of pH. The formation of reactive oxygen species was followed with the use of spectrophotometric indicators, NDMA and NBT. The results indicate that the ability of these complexes to generate hydroxyl-like radicals correlates with the formation of active Cu(III) complexes resulting from the oxidation of Cu(II) by H2O2, which interact with further H2O2 molecules specifically.     

Determination of oxygen content in YBa2Cu3O6.5+x

A method for determining the oxygen content of the high-temperature superconductor YBa₂Cu₃O_6.5+x is described. The superconductor is dissolved in 4.4 M hydrobromic acid, forming bromine. The mixture is then diluted with hydrochloric acid to obtain a solution of bromine and Cu(II) in 0.44 M hydrobromic acid and 1.1 M hydrochloric acid. As(III) is added in slight excess of that required to react with the bromine and the unreacted As(III) is determined by titration with potassium bromate. Oxygen does not interfere. The results of this method are in agreement with those of other iodimetric procedures. The dissolution of the superconductor in 4.4 M hydrobromic acid is much faster than in hydrochloric acid, the medium used in one iodimetric technique. YBa₂Cu₃O_6.5+x sintered fibers and powder samples weighing from ca. 0.5 to 200 mg were analyzed for oxygen content.     

ContinuousK-theory

We study arithmetical properties of homotopy groups of thel-adic completion of Quillen'sK-theory space of number field, with a view on the Dwyer-Friedlander comparison map into étaleK-theory. The relation of these groups toK-theory is a complete analogy to the relation of continuous étale cohomology to étale cohomology. We identify the torsion subgroup of the resulting term with the subgroup of divisible elements inK _2n (F). We prove that this term is sent isomorphically into étaleK-theory, giving some further evidence for the Lichtenbaum-Quillen conjectures.     

Isomerization of alkylaromatic hydrocarbons on nickel-boron-alumina catalysts

The activity of alumina and silica-alumina modified with nickel and/or boron trifluoride etherate in the transformations of o-xylene and -methylnaphthalene in the presence of gaseous hydrogen has been measured. Dependence between the yields of isomerization reaction and the concentration of Brönsted acid centers on the surface of the catalysts investigated was observed.     

Influence of substituents on positron annihilation in styrene copolymers

Results of angular correlation of annihilation radiation (ACAR) and positron annihilation lifetime (PAL) measurements are presented for five styrene copolymers: poly(co-styrene-phenylmaleimide) and its three derivatives with chlorine as well as for one with the OH group substituted at the benzene ring. It occurs that the chlorine substituted at three different positions at the benzene ring poly(co-styrene-o (or-m,-p)-chlorophenylmaleimide) inhibits the formation of the positronium to different extent. The greatest effect is observed in case of the chlorine atom substituted at the benzene ring at the ortho-position towards the nitrogen atom. The two long lifetimes (₃ and ₄) observed in the lifetime spectra are connected with the bimodal distributions of the free volume radius in the samples.     

Cramér theorem on symmetric spaces of noncompact type

We prove the Cramér theorem forK-invariant Gaussian measures on irreducible symmetric spacesX=G/K withG semisimple noncompact. To do this we use a kind of Abel transform ofK-invariant measures onX.This research is supported by KBN Grant.     

Measurement of γp→K + Λ and γp→K + Σ 0 at photon energies up to 1.47 GeV

The reactions pK ⁺ and pK ^{+ 0} have been measured with the multiparticle detector system SAPHIR at ELSA in Bonn. Besides the differential cross sections the polarization and, for the first time, the ⁰ polarization have been determined in a photon induced reaction. All data are presented as functions of the photon energy (from threshold up to 1.47 GeV) and of the kaon production angle (0°–180°). The polarization of both and ⁰ is substantial at all energies and varies strongly with the production angle.This work is supported by the Bundesminister für Forschung und Technologie (BMFT), FK 06 BN 621 I     

Novel Rearrangements of 2,3-Dimercapto-1-propanol Derivatives: Formation of Dialkyl Sulfide, Dialkyl Disulfide, and 1,2,3-Tris(alkylthio)propane

The base alkylation of 2,3-dimercapto-1-propanol with alkyl halides leads in good yield to 2,3-bis(alkylthio)-1-propanol and dialkyl sulfide. The reaction of 2,3-bis(alkylthio)-1-propanol with catalytic concentrated sulfuric acid proceeds with rearrangement to give 1,2,3-tris(alkylthio)propane and dialkyl disulfide. The rearrangement reaction takes place through a common intermediate thiaranium intermediate 8.