Thermal decomposition of mineral zircon by alkali metal hydroxides

Thermal decomposition of zircon mineral was studied in the presence of sodium and potassium hydroxides and in the presence of a waste mixture of hydroxides containing NaOH and KOH in a weight ratio of 23. The process was controlled in such a way that the decomposition products might contain the minimum possible amount of alkali and could thus be applied for the syntheses of zircon pigments without any further exacting treatment.

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Zusammenfassung Es wurde die thermische Zersetzung eines Zirkonminerals in Gegenwart von Natrium- und Kaliumhydroxid-sowie in Gegenwart einer Altlauge mit einem Gehalt an NaOH und KOH im Verhältnis zwei zu drei untersucht. Der Prozeß wird derart gesteuert, daß die Zersetzungsprodukte einen möglichst geringen Anteil an Lauge besitzen und so ohne weitere arbeitsaufwändige Behandlungen zur Synthese von Zirkonpigmenten verwendet werden können.

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Sulfide ion electrooxidation catalysed by cobalt phthalocyanine microcrystals

Electrooxidation of sulfide ion catalysed by microcrystals of cobalt phthalocyanine was investigated by cyclic voltammetry in 0.5M KNO₃ at pH 9.22. Traces of catalyst were immobilized at the surface of a paraffin-impregnated graphite electrode by the mechanical transfer of its powder. The electro-oxidation of HS^– proceeds in two irreversible steps, with the first peak between 0 V and –0.12 V and the second at 0.17 V. The first step is second order in HS^– and its product is the adsorbed disulfide, which may further dissociate to give adsorbed sulfur atoms. The reduction of sulfur occurs at –0.1 V.     

Zur Konfiguration des Vitamin-D3-Metaboliten 25, 26-Dihydroxycholecalciferol: Synthese von (25S,26)- und (25R,26)-Dihydroxycholecalciferol

Configuration of the Vitamin-D₃-Metabolite 25,26-Dihydroxycholecalciferol: Synthesis of (25S,26)- and (25R,26)-Dihydroxycholecalciferol For selective synthesis of the title compounds, (25S)- 1b and (25R)- 1b (Scheme 1), the protected cholesterol precursors (25S)- 6 and (25R)- 6 were prepared from stigmasterol-derived steroid-units 4a-d and C₅-side chain building blocks 5a–d by Grignard- or Wittig-coupling (Scheme 2), the configuration at C(25) of the target compounds being already present in the C₅-units. Conversion of the cholesterol intermediates to the corresponding vitamin-D₃ derivatives was carried out via the 7,8-didehydrocholesterol compounds (25S)- 2b and (25R)- 2b (Scheme 1), using the established photochemical-thermal transformation of the 5,7-diene system to the seco-triene system of cholecalciferol. The configuration at C(25) of the cholesterol precursors as assigned on basis of the known configuration of the C₅-units used, was found to be in agreement with the result of a single crystal X-ray analysis on compound 11 . The configuration at C(25) remained untouched on conversion of the cholesterol ring system to the seco-triene system of vitamin D₃ as evident from comparison of the lanthanide-induced CD. Cotton effects observed for (25S)- 3b and (25S) 1b . 25,26-Dihydroxycholecalciferol observed as a natural vitamin-D₃ metabolite has (25S)-configuration.     

Photocatalytic TiO2 Coatings: Effect of Substrate and Template

Summary. Transparent TiO₂ films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles, higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template (i.e. Pluronic F127) to the sol.     

Sorption of radionuclides on inorganic sorbents

Inorganic sorbents are often used in separation of metals and radionuclides in radioanalytical application and they were also used in technological scale for separation of radionuclides in cleanup of Three Mile Island NPP. Inorganic sorbents become popular in the last years because no problem with organic contamination, there are stable against radiation, sorption efficiency can be tailor made for selective separation of chosen metal. Contrary to the organic sorbents they have usually lower capacity and chemical stability is limited to narrower pH. Nevertheless of some problems, many good properties of inorganic sorbents make them very attractive for sorption study.     

Correlation between Lipophilicity of the Ligands and the Hepatobiliary Properties of the Radiopharmaceuticals: Approach to the Development of New IDA Derivatives

The partition coefficient (log P) for n-octanol/water system was calculated applying PACO program for various theoretically possible mono and dihalogenated IDA derivatives. Some of the synthesized ligands (SOLCOIODIDA, IODIDA and DIIODIDA) were labeled with the technetium-99m. The biodistribution and influence of bilirubin on their biokinetics were investigated in rats. The correlation between partition coefficients of ligands increase (log P) and better hepatobiliary properties of ^99mTc-IDA derivatives was determined. The values of log P increase from 1.16 for SOLCOIODIDA, 3.11 for IODIDA to 3.47 for DIIODIDA. In correlation with these results, biliary excretion decreased for 59% for ^99mTc-SOLCOIODIDA and 11% for ^99mTc-IODIDA and ^99mTc-DIIODIDA under hyperbilirubinemia (3.5 min after injection) and 45%, 11% and 0.38% respectively (15 min after injection). The highest biliary excretion had ^99mTc-DIIODIDA (55.4% for 3.5 min). Considering the correlation between hepatobiliary properties and log P, the evaluation of biological properties for various trifluoromethyl mono and dihalogenated IDA derivatives was performed on the basis of the calculated log P in order to synthetize a new radiopharmaceutical for hepatobiliary scintigraphy.     

Indications for the Occurrence of Nitric Oxide Synthases in Fungi and Plants and the Involvement in Photoconidiation of Neurospora crassa*

Indications for the occurrence of nitric oxide synthases in Dictyostelium, Neurospora, Phycomyces and the leguminous plant Mucuna hassjoo as well as a physiological role of nitric oxide in Neurospora crassa are demonstrated. An exogenous nitric oxide donor, sodium nitroprus-side, inhibited light-stimulated conidiation in N. crassa. Specific inhibitors of nitric oxide synthase, like the arginine derivatives N^G-nitro-L-arginine (L-NA) and N^G-nitro-L-arginine-methyl ester (L-NAME), enhanced conidiation in darkness and in the light, whereas the stereo-isomer D-NAME was inactive. This communication reports to our knowledge the first time the presence of enzymatic activity of nitric oxide synthase in fungi and a higher plant and an effect of nitric oxide in fungal photophysiology.     

Electrospray ionization ion-trap multistage mass spectrometric study of sodium cationized aldobiuronic and pseudoaldobiuronic acid derivatives

Fragmentation mechanisms of electrospray ionization (ESI) mass spectrometry of aldobiuronic and pseudoaldobiuronic acid derivatives were elucidated by multistage mass spectrometric (MS(n), n = 2-5) measurements of selected ions. Characteristic under the conditions of ESI-MS analysis is the production of alkali metal (Na and K) cationized adducts. The probability the of locations of Na cations in per-O-methylated compounds was proved by quantum chemical calculations, using the Jaguar program. The most probably position of alkali metal attachment is the carboxy group of the methoxycarbonyl C-5 group of the uronic acid unit. Characteristic cleavages vary according the kind of O-derivatization. In most cases they take place on the acidic part of the dimer and at the interglycosidic oxygen atom. As a result, the criteria for the differentiation of aldobiouronic and pseudoaldobiouronic acids derivatives were elucidated.     

Liquid chromatography of benzene derivatives on a porous methacrylate copolymer containing epoxy groups

Summary The retention of benzene derivatives with nonpolar and polar substituents on a porous methacrylate copolymer containing epoxy groups using both nonpolar and polar eluents was investigated. When n-hexane is used as the eluent, the retention of n-alkylbenzenes and polymethylbenzenes is weaker than that of benzene. In the case of benzene derivatives containing polar functional groups their capacity ratios (k) on this porous polymer increases approximately linearly with the increase of the adsorbate molecules dipole moment. The retention characteristics of the methacrylate copolymer were compared with that of a styrene-divinylbenzene copolymer and silica gels with a hydroxylated surface and with a surface modified by chemically bonded alkylsilyl groups.     

Synthesis and structure of a new rhodium(I) complex [Rh{P(OPh)3}3CN]

Summary The [Rh(acac){P(OPh)₃)}₂] complex (Hacac = 2,4-pentadione) reacts in solution with gaseous HCN in the presence of P(OPh)₃ to give [Rh{P(OPh)₃}₃CN]. Structural investigations of this complex including its³¹P n.m.r. spectra are reported.