X-ray spectroscopic characterization of Cu2+-phenanthroline complexes intercalated in α-zirconium phosphate

X-ray photoelectron spectroscopy provides evidence that when [Cu(phen)₂]²⁺(phen = 1,10-phenanthroline) is diffused between the layers of -zirconium phosphate, the complex species does not remain intact after intercalation, but some Cu-N bonds are broken, replaced with Cu-O bonds and the released nitrogen atoms can now interact with the PO₃-OH groups of the host. XPS also provides evidence for coordination of the Cu²⁺ ions when they are diffused by ion exchange in the phenanthroline--zirconium phosphate intercalation compound. Although Cu²⁺ and phen are in a 1 : 1 molar ratio in the interlayer region of the host, so that a 1 : 1 coordination could be expected between the two species, the characteristic peaks of the uncoordinated phenanthroline, even though at a low intensity, are still present. The differences between the two Cu(II)-intercalation compounds are discussed.     

Chemical and radiochemical characterization of depleted uranium (DU) in Kosovo soils

As is well known ammunitions containing depleted uranium (DU) were used by NATO during the Balkan war. The paper deals with the determination of uranium alpha emitting radiosotopes in Kosovo soils by chemical separation and alpha spectrometry. The samples were collected by CISAM (Centro Interforze Studi ed Applicazioni Militari, S. Piero a Grado, Livorno) in the period November 1999-April 2000. The DU distribution in soil appeared very disomogeneous; the isotope weight percentages for U-238, U-235 and U-234 resulted 99.76, 0.24 and 7.24.10(-4) respectively; consequently the activity distribution was 86.42%, 1.31%, 11.63% and the isotope ratios were 1.52.10(-2) and 0.134 for U-235/U-238 and U-234/U-238 showing clearly the presence of DU. A small peak at 4.49 MeV (U-236) in the alpha spectrum indicated that the used DU was the by-product of exhausted uranium reprocessing. In order to determine the chemical and physiological solubility of uranium a fractionation study was carried out by using the Tessier method: 55% of uranium showed a fair solubility, but 45% was solubilized only by 8 M HNO3.     

Crystal,molecular and electronic structure of 1,1-diaryl-2-halogenoethylenes

On the basis of semiempirical calculations, the conformation of the isolated molecule of 2-bromo-1,1-diphenylprop-1-ene corresponding to the minimum of total energy was determined. Assuming some information on the localization of the molecules in the crystal, also the conformation in a theoretical crystal was studied. The results have been compared with the crystal structure of 2-bromo-1,1-diphenylprop-1-ene, as obtained by X-ray diffraction. From the comparison a slight displacement of the C2 atom was suggested.

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Zusammenfassung Die dem Minimum der Gesamtenergie entsprechende Konformation des isolierten Moleküls von 2-Brom-1,1-diphenylprop-1-en wurde durch halb-empirische Methoden bestimmt. Gewisse Ergebnisse über die Anordnung der Moleküle im Kristall machten es möglich, die Konformation in einem theoretischen Kristall zu untersuchen. Nach Vergleich der Resultate mit der durch Röntgen-Analyse bestimmten Kristallstruktur des 2-Brom-1,1-diphenylprop-1-en wurde eine kleine Verschiebung des C2-Atoms vorgeschlagen.

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Résumé Par le moyen de calculs semiempiriques on a déterminé la conformation de la molécule isolée de 2-bromo-1, 1-diphénilprop-1-ène, correspondant au minimum d'énergie totale. On a aussi étudié la conformation dans le cristal théorique en se basant sur des informations concernant la localisation des molécules dans le cristal. On a comparé ces résultats avec ceux que nous avons obtenus par la détermination de la structure cristalline du 2-bromo-1, 1-diphénilprop-1-ène avec la diffraction des rayons X: cette comparaison nous a porté à déplacer un petit peu l'atome C 2.

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This work was supported by a grant from the Italian Consiglio Nazionale delle Ricerche.     

Molecular structure-activity relationships for the oxidation of organic compounds using mesoporous silica catalysts derivatised with bis(halogeno)dioxomolybdenum(VI) complexes

Mo K-edge XAFS spectra have been measured for ordered mesoporous silica MCM-41 grafted with the complexes [MoO2X2(thf)2] (X=Cl, Br). For grafting reactions in the absence of triethylamine, materials with 1 wt. % Mo are obtained; the Mo K-edge EXAFS results indicate the co-existence of isolated surface-fixed monomeric species [MoO2[(-O)3SiO]2(thf)(n)] and [MoO2[(-O)3SiO]X(thf)(n)]. When Et3N is used in the grafting reactions, materials with 4 wt. % Mo are obtained. The EXAFS data for the material prepared using [MoO2Cl2(thf)2] and Et3N indicate the presence of dinuclear species with two Mo(VI) centres, each with two Mo=O groups and each linked by one or two oxo bridges (Mo...Mo 3.27 A). The molybdenum centres in the material prepared using the dibromo complex comprise mainly isolated four-coordinate dioxomolybdenum(VI) and trioxomolybdenum(VI) monomeric species, with a small contribution from dimeric species. All materials were further characterised in the solid state by powder X-ray diffraction, N2 adsorption analysis, MAS NMR (13C, 29Si) and FTIR spectroscopy. The derivatised MCMs perform differently as catalysts in the liquid-phase oxidation of various olefins and alcohols with tert-butyl hydroperoxide. The highest alkene epoxidation activity was recorded for the catalysts with low metal loading, whereas the material containing oxo-bridged dimers had the highest activity for oxidation of alcohols. The recyclability of all the catalysts was tested: the catalytic activity of the derivatised materials tended to stabilize with ageing.     

Synthesis and biological evaluation of 5-substituted-4-nitroimidazole ribonucleosides

The imidazole nucleosides, 4(5)-bromo-5(4)-nitro-1-β-D-ribofuranosylimidazoles, have been prepared via glycosylation of the trimethylsilylated aglycone, 4(5)-bromo-5(4)-nitroimidazole, with tetra-O-acetyl-β-D-ribo-furanose followed by removal of the acetyl protecting groups. The 5-bromo-4-nitro-1-β-D-ribofuranosylimidazole nucleoside was acetonated to produce 5-bromo-4-nitro-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-imidazole which was cyclized to provide the corresponding anhydronucleoside 5,5′-anhydro-4-nitro-5-oxo-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole. Sodium hydrosulfide treatment of 5-bromo-4-nitroimidazole nucleoside provided 5-mercapto-4-nitro-1-β-D-ribofuranosylimidazole 5-sodium salt which was alkylated with E-1,5-diiodopent-1-ene to yield 5-(E-1-iodo-1-penten-5-yl)thio-4-nitro-1-β-D-ribofuranosylimidazole. The corresponding iodine-125-labeled compound was prepared similarly using radiolabeled diiodopentene. The 5-bromo-4-nitroimidazole, 5-mercapto-4-nitroimidazole, and 5-iodopentenylthio-4-nitroimidazole nucleosides were cytotoxic to Molt-3 cells in vitro at concentrations higher than 10 μg/mL. The radiolabeled 5-iodopentenylthio-4-nitroimidazole nucleoside showed 2-fold higher uptake in a rapidly growing tumor as compared to uptake in a relatively slower growing tumor in mice.     

Gadolinium‐Decorated Silica Microspheres as Redox‐Responsive MRI Probes for Applications in Cell Therapy Follow‐Up

The redox microenvironment within a cell graft can be considered as an indicator to assess whether the graft is metabolically active or hypoxic. We present a redox‐responsive MRI probe based on porous silica microparticles whose surface has been decorated with a Gd‐chelate through a disulphide bridge. Such microparticles are designed to be interspersed with therapeutic cells within a biocompatible hydrogel. The onset of reducing conditions within the hydrogel is paralleled by an increased clearance of Gd, that can be detected by MRI.     

Influence of trace elements supplementation on the production of recombinant frutalin by Pichia pastoris KM71H in fed-batch process

Frutalin, a galactose-specific lectin used to detect specific tumour markers, is a protein with low expression level in breadfruit. In the present study, fed-batch fermentation in a stirred tank bioreactor was used as a strategy to enhance protein production by a recombinant Pichia pastoris KM71H. By using this process, the production of recombinant frutalin was 4-fold higher than the value obtained in shaker flasks batch assays. Supplementation of the fermentation medium with trace elements (Pichia trace minerals, PTM) was also evaluated in order to stimulate production of the recombinant protein. The addition of PTM to the minimum medium afforded a recombinant protein production of 13.4 mg L^?1, which was 2.5-fold higher than that achieved from the culture medium without PTM supplementation. These results are significant as the development of strategies to improve the production of recombinant frutalin may broaden its application in cancer diagnosis.