The application of column redox-extraction chromatography to the separation of some actinide elements

The application of a new technique to the separation of some actinide elements by means of a single reducing and extracting column is described. Tri-n-octylphosphine oxide (TOPO) was used as the extractant. The following reducing agents were supported on microporous polyethylene together with TOPO: tetrachlorohydroquinone, 2,3-dichloro-1,4-naphthahydroquinone, 2,5-di-tert-butylhydroquinone and 2,5-di-tert-pentylhydroquinone. The last compound was chosen for the separation experiments; it allowed quantitative reduction of plutonium to Pu(III) and of neptunium to Np(IV). The separations Pu(III)-Np(IV), Pu(III)-U(VI) and Am(III)-Np(IV) in 6 M hydrochloric acid were obtained.     

Enhancing selectivity in oxidation catalysis with sol-gel nanocomposites

Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis.     

Di-2-pyridylketone semicarbazone as ligand in metal complexes: synthesis and X-ray crystal structure

A series of complexes of di-2-pyridylketone semicarbazone (Hdips) and Mn(II), Co(II), Co(III), Ni(II) and Cu(II) nitrates were synthesized and characterized by means of IR spectroscopy and for cobalt and nickel by X-ray crystal structures. The results are in agreement with the formulae: Mn(Hdips)₂(NO₃)₂·2H₂O, [Co(Hdips)₂](NO₃)₂·H₂O (I), [Ni(Hdips)₂](NO₃)₂·H₂O (II), Cu(Hdips)(NO₃)₂·2H₂O, [Co(dips)₂](NO₃)·2H₂O (III). The structure of I and II are monoclinic, space groupP2₁/c, with, I,a=15.980(4),b=11.531(2),c=16.170(2)Å;=104.20(2)°,Z=4,R=0.032; II,a=16.109(5),b=11.480(3),c=16.135(6)Å;=104.15(2)°,Z=4,R=0.069. Compound III is also monoclinic, space groupP2₁/c witha=12.173(5),b=15.619(5),c=15.338(8)Å;=111.40(4)°,Z=4,R=0.059. In these complexes the ligand is tridentate via carbonylic oxygen, semicarbazone and pyridine nitrogens forming each two five membered chelate rings with the metal in a distorted octahedral geometry.     

Radium,uranium and thorium concentrations in low specific activity scales and in waters of some oil and gas production plants

Low specific activity scales consisting of alkaline earth metal carbonates and sulfates are often present in some gaseous and liquid hydrocarbon plants; these scales contain a certain concentration of radium, uranium and thorium, which can cause a risk of -irradiation and of internal radiocontamination when they must be mechanically removed. That being stated,²³⁸U,²³²Th and²²⁶Ra were determined in scales, sludges and waters coming from different plants.²³⁸U and²³²Th concentrations were found very low; the isotopes²³⁸U and²³⁴U resulted in radioactive equilibrium, whilst²³²Th and²²⁸Th were not always in equilibrium.²²⁶Ra concentration was higher in scales and sludges than in waters.     

Ultrasound effects on the Mn(III) - promoted addition of amidoalkyl radicals to olefins

Amidoalkyl radicals, generated from amides by Mn(OAc)₃ in acetic acid react with phenyl substituted alkenes to generate five-membered lactones or lactams. Ultrasound at ambient temperature significantly accelerates these single electron transfer reactions even when compared with conventional conditions under reflux or simple mechanical stirring. In some cases sonication leads to unusual products.     

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.     

R.F. (280 MHz) EPR imaging of extended samples: Apparatus and preliminary results

This paper presents the preliminary results obtained using an Electron Paramagnetic Resonance imaging apparatus operating at 280 MHz. The acquisition technique and the procedure used to obtain the spin density spatial localization are presented and specimen images of extended samples are given. The accuracy of the images and the spatial resolution are also discussed.     

A remark on the KAM theorem applied to a four-vortex system

We consider a planar four-vortex system with unit intensities and apply the KAM theorem for two-dimensional tori with fixed frequency. We obtain a rigorous lower bound for the stochasticity threshold of the torus with rotation number=(5—1)/2 and compare our result with numerical experiments.     

Numerical calculation of domains of analyticity for perturbation theories in the presence of small divisors

We study numerically the complex domains of validity for KAM theory in generalized standard mappings. We compare methods based on Padé approximants and methods based on the study of periodic orbits.     

Time-division multiplexing of the orbital angular momentum of light

We present an optical setup for generating a sequence of light pulses in which the orbital angular momentum (OAM) degree of freedom is correlated with the temporal one. The setup is based on a single q plate within a ring optical resonator. By this approach, we demonstrate the generation of a train of pulses carrying increasing values of OAM, or, alternatively, of a controlled temporal sequence of pulses having prescribed OAM superposition states. Finally, we exhibit an "OAM-to-time conversion" apparatus that divides different input OAM states into different time bins. The latter application provides a simple approach to digital spiral spectroscopy of pulsed light.