Solvent extraction of scandium(III), yttrium(III), lanthanum(III) and gadolinium(III) using Cyanex 302 in heptane from hydrochloric acid solutions

The extractions of the selected rare earths (Sc, Y, La and Gd) from hydrochloric acid solutions have been investigated using bis(2,4,4-trimethylpentyl)-mono thiophosphinic acid (Cyanex 302, HL) in heptane as an extractant. The results demonstrate that the extractions of rare earths occur via the following reaction: Sc(OH)(2+) + 2[(HL)(2)]((O)) double left right arrow [Sc(OH)L-2 (.) 2(HL)]((O)) + 2H(+) Y3+ + 3[(HL)(2)]((O)) double left right arrow [Y(HL2)(3)]((O)) + 3H(+) La(OH)(2)(+) + 3[(HL)(2)](O) double left right arrow [La(OH)(2)L (.) 5(HL)]((O)) + H+ Gd(OH)(2+) + 3[(HL)(2)]((O)) double left right arrow [Gd(OH)L-2 (.) 4(HL)]((O)) + 2H(+) The pH(1/2) values and equilibrium constants of the extracted complexes have been deduced by taking into account the aqueous phase complexation of the metal ion with hydroxyl ligands and plausible complexes extracted into the organic phase. According to the pH(1/2) values, it is possible to realize mutual separation among Sc(III), Y(III), La(III) and Gd(III) with Cyanex 302 by controlling aqueous acidity.

Synthesis and evaluation of novel polysaccharide-Gd-DTPA compounds as contrast agent for MRI

Macromolecular conjugates of two kinds of natural polysaccharides, that from Panax quinquefolium linn (PQPS) and Ganoderma applanatum pat (GAPS), with gadolinium-diethylenetriaminepenta-acetic acid (Gd-DTPA) have been synthesized and characterized by means of FTIR, elementary analysis and ICP-AES. Their stability was investigated by competition study with Ca2+, EDTA (ethylenediaminetetraacetic acid) and DTPA. Polysaccharide-bound complexes exhibit T-1 relaxivities of 1.5-1.7 times that of Gd-DTPA in D2O at 25degreesC and 9.4T. MR imaging of Sprague-Dawley (SD) rats showed remarkable enhancement in rat liver and kidney after i.v. injection of these two complexes: liver parenchyma 60.9+/-5.6%, 57.8+/-7.4% at 65-85 min; kidney 144.9+/-14.5%, 199.9+/-25.4% at 10-30 min for PQPS-GdDTPA, GAPS-Gd-DTPA at gadolinium dose of 0.083 and 0.082 mmol/kg, respectively. Our preliminary in vivo and in vitro study indicates that the two kinds of polysaccharide-bound complexes are potential tissue-specific contrast agents for MRI.

An evaluation of gadolinium polyoxornetalates as possible MRI contrast agent

Two gadolinium polyoxometalates, K9GdW10O36 and K-11 [Gd(PW11O39)(2)], have been evaluated both in vivo and in vitro as candidates for tissue-specific MRI contrast agents. T-1-relaxivities of 6.89 mM(-1) . s(-1) for K9GdW10O36 and 5.27 mM(-1) . s(-1) for K-11[Gd(PW11O39)(2)] are slightly higher than that of the commercial MRI contrast agent (Gd-DTPA). Both compounds bind with bovine serum albumin and human serum transferrin and favorable liver-specific contrast enhancement in in vivo MRI with Sprague-Dawley rats after i.v. administration has been demonstrated. Imaging studies demonstrate that the two agents have a long residence time, showing MR signal enhancement in the liver for more than 40 min, longer than commercially available contrast agents. In vivo and in vitro assays showed that GdW10 and Gd(PW11)(2) are promising liver-specific MRI contrast agents and GdW10 may be used in the diagnosis of the pathological state. However, with the higher acute toxicity, the two gadolinium polyoxometalates need to be modified and studied further before clinical use.

PREPARATION AND MOLECULAR-STRUCTURE OF METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)NEODYMIUM AND METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)GADOLINIUM

Bis(t-butylcyclopentadienyl)lanthanide chloride (Ln = Nd or Gd) reacts with one equivalent of methyllithium in ether/tetrahydrofuran to give the complex [(C5H4tBu)2LnCH3]2 (Ln = Nd or Gd). The structure of [(C5H4tBu)2NdCH3]2 has been determined by X-ray analysis. The crystals are monoclinic of space group Cm with a = 9.538(2), b = 23.298(4), c = 9.505(3) angstrom, beta = 119.53(2)-degrees, V = 1828.0(7) angstrom 3, D(calc.) = 1.458 g/cm3 and Z = 2 for the dimer. The two (C5H4tBu)2Nd units in the dimer are connected by asymmetrical methyl bridges with independent Nd-C bond lengths of 2.70(2) and 2.53(2) angstrom and Nd-C-Nd angles of 94.7(9) and 87.3(6)-degrees.

Red and blue emissions of europium doped gadolinium silicate from porous silica matrix and hydroxide carbonate with spherical shaped particles

In this work, Eu(III) and Eu(II) doped gadolinium silicates has been obtained as compact tubes starting from spherical gadolinium hydroxide carbonate using the pores of silica matrix as support and its surface as reagent. Eu(III) doped gadolinium silicate with hexagonal phase shows an interesting visible shifted charge transfer band when compared to disilicate with orthorhombic phase that was also obtained. Eu(II) gadolinium silicate has been prepared using CO atmosphere presenting an intense blue emission. The divalent europium system shows a potential application as an UV-blue converter. The samples were characterized by scanning electron microscopy (SEM), X-ray powder diffractometry (XRD) and photoluminescence spectroscopy. (C) 2002 Elsevier B.V. B.V. All rights reserved.

High-density nanoparticle ceramic bodies: A study of heating rates in the sinterization of Gadolinium-doped Ceria

An investigation on the sinterization of Gd:CeO2 (Ce 0.85Gd0.15O1.9-δ ceramic system) 3-10 nm nanoparticles in pressed bodies was done. The heating rate was taken as a key parameter and two competing sinterization processes were identified, associated with different diffusional mechanisms. Using heating rates of 113 C min -1, a high-final density (98 % of the theoretical) was obtained by superposing the two aforementioned mechanisms, resulting in a homogeneous microstructure at lower temperatures. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Synthesis, characterisation and thermal behaviour of solid state compounds of 4-methylbenzylidenepyruvate with heavier trivalent lanthanides and yttrium(III)

Solid state Ln-4-Me-BP compounds, where Ln stands for heavier trivalent lanthanides (gadolinium to lutetium) and yttrium(III) and 4-Me-BP is 4-methylbenzylidenepyruvate (CH3-C6H4-CH=CH-COCOO-), have been synthesized. Elemental analysis, complexometry, X-ray powder diffractometry, infrared spectroscopy and simultaneous thermogravimetry-differential thermal analysis (TG-DTA), have been used to characterise and to study the thermal behaviour of these compounds. The results provided information concerning the stoichiometry, crystallinity, ligand's denticity, thermal stability and thermal decomposition. © 2002 Elsevier Science B.V. All rights reserved.

HIGH TEMPERATURE RARE EARTH COMPOUNDS: SYNTHESIS, CHARACTERIZATION AND APPLICATIONS IN DEVICE FABRICATION

As the area of nanotechnology continues to grow, the development of new nanomaterials with interesting physical and electronic properties and improved characterization techniques are several areas of research that will be remain vital for continued improvement of devices and the understanding in nanoscale phenomenon. In this dissertation, the chemical vapor deposition synthesis of rare earth (RE) compounds is described in detail. In general, the procedure involves the vaporization of a REClx (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho) in the presence of hydride phase precursors such as decaborane and ammonia at high temperatures and low pressures. The vapor-liquid-solid mechanism was used in combination with the chemical vapor deposition process to synthesize single crystalline rare earth hexaboride nanostructures. The crystallographic orientation of as-synthesized rare earth hexaboride nanostructures and gadolinium nitride thin films was controlled by judicious choice of specific growth substrates and modeled by analyzing x-ray diffraction powder patterns and crystallographic models. The rare earth hexaboride nanostructures were then implemented into two existing technologies to enhance their characterization capabilities. First, the rare earth hexaboride nanowires were used as a test material for the development of a TEM based local electrode atom probe tomography (LEAP) technique. This technique provided some of the first quantitative compositional information of the rare earth hexaboride systems. Second, due to the rigidity and excellent conductivity of the rare earth hexaborides, nanostructures were grown onto tungsten wires for the development of robust, oxidation resistant nanomanipulator electronic probes for semiconductor device failure analysis.

Novel europium and gadolinium complexes with methaneseleninate as ligand: Synthesis, characterization and spectroscopic study

The methaneseleninate and 1,10-phenanthroline were used as ligands in the synthesis of new lanthanide complexes. The photostability, emission quantum yield (q) and quantum efficiency (eta) of the D-5(0) emitting level of the Eu3+ ion were determined. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal intramolecular energy transfer process. The nephelauxetic effect was investigated to assess the covalency of the ligand-metal chemical bond. The values of the experimental 4f-4f intensity parameters, suggest that this ion is in a chemical environment less polarisable than in the case of complexes with beta-diketonates as ligands. (C) 2011 Elsevier B.V. All rights reserved.

Zero- one- and two-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the monocyclic heteroaromatic Lewis bases 2-aminopyrimidine, nicotinamide and isonicotinamide

The structures of the anhydrous 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the monocyclic heteroaromatic Lewis bases 2-aminopyrimidine, 3-(aminocarboxy) pyridine (nicotinamide) and 4-(aminocarbonyl) pyridine (isonicotinamide), namely 2-aminopyrimidinium 2-carboxy-4,5-dichlorobenzoate C4H6N3+ C8H3Cl2O4- (I), 3-(aminocarbonyl) pyridinium 2-carboxy-4,5-dichlorobenzoate C6H7N2O+ C8H3Cl2O4- (II) and the unusual salt adduct 4-(aminocarbonyl) pyridinium 2-carboxy-4,5-dichlorobenzoate 2-carboxymethyl-4,5-dichlorobenzoic acid (1/1/1) C6H7N2O+ C8H3Cl2O4-.C9H6Cl2O4 (III) have been determined at 130 K. Compound (I) forms discrete centrosymmetric hydrogen-bonded cyclic bis(cation--anion) units having both R2/2(8) and R2/1(4) N-H...O interactions. In compound (II) the primary N-H...O linked cation--anion units are extended into a two-dimensional sheet structure via amide-carboxyl and amide-carbonyl N-H...O interactions. The structure of (III) reveals the presence of an unusual and unexpected self-synthesized methyl monoester of the acid as an adduct molecule giving one-dimensional hydrogen-bonded chains. In all three structures the hydrogen phthalate anions are

Proton-transfer versus nontransfer in compounds of the diazo-dye precursor 4-(phenyldiazenyl) aniline (aniline yellow) with strong organic acids: the 5-sulfosalicylate and the dichroic benzenesulfonate salts, and the 1:2 adduct with 3,5-dinitrobenzoic

The structures of two 1:1 proton-transfer red-black dye compounds formed by reaction of aniline yellow [4-(phenyldiazenyl)aniline] with 5-sulfosalicylic acid and benzenesulfonic acid, and a 1:2 nontransfer adduct compound with 3,5-dinitrobenzoic acid have been determined at either 130 or 200 K. The compounds are 2-(4-aminophenyl)-1-phenylhydrazin-1-ium 3-carboxy-4-hydroxybenzenesulfonate methanol solvate, C12H12N3+.C7H5O6S-.CH3OH (I), 2-(4-aminophenyl)-1-hydrazin-1-ium 4-(phenydiazinyl)anilinium bis(benzenesulfonate), 2C12H12N3+.2C6H5O3S-, (II) and 4-(phenyldiazenyl)aniline-3,5-dinitrobenzoic acid (1/2) C12H11N3.2C~7~H~4~N~2~O~6~, (III). In compound (I) the diaxenyl rather than the aniline group of aniline yellow is protonated and this group subsequently akes part in a primary hydrogen-bonding interaction with a sulfonate O-atom acceptor, producing overall a three-dimensional framework structure. A feature of the hydrogen bonding in (I) is a peripheral edge-on cation-anion association involving aromatic C--H...O hydrogen bonds, giving a conjoint R1/2(6)R1/2(7)R2/1(4)motif. In the dichroic crystals of (II), one of the two aniline yellow species in the asymmetric unit is diazenyl-group protonated while in the other the aniline group is protonated. Both of these groups form hydrogen bonds with sulfonate O-atom acceptors and thee, together with other associations give a one-dimensional chain structure. In compound (III), rather than proton-transfer, there is a preferential formation of a classic R2/2(8) cyclic head-to-head hydrogen-bonded carboxylic acid homodimer between the two 3,5-dinitrobenzoic acid molecules, which in association with the aniline yellow molecule that is disordered across a crystallographic inversion centre, result in an overall two-dimensional ribbon structure. This work has shown the correlation between structure and observed colour in crystalline aniline yellow compounds, illustrated graphically in the dichroic benzenesulfonate compound.