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At least 19 recordsLinked to original sources
PubMed2005

Distribution of elements in the millipede, Oxidus gracilis C. L. Koch (Polydesmida: Paradoxosomatidae) and the relation to environmental habitats.

The concentrations of 55 elements in the millipede, Oxidus gracilis, soil and plant in the habitat were examined using inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). In all the millipedes, Ca concentration derived from calcium carbonate in the exoskeleton was the highest at average 94 microg/mg-weight. The other major elements were the following: Mg, K, Na, Zn, Fe, Al, Cu, Sr, Ba, Mn and Ti (>1 ng/mg-body weight), whereas Se, Mo, Ag, Cd, Co, Li and Ce etc. were in trace levels. Interestingly, the various 15 elements such as Ca, Na, Zn, Al, Ba, Ga, Ag, Cd, Co and Y in environmental habitats were well reflected in the body of the millipede. Although the heavy metal contents, in the order of Cu>Pb>Cd, were similar to those of other invertebrates, Cu in the millipede was remarkably high concentration. Zn was maintained in a range of 72-394 ng/mg-weight as essential element in the body and no difference was found in the sexes. The C1 chondrite normalization pattern for lanthanoid series elements in the millipede, soil and plant indicated that the environmental habitats were well protected from pollution. These characteristics of internal elements and metal accumulation in the millipede or relation to their habitats would be useful information for the environmental pollution studies.

Animals↗
PubMed2006

Self-assembled microspheres from f-block elements and nucleoamphiphiles.

Hollow microspheres featuring a hybrid lipid-cation multilamellar shell are prepared by hydration of a nucleoside based amphiphile with an aqueous solution containing either actinide or lanthanide salts. The physico-chemical data collected clearly indicate that the formation of these microspheres is a consequence of the following concomitant stabilizing factors: (i) hydrophobic interactions, (ii) nucleobase dimer formation and (iii) phosphate/f-block element salt binding.

Actinoid Series Elements↗
PubMed2002

Synergic extraction of lanthanoids by mixtures of LIX 54 (high molecular weight beta-diketone) and bidentate neutral amines.

The synergic extraction of lanthanoids has been investigated using mixtures of high molecular weight beta-diketone, LIX 54 (HA; major component, 1-phenyl-3-isoheptyl-1,3-propanedion) and bidentate neutral ligands (S) in toluene. The distribution behavior of bidentate amines (2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp)) was investigated and their related equilibrium constants were evaluated. The synergic effect is produced by the formation of such adduct complexes as MA3 x S. The extraction constants with LIX 54 alone and those in the presence of bidentate ligands were determined for lanthanoid-series elements.

Journal Article↗
PubMed2003

Analytical separations of lanthanides and actinides by capillary electrophoresis.

The separation of lanthanide and actinide elements belongs to one of the most challenging tasks of the separation science, due to a great similarity in their physical and chemical properties. The electrophoretic separation can be accomplished in the presence of suitable complex-forming agents, from which alpha-hydroxyisobutyric acid (HIBA) has been used most often. In the most effective capillary electrophoretic mode--capillary zone electrophoresis (CZE)--a complete separation of lanthanide ions can be accomplished within a few minutes. Various electrophoretic methods can be relatively easily adopted for the determinations of individual lanthanide elements in certain kinds of technical materials, concentrates, precursors, etc., where the high speed and low costs of analysis characteristics of capillary electrophoresis (CE) may be advantageously exploited. Electrophoretic techniques may also be employed for speciation studies, especially for examinations of the behavior of actinides in the environment.

Actinoid Series Elements↗
PubMed2005

Infrared and Raman spectroscopic and theoretical studies of nonaaqua complexes of trivalent rare earth metal ions.

Infrared (IR), far-infrared (far-IR) and Raman spectra have been recorded of the hydrated lanthanide(III) trifluoromethanesulfonates, [Ln(OH2)9](CF3SO3)3, (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), and also for the deuterated [La(OD2)9](CF3SO3)3 compound. This has enabled complete assignments of all seven metal-oxygen stretching modes for the first time. Force constant calculations have been performed for an LnO9(3+) moiety, with a tricapped trigonal prismatic oxygen atom arrangement in D3h point group symmetry. The lanthanide contraction in reflected in continuously increasing trends for the averaged LnO stretching frequencies and force constants with increasing inverse of ionic radii. The stretching force constants increased from 0.81 to 1.16 Ncm-1 for the LnO6 prism in the series from La to Lu, while those for the capping LnO3 bonds increased from 0.49 to 0.65 Ncm-1. The LnO stretching force constants showed a smooth correlation with the LnO bond distances to the prism oxygen atoms, while the correlation to the LnO capping oxygen atoms has a different shape, reflecting the increased ligand-ligand repulsion with decreasing lanthanide ion size.

Elements↗
PubMed2004

Effect of alcohols on elution chromatography of trivalent actinides and lanthanides using tertiary pyridine resin with hydrochloric acid-alcohol mixed solvents.

Elution chromatography with a tertiary pyridine resin has been used to separate the trivalent actinides (An3+) from the lanthanides (Ln3+) using an alcoholic hydrochloric acid solvent. Trivalent Am and Cm were separated from the Ln by employing a 1 cm(phi) x 10 cm resin column with the mixed solvent system composed of concentrated hydrochloric acid (HCl) and alcohols. The distribution coefficients (Kd) and the separation factors between An and Ln (alpha(An)(Ln)) increased as the alcohol content of the solvent mixture increased. On the other hand, the Kd and alpha(An)(Ln) decreased drastically upon the addition of water to the solvent mixture. Among the four alcohols investigated (methanol, ethanol, n-propanol and n-butanol), the ethanol-HCl mixed solvent system showed the largest Kd and alpha(An)(Ln). The mechanism of adsorption for An and Ln cations on the pyridine resin is discussed in addition to the results presented herein.

Actinoid Series Elements↗
PubMed2005

Sorption of 243Am(III) to multiwall carbon nanotubes.

Carbon nanotubes have attracted great interest in multidisciplinary study since their discovery. Herein, radionuclide 243Am(III) sorption to uncapped multiwall carbon nanotubes (MWCNTs) was carried out at 20+/-2 degrees C in 0.01 and 0.1 M NaClO4 solutions. Effects of 243Am(III) solution concentration, ionic strength, and pH on 243Am(III) sorption to MWCNTs were also investigated. The sorption is strongly dependent on pH values and weakly dependent on the ionic strength in the experimental conditions. The results show that MWCNTs can adsorb 243Am(III) with extraordinarily high efficiency by forming very stable complexes. Chemisorption or chemicomplexation is the main mechanism of 243Am(III) sorption on the surface of MWCNTs. MWCNTs can be a promising candidate for the preconcentration and solidification of 243Am(III) or its analogue lanthanides and actinides from large volumes of aqueous solution, as required for remediation purposes, and perhaps also as a sorbent for the removal of heavy metal ions from the industry wastewater.

Actinoid Series Elements↗
PubMed2004

Lanthanide(III)/actinide(III) differentiation in coordination of azine molecules to tris(cyclopentadienyl) complexes of cerium and uranium.

Reaction of azine molecules L with the trivalent metallocenes [M(C5H4R)3](M = Ce, U; R = But, SiMe3) in toluene gave the Lewis base adducts [M(C5H4R)3(L)](L = pyridine, 3-picoline, 3,5-lutidine, 3-chloropyridine, pyridazine, pyrimidine, pyrazine, 3,5-dimethylpyrazine and s-triazine), except in the cases of M = U and L = 3-chloropyridine, pyridazine, pyrazine and s-triazine where oxidation of U(III) was found to occur. In the pairs of analogous compounds of Ce(III) and U(III), i.e.[M(C5H4But)3(L)](L = pyridine, picoline) and [M(C5H4SiMe3)3(L)](L = pyridine, lutidine, pyrimidine and dimethylpyrazine), the M-N and average M-C distances are longer for M = Ce than for M = U; however, within a series of azine adducts of the same metallocene, no significant variation is noted in the M-N and average M-C distances. The equilibria between [M(C5H4R)3], L and [M(C5H4R)3(L)] were studied by 1H NMR spectroscopy. The stability constants of the uranium complexes, KUL, are greater than those of the cerium counterparts, KCeL. The values of KML are much greater for R = SiMe3 than for R = But and a linear correlation is found between the logarithms of KML and the hydrogen-bond basicity pKHB scale of the azines. Thermodynamic parameters indicate that the enthalpy-entropy compensation effect holds for these complexation reactions. Competition reactions of [Ce(C5H4R)3] and [U(C5H4R)3] with L show that the selectivity of L in favour of U(III) increases with the [small pi] donor character of the metallocene and is proportional to the pi accepting ability of the azine molecule, measured by its reduction potential.

Actinoid Series Elements↗
PubMed2001

Analytical microscopy observations of rat enterocytes after oral administration of soluble salts of lanthanides, actinides and elements of group III-A of the periodic chart.

The behavior in the intestinal barrier of nine elements (three of the group III-A, four lanthanides and two actinides), absorbed as soluble salts, has been studied by two microanalytical methods: electron probe X-ray micro analysis (EPMA) and secondary ion mass spectrometry (SIMS). It has been shown that the three elements of group III-A, aluminium, gallium and indium; and the four lanthanides, lanthanum, cerium, europium and thulium, are selectively concentrated and precipitated as non-soluble form in enterocytes of proximal part of the intestinal tract. SIMS microscopy has shown that these elements are concentrated as a number of submicroscopic precipitates, most of them localized in the apical part of the duodenum enterocytes, where they are observed from one hour to 48 hr after a single intragastric administration. No precipitate is observed after three days. It is suggested that this mechanism of local concentration limits the diffusion of these elements through the digestive barrier, some of them being toxic and none of them having a recognized physiological role. Additionally, the precipitation in duodenal enterocytes, the life time of which is on the order of 2-3 days, allows the elements absorbed as soluble form to be eliminated as a non-soluble form in the digestive lumen along with the desquamation of the apoptotic enterocytes. The intracytoplasmic localization of the precipitates are supposed to be the lysosomes although no direct evidence could be given here due to the very small sizes of the lysosomes of enterocytes. The same results were not observed with the two studied actinides. After administration of thorium, only some very sparse microprecipitates could be observed in intestinal mucosa and, after administration of uranium, no precipitates were observed with the exception of some in the conjunctive part of the duodenal villi.

Actinoid Series Elements↗
PubMed2003

A generic biokinetic model for predicting the behaviour of the lanthanide elements in the human body.

Information on the biokinetics of the 15 elements of the lanthanide series, 57La to 71Lu, is too sparse to permit individual development of meaningful biokinetic models to describe the behaviour of each of the elements in humans. The lanthanides show a regular gradation in chemical properties across the series, and animal studies indicate that this is reflected in regular differences in their deposition in tissues such as the liver and skeleton. These regular differences in chemical and biological behaviour have been utilised to construct a generic lanthanide biokinetic model and to define element-specific parameters for each element in the series. This report describes the use of the available biokinetic data for humans and animals to derive the parameters for each of the elements.

Animals↗
PubMed2002

High contents of rare earth elements (REEs) in stream waters of a Cu-Pb-Zn mining area.

Stream waters draining an old mining area present very high rare earth element (REE) contents, reaching 928 microg/l as the maximum total value (sigmaREE). The middle rare earth elements (MREEs) are usually enriched with respect to both the light (LREEs) and heavy (HREEs) elements of this group, producing a characteristic "roof-shaped" pattern of the shale Post-Archean Australian Shales-normalized concentrations. At the Fenice Capanne Mine (FCM), the most important base metal mine of the study area, the REE source coincides with the mine tailings, mostly the oldest ones composed of iron-rich materials. The geochemical history of the REEs released into Noni stream from wastes in the FCM area is strictly determined by the pH, which controls the REE speciation and in-stream processes. The formation of Al-rich and mainly Fe-rich flocs effectively scavenges the REEs, which are readily and drastically removed from the solution when the pH approaches neutrality. Leaching experiments performed on flocs and waste materials demonstrate that Fe-oxides/oxyhydroxides play a key role in the release of lanthanide elements into stream waters. The origin of the "roof-shaped" REE distribution pattern as well as the peculiar geochemical behavior of some lanthanide elements in the aqueous system are discussed.

Aluminum↗
PubMed2006

Trinuclear lanthanide complexes of a compartmental ligand N,N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide: a spectroscopic investigation.

Trinuclear lanthanide complexes of the formula [Ln(3)(PPDA)(NO(3))(6)(H(2)O)(2)].NO(3).2H(2)O where Ln=La(III), Pr(III), Sm(III), Nd(III), Eu(III) Gd(III) Tb(III), Dy(III) and Y(III); H(2)PPDA=N,N'-bis(2-pyridinyl)-2,6-pyridinedicarboxamide, have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility measurements and spectral (IR, NMR, UV-vis, fluorescence, FAB and EPR) and thermal studies.

Lanthanoid Series Elements↗
PubMed2007

Facile construction of lanthanide metallomacrocycles with the bridging imidazolate and triazolate ligands and their ring expansions.

Four novel tri- or tetranuclear organolanthanide metallomacrocycles [Cp2Ln(mu-Im)(THF)3 (Cp = C5H5, Ln = Yb (1), Er (2)], [Cp2Dy(mu-Im)]4(THF)]3 x 2THF (3), and [Cp'2Yb(mu-eta1:eta2-Tz)]4 x 2THF (Cp' = CH3C5H4) (4) have been synthesized through protolysis of Cp3Ln or Cp'3Yb with imidazole or triazole, indicating that both the bridge-ligand size and the lanthanide-ion radii can be applied in the modulation of the metallomacrocycles. Further investigations on the reactivity of complexes 1, 3, and 4 toward phenyl isocyanate reveal that PhNCO inserts readily into the simple bridge Ln-N bonds of 1 and 3 to yield the corresponding insertion products [Cp2Ln(mu-eta1:eta2-OC(Im)NPh)]3 (Ln = Yb (5), Dy (6)) but cannot insert into the Ln-N bond with a mu-eta1:eta2-bonding mode in 4. The novel bridge ligand [OC(Im)NPh] can expand the numbers of the ring members from 12 to 18 in 5 or 16 to 18 in 6. The number of metal atoms in the metallacycles with the ligand [OC(Im)NPh] is independent of the lanthanide-ion size; both trinuclear lanthanide macrocycles are observed in 5 and 6. All of these new complexes have been characterized by elemental analysis and spectroscopic properties, and their structures have also been determined through X-ray single-crystal diffraction analysis.

Crystallography, X-Ray↗
PubMed2006

Benefiting from the unique properties of lanthanide ions.

The recent upsurge of interest in contrast agents for magnetic resonance imaging, of luminescent chemosensors for medical diagnostic, and lately, for optical imaging of cells has generated an impressive momentum for the coordination and supramolecular chemistry of trivalent lanthanide ions. We shortly review the synthetic methods allowing the introduction of these spherical ions with fascinating optical and magnetic properties into elaborate mono- and polymetallic edifices. We then illustrate these methods by selected examples describing the use of (i) a coronand to produce luminescent liquid crystals, (ii) derivatized calixarenes for 4f-5f element separation, (iii) podates for the production of nanoparticles with high relaxivity and for sensitizing the near-infrared (NIR) emission, and (iv) self-assembly processes for producing functional bimetallic edifices.

Ions↗
PubMed2004

Separation and determination of lanthanides, thorium and uranium using a dual gradient in reversed-phase liquid chromatography.

Separation and determination of lanthanides, Th and U is of great relevance in different fields of science and technology. Reversed-phase high-performance liquid chromatography (RP-HPLC) using alpha-hydroxy isobutyric acid (alpha-HIBA) as an eluent on reversed-phase column modified to cation exchanger has been reported to achieve the separation. However, under those conditions, Th and U are eluted amongst lanthanides, making their quantification difficult due to overlapping with some of the lanthanides peaks. In this work, different chromatographic parameters (concentrations of eluent and ion interaction reagent, pH, etc.) were studied systematically to arrive at optimum chromatographic conditions. Using the dual (concentration and pH) gradient conditions, lanthanides, Th and U could be separated in 11 min by RP-HPLC with sequential elution of Th and U after the elution of all the lanthanides. The separation methodology was tested using SY-3 rock sample for the separation and determination of lanthanides, Th and U. The method allows an accurate determination of these elements in a single run using a single column. Also, the method is fast and cost-effective compared to the reported methods.

Butyrates↗
PubMed2001

Distribution of lanthanoids, Be, Bi, Ga, Te, Tl, Th and U on the territory of Bulgaria using Populus nigra 'Italica' as an indicator.

The concentrations of lanthanoids, Be, Bi,Ga, Te, Tl, Th and U have been determined using ICP-MS for 100 standardized samples of poplar leaves collected from the territory of Bulgaria. The investigated elements are log-normally distributed on the territory. Using cluster analysis of the analytical data the samples were grouped according soil type on which the plants are growing.

Bulgaria↗