Separation of trivalent americium and europium by purified Cyanex 301 immobilized in macro porous polymer

The present work confirms the high separation ability of purified Cyanex 301 towards trivalent americium over europium in liquid-liquid extraction. Solvent 2-nitrophenyl octyl ether (NPOE) lowered the partitioning of Am³⁺ but remained the separation ability over europium. Solvent toluene and 3-octanone lowered the separation factor to 1000. It is feasible to separate Am³⁺ from Eu³⁺ by Cyanex 301 which was immobilized in the macro porous polymer (MPP). 3-Octanone is a suitable solvent for dissolving NH₄OH-saponified Cyanex 301 and MPP is a suitable solid supported material for column operation. A five-step column experiment demonstrated the feasibility to separate Am³⁺ from Eu³⁺ in column which was packed with Cyanex 301-impregnated MPP.     

Selective adsorption of europium/III/ and americium/III/ in non-proliferative mycobacterial suspensions

The absorption effect of 5% w/w non-proliferative cell suspensions of Mycobacterium smegmatis on labelled solutions of Eu³⁺ ions, both alone and in admixtures with Am³⁺, Co²⁺ and Cs⁺, was studied at pH 1.0 as a function of time and cationic concentration. For 10 M concentrations of Eu, Co and Cs, selective adsorption of the trivalent lanthanide and actinide ions was practically quantitative after 90 min; no significant adsorption was observed for cobalt and cesium ions. Column adsorption measurements with the mycobacterial biomass showed that desorption of the M³⁺ ions did not occur at less than 2M HCl and remained incomplete even at higher acidities.     

Influence of organic additives on the colour reaction between trivalent americium and arsenazo III

The colour reaction of Am(III) with Arsenazo III in several hydroorganic media has been examined systematically on the addition of certain polar water-miscible organic solvents in the course of a search for improved and simple spectrophotometric methods for the estimation of americium. Addition of these substances resulted in the stabilization of colour and brought about a drastic enhancement in the absorbance values. The organic additives studied include acetone, acetonitrile, dimethylformamide, dioxane and ethanol. Among the many solvents tested, alcohol and dioxane proved to be the most effective; highest sensitivity is obtained by using a 60% dioxane-ethanol (11) mixture. The apparent molar absorptivity based on Am content is 184616±9931 mol^–1 cm^–1 at 655 nm which is about 3 times that attained for the reaction in aqueous medium (65178±1243). Strikingly, this is the highest value reported as yet for its determination. Beer's law is obeyed both in mixed as well as aqueous media. The effects of some experimental variables on colour development have also been studied to optimize the conditions for the assay of Am.     

Carbamoylmethylphosphine oxide derivatives of adamantane as extracting agents of americium and europium

Adamantane di-1,3-carbamoylmethylphosphine oxide derivatives were synthesized. Their efficiency in extraction of americium(III) and europium(III) from nitric acid solutions was shown. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 110–115, January, 2007.     

Ionic liquid modified silica gel for the sorption of americium(III) and europium(III) from dilute nitric acid medium

The imidazolium bis(2-ethylhexyl) phosphate moiety was chemically attached on silica gel by chemical modification. The resulting product ([SG-Im]⁺ [DEHP]^?) was characterized by FT-IR spectroscopy, thermogravimetry and elemental analysis. The sorption behavior of Am(III) and Eu(III) on [SG-Im]⁺ [DEHP]^? was studied from dilute nitric acid medium for the separation of Am(III) and Eu(III) from aqueous waste. The effect of time, concentrations of nitric acid and europium in aqueous phase on the distribution coefficient (K _d) was studied. The study indicated the possibility of using modified silica for the separation of Eu(III) from Am(III) with high separation factors (>50 at 0.1 M HNO₃).     

Adsorption of europium(III) and americium(III) on kaolinite and montmorillonite in the presence of humic acid

Distribution of trace amount of Eu(III), or Am(III), in the aqueous/solid system containing humic acid and kaolinite, or montmorillonite, was studied by batch experiments. Humic acid was also adsorbed on the clay minerals and its adsorption isotherm can be regarded as a Langmuir type. It is shown that Eu(III), or Am(III), exists as humate complex either in the aqueous or on solid phase in the system including kaolinite, or montmorillonite. These results suggest that the organic-inorganic complex like clay minerals coated with humic substances is important as metal reservoir in the environment.     

The conjugate base of malonaldehyde as antenna-ligand towards trivalent europium and terbium ions

Coordination compounds having formulae [M(MA)₃] _n and M(MA)(^Me2Tp)₂ (M = Y, Eu, Tb; MA = conjugate base of malonaldehyde; ^Me2Tp = tris(3,5-dimethyl-pyrazol-1-yl)borate) were synthesized and characterized. The photoluminescence features of the europium and terbium derivatives were investigated. By comparing the herein reported photoluminescence data with those relative to analogous nitro- and bromomalonaldehyde derivatives, it appears that the conjugate base of malonaldehyde is a more efficient antenna-ligand for the sensitization of Tb(III) luminescence. The experimental data were rationalized on the basis of DFT calculations. Tb(MA)(^Me2Tp)₂ was used as dopant for the preparation of luminescent plastic materials based on poly(methyl methacrylate).     

A europium(III) chelate as an efficient time-gated luminescent probe for nitric oxide

The first Eu(3+) chelate-based luminescent probe specific for nitric oxide (NO) has been designed and synthesized for highly sensitive and selective time-gated luminescence detection of NO. Based on the probe, a time-gated luminescence imaging technique was developed for imaging the endogenous NO production in living plant cells/tissues.     

A europium(III) complex as an efficient singlet oxygen luminescence probe

A new europium(III) complex, [4'-(10-methyl-9-anthryl)-2,2':6',2"-terpyridine-6,6"-diyl]bis(methylenenitrilo) tetrakis(acetate)-Eu(3+), was designed and synthesized as a highly sensitive and selective time-gated luminescence probe for singlet oxygen ((1)O2). The new probe is highly water soluble with a large stability constant of approximately 10(21) and a wide pH available range (pH 3-10), and can specifically react with (1)O2 to form its endoperoxide (EP-MTTA-Eu(3+)) with a high reaction rate constant at 10(10) M(-1) s(-1), accompanied by the remarkable increases of luminescence quantum yield from 0.90% to 13.8% and lifetime from 0.80 to 1.29 ms, respectively. The wide applicability of the probe was demonstrated by detection of (1)O2 generated from a MoO(4)(2-)/H(2)O2 system, a photosensitization system of 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP), and a horseradish peroxidase catalyzed aerobic oxidation system of indole-3-acetic acid (IAA). In addition, it was found that the new probe could be easily transferred into living HeLa cells by incubation with TMPyP. A time-gated luminescence imaging technique that can fully eliminate the short-lived background fluorescence from TMPyP and cell components has been successfully developed for monitoring the time-dependent generation of (1)O2 in living cells.     

Synergic extraction of trivalent gadolinium,europium and americium radionuclides by 15-crown-5 or 18-crown-6 mixed with thenoyltrifluoroacetone from perchlorate medium

Synergic extraction of trivalent Eu, Gd and Am from aqueous perchlorate medium has been studied using mixtures of thenoyltrifluoroacetone (HTTA) and 15-crown-5 or 18-crown-6 (CE) in chloroform at (25±1) °C. Slope analysis of the extraction results indicated a general formula of M(TTA)₃·(CE)₂ for the extracted species. The stability order took the sequence Eu(TTA)₃·(CE)₂>Am(TTA)₃)·(CE)_2>>Gd(TTA)₃·(CE)₂ with 15C5 and Am(TTA)₃·(CE)₂>Eu(TTA)₃·(CE)₂>Gd(TTA)₃·(CE)₂ with 18C6. The synergic factors, extracton constants and formation constants of the extracted species were determined and discussed in terms of the correspondence between cavity size of the crown ethers and ionic crystal radii.     

Bis(2-ethylhexyl)sulfoxide as an extractant for americium(III) from aqueous nitrate media

Solven extraction separation of americium(III) from dilute aqueous nitrate media into n-dodecane by bis(2-ethylhexyl)sulfoxide (BESO) has been investigated over a wide range of experimentgal conditioins. Very poor extractablity of Am(III), necessitated the use of calcium nitrate as the salting-out agent. Effects of certain variables such as acidity, extractant concentration, salting-out agent concentration, organic diluents on the metal extraction by BESO have been examined in detail. By increasing the concentration of BESO in organic phase or calcium nitrate in aqueous phase, nearly quantitative extraction of americium even from moderate acidity is accomplished. Slope analyses applied to Am(III) distribution experiments from acidic nitrate solutions indicate predominant formation of the risolvated organic phase complex, Am(NO₃)₃)·3BESO for which equilibrium constant is found to be, log K_x=1.99. Extraction behavior of Am(III) has also been evlauated in the presence of several water-miscible polar organic solvents to stuy their possible synergistic effects on its extraction. Extractability of americium increased 5 to 10-fold withi increasing conentration of some of these additives, with maximum enhancement being observed in the presence of acetone or acetonitrile. Recovery of BESO from loaded americium is easily obtained using dilute nitric acid as the strippant.     

Extraction of europium and americium by a mixture of CMPO and dicarbollide

The extraction of Eu³⁺ and Am³⁺ by a mixture of CMPO and dicarbollide in nitrobenzene has been studied. The synergetic effect of dicarbollide is pronounced at low acidities but still lower than for previously studied DBDECMP. Separation properties towards Am/Eu pair are small.     

Effect of gamma-radiation on the extraction of europium and americium by benzyldibutylamine

The effect of gamma irradiation on benzene solutions of benzyldibutylamine with cetyl alcohol used for the extraction of europium and americium from nitrate solutions was investigated. The dependence of the distribution coefficient on the dose absorbed either by the whole system or some efficient component was measured. Nitric acid present during irradiation significantly lowers the radiation stability, while benzyldibutylamine and cetyl alcohol appear to be radiostable components. Up to tens of kGy's—the doses expected in an extraction process from highly active solutions—the system seems to be quite stable.     

Vanadium(III) chloride as an effective catalyst for the Pechmann reaction

Good yields of substituted coumarins were obtained by a synthetic method involving the Pechmann reaction using vanadium(III)chloride (VCl₃) reagent to effect this condensation under solvent-free conditions. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 197–200, February, 2006.     

Magnesium/methanol: an effective reducing agent for peroxides

Magnesium in methanol is an effective reagent for the chemoselective reduction of peroxides, including ozonides. Mg/MeOH is significantly more reactive than Me(2)S or PPh(3) and somewhat more reactive than Zn/HOAc.     

Effect of gamma-radiation on the extraction of europium and americium by benzyldimethyldodecylammonium nitrate

Previously it was found that in the extraction separation on lanthanides and americium from acidic nitrate solutions of nuclear fission products, benzyldimethyldodecylammonium nitrate gives high values of separation coefficients. The change in the extraction capacity of this agent and its solutions in benzene in the extraction of Eu(III) and Am(III) was investigated as a function of the adsorbed dose of ionizing radiation. The slight reduction in the extraction of both metals is caused mainly by the radiolysis products of nitric acid in the organic phase that enter into secondary reactions with both the solvent and the extractant. Comparison of the radiation stability of benzyldimethyldodecylammonium nitrate systems with tertiary amines show that the changes in distribution coefficients in the range of investigated absorbed doses are significantly lower in the former case. The investigated system may be characterized as radiation stable up to about 100 kGy even in the presence of nitric acid.     

Selective americium(III) complexation by dithiophosphinates: a density functional theoretical validation for covalent interactions responsible for unusual separation behavior from trivalent lanthanides

The separation of trivalent actinides and lanthanides is a challenging task for chemists because of their similar charge and chemical behavior. Soft donor ligands like Cyanex-301 were found to be selective for the trivalent actinides over the lanthanides. Formation of different extractable species for Am(3+) and various lanthanides (viz. La(3+), Eu(3+), and Lu(3+)) was explained on the basis of their relative stabilities as compared to their corresponding trinitrato complexes calculated using the density functional method. Further, the metal-ligand complexation energy was segregated into electrostatic, Pauli repulsion, and orbital interaction components. Higher covalence in the M-S bond in the dithiophosphinate complexes as compared to the M-O bond in the nitrate complexes was reflected in the higher orbital and lower electrostatic interactions for the complexes with increasing number of dithiophosphinate ligands. Higher affinity of the dithiophosphinate ligands for Am(3+) over Eu(3+) was corroborated with higher covalence in the Am-S bond as compared to the Eu-S bond, which was reflected in shorter bond length in the case of the former and higher ligand to metal charge transfer in Am(III)-dithiophosphinate complexes. The results were found to be consistent in gas phase density functional theory (DFT) calculations using different GGA functional. More negative complexation energies in the case of Eu(3+) complexes of Me(2)PS(2)(-) as compared to the corresponding Am(3+) complexes in spite of marginally higher covalence in the Am-S bond as compared to the Eu-S bond might be due to higher ionic interaction in the Eu(3+) complexes in the gas phase calculations. The higher covalence in the Am-S bond obtained from the gas phase studies of their geometries and electronic structures solely cannot explain the selectivity of the dithiophosphinate ligands for Am(3+) over Eu(3+). Presence of solvent may also play an important role to control the selectivity as observed from higher complexation energies for Am(3+) in the presence of solvent. Thus, the theoretical results were able to explain the experimentally observed trends in the metal-ligand complexation affinity.