Solvent extraction behaviour of lanthanum(III), cerium(III), europium(III), thorium(IV) and uranium(VI) with 3-phenyl-4-benzoyl-5-isoxazolone

The extraction behaviour of La(III), Ce(III), Eu(III), Th(IV) and U(VI) with 3-phenyl-4- benzoyl-5-isoxazolone (HPBI) in chloroform has been studied. The mechanism of extraction and the species extracted have been identified. Extraction constants for each system have been calculated. The system has been used to separate Th(IV) from U(VI) and from La(III), Ce(III) and Eu(III). A comparison of the extraction constants with those for the 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) and thenoyltrifluoroacetone (HTTA) systems indicates that HPBI extracts these metal species better than HPMBP and HTTA do.     

Interaction features of cerium (III) and europium (III) acetate and pivalate with monoethanolamine

The composition of mixed-ligand complexes of cerium (III) and europium (III) acetates and pivalates with monoethanolamine (MEA) depends on the synthesis conditions and the nature of carboxylate ligand. We prepared solid complexes [Ln(Piv)₃(MEA) _x ], where Ln = Ce, Eu; HPiv-2,2-dimethylpropionic (pivalic) acid; x = 1, 1.5, and gel-like hydroxocomplexes [Ln(Carb) _{n − x − y} ,(NO₃) _x (OH) _y (MEA) _w (H₂O) _z ], where Ln = Ce, n = 4; Ln = Eu, n = 3; HCarb is acetic acid (HAcet) or HPiv. The values of the coefficients x, y, w, and z depend on the synthesis conditions and heat treatment. Prepared compounds were characterized by IR and ¹H NMR spectroscopies, elemental and thermal analyses, and MALDI-MS. The ESI-MS method was used to characterize the processes occurring in the solutions.     

Crystal structure and luminescence of europium(III) acrylate

The atomic structure of europium acrylate crystals [Eu₂(Acr)₅OH·3H₂O]·2(0.5H₂O) was studied by X-ray analysis (a = 24.360(3) Å, b = 18.466(2) Å, c = 8.5818(9) Å, β = 96.087(2)°, space group C2/c, Z = 6, ρ_calc = 2.036 g/cm³). The crystal structure involves chains of binuclear [Eu₂(C₃H₃O₂)₅OH·3H₂O] molecules, running infinitely in the [101] direction and having pairs of C₉H₉EuO₇H₂O molecules alternating with C₆H₆EuO₄OH·2H₂O molecules that link the pairs. The infinite chains are linked by hydrogen bonds and van der Waals interactions. The thermal behavior of luminescence of the europium(III) complex is discussed.     

Double cerium(III) cerium(IV) sulfate K5Ce2(SO4)6·H2O

All Union Scientific Research Institute for Chemical Reagents and Highly Pure Chemical Substances. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 1, pp. 135–140, January–February, 1989.     

Anti-Stokes luminescence of europium(III)-doped lanthanum oxychloride

The anti-Stokes luminescence from the ⁵D_1,2,3 levels of Eu³⁺-doped LaOCl was observed at 300 and 77 K under dye-laser excitation to the ⁵D₀ level. A two-photon absorption from the ⁷F₀ ground level to charge-transfer states via the ⁵D₀ level was concluded to be the mechanism involved. The absorption of the first photon through the forbidden ⁵D₀→⁷F₀ transition determines the upconversion efficiency. The two-photon absorption seems to occur as an intra-ion process without interionic energy transfer.     

Laser-induced luminescence study of europium(III) polyacrylate and polymaleate complexes

Luminescence lifetime of Eu(III) in polyacrylate and polymaleate complexes has been measured to evaluate the number of water molecules bound to the ion. The number of residual water molecules hydrated to Eu(III) in the polyacrylate and polymaleate complexes ranged from 3.5 to 4.5 when the supporting electrolyte concentration was 0.01. The residual hydration number decreased with the addition of supporting electrolyte. These results indicate that Eu(III) is surrounded by polymolecular ligands in these complexes.     

Solvent extraction of lanthanum(III), europium(III) and lutetium(III) with fluorinated 1-phenyl-3-methyl-4-benzoyl-5-pyrazolones into chloroform

A series of chelating reagents, 1-phenyl-3-methyl-4-(2-fluorobenzoyl)-5-pyrazolone, 1-phenyl-3-methyl-4-(3-fluorobenzoyl)-5-pyrazolone and 1-phenyl-3-methyl-4-(4-fluorobenzoyl)-5-pyrazolone, has been synthesized. The extraction of Ln(III), (Ln = La, Eu and Lu) into chloroform with these reagents at 30 +/- 1 degrees has been studied. The composition of the complexes extracted has been determined by the slope method, and the extraction constants K(ex), were measured. The presence of the fluorine atom in the reagents does not make the K(ex), values much different from those obtained with the parent pyrazolone.     

Modified dipicolinic acid ligands for sensitization of europium(III) luminescence

The effect of substitution at the 4 and 3,5 positions in the pyridine ring of europium(III) pyridine-2,6-dicarboxylate complexes has been investigated with particular emphasis on sensitization of the Eu3+ ion. Sensitization of the Eu3+ 615-nm emission was achieved through excitation of the ligands in which the 4 substituent was -H, -OH, and -Cl and the 3,5 position was -H. In these cases, the ligand-to-Eu3+ ratio was confirmed as being 3:1. The sensitization was found to increase following substitution of the 4 position in the order Cl > H > OH. This is attributed to energy transfer occurring from the ligands into different Eu3+ intra-atomic energy levels, with spin selection rules governing the efficiency of this process. The Eu3+ luminescence lifetime was measured and found to vary from 1.16 to 2.90 ms depending on the excitation energy, ligand, and solvent. For the case of the 3,5-dibromo-4-hydroxy derivative, no sensitization was observed and a ligand-to-Eu3+ ratio of 1:1 was found. The solubility of these complexes in water and their long emission lifetime make them attractive for use as probes in biological systems.     

Facile synthesis and luminescence properties of europium(III)-doped silica nanotubes

Photoluminescent nanomaterials had emerged as an amazing field in a wide range of applications during the past few decades. In this article, fibrous europium tartrates and photoluminescent silica nanotubes were conveniently synthesized by using sol–gel method, in which europium ions entered silica matrix. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction analysis, fourier transform infrared spectra, energy-dispersive X-ray spectroscopy and photoluminescence (PL) spectra analysis were used to characterize the growth, structure, morphology and optical property of the products. The results indicated that europium tartrates nanofibers as a template can transform tetraethylorthosilicate into silica nanotubes effectively. Meanwhile, europium(III) was transferred from the fibers to the tubes successfully. A hard template mechanism was proposed to explain the formation process of europium(III)-doped silica nanotubes. Moreover, different morphologies of silica-based nanomaterials were obtained due to varying NH₄OH addition or stirring time. PL spectra from nanofiber and nanotube show a typical emission of europium(III), and 13 % is the quenching concentration of europium(III) in silica matrix for this system. The novel silica nanotubes can be applied potentially in optical and biological areas.     

Interaction between 1,2-dimethyl-3-hydroxypyrid-4-one and europium(III)

The interaction of the clinically used 1,2-dimethyl-3-hydroxypyrid-4-one with trivalent europium Eu(III), was investigated by using potentiometric and spectroscopic methods. The stability constants of the EuL_n ⁽³⁻ⁿ⁾⁺ complexes determined by spectroscopic and potentiometric measurements were found to be log β₁₁ = 6.5±0.3 and log β₁₂ = 12.0±0.5. However, at pH ≥ 5, hydrolysis of the Eu-L complexes starts, resulting in the formation of needle-type, yellow crystals. The low solubility of the Eu-L complexes in the neutral pH range is disadvantageous with respect to the use of deferiprone as chelating agent for decorporation of trivalent f-elements.     

Determination of citrate in tablets and of oxytetracycline in serum using europium (III) luminescence

A direct method for the determination of citrate and oxytetracycline in samples containing complex matrices like tablets or serum has been developed using the luminescence of the ternary complex formed with Eu(III) ions. The triplet-state energy level of oxytetracycline (OxTc), the excitation maximum (412 nm) and the luminescence lifetime of Eu-OxTc (58 μs) were determined. A 17-fold luminescence enhancement at 615 nm occurs upon addition of citrate within a short 5-min incubation time at neutral pH. This is accompanied by a threefold increase of the luminescence decay time. The optimal conditions for determination of OxTc are equal concentrations of Eu (III) and citrate (C = 1 · 10^− 4 mol L^− 1) and pH 7.2. For determination of citrate, the optimal concentrations of Eu(III) and OxTc are 1 : 0.5 (C_Eu = 1 · 10^− 4 mol L^− 1, C_OxTc = 5 · 10^− 5 mol L^− 1) at pH 7.2. The linear range for determination of OxTc in serum is 0.25-250 μg mL^− 1, and for citrate in tablets from 0.5 to 10.0 μg mL^− 1 (2.3 · 10^− 6- 4 · 10^− 5 mol L^− 1). The detection limit was 0.1 μg mL^− 1 for OxTc and 0.2 μg mL^− 1 (1 · 10^-6 mol L^− 1) for citrate, respectively. A comparison of the new method with other methods for determination of citrate is given.     

Temperature-driven luminescence switching of europium(III) in a glass dispersed liquid crystal film

Glass dispersed liquid crystal films doped with the tris(β-diketonato)europium(III) complex [Eu(dbm)₃(gly)] (Hdbm=dibenzoylmethane, gly=1,2-dimethoxyethane) were prepared. The liquid crystal host was 4-pentyl-4'-cyanobiphenyl (5CB); a mixed silica-titania glass with a refractive index close to that of 5 CB was chosen as the glass matrix. The photoluminescence intensity was measured as a function of temperature. A strong intensity change was observed at the nematic-to-isotropic transition.     

Temperature-driven luminescence switching of europium(III) in a glass dispersed liquid crystal film

Glass dispersed liquid crystal films doped with the tris(β-diketonato)europium(III) complex [Eu(dbm)₃(gly)] (Hdbm=dibenzoylmethane, gly=1,2-dimethoxyethane) were prepared. The liquid crystal host was 4-pentyl-4′-cyanobiphenyl (5CB); a mixed silica–titania glass with a refractive index close to that of 5 CB was chosen as the glass matrix. The photoluminescence intensity was measured as a function of temperature. A strong intensity change was observed at the nematic-to-isotropic transition.     

Structure, spectral and luminescence properties of compounds of europium(III) with nicotinic acid and enrofloxacin

The compounds of Eu(III) with nicotinic acid and enrofloxacin are synthesized. Their composition and structure are proved by the data of elemental analysis, IR and luminescence spectroscopy, powder and single crystal X-ray diffraction. By single crystal X-ray diffraction, the structure of the compound of Eu with nicotinic acid is identified as a centrosymmetric dimer with 4 carboxylate bridges of the composition Eu₂(C₆H₄NO₂)₆·4H₂O. The Stark structure of the ⁵ D ₀-⁷ F _j transitions in the mixed-ligand compounds of Eu(III) with nicotinic acid and enrofloxacin is determined. The bands of IR spectra are assigned; the conclusion about the bidentate coordination of ligands is made.     

Nonradiative deactivation of europium(III) luminescence as a detection scheme for moisture

The nonradiative deactivation of the excited state of europium(III)-based phosphors via OH-vibrations in the presence of water allows the detection of moisture in nitrogen at concentration levels down to at least 25 ppm (0.09% RH).     

Spectrofluorimetric determination of trace amounts of europium(III) ion with lutetium(III)-sparfloxacin-sodium dodecyl sulfate luminescence enhancement system.

A new luminescence-enhancement system based on complex formation between europium and sparfloxacin in the presence of lutetium in a sodium dodecyl sulfate solution has been discovered. By adding a suitable amount of Lu3+ to the Eu-sparfloxacin-sodium dodecyl sulfate system, the luminescence can be enhanced by approximately 5-fold compared with that of the system without Lu3+. Under the optimum conditions, the luminescence intensity of the system is a linear function of the concentration of europium in the range of 1.0 x 10(-10) - 5.0 x 10(-7) mol L(-1). The detection limit of europium is 2.0 x 10(-13) mol L(-1) (S/N = 3). The system was used for the determination of trace amounts of europium in rare earth samples with satisfactory results.     

Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.