Structure of Complexes of Lanthanides with N,N''-Dimethyl-3-Oxa-Glutaramic Acid

A new stripping agent N,N-dimethyl-3-oxa-glutaramic Acid (DOGA) was used in TRPO process to simplify the TRPO process. The structures of the complexes of the DOGA with Eu(Ⅲ), Nd(Ⅲ), La(Ⅲ) were characterized with extended X-ray absorption fine structure spectroscopy (EXAFS), infrared spectra (IR) and mass spectra (MS). The molecular formula of the complexes of Eu(Ⅲ) and Nd(Ⅲ) is deduced to be M(DOGA)3, and only La(Ⅲ) can form the complex HM(DOGA)4 under condition of high consistency of the DOGA. The coordination number of Ln(Ⅲ) in the complexes is 8, and all of coordinated donor atoms are O atoms. For Eu(Ⅲ), Nd(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of Ln-O are 0.240 nm, 0.244 nm respectively, while the numbers of the second O shell are 2.4, and the average coordination bond lengths of Ln-O are 0.260 nm, 0.262 nm. For La(Ⅲ), the coordination numbers of O atom in the first coordination shell is 6 and the average coordination bond lengths of La-O are 0.258 nm, while the number of O atom in the second coordination shell is 4.4, and the average coordination bond length of La-O is 0.28 nm. The results of IR and MS show that there is no water coordinating with Ln(Ⅲ) in the complexes.     

Microwave assisted synthesis, spectroscopic, thermal, and antifungal studies of some lanthanide(Ⅲ) complexes with a heterocyclic bishydrazone

A bishydrazone formed by the condensation of isatinmonohydrazone and salicylaldehyde reacted with lanthanide(Ⅲ) chloride to form complexes of the type [Ln(HISA)2Cl3], where, Ln=La(Ⅲ), ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sin(Ⅲ), Eu(Ⅲ), or Gd(Ⅲ) and HISA=[(2-hydroxybenzaldehyde)-3-isatin]bishydrazone. Both reactions were carried out under microwave conditions. The ligand and the metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV visible, infrared, far infrared, and proton NMR spectral data. The ligand acted as neutral tridentate, coordinating through the carbonyl oxygen, azomethine nitrogen, and phenolic oxygen without deprotonation. The ligand and lanthanum(Ⅲ) complex were subjected to X-ray diffraction studies. The X-ray diffraction pattern of ligand exhibited its crystalline nature and that of the lanthanum(Ⅲ) complex indicated its amorphous character. The thermal decomposition behaviour of the complex, [La(HISA)2Cl3], was examined in the temperature range of 40-800 ℃ using TG, DTG, and DTA. The ligand and the metal complexes were screened for their antifungal activities.     

Electrochemical behavior of Ce（III） in LiF-BaF2 melts

The electrochemical behavior of Ce(III) was investigated in the molten LiF-BaF2 (81 mol.%-19 mol.%) on a molybdenum elec-trode in the temperature range of 1098-1188 K using cyclic voltammetry and chronopotentiometry. It was observed that CeF3 could be re-duced into cerium metal in a reversible one-step process exchanging three electrons (Ce(III)+3e-→Ce(0)) at the operating temperatures on a molybdenum cathode. The electrochemical reduction process was controlled by the diffusion of Ce(III) in the solution. The Ce(III) diffusion coefficients were calculated at different temperatures and the values obeyed the Arrhenius law with an activation energy of 87.5 kJ/mol.     

Effect of pH on sorption for RE(Ⅲ) and sorption behaviors of Sm(Ⅲ) by D152 resin

The pH dependent sorption of rare earth ions (La(Ⅲ), Ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Y(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Tb(Ⅲ), Dy(Ⅲ), Ho(Ⅲ), Er(Ⅲ), Lu(Ⅲ), and Yb(Ⅲ)) from HAC-NaAC buffer solution at 298 K by D152 resin containing-COOH function groups were presented. The sorption behaviors of D152 resin for Sm(Ⅲ) were discussed as an example. The effects of operational conditions such as pH, temperature, and contact time were studied. The statically saturated sorption capacity was 510 mg/g resin at pH 6.70 in HAc-NaAc medium at 298 K. The sorption behaviors obeyed the Freundlich isotherm. The capacity value for column study was obtained by graphical integration as 495 mg/g resin. Thomas model was applied to experimental data to predict the breakthrough curve and to determine the characteristic pa-rameters of the column useful for process design.     

Synthesis and spectral characteristics of La2MoO6：Ln3＋ （Ln=Eu, Sm, Dy, Pr, Tb） polycrystals

The novel phosphors of La 2 MoO 6 activated with the trivalent rare earth Ln 3+ (Ln=Eu, Sm, Dy, Pr, Tb) ions were synthesized by solid state reactions at high temperature in air atmosphere, and their phase impurities and luminescent properties were studied. The photoluminescence (PL) excitation and emission spectra, and decay curves were employed to study their luminescence properties. The lifetimes of the characteristic emissions from Ln 3+ ions were in the order of millisecond except Pr 3+ ions. (LaEu 1-x ) 2 MoO 6 was a promising phosphor for practical application and the optimum concentration was x=0.075. The concentration quenching mechanism of Eu 3+ was also discussed by theoretical fitting using Burshtein model.     

A novel red phosphor:Ca2GeO4:Eu3+

A novel red phosphor Ca2GeO4:Eu3+ was prepared by the traditional solid state reaction. X-ray powder diffraction (XRD) analysis suggested that there was no impurity phase. The study on the diffusion reflection spectra of the undoped and Eu3+ doped Ca2GeO4 phosphors revealed an absorption band superposed of that of the host material and the Eu3+ ions. And the excitation spectrum presented a dominating broad band at 250–300 nm which was attributed to both the host material absorption and the charge transfer band (CTB) of the Eu3+ ions. The investigation on the excitation and diffusion spectra showed that there was an effective energy transfer from the host material to the Eu3+ ions. This was favorable to the red emission of the phosphor. Photoluminescence measurements indicated that the phosphor presents bright red emission at 611 nm under UV excitation. In addition, the Al3+ or Li+ codoping enhanced the red emission from Ca2GeO4:Eu3+ by about 3 and 2 times respectively under UV excitation.     

Cytotoxicity of new Ho(Ⅲ) and Pr(Ⅲ) complexes

New complexes of coumarin-3-carboxylic acid(HCCA) with Ho(Ⅲ) and Pr(Ⅲ) were synthesized and their structures and spectral properties were investigated by elemental analysis,IR,Raman and NMR measurements.According to the experimental data the complexes’ formula and geometries were suggested.Vibrational frequencies,IR intensities and Raman activities as well as 1H NMR chemical shifts of HCCA and its Ho(Ⅲ) and Pr(Ⅲ) complexes were presented.The comparative experimental vibrational and NMR analyses of both the ligand and the Ln(Ⅲ) complexes predicted the bidentate binding to Ho(Ⅲ) and Pr(Ⅲ) through the deprotonated carboxylic oxygen and the carbonylic oxygen of the ligand.The cytotoxic/cytostatic properties of the ligand and the newly synthesized complexes of coumarin-3-carboxylic acid with Ho(Ⅲ) and Pr(Ⅲ) were tested by MTT reduction assay against two mouse tumor cell lines:melanoma B16 and fibrosarcoma L929.They were also tested for cytotoxicity against normal mouse peritoneal macrophages.The proliferation inhibitory effect of the complexes compared to that of the ligand proved their cytotoxic/cytostatic properties against both the tumor cell lines.In addition,the complexes were less cytotoxic against normal mouse macrophages and were able to modulate NO release by activated macrophages.The obtained results were in accordance with our previously published data concerning the activity of lanthanide(Ⅲ) complexes with other coumarin derivatives.     

Synthesis, characterization, fluorescence and DNA-binding studies of europium（Ⅲ） pirates complexes with amide-based 2,3-dihydroxynaphthalene derivatives

Two ligands 2,2′-[2,3-naphthylenebis(oxy)]-bis(N-benzyl(acetamide))(L1) and 2,2′-[2,3-naphthylenebis (oxy)]-bis(N,N-diphenyl (acetamide))(L2) and their europium(Ⅲ) picrate complexes were synthesized. The complexes were characterized by elemental analysis, infra-red (IR), thermogravimetry and differential thermal analysis (TG-DTA) and molar conductivity. Fluorescent experiments showed that the resonance level of the Eu) matched better to the triplet state energy level of the ligand L2 than that of the ligand L1 and the fluorescence in-tensities of the complexes were reduced with the raising coordination ability of solvent. In addition, the interactions between the complexes and DNA were studied by means of spectrometry and cyclic voltammetry. The results suggested that the complexes could bind to DNA through intercalation and the complex 1 binded to DNA more strongly than the complex 2.     

Electroreduction of Y(Ⅲ)in Molten Chlorides and Alloying

The electroreduction of Y(Ⅲ)on tungsten electrode in NaCl-KCl-YCl_3 melt has been investi-gated by cyclic voltammetry.Deposition of Y(Ⅲ)to Y(0)is reversible in one step.The cyclic voltammetry,convolution voltammetry,potential-time curve after potentiostatic electrolysis and X-ray diffraction analy-sis were used to study the electrode process of Y(Ⅲ)reduced on iron electrode.Several Y-Fe intermetalliccompounds are formed before the deposition of metallic yttrium.The diffusion coefficient anddiffusion activation energy of Y in Y_6Fe_(23) were determined by current-time curve at potential step.The results indicate the diffusion of Y in its alloy phase is so slow that this step will control the electrode pro-cess.     

Electrochemical behavior of cerium ion in molten LiCI-KCI

The electrode process of cerium(Ⅲ) on the Mo electrode in eutectic LiCl-KCl melt was investigated by electrochemical transient techniques in the temperature range of 673-783 K,respectively.These results unanimously indicated that the reduction process of cerium(Ⅲ) to cerium metal was a single step exchanging three electrons which was controlled by diffusion of cerium(Ⅲ).Diffusion coefficients(D Ce(Ⅲ)) in eutectic LiCl-KCl melt were determined by cyclic voltammetry,chronopotentiometry and square wave voltammetry.An empirical diffusion coefficient function depending on temperature was proposed:lnD Ce(Ⅲ) =-2.129-5704/T.The formal potentials(Eθ’ Ce(Ⅲ)/Ce(0) versus Ag/AgCl reference electrode) at different temperatures were obtained from chronopotentiometry,which were-2.10 V(673 K) and-2.07 V(733 K),respectively.     

Study on the adsorption of lanthanum(Ⅲ) from aqueous solution by bamboo charcoal

The adsorption behaviors of La(Ⅲ) ion on bamboo charcoal were investigated with various chemical methods and IR spectrometry. Parameters studied include the effects of pH,average particle size,initial ion concentration,contact time and temperature by batch method. The results showed that bamboo charcoal could remove La(Ⅲ) ions effectively from aqueous solution. The loading of La(Ⅲ) ions was strongly dependent on pH of the medium and the optimal adsorption condition was in HNO3-TEA medium with pH value of 7.20. In the batch system,the modified bamboo charcoal exhibited the highest La(Ⅲ) ion uptake as 120 mg/g at 298 K,at an initial pH value of 7.20. The adsorption kinetics were tested with Lagergren-first-order model and pseudo-second-order model. The adsorption data were conformed to the Langmuir and Freundlich isotherms,and the correlation coefficients had been evaluated. Thermodynamic parameters such as free energy(ΔG) ,which were all negative,indicated that the adsorption of La(Ⅲ) ion onto bamboo charcoal was spontaneous and the positive value of enthalpy(ΔH) showed that the adsorption was endothermic in nature. Thomas model was applied to experimental column data to determine the characteristic parameters of column useful for process design. The characterization of both before and after adsorption of La(Ⅲ) ion on bamboo charcoal was undertaken using IR spectroscopic technique. The results revealed that bamboo charcoal was a good choice as a biosorbent for the recovery of lanthanum from aqueous solution.     

Ultraviolet to visible frequency-conversion properties of rare earths doped glass ceramics

Nd3+,Eu3+ and Tb3+ ions doped transparent chlorophosphate glass ceramics were prepared and their frequency-conversion properties were studied. X-ray diffraction (XRD) patterns evidenced the formation of expected halide nanocrystals. The absorption,excitation and emission spectra investigation indicated that some of rare earth (RE) ions were trapped in low phonon energy halide nanocrystals,and therefore an efficient down frequency-conversion was observed. The comparative spectroscopic studies of RE doped samples suggested that the glass ceramics systems are potentially applicable as efficient ultraviolet to visible frequency-conversion photonics materials.     

Origin of light emission and enhanced Eu3+photoluminescence in tin-containing glass

A barium-phosphate glass matrix was co-doped with Sn O and Eu2O3 for investigating on material luminescent properties. Optical absorption and X-ray photoelectron spectroscopy(XPS) were employed in the characterization of tin species. The prevalence of divalent tin was indicated by the XPS data in accord with a conspicuous absorption band detected around 285 nm ascribed to twofold-coordinated Sn centers(isoelectronic with Sn2+). Photoluminescence(PL) excitation spectra obtained by monitoring Eu3+ emission from the 5D0 state revealed a broad excitation band from about 250 to 340 nm, characteristic of donor/acceptor energy transfer. Under excitation of such at 290 nm, the co-doped material exhibited a bright whitish luminescence, and a four-fold enhanced Eu3+ emission relative to a purely Eu-doped reference. Time-resolved PL spectra recorded under the excitation at 290 nm exposed a broad band characteristic of the twofold-coordinated Sn centers and emission bands of Eu3+ ions, which appeared well separated in time in accord with their emission decay dynamics. The data suggested that light absorption took place at the Sn centers(donors) followed by energy transfer to Eu3+ ions(acceptors) which resulted in populating the 5D0 emitting state. Energy transfer pathways likely resulting in the enhanced Eu3+ photoluminescence and the consequential light emission were discussed.     

Effect of Lanthanum (Ⅲ) on Reactive Oxygen Metabolism of Soybean Seedlings under Supplemental UV-B Irradiation

The effect of lanthanum (Ⅲ) on reactive oxygen metabolism of soybean seedlings under elevated ultraviolet-B radiation (UV-B: 280～320 nm) at 0.15 and 0.45 W·cm-2 levels respectively was studied through hydroponics in the laboratory. Plasmolemma permeability and contents of malonadialdehyde (MDA), hydrogen peroxide (H2O2), and proline gradually increased during the imposition of UV-B radiation and subsequently decreased during recovery from UV-B stress. The dynamic tendency of catalase (CAT) activity was similar to that of the above four indices. The activity of peroxidase (POD) initially increased, then remained at a high level, and finally dropped steeply when soybean seedlings were exposed to a low dosage of UV-B radiation. However, POD activity rose throughout and declined slightly on the eleventh day when soybean seedlings were stressed by a high dosage. With the addition of La(Ⅲ) of 20 mg·L-1, the rising tendency of plasmolemma permeability and contents of MDA, H2O2, and proline were slowed down during the stress period, whereas the declining speed was accelerated during the recovery period. The activities of CAT and POD were higher than those without La(Ⅲ) in all experiments. It suggested that the regulative effect of La(Ⅲ) on antioxidant enzymes such as CAT and POD could strengthen their capacities to scavenge reactive oxygen species (ROS), decrease contents of MDA and proline, and maintain normal plasmolemma permeability. Further more, the protective potential of La(Ⅲ) was better under low UV-B radiation than under a high one.     

Luminescence study of europium(III) tris(β-diketonato)/phosphonate complexes in chloroform

The extraction of Eu(III) with β-diketone, HA, and monodentate or bidentate Lewis bases, B, into chloroform and the luminescence properties of the extracted species were studied. Pivaloyltrifluoroacetone, Hpta, and 2-thenoyltrifluoroacetone, Htta, were used as the β-diketones. The Lewis bases, B, were tetraethyl methylene diphosphonate, POPO, which was bidentate, and diethyl benzylphosphonate, PhPO which was monodentate. Based on the extraction data, the stability constants, log β of the first complexes between tris(β-diketonato)Eu(III) and the phosphonate, EuA3B, were determined to be 6.0 for the POPO complex and 3.40 for the PhPO complex. The Eu(III) luminescence intensity in the EuA3POPO was larger than EuA3 where A was either pta or tta at similar concentrations of Eu(III), while that in Eu(pta)3PhPO was stronger than EuA3; however, in Eu(tta)3PhPO, it was weaker than Eu(tta)3. The POPO functions as a sensitizer, and the PhPO functions as a quencher for the tta chelate and as a sensitizer for the pta chelate. From the lifetime and quantum yield, φ, of the Eu(III) luminescence in the complexes as well as the observation of the extractability of Eu(III) with the Hpta and the phosphonates and of the luminescence spectra of the complexes, it was confirmed that the extraction of Eu(III) was remarkably enhanced with a β-diketonate and a strong Lewis base, and also the ternary complex that was formed as the extracted species, showed luminescence enhancement. This phenomenon may be due the formation of a strong bond between the Eu(III) and the strong Lewis base leading to more hydrophobicity in the extracted species and also to more effective energy transfer from the Lewis base to the Eu(III). It was not significant whether the donor atoms were N or O.     

Electrochemistry of samarium in lithium-beryllium fluoride salt mixture

The electrochemical behaviour of samarium was investigated in LiF-BeF2 system on an inert (Mo) electrode by cyclic voltammetry and chronopotentiometry at 804, 833, 847 and 872 K. Redox process Sm3++e-→Sm2+ was recognized and analysed. Cyclic voltammetry data suggested that at potential sweep rates lower than 0.25 V/s, the reduction was limited by the diffusion of Sm3+ ions. It was not possible to observe reduction process of Sm2++2e-→Sm0 due to insufficient electrochemical stability of LiF-BeF2. Diffusion coefficients of Sm3+ ions in LiF-BeF2 were calculated from voltammetric and chronopotentiometric data in the temperature range 804-872 K. Diffusion coefficient values obeyed Arrhenius law. Activation energy was calculated to be 102.5 kJ/mol.     

Mesomorphism of Lanthanide（ Ⅲ ） 4-Hexyloxybenzoates

The 4-alkoxybenzoic acids are well-known liquid crystals showing several mesophases (nematic, smectic C phase or both) depending on the alkoxy chain length and whereby the rigid core of the mesogen is formed by intermolecular hydrogen bo..ds. In this paper it is shown that the thermal behaviour of lanthanide salts of 4-hexyloxybenzoic acids depends on the lanthanide ion (Ln = La, Pr, Nd, Sm, Eu). The lanthanum (Ⅲ) and praseodymium (Ⅲ) 4-hexyloxybenzoates exhibit a smectic A mesophase. No mesophase is found for the corresponding compounds of heavier lanthanides. The thermal properties of the lanthanide(Ⅲ) 4-hexyloxybenzoates were investigated by differential scanning calorimetry (DSC), polarising thermo-optical microscopy and synchrotron X-ray radiation.     

Metal-organic frameworks of lanthanide iminodiacetates and tartrates:Synthesis,structural characterization and luminescence properties——Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Two series of lanthanide-containing metal-organic frameworks(Ln-MOFs) of the general formula{[Ln(HIDA)_2 H_2 O]ClO_4·H_2 O}_n(Ln = La(1),Nd(2),Eu(3),Gd(4),Tb(5),Eu:Tb(6);H_2 IDA=iminodiacetic acid) and [Ln(TT)(HTT)(H_2 O)_3]_n(Ln=Eu(7),Gd(8),Tb(9),Dy(10),and Eu:Tb(11);H_2 TT=tartaric acid)were synthesized by reacting Ln(ClO_4)_3 with iminodiacetic acid and L-tartaric acid,respectively.All compounds were structurally characterized by single-crystal X-ray diffraction.Elemental analyses are co nsistent with the corre sponding crystallographically generated formulas.Mo reover,the luminescence properties of both the single and mixed-lanthanide complexes were studied.Near infrared,red,and green emissions that are characteristic of Nd(Ⅲ),Eu(Ⅲ),and Tb(Ⅲ) are observed for 2,3/7,and 5/9,respectively.For the two mixed-lanthanide complex systems 6 and 11,depending on the relative amount of Eu(Ⅲ) and Tb(Ⅲ),the color of emission can be fine-tuned.It is found that a small amount of Eu(Ⅲ) is adequate for the observation of the most intense transition of Eu(Ⅲ).This is believed to be a result of energy transfer from Tb(Ⅲ) to Eu(Ⅲ) within the same complex-a conclusion supported by the significantly shortened lifetime of Tb(Ⅲ) and the accompanying enhanced lifetime of Eu(Ⅲ) in the mixedlanthanide complex with respect to the corresponding values for the pure Tb(Ⅲ) and Eu(Ⅲ) complexes with the same ligand.     

Electrochemical behavior of dysprosium(Ⅲ) in eutectic LiF-DyF_3 at tungsten and copper electrodes

Electrochemical behavior of dysprosium(Dy) ions in LiF-DyF_3(24 mol%) was investigated by cyclic voltammetry,chronoamperometry and chronopotentiometry.Dy-Cu alloy samples were prepared by constant-potential electrolysis in LiF-DyF_3(24 mol%) at the Cu electrode.The Cu_5 Dy and Cu phases were characterized by an X-ray diffractometer and a scanning electron microscope equipped with an energy dispersive spectrometer.The results show that the reduction of Dy(Ⅲ) ions in a LiF-DyF_3(24 mol%)molten salt system is found to be a quasi-reversible diffusion-controlled process which occurs via a onestep reaction involving the transfer of three electrons.The electro-crystallization processes of the Dy metal at the W electrode and the mode of nucleation confirm that progressive nucleation is dominant at high concentrations of Dy ions in the LiF-DyF_3 salt.At lower concentrations,the instantaneous nucleation of Dy with three-dimensional growth of the nuclei is dominant.     

Synthesis and photoluminescence studies of Ba(Gd,Ln)B9O16:Eu3+(Ln=La,Y) phosphors for n-UV LED lighting and display devices

BaGdB9O16:Eu3+ and Ba(Gd,Ln)B9O16:Eu3+(Ln=La, Y) phosphors were synthesized by solid state diffusion method. The X-ray diffraction, scanning electron microscopy(SEM) and photoluminescence properties were investigated. The as-synthesized BaGdB9O16:Eu3+ and Ba(Gd,Ln)B9O16:Eu3+(Ln=La, Y) phosphors showed strong red emission under ultraviolet light excitation. By partially substituting Gd3+ by La3+ and Y3+ ions in the host BaGdB9O16:Eu3+ materials, the maximum emission intensity was observed for the optimum composition of BaGd0.91La0.8B9O16Eu0.01 phosphor. The experimental results indicated that the Eu doped BaGdB9O16 and Ba(Gd,Ln)B9O16(Ln=La, Y) phosphors were promising red phosphors, which might find potential applications in near-UV excited LED lighting as well as display devices. Comparison of as-synthesized phosphors with standard phosphor used in CFL(compact fluorescent lamp) was also done. Energy transfer mechanism of Gd3+ to Eu3+ was also discussed in this paper.