• Title/Summary/Keyword: Lanthanide

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Contact-Only and Dipolar-Only Mixtures of Lanthanide NMR Shift Reagents

  • Lee, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.433-438
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    • 1986
  • Two new types of NMR shift reagents, one giving dipolar-only and the other giving contact-only shifts, can be prepared simply by mixing two appropriate $Ln(fod)_3$(Ln = Pr, Nd, Eu, and Yb) reagents in certain ratios. The $^1H$ and $^{13}C$ NMR spectra of pyridine-type substrates, quinoline and isoquinoline, whose paramagnetic shifts are normally a composite of contact and dipolar contributions with single lanthanide shift reagents, show the feasibility of this approach.

Electrochemical study on the Lanthanide-Alizarin Complexone Complexes (란탄족원소-ALC 착물의 전기화학적 연구)

  • Son, Byeong-Chan;Kim, Jae-Gyun;Park, Jong-Min
    • The Journal of Natural Sciences
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    • v.7
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    • pp.37-46
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    • 1995
  • Electrochemical behavior of $Ln^{3+},$-ALC complexes($Gd^{3+},$ $Tb^{3+},$ $Dy^{3+},$ $Ho^{3+},$ $Er^{3+},$ $Yb^{3+}$ and $Lu^{3+}$-alizarin complex-one) has been investgated by d.c polarography, differential pulse polarography and cyclic voltammetry. The reduction mechanism of ALC comes to the conclusion that the two electron make one step of reversible processes, and that there is few adsorption in the electrode reaction. The new complex is made from one lanthanide ion and one ALC. This complex is proven to make an adsorptive complex wave, by the experiments of differential pulse polarography and cyclic voltammetry. The reduction potential of complex wave($P_2$)turns up more negatively than ligand wave($P_1$) does. Linear calibration curves of the decreasing P1 and increasing $P_2$ is obtained when the lanthanide concentration varys from $2.5X10^5$M to $1X10^4M$.

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Interaction Behavior between Lanthanide Element and Ferritic-Martensitic Steel (란탄족 원소와 Ferritic-Martensitic 강의 반응 거동)

  • Kim, Jun Hwan;Baek, Jong Hyuk;Lee, Byoung Oon;Lee, Chan Bock;Yoon, Young Soo
    • Korean Journal of Metals and Materials
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    • v.48 no.8
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    • pp.691-698
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    • 2010
  • A study has been carried out to evaluate the interaction behavior between a lanthanide element and clad material in order to analyze the effect of the lanthanide element on the fuel cladding chemical interaction (FCCI). A diffusion couple test between Misch metal (70Ce-30La) and ferritic-martensitic steel (Gr.92) was performed at $660^{\circ}C$, followed by a microstructural analysis of the coupled sample. The results showed that Ce in the Misch metal, rather than La, reacted with the ferritic-martensitic steel (FMS) to form an interaction layer that penetrated the clad thickness. Fe diffused outside the clad interface to form an $Fe_2Ce$ compound, leaving a depletion of Fe caused by excess diffusion as well as by the formation of Cr-rich precipitation inside the interaction layer. The rate of growth followed the cubic rate law, which indicated that Fe depletion was caused by the diffusion of Fe and that the associated Cr-rich phase formation controlled the whole diffusion process.

Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

  • Ma, De-Yun;Guo, Hai-Fu;Qin, Liang;Xu, Jun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2774-2780
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    • 2013
  • Two new isostructural dinuclear complexes, $Ln_2(4-cpa)_6(bpy)_2$ (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenylacetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with $Ln{\cdots}Ln$ separations of 3.967(2) and 3.956(3) ${\AA}$, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

Synthesis and Structures of Two Lanthanide Complexes Containing a Mixed Ligand System: [Ln(Phen)2(L)3(HL)]·H2O [Ln = La, Ce: Phen = Phenanthroline: HL = Salicylic Acid]

  • Iravani, Effat;Nami, Navabeh;Nabizadeh, Fatemeh;Bayani, Elham;Neumuller, Bernhard
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3420-3424
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    • 2013
  • The reaction of $LnCl_3{\cdot}7H_2O$ [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at $20^{\circ}C$ in $H_2O$/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula $[Ln(Phen)_2(L)_3(HL)]{\cdot}H_2O$. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain $Ln^{3+}$ ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to $Ln^{3+}$). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give $Ln_2O_3$.

Solvent Extraction of Eu3+ and Tb3+ Ions with 12-Crown-4 15-Crown-5 and 18-Crown-6 (12-Crown-4, 15-Crown-5 및 18-Crown-6에 의한 Eu(Ⅲ) 및 Tb(Ⅲ)의 용매추출)

  • Kim, Eun-Jeong;Yoon, Soo-Kyung;Bae, Jun-Hyun;Kang, Jun-Gil;Kim, Youn-Doo
    • Journal of the Korean Chemical Society
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    • v.39 no.4
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    • pp.266-274
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    • 1995
  • The extractions of aqueous Eu3+ and Tb3+ ions into ethylacetate or dichloromethane were conducted by using 12-crown-4, 15-crown-5 and 18-crown-6 ethers as ligand. Benzoate ion was selected as counter anion for the complexes formed between the lanthanide ions and crown ethers. Fluorescence spectra of the lanthanide ions induced by the energy transfer from benzoate anion to the cations were also measured. The quantitative analysis of the lanthanide ions extracted into organic phase were made on the basis of the results of fluorescence. The measured extractivity is interpreted in terms of the ion-dipole interaction.

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Electrochemical Behavior of Mordant Red 19 and its Complexes with Light Lanthanides

  • Sang Kwon Lee;Taek Dong Chung;Song-Ju Lee;Ki-Hyung Chjo;Young Gu Ha;Ki-Won Cha;Hasuck Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.567-574
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    • 1993
  • Mordant Red 19(MR19) is reduced at mercury electrode at -0.67 V vs. Ag/AgCl with two electrons per molecule in pH 9.2 buffer by differential pulse polarography and linear sweep voltammetry. The peak potential is dependent on the pH of solution. The exhaustive electrolysis, however, gives 4 electrons per molecule because of the disproportionation of the unstable hydrazo intermediate. The electrochemical reduction of lanthanide-MR19 complexes is observed at more cathodic potential than that of free ligand. The difference in peak potentials between complex and free ligand varies from 75 mV for $La^{3+}$ to 165 mV for $Tb^{3+}$ and increases with increasing the atomic number of lanthanide. The electrochemical reduction of lanthanide complexes with MR19 is due to the reduction of ligand itself, and it can be potentially useful as an indirect method for the determination of lanthanides. The shape of i-E curves and the scan rate dependence indicates the presence of adsorption and the adsorption was confirmed by potential double-step chronocoulometry and the effect of standing time. Also the surface excess of the adsorbed species and diffusion coefficients are determined. The composition of the complex is determined to be 1 : 2 by spectrophotometric and electrochemical methods.

Oxalate Precipitation of Lanthanide and Actinide in a Simulated Radioactive Liquid Waste (모의 방사성용액에서 란탄족과 악티늄족원소의 옥살산침전)

  • Chung, Dong-Yong;Kim, Eung-Ho;Lee, Eil-Hee;Yoo, Jae-Hyung;Park, Hyun-Soo
    • Applied Chemistry for Engineering
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    • v.10 no.7
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    • pp.996-1002
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    • 1999
  • The oxalate precipitation of lanthanide and actinide by oxalic acid was investigated in the simulated radioactive liquid waste, which was composed of 17 elements of alkali, alkaline earth(Cs, Rb, Ba, Sr), transition metal(Zr, Fe, Mo, Ni, Pd, Rh), lanthanide(La, Y, Nd, Ce, Eu) and actinide(Np, Am) in nitric acid solution. The effect of concentrations of nitric acid and ascorbic acid on the precipitation yield of each element in the simulated solution was examined at 0.5 M oxalic acid concentration. The precipitation yields of the elements were usually decreased with nitric acid concentration, nevertheless, the precipitation yields of lanthanide and actinide were more than 99%. Palladium was precipitated due to the reduction of Pd(II) into Pd metal by the addition of ascorbic acid in the oxalate precipitation and then, the precipitation yields of Mo, Fe, Ni, Ba decreased by 10~20% with concentration of ascorbic acid. The reductive precipitation of Pd(II) into Pd metal by the addition of ascorbic acid into the simulated radwaste occurred at below 1 M nitric acid concentration and its yield showed maximum at the ascorbic acid concentration of 0.01~0.02 M. The hydrazine suppressed the reductive precipitation of Pd by the ascorbic acid.

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Luminescent Lanthanide Complexes for Advanced Photonics Applications

  • Eom, Yu Kyung;Ryu, Jung Ho;Kim, Hwan Kyu
    • Rapid Communication in Photoscience
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    • v.1 no.1
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    • pp.1-9
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    • 2012
  • Luminescent lanthanide complexes have been overviewed for advanced photonics applications. Lanthanide(III) ions ($Ln^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins, naphthalenes, anthracene, push-pull diketone derivatives and boron dipyrromethene(bodipy). The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to $Ln^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of $Ln^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent $Ln^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent $Ln^{3+}$ complexes, yielding novel $Ln^{3+}$-cored dendrimer complex such as metalloporphyrins, naphthalenes, and anthracenes bearing the Fr$\acute{e}$chet aryl-ether dendrons, namely, ($Er^{3+}-[Gn-Pt-Por]_3$ (terpy), $Er^{3+}-[Gn-Naph]_3$(terpy) and $Er^{3+}-[Gn-An]_3$(terpy)). These complexs showed much stronger near-IR emission bands at 1530 nm, originated from the 4f-4f electronic transition of the first excited state ($^4I_{13/2}$) to the ground state ($^4I_{15/2}$) of the partially filled 4f shell. A significant decrease in the fluorescence of metalloporphyrins, naphthalenes and anthracene ligand were accompanied by a strong increase in the near IR emission of the $Ln^{3+}$ ions. The near IR emission intensities of $Ln^{3+}$ ions in the lanthanide(III)-encapsulated dendrimer complexes were dramatically enhanced with increasing the generation number (n) of dendrons, due to the site-isolation and the light-harvesting(LH) effects. Furthermore, it was first attempted to distinguish between the site-isolation and the light-harvesting effects in the present complexes. In this review, synthesis and photophysical studies of inert and stable luminescent $Ln^{3+}$ complexes will be dealt for the advanced photonics applications. Also, the review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to $Ln^{3+}$ ions with $Ln^{3+}$-chelated prototype complexes.