• Title/Summary/Keyword: Lanthanide ions

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Lanthanide-Cored Supramolecular Systems with Highly Efficient Light-Harvesting Dendritic Arrays towards Tomorrow′s Information Technology

  • Kim, Hwan-Kyu;Roh, Soo-Gyun;Hong, Kyong-Soo;Ka, Jae-Won;Baek, Nam-Seob;Oh, Jae-Buem;Nah, Min-Kook;Cha, Yun-Hui;Jin Ko
    • Macromolecular Research
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    • v.11 no.3
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    • pp.133-145
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    • 2003
  • We have developed novel lanthanide-cored supramolecular systems with highly efficient light-harvesting dendritic arrays for integrated planar waveguide-typed amplifiers. Er$^{3+}$ ions were encapsulated by the supramolecular ligands, such as porphyrins and macrobicyclics. The supramolecular ligands have been designed and synthesized to provide enough coordination sites for the formation of stable Er(III)-chelated complexes. For getting a higher optical amplification gain, also, the energy levels of the supramolecular ligands were tailored to maintain the effective energy transfer process from supramolecular ligands to erbium(III) ions. Furthermore, to maximize the light-harvesting effect, new aryl ether-functionalized dendrons as photon antennas have been incorporated into lanthanide-cored supramolecular systems. In this paper, molecular design, synthesis and luminescent properties of novel lanthanide-cored integrated supramolecular systems with highly efficient light-harvesting dendritic arrays will be discussed.d.

Electrochemical Behavior of Light Lanthanide Ions in Nonaqueous Solution, Flow Injection Determination and Photochemical Characterization of Eight Coordinated Chelates of Heavy Metal Ions (Part I) Electrochemical Behavior of Light Lanthanide Ions in Nonaqueous Solution (물아닌용매에서 가벼운 란탄족 이온의 전기화학적 거동, 흐름주입에 의한 정량 및 중금속이온의 킬레이트형 8-배위 착물의 광화학적 특성 (제 1 보) 물아닌용매에서 가벼운 란탄족이온의 전기화학적 거동)

  • Kang, Sam-Woo;Pak, Chong-Min;Do, Lee-Mi;Song, Myoung-Kyu;Kim, Il-Kwang
    • Analytical Science and Technology
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    • v.7 no.3
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    • pp.361-369
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    • 1994
  • Voltammetric behavior of some light lanthanide ions($La^{3+}$, $Pr^{3+}$, $Nd^{3+}$, $Sm^{3+}$ and $Eu^{3+}$) in acetonitrile(AN) and dimethylformamide(DMF) has been investigated by direct current, differential pulse polarography and cyclic voltammetry. The reduction of $La^{3+}$, $Pr^{3+}$ and $Nd^{3+}$ in 0.1M TEAP proceeded directly to the metallic state through three-electron charge transfer of irreversible process where as $Sm^{3+}$ and $Eu^{3+}$ proceeded by charge transfer of two steps. As the results of the cyclic voltammetric investigation, the first step reduction of $Sm^{3+}$ and $Eu^{3+}$ were a quasireversible reaction, the second step reductions were an irreversible reaction. The cathodic peak currents of the differential pulse polarogram showed adsorptive properties at lower sweep rates and high concentrations of these metal ions. The peak potenital was shifted to a negative petential and the peak current decreased with the increase of percentage of water in AN. On the other hand, the peak potential was shifted to a positive potential and the peak current decreased with an increased percentage of water in DMF.

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Synthesis and Electrochemical Characteristics of Lantanium and Neodynium Metal Complexes (란탄늄 및 네오디늄 금속의 착물합성과 전기화학적 특성)

  • Oh, Je Jik
    • Analytical Science and Technology
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    • v.6 no.1
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    • pp.83-92
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    • 1993
  • The electrochemical behaviors of lanthanide ion(La and Nd) and lanthanide complexes with 2, 2, 6, 6-tetramethyl-3, 5-heptanedione(THD), sym-hydroxydibenzo-16-crown-5(HD16C5) and sym-dibenzo-16-crown-5-oxyacetic acid(D16C5A) ligands in acton solution have been investigated by the use of cyclic voltammetry and direct current polarography. The peak potential and peak current, their dependency on the concentration, temperature, the reversibility of the eleotrode reactions are described. The reduction of the lanthanide ions and complexes in 0.05 M TEAP proceeded one-electron step in first step and one two-electron step in second step. These reduction step was irreversible and the reduction current was diffusion controlled. Macrovcyclic crown ethers, sym-hydroxydibenzo-16-crown-5(HD16C5) and sym-dibenzo-16-crown-5-oxyacetic acid(D16C5A), were prepared from 1, 5-bis-(2-hydroxyphenoxy)-3-oxapentane with epichlorohydrin. The voltammetric behaviors of Ln(III)-HD16C5 and Ln-D16C5A complexes in aceton solution have been investigated by the voltammetric method. The composition and stability constants of lanthanide complexes were determined.

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Studies on the Intercalation between Montmorillonite and Lanthanides (몬모리노나이트와 란탄족 원소들과의 인터카레이숀에 관한 연구)

  • Young Gu Ha
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.488-492
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    • 1986
  • The $Ca^{++}$ and $Mg^{++}$ released during Ca, Mg-Na exchange on Kampo 78 montmorillonite which was treated with various concentrations of NaCl solution, were measured with EDTA titration metbod in the leaching solutions. Lanthanide montmorillonite was prepared with various neutral lanthanide ions from sodium montmorillonite in which the exchangeable ions are displaced from the exchanger, such as the displacement of $Na^+$ by $Ln^{3+}$ ions, Cation exchange capacity (CEC) is determined on remaining lanthanides in the leaching solutions with E. D. T. A titration method. As a results of this study, there were no difference of C. E. C in series of lanthanide contraction, but C. E. C depends on charge density of montmorillonite. When we conformed the structure of Ln-montmorillonite by X-ray diffraction. It was found that there was much difference of pattern between Na-montmorillonite and Ln-montmorillonite.

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The Successive Complex Formation of Trivalent Lanthanide Ions with Ionophore ETH4120 at the Liquid/Liquid Interface (액체/액체계면에서 삼가 란탄족원소 이온과 중성담체(ETH4120)의 연속적인 착물형성 연구)

  • Choi, In Kyu;Yu, Zemu;Yeon, Jei Won;Chun, Kwan Sik;Kim, Won Ho;Eom, Tae Yoon
    • Journal of the Korean Chemical Society
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    • v.43 no.2
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    • pp.161-166
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    • 1999
  • Transfer of lanthanide ions across the liquid/liquid interface facilitated by ionopore ETH4120 has been studied by using cyclic voltammetry (CV) and chronopotentiometry with cyclic linear current-scanning (CPCLCS) under the condition where the concentration of ETH4120 in nitrobenzene was much smaller than the concentration of lanthanide ions in aqueous solution. One cathodic current peak (transfer from aqueous to nitrobenzene phase) and two anodic current waves (transfer from nitrobenzene to aqueous phase) were observed. The cathodic wave was due to the formation of 1:1 (metal:ligand) complex and two anodic waves showed successive formation of 1:2 and 1:3 complexes in nitrobenzene solution. But there was no cathodic wave corresponding to two anodic waves. The ion transfer mechanism has also been discussed.

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Studies on Electrochemical Behavior of Some Light Lanthanide Ions in Nonaqueous Solution, Flow Injection Determination and Photochemical Characterization of Heavy Metal Ion Chelate Eight Coordinated Complexes. (Part 2) (비수용액에서 가벼운 란탄족 이온의 전기화학적 거동, 흐름 주입법에 의한 정량 및 중금속 이온의 킬레이트형 8-배위 착물의 광화학적 특성 연구 (제 2 보) : 계면활성제 존재하에서 Chromeazurol S를 사용하여 몇 가지 란탄이온의 흐름주입법에 의한 정량)

  • Gang, Sam U;Jang, Ju Hwan;Kim, Il Gwang;Han, Hong Seok;Jo, Gwang Hui
    • Journal of the Korean Chemical Society
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    • v.38 no.1
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    • pp.50-54
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    • 1994
  • Spectrophotometric determination of some light lanthanide ions by flow injection method is described. Chromeazurol S forms water soluble complex with lanthanide ions in the presence of DTAB. The absorption maximum of the complexes are from 650 nm to 655 nm and the molar absorptivities were ca. $1.8{\times}10^5\;L mol^{-1}cm^{-1}$ on Tris buffer (pH 10.5). The calibration curves for Nd(III), Eu(III) and Sm(III) obtained by FIA are over the range of 0.1 to 0.6 ppm and the correlation coefficient were ca. 0.9993. The detection limits (S/N) were from 10 ppb for Nd(III) and Eu(III) to 20 ppb for Sm(III). The relative standard deviations was ${\pm}$.2% for 0.4 ppm sample. The samples throughput was ca. $50\;cm^{-1}$.

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Stability Constants of Divalent Transition and Trivalent Lanthanide Metal Ion Complexes of Macrocyclic Triazatri(Methylacetic Acid)

  • 김동원;홍춘표;최기영;김창숙;이남수;장영훈;이재국
    • Bulletin of the Korean Chemical Society
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    • v.17 no.9
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    • pp.790-793
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    • 1996
  • The azacrown compound, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N"-tri(methyl-acetic acid)(N3O2-tri(methylacetic acid)) was synthesized by modified procedure of Krespan. Potentiometric method has been used to determine the protonation constants of N3O2-tri(methylacetic acid) and stability constants of complexes on the divalent transition metal ions (Co2+, Ni2+, Cu2+, and Zn2+) and trivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with N3O2-tri(methylacetic acid). The stability constants for the complexes of the divalent transition metal ions studied in the present work with N3O2-tri(methylacetic acid) were 11.4 for Co2+, 11.63 for Ni2+, 13.51 for Cu2+, and 11.65 for Zn2+, respectively. Thus, the order of the stability constants for complexes on the transition metal ions with N3O2-tri(methylacetic acid) was shown Co2+ < Ni2+ < Cu2+ > Zn2+ as same as the order of Irving-Williams series. The stability constants of Ce3+, Eu3+, Gd3+, and Yb3+ trivalent lanthanide metal ion complexes of N3O2-tri(methylacetic acid) were, respectively, 11.26 for Ce3+, 11.56 for Eu3+, 11.49 for Gd3+, and 11.80 for Yb3+. The values of the stability constants on trivalent metal ions with the ligand are increasing according to increase atomic number, due to increase acidity. But the value of stability constant of Gd3+ ion is less than the value of Eu3+ ion. This disordered behavior is also reported by Moeller.