• Title/Summary/Keyword: Lanthanide

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Preparati on and Characterization of $LnTaO_4$ (Ln = La, Nd, Sm, Dy, Er and Tm)

  • Fujita, Atsushi;Matsushita, Hiroaki;Katsui, Akinori
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2006.09b
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    • pp.1116-1117
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    • 2006
  • Lanthanide tantalite $LnTaO_4$ (Ln= La, Nd, Sm, Dy, Er and Tm) was synthesized by a solid state reaction between mixed powders of $Ln_2O_3$ and $Ta_2O_5$. The single-phase $LnTaO_4$ was prepared by sintering at temperatures of 1423-1673 K in air. The SEM observation showed that the particles were provided with the growth steps and the depeloped facets. The photocatalytic activity for water splitting of $LnTaO_4$ prepared was measured under UV light irradiation. The activity obtained was higher than that previously reported. These results suggested the crystallinity of $LnTaO_4$ photocatalysts correlates closely with the efficiency of water splitting.

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Dissociation Kinetics of Linear polyaminopolycarboxylate Complexes of Lanthanides(III)

  • Ki-Young Choi;Ki Sung Kim;Choon Pyo Hong
    • Bulletin of the Korean Chemical Society
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    • v.15 no.9
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    • pp.782-785
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    • 1994
  • The dissociation kinetics of linear polyaminopolycarboxylate complexes of lanthanide ions (L$n^{3+}: Ce^{3+},\;Eu^{3+}\;and\;Yb^{3+}$) has been studied in an aqueous solution of 0.10 M (NaCl$O_4$) at 25.0${\pm}0.1^{\circ}C$ using Cu(II) ions as a scavenger. The dissociation rates of acid-catalyzed pathway decrease in the order Ln(EPDTA$)^- > Ln(DPOT)^- > In(TMDTA)^- > Ln(MPDTA)^- > Ln(EDTA)^- > Ln(PDTA)^- > Ln(DCTA)^-$ according to the present and literature data. An increase in the N-Ln-N chelate ring from 5 to 6 and substitution of two methyl groups, one ethyl and hydroxyl group on a chelate ring carbon of these ligands leads to a decrease in kinetic stabilities of the complexes. The substitution of one methyl group and cyclohexyl ring on a ring carbon, however, results in a significant increase in the kinetic stability of the resulting $Ln^{3+}$ complexes. Individual reaction steps taking place for each system, with different copper, acetate buffer concentration and pH dependence, are also discussed.

The Design of Photobiological Active Molecular Model For Photodynamic Therapy

  • Choi, Chang-Shik
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • 2019.05a
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    • pp.521-524
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    • 2019
  • The design of photobiological active photosensitizing molecular model for photodynamic therapy has been attracted as a research for the development of cancer treatment, and has been interested in the effective method for cancer treatment and the photosensitizer having more stable wavelength. Furthermore, the development of photosensitizer has been already carried out from the first generation molecule to the third one, and the research of smart photosensitizer as the fourth generation has been requested. As a fact, the selective killing of the only cancer cell is very difficult problem, and the present photodynamic therapy has the problem of killing of the normal cell. So, I have designed the new modelling of photosensitizer having the smart recognizing unit and the magnetic nanoparticle as well as having the several effective recognizing unit. In particular, the new model design of the photosensitizer having lanthanide metal has suggested for the development of photodynamic therapy. The model design of these new photosensitizing molecules will be introduced in the poster section for the new turning point of the development of photosensitizer.

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The Stability Constant of 1, 7, 10, 16-Tetraoxa-4, 13-Diazacyclooctadecane-Uranium (Ⅵ) Complex in Aqueous Solution

  • Suh, Moo-Yul;Eom, Tae-Yoon;Kim, Si-Joong
    • Bulletin of the Korean Chemical Society
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    • v.4 no.5
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    • pp.231-234
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    • 1983
  • The stability constant for the complex of $UO_2^{2+}$ with a macrocyclic aminoether ligand, 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane, has determined in aqueous solution. The conductivity and pH metric measurements suggest that the ligand forms a stable 1:1 complex with $UO_2^{2+}$ ion, and the complex is an ionic form, $UO_2L^{2+}$, in aqueous solution. The fact that the ligand does not form a complex with lanthanides, such as $Ce^{3+}$, $Sm^{3+}$, and $Nd^{3+}$ ions, in aqueous solution suggests a possibility of separation of the lanthanide elements from uranium matrix using the macrocyclic aminoether ligand.

Wavelength Conversion Lanthanide(III)-cored Complex for Highly Efficient Dye-sensitized Solar Cells

  • Oh, Jung-Hwan;Song, Hae-Min;Eom, Yu-Kyung;Ryu, Jung-Ho;Ju, Myung-Jong;Kim, Hwan-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2743-2750
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    • 2011
  • Lanthanide(III)-cored complex as a wavelength conversion material has been successfully designed and synthesized for highly efficient dye-sensitized solar cells, for the first time, since light with a short wavelength has not been effectively used for generating electric power owing to the limited absorption of these DSSCs in the UV region. A black dye (BD) was chosen and used as a sensitizer, because BD has a relatively weak light absorption at shorter wavelengths. The overall conversion efficiency of the BD/WCM device was remarkably increased, even with the relatively small amount of WCM added to the device. The enhancement in $V_{oc}$ by WCM, like DCA, could be correlated with the suppression of electron recombination between the injected electrons and $I_3{^-}$ ions. Furthermore, the short-circuit current density was significantly increased by WCM with a strong UV light-harvesting effect. The energy transfer from the Eu(III)-cored complex to the $TiO_2$ film occurred via the dye, so the number of electrons injected into the $TiO_2$ surface increased, i.e., the short-circuit current density was increased. As a result, BD/WCM-sensitized solar cells exhibit superior device performance with the enhanced conversion efficiency by a factor of 1.22 under AM 1.5 sunlight: The photovoltaic performance of the BD/WCM-based DSSC exhibited remarkably high values, $J_{sc}$ of 17.72 mA/$cm^2$, $V_{oc}$ of 720 mV, and a conversion efficiency of 9.28% at 100 mW $cm^{-2}$, compared to a standard DSSC with $J_{sc}$ of 15.53 mA/$cm^2$, $V_{oc}$ of 689 mV, and a conversion efficiency of 7.58% at 100 mW $cm^{-2}$. Therefore, the Eu(III)-cored complex is a promising candidate as a new wavelength conversion coadsorbent for highly efficient dye-sensitized solar cells to improve UV light harvesting through energy transfer processes. The abstract should be a single paragraph which summaries the content of the article.

Studies on the Coordination of Acetamide to Rare Earth Metal Ion (Ln(II) (희토류 금속이온 (Ln(III))과 Acetamide 사이의 상호작용에 대한 연구)

  • Sang-Won Lee;Jeonga Yu;Chang-Ju Yoon;Yoo-Hyek Jun;Young-Sang Choi
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.205-211
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    • 1992
  • The $2{\nu}_{C=0}$ + amide III combination band spectrum of acetamide (AA) was obtained in very dilute solutions of AA+lanthanide shift reagents (LSR) in carbon tetrachloride over the range of $15^{\circ}$ to $45^{\circ}C$. It was found that only 1 : 1 AA-LSR complex is formed by the interaction between carbonyl oxygen of AA and central metal ion(Ln(Ⅲ)) in LSR. The thermodynamic parameters for Ln(III)${\cdot}$O=C bond were determined by computer analysis of concentration and temperature dependent spectra. ${\Delta}H^{\circ}$ for the coordination of AA to Eu$(dpm)_3$, Yb$(dpm)_3$, and Pr$(dpm)_3$ have been found to be -39.1, -28.4, and -25.5 kJ/mol, respectively. It has shown that this type of ion-dipole interaction is more than twice stronger compared to the dipole-dipole interaction in the amide linkage, and largely depending on the steric hindrence effect by the bulky dpm groups around central metal ion (Ln(III)) rather than the ionic potential effect of central metal ion itself.

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Thermodynamic Parameters of Complexation of Lanthanides by L-proline (Lanthanides-L-proline 착물의 형성에 관한 열역학적 연구)

  • Choi Im-Yeon;Kim Young-Inn;Choi Sung-Nak;Hyun Myung-Ho
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.105-111
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    • 1993
  • The stability constants for lanthanides complexes with optically active L-proline (1 : 1) were determined in aqueous solution in the ionic medium of 0.1 M $NaClO_4$ at 25$^{\circ}C$ using a pH titration method. The results show called "gadolinium break" between lighter and heavier lanthanides. The linear relation between the stability constant (log$\beta$1) and the pKa values of ligands indicates that L-proline acts as a bidentate ligand in the complexation. The thermodynamic parameters (${\Delta}H$ and ${\Delta}S$) were also determined using an enthalpy titration method at the same condition. The positive endothermic enthalpy change and positive entropy change clearly indicate that the driving force for the complexation is an entropy effect. The comparison of the thermodynamic parameters of L-proline complexes with anthranilate complexes supports the conclusion that the heterocyclic nitrogen atom and carboxylate of L-proline are involved in the chleate formation. The enthalpy values for L-proline are more positive than the ones for anthranilate complex. The difference in enthalpy change for the complex formation between L-proline complex and anthranilate complex is explained in terms of the basicity of the nitrogen donor atom in the ligand. The relatively large entropy change may be described by the extra dehydration related to the rigidity of L-proline ring.

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Studies on the Optical and the Electrical Characterization of Organic Electroluminescence Devices of Europium Complex Fabricated with PVD(Physical Vopor Deposition) Technique (진공 증착법에 의하여 제작한 Europium complex 유기 박막 전기발광소자의 광학적.전기적 특성에 관한 연구.)

  • Lee, Myeong-Ho;Lee, Han-Seong;Kim, Yeong-Gwan;Kim, Jeong-Su
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.48 no.5
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    • pp.285-295
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    • 1999
  • Electroluminescent(EL) devices based on organic materials have been of great interest due to their possible applications for large-area flat-panel displays. They are attractive because of their capability of multi-color emission, and low operation voltage. An approach to realize such device characteristics is to use active layers of lanthanide complexes with their inherent extremely sharp emission bands in stead of commonly known organic dyes. In general, organic molecular compounds show emission due to their $\pi$-$\pi*$ transitions resulting in luminescence bandwidths of about 80 to 100nm. Spin statistic estimations lead to an internal quantum efficiency of dye-based EL devices limited to 25%. On the contrary, the fluorescence of lanthanide complexes is based on an intramolecular energy transfer from the triplet of the organic ligand to the 4f energy states of the ion. Therefore, theoretical internal quantum efficiency is principally not limited. In this study, Powders of TPD, $Eu(TTA)_3(phen) and AlQ_3$ in a boat were subsequently heated to their sublimation temperatures to obtain the growth rates of 0.2~0.3nm/s. Organic electrolumnescent devices(OELD) with a structure of $glass substrate/ITO/Eu(TTA)_3(phen)/AI, glass substrate/ITO/TPD/Eu(TTA)_3(phen)/AI and glass substrate/ITO/TPD/Eu(TTA)_3(phen)/AIQ_3AI$ structures were fabricated by vacuum evaporation method, where aromatic diamine(TPD) was used as a hole transporting material, $Eu(TTA)_3(phen)$ as an emitting material, and Tris(8-hydroxyquinoline)Aluminum$(AlQ_3)$ as an electron transporting layer. Electroluminescent(EL) and current density-voltage(J-V) characteristics of these OELDs with various thickness of $Eu(TTA)_3(phen)$ layer were investigated. The triple-layer structure devices show the red EL spectrum at the wavelength of 613nm, which is almost the same as the photoluminescent(PL) spectrum of $Eu(TTA)_3(phen)$.It was found from the J-V characteristics of these devices that the current density is not dependent on the applied field, but on the electric field.

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Novel Tm(III) Membrane Sensor Based on 2,2'-Dianiline Disulfide and Its Application for the Fluoride Monitoring of Mouth Wash Preparations

  • Ganjali, Mohammad Reza;Norouzi, Parviz;Tamaddon, Atefeh;Husain, Syed Waqif
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1418-1422
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    • 2006
  • In this work the construction of a novel poly(vinyl chloride) membrane sensor based on 2,2'-dianiline disulfide (DADS) as a neutral carrier, o-nitrophenyloctyl ether (NPOE) as a plasticizer and sodium tetraphenyl borate (NaTPB) as an anionic site with unique selectivity towards Tm(III) ions is reported. The electrode has a linear dynamic range between $1.0\;{\times}\;10^{-6}$ and $1.0\;{\times}\;10^{-2}$ M, with a nice Nernstian slope of 19.5 ${\pm}$ 0.3 mV per decade and a detection limit of $4.0\;{\times}\;10^{-7}$ M at the pH range of 4.8-8.5. It has a very fast response time (<15 s) in the whole concentration range, and can be used for at least 4 weeks without any considerable divergence in the electrode potentials. The proposed sensor revealed comparatively good selectivity with respect to most common metal ions, and especially lanthanide ions. It was used as an indicator electrode in the potentiometric titration of Tm(III) ions with EDTA and in direct determination of concentration of Tm(III) ions in binary mixtures. It was also applied in determination of fluoride ions in mouth wash preparations.