• Title/Summary/Keyword: Metal complexes

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Investigation of Eu(Ⅲ)-Polyfunctional Organic Acid Complexes by Eu(Ⅲ) Luminescence Spectroscopy (Eu(Ⅲ) 발광 분광법을 이용한 Eu(Ⅲ)과 다가 유기산 착물 연구)

  • Lee, Byoung Ho;Shin, Hyun Sang;Moon, HiChung
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.59-64
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    • 1996
  • The 7F0→5D0excitation spectra of Eu(Ⅲ) complexed with polyfunctional monocarboxylic acid(glycolic acid, glycine and thioglycolic acid) containing a terminal O, N and S neutral donors and propionic acid were investigated using Eu(Ⅲ) luminescence spectroscopy. In the excitation spectra of Eu(Ⅲ)-propionate system, the stepwise appearance of the peaks was observed at 579.0, 579.2 and 579.5 nm with increasing in the ligand-to-metal ratio, which correspond to the formation of Eu(propionate)2+, Eu(propionate)2+ and Eu(propionate)3 species. Three maximum peaks were also obtained for Eu(Ⅲ)-glycolate, Eu(Ⅲ)-glycinate and Eu(Ⅲ)-thioglycolate systems and were found to be quite similar to those of Eu(Ⅲ)-propionate system. The q values (number of coordinated water molecules of Eu(Ⅲ) ion) obtained from the luminescence decay constants of Eu(Ⅲ)-glycolate and Eu(Ⅲ)-thioglycolate were 7.0 and 7.1, and compare well with 7.3 for Eu(Ⅲ)-propionate: Each ligand units replace around two coordinated water molecules. These results show that the polyfunctional monocarboxylates behaves like the propionate for Eu(Ⅲ) ion coordination.

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The synergistic solvent extraction effect of europium and yttrium using the hexanoic acid -crown ether system (Hexanoic acid - crown ether system을 이용한 europium과 yttrium의 용매추출효과의 향상)

  • Sim, Dea-Seon;Han, Hye-Rim;Kim, Se-Mi;Kim, Jeong-Hoon;Kim, Young-Wun;Jeong, Noh-Hee;Kang, Ho-Cheol
    • Journal of the Korean Applied Science and Technology
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    • v.32 no.1
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    • pp.31-39
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    • 2015
  • The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded $MLR_3{\cdot}3RH$ form when added the crown ether.

A study on the Recovery of waste fluids of the conservation treatment of waterlogged wooden artifacts (수침목재유물보존처리 폐액의 재활용에 관한 연구)

  • Yang, Seok-Jin;Kim, Jong-Hwa;Song, Ju-Yeong;Lee, Soo
    • Journal of the Korean Applied Science and Technology
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    • v.29 no.1
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    • pp.108-115
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    • 2012
  • Archaeological waterlogged woods found under the sea, in lakes, or in swamp environments are generally weak and fragile. If waterlogged wood materials were taken out of the water and left without modification, they would collapse and lose their original dimensions completely. Conservation is performed to replace the water with chemical agents and to give dimensional stabilization and durability. EDTA and PEG are the most commonly used in the preservation of wood. pH control-precipitation method is used for recovery of EDTA from waste fluid of archeological waterlogged wood conservation treatment. The black substance is eliminated from wood as Fe-EDTA complex are formed and EDTA is separated and precipitated from Fe-EDTA complexes at pH 2.68 or less. The result of analysis of the precipitated products and the commercial EDTA by FT-IR and FE-SEM showed that precipitated product by pH adjusted was not a type of Fe-EDTA complex, but pure EDTA. Waste fluid produced in PEG treatment shows the black color and has an offensive odor by organic matter extracted from wood. Color of waste fluid is decolored with oxidation reaction by peroxy hydrate. In FT-IR and SEM-EDX of PEG after freeze-drying process, no significant change of functional groups induced from oxidation is observed, and any metal ion does not exist in the solid PEG specimen. The molecular weight of PEG is measured using GPC and viscometry. Properties of PEG before and after preservation treatment, and after oxidation with $H_2O_2$ were not changed. Consequently, the peroxidation with $H_2O_2$ is a reasonable and simple method to decolor the used PEG solution.

Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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Conversion of Coordinated Sulfur Atom into Sulfoxide Group via Oxidation Reaction of Metal Complexes of Tetradentates and Sulfur Amino Acids (네자리 리간드-황아미노산 금속착물의 산화반응에 의한 배위된 황원자의 sulfoxide 원자단으로의 전환)

  • Sung Sil Lee;Peter Fu;Sung Rack Choi;Moo Jin Jun
    • Journal of the Korean Chemical Society
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    • v.33 no.5
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    • pp.516-521
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    • 1989
  • Reaction between the $N_2O_2-type$ tetradentate ligand, ethylenediamine-N,N'-di-S-${\alpha}$-isobutylacetic acid (SS-emiba) and $RhCl_3{\cdot}3H_2O$ has yielded ${\Delta}-s-cis-\;and\;{\wedge}-uns-cis-[Rh(SS-eniba)Cl_2]-$. ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]^-$ has been utilized to react with S-methyl-L-cystcine(Smc) to give ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$. The oxidation of ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ using $H_2O_2$ has produced ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$, in which the coordinated sulfur has been converted into the sulfoxide group. In a separate series of experiments the S-methyl-L-cysteine is oxidized by $H_2O_2$ to give S-methyl-L-cysteine sulfoxide, which is then coordinated to ${\Delta}-s-cis-[Rh(SS-eniba)Cl2]^-$ to make the standard complet of ${\Delta}-s-cis-[Rh(SS-eniba)(Sme-o)]+$ for comparison with the complex obtained from the oxidation of ${\Delta}-s-cis-[Rh(SS-eniba)(Smc)]^+\;by\;H_2O_2.$

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Evaluation of the fracture resistance of all-ceramic zirconia posts by 3 different methods

  • Jeong, Seung-Mi;Chung, Chae-Heon;Kang, Dong-Wan;Ludwig, Klaus;Kern, Matthias;Huels, Alfons
    • The Journal of Korean Academy of Prosthodontics
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    • v.38 no.6
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    • pp.757-764
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    • 2000
  • Statement of the problem. All-ceramic post-and-core restorations offer a number of advantages compared with systems that use metal build-ups. In certain clinical cases, however, fractures at the joint between the post and core build-up have been reported. Purpose. The objective, therefore, is to improve the joint between the post and the core build-up. Material and methods. Three different methods were used to prepare all-ceramic post-and-core restorations; pressing IPS Empress core build-ups to CosmoPost zirconia posts, cement-ing IPS Empress core build-ups to CosmoPost zirconia posts and Celay-milling of zirconia blanks. A series of ten restorations was prepared for each of the three methods. The post-and-core complexes were tested to failure with the load applied perpendicular to the post axis. The load and deflection at fracture were recorded. Results. The highest breaking load and highest deflection were recorded for the cementing technique with values of 25.3 N and $394{\mu}m$, respectively, The corresponding values for the pressed core build-ups and the milled zirconia core build-ups were 22 N and $301{\mu}m$, and 13 N and $160{\mu}m$, respectively. All the differences are statistically significant (p=0.05). Regarding the load-dependence of the deflection, the cemented core build-ups again demonstrated the highest value with $15.5{\mu}m/N$. The difference in the values of $13.6{\mu}m/N\;and\;13{\mu}m/N$ recorded for the pressed-on and milled core build-ups, respectively, were statistically insignificant. Conclusion. In regard to the high fracture resistance of zirconia post, adhesive cementing the core build-up to the post offers a viable alternative to the conventional pressing technique. The elastic bond between the rigid high-strength zirconia post and the core build-up presents an additional advantage.

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Studies on Solvent Extraction and Analytical Applications of Metal-Dithiocarbamate Complexes(Ⅰ). Extraction and Determination of Trace Bismuth, Cadmium and Indium in Sea Water (Dithiocarbamate 금속착물의 용매추출 및 분석적 응용(제 1 보). 해수중 흔적량 비스무트, 카드뮴, 인듐의 용매추출 및 정량)

  • Jeon, Moon Kyo;Choi, Jong Moon;Choi, Hee Seon;Kim, Young Sang
    • Journal of the Korean Chemical Society
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    • v.40 no.7
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    • pp.492-500
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    • 1996
  • The solvent extraction of trace Bi, Cd and In in seawater samples using ammonium pyrrolidine dithiocarbamate(APDC) as a complexing agent was studied. The pH of sample solution, the amount of APDC, the type of solvent and the shaking time were investigated together with back-extraction conditions. After the pH of 200 mL seawater was adjusted to 4.0 and 5.0 mL of 1% APDC was added, analytes were extracted with 10.0 mL of MIBK by shaking for 35 minutes. The organic phase seperated was washed with a 0.05 M NaOH 10.0 mL to remove HPDC. The analytes were stripped by the back-extraction of 5 minute shaking with 5 mL of 4 M HNO3 containing 150 ㎍/mL Pd(Ⅱ). Detection limits of Bi, Cd and In were 0.038, 0.0057 and 0.023 ng/mL, respectively. Both of Bi(Ⅲ) and In(Ⅲ) were not detected in two kinds of water samples of the East Sea and the contents of Cd(Ⅱ) were 0.018 and 0.016 ng/mL. The recoveries of over 90% showed that this procedure was applicable to the determination of such trace elements in seawater samples.

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Selective Dimerization and Cyclotrimerization of Phenylacetylene with Rhodium and Iridium Complexes

  • Chin, Chong-Shik;Won, Gyong-Shik;Song, Joong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.961-966
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    • 1994
  • Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

Efficient Synthesis of hypho-2,5-$S_2B_7H_{11}$ and Preparation of New nido-, arachno-, and hypho-Metalladithiaborane Clusters Derived from Its Anion hypho-$S_2B_7H_{10}{^-}$

  • 강창환;김성준;고재정;강상욱
    • Bulletin of the Korean Chemical Society
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    • v.16 no.11
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    • pp.1067-1074
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    • 1995
  • Reaction of arachno-S2B7H8- with either THF or 1,2-dimethoxyethane upon refluxing condition results in the formation of the previously known compound hypho-S2B7H10-. Protonation of hypho-S2B7H10- with HCl/Et2O generates hypho-2,5-S2B7H11 in good yield. This hypho-S2B7H10- anion has been employed to generate a series of new nido-, arachno-, and hypho-metalladithiaborane clusters. Reaction of the anion with Cp(CO)2FeCl results in direct metal insertion and the formation of a complex containing the general formula (η5-C5H5)FeS2B7H8. Spectroscopic studies of nido-6-CpFe-7,9-S2B7H8 Ⅰ demonstrated that compound Ⅰ was shown to have an nido-type cage geometry derived from an octadecahedron missing one vertex, with the iron atom occupying the three-coordinate 6-position in the cage and the two sulfurs occupying positions on the open face of the cage. Reaction of hypho-S2B7H10- with CoCl2/Li+[C5H5]- gave the previously known complex arachno-7-CpCo-6,8-S2B6H8 Ⅱ. Also, the reaction of the anion with [Cp*RhCl2]2 gave the complex arachno-7-Cp*Rh-6,8-S2B6H8 Ⅲ, the structure of which was shown to be that of complex Ⅱ. The similarity of the NMR spectra of Ⅱ and Ⅲ suggest that Ⅲ adopts cage structure similar to that previously confirmed for Ⅱ. A series of 9-vertex hypho clusters in which the sulfur atoms are bridged by different species isoelectronic with a BH3 unit, such as HMn(CO)4 or SiR2 have been prepared. Compounds Ⅳ,Ⅴ and Ⅵ are each 2n+4 skeletal electron systems and would be expected according to skeletal electron counting theory to adopt hypho-type polyhedral structures derived from an icosahedron missing three vertices. The complex hypho-1-(CO)4Mn-2,5-S2B6H9 Ⅳ was obtained by the reaction of the anion with (CO)5MnBr and has been shown from spectroscopic data to consist of a (CO)4Mn fragment bound to the two sulfur atoms S2 and S5 of hypho-S2B7H10-. Also, similar hypho-type complexes hypho-1-R2Si-2,5-S2B6H8 (R=CH3 Ⅴ, R=C6H5 Ⅵ) have been prepared from the reaction of hypho-S2B7H10- with R2SiHCl.

A Comparative Study on Chemistry Education Contents of South Korea and North Korea (남한과 북한의 화학교육 내용 요소 비교 연구)

  • Min, Byoung Wook;Park, Hyun Ju
    • Journal of the Korean Chemical Society
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    • v.66 no.2
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    • pp.124-135
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    • 2022
  • The purpose of this study was to analyze the chemisry education contents of South Korea and North Korea for understanding chemistry education of North Korea. Chemistry education in South and North Korea was investigated in terms of learning period and learning quantaty. Especially, what content North Korea learned prior to South Korea and what contents learned more were analyzed. The subjects of this study were South Korean 2015 revised National Science Curriculum and North Korean science textbooks in Kim Jong-un era. The North Korean textbooks analyzed are 'Nature' for North Korean elementary school 3, 'Natural Science' for North Korean middle school 1 and 2, and 'Chemistry' for North Korean high school 1 and 2. The analysis results are as follows. First, the content elements to be learned in advance in North Korean textbooks were density, oxidation and reduction, battery, and atomic weight. Second, the content elements additionally learned in North Korean textbooks include separation of mixtures, fuels, oxidation and reduction, metals, organic and inorganic substances, metals and non-metal oxides and hydroxides, inorganic substances used as fertilizers, nutritional substances, and salt reaction and utilization, atomic orbitals, hybridization of orbitals, coordination bonds and complexes. As a future research task, a qualitative analysis of the elements of North Korean chemistry, the activities of textbooks, and an experimental analysis were proposed.