• Title/Summary/Keyword: Binuclear

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Electrochemical Properties of Binuclear Cobalt (II) Complexes with Tetradentate Schiff Base in Aprotic Solvents (III) (비수용매에서 이핵성 네자리 Schiff Base Cobalt(II) 착물들의 전기화학적 성질 (제 3 보))

  • Chjo Ki-Hyung;Choi Yong-Kook;Seo Seong-Seob;Lee Song-Ju
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.379-388
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    • 1991
  • We synthesized the binuclear Tetradentate Schiff base cobalt (II) complexes; [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] (where, SMPD: N,N'-bis(salicylaldehyde)-m-phenylenediimine, SPPD: N,N'-bis(salicylaldehyde)-p-phenylenediimine, L: Py, DMSO and DMF). We identified the binuclear structure of these complexes by elemental analysis, IR-spectrum, and T. G. A. According to the results of cyclic voltammetry and DPP measurements in aprotic solvents containing 0.1M TEAP as supporting electrolyte, it was found that diffusionally controlled redox process of two step for one electron was reversible or quasi reversible process in 0.1M TEAP-pyridine and 0.1M TEAP-DMSO solution at mononuclear complexes; [Co(II)(SOPD)(L)$_2$]. But, we knew that diffusionally controlled reduction processes of four steps with one electron for binuclear [Co(II)$_2$(SMPD)$_2$(L)$_2$] and [Co(II)$_2$(SPPD)$_2$(L)$_2$] complexes was Co(III)$_2\;{\longrightarrow^e}$ Co(III)Co(II) ${\longrightarrow^e}$ Co(II)$_2\;{\longrightarrow^e}$ Co(II)Co(I) ${\longrightarrow^e}$ Co(I)$_2$ in aprotic solvents.

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Structure function relationships amongst the purple acid phosphatase family of binuclear metal-containing enzymes

  • Hamilton, Susan
    • Proceedings of the Korean Society for Bioinformatics Conference
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    • 2003.10a
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    • pp.5-5
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    • 2003
  • The purple acid phosphatases comprise a family of binuclear metal-containing enzymes. The metal centre contains one ferric ion and one divalent metal ion. Spectroscopic studies of the monomeric, ${\sim}$36 kDa mammalian purple acid phosphatases reveal the presence of an Fe(III)Fe(II) centre in which the metals are weakly antiferromagnetically coupled, whereas the dimeric, ${\sim}$110 000 kDa plant enzymes contain either Fe(III)Zn(II) or Fe(III)Mn(II). The three dimensional structures of the red kidney bean and pig enzymes show very similar arrangements of the metal ligands but some significant differences beyond the immediate vicinity of the metals. In addition to the catalytic domain, the plant enzyme contains a second domain of unknown function. A search of sequence databases was undertaken using a sequence pattern which includes the conserved metal-binding residues in the plant and animal enzymes. The search revealed the presence in plants of a 'mammalian-type' low molecular weight purple acid phosphatase, a high molecular weight form in some fungi, and a homologue in some bacteria. The catalytic mechanism of the enzyme has been investigated with a view to understanding the marked difference in specificity between the Fe-Mn sweet potato enzyme, which exhibits highly efficient catalysis towards both activated and unactivated phosphate esters, and other PAPs, which hydrolyse only activated esters. Comparison of the active site structures of the enzymes reveal some interesting differences between them which may account for the difference. The implications fur understanding the physiological functions of the enzymes will be discussed.

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Crystal Structures and Thermal Properties of Two Binuclear Cd(II) Supramolecular Complexes Based on Quinolinecarboxylate Ligand

  • Hao, Hu-Jun;Yin, Xian-Hong;Lin, Cui-Wu;Wei, Shui-Qiang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3255-3260
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    • 2011
  • Two novel binuclear metal-organic coordination complexes $[Cd_2(L)_2(bpy)_2(H_2O)_2]{\cdot}6H_2O$ (1), $[Cd_2(L)_2(phen)_2-(H_2O)_2]{\cdot}2H_2O$ (2) (where L = 2-methylquinoline-3,4-dicarboxylate dianion, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by single crystal Xray diffraction, spectral method (IR), elemental analysis and thermal gravimetric analysis (TGA). Both 1 and 2 consist of two Cd(II) atoms bridged by two monoatomic bridging carboxylate groups from two L ligands, and the second carboxylate group of each L is monodentately coordinated to Cd(II), creating a sevenmembered chelating ring. The coordination at each metal nucleus is completed by a water molecule and a chelating bidentate molecule. The 3D structures of the complexes are stabilized by ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds.

QUANTUM EFFICIENCY OF PHOTOGENERATION OF SINGLET OXYGEN FROM THE CLUSTER TYPE OF BINUCLEAR IRON-SULFUR CENTER [2Fe-2S]

  • Choi, Jong-Keun;Kim, Chang-Sook
    • Journal of Photoscience
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    • v.3 no.2
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    • pp.77-83
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    • 1996
  • Photosensitization via the singlet oxygen ($^1O_2$) mechanism by the binuclear iron-sulfur center, denoted as [2Fe-2S], was investigated, using a highly purified ferredoxin (Fd) preparation from spinach leaves. Since the apoprotein of Fd contains a good number of amino acid residues that are readily reactive with $^1O_2$ and thus interfere with the detection of $^1O_2$ generated from [2Fe-2S], we attempted to deprive the $^1O_2$-sensitive residues of their $^1O_2$-scavenging capacity as much as possible by treating Fd with rose bengal plus 550 nm monochromatic light and thereby photooxidatively degrading these residues. The photochemically modified Fd was found to keep the structural integrity of its Fe-S group virtually unaffected by the treatment. By employing chemical trap method for measurement and examining the kinetic effects of azide and deuterium oxide on the reactions of $^1O_2$ with various trap compounds, we were able to demonstrate that [2Fe-2S] indeed acts as a photosensitizer via $^1O_2$. Further, the minimum quantum yield of $^1O_2$ production by [2Fe-2S] was estimated to be 0.0047.

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Monooxo-bridged Binuclear Molybdenum (V) Complexes (IV) (한 개 산소 가교 이핵몰리브덴 (V) 착물 (제4보))

  • Sang Oh Oh;Jong Dal Rhee
    • Journal of the Korean Chemical Society
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    • v.26 no.2
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    • pp.81-87
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    • 1982
  • The monooxo-bridged binuclear molybdenum(V) complexes, $Mo_2O_3(NCS)_4(Bipy)_2\;(Bipy = bipyridine),\;Mo_2O_3(NCS)-4(Phen)-2$ (Phen = 1,10-phenanthroline), and $Mo_2O_3(NCS)_4(Ox)_2(OxH)_2$ (Ox = oxinato and OxH = oxine) have been prepared. Their electronic and IR spectra, electric conductivity, and magnetic susceptibility were measured. From the results all of th complexes turned out to be electroneutral dimers with about 0.5 BM, and in the oxine complex, $Mo_2O_3(NCS)_2(Ox)_2(OxH)_2$, the oxine seems to bind partly as monodentate and partly as bidentate molecule.

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Synthesis, Crystal Structures and Properties of Two Binuclear Supramolecular Complexes Based on Biphenyl-2,2'-dicarboxylic Acid Ligand

  • Tang, Jin-Niu;Pan, Gang-Hong;Li, Long;Tian, Wei-Man;Huang, Zhong-Jing
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.374-378
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    • 2013
  • Two novel binuclear metal-organic coordination complexes [$Cd_2(Hdpa)_4(bpy)_2$] (1), [$Dy_2(dpa)_2(bpy)_2(NO_3)_2-(H_2O)_2$](bpy) (2) (where $H_2dpa$ = biphenyl-2,2'-dicarboxylic acid, bpy = 2,2'-bipyridine) have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, spectral method (IR), elemental analysis (EA), powder X-ray diffraction (XRD), electronic spectra (UV-vis), fluorescent in the solid state and thermogravimetric analysis (TGA). Complexes 1-2 crystallizes isomorphously in the Triclinic space group P-1. The ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds play a vital role in determining the crystal packing and construction of the extended 3-D supramolecular network.

Oxygen Ring Formation Reaction of Mono-Oxo-Bridged Binuclear Molybdenum(V) Complex (II). Reaction of $[Mo_2O_3(Phen)_2(NCS)_4]$ with Solvent Water in Water + Co-Solvent Mixtures (한개의 산소다리를 가진 몰리브덴(V) 착물의 산소고리화 반응 (II). 2성분 혼합용매에서 용매물과 $[Mo_2O_3(Phen)_2(NCS)_4]$의 반응)

  • Sang-Oh Oh;Huee-Young Seok
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.203-210
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    • 1988
  • Mono-oxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_3(Phen)_2(NCS)_4]$ produces di-oxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_4(Phen)_2(NCS)_2]$ in water + co-solvent, where the co-solvent are acetone, acetonitrile and N,N-dimethylformamide. The rate of conversion of $[Mo_2O_3(Phen)_2(NCS)_4]\;into\;[Mo_2O_4(Phen)_2(NCS)_2]$ has been measured by spectrophotometric method. Temperature was $10^{\circ}C$ to $40^{\circ}C$ and pressure was varied up to 1500 bar. The rate constants are increased with increasing water mole fraction and decreased with increasing concentration of hydrogen ion. The order of oxygen ring formation reaction rate in various cosolvent is as follows, ACT > AN > DMF which is agreed with solvent dielectric constants. The observed negative activation entropy ($[\Delta}S^{\neq}$), activation volume($[\Delta}V^{\neq}$) and activation compressibility coefficient(${\Delta}{\beta}^{\neq}$) values show that the solvent water molecule is strongly attracted to the complex at transition state. From these results, the oxygen ring formation reaction of $[Mo_2O_3(Phen)_2(NCS)_4]$ is believed association mechanism.

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