• 제목/요약/키워드: Binuclear

검색결과 63건 처리시간 0.026초

비수용매에서 이핵성 다섯자리 Schiff Base Cobalt(Ⅱ) 및 Manganese(Ⅱ) 착물들의 전기화학적 성질 (Electrochemical Properties of Pentadentate Binucleated Schiff Base Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes in Nonaqueous Solvent)

  • 조기충;최용국;이송주;서성섭
    • 대한화학회지
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    • 제36권3호
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    • pp.428-441
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    • 1992
  • 이핵성 다섯자리 Schiff base 착물계인 $Co(II)_2$ (BSPP)($H_2O)_2$, $Co(II)_2$ (BSPD)($H_2O)_2$, $Mn(II)_2$ (BSPP)($H_2O)_2$$Mn(II)_2$ (BSPD)($H_2O)_2$와 일핵성 다섯자리 Schiff base 착물계인 Co(II)(BSP)($H_2O)$ 및 Mn(II)(BSP)($H_2O)$들을 합성하였다. 이들 착물들의 조성을 원소분석, IR, UV-visible spectrum, T.G.A. 및 DSC 측정으로 알아보았다. 지지전해질용액 0.1M의 TEAP-Py (-DMSO 및 DMF)을 포함한 10mM 착물용액에서 유리질 탄소전극을 사용한 순환전압전류법과 DPP법으로 전기화학적 성질을 측정한 결과 이핵성 cobalt(II) 및 manganese(II) 착물들은 $M(III)_2$ / $Mn(II)_2$$Mn(II)_2$ / $M(I)_2$ (M; Co 및 Mn)의 두 과정에서 일전자의 환원과정이 각각 두 단계 환원과정에서 네 단계로 일어나지만 일핵성 착물들은 M(III) / M(II) 와 M(II) / M(I) 의 두 과정에서 각각 한 단계 산화${\cdot}$환원과정으로 일어남을 알았다.

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Synthesis of Binuclear Bismacrocyclic Iron(II) Complex by the Aerobic Oxidation of Iron(II) Complex of 1,4,8,11-Tetraazacyclotetradecane

  • Myunghyun Paik Suh;Gee-Yeon Kong;Il-Soon Kim
    • Bulletin of the Korean Chemical Society
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    • 제14권4호
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    • pp.439-444
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    • 1993
  • The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

Microspore Division and Plant Regeneration from Shed Pollen Culture in Rice

  • Kim, Hyun-Soon;Kang, Hyeon-Jung;Lee, Young-Tae;Lee, Seung-Yeob;Nam, Jeong-Kwon;Kim, Tae-Soo;Rha, Eui-Shik;Jin, Il-Doo
    • 한국작물학회지
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    • 제47권1호
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    • pp.62-67
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    • 2002
  • An efficient system of rice microspore culture could contribute to the production of genetically modified rice. The microspores were isolated by mechanical or shed methods. The number of microspores per 100 anthers isolated at uninucleate stage was higher than (or similar to) those at binucleate stage in isolation method with pestle or spatular, but microspore divisions were not easily observed on both stages. On the other hand, pollen division in shed pollen culture was observed more frequently at uninuclear than at binuclear stage. Cold pretreatment at 1$0^{\circ}C$ for 10 days resulted in the best multicellular division to produce microcalli at 12.5% efficiency in shed microspores. Heat shock at 33$^{\circ}C$ for one hour before or after pollen shedding enhanced cell division and callus formation. Out of twelve green regenerants, two were haploids and ten were diploids based on the chromosome analysis of root tips. The size of stoma was 12$^{m}$ m in haploids and 15 ${\mu}{\textrm}{m}$ in diploids determined by scanning electron microscope (SEM).

정사면체 구조를 갖는 Cu(II) 착물과 수은(II) 및 수은(0)과의 금속 교환반응 연구 (Studies on the Metal-Exchange Reaction of Tetrahedral Cu(II) Complex with Mercuric Ion and Mercury Metal)

  • 공영태;최성락;심윤보
    • 대한화학회지
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    • 제36권2호
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    • pp.223-229
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    • 1992
  • 정사면체 구조를 갖는 $SpCuCl_2$와 수은(II) 이온 및 수은 금속간의 금속 교환반응의 속도론적인 연구를 순환 전압전류법과 자외 가시선 분광법을 사용하여 실험하였다. 수은(II) 이온 및 수은 금속과$SpCuCl_2$와의 교환 반응은 유사일차속도식을 따른다. 교환반응의 속도상수와 활성화 계수들의 값을 구하고 이들을 정리하여 나타내었다. 이러한 실험결과들로부터 Sp 배위자에 동시에 결합되어 있는 구리와 수은의 이핵 착물에서 구리와 질소간의 결합이 끊어지는 과정이 교환반응의 속도결정단계임을 알 수 있다.

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A Two-dimensional Supramolecular Network Built through Unique π-πStacking: Synthesis and Characterization of [Cu(phen)2(μ-ID A)Cu(phen)·(NO3)](NO3)·4(H2O)

  • Lin, Jian-Guo;Qiu, Ling Qiu;Xu, Yan-Yan
    • Bulletin of the Korean Chemical Society
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    • 제30권5호
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    • pp.1021-1025
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    • 2009
  • A novel supramolecular network containing binuclear copper unit $[Cu(phen)_{2}({\mu}-ID\;A)Cu(phen){\cdot}(NO_{3})](NO_{3}){\cdot}4(H_{2}O)$ (1) was synthesized through the self-assembly of iminodiacetic acid ($H_2IDA$) and 1,10-phenanthroline (phen) in the condition of pH = 6. It has been characterized by the infrared (IR) spectroscopy, elemental analysis, single crystal X-ray diffraction, and thermogravimetric analysis (TGA). 1 shows a 2-D supramolecular structure assembled through strong and unique $\pi-\pi$ packing interactions. Density functional theory (DFT) calculations show that theoretical optimized structures can well reproduce the experimental structure. The TGA and powder X-ray diffraction (PXRD) curves indicate that the complex 1 can maintain the structural integrity even at the loss of free water molecules. The magnetic property is also reported in this paper.

건초거대세포종의 압착도말 및 세포흡인 세포소견 - 1예 보고 - (Touch Imprint and Fine Needle Aspiration Cytology of Giant Cell Tumor of Tendon Sheath - A Case Report -)

  • 이종임
    • 대한세포병리학회지
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    • 제19권1호
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    • pp.57-64
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    • 2008
  • Giant cell tumor of the tendon sheath (GCTTS) is a slowly growing, benign soft tissue tumor. The tumors occur predominantly on the hands and feet. Although the clinical and histopathologic features are well-defined, only a few reports have described the cytologic appearance of this entity. A 26-year-old woman presented with a gradually developing circumscribed soft tissue mass near the proximal phalanx of her left little finger for one year. Imprint and fine needle aspiration (FNA) smears were obtained from the excisional biopsy specimen. The imprint smears were composed of predominantly singly dispersed bland mononuclear cells and several giant cells. The mononuclear cells were polygonal to round, and they showed a histiocyte-like appearance. Osteoclast-type multinucleated giant cells of various sizes were randomly scattered throughout the smears, and these cells contained 3 to 50 nuclei. Nuclear atypia and pleomorphism were absent in both the single and giant cells. Loose aggregates of hemosiderin-laden macrophages and binuclear stromal cells were also seen. The cytologic features of the FNA smears were similar with those of the imprint, Additionally, the FNA smears contained several clumps of densely collagenous stromal tissue that were seldom noted in previously reported cytologic material. The cytologic features were well-correlated with the concurrent histologic findings and the diagnosis of GCTTS was made. When the clinical and radiologic datas are integrated, the diagnosis of GCTTS can be strongly suggested, based on the pre-operative cytologic specimen.

Electrocatalytic Effects for the Reduction of Thionyl Chloride in $Li/SOCl_2$ Cell Containing Schiff Base Metal(II) Complexes

  • 김우성;정광일;김신국;전성원;김연희;성용은;최용국
    • Bulletin of the Korean Chemical Society
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    • 제21권6호
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    • pp.571-576
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    • 2000
  • Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.

Reaction and Theoretical Study of the Coordination of an N2O-Donor Amino Alcoholic Ligand Toward Group 12 Metals Mixtures

  • Mardani, Zahra;Moeini, Keyvan;Kazemshoar-Duzduzani, Reza
    • 대한화학회지
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    • 제63권3호
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    • pp.160-165
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    • 2019
  • A series of reactions between an amino alcoholic ligand, cis-2-((2-((2-hydroxyethyl)amino)ethyl)amino)cyclohexan-1-ol (HEAC), with the mixtures of group 12 metals including, $HgCl_2/CdCl_2$, $HgCl_2/CdI_2$, $ZnCl_2/CdCl_2$ and $ZnCl_2/CdCl_2/HgCl_2$ was experimentally and theoretically studied to determine the most stable product of these reactions. Furthermore, the Cambridge Structural Database (CSD) studies were done to evaluate the theoretical results. The products were characterized by elemental analysis, FT-IR, Raman, $^1H$ NMR spectroscopy and single-crystal X-ray diffraction. Based on these investigations a binuclear structure of cadmium, [$Cd_2(HEAC)_2({\mu}-Cl)_2Cl_2$] (1), is the most stable product that was formed in all studied reactions between HEAC and metals mixtures. In this structure, the cadmium atom has a $CdN_2O({\mu}-Cl)_2Cl$ environment and distorted octahedral geometry.

Thermus thermophilus HJ6 유래 내열성 laccase의 유전자 클로닝 및 효소학적 특성 (Gene Cloning and Enzymatic Properties of Thermostable Laccase from Thermus thermophilus HJ6)

  • 이소영;정영훈;서민호;전숭종
    • KSBB Journal
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    • 제27권4호
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    • pp.257-262
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    • 2012
  • The gene encoding Thermus thermophilus HJ6 laccase (Tt-laccase) was cloned, sequenced, and comprised of 1,389 nucleotides encoding a protein (462 amino acids) with a predicted molecular mass of 51,049 Da. The deduced amino acid sequence of Tt-laccase showed 99.7% and 44.3% identities to the Thermus thermophilus HB27 laccase and Synechococcus sp. RS9917 laccase, respectively. Tt-laccase gene was expressed as a fusion protein with six histidine residues in E. coli Rosetta-gami (DE3) cells, and the recombinant protein was purified to homogeneity. UV-Vis spectrum analysis revealed that the enzyme has copper atoms, a type I Cu(II) and a type III binuclear Cu(II). The optimum pH for the oxidation of guaiacol was 5.0 and the optimum temperature was $90^{\circ}C$ The half-life of heat inactivation was about 120 min at $90^{\circ}C$ The enzyme reaction was inhibited by sodium azide, L-cystein, EDTA, dithiothreitol, tropolone, and kojic acid. The enzyme oxidized various known laccase substrates, its lowest $K_m$ value being for 4-hydroxyindole, highest $k_{cat}$ value for syringaldazine, and highest $k_{cat}/K_m$ for guaiacol.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part II); Synthesis and Characterization of Cr(III)-Citrato Macrocyclic Complex

  • Byun, Jong-Chul;Park, Yu-Chul;Youn, Jeung-Su;Han, Chung-Hun;Lee, Nam-Ho
    • Bulletin of the Korean Chemical Society
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    • 제26권4호
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    • pp.634-640
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    • 2005
  • The reaction of cis-[Cr([14]-decane)(OH$_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = citrate(cit)} leads to a new dimeric complex cis-[{Cr([14]-decane)($\mu$-cit)}$_2](ClO_4)_2$. This binuclear complex has been structurally characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ reveals that each chromium has a distorted octahedral coordination environment and citrato ligands are monodentate to the two chromium atoms via the carboxyl groups. For dimeric complex the bridging geometry is as follows: Cr$\ldots$Cr = 7.361 $\AA$; Cr-O(average) = 1.958 (8) $\AA$; Cr-N range = 2.108 (9)-2.147(9) $\AA$; N(1)-Cr-N(3) (equatorial position) = 98.0(4)$^{\circ}$; N(2)-Cr-N(4) (axial position) = 166.4(4)$^{\circ}$; O(1)-Cr-N(2) = 98.1(4)$^{\circ}$; O(3)-Cr-N(4) = 96.6(3)$^{\circ}$; O(1)-Cr-O(3) = 90.4$^{\circ}$. The FAB mass spectrum of the dimeric complex displays peak due to the molecular ions cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ at m/z 1053.