• Title/Summary/Keyword: N ligand

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Structure and Heme-Independent Peroxidase Activity of a Fully-Coordinated Mononuclear Mn(II) Complex with a Schiff-Base Tripodal Ligand Containing Three Imidazole Groups

  • Sarkar, Shuranjan;Moon, Do-Hyun;Lah, Myoung-Soo;Lee, Hong-In
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3173-3179
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    • 2010
  • New complex $[Mn(II)H_{1.5}L]_2[Mn(II)H_3L]_2(ClO_4)_5{\cdot}3H_2O$ (1), where $H_3L$ is tris {2-(4-imidazolyl)methyliminoethyl} amine (imtren), has been prepared by reacting manganese(II) perchlorate hexahydrate with the imtren ligand in methanol. X-ray crystallographic study revealed that the imtren ligand hexadentately binds to Mn(II) ion through the three Schiff-base imine N atoms and three imidazole N atoms with a distorted octahedral geometry, and the apical tertiary amine N atom of the ligand pseudo-coordinates to Mn(II), forming overall a pseudo-seven coordination environment. The hydrogen-bonds between imidazole and imidazolate of $[Mn(II)H_{1.5}L]^{0.5+}$ complex ions are extended to build a 2D puckered network with trigonal voids. $[Mn(II)H_3L]^{2+}$ complex ions constitutes another extended 2D puckered layer without hydrogen bonds. Two layers are wedged each other to constitute overall stack of the crystal. Peroxidase activity of complex 1 was examined by observing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with hydrogen peroxide in the presence of complex 1. Generation of $ABTS^{+{\cdot}}$ was observed by UV-vis and EPR spectroscopies, indicating that the complex 1, a fully-coordinated mononuclear Mn(II) complex with nitrogen-only ligand, has a heme-independent peroxidase activity.

Synthesis and Characterization of Transition Metal(Ⅱ) Complexes with Tridentate Schiff Base in DMF Solution (DMF용액에서 세자리 Schiff Base를 가진 전이금속(II) 착물들의 합성과 구조결정)

  • Oh, Jeong Geun;Choi, Yong Kook
    • Journal of the Korean Chemical Society
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    • v.43 no.5
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    • pp.511-516
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    • 1999
  • Shiff Base ligand such as [NOIPH] have been synthesized from 2-hydroxy-1-naphthaldehyde and arometic amine. Co(II), Ni(II), and Cu(II) complexes from the reaction metal salts with Tridentate Schiff Base [NOIPH] were sythesized. The ligand and metal(II) complexes were characterized by the elementary analysis, IR, UV-Vis, NMR spectra, and thermogravimetric analysis. Metal(II) complexes in solid state have been shown that the mole raio of Schiff base [NOIPH] as $N_2O$ type to Metal(II) is 2:1 and the metal(II) complexes of $N_2O$ ligand type were four-coordinated configuration.

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Iron Catalyzed Atom Transfer Radical Polymerization of Methyl Methacrylate Using Diphenyl-2-pyridylphosphine as a Ligand

  • Xue, Zhigang;Noh, Seok-Kyun;Lyoo, Won-Seok
    • Macromolecular Research
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    • v.15 no.4
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    • pp.302-307
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    • 2007
  • The living radical polymerization of methyl methacrylate (MMA) by atom transfer radical polymerization, (ATRP) employing a $Fe(II)X_2/diphenyl-2-pyridyl$ phosphine (PyP) catalytic system (X=Cl, Br), was investigated using several initiators and solvents at various temperatures. Most of the polymerizations with the PyP ligand were well controlled, with a linear increase in the number average molecular weights ($M_n$) vs. conversion, with relatively low molecular weight distributions ($M_w/M_n=1.2-1.4$) throughout the reactions. The measured weights matched those of the predicted values. The ethyl-2-bromoisobutyrate (EBriB) initiated ATRP of MMA, with the $Fe(II)X_2/diphenyl-2-pyridyl$ phosphine catalytic system (X=Cl, Br), was better controlled in p-xylene at $80^{\circ}C$ than the other solvents used in this study.

$^{15}N$ NMR Relaxation Studies of Backbone Motion of the catalytic Residues in Free and Steroid-bound ${\Delta}^5$-3-Ketosteroid Isomerase

  • Lee, Hee-Cheon;Sunggoo Yun
    • Journal of the Korean Magnetic Resonance Society
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    • v.5 no.2
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    • pp.130-137
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    • 2001
  • Backbone dynamics of the catalytic residues in free and steroid-bound $\Delta$$^{5}$ -3- ketosteroid isomerase from Pseudomonas testosteroni has been examined by $^{15}$ N relaxation measurements. The relaxation data were analyzed using the model-free formalism to extract the model-free parameters (S$^2$, $\tau$$_{e}$, and R$_{ex}$). Tyr-34 and Asp-99 exhibit enhanced high-frequency (pico- to nanosecond) internal motions in the free enzyme, which are restricted upon ligand binding, while Asp-38 experiences severe restriction of the internal motions in the fee enzyme, suggesting that Tyr-14 and Asp-99 are more actively involved in the ligand binding than Asp-38. The results also indicate that the H-bond network in the catalytic cavity might be slightly strengthened upon ligand binding, which may have some implications on the enzyme mechanism.he enzyme mechanism.m.

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Cobalt(III) Complexes of Various Salen-Type Ligand Bearing Four Quaternary Ammonium Salts and Their Reactivity for CO2/Epoxide Copolymerization

  • Kim, Bo-Eun;Varghese, Jobi Kodiyan;Han, Yong-Gyu;Lee, Bun-Yeoul
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.829-834
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    • 2010
  • Ligand variation was carried out on a cobalt(III) complex of Salen-type ligand comprised of 1,2-cyclohexenediamine and salicylaldehyde bearing a methyl substituent on 3-position and -[$CMe(CH_2CH_2CH_2N^+Bu_3)_2$] on 5-position, which is a highly active catalyst for $CO_2$/propylene oxide copolymerization. Replacement of the methyl substituent with bulky isopropyl group resulted in alteration of the binding mode, consequently lowering turnover frequency significantly. Replacement with an ethyl group preserved binding mode and activity. Replacement of the tributylammonium unit with trihexylammonium or trioctylammonium, or replacement of 1,2-cyclohexenediamino unit with -$NC(Me)_2CH_2N$- decreased activity, even though the binding mode was unaltered.

Effect of ligand orientation on hepatocyte attachment onto the poly(N-p-vinyl benzyl-o-$\beta$-D-galactopyranosyl-D-gluconamide)

  • Jo, Jong-Su;Goto, M.;Kobayashi, A.;Kobayashi, K.;Akaike, T.
    • Proceedings of the KOSOMBE Conference
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    • v.1996 no.05
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    • pp.123-125
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    • 1996
  • The orientation effect of galactose ligand on hepatocyte attachment was investigated. Poly(N-p-vinyl benzyl-o-${\beta}$-D-galactopyranosyl-D-gluconamide) (PVLA), a ${\beta}$-galactose-carrying styrene homo-polymer, was used as a model ligand for the asialoglycoprotein receptors on hepatocytes. PYVA was transferred onto the poly(${\gamma}$-benzyl L-glutamate)(PBLG) or PBLG/ poly(ethylene glycol)(PEG)/PBLG Langmuir-Blodgett (LB) films as the monolayer level. The dichroic fluorescence values of confocal microscope indicated that the PVLA transferred onto the LB films was located with a preferential orientation of its molecular axes with regard to the direction of the a-helix of polypeptide. Hepatocyte recognized well-oriented galactose moieties of the surface of PVLA through asialoglycoprotein receptors.

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Optical Resolution of Dansyl Amino Acids with Addition of Benzyl-L-Hydroxyproline Copper(II) Chelate by High Performance Liquid Chromatography

  • Sun Haing Lee;Tae Sub Oh;Sang Hyun Bak
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.491-495
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    • 1989
  • Resolution of enantiomers of DNS-amino acids has been achieved by a reversed phase liquid chromatography with an addition of a copper(Ⅱ) complex of N-benzyl-L-hydroxyproline to the mobile phase. N-Benzyl-L-hydroxyproline was prepared and used as a chiral ligand of copper(Ⅱ) chelate for the optical resolution. The pH and the concentration of copper(Ⅱ) chelate, organic solvent, and buffer agent in the mobile phase all affect the optical resolutions of dansyl amino acids. The elution orders between D and L-DNS-amino acids were different depending on the structure of the side chain of the amino acids. The retention mechanism for the chiral separation of the dansyl amino acids can be illustrated by the equilibrium of ligand exchange and by hydrophobic interaction with $C_{18}$ stationary phase. The chiral separation can be illustrated with cis and trans effect of the ligand exchange reaction.

Mechanistic Studies on the Oxidation of Triphenylphosphine by $[(tpy)(bpy)Ru^{IV}=O]^{2+}$, Structure of the Parent Complex $[(tpy)(bpy)Ru^{II}-OH_2]^{2+}$

  • 석원경;김미영;Yoshinobu Yokomori;Derek J. Hodgson;Thomas J. Meyer
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.619-624
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    • 1995
  • Oxidation of triphenylphosphine to triphenylphosphine oxide by [(tpy)(bpy)Ru(O)]2+ (tpy is 2,2':6',2"-terpyridine and bpy is 2,2'-bipyridine) in CH3CN has been studied. Experiments with the 18O-labeled oxo complex show that transfer of oxygen from [(tpy)(bpy)RuⅣ=O]2+ to triphenylphosphine is quantitative within experimental error. The reaction is first order in each reactant with k (25.3 ℃)=1.25 × 106 M-1s-1. The inital product, [(tpy)(bpy)RuⅡ-OPPh3]2+, is formed as an observable intermediate and undergoes slow k (25 ℃)=6.7 × 10-5 s-1 solvolysis. Activation parameters for the oxidation step are ΔH≠=3.5 kcal/mol and ΔS≠=-23 eu. The geometry at ruthenium in the complex cation, [(tpy)(bpy)RuⅡ(OH2)]2+, is approximately octahedral with the ligating atoms being the three N atoms of the tpy ligand, the two N atoms of the bpy ligand, and the oxygen atom of the aqua ligand. The Ru-O bond length is 2.136(5) Å.

Template Synthesis and Characterization of Copper(Ⅱ) Complexes of a Polyaza Non-Macrocyclic or a Bis(macrocyclic) Ligand

  • 강신걸;유기석;정수경;김창수
    • Bulletin of the Korean Chemical Society
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    • v.17 no.4
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    • pp.331-334
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    • 1996
  • New copper(Ⅱ) complex of the pentaaza non-macrocyclic ligand 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl)-1,3-diazacyclohexane (2) and a dinuclear copper(Ⅱ) compex of the bis(macrocyclic) ligand 3, in which two 1,5,8,10,12,15-hexaazabicyclo[11.3.11.5]heptadecane subunits are linked together by an ethylene chain through the uncoordinated nitrogen (N10) atoms, have been prepared selectively by the reaction of the metal ion, 1,4,8-triazaoctane, ethylenediamine, and formaldehyde. The dinuclear complex [Cu2(3)]4+ has been also prepared by the reaction of [Cu(2)]2+ with ethylenediamine and formaldehyde. The reaction products largely depend on the molar ratio of the reactants employed. The mononuclear complex or each macrocyclic subunit of the dinuclear complex contains one 1,3-diazacyclohexane ring and has a square-planar geometry with a 5-6-5 or 5-6-5-6 chelate ring sequence. In acidic solution, the copper(Ⅱ) complex of 2 dissociates more slowly than those of other related non-cyclic polyamines.