• Title/Summary/Keyword: Coordination chemistry

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Circadian rhythm of melatonin secretion and growth-related gene expression in the tiger puffer Takifugu rubripes

  • Kim, Byeong-Hoon;Hur, Sung-Pyo;Hur, Sang-Woo;Takeuchi, Yuki;Takemura, Akihiro;Lee, Young-Don
    • Fisheries and Aquatic Sciences
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    • v.20 no.8
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    • pp.17.1-17.8
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    • 2017
  • Somatostatin (SS) and growth hormone-releasing hormone (GHRH) are primary factors regulating growth hormone (GH) secretion in the pituitary. To date, it remains unknown how this rhythm is controlled endogenously, although there must be coordination of circadian manners. Melatonin was the main regulator in biological rhythms, and its secretion has fluctuation by photic information. But relationship between melatonin and growth-related genes (ghrh and ss) is unclear. We investigated circadian rhythms of melatonin secretion, ghrh and ss expressions, and correlation between melatonin with growth-related genes in tiger puffer Takifugu rubripes. The melatonin secretion showed nocturnal rhythms under light and dark (LD) conditions. In constant light (LL) condition, melatonin secretion has similar patterns with LD conditions. ss1 mRNA was high during scotophase under LD conditions. But ss1 rhythms disappeared in LL conditions. Ghrh appeared opposite expression compared with melatonin levels or ss1 expression under LD and LL. In the results of the melatonin injection, ghrh and ss1 showed no significant expression compared with control groups. These results suggested that melatonin and growth-related genes have daily or circadian rhythms in the tiger puffer. Further, we need to know mechanisms of each ss and ghrh gene regulation.

Kinetic Studies on the Aquation of Tetrahedral Copper (II) and Cobalt (II) Complexes (정사면체 구조를 갖는 Cu (II) 및 Co (II) 착화물들의 아쿠오화반응에 관한 연구)

  • Kim, Young-Inn;Choi, Sung-Nak;Kim, Jung-Sook;Kim, Hae-Kyung
    • Journal of the Korean Chemical Society
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    • v.32 no.2
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    • pp.122-129
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    • 1988
  • The rates of aquation of sparteine cobalt(II) halide and sparteine copper(II) halide were investigated in the citrate buffer solutions. The aquation of cobalt(II) complexes proceeds via D-mechanism and the catalytic effect of halide ions is not observed. The aquation of copper(II) complexes proceeds via $I_d$-mechanism and is catalyzed by the presence of cyanide and halide ions, and the aquation rate is pH dependent. The different mechanistic behavior of cobalt(II) complexes from corresponding copper(II) complexes seems to be attributed to the weakness of Co-N bond in the coordination sphere.

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Transition Metal Catalysed Oxidation Reactions and Ligand Effects in Aprotic Solvents (전이금속 촉매작용의 산화반응과 리간드 효과)

  • Kim, Sang-Bock
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.585-590
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    • 2003
  • Cobalt oxygen carrier complex N,N'-ethylenebis(3-methoxysalycylideneiminato)cobalt(II), Co(3MeOsalen) was prepared at $25{\circ}C$. UV and visible absorption spectra of the complex and hydrazobenzene were studied in non-aqueous solvent methanol in the range of wavelength 200-600 nm. The oxidation of hydrazobenzene by oxygen in non-aqueous solvent is catalysed by Co(3MeOsalen). In the presence of triphenylphosphine($PPh_3$), the rate decreases in methanol. This is presumably attributable to the coordination of $PPh_3$ to the Co(3MeOsalen), resulting in the catallytically inactive compound. The initial rates of the oxidation of hydrazobenzene with the ligand triphenylphosphine were measured by the theoretical values of the rates, Rate=$k_1+k_2K_1[P]/1+K_1[P]+K_1K_2[P]^2$. This fact would be a poorer σ-donor ligand than methanol.

Magnetic Exchange Interactions in a 2D Grid-like Copper(II) Polymer with Bridging End-on Cyanato and Pyrazine Ligands: A DFT Study

  • Kang, Dae-Bok
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1704-1710
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    • 2010
  • The structure of a 2D grid-like copper(II) complex [Cu$(NCO)_2$(pyz)](pyz=pyrazine) (1) consists of 1D chains of Cu-pyz units connected by double end-on (EO) cyanato bridges. Each Cu(II) ion has a distorted octahedral coordination, completed by the four EO cyanato and two pyrazine ligands. Magnetic interactions through EO cyanato and pyrazine bridges in 1 are discussed on the basis of DFT broken-symmetry calculations at the B3LYP level. For model dicopper(II) complexes I (bridged by cyanato) and II (bridged by pyrazine), electronic structure calculations reproduce very well the experimental couplings for the S = 1/2 ferromagnetic and antiferromagnetic exchange-coupled 2D system: the calculated exchange parameters J are +1.25 $cm^{-1}$ and -3.07 $cm^{-1}$ for I and II, respectively. The $\sigma$ orbital interactions between the Cu $x^2-y^2$ magnetic orbitals and the nitrogen lone-pair orbitals of pyrazine are analyzed from the viewpoint of through-bond interaction. The energy splitting of 0.106 eV between two SOMOs indicates that the superexchange interaction should be antiferromagnetic in II. On the other hand, there are no bridging orbitals that efficiently connect the two copper(II) magnetic orbitals in I because the HOMOs of the basal-apical NCO bridge do not play a role in the formation of overlap interaction pathway. The energy separation in the pair of SOMOs of I is calculated to be very small (0.054 eV). This result is consistent with the occurrence of weakly ferromagnetic properties in I.

Persistence and Degradation Pattern of Acequinocyl and Its Metabolite, Hydroxyl-Acequinocyl and Fenpyroximate in Butterburs (Petasites japonicus Max.)

  • Leesun Kim;Geun-Hyoung Choi;Hyun Ho Noh;Hee-Dong Lee;Hak-won Lee;Kee Sung Kyung;Jin-Ho Ro
    • Korean Journal of Environmental Agriculture
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    • v.42 no.2
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    • pp.93-103
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    • 2023
  • Persistence and degradation patterns of acequinocyl and its metabolite, hydroxyl-acequinocyl (acequinocyl-OH) and fenpyroximate in butterburs (Petasites japonicus Max.) were investigated after pesticide application. Butterburs, one of the minor crops in South Korea, was planted in two plots (plot A for double and plot B for single application) in a greenhouse. Butterburs samples were also planted in a separate plot without pesticide treatment, as the control. A commercial pesticide containing acequinocyl and fenpyroximate was applied to the foliage of butterburs at hourly intervals after dilution. Recoveries of acequinocyl and acequinocyl-OH were 78.6-84.7% and 83.7-95.5%, respectively; the relative standard deviation of the two compounds were less than 5%. The method limit of quantification was 0.01 mg/kg. The total (Ʃ) acequinocyl residues in butterburs reduced by 96.0% at 14 days and 75.9% at 7 days, in plot A and B, respectively, after final pesticide applications. The biological half-life (DT50) of Ʃ acequinocyl and fenpyroximate, calculated using the dissipation rate, was 3.0 days and 4.0 days, respectively. These data were used to set up maximum residue and safe standard levels when the pesticides are applied to control pests during butterbur cultivation. Risk assessment results showed that the maximum % acceptable daily intake was 7.74% for Ʃ acequinocyl and 0.16% for Ʃ fenpyroximate. The theoretical maximum daily intake of Ʃ acequinocyl and fenpyroximate was 26.3% and 35.8%, respectively. In conclusion, the concentrations of Ʃ acequinocyl and fenpyroximate in butterburs pose no significant health risks to Koreans.

Interaction of Proline with Cu+ and Cu2+ Ions in the Gas Phase (기체상에서 Cu+ 및 Cu2+ 이온과 proline의 상호작용)

  • Lee, Gab-Yong
    • Journal of the Korean Chemical Society
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    • v.53 no.3
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    • pp.257-265
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    • 2009
  • The structures and metal affinities of the binding configurations of $Cu^{+}$ and $Cu^{2+}$ to proline have been investigated using the hybrid three-parameter Density Functional Theory(DFT/B3LYP). We found that the metal-proline bonding and the energy ordering of several conformers were very different in $Cu^{+}$-proline and $Cu^{2+}$-proline. For $Cu^{+}$-proline, the ground state structure was found to have a bidentated coordination in which $Cu^{+}$ was coordinated to the carbonyl oxygen and imino group nitrogen of neutral proline. On the contrary, the ground state structure of $Cu^{2+}$-proline involves chelation between the two oxygens of the carboxylate group in a zwitterionic proline. The metal ion affinity of proline of the most stable $Cu^{+}$-proline complex was calculated as 76.0 kcal/mol at 6-311++G(d,p) level, whereas the $Cu^{2+}$ ion affinity of proline was calculated as 258.5 kcal/mol.

The Crystal and Molecular Structure of Sodium Sulfisoxazole hexahydrate (Sodium Sulfisoxazole Hexahydrate의 결정 및 분자구조와 수소결합에 관한 연구)

  • Young Ja Park;Chung Hoe Koo
    • Journal of the Korean Chemical Society
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    • v.20 no.1
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    • pp.19-34
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    • 1976
  • The crystal structure of sodium sulfisoxazole hexahydrate, $C_{11}H_{12}N_3O_3SNa{\cdot}6H_2O$,has been determined by X-ray diffraction method. The compound crystallizes in the monoclinic space group $$P2_1}c$$ with a = 15.68(3), b = 7.70(2), c = 17.94(4)${\AA}$, ${\beta}$ = $118(2)^{\circ}$ and Z = 4. A total of 1717 observed reflections were collected by the Weissenberg method with $CuK{\alpha}$ radiation. Structure was solved by heavy atom method and refined by block-diagonal least-squares methods to the R value of 0.14. The conformational angle formed by the S-C(l) bond with that of N(2)-C(7), when the projection in taken along the S-N(2), is $73^{\circ}.$ The benzene ring is planar and makes an angle of $60^{\circ}$ with the plane of the isoxazole ring, which is also planar. The sodium atom has a distorted octahedral coordination of N(l) and five oxygen atoms from hydrate molecules. Sodium sulfisoxazole hexahydrate shows fourteen different hydrogen bondings in the crystal. These are six $O-H{\cdots}O-H bonds, three $O-H{\cdots}O$ bonds, two $O-N{\cdots}N,$ one $N-H{\cdots}O,O-H{\cdots}N,N-H{\cdots}O-H$ bond, with the distances in the range of 2.71 to $3.04{\AA}.$.

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Synthesis of Self-doped Poly(PEGMA-co-BF3LiMA) Electrolytes and Effect of PEGMA Molecular Weight on Ionic Conductivities (자기-도핑형 poly(PEGMA-co-BF3LiMA) 전해질의 합성과 이온전도도에 대한 PEGMA분자량의 영향)

  • Kim, Kyung-Chan;Ryu, Sang-Woog
    • Journal of the Korean Electrochemical Society
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    • v.15 no.4
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    • pp.230-235
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    • 2012
  • Polymer electrolytes consisted of $BF_3LiMA$ and 300 (PEGMA300) or 1100 (PEGMA1100) g $mol^{-1}$ of PEGMA were prepared and the electrochemical properties were characterized. Interestingly, the AC-impedance measurement shows $1.22{\times}10^{-5}S\;cm^{-1}$ of room temperature ionic conductivity from PEGMA1100 based solid polymer electrolytes while $8.54{\times}10^{-7}S\;cm^{-1}$ was observed in PEGMA300 based liquid polymer electrolytes. The more suitable coordination between lithium ion and ethylene oxide (EO) unit might be the reason of higher ionic conductivity which can be possible in PEGMA1100 based electrolytes since it has 23 EO units in monomer. The lithium ion transference number was found to be 0.6 due to the side reactions between $BF_3$ and lithium metal expecially for longer time but 0.9 was observed within 3000 seconds of measuring time which is strong evidence of a single-ion conductor.

Electrocatalytic Effect of Dioxygen Reduction at Glassy Carbon Electrode Modified with Schiff Base Co(II) Complexes (Schiff Base Co(II) 착물이 변성된 유리질 탄소전극에서 산소 환원의 전기촉매 효과)

  • Seong, Jeong-Sub;Chae, Hee-Nam;Choi, Yong-Kook
    • Analytical Science and Technology
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    • v.11 no.6
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    • pp.460-468
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    • 1998
  • Schiff base ligands such as $SOPDH_2$, $SNDH_2$, $EBNH_2$, and $PBNH_2$ and their Co(II) complexes such as [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], and [$Co(II)(PBN)(H_2O)$] have been synthesized. The mole ratio of Shiff base ligand to cobalt(II) for the Co(II) complexes was found to be 1:1. Also these complexes have been configurated with hexa-coordination. Reduction of dioxygen was investigated by cyclic voltammetry at glassy carbon electrodes modified with Schiff base Co(II) complexes in 1 M KOH aqueous solution. At modified glassy carbon electrode with Schiff base Co(II) complexes, reduction peak current of oxygen was increased and peak potential was shifted to more positive direction compared to bare glassy carbon electrode. The electrokinetic parameters such as number of electron and exchange rate constant were calculated from the results of cyclic voltammogrms. The reduction of dioxygen at glassy carbon electrode has been $2e^-$ reaction pathway. Exchange rate constant at glassy carbon electrode modified with Co(II) complexes was increased 2~10 times compared to bare electrode.

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X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides (α-케토안정화된 일리드화 인의 수은(II) 및 은(I) 착물에 대한 X-선 및 분광학적 연구)

  • Karami, K.;Buyukgungor, O.;Dalvand, H.
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.38-45
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    • 2011
  • The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.