• Title/Summary/Keyword: Metal coordination

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Compositions and Provenience Studies on Horse Armour Excavated from Changnyeong Gyo-dong and Songhyeon-dong Tumuli (창녕 교동과 송현동 고분군 출토 마구류(馬具類)의 조성 및 원료 산지 추정)

  • Han, Woorim;Park, Jiyeon;Kim, Sojin
    • Korean Journal of Heritage: History & Science
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    • v.54 no.1
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    • pp.4-17
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    • 2021
  • This study analyzed 19 samples of harness fittings and pendants, which were excavated in Tomb No. 15 in Songhyeon-dong, Changnyeong. Harness fittings and pendants are used for ostentation, rather than practicality, and were excavated from ancient tombs in Gaya culture. So, they are considered artifacts that compare the production techniques and raw materials. This study aimed to examine the production techniques and provenience studies of Bihwa Gaya, which is estimated to be from the 5th to 6th centuries. According to the research, harness fittings were made of pure copper and were gilded with Au·Ag alloys on their surfaces. Hg was detected together and plated with a mercury amalgam method. As a result of the pendant (fish scales-pattern, oval and fish-tail shape), analysis showed that Fe in the background metal, Cu in the middle layer, and Au and Ag on the surface were the main components. The method of adhesion between Cu and Au·Ag gilded layers are plated by a mercury amalgamation method. So, it was identified by the gilt-iron·gold·bronze technique. Since the pendant (heart shaped) is found to be the main component of Fe in the background metal and Ag in the surface layer, the metal was made gilt-iron·silver technique. The background metal and gilding were additionally fixed using a rivet. The raw materials of 3 harnesses excavated from Changnyeong are plotted in zone 2 in the southern Korean Peninsula. And 16 harnesses were plotted in Chinese copper ore by Mabuchi Hishao in the Chinese Peninsula.

Structural characterization and thermal behaviour of the bis(2-aminothiazole)bis(isothiocyanato)zinc(II) complex, Zn(NCS)2(C3H4N2S)2

  • Suh, Seung Wook;Kim, Inn Hoe;Kim, Chong-Hyeak
    • Analytical Science and Technology
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    • v.18 no.5
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    • pp.386-390
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    • 2005
  • The zinc(II) complex, $Zn(NCS)_2(C_3H_4N_2S)_2$, I, has been synthesized and characterized by single crystal X-ray diffraction, thermal analysis and infrared spectroscopy. The complex I crystallizes in the triclinic system, $P\bar{1}$ space group with a = 7.587(1), b = 8.815(1), $c=12.432(2){\AA}$, ${\alpha}=75.584(8)$, ${\beta}=83.533(9)$, ${\gamma}=68.686(8)^{\circ}$, $V=750.0(2){\AA}^3$, Z = 2, $R_1=0.036$ and ${\omega}R_2=0.101$. The central Zn(II) atom has a tetrahedral coordination geometry, with the heterocyclic nitrogen atoms of 2-aminothiazole ligands and the nitrogen atoms of isothiocyanate ligands. The crystal structure is stabilized by one-dimensional networks of the intermolecular $N-H{\cdots}S$ hydrogen bonds between the amino group of 2-aminothiazole ligands and the sulfur atom of isothiocyanate ligands. Based on the results of thermal analysis, the thermal decomposition reaction of complex I was analyzed to have three distinctive stages such as the loss of 2-aminothiazole, the decomposition of isothiocyanate and the formation of metal oxide.

Switching and sensing molecular spins by chemical reactions on metal surfaces

  • Kahng, Se-Jong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2015.08a
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    • pp.63.2-63.2
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    • 2015
  • Controlling and sensing spin states of magnetic molecules such as metallo-porphyrins at the single molecule level is essential for spintronic molecular device applications. Axial coordinations of diatomic molecules to metallo-porphyrins also play key roles in dynamic processes of biological functions such as blood pressure control and immune response. However, probing such reactions at the single molecule level to understand their physical mechanisms has been rarely performed. Here we present on our single molecule association and dissociation experiments between diatomic and metallo-porphyrin molecules on Au(111) describing its adsorption structures, spin states, and dissociation mechanisms. We observed bright ring shapes in NO adsorbed metallo-porphyrin compelxes and explained them by considering tilted binding and precession motion of NO. Before NO exposure, Co-porphryin showed a clear zero-bias peak in scanning tunneling spectroscopy, a signature of Kondo effect in STS, whereas after NO exposures it formed a molecular complex, NO-Co-porphyrin, that did not show any zero-bias feature implying that the Kondo effect was switched off by binding of NO. Under tunneling junctions of scanning tunneling microscope, both positive and negative energy pulses. From the observed power law relations between dissociation rate and tunneling current, we argue that the dissociations were inelastically induced with molecular orbital resonances. Our study shows that single molecule association and dissociation can be used to probe spin states and reaction mechanisms in a variety of axial coordination between small molecules and metallo-porphyrins.

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Colour Change of Black-dyed PET Fabrics by Sputter Coloration and Their Physical Properties (Sputter 착색에 의한 Black-dyed PET 직물의 색상 및 물성변화)

  • Koo, Kang;Won, Eun-Hee;Park, Young-Mi
    • Textile Coloration and Finishing
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    • v.18 no.4
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    • pp.11-19
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    • 2006
  • Black-dyed PET fabrics were sputtered with stainless steel through DC-magnetron type device to investigate the possibility of coloration effect, and then considered the morphological structure and physical characteristics such as water permeation ability and washing fastness. Change in color was estimated on the basis of CIELAB color system. The color coordination of metal plated PET was shifted to yellow-red from red-blue. Colour difference$({\Delta}E^*)$ was increased by sputtering conditions with increasing ion current and treatment time. Especially, $Lightness(L^*)$ value of PET was remarkably increased by sputtering, whereas $Chroma(C^*)$ increased gradually. From SEM analysis, rough and uneven craters were found and thickened on the fiber surfaces with longer sputtering time. And washing fastness was a little poor and absorption ability slightly decreased. There were little changes of breaking load and breaking extension. It was evident that observed uneven craters in the plated thin layer resulted in the colour change of PET fabrics by sputtering treatments.

Structural Studies of Copper(II)-Hippuryl-L-histidyl-L-leucine(HHL) Complex by NMR Methods

  • Lee Seong-Ran;Jun Ji-Hyun;Won Ho-Shik
    • Journal of the Korean Magnetic Resonance Society
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    • v.10 no.1
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    • pp.115-125
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    • 2006
  • Hippuryl-L-histidyl-L-leucine(HHL) is widely used as a substrate of angiotensin converting enzyme(ACE) cleaving the neurotransmitter angiotensin(I) to the octapeptide angiotensin(II). The structure of the substrate molecules should provide information regarding the geometric requirements of the ACE active site. For the purpose of determination of in vivo reaction, metallo(Cu, Zn)-HHL complexes were synthesized and the degree of complex formation were identified by MALDITOF, ESI mass spectrometric analysis. Tn addition, the pH-dependent species distribution curves were obtained by potentiometric titration. Nitrogen atoms of imidazole ring and oxygen atom of caboxylate groups in the peptide chain were observed to be participated in the metal complex formation. After purification of complexes further structural characterization were made by utilizing UV-Vis, electrochemical methods and NMR. Complete NMR signal assignments were carried out by using 2D-spectrum techniques COSY, TOCSY, NOESY, HETCOR. A complex that two imidazole and carboxylate groups are asymmetrically participating to coordination mode was predicted to the solution-state structure of $Cu(II)-HHL_2$ based on $^{13}C-NMR$ signal assignment and NOE information.

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Syntheses of Amide Bonds and Activations of N-C(sp3) Bonds

  • Hong, Jang-Hwan
    • Journal of Integrative Natural Science
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    • v.10 no.4
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    • pp.175-191
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    • 2017
  • In organic chemistry amide synthesis is performed through condensation of a carboxylic acid and an amine with releasing one equivalent of water via the corresponding ammonium carboxylate salt. This method is suffering from tedious processes and poor atom-economy due to the adverse thermodynamics of the equilibrium and the high activation barrier for direct coupling of a carboxylic acid and an amine. Most of the chemical approaches to amides formations have been therefore being developed, they are mainly focused on secondary amides. Direct carbonylations of tertiary amines to amides have been an exotic field unresolved, in particular direct carbonylation of trimethylamine in lack of commercial need has been attracted much interests due to the versatile product of N,N-dimethylacetamide in chemical industries and the activation of robust N-C($sp^3$) bond in tertiary amine academically. This review is focused mainly on carbonylation of trimethylamine as one of the typical tertiary amines by transition metals of cobalt, rhodium, platinum, and palladium including the role of methyl iodide as a promoter, the intermediate formation of acyl iodide, the coordination ability of trimethylamine to transition metal catalysts, and any possibility of CO insertion into the bond of Me-N in trimethylamine. In addition reactions of acyl halides as an activated form of acetic acid with amines are reviewed in brief since acyl iodide is suggested as a critical intermediate in those carbonylations of trimethylamine.

Crystal Structure and Molecular Stereochemistry of Novel Polymeric Cu2(DMP)44(DMSO) as a Platform for Phosphate Diester Binding

  • Rafizadeh, Massoud;Tayebee, Reza;Amani, Vahid;Nasseh, Mohammad
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.594-598
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    • 2005
  • Treatment of a solution of $CuCl_2$ in dimethyl phosphate (DMP) with DMSO under nitrogen atmosphere afforded to a light blue fluorescence powder. Slow evaporation of $H_2O$-DMSO solution of this powder resulted in blue-sky crystals of a new polymeric Cu(II) complex, with a unit cell composed of $Cu_2(DMP)_4$(DMSO), (1). The crystal and molecular structure of the complex acquired crystallographically. Compound (1) crystallizes in the monoclinic space group $P2_1$/n with a = 12.8920(11) $\AA$, b = 13.1966(11) $\AA$, c = 14.7926(13) $\AA$, $\alpha$ = 90$^{\circ}$, $\beta$ = 98.943(2)$^{\circ}$, $\gamma$ = 90$^{\circ}$, V= 2486.1(4) ${\AA}^3$, and Z = 4. A square pyramidal environment for the metal center was established by coordination of oxygen atoms of four bridging DMP ligands in the basal positions and binding a tri-centered oxygen atom of DMSO in the apical disposition of Cu(II). The sixth position was also affected by a weak interaction with the sulfur atom of another DMSO. The phosphorous atom in the bridging DMP was arranged in a deformed tetrahedron with (gg) conformation for methyl esters with $C_{2v}$ symmetry.

Preparation of Novel Magnesium Precursors and MgO Thin Films Growth by Atomic Layer Deposition (ALD)

  • Kim, Hyo-Suk;park, Bo Keun;Kim, Chang Gyoun;Son, Seung Uk;Chung, Taek-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.364.2-364.2
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    • 2014
  • Magnesium oxide (MgO) thin films have attracted great scientific and technological interest in recent decades. Because of its distinguished properties such as a wide band gap (7.2 eV), a low dielectric constant (9.8), a low refractive index, an excellent chemical, and thermal stability (melting point=$2900^{\circ}C$), it is widely used as inorganic material in diverse areas such as fire resistant construction materials, optical materials, protective layers in plasma display panels, buffer layers of multilayer electronic/photonic devices, and perovskite ferroelectric thin films. Precursor used in the ALD requires volatility, stability, and low deposition temperature. Precursors using a heteroleptic ligands with different reactivity have advantage of selective reaction of the heteroleptic ligands on substrate during ALD process. In this study, we have synethesized new heteroleptic magnesium precursors ${\beta}$-diketonate and aminoalkoxide which have been widely used for the development of precursor because of the excellent volatility, chelating effects by increasing the coordination number of the metal, and advantages to synthesize a single precursor. A newly-synthesized Mg(II) precursor was adopted for growing MgO thin films using ALD.

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Microwave Synthesis of a Porous Metal-Organic Framework, Nickel(II) Dihydroxyterephthalate and its Catalytic Properties in Oxidation of Cyclohexene

  • Lee, Ji-Sun;Halligudi, Shiva B.;Jang, Nak-Han;Hwang, Dong-Won;Chang, Jong-San;Hwang, Young-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.31 no.6
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    • pp.1489-1495
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    • 2010
  • A porous coordination solid of nickel(II) dihydroxyterephthalate has been synthesized by the microwave-assisted (MW) method. The synthesized nickel(II) dihyroxylterephthalate was designated by the general formula of [$Ni_2$(dhtp) $(H_2O)_2]{\cdot}8H_2O$ (where, dhtp = 2,5-dihydroxyterephthalate, denoted by Ni-DHTP). The effect of microwave-irradiation temperature and time of irradiation on the porosity and morphological changes in the solids have also been investigated. The catalytic performance of Ni-DHTP synthesized by MW method has been studied in the oxidation of cyclohexene with aqueous $H_2O_2$, which gave cyclohexene oxide as the primary product and 2-cyclohexene-1-ol as a major product.

A Study on the Lightning Overvoltage Analysis and Lightning Surge Protection Methods in Underground Distribution System (지중배전계통의 뇌과전압 해석 및 뇌써지 보호방안에 관한 연구)

  • Kim, Sang-Kuk;Jung, Chae-Kyun;Lee, Jong-Beom;Ha, Dong-Hyuk
    • Proceedings of the KIEE Conference
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    • 2003.07a
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    • pp.558-560
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    • 2003
  • The effects of surge arresters for protection of transmission systems against direct lightning strokes have already been investigated using the digital simulation program EMTP. Distribution lines are spanned on a much large area as compared to transmission lines, and therefore, are more often susceptible to lightning strokes. This paper analyzes the overvoltages on underground cable system against direct lightning strokes to the overhead ground wire using the digital simulation. The effects of lightning protection methods, such as lowering the grounding resistance and installing the surge arrester, for preventing overvoltages on underground cable system caused by direct lightning strokes to the overhead ground wire is investigated. Several schemes have been proposed to protect underground cables. This paper summarizes the main results of a study aimed at analysis of lightning overvoltages in variety underground feeders protected by metal-oxide arresters. This study will provide insulation coordination methods for reasonable system design in 22.9kV underground cable system.

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