• Title/Summary/Keyword: copper complexes

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Separation of D and L Amino Acids by High-Performance Liquid Chromatography

  • Lee, Sun-Haing;Ryu, Jae-Wook;Park ,Kyoung-Sug
    • Bulletin of the Korean Chemical Society
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    • v.7 no.1
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    • pp.45-50
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    • 1986
  • Separation of optical isomers of some derivatives of amino acids by reversed-phase HPLC has been accomplished by adding a chelate of an optically active amino acid to copper(Ⅱ) to the mobile phase. Cu(Ⅱ) complexes of L-proline and L-hydroxyproline in the mobile phase showed different degrees of separation. Optical isomers of DNS derivatives of amino acids are selectively separated, but those of several other derivatives are not at all. The kinds of buffer agents, the pH, and the concentrations of acetonitrile and the Cu(Ⅱ) ligand all affect the separations. The elution behavior between D and L DNS-amino acids appears to depend on the alkyl side chain of the amino acids. A chromatographic mechanism is proposed that is based on a stereospecificity of the formation of ternary complexes by the D, L-DNS-amino acids and the chiral additive associated with the stationary phase. The steric effects of the ligand exchange reactions are related with the feasibility of cis and/or trans attack of the amino acids to the binary chiral chelate retained on the stationary phase.

Cupric Complexes Produced from the Reaction of Cupric Nitrate Trihydrate with S-2-Pyridyl Thioates

  • Choi, Young-Nam;So, Hyun-Soo;Lee, Jae-In;Kim, Sung-Gak
    • Bulletin of the Korean Chemical Society
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    • v.7 no.5
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    • pp.385-388
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    • 1986
  • The reaction of cupric nitrate trihydrate with S-2-pyridyl thioates in acetonitrile was studied. The major products were the corresponding carboxylic acids and $[Cu(NO_3)(C_5H_4NS)(C_5H_5NS$)] (Complex A). Sometimes $[Cu(NO_3)(C_5H_4NS)(H_2O$)] was also obtained in addition to Complex A. When Complex A was recrystallized in dimethylsulfoxide, $[Cu(NO_3)(C_5H_4NS)(C_5H_5NS)$ {$(CH_3)_2SO$}$_2]{\cdot}2H_2O$ was crystallized. The structures of these copper complexes and the role of cupric nitrate in the hydrolysis of S-2-pyridyl thioates are discussed.

Spectroscopic, Redox and Biological Studies of Push-Pull Porphyrins and Their Metal Complexes

  • Rajesh, K.;Rahiman, A. Kalilur;Bharathi, K. Shanmuga;Sreedaran, S.;Gangadevi, V.;Narayanan, V.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2656-2664
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    • 2010
  • We have synthesized a series of push-pull porphyrins containing both donor and acceptor substituents at the mesopositions and have examined their spectral and biological properties. The push-pull porphyrins containing both strong donor $NH_2$ and acceptor $NO_2$ at meso-positions, in which donor group condensed with the ligand, (2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formlyphenol (L) to form imine linkages with porphyrin. The Schiff base ligand 5-[4-(2,6-bis(4-methylpiperazine-1-yl-methyl)-4-iminomethylphenol)phenyl]-10,15,20-tris(4-nitrophenyl) porphyrin [$an_3$(TPP)L] can be synthesized from 2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formylphenol (L) and 5-(4-aminophenyl)-10, 15,20-tris(4-nitrophenyl)porphyrin. The push-pull porphyrin [$an_3$(TPP)L] was metallated to get copper, nickel and zinc complexes. The spectral, electrochemical, antibacterial, antifungal and cytotoxicity properties of all the donor- acceptor push-pull porphyrins and their complexes were characterized and studied.

Protonation and Energetical Investigations of Calix[4]-cyclen-benzo-crown-6 and Its Complexes with Zinc and Copper

  • Boonchoo, Thanaporn;Pulpoka, Buncha;Ruangpprnvisuti, Vithaya
    • Bulletin of the Korean Chemical Society
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    • v.25 no.6
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    • pp.819-822
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    • 2004
  • Protonation constants of calix[4]-cyclen-benzo-crown-6, L in 1X$10^{-2}$ M $Bu_4NCF_3SO_3$ in 40% $CH_2Cl_2/CH_3OH$ at $25^{\circ}C$ determined by potentiometric titration are log $K_1$ = 10.91, log $K_2$ = 10.30, log $K_3$ = 6.24 and log $K_4$ = 2.55. Stability constants for the receptor L complexes with Cu(II) and Zn(II) in 1X$10^{-2}$ M $Bu_4NCF_3SO_3$ in 40% $CH_2Cl_2/CH_3OH$ at $25^{\circ}C$ were determined by UV-VIS spectrometric titration. Stability constants of the CuL and ZnL complexes as log $\beta$ are 4.37 and 3.45, respectively. Stabilization energies for protonations of receptor L, derived from ab initio Hartree-Fock method with 6-31G basis set, are ${\Delta}E_1$ = -290.1, ${\Delta}E_2$ = -205.0, ${\Delta}E_3$ = -124.9 and ${\Delta}E_4$ = -26.9 kcal/mol and complexation energy of ZnL complex is -370.3 kcal/mol.

Preparation of silver stabilizer layer on coated conductor by continuous dip coating method using organic silver complexes (유기 은 착체 화합물을 코팅용액으로 사용하여 연속적인 담금코팅방법에 의한 은 안정화층 제조)

  • Lee, Jong-Beom;Kim, Ji-Cheol;Park, Sin-Keun;Kim, Byeong-Joo;Kim, Jae-Geun;Lee, Hee-Gyoun;Hong, Gye-Won
    • Progress in Superconductivity and Cryogenics
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    • v.12 no.1
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    • pp.1-5
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    • 2010
  • Silver stabilizing layer of coated conductor has been prepared by dip coating method using organic silver complexes containing 10 wt% silver as a starting material. Coated silver complex layer was dried in situ with hot air and converted to crystalline silver by post heat treatment in flowing oxygen atmosphere. A dense continuous silver layer with good surface coverage and proper thickness of 230 nm is obtained by multiple dip coatings and heat treatments. The film heat treated at $500^{\circ}C$ showed good mechanical adhesion and crystallographic property. The interface resistivity between superconducting YBCO layer and silver layer prepared by dip coating was measured as $0.67\;{\times}\;10^{-13}\;{\Omega}m^2$. Additional protecting copper layer with the thickness of $20\;{\mu}m$ was successfully deposited by electroplating. The critical current measured with the specimen prepared by dip coating and sputtering on same quality YBCO layer showed similar value of ~140 A and proved its ability to replace sputtering method for industrial production of coated conductor.

Photodynamic and Antioxidant Activities of Divalent Transition Metal Complexes of Methyl Pheophorbide-a

  • Yoon, Il;Park, Ho-Sung;Cui, Bing Cun;Li, Jia Zhu;Kim, Jung-Hwa;Lkhagvadulam, Byambajav;Shim, Young-Key
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.2981-2987
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    • 2011
  • A comparative study of the photodynamic and antioxidant activities of methyl pheophorbide-a (MPa, 1) and its transition metal(II) complexes (2-5) is described. Four transition metal complexes (palladium(II): 2, zinc(II): 3, cobalt(II): 4 and copper(II): 5) of MPa were prepared by reaction between the corresponding transition metal and 1, respectively, and were characterized by $^1H$-NMR and UV-vis spectroscopic and mass spectrometric analyses. In vitro results show a photodynamic therapy (PDT) efficacy with A549 cells might be attributed to a heavy atom effect of the transition metal complexes of MPa. Among them, 4 and 5 showed higher photodynamic activity than that of 1 at the concentration of 5 ${\mu}M$ at 24 h incubation after photoirradiation. The images of morphological change for 2-5 show evidence for the PDT effect with A549 cells. And the all transition metal complexes of MPa showed higher antioxidant activity than that of MPa, in which 4 showed the highest antioxidant activity.

Tautomerism of Cytosine on Silver, Gold, and Copper: Raman Spectroscopy and Density Functional Theory Calculation Study

  • Cho, Kwang-Hwi;Joo, Sang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.29 no.1
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    • pp.69-75
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    • 2008
  • Tautomerism of pyrimidine base cytosine has been comparatively examined on nanoparticle and roughened plate surfaces of silver, gold, and copper by surface-enhanced Raman scattering (SERS). The SERS spectrum was found to be different depending on the metals and their substrate conditions suggesting the dissimilar population of various tautomers of cytosine on the surfaces. The ab initio calculations were performed at the levels of B3LYP, HF, and MP2 levels of theory with the LanL2DZ basis set to estimate the energetic stability of the tautomers with the metal complexes as well as the gas phase state. The amino group and N3-coordinated tautomer was predicted to be more favorable for bonding to Au, whereas the hydroxyl and N1-coordinated zwitter ionic form is most stable with Ag and Cu as a bidentate form from the DFT calculation. The binding energy with the Ag atom is calculated to be smaller than those with the Au and Cu atoms in line with the temperature-dependent SERS spectra of cytosine.