• 제목/요약/키워드: Cu(II) EPR

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Formation of Au Particles in Cu2-xICu2IIO3-δ (x ≈ 0.20; δ ≈ 0.10) Oxide Matrix by Sol-Gel Growth

  • Das, Bidhu Bhusan;Palanisamy, Kuppan;venugopal, Potu;Sandeep, Eesam;Kumar, Karrothu Varun
    • Journal of the Korean Chemical Society
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    • v.61 no.1
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    • pp.29-33
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    • 2017
  • Formation of Au particles in nonstoichiometric $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxide from aniline + hydrochloric acid mixtures and chloroauric acid in the ratios 30 : 1; 60 : 1; 90 : 1 (S1-S3) by volume and 0.01 mol of copper acetate, $Cu(OCOCH_3)_2.H_2O$, in each case is performed by sol-gel growth. Powder x-ray diffraction (XRD) results show Au particles are dispersed in tetragonal nonstoichiometric dicopper (I) dicopper (II) oxides, $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$). Average crystallite sizes of Au particles determined using Scherrer equation are found to be in the approximate ranges ${\sim}85-140{\AA}$, ${\sim}85-150{\AA}$ and ${\sim}80-150{\AA}$ in S1-S3, respectively which indicate the formation of Au nano-micro size particles in $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Hysteresis behaviour at 300 K having low loop areas and magnetic susceptibility values ${\sim}5.835{\times}10^{-6}-9.889{\times}10^{-6}emu/gG$ in S1-S3 show weakly ferromagnetic nature of the samples. Broad and isotropic electron paramagnetic resonance (EPR) lineshapes of S1-S4 at 300, 77 and 8 K having $g_{iso}$-values ${\sim}2.053{\pm}0.008-2.304{\pm}0.008$ show rapid spin-lattice relaxation process in magnetic $Cu^{2+}$ ($3d^9$) sites as well as delocalized electrons in Au ($6s^1$) nano-micro size particles in the $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Broad and weak UV-Vis diffuse reflectance optical absorption band ~725 nm is assigned to $^2B_{1g}{\rightarrow}^2A_{1g}$ transitions, and the weak band ~470 nm is due to $^2B_{1g}{\rightarrow}^2E_g$ transitions from the ground state $^2B_{1g}$(${\mid}d_{x^2-y^2}$>) of $Cu^{2+}$ ($3d^9$) ions in octahedral coordination having tetragonal distortion.

Geochemistry of Heavy Metals and Rare Earth Elements in Core Sediments from the Korea Deep-Sea Environmental Study (KODES)-96 Area, Northeast Equatorial Pacific (한국심해환경연구(KODES) 지역 주상 퇴적물중 금속 및 희토류원소의 지구화학적 특성)

  • Jung, Hoi-Soo;Park, Sung-Hyun;Kim, Dong-Seon;Choi, Man-Sik;Lee, Kyeong-Young
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.2 no.2
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    • pp.125-137
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    • 1997
  • To study the vertical variation of heavy metal and Rare Earth Element (REE) contents in deep-sea sediments, eighteen cores were sampled from the Korea Deep-sea Environmental Study (KODES)-96 area in the C-C zone (Clarion-Clipperton fracture zone), northeast equatorial Pacific. Sediment columns can be divided into three units based on sediment colors and geochemical characters; uppermost Unit I with brown color, middle Unit II with pale brown color and smaller Ni/Cu ratio than the ratio in Unit I, and lowermost Unit III with dark (brown) colors and higher contents of Mn, Ni, Cu, and REEs than those in Unit I and II. Unit II can be divided more into two layers of upper Unit IIa and lower Unit IIb. Unit IIb is characterized by high contents of Cu, 3+REEs (REEs except Ce), smectite, and severely deteriorated fossil tests. Unit III can also be divided into two units; upper Unit IIIa with dark brown color, and lower Unit IIIb with black color and enriched Mn and Fe. The KODES area was located near from the East Pacific Rise (EPR) When Unit III Sediments were deposited, considering the hiatus between Unit II and III (Quaternary-Tertiary boundary) and the spreading rate (10 cm/yr) and direction (north southern west) of the Pacific plate from the EPR. High contents of Mn and Fe in Unit IIIb may be related with hydrothermal influence from the EPR. Meanwhile, Unit IIb (about 2~3 Ma) and Unit III (11~30 Ma) layers were probably formed near (or under) the equatorial high productivity zone, and accordingly received a lot of organic materials. As a result, Cu and 3+REEs, closely associated with organic materials, are enriched in smectite and/or Ca-P composites (fish bone debrise, biogenic apatite) after decomposition and reprecipitation on the sea floor. Higher contents of Cu and 3+REEs in Unit IIb and III are suggested to be the result of abundant supply of organic substances in the equatorial high productivity zone.

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Synthesis and Physicochemical Properties of Schiff Base Macrocyclic Ligands and Their Transition Metal Chelates

  • Rafat, Fouzia;Siddiqi, K.S.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.912-918
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    • 2011
  • Tetraaza Schiff base macrocyclic ligands, $L^1$,$L^2$ and their transition metal chelates have been synthesized and characterized by elemental analyses, IR, electronic, EPR and $^1H$ NMR spectra, TGA and magnetic measurements. The molar conductance of one milli-molar solution of the complexes measured in DMF indicates that the divalent metal complexes are nonelectrolyte while those of trivalent metal ion, are 1:1 electrolytic in the same solvent. The reduction of Racah parameter from the free ion value confirms the presence of considerable covalence of metal ligand sigma bond in the Co(II) and Mn(II) complexes. The EPR spectra of Cu(II) complexes at room temperature shows axial symmetry indicating a $d_x{^2}_{-y}{^2}$ ground state with significant covalent character. The thermal analysis suggests that the complexes do not contain water molecules because only the metal is left as residue.

Cu(II) Adsorption by Quartz: An EPR Study (석영에 의한 구리(II) 흡착: 전자상자성공명 연구)

  • 현성필;조영환;한필수;김수진
    • Proceedings of the Mineralogical Society of Korea Conference
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    • 2001.06a
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    • pp.44-44
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    • 2001
  • 구리(II)의 전자상자성공명 흉수선의 모양과 선 폭에 대한 해석을 통해 석영-물 계면에서의 구리(II) 및 흡착수와 석영 표면과의 상호 작용에 대해 연구하였다. 두 가지 흡수선이 중첩하여 흡수선을 구성하며 따라서 석영 표면에 적어도 두 종류의 구리(II)가 존재함을 알 수 있었다. 하나는 g=2.18에 중심을 둔 초미세 갈라짐이 분해되지 않는 등방성 단일 흡수선을 보여 주는 구리(II) 이온이다. 이는 수용액 중에서와 유사한 빠른 자유 회전 운동이 가능한 상태로 표면에 매우 약하게 결합된 구리 이온(Cu($H_2O$)$_{6}$$^{2+}$)인 것으로 해석된다. 다른 하나는 축 대칭 흡수선 $g_{∥}$=2.40, $g_{⊥}$=2.08)을 가지는 구리(II)로서 이는 표면에 강하게 결합된 것으로 해석된다. 본 결과는 흡착 현상에 대한 열역학적 접근법인 표면 착물화 모델들이 제시하는 광물 표면에서의 금속 이온 흡착 모델이 거시적 관점에서 흡착 현상을 잘 모사할지라도 분자 수준의 미시적 관점에서 흡착 메커니즘을 규명하기 위해서는 독립적인 분광학적 정보가 제시되어야함을 보여 준다.다.

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NMR Studies of Metal-binding Luteinizing Hormone Releasing Hormone

  • Won, Ho-Shik
    • Bulletin of the Korean Chemical Society
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    • v.32 no.11
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    • pp.4021-4026
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    • 2011
  • Functions of the luteinizing hormone releasing hormone (LHRH) and its induced release by divalent metal ions have received great attention because this neurotransmitter subsequently regulates the secretion of luteinizing hormone (LH). Metal-LHRH complexes were synthesized by addition of various Cu(II),Ni(II),Zn(II) ions into LHRH in order to understand how the induced release of LHRH is possible. The degree of complexation was monitored by $^1H$, $^{13}C$-NMR chemical shifts, and final products were identified by Mass spectrometry. Solutionstate structure determination of Zn(II)-LHRH out of metal-complexes was accomplished by using NMR and NMR-based distance geometry (DG). Interproton distance information from nuclear Overhauser effect spectroscopy was utilized for structure determination. Structure obtained in this study has a cyclic conformation exhibiting a specific ${\alpha}$-helical turn with residue numbers His[2]-Leu[7] out of 10 amino acids. Comparison of chemical shifts and EPR studies of Ni(II),Cu(II)-LHRH complexes exhibit that these metal complexes have 4-coordination geometry.

Structural and Magnetic Properties of Monomeric and Dimeric Copper(II) Complexes with Phenyl-N-[(pyridine-2-yl)methylene]methaneamide

  • Lee, Hong-Woo;Sengottuvelan, Nallathambi;Seo, Hoe-Joo;Choi, Jae-Soo;Kang, Sung-Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.29 no.9
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    • pp.1711-1716
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    • 2008
  • The reaction of copper(II) chloride with phenyl-N-[(pyridine-2-yl)methylene]methaneamide (ppmma) leads to a new $\mu$ -chloro bridged dimeric [Cu(ppmma)$Cl_2$]$_2$ complex, whereas a reaction of copper(II) bromide with ppmma affords a monomeric Cu(ppmma)$Br_2$ complex. Both complexes have been characterized by X-ray crystallography and electronic absorption spectroscopy. The crystal structural analysis of [Cu(ppmma)$Cl_2$]$_2$ shows that the two Cu(II) atoms are bridged by two chloride ligands, forming a dimeric copper(II) complex and the copper ion has a distorted square-pyramidal geometry ($\tau$ = 0.2). The dimer units are held through a strong intermolecular $\pi-\pi$ interactions between the nearest benzyl rings. On the other hand, Cu(ppmma)Br2 displayed a distorted square planar geometry with two types of strong intermolecular π-π interaction. EPR spectrum of [Cu(ppmma)$Cl_2$]$_2$ in frozen glas s at 77 K revealed an equilibrium between the mononuclear and binuclear species. The magnetic susceptibilities data of [Cu(ppmma)$Cl_2$]$_2$ and Cu(ppmma)$Br_2$ follow the Curie-Weiss law. No significant intermolecular magnetic interactions were examined in both complexes, and magnetic exchange interactions are discussed on the basis of the structural features.

Synthesis and Characterization of Paramagnetic Copper(Ⅱ) Complexes (상자성 구리(Ⅱ) 화합물의 합성과 그 특성 연구)

  • Oh, Yeong-Hee
    • Journal of the Korean Chemical Society
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    • v.44 no.6
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    • pp.507-512
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    • 2000
  • A new copper(II) complex, Cu(dpb)(NO$_3$)$_2$(H$_2$O) (dpb=2,2'-dipyridylbenzylamine) (1) was synthesized from the reaction of Cu(NO$_3$)$_2$·3H$_2$O and dpb in ethanol solution followed by recrystallization in acetonitrile. The structure of 1 was determined by X-ray diffraction methods. The single crystal structure was characterized as follows: space group P2$_1$/c, Z=4, a=12.501(9)$\AA$, b=9.231(10)$\AA$, c=17.119(6)$\AA$, $\alpha$=90$^{\circ}$, $\beta$=107.33(4)$^{\circ}$, $\gamma$=90$^{\circ}$, V=1885.8(2)$\AA^3$, R$_1$=0.0647, $_{w}R$_2$$=0.1866 for 3258 reflections. Compound was a typical paramagnetic copper(II) complex coordinated by 2,2'-dipyridylamine derivative ligand, which was confirmed by EPR, NMR, UV/VIS, and IR spectroscopy.

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Recovery of Pd(II), Pt(IV), and Rh(III) Using Polyelectrolytes

  • Lee, You-Sean;Lee, Hoosung;Chung, Koo-Soon
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.561-568
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    • 1995
  • Two methods, precipitation and ultrafiltration, were applied in order to recover platinum group metals(PGM) by complexing them with water-soluble polyelectrolytes, e.g., polyethyleneimine [PEl], poly(2-vinylpyridine) [2-PVP], poly (4-vinylpyridine) [4-PVP], and poly (styrene sulfonic acid) [PSSA]. In the precipitation method, the PGM-polyelectrolyte complex that was formed by mixing first with polybase, e.g.,4-PVP at pH 1 was precipitated by further mixing with polyacid, e.g., PSSA. However, the recovery of PGM obtained by this method was not quantitative(less than 70%). The "sandwiching" binding between the metal anions and two polyelectrolytes was examined by X-ray photoelectron spectroscopy(XPS). The XPS studies indicated that the PGM atom was bound with the acdic and basic polyelectrolyte via its oxygen and nitrogen atom, respectively. The recovery of PGM using polyelectrolyte was further studied by ultrafiltration methods as follows : The PGM ions, eomplexed at pH 1 with polyelectrolyte, allowed the applicntion of membrane filtration by virtue of the great differences in molecular weights between PGM and other low molecular weight species. By applying this method, Pd and Pt (ca. $10^{-4}M$) were selectively separated almost quantitatively from coexisting metal ions, e.g., $Cu^{2+}$ and $Ni^{2+}$. The EPR spectra and viscosity measurements indicated that these polyelectrlytes were not bound to $Cu^{2+}$ and $Ni^{2+}$ ions at this pH, which provided the basis for selective separation of PGM(Pd, Pt and Rh) from these coexisting ions.

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