Hypoxia targeting copper complexes

International Nuclear Information System (INIS)

Dearling, J.L.

1998-11-01

The importance and incidence of tumour hypoxia, its measurement and current treatments available, including pharmacological and radiopharmacological methods of targeting hypoxia, are discussed. A variety of in vitro and in vivo methods for imposing hypoxia have been developed and are reviewed. Copper, its chemistry, biochemistry and radiochemistry, the potential for use of copper radionuclides and its use to date in this field is considered with particular reference to the thiosemicarbazones. Their biological activity, metal chelation, in vitro and in vivo studies of their radiocopper complexes and the potential for their use as hypoxia targeting radiopharmaceuticals is described. The reduction of the copper(II) complex to copper(l), its pivotal importance in their biological behaviour, and the potential for manipulation of this to effect hypoxia selectivity are described. An in vitro method for assessing the hypoxia selectivity of radiopharmaceuticals is reported. The rapid deoxygenation and high viability of a mammalian cell culture in this system is discussed and factors which may affect the cellular uptake of a radiopharmaceutical are described. The design, synthesis and complexation with copper and radiocopper of a range of bis(thiosemicarbazones) is reported. Synthesis of these compounds is simple giving high yields of pure products. The characteristics of the radiocopper complexes ( 64 Cu) including lipophilicity and redox activity are reported (reduction potentials in the range -0.314 - -0.590 V). High cellular uptakes of the radiocopper complexes of the ligands, in hypoxic and normoxic EMT6 and CHO320 cells, were observed. Extremes of selectivity are shown ranging from the hypoxia selective 64 Cu(II)ATSM to normoxic cell selective 64 Cu(II)GTS. The selectivities observed are compared with the physico chemical characteristics of the complexes. A good correlation exists between selectivity of the complex and its Cu(II)/Cu(I) reduction potential, with hypoxia

21 CFR 73.1125 - Potassium sodium copper chloropyhllin (chlorophyllin-copper complex).

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Potassium sodium copper chloropyhllin (chlorophyllin-copper complex). 73.1125 Section 73.1125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT....1125 Potassium sodium copper chloropyhllin (chlorophyllin-copper complex). (a) Identity. (1) The color...

21 CFR 73.2125 - Potassium sodium copper chlorophyllin (chlorophyllin-copper complex).

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Potassium sodium copper chlorophyllin (chlorophyllin-copper complex). 73.2125 Section 73.2125 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT... § 73.2125 Potassium sodium copper chlorophyllin (chlorophyllin-copper complex). (a) Identity and...

From a Dy(III) single molecule magnet (SMM) to a ferromagnetic [Mn(II)Dy(III)Mn(II)] trinuclear complex.

Science.gov (United States)

Bhunia, Asamanjoy; Gamer, Michael T; Ungur, Liviu; Chibotaru, Liviu F; Powell, Annie K; Lan, Yanhua; Roesky, Peter W; Menges, Fabian; Riehn, Christoph; Niedner-Schatteburg, Gereon

2012-09-17

The Schiff base compound 2,2'-{[(2-aminoethyl)imino]bis[2,1-ethanediyl-nitriloethylidyne]}bis-2-hydroxy-benzoic acid (H(4)L) as a proligand was prepared in situ. This proligand has three potential coordination pockets which make it possible to accommodate from one to three metal ions allowing for the possible formation of mono-, di-, and trinuclear complexes. Reaction of in situ prepared H(4)L with Dy(NO(3))(3)·5H(2)O resulted in the formation of a mononuclear complex [Dy(H(3)L)(2)](NO(3))·(EtOH)·8(H(2)O) (1), which shows SMM behavior. In contrast, reaction of in situ prepared H(4)L with Mn(ClO(4))(2)·6H(2)O and Dy(NO(3))(3)·5H(2)O in the presence of a base resulted in a trinuclear mixed 3d-4f complex (NHEt(3))(2)[Dy{Mn(L)}(2)](ClO(4))·2(H(2)O) (2). At low temperatures, compound 2 is a weak ferromagnet. Thus, the SMM behavior of compound 1 can be switched off by incorporating two Mn(II) ions in close proximity either side of the Dy(III). This quenching behavior is ascribed to the presence of the weak ferromagnetic interactions between the Mn(II) and Dy(III) ions, which at T > 2 K act as a fluctuating field causing the reversal of magnetization on the dysprosium ion. Mass spectrometric ion signals related to compounds 1 and 2 were both detected in positive and negative ion modes via electrospray ionization mass spectrometry. Hydrogen/deuterium exchange (HDX) reactions with ND(3) were performed in a FT-ICR Penning-trap mass spectrometer.

Long-Range Intramolecular Electronic Communication in a Trinuclear Ruthenium Tropolonate Complex.

Science.gov (United States)

Yoshida, Jun; Kuwahara, Kyohei; Suzuki, Kota; Yuge, Hidetaka

2017-02-20

Dinuclear and trinuclear ruthenium complexes, [Ru(trop) 2 (C 2 trop)Ru(dppe)Cp] [2b; trop = tropolonato, C 2 trop = ethynyltropolonato, dppe = 1,2-bis(diphenylphosphino)ethane] and [Ru(trop){(C 2 trop)Ru(dppe)Cp} 2 ] (3), were synthesized, and their electronic and electrochemical properties were investigated in comparison with our previously reported complex [Ru(acac) 2 (C 2 trop)Ru(dppe)Cp] (2a). The electron-donating Ru II (dppe)Cp unit and electron-accepting Ru III O 6 unit are connected by C 2 trop in these complexes. 2a incorporates acetylacetonate as an ancillary ligand, while 2b and 3 incorporate tropolonate as an ancillary ligand. Every complex, 2a, 2b, and 3, exhibits similar UV-vis-near-IR (NIR) absorption spectra, demonstrating the lack of explicit intramolecular electronic communication between the units at least in the neutral state. The weak NIR absorption in 2a further diminished upon electrochemical oxidation, indicating almost no electronic communication between the units. In contrast, 2b and 3 exhibit broad NIR absorptions upon oxidation. Additionally, 3 exhibits four stepwise redox couples in the electrochemical study, which are formally attributed to [Ru II (trop) 3 ] - /[Ru III (trop) 3 ], two [Ru II (dppe)Cp]/[Ru III (dppe)Cp] + , and [Ru III (trop) 3 ]/[Ru IV (trop) 3 ] + couples. Clear separation of the redox couples attributed to the two terminal [Ru(dppe)Cp] units demonstrates the thermodynamic stability of the intermediate oxidation states with respect to disproportionation. Further electrochemical studies using an electrolyte including perfluorinated weakly coordinating anions and density functional theory/time-dependent density functional theory calculations confirmed the effect of ancillary ligands, acetylacetonate and tropolonate. In the case of 2a, electronic delocalization over the whole complex, especially over the [Ru(acac) 2 (trop)] unit, appears to be small. In contrast, the electronic communication between [Ru(dppe)Cp] and [Ru

Design and synthesis of a novel trinuclear palladium(II) complex containing an oxime chelate ligand: determining the interaction mechanism with the DNA groove and BSA site I by spectroscopic and molecular dynamics simulation approaches

Czech Academy of Sciences Publication Activity Database

Karami, K.; Lighvan, Z.M.; Barzani, S.A.; Faal, A.Y.; Poshteh-Shirani, M.; Khayamian, T.; Eigner, Václav; Dušek, Michal

2015-01-01

Roč. 39, č. 11 (2015), s. 8708-8719 ISSN 1144-0546 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : single-crystal structure analysis * paladium complex * trinuclear complex Subject RIV: CC - Organic Chemistry Impact factor: 3.277, year: 2015

A new trinuclear Zn(II) complex {[Zn(μ-ONN)(μ.sub.2./sub.-O)(μ-OO)].sub.2./sub.Zn}: Synthesis, characterization, thermal decomposition and antibacterial activity

Czech Academy of Sciences Publication Activity Database

Far, B.S.; Grivani, G.; Khalaji, A.D.; Khorshidi, M.; Eigner, Václav; Dušek, Michal

2017-01-01

Roč. 28, č. 6 (2017), s. 3217-3227 ISSN 1040-7278 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : trinuclear complex * Schiff base * single-crystal structure analysis * ZnO nano particle * antibacterial activity Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.471, year: 2016

Electrochemical behaviour of alkaline copper complexes

Indian Academy of Sciences (India)

Abstract. A search for non-cyanide plating baths for copper resulted in the development of alkaline copper complex baths containing trisodium citrate [TSC] and triethanolamine [TEA]. Voltammetric studies were carried out on platinum to understand the electrochemical behaviour of these complexes. In TSC solutions, the.

Evidence for organic complexed copper in sea water

Energy Technology Data Exchange (ETDEWEB)

Slowey, J F; Jeffrey, L M; Hood, D W

1967-04-22

A few attempts have been made to characterize the chemical components contributing to the copper content of seawater. About 0.3 mu/liter of particulate copper in 2 stations in the English Channel and 15 mu/liter of ultrafilterable (10 mu) but non-dialyzable copper in a sample from Texas Bay has been reported. Also the evidence has been shown for copper in the organic form in waters of the Florida Current. The occasional presence of non- dialyzable copper for many samples from the Gulf of Mexico suggests that strongly complexed copper-organic compounds are present in seawater. This communication presents evidence for such complexes that are extractable into a nonpolar solvent in the absence of any added chelating agent. Preliminary results have shown that the copper- organic complex isolated by chloroform extraction occurs in the eighth fraction of the Hirsch and Ahrens lipid separation method using silica gel chromatography. This would indicate that copper complex is associated with the phospholipid, amino lipid, or porphyrin fraction of the lipids.

Thiolato-bridged RuIIAgIRuII trinuclear complex composed of bis(bipyridine)ruthenium(II) units with chelating 2-aminoethanethiolate: conversion to a disulfide-bridged RuIIRuII dinuclear complex.

Science.gov (United States)

Tamura, Motoshi; Matsuura, Noriyuki; Kawamoto, Tatsuya; Konno, Takumi

2007-08-20

The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2'-bipyridine) with Haet (2-aminoethanethiol) in ethanol/water in the presence of Ag+ gave a thiolato-bridged RuIIAgIRuII trinuclear complex, [Ag{Ru(aet)(bpy)2}2]3+, in which two [RuII(aet)(bpy)2]+ units are linked by an AgI atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged RuIIRuII dinuclear complex, [Ru2(cysta)(bpy)4]4+ (cysta = cystamine), was produced as a result of the removal of an AgI atom and the autoxidation of thiolato groups. It was found that the dinuclear structure in [Ru2(cysta)(bpy)4]4+ is reverted back to [Ag{Ru(aet)(bpy)2}2]3+ by treatment with Ag+ assisted by Zn reduction.

Photocleavage of DNA by copper (II) complexes

Indian Academy of Sciences (India)

The chemistry of ternary and binary copper(II) complexes showing efficient visible lightinduced DNA cleavage activity is summarized in this article. The role of the metal in photo-induced DNA cleavage reactions is explored by designing complex molecules having a variety of ligands. Ternary copper(II) complexes with amino ...

Photocleavage of DNA by copper(II) complexes

Indian Academy of Sciences (India)

The chemistry of ternary and binary copper(II) complexes showing efficient visible lightinduced DNA cleavage activity is summarized in this article. The role of the metal in photo-induced DNA cleavage reactions is explored by designing complex molecules having a variety of ligands. Ternary copper(II) complexes with amino ...

Mössbauer spectroscopic and powder X-ray diffraction studies on incorporation of gaseous organic molecules into intermolecular nano-voids of mixed-valence trinuclear iron pentafluorobenzoate complex

International Nuclear Information System (INIS)

Sakai, Yoichi; Onaka, Satoru; Ogiso, Ryo; Takayama, Tsutomu; Takahashi, Masashi; Nakamoto, Tadahiro

2013-01-01

Incorporation of gaseous organic molecules into polycrystalline mixed-valence trinuclear iron (Fe 3+ ,Fe 3+ ,Fe 2+ ) pentafluorobenzoate complex Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 with intermolecular nano-voids was studied by 57 Fe-Mössbauer spectroscopic and powder XRD measurements. Organic-molecule incorporation was mainly chased by using iron-valence fluctuation observed in a Mössbauer spectrum, and also researched supportively by a powder XRD technique. (author)

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

Science.gov (United States)

Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

2008-09-01

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate ( I), bromo-(2-formylpyridinethiosemicarbazono)copper ( II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate ( III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I III at a concentration of 10-5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

International Nuclear Information System (INIS)

Chumakov, Yu. M.; Tsapkov, V. I.; Jeanneau, E.; Bairac, N. N.; Bocelli, G.; Poirier, D.; Roy, J.; Gulea, A. P.

2008-01-01

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10 -5 mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Crystal structures of copper(II) chloride, copper(II) bromide, and copper(II) nitrate complexes with pyridine-2-carbaldehyde thiosemicarbazone

Energy Technology Data Exchange (ETDEWEB)

Chumakov, Yu. M., E-mail: chumakov.xray@phys.asm.md [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I. [State University of Moldova (Moldova, Republic of); Jeanneau, E. [Universite Claude Bernard, Laboratoire des Multimateriaux et Interfaces (France); Bairac, N. N. [State University of Moldova (Moldova, Republic of); Bocelli, G. [National Research Council (IMEM-CNR), Institute of Materials for Electronics and Magnetism (Italy); Poirier, D.; Roy, J. [Centre Hospitalier Universitaire de Quebec (CHUQ) (Canada); Gulea, A. P. [State University of Moldova (Moldova, Republic of)

2008-09-15

The crystal structures of chloro-(2-formylpyridinethiosemicarbazono)copper dimethyl sulfoxide solvate (I), bromo-(2-formylpyridinethiosemicarbazono)copper (II), and (2-formylpyridinethiosemicarbazono)copper(II) nitrate dimethyl sulfoxide solvate (III) are determined using X-ray diffraction. In the crystals, complexes I and II form centrosymmetric dimers in which the thiosemicarbazone sulfur atom serves as a bridge and occupies the fifth coordination site of the copper atom of the neighboring complex related to the initial complex through the center of symmetry. In both cases, the coordination polyhedron of the complexing ion is a distorted tetragonal bipyramid. Complex III in the crystal structure forms polymer chains in which the copper atom of one complex forms the coordination bond with the thicarbamide nitrogen atom of the neighboring complex. In this structure, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid. It is established that complexes I-III at a concentration of 10{sup -5} mol/l selectively inhibit the growth of 60 to 90 percent of the cancer tumor cells of the human myeloid leukemia (HL-60).

Copper complexes as 'radiation recovery' agents

International Nuclear Information System (INIS)

Sorenson, J.R.J.

1989-01-01

Copper and its compounds have been used for their remedial effects since the beginning of recorded history. As early as 3000 BC the Egyptians used copper as an antiseptic for healing wounds and to sterilise drinking water; and later, ca 1550 BC, the Ebers Papyrus reports the use of copper acetate, copper sulphate and pulverised metallic copper for the treatment of eye infections. These historical uses of copper and its compounds are particularly interesting in the light of modern evidence concerning the use of certain copper complexes for the treatment of radiation sickness and more recently as an adjunct to radiotherapy for cancer patients. (author)

A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

Science.gov (United States)

Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

2009-11-01

Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

Moessbauer spectroscopic study on valence-detrapping and trapping of mixed-valence trinuclear iron (III, III, II) fluorine-substitute benzoate complexes

International Nuclear Information System (INIS)

Sakai, Y.; Onaka, S.; Ogiso, R.; Takayama, T.; Takahashi, M.; Nakamoto, T.

2012-01-01

Four mixed-valence trinuclear iron(III, III, II) fluorine-substituted benzoate complexes were synthesized; Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 ·CH 2 Cl 2 (1), Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 (2), Fe 3 O(2H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (3), and Fe 3 O(4H-C 6 F 4 COO) 6 (C 5 H 5 N) 3 (4). By means of 57 Fe-Moessbauer spectroscopy, valence-detrapping and trapping phenomena have been investigated for the four mixed-valence complexes. The valence state of three iron ions is trapped at lower temperatures while it is fully detrapped at higher temperatures for 1. Valence detrapping is not observed for 2, 3, and 4 even at room temperature, although Moessbauer spectra for 3 and 4 show a complicated temperature dependence. (author)

Crystal structures of E. coli laccase CueO at different copper concentrations

International Nuclear Information System (INIS)

Li Xu; Wei Zhiyi; Zhang Min; Peng Xiaohui; Yu Guangzhe; Teng Maikun; Gong Weimin

2007-01-01

CueO protein is a hypothetical bacterial laccase and a good laccase candidate for large scale industrial application. Four CueO crystal structures were determined at different copper concentrations. Low copper occupancy in apo-CueO and slow copper reconstitution process in CueO with exogenous copper were demonstrated. These observations well explain the copper dependence of CueO oxidase activity. Structural comparison between CueO and other three fungal laccase proteins indicates that Glu106 in CueO constitutes the primary counter-work for reconstitution of the trinuclear copper site. Mutation of Glu106 to a Phe enhanced CueO oxidation activity and supported this hypothesis. In addition, an extra α-helix from Leu351 to Gly378 covers substrate biding pocket of CueO and might compromises the electron transfer from substrate to type I copper

Roles of Bridging Ligand Topology and Conformation in Controlling Exchange Interactions between Paramagnetic Molybdenum Fragments in Dinuclear and Trinuclear Complexes.

Science.gov (United States)

Ung VÂ, V&acaron;n Ân; Cargill Thompson, Alexander M. W.; Bardwell, David A.; Gatteschi, Dante; Jeffery, John C.; McCleverty, Jon A.; Totti, Federico; Ward, Michael D.

1997-07-30

The magnetic properties of two series of dinuclear complexes, and one trinuclear complex, have been examined as a function of the bridging pathway between the metal centers. The first series of dinuclear complexes is [{Mo(V)(O)(Tp)Cl}(2)(&mgr;-OO)], where "OO" is [1,4-O(C(6)H(4))(n)O](2)(-) (n = 1, 1; n = 2, 3), [4,4'-O(C(6)H(3)-2-Me)(2)O](2)(-) (4), or [1,3-OC(6)H(4)O](2)(-) (2) [Tp = tris(3,5-dimethylpyrazolyl)hydroborate]. The second series of dinuclear complexes is [{Mo(I)(NO)(Tp)Cl}(2)(&mgr;-NN)], where "NN" is 4,4'-bipyridyl (5), 3,3'-dimethyl-4,4'-bipyridine (6), 3,8-phenanthroline (7), or 2,7-diazapyrene (8). The trinuclear complex is [{Mo(V)(O)(Tp)Cl}(3)(1,3,5-C(6)H(3)O(3))] (9), whose crystal structure was determined [9.5CH(2)Cl(2): C(56)H(81)B(3)Cl(13)Mo(3)N(18)O(6); monoclinic, P2(1)/n; a = 13.443, b = 41.46(2), c = 14.314(6) Å; beta = 93.21(3) degrees; V = 7995(5) Å(3); Z = 4; R(1) = 0.106]. In these complexes, the sign and magnitude of the exchange coupling constant J is clearly related to both the topology and the conformation of the bridging ligand [where J is derived from H = -JS(1)().S(2)() for 1-8 and H = -J(S(1)().S(2)() + S(2)().S(3)() + S(1)().S(3)()) for 9]. The values are as follows: 1, -80 cm(-)(1); 2, +9.8 cm(-)(1); 3, -13.2 cm(-)(1); 4, -2.8 cm(-)(1); 5, -33 cm(-)(1); 6, -3.5 cm(-)(1); 7, -35.6 cm(-)(1); 8, -35.0 cm(-)(1); 9, +14.4 cm(-)(1). In particular the following holds: (1) J is negative (antiferromagnetic exchange) across the para-substituted bridges ligands of 1 and 3-8 but positive (ferromagnetic exchange) across the meta-substituted bridging ligands of 2 and 9. (2) J decreases in magnitude dramatically as the bridging ligand conformation changes from planar to twisted (compare 3 and 4, or 6 and 8). These observations are consistent with a spin-polarization mechanism for the exchange interaction, propagated across the pi-system of the bridging ligand by via overlap of bridging ligand p(pi) orbitals with the d(pi) magnetic

Effects of 3d-4f magnetic exchange interactions on the dynamics of the magnetization of Dy(III)-M(II)-Dy(III) trinuclear clusters.

Science.gov (United States)

Pointillart, Fabrice; Bernot, Kevin; Sessoli, Roberta; Gatteschi, Dante

2007-01-01

[{Dy(hfac)(3)}(2){Fe(bpca)(2)}] x CHCl(3) ([Dy(2)Fe]) and [{Dy(hfac)(3)}(2){Ni(bpca)(2)}]CHCl(3) ([Dy(2)Ni]) (in which hfac(-)=1,1,1,5,5,5-hexafluoroacetylacetonate and bpca(-)=bis(2-pyridylcarbonyl)amine anion) were synthesized and characterized. Single-crystal X-ray diffraction shows that [Dy(2)Fe] and [Dy(2)Ni] are linear trinuclear complexes. Static magnetic susceptibility measurements reveal a weak ferromagnetic exchange interaction between Ni(II) and Dy(III) ions in [Dy(2)Ni], whereas the use of the diamagnetic Fe(II) ion leads to the absence of magnetic exchange interaction in [Dy(2)Fe]. Dynamic susceptibility measurements show a thermally activated behavior with the energy barrier of 9.7 and 4.9 K for the [Dy(2)Fe] and [Dy(2)Ni] complexes, respectively. A surprising negative effect of the ferromagnetic exchange interaction has been found and has been attributed to the structural conformation of these trinuclear complexes.

CONSIDERATIONS ON THE INFLUENCE OF COMPLEXATION IN THE COPPER UPTAKE AND TRANSLOCATION

Directory of Open Access Journals (Sweden)

SEMAGHIUL BIRGHILA

2014-07-01

Full Text Available The actual knowledge about food and the environment underlines the fact that agricultural and environmental sciences must solve various problems regarding copper uptake from soil to plants and its bioaccumulation, being important issues for copper concentration in crops and also for phytoremediation of polluted soils. We studied the relation between the form in which copper is applied to soil and the consequential copper bioavailability, uptake and translocation, using as examples simple and complex copper compounds. The copper concentration in basil plants harvested from soils treated with copper compounds and the calculated values of transfer coefficient, translocation factor, bioaccumulation factor, and uptake coefficient demonstrated that the ionic copper (from simple salts is not necessarily easier to uptake than complex ions, but is easier translocated in plants, while the copper given as complex ions is most likely to be retained by roots. The results indicated that the involvement of copper complexes in agricultural treatments is a solution for soils phytoremediation, concerning the phytostabilization technology.

Leaching behavior and chemical stability of copper butyl xanthate complex under acidic conditions.

Science.gov (United States)

Chang, Yi Kuo; Chang, Juu En; Chiang, Li Choung

2003-08-01

Although xanthate addition can be used for treating copper-containing wastewater, a better understanding of the leaching toxicity and the stability characteristics of the copper xanthate complexes formed is essential. This work was undertaken to evaluate the leaching behavior of copper xanthate complex precipitates by means of toxicity characteristics leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) using 1 N acetic acid solution as the leachant. Also, the chemical stability of the copper xanthate complex during extraction has been examined with the studying of variation of chemical structure using UV-vis, Fourier transform infrared and X-ray photoelectron spectroscopies (XPS). Both TCLP and SDLT results showed that a negligible amount of copper ion was leached out from the copper xanthate complex precipitate, indicating that the complex exhibited a high degree of copper leaching stability under acidic conditions. Nevertheless, chemical structure of the copper xanthate complex precipitate varied during the leaching tests. XPS data suggested that the copper xanthate complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acid extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the copper xanthate complex.

A serials of sandwich-like trinuclear and one-dimensional chain cyanide-bridged iron(III)-copper(II) complexes: Syntheses, crystal structures and magnetic properties

Science.gov (United States)

Shi, Jingwen; Lan, Wenlong; Ren, Yanjie; Liu, Qingyun; Liu, Hui; Dong, Yunhui; Zhang, Daopeng

2018-04-01

Four pyridinecarboxamide trans-dicyanideiron(III) building blocks and one macrocyclic copper(II) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in a serials of cyanide-bridged FeIII-CuII complexes with different structure types. The series of complexes can be formulated as: {[Cu(Cyclam)][Fe(bpb)(CN)2]2}·4H2O (1), {{[Cu(Cyclam)][Fe(bpb)(CN)2]}ClO4}n·nH2O (2), and {[Cu(Cyclam)][Fe(bpmb)(CN)2]2}·4H2O (3), {[Cu(Cyclam)][Fe(bpClb)(CN)2]2}·4H2O (4) and {{[Cu(Cyclam)][Fe(bpdmb)(CN)2]}ClO4}n·2nCH3OH (5) (bpb2- = 1,2-bis(pyridine-2-carboxamido)benzenate, bpmb2- = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate, bpClb2- = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate, bpdmb2- = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate, Cyclam = 1,4,8,11-tetraazacyclotetradecane). All the complexes have been characterized by elemental analysis, IR spectra and structural determination. Single X-ray diffraction analysis shows the similar neutral sandwich-like structures for complexes 1, 3 and 4, in which the two cyano precursors acting as monodentate ligand through one of their two cyanide groups were coordinated face to face to central Cu(II) ion. The complexes 2 and 5 can be structurally characterized as one-dimensional cationic single chain consisting of alternating units of [Cu(Cyclam)]2+ and [Fe(bpb/bpdmb)(CN)2]- with free ClO4- as balanced anion. Investigation over magnetic properties of the whole serials of complexes reveals the antiferromagnetic magnetic coupling between the neighboring cyanide-bridged Fe(III) and Cu(II) ions in complexes 3 and 4 and the ferromagnetic interaction in complexes 1, 2 and 5, respectively.

Copper complexes as chemical nucleases

Indian Academy of Sciences (India)

Unknown

anticancer drug famotidine has been shown as a better catalyst than CuCl2 for sulfite ... Effect of addition of bis-chelate copper(II) complexes (dpq, •; phen, ; ..... Reproduction, Development & Genetics for their help in the DNA cleavage studies ...

Ferro- to antiferromagnetic crossover angle in diphenoxido- and carboxylato-bridged trinuclear Ni(II)₂-Mn(II) complexes: experimental observations and theoretical rationalization.

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Seth, Piya; Figuerola, Albert; Jover, Jesús; Ruiz, Eliseo; Ghosh, Ashutosh

2014-09-02

Three new trinuclear heterometallic Ni(II)-Mn(II) complexes have been synthesized using a [NiL] metalloligand, where H2L = N,N'-bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)2Mn(OCnn)2(CH3OH)2]·CH3OH (1), [(NiL)2Mn(OPh)2(CH3OH)2][(NiL)2Mn(OPh)2]·H2O (2), and [(NiL)2Mn(OSal)2(CH3OH)2]·2[NiL] (3) (where OCnn = cinnamate, OPh = phenylacetate, OSal = salicylate) have been structurally characterized. In all three complexes, in addition to the double phenoxido bridge, the two terminal Ni(II) atoms are linked to the central Mn(II) by means of a syn-syn bridging carboxylate, giving rise to a linear structure. Complexes 1 and 2 with Ni-O-Mn angles of 97.24 and 96.43°, respectively, exhibit ferromagnetic interactions (J(Ni-Mn) = +1.38 and +0.50 cm(-1), respectively), whereas 3 is antiferromagnetic (J(Ni-Mn) = -0.24 cm(-1)), having an Ni-O-Mn angle of 98.51°. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni-O-Mn angle and J(Ni-Mn) values, which is in agreement with the experimental results.

Doubly end-on azido bridged mixed-valence cobalt trinuclear complex: Spectral study, VTM, inhibitory effect and antimycobacterial activity on human carcinoma and tuberculosis cells

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Datta, Amitabha; Das, Kuheli; Sen, Chandana; Karan, Nirmal Kumar; Huang, Jui-Hsien; Lin, Chia-Her; Garribba, Eugenio; Sinha, Chittaranjan; Askun, Tulin; Celikboyun, Pinar; Mane, Sandeep B.

2015-09-01

Doubly end-on azido-bridged mixed-valence trinuclear cobalt complex, [Co3(L)2(N3)6(CH3OH)2] (1) is afforded by employing a potential monoanionic tetradentate-N2O2 Schiff base precursor (2-[{[2-(dimethylamino)ethyl]imino}methyl]-6-methoxyphenol; HL). Single crystal X-ray structure reveals that in 1, the adjacent CoII and CoIII ions are linked by double end-on azido bridges and thus the full molecule is generated by the site symmetry of a crystallographic twofold rotation axis. Complex 1 is subjected on different spectral analysis such as IR, UV-vis, emission and EPR spectroscopy. On variable temperature magnetic study, we observe that during cooling, the χMT values decrease smoothly until 15 K and then reaches to the value 1.56 cm3 K mol-1 at 2 K. Complex 1 inhibits the cell growth on human lung carcinoma (A549 cells), human colorectal (COLO 205 and HT-29 cells), and human heptacellular (PLC5 cells) carcinoma cells. Complex 1 exhibits anti-mycobacterial activity and considerable efficacy on Mycobacterium tuberculosis H37Rv ATCC 27294 and H37Ra ATCC 25177 strains.

Synthesis, characterization and biological activities of semicarbazones and their copper complexes.

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Venkatachalam, Taracad K; Bernhardt, Paul V; Noble, Chris J; Fletcher, Nicholas; Pierens, Gregory K; Thurecht, Kris J; Reutens, David C

2016-09-01

Substituted semicarbazones/thiosemicarbazones and their copper complexes have been prepared and several single crystal structures examined. The copper complexes of these semicarbazone/thiosemicarbazones were prepared and several crystal structures examined. The single crystal X-ray structure of the pyridyl-substituted semicarbazone showed two types of copper complexes, a monomer and a dimer. We also found that the p-nitrophenyl semicarbazone formed a conventional 'magic lantern' acetate-bridged dimer. Electron Paramagnetic Resonance (EPR) of several of the copper complexes was consistent with the results of single crystal X-ray crystallography. The EPR spectra of the p-nitrophenyl semicarbazone copper complex in dimethylsulfoxide (DMSO) showed the presence of two species, confirming the structural information. Since thiosemicarbazones and semicarbazones have been reported to exhibit anticancer activity, we examined the anticancer activity of several of the derivatives reported in the present study and interestingly only the thiosemicarbazone showed activity while the semicarbazones were not active indicating that introduction of sulphur atom alters the biological profile of these thiosemicarbazones. Copyright © 2016 Elsevier Inc. All rights reserved.

Copper Recovery from Yulong Complex Copper Oxide Ore by Flotation and Magnetic Separation

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Han, Junwei; Xiao, Jun; Qin, Wenqing; Chen, Daixiong; Liu, Wei

2017-09-01

A combined process of flotation and high-gradient magnetic separation was proposed to utilize Yulong complex copper oxide ore. The effects of particle size, activators, Na2S dosage, LA (a mixture of ammonium sulfate and ethylenediamine) dosage, activating time, collectors, COC (a combination collector of modified hydroxyl oxime acid and xanthate) dosage, and magnetic intensity on the copper recovery were investigated. The results showed that 74.08% Cu was recovered by flotation, while the average grade of the copper concentrates was 21.68%. Another 17.34% Cu was further recovered from the flotation tailing by magnetic separation at 0.8 T. The cumulative recovery of copper reached 91.42%. The modifier LA played a positive role in facilitating the sulfidation of copper oxide with Na2S, and the combined collector COC was better than other collectors for the copper flotation. This technology has been successfully applied to industrial production, and the results are consistent with the laboratory data.

[Biohydrometallurgical technology of a complex copper concentrate process].

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Murav'ev, M I; Fomchenko, N V; Kondrat'eva, T F

2011-01-01

Leaching of sulfide-oxidized copper concentrate of the Udokan deposit ore with a copper content of 37.4% was studied. In the course of treatment in a sulfuric acid solution with pH 1.2, a copper leaching rate was 6.9 g/kg h for 22 h, which allowed extraction of 40.6% of copper. As a result of subsequent chemical leaching at 80 degrees C during 7 h with a solution of sulphate ferric iron obtained after bio-oxidation by an association of microorganisms, the rate of copper recovery was 52.7 g/kg h. The total copper recovery was 94.5% (over 29 h). Regeneration of the Fe3+ ions was carried out by an association of moderately thermophilic microorganisms, including bacteria of genus Sulfobacillus and archaea of genus Ferroplasma acidiphilum, at 1.0 g/l h at 40 degrees C in the presence of 3% solids obtained by chemical leaching of copper concentrate. A technological scheme of a complex copper concentrate process with the use of bacterial-chemical leaching is proposed.

Hydrothermal growth of cross-linked hyperbranched copper dendrites using copper oxalate complex

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Truong, Quang Duc; Kakihana, Masato

2012-06-01

A facile and surfactant-free approach has been developed for the synthesis of cross-linked hyperbranched copper dendrites using copper oxalate complex as a precursor and oxalic acid as a reducing and structure-directing agent. The synthesized particles are composed of highly branched nanostructures with unusual cross-linked hierarchical networks. The formation of copper dendrites can be explained in view of both diffusion control and aggregation-based growth model accompanied by the chelation-assisted assembly. Oxalic acid was found to play dual roles as reducing and structure-directing agent based on the investigation results. The understanding on the crystal growth and the roles of oxalic acid provides clear insight into the formation mechanism of hyperbranched metal dendrites.

Copper(II)-bis(thiosemicarbazonato) complexes as anti-chlamydial agents.

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Marsh, James W; Djoko, Karrera Y; McEwan, Alastair G; Huston, Wilhelmina M

2017-09-29

Lipophilic copper (Cu)-containing complexes have shown promising antibacterial activity against a range of bacterial pathogens. To examine the susceptibility of the intracellular human pathogen Chlamydia trachomatis to copper complexes containing bis(thiosemicarbazone) ligands [Cu(btsc)], we tested the in vitro effect of CuII-diacetyl- and CuII-glyoxal-bis[N(4)-methylthiosemicarbazonato] (Cu(atsm) and Cu(gtsm), respectively) on C. trachomatis. Cu(atsm) and to a greater extent, Cu(gtsm), prevented the formation of infectious chlamydial progeny. Impacts on host cell viability and respiration were also observed in addition to the Chlamydia impacts. This work suggests that copper-based complexes may represent a new lead approach for future development of new therapeutics against chlamydial infections, although host cell impacts need to be fully explored. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Magnetic properties of cyano-bridged Ln3+-M3+ complexes. Part I: trinuclear complexes (Ln3+ = La, Ce, Pr, Nd, Sm; M3+ = FeLS, Co) with bpy as blocking ligand.

Science.gov (United States)

Figuerola, Albert; Ribas, Joan; Llunell, Miquel; Casanova, David; Maestro, Miguel; Alvarez, Santiago; Diaz, Carmen

2005-10-03

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.

Copper Complexes of Nicotinic-Aromatic Carboxylic Acids as Superoxide Dismutase Mimetics

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Virapong Prachayasittikul

2008-12-01

Full Text Available Nicotinic acid (also known as vitamin B3 is a dietary element essential for physiological and antihyperlipidemic functions. This study reports the synthesis of novel mixed ligand complexes of copper with nicotinic and other select carboxylic acids (phthalic, salicylic and anthranilic acids. The tested copper complexes exhibited superoxide dismutase (SOD mimetic activity and antimicrobial activity against Bacillus subtilis ATCC 6633, with a minimum inhibition concentration of 256 μg/mL. Copper complex of nicotinic-phthalic acids (CuNA/Ph was the most potent with a SOD mimetic activity of IC50 34.42 μM. The SOD activities were observed to correlate well with the theoretical parameters as calculated using density functional theory (DFT at the B3LYP/LANL2DZ level of theory. Interestingly, the SOD activity of the copper complex CuNA/Ph was positively correlated with the electron affinity (EA value. The two quantum chemical parameters, highest occupied molecular orbital (HOMO and lowest unoccupied molecular orbital (LUMO, were shown to be appropriate for understanding the mechanism of the metal complexes as their calculated energies show good correlation with the SOD activity. Moreover, copper complex with the highest SOD activity were shown to possess the lowest HOMO energy. These findings demonstrate a great potential for the development of value-added metallovitamin-based therapeutics.

Copper-based nanoparticles prepared from copper (II acetate bipyridine complex

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Lastovina Tatiana A.

2016-01-01

Full Text Available We report the synthesis of CuO, Cu/Cu2O and Cu2O/CuO nanoparticles (NPs from the single copper (II acetate bipyridine complex by three different methods:microwave-assisted, solvothermal and borohydride. Presence of bipyridine ligand in the copper complex would impose no need in additional stabilization during synthesis. The phases of formed NPs were identified by X-ray diffraction. CuO NPs of ~11 nm were obtained via solvothermal synthesis from alkaline solution at 160°C. The Cu/Cu2O NPs of ~80 nm were produced via microwave-assisted polyol procedure at 185-200°C, where ethylene glycol can play a triple role as a solvent, a reducing agent and a surfactant. The Cu2O/CuO NPs of ~16 nm were synthesized by a borohydride method at room temperature. Interplanar spacing calculated from the selected-area electron diffraction data confirmed the formation of Cu, CuO and Cu2O phases in respective samples. All NPs are stable and can be used for various applications including biomedicine.

Coordination-organometallic hybrid materials based on the trinuclear M(II)-Ru(II) (M=Ni and Zn) complexes: Synthesis, structural characterization, luminescence and electrochemical properties

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Pawal, S. B.; Lolage, S. R.; Chavan, S. S.

2018-02-01

A new series of trinuclear complexes of the type Ni[R-C6H4Ndbnd CH(O)C6H3Ctbnd CRu(dppe)2Cl]2 (1a-c) and Zn[Rsbnd C6H4Ndbnd CH(O)C6H3Ctbnd CRu(dppe)2Cl]2 (2a-c) have been prepared from the reaction of trans-[RuCl(dppe)2Ctbnd Csbnd C6H3(OH)(CHO)] (1) with aniline, 4-nitroaniline and 4-methoxyaniline (R1-3) in presence of nickel acetate and zinc acetate in CH2Cl2/MeOH (1:1) mixture. The structural properties of the complexes have been characterized by elemental analyses and spectroscopic techniques viz. FTIR, UV-Visible, 1H NMR and 31P NMR spectral studies. The crystal structure and morphology of the hybrid complexes was investigated with the help of X-ray powder diffraction (XRPD), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). The thermal properties of 1a-c and 2a-c were studied by thermogravimetric (TG) analysis. The electrochemical behaviour of the complexes reveals that all complexes displayed a quasireversible redox behaviour corresponding to Ru(II)/Ru(III) and Ni(II)/Ni(III) couples for 1a-c and only Ru(II)/Ru(III) couple for 2a-c. All complexes are emissive in solution at room temperature revealing the influence of substituents and solvent polarity on emission properties of the complexes.

Mixed-ligand complexes of copper (II with ditiolfenols and heterocyclic diamines

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K. A. Kuliev

2017-01-01

Full Text Available By the methods spectrophotometric methods was investigated complex formation of copper with 2,6-ditiolphenol and its derivatives (2,6-ditiol-4-methylphenol, 2,6-ditiol-4-ethylphenol and 2,6-ditiol-4-tert-buthylphenol in the presence of heterocyclic diamines. As heterocyclic diamines phenantroline (Fen, batophenantroline and dipyridile were used. It was established, that mixedligand complex were formed in weak acidic medium (pHop=6,0-8,5. Maximum of light absorption observed at (=522–550 nm. Molar coefficient of light absorption was ( = (3.08–4.92?104. The stoichiometry of complexes had been discovered using shift the equilibrium and relative yield methods. During the extraction of copper(II complexes with ditiol-phenols with the presence of heterocyclic diamines there was discovered that there is no chlorophorm molecules in the composition of the extracted complexes. IR spectra shows that hydroxyl group is involved to the formation of a bond with the metal and that phenantroline is included in the composition of the copper complex. In the organic phase mixed-ligand complexes have the monomeric form and can’t polymerize; that fact can be proved by calculations. By dint of spectrophotometric, IR-spectroscopic, thermogravimetric experiments and some published data we were able to determine the structural formula of complexes. Also had been determined main spectrophotometric characteristics of copper(II mixed-ligand complexes: pH of the beginning of the deposition, optimal pH, detection limit and sensivity. For separation and finding copper, we studied the effect of interfering foreign ions: alkali, alkaline earth and rare earth elements, as well as acid anions selected masking reagents. On the base of the results was offered photometric method for determination of copper in steel different trade-marks and in food. This method characterized by good reproduction (relatively standard deviation no more 0.05 and low limit of discovery.

Reconnaissance and economic geology of Copper Mountain metamorphic complex, Owl Creek Mountains, Wyoming

International Nuclear Information System (INIS)

Hausel, W.D.

1983-01-01

The Copper Mountain metamorphic complex lies within a westerly trending belt of Precambrian exposures known as the Owl Creek Mountains uplift. The metamorphic complex at Copper Mountain is part of a larger complex known as the Owl Creek Mountains greenstone belt. Until more detailed mapping and petrographic studies can be completed, the Copper Mountain area is best referred to as a complex, even though it has some characteristics of a greestone belt. At least three episodes of Precambrian deformation have affected the supracrustals, and two have disturbed the granites. The final Precambrian deformation event was preceded by a weak thermal event expressed by retrogressive metamorphism and restricted metasomatic alteration. During this event, a second phase of pegmatization was accompanied by hydrothermal solutions. During the Laramide orogeny, Copper Mountain was again modified by deformation. Laramide deformation produced complex gravity faults and keystone grabens. Uranium deposits were formed following major Laramide deformation. The genesis of these deposits is attributable to either the leaching of granites or the leaching of overlying tuffaceous sediments during the Tertiary. Production of metals and industrial minerals has been limited, although some gold, copper, silver, tungsten, beryl, feldspar, and lithium ore have been shipped from Copper Mountain. A large amount of uranium was produced from the Copper Mountain district in the 1950s

Intrinsic gas-phase reactivity toward methanol of trinuclear tungsten W(3)S(4) complexes bearing W-X (X = Br, OH) groups.

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Vicent, Cristian; Feliz, Marta; Llusar, Rosa

2008-12-11

Electrospray ionization (ESI) tandem mass spectrometry is used to investigate the gas-phase dissociation of trinuclear sulfide W(3)S(4) complexes containing three diphosphane ligands and three terminal bromine atoms, namely, [W(3)S(4)(dmpe)(3)(Br)(3)](+) (1(+)) or hydroxo groups, [W(3)S(4)(dmpe)(3)(OH)(3)](+) (2(+)) (dmpe = 1,2-bis(dimethylphosphanyl)ethane). Sequential evaporation of two diphosphane ligands is the sole fragmentation channel for the 1(+) cation that yields product ions with one or two unsaturated W-Br functional groups, respectively. Conversely, evaporation of one diphosphane ligand followed by two water molecules is observed for cation 2(+). Complementary deuterium-labeling experiments in conjunction with computational studies provide deep insight into the thermodynamically favored product ion structures found along the fragmentation pathways. From these results, the formation of a series of cluster cations with WBr, WOH, and WO functional groups either on saturated or unsaturated metal sites is proposed. The effect of the properties of these cluster cations, among them chemical composition and coordinative saturation, on their reactivity toward methanol is discussed.

Antibacterial activity of nicotine and its copper complex

International Nuclear Information System (INIS)

Zaidi, M.I.; Gul, A.

2005-01-01

Nicotine and its metal complex; Cu(II)-nicotine was isolated from leaves of Nicotiana tabacum using metal ions following the method of Munir et al., 1994. Their antibacterial activity against ten different species of gram positive and gram negative bacteria were studied. For comparative study, pure sample of nicotine and metal salts used for complexation; Copper(II) chloride were also subjected to antibacterial tests with the same species of bacteria under similar conditions. Results indicated that nicotine had no effect on all the bacteria tested except Escherichia coli, Pseudomonas aeroginosa and Enterococcus faecalis, which showed 14 mm zone of inhibition at 200 mu g l00 mul/sup -1/ Copper(II) chloride was found to be effective against seven species and ineffective against three species of selected bacteria. On the other hand, Cu(II)-nicotine complex was ineffective against five species of bacteria at lower level while at higher level, only one species of bacteria showed resistance against this complex. The complex was compared with three standard antibiotics. Thus, this complex can be used against a variety of microorganisms at higher level. (author)

40 CFR 721.2577 - Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine...

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2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Copper complex of (substituted... Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine salt... substances identified generically as copper complex of (substituted sulfonaphthyl azo substituted phenyl...

Long-Lived Photoinduced Charge Separation in a Trinuclear Iron-μ ₃ -oxo-based Metal–Organic Framework

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Hanna, Lauren [Department; Kucheryavy, Pavel [Department; Liu, Cunming [X-ray; Zhang, Xiaoyi [X-ray; Lockard, Jenny V. [Department

2017-06-14

The presence of long-lived charge-separated excited states in metal-organic frameworks (MOFs) can enhance their photocatalytic activity by decreasing the probability that photogenerated electrons and holes recombine before accessing adsorbed reactants. Detecting these charge separated states via optical transient absorption, however, can be challenging when they lack definitive optical signatures. Here, we investigate the long-lived excited state of a MOF with such vague optical properties, MIL-100(Fe), comprised of Fe3-μ3-oxo clusters and trimesic acid linkers using Fe K-edge X-ray transient absorption (XTA) spectroscopy, to unambiguously determine its ligand-to-metal charge transfer character. Spectra measured at time delays up to 3.6 μs confirm the long lived nature of the charge separated excited state. Several trinuclear iron μ3- oxo carboxylate complexes, which model the trinuclear cores of the MOF structure, are measured for comparison using both steady state XAS and XTA to further support this assignment and corresponding decay time. The MOF is prepared as a colloidal nanoparticle suspension for these measurements so both its fabrication and particle size analysis are presented, as well.

XAFS Study of the Ferro- and Antiferromagnetic Binuclear Copper(II) Complexes of Azomethine Based Tridentate Ligands

International Nuclear Information System (INIS)

Vlasenko, Valery G.; Vasilchenko, Igor S.; Shestakova, Tatiana E.; Uraev, Ali I.; Burlov, Anatolii S.; Garnovskii, Alexander D.; Pirog, Irina V.

2007-01-01

Binuclear copper complexes are known to be models for metalloenzymes containing copper active sites, and some of them are of considerable interest due to their magnetic and charge transfer properties. The reactions of the complex formation of bibasic tridentate heterocyclic imines with copper acetate leads to two types of chelates with mono deprotonated ligands and with totally deprotonated ligands. Cu K-edge EXAFS has been applied to determine the local structure around the metal center in copper(II) azomethine complexes with five tridentate ligands: 1-(salycilideneimino)- or 1-(2-tosylaminobenzilideneimino)-2-amino(oxo, thio)benzimidazoles. It has been found that some of the chelates studied are bridged binuclear copper complexes, and others are mononuclear complexes. The copper-copper interatomic distances in the bridged binuclear copper complexes were found to be 2.85-3.01 A. Variable temperature magnetic susceptibility data indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former is dominating at low temperatures and the latter at high temperatures

Effects of Copper Exchange Levels on Complexation of Ammonia in ...

African Journals Online (AJOL)

NJD

Cation exchange, catalysis, copper, complexation, copper ammines. 1. Introduction ... ammonia is able to de-link Cu2+ ions away from the influence of .... Figure 1 DRS of CuX at different concentration levels of Cu/UC: (a). 38 Cu/UC, (b) 24 ...

Amplification of light emission of chiral pyridine Eu(III) complex by copper nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Reisfeld, Renata; Levchenko, Viktoria [Institute of Chemistry, The Hebrew University of Jerusalem, Givat Ram, Jerusalem 91904 (Israel); Piccinelli, Fabio; Bettinelli, Marco [Laboratorio Materiali Luminescenti, DB, Universita di Verona and INSTM, UdR Verona, Strada Le Grazie 15, 37134 Verona (Italy)

2016-02-15

We outline the applications of lanthanides luminescence in a number of modern fields. The intensity of the luminescence of the expensive lanthanides can be increased by their interaction with nanoparticles of inexpensive copper. As a typical example the chiral pyridine-based Eu{sup 3+} complex was incorporated into amorphous films of polyvinyl alcohol with hydroxyethyl cellulose. The luminescence intensity of the complex is increased by three hundred percent by its interaction with copper nanoparticles. The synthesis and steady state spectroscopy of the materials are presented. - Highlights: • Nanoparticles of copper were for the first time synthesized at 80 °C. • Copper NPs were incorporated with a luminescent Eu{sup 3+} complex in a polymeric matrix. • The films produced were characterized by photoluminescence spectroscopy. • The luminescence of Eu{sup 3+} complex with Cu NPs is 3 times higher than the original one.

Self-reduction of a copper complex MOD ink for inkjet printing conductive patterns on plastics.

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Farraj, Yousef; Grouchko, Michael; Magdassi, Shlomo

2015-01-31

Highly conductive copper patterns on low-cost flexible substrates are obtained by inkjet printing a metal complex based ink. Upon heating the ink, the soluble complex, which is composed of copper formate and 2-amino-2-methyl-1-propanol, decomposes under nitrogen at 140 °C and is converted to pure metallic copper. The decomposition process of the complex is investigated and a suggested mechanism is presented. The ink is stable in air for prolonged periods, with no sedimentation or oxidation problems, which are usually encountered in copper nanoparticle based inks.

Fluorescent copper(II complexes: The electron transfer mechanism, interaction with bovine serum albumin (BSA and antibacterial activity

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Madhumita Hazra

2017-01-01

Full Text Available Dinuclear copper(II complexes with formula [Cu2(L2(N32] (1 and [Cu2(L2(NCS2] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized by controlling the molar ratio of Cu(OAC2·6H2O, HL, sodium azide (1 and ammonium thiocyanate (2. The end on bridges appear exclusively in azide and thiocyanate to copper complexes. The electron transfer mechanism of copper(II complexes is examined by cyclic voltammetry indicating copper(II complexes are Cu(II/Cu(I couple. The interactions of copper(II complexes towards bovine serum albumin (BSA were examined with the help of absorption and fluorescence spectroscopic tools. We report a superficial solution-based route for the synthesis of micro crystals of copper complexes with BSA. The antibacterial activity of the Schiff base and its copper complexes were investigated by the agar disc diffusion method against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia and Bacillus cereus. It has been observed that the antibacterial activity of all complexes is higher than the ligand.

The impact of tertiary wastewater treatment on copper and zinc complexation.

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Constantino, C; Gardner, M; Comber, S D W; Scrimshaw, M D; Ellor, B

2015-01-01

Tightening quality standards for European waters has seen a move towards enhanced wastewater treatment technologies such as granulated organic carbon treatment and ozonation. Although these technologies are likely to be successful in degrading certain micro-organic contaminants, these may also destroy compounds which would otherwise complex and render metals significantly less toxic. This study examined the impact of enhanced tertiary treatment on the capacity of organic compounds within sewage effluents to complex copper and zinc. The data show that granulated organic carbon treatment removes a dissolved organic carbon (DOC) fraction that is unimportant to complexation such that no detrimental impact on complexation or metal bioavailability is likely to occur from this treatment type. High concentrations of ozone (>1 mg O3/mg DOC) are, however, likely to impact the complexation capacity for copper although this is unlikely to be important at the concentrations of copper typically found in effluent discharges or in rivers. Ozone treatment did not affect zinc complexation capacity. The complexation profiles of the sewage effluents show these to contain a category of non-humic ligand that appears unaffected by tertiary treatment and which displays a high affinity for zinc, suggesting these may substantially reduce the bioavailability of zinc in effluent discharges. The implication is that traditional metal bioavailability assessment approaches such as the biotic ligand model may overestimate zinc bioavailability in sewage effluents and effluent-impacted waters.

Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides

KAUST Repository

Huang, Ronglu

2015-03-17

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation, and tetrafluoropropoxylation of aryl and heteroaryl bromides were investigated. Efficiency drive: A series of copper(I) fluoroalkoxide complexes bearing N,N ligands have been prepared and structurally characterized. These well-defined complexes serve as efficient reagents for the fluoroalkoxylation of aryl and heteroaryl bromides to produce a wide range of trifluoroethyl, pentafluoropropyl, and tetrafluoropropyl (hetero)aryl ethers in good to excellent yields.

Spectroscopic and molecular docking studies on the interaction of human serum albumin with copper(II) complexes

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Guhathakurta, Bhargab; Pradhan, Ankur Bikash; Das, Suman; Bandyopadhyay, Nirmalya; Lu, Liping; Zhu, Miaoli; Naskar, Jnan Prakash

2017-02-01

Two osazone based ligands, butane-2,3-dione bis(2‧-pyridylhydrazone) (BDBPH) and hexane-3,4-dione bis(2‧-pyridylhydrazone) (HDBPH), were synthesized out of the 2:1 M Schiff base condensation of 2-hydrazino pyridine respectively with 2,3-butanedione and 3,4-hexanedione. The X-ray crystal structures of both the ligands have been determined. The copper(II) complex of HDBPH has also been synthesized and structurally characterized. HDBPH and its copper(II) complex have thoroughly been characterized through various spectroscopic and analytical techniques. The X-ray crystal structure of the copper complex of HDBPH shows that it is a monomeric Cu(II) complex having 'N4O2' co-ordination chromophore. Interaction of human serum albumin (HSA) with these ligands and their monomeric copper(II) complexes have been studied by various spectroscopic means. The experimental findings show that the ligands as well as their copper complexes are good HSA binders. Molecular docking investigations have also been done to unravel the mode of binding of the species with HSA.

Immobilized copper(II) macrocyclic complex on MWCNTs with antibacterial activity

Energy Technology Data Exchange (ETDEWEB)

Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Lab., Chemistry & Chemical Engineering Research Center of Iran, Pajoohesh Blvd., km 17, Karaj Hwy, Tehran 14968-13151 (Iran, Islamic Republic of); Mohammadipanah, Fatemeh; Hamedi, Javad [Department of Microbial Biotechnology, School of Biology and Center of Excellence in Phylogeny of Living Organisms, College of Science, University of Tehran, Tehran 14155-6455 (Iran, Islamic Republic of); University of Tehran Biocompound Collection (UTBC), Microbial Technology and Products Research Center, University of Tehran, Tehran (Iran, Islamic Republic of); Tahermansouri, Hasan [Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, Amol (Iran, Islamic Republic of); Amini, Mostafa M. [Department of Chemistry, Shahid Behshti University, 1983963113, Tehran (Iran, Islamic Republic of)

2015-06-30

Graphical abstract: In an antibacterial test, grafted copper(II) macrocyclic complex on the surface of MWCNT showed higher antibacterial activity against Bacillus subtilis compared to the individual MWCNT-COOH and the complex. - Highlights: • Copper(II) tetraaza macrocyclic complex covalently bonded to modified MWCNT. • Grafting of the complex carried out via an interaction between −C(=O)Cl group and NH of the ligand. • The samples were subjected in an antibacterial assessment to compare their activity. • Immobilized complex showed higher antibacterial activity against Bacillus subtilis ATCC 6633 compared to separately MWCNT-C(C=O)-OH and CuTAM. - Abstract: In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the I{sub D}/I{sub G} ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex.

Science.gov (United States)

Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius

2018-04-06

Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

COPPER(II) COMPLEXES OF o -VANILLIN ACETYLHYDRAZONE ...

African Journals Online (AJOL)

A hydrazonic ligand, o-vanillin acetylhydrazone (H2L) has been prepared and used as chelating agent towards copper(II) ion. The ligand acts like a tridentate ligand in the monodeprotonated (HL-) and dideprotonated (L2-) states. Monoanionic complexes [{Cu(HL)(H2O)}2]•2BF4 and [{Cu(HL)(Hpz)(H2O)}]•NO3 have been ...

Anti-inflammatory activity of copper-protein complexes with reference to rheumatoid arthritis

International Nuclear Information System (INIS)

Bibi, S.; Sajjad, I.; Akram, W.; Karim, H.M.A.; Iqbal, M.Z.

1996-01-01

Work was carried out on the serum of 100 healthy subjects and hundred Rheumatoid Arthritus patients by electrophoresis and atomic absorption model Hitachi-180-80. The different proteins fractions separated by electrophoresis were subjected for estimation of Cu-Concentration. It was found that only 5% copper is present in albumin which remains constant in normal and Rheumatoid Arthritus patients. The other important group of proteins were a2-globulins, in which Cu concentration was found high in Rheumatoid Arthritus patients as compared to normal subject. There was no copper detected in beta and gamma globulins. The study can be used for diagnostic purposes. Copper complexes of alpha 2-Globulins were found anti inflammatory in nature and this quality of self defense can bring revolution in the history of all infectious diseases including Rheumatoid Arthritus simply by separating the copper complexes of alpha 2-globulins (most probably ceruloplasmin) from the blood of donors and injecting into the body of patients. It is possible by this method that the disease-Rheumatoid Arthritus may be eradicated completely. These complexes have also shown antibiotic activity in gynae patients. (author)

Copper (II) complexes of bidentate ligands exhibit potent anti-cancer activity regardless of platinum sensitivity status.

Science.gov (United States)

Wehbe, Mohamed; Lo, Cody; Leung, Ada W Y; Dragowska, Wieslawa H; Ryan, Gemma M; Bally, Marcel B

2017-12-01

Insensitivity to platinum, either through inherent or acquired resistance, is a major clinical problem in the treatment of many solid tumors. Here, we explored the therapeutic potential of diethyldithiocarbamate (DDC), pyrithione (Pyr), plumbagin (Plum), 8-hydroxyquinoline (8-HQ), clioquinol (CQ) copper complexes in a panel of cancer cell lines that differ in their sensitivity to platins (cisplatin/carboplatin) using a high-content imaging system. Our data suggest that the copper complexes were effective against both platinum sensitive (IC 50  ~ 1 μM platinum) and insensitive (IC 50  > 5 μM platinum) cell lines. Furthermore, copper complexes of DDC, Pyr and 8-HQ had greater therapeutic activity compared to the copper-free ligands in all cell lines; whereas the copper-dependent activities of Plum and CQ were cell-line specific. Four of the copper complexes (Cu(DDC) 2 , Cu(Pyr) 2 , Cu(Plum) 2 and Cu(8-HQ) 2 ) showed IC 50 values less than that of cisplatin in all tested cell lines. The complex copper DDC (Cu(DDC) 2 ) was selected for in vivo evaluation due to its low nano-molar range activity in vitro and the availability of an injectable liposomal formulation. Liposomal (Cu(DDC) 2 ) was tested in a fast-growing platinum-resistant A2780-CP ovarian xenograft model and was found to achieve a statistically significant reduction (50%; p < 0.05) in tumour size. This work supports the potential use of copper-based therapeutics to treat cancers that are insensitive to platinum drugs.

Mixed-ligand copper(II) complexes of dipicolylamine and 1,10 ...

Indian Academy of Sciences (India)

Unknown

DNA repair mechanism.13,14 Copper(II) complexes containing heterocyclic bases have received consid- erable current interest in nucleic acid chemistry due to their diverse applications following the discovery of the “chemical nuclease” activity of the [Cu. (phen)2]+ (phen = 1,10-phenanthroline) complex in the presence of ...

The in vivo behavior of copper-64-labeled azamacrocyclic complexes

International Nuclear Information System (INIS)

Jones-Wilson, Teresa M.; Deal, Kim A.; Anderson, Carolyn J.; McCarthy, Deborah W.; Kovacs, Zoltan; Motekaitis, Ramunas J.; Sherry, A. Dean; Martell, Arthur E.; Welch, Michael J.

1998-01-01

The use of copper radioisotopes in imaging and therapy applications has created a greater need for bifunctional chelates (BFCs) for complexing copper radioisotopes to biomolecules. It has been demonstrated that the charge and lipophilicity of the Cu-BFC complex has a significant effect on the in vivo behavior of the radiolabeled Cu-BFC-biomolecule conjugate. To evaluate the effects of charge, stability, and macrocyclic backbone size on the biological behavior of 64 Cu complexes, a series of macrocyclic 64 Cu complexes have been prepared, and the biodistributions of these agents were evaluated in normal Sprague-Dawley rats. Two macrocyclic backbones, dodecane and tetradecane, were evaluated; cyclen, DOTA, and DO2A were dodecane backbone derivatives, and cyclam, TETA, and et-cyclam were tetradecane backbone derivatives. The biodistributions of the 64 Cu-labeled complexes correlated with differences in the size of the macrocycle backbone and the formal charge of the complex. All compounds showed uptake and clearance through the liver and kidneys; however, the positively charged 64 Cu complexes showed significantly higher uptake in both of these organs than did the negatively charged or neutral complexes. 64 Cu-TETA, a negatively charged complex with the tetradecane backbone, had the most efficient clearance by 24 hours' postinjection. These data suggest that negatively charged complexes may have more favorable clearance properties when used as BFCs

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Directory of Open Access Journals (Sweden)

Patrícia M. Dias

2010-01-01

Full Text Available Herein, the immobilization of some Schiff base-copper(II complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Oxidation of aromatic alcohols on zeolite-encapsulated copper amino acid complexes

Energy Technology Data Exchange (ETDEWEB)

Ernst, S.; Teixeira Florencio, J.M. [Kaiserslautern Univ. (Germany). Dept. of Chemistry, Chemical Technology

1998-12-31

Copper complexes of the amino acids histidine, arginine and lysine have been introduced into the supercages of zeolite Y and, for the first time, into the large intracrystalline cavities of zeolites EMT and MCM-22. The resulting host/guest compounds are characterized by X-ray powder diffraction, UV/VIS-spectroscopy in the diffuse reflectance mode and by catalytic tests in the liquid-phase oxidation of aromatic alcohols (viz. benzyl alcohol, 2- and 3-methylbenzyl alcohol and 2,5-dimethylbenzyl alcohol) with tertiary-butylhydroperoxide as oxidant. It was observed that intracrystalline copper-amino acid complexes possess remarkable catalytic activity, yielding the corresponding aromatic aldehydes and acids. (orig.)

Geometry and Framework Interactions of Zeolite-Encapsulated Copper(II)-Histidine Complexes

NARCIS (Netherlands)

Weckhuysen, B.M.; Grommen, R.; Manikandan, P.; Gao, Y.; Shane, T.; Shane, J.J.; Schoonheydt, R.A.; Goldfarb, D.

2000-01-01

The coordination geometry of zeolite-encapsulated copper(II)-histidine (CuHis) complexes, prepared by ion exchange of the complexes from aqueous solutions into zeolite NaY, was determined by a combination of UV-vis-NIR diffuse reflectance spectroscopy (DRS), X-band EPR, electron-spin-echo envelope

Vectorization of copper complexes via biocompatible and biodegradable PLGA nanoparticles.

Science.gov (United States)

Courant, T; Roullin, V G; Cadiou, C; Delavoie, F; Molinari, M; Andry, M C; Gafa, V; Chuburu, F

2010-04-23

A double emulsion-solvent diffusion approach with fully biocompatible materials was used to encapsulate copper complexes within biodegradable nanoparticles, for which the release kinetics profiles have highlighted their potential use for a prolonged circulating administration.

Vectorization of copper complexes via biocompatible and biodegradable PLGA nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Courant, T; Roullin, V G; Andry, M C [Institut de Chimie Moleculaire de Reims, CNRS UMR 6229, UFR Pharmacie Reims, 51 rue Cognacq-Jay, F-51100 Reims (France); Cadiou, C; Chuburu, F [Institut de Chimie Moleculaire de Reims, CNRS UMR 6229, UFR des Sciences Exactes et Naturelles, Batiment 18-Europol' Agro, BP 1039, F-51687 Reims Cedex 2 (France); Delavoie, F [Laboratoire de Microscopie Electronique Analytique, INSERM UMRS 926, 21 rue Clement Ader, F-51685 Reims Cedex 2 (France); Molinari, M [Laboratoire de Microscopies et d' Etudes des Nanostructures, UFR des Sciences, Universite de Reims Champagne-Ardenne, 21 rue Clement Ader, F-51685 Reims Cedex 2 (France); Gafa, V, E-mail: gaelle.roullin@univ-reims.fr, E-mail: francoise.chuburu@univ-reims.fr [EA4303 ' Inflammation et Immunite de l' Epithelium Respiratoire' , IFR53, UFR de Pharmacie, Universite de Reims Champagne-Ardenne, 51 rue Cognacq-Jay, F-51100 Reims (France)

2010-04-23

A double emulsion-solvent diffusion approach with fully biocompatible materials was used to encapsulate copper complexes within biodegradable nanoparticles, for which the release kinetics profiles have highlighted their potential use for a prolonged circulating administration.

Vectorization of copper complexes via biocompatible and biodegradable PLGA nanoparticles

International Nuclear Information System (INIS)

Courant, T; Roullin, V G; Andry, M C; Cadiou, C; Chuburu, F; Delavoie, F; Molinari, M; Gafa, V

2010-01-01

A double emulsion-solvent diffusion approach with fully biocompatible materials was used to encapsulate copper complexes within biodegradable nanoparticles, for which the release kinetics profiles have highlighted their potential use for a prolonged circulating administration.

Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

Directory of Open Access Journals (Sweden)

Akinori Honda

2016-10-01

Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

Trinuclear rhenium(III) halide clusters with carboxylate ligands

Science.gov (United States)

Dougan, Jeffrey Steven

Four mono(carboxylato)trirhenium complexes and three bis(carboxylato)trirhenium complexes have been synthesized and characterized, principally by mass spectrometry, with supporting evidence from X-ray diffraction. These compounds represent the first trinuclear rhenium carboxylate complexes. The reactions generally proceed readily under comparatively mild conditions. Mass spectrometry has again proved its usefulness as a technique in the field of metal cluster chemistry, having provided the initial identification of the products of the reactions studied. These compounds provide a further base to which future mass spectra of metal cluster compounds can be compared. Re-examination of a reaction reported by Taha and Wilkinson has also cast considerable doubt onto the validity of a conversion widely reported in the literature that transforms (Re3Cl9) x into [Re2(O2CCH3)4Cl 2]. We believe that the literature result is a consequence of the purity of the metal precursor, and suggest that the starting material in the earlier work may have contained ReCl4 or ReCl5. The importance of mass spectrometry in the characterization of the new compounds synthesized in this project has led to a thorough study of calculated isotopic distributions. The information gathered suggests that for isotopically simple molecules, the choice of algorithm for computing an isotopic distribution is unimportant. However, it is important to compute the mass spectrum of an isotopically complex molecule using an algorithm that can, if desired, show the underlying isotopic fine structure of a peak of interest. In the last chapter of this thesis, the results of a project in chemistry education research are presented. Predicting the success of students in general chemistry has long been of interest to the chemistry education community, and several factors have been identified as contributing factors. An off-hand comment by a student inspired an examination of whether continuity with the same instructor for

Trinuclear Lanthanoid Complexes of 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol with a Unique, Sandwich-Type Cage Structure(1).

Science.gov (United States)

Hedinger, Roman; Ghisletta, Michele; Hegetschweiler, Kaspar; Tóth, Eva; Merbach, André E.; Sessoli, Roberta; Gatteschi, Dante; Gramlich, Volker

1998-12-28

A variety of trinuclear complexes [M(3)(H(-)(3)L)(2)](3+) [M = Y, La, Eu, Gd, Dy; L = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci)] was prepared as solid materials of the composition M(3)(H(-)(3)L)(2)X(3).pH(2)O.qEtOH (X = Cl, NO(3); 2.5 complex crystallizes in the orthorhombic space group Pbca, a = 17.10(2) Å, b = 16.20(4) Å, c = 20.25(4) Å, Z = 8 for C(12)Cl(3)H(38)La(3)N(6)O(13). The Gd complex crystallizes in the monoclinic space group P2(1)/n, a = 10.294(3) Å, b = 15.494(5) Å, c = 19.994(6) Å, beta = 95.36(2) degrees, Z = 4 for C(12)Cl(3)Gd(3)H(42)N(6)O(15). The two complexes exhibited a unique, sandwich-type cage structure, where the two triply deprotonated taci ligands encapsulate an equilateral triangle of the three metal centers. The metal cations are coordinated to the equatorial, terminal amino groups and are bridged by the axial &mgr;(2)-alkoxo groups. The coordination spheres are completed by additional peripheral ligands such as H(2)O or Cl(-) counterions. The coordination number of the metal cations is 8. Magnetic susceptibility measurements of the Gd complex revealed very weak antiferromagnetic coupling interactions between the three Gd centers. Complex formation and species distribution in aqueous solution was investigated by potentiometry and pD-dependent NMR spectroscopy. An exclusive formation of the [Eu(3)(H(-)(3)taci)(2)](3+) unit in solution was found in the range 7 complexes with taci. The stability of the lanthanoid complexes increased monotonically with decreasing ionic radius of

Well-Defined Copper(I) Fluoroalkoxide Complexes for Trifluoroethoxylation of Aryl and Heteroaryl Bromides

KAUST Repository

Huang, Ronglu; Huang, Yangjie; Lin, Xiaoxi; Rong, Mingguang; Weng, Zhiqiang

2015-01-01

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Copper(I) fluoroalkoxide complexes bearing dinitrogen ligands were synthesized and the structure and reactivity of the complexes toward trifluoroethoxylation, pentafluoropropoxylation

Adsorptive stripping voltammetric behaviour of copper complexes of some heterocyclic azo compounds.

Science.gov (United States)

Farias, P A; Ferreira, S L; Ohara, A K; Bastos, M B; Goulart, M S

1992-10-01

Controlled adsorptive accumulation of copper complexed with TAN, TAC, TAR and TAM (heterocyclic azo-compounds) on a static mercury drop electrode provides the basis for the direct stripping measurement of this element in the nanomolar concentration level. The ligand TAN exhibited great sensitivity and better separation of the peak current of the ligand in relation to the complex. The reduction current of adsorbed complex ions of copper is measured by linear scan cathodic stripping voltammetry, preceded by a period of accumulation of a few minutes. The peak potential is at approximately -0.37 V vs. Ag/AgCl. Optimal experimental parameters were found to be a TAN concentration of 1 x 10(-5)M, an accumulation potential of -0.22 V, and a solution pH of 3.7 (acetate buffer). The detection limit is 0.8nM after a 5-min accumulation with a stirred solution, and the response is linear up to 50 mug/l. Many common cations and anions do not interfere in the determination of copper. The interference of titanium is eliminated by addition of fluoride ion. Results are reported for a fresh water sample.

Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study.

Science.gov (United States)

Yu, Yang; Li, Chen; Yin, Bing; Li, Jian-Li; Huang, Yuan-He; Wen, Zhen-Yi; Jiang, Zhen-Yi

2013-08-07

The structures, relative stabilities, vertical electron detachment energies, and magnetic properties of a series of trinuclear clusters are explored via combined broken-symmetry density functional theory and ab initio study. Several exchange-correlation functionals are utilized to investigate the effects of different halogen elements and central atoms on the properties of the clusters. These clusters are shown to possess stronger superhalogen properties than previously reported dinuclear superhalogens. The calculated exchange coupling constants indicate the antiferromagnetic coupling between the transition metal ions. Spin density analysis demonstrates the importance of spin delocalization in determining the strengths of various couplings. Spin frustration is shown to occur in some of the trinuclear superhalogens. The coexistence of strong superhalogen properties and spin frustration implies the possibility of trinuclear superhalogens working as the building block of new materials of novel magnetic properties.

Infrared spectroscopy of copper-resveratrol complexes: A joint experimental and theoretical study

Energy Technology Data Exchange (ETDEWEB)

Chiavarino, B.; Crestoni, M. E.; Fornarini, S. [Dipartimento di Chimica e Tecnologie del Farmaco, Sapienza - Universita di Roma, Piazzale A. Moro 5, 00185 Rome (Italy); Taioli, S. [Interdisciplinary Laboratory for Computational Science, FBK-CMM and University of Trento, Via Sommarive 18, 38123 Trento (Italy); Department of Physics, University of Trento, Via Sommarive 14, 38123 Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Perugia (Italy); Department of Chemistry, University of Bologna, Via F. Selmi 2, I-40126 Bologna (Italy); Mancini, I.; Tosi, P. [Department of Physics, University of Trento, Via Sommarive 14, 38123 Trento (Italy)

2012-07-14

Infrared multiple-photon dissociation spectroscopy has been used to record vibrational spectra of charged copper-resveratrol complexes in the 3500-3700 cm{sup -1} and 1100-1900 cm{sup -1} regions. Minimum energy structures have been determined by density functional theory calculations using plane waves and pseudopotentials. In particular, the copper(I)-resveratrol complex presents a tetra-coordinated metal bound with two carbon atoms of the alkenyl moiety and two closest carbons of the adjoining resorcinol ring. For these geometries vibrational spectra have been calculated by using linear response theory. The good agreement between experimental and calculated IR spectra for the selected species confirms the overall reliability of the proposed geometries.

Photochemical activation and reactivity of polynuclear transition metal complex molecules. Final report

International Nuclear Information System (INIS)

Endicott, J.F.; Lintvedt, R.L.

1982-06-01

Several bi- and trinuclear metal complexes containing ligands from β-polyketonates have been synthesized and characterized including homo- and hetero-polynuclear complexes. New synthetic approaches to the preparation of heterobi- and trinuclear complexes have been developed that allow the preparation of a large number of molecules containing heavy-metal ions such as Pd 2+ or UO 2 2+ and a first-row transition-metal ion. The electrochemical properties of these complexes have been investigated and many exhibit the ability to transfer two electrons at very nearly the same potential. Photochemical studies on binuclear Cu(II) and Ni(II) showed that these compounds yielded reduced metal species and decomposition upon irradiation. Luminescence of hetero-complexes of uranyl polyketonates is observed at 77 0 K with the UO 2 2+ moiety functioning as an isolated chromophore in which emission is observed only on direct excitation of UO 2 2+ and energy transfer to lower states in the molecule is not observed

Spectroscopic and structural study of the newly synthesized heteroligand complex of copper with creatinine and urea.

Science.gov (United States)

Gangopadhyay, Debraj; Singh, Sachin Kumar; Sharma, Poornima; Mishra, Hirdyesh; Unnikrishnan, V K; Singh, Bachcha; Singh, Ranjan K

2016-02-05

Study of copper complex of creatinine and urea is very important in life science and medicine. In this paper, spectroscopic and structural study of a newly synthesized heteroligand complex of copper with creatinine and urea has been discussed. Structural studies have been carried out using DFT calculations and spectroscopic analyses were carried out by FT-IR, Raman, UV-vis absorption and fluorescence techniques. The copper complex of creatinine and the heteroligand complex were found to have much increased water solubility as compared to pure creatinine. The analysis of FT-IR and Raman spectra helps to understand the coordination properties of the two ligands and to determine the probable structure of the heteroligand complex. The LIBS spectra of the heteroligand complex reveal that the complex is free from other metal impurities. UV-visible absorption spectra and the fluorescence emission spectra of the aqueous solution of Cu-Crn-urea heteroligand complex at different solute concentrations have been analyzed and the complex is found to be rigid and stable in its monomeric form at very low concentrations. Copyright © 2015 Elsevier B.V. All rights reserved.

Template Syntheses, Crystal Structures and Supramolecular Assembly of Hexaaza Macrocyclic Copper(II) Complexes

International Nuclear Information System (INIS)

Kim, Taehyung; Kim, Ju Chang; Lough, Alan J.

2013-01-01

Two new hexaaza macrocyclic copper(II) complexes were prepared by a template method and structurally characterized. In the solid state, they were self-assembled by intermolecular interactions to form the corresponding supramolecules 1 and 2, respectively. In the structure of 1, the copper(II) macrocycles are bridged by a tp ligand to form a macrocyclic copper(II) dimer. The dimer extends its structure by intermolecular forces such as hydrogen bonds and C-H···π interactions, resulting in the formation of a double stranded 1D supramolecule. In 2, the basic structure is a monomeric copper(II) macrocycle with deprotonated imidazole pendants. An undulated 1D hydrogen bonded array is achieved through hydrogen bonds between imidazole pendants and secondary amines, where the imidazole pendants act as a hydrogen bond acceptor. The 1D hydrogen bonded supramolecular chain is supported by C-H···π interactions between the methyl groups of acetonitrile ligands and imidazole pendants of the copper(II) macrocycles. In both complexes, the introduction of imidazoles to the macrocycle as a pendant plays an important role for the formation of supramolecules, where they act as intermolecular hydrogen bond donors and/or acceptors, C-H···π and π-π interactions

Low-dimensional compounds containing cyanido groups. XXVIII. Crystal structure, spectroscopic and magnetic properties of two copper(II) tetracyanidoplatinate complexes with 1,2-diaminopropane

International Nuclear Information System (INIS)

Vavra, Martin; Potočňák, Ivan; Dušek, Michal; Čižmár, Erik; Ozerov, Mykhaylo; Zvyagin, Sergei A.

2015-01-01

Violet crystals of ([Cu(pn) 2 ] 2 [Pt(CN) 4 ])[Pt(CN) 4 ]·2H 2 O (1, pn=1,2-diaminopropane) and blue crystals of [Cu(pn)Pt(CN) 4 ] n ·nH 2 O (2) were prepared under hydrothermal conditions and characterized using elemental analysis, IR and UV–vis spectroscopy and by X-ray crystal structure analysis. Different number of ν(C≡N) absorption bands of these two compounds reflects their different structures. An X-ray crystal structure analysis has shown that complex 1 is of ionic character and is formed from trinuclear [Cu(pn) 2 –Pt(CN) 4 –Cu(pn) 2 ] 2+ complex cation and discrete [Pt(CN) 4 ] 2– anion together with two molecules of crystal water. On the other hand, complex 2 is of polymeric character and is formed by 2D networks of [Cu(pn)Pt(CN) 4 ] n composition and completed by n molecules of crystal water. Magnetic measurements show the presence of a weak antiferromagnetic exchange interaction in complex 1 (Θ=–0.2 K), while the magnetic susceptibility of complex 2 is well described by the model of uniform S=1/2 spin chain with exchange interaction J/k B =–1.64 K. - Graphical abstract: Two complexes of different structural types from the system Cu(II) – 1,2–diaminopropane – [Pt(CN) 4 ] 2– have been isolated. These were characterized by IR and UV–VIS spectroscopy, X–ray crystal structure analysis together with the magnetic measurements. On one hand ([Cu(pn) 2 ] 2 [Pt(CN) 4 ])[Pt(CN) 4 ]∙2H 2 O is of ionic character and is formed from trinuclear complex cation and discrete anion together with two molecules of crystal water. On the other hand, [Cu(pn)Pt(CN) 4 ] n ∙nH 2 O is of polymeric character and is formed by 2D networks of [Cu(pn)Pt(CN) 4 ] n composition and completed by n molecules of crystal water. - Highlights: • Two complexes of different compositions from one system have been isolated. • First complex is of ionic character and second one is of polymeric character. • Polymeric complex described as a spin chain in contrast to

Structural measurements and cell line studies of the copper-PEG-Rifampicin complex against Mycobacterium tuberculosis.

Science.gov (United States)

Manning, Thomas; Mikula, Rachel; Wylie, Greg; Phillips, Dennis; Jarvis, Jackie; Zhang, Fengli

2015-02-01

The bacterium responsible for tuberculosis is increasing its resistance to antibiotics resulting in new multidrug-resistant Mycobacterium tuberculosis (MDR-TB) and extensively drug-resistant tuberculosis (XDR-TB). In this study, several analytical techniques including NMR, FT-ICR, MALDI-MS, LC-MS and UV/Vis are used to study the copper-Rifampicin-Polyethylene glycol (PEG-3350) complex. The copper (II) cation is a carrier for the antibiotic Rifampicin as well as nutrients for the bacterium. The NIH-NIAID cell line containing several Tb strains (including antibiotic resistant strains) is tested against seven copper-PEG-RIF complex variations. Copyright © 2014 Elsevier Ltd. All rights reserved.

X-ray absorption near edge structure (XANES) study of some hydroxamic mixed ligand copper complexes

International Nuclear Information System (INIS)

Mishra, A; Parsai, N; Shrivastava, B D; Soni, N

2012-01-01

With the advent of modern bright synchrotron radiation sources, X-ray absorption spectra has emerged as a powerful technique for local structure determination, which can be applied to any type of material. The X-ray absorption measurements of four hydroxamic mixed ligand copper complexes have been performed at the recently developed BL-8 Dispersive EXAFS beamline at 2.5 GeV Indus-2 synchrotron at RRCAT, Indore, India. The X-ray absorption near edge structure (XANES) data obtained has been processed using data analysis program Athena. The energies of the K absorption edge, chemical shifts, edge-widths, shifts of the principal absorption maximum in the complexes have been determined. The values of the chemical shift suggest that copper is in oxidation state +2 in all of the complexes. The chemical shift data has been utilized to estimate effective nuclear charge on copper atom. The order of the chemical shifts has been correlated to the relative ionic character of the bonding in these complexes.

Infrared spectroscopy of copper-resveratrol complexes: A joint experimental and theoretical study

International Nuclear Information System (INIS)

Chiavarino, B.; Crestoni, M. E.; Fornarini, S.; Taioli, S.; Mancini, I.; Tosi, P.

2012-01-01

Infrared multiple-photon dissociation spectroscopy has been used to record vibrational spectra of charged copper-resveratrol complexes in the 3500–3700 cm −1 and 1100–1900 cm −1 regions. Minimum energy structures have been determined by density functional theory calculations using plane waves and pseudopotentials. In particular, the copper(I)-resveratrol complex presents a tetra-coordinated metal bound with two carbon atoms of the alkenyl moiety and two closest carbons of the adjoining resorcinol ring. For these geometries vibrational spectra have been calculated by using linear response theory. The good agreement between experimental and calculated IR spectra for the selected species confirms the overall reliability of the proposed geometries.

Physicochemical characterization of functionalized-nanostructured-titania as a carrier of copper complexes for cancer treatment

International Nuclear Information System (INIS)

López, Tessy; Ortiz, Emma; Guevara, Patricia; Gómez, Esteban; Novaro, Octavio

2014-01-01

In the present paper we report the preparation and characterization of functionalized-TiO 2 (F-TiO 2 ) to obtain a biocompatible material to be used as carrier of alternative anticancer agents: copper acetate and copper acetylacetonate. The sol–gel procedure was used to prepare the fuctionalized titania material through hydrolysis and condensation of the titanium's butoxide. Sulfate, amine and phosphate ions served as functional groups which were anchored to the titania's surface. Mineral acids and gamma amine butyric acid were the precursors and they were added at the initial step of the synthesis. The copper complexes were loaded on titania and were also added to the reactor synthesis from the beginning. Infrared and ultraviolet–visible spectroscopies were the principal techniques used to the characterization of F-TiO 2 and copper complexes loaded on titania materials. Transmission Electronic Microscopy (TEM) was used to complement the characterization's studies. The biocompatibility of F-TiO 2 was evaluated by treating different cancer cell lines with increased concentration of this compound. The amine, the sulfate and the phosphate on the titania's surface, as well as the integral structures of the metal complexes on titania were well identified by infrared and ultraviolet–visible spectroscopies. The TEM photographs of Cu(acac) 2 /F-TiO 2 and Cu(Oac) 2 /F-TiO 2 materials showed the formation of nanoparticles, which have sizes ranging from 4 to 10 nm, with no morphology alterations in comparison with F-TiO 2 nanoparticles, suggesting that the presence of low quantities of copper do not affect the structure of the nanoparticles. The Energy Dispersive Spectroscopy (EDS) confirms the presence of copper on the titania's nanoparticles. The biological results indicate that there is more than 90% cell survival, thus suggesting that F-TiO 2 does not cause damage to the cells. Therefore, highly biocompatible titania was obtained by

Mechanism and kinetics of thermal decomposition of ammoniacal complex of copper oxalate

International Nuclear Information System (INIS)

Prasad, R.

2003-01-01

A complex precursor has been synthesized by dissolving copper oxalate in liquor ammonia followed by drying. The thermal decomposition of the precursor has been studied in different atmospheres, air/nitrogen. The mechanism of decomposition of the precursor in air is not as simple one as in nitrogen. In nitrogen, it involves endothermic deammoniation followed by decomposition to finely divided elemental particles of copper. Whereas in air, decomposition and simultaneous oxidation of the residual products (oxidative decomposition), make the process complex and relatively bigger particle of cupric oxide are obtained as final product. The products of decomposition in different atmospheres have been characterized by X-ray diffraction and particle size analysis. The stoichiometric formula, Cu(NH 3 ) 2 C 2 O 4 of the precursor is established from elemental analysis and TG measurements, and it is designated as copper amino oxalate (CAO). In nitrogen atmosphere, the deammoniation and decomposition have been found to be zero and first order, respectively. The values of activation energy have been found to be 102.52 and 95.38 kJ/mol for deammoniation and decomposition, respectively

Copper complexation capacity in surface waters of the Venice Lagoon.

Science.gov (United States)

Delgadillo-Hinojosa, Francisco; Zirino, Alberto; Nasci, Cristina

2008-10-01

Total copper (Cu(T)), copper ion activity (pCu) and the copper complexation capacity (CuCC) were determined in samples of seawater collected in July 2003 from the Venice Lagoon. Cu(T) and CuCC showed considerable spatial variability: Cu(T) ranged from 1.8 to 70.0nM, whereas the CuCC varied from 195 to 573nM. pCu values varied from 11.6 to 12.6 and are consistent with those previously reported in estuarine and coastal areas (10.9-14.1). The range of Cu(T) values compares well with those reported in the past in the lagoon and in the adjacent Adriatic Sea. The highest concentrations of Cu(T) were found in samples collected near the industrial area of Porto Marghera, whereas the lowest were measured near the Chioggia and Malamocco inlets, where an intense tidally-driven renewal of seawater takes place. Although CuCC showed a high degree of spatial variability, the values recorded in the Venice Lagoon are comparable to those reported in other estuarine systems. In addition, CuCC was positively correlated with dissolved organic carbon (DOC), suggesting that organic ligands responsible for Cu complexation are part of the bulk organic matter pool in the lagoon. The CuCC:Cu(T) molar ratio was, on average 55:1, indicating that a large excess of complexation capacity exists in the Venice Lagoon. The high levels of CuCC and the narrow range of pCu indicates the importance of the role played by organic ligands in controlling the free ion Cu concentrations in the lagoon, and as a consequence, regulating its availability and/or toxicity.

EXAFS Studies of Some Copper(II) Mixed-Ligand Complexes

International Nuclear Information System (INIS)

Joshi, S. K.; Katare, R. K.; Shrivastava, B. D.

2007-01-01

X-ray K-absorption spectroscopic studies have been carried out on copper (II) mixed-ligand complexes with glutamic acid and aspartic acid as the primary ligands, where as water, pyridine, imidazole and benz-imidazole have been used as secondary ligands. Chemical shifts obtained from the X-ray absorption data have indicated that the glutamic acid complexes are more ionic as compared to their corresponding aspartic acid complexes having similar secondary ligands. Further, we have estimated the average metal-ligand bond distances from the from structure data. For the different complexes studied under the present investigation, the studies reveal that the bonding parameter α1 decreases with the increase in the percentage covalency of the metal-ligand bond. Thus, the bonding parameter α1 may be used for the estimation of percentage covalency of the metal-ligand bond in other similar complexes

Physicochemical characterization of functionalized-nanostructured-titania as a carrier of copper complexes for cancer treatment

Energy Technology Data Exchange (ETDEWEB)

López, Tessy [Nanotechnology and Nanomedicine Laboratory, Metropolitan Autonomous University-Xochimilco, Calzada del Hueso 1100, Villa Quietud, Coyoacán, 04960 México D.F. (Mexico); Nanotechnology Laboratory, National Institute of Neurology and Neurosurgery “MVS”, Avenida Insurgentes Sur 3877, La Fama, Tlalpan, 14269 México D.F. (Mexico); Department of Chemical and Biomolecular Engineering, Tulane University, 6823 St. Charles Avenue, New Orleans (United States); Ortiz, Emma, E-mail: emma170@hotmail.com [Nanotechnology Laboratory, National Institute of Neurology and Neurosurgery “MVS”, Avenida Insurgentes Sur 3877, La Fama, Tlalpan, 14269 México D.F. (Mexico); Guevara, Patricia [Neuroimmunology Laboratory, National Institute of Neurology and Neurosurgery “MVS”, Insurgentes Sur 3877, La Fama, Tlalpan, 14269 México D.F. (Mexico); Gómez, Esteban [Nanotechnology Laboratory, National Institute of Neurology and Neurosurgery “MVS”, Avenida Insurgentes Sur 3877, La Fama, Tlalpan, 14269 México D.F. (Mexico); Novaro, Octavio [Institute of Physics-UNAM, Circuito de la Investigación Científica Ciudad Universitaria, CP 04510 México D.F. (Mexico)

2014-07-01

In the present paper we report the preparation and characterization of functionalized-TiO{sub 2} (F-TiO{sub 2}) to obtain a biocompatible material to be used as carrier of alternative anticancer agents: copper acetate and copper acetylacetonate. The sol–gel procedure was used to prepare the fuctionalized titania material through hydrolysis and condensation of the titanium's butoxide. Sulfate, amine and phosphate ions served as functional groups which were anchored to the titania's surface. Mineral acids and gamma amine butyric acid were the precursors and they were added at the initial step of the synthesis. The copper complexes were loaded on titania and were also added to the reactor synthesis from the beginning. Infrared and ultraviolet–visible spectroscopies were the principal techniques used to the characterization of F-TiO{sub 2} and copper complexes loaded on titania materials. Transmission Electronic Microscopy (TEM) was used to complement the characterization's studies. The biocompatibility of F-TiO{sub 2} was evaluated by treating different cancer cell lines with increased concentration of this compound. The amine, the sulfate and the phosphate on the titania's surface, as well as the integral structures of the metal complexes on titania were well identified by infrared and ultraviolet–visible spectroscopies. The TEM photographs of Cu(acac){sub 2}/F-TiO{sub 2} and Cu(Oac){sub 2}/F-TiO{sub 2} materials showed the formation of nanoparticles, which have sizes ranging from 4 to 10 nm, with no morphology alterations in comparison with F-TiO{sub 2} nanoparticles, suggesting that the presence of low quantities of copper do not affect the structure of the nanoparticles. The Energy Dispersive Spectroscopy (EDS) confirms the presence of copper on the titania's nanoparticles. The biological results indicate that there is more than 90% cell survival, thus suggesting that F-TiO{sub 2} does not cause damage to the cells. Therefore

Preparation of Some Novel Copper(I) Complexes and their Molar Conductances in Organic Solvents

Science.gov (United States)

Gill, Dip Singh; Rana, Dilbag

2009-04-01

Attempts have been made to prepare some novel copper(I) nitrate, sulfate, and perchlorate complexes. Molar conductances of these complexes have been measured in organic solvents like acetonitrile (AN), acetone (AC), methanol (MeOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), and dimethylsulfoxide (DMSO) at 298 K. The molar conductance data have been analyzed to obtain limiting molar conductances (λ0) and ion association constants (KA) of the electrolytes. The results showed that all these complexes are strong electrolytes in all organic solvents. The limiting ionic molar conductances (λo± ) for various ions have been calculated using Bu4NBPh4 as reference electrolyte. The actual radii for copper(I) complex ions are very large and different in different solvents and indicate some solvation effects in each solvent system

Pilot Study of Topical Copper Chlorophyllin Complex in Subjects With Facial Acne and Large Pores.

Science.gov (United States)

Stephens, Thomas J; McCook, John P; Herndon, James H

2015-06-01

Acne vulgaris is one of the most common skin diseases treated by dermatologists. Salts of copper chlorophyllin complex are semi-synthetic naturally-derived compounds with antioxidant, anti-inflammatory and wound healing activity that have not been previously tested topically in the treatment of acne-prone skin with enlarged pores. This single-center pilot study was conducted to assess the efficacy and safety of a liposomal dispersion of topically applied sodium copper chlorophyllin complex in subjects with mild-moderate acne and large, visible pores over a course of 3 weeks. Subjects were supplied with the test product, a topical gel containing a liposomal dispersion of sodium copper chlorophyllin complex (0.1%) with directions to apply a small amount to the facial area twice daily. Clinical assessments were performed at screening/baseline and at week 3. VISIA readings were taken and self-assessment questionnaires were conducted. 10 subjects were enrolled and completed the 3-week study. All clinical efficacy parameters showed statistically significant improvements over baseline at week 3. The study product was well tolerated. Subject questionnaires showed the test product was highly rated. In this pilot study, a topical formulation containing a liposomal dispersion of sodium copper chlorophyllin complex was shown to be clinically effective and well tolerated for the treatment of mild-moderate acne and large, visible pores when used for 3 weeks.

Optimizing the Readout of Lanthanide-DOTA Complexes for the Detection of Ligand-Bound Copper(I).

Science.gov (United States)

Hanna, Jill R; Allan, Christopher; Lawrence, Charlotte; Meyer, Odile; Wilson, Neil D; Hulme, Alison N

2017-05-14

The CuAAC 'click' reaction was used to couple alkyne-functionalized lanthanide-DOTA complexes to a range of fluorescent antennae. Screening of the antenna components was aided by comparison of the luminescent output of the resultant sensors using data normalized to account for reaction conversion as assessed by IR. A maximum 82-fold enhanced signal:background luminescence output was achieved using a Eu(III)-DOTA complex coupled to a coumarin-azide, in a reaction which is specific to the presence of copper(I). This optimized complex provides a new lead design for lanthanide-DOTA complexes which can act as irreversible 'turn-on' catalytic sensors for the detection of ligand-bound copper(I).

Optimizing the Readout of Lanthanide-DOTA Complexes for the Detection of Ligand-Bound Copper(I

Directory of Open Access Journals (Sweden)

Jill R. Hanna

2017-05-01

Full Text Available The CuAAC ‘click’ reaction was used to couple alkyne-functionalized lanthanide-DOTA complexes to a range of fluorescent antennae. Screening of the antenna components was aided by comparison of the luminescent output of the resultant sensors using data normalized to account for reaction conversion as assessed by IR. A maximum 82-fold enhanced signal:background luminescence output was achieved using a Eu(III-DOTA complex coupled to a coumarin-azide, in a reaction which is specific to the presence of copper(I. This optimized complex provides a new lead design for lanthanide-DOTA complexes which can act as irreversible ‘turn-on’ catalytic sensors for the detection of ligand-bound copper(I.

Study of copper and purine-copper complexes on modified carbon electrodes by cyclic and elimination voltammetry

Czech Academy of Sciences Publication Activity Database

Trnková, L.; Zerzánková, L.; Dyčka, F.; Mikelová, R.; Jelen, František

2008-01-01

Roč. 8, č. 1 (2008), s. 429-444 ISSN 1424-8220 R&D Projects: GA AV ČR(CZ) IAA100040602; GA AV ČR(CZ) IAA400040804 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : copper-purine complexes * paraffin-impregnated graphite electrode * mercury-film electrode Subject RIV: BO - Biophysics Impact factor: 1.870, year: 2008

Performances and improvement of copper-hydrazine complexation deoxidising resin

International Nuclear Information System (INIS)

Liu Fenfen; Zhang Hao; Sun Haijun; Liu Xiaojie

2012-01-01

Copper-hydrazine complexation deoxidising resin is tested to examine its performances including effluent water quality and capacity of deoxidisation. By the means of changing the resin type and regeneration, the deoxidising capacity of the resin can be improved to 13 times more than before. At the same time, physical performances of the resin are also greatly improved while maintaining its velocity of deoxidisation and effluent quality. (authors)

Copper(II) Schiff base complexes and their mixed thin layers with ...

Indian Academy of Sciences (India)

Thin layer; ZnO nanoparticles; copper complexes; AFM; SEM; fluorescence. 1. Introduction ... ZnO nanopowders29,30 and ZnO nanoparticles doped by different metal ...... Roy S, Choubey S, Bhar K, Khan S, Mitra P and Ghosh. B K 2013 J. Mol ...

Preparation of phenacylchloride, morpholinophenacyl and N-Piperidinophenacyl oximes and study of their complexation with Copper (II) and Cobalt (II) ions

International Nuclear Information System (INIS)

Ali, Kamal Eldin Ahmed

1999-01-01

The aim of the present work is to prepare phenacyl chloride oxime and phenacyl of N-Piperidine and morpholine derivatives, and mainly to study their complexes with Cu(II) and Co(II) ions with objective ascertaining that one of these ligands can be used in quantitative extraction of these metal ions from the aqueous solution. Copper (II) salts form 1:1 complexes with the phenyacyl oximes of N-piperidine and morpholine and 1:2 complex with phenacyl chloride oxime. However, cobalt(II) salts form 1:2 complexes with phenacyl oxime of N-piperidine and morpholine but does not complex with phenacyl chloride oxime. The stoichiometry of these complexes were determined by UV/VIS spectrophotometry using the mole ratio, continuous variation and slope ratio methods.The stability constants of the five complexes were calculated from aberrances using Job's method. They showed that the copper (II) and cobalt (II) complexes with N-piperidinophenacy oxime are more stable than those with morpholinophenacyl oxime. Copper (II) complexes with any of these two ligands are more stable than those of cobalt (II). IR spectra of the complexes of copper (II) and cobalt (II) with phenacyl oxime of N-piperidine and morpholine show diminished peaks of hydrogen bonds between N and O atoms of the ligand. Specific extractabilities using amylalcohol of copper (II) complexes with the three ligands increase from PH4 to reach its maximum at PH8. The high value for N-piperidinophenacyl oxime ligand (96%-97%) indicates that, this ligand can be used as analytical reagent for the quantitative spectrophotometric determination of copper (II) salts in aqueous media. Cobalt (II) complexes were formed and extracted from solution only at PH6 (specific PH). The extractabilities ranging from 81.6-87.2% warrants the use of these ligands in quantitative spectrophotometric determination of cobalt (II).(Author)

Distinctive EPR signals provide an understanding of the affinity of bis-(3-hydroxy-4-pyridinonato) copper(II) complexes for hydrophobic environments.

Science.gov (United States)

Rangel, Maria; Leite, Andreia; Silva, André M N; Moniz, Tânia; Nunes, Ana; Amorim, M João; Queirós, Carla; Cunha-Silva, Luís; Gameiro, Paula; Burgess, John

2014-07-07

In this work we report the synthesis and characterization of a set of 3-hydroxy-4-pyridinone copper(ii) complexes with variable lipophilicity. EPR spectroscopy was used to characterize the structure of copper(ii) complexes in solution, and as a tool to gain insight into solvent interactions. EPR spectra of solutions of the [CuL2] complexes recorded in different solvents reveal the presence of two copper species whose ratio depends on the nature of the solvent. Investigation of EPR spectra in the pure solvents methanol, dimethylsulfoxide, dichloromethane and their 50% (v/v) mixtures with toluene allowed the characterization of two types of copper signals (gzz = 2.30 and gzz = 2.26) whose spin-Hamiltonian parameters are consistent with solvated and non-solvated square-planar copper(ii) complexes. Regarding the potential biological application of ligands and complexes and to get insight into the partition properties in water-membrane interfaces, EPR spectra were also obtained in water-saturated octanol, an aqueous solution buffered at pH = 7.4 and liposome suspensions, for three compounds representative of different hydro-lipophilic balances. Analysis of the EPR spectra obtained in liposomes allowed establishment of the location of the complexes in the water and lipid phases. In view of the results of this work we put forward the use of EPR spectroscopy to assess the affinity of copper(ii) complexes for a hydrophobic environment and also to obtain indirect information about the lipophilicity of the ligands and similar EPR silent complexes.

Capacity of waters in the Magela Creek system, Northern Territory, to complex copper and cadmium

International Nuclear Information System (INIS)

Hart, B.T.; Davies, S.H.R.

1984-08-01

Two methods were used to determine the concentrations of copper-binding ligand (complexing capacity) and conditional formation constants for waters collected from the Magela Creek system, Northern Territory. These data are particularly important in estimating the concentrations of toxic forms of copper that may result from particular effluent discharge strategies from the Ranger uranium operation

Trinuclear ruthenium dioxolene complexes based on the bridging ligand hexahydroxytriphenylene: electrochemistry, spectroscopy, and near-infrared electrochromic behaviour associated with a reversible seven-membered redox chain.

Science.gov (United States)

Grange, Christopher S; Meijer, Anthony J H M; Ward, Michael D

2010-01-07

The trinuclear complexes [{(R2bipy)2Ru}3(mu3-HHTP)](PF6)3 [1(PF6)3, R = H; 2(PF6)3, R = 4-tBu] contain three {Ru(R2bipy)2}2+ fragments connected to the triangular tris-chelating ligand hexahydroxytriphenylene (H6HHTP). This bridging ligand contains three dioxolene-type binding sites, each of which can reversibly convert between dianionic catecholate (cat), monoanionic semiquinone (sq) or neutral quinone (q) redox states. The bridging ligand as a whole can therefore exist in seven different redox states from fully reduced [cat,cat,cat]6- through to fully oxidised, neutral [q,q,q]. Cyclic voltammetry of 1(PF6)3 in MeCN reveals six redox processes of which the three at more positive potentials (the sq/q couples) are reversible but the three at more negative potentials (the sq/cat couples) are irreversible with distorted wave shapes due to the insolubility of the reduced forms of the complex. In contrast, the more soluble complex 2(PF6)3 displays six reversible one-electron redox processes making all components of a seven-membered redox chain accessible. UV/Vis/NIR spectro-electrochemical studies reveal rich spectroscopic behaviour, with--in particular--very intense transitions in the near-IR region in many of the oxidation states associated with Ru(II)-->(dioxolene) MLCT and bridging ligand centred pi-pi* transitions. TDDFT calculations were used to analyse the electronic spectra in all seven oxidation states; the calculated spectra generally show very good agreement with experiment, which has allowed a fairly complete assignment of the low-energy transitions. The strong electrochromism of the complexes in the near-IR region has formed the basis of an optical window in which a thin film of 1(PF6)3 or 2(PF6)3 on a conductive glass surface can be reversibly and rapidly switched between redox states that alternate between strongly absorbing or near-transparent at 1100 nm, with--for 2(PF6)3--the switching being stable and reversible in water over thousands of cycles.

Valence-delocalization of the mixed-valence oxo-centered trinuclear iron propionates [FeIII2FeIIO(C2H5CO2)6(py)3[npy; n = 0, 1.5

International Nuclear Information System (INIS)

Nakamoto, Tadahiro; Katada, Motomi; Kawata, Satoshi; Kitagawa, Susumu; Sano, Hirotoshi; Konno, Michiko

1994-01-01

Mixed-valence trinuclear iron propionates [Fe III 2 Fe II O(C 2 H 5 CO 2 ) 6 (py) 3 [npy, where n = 0, 1.5, were synthesized and the structure of the pyridine-solvated complex was determined by single-crystal X-ray diffraction. Moessbauer spectra of the solvated propionate complex showed a temperature-dependent mixed-valence state related to phase transitions, reaching an almost delocalized valence state at room temperature. On the other hand, the non-solvated propionate showed a remarkable change of the spectral shape related to a phase transition, remaining in a localized valence state at higher temperatures up to room temperature. (orig.)

Preparation of CuO nanoparticles by thermal decomposition of double-helical dinuclear copper(II Schiff-base complexes

Directory of Open Access Journals (Sweden)

Aliakbar Dehno Khalaji

2015-12-01

Full Text Available In this paper, two double helical dinuclear copper(II complexes of bis-N,O-bidentate Schiff base ligands bis(3-methoxy-N-salicylidene-4,4'-diaminodiphenylsulfone (L1 and bis(5-bromo-N-salicylidene-4,4'-diaminodiphenylsulfone (L2 were prepared and characterized by elemental analyses (CHN, as well as thermal analysis. Elemental analyses (CHN suggested that the reaction between ligands and copper salt has been occurred in 1:1 molar ratio. In these complexes the Schiff base ligands behaves as an anionic and bis-bidentate chelate and is coordinated to the copper(II ion via two phenolic oxygen and two iminic nitrogen atoms. In these double helical dinuclear complexes, each copper(II center has a pseudo-tetrahedral coordination sphere two-wrapped ligands. Thermal analysis of ligands and their complexes were studied in the range of room temperature to 750 °C with a heating rate of 10 °C min-1. TG plots show that the ligands and their complexes are thermally decomposed via 2 and 3 thermal steps, respectively. In addition, the complexes thermally decomposed in air at 520 °C for 3 h. The obtained solids characterized by Fourier transform infrared spectroscopy (FT-IR, X-ray powder diffraction (XRD and transmission electron microscopy (TEM. The X-ray pattern result shows that the CuO nanoparticles are pure and single phase. The TEM result shows the as prepared CuO nanoparticles were very small and similar shape with particle size about

The oxidative p-dichlorobenzene dechlorinating in the presence of copper (ΙΙ complexes and nitrogen (ΙΙ, ΙV oxides

Directory of Open Access Journals (Sweden)

Valentina Yemelyanova

2012-12-01

Full Text Available The results of dechlorination in the solution CuCl2–TBP–NaNO2–О2–Н2О kinetics research are presented in the article. All system components influence to the dechlorination process is studied and quantitatively described. The composition of copper intermediate complexes participating in reaction is studied by the instrumentality of UV-spectroscopy. Established part of binuclear copper complexes in the catalytic intermediate complex constants of formation were estimated and compared with the kinetic and spectrophotometric methods. The composition of the intermediate complexes responsible for process is defined, the mechanism scheme is offered, the p-dichlorobenzene dechlorination limiting stage including redox-disintegration of the intermediate complex consisting of dimeric complex of copper (II, I chloride, nitrogen oxide and p-dichlorobenzene is defined.

Three-dimensional imaging of a complex concaved cuboctahedron copper sulfide crystal by x-ray nanotomography

International Nuclear Information System (INIS)

Chen Jie; Tian Jinping; Li Wenjie; Tian Yangchao; Wu Chunyan; Yu Shuhong

2008-01-01

By combining Fresnel zone-plate based transmission x-ray microscopy with computed tomography, the nanoscale features in materials with complex shapes can be imaged using synchrotron radiation. The tomographic data sets of a complex copper sulfide crystal were acquired in the angle range ±70 deg. at photon energy of 8.0 keV and then were reconstructed by a standard filtered-back-projection algorithm. This experiment shows the quantifiable three-dimensional information of the copper sulfide crystal, which offers a complete understanding of the concaved cuboctahedron structure with 14 faces comprising of six squares and eight triangles

Synthesis and physicochemical investigation of complexes of rare earth, alkaline earth elements and copper with some β-diketones

International Nuclear Information System (INIS)

Nichiporuk, R.V.; Pechurova, N.I.; Snezhko, N.I.; Martynenko, L.I.; Kaul', A.R.; Zanina, A.S.; Shergina, S.I.; Sokolov, I.E.

1991-01-01

Complexes of rare earth, alkaline earth elements and copper with 2-methoxy-2,6,6-trimethylheptanedion-3,5 as well as complexes of yttrium and barium with 2-methoxy-2,6-dimethylheptanedion-3,5 were synthesized. Prepared complexes were investigated by the methods of chemical, thermal, X-ray phase analyses, IR spectroscopy. Complex sublimation was studied at 10 -1 -10 -2 mm Hg. Complexes of rare earths and copper don't change their composition during sublimation, and sublimation of hydrated complexes of barium, strontium and calcium leads to formation of anhydrous complexes. All prepared complexes are able to transsublimate multiply and qualitatively without change of composition. All isolated complexes can be used for preparation of film oxide coatings by CVD method

Comparative study of copper(II)-curcumin complexes as superoxide dismutase mimics and free radical scavengers.

Science.gov (United States)

Barik, Atanu; Mishra, Beena; Kunwar, Amit; Kadam, Ramakant M; Shen, Liang; Dutta, Sabari; Padhye, Subhash; Satpati, Ashis K; Zhang, Hong-Yu; Indira Priyadarsini, K

2007-04-01

Two stoichiometrically different copper(II) complexes of curcumin (stoichiometry, 1:1 and 1:2 for copper:curcumin), were examined for their superoxide dismutase (SOD) activity, free radical-scavenging ability and antioxidant potential. Both the complexes are soluble in lipids and DMSO. The formation constants of the complexes were determined by voltammetry. EPR spectra of the complexes in DMSO at 77K showed that the 1:2 Cu(II)-curcumin complex is square planar and the 1:1 Cu(II)-curcumin complex is distorted orthorhombic. Cu(II)-curcumin complex (1:1) with larger distortion from square planar structure shows higher SOD activity. These complexes inhibit gamma-radiation induced lipid peroxidation in liposomes and react with DPPH acting as free radical scavengers. One-electron oxidation of the two complexes by radiolytically generated azide radicals in Tx-100 micellar solutions produced phenoxyl radicals, indicating that the phenolic moiety of curcumin in the complexes participates in free radical reactions. Depending on the structure, these two complexes possess different SOD activities, free radical neutralizing abilities and antioxidant potentials. In addition, quantum chemical calculations with density functional theory have been performed to support the experimental observations.

Voltammetric study of adenine complex with copper on mercury electrode

Czech Academy of Sciences Publication Activity Database

Jelen, František; Kouřilová, Alena; Hasoň, Stanislav; Kizek, R.; Trnková, L.

2009-01-01

Roč. 21, 3-5 (2009), s. 439-444 ISSN 1040-0397 R&D Projects: GA AV ČR(CZ) IAA100040602; GA AV ČR(CZ) IAA400040804; GA AV ČR(CZ) KAN200040651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : cyclic voltammetry * elimination voltammetry * copper-adenine complex Subject RIV: BO - Biophysics Impact factor: 2.630, year: 2009

A monomeric copper-phosphoramide complex: synthesis, structure, and electronic properties

Czech Academy of Sciences Publication Activity Database

Henriques, Margarida Isabel Sousa; Gorbunov, D.I.; Ponomaryov, A.Y.; Saneei, A.; Pourayoubi, M.; Dušek, Michal; Zvyagin, S.; Uhlarz, M.; Wosnitza, J.

2016-01-01

Roč. 118, Nov (2016), s. 154-158 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA14-03276S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : phosphoramide * magnetization * EPR * mononuclear copper complex * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.926, year: 2016

Investigation of gadolinium (3)-, calcium (2)- and copper (2) complexes with riboflavin in acetonitrile

International Nuclear Information System (INIS)

Lugina, L.N.

1984-01-01

Electron and IR spectra of gadolinium-(3), calcium (2), and copper (2) complexes with riboflavin (RF) in acetopitrile against the background of LiClO 4 x3H 2 O are studied. The way of RF coordination by the atom of metal is shown to depend on the nature of metal. Gadolinium (3) coordinates RF through N and O atoms; copper - through O metal, calcium - through O atom and, evidently, through hydroxyl groups of ribitol. Directions of RF line shifts of π-π * electron transitions at RF complexing with metals are compared with the calculated results and directions of RF line shifts during the formation of hydrogen bonds with different donor atoms of the isoalloxazine ring

Copper complexing ligands and organic matter characterization in the northern Adriatic Sea

Science.gov (United States)

Plavšić, Marta; Gašparović, Blaženka; Strmečki, Slađana; Vojvodić, Vjeročka; Tepić, Nataša

2009-11-01

The study on dissolved organic ligands capable to complex copper ions (L T), surface-active substances (SAS) and dissolved organic carbon (DOC) in the Northern Adriatic Sea station (ST 101) under the influence of Po River was conducted in period from 2006-2008. The acidity of surface-active organic material (Ac r) was followed as well. The results are compared to temperature and salinity distributions. On that way, the contribution of the different pools of ligands capable to complex Cu ions could be determined as well as the influence of aging and transformation of the organic matter. The L T values in the investigated period were in the range of 40-300 nmol l -1. The range of DOC values for surface and bottom samples were 0.84-1.87 mg l -1 and 0.80-1.30 mg l -1, respectively. Total SAS concentrations in the bottom layer were 0.045-0.098 mg l -1 in equiv. of Triton-X-100 while those in the surface layer were 0.050-0.143 mg l -1 in equiv. of Triton-X-100. The majority of organic ligands responsible for Cu binding in surface water originate from new phytoplankton production promoted by river borne nutrients. Older, transformed organic matter, possessing higher relative acidity, is the main contributor to the pool of organic ligands that bind copper in the bottom samples. It was estimated that ˜9% of DOC in surface samples and ˜12% of DOC in the bottom samples are present as ligands capable to complex copper ions.

Copper bis(diphosphine) complexes: radiopharmaceuticals for the detection of multi-drug resistance in tumours by PET

International Nuclear Information System (INIS)

Lewis, J.S.; Dearling, J.L.S.; Blower, P.J.; Sosabowski, J.K.; Zweit, J.; Carnochan, P.; Kelland, L.R.; Coley, H.M.

2000-01-01

Experience with imaging of the multi-drug resistance (MDR) phenotype in tumours using technetium-99m sestamibi, a substrate of the P-glycoprotein (Pgp) transporter, suggests that better quantification of images and separation of MDR from other variables affecting tracer uptake in tumours are required. One approach to these problems is the development of short half-life positron-emitting tracers which are substrates of Pgp. Several lipophilic cationic copper(I) bis(diphosphine) complexes labelled with copper-64 have been synthesised and evaluated in vitro as substrates for Pgp. The synthesis is rapid and efficient with no need for purification steps. The chemistry is suitable for use with very short half-life radionuclides such as copper-62 (9.7 min) and copper-60 (23.7 min). Incubation of the complexes with human serum in vitro showed that they are sufficiently stable in serum to support clinical imaging, and the more lipophilic members of the series are taken up rapidly by cells (Chinese hamster ovary and human ovarian carcinoma) in vitro with great avidity. Uptake in human ovarian carcinoma cells is significantly reduced after several months of conditioning in the presence of doxorubicin, which induces increased Pgp expression. Uptake in hooded rat sarcoma (HSN) cells, which express Pgp, is significantly increased in the presence of the MDR modulator cyclosporin A. Biodistribution studies in hooded rats show rapid blood clearance, excretion through both kidneys and liver, and low uptake in other tissues. The one complex investigated in HSN tumour-bearing rats showed uptake in tumour increasing up to 30 min p.i. while it was decreasing in other tissues. We conclude that diphosphine ligands offer a good basis for development of radiopharmaceuticals containing copper radionuclides, and that this series of complexes should undergo further evaluation in vivo as positron emission tomography imaging agents for MDR. (orig.)

Organically complexed copper, zinc, and chelating agents in the rivers of Western Puerto Rico

International Nuclear Information System (INIS)

Montgomery, J.R.; Echevarria, J.E.

1975-01-01

The method for determining soluble chelators gives their concentration in copper-equivalent chelating capacity units in fresh or slightly brackish (less than 3 percent salinity) water. The mean concentration of chelators in the Rio Guanajibo for December 1973 and January 1974 was 0.4 mg of copper per liter of water (N = 21, SD = 0.2) and for February 1974, 0.9 mg/liter (N = 8, SD = 0.4). The combined mean for the Rio Anasco and Culebrinas was 0.5 mg/liter (N = 7, SD = 0.4) in January and February 1974. The mean concentration of ionic copper was 0.5 μg/liter (N = 7, SD = 0.6) and of ionic zinc, 0.2 μg/liter (N = 8, SD = 0.1) in the Rio Guanajibo from November 1972 to February 1973. The concentration of organically bound copper was 0.3 μ/liter (N = 7, SD = 0.2) and that of organically bound zinc was 0.6 μg/liter (N = 8, SD = 0.6); this indicates that there was more than a sufficient quantity of chelator available in the river to complex all the soluble copper. The presence of a high ratio of Ca 2+ to Cu 2+ probably prevents the formation of larger concentrations of organically complexed copper. The mean concentration of chelating agents in the Guanajibo River seems to be directly related to the increased organic input from municipalities and a sugar mill. The concentration of chelators in tropical rivers appears to be higher than that found in Canadian lakes. The mean concentration for particulate organic carbon (POC) was 3653 μg atoms/liter (SD = 3653, N = 29). The dissolved reactive phosphate (DRP) ranged from a mean of 1.1 μg atom/liter. No significant correlation could be found between POC, DRP, and the concentration of chelators

Copper(II) Complexes of Phenanthroline and Histidine Containing Ligands: Synthesis, Characterization and Evaluation of their DNA Cleavage and Cytotoxic Activity.

Science.gov (United States)

Leite, Sílvia M G; Lima, Luís M P; Gama, Sofia; Mendes, Filipa; Orio, Maylis; Bento, Isabel; Paulo, António; Delgado, Rita; Iranzo, Olga

2016-11-21

Copper(II) complexes have been intensely investigated in a variety of diseases and pathological conditions due to their therapeutic potential. The development of these complexes requires a good knowledge of metal coordination chemistry and ligand design to control species distribution in solution and tailor the copper(II) centers in the right environment for the desired biological activity. Herein we present the synthesis and characterization of two ligands HL1 and H 2 L2 containing a phenanthroline unit (phen) attached to the amino group of histidine (His). Their copper(II) coordination properties were studied using potentiometry, spectroscopy techniques (UV-vis and EPR), mass spectrometry (ESI-MS) and DFT calculations. The data showed the formation of single copper complexes, [CuL1] + and [CuL2], with high stability within a large pH range (from 3.0 to 9.0 for [CuL1] + and from 4.5 to 10.0 for [CuL2]). In both complexes the Cu 2+ ion is bound to the phen unit, the imidazole ring and the deprotonated amide group, and displays a distorted square pyramidal geometry as confirmed by single crystal X-ray crystallography. Interestingly, despite having similar structures, these copper complexes show different redox potentials, DNA cleavage properties and cytotoxic activity against different cancer cell lines (human ovarian (A2780), its cisplatin-resistant variant (A2780cisR) and human breast (MCF7) cancer cell lines). The [CuL2] complex has lower reduction potential (E pc = -0.722 V vs -0.452 V for [CuL1] + ) but higher biological activity. These results highlight the effect of different pendant functional groups (carboxylate vs amide), placed out of the coordination sphere, in the properties of these copper complexes.

Synthesis, Structural Characterization, Antimicrobial Activity, and In Vitro Biocompatibility of New Unsaturated Carboxylate Complexes with 2,2'-Bipyridine.

Science.gov (United States)

Vasile Scăețeanu, Gina; Chifiriuc, Mariana Carmen; Bleotu, Coralia; Kamerzan, Crina; Măruţescu, Luminiţa; Daniliuc, Constantin G; Maxim, Cătălin; Calu, Larisa; Olar, Rodica; Badea, Mihaela

2018-01-12

The synthesis, structural characterization, cytotoxicity, and antimicrobial properties of four new complexes formed by employing acrylate anion and 2,2'-bipyridine are reported herein. X-ray crystallography revealed the trinuclear nature of [Mn₃(2,2'-bipy)₂(C₃H₃O₂)₆] ( 1 ), meanwhile complexes with general formula [M(2,2'-bipy)(C₃H₃O₂)₂(H₂O) x ]∙ y H₂O (( 2 ) M: Ni, x = 1, y = 0; ( 3 ) M: Cu, x = 1, y = 0; ( 4 ) M: Zn, x = 0, y = 1; 2,2'-bipy: 2,2'-bipyridine; C₃H₃O₂: acrylate anion) were shown to be mononuclear. The lowest minimum inhibitory concentration (MIC) of 128 μg mL -1 was recorded for all four tested complexes against Candida albicans , for complex ( 3 ) against Escherichia coli , and for complex ( 4 ) against Staphylocococcus aureus . Compounds ( 3 ) and ( 4 ) were also potent efflux pumps activity inhibitors (EPI), proving their potential for use in synergistic combinations with antibiotics. Complexes ( 1 )-( 4 ) revealed that they were not cytotoxic to HCT-8 cells. They also proved to interfere with the cellular cycle of tumour HCT-8 cells by increasing the number of cells found in the S and G2/M phases. Taken together, these results demonstrate the potential of zinc and copper complexes for use in the development of novel antimicrobial and anti-proliferative agents.

Quantum chemical and thermodynamic calculations of fulvic and humic copper complexes in reactions of malachite and azurite formation

International Nuclear Information System (INIS)

Fomin, Vitaliy N.; Gogol, Daniil B.; Rozhkovoy, Ivan E.; Ponomarev, Dmitriy L.

2017-01-01

This article provides a thermodynamic evaluation of the reactions of humic and fulvic acids in the process of malachite and azurite mineralogenesis. Semi-empirical methods AM/1, MNDO, PM3, PM5, PM6 and PM7 were used to compute the heat of formation, enthalpy and entropy for thermodynamic calculations of the reactions performed on the basis of Hess's law. It is shown that methods PM6 and PM7 in the MOPAC software package provide good compliance with experimental and calculated heats of formation for copper complexes and alkaline earth metal complexes with organic acids. It is found that the malachite and azurite formation processes involving humus complexing substances are thermodynamically possible. - Highlights: • Copper and alkali-earth metal complexes with humic and fulvic acids are considered. • Quantum chemical calculation of thermodynamics for the structures was performed. • Semi-empirical methods PM6 and PM7 provide best correlation for the properties. • Parameters of basic copper carbonate formation reactions were obtained by Hess's law. • Processes of malachite and azurite formation from humus complexes are possible.

Blue copper model complexes with distorted tetragonal geometry acting as effective electron-transfer mediators in dye-sensitized solar cells.

Science.gov (United States)

Hattori, Shigeki; Wada, Yuji; Yanagida, Shozo; Fukuzumi, Shunichi

2005-07-06

The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/)(-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(phen)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I(3)(-)/I(-) couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dmp)(2)](2+/+), and [Cu(SP)(mmt)](0/)(-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dmp)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I(3)(-)/I(-) couple.

Gadolinium-, Calcium-, copper- and zirc complexes with riboflavin in acetone and acetonitrile

International Nuclear Information System (INIS)

Lugina, L.N.; Romanenko, V.I.; Davidenko, N.K.

1983-01-01

Using the methods of solubility and spectrophotometry, stability copstants Of complexes RFMSSUp(n+) (RF=riboflavin, Mnsup(n+)=Cdsup(3+), Ca 2+ , Cu 2+ and Zn 2+ ) in acetone and acetonitrile against the background of 1 mol/l LiClO 4 x3H 2 O have been determined. It was found that stability of copper and zinc complexes with riboflavin in acetone is higher than in acetonitrile, whereas the stability of gadolinium and calcium complexes, on the contrary, is higher in acetonitrile than in acetone. It is shown that the character of the absorption spectrum change of riboflavin in complexing with metal ions depends on the nature of coordinating cation

Structure and spectroscopic properties of the dimeric copper(I) N-heterocyclic carbene complex [Cu₂(CNC(t-Bu))₂](PF₆)₂.

Science.gov (United States)

Riener, Korbinian; Pöthig, Alexander; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

2015-08-01

In recent years, the use of copper N-heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[μ-1,3-bis(3-tert-butylimidazolin-2-yliden-1-yl)pyridine]-1κ(4)C(2),N:N,C(2');2κ(4)C(2),N:N,C(2')-dicopper(I) bis(hexafluoridophosphate), [Cu2(C19H25N5)2](PF6)2, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N-heterocyclic carbene)pyridine, ligands. Each Cu(I) atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV-Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported.

Phosphorescent emissions of phosphine copper(I) complexes bearing 8-hydroxyquinoline carboxylic acid analogue ligands

Energy Technology Data Exchange (ETDEWEB)

Małecki, Jan G., E-mail: gmalecki@us.edu.pl [Department of Crystallography, Institute of Chemistry, University of Silesia, Szkolna 9 street, 40-006 Katowice (Poland); Łakomska, Iwona, E-mail: iwolak@chem.umk.pl [Department of Chemistry, Nicolaus Copernicus University, Toruń (Poland); Maroń, Anna [Department of Crystallography, Institute of Chemistry, University of Silesia, Szkolna 9 street, 40-006 Katowice (Poland); Szala, Marcin [Institute of Chemistry, University of Silesia, ul. Szkolna 9, 40-006 Katowice (Poland); Fandzloch, Marzena [Department of Chemistry, Nicolaus Copernicus University, Toruń (Poland); Nycz, Jacek E., E-mail: jacek.nycz@us.edu.pl [Institute of Chemistry, University of Silesia, ul. Szkolna 9, 40-006 Katowice (Poland)

2015-05-15

The pseudotetrahedral complexes of [Cu(PPh{sub 3}){sub 2}(L)], where L=8-hydroxy-2-methylquinoline-7-carboxylic acid (1), 8-hydroxy-2,5-dimethylquinoline-7-carboxylic acid (2) or 5-chloro-8-hydroxy-2-methylquinoline-7-carboxylic acid (3) have been synthesized and structurally characterized by X-ray crystallography. Their properties have been examined through combinations of IR, NMR, electronic absorption spectroscopy and cyclic voltammetry. The complexes exhibit extraordinary photophysical properties. Complex (1) in solid state exhibits an emission quantum yield of 4.67% and an excited life time of 1.88 ms (frozen DCM solution up to 6.7 ms). When dissolved in a coordinating solvent (acetonitrile) the charge transfer emission was quenched on a microsecond scale. - Highlights: • Synthesis of copper(I) complexes with 8-hydroxyquinoline carboxylic acid ligands. • Very long lived phosphorescent copper(I) complexes. • [Cu(PPh{sub 3}){sub 2}(L)] where L=8-hydroxy-2-methylquinoline-7-carboxylic acid luminesce in the solid state exhibits extremely long lifetime on millisecond scale (1.9 ms). • In frozen MeOH:EtOH solution lifetime increases to 7 ms. • Quantum efficiency equal to 4.7%.

Structural influence in the interaction of cysteine with five coordinated copper complexes: Theoretical and experimental studies

Science.gov (United States)

Huerta-Aguilar, Carlos Alberto; Thangarasu, Pandiyan; Mora, Jesús Gracia

2018-04-01

Copper complexes of N,N,N‧,N‧-tetrakis(pyridyl-2-ylmethyl)-1,2-diaminoethane (L1) and N,N,N‧,N‧-tetrakis(pyridyl-2-ylmethyl)-1,3-diaminopropane (L2) prepared were characterized completely by different analytical methods. The X-structure of the complexes shows that Cu(II) presents in trigonal bi-pyramidal (TBP) geometry, consisting with the electronic spectra where two visible bands corresponding to five coordinated structure were observed. Thus TD-DFT was used to analyze the orbital contribution to the electronic transitions for the visible bands. Furthermore, the interaction of cysteine with the complexes was spectrally studied, and the results were explained through DFT analysis, observing that the geometrical parameters and oxidation state of metal ions play a vital role in the binding of cysteine with copper ion. It appears that the TBP structure is being changed into octahedral geometry during the addition of cysteine to the complexes as two bands (from complex) is turned to a broad band in visible region, signifying the occupation of cysteine molecule at sixth position of octahedral geometry. In the molecular orbital analysis, the existence of a strong overlapping of HOMOs (from cysteine) with LUMOs of Cu ion was observed. The total energy of the systems calculated by DFT shows that cysteine binds favorably with copper (I) than that with Cu(II).

Intralesional copper wire retention and pingyangmycin injection: an effective combinational therapy for complex venous malformation in soft tissue.

Science.gov (United States)

Yuan, S-M; Hong, Z-J; Jiang, H-Q; Wang, J; Hu, X-B

2014-04-01

Complex venous malformations (VMs) may extensively involve the soft tissue. The treatment remains a challenge till now. Here we introduce a combinational therapy of copper wires and pingyangmycin (bleomycin A5,PYM). Copper wires were retained in VMs by repeated penetration with a straight needle. Subsequently, PYM solution was injected into the lesion. Eight to 10 days later, copper wires were removed. The dressing was changed every day until the puncture pores healed. Magnetic resonance imaging scanning was performed to observe the change of VMs. From January 2001 to December 2011, 56 patients were treated. During the follow-up period, most of the VMs shrunk obviously. The symptoms were relieved or disappeared. The complications included local pain, temporary paraesthesia and moderate fever, which disappeared quickly after the removal of copper wires. This combinational therapy is a safe and effective approach for the complex VMs in soft tissue.

The effect of pH and storage on copper speciation and bacterial growth in complex growth media

DEFF Research Database (Denmark)

Hasman, Henrik; Bjerrum, Morten J.; Christiansen, Lasse Engbo

2009-01-01

correlation between the free copper concentration and bacterial growth, than for the total copper concentration and growth. Furthermore, it is shown that the initial pH influences the amount of free copper ions in the media and that this has a direct effect on the ability of bacterial cultures to grow......In this paper we examine how the bacterial growth is influenced by the availability of copper ions in complex Mueller Hinton growth media. The data shows that the free copper concentration is seven to eight orders of magnitude lower the total copper concentration and that there seems to be a better....... However, there still remains an effect of pH on bacterial growth which cannot be attributed to the influence of the Cu2+ concentration alone. The study also shows that the sterilization treatment can have some effect on the availability of copper ions in the media over time. Freshly autoclaved and sterile...

Induction of Laccase, Lignin Peroxidase and Manganese Peroxidase Activities in White-Rot Fungi Using Copper Complexes

Directory of Open Access Journals (Sweden)

Martina Vrsanska

2016-11-01

Full Text Available Ligninolytic enzymes, such as laccase, lignin peroxidase and manganese peroxidase, are biotechnologically-important enzymes. The ability of five white-rot fungal strains Daedaleopsis confragosa, Fomes fomentarius, Trametes gibbosa, Trametes suaveolens and Trametes versicolor to produce these enzymes has been studied. Three different copper(II complexes have been prepared ((Him[Cu(im4(H2O2](btc·3H2O, where im = imidazole, H3btc = 1,3,5-benzenetricarboxylic acid, [Cu3(pmdien3(btc](ClO43·6H2O and [Cu3(mdpta3(btc](ClO43·4H2O, where pmdien = N,N,N′,N′′,N′′-pentamethyl-diethylenetriamine and mdpta = N,N-bis-(3-aminopropylmethyl- amine, and their potential application for laccase and peroxidases induction have been tested. The enzyme-inducing activities of the complexes were compared with that of copper sulfate, and it has been found that all of the complexes are suitable for the induction of laccase and peroxidase activities in white-rot fungi; however, the newly-synthesized complex M1 showed the greatest potential for the induction. With respect to the different copper inducers, this parameter seems to be important for enzyme activity, which depends also on the fungal strains.

Complex strain paths in polycrystalline copper: microstructural aspects

Directory of Open Access Journals (Sweden)

M.F. Vieira

1999-07-01

Full Text Available Microstructural aspects of polycrystalline copper sheets subjected to complex strain paths were analysed in this work. Dislocation structures developed during the strain paths (rolling and tension and the evolution of this microstructure during reloading have been studied. The active slip systems developed in each strain path were used to explain the microstructural evolution. The heterogeneous surface deformation observed on polished tensile specimens prestrained in rolling was also analysed. The structural aspects are related with the mechanical behaviour of the material, namely with the increase in yield stress in reloading, the work hardening evolution and the premature occurrence of plastic instability for some prestrain values.

Formation of complexes between functionalized chitosan membranes and copper: A study by angle resolved XPS

Energy Technology Data Exchange (ETDEWEB)

Jurado-López, Belén [Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Málaga, 29071 Málaga (Spain); Vieira, Rodrigo Silveira [Chemical Engineering Department, Universidade Federal do Ceará, UFC, 60455-760 Fortaleza, CE (Brazil); Rabelo, Rodrigo Balloni; Beppu, Marisa Masumi [School of Chemical Engineering, University of Campinas, UNICAMP, P.O. Box 6066, 13081-970 Campinas, SP (Brazil); Casado, Juan [Departamento de Química-Física, Facultad de Ciencias, Universidad de Málaga, 29071 Málaga (Spain); Rodríguez-Castellón, Enrique, E-mail: castellon@uma.es [Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Málaga, 29071 Málaga (Spain)

2017-01-01

Chitosan is a biopolymer with potential applications in various fields. Recently, it has been used for heavy metals removal like copper, due to the presence of amino and hydroxyl groups in its structure. Chitosan membranes were crosslinked with epichlorohydrin and bisoxirano and functionalized with chelating agents, such as iminodiacetic acid, aspartic acid and tris-(2-amino-ethyl) polyamine. These membranes were used for copper adsorption and the formed complexes were characterized. Thermal and crystalline properties of chitosan membranes were studied by TG-DCS and X-ray diffraction. Raman, XPS and FT-IR data confirmed that copper is linked to the modified chitosan membranes by the amino groups. The oxidation state of copper-chitosan membranes were also studied by angle resolved XPS, and by UV–Vis diffuse reflectance spectroscopy. - Highlights: • Chitosan membranes were crosslinked with epichlorohydrin and bisoxirano and functionalized with chelating agents. • The chelating agent were iminodiacetic acid, aspartic acid and tris-(2-amino-ethyl) polyamine. • The functionalized membranes were used for copper adsorption and studied by ARXPS, Raman, TG-DCS, FT-IR and XRD. • Spectroscopic data confirmed that copper is linked to the modified chitosan membranes by the amino groups.

Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

Science.gov (United States)

Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

2010-06-28

With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

Antimicrobial mechanism of copper (II 1,10-phenanthroline and 2,2′-bipyridyl complex on bacterial and fungal pathogens

Directory of Open Access Journals (Sweden)

S. Chandraleka

2014-12-01

Full Text Available Copper based metallo drugs were prepared and their antibacterial, antifungal, molecular mechanism of [Cu(SAlaPhen]·H2O and [Cu(SAlabpy]·H2O complexes were investigated. The [Cu(SAlaPhen]·H2O and [Cu(SAlabpy]·H2O were derived from the Schiff base alanine salicylaldehyde. [Cu(SAlaPhen]·H2O showed noteworthy antibacterial and antifungal activity than the [Cu(SAlabpy]·H2O and ligand alanine, salicylaldehyde. The [Cu(SAlaPhen]·H2O complex showed significant antibacterial activity against Salmonella typhi, Staphylococcus aureus, Salmonella paratyphi and the antifungal activity against Candida albicans and Cryptococcus neoformans in well diffusion assay. The mode of action of copper (II complex was analyzed by DNA cleavage activity and in silico molecular docking. The present findings provide important insight into the molecular mechanism of copper (II complexes in susceptible bacterial and fungal pathogens. These results collectively support the use of [Cu(SAlaPhen]·H2O complex as a suitable drug to treat bacterial and fungal infections.

EPR studies on binuclear copper(II) complexes with N,N',N'',N'''-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraaza-cyclotetradecane in solutions

International Nuclear Information System (INIS)

Jezierska, J.; Ozarowski, A.; Vuckovic, G.

1997-01-01

Binuclear copper(II) complexes of macrocyclic ligand TMPC (tetraazamacrocycle with four pendant 2-pirydylmethyl groups attached to the ring nitrogen atoms) with various anions forming bridge between copper ions, or coordinating to copper(II) ions at the apex, were prepared and their frozen solutions in DMF and NMF were investigated by EPR. The spectroscopic results have been interpreted in terms of molecular structure of investigated complexes

Spontaneous and Directional Bubble Transport on Porous Copper Wires with Complex Shapes in Aqueous Media.

Science.gov (United States)

Li, Wenjing; Zhang, Jingjing; Xue, Zhongxin; Wang, Jingming; Jiang, Lei

2018-01-24

Manipulation of gas bubble behaviors is crucial for gas bubble-related applications. Generally, the manipulation of gas bubble behaviors generally takes advantage of their buoyancy force. It is very difficult to control the transportation of gas bubbles in a specific direction. Several approaches have been developed to collect and transport bubbles in aqueous media; however, most reliable and effective manipulation of gas bubbles in aqueous media occurs on the interfaces with simple shapes (i.e., cylinder and cone shapes). Reliable strategies for spontaneous and directional transport of gas bubbles on interfaces with complex shapes remain enormously challenging. Herein, a type of 3D gradient porous network was constructed on copper wire interfaces, with rectangle, wave, and helix shapes. The superhydrophobic copper wires were immersed in water, and continuous and stable gas films then formed on the interfaces. With the assistance of the Laplace pressure gradient between two bubbles, gas bubbles (including microscopic gas bubbles) in the aqueous media were subsequently transported, continuously and directionally, on the copper wires with complex shapes. The small gas bubbles always moved to the larger ones.

Validation data supporting the characterization of novel copper complexes as anticancer agents

Directory of Open Access Journals (Sweden)

Ceyda Acilan

2016-12-01

Full Text Available Three copper(II complexes, Cu(Sal-Gly(phen, Cu(Sal-Glypheamine, Cu(Sal-Glyphepoxy were synthesized and characterized for their anticancer properties and mechanism of action (Acilan et al., in press [1]. Here, we provide supporting data on colon cancer cell lines complementing our previous findings in cervix cells. This paper also contains a data table for the fold changes and p-values of all genes analyzed in this study via a custom RT-qPCR array. All compounds induced DNA damage (based on 8-oxo-guanidine, ɣH2AX staining in cells and apoptosis (based on elevated DNA condensation/fragmentation, Annexin V staining, caspase 3/7 activity and mitochondrial membrane depolarization in HCT-116 colon cancer cells. The increase in oxidative stress was also further confirmed in these cells. Further interpretation of the data presented here can be found in the article entitled “Synthesis, biological characterization and evaluation of molecular mechanisms of novel copper complexes as anticancer agents” (Acilan et al., in press [1].

Synthesis and complexation of acyclic dithiolate ligands

International Nuclear Information System (INIS)

Ashford, L.

1999-11-01

-[N,N'-bis(p-nitro-o-mereaptobenzyliden)propylenediaminate, Copper- [N,N'-bis(p-nitro-o-mercaptobenzyliden)propylenediaminate and Nickel-[N,N'-bis(o-mercaptobenzyliden)propylenediaminate] are analysed. Comparison of the data of the Ni(II) species show the major effects of the para-nitro group arise from electron withdrawal from the thiolate donors. The synthesis and complexation of the (2-mercaptomethyl)thiophenolato series of ligands, via the corresponding (2-hydroxymethyl)thiophenolato compounds, is detailed. Removal of β-elimination pathways by use of an o-xylyl linker allows the synthesis of α,α'-di[(2-mercaptomethyl)thiophenolato]-o-xylene. Reaction of α,α'-di[(2-mercaptomethyl)thiophenolato]-o-xylene with Group 10 metal ions Ni(II) and Pd(ll) monomers and a Pt(ll) trinuclear complex. Potential causes of the broad and featureless resonances in the 1 H NMR spectra of the complexes are investigated. The Ni(II) and Pd(ll) monomers are reacted with Pt(ll) salts to give trinuclear species. (author)

Template synthesis of poly aza macrocyclic copper(II) and nickel(II) complexes: Spectral characterization and antimicrobial studies

Energy Technology Data Exchange (ETDEWEB)

Gurumoorthy, P.; Ravichandran, J.; Kaliur Rahiman, A. [The New College, Chennai (India); Karthikeyan, N.; Palani, P. [Univ. of Madras, Chennai (India)

2012-07-15

The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-amino propylamino)ethane produce the 12-membered N{sub 3}O and 17-membered N{sub 4}O macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear N{sub 3}O and N{sub 4}O copper(II) complexes show one irreversible one electron reduction wave at E{sup pc} = .1.35 and .1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at E{sup pc} = .1.25 and .1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at Epa = +0.84 and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

High stability and biological activity of the copper(II) complexes of alloferon 1 analogues containing tryptophan.

Science.gov (United States)

Kadej, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Urbański, Arkadiusz; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2016-10-01

Copper(II) complex formation processes between the alloferon 1 (Allo1) (HGVSGHGQHGVHG) analogues where the tryptophan residue is introducing in the place His residue H1W, H6W, H9W and H12W have been studied by potentiometric, UV-visible, CD and EPR spectroscopic, and MS methods. For all analogues of alloferon 1 complex speciation have been obtained for a 1:1 metal-to-ligand molar ratio and 2:1 of H1W because of precipitation at higher (2:1, 3:1 and 4:1) ratios. At physiological pH7.4 and a 1:1 metal-to-ligand molar ratio the tryptophan analogues of alloferon 1 form the CuH -1 L and/or CuH -2 L complexes with the 4N binding mode. The introduction of tryptophan in place of histidine residues changes the distribution diagram of the complexes formed with the change of pH and their stability constants compared to the respective substituted alanine analogues of alloferon 1. The CuH -1 L, CuH -2 L and CuH -3 L complexes of the tryptophan analogues are more stable from 1 to 5 log units in comparison to those of the alanine analogues. This stabilization of the complexes may result from cation(Cu(II))-π and indole/imidazole ring interactions. The induction of apoptosis in vivo, in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 was studied. The biological results show that copper(II) ions in vivo did not cause any apparent apoptotic features. The most active were the H12W peptide and Cu(II)-H12W complex formed at pH7.4. Copyright © 2016 Elsevier Inc. All rights reserved.

Fabrication of Chitosan-complexed Electrode and Evaluation of Its Efficiency in Removal of Copper Ion from Aqueous Solution

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Yoon Young-Chan

2016-01-01

Full Text Available In this study, we fabricated chitosan/PVA/activated carbon complexed electrode to remove copper ion from aqueous solution. The prepared composite electrode was analyzed by BET and SEM to investigate its physicochemical properties. Electrochemical properties of prepared composite electrodes were analyzed via cyclic voltammetry. Adsorption performance of copper ion on chitosan composite complexed electrodes was evaluated. Almost similar pore size distribution results were observed in the series of ACP not included electrodes while observed differences in pore size distribution for the ACP included one. Cyclic voltammetry results exhibited that oxidation-reduction reaction does not occur in a potential range of -1.0 ~ 1.0 V. The amount of copper ion during adsroption reaction is increase according to increase of adsorption potential to 1.0 V.

Trialkylphosphine-stabilized copper(I) gallium(III) phenylchalcogenolate complexes: crystal structures and generation of ternary semiconductors by thermolysis.

Science.gov (United States)

Kluge, Oliver; Krautscheid, Harald

2012-06-18

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R(3)P)(m)Cu(n)Me(2-x)Ga(EPh)(n+x+1)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga-E bonds are relatively rigid, in contrast to flexible Cu-E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga-E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga-E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE(2). The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me(3)Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors.

Voltammetry and single-molecule in situ scanning tunneling microscopy of laccases and bilirubin oxidase in electrocatalytic dioxygen reduction on Au(111) single-crystal electrodes

DEFF Research Database (Denmark)

Climent, Victor; Zhang, Jingdong; Friis, Esben Peter

2012-01-01

Laccases (E.C. 1.10.3.2) are multicopper oxidases catalytically active in the oxidation of diphenolics and related compounds by molecular dioxygen. The laccases contain a single-copper type I center and a trinuclear cluster of a single-copper type II and a dinuclear type III center. The oxidation...

Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes.

Science.gov (United States)

Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas

2013-12-15

The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

Geometric control of nuclearity in copper(I)/dioxygen chemistry.

Science.gov (United States)

Abe, Tsukasa; Morimoto, Yuma; Tano, Tetsuro; Mieda, Kaoru; Sugimoto, Hideki; Fujieda, Nobutaka; Ogura, Takashi; Itoh, Shinobu

2014-08-18

Copper(I) complexes supported by a series of N3-tridentate ligands bearing a rigid cyclic diamine framework such as 1,5-diazacyclooctane (L8, eight-membered ring), 1,4-diazacycloheptane (L7, seven-membered ring), or 1,4-diazacyclohexane (L6, six-membered ring) with a common 2-(2-pyridyl)ethyl side arm were synthesized and their reactivity toward O2 were compared. The copper(I) complex of L8 preferentially provided a mononuclear copper(II) end-on superoxide complex S as reported previously [Itoh, S., et al. J. Am. Chem. Soc. 2009, 131, 2788-2789], whereas a copper(I) complex of L7 gave a bis(μ-oxido)dicopper(III) complex O at a low temperature (-85 °C) in acetone. On the other hand, no such active-oxygen complex was detected in the oxygenation reaction of the copper(I) complex of L6 under the same conditions. In addition, O2-reactivity of the copper(I) complex supported by an acyclic version of the tridentate ligand (LA, PyCH2CH2N(CH3)CH2CH2CH2N(CH3)2; Py = 2-pyridyl) was examined to obtain a mixture of a (μ-η(2):η(2)-peroxido)dicopper(II) complex (S)P and a bis(μ-oxido)dicopper(III) complex O. Careful inspection of the crystal structures of copper(I) and copper(II) complexes and the redox potentials of copper(I) complexes has revealed important geometric effects of the supporting ligands on controlling nuclearity of the generated copper active-oxygen complexes.

Dimeric Self-assembling via Hydrogen Bonding and Emissive Behavior of a New Copper (I Complex

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Juciely M. dos Reis

2017-04-01

Full Text Available This work describes the synthesis, structural characterization and emissive behavior of a new copper (I complex based on 1-thiocarbamoyl-5-(4-methoxiphenyl-3-phenyl-4,5-dihydro-1H-pyrazole ligand. A dimeric self-assembling via hydrogen bonding was determined by analyzing the short contacts present in the solid-state structure by means of X-ray crystallography. The spectroscopic properties were determined using UV-Vis and fluorescence experiments and an interesting behavior as bluish luminescence was assigned mainly to the mixed (MLCT + IL electronic transitions of the Cu(Id10 ® (S=C–Nligand type. The complete characterization of the new copper (I complex also included elemental analyses and IR spectroscopy. DOI: http://dx.doi.org/10.17807/orbital.v9i1.952

Polynuclear complexes of copper(I) halides: coordination chemistry and catalytic transformations of alkynes

International Nuclear Information System (INIS)

Mykhalichko, B M; Mys'kiv, M G; Temkin, Oleg N

2000-01-01

Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H 2 O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH 2 OH, CH=CH 2 , etc.) are analysed based on studies of the compositions and structures of copper(I) chloride (bromide) complexes, alkyne π-complexes and ethynyl organometallic polynuclear compounds formed in this system in solutions and in the crystalline state. The role of polynuclear complexes in various reactions of alkynes is discussed. The bibliography includes 149 references.

Synthesis, crystal structure and DFT studies of a novel dinuclear copper(I) complex with triphenylphosphine and 2-mercaptonicotinic acid

Science.gov (United States)

Ahmad, Tayyaba; Mahmood, Rashid; Georgieva, Ivelina; Zahariev, Tsvetan; Tahir, Muhammad Nawaz; Shaheen, Muhammad Ashraf; Gilani, Mazhar Amjad; Ahmad, Saeed

2018-02-01

A novel dinuclear copper(I) complex, {[Cu2(Mnt)2(PPh3)2Cl2].2H2O.CH3CN}2 (1) (Mnt = Mercaptonicotinic acid, PPh3 = triphenylphosphine) was prepared and its structure was determined by X-ray crystallography. The complex 1 consists of two dinuclear molecules and in each molecule, the two copper atoms are bridged by S atoms of N-protonated mercaptonicotinic acid forming a four-membered ring. The planar Cu2S2 core is characterized by significant cuprophilic interactions (Cusbnd Cu distance = 2.7671(8), 2.8471(8) Å). Each copper atom in 1 is coordinated by two sulfur atoms of Mnt, one phosphorus atom of PPh3 and a chloride ion adopting a tetrahedral geometry. The calculated Gibbs energies for reaction in CH3CN supported the experimental structure and predicted more favorable formation of dinuclear Cu(I) complex as compared to the mononuclear Cu(I) complex. The dinuclear complex is stabilized by 65.98 kJ mol-1 by coupling of two mononuclear Cu(I) complexes. The IR spectra of 1 and Mnt ligand were reliably interpreted and the Mnt vibrations, which are sensitive to the ligand coordination to Cu(I) ion in 1 were selected with the help of DFT/ωB97XD calculations.

Synthesis, characterization, DNA binding and cleavage studies of mixed-ligand copper (II complexes

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M. Sunita

2017-05-01

Full Text Available New two copper complexes of type [Cu(Bzimpy(LH2O]SO4 (where L = 2,2′ bipyridine (bpy, and ethylene diamine (en, Bzimpy = 2,6-bis(benzimidazole-2ylpyridine have been synthesized and characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, IR, electronic and EPR spectral studies. Based on elemental and spectral studies six coordinated geometries were assigned to the two complexes. DNA-binding properties of these metal complexes were investigated using absorption spectroscopy, fluorescence spectroscopy, viscosity measurements and thermal denaturation methods. Experimental studies suggest that the complexes bind to DNA through intercalation. These complexes also promote the cleavage of plasmid pBR322, in the presence of H2O2.

Towards a selective adsorbent for arsenate and selenite in the presence of phosphate: Assessment of adsorption efficiency, mechanism, and binary separation factors of the chitosan-copper complex.

Science.gov (United States)

Yamani, Jamila S; Lounsbury, Amanda W; Zimmerman, Julie B

2016-01-01

The potential for a chitosan-copper polymer complex to select for the target contaminants in the presence of their respective competitive ions was evaluated by synthesizing chitosan-copper beads (CCB) for the treatment of (arsenate:phosphate), (selenite:phosphate), and (selenate:sulfate). Based on work by Rhazi et al., copper (II) binds to the amine moiety on the chitosan backbone as a monodentate complex (Type I) and as a bidentate complex crosslinking two polymer chains (Type II), depending on pH and copper loading. In general, the Type I complex exists alone; however, beyond threshold conditions of pH 5.5 during synthesis and a copper loading of 0.25 mol Cu(II)/mol chitosan monomer, the Type I and Type II complexes coexist. Subsequent chelation of this chitosan-copper ligand to oxyanions results in enhanced and selective adsorption of the target contaminants in complex matrices with high background ion concentrations. With differing affinities for arsenate, selenite, and phosphate, the Type I complex favors phosphate chelation while the Type II complex favors arsenate chelation due to electrostatic considerations and selenite chelation due to steric effects. No trend was exhibited for the selenate:sulfate system possibly due to the high Ksp of the corresponding copper salts. Binary separation factors, α12, were calculated for the arsenate-phosphate and selenite-phosphate systems, supporting the mechanistic hypothesis. While, further research is needed to develop a synthesis method for the independent formation of the Type II complexes to select for target contaminants in complex matrices, this work can provide initial steps in the development of a selective adsorbent. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interpretation of the Electron Paramagnetic Resonance Spectra of Copper(II)-Tyrosine Complex

Science.gov (United States)

Xu, Xiao-Hui; Kuang, Min-Quan

2017-12-01

The electron paramagnetic resonance (EPR) spectra of [Cu(l-tyrosine)2]n (CuA) were interpreted based on the fourth-order perturbation treatments where the contributions due to the local distortion, ligand orbit and spin-orbit coupling were included. The calculated band transitions d_{x^2} - y^2 to dxy (≈16412 cm-1) and d_{z^2} (≈14845 cm-1) agree well with the band analysis results (d_{x^2} - y^2 \\to d_{xy} ≈16410 and d_{x^2} - y^2 \\to d_{z^2} ≈14850 cm-1). The unresolved separations d_{x^2} - y^2 \\to d_{xz} and d_{x^2} - y^2 \\to d_{yz} in the absorption spectra were evaluated as 26283 and 26262 cm-1, respectively. For CuA, copper chromophores in 1,3-diaminorpropane isophtalate copper(II) complex (CuB) and N-methyl-1,2-diaminoetaane-bis copper(II) polymer (CuC), the transition d_{x^2} - y^2 \\to d_{xy} (=E1≈10Dq) suffered an increase with a decrease in R̅L which was evaluated as the mean value of the copper-ligand bond lengths. The correlations between the tetragonal elongation ratio ρ (=(Rz-R̅L)/R̅L) (or the ratio G=(gz-ge)/((gx+gy)/2-ge)) and the g isotropy gav (=(gx+gy+gz)/3) (or the covalency factor N) for CuA, CuB and CuC were acquired and all the results were discussed.

Synthesis, Structural Characterization, Antimicrobial Activity, and In Vitro Biocompatibility of New Unsaturated Carboxylate Complexes with 2,2′-Bipyridine

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Gina Vasile Scăețeanu

2018-01-01

Full Text Available The synthesis, structural characterization, cytotoxicity, and antimicrobial properties of four new complexes formed by employing acrylate anion and 2,2′-bipyridine are reported herein. X-ray crystallography revealed the trinuclear nature of [Mn3(2,2′-bipy2(C3H3O26] (1, meanwhile complexes with general formula [M(2,2′-bipy(C3H3O22(H2Ox]∙yH2O ((2 M: Ni, x = 1, y = 0; (3 M: Cu, x = 1, y = 0; (4 M: Zn, x = 0, y = 1; 2,2′-bipy: 2,2′-bipyridine; C3H3O2: acrylate anion were shown to be mononuclear. The lowest minimum inhibitory concentration (MIC of 128 μg mL−1 was recorded for all four tested complexes against Candida albicans, for complex (3 against Escherichia coli, and for complex (4 against Staphylocococcus aureus. Compounds (3 and (4 were also potent efflux pumps activity inhibitors (EPI, proving their potential for use in synergistic combinations with antibiotics. Complexes (1–(4 revealed that they were not cytotoxic to HCT-8 cells. They also proved to interfere with the cellular cycle of tumour HCT-8 cells by increasing the number of cells found in the S and G2/M phases. Taken together, these results demonstrate the potential of zinc and copper complexes for use in the development of novel antimicrobial and anti-proliferative agents.

Copper(II) complexes of methimazole, an anti Grave's disease drug. Synthesis, characterization and its potential biological behavior as alkaline phosphatase inhibitor.

Science.gov (United States)

Urquiza, Nora M; Manca, Silvia G; Moyano, María A; Dellmans, Raquel Arrieta; Lezama, Luis; Rojo, Teófilo; Naso, Luciana G; Williams, Patricia A M; Ferrer, Evelina G

2010-04-01

Methimazole (MeimzH) is an anti-thyroid drug and the first choice for patients with Grave's disease. Two new copper(II) complexes of this drug: [Cu(MeimzH)(2)(NO(3))(2)]*0.5H(2)O and [Cu(MeimzH)(2)(H(2)O)(2)](NO(3))(2)*H(2)O were synthesized and characterized by elemental analysis, dissolution behavior, thermogravimetric analysis and UV-vis, diffuse reflectance, FTIR and EPR spectroscopies. As it is known that copper(II) cation can act as an inhibitor of alkaline phosphatase (ALP), the inhibitory effect of methimazole and its copper(II) complexes on ALP activity has also been investigated.

Investigation into cobalt, copper and vanadium complexes with phenylbenzimidazolylazoketoxime and o-phenanthroline

Energy Technology Data Exchange (ETDEWEB)

Dubinina, L F; Lipunova, G N; Medvedeva, L I; Mertsalov, S L [Ural' skij Politekhnicheskij Inst., Sverdlovsk (USSR)

1983-01-01

Complex formation of phenylbenzimidozolylazoketoxime (PhBAKO) with Co(2), Cu(2) and V(5) ions in aqueous-ethanol medium at different pH values, is investigated. In aqueous-ethanol medium PhBAKO forms coloured complexes. Reagent has a low selectivity under these conditions. It is found that the addition of phenanthroline not only increases the contrast of the reaction but considerably increases its selectivity. The optimum range of pH value of complex formation for vanadium is 6.0-8.2. A high selectivity of PhBAKO and the contrast nature of complex formation reaction of the reagent with cobalt copper and vanadium ions, different stability of complexes in the acidic medium have permitted to develop the photometric method of determination of these elements in natural waters in the case of their mutual presence. The limit of vanadium detection is 0.01 ..mu..g/ml.

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu-(cytidine) and Cu-(uridine)

Science.gov (United States)

Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H.; Guevara-García, Alfredo; Martínez, Ana

2011-02-01

The copper-nucleoside anions, Cu-(cytidine) and Cu-(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu-(cytidine) and Cu-(uridine), respectively. According to our calculations, Cu-(cytidine) and Cu-(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu-(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

Photoelectron and computational studies of the copper-nucleoside anionic complexes, Cu(-)(cytidine) and Cu(-)(uridine).

Science.gov (United States)

Li, Xiang; Ko, Yeon-Jae; Wang, Haopeng; Bowen, Kit H; Guevara-García, Alfredo; Martínez, Ana

2011-02-07

The copper-nucleoside anions, Cu(-)(cytidine) and Cu(-)(uridine), have been generated in the gas phase and studied by both experimental (anion photoelectron spectroscopy) and theoretical (density functional calculations) methods. The photoelectron spectra of both systems are dominated by single, intense, and relatively narrow peaks. These peaks are centered at 2.63 and 2.71 eV for Cu(-)(cytidine) and Cu(-)(uridine), respectively. According to our calculations, Cu(-)(cytidine) and Cu(-)(uridine) species with these peak center [vertical detachment energy (VDE)] values correspond to structures in which copper atomic anions are bound to the sugar portions of their corresponding nucleosides largely through electrostatic interactions; the observed species are anion-molecule complexes. The combination of experiment and theory also reveal the presence of a slightly higher energy, anion-molecule complex isomer in the case of the Cu(-)(cytidine). Furthermore, our calculations found that chemically bond isomers of these species are much more stable than their anion-molecule complex counterparts, but since their calculated VDE values are larger than the photon energy used in these experiments, they were not observed.

Synthesis and characterization of mononuclear copper(II complex of tetradentate N2S2 donor set and the study of DNA and bovine serum albumin binding

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Sandipan Sarkar

2014-12-01

Full Text Available One mononuclear copper(II complex, containing neutral tetradentate NSSN-type ligands, of formulation [Cu II(L 1Cl]ClO 4 (1, was synthesized and isolated in pure form [where L 1˭ 1,3-bis(3-pyridylmethylthiopropane]. Green-colored copper(II complex was characterized by physicochemical, spectroscopic methods and conductivity measurement. These experimental data matched well with the proposed structure of the complex. Biological activity of the complex (1 toward calf thymus DNA and bovine serum albumin has been examined systematically and groove-binding behavior of the Copper(II complex 1 with calf thymus DNA has been observed from the spectral study.

Two new coordination polymers with flexible alicyclic carboxylate and bipyridyl co-ligands bearing trinuclear [Ni3(COO)6] SBUs: Synthesis, crystal structures, and magnetic properties

Science.gov (United States)

Zhu, Xian-Dong; Li, Yong; Gao, Jian-Gang; Wang, Fen-Hua; Li, Qing-Hai; Yang, Hong-Xun; Chen, Lei

2017-02-01

Two new coordination polymers generally formulated as [Ni3(Hchda)2(chda)2(bpy)2(H2O)2]n (1) and [Ni3(Hchda)2(chda)2(bpp)2(H2O)2]n (2) [H2chda = 1,1'-cyclohexanediacetic acid, bpy = 4,4'-bipyridine and bpp = 1,3-bis(4-pyridyl)propane], have been successfully assembled through mixed-ligands synthetic strategy with flexible alicyclic carboxylate and bipyridyl ligands. There structures feature trinuclear nickel secondary building units connected via the bridging bipyridyl spacers to form two-dimensional (4,4) grid layer. The nature of the different N-donor auxiliary ligands leads to the discrepancy in supramolecular structure of the two compounds. Magnetic studies indicate the ferromagnetic intra-complex magnetic interaction in the molecule for 1 and 2.

Determination of formal redox potentials in aqueous solution of copper(II) complexes with ligands having nitrogen and oxygen donor atoms and comparison with their EPR and UV-Vis spectral features.

Science.gov (United States)

Tabbì, Giovanni; Giuffrida, Alessandro; Bonomo, Raffaele P

2013-11-01

Formal redox potentials in aqueous solution were determined for copper(II) complexes with ligands having oxygen and nitrogen as donor atoms. All the chosen copper(II) complexes have well-known stereochemistries (pseudo-octahedral, square planar, square-based pyramidal, trigonal bipyramidal or tetrahedral) as witnessed by their reported spectroscopic, EPR and UV-visible (UV-Vis) features, so that a rough correlation between the measured redox potential and the typical geometrical arrangement of the copper(II) complex could be established. Negative values have been obtained for copper(II) complexes in tetragonally elongated pseudo-octahedral geometries, when measured against Ag/AgCl reference electrode. Copper(II) complexes in tetrahedral environments (or flattened tetrahedral geometries) show positive redox potential values. There is a region, always in the field of negative redox potentials which groups the copper(II) complexes exhibiting square-based pyramidal arrangements. Therefore, it is suggested that a measurement of the formal redox potential could be of great help, when some ambiguities might appear in the interpretation of spectroscopic (EPR and UV-Vis) data. Unfortunately, when the comparison is made between copper(II) complexes in square-based pyramidal geometries and those in square planar environments (or a pseudo-octahedral) a little perturbed by an equatorial tetrahedral distortion, their redox potentials could fall in the same intermediate region. In this case spectroscopic data have to be handled with great care in order to have an answer about a copper complex geometrical characteristics. © 2013.

Crystal structure of the Copper(I) complex Cu(py-Clan)(PPh.sub.3./sub.)I

Czech Academy of Sciences Publication Activity Database

Khalaji, A.D.; Jafari, K.; Fejfarová, Karla; Dušek, Michal

2015-01-01

Roč. 56, č. 1 (2015), s. 175-178 ISSN 0022-4766 Grant - others:AV ČR(CZ) Praemium Academiae Institutional support: RVO:68378271 Keywords : copper(I) complex * Schiff base * crystal structure Subject RIV: CC - Organic Chemistry Impact factor: 0.536, year: 2015

N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

Science.gov (United States)

Zhou, Zhi-Hang; Han, Min-Le; Wu, Ya-Pan; Dong, Wen-Wen; Li, Dong-Sheng; Lu, Jack Y.

2016-10-01

Two new Co(II) coordination polymers(CPs), namely [Co2(bpe)2(Hbppc)]n (1) and [Co3(μ3-OH)(bppc)(bpm)(H2O)]·3H2O (2) (H5bppc=biphenyl-2,4,6,3‧,5‧-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (44·610·8)(44·62) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)]5+ units with unusual (3.46.52.6)(32.46.57.65.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system.

Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

International Nuclear Information System (INIS)

Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

1988-01-01

Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The 31 P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs

Template Synthesis, Crystal Structure, and Magnetic Properties of a Dinuclear Copper(II) Complex with Cooperative Hydrogen Bonding

International Nuclear Information System (INIS)

Kang, Shin Geol; Nam, Kwang Hee; Min, Kil Sik; Lee, Uk

2011-01-01

The dinuclear complex with cooperative hydrogen bonds can be prepared by the metal-directed reaction of Eq. This work shows that the coordinated hydroxyl group trans to the secondary amino group is deprotonated more readily than that trans to the tertiary amino group and acts as the hydrogen-bond accepter. The lattice water molecules in act as bridges between the two mononuclear units through hydrogen bonds. The complex is quite stable as the dimeric form even in various polar solvents. The complex exhibits a weak antiferromagnetic interaction between the metal ions in spite of relatively long Cu···Cu distance. This strongly supports the suggestion that the antiferromagnetic behavior is closely related to the cooperative hydrogen bonds. The design and synthesis of polynuclear transition metal complexes have received much attention because of their potential applications in various fields, such as catalysis, supramolecular chemistry, and materials chemistry. Until now, various types of dinuclear copper(II) complexes have been prepared and investigated. Some dinuclear copper(II) complexes resulting from cooperative hydrogen bonding, such as containing two N_2O_2 donor sets, are also reported

A New Heterotrophic Strain for Bioleaching of Low Grade Complex Copper Ore

Directory of Open Access Journals (Sweden)

Kaijian Hu

2016-02-01

Full Text Available A new heterotrophic strain, named Providencia sp. JAT-1, was isolated and used in bioleaching of low-grade complex copper ore. The strain uses sodium citrate as a carbon source and urea as a nitrogen source to produce ammonia. The optimal growth condition of the strain is 30 C, initial pH 8, sodium citrate 10 g/L and urea 20 g/L, under which the cell density and ammonia concentration in the medium reached a maximum of 4.83 × 108 cells/mL and 14 g/L, respectively. Ammonia produced by the strain is used as the main lixiviant in bioleaching. Bioleaching results revealed that higher strain growth led to a higher copper recovery, while higher pulp density will cause a greater inhibitory effect on strain growth and ammonia production. The copper extraction reached the highest value of 54.5% at the pulp density of 1%. Malachite, chrysocolla and chalcocite are easy to leach out in this bioleaching system while chalcopyrite is difficult. Results of comparative leaching experiments show that bioleaching using JAT-1 is superior to ammonia leaching at the same condition. The metabolites produced by the strain other than ammonia are also involved in bioleaching.

Synthesis, catalytic and biological activity of novel dinuclear copper complex with Schiff base

Institute of Scientific and Technical Information of China (English)

WEI Danyi; LI Ning; LU Gui; YAO Kemin

2006-01-01

A novel dinuclear copper complex with tetraglycol aldehyde-phenylalanine Schiff base has been synthesized. It was characterized and formulated as [Cu2L(NO3)]NO3 by elemental analysis,magnetic susceptibility, TG-DTA, IR, EPR and 1H NMR spectra. The obtained complex can be used as a good catalyst for the polymerization of methyl methacrylate (MMA). The optimum polymerization conditions are: MMNcatalyst = 500 (molar ratio); [catalyst] = 7.5×10-3 mol. L-1; dioxane as solvent;80℃; 6 h. Polymethyl methacrylate (PMMA) with 80% conversion, 7.2×105 viscosity-average molecular weight and 60.5% syndiotacticity was obtained. This complex has also been shown to play an important role in scavenging O-·2.

Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration.

Science.gov (United States)

Olchowka, Jakub; Falaise, Clément; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2013-02-04

The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO(2)(2+)-Cu(2+) coordination polymers: (UO(2))Cu(H(2)O)(2)(1,2-bdc)(2) (1; 1,2-bdc = phthalate), (UO(2))Cu(H(2)O)(2)(btec)⋅4 H(2)O (2) and (UO(2))Cu(btec) (2'; btec = pyromellitate), (UO(2))(2)Cu(H(2)O)(4)(mel) (3; mel = mellitate), and (UO(2))(2)O(OH)(2)Cu(H(2)O)(2)(1,3-bdc)⋅H(2)O (4; 1,3-bdc = isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO(8) and CuO(4)(H(2)O)(2) units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH(2)) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO(4)(OH(2))(2), was linked to two uranium units, UO(5)(H(2)O)(2). The assembly of this trimer, "U(2)Cu", with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO(5)(OH)(2) and UO(6)(OH) units that were linked to two copper centers, CuO(OH)(2)(H(2)O)(2), which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Å. In the case of a shorter Cu-O distance, a slight lengthening

Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration

International Nuclear Information System (INIS)

Olchowka, Jakub; Falaise, Clement; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

2013-01-01

The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO 2 2+ -Cu 2+ coordination polymers: (UO 2 )Cu(H 2 O) 2 (1,2-bdc) 2 (1; 1,2-bdc=phthalate), (UO 2 )Cu(H 2 O) 2 (btec).4 H 2 O (2) and (UO 2 )Cu(btec) (2'; btec=pyromellitate), (UO 2 ) 2 Cu(H 2 O) 4 (mel) (3; mel=mellitate), and (UO 2 ) 2 O(OH) 2 Cu(H 2 O) 2 (1,3-bdc).H 2 O (4; 1,3-bdc=isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO 8 and CuO 4 (H 2 O) 2 units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH 2 ) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO 4 (OH 2 ) 2 , was linked to two uranium units, UO 5 (H 2 O) 2 . The assembly of this trimer, ''U 2 Cu'', with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO 5 (OH) 2 and UO 6 (OH) units that were linked to two copper centers, CuO(OH) 2 (H 2 O) 2 , which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U=O-Cu type, which is reflected by apical Cu-O distances in the range 2.350(3)-2.745(5) Aa. In the case of a shorter Cu-O distance, a slight

VARIABILITY OF COORDINATION COMPLEXES OF COPPER ACCUMULATED WITHIN FUNGAL COLONY IN THE PRESENCE OF COPPER-CONTAINING MINERALS

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M. O. Fomina

2014-04-01

Full Text Available The aim of work was to elucidate the mechanisms of bioaccumulation of copper leached from minerals by fungus Aspergillus niger with great bioremedial potential due to its ability to produce chelating metabolites and transform toxic metals and minerals. The special attention was paid to the chemical speciation of copper bioaccumulated within fungal colony in the process of fungal transformation of copper-containing minerals. Chemical speciation of copper within different parts of the fungal colony was studied using solid-state chemistry methods such as synchrotron-based X-ray absorption spectroscopy providing information about the oxidation state of the target element, and its coordination environment. The analysis of the obtained X-ray absorption spectroscopy spectra was carried out using Fourier transforms of Extended X-ray Absorption Fine Structure regions, which correspond to the oscillating part of the spectrum to the right of the absorption edge. Results of this study showed that fungus A. niger was involved in the process of solubilization of copper-containing minerals resulted in leaching of mobile copper and its further immobilization by fungal biomass with variable coordination of accumulated copper within fungal colony which depended on the age and physiological/reproductive state of fungal mycelium. X-ray absorption spectroscopy data demonstrated that copper accumulated within outer zone of fungal colony with immature vegetative mycelium was coordinated with sulphur–containing ligands, in contrast to copper coordination with phosphate ligands within mature mycelium with profuse conidia in the central zone of the colony. The findings of this study not only broaden our understanding of the biogeochemical role of fungi but can also be used in the development of various fungal-based biometallurgy technologies such as bioremediation, bioaccumulation and bioleaching and in the assessment of their reliability. The main conclusion is that

Copper Complexes with Tetradentate Ligands for Enhanced Charge Transport in Dye-Sensitized Solar Cells

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Hannes Michaels

2018-05-01

Full Text Available In dye-sensitized solar cells (DSCs, the redox mediator is responsible for the regeneration of the oxidized dye and for the hole transport towards the cathode. Here, we introduce new copper complexes with tetradentate 6,6′-bis(4-(S-isopropyl-2-oxazolinyl-2,2′-bipyridine ligands, Cu(oxabpy, as redox mediators. Copper coordination complexes with a square-planar geometry show low reorganization energies and thus introduce smaller losses in photovoltage. Slow recombination kinetics of excited electrons between the TiO2 and CuII(oxabpy species lead to an exceptionally long electron lifetime, a high Fermi level in the TiO2, and a high photovoltage of 920 mV with photocurrents of 10 mA∙cm−2 and 6.2% power conversion efficiency. Meanwhile, a large driving force remains for the dye regeneration of the Y123 dye with high efficiencies. The square-planar Cu(oxabpy complexes yield viscous gel-like solutions. The unique charge transport characteristics are attributed to a superposition of diffusion and electronic conduction. An enhancement in charge transport performance of 70% despite the higher viscosity is observed upon comparison of Cu(oxabpy to the previously reported Cu(tmby2 redox electrolyte.

Copper(II)–imida‐salen Complexes Encapsulated into NaY Zeolite for Oxidations Reactions

DEFF Research Database (Denmark)

Kuźniarska‐Biernacka, Iwona; Carvalho, M. Alice; Rasmussen, Søren Birk

2013-01-01

The oxidation of phenol, cychohexanol and hydroquinone has been screened in the presence of copper(II) complexes with the Schiff‐base salen ligand, 1,5‐bis[(E)‐5‐chloro‐2‐hydroxybenzylideneamino]‐1H‐imidazole‐4‐carbonitrile, and encapsulated into NaY zeolite by using two different methods. The new...

Identifying Marine Copper-Binding Ligands in Seawater

Science.gov (United States)

Whitby, H.; Hollibaugh, J. T.; Maldonado, M. T.; Ouchi, S.; van den Berg, S. M.

2016-02-01

Complexation reactions are important because they affect the bioavailability of trace metals such as copper and iron. For example, organic complexation can determine whether copper is a limiting or a toxic micronutrient at natural levels. Copper competes with iron for complexing ligands, and when iron is limiting, copper can also substitute for iron in some metabolic pathways. The speciation of copper can be measured using complexing capacity titrations, which provide the concentration of individual ligand classes (L1, L2 etc.) and the complex stabilities (log K). Using methods recently developed in our laboratory, we show that the ligands within these classes can be measured independently of titrations, thus confirming the titration method and simultaneously identifying the ligands within each class. Thiols were identified as the L1 ligand class and humic compounds as the weaker L2 class in samples from coastal Georgia, USA, collected monthly from April to December. Log K values of the ligand complexes were consistent with values expected for thiols and humic substances. Recent results from culture studies and from samples collected along Line P, a coastal - oceanic transect in the HNLC region of the NE subarctic Pacific, will be presented in comparison to the estuarine results. This comparison will help to broaden our perspective on copper complexation and the ligands responsible, furthering our understanding of ligand sources and life cycles.

Efficient SN2 fluorination of primary and secondary alkyl bromides by copper(I) fluoride complexes

KAUST Repository

Liu, Yanpin; Chen, Chaohuang; Li, Huaifeng; Huang, Kuo-Wei; Tan, Jianwei; Weng, Zhiqiang

2013-01-01

Copper(I) fluoride complexes ligated by phenanthroline derivatives have been synthesized and structurally characterized by X-ray crystallography. These complexes adopt as either ionic or neutral forms in the solid state, depending on the steric bulkiness of the substituent groups on the phenanthroline ligands. These complexes react with primary and secondary alkyl bromides to produce the corresponding alkyl fluorides in modest to good yields. This new method is compatible with a variety of important functional groups such as ether, thioether, amide, nitrile, methoxyl, hydroxyl, ketone, ester, and heterocycle moieties. © 2013 American Chemical Society.

Efficient SN2 fluorination of primary and secondary alkyl bromides by copper(I) fluoride complexes

KAUST Repository

Liu, Yanpin

2013-11-11

Copper(I) fluoride complexes ligated by phenanthroline derivatives have been synthesized and structurally characterized by X-ray crystallography. These complexes adopt as either ionic or neutral forms in the solid state, depending on the steric bulkiness of the substituent groups on the phenanthroline ligands. These complexes react with primary and secondary alkyl bromides to produce the corresponding alkyl fluorides in modest to good yields. This new method is compatible with a variety of important functional groups such as ether, thioether, amide, nitrile, methoxyl, hydroxyl, ketone, ester, and heterocycle moieties. © 2013 American Chemical Society.

N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

Energy Technology Data Exchange (ETDEWEB)

Zhou, Zhi-Hang [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Han, Min-Le [College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471022 (China); Wu, Ya-Pan; Dong, Wen-Wen [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Lu, Jack Y., E-mail: lu@uhcl.edu [Department of Chemistry, University of Houstons-Clear Lake, Houston, TX 77058 (United States)

2016-10-15

Two new Co(II) coordination polymers(CPs), namely [Co{sub 2}(bpe){sub 2}(Hbppc)]{sub n} (1) and [Co{sub 3}(μ{sub 3}-OH)(bppc)(bpm)(H{sub 2}O)]·3H{sub 2}O (2) (H{sub 5}bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co{sub 3}(μ{sub 3}-OH)]{sup 5+} units with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system. - Graphical abstract: Two new Co(II) coordination polymers with bi- and trinuclear units have been obtained. 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology and antiferromagnetic interactions between the adjacent Co(II) ions, while 2 is a binodal (5,7)-connected 3D network with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology and a ferromagnetic system. - Highlights: • Two Co(II) coordination polymers with different multimetallic clusters as building units. • A (4,6)-connected fsc net and a (5,7)-connected 3D network. • A antiferromagnetic coupling for 1 and A ferromagnetic coupling for 2.

Silver(I), Copper(I) and Copper(II) Complex of the New N,Se-Chelate Ligand 2-Phenylselenomethyl-1H-benzimidazole: Electrochemistry and Structure

Czech Academy of Sciences Publication Activity Database

Leboschka, M.; Sieger, M.; Sarkar, B.; Niemeyer, M.; Schurr, T.; Fiedler, Jan; Záliš, Stanislav; Kaim, W.

2009-01-01

Roč. 635, 6-7 (2009), s. 1001-1007 ISSN 0044-2313 R&D Projects: GA AV ČR KAN100400702; GA MŠk OC 139 Institutional research plan: CEZ:AV0Z40400503 Keywords : copper compounds * solid-state structures * electrochemistry * selenother ligand * silver complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.226, year: 2009

Hetero-metallic {3d-4f-5d} complexes: preparation and magnetic behavior of trinuclear [(L(Me2)Ni-Ln){W(CN)(8)}] compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; L(Me2) = Schiff base) and variable SMM characteristics for the Tb derivative.

Science.gov (United States)

Sutter, Jean-Pascal; Dhers, Sébastien; Rajamani, Raghunathan; Ramasesha, S; Costes, Jean-Pierre; Duhayon, Carine; Vendier, Laure

2009-07-06

Assembling bimetallic {Ni-Ln}(3+) units and {W(CN)(8)}(3-) is shown to be an efficient route toward heteronuclear {3d-4f-5d} compounds. The reaction of either the binuclear [{L(Me2)Ni(H(2)O)(2)}{Ln(NO(3))(3)}] complexes or their mononuclear components [L(Me2)Ni] and Ln(NO(3))(3) with (HNBu(3))(3){W(CN)(8)} in dmf followed by diffusion of tetrahydrofuran yielded the trinuclear [{L(Me2)NiLn}{W(CN)(8)}] compounds 1 (Ln = Y), 2a,b (Gd), 3a,b (Tb), 4 (Dy), 5 (Ho), and 6 (Er) as crystalline materials. All of the derivatives possess the trinuclear core resulting from the linkage of the {W(CN)(8)} to the Ni center of the {Ni-Ln} unit. Differences are found in the solvent molecules acting as ligands and/or in the lattice depending on the crystallization conditions. For all the compounds ferromagnetic {Ni-W} and {Ni-Ln} (Ln = Gd, Tb, Dy, and Er} interactions are operative resulting in high spin ground states. Parameterization of the magnetic behaviors for the Y and Gd derivatives confirmed the strong cyano-mediated {Ni-W} interaction (J(NiW) = 27.1 and 28.5 cm(-1)) compared to the {Ni-Gd} interaction (J(NiGd) = 2.17 cm(-1)). The characteristic features for slow relaxation of the magnetization are observed for two Tb derivatives, but these are modulated by the crystal phase. Analysis of the frequency dependence of the alternating current susceptibility data yielded U(eff)/k(B) = 15.3 K and tau(0) = 4.5 x 10(-7) s for one derivative whereas no maxima of chi(M)'' appear above 2 K for the second one.

DNA binding, cytotoxicity and apoptosis induction activity of a mixed-ligand copper(II) complex with taurine Schiff base and imidazole

Science.gov (United States)

Li, Mei; kong, Lin Lin; Gou, Yi; Yang, Feng; Liang, Hong

2014-07-01

A novel binuclear copper(II) complex (complex 1) with taurine Schiff base and imidazole has been synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, ESI-MS spectrometry, UV-vis and IR spectroscopy. Single-crystal analysis revealed that 1 displays the sulfonate-bridged dinuclear copper(II) centers. Both copper atoms are five-coordinated and exhibit slightly distorted square pyramidal geometries. Each of copper atom is surrounded by three oxygen atoms and one nitrogen atom from different taurine Schiff base ligands, and one nitrogen atom from one imidazole ligand. The interaction between 1 and calf thymus DNA (CT-DNA) was investigated by UV-vis, fluorescence, circular dichroism (CD) spectra and agarose gel electrophoresis. The experimental results indicated that 1 could bind to CT-DNA via an intercalative mode and show efficient cleavage activity. In addition, 1 showed an antitumor effect on cell cycle and apoptosis. Flow cytometric analysis revealed that MGC-803 cells were arrested in the S phase after treatment with 1. Fluorescence microscopic observation indicated that 1 could induce apoptosis of MGC-803 cells.

COPPER AND COPPER-CONTAINING PESTICIDES: METABOLISM, TOXICITY AND OXIDATIVE STRESS

Directory of Open Access Journals (Sweden)

Viktor Husak

2015-05-01

Full Text Available The purpose of this paper is to provide a brief review of the current knowledge regarding metabolism and toxicity of copper and copper-based pesticides in living organisms. Copper is an essential trace element in all living organisms (bacteria, fungi, plants, and animals, because it participates in different metabolic processes and maintain functions of organisms. The transport and metabolism of copper in living organisms is currently the subject of many studies. Copper is absorbed, transported, distributed, stored, and excreted in the body via the complex of homeostatic processes, which provide organisms with a needed constant level of this micronutrient and avoid excessive amounts. Many aspects of copper homeostasis were studied at the molecular level. Copper based-pesticides, in particularly fungicides, bacteriocides and herbicides, are widely used in agricultural practice throughout the world. Copper is an integral part of antioxidant enzymes, particularly copper-zinc superoxide dismutase (Cu,Zn-SOD, and plays prominent roles in iron homeostasis. On the other hand, excess of copper in organism has deleterious effect, because it stimulates free radical production in the cell, induces lipid peroxidation, and disturbs the total antioxidant capacity of the body. The mechanisms of copper toxicity are discussed in this review also.

Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

Science.gov (United States)

Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

2018-03-21

X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

A Novel Pentadentate Coordination Mode for the Carbonato Bridge: Synthesis, Crystal Structure, and Magnetic Behavior of (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)], a New Trinuclear Nickel(II) Carbonato-Bridged Complex with Strong Antiferromagnetic Coupling.

Science.gov (United States)

Escuer, Albert; Vicente, Ramon; Kumar, Sujit B.; Solans, Xavier; Font-Bardía, Mercé; Caneschi, Andrea

1996-05-22

The trinuclear complex (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)] was obtained by reaction of basic solutions of nickel(II), Medpt (bis(3aminopropyl)methylamine) and thiocyanate ligand with atmospheric CO(2) or by simple reaction with carbonate anion. (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)] crystallizes in the triclinic system, space group P&onemacr;, with a = 12.107(5) Å, b = 12.535(7) Å, c = 16.169(9) Å, alpha = 102.69(5) degrees, beta = 92.91(5) degrees, gamma = 118.01(4) degrees, Z = 2, and R = 0.043. The three nickel atoms are asymmetrically bridged by one pentadentate carbonato ligand, which shows a novel coordination mode. The (&mgr;(3)-CO(3))[Ni(3)(Medpt)(3)(NCS)(4)] compound shows a very strong antiferromagnetic coupling. Fit as irregular triangular arrangement gave J(1) = -88.4, J(2) = -57.7, and J(3) = -9.6 cm(-)(1), which is the strongest AF coupling observed to date for Ni(3) compounds. The magnetic behavior of the carbonato bridge is discussed.

RECYCLING OF SCRAP AND WASTE OF COPPER AND COPPER ALLOYS IN BELARUS

Directory of Open Access Journals (Sweden)

S. L. Rovin

2017-01-01

Full Text Available The construction of a new casting and mechanical shop of unitary enterprise «Tsvetmet» in December 2015 has allowed to solve the complex problem of processing and utilization of scrap and wastes of copper and copper alloys in the Republic of Belarus. The technological processes of fire refinement of copper and manufacturing of copper rod from scrap and production of brass rod by hot pressing (extrusion of the continuously casted round billet have been mastered for the first time in the Republic of Belarus.

potentiometric studies of the complexes formed by copper (ii)

African Journals Online (AJOL)

MBI

The overall stability constants of copper (II) and zinc (II) ions with some polar ... The average number of coordinated amino acids to the copper (II) and zinc (II) ions .... of chelated rings (Yamuchi and Odani, 1996). ... Synthesis and techniques in.

Interesting properties of some iron(II), copper(I) and copper(II ...

Indian Academy of Sciences (India)

Administrator

Tridendate ligands with nitrogen centers, generally well-known as the tripod ligands, have been of considerable interest to inorganic chemists dealing with the preparation of model compounds for hemocyanin, tyrosinase etc. We have found that such ligands when complexed with iron(II) and copper(II) and copper(I) ions ...

Action of copper (3) in periodate complex on hexavalent neptunium and plutonium in alkaline medium

International Nuclear Information System (INIS)

Shatokhina, O.B.; Alekseeva, D.P.; Peretrukhin, B.F.; Krot, N.N.

1977-01-01

A complex of trivalent copper connected with periodate has been studied in order to determine its possible use for oxidizing hexavalent transuranium elements. Proceeding from the dependence of formal potentials of the pairs Cusup((3))-Cusup((2)), Npsup((7))-Npsup((6)), Pusup((7))-Pusup((6)) on alkali concentration, it has been established that beginning with concentration 1M the potential of the pair Cusup((3))-Cusup((2)) is higher than that of the pair Npsup((7))-Npsup((6)) by approximately 50 mV. This means that a rather complete oxidation of hexavalent neptunium to heptavalent is possible by the action of copper (3) excess on neptunium (6) when KOH concentration is 1M and higher. Oxidation close to quantitative is attained in 1M KOH when excess of copper(3) is used and the ratio Npsup((6)): Cusup((3)) is 1:4 and higher. When KOH concentration is more than 1M a sufficiently complete oxidation (96-97%) of neptunium (6) is attained at Npsup((6)):Cusup((3))=1:2 or 1:3. Optimum conditions for oxidizing plutonium are 11M KOH and 2-3-fold excess of copper (3) reagent. At 9M KOH and a ratio Pusup((6)):Cusup((3))=1:2 the yield of Pu (7) is 33 %

Enhanced reactive oxygen species through direct copper sulfide nanoparticle-doxorubicin complexation

Science.gov (United States)

Li, Yajuan; Cupo, Michela; Guo, Liangran; Scott, Julie; Chen, Yi-Tzai; Yan, Bingfang; Lu, Wei

2017-12-01

CuS-based nanostructures loading the chemotherapeutic agent doxorubicin (DOX) exerted excellent cancer photothermal chemotherapy under multi-external stimuli. The DOX loading was generally designed through electrostatic interaction or chemical linkers. However, the interaction between DOX molecules and CuS nanoparticles has not been investigated. In this work, we use PEGylated hollow copper sulfide nanoparticles (HCuSNPs) to directly load DOX through the DOX/Cu2+ chelation process. Distinctively, the synthesized PEG-HCuSNPs-DOX release the DOX/Cu2+ complexes into surrounding environment, which generate significant reactive oxygen species (ROS) in a controlled manner by near-infrared laser. The CuS nanoparticle-mediated photothermal ablation facilitates the ROS-induced cancer cell killing effect. Our current work reveals a DOX/Cu2+-mediated ROS-enhanced cell-killing effect in addition to conventional photothermal chemotherapy through the direct CuS nanoparticle-DOX complexation.

Crystal Structure and Magnetic Behavior of Two New Dinuclear Carbonato-Bridged Copper(II) Compounds. Superexchange Pathway for the Different Coordination Modes of the Carbonato Bridge in Polynuclear Copper(II) Compounds.

Science.gov (United States)

Escuer, Albert; Mautner, Franz A.; Peñalba, Evaristo; Vicente, Ramon

1998-08-24

Four new &mgr;-CO(3)(2-) copper(II) complexes with different coordination modes for the carbonato bridge have been obtained by fixation of atmospheric CO(2): {(&mgr;(3)-CO(3))[Cu(3)(ClO(4))(3)(Et(3)dien)(3)]}(ClO(4)) (1), Et(3)dien = N,N',N"-triethylbis(2-aminoethane)amine; {(&mgr;-CO(3))[Cu(2)(H(2)O)(Et(4)dien)(2)]}(ClO(4))(2).H(2)O (2), Et(4)dien = N,N,N",N"-tetraethyl-bis(2-aminoethane)amine; {(&mgr;-CO(3))[Cu(2)(H(2)O)(2)(EtMe(4)dien)(2)]} (ClO(4))(2).2H(2)O (3), EtMe(4)dien = N'-ethyl-N,N,N",N"-tetramethylbis(2-aminoethane)amine; and {(&mgr;-CO(3))[Cu(2)(H(2)O)(Me(5)dien)(2)]}(ClO(4))(2).H(2)O (4), Me(5)dien = N,N,N',N",N"-pentamethylbis(2-aminoethane)amine. The crystal structures have been solved for 2, monoclinic system, space group P2(1)/n, formula [C(25)H(62)Cl(2)Cu(2)N(6)O(13)] with a = 12.763(6) Å, b = 25.125(8) Å, c = 13.261(4) Å, beta = 111.85(3) degrees, Z = 4, and for 3, triclinic system, space group P&onemacr;, formula [C(21)H(58)Cl(2)Cu(2)N(6)O(15)] with a = 8.412(3) Å, b = 14.667(4) Å, c = 16.555(5) Å, alpha = 99.66(2) degrees, beta = 102.14(2) degrees, gamma = 104.72(2) degrees, Z = 2. Susceptibility measurements show ferromagnetic behavior (J = +6.7(6) cm(-)(1)) for the trinuclear compound 1 whereas 2-4 are antiferromagnetically coupled with J = -17.8(8), -125.5(9), and -21.2(3) cm(-)(1) respectively. Certain synthetic aspects that may be related to the nuclearity of the copper(II) &mgr;-CO(3)(2-) compounds and the superexchange pathway for the different coordination modes of the carbonato bridge are discussed.

Antimalarial, antimicrobial, cytotoxic, DNA interaction and SOD like activities of tetrahedral copper(II) complexes

Science.gov (United States)

Mehta, Jugal V.; Gajera, Sanjay B.; Patel, Mohan N.

2015-02-01

The mononuclear copper(II) complexes with P, O-donor ligand and different fluoroquinolones have been synthesized and characterized by elemental analysis, electronic spectra, TGA, EPR, FT-IR and LC-MS spectroscopy. An antimicrobial efficiency of the complexes has been tested against five different microorganisms in terms of minimum inhibitory concentration (MIC) and displays very good antimicrobial activity. The binding strength and binding mode of the complexes with Herring Sperm DNA (HS DNA) have been investigated by absorption titration and viscosity measurement studies. The studies suggest the classical intercalative mode of DNA binding. Gel electrophoresis assay determines the ability of the complexes to cleave the supercoiled form of pUC19 DNA. Synthesized complexes have been tested for their SOD mimic activity using nonenzymatic NBT/NADH/PMS system and found to have good antioxidant activity. All the complexes show good cytotoxic and in vitro antimalarial activities.

Preconcentration and Determination of Copper and Zinc in Natural Water Samples by ICP-AES After Complexation and Sorption on Amberlite XAD-2

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Ferreira Sérgio Luis Costa

1998-01-01

Full Text Available The present paper describes a procedure for separation, preconcentration and sequential determination of trace amounts of copper and zinc in natural water samples, by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES. The proposed method is based on the complexation of copper(II and zinc(II ions by 1-(2-thiazolylazo-2-naphthol (TAN and sorption on to Amberlite XAD-2 resin. Parameters such as: TAN amount, pH effect on the complexation and sorption of TAN complexes, agitation time for complete sorption, concentration of metal ion, mass of Amberlite XAD-2, desorption of metal ions from XAD-2 resin and sample volume were studied. The results demonstrated that the copper(II and zinc(II ions, in the range of 0.10 to 100.00 mug, contained in a solution sample volume of 400 mL, in the pH range of 5.7 to 8.3, on the form of TAN complexes had been quantitatively retained on to XAD-2 resin. The shaking time required for sorption is 1 h using a resin mass of 1.4 g. The solution for determination of copper and zinc by ICP-AES is obtained, after desorption of the ions from the XAD-2 resin, using 5 mL of 2 mol L-1 hydrochloric acid and shaking the system for 5 min. The procedure was applied to the determination of copper and zinc in several natural water samples. The standard addition technique was applied and the obtained recoveries revealed that the proposed procedure has a good accuracy. A high enrichment factor (80 and simplicity are the main advantages in this analytical protocol.

Fluorescence-based detection of nitric oxide in aqueous and methanol media using a copper(II) complex.

Science.gov (United States)

Mondal, Biplab; Kumar, Pankaj; Ghosh, Pokhraj; Kalita, Apurba

2011-03-14

The quenched fluorescent intensity of a copper(II) complex, 1, of a fluorescent ligand, in degassed methanol or aqueous (buffered at pH 7.2) solution, was found to reappear on exposure to nitric oxide. Thus, it can function as a fluorescence based nitric oxide sensor. It has been found that the present complex can be used to sense nanomolar quantities of nitric oxide in both methanol and pH 7.2 buffered-water medium.

Native copper in Permian Mudstones from South Devon: A natural analogue of copper canisters for high-level radioactive waste

International Nuclear Information System (INIS)

Milodowski, A.E.; Styles, M.T.; Werme, L.; Oversby, V.M.

2001-01-01

Native copper (>99.9% Cu) sheets associated with complex uraniferous and vanadiferous concretions in Upper Permian Mudstones from south Devon (United Kingdom) have been studied as a 'natural analogue' for copper canisters designed to be used in the isolation of spent fuel and high-level radioactive wastes (HLW) for deep geological disposal. Detailed analysis demonstrates that the copper formed before the mudstones were compacted. The copper displays complex corrosion and alteration. The earliest alteration was to copper oxides, followed sequentially by the formation of copper arsenides, nickel arsenide and copper sulphide, and finally nickel arsenide accompanied by nickel-copper arsenide, copper arsenide and uranium silicates. Petrographic observations demonstrate that these alteration products also formed prior to compaction. Consideration of the published history for the region indicates that maximum compaction of the rocks will have occurred by at least the Lower Jurassic (i.e. over 176 Ma ago). Since that time the copper sheets have remained isolated by the compacted mudstones and were unaffected by further corrosion until uplift and exposure to present-day surface weathering

Complex crystals formed in the aqueous solution of copper(I) iodide and sodium iodide

International Nuclear Information System (INIS)

Sugasaka, Kazuhiko; Fujii, Ayako

1977-01-01

Crystals of different crystal habits were separated from the copper(I) iodide and sodium iodide solution and the thermal changes of the composition of copper(I) iodide and sodium iodide complexes were studied by chemical analysis, thermal analysis and X-ray diffractometry. Granular and columnar crystals were determined to be copper(I) iodide and sodium iodide dihydrate by X-ray diffraction analysis, respectively. Needle crystal (A) which was separated from the solution at 25 0 C was assumed to be Na 2 CuI 3 .6H 2 O. (A) was stable in its appearance in the air, but the X-ray diffraction pattern of (A) changed. Needle crystal (B) which was recrystallized at 10 0 C from mother liquor after the separation of crystal (A) was assumed to be NaCuI 2 .4H 2 O. (B) was hygroscopic and decomposed to precipitate copper(I) iodide with moisture in the air. (A) and (B) were found to change by heating and or drying, respectively, as follows: Na 2 CuI 3 .6H 2 O → (-2H 2 O, 80 0 C) → 2NaI.2H 2 O + CuI → (-4H 2 O, 160 0 C) → 2NaI + CuI → (+1/2O 2 , 450 0 C) → 2NaI + CuO + 1/2I 2 , NaCuI 2 .4H 2 O → (-4H 2 O, Dried) → NaI + CuI. (auth.)

Synthesis, characterization, and antimicrobial activity of silver(I) and copper(II) complexes of phosphate derivatives of pyridine and benzimidazole.

Science.gov (United States)

Kalinowska-Lis, Urszula; Szewczyk, Eligia M; Chęcińska, Lilianna; Wojciechowski, Jakub M; Wolf, Wojciech M; Ochocki, Justyn

2014-01-01

Two silver(I) complexes--[Ag(4-pmOpe)]NO₃}(n) and [Ag(2-bimOpe)₂]NO₃--and three copper(II) complexes--[Cu₄Cl₆O(2-bimOpe)₄], [CuCl₂(4-pmOpe)₂], and [CuCl₂(2-bis(pm)Ope]--were synthesized by reaction of silver(I) nitrate or copper(II) chloride with phosphate derivatives of pyridine and benzimidazole, namely diethyl (pyridin-4-ylmethyl)phosphate (4-pmOpe), 1H-benzimidazol-2-ylmethyl diethyl phosphate (2-bimOpe), and ethyl bis(pyridin-2-ylmethyl)phosphate (2-bis(pm)Ope). These compounds were characterized by ¹H, ¹³C, and ³¹P NMR as well as IR spectroscopy, elemental analysis, and ESIMS spectrometry. Additionally, molecular and crystal structures of {[Ag(4-pmOpe)]NO₃}n and [Cu₄Cl₆O(2-bimOpe)₄] were determined by single-crystal X-ray diffraction analysis. The antimicrobial profiles of synthesized complexes and free ligands against test organisms from the ATCC and clinical sources were determined. Silver(I) complexes showed good antimicrobial activities against Candida albicans strains (MIC values of ∼19 μM). [Ag(2-bimOpe)₂]NO₃ was particularly active against Pseudomonas aeruginosa and methicillin-resistant Staphylococcus epidermidis, with MIC values of ∼5 and ∼10 μM, respectively. Neither copper(II) complexes nor the free ligands inhibited the growth of test organisms at concentrations below 500 μg mL⁻¹. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poly(N-4-vinylbenzyl-1,4,7-triazacyclononane Copper Complex Grafted Solid Catalyst for Oxidative Polymerization of 2,6-Dimethylphenol

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Kei Saito

2016-01-01

Full Text Available A new solid phase catalyst, poly(N-4-vinylbenzyl-1,4,7-triazacyclononane copper(I complex, grafted onto polystyrene particles, has been employed for the oxidative polymerization of 2,6-dimethylphenol using an aqueous biphasic (water/toluene solvent system. The solid catalyst was synthesized by first grafting N-(4-vinylbenzyl-1,4,7-triaza-cyclononane onto polystyrene particles using a radical mediated polymerization method and next by creating the polymer-metal complex of copper-triazacyclononane with these modified particles. Poly(2,6-dimethyl-1,4-phenylene oxide was successfully obtained from the polymerization of 2,6-dimethylphenol using this new metal-organic solid phase catalyst.

Determination of sub-parts per billion levels of copper in complex matrices by adsorptive string voltammetry on a mercury electrode

International Nuclear Information System (INIS)

Shahbaazi, H.R.; Shahbaazi, H.R.; Safavi, A.; Maleki, N.

2008-01-01

The voltammetric characteristics of Cu(II)-SSA complex at the mercury electrode were investigated. An analytical method that based on the adsorptive accumulation of Cu(II)-SSA complex followed by the reduction of the complexed copper was developed for the copper determination in complex matrices in presence of the large amount of foreign ions. Adsorptive voltammetry determination showed that the Cu(II)-SSA complex behaves irreversibly exchanging two electrons on the hanging mercury drop electrode (HMDE). Factor affecting on the complextion, accumulation and stripping steps were studied and a procedure was developed. The instrumental parameters in the measurement step were also tested. The optimum conditions of pH, SSA concentration, accumulation potential and accumulation time were studied. Under optimal conditions (pH=12.9 glycin Buffer, 7 x 10 - '3 M SSA and accumulation potential -100 mV vs. Ag/ AgCl), a linear calibration graph in the range 1.25 μg L -1 to 42.5 μg L'- 1 and a detection limit of 0.8 μ L -1 were obtained. The average relative standard deviation (RSD) for seven determinations was calculated as 7 %, 5.5 % and 3 % for the concentrations between 3, 15 and 23 μg L'- 1 . The effect of foreign ions and surfactants on the peak height of Cu(II)-SSA complex was evaluated. The method was applied for the determination of the copper in different real samples such as crude oil, crude oil tank button sludge, waste water and tap water samples. The accuracy of the results was checked by ICP. (author)

Fabrication of copper-selective PVC membrane electrode based on newly synthesized copper complex of Schiff base as carrier

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Sulekh Chandra

2016-09-01

Full Text Available The newly synthesized copper(II complex of Schiff base p-hydroxyacetophenone semicarbazone was explored as neutral ionophore for the fabrication of poly(vinylchloride (PVC based membrane electrode selective to Cu(II ions. The electrode shows a Nernstian slope of 29.8 ± 0.3 mV/decade with improved linear range of 1.8 × 10−7 to 1.0 × 10−1 M, comparatively lower detection limit 5.7 × 10−8 M between pH range of 2.0–8.0, giving a relatively fast response within 5s and can be used for at least 16 weeks without any divergence in potential. The selectivity coefficient was calculated using the fixed interference method (FIM. The electrode can also be used in partially non-aqueous media having up to 25% (v/v methanol, ethanol or acetone content with no significant change in the value of slope or working concentration range. It was successfully applied for the direct determination of copper content in water and tea samples with satisfactory results. The electrode has been used in the potentiometric titration of Cu2+ with EDTA.

Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations.

Science.gov (United States)

Hänninen, Mikko M; Välivaara, Juha; Mota, Antonio J; Colacio, Enrique; Lloret, Francesc; Sillanpää, Reijo

2013-02-18

A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.

Synthesis, spectral characterization and structural studies of a novel O, N, O donor semicarbazone and its binuclear copper complex with hydrogen bond stabilized lattice

Science.gov (United States)

Layana, S. R.; Saritha, S. R.; Anitha, L.; Sithambaresan, M.; Sudarsanakumar, M. R.; Suma, S.

2018-04-01

A novel O,N,O donor salicylaldehyde-N4-phenylsemicarbazone, (H2L) has been synthesized and physicochemically characterized. Detailed structural studies of H2L using single crystal X-ray diffraction technique reveals the existence of intra and inter molecular hydrogen bonding interactions, which provide extra stability to the molecule. We have successfully synthesized a binuclear copper(II) complex, [Cu2(HL)2(NO3)(H2O)2]NO3 with phenoxy bridging between the two copper centers. The complex was characterized by elemental analysis, magnetic susceptibility and conductivity measurements, FT-IR, UV-Visible, mass and EPR spectral methods. The grown crystals of the copper complex were employed for the single crystal X-ray diffraction studies. The complex possesses geometrically different metal centers, in which the ligand coordinates through ketoamide oxygen, azomethine nitrogen and deprotonated phenoxy oxygen. The extensive intermolecular hydrogen bonding interactions of the coordinated and the lattice nitrate groups interconnect the complex units to form a 2D supramolecular assembly. The ESI mass spectrum substantiates the existence of 1:1 complex. The g values obtained from the EPR spectrum in frozen DMF suggest dx2 -y2 ground state for the unpaired electron.

COMMD1 is linked to the WASH complex and regulates endosomal trafficking of the copper transporter ATP7A

NARCIS (Netherlands)

Phillips-Krawczak, Christine A.; Singla, Amika; Starokadomskyy, Petro; Deng, Zhihui; Osborne, Douglas G.; Li, Haiying; Dick, Christopher J.; Gomez, Timothy S.; Koenecke, Megan; Zhang, Jin-San; Dai, Haiming; Sifuentes-Dominguez, Luis F.; Geng, Linda N.; Kaufmann, Scott H.; Hein, Marco Y.; Wallis, Mathew; McGaughran, Julie; Gecz, Jozef; De Sluis, Bart van; Billadeau, Daniel D.; Burstein, Ezra

2015-01-01

COMMD1 deficiency results in defective copper homeostasis, but the mechanism for this has remained elusive. Here we report that COMMD1 is directly linked to early endosomes through its interaction with a protein complex containing CCDC22, CCDC93, and C16orf62. This COMMD/CCDC22/CCDC93 (CCC) complex

A Novel Coordination Polymer Based on Trinuclear Cobalt Building Blocks Cluster: Synthesis, Crystal Structure, and Properties

Science.gov (United States)

Lu, J. F.; Tang, Z. H.; Shi, J.; Ge, H. G.; Jiang, M.; Song, J.; Jin, L. X.

2017-12-01

The title compound {[Co3(μ3-OH)(μ2-H2O)2(H2O)5(BTC)2] · 6H2O} n (H3BTC is a 1,3,5-benzenetricarboxylic acid) was prepared and characterized by single crystal and powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric and elemental analyses. The single crystal X-ray diffraction reveals that the title compound consists of 1D infinite zigzag chains which were constructed by trinuclear cobalt cluster and BTC3- ligand. Neighbouring above-mentioned 1D infinite zigzag chains are further linked by intermolecular hydrogen bonding to form a 3D supermolecular structure. In addition, the luminescent properties of the title compound were investigated.

Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

Science.gov (United States)

Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

2016-06-30

A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

Copper(II) and palladium(II) complexes with tridentate NSO donor Schiff base ligand: Synthesis, characterization and structures

Science.gov (United States)

Kumar, Sujit Baran; Solanki, Ankita; Kundu, Suman

2017-09-01

Mononuclear copper(II) complex [CuL2] and palladium(II) complexes [Pd(X)L] where X = benzoate(bz) or salicylate(sal) and HL = 2-(methylthio)phenylimino)methyl)phenol, a Schiff base ligand with NSO coordination sites have been synthesized and characterized by microanalyses, IR, UV-Visible spectra, conductivity measurement and magnetic studies. Crystal structures of all the complexes have been solved by single crystal X-ray diffraction studies and showed that there are two molecules in a unit cell in the [CuL2] complex - one molecule has square planar geometry whereas second molecule has distorted square pyramidal geometry and palladium(II) complexes have distorted square planar geometry.

Synthesis, CMC Determination, Antimicrobial Activity and Nucleic Acid Binding of A Surfactant Copper(II) Complex Containing Phenanthroline and Alanine Schiff-Base.

Science.gov (United States)

Nagaraj, Karuppiah; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

2014-03-01

A new water-soluble surfactant copper(II) complex [Cu(sal-ala)(phen)(DA)] (sal-ala = salicylalanine, phen = 1,10-phenanthroline, DA = dodecylamine), has been synthesized and characterized by physico-chemical and spectroscopic methods. The critical micelle concentration (CMC) values of this surfactant-copper(II) complex in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303, 308, 313. 318 and 323 K) served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG(0)m, ΔH(0)m and ΔS(0)m). The interaction of this complex with nucleic acids (DNA and RNA) has been explored by using electronic absorption spectral titration, competitive binding experiment, cyclic voltammetry, circular dichroism (CD) spectra, and viscosity measurements. Electronic absorption studies have revealed that the complex can bind to nucleic acids by the intercalative binding mode which has been verified by viscosity measurements. The DNA binding constants have also been calculated (Kb = 1.2 × 10(5) M(-1) for DNA and Kb = 1.6 × 10(5) M(-1) for RNA). Competitive binding study with ethidium bromide (EB) showed that the complex exhibits the ability to displace the DNA-bound-EB indicating that the complex binds to DNA in strong competition with EB for the intercalative binding site. The presence of hydrophobic ligands, alanine Schiff-base, phenanthroline and long aliphatic chain amine in the complex were responsible for this strong intercalative binding. The surfactant-copper (II) complex was screened for its antibacterial and antifungal activities against various microorganisms. The results were compared with the standard drugs, amikacin(antibacterial) and ketokonazole(antifungal).

Structural observations of heterometallic uranyl copper(II) carboxylates and their solid-state topotactic transformation upon dehydration

Energy Technology Data Exchange (ETDEWEB)

Olchowka, Jakub; Falaise, Clement; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS), UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

2013-02-04

The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO{sub 2}{sup 2+}-Cu{sup 2+} coordination polymers: (UO{sub 2})Cu(H{sub 2}O){sub 2}(1,2-bdc){sub 2} (1; 1,2-bdc=phthalate), (UO{sub 2})Cu(H{sub 2}O){sub 2}(btec).4 H{sub 2}O (2) and (UO{sub 2})Cu(btec) (2'; btec=pyromellitate), (UO{sub 2}){sub 2}Cu(H{sub 2}O){sub 4}(mel) (3; mel=mellitate), and (UO{sub 2}){sub 2}O(OH){sub 2}Cu(H{sub 2}O){sub 2}(1,3-bdc).H{sub 2}O (4; 1,3-bdc=isophthlalate). Single-crystal X-ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO{sub 8} and CuO{sub 4}(H{sub 2}O){sub 2} units that were connected through the phthalate ligands. In compound 2, these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open-framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu-OH{sub 2}) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid-state topotactic transformation with the formation of a new set of Cu-O interactions in the crystalline anhydrous structure (2'), in order to keep the square-planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO{sub 4}(OH{sub 2}){sub 2}, was linked to two uranium units, UO{sub 5}(H{sub 2}O){sub 2}. The assembly of this trimer, ''U{sub 2}Cu'', with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO{sub 5}(OH){sub 2} and UO{sub 6}(OH) units that were linked to two copper centers, CuO(OH){sub 2}(H{sub 2}O){sub 2}, which were then connected to each other through isophthalate ligands and U=O-Cu interactions to create a 3D structure. The common structural feature of these different compounds is

Synthesis, structure, terahertz spectroscopy and luminescent properties of copper (I) complexes with bis(diphenylphosphino)methane and N-donor ligands

Science.gov (United States)

Fan, Wei-Wei; Li, Zhong-Feng; Li, Jiao-Bao; Yang, Yu-Ping; Yuan, Yuan; Tang, Han-Qin; Gao, Ling-Xiao; Jin, Qiong-Hua; Zhang, Zhen-Wei; Zhang, Cun-Lin

2015-11-01

The reactions of copper(I) salts CuX [X = Cl, OTf (OTf = CF3SO3) and ClO4] and bis(diphenylphosphino)methane (dppm) with 4,4-bipyridine (4,4-bipy), 2,2-bipyridine (2,2-bipy), isoquinoline (i-C9H7N) and 1,10-phenanthroline (phen) lead to five new copper(I) complexes: [CuCl(dppm)(i-C9H7N)]2 (1), {[CuCl(dppm)(phen)]2•5H2O}n (2), [Cu2Cl2(dppm)2(4,4-bipy)]•4CH3CN (3), [Cu(dppm)(2,2-bipy)]2(OTf)2 (4), {[Cu2Cl(dppm)2(4,4-bipy)](ClO4)}n (5). Complexes 1, 3 and 4 are of dinuclear structure with eight-membered Cu2P4C2 rings. The structure of compound 2 can be simplified as three-dimensional topology. Complex 5 is of infinite chain structure linked by 4,4-bipy. All these complexes are characterized by IR, elemental analyses, single-crystal X-ray diffraction analysis, luminescence, NMR and terahertz time-domain spectroscopy.

Synthesis, structures and Helicobacter pylori urease inhibitory activity of copper(II) complexes with tridentate aroylhydrazone ligands.

Science.gov (United States)

Pan, Lin; Wang, Cunfang; Yan, Kai; Zhao, Kedong; Sheng, Guihua; Zhu, Hailiang; Zhao, Xinlu; Qu, Dan; Niu, Fang; You, Zhonglu

2016-06-01

A series of new copper(II) complexes were prepared. They are [CuL(1)(NCS)] (1), [CuClL(1)]·CH3OH (2), [CuClL(2)]·CH3OH (3), [CuL(3)(NCS)]·CH3OH (4), [CuL(4)(NCS)]·0.4H2O (5), and [CuL(5)(bipy)] (6), where L(1), L(2), L(3) and L(4) are the deprotonated form of N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide, 4-bromo-N'-(2-hydroxy-5-methoxybenzylidene)benzohydrazide, N'-(2-hydroxy-5-methoxybenzylidene)-3-methylbenzohydrazide and 2-chloro-N'-(2-hydroxy-5-methoxybenzylidene)benzohydrazide, respectively, L(5) is the dianionic form of N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide, and bipy is 2,2'-bipyridine. The complexes were characterized by infrared and UV-Vis spectra and single crystal X-ray diffraction. The Cu atoms in complexes 1, 2, 3, 4 and 5 are coordinated by the NOO donor set of the aroylhydrazone ligands, and one Cl or thiocyanate N atom, forming square planar coordination. The Cu atom in complex 6 is in a square pyramidal coordination, with the NOO donor set of L(1), and one N atom of bipy defining the basal plane, and with the other N atom of bipy occupying the apical position. Complexes 1, 2, 3, 4 and 5 show effective urease inhibitory activities, with IC50 values of 5.14, 0.20, 4.06, 5.52 and 0.26μM, respectively. Complex 6 has very weak activity against urease, with IC50 value over 100μM. Molecular docking study of the complexes with the Helicobacter pylori urease was performed. The relationship between structures and urease inhibitory activities indicated that copper complexes with square planar coordination are better models for urease inhibition. Copyright © 2016 Elsevier Inc. All rights reserved.

Synthesis, characterization and behavior to gamma radiation of copper (II) complex and l-asparagine

International Nuclear Information System (INIS)

Rodrigues, E.R.

1982-01-01

Synthesis and caracterization of coordination compound formed by interation between l-asparagina (HL) and copper (II) ion are discussed. Elemental analysis, Visible and Ultraviolet electronic Spectroscopy, Infrared Vibrational Spectroscopy, Proton Nuclear Magnetic Resonance and melting and/or decomposition point are made; it is also possible to: a) Synthesize the complex with high degree of purity; b)determine the #betta# sub(max) for absorption in the Visible and Ultraviolet, as well as the molar absorption coefficient; c) determine the probable structure of the complex; d) calculate the kinetic parameters and the break factor by means of radiolysis in ammoniacal aqueous solution of sample submitted by a 60 Co source of #betta#-radiation (Gamma Cell); e) separate the complex from the ionic fractions formed by radiolysis, by means of cromatography in their layers; f) determine the porcentage of Cu in this complex by neutron activation; g) justify the complex resistence in solid phase, to gamma radiation. (A.R.H.) [pt

Influence of ocean acidification on the organic complexation of iron and copper in Northwest European shelf seas; a combined observational and model study

Directory of Open Access Journals (Sweden)

Lizeth eAvendaño

2016-04-01

Full Text Available The pH of aqueous solutions is known to impact the chemical speciation of trace metals. In this study we conducted titrations of coastal seawaters with iron and copper at pH 7.91, 7.37 and 6.99 (expressed on the total pH scale. Changes in the concentration of iron and copper that complexed with the added ligands 1-nitroso-2-napthol and salicylaldoxime respectively were determined by adsorptive cathodic stripping voltammetry - competitive ligand equilibrium (AdCSV-CLE. Interpretation of the results, assuming complexation by a low concentration of discrete ligands, showed that conditional stability constants for iron complexes increased relative to inorganic iron complexation as pH decreased by approximately 1 log unit per pH unit, whilst those for copper did not change. No trend was observed for concentrations of iron and copper complexing ligands over the pH range examined. We also interpreted our titration data by describing chemical binding and polyelectrolytic effects using non-ideal competitive adsorption in Donnan-like gels (NICA-Donnan model in a proof of concept study. The NICA-Donnan approach allows for the development of a set of model parameters that are independent of ionic strength and pH, and thus calculation of metal speciation can be undertaken at ambient sample pH or the pH of a future, more acidic ocean. There is currently a lack of basic NICA-Donnan parameters applicable to marine dissolved organic matter (DOM so we assumed that the measured marine dissolved organic carbon could be characterized as terrestrial fulvic acids. Generic NICA-Donnan parameters were applied within the framework of the software program visual MINTEQ and the metal –added ligand concentrations [MeAL] calculated for the AdCSV-CLE conditions. For copper, calculated [MeAL] using the NICA-Donnan model for DOM were consistent with measured [MeAL], but for iron an inert fraction with kinetically inhibited dissolution was required in addition to the NICA

Integrated copper-containing wastewater treatment using xanthate process.

Science.gov (United States)

Chang, Yi-Kuo; Chang, Juu-En; Lin, Tzong-Tzeng; Hsu, Yu-Ming

2002-09-02

Although, the xanthate process has been shown to be an effective method for heavy metal removal from contaminated water, a heavy metal contaminated residual sludge is produced by the treatment process and the metal-xanthate sludge must be handled in accordance with the Taiwan EPA's waste disposal requirements. This work employed potassium ethyl xanthate (KEX) to remove copper ions from wastewater. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) were used to determine the leaching potential and stability characteristics of the residual copper xanthate (Cu-EX) complexes. Results from metal removal experiments showed that KEX was suitable for the treatment of copper-containing wastewater over a wide copper concentration range (50, 100, 500, and 1000 mg/l) to the level that meets the Taiwan EPA's effluent regulations (3mg/l). The TCLP results of the residual Cu-EX complexes could meet the current regulations and thus the Cu-EX complexes could be treated as a non-hazardous material. Besides, the results of SDLT indicated that the complexes exhibited an excellent performance for stabilizing metals under acidic conditions, even slight chemical changes of the complexes occurred during extraction. The xanthate process, mixing KEX with copper-bearing solution to form Cu-EX precipitates, offered a comprehensive strategy for solving both copper-containing wastewater problems and subsequent sludge disposal requirements.

Novel rare earth quinolinolate complexes

International Nuclear Information System (INIS)

Deacon, Glen B.; Forsyth, Craig M.; Junk, Peter C.; Kynast, Ulrich; Meyer, Gerd; Moore, Joanne; Sierau, Jennyfer; Urbatsch, Aron

2008-01-01

The reaction of europium 8-quinolinolate Eu(OQ) 3 with calcium 8-quinolinolate, Ca(OQ) 2 , in the flux 1,2,4,5-tetramethylbenzene (TMB) at 210 deg. C yields the bimetallic [Eu 2 Ca(OQ) 8 ], which is a linear tri-nuclear complex with two eight coordinate europium atoms flanking a six coordinate calcium atom bonded by six bridging phenolate oxygen atoms. A similar reaction between La(OQ) 3 and Co(OQ) 2 gave [LaCo 2 (OQ) 7 ], in which two six coordinate cobalt atoms flank an eight coordinate lanthanum atom with six bridging phenolate oxygen atoms and a terminal OQ group

Complexes cobalt(II, zinc(II and copper(II with some newly synthesized benzimidazole derivatives and their antibacterial activity

Directory of Open Access Journals (Sweden)

S. O. PODUNAVAC-KUZMANOVIC

1999-05-01

Full Text Available The preparation and properties of some complexes of cobalt(II, zinc(II and copper(II with several newly synthesized benzimidazole derivatives (L are reported. The complexes, of the general formula [MCl2L2] (M=Co(II, Zn(II and [CuCl2L(H2O], have a tetrahedral structure. The complexes were characterized by elemental analysis, molar conductivity, magnetic susceptibility measurements, IR and absorption electronic spectra. The antibacterial activitiy of the benzimidazoles and their complexes was evaluated against Erwinia carotovora subsp. carotovora and Erwinia amylovora. The complexes were found to be more toxic than the ligands.

Present status and prospect of copper radiopharmaceuticals

International Nuclear Information System (INIS)

Chen Huawei; Li Hongfeng; Liu Boli

1996-01-01

In the past decade most of the efforts of copper radiopharmaceuticals research has been focused on bis(thiosemicarbazonato) copper complexes for use in myocardial and brain imaging agents. In the present work, the analogs of bis(thiosemicarbazone) is studied in labeling antibodies and tumors. The retention mechanism of Cu-PTSM is investigated. Other kinds of ligands, BAT (N 2 S 2 ) for example, can be used to prepare neutral copper complexes in order to obtain brain radiopharmaceuticals in future. (60 refs.)

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N4-methyl-3-thiosemicarbazone: Crystal structure of a novel sulfur bridged copper(II) box-dimer

Science.gov (United States)

Jayakumar, K.; Sithambaresan, M.; Aiswarya, N.; Kurup, M. R. Prathapachandra

2015-03-01

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N4-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ = 0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)sbnd I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g|| > g⊥ > 2.0023 and the g values in frozen DMF are consistent with the dx2-y2 ground state. The thermal stabilities of some of the complexes were also determined.

Structures of nitrato-(2-hydroxybenzaldehydo) (2,2 Prime -bipyridyl)copper and nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2 Prime -bipyridyl)copper

Energy Technology Data Exchange (ETDEWEB)

Chumakov, Yu. M. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Paladi, L. G. [Moldova State University (Moldova, Republic of); Antosyak, B. Ya.; Simonov, Yu. A. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I., E-mail: vtsapkov@gmail.com [Moldova State University (Moldova, Republic of); Bocelli, G. [Institute of Materials for Electronics and Magnetism (Italy); Gulea, A. P. [Moldova State University (Moldova, Republic of); Ginju, D. [Alexandru Ioan Cuza University of Iasi (Romania); Palomares-Sanchez, S. A. [Autonomous University of San Luis Potosi (Mexico)

2011-03-15

Nitrato-(2-hydroxy-5-nitrobenzaldehydo)(2,2 Prime -bipyridyl)copper (I) and nitrato-(2-hydroxybenzaldehydo)(2,2 Prime -bipyridyl)copper (II) were synthesized and characterized by X-ray diffraction. The coordination polyhedron of the central copper atom in complex I can be described as a distorted tetragonal pyramid whose base is formed by the phenol and carbonyl oxygen atoms of the monodeprotonated 2-hydroxy-5nitrobenzaldehyde molecule and the nitrogen atoms of the 2,2 Prime -bipyridyl ligand and whose apex is occupied by the oxygen atom of the nitrato group. In the crystal structure, complexes I are linked by the acido ligands and the NO{sub 2} groups of the aldehyde molecule into infinite chains. In complex II, the central copper atom is coordinated by 2-hydroxybenzaldehyde, 2,2 Prime -bipyridyl, and the nitrato group, resulting in the formation of centrosymmetric dimers. The coordination polyhedron of the central copper atom can be described as a bipyramid (4 + 1 + 1) with the same base as in complex I. The axial vertices of the bipyramid are occupied by the oxygen atom of the nitrato group and the bridging phenol oxygen atom of the adjacent complex related to the initial complex by a center of symmetry. In the crystal structure, complexes II are hydrogen bonded into infinite chains.

Bis(bipyridine)ruthenium(II) complexes with an aliphatic sulfinato donor: synthesis, characterization, and properties.

Science.gov (United States)

Tamura, Motoshi; Tsuge, Kiyoshi; Igashira-Kamiyama, Asako; Konno, Takumi

2011-06-06

Treatment of a thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex, [Ag{Ru(aet)(bpy)(2)}(2)](3+) (aet = 2-aminoethanthiolate; bpy = 2,2'-bipyridine), with NaI in aqueous ethanol under an aerobic condition afforded a mononuclear ruthenium(II) complex having an S-bonded sulfinato group, [1](+) ([Ru(aesi-N, S)(bpy)(2)](+) (aesi = 2-aminoethanesulfinate)). Similar treatment of optically active isomers of an analogous Ru(II)Ag(I)Ru(II) trinuclear complex, Δ(D)Δ(D)- and Λ(D)Λ(D)-[Ag{Ru(d-Hpen-O,S)(bpy)(2)}(2)](3+) (d-pen = d-penicillaminate), with NaI also produced mononuclear ruthenium(II) isomers with an S-bonded sulfinato group, Δ(D)- and Λ(D)-[2](+) ([Ru(d-Hpsi-O,S)(bpy)(2)](+) (d-psi = d-penicillaminesulfinate)), respectively, retaining the bidentate-O,S coordination mode of a d-Hpen ligand and the absolute configuration (Δ or Λ) about a Ru(II) center. On refluxing in water, the Δ(D) isomer of [2](+) underwent a linkage isomerization to form Δ(D)-[3] (+) ([Ru(d-Hpsi-N,S)(bpy)(2)](+)), in which a d-Hpsi ligand coordinates to a Ru(II) center in a bidentate-N,S mode. Complexes [1](+), Δ(D)- and Λ(D)-[2](+), and Δ(D)-[3](+) were fully characterized by electronic absorption, CD, NMR, and IR spectroscopies, together with single-crystal X-ray crystallography. The electrochemical properties of these complexes, which are highly dependent on the coordination mode of sulfinate ligands, are also described. © 2011 American Chemical Society

Synthesis and spectral characterization of mono- and binuclear copper(II) complexes derived from 2-benzoylpyridine-N⁴-methyl-3-thiosemicarbazone: crystal structure of a novel sulfur bridged copper(II) box-dimer.

Science.gov (United States)

Jayakumar, K; Sithambaresan, M; Aiswarya, N; Kurup, M R Prathapachandra

2015-03-15

Mononuclear and binuclear copper(II) complexes of 2-benzoylpyridine-N(4)-methyl thiosemicarbazone (HL) were prepared and characterized by a variety of spectroscopic techniques. Structural evidence for the novel sulfur bridged copper(II) iodo binuclear complex is obtained by single crystal X-ray diffraction analysis. The complex [Cu2L2I2], a non-centrosymmetric box dimer, crystallizes in monoclinic C2/c space group and it was found to have distorted square pyramidal geometry (Addison parameter, τ=0.238) with the square basal plane occupied by the thiosemicarbazone moiety and iodine atom whereas the sulfur atom from the other coordinated thiosemicarbazone moiety occupies the apical position. This is the first crystallographically studied system having non-centrosymmetrical entities bridged via thiolate S atoms with Cu(II)I bond. The tridentate thiosemicarbazone coordinates in mono deprotonated thionic tautomeric form in all complexes except in sulfato complex, [Cu(HL)(SO4)]·H2O (1) where it binds to the metal centre in neutral form. The magnetic moment values and the EPR spectral studies reflect the binuclearity of some of the complexes. The spin Hamiltonian and bonding parameters are calculated based on EPR studies. In all the complexes g||>g⊥>2.0023 and the g values in frozen DMF are consistent with the d(x2-y2) ground state. The thermal stabilities of some of the complexes were also determined. Copyright © 2014 Elsevier B.V. All rights reserved.

A novel aggregation induced emission active cyclometalated Ir(III) complex as a luminescent probe for detection of copper(II) ion in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Shen, Wei; Yan, Liqiang; Tian, Wenwen; Cui, Xia; Qi, Zhengjian, E-mail: qizhengjian@seu.edu.cn; Sun, Yueming, E-mail: sun@seu.edu.cn

2016-09-15

We report the synthesis and characterization of a novel aggregation induced emission (AIE) active cyclometalated Ir(III) complex, namely [Ir(dfppy){sub 2}(phen-DPA)]PF{sub 6}, where dfppy and phen-DPA represent 2-(2,4-difluorophenyl)pyridine and 2-(bis(pyridin-2-ylmethyl)amino)-N-(1,10-phenanthrolin-5-yl)acetamide, respectively. The complex showed remarkable selectivity for copper(II) in aqueous solution over other competitive ions. Furthermore, this sensor showed a rapid and reversible response to copper(II) in aqueous solution with a detection limit of 65 nM.

Sulfonato-imino copper(ii) complexes: fast and general Chan-Evans-Lam coupling of amines and anilines.

Science.gov (United States)

Hardouin Duparc, V; Schaper, F

2017-10-14

Sulfonato-imine copper complexes with either chloride or triflate counteranions were prepared in a one-step reaction followed by anion-exchange. They are highly active in Chan-Evans-Lam couplings under mild conditions with a variety of amines or anilines, in particular with sterically hindered substrates. No optimization of reaction conditions other than time and/or temperature is required.

Some actinide complexes of pyridin-, pyrrol-, furan- and thiophen-aldazine Schiff bases

International Nuclear Information System (INIS)

Dawod, M.M.; Khalili, F.I.; Seyam, A.M.

1990-01-01

Actinide chloride complexes with pyridinaldazine (PAA), pyrrolaldazine(PyAA-H 2 ), furanaldazine (FAA), and thiophenaldazine (TAA): An(L)Cl n ·m-H 2 O, where An = Th, UO 2 ; L PAA, PyAA-H 2 , FAA, TAA; n = 2,4; m = 0, 2, 3, 5 (also, mononuclear with 2L, dinuclear and trinuclear complexes) have been prepared by the reaction of ThCl 4 , UO 2 Cl 2 or UO 2 (Ac) 2 ·2H 2 O with PAA, PyAA-H 2 , FAA or TAA and characterized by spectral data, electrical conductance, thermal and elemental analysis. (author)

Luminescent zinc(ii) and copper(i) complexes for high-performance solution-processed monochromic and white organic light-emitting devices.

Science.gov (United States)

Cheng, Gang; So, Gary Kwok-Ming; To, Wai-Pong; Chen, Yong; Kwok, Chi-Chung; Ma, Chensheng; Guan, Xiangguo; Chang, Xiaoyong; Kwok, Wai-Ming; Che, Chi-Ming

2015-08-01

The synthesis and spectroscopic properties of luminescent tetranuclear zinc(ii) complexes of substituted 7-azaindoles and a series of luminescent copper(i) complexes containing 7,8-bis(diphenylphosphino)-7,8-dicarba- nido -undecaborate ligand are described. These complexes are stable towards air and moisture. Thin film samples of the luminescent copper(i) complexes in 2,6-dicarbazolo-1,5-pyridine and zinc(ii) complexes in poly(methyl methacrylate) showed emission quantum yields of up to 0.60 (for Cu-3 ) and 0.96 (for Zn-1 ), respectively. Their photophysical properties were examined by ultrafast time-resolved emission spectroscopy, temperature dependent emission lifetime measurements and density functional theory calculations. Monochromic blue and orange solution-processed OLEDs with these Zn(ii) and Cu(i) complexes as light-emitting dopants have been fabricated, respectively. Maximum external quantum efficiency (EQE) of 5.55% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.16, 0.19) were accomplished with the optimized Zn-1 -OLED while these values were, respectively 15.64% and (0.48, 0.51) for the optimized Cu-3 -OLED. Solution-processed white OLEDs having maximum EQE of 6.88%, CIE coordinates of (0.42, 0.44), and colour rendering index of 81 were fabricated by using these luminescent Zn(ii) and Cu(i) complexes as blue and orange light-emitting dopant materials, respectively.

Intramolecular electron transfer in ascorbate oxidase is enhanced in the presence of oxygen

DEFF Research Database (Denmark)

Farver, O; Wherland, S; Pecht, I

1994-01-01

Intramolecular electron transfer from the type 1 copper center to the type 3 copper(II) pair is induced in the multi-copper enzyme, ascorbate oxidase, following pulse radiolytic reduction of the type 1 Cu(II) ion. In the presence of a slight excess of dioxygen over ascorbate oxidase, interaction...... between the trinuclear copper center and O2 is observed even with singly reduced ascorbate oxidase molecules. Under these conditions, the rate constant for intramolecular electron transfer from type 1 Cu(I) to type 3 Cu(II) increases 5-fold to 1100 +/- 300 s-1 (20 degrees C, pH 5.8) as compared...

Hemoglobin and Myoglobin as Reducing Agents in Biological Systems. Redox Reactions of Globins with Copper and Iron Salts and Complexes.

Science.gov (United States)

Postnikova, G B; Shekhovtsova, E A

2016-12-01

In addition to reversible O2 binding, respiratory proteins of the globin family, hemoglobin (Hb) and myoglobin (Mb), participate in redox reactions with various metal complexes, including biologically significant ones, such as those of copper and iron. HbO 2 and MbO 2 are present in cells in large amounts and, as redox agents, can contribute to maintaining cell redox state and resisting oxidative stress. Divalent copper complexes with high redox potentials (E 0 , 200-600 mV) and high stability constants, such as [Cu(phen) 2 ] 2+ , [Cu(dmphen) 2 ] 2+ , and CuDTA oxidize ferrous heme proteins by the simple outer-sphere electron transfer mechanism through overlapping π-orbitals of the heme and the copper complex. Weaker oxidants, such as Cu2+, CuEDTA, CuNTA, CuCit, CuATP, and CuHis (E 0 ≤ 100-150 mV) react with HbO 2 and MbO 2 through preliminary binding to the protein with substitution of the metal ligands with protein groups and subsequent intramolecular electron transfer in the complex (the site-specific outer-sphere electron transfer mechanism). Oxidation of HbO 2 and MbO 2 by potassium ferricyanide and Fe(3) complexes with NTA, EDTA, CDTA, ATP, 2,3-DPG, citrate, and pyrophosphate PP i proceeds mainly through the simple outer-sphere electron transfer mechanism via the exposed heme edge. According to Marcus theory, the rate of this reaction correlates with the difference in redox potentials of the reagents and their self-exchange rates. For charged reagents, the reaction may be preceded by their nonspecific binding to the protein due to electrostatic interactions. The reactions of LbO 2 with carboxylate Fe complexes, unlike its reactions with ferricyanide, occur via the site-specific outer-sphere electron transfer mechanism, even though the same reagents oxidize structurally similar MbO 2 and cytochrome b 5 via the simple outer-sphere electron transfer mechanism. Of particular biological interest is HbO 2 and MbO 2 transformation into met-forms in the presence

Synthesis, X-ray crystal structures, and phosphate ester cleavage properties of bis(2-pyridylmethyl)amine copper(II) complexes with guanidinium pendant groups.

Science.gov (United States)

Belousoff, Matthew J; Tjioe, Linda; Graham, Bim; Spiccia, Leone

2008-10-06

Three new derivatives of bis(2-pyridylmethyl)amine (DPA) featuring ethylguanidinium (L (1)), propylguanidinium (L (2)), or butylguanidinium (L (3)) pendant groups have been prepared by the reaction of N, N- bis(2-pyridylmethyl)alkane-alpha,omega-diamines with 1 H-pyrazole-1-carboxamidine hydrochloride. The corresponding mononuclear copper(II) complexes were prepared by reacting the ligands with copper(II) nitrate and were isolated as [Cu(LH (+))(OH 2)](ClO 4) 3. xNaClO 4. yH 2O ( C1: L = L (1), x = 2, y = 3; C2: L = L (2), x = 2, y = 4; C3: L = L (3), x = 1, y = 0) following cation exchange purification. Recrystallization yielded crystals of composition [Cu(LH (+))(X)](ClO 4) 3.X ( C1': L = L (1), X = MeOH; C2': L = L (2), X = H 2O; C3': L = L (3), X = H 2O), which were suitable for X-ray crystallography. The crystal structures of C1', C2', and C3' indicate that the DPA moieties of the ligands coordinate to the copper(II) centers in a meridional fashion, with a water or methanol molecule occupying the fourth basal position. Weakly bound perchlorate anions located in the axial positions complete the distorted octahedral coordination spheres. The noncoordinating, monoprotonated guanidinium groups project away from the Cu(II)-DPA units and are involved in extensive charge-assisted hydrogen-bonding interactions with cocrystallized water/methanol molecules and perchlorate anions within the crystal lattices. The copper(II) complexes were tested for their ability to promote the cleavage of two model phosphodiesters, bis( p-nitrophenyl)phosphate (BNPP) and uridine-3'- p-nitrophenylphosphate (UpNP), as well as supercoiled plasmid DNA (pBR 322). While the presence of the guanidine pendants was found to be detrimental to BNPP cleavage efficiency, the functionalized complexes were found to cleave plasmid DNA and, in some cases, the model ribose phosphate diester, UpNP, at a faster rate than the parent copper(II) complex of DPA.

Interaction of a copper (II) complex containing an artificial sweetener (aspartame) with calf thymus DNA.

Science.gov (United States)

Shahabadi, Nahid; Khodaei, Mohammad Mehdi; Kashanian, Soheila; Kheirdoosh, Fahimeh

2014-01-01

A copper (II) complex containing aspartame (APM) as ligand, Cu(APM)2Cl2⋅2H2O, was synthesized and characterized. In vitro binding interaction of this complex with native calf thymus DNA (CT-DNA) was studied at physiological pH. The interaction was studied using different methods: spectrophotometric, spectrofluorometric, competition experiment, circular dichroism (CD) and viscosimetric techniques. Hyperchromicity was observed in UV absorption band of Cu(APM)2Cl2⋅2H2O. A strong fluorescence quenching reaction of DNA to Cu(APM)2Cl2⋅2H2O was observed and the binding constants (Kf) and corresponding numbers of binding sites (n) were calculated at different temperatures. Thermodynamic parameters, enthalpy change (ΔH) and entropy change (ΔS) were calculated to be+89.3 kJ mol(-1) and+379.3 J mol(-1) K(-1) according to Van't Hoff equation which indicated that reaction is predominantly entropically driven. Experimental results from spectroscopic methods were comparable and further supported by viscosity measurements. We suggest that Cu(APM)2Cl2⋅2H2O interacts with calf thymus DNA via a groove interaction mode with an intrinsic binding constant of 8×10+4 M(-1). Binding of this copper complex to DNA was found to be stronger compared to aspartame which was studied recently. Copyright © 2013 Elsevier B.V. All rights reserved.

Selective Production of 2-Methylfuran by Gas-Phase Hydrogenation of Furfural on Copper Incorporated by Complexation in Mesoporous Silica Catalysts.

Science.gov (United States)

Jiménez-Gómez, Carmen Pilar; Cecilia, Juan A; Moreno-Tost, Ramón; Maireles-Torres, Pedro

2017-04-10

Copper species have been incorporated in mesoporous silica (MS) through complexation with the amine groups of dodecylamine, which was used as a structure-directing agent in the synthesis. A series of Cu/SiO 2 catalysts (xCu-MS) with copper loadings (x) from 2.5 to 20 wt % was synthesized and evaluated in the gas-phase hydrogenation of furfural (FUR). The most suitable catalytic performance in terms of 2-methylfuran yield was obtained with an intermediate copper content (10 wt %). This 10Cu-MS catalyst exhibits a 2-methylfuran yield higher than 95 mol % after 5 h time-on-stream (TOS) at a reaction temperature of 210 °C with a H 2 /FUR molar ratio of 11.5 and a weight hourly space velocity (WHSV) of 1.5 h -1 . After 14 h TOS, this catalyst still showed a yield of 80 mol %. In all cases, carbonaceous deposits on the external surface were the cause of the catalyst deactivation, although sintering of the copper particles was observed for higher copper loadings. This intermediate copper loading (10 wt %) offered a suitable balance between resistance to sintering and tendency to form carbonaceous deposits. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of glutamic acid on copper sorption onto kaolinite. Batch experiments and surface complexation modeling

Energy Technology Data Exchange (ETDEWEB)

Karimzadeh, Lotfallah; Barthen, Robert; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Reactive Transport; Stockmann, Madlen [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

2017-06-01

In this work, we study the mobility behavior of Cu(II) under conditions related to an alternative, neutrophile biohydrometallurgical Cu(II) leaching approach. Sorption of copper onto kaolinite influenced by glutamic acid (Glu) was investigated in the presence of 0.01 M NaClO{sub 4} by means of binary and ternary batch adsorption measurements over a pH range of 4 to 9 and surface complexation modeling.

Effect of glutamic acid on copper sorption onto kaolinite. Batch experiments and surface complexation modeling

International Nuclear Information System (INIS)

Karimzadeh, Lotfallah; Barthen, Robert; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna; Stockmann, Madlen

2017-01-01

In this work, we study the mobility behavior of Cu(II) under conditions related to an alternative, neutrophile biohydrometallurgical Cu(II) leaching approach. Sorption of copper onto kaolinite influenced by glutamic acid (Glu) was investigated in the presence of 0.01 M NaClO_4 by means of binary and ternary batch adsorption measurements over a pH range of 4 to 9 and surface complexation modeling.

Isolation of a new two-dimensional honeycomb carbonato-bridged copper(II) complex exhibiting long-range ferromagnetic ordering.

Science.gov (United States)

Majumder, Arpi; Choudhury, Chirantan Roy; Mitra, Samiran; Rosair, Georgina M; El Fallah, M Salah; Ribas, Joan

2005-04-28

Atmospheric CO2 fixation by an aqueous solution containing Cu(ClO4)2.6H2O and 4-aminopyridine (4-apy) yields a novel example of a two-dimensional mu3-CO3 bridged copper(II) complex {[Cu(4-apy)2]3(mu3-CO3)2(ClO4)2.(1/2)CH3OH}n that has been characterized by IR, UV and X-ray crystallography; preliminary magnetic measurements show that complex exhibits long-range ordered ferromagnetic coupling.

Synthesis, characterization and catalytic oxidation properties of multi-wall carbon nanotubes with a covalently attached copper(II) salen complex

Science.gov (United States)

Salavati-Niasari, Masoud; Bazarganipour, Mehdi

2009-06-01

Hydroxyl functionalized copper(II) Schiff-base, N,N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diaminecopper(II), [Cu((OH) 2-salen)], has been covalently anchored on modified MWCNTs. The new modified MWCNTs ([Cu((OH) 2-salen)]-MWCNTs) have been characterized by TEM, thermal analysis, XRD, XPS, UV-vis, DRS, FT-IR spectroscopy and elemental analysis. The modified copper(II) MWCNTs solid was used to affect the catalytic oxidation of ethylbenzene with tert-butylhydroperoxide as the oxidant at 333 K. The system is truly heterogeneous (no leaching observed) and reusable (no decrease in activity) in three consecutive runs. Acetophenone was the major product though small amounts of o- and p-hydroxyacetophenones were also formed revealing that C-H bond activation takes place both at benzylic and aromatic ring carbon atoms. Ring hydroxylation was more over the "neat" complexes than over the encapsulated complexes.

Copper(II) and molybdenum(VI) complexes of a tridentate ONN donor isothiosemicarbazone: synthesis, characterization, X-ray, TGA and DFT

Czech Academy of Sciences Publication Activity Database

Fasihizad, A.; Akbari, A.; Ahmadi, M.; Dušek, Michal; Henriques, Margarida Isabel Sousa; Pojarová, Michaela

2016-01-01

Roč. 115, Sep (2016), s. 297-305 ISSN 0277-5387 R&D Projects: GA ČR(CZ) GA14-03276S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : isothiosemicarbazone * Copper(II) complex * molybdenum(VI) complex * crystal structure * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.926, year: 2016

2-Organoselenomethyl-1H-benzimidazole Complexes of Copper(II) and Copper(I)

Czech Academy of Sciences Publication Activity Database

Leboschka, M.; Sieger, M.; Sarkar, B.; Heck, J.; Niemeyer, M.; Bubrin, D.; Lissner, F.; Schleid, T.; Záliš, Stanislav; Su, Ch. Y.; Kaim, W.

2009-01-01

Roč. 635, 13-14 (2009), s. 2177-2184 ISSN 0044-2313 R&D Projects: GA MŠk OC 139; GA AV ČR KAN100400702 Institutional research plan: CEZ:AV0Z40400503 Keywords : coordination models * copper * imidazole ligands * selenoether ligands Subject RIV: CG - Electrochemistry Impact factor: 1.226, year: 2009

Copper complexes containing thiosemicarbazones derived from 6-nitropiperonal: Antimicrobial and biophysical properties

Science.gov (United States)

Beckford, Floyd A.; Webb, Kelsey R.

2017-08-01

A series of four thiosemicarbazones from 6-nitropiperonal along with the corresponding copper complexes were synthesized. The biophysical characteristics of the complexes were investigated by the binding to DNA and human serum albumin. The binding to DNA is moderate; the binding constants run from (0.49-7.50) × 104 M- 1. In relation to HSA, the complexes interact strongly with binding constants on the order of 105 M- 1. The complexes also display antioxidant behavior as determined by the ability to scavenge diphenylpicrylhydrazyl (dpph) and nitric oxide radicals. The antimicrobial profiles of the compounds, tested against a panel of microbes including five of the ESKAPE pathogens (Staphylococcus aureus, MRSA, Escherichia coli, Klebsiella pneumoniae, MDR, Acinetobacter baumannii, Pseudomonas aeruginosa) and two yeasts (Candida albicans and Cryptococcus neoformans var. grubii), are also described. The compounds contain a core moiety that is similar to oxolinic acid, a quinolone antibiotic that targets DNA gyrase and topoisomerase (IV). The binding interaction between the complexes and these important antibacterial targets were studied by computational methods, chiefly docking studies. The calculated dissociation constants for the interaction with DNA gyrase B (from Staphylococcus aureus) range from 4.32 to 24.65 μM; the binding was much stronger to topoisomerase IV, with dissociation constants ranging from 0.37 to 1.27 μM.

Cytokinin oxidase from Phaseolus vulgaris callus tissues. Enhanced in vitro activity of the enzyme in the presence of copper-imidazole complexes

International Nuclear Information System (INIS)

Chatfield, J.M.; Armstrong, D.J.

1987-01-01

The effects of metal ions on cytokinin oxidase activity extracted from callus tissues of Phaseolus vulgaris L. cv Great Northern have been examined using an assay based on the oxidation of N 6 -(Δ 2 -isopentenyl)-adenine-2,8- 3 H (i 6 Ade) to adenine (Ade). The addition of cupric ions to reaction mixtures containing imidazole buffer markedly enhanced cytokinin oxidase activity. In the presence of optimal concentrations of copper and imidazole, cytokinin oxidase activity was stimulated more than 20-fold. The effect was enzyme dependent, specific for copper, and observed only in the presence of imidazole. The substrate specificity of the copper-imidazole enhanced reaction, as judged by substrate competition tests, was the same as that observed in the absence of copper and imidazole. Similarly, in tests involving DEAE-cellulose chromatography, elution profiles of cytokinin oxidase activity determined using a copper-imidazole enhanced assay were identical to those obtained using an assay without copper and imidazole. On the basis of these results, the addition of copper and imidazole to reaction mixtures used to assay for cytokinin oxidase activity is judged to provide a reliable and specific assay of greatly enhanced sensitivity for the enzyme. The mechanism by which copper and imidazole enhance cytokinin oxidase activity is not certain, but the reaction catalyzed by the enzyme was not inhibited by anaerobic conditions when these reagents were present. This observation suggests that copper-imidazole complexes are substituting for oxygen in the reaction mechanism by which cytokinin oxidase effects cleavage of the N 6 -side chain of i 6 Ade

Copper(I) in fogwater: Determination and interactions with sulfite

Energy Technology Data Exchange (ETDEWEB)

Hanbin Xue; Reutlinger, M.; Sigg, L.; Stumm, W. (Swiss Federal Inst. of Tech., Duebendorf (Switzerland)); Lurdes S. Goncalves, M. de (Inst. Superior Tecnico, Lisbon (Portugal))

1991-10-01

The copper(I)/(II) redox system was examined in fogwater with respect to the occurrence of Cu(I), the role of sulfite as a reductant of Cu(II) and as a complexing ligand, and the speciation of Cu(I) and Cu(II). Copper(I) was measured in fogwater by the bathocuproine method, which was evaluated for the conditions typically encountered in atmospheric water droplets. Concentrations of Cu(I) in the range 0.1-1 {mu}M were found, which represented between 4 and > 90% of the total copper in these samples. In experiments using concentration ranges of copper and S(IV) close to that of fogwater, the reduction of copper(II) to copper(I) by sulfite was shown to be pH-dependent and to occur rapidly at pH > 6. Calculations of the equilibrium complexation of Cu(I) and Cu(II) under fogwater conditions show that complexes of Cu(I) with sulfite predominate, while for Cu(II) oxalato complexes are important. Sulfite plays an important role as a ligand for Cu(I) in fogwater; Cu(I) may be produced by various reduction reactions, e.g., by organic compounds, and appears to be oxidized only slowly in the presence of S(IV).

Synthesis, spectroscopic characterization, crystallographic studies and antibacterial assays of new copper(II) complexes with sulfathiazole and nimesulide

Science.gov (United States)

Nunes, Julia Helena Bormio; de Paiva, Raphael Enoque Ferraz; Cuin, Alexandre; da Costa Ferreira, Ana Maria; Lustri, Wilton Rogério; Corbi, Pedro Paulo

2016-05-01

New ternary copper(II) complexes of sulfathiazole (SFT, C9H8N3O2S2) or nimesulide (NMS, C13H11N2O5S) and 2,2‧-bipyridine (bipy) were synthesized, and characterized by chemical and spectroscopic techniques. Elemental analyses indicated a 2:1:1 sulfonamide/copper/bipy composition for both complexes. Mass spectrometric measurements permitted identifying the molecular ions [Cu(SFT)2(bipy)+H]+ and [Cu(NMS)2(bipy)+H]+ at m/z 728 and 835, respectively, confirming the proposed compositions. Crystal structure of the [Cu(SFT)2(bipy)] complex was solved by powder X-ray diffraction analysis (PXRD), attesting that the Cu(II) ion is hexacoordinated in a distorted octahedral geometry. Each SFT molecule coordinates to the metal ion by the nitrogen atoms of the SO2-N group and of the heterocyclic ring. The coordination sphere is completed by a bipyridine. Electronic paramagnetic resonance (EPR) studies were carried out for the [Cu(NMS)2(bipy)] complex, indicating a tetragonal environment around the metal ion. It was suggested that NMS coordinates to Cu(II) by the nitrogen and oxygen atoms of the SO2-N group, which was confirmed by infrared spectroscopic studies. Biological studies showed the antibacterial activity of both Cu-SFT and Cu-NMS complexes, with the minimum inhibitory concentration (MIC) values ranging from 0.10 to 0.84 mmol L-1 against Gram-negative bacteria for [Cu(SFT)2(bipy)], and from 1.50 to 3.00 mmol L-1 against Gram-positive and -negative bacteria for [Cu(NMS)2(bipy)].

Synthesis, Characterization and DNA Cleavage of Copper(II ...

African Journals Online (AJOL)

Purpose: To study deoxyribonucleic acid (DNA) shearing capability of copper(II) complex of dithiothreitol (DTT) and to fevaluate its potential application in cancer therapy. Methods: A parrot green complex was synthesized by grinding copper acetate monohydrate and DTT in 1:2 molar ratio in a mortar until no fumes of acetic ...

Synthesis of an S T = 7 [Mn 3 ] Mixed-Valence Complex Based on 1,3-Propanediol Ligand Derivatives and Its One-Dimensional Assemblies

KAUST Repository

Huang, Jian; Wu, Gang; Bai, Jiaquan; Jiang, Yuan; Li, Guanghua; Qiu, Shilun; Clé rac, Rodolphe

2013-01-01

. In this work, a new ST = 7 trinuclear mixed-valence Mn complex, [MnIIIMnII 2(LA) 2(Br)4(CH3OH)6] ·Br· (CH3OH)1.5·(H2O)0.5 (1), is reported using a pyridinium-functionalized 1,3-propanediol ligand (H 2LABr = 1-(3-bromo-2,2-bis

Chalcogenhalide cluster rhenium- and molybdenum complexes

International Nuclear Information System (INIS)

Fedin, V.P.; Gubin, S.P.; Mishchenko, A.V.; Fedorov, V.E.

1984-01-01

The interaction of rhenium- and molybdenum chalcogenhalides with n-donor ligands (L) is studied. At heating Re 3 X 2 Hal 5 complexes up to 100 deg in DMSO in the L presence obtained are the complexes of the 1-6 composition Re 3 X 2 Hal 5 -x Lx DMSO (X=Se, Hal=Cl, L=Et 3 N(1); X=Se, Hal=Cl, L=Bipy(2); X=Se, Hal=Br, L=Et 3 N(3); X=Se, Hal=Br, L=Bipy(4); X=Te, Hal=Br, L=Et 3 N(5); X=Te, Hal=Br, L=(Me 2 NCH 2 ) 2 (6). In the course of boiling of Mo 3 S 7 Hal 4 with PPh 3 in MeCN the Mo 3 S 7 Hal 4 2PPh 3 complexes (Hal=Cl(7); Br(8)) are obtained. For 1 through 8 complexes the chemical analysis data and IR spectra are given. For 4 and 8 complexes the molecular mass is measured. A possible method of obtaining molecular trinuclear clusters from polymer clusters is discussed

Unprecedented hetero-geometric discrete copper(II) complexes ...

Indian Academy of Sciences (India)

Copper; X-ray structure; radical activity; catechol oxidase activity. 1. Introduction ... dylamine and thiocyanate ions but none of these groups .... Independent reflections. 7978 ... was added to it to achieve the ultimate concentration of .... as exchange couples so as to form a single species with ... cantly on central Cu(II) ion.

Bonding and structure of copper nitrenes.

Science.gov (United States)

Cundari, Thomas R; Dinescu, Adriana; Kazi, Abul B

2008-11-03

Copper nitrenes are of interest as intermediates in the catalytic aziridination of olefins and the amination of C-H bonds. However, despite advances in the isolation and study of late-transition-metal multiply bonded complexes, a bona fide structurally characterized example of a terminal copper nitrene has, to our knowledge, not been reported. In anticipation of such a report, terminal copper nitrenes are studied from a computational perspective. The nitrene complexes studied here are of the form (beta-diketiminate)Cu(NPh). Density functional theory (DFT), complete active space self-consistent-field (CASSCF) electronic structure techniques, and hybrid quantum mechanical/molecular mechanical (QM/MM) methods are employed to study such species. While DFT methods indicate that a triplet (S = 1) is the ground state, CASSCF calculations indicate that a singlet (S = 0) is the ground state, with only a small energy gap between the singlet and triplet. Moreover, the ground-state (open-shell) singlet copper nitrene is found to be highly multiconfigurational (i.e., biradical) and to possess a bent geometry about the nitrene nitrogen, contrasting with the linear nitrene geometry of the triplet copper nitrenes. CASSCF calculations also reveal the existence of a closed-shell singlet state with some degree of multiple bonding character for the copper-nitrene bond.

Preparation, characterization, and kinetics of thermolysis of nickel and copper nitrate complexes with 2,2 Prime -bipyridine ligand

Energy Technology Data Exchange (ETDEWEB)

Kumar, Dinesh; Kapoor, I.P.S. [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273 009 (India); Singh, Gurdip, E-mail: gsingh4us@yahoo.com [Department of Chemistry, DDU Gorakhpur University, Gorakhpur 273 009 (India); Froehlich, Roland [Institut fuer Organische Chemie, Universitaet Muenster, D-48149 Muenster (Germany)

2012-10-10

Graphical abstract: Nickel and copper nitrate complexes with 2,2 Prime -bipyridine, nitrate and water ligands have been prepared and characterized by single crystal X-ray diffraction, FT-IR and CHN analyses. Thermolysis was performed by using TG, DTA and ignition delay measurements. The kinetics of thermolysis were also evaluated. Highlights: Black-Right-Pointing-Pointer Preparation and characterization of Ni and Cu nitrate complexes have been reported. Black-Right-Pointing-Pointer Thermolysis has been carried out using TG-DTA and ignition delay measurements. Black-Right-Pointing-Pointer Their thermal decomposition pathways have been proposed. Black-Right-Pointing-Pointer Oxides residues as end product of thermolysis were revealed by XRD patterns. Black-Right-Pointing-Pointer Kinetics of their isothermal decomposition was evaluated. - Abstract: Nickel and copper nitrate complexes with 2,2 Prime -bipyridine (bipy) as a N donor and nitrate and water as oxygen donor ligands of the general formula [M(NO{sub 3})(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O){sub 3}](NO{sub 3}), where M = Ni and Cu, have been obtained from the corresponding metal nitrate salts. These complexes were characterized by X-ray crystallography, FT-IR, and CHN analysis. Both the complexes have been found to be six coordinated. Their thermal decomposition behaviour was investigated by TG, DTA, and ignition delay measurements. TG-DTA examinations of these complexes revealed multistep thermal decomposition. The corresponding metal oxide residues obtained after thermolysis were identified from their X-ray diffraction patterns (XRD). Kinetics of isothermal decomposition of the complexes was established from both the model-fitting as well as isoconversional methods.

Copper (II) and zinc (II) complexes with flavanone derivatives: Identification of potential cholinesterase inhibitors by on-flow assays.

Science.gov (United States)

Sarria, André Lucio Franceschini; Vilela, Adriana Ferreira Lopes; Frugeri, Bárbara Mammana; Fernandes, João Batista; Carlos, Rose Maria; da Silva, Maria Fátima das Graças Fernandes; Cass, Quezia Bezerra; Cardoso, Carmen Lúcia

2016-11-01

Metal chelates strongly influence the nature and magnitude of pharmacological activities in flavonoids. In recent years, studies have shown that a promising class of flavanone-metal ion complexes can act as selective cholinesterase inhibitors (ChEIs), which has led our group to synthesize a new series of flavanone derivatives (hesperidin, hesperetin, naringin, and naringenin) complexed to either copper (II) or zinc (II) and to evaluate their potential use as selective ChEIs. Most of the synthesized complexes exhibited greater inhibitory activity against acetylcholinesterase (AChE) than against butyrylcholinesterase (BChE). Nine of these complexes constituted potent, reversible, and selective ChEIs with inhibitory potency (IC 50 ) and inhibitory constant (K i ) ranging from 0.02 to 4.5μM. Copper complexes with flavanone-bipyridine derivatives afforded the best inhibitory activity against AChE and BChE. The complex Cu(naringin)(2,2'-bipyridine) (11) gave IC 50 and K i values of 0.012±0.002 and 0.07±0.01μM for huAChE, respectively, which were lower than the inhibitory values obtained for standard galanthamine (IC 50 =206±30.0 and K i =126±18.0μM). Evaluation of the inhibitory activity of this complex against butyrylcholinesterase from human serum (huBChE) gave IC 50 and K i values of 8.0±1.4 and 2.0±0.1μM, respectively. A Liquid Chromatography-Immobilized Capillary Enzyme Reactor by UV detection (LC-ICER-UV) assay allowed us to determine the IC 50 and K i values and the type of mechanism for the best inhibitors. Copyright © 2016 Elsevier Inc. All rights reserved.

Adsorption of 2-mercaptobenzothiazole on copper surface from phosphate solutions

International Nuclear Information System (INIS)

Kazansky, L.P.; Selyaninov, I.A.; Kuznetsov, Yu.I.

2012-01-01

Analysis of the electrochemical and XPS results has shown that adsorption of 2-mercaptobenzothiazole (MBT) on copper electrodes in neutral phosphate solutions proceeds through the formation of the chemical bonds by copper (I) cations with exo-sulfur and nitrogen atoms. A protection layer formed of Cu(I)MBT complex prevents precipitation of copper (II) phosphate on a copper surface. The thickness of the surface film consisting of a complex [Cu(I)MBT] n (having probably polymeric nature), where MBT acts as at least three-dentate ligand, increases depending on the exposure time, reaching 8-9 nm after immersing for 12 h in test solution. Even in a case of the preliminary formation of copper (II) phosphate on the copper electrode at the anodic potential addition of small amounts of MBT results in complete removal of copper (II) phosphate from the surface.

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of N'-(furan-3-ylmethylene)-2-(4-methoxyphenylamino)acetohydrazide.

Science.gov (United States)

Emam, Sanaa M; El-Saied, Fathy A; Abou El-Enein, Saeyda A; El-Shater, Heba A

2009-03-01

Cobalt(II), nickel(II), copper(II), zinc(II) and hafnium(IV) complexes of furan-2-carbaldehyde 4-methoxy-N-anilinoacetohydrazone were synthesized and characterized by elemental and thermal (TG and DTA) analyses, IR, UV-vis and (1)H NMR spectra as well as magnetic moment and molar conductivity. Mononuclear complexes are obtained with 1:1 molar ratio except complexes 3 and 9 which are obtained with 1:2 molar ratios. The IR spectra of ligand and metal complexes reveal various modes of chelation. The ligand behaves as a neutral bidentate one and coordination occurs via the carbonyl oxygen atom and azomethine nitrogen atom. The ligand behaves also as a monobasic tridentate one and coordination occurs through the enolic oxygen atom, azomethine nitrogen atom and the oxygen atom of furan ring. Moreover, the ligand behaves as a neutral tridentate and coordination occurs via the carbonyl oxygen, azomethine nitrogen and furan oxygen atoms as well as a monobasic bidentate and coordination occurs via the enolic oxygen atom and azomethine nitrogen atom. The electronic spectra and magnetic moment measurements reveal that all complexes possess octahedral geometry except the copper complex 10 possesses a square planar geometry. The thermal studies showed the type of water molecules involved in metal complexes as well as the thermal decomposition of some metal complexes.

Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding.

Science.gov (United States)

Bag, Pradip; Dutta, Supriya; Biswas, Papu; Maji, Swarup Kumar; Flörke, Ulrich; Nag, Kamalaksha

2012-03-28

A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).

In vitro antioxidant activity, enzyme kinetics, biostability and cellular SOD mimicking ability of 1:1 curcumin-copper (II) complex

International Nuclear Information System (INIS)

Kunwar, A.; Mishra, B.; Barik, A.; Priyadarsini, K.I.; Narang, H.; Krishna, M.

2008-01-01

In vitro antioxidant activity of 1:1 curcumin copper (II) complex was evaluated by following the inhibition of γ-radiation induced lipid peroxidation and protein oxidation in model systems. The SOD enzyme kinetic parameters K m and V max values and the turn over number of the complex were determined. The complex is stable in bio-fluids and prevents oxidation of lipid and protein solution in presence of H 2 O 2 and showed reduction in MnSOD level in spleen cells without having any effect on cell viability. (author)

In vitro antioxidant activity, enzyme kinetics, biostability and cellular SOD mimicking ability of 1:1 curcumin-copper (II) complex

Energy Technology Data Exchange (ETDEWEB)

Kunwar, A; Mishra, B; Barik, A; Priyadarsini, K I [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India); Narang, H; Krishna, M [Radiation Biology and Health Sciences Div., Bhabha Atomic Research Centre, Mumbai (India)

2008-01-15

In vitro antioxidant activity of 1:1 curcumin copper (II) complex was evaluated by following the inhibition of {gamma}-radiation induced lipid peroxidation and protein oxidation in model systems. The SOD enzyme kinetic parameters K{sub m} and V{sub max} values and the turn over number of the complex were determined. The complex is stable in bio-fluids and prevents oxidation of lipid and protein solution in presence of H{sub 2}O{sub 2} and showed reduction in MnSOD level in spleen cells without having any effect on cell viability. (author)

Albumin has no role in the uptake of copper by human fibroblasts

International Nuclear Information System (INIS)

McArdle, H.J.; Guthrie, J.R.; Ackland, M.L.; Danks, D.M.

1987-01-01

The mechanism of copper uptake by cells has been the subject of controversy for some time. This paper examines the possibility of a role for albumin in the uptake of copper by fibroblasts. Although the cells could accumulate copper from a copper-albumin complex, there was no evidence for either copper-albumin or albumin receptors on the cell surface. The possibility of a surface exchange mechanism for copper was examined. While copper uptake showed saturation with increasing concentrations of labelled copper-albumin, adding unlabelled copper to the incubation medium did not inhibit uptake. Adding albumin or histidine to the copper-albumin complex resulted in an inhibition of copper uptake. The results can only be explained by the cell taking up free copper from the incubation medium, with the albumin then releasing its copper to maintain the equilibrium between free and bound metal. Since, in vivo there is essentially no free copper in serum, it is concluded that albumin is most unlikely to play a role in the uptake of copper by fibroblasts

Electronic Structural Analysis of Copper(II)–TEMPO/ABNO Complexes Provides Evidence for Copper(I)–Oxoammonium Character

International Nuclear Information System (INIS)

Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.; MacMillan, Samantha N.; Stahl, Shannon S.; Lancaster, Kyle M.

2017-01-01

Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and here we probe this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L 2,3 - edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-driven alcohol oxidation reactions, with similar findings. On the whole, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co- catalyst system.

Effectiveness acidic pre-cleaning for copper-gold ore

Directory of Open Access Journals (Sweden)

Antonio Clareti Pereira

Full Text Available Abstract The presence of copper-bearing minerals is known to bring on many challenges during the cyanidation of gold ore, like high consumption of cyanide and low extraction of metal, which are undesirable impacts on the auriferous recovery in the subsequent process step. The high copper solubility in cyanide prevents the direct use of classical hydrometallurgical processes for the extraction of gold by cyanidation. Additionally, the application of a conventional flotation process to extract copper is further complicated when it is oxidized. As a result, an acid pre-leaching process was applied in order to clean the ore of these copper minerals that are cyanide consumers. The objective was to evaluate the amount of soluble copper in cyanide before and after acidic cleaning. From a gold ore containing copper, the study selected four samples containing 0.22%, 0.55%, 1.00% and 1.36% of copper. For direct cyanidation of the ore without pre-treatment, copper extraction by cyanide complexing ranged from 8 to 83%. In contrast, the pre-treatment carried out with sulfuric acid extracted 24% to 99% of initial copper and subsequent cyanidation extracted 0.13 to 1.54% of initial copper. The study also showed that the copper contained in the secondary minerals is more easily extracted by cyanide (83%, being followed by the copper oxy-hydroxide minerals (60%, while the copper contained in the manganese oxide is less complexed by cyanide (8% a 12%. It was possible to observe that minerals with low acid solubility also have low solubility in cyanide. Cyanide consumption decreased by about 2.5 times and gold recovery increased to above 94% after acidic pre-cleaning.

Studies on Cementation of Tin on Copper and Tin Stripping from Copper Substrate

Directory of Open Access Journals (Sweden)

Rudnik E.

2016-06-01

Full Text Available Cementation of tin on copper in acid chloride-thiourea solutions leads to the formation of porous layers with a thickness dependent on the immersion time. The process occurs via Sn(II-Cu(I mechanism. Chemical stripping of tin was carried out in alkaline and acid solutions in the presence of oxidizing agents. It resulted in the dissolution of metallic tin, but refractory Cu3Sn phase remained on the copper surface. Electrochemical tin stripping allows complete tin removal from the copper substrate, but porosity and complex phase composition of the tin coating do not allow monitoring the process in unambiguous way.

A differential genome-wide transcriptome analysis: impact of cellular copper on complex biological processes like aging and development.

Directory of Open Access Journals (Sweden)

Jörg Servos

Full Text Available The regulation of cellular copper homeostasis is crucial in biology. Impairments lead to severe dysfunctions and are known to affect aging and development. Previously, a loss-of-function mutation in the gene encoding the copper-sensing and copper-regulated transcription factor GRISEA of the filamentous fungus Podospora anserina was reported to lead to cellular copper depletion and a pleiotropic phenotype with hypopigmentation of the mycelium and the ascospores, affected fertility and increased lifespan by approximately 60% when compared to the wild type. This phenotype is linked to a switch from a copper-dependent standard to an alternative respiration leading to both a reduced generation of reactive oxygen species (ROS and of adenosine triphosphate (ATP. We performed a genome-wide comparative transcriptome analysis of a wild-type strain and the copper-depleted grisea mutant. We unambiguously assigned 9,700 sequences of the transcriptome in both strains to the more than 10,600 predicted and annotated open reading frames of the P. anserina genome indicating 90% coverage of the transcriptome. 4,752 of the transcripts differed significantly in abundance with 1,156 transcripts differing at least 3-fold. Selected genes were investigated by qRT-PCR analyses. Apart from this general characterization we analyzed the data with special emphasis on molecular pathways related to the grisea mutation taking advantage of the available complete genomic sequence of P. anserina. This analysis verified but also corrected conclusions from earlier data obtained by single gene analysis, identified new candidates of factors as part of the cellular copper homeostasis system including target genes of transcription factor GRISEA, and provides a rich reference source of quantitative data for further in detail investigations. Overall, the present study demonstrates the importance of systems biology approaches also in cases were mutations in single genes are analyzed to

In vitro and in vivo anti-inflammatory active copper(II-lawsone complexes.

Directory of Open Access Journals (Sweden)

Ján Vančo

Full Text Available We report in vitro and in vivo anti-inflammatory activities of a series of copper(II-lawsone complexes of the general composition [Cu(Law2(LNx(H2O(2-x]·yH2O; where HLaw = 2-hydroxy-1,4-naphthoquinone, x = 1 when LN = pyridine (1 and 2-aminopyridine (3 and x = 2 when LN = imidazole (2, 3-aminopyridine (4, 4-aminopyridine (5, 3-hydroxypyridine (6, and 3,5-dimethylpyrazole (7. The compounds were thoroughly characterized by physical techniques, including single crystal X-ray analysis of complex 2. Some of the complexes showed the ability to suppress significantly the activation of nuclear factor κB (NF-κB both by lipopolysaccharide (LPS and TNF-alpha (complexes 3-7 at 100 nM level in the similar manner as the reference drug prednisone (at 1 μM level. On the other hand, all the complexes 1-7 decreased significantly the levels of the secreted TNF-alpha after the LPS activation of THP-1 cells, thus showing the anti-inflammatory potential via both NF-κB moderation and by other mechanisms, such as influence on TNF-alpha transcription and/or translation and/or secretion. In addition, a strong intracellular pro-oxidative effect of all the complexes has been found at 100 nM dose in vitro. The ability to suppress the inflammatory response, caused by the subcutaneous application of λ-carrageenan, has been determined by in vivo testing in hind-paw edema model on rats. The most active complexes 1-3 (applied in a dose corresponding to 40 μmol Cu/kg, diminished the formation of edema simalarly as the reference drug indomethacine (applied in 10 mg/kg dose. The overall effect of the complexes, dominantly 1-3, shows similarity to anti-inflammatory drug benoxaprofen, known to induce intracellular pro-oxidative effects.

Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

Science.gov (United States)

Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

2015-01-01

A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

A New Polynuclear Coordination Type for (Salicylaldoxime)copper(II) Complexes: Structure and Magnetic Properties of an (Oxime)Cu₆ Cluster

DEFF Research Database (Denmark)

Wenzel, Marco; Forgan, Ross S.; Faure, Anaëlle

2009-01-01

A previously unseen coordination mode is reported for (salicylaldoxime)copper complexes utilising a linked zwitterionic NO22- donor set. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)...

Unusual saccharin-N,O (carbonyl) coordination in mixed-ligand copper(II) complexes: Synthesis, X-ray crystallography and biological activity

Science.gov (United States)

Mokhtaruddin, Nur Shuhada Mohd; Yusof, Enis Nadia Md; Ravoof, Thahira B. S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhi; Tahir, Mohamed Ibrahim Mohamed

2017-07-01

Three tridentate Schiff bases containing N and S donor atoms were synthesized via the condensation reaction between S-2-methylbenzyldithiocarbazate with 2-acetyl-4-methylpyridine (S2APH); 4-methyl-3-thiosemicarbazide with 2-acetylpyridine (MT2APH) and 4-ethyl-3-thiosemicarbazide with 2-acetylpyridine (ET2APH). Three new, binuclear and mixed-ligand copper(II) complexes with the general formula, [Cu(sac)(L)]2 (sac = saccharinate anion; L = anion of the Schiff base) were then synthesized, and subsequently characterized by IR and UV/Vis spectroscopy as well as by molar conductivity and magnetic susceptibility measurements. The Schiff bases were also spectroscopically characterized using NMR and MS to further confirm their structures. The spectroscopic data indicated that the Schiff bases behaved as a tridentate NNS donor ligands coordinating via the pyridyl-nitrogen, azomethine-nitrogen and thiolate-sulphur atoms. Magnetic data indicated a square pyramidal environment for the complexes and the conductivity values showed that the complexes were essentially non-electrolytes in DMSO. The X-ray crystallographic analysis of one complex, [Cu(sac)(S2AP)]2 showed that the Cu(II) atom was coordinated to the thiolate-S, azomethine-N and pyridyl-N donors of the S2AP Schiff base and to the saccharinate-N from one anion, as well as to the carbonyl-O atom from a symmetry related saccharinate anion yielding a centrosymmetric binuclear complex with a penta-coordinate, square pyramidal geometry. All the copper(II) saccharinate complexes were found to display strong cytotoxic activity against the MCF-7 and MDA-MB-231 human breast cancer cell lines.

Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2).

Science.gov (United States)

AbouEl-Enein, S A; El-Saied, F A; Kasher, T I; El-Wardany, A H

2007-07-01

Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.

Enrichment of copper and recycling of cyanide from copper-cyanide waste by solvent extraction

Science.gov (United States)

Gao, Teng-yue; Liu, Kui-ren; Han, Qing; Xu, Bin-shi

2016-11-01

The enrichment of copper from copper-cyanide wastewater by solvent extraction was investigated using a quaternary ammonium salt as an extractant. The influences of important parameters, e.g., organic-phase components, aqueous pH values, temperature, inorganic anion impurities, CN/Cu molar ratio, and stripping reagents, were examined systematically, and the optimal conditions were determined. The results indicated that copper was effectively concentrated from low-concentration solutions using Aliquat 336 and that the extraction efficiency increased linearly with increasing temperature. The aqueous pH value and concentrations of inorganic anion impurities only weakly affected the extraction process when varied in appropriate ranges. The CN/Cu molar ratio affected the extraction efficiency by changing the distribution of copper-cyanide complexes. The difference in gold leaching efficiency between using raffinate and fresh water was negligible.

Neurokinin B and serum albumin limit copper binding to mammalian gonadotropin releasing hormone.

Science.gov (United States)

Gul, Ahmad Samir; Tran, Kevin K; Jones, Christopher E

2018-02-26

Gonadotropin releasing hormone (GnRH) triggers secretion of luteinizing hormone and follicle stimulating hormone from gonadotropic cells in the anterior pituitary gland. GnRH is able to bind copper, and both in vitro and in vivo studies have suggested that the copper-GnRH complex is more potent at triggering gonadotropin release than GnRH alone. However, it remains unclear whether copper-GnRH is the active species in vivo. To explore this we have estimated the GnRH-copper affinity and have examined whether GnRH remains copper-bound in the presence of serum albumin and the neuropeptide neurokinin B, both copper-binding proteins that GnRH will encounter in vivo. We show that GnRH has a copper dissociation constant of ∼0.9 × 10 -9  M, however serum albumin and neurokinin B can extract metal from the copper-GnRH complex. It is therefore unlikely that a copper-GnRH complex will survive transit through the pituitary portal circulation and that any effect of copper must occur outside the bloodstream in the absence of neurokinin B. Copyright © 2018 Elsevier Inc. All rights reserved.

Two new barium-copper-ethylene glycol complexes: Synthesis and structure of BaCu(C2H6O2)n(C2H4O2)2 (N = 3, 6)

International Nuclear Information System (INIS)

Love, C.P.; Page, C.J.; Torardi, C.C.

1992-01-01

Two crystalline barium-copper-ethylene glycol complexes have been isolated and structurally characterized by single-crystal x-ray diffraction. The solution-phase complex has also been investigated as a molecular precursor for use in sol-gel synthesis of high-temperature superconductors. The first crystalline form has the formula BaCu(C 2 H 6 O 2 ) 6 (C 2 H 4 O 2 ) 2 (1) and has been isolated directly from ethylene glycol solutions of the barium-copper salt. In this molecule, copper is coordinated to the four xygens of two ethylene glycolate ligands in a nearly square planar geometry. Barium is coordinated by three bidentate ethylene glycol molecules and three monodentate ethylene glycol molecules; the 9-fold coordination resembles a trigonal prism with each rectangular face capped. Copper and barium moieties do not share any ethylene glycol or glycolate oxygens; they are found by hydrogen bonding to form linear chains. The second crystal type has formula BaCu(C 2 H 6 O 2 ) 3 (C 2 H 4 O 2 ) 2 (2). It was prepared via crystallization of the mixed-metal alkoxide from an ethylene glycol/methyl ethyl ketone solution. As for 1, the copper is coordinated to four oxygen atoms of two ethylene glycolate ligands in a nearly square planar arrangement. Barium is 8-coordinate in a distorted cubic geometry. It is coordinated to three bidentate ethylene glycol molecules and shares two of the oxygen atoms bound to the copper (one from each coordinated ethylene glycol) to form a discrete molecular barium-copper complex

Uranyl complexes of ν-polyketonates. Crystal and molecular structure of a mononuclear uranyl 1,3,5-triketonate and a novel trinuclear uranyl 1,3,5-triketonate with a trigonal-planar bridging oxide

International Nuclear Information System (INIS)

Lintvedt, R.L.; Heeg, M.J.; Ahmad, N.; Glick, M.D.

1982-01-01

Two uranyl complexes of 1,3,5-triketonate ligands have been crystallized and examined by X-ray diffraction techniques. The first is the mononuclear bis[1,5-diphenyl-1,3,5-pentanetrionato(1-)](methanol)dioxouranium(VI)-methanol,[UO 2 -(C 35 H 30 O 7 )(CH 3 OH)],UO 2 (H(DBA)) 2 (CH 3 OH).CH 3 OH, in which the uranium atom is bound to four enolic oxygens, two uranyl oxygens, and one methanolic oxygen. The triketonate ligands are in a cis configuration presumably due to the steric constraints of the methanol coordination. Crystal data are as follows: P2 1 /c, a = 9.932 (4), b = 30.29 (4), c = 11.671 (4) angstrom; ν = 103.03 0 , V = 3421 (2) angstrom 3 ; Z = 4, R 1 = 0.048, R 2 = 0.050. The second is a trinuclear UO 2 2 + anion containing a trigonal, tribridging oxide ion that results during attempts to prepare binuclear UO 2 2 + complexes of 1,3,5-triketonates. The compound bis(triethylammonium) tris(2,2',8,8'-tetramethyl-3,5,7-nonanetrionato)-μ 3 -oxo-tris(dioxo-uranate)(2-), [(C 2 H 5 ) 3 NH] 2 [U 3 O 6 (C 39 H 60 O 9 )O], [(C 2 H 5 ) 3 NH] 2 [(UO 2 ) 3 (DPA) 3 O], contains a nearly equilateral triangle of UO 2 2 + ions with a central O 2 - ion trigonally bonded to the three U atoms. One triketonate occupies each edge of the trangle with the central enolic oxygen bridging two U atoms and the terminal oxygens bound to one U atom. Each U is seven-coordinate in nearly pentagonal-bipyramidal geometry. Crystal data are as follows: C2/c, a = 27.90 (2), b = 15.65 (2), c = 31.81 (3) angstrom; ν = 107.8 (1) 0 , V = 13220 (20), angstrom 3 ; Z = 8, R 1 = 0.062, R 2 = 0.078

Synthesis and properties of complexes of copper(II), nickel(II), cobalt(II) and uranyl ions with 3-(p-tolylsulphonamido)rhodamine

International Nuclear Information System (INIS)

El-Bindary, A.A.; El-Sonbati, A.Z.

2000-01-01

Metal complexes of copper(II), nickel(II), cobalt(II) and uranyl ions with 3-(p-tolylsulphonamido)rhodamine (HL) have been prepared and characterized by chemical and thermal analyses, molar conductivity , magnetic susceptibility measurements, and infrared, electronic and EPR spectra. The visible and EPR spectra indicated that the Cu(II) complex has a tetragonal geometry. From EPR spectrum of the Cu(II) complex,various parameters were calculated. The crystal field parameters of Ni(II) complex were calculated and were found to agree fairly well with the values reported for known square pyramidal complexes. The infrared spectral studies showed a monobasic bidentate behaviour with the oxygen and nitrogen donor system. Thermal stabilities of the complexes are also reported. (author)

Copper(II) cyanido-bridged bimetallic nitroprusside-based complexes: Syntheses, X-ray structures, magnetic properties, 57Fe Moessbauer spectroscopy and thermal studies

International Nuclear Information System (INIS)

Travnicek, Zdenek; Herchel, Radovan; Mikulik, Jiri; Zboril, Radek

2010-01-01

Three heterobimetallic cyanido-bridged copper(II) nitroprusside-based complexes of the compositions [Cu(tet)Fe(CN) 5 NO].H 2 O (1), where tet=N,N'-bis(3-aminopropyl)ethylenediamine, [Cu(hto)Fe(CN) 5 NO].2H 2 O (2), where hto=1,3,6,9,11,14-hexaazatricyclo[12.2.1.1 6,9 ]octadecane and [Cu(nme) 2 Fe(CN) 5 NO].H 2 O (3), where nme=N-methylethylenediamine, were synthesized and characterized by elemental analyses, 57 Fe Moessbauer and FTIR spectroscopies, thermal analysis, magnetic measurements and single-crystal X-ray analysis. The products of thermal degradation processes of 2 and 3 were studied by XRD, 57 Fe Moessbauer spectroscopy, SEM and EDS, and they were identified as mixtures of CuFe 2 O 4 and CuO. - Three heterobimetallic cyano-bridged copper(II) nitroprusside-based complexes of the general compositions of [Cu(L)Fe(CN) 5 NO].xH 2 O, where L=N,N'-bis(3-aminopropyl)ethylenediamine (complex 1), 1,3,6,9,11,14-hexaazatricyclo[12.2.1.1 6,9 ]-octadecane (complex 2) and N-methylethylenediamine (complex 3), were synthesized, and fully structurally and magnetically characterized. SEM, EDS, XRD and 57 Fe Moessbauer experiments were used for characterization of thermal decomposition products of complexes 2 and 3.

A curcumin-based TPA four-branched copper(II) complex probe for in vivo early tumor detection

Energy Technology Data Exchange (ETDEWEB)

Pi, Zongxin [Department of Chemical and Chemical Engineering, Hefei Normal University, Hefei 230001 (China); Wang, Jiafeng; Jiang, Bo [Department of Pharmacy, Anhui University of Chinese Medicine, Hefei 230038 (China); Cheng, Gang [Department of Chemical and Chemical Engineering, Hefei Normal University, Hefei 230001 (China); Zhou, Shuangsheng, E-mail: zshuangsheng@126.com [Department of Pharmacy, Anhui University of Chinese Medicine, Hefei 230038 (China); Center of Modern Experimental Technology, Anhui University, Hefei 230038 (China)

2015-01-01

A multibranched Cu(II) complex CuL{sub 2} curcumin-based was synthesized and characterized by single-crystal X-ray diffraction analysis. The photophysical properties of the complex have been investigated both experimentally and theoretically. The results show that the target complex exhibits higher quantum yield and larger two-photon absorption (TPA) cross-section in the near infrared (NIR) region compared with its free ligand. The cell imaging studies in vitro and in vivo reveal that the complex shows good photostability and excellent tumor targeting capability to tested cancerous cells, which can be potentially used for early tumor detection. - Graphical abstract: A multibranched Cu(II) complex was prepared from curcumin. The photophysical properties of the obtained complex have been investigated. The results exhibit that the complex has high capability to test cancerous cells and can distinguish between the cancerous and noncancerous cells, which should be potentially used for early tumor detection. - Highlights: • A novel multi-branched copper complex was synthesized. • The obtained compounds exhibited obvious TPA in high polar solvents. • The complex is a low toxicity at low-micromolar concentrations. • The complex exhibits larger TPA cross-section and brighter TPF imaging. • The complex has excellent targeting capability to tested cancerous cells.

Improved dust handling at Inco's Copper Cliff smelter

International Nuclear Information System (INIS)

Dutton, A.; Warner, A.E.M.; Humphris, M.J.

1989-01-01

The Cooper Cliff Smelter Complex comprises three major production departments - a Nickel Smelter for the processing of nickel concentrated to a low iron, nickel - copper sulphide (Bessemer) matte; a Matte Processing plant for the separation of matte sulphides and the production of market nickel oxides and refinery feeds and a Copper Smelter to process copper concentrates to blister copper. Annual production is currently -114,000 tonnes of copper as blister and -110,000 tonnes of nickel. The nickel concentrate (11-13% Ni, 2-3% Cu) is roasted in multi-hearth roasters, smelted in oxy-fuel fired reverberatory furnaces to a 30-35% CuNiCo matte and converted to Bessemer matte (75% CuNiCo) in Peirce-Smith converters. The Bessemer matte is slow cooled and crushed for subsequent separation by mineral dressing techniques in the Matte Processing plant into nickel (sulphide and metallic) concentrates and a copper (chalcocite) concentrate. Nickel sulphides are further processed in fluid bed reactors to oxide market product or refinery feedstock. The copper concentrate (29-30% Cu, 0.9% No.) is dried in fluid bed driers, smelted to a 40-50% copper matte in an Inco oxygen flash furnace and converted to blister copper in Peirce-Smith converters. The chalcocite concentrate from the matte separation stage is flash converted to a semi-blister (3-4% S, 4-5% Ni) and then finished to lighter conventionally. A schematic process flowsheet of the Smelter Complex is shown in this paper

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) and beyond: new reactivity of copper(i) acetylides†

OpenAIRE

Hein, Jason E.; Fokin, Valery V.

2010-01-01

Copper-catalyzed azide–alkyne cycloaddition (CuAAC) is a widely utilized, reliable, and straightforward way for making covalent connections between building blocks containing various functional groups. It has been used in organic synthesis, medicinal chemistry, surface and polymer chemistry, and bioconjugation applications. Despite the apparent simplicity of the reaction, its mechanism involves multiple reversible steps involving coordination complexes of copper(i) acetylides of varying nucle...

Copper Promoted Synthesis of Diaryl Ethers

OpenAIRE

Ghosh, Rajshekhar; Samuelson, Ashoka G

2004-01-01

An efficient protocol using copper based reagents for the coupling of aryl halides with phenols to generate diaryl ethers is described. Acopper( I) complex, [ Cu( CH3CN) (4)] ClO4, or the readily available copper( II) source, CuCO3 . Cu( OH) (2) . H2O ( in combination with potassium phosphate), can be used. Aryl halides and phenols with different steric and electronic demands have been used to assess the efficiency of the procedure. The latter source of copper gives better yields under all co...

Synthesis of mononuclear copper(II) complexes of N3O2 and N4O2 donors containing Schiff base ligands: Theoretical and biological observations

Science.gov (United States)

Mancha Madha, K.; Gurumoorthy, P.; Arul Antony, S.; Ramalakshmi, N.

2017-09-01

A new series of six mononuclear copper(II) complexes were synthesized from N3O2 and N4O2 donors containing Schiff base ligands, and characterized by various spectral methods. The geometry of the complexes was determined using UV-Vis, EPR and DFT calculations. The complexes of N3O2 donors (1-3) adopted square pyramidal geometry and the remaining complexes of N4O2 donors (4-6) show distorted octahedral geometry around copper(II) nuclei. Redox properties of the complexes show a one-electron irreversible reduction process in the cathodic potential (Epc) region from -0.74 to -0.98 V. The complexes show potent antioxidant activity against DPPH radicals. Molecular docking studies of complexes showed σ-π interaction, hydrogen bonding, electrostatic and van der Waals interactions with VEGFR2 kinase receptor. In vitro cytotoxicity of the complexes was tested against human breast cancer (MDA-MB-231) cell lines and one normal human dermal fibroblasts (NHDF) cell line through MTT assay. The morphological assessment data obtained by Hoechst 33258 and AO/EB staining revealed that the complexes induce apoptosis pathway of cell death.

Production of Copper as a Complex Mining and Metallurgical Processing System in Polish Copper Mines of the Legnica-Glogów Copper Belt

Science.gov (United States)

Malewski, Jerzy

2017-12-01

Geological and technological conditions of Cu production in the Polish copper mines of the Legnica-Glogów Copper Belt are presented. Cu production is recognized as a technological fractal consisting of subsystems for mineral exploration, ore extraction and processing, and metallurgical treatment. Qualitative and quantitative models of these operations have been proposed, including estimation of their costs of process production. Numerical calculations of such a system have been performed, which allow optimize the system parameters according to economic criteria under variable Cu mineralization in the ore deposit. The main objective of the study is to develop forecasting tool for analysis of production efficiency in domestic copper mines based on available sources of information. Such analyses are primarily of social value, allowing for assessment of the efficiency of management of local mineral resources in the light of current technological and market constraints. At the same time, this is a concept of the system analysis method to manage deposit exploitation on operational and strategic level.

Synthesis and Crystal Structure of a 4,4'-bipyridine Linked Dinuclear Copper(II) Complex Derived from 2-{[2-(2-hydroxyethylamino)ethylimino]methyl}-6-methylphenol.

Science.gov (United States)

Zhang, Xiu-Zhen; Gu, Yitong; Li, Yuntong; Liu, Andong; Liu, Fuyao; You, Zhonglu; Zhu, Hai-Liang

2016-12-01

A novel 4,4'-bipyridine linked dinuclear copper(II) complex, [Cu2L2(bipy)](NO3)2·bipy (L = 2-[2-(2-hydroxyethylamino) ethylimino]methyl-6-methylphenol; bipy = 4,4'-bipyridine), was prepared and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The Cu···Cu distance is 11.129(2) Å. The CuII atom is coordinated by one phenolate O, one imine N, and one amine N atoms of a Schiff base ligand, and one N atom of the bridging 4,4'-bipyridine ligand, forming a square planar geometry. In the crystal structure of the complex, the dinuclear copper complex cations are linked by 4,4'-bipyridine molecules through intermolecular O-H···N hydrogen bonds, to form 1D chains running in the [2 0 -1] direction.

Antioxidant, DNA interaction, VEGFR2 kinase, topoisomerase I and in vitro cytotoxic activities of heteroleptic copper(II) complexes of tetrazolo[1,5-a]pyrimidines and diimines

Energy Technology Data Exchange (ETDEWEB)

Haleel, A.; Mahendiran, D. [Post-Graduate and Research Department of Chemistry, The New College (Autonomous), Chennai 600 014 (India); Veena, V.; Sakthivel, N. [Department of Biotechnology, Pondicherry University, Pondicherry 605 014 (India); Rahiman, A. Kalilur, E-mail: akrahmanjkr@gmail.com [Post-Graduate and Research Department of Chemistry, The New College (Autonomous), Chennai 600 014 (India)

2016-11-01

A series of heteroleptic mononuclear copper(II) complexes of the type [Cu(L{sup 1–3})(diimine)]ClO{sub 4} (1–6) containing three tetrazolo[1,5-a]pyrimidine core ligands, ethyl 5-methyl-7-(2-hydroxyphenyl)-4,7-dihydrotetrazolo[1,5-a] pyrimidine-6-carboxylate (HL{sup 1}), ethyl 5-methyl-7-(4-diethylamino-2-hydroxyphenyl)-4,7-dihydrotetrazolo[1,5-a] pyrimidine-6-carboxylate (HL{sup 2}) or ethyl 5-methyl-7-(2-hydroxy-4-nitrophenyl)-4,7-dihydrotetrazolo[1,5-a] pyrimidine-6-carboxylate (HL{sup 3}), and two diimine coligands, 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen) have been synthesized and characterized by spectral methods. The geometry of complexes have been determined with the help of electronic absorption and EPR splitting patterns, which suggest four coordinated square planar geometry around copper(II) ion. The lowering of HOMO–LUMO band gap value of complex 4 implies its higher biological activity compared to other complexes. Antioxidant studies revealed that the complexes possess considerable radical scavenging potency against DPPH. The binding studies of the complexes with calf thymus DNA (CT–DNA) revealed groove mode of binding, which was further supported by docking simulation. The complexes 3 and 4 strongly inhibit the topoisomerase I, and also strongly interact with VEGFR2 kinase receptor via π–π, σ–π and hydrogen bonding interaction. Gel electrophoresis experiments demonstrated the ability of the complexes to cleave plasmid DNA in the absence of activators. In vitro cytotoxic activities of the complexes were examined on three cancerous cell lines such as human lung (A549), cervical (HeLa) and colon (HCT-15), and two normal cells such as human embryonic kidney (HEK) and peripheral blood mononuclear cells (PBMCs). The live cell and fluorescent imaging of cancer cells were observed with acridine orange/ethidium bromide staining assay. All encouraging chemical and biological findings indicate that the complex 4 is a suitable candidate

Investigating the Structure and Reactivity of Azolyl-Based Copper(I)–NHC Complexes: The Role of the Anionic Ligand

KAUST Repository

Trose, Michael; Nahra, Fady; Poater, Albert; Cordes, David B.; Slawin, Alexandra M. Z.; Cavallo, Luigi; Cazin, Catherine S. J.

2017-01-01

A family of copper(I)–NHC azolyl complexes was synthesized and deployed in the hydrosilylation of dicyclo-hexylketone to probe the role of the anionic ligand on catalytic performance. The azolyl ligand is shown to have a crucial role in catalytic activity without the need for additives, and this at very low catalyst loading.

Investigating the Structure and Reactivity of Azolyl-Based Copper(I)–NHC Complexes: The Role of the Anionic Ligand

KAUST Repository

Trose, Michael

2017-11-01

A family of copper(I)–NHC azolyl complexes was synthesized and deployed in the hydrosilylation of dicyclo-hexylketone to probe the role of the anionic ligand on catalytic performance. The azolyl ligand is shown to have a crucial role in catalytic activity without the need for additives, and this at very low catalyst loading.

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

Science.gov (United States)

Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

2013-03-01

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis, molecular docking and DNA binding studies of phthalimide-based copper(II) complex: In vitro antibacterial, hemolytic and antioxidant assessment

Science.gov (United States)

Arif, Rizwan; Nayab, Pattan Sirajuddin; Ansari, Istikhar A.; Shahid, M.; Irfan, Mohammad; Alam, Shadab; Abid, Mohammad; Rahisuddin

2018-05-01

In the present research work, we prepared N-substituted phthalimide, 2-(-(2-(2-(2-(1,3-dioxoisoindoline-2-yl-ethylamino)ethylamino)ethyl)isoindoline-1,3-dione (DEEI) and its copper(II) complex. The ligand (DEEI) and its Cu(II) complex were structurally identified using absorption, FTIR, NMR, electron spin resonance, X-ray diffraction spectral studies, thermogravimetric and elemental analyses. The electronic spectrum and magnetic moment value proposed that Cu(II) complex has square planar geometry. The DNA interaction ability of the ligand (DEEI) and Cu(II) complex was studied by means of absorption and fluorescence spectrophotometer, viscosity measurements, cyclic voltammetery, and circular dichroism methods. The extent of DNA binding (Kb) with Calf thymus (Ct-DNA) follows the order of Cu(II) complex (1.11 × 106 M-1) > DEEI (1.0 × 105 M-1), indicating that Cu(II) complex interact with Ct-DNA through groove binding mode and more sturdily than ligand (DEEI). Interestingly, in silico predictions were corroborated with in vitro DNA binding studies. The antibacterial evaluation of these compounds was screened against a panel of bacterial strains Pseudomonas aeruginosa (MTCC 2453), Salmonella enterica (MTCC 3224), Streptococcus pneumoniae (MTCC 655), Enterococcus faecalis (MTCC 439), Klebsiella pneumonia and Escherichia coli (ATCC 25922). The results showed that the copper(II) complex has significant antibacterial potential (IC50 = 0.0019 μg/mL) against Salmonella enteric comparable with ligand (DEEI) and standard drug ciprofloxacin. Growth curve study of Cu(II) complex against only three bacterial strains S. enterica, E. faecalis and S. pneumoniae showed its bactericidal nature. Cu(II) complex showed less than 2% hemolysis on human RBCs indicating its non toxic nature. The results of antioxidant assay demonstrated that scavenging activity of Cu(II) complex is higher as compared to ligand and ascorbic acid as standard.

Synthesis, thermogravimetric, spectroscopic and theoretical characterization of copper(II) complex with 4-chloro-2-nitrobenzenosulfonamide

Science.gov (United States)

Camí, G.; Chacón Villalba, E.; Di Santi, Y.; Colinas, P.; Estiu, G.; Soria, D. B.

2011-05-01

4-Chloro-2-nitrobenzenesulfonamide (ClNbsa) was purified and characterized. A new copper(II) complex, [Cu(ClNbsa) 2(NH 3) 2], has been prepared using the sulfonamide as ligand. The thermal behavior of both, the ligand and the Cu(II) complex, was investigated by thermogravimetric analyses (TG) and differential thermal analysis (DT), and the electronic characteristics analyzed by UV-VIS, FTIR, Raman and 1H NMR spectroscopies. The experimental IR, Raman and UV-VIS spectra have been assigned on the basis of DFT calculations at the B3LYP level of theory using the standard (6-31 + G ∗∗) basis set. The geometries have been fully optimized in vacuum and in modeled dimethylsulfoxide (DMSO) solvent, using for the latter a continuum solvation model that reproduced the experimental conditions of the UV-VIS spectroscopy. The theoretical results converged to stable conformations for the free sulfonamide and for the complex, suggesting for the latter a distorted square planar geometry in both environments.

Application of Box-Behnken design in the optimization of catalytic behavior of a new mixed chelate of copper (II) complex in chemiluminescence reaction of luminol

International Nuclear Information System (INIS)

Khajvand, Tahereh; Chaichi, Mohammad Javad; Nazari, OmLeila; Golchoubian, Hamid

2011-01-01

In this work, we observed an enhancement of chemiluminescence (CL) emission of luminol when a new mixed chelate of copper complex (N-(2-(2-aminoethylamino)ethyl)-1H-pyrrole-2-carboxamide-Cu(II)) was mixed with a solution containing luminol in methanol/water. The Box-Behnken design matrix and response surface methodology (RSM) have been applied to design the experiments to evaluate the interactive effects of the three most important operating variables-luminol (10 -4 -10 -2 M), fluorescein (10 -5 -10 -3 M) and hydrogen peroxide (1-3 M) concentrations on the CL emission of luminol. The total 15 experiments were conducted in the present study towards the construction of a quadratic model. Independent variables luminol and hydrogen peroxide have significant value P F less than 0.0500 indicate that model terms are significant for the CL emission of luminol. The regression equation coefficients were calculated and the data fitted to a second-order polynomial equation for CL emission of luminol. The new introduced inorganic catalyst of luminol CL reaction can be effect more than that of the common ones such as potassium hexacyanoferrate (III) and copper (II) acetate. - Research highlights: → In this study we introduce a new mixed chelate of copper complex as a catalyst of luminol chemiluminescence (CL) reaction. → The copper complex (N-(2-(2-aminoethylamino)ethyl)-1H-pyrrole-2-carboxamide-Cu(II)) catalyst luminol reaction more than that of copper acetate and potassium hexacyanoferrate (III). → The Box-Behnken design matrix and response surface methodology are used for prediction of CL intensity of luminol. → There are good correlation between experimental and expected CL intensity that predicted by the theoretical model. → Fluorescein used as a fluorescer in the luminol CL reaction in presence of the new catalyst.

High-fidelity DNA replication in Mycobacterium tuberculosis relies on a trinuclear zinc center.

Science.gov (United States)

Baños-Mateos, Soledad; van Roon, Anne-Marie M; Lang, Ulla F; Maslen, Sarah L; Skehel, J Mark; Lamers, Meindert H

2017-10-11

High-fidelity DNA replication depends on a proofreading 3'-5' exonuclease that is associated with the replicative DNA polymerase. The replicative DNA polymerase DnaE1 from the major pathogen Mycobacterium tuberculosis (Mtb) uses its intrinsic PHP-exonuclease that is distinct from the canonical DEDD exonucleases found in the Escherichia coli and eukaryotic replisomes. The mechanism of the PHP-exonuclease is not known. Here, we present the crystal structure of the Mtb DnaE1 polymerase. The PHP-exonuclease has a trinuclear zinc center, coordinated by nine conserved residues. Cryo-EM analysis reveals the entry path of the primer strand in the PHP-exonuclease active site. Furthermore, the PHP-exonuclease shows a striking similarity to E. coli endonuclease IV, which provides clues regarding the mechanism of action. Altogether, this work provides important insights into the PHP-exonuclease and reveals unique properties that make it an attractive target for novel anti-mycobacterial drugs.The polymerase and histidinol phosphatase (PHP) domain in the DNA polymerase DnaE1 is essential for mycobacterial high-fidelity DNA replication. Here, the authors determine the DnaE1 crystal structure, which reveals the PHP-exonuclease mechanism that can be exploited for antibiotic development.

Synthesis, physico-chemical characterization and biological activity of copper(ii and nickel(ii complexes with l-benzoyl-2-methylbenzimidazole derivatives

Directory of Open Access Journals (Sweden)

Podunavac-Kuzmanović Sanja O.

2002-01-01

Full Text Available Chlorides of copper(II and nickel(ll react with 1-benzoyl-2-methylbenzimidazole or 1-(4-chlorobenzoyl-2-methylbenzimidazole to give complexes of the type [M(LnCln(H20∙Cln (M = Cu or Ni; L = (1-benzoyl-2-methylbenzimidazole or 1-(4-chlorobenzoyl-2-methylbenzimidazole; n=O, 1 or 2. The complexes were synthesized and characterized by elemental analysis, molar conductivity magnetic susceptibility measurements and IR spectra. These studies suggest that all the complexes possess an octahedral stereochemistry. The antibacterial activity of (1-benzoyl-2-methylbenzimidazole or 1-(4-chlorobenzoyl-2-methylbenzimidazole and their complexes was evaluated against Escherichia coli and Bacillus sp.

Synthesis, spectroscopic and thermal studies of the copper(II) aspartame chloride complex

Science.gov (United States)

Çakır, S.; Coşkun, E.; Naumov, P.; Biçer, E.; Bulut, İ.; İçbudak, H.; Çakır, O.

2002-08-01

Aspartame adduct of copper(II) chloride Cu(Asp) 2Cl 2·2H 2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions.

Copper(II) complexes of alloferon 1 with point mutations (H1A) and (H9A) stability structure and biological activity.

Science.gov (United States)

Matusiak, Agnieszka; Kuczer, Mariola; Czarniewska, Elżbieta; Rosiński, Grzegorz; Kowalik-Jankowska, Teresa

2014-09-01

Mono- and polynuclear copper(II) complexes of the alloferon 1 with point mutations (H1A) A(1)GVSGH(6)GQH(9)GVH(12)G (Allo1A) and (H9A) H(1)GVSGH(6)GQA(9)GVH(12)G (Allo9A) have been studied by potentiometric, UV-visible, CD, EPR spectroscopic and mass spectrometry (MS) methods. To obtain a complete complex speciation different metal-to-ligand molar ratios ranging from 1:1 to 4:1 for Allo1A and to 3:1 for Allo9A were studied. The presence of the His residue in first position of the peptide chain changes the coordination abilities of the Allo9A peptide in comparison to that of the Allo1A. Imidazole-N3 atom of N-terminal His residue of the Allo9A peptide forms stable 6-membered chelate with the terminal amino group. Furthermore, the presence of two additional histidine residues in the Allo9A peptide (H(6),H(12)) leads to the formation of the CuL complex with 4N {NH2,NIm-H(1),NIm-H(6),NIm-H(12)} binding site in wide pH range (5-8). For the Cu(II)-Allo1A system, the results demonstrated that at physiological pH7.4 the predominant complex the CuH-1L consists of the 3N {NH2,N(-),CO,NIm} coordination mode. The inductions of phenoloxidase activity and apoptosis in vivo in Tenebrio molitor cells by the ligands and their copper(II) complexes at pH7.4 were studied. The Allo1A, Allo1K peptides and their copper(II) complexes displayed the lowest hemocytotoxic activity while the most active was the Cu(II)-Allo9A complex formed at pH7.4. The results may suggest that the N-terminal-His(1) and His(6) residues may be more important for their proapoptotic properties in insects than those at positions 9 and 12 in the peptide chain. Copyright © 2014 Elsevier Inc. All rights reserved.

Lanthanide Single-Molecule Magnets Framed by Alkali Metals & Magnetic and Spectroscopic Studies of 3d Transition Metal Complexes

DEFF Research Database (Denmark)

Konstantatos, Andreas

-molecule magnets (SMMs). Starting from the archetype SMM Mn12 we present the details of the mechanisms governing the relaxation of the magnetization of these systems. In Chapter 2 we present our work on the coordination chemistry of lanthanides with a new Schiff-base ligand, H3L [(E)-3-((2-hydroxyphenyl...... complexes of M3+ or M2+ metal ions (M: 3d transition metal) with the preference to either approximate octahedral or trigonal prismatic coordination geometry. A detailed magnetic characterization for most of the complexes is presented where a trinuclear Co2+ cluster stands out for its pronounced SMM...

Synthesis, spectral, thermal and antimicrobial studies on cobalt(II), nickel(II), copper(II), zinc(II) and palladium(II) complexes containing thiosemicarbazone ligand

Science.gov (United States)

El-Sawaf, Ayman K.; El-Essawy, Farag; Nassar, Amal A.; El-Samanody, El-Sayed A.

2018-04-01

The coordination characteristic of new N4-morpholinyl isatin-3-thiosemicarbazone (HL) towards Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) has been studies. The structures of the complexes were described by elemental analyses, molar conductivity, magnetic, thermal and spectral (IR, UV-Vis, 1H and 13C NMR and ESR) studies. On the basis of analytical and spectral studies the ligand behaves as monobasic tridentate ONS donor forming two five membered rings towards cobalt, copper and palladium and afforded complexes of the kind [M(L)X], (Mdbnd Co, Cu or Pd; Xdbnd Cl, Br or OAc). Whereas the ligand bound to NiCl2 as neutral tridentate ONS donor and with ZnCl2 as neutral bidentate NS donor. The newly synthesized thiosemicarbazone ligand and some of its complexes were examined for antimicrobial activity against 2 gram negative bacterial strains (Escherichia coli Pseudomonas and aeruginosa), 2 gram positive bacterial strains (Streptococcus pneumoniae and Staphylococcus aureus)} and two Pathogenic fungi (Aspergillus fumigatus and Candida albicans). All metal complexes possess higher antimicrobial activity comparing with the free thiosemicarbazone ligand. The high potent activities of the complexes may arise from the coordination and chelation, which tends to make metal complexes act as more controlling and potent antimicrobial agents, thus hindering the growing of the microorganisms. The antimicrobial results also show that copper bromide complex is better antimicrobial agent as compared to the Schiff base and its metal complexes.

Aspergillus fumigatus Copper Export Machinery and Reactive Oxygen Intermediate Defense Counter Host Copper-Mediated Oxidative Antimicrobial Offense

Directory of Open Access Journals (Sweden)

Philipp Wiemann

2017-05-01

Full Text Available The Fenton-chemistry-generating properties of copper ions are considered a potent phagolysosome defense against pathogenic microbes, yet our understanding of underlying host/microbe dynamics remains unclear. We address this issue in invasive aspergillosis and demonstrate that host and fungal responses inextricably connect copper and reactive oxygen intermediate (ROI mechanisms. Loss of the copper-binding transcription factor AceA yields an Aspergillus fumigatus strain displaying increased sensitivity to copper and ROI in vitro, increased intracellular copper concentrations, decreased survival in challenge with murine alveolar macrophages (AMΦs, and reduced virulence in a non-neutropenic murine model. ΔaceA survival is remediated by dampening of host ROI (chemically or genetically or enhancement of copper-exporting activity (CrpA in A. fumigatus. Our study exposes a complex host/microbe multifactorial interplay that highlights the importance of host immune status and reveals key targetable A. fumigatus counter-defenses.

Theoretical description of copper Cu(I)/Cu(II) complexes in mixed ammine-aqua environment. DFT and ab initio quantum chemical study

International Nuclear Information System (INIS)

Pavelka, Matej; Burda, Jaroslav V.

2005-01-01

This work is devoted to investigate the interactions of the Cu(I)/Cu(II) cation with variable ammonia-water ligand field by the quantum chemical approach. For that purpose, the optimization of the [Cu(NH 3 ) m (H 2 O) n ] 2+/+ complexes (where n varies from 0 to 4 or 6 and m + n = 4 or 6) has been performed at the DFT/6-31+G(d) level of theory in conjunction with the B3PW91 hybrid functional. Based on the results of the single-point B3LYP/6-311++G(2df,2pd) calculations, the stabilization energies were determined. The two-coordinated copper(I) complexes appeared to be the most stable compounds with the remaining water or ammonia molecules in the second solvation shell. In the case of the Cu(II) systems, four-coordinated complexes were found to be the most stable. In order to examine and explain bonding characteristics, Morokuma interaction energy decomposition (for selected Cu + complexes) and Natural Population Analysis for all systems were performed. It was found that the most stable structures correlate with the highest donation effects. Therefore, more polarizable ammonia molecules exhibit higher donation than water and thus make stronger bonds to copper. This can be demonstrated by the fact that the NH 3 molecule always tries to occupy the first solvation shell in mixed ammine-aqua complexes

Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper(i) complex.

Science.gov (United States)

Weber, Michael D; Garino, Claudio; Volpi, Giorgio; Casamassa, Enrico; Milanesio, Marco; Barolo, Claudia; Costa, Rubén D

2016-06-07

This work provides the synthesis, structural characterization, electrochemical and photophysical features, as well as the application in light-emitting electrochemical cells (LECs) of a novel heteroleptic copper(i) complex - [Cu(impy)(POP)][PF6], where impy is 3-(2-methoxyphenyl)-1-(pyridine-2-yl)imidazo[1,5-a]pyridine and POP is bis{2-(diphenylphosphanyl)phenyl}ether. This compound shows blue photoluminescence (PL, λ = 450 nm) in solution and solid-state and excellent redox stability. Despite these excellent features, the electroluminescence (EL) response is located at ∼550 nm. Although the EL spectrum of LECs is typically red-shifted compared to the PL of the electroluminescent material, a shift of ca. 100 nm represents the largest one reported in LECs. To date, the large shift phenomena have been attributed to (i) a change in the nature of the lowest emitting state due to a concentration effect of the films, (ii) a reversible substitution of the ligands due to the weak coordination to the Cu(i), and (iii) a change in the distribution of the excited states due to polarization effects. After having discarded these along with others like the irreversible degradation of the emitter during device fabrication and/or under operation conditions, driving conditions, active layer composition, and changes in the excited states under different external electrical stimuli, we attribute the origin of this unexpected shift to a lack of a thermally activated delayed fluorescence (TADF) process due to the solely ligand-centered character of the excited states. As such, the lack of a charge transfer character in the excited states leads to a blue-fluorescence and yellow-phosphorescence photo- and electro-responses, respectively. This corroborates recent studies focused on the design of TADF for heteroleptic copper(i) complexes. Overall, this work is a clear insight into the design of new copper(i) complexes towards the preparation of blue LECs, which are still unexplored.

Synthesis of copper hydroxide branched nanocages and their transformation to copper oxide

KAUST Repository

LaGrow, Alec P.; Sinatra, Lutfan; Elshewy, Ahmed M.; Huang, Kuo-Wei; Katsiev, Khabiboulakh; Kirmani, Ahmad R.; Amassian, Aram; Anjum, Dalaver H.; Bakr, Osman

2014-01-01

Copper oxide nanostructures have been explored in the literature for their great promise in the areas of energy storage and catalysis, which can be controlled based on their shape. Herein we describe the synthesis of complex branched nanocages

Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives

International Nuclear Information System (INIS)

Pasquale, M.A.; Gassa, L.M.; Arvia, A.J.

2008-01-01

Copper electrodeposition on copper from still plating solutions of different compositions was investigated utilising electrochemical impedance spectroscopy (EIS), cyclic voltammetry, and scanning electron microscopy (SEM). An acid copper sulphate plating base solution was employed either with or without sodium chloride in the presence of a single additive, either polyethylene glycol (PEG) or 3-mercapto-2-propanesulphonic acid (MPSA), and their mixture. Thallium underpotential deposition/anodic stripping was employed to determine the adsorption capability of additives on copper. In the absence of chloride ions, MPSA shows a moderate adsorption on copper, whereas PEG is slightly adsorbed. At low cathodic overpotentials, the simultaneous presence of MPSA and chloride ions accelerates copper electrodeposition through the formation of an MPSA-chloride ion complex in the solution, particularly for about 220 μM sodium chloride. The reverse effect occurs in PEG-sodium chloride plating solutions. In this case, from EIS data the formation of a film that interferes with copper electrodeposition can be inferred. At higher cathodic overpotentials, when copper electrodeposition is under mass transport control, the cathode coverage by a PEG-copper chloride-mediated film becomes either partially or completely detached as the concentration of chloride ions at the negatively charged copper surface diminishes. The copper cathode grain topography at the μm scale depends on the cathodic overpotential, plating solution composition and average current density. Available data about the solution constituents and their adsorption on copper make it possible to propose a likely complex mechanism to understand copper electrodeposition from these media, including the accelerating effect of MPSA and the dynamics of PEG-copper chloride complex adsorbate interfering with the surface mobility of depositing copper ad-ions/ad-atoms

Copper complexation by tannic acid in aqueous solution

NARCIS (Netherlands)

Kraal, P.; Jansen, B.; Nierop, K.G.J.; Verstraten, J.M.

2006-01-01

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon ((OC)/l was investigated in a nine-step titration experiment (Cu/oC molar ratio = 0.0030-0.0567). We differentiated between soluble and insoluble Cu species by 0.45 mu m

Theoretical Study of Copper Complexes: Molecular Structure, Properties, and Its Application to Solar Cells

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Jesus Baldenebro-Lopez

2013-01-01

Full Text Available We present a theoretical investigation of copper complexes with potential applications as sensitizers for solar cells. The density functional theory (DFT and time-dependent DFT were utilized, using the M06 hybrid meta-GGA functional with the LANL2DZ (D95V on first row and DZVP basis sets. This level of calculation was used to find the optimized molecular structure, the absorption spectra, the molecular orbitals energies, and the chemical reactivity parameters that arise from conceptual DFT. Solvent effects have been taken into account by an implicit approach, namely, the polarizable continuum model (PCM, using the nonequilibrium version of the IEF-PCM model.

Standard molar enthalpies of formation of copper(II) β-diketonates and monothio-β-diketonates

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Santos, Luis M.N.B.F.

2006-01-01

The standard (p o =0.1MPa) molar enthalpies of formation of the crystalline complexes of dibenzoylmethane (Hdbm), thenoyltrifluoroacetone (Httfa), monothiodibenzoylmethane (HdbmS), and monothiothenoyltrifluoroacetone (HttfaS) of copper(II) were determined, at T=298.15K, by high precision solution-reaction calorimetry. The standard molar enthalpies of sublimation of the copper(II) β-diketonate complexes were measured by high-temperature Calvet microcalorimetry. From the standard molar enthalpies of formation of the complexes in the gaseous state, the mean molar dissociation enthalpies copper(II)-ligand, m >(Cu-L), were derived. Δ f H m o (cr)Δ cr g H m o kJ.mol -1 kJ.mol -1 Bis(dibenzoylmethanate)copper(II), Cu(dbm) 2 -364.0+/-3.9230.7+/-8.2Bis(thenoyltrifluoroacetonate)copper(II), Cu(ttfa) 2 -1824.3+/-8.3167.9+/-7.4Bis(monothiodibenzoylmethanate)copper(II), Cu(dbmS) 2 35.6+/-7.7[241+/-15]Bis(monothiothenoyltrifluoroacetonate) copper(II), Cu(ttfaS) 2 -1405.7+/-8.3[177+/-15

Leaching of copper concentrates using NaCl and soluble copper contributed by the own concentrate

International Nuclear Information System (INIS)

Herrero, O.; Bernal, N.; Quiroz, R.; Fuentes, G.; Vinals, J.

2005-01-01

Leaching of copper concentrates using cupric chloro complexes, generated in situ by the reaction between Cu(II), aported by the soluble copper content of the concentrate, and sodium chloride in acid media was studied. The concentrate samples were obtained from mineral processing plants from Antofagasta, Chile. Chemical and mineralogical characterization from original concentrates was made. Typical variable such as a chloride concentration, soluble copper concentration, leaching time, solid percentage and temperature were studied. DRX and EDS analyzed some of the residues. the experimental results indicated that it is possible to obtain solutions having high copper content (15 to 35 g/L) and 2 to 5 g/L free acid in order to submit this solution directly to a solvent extraction stage. The leaching tests use common reactive and low cost such as sodium chloride and sulfuric acid. (Author) 16 refs

Assessment of serum copper, iron and immune complexes in potentially malignant disorders and oral cancer

Directory of Open Access Journals (Sweden)

Ritu TIWARI

Full Text Available Abstract Potentially malignant disorders (PMDs of oral cavity and oral cancer remain a cause of serious concern despite intensive research and development. Diet and immunity have been identified to play a crucial role as modifying factors in these diseases. Our study intended to explore this relationship by estimating and comparing the serum levels of copper, iron and circulating immune complexes (CICs in patients diagnosed with PMDs and oral cancer and normal healthy individuals. In this study, 40 histopathologically diagnosed cases of PMDs and oral cancer were included along with 30 healthy controls and 5 ml of venous blood was drawn using venipuncture. Serum estimation of copper, iron and CIC then followed using the colorimetric and spectrophotometric methods. The data obtained was subjected to statistical analysis using one way ANOVA and Pearson’s Product-Moment Correlation Test. The mean serum copper level was measured as 138.98 ± 10.13µg/100ml in the PMD group and 141.99 ± 21.44 µg/100ml in the oral cancer as compared to 105.5 + 18.81µ/100ml in the controls. The mean serum CIC levels was highest in the oral cancer (9.65 ± 0.16OD470 followed by the PMD group (0.18 + 0.21 OD470 and least in the control group (0.048 ± 0.02OD470. Whereas, the serum levels of iron showed a significant decrease in the PMD group (110.9 ± 10.54 µg/100ml and the oral cancer group (114.29 ± 25.83 µg/100ml as compared with the control group (136.85 ± 14.48 µg/100ml. There was no positive correlation obtained between the three groups with respect to the chosen parameters indicating that the variables were independent of each other. It can be thus be ascertained that trace elements like copper and iron as well as humoral responses (CICs have a close relationship with PMDs and oral cancers.

Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

Science.gov (United States)

Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

2016-06-06

We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

and copper(II)

Indian Academy of Sciences (India)

Unknown

(II) and copper(II)–zinc(II) complexes. SUBODH KUMAR1, R N PATEL1*, P V KHADIKAR1 and. K B PANDEYA2. 1 Department of Chemistry, APS University, Rewa 486 003, India. 2 CSJM University, Kanpur 208 016, India e-mail: (R N Patel) ...

Design of copper DNA intercalators with leishmanicidal activity.

Science.gov (United States)

Navarro, Maribel; Cisneros-Fajardo, Efrén José; Sierralta, Aníbal; Fernández-Mestre, Mercedes; Silva, Pedro; Arrieche, Dwight; Marchán, Edgar

2003-04-01

The complexes [Cu(dppz)(NO(3))]NO(3) (1), [Cu(dppz)(2)(NO(3))]NO(3) (2), [Cu(dpq)(NO(3))]NO(3) (3), and [Cu(dpq)(2)(NO(3))]NO(3) (4) were synthesized and characterized by elemental analysis, FAB-mass spectrometry, EPR, UV, and IR spectroscopies, and molar conductivity. DNA interaction studies showed that intercalation is an important way of interacting with DNA for these complexes. The biological activity of these copper complexes was evaluated on Leishmania braziliensis promastigotes, and the results showed leishmanicidal activity. Preliminary ultrastructural studies with the most active complex (2) at 1 h revealed parasite swelling and binucleated cells. This finding suggests that the leishmanicidal activity of the copper complexes could be associated with their interaction with the parasitic DNA.

Ultrasonic-bath-assisted preparation of mononuclear copper(I) thiosemicarbazone complex particles: crystal structure, characterization and antimicrobial activity

Czech Academy of Sciences Publication Activity Database

Khalaji, A.D.; Shahsavani, E.; Feizi, N.; Kučeráková, Monika; Dušek, Michal; Mazandarani, R.; Amiri, A.

2017-01-01

Roč. 20, č. 2 (2017), s. 125-131 ISSN 1631-0748 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA15-12653S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : thiosemicarbazone * copper(I) complex * spectroscopy * X-ray crystallography Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.879, year: 2016

Metal complexation in near field conditions of nuclear waste repository - stability constant of copper complexation with cellulose degradation products, in alkaline conditions

International Nuclear Information System (INIS)

Guede, Kipre Bertin

2005-11-01

Copper is a stable element and spent fuel component which constitutes the radioactive waste. The reaction of Copper with cellulose degradation products in alkaline conditions was performed to mimic what occurs in near field conditions of nuclear waste repository. From the characteristics of Cu (II), this thesis aims at inferring the behaviour of radionuclides vis a vis the degradation products of cellulose. The contribution of the present work is therefore the assessment of the stability of the major cellulose degradation product, its affinity for Copper and the extent of the complexation function 13 between Cu (II) and the organic moieties. The formation of cellulose degradation products was followed by measurement of p11, Conductivity, Angle of rotation, relative abundance of aliphatics and aromatics (E4/E6 ) aid by UV-visible spectroscopy. The TOC was determined using the Walkley and Black titration after respectively 31 weeks and 13 weeks of degradation for the reaction mixtures T and A, N. The stability of the major degradation products gave the following figures: ISA(A): - 13 43.39 <ΔG -10639.88 ISA(N): - Ii 436.45<ΔG< -9103.6. The study of the characteristics of Gluconic Acid, as a model compound, was carried out in an attempt to give a general picture of the roper ties of cellulose degradation products. The Complexation between Cu (II) and the organic ligand (Cellulose degradation products) was performed using UV-visible spectroscopy and Ion Distribution technique. The Log B value obtained from the complexation studies at 336 nm for 1 = 0. I Ni NaClO4 and I = 0.01 M NaClO4, falls within a range of 3.48 to 3.74 for the standard reference material (Gluconic Acid), and within I .87 to 2.3 I, and I .6 to 2.01, respectively for the degradation Products ISA (A) and ISA(N). The ion distribution studies showed that: • In (he absence of the degradation product ISA and at pH = 3.68. 56. 17 % of Cu (II) was bound to the resin. • In the presence of ISA and at 2

Colloidal and electrochemical aspects of copper-CMP

Science.gov (United States)

Sun, Yuxia

Copper based interconnects with low dielectric constant layers are currently used to increase interconnect densities and reduce interconnect time delays in integrated circuits. The technology used to develop copper interconnects involves Chemical Mechanical Planarization (CMP) of copper films deposited on low-k layers (silica or silica based films), which is carried out using slurries containing abrasive particles. One issue using such a structure is copper contamination over dielectric layers (SiO2 film), if not reduced, this contamination will cause current leakage. In this study, the conditions conducive to copper contamination onto SiO2 films during Cu-CMP process were studied, and a post-CMP cleaning technique was discussed based on experimental results. It was found that the adsorption of copper onto a silica surface is kinetically fast (electrocoagulation was investigated to remove both copper and abrasive slurry particles simultaneously. For effluent containing ˜40 ppm dissolved copper, it was found that ˜90% dissolved copper was removed from the waste streams through electroplating and in-situ chemical precipitation. The amount of copper removed through plating is impacted by membrane surface charge, type/amount of complexing agents, and solid content in the slurry suspension. The slurry particles can be removed ˜90% within 2 hours of EC through multiple mechanisms.

Biochar and compost as amendments in copper-enriched vineyard soils - stabilization or mobilization of copper?

Science.gov (United States)

Soja, Gerhard; Fristak, Vladimir; Wimmer, Bernhard; Bell, Stephen; Chamier Glisczinski, Julia; Pardeller, Georg; Dersch, Georg; Rosner, Franz; Wenzel, Walter; Zehetner, Franz

2016-04-01

Copper is an important ingredient for several fungicides that have been used in agriculture. For organic viticulture, several diseases as e.g. downy mildew (Plasmopara viticola) can only be antagonized with Cu-containing fungicides. This long-lasting dependence on Cu-fungicides has led to a gradual Cu enrichment of vineyard soils in traditional wine-growing areas, occasionally exceeding 300 mg/kg. Although these concentrations do not affect the vines or wine quality, they may impair soil microbiological functions in the top soil layer or the root growth of green cover plants. Therefore measures are demanded that reduce the bioavailability of copper, thereby reducing the ecotoxicological effects. The use of biochar and compost as soil amendment has been suggested as a strategy to immobilize Cu and reduce the exchangeable fractions. This study consisted of lab and greenhouse experiments that were designed to test the sorption and desorption behavior of copper in vineyard soils with or without biochar and/or compost as soil amendment. Slightly acidic soils (pHeffects were more evident for a reduction of the ionic form Cu2+ than for total soluble copper, even in alkaline soils. Biochar modified with citric or tartaric acid did not significantly decrease the solubility of copper based on total dissolved concentrations although CEC was higher than in unmodified biochar. Treatments consisting of compost only or that had an equal amount of compost and biochar rather had a mobilizing effect on biochar. Sorption experiments with different DOC concentrations and biochar, however, showed a positive effect on copper sorption. Apparently in vineyard soils the predisposition to form organic-Cu-complexes may outbalance the binding possibilities of these complexes to biochar, occasionally resulting in enhanced mobilization. Presumably immobilization of copper with biochar would work best in acidic soils low in organic carbon and with low or no compost addition although this might

Toxicity of copper to the marine amphipod Allorchestes compressa in the presence of water- and lipid-soluble ligands

Energy Technology Data Exchange (ETDEWEB)

Ahsanullah, M; Florence, T M

1984-12-01

Acute toxicity tests were carried out on the marine amphipod Allorchestes compressa Dana using copper sulfate and some organocopper complexes. For copper sulfate, 96 h LC50 values of 0.11 and 0.5 mg Cu/liter were determined for the juveniles and the adults, respectively. Juveniles were about 4.5 times more sensitive to copper than adults Organocopper complexes were tested on adults only. The three water soluble ligands nitrotriacetic acid, 8-hydroxyquinoline-5-sulfoic acid and tannic acid ameliorated copper toxicity by decreasing the concentration of free ionic copper while lipid-soluble ligands such as oxine and potassium ethylxanthogenate increased copper toxicity, presumably as a result of the complexes diffusing through the cell membrane and participating in injurious reaction. The copper complex with 2,9-dimethyl-1,10-phenanthroline was the most toxic complex tested. It is suggested that the presence of these ligands in the receiving water should be taken into consideration when establishing water quality criteria. 19 references, 2 figures, 3 tables.

Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

Science.gov (United States)

Domracheva, N. E.; Mirea, A.; Schwoerer, M.; Torre-Lorente, L.; Lattermann, G.

2007-07-01

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO4) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B 0 = 8000 G). The degree of orientation of these complexes is rather high (S z = 0.76) and close to that of systems with a complete ordering (S z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH4, N2H4 · H2O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.

Spectroscopic study of divalent copper complexes forming in the systems CuCl2-MCl (M= Na, K, Rb, Cs)

International Nuclear Information System (INIS)

Utorov, N.P.; Bakshi, Yu.M.; Bazov, V.P.; Gel'bshtejn, A.I.

1982-01-01

The structure of complex ions formed in salt systems CuCl 2 -MCl depending on the nature of cation of alkali metal chloride at different mole ratios (n=MCl/CuCl 2 ) is studied. The data obtained using the methods of oscillation and electron spectroscopy enable to consider that during the melting of CuCl 2 and CsCl at n 4 2- ions, have the symmetry Csub(2v) at n=1. π-bonding, which is realized with participation of of Cl - p-orbitals and Cu 2+ d-orbitals plays a very important role in the formation of dimers and polymer chains. π-conjugated systems are characterized by the spectrum of charge transfer in the visible region. Charge transfer promotes metal reduction in the excited state which is adequate to the change of electron configuration of copper from d 9 for d 10 . It results in the decrease of acceptor and increase of dative ability of copper cation in the composition of salt complex. Big (n >= 2) additions of CsCl lead to the formation of separate stable ions of CuCl 4 2- type with the symmetry Dsub(2d)

Photochemical activation and reactivity of polynuclear transition-metal-complex molecules. Progress report, June 1981-May 31, 1982

International Nuclear Information System (INIS)

Endicott, J.F.; Lintvedt, R.L.

1982-01-01

Significant results obtained during the year are summarized for the following programs: (1) reversible, two electron transfer at a single potential in binuclear complexes; (2) photophysics of polyketonate complexes; (3) synthetic strategies and characterization of heavy metal heterobinuclear complexes; (4) high yield synthesis of ligands capable of binding 3 and 4 metal ions per molecule. Electrochemical studies have uncovered a number of new binuclear metal complexes that undergo reversible two-electron reduction at single potential including Cu(II) complexes with two different coordination environments, mixed Ni(II), Cu(II) complexes and binuclear Ni(II) complexes. In each case the species that exhibit these electron transfer properties have been shown to be Na + ion-paired complexes. Several new trinuclear molecular complexes have been prepared and characterized that contain two UO 2 2+ ions and one transition metal ion. The electrochemistry, absorption spectra, and luminescence have been investigated

Photoluminescent Copper(I) Complex Based on 3-(2-(Cyclohexylthio) ethoxy)pyridine: Synthesis, Structure, and Physical Properties

Energy Technology Data Exchange (ETDEWEB)

Park, Hyunjin; Kwon, Eunjin; Kang, Gihaeng; Kim, Jieun; Kim, Tae Ho [Gyeongsang National University, Jinju (Korea, Republic of)

2016-07-15

In recent years, the Cu(I) complexes, with d 10 electronic configuration, have been attracting interest due to their diverse structures and photophysical properties. A copper(I) coordination polymer 1 based on a sulfur-containing pyridyl ligand L was synthesized and identified by X-ray crystallography. Photophysical and thermal properties of 1 have been investigated. More Cu(I) coordination polymers based on mixed donor ligands are under investigation in order to discover factors governing luminescence wavelength, such as Cu[BOND]Cu distances, intermolecular interactions, structures of ligands, and so on.

Silver(I) and copper(I) complexes with the closo-decaborate anion B10H102- as a ligand

International Nuclear Information System (INIS)

Malinina, E.A.; Zhizhin, K.Yu.; Polyakova, I.N.; Lisovskij, M.V.; Kuznetsov, N.T.

2002-01-01

Studying the process of silver(I) and copper(I) complexing with closo-borate anion B 10 H 10 2- it is determined that the last can to play a role of intraspherical ligand forming stable coordination compounds of two types: Cat[MB 10 H 10 ] and [M 2 B 10 H 10 ] (M=Ag(I), Cu(I)). In these compounds the bond metal-boron skeleton is realized by means of formation of three-center bonds M-H-B. Structure of the complexes Cs[AgB 10 H 10 ] and [(C 2 H 5 ) 3 NH][AgB 10 H 10 ] and possible mechanism of their formation are discussed [ru

Synthesis, structures, spectroscopy and antimicrobial properties of complexes of copper(II) with salicylaldehyde N-substituted thiosemicarbazones and 2,2'-bipyridine or 1,10-phenanthroline.

Science.gov (United States)

Lobana, Tarlok S; Indoria, Shikha; Jassal, Amanpreet Kaur; Kaur, Harpreet; Arora, Daljit S; Jasinski, Jerry P

2014-04-09

Among the biometals (Cu, Co, Ni-cofactors in many enzymes), copper derivatives of O, N, S-donor salicylaldehyde thiosemicarbazones have received considerable attention owing to their potential biological applications. Eight new complexes of salicylaldehyde-N-substituted thiosemicarbazones [5-MeO-2-HO-C₆H₄-C(2)(H)N(3)-N(2)H-C(1)(S)-N(1)HR; R = Me, H2L(1); Et, H₂L(1), Ph, H₂L(3), H, H₂L(4)] with copper(II), namely, [Cu(κ(3)-O,N,S-L)( κ(2)-N,N-L')] {(L)(2-) = (L(1))(2-), L' = bipy, 1, phen, 2; (L)(2-) = (L(2))(2-), L' = bipy, 3, phen, 4; (L)(2-) = (L(3))(2-), L' = bipy, 5, phen, 6; (L)(2-) = (L(4))(2-), L' = bipy, 7, phen, 8} have been isolated. Complexes have slightly distorted square pyramidal geometry around the metal center (τ parameter = 0.243-0.357) and display weak to intense fluorescence in the region, 375-475 nm. These copper complexes have shown significant growth inhibitory activity (antimicrobial activity) against Staphylococcus aureus (MTCC740), methicillin resistant Staphylococcus aureus (MRSA), Klebsiella pneumoniae 1 (MTCC109), Shigella flexneri (MTCC1457), Pseudomonas aeruginosa (MTCC741) and Candida albicans (MTCC227). The activity against MRSA is an interesting observation as the commercially available gentamycin is found to be inactive against this bacterial strain. Specifically complex 5 formed by 5-methoxysalicylaldehyde-N-phenylthiosemicatbazone has shown novel antimicrobial activity against various bacteria and yeast investigated. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Copper in the sea: a bibliography

Energy Technology Data Exchange (ETDEWEB)

Schmidt, R.L.

1977-04-01

Life in the sea is vulnerable to the influx of trace metals resulting from man's activities. Although many pollutants introduced to the sea eventually degrade to less harmful forms, trace metals accumulate in sediments and have a continued potential for effect on biota. Copper has a toxic potential exceeding all other metals due to the quantity discharged and its toxicological effect. Fortunately, copper in the oceans is rendered less bioavailable or less toxic by its ready interaction with the complex chemical components of seawater. This bibliography was prepared to illustrate the status of current knowledge of the biogeochemistry of copper and to aid the development of research programs to define the effects of copper discharged to the marine environment. The references are categorized to aid the reader to locate literature concerning specific aspects of the biogeochemistry of copper. A brief comment describing the important findings in each category is given. Although this bibliography is not exhaustive, the listed references are likely representative of current knowledge.

Standard molar enthalpies of formation of copper(II) {beta}-diketonates and monothio-{beta}-diketonates

Energy Technology Data Exchange (ETDEWEB)

Ribeiro da Silva, Manuel A.V. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)]. E-mail: risilva@fc.up.pt; Santos, Luis M.N.B.F. [Centro de Investigacao em Quimica, Departamento de Quimica, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

2006-07-15

The standard (p{sup o}=0.1MPa) molar enthalpies of formation of the crystalline complexes of dibenzoylmethane (Hdbm), thenoyltrifluoroacetone (Httfa), monothiodibenzoylmethane (HdbmS), and monothiothenoyltrifluoroacetone (HttfaS) of copper(II) were determined, at T=298.15K, by high precision solution-reaction calorimetry. The standard molar enthalpies of sublimation of the copper(II) {beta}-diketonate complexes were measured by high-temperature Calvet microcalorimetry. From the standard molar enthalpies of formation of the complexes in the gaseous state, the mean molar dissociation enthalpies copper(II)-ligand, (Cu-L), were derived. {delta}{sub f}H{sub m}{sup o} (cr){delta}{sub cr}{sup g}H{sub m}{sup o} kJ.mol{sup -1}kJ.mol{sup -1}Bis(dibenzoylmethanate)copper(II), Cu(dbm){sub 2}-364.0+/-3.9230.7+/-8.2Bis(thenoyltrifluoroacetonate)copper(II), Cu(ttfa){sub 2}-1824.3+/-8.3167.9+/-7.4Bis(monothiodibenzoylmethanate)copper(II), Cu(dbmS){sub 2}35.6+/-7.7[241+/-15]Bis(monothiothenoyltrifluoroacetonate) copper(II), Cu(ttfaS){sub 2}-1405.7+/-8.3[177+/-15].

Metal complex derivatives of hydrogen uranyl phosphate

International Nuclear Information System (INIS)

Grohol, D.; Blinn, E.L.

1994-01-01

Derivatives of hydrogen uranyl phosphate were prepared by incorporating transition metal complexes into the uranyl phosphate matrix. The transition metal complexes employed include bis(ethylenediamine)copper(II), bis(1,3-propanediamine)copper(II) chloride, (triethylenetetramine)copper(II), (1,4,8,11-tetraazacyclotetradecane)copper(II), (1,4,8,12-tetraazacyclopentadecane)copper(II), (1,4,8,11-tetraazacyclotetradecane)nickel(II) chloride, (triethylenetetramine)nickel(II) and others. The chemical analyses of these derivatives indicated that the incorporation of the transition metal complexes into the uranyl phosphate matrix via ion exchange was not stoichiometric. The extent of ion exchange is dependent on the size and structure of the transition metal complex. All complexes were characterized by X-ray powder diffractometry, electronic and infrared spectra, thermal analyses and chemical analysis. An attempt was made to correlate the degree of quenching of the luminescence of the uranyl ion to the spacing between the uranyl phosphate layers in the derivatives

Steric Effects on the Binding of Phosphate and Polyphosphate Anions by Zinc(II) and Copper(II) Dinuclear Complexes of m-Xylyl-bis-cyclen.

Science.gov (United States)

Esteves, Catarina V; Esteban-Gómez, David; Platas-Iglesias, Carlos; Tripier, Raphaël; Delgado, Rita

2018-05-11

The triethylbenzene-bis-cyclen (cyclen = 1,4,7,10-tetraazacyclododecane) compound (tbmce) was designed with an imposed structural rigidity at the m-xylyl spacer to be compared to a less restrained and known parent compound (bmce). The framework of both compounds differs only in the substituents of the m-xylyl spacer. The study was centered in the differences observed in the acid-base reactions of both compounds, their copper(II) and zinc(II) complexation behaviors, as well as in the uptake of phosphate and polyphosphate anions (HPPi 3- , ATP 4- , ADP 3- , AMP 2- , PhPO 4 2- , and HPO 4 2- ). On the one hand, the acid-base reactions showed lower values for the third and fourth protonation constants of tbmce than for bmce, suggesting that the ethyl groups of the spacer in tbmce force the two cyclen units to more conformational restricted positions. On the other hand, the stability constant values for copper(II) and zinc(II) complexes revealed that bmce is a better chelator than tbmce pointing out to additional conformational restraints imposed by the triethylbenzene spacer. The binding studies of phosphates by the dinuclear copper(II) and zinc(II) complexes showed much smaller effective association constants for the dicopper complexes. Single-crystal X-ray and computational (density functional theory) studies suggest that anion binding promotes the formation of tetranuclear entities in which anions are bridging the metal centers. Our studies also revealed the dinuclear zinc(II) complex of bmce as a promising receptor for phosphate anions, with the largest effective association constant of 5.94 log units being observed for the formation of [Zn 2 bmce(HPPi)] + . Accordingly, a colorimetric study via an indicator displacement assay to detect phosphates in aqueous solution found that the [Zn 2 bmce] 4+ complex acts as the best receptor for pyrophosphate displaying a detection limit of 2.5 nM by changes visible to naked eye.

A Nanostructured Lipid System as a Strategy to Improve the in Vitro Antibacterial Activity of Copper(II Complexes

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Patricia B. da Silva

2015-12-01

Full Text Available The aim of this study was to construct a nanostructured lipid system as a strategy to improve the in vitro antibacterial activity of copper(II complexes. New compounds with the general formulae [CuX2(INH2]·nH2O (X = Cl− and n = 1 (1; X = NCS− and n = 5 (2; X = NCO− and n = 4 (3; INH = isoniazid, a drug widely used to treat tuberculosis derived from the reaction between the copper(II chloride and isoniazid in the presence or absence of pseudohalide ions (NCS− or NCO− were synthesized and characterized by infrared spectrometry, electronic absorption spectroscopy, electron paramagnetic resonance (EPR spectroscopy, elemental analysis, melting points and complexometry with 2,2′,2′′,2′′′-(Ethane-1,2-diyldinitrilotetraacetic acid (EDTA. The characterization techniques allowed us to confirm the formation of the copper(II complexes. The Cu(II complexes were loaded into microemulsion (MEs composed of 10% phase oil (cholesterol, 10% surfactant [soy oleate and Brij® 58 (1:2] and 80% aqueous phase (phosphate buffer pH = 7.4 prepared by sonication. The Cu(II complex-loaded MEs displayed sizes ranging from 158.0 ± 1.060 to 212.6 ± 1.539 nm, whereas the polydispersity index (PDI ranged from 0.218 ± 0.007 to 0.284 ± 0.034. The antibacterial activity of the free compounds and those that were loaded into the MEs against Staphylococcus aureus ATCC® 25923 and Escherichia coli ATCC® 25922, as evaluated by a microdilution technique, and the cytotoxicity index (IC50 against the Vero cell line (ATCC® CCL-81TM were used to calculate the selectivity index (SI. Among the free compounds, only compound 2 (MIC 500 μg/mL showed activity for S. aureus. After loading the compounds into the MEs, the antibacterial activity of compounds 1, 2 and 3 was significantly increased against E. coli (MIC’s 125, 125 and 500 μg/mL, respectively and S. aureus (MICs 250, 500 and 125 μg/mL, respectively. The loaded compounds were less toxic against the Vero

Non-covalent interactions in 2-methylimidazolium copper(II) complex (MeImH)2[Cu(pfbz)4]: Synthesis, characterization, single crystal X-ray structure and packing analysis

Science.gov (United States)

Sharma, Raj Pal; Saini, Anju; Kumar, Santosh; Kumar, Jitendra; Sathishkumar, Ranganathan; Venugopalan, Paloth

2017-01-01

A new anionic copper(II) complex, (MeImH)2 [Cu(pfbz)4] (1) where, MeImH = 2-methylimidazolium and pfbz = pentafluorobenzoate has been isolated by reacting copper(II) sulfate pentahydrate, pentafluorobenzoic acid and 2-methylimidazole in ethanol: water mixture in 1:2:2 molar ratio. This complex 1 has been characterized by elemental analysis, thermogravimetric analysis, spectroscopic techniques (UV-Vis, FT-IR) and conductance measurements. The complex salt crystallizes in monoclinic crystal system with space group C2/c. Single crystal X-ray structure determination revealed the presence of discrete ions: [Cu(pfbz)4]2- anion and two 2-methylimidazolium cation (C4H7N2)+. The crystal lattice is stabilized by strong hydrogen bonding and F⋯F interactions between cationic-anionic and the anionic-anionic moieties respectively, besides π-π interactions.

Chemical Speciation of Copper in a Salt Marsh Estuary and Bioavailability to Thaumarchaeota

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Hannah Whitby

2017-06-01

Full Text Available The concentrations of dissolved copper (Cud, copper-binding ligands, thiourea-type thiols, and humic substances (HSCu were measured in estuarine waters adjacent to Sapelo Island, Georgia, USA, on a monthly basis from April to December 2014. Here we present the seasonal cycle of copper speciation within the estuary and compare it to the development of an annually occurring bloom of Ammonia Oxidizing Archaea (AOA, which require copper for many enzymes. Two types of complexing ligands (L1 and L2 were found to dominate with mean complex stabilities (log KCuL′ of 14.5 and 12.8. Strong complexation resulted in lowering the concentration of free cupric ion (Cu2+ to femtomolar (fM levels throughout the study and to sub-fM levels during the summer months. A Thaumarchaeota bloom during this period suggests that this organism manages to grow at very low Cu2+ concentrations. Correlation of the concentration of the L1 ligand class with a thiourea-type thiol and the L2 ligand class with HSCu provide an interesting dimension to the identity of the ligand classes. Due to the stronger complex stability, 82–99% of the copper was bound to L1. Thiourea-type thiols typically form Cu(I species, which would suggest that up to ~90% copper could be present as Cu(I in this region. In view of the very low concentration of free copper (pCu > 15 at the onset and during the bloom and a reputedly high requirement for copper, it is likely that the Thaumarchaeota are able to access thiol-bound copper directly.

Effect of acrylonitrile on the electrode processes ivolving copper cations

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Viktor F. Vargalyuk

2016-03-01

Full Text Available Based on the results of cyclic voltammetry and study of deposits morphology, it has been shown that acrylonitrile does not have significant effect on the mechanism of Cu2+ + 2ē → Cu0 reaction. This distinguishes acrylonitrile from the unsaturated polyfunctional organic substances (acrylic acid, acrylamide which forms stable complexes with Cu2+ ions. Acrylonitrile just inhibits cathodic process by adsorbing on the surface of electrode thus blocking its active sites. But the presence of acrylonitrile significantly changes the mechanism of the anodic process. It has been found that acrylonitrile interacts with surface copper atoms thus forming thermodynamically stable [Cu π-AN]0 π‑complexes. Ionization potential of these π‑complexes is more negative if compare to copper atoms. As the result acceleration of anodic process takes place in the low polarization area. However, since the chemisorption is a slow process the presence of acrylonitrile mainly affects dissolution of the first surface layers of copper atoms. Further ionization of copper atoms runs out directly and requires higher polarization.

Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen

Energy Technology Data Exchange (ETDEWEB)

Winkler, H; Wannowius, K J; Elias, H [Technische Hochschule Darmstadt (Germany, F.R.). Fachbereich Anorganische Chemie und Kernchemie

1977-01-01

The kinetics of isotopic copper exchange between various (bis-(N-phenyl-salicylaldiminato))copper(II)complexes (= CuL/sub 2/) and mono(pyridine)copper(II)acetate (= CuAc/sub 2/py) was studied in dichloromethane as solvent in the temperature range -20 to +20/sup 0/C. The exchange follows the experimental rate law (5), which is simplified in certain cases due to k''((CuAc/sub 2/py)/sub 2/)/sup 1///sup 2/ < 1. The variation of substituents X on the salicylaldehyde ring and of substituents Y on the N-phenyl ring leads via Hammett plots to the conclusion that substituent effects become apparent as rate increasing or rate decreasing only in those cases, in which they cause an increase or decrease in electron density at the donor oxygen. Substituents Y in 2-position, and especially in 2.6-position, reduce the rate of exchange with increasing van der Waals radius of Y. The mechanistic implications of the results are discussed. (orig.) 891 HK.

Synthesis, crystal structure and excellent photoluminescence properties of copper (II and cobalt (II complexes with Bis(1[(4-butylphenylimino]methyl naphthalen-2-ol Schiff base

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V.B. Nagaveni

2018-03-01

Full Text Available Copper (II and Cobalt (II metal complexes (4a- and 4b-complexes using Schiff base ligand 1-[(4-butylphenylimino]methyl naphthalen-2-ol (3 have been synthesized. The single crystals of Copper (II and Cobalt (II complex phosphors were grown and characterized by Fourier-Transform Infrared (FT-IR, single crystal X-ray diffraction (XRD, SEM (Scanning Electron Microscope and EDS (Energy Dispersive X-ray spectroscopy. Photoluminescence study of the phosphors revealed the presence of excitation peaks at 333 nm and 360 nm for 4a-complex (λemi = 495 nm and excitation peaks at 300 nm and 360 nm for 4b-complex (λemi = 496 nm. The calculated CCT values of the complexes pointed out that these materials can be used to obtain cold white light from the light emitting devices. Diffuse reflectance spectra (DRS showed the measured band gap energies of 1.78 eV and 1.44 eV for Cu (II and Co (II complexes, respectively. It is concluded that the 4a- and 4b-complexes become white and blue green light emitting diodes respectively and will be useful in the development of strong electroluminescent materials. Keywords: 1[(4-butylphenylimino]methylnaphthalen-2-ol, Schiff base, Cu (II and Co (IIcomplex, Photoluminescence, Single crystal XRD, OLED

The cardiac copper chaperone proteins Sco1 and CCS are up-regulated, but Cox 1 and Cox4 are down-regulated, by copper deficiency.

Science.gov (United States)

Getz, Jean; Lin, Dingbo; Medeiros, Denis M

2011-10-01

Copper is ferried in a cell complexed to chaperone proteins, and in the heart much copper is required for cytochrome c oxidase (Cox). It is not completely understood how copper status affects the levels of these proteins. Here we determined if dietary copper deficiency could up- or down-regulate select copper chaperone proteins and Cox subunits 1 and 4 in cardiac tissue of rats. Sixteen weanling male Long-Evans rats were randomized into treatment groups, one group receiving a copper-deficient diet (CCS, Sco1, Ctr1, Cox17, Cox1, and Cox4 by SDS-PAGE and Western blotting. No changes were observed in the concentrations of CTR1 and Cox17 between copper-adequate and copper-deficient rats. CCS and Sco1 were up-regulated and Cox1 and Cox4 were both down-regulated as a result of copper deficiency. These data suggest that select chaperone proteins and may be up-regulated, and Cox1 and 4 down-regulated, by a dietary copper deficiency, whereas others appear not to be affected by copper status.

X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

Science.gov (United States)

Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

2017-05-01

Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

Proteomic and physiological responses of Kineococcus radiotolerans to copper.

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Christopher E Bagwell

Full Text Available Copper is a highly reactive, toxic metal; consequently, transport of this metal within the cell is tightly regulated. Intriguingly, the actinobacterium Kineococcus radiotolerans has been shown to not only accumulate soluble copper to high levels within the cytoplasm, but the phenotype also correlated with enhanced cell growth during chronic exposure to ionizing radiation. This study offers a first glimpse into the physiological and proteomic responses of K. radiotolerans to copper at increasing concentration and distinct growth phases. Aerobic growth rates and biomass yields were similar over a range of Cu(II concentrations (0-1.5 mM in complex medium. Copper uptake coincided with active cell growth and intracellular accumulation was positively correlated with Cu(II concentration in the growth medium (R(2=0.7. Approximately 40% of protein coding ORFs on the K. radiotolerans genome were differentially expressed in response to the copper treatments imposed. Copper accumulation coincided with increased abundance of proteins involved in oxidative stress and defense, DNA stabilization and repair, and protein turnover. Interestingly, the specific activity of superoxide dismutase was repressed by low to moderate concentrations of copper during exponential growth, and activity was unresponsive to perturbation with paraquot. The biochemical response pathways invoked by sub-lethal copper concentrations are exceptionally complex; though integral cellular functions are preserved, in part, through the coordination of defense enzymes, chaperones, antioxidants and protective osmolytes that likely help maintain cellular redox. This study extends our understanding of the ecology and physiology of this unique actinobacterium that could potentially inspire new biotechnologies in metal recovery and sequestration, and environmental restoration.

Proteomic and physiological responses of Kineococcus radiotolerans to copper.

Science.gov (United States)

Bagwell, Christopher E; Hixson, Kim K; Milliken, Charles E; Lopez-Ferrer, Daniel; Weitz, Karl K

2010-08-26

Copper is a highly reactive, toxic metal; consequently, transport of this metal within the cell is tightly regulated. Intriguingly, the actinobacterium Kineococcus radiotolerans has been shown to not only accumulate soluble copper to high levels within the cytoplasm, but the phenotype also correlated with enhanced cell growth during chronic exposure to ionizing radiation. This study offers a first glimpse into the physiological and proteomic responses of K. radiotolerans to copper at increasing concentration and distinct growth phases. Aerobic growth rates and biomass yields were similar over a range of Cu(II) concentrations (0-1.5 mM) in complex medium. Copper uptake coincided with active cell growth and intracellular accumulation was positively correlated with Cu(II) concentration in the growth medium (R(2)=0.7). Approximately 40% of protein coding ORFs on the K. radiotolerans genome were differentially expressed in response to the copper treatments imposed. Copper accumulation coincided with increased abundance of proteins involved in oxidative stress and defense, DNA stabilization and repair, and protein turnover. Interestingly, the specific activity of superoxide dismutase was repressed by low to moderate concentrations of copper during exponential growth, and activity was unresponsive to perturbation with paraquot. The biochemical response pathways invoked by sub-lethal copper concentrations are exceptionally complex; though integral cellular functions are preserved, in part, through the coordination of defense enzymes, chaperones, antioxidants and protective osmolytes that likely help maintain cellular redox. This study extends our understanding of the ecology and physiology of this unique actinobacterium that could potentially inspire new biotechnologies in metal recovery and sequestration, and environmental restoration.

Interaction between metals and nucleic acids. Part 3. Synthesis and structural studies of copper(II) complexes with Schiff base ligands derived from barbituric acid

Energy Technology Data Exchange (ETDEWEB)

Sasaki, I.; Gaudemer, A.; Chiaroni, A.; Riche, C.

1986-02-17

Schiff bases have been prepared from 5-formylbarbituric acid and 5-formyl-1,3-dimethyl-barbituric acid and various di- or tri-amines. The structure of the corresponding copper(II) complexes have been established by elemental analysis and spectroscopic methods. The molecular structure of one of the complexes, Cu(DiMeBardpt), was determined by X-ray diffraction. Electrochemical study shows that these complexes are reduced at slightly more negative potentials than the corresponding complexes obtained from uracil, which suggests that these new ligands are better electron-donors.

Nonlinear optical and G-Quadruplex DNA stabilization properties of novel mixed ligand copper(II) complexes and coordination polymers: Synthesis, structural characterization and computational studies

Science.gov (United States)

Rajasekhar, Bathula; Bodavarapu, Navya; Sridevi, M.; Thamizhselvi, G.; RizhaNazar, K.; Padmanaban, R.; Swu, Toka

2018-03-01

The present study reports the synthesis and evaluation of nonlinear optical property and G-Quadruplex DNA Stabilization of five novel copper(II) mixed ligand complexes. They were synthesized from copper(II) salt, 2,5- and 2,3- pyridinedicarboxylic acid, diethylenetriamine and amide based ligand (AL). The crystal structure of these complexes were determined through X-ray diffraction and supported by ESI-MAS, NMR, UV-Vis and FT-IR spectroscopic methods. Their nonlinear optical property was studied using Gaussian09 computer program. For structural optimization and nonlinear optical property, density functional theory (DFT) based B3LYP method was used with LANL2DZ basis set for metal ion and 6-31G∗ for C,H,N,O and Cl atoms. The present work reveals that pre-polarized Complex-2 showed higher β value (29.59 × 10-30e.s.u) as compared to that of neutral complex-1 (β = 0.276 × 10-30e.s.u.) which may be due to greater advantage of polarizability. Complex-2 is expected to be a potential material for optoelectronic and photonic technologies. Docking studies using AutodockVina revealed that complex-2 has higher binding energy for both G-Quadruplex DNA (-8.7 kcal/mol) and duplex DNA (-10.1 kcal/mol). It was also observed that structure plays an important role in binding efficiency.

Novel Microbial Assemblages Dominate Weathered Sulfide-Bearing Rock from Copper-Nickel Deposits in the Duluth Complex, Minnesota, USA.

Science.gov (United States)

Jones, Daniel S; Lapakko, Kim A; Wenz, Zachary J; Olson, Michael C; Roepke, Elizabeth W; Sadowsky, Michael J; Novak, Paige J; Bailey, Jake V

2017-08-15

The Duluth Complex in northeastern Minnesota hosts economically significant deposits of copper, nickel, and platinum group elements (PGEs). The primary sulfide mineralogy of these deposits includes the minerals pyrrhotite, chalcopyrite, pentlandite, and cubanite, and weathering experiments show that most sulfide-bearing rock from the Duluth Complex generates moderately acidic leachate (pH 4 to 6). Microorganisms are important catalysts for metal sulfide oxidation and could influence the quality of water from mines in the Duluth Complex. Nevertheless, compared with that of extremely acidic environments, much less is known about the microbial ecology of moderately acidic sulfide-bearing mine waste, and so existing information may have little relevance to those microorganisms catalyzing oxidation reactions in the Duluth Complex. Here, we characterized the microbial communities in decade-long weathering experiments (kinetic tests) conducted on crushed rock and tailings from the Duluth Complex. Analyses of 16S rRNA genes and transcripts showed that differences among microbial communities correspond to pH, rock type, and experimental treatment. Moreover, microbial communities from the weathered Duluth Complex rock were dominated by taxa that are not typically associated with acidic mine waste. The most abundant operational taxonomic units (OTUs) were from the genera Meiothermus and Sulfuriferula , as well as from diverse clades of uncultivated Chloroflexi , Acidobacteria , and Betaproteobacteria Specific taxa, including putative sulfur-oxidizing Sulfuriferula spp., appeared to be primarily associated with Duluth Complex rock, but not pyrite-bearing rocks subjected to the same experimental treatment. We discuss the implications of these results for the microbial ecology of moderately acidic mine waste with low sulfide content, as well as for kinetic testing of mine waste. IMPORTANCE Economic sulfide mineral deposits in the Duluth Complex may represent the largest

Photochemical synthesis of copper nanoparticles incorporated in poly(vinyl pyrrolidone)

International Nuclear Information System (INIS)

Giuffrida, Salvatore; Costanzo, Lucia L.; Ventimiglia, Giorgio; Bongiorno, Corrado

2008-01-01

The effect of the presence of poly(vinyl pyrrolidone) (PVP) on the copper nanoparticle formation, obtained by UV irradiation of ethanol solution of Cu(acac) 2 (acac = 2,4-pentanedionato), was investigated. At 254 nm, in conditions of light completely absorbed by complex, the PVP exhibited protective and stabilizing effects, as shown by the formation of a colloidal copper solution and by a block of the heterogeneous process, which leads to thin film formation on the quartz walls. The colloidal solution was tested for several months by plasmon position and it was found that it remained unaltered in inert atmosphere, but returned to the starting complex on contact with air. The PVP ability to control the particle size was investigated by carrying out photoreduction sensitized by Hacac at 254 and 300 nm, in the presence of PVP concentration varying from 0 to 0.2 M. In this range it was possible to obtain copper nanoparticles of dimensions decreasing from 30 to 4 nm. Besides this, the PVP (0.005-0.05 M) role as sensitizer was investigated by irradiating solutions of Cu(acac) 2 at 300 nm which is an inactive wavelength for copper reduction by direct light absorption. It was found that the PVP was an efficient sensitizer of the copper photoreduction. The nanoparticles were characterized by plasmon band, Trasmission Electron Microscope (TEM) as well as Dynamic Light Scattering (DSL) analysis. The overall results evidence the advantages of the PVP use in the nanoparticle copper formation through the photochemical technique such as the exclusive formation of colloidal copper, their size control, stable colloidal solution and complete return to the starting complex.

Visual Observation of Dissolution of Copper Ions from a Copper Electrode

Science.gov (United States)

Ikemoto, Isao; Saitou, Kouichi

2013-01-01

During electrolysis, to visually observe the conversion of a metal to its cation, either the cation or its complex ion should have a distinct color while the electrolyte solution must be colorless and transparent. A demonstration is described in which copper is used as the electrodes and sodium polyacrylate (a superabsorbent polymer) solution is…

Forming Refractory Insulation On Copper Wire

Science.gov (United States)

Setlock, J.; Roberts, G.

1995-01-01

Alternative insulating process forms flexible coat of uncured refractory insulating material on copper wire. Coated wire formed into coil or other complex shape. Wire-coating apparatus forms "green" coat on copper wire. After wire coiled, heating converts "green" coat to refractory electrical insulator. When cured to final brittle form, insulating material withstands temperatures above melting temperature of wire. Process used to make coils for motors, solenoids, and other electrical devices to be operated at high temperatures.

Enhanced reactivity of dinuclear Copper(I) acetylides in dipolar cycloadditions

DEFF Research Database (Denmark)

Ahlquist, Mårten Sten Gösta; Fokin, V.V.

2007-01-01

Dinuclear alkynyl copper(I) complexes exhibit superior reactivity toward organic azides compared to their monomeric analogues. DFT studies indicate that the second copper center facilitates the formation of the cupracycle in the rate-determining step and stabilizes the metallacycle intermediate i...

Electrical characterization of copper related defect reactions in silicon

Energy Technology Data Exchange (ETDEWEB)

Heiser, T. [Centre National de la Recherche Scientifique, 67 - Strasbourg (France). Lab. PHASE; Istratov, A.A.; Flink, C.; Weber, E.R. [Department of Material Science and Mineral Engineering, University of California at Berkeley, 577 Evans Hall, Berkeley, CA 94720 (United States)

1999-02-12

Defect reactions involving interstitial copper impurities (Cu{sub i}) in silicon are reviewed. The influence of the Coulomb interaction between positively charged copper and negatively charged defects, such as acceptor states of transition metals and lattice defects, on the complex formation rate is discussed in detail. The diffusivity of interstitial copper and the dissociation kinetics of copper-acceptor pairs are studied using the recently introduced transient ion drift (TID) method. TID results reveal that most interstitial copper impurities remain dissolved immediately after the quench and form pairs with shallow acceptors. It is shown that in moderately and heavily doped silicon the diffusivity of copper is trap limited, while in low B-doped silicon the interstitial copper-acceptor pairing is weak enough to allow the assessment of the copper intrinsic diffusion coefficient. The intrinsic diffusion barrier is estimated to be 0.18{+-}0.01 eV. It is concluded that the Coulomb potential used in previous publications underestimated considerably the acceptor-copper interaction. In light of these results, a general discussion on Cu related defect reactions is given. (orig.) 44 refs.

Electrodialytic remediation of copper mine tailings: Comparing different operational conditions

DEFF Research Database (Denmark)

Rojo, Adrian; Hansen, Henrik K.; Ottosen, Lisbeth M.

2006-01-01

This work compares and evaluates sixteen electrodialytic laboratory remediation experiments on copper mine tailings. Different parameters were analyzed, such as remediation time, voltage drop, addition of desorbing agents, and the use of pulsed electrical fields. The results show that electric...... of copper citrate complexes. Using pulsed electric fields the remediation process with sulphuric acid addition was also improved by a decrease in the polarization cell. Main results: considering remediation with watery tailing as the base line, for three weeks experiments no copper removal was observed......, adding sulphuric acid total copper removal reached 39%. Adding citric acid, total copper removal was improved in terms of remediation time: after 5h experiment copper removal was 16% instead of 9% obtained after 72h with sulphuric acid addition. Using pulsed electric fields total copper removal was also...

Polymer complexes.. XXXX. Supramolecular assembly on coordination models of mixed-valence-ligand poly[1-acrylamido-2-(2-pyridyl)ethane] complexes

Science.gov (United States)

El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.

2003-02-01

The build-up of polymer metallic supramolecules based on homopolymer (1-acrylamido-2-(2-pyridyl)ethane (AEPH)) and ruthenium, rhodium, palladium as well as platinum complexes has been pursued with great interest. The homopolymer shows three types of coordination behaviour. In the mixed valence paramagnetic trinuclear polymer complexes [( 11)+( 12)] in the paper and in mononuclear polymer complexes ( 1)-( 5) it acts as a neutral bidentate ligand coordinating through the N-pyridine and NH-imino atoms, while in the mixed ligand diamagnetic poly-chelates, which are obtained from the reaction of AEPH with PdX 2 and KPtCl 4 in the presence of N-heterocyclic base consisting of polymer complexes ( 9)+( 10), and in monouclear compounds ( 6)-( 8), it behaves as a monobasic bidentate ligand coordinating through the same donor atoms. In mononuclear compounds ( 13)+( 14) it acts as a monobasic and neutral bidentate ligand coordinating only through the same donor atoms. Monomeric distorted octahedral or trimeric chlorine-bridged, approximately octahedral structures are proposed for these polymer complexes. The poly-chelates are of 1:1, 1:2 and 3:2 (metal-homopolymer) stoichiometry and exhibit six coordination. The values of ligand field parameters were calculated. The homopolymer and their polymer complexes have been characterized physicochemically.

Studies on the optical absorption of copper-dopped myoglobin: conformational changes

International Nuclear Information System (INIS)

Lamy, M.T.M.

1976-03-01

Optical absorption changes in the visible and near U.V. spectrum of myoglobin molecules are observed when copper ions are added to the macromolecule. The heme optical transitions are investigated through a theoretical simulation of the optical absorption spectrum. A study of the absorption band in the region of 700 nm associated with the copper - myoglobin complexes indicated the existence of two kinds of metal-protein complexes: one associated with the six or eitht first added copper ions and the other related with the higher concentrations. Conformational changes caused by thermal treatment are studied in myoglobin water solutions and solutions containing copper ions. The phenomenon named pre-denaturation is observed through the optical absorption at 245 nm. It is shown that interactions between myoglobin molecules occur in the pre-denaturation phenomenon. (Author) [pt

Drastic Effect of the Peptide Sequence on the Copper-Binding Properties of Tripeptides and the Electrochemical Behaviour of Their Copper(II) Complexes.

Science.gov (United States)

Mena, Silvia; Mirats, Andrea; Caballero, Ana B; Guirado, Gonzalo; Barrios, Leoní A; Teat, Simon J; Rodriguez-Santiago, Luis; Sodupe, Mariona; Gamez, Patrick

2018-04-06

The binding and electrochemical properties of the complexes Cu II -HAH, Cu II -HWH, Cu II -Ac-HWH, Cu II -HHW, and Cu II -WHH have been studied by using NMR and UV/Vis spectroscopies, CV, and density functional calculations. The results obtained highlight the importance of the peptidic sequence on the coordination properties and, consequently, on the redox properties of their Cu II complexes. For Cu II -HAH and Cu II -HWH, no cathodic processes are observed up to -1.2 V; that is, the complexes exhibit very high stability towards copper reduction. This behaviour is associated with the formation of very stable square-planar (5,5,6)-membered chelate rings (ATCUN motif), which enclose two deprotonated amides. In contrast, for non-ATCUN Cu II -Ac-HWH, Cu II -HHW complexes, simulations seem to indicate that only one deprotonated amide is enclosed in the coordination sphere. In these cases, the main electrochemical feature is a reductive irreversible one electron-transfer process from Cu II to Cu I , accompanied with structural changes of the metal coordination sphere and reprotonation of the amide. Finally, for Cu II -WHH, two major species have been detected: one at low pH (10) with an ATCUN motif, both species coexisting at intermediate pH. The present study shows that the use of CV, using glassy carbon as a working electrode, is an ideal and rapid tool for the determination of the redox properties of Cu II metallopeptides. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of hypoxia-targeting radiopharmaceuticals: selective uptake of copper-64 complexes in hypoxic cells in vitro

International Nuclear Information System (INIS)

Dearling, J.L.J.; Lewis, J.S.; Mullen, G.E.D.; Rae, M.T.; Zweit, J.; Blower, P.J.

1998-01-01

The well-known perfusion tracer CuPTSM, labelled with 62 Cu or 64 Cu, is believed to be trapped in cells non-selectively by a bioreductive mechanism. It is proposed that by modifying the ligand to increase its electron donor strength (for example by adding alkyl functionality or replacing sulphur ligands with oxygen ligands), the copper complexes will become less easily reduced and tracers with selectivity for hypoxic tissues could thus be developed. The aim of this work was to prepare 64 Cu-labelled complexes of two series of ligands, based on the bis(thiosemicarbazone) (13 ligands) and bis(salicylaldimine) (3 ligands) skeletons, and to evaluate the hypoxia dependence of their uptake in cells. The complexes were incubated with Chinese hamster ovary cells under normoxic and hypoxic conditions, and the cells isolated by centrifugation to determine radioactivity uptake at various time points up to 90 min. Several members of both series demonstrated significant (P 60 Cu, 61 Cu, 62 Cu, 64 Cu) and targeted radiotherapy ( 64 Cu, 67 Cu). (orig.)

Catalytic aspects of a copper(II) complex: biological oxidase to ...

Indian Academy of Sciences (India)

BISWAJIT CHOWDHURY

2017-10-03

Oct 3, 2017 ... made with a Jasco model V-730 UV-Vis spectrophotometer. ..... Ligand-induced coordination changes ... Fet3 protein from yeast, a multinuclear copper oxidase ... of mutants of the multicopper oxidase Fet3p Biochem-.

Regulation of the copper chaperone CCS by XIAP-mediated ubiquitination.

Science.gov (United States)

Brady, Graham F; Galbán, Stefanie; Liu, Xuwen; Basrur, Venkatesha; Gitlin, Jonathan D; Elenitoba-Johnson, Kojo S J; Wilson, Thomas E; Duckett, Colin S

2010-04-01

In order to balance the cellular requirements for copper with its toxic properties, an elegant set of mechanisms has evolved to regulate and buffer intracellular copper. The X-linked inhibitor of apoptosis (XIAP) protein was recently identified as a copper-binding protein and regulator of copper homeostasis, although the mechanism by which XIAP binds copper in the cytosol is unclear. Here we describe the identification of the copper chaperone for superoxide dismutase (CCS) as a mediator of copper delivery to XIAP in cells. We also find that CCS is a target of the E3 ubiquitin ligase activity of XIAP, although interestingly, ubiquitination of CCS by XIAP was found to lead to enhancement of its chaperone activity toward its physiologic target, superoxide dismutase 1, rather than proteasomal degradation. Collectively, our results reveal novel links among apoptosis, copper metabolism, and redox regulation through the XIAP-CCS complex.

Physicochemical, antioxidant, DNA cleaving properties and antimicrobial activity of fisetin-copper chelates.

Science.gov (United States)

Łodyga-Chruscińska, Elżbieta; Pilo, Maria; Zucca, Antonio; Garribba, Eugenio; Klewicka, Elżbieta; Rowińska-Żyrek, Magdalena; Symonowicz, Marzena; Chrusciński, Longin; Cheshchevik, Vitalij T

2018-03-01

Fisetin (3,3',4',7-tetrahydroxyflavone) metal chelates are of interest as this plant polyphenol has revealed broad prospects for its use as natural medicine in the treatment of various diseases. Metal interactions may change or enhance fisetin biological properties so understanding fisetin metal chelation is important for its application not only in medicine but also as a food additive in nutritional supplements. This work was aimed to determine and characterize copper complexes formed in different pH range at applying various metal/ligand ratios. Fisetin and Cu(II)-fisetin complexes were characterized by potentiometric titrations, UV-Vis (Ultraviolet-visible spectroscopy), EPR, ESI-MS, FTIR and cyclic voltammetry. Their effects on DNA were investigated by using circular dichroism, spectrofluorimetry and gel electrophoresis methods. The copper complex with the ratio of Cu(II)/fisetin 1/2 exhibited significant DNA cleavage activity, followed by complete degradation of DNA. The influence of copper(II) ions on antioxidant activity of fisetin in vitro has been studied using DPPH, ABTS and mitochondrial assays. The results have pointed out that fisetin or copper complexes can behave both as antioxidants or pro-oxidants. Antimicrobial activity of the compounds has been investigated towards several bacteria and fungi. The copper complex of Cu(II)/fisetin 1/2 ratio showed higher antagonistic activity against bacteria comparing to the ligand and it revealed a promising antifungal activity. Copyright © 2017 Elsevier Inc. All rights reserved.

Toxicity of copper chelates of azomethines and amino acids for Chlorella pyrenoidosa

Energy Technology Data Exchange (ETDEWEB)

Barashkov, G.K.; Rukhadze, E.G.; Talyzenkova, G.P.

1979-01-01

The authors have attempted to assess the toxicity of copper-containing compounds from the point of view of their interrelationship with the structural characteristics of the chelate compound and the structure of the ligand. The copper chelates of the azomethines tested may be provisionally divided into three types: A - complexes with N-alkly-azomethines; B - complexes with N-aryl-azomethines; C - binuclear complexes. Consideration was also given to chelates with aromatic and heterocyclic amino acids and to heteroligand chelates in which the copper atom coordinates azomethine and an amino acid simultaneously. Toxicity was determined by the method previously described and expressed as a critical concentration (C/sub cr/, mg Cu/liter) and in relative toxicity units (T/sub c/). The compounds investigated were obtained from the interaction between a bidentant ligand of an azomethine or anamino acid and copper acetate in a water-alcohol medium at pH 6-8. Since they are not very soluble in water, true solutions were obtained by using dimethyl sulfoxide.

Synthesis, Crystal Structure, Luminescence, Electrochemical and Antimicrobial Properties of Bis(salamo-Based Co(II Complex

Directory of Open Access Journals (Sweden)

Li Wang

2017-09-01

Full Text Available A newly designed Co(II complex, [Co3(L(OAc2(CH3OH2]·CH3OH, by the reaction of a bis(salamo-type tetraoxime ligand (H4L with Co(II acetate tetrahydrate was synthesized and characterized by elemental analyses, IR, UV-vis spectra and single-crystal X-ray crystallography. The UV-vis titration experiment manifested that a trinuclear (L:M = 1:3 complex was formed. It is worth noting that the two terminal Co(II (Co1 and Co3 atoms of the Co(II complex have different coordination modes and geometries unreported earlier. Furthermore, through intermolecular interactions (C–H···O, C–H···π and O–H···O, a 2D layer-like network is constructed. In addition, the fluorescence behaviors, antimicrobial activities and electrochemical properties of H4L and its Co(II complex were investigated.

Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions.

Science.gov (United States)

Papadakis, Raffaello; Rivière, Eric; Giorgi, Michel; Jamet, Hélène; Rousselot-Pailley, Pierre; Réglier, Marius; Simaan, A Jalila; Tron, Thierry

2013-05-20

A novel tetranuclear copper(II) complex (1) was synthesized from the self-assembly of copper(II) perchlorate and the ligand N-benzyl-1-(2-pyridyl)methaneimine (L(1)). Single-crystal X-ray diffraction studies revealed that complex 1 consists of a Cu4(OH)4 cubane core, where the four copper(II) centers are linked by μ3-hydroxo bridges. Each copper(II) ion is in a distorted square-pyramidal geometry. X-ray analysis also evidenced an unusual metal cation-π interaction between the copper ions and phenyl substituents of the ligand. Calculations based on the density functional theory method were used to quantify the strength of this metal-π interaction, which appears as an important stabilizing parameter of the cubane core, possibly acting as a driving parameter in the self-aggregation process. In contrast, using the ligand N-phenethyl-1-(2-pyridyl)methaneimine (L(2)), which only differs from L(1) by one methylene group, the same synthetic procedure led to a binuclear bis(μ-hydroxo)copper(II) complex (2) displaying intermolecular π-π interactions or, by a slight variation of the experimental conditions, to a mononuclear complex (3). These complexes were studied by X-ray diffraction techniques. The magnetic properties of complexes 1 and 2 are reported and discussed.

Phosphorylated α-Synuclein-Copper Complex Formation in the Pathogenesis of Parkinson’s Disease

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Juan Antonio Castillo-Gonzalez

2017-01-01

Full Text Available Parkinson’s disease is the second most important neurodegenerative disorder worldwide. It is characterized by the presence of Lewy bodies, which are mainly composed of α-synuclein and ubiquitin-bound proteins. Both the ubiquitin proteasome system (UPS and autophagy-lysosomal pathway (ALS are altered in Parkinson’s disease, leading to aggregation of proteins, particularly α-synuclein. Interestingly, it has been observed that copper promotes the protein aggregation process. Additionally, phosphorylation of α-synuclein along with copper also affects the protein aggregation process. The interrelation among α-synuclein phosphorylation and its capability to interact with copper, with the subsequent disruption of the protein degradation systems in the neurodegenerative process of Parkinson’s disease, will be analyzed in detail in this review.

New Approach to Remove Metals from Chromated Copper Arsenate (CCA)-Treated Wood

Science.gov (United States)

Todd F. Shupe; Chung Y. Hse; Hui Pan

2012-01-01

Recovery of metals from chromated copper arsenate (CCA)-treated southern pine wood particles was investigated using binary acid solutions consisting of acetic, oxalic, and phosphoric acids in a microwave reactor. Formation of an insoluble copper oxalate complex in the binary solution containing oxalic acid was the major factor for low copper removal. Furthermore, the...

solution growth and characterization of copper oxide thin films ...

African Journals Online (AJOL)

Thin films of copper oxide (CuO) were grown on glass slides by using the solution growth technique. Copper cloride (CuCl ) and potassium telluride (K T O ) were used. Buffer 2 2e 3 solution was used as complexing agent. The solid state properties and optical properties were obtained from characterization done using PYE ...

Copper and Copper Proteins in Parkinson's Disease

Science.gov (United States)

Rivera-Mancia, Susana; Diaz-Ruiz, Araceli; Tristan-Lopez, Luis; Rios, Camilo

2014-01-01

Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson's disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson's disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased protein-bound copper in brain may enhance iron accumulation and the associated oxidative stress. The function of other copper-binding proteins such as Cu/Zn-SOD and metallothioneins is also beneficial to prevent neurodegeneration. Copper may regulate neurotransmission since it is released after neuronal stimulus and the metal is able to modulate the function of NMDA and GABA A receptors. Some of the proteins involved in copper transport are the transporters CTR1, ATP7A, and ATP7B and the chaperone ATOX1. There is limited information about the role of those biomolecules in the pathophysiology of Parkinson's disease; for instance, it is known that CTR1 is decreased in substantia nigra pars compacta in Parkinson's disease and that a mutation in ATP7B could be associated with Parkinson's disease. Regarding copper-related therapies, copper supplementation can represent a plausible alternative, while copper chelation may even aggravate the pathology. PMID:24672633

Effects of copper source and concentration on in vitro phytate phosphorus hydrolysis by phytase.

Science.gov (United States)

Pang, Yanfang; Applegate, Todd J

2006-03-08

Five copper (Cu) sources were studied at pH 2.5, 5.5, and 6.5 to determine how Cu affects phytate phosphorus (PP) hydrolysis by phytase at concentrations up to 500 mg/kg diet (60 min, 40-41 degrees C). Subsequently, Cu solubility with and without sodium phytate was measured. Adding Cu inhibited PP hydrolysis at pH 5.5 and pH 6.5 (P copper chloride and copper lysinate inhibited PP hydrolysis much less than copper sulfate pentahydrate, copper chloride, and copper citrate (P copper-phytin complexes.

Separation of copper-64 from copper phthalocyanine

International Nuclear Information System (INIS)

Battaglin, R.I.M.

1979-01-01

The separation of copper-64 from irradiated copper phthalocyanine by Szilard-Chalmers effect is studied. Two methods of separation are used: one of them is based on the dissolution of the irradiated dry compound in concentrated sulfuric acid following its precipitation in water. In the other one the compound is irradiated with water in paste form following treatment with water and hydrochloric acid. The influence of the crystal form of the copper phthalocyanine on the separation yield of copper-64 is shown. Preliminary tests using the ionic exchange technique for purification and changing of copper-64 sulfate to chloride form are carried out. The specific activity using the spectrophotometric technique, after the determination of the copper concentration in solution of copper-64, is calculated. (Author) [pt

Ternary copper(II) complex: NCI60 screening, toxicity studies, and evaluation of efficacy in xenograft models of nasopharyngeal carcinoma

Science.gov (United States)

Chu, Tai-Lin; Abdul Aziz, Norazlin; Mohd Kornain, Noor-Kaslina; Samiulla, D. S.; Lo, Kwok-Wai; Ng, Chew-Hee

2018-01-01

Copper(II) ternary complex, [Cu(phen)(C-dmg)(H2O)]NO3 was evaluated against a panel of cell lines, tested for in vivo efficacy in nasopharyngeal carcinoma xenograft models as well as for toxicity in NOD scid gamma mice. The Cu(II) complex displayed broad spectrum cytotoxicity against multiple cancer types, including lung, colon, central nervous system, melanoma, ovarian, and prostate cancer cell lines in the NCI-60 panel. The Cu(II) complex did not cause significant induction of cytochrome P450 (CYP) 3A and 1A enzymes but moderately inhibited CYP isoforms 1A2, 2C9, 2C19, 2D6, 2B6, 2C8 and 3A4. The complex significantly inhibited tumor growth in nasopharyngeal carcinoma xenograft bearing mice models at doses which were well tolerated without causing significant or permanent toxic side effects. However, higher doses which resulted in better inhibition of tumor growth also resulted in toxicity. PMID:29329342

Effect of Grafted Hydroquinone on the Acid-Base Properties of Poly(acrylic acid in the Presence of Copper (II

Directory of Open Access Journals (Sweden)

Nabila Bensacia

2015-01-01

Full Text Available Potentiometric titration of poly(acrylic acid and hydroquinone-functionalized poly(acrylic acid was conducted in the presence of copper (II. The effects of hydroquinone functionalizing and copper (II complexing on the potentiometric titration of poly(acrylic acid were studied in an ionic environment and in its absence. Henderson-Hasselbalch equation was applied to assess its validity for this titration. Coordination number and the stability constants of the copper- (II-complexed polymers were determined, and results showed the formation of mostly monodentate and bidentate copper- (II-polymer complexes.

Electrodeposition and Properties of Copper Layer on NdFeB Device

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LI Yue

2017-06-01

Full Text Available To decrease the impact of the regular Ni/Cu/Ni coating on the magnetic performance of sintered NdFeB device, alkaline system of HEDP complexing agent was applied to directly electro-deposit copper layer on NdFeB matrix, then nickel layer was electrodeposited on the copper layer and Cu/Ni coating was finally obtained to replace the regular Ni/Cu/Ni coating. The influence of concentration of HEDP complexing agent on deposition course was tested by electrochemical testing; morphology of copper layer was characterized by SEM, XRD and TEM; the binding force of copper layer and the thermal reduction of magnetic of NdFeB caused by electrodeposited coating were respectively explored through the thermal cycle test and thermal demagnetization test. The results show that the concentration of HEDP has great impact on the deposition overpotential of copper. In the initial electrodepositing stage, copper particles precipitate at the grain boundaries of NdFeB magnets with a preferred (111 orientation. The copper layer is compact and has enough binding force with the NdFeB matrix to meet the requirements in SJ 1282-1977. Furthermore, the thermal demagnetization loss rate of the sintered NdFeB with the protection of Cu/Ni coating is significantly less than that with the protection of Ni/Cu/Ni coating.

Pharmacological and spectral studies of synthetic biomimetic copper complexes derived from 3-hydroxyflavone derivatives as anti-inflammatory agents

Directory of Open Access Journals (Sweden)

K. Nagashri

2016-09-01

Full Text Available Novel biomimetic ligands were synthesized by the condensation of 3-hydroxyflavone, 2-aminophenol(L1/2-aminobenzoic acid (L2 and-aminothiazole (L3. Their Cu(II complexes have also been synthesized and characterized on the basis of 1H NMR, IR, UV–Vis spectra, elemental analyses, molar conductivity, ESR, electrochemical behaviour and thermal analyses. The antimicrobial activities (MIC values of the ligands, copper complexes and standard drugs have been evaluated using the serial dilution technique against the bacterial species Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Proteus vulgaris and Pseudomonas aeruginosa and fungal species Aspergillus niger, Rhizopus stolonifer, Aspergillus flavus, Rhizoctonia bataicola and Candida albicans. The anti-inflammatory and SOD activities of the investigated compounds are also promising and allow the selection of a lead compound for further biological studies.

A bioinspired copper 2,2-bipyridyl complex immobilized MWCNT modified electrode prepared by a new strategy for elegant electrocatalytic reduction and sensing of hydrogen peroxide

International Nuclear Information System (INIS)

Mayuri, Pinapeddavari; Saravanan, Natarajan; Senthil Kumar, Annamalai

2017-01-01

Owing to facile electron-transfer reaction, metal complex based molecular architecture has attracted much interest in electrochemistry, especially for bioinspired electrocatalytic and electrochemical sensor applications. Indeed, preparation of stable surface-confined molecular system is a challenging task. In general, derivatization methodology, in which, a specific functional groups such as thiol, carboxylic acid, pyrene and amino bearing inorganic complexes synthesized discreetly by chemical approach have been attached suitably on electrode surface via any one of the following techniques; self-assembly, covalent immobilization, electrostatic interaction, ionic exchange and encapsulation. Herein, we report a copper-bipyridyl complex immobilized multiwalled carbon nanotube (MWCNT)-Nafion (Nf) modified glassy carbon electrode (GCE/Nf-MWCNT@bpy-Cu"2"+) prepared by a new strategy in which sequential modification of bipyridyl (bpy) ligand on MWCNT via π-π interaction followed by in-situ complexation with copper ion for efficient electrochemical reduction of H_2O_2. The copper species chemically modified electrode showed highly stable and well-defined surface-confined Cu"2"+"/"1"+ redox peak response, without any Cu"1"+"/"0 redox transition, at an equilibrium potential, E_1_/_2 = −135 mV vs Ag/AgCl in a pH 7 phosphate buffer solution. Detailed physico-chemical characterization by SEM, FT-IR, Raman and ESI-MS and electrochemical characterization reveals that [Cu(bpy)_2(H_2O)_2]"+ (molecular weight 413.4) like species was immobilized as a major species on the modified electrode. A bioinspired electro-catalytic reduction of H_2O_2 was studied using cyclic voltammetric and rotating disc electrode techniques. In further, electrochemical sensing of H_2O_2 by amperometric i-t and flow injection analysis methods with a detection limit values 4.5 and 0.49 μM respectively were demonstrated.

A copper-relates shallow acceptor in quenched germanium

International Nuclear Information System (INIS)

Kamiura, Yoichi; Hashimoto, Fumio; Sugiyama, Hazime; Yoneyama, Shin-ichiro

1982-01-01

The temperature variation of hole density was measured in the range 5-200 K after successive annealings at 320sup(o)C. It was found that a shallow acceptor at Esub(v) + 9 meV disappears on annealing, being replaced by a just equal additional density of substitutional copper. This provides experimental proof that the shallow acceptor is a defect complex containing at least one copper atom. (author)

The interaction of taurine-salicylaldehyde Schiff base copper(II) complex with DNA and the determination of DNA using the complex as a fluorescence probe

Science.gov (United States)

Zhang, Xiaoyan; Wang, Yong; Zhang, Qianru; Yang, Zhousheng

2010-09-01

The interaction of taurine-salicylaldehyde Schiff base copper(II) (Cu(TSSB) 22+) complex with DNA was explored by using UV-vis, fluorescence spectrophotometry, and voltammetry. In pH 7.4 Tris-HCl buffer solution, the binding constant of the Cu(TSSB) 22+ complex interaction with DNA was 3.49 × 10 4 L mol -1. Moreover, due to the fluorescence enhancing of Cu(TSSB) 22+ complex in the presence of DNA, a method for determination of DNA with Cu(TSSB) 22+ complex as a fluorescence probe was developed. The fluorescence spectra indicated that the maximum excitation and emission wavelength were 389 nm and 512 nm, respectively. Under optimal conditions, the calibration graphs are linear over the range of 0.03-9.03 μg mL -1 for calf thymus DNA (CT-DNA), 0.10-36 μg mL -1 for yeast DNA and 0.01-10.01 μg mL -1 for salmon DNA (SM-DNA), respectively. The corresponding detection limits are 7 ng mL -1 for CT-DNA, 3 ng mL -1 for yeast DNA and 3 ng mL -1 for SM-DNA. Using this method, DNA in synthetic samples was determined with satisfactory results.

Spatial Pattern of Copper Phosphate Precipitation Involves in Copper Accumulation and Resistance of Unsaturated Pseudomonas putida CZ1 Biofilm.

Science.gov (United States)

Chen, Guangcun; Lin, Huirong; Chen, Xincai

2016-12-28

Bacterial biofilms are spatially structured communities that contain bacterial cells with a wide range of physiological states. The spatial distribution and speciation of copper in unsaturated Pseudomonas putida CZ1 biofilms that accumulated 147.0 mg copper per g dry weight were determined by transmission electron microscopy coupled with energy dispersive X-ray analysis, and micro-X-ray fluorescence microscopy coupled with micro-X-ray absorption near edge structure (micro-XANES) analysis. It was found that copper was mainly precipitated in a 75 μm thick layer as copper phosphate in the middle of the biofilm, while there were two living cell layers in the air-biofilm and biofilm-medium interfaces, respectively, distinguished from the copper precipitation layer by two interfaces. The X-ray absorption fine structure analysis of biofilm revealed that species resembling Cu₃(PO₄)₂ predominated in biofilm, followed by Cu-Citrate- and Cu-Glutathione-like species. Further analysis by micro-XANES revealed that 94.4% of copper were Cu₃(PO₄)₂-like species in the layer next to the air interface, whereas the copper species of the layer next to the medium interface were composed by 75.4% Cu₃(PO₄)₂, 10.9% Cu-Citrate-like species, and 11.2% Cu-Glutathione-like species. Thereby, it was suggested that copper was initially acquired by cells in the biofilm-air interface as a citrate complex, and then transported out and bound by out membranes of cells, released from the copper-bound membranes, and finally precipitated with phosphate in the extracellular matrix of the biofilm. These results revealed a clear spatial pattern of copper precipitation in unsaturated biofilm, which was responsible for the high copper tolerance and accumulation of the biofilm.

Copper and copper-nickel alloys as zebra mussel antifoulants

Energy Technology Data Exchange (ETDEWEB)

Dormon, J.M.; Cottrell, C.M.; Allen, D.G.; Ackerman, J.D.; Spelt, J.K. [Univ. of Toronto, Ontario (Canada)

1996-04-01

Copper has been used in the marine environment for decades as cladding on ships and pipes to prevent biofouling by marine mussels (Mytilus edulis L.). This motivated the present investigation into the possibility of using copper to prevent biofouling in freshwater by both zebra mussels and quagga mussels (Dreissena polymorpha and D. bugensis collectively referred to as zebra mussels). Copper and copper alloy sheet proved to be highly effective in preventing biofouling by zebra mussels over a three-year period. Further studies were conducted with copper and copper-nickel mesh (lattice of expanded metal) and screen (woven wire with a smaller hole size), which reduced the amount of copper used. Copper screen was also found to be strongly biofouling-resistant with respect to zebra mussels, while copper mesh reduced zebra mussel biofouling in comparison to controls, but did not prevent it entirely. Preliminary investigations into the mechanism of copper antifouling, using galvanic couples, indicated that the release of copper ions from the surface of the exposed metal into the surrounding water is directly or indirectly responsible for the biofouling resistance of copper.

Synthesis, Characterization and Antimicrobial Studies of a New Mannich Base N-[Morpholino(phenylmethyl]acetamide and Its Cobalt(II, Nickel(II and Copper(II Metal Complexes

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L. Muruganandam

2012-01-01

Full Text Available A new Mannich base N-[morpholino(phenylmethyl]acetamide (MBA, was synthesized and characterized by spectral studies. Chelates of MBA with cobalt(II, nickel(II and copper(II ions were prepared and characterized by elemental analyses, IR and UV spectral studies. MBA was found to act as a bidentate ligand, bonding through the carbonyl oxygen of acetamide group and CNC nitrogen of morpholine moiety in all the complexes. Based on the magnetic moment values and UV-Visible spectral data, tetracoordinate geometry for nitrato complexes and hexacoordinate geometry for sulphato complexes were assigned. The antimicrobial studies show that the Co(II nitrato complex is more active than the other complexes.

Environmental significance of copper, lead, manganese, uranium and zinc speciation in the event of contaminated waters release from the Ranger Uranium Mining Complex

International Nuclear Information System (INIS)

Noller, B.N.; Currey, N.A.

1983-01-01

The likely impact of the accidental release of tailings dam water during the dry season at the Ranger Uranium Mining Complex was examined. A speciation scheme utilising sizing by filtration and ion-exchange with Chelex 100 has given an insight into the likely partitioning of zinc, copper, lead, manganese and uranium following the addition of tailings dam water to samples from waterbodies in the vicinity of the uranium mining/milling complex. The speciation findings are discussed in terms of likely toxic effects on fish

The ligational behavior of an isatinic quinolyl hydrazone towards copper(II- ions

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Mousa Marwa A

2011-04-01

Full Text Available Abstract Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring. Quinoline ring has therapeutic and biological activities whereas, the indole ring occurs in Jasmine flowers and Orange blossoms. As a ligand, the isatin moiety is potentially ambidentate and can coordinate the metal ions either through its lactam or lactim forms. In a previous study, the ligational behavior of a phenolic quinolyl hydrazone towards copper(II- ions has been studied. As continuation of our interest, the present study is planned to check the ligational behavior of an isatinic quinolyl hydrazone. Results New homo- and heteroleptic copper(II- complexes were obtained from the reaction of an isatinic quinolyl hydrazone (HL with several copper(II- salts viz. Clˉ, Brˉ, NO3ˉ, ClO4-, SO42- and AcO-. The obtained complexes have Oh, Td and D4h- symmetry and fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions. Depending on the type of the anion, the ligand coordinates the copper(II- ions either through its lactam (NO3ˉ and ClO4- or lactim (the others forms. Conclusion The effect of anion for the same metal ion is obvious from either the geometry of the isolated complexes (Oh, Td and D4h or the various modes of bonding. Also, the obtained complexes fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions in consistency with the donor ability of the anions. In case of copper(II- acetate, a unique homoleptic complex (5 was obtained in which the AcO- anion acts as a base enough to quantitatively deprotonate the hydrazone. The isatinic hydrazone uses its lactim form in most complexes.

Cupriferous peat: embryonic copper ore

Energy Technology Data Exchange (ETDEWEB)

Fraser, D C

1961-07-01

A Canadian peat was found to contain up to 10% (dry weight) Cu, and a mechanism for Cu accumulation in peat was discussed. Wet chemical techniques and x-ray diffraction were utilized to identify Cu compounds. Copper was organically bound in peat as a chelate complex and did not occur as an oxide, sulfide, or as elemental Cu. Because of the low S content of peat the Cu was assumed to be bound to nitrogen or oxygen-containing components. Copper, having a greater affinity for N, tended to form the more stable Cu-N chelate. The element was concentrated as circulating cupriferous ground waters filtered through the peat.

Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu4 core structural changes.

Science.gov (United States)

Kato, Merii; Sah, Ajay Kumar; Tanase, Tomoaki; Mikuriya, Masahiro

2006-08-21

Tetranuclear copper(II) complexes containing alpha-D-glucose-1-phosphate (alpha-D-Glc-1P), [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(bpy)4(H2O)2]X3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(phen)4(H2O)2](NO3)3 (2) were prepared by reacting the copper(II) salt with Na2[alpha-D-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}2+ fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu4-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-D-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-CA)2(bpy)4](NO3)2 [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)2] also gave the discrete tetracopper(II) cationic complex [Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)(CH2COOH))2(bpy)4](NO3)2 (5a) as well as the cluster polymer formulated as {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)2)(bpy)4](NO3)2}n (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu(II) ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta

The Menkes and Wilson disease genes counteract in copper toxicosis in Labrador retrievers: a new canine model for copper-metabolism disorders

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Hille Fieten

2016-01-01

Full Text Available The deleterious effects of a disrupted copper metabolism are illustrated by hereditary diseases caused by mutations in the genes coding for the copper transporters ATP7A and ATP7B. Menkes disease, involving ATP7A, is a fatal neurodegenerative disorder of copper deficiency. Mutations in ATP7B lead to Wilson disease, which is characterized by a predominantly hepatic copper accumulation. The low incidence and the phenotypic variability of human copper toxicosis hamper identification of causal genes or modifier genes involved in the disease pathogenesis. The Labrador retriever was recently characterized as a new canine model for copper toxicosis. Purebred dogs have reduced genetic variability, which facilitates identification of genes involved in complex heritable traits that might influence phenotype in both humans and dogs. We performed a genome-wide association study in 235 Labrador retrievers and identified two chromosome regions containing ATP7A and ATP7B that were associated with variation in hepatic copper levels. DNA sequence analysis identified missense mutations in each gene. The amino acid substitution ATP7B:p.Arg1453Gln was associated with copper accumulation, whereas the amino acid substitution ATP7A:p.Thr327Ile partly protected against copper accumulation. Confocal microscopy indicated that aberrant copper metabolism upon expression of the ATP7B variant occurred because of mis-localization of the protein in the endoplasmic reticulum. Dermal fibroblasts derived from ATP7A:p.Thr327Ile dogs showed copper accumulation and delayed excretion. We identified the Labrador retriever as the first natural, non-rodent model for ATP7B-associated copper toxicosis. Attenuation of copper accumulation by the ATP7A mutation sheds an interesting light on the interplay of copper transporters in body copper homeostasis and warrants a thorough investigation of ATP7A as a modifier gene in copper-metabolism disorders. The identification of two new functional

Copper and Copper Proteins in Parkinson’s Disease

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Sergio Montes

2014-01-01

Full Text Available Copper is a transition metal that has been linked to pathological and beneficial effects in neurodegenerative diseases. In Parkinson’s disease, free copper is related to increased oxidative stress, alpha-synuclein oligomerization, and Lewy body formation. Decreased copper along with increased iron has been found in substantia nigra and caudate nucleus of Parkinson’s disease patients. Copper influences iron content in the brain through ferroxidase ceruloplasmin activity; therefore decreased protein-bound copper in brain may enhance iron accumulation and the associated oxidative stress. The function of other copper-binding proteins such as Cu/Zn-SOD and metallothioneins is also beneficial to prevent neurodegeneration. Copper may regulate neurotransmission since it is released after neuronal stimulus and the metal is able to modulate the function of NMDA and GABA A receptors. Some of the proteins involved in copper transport are the transporters CTR1, ATP7A, and ATP7B and the chaperone ATOX1. There is limited information about the role of those biomolecules in the pathophysiology of Parkinson’s disease; for instance, it is known that CTR1 is decreased in substantia nigra pars compacta in Parkinson’s disease and that a mutation in ATP7B could be associated with Parkinson’s disease. Regarding copper-related therapies, copper supplementation can represent a plausible alternative, while copper chelation may even aggravate the pathology.

Effect of physicochemical form on copper availability to aquatic organisms

International Nuclear Information System (INIS)

Harrison, F.L.

1983-11-01

Copper concentration and speciation were determined in influent and effluent waters collected from eight power stations that used copper alloys in their cooling systems. Quantities of copper associated with particles, colloids, and organic and inorganic ligands differed with the site, season, and mode of operation of the station. Under normal operating conditions, the differences between influent and effluent waters were generally small, and most of the copper was in bound (complexed) species. However, copper was high in concentration and present in labile species during start-up of water circulation through some cooling systems and during changeover from an open- to closed-cycle operation. Copper sensitivity of selected ecologically and economically important aquatic organisms was also evaluted. Our primary emphasis was on acute effects and most of the testing was performed under controlled laboratory conditions. However, sublethal effects of copper on a population of bluegills living in a power station cooling lake containing water of low pH were also assessed. The toxic response to copper differed with the species and life stage of the animal and with the chemical form of copper in the water

Copper imbalances in ruminants and humans: unexpected common ground.

Science.gov (United States)

Suttle, Neville F

2012-09-01

Ruminants are more vulnerable to copper deficiency than humans because rumen sulfide generation lowers copper availability from forage, increasing the risk of conditions such as swayback in lambs. Molybdenum-rich pastures promote thiomolybdate (TM) synthesis and formation of unabsorbable Cu-TM complexes, turning risk to clinical reality (hypocuprosis). Selection pressures created ruminant species with tolerance of deficiency but vulnerability to copper toxicity in alien environments, such as specific pathogen-free units. By contrast, cases of copper imbalance in humans seemed confined to rare genetic aberrations of copper metabolism. Recent descriptions of human swayback and the exploratory use of TM for the treatment of Wilson's disease, tumor growth, inflammatory diseases, and Alzheimer's disease have created unexpected common ground. The incidence of pre-hemolytic copper poisoning in specific pathogen-free lambs was reduced by an infection with Mycobacterium avium that left them more responsive to treatment with TM but vulnerable to long-term copper depletion. Copper requirements in ruminants and humans may need an extra allowance for the "copper cost" of immunity to infection. Residual cuproenzyme inhibition in TM-treated lambs and anomalies in plasma copper composition that appeared to depend on liver copper status raise this question "can chelating capacity be harnessed without inducing copper-deficiency in ruminants or humans?" A model of equilibria between exogenous (TM) and endogenous chelators (e.g., albumin, metallothionein) is used to predict risk of exposure and hypocuprosis; although risk of natural exposure in humans is remote, vulnerability to TM-induced copper deficiency may be high. Biomarkers of TM impact are needed, and copper chaperones for inhibited cuproenzymes are prime candidates.

Using Pd-salen complex as an efficient catalyst for the copper- and solvent-free coupling of acyl chlorides with terminal alkynes under aerobic conditions

Institute of Scientific and Technical Information of China (English)

Mohammad

2010-01-01

The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-l,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base, giving excellent ynones under aerobic conditions.

Characterization of a meso-chiral isomer of a hexanuclear Cu(II) cage from racemization of the L-alanine Schiff base.

Science.gov (United States)

Rajesh, Chinnaiyan Mahalingam; Ray, Manabendra

2014-09-14

We are reporting structural characterization of two new hexanuclear cages (H3O)2[Cu3(μ3-OH)(μ3-NH3)(0.5)(L)3]2·8H2O (1) and (H3O)2[Cu3(μ3-OH)(μ3-H2O)(0.5)(L)3]2·8H2O (1a) where L(2-) is the dianionic form of the Schiff base of L-alanine and salicylaldehyde. The complex 1 has two C3 symmetric hydroxo bridged trinuclear halves joined by an ammonia or water molecule at the center through H-bonding. Each of the trinuclear halves is enantiopure but of opposite chirality to the other half, making the hexanuclear unit a meso isomer. Temperature dependent magnetic measurements showed the presence of ferromagnetic interactions among trinuclear Cu(II) units, a rare occurrence among trinuclear Cu(II) complexes. Characterization of the LiHL showed it to be enantiopure. Addition of a base, monitored using optical rotation, showed that racemization occurs as a result of base addition. The racemization depends on the base as well as the temperature. Base or Cu(II) induced racemization of amino acid derivatives has been indicated in a number of cases in the past but structural characterization of the products or formation of this type of chiral hexanuclear architecture was never reported. Structures of the complex and the ligand have a number of interesting H-bonding situations.

Copper carrier protein in copper toxic sheep liver

Energy Technology Data Exchange (ETDEWEB)

Harris, A L; Dean, P D.G.

1973-01-01

The livers of copper-toxic sheep have been analyzed by gel electrophoresis followed by staining the gels for copper with diethyldithiocarbamate and for protein with amido schwartz. These gels were compared with similar gels obtained from the livers of normal and copper-deficient animals. The copper-toxic livers contained an extra protein band which possessed relatively weakly bound copper. Possible origins of this protein are discussed. 8 references, 1 figure, 2 tables.

Synthesis of Well-Defined Copper "N"-Heterocyclic Carbene Complexes and Their Use as Catalysts for a "Click Reaction": A Multistep Experiment that Emphasizes the Role of Catalysis in Green Chemistry

Science.gov (United States)

Ison, Elon A.; Ison, Ana

2012-01-01

A multistep experiment for an advanced synthesis lab course that incorporates topics in organic-inorganic synthesis and catalysis and highlights green chemistry principles was developed. Students synthesized two "N"-heterocyclic carbene ligands, used them to prepare two well-defined copper(I) complexes and subsequently utilized the complexes as…

Bis[2-(cyclopentyliminomethyl-5-methoxyphenolato]copper(II

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Xiao-Hui Ji

2010-08-01

Full Text Available The title compound, [Cu(C13H16NO22], is a mononuclear copper(II complex derived from the Schiff base ligand 2-(cyclopentyliminomethyl-5-methoxyphenol and copper acetate. The CuII atom is four-coordinated by the phenolate O atoms and imine N atoms from two Schiff base ligands, in a highly distorted square-planar geometry. The O- and N-donor atoms are mutually trans and the dihedral angle between the two benzene rings is 55.8 (3°.

Computational Molecular Nanoscience Study of the Properties of Copper Complexes for Dye-Sensitized Solar Cells

Science.gov (United States)

Baldenebro-López, Jesús; Castorena-González, José; Flores-Holguín, Norma; Almaral-Sánchez, Jorge; Glossman-Mitnik, Daniel

2012-01-01

In this work, we studied a copper complex-based dye, which is proposed for potential photovoltaic applications and is named Cu (I) biquinoline dye. Results of electron affinities and ionization potentials have been used for the correlation between different levels of calculation used in this study, which are based on The Density Functional Theory (DFT) and time-dependent (TD) DFT. Further, the maximum absorption wavelengths of our theoretical calculations were compared with the experimental data. It was found that the M06/LANL2DZ + DZVP level of calculation provides the best approximation. This level of calculation was used to find the optimized molecular structure and to predict the main molecular vibrations, the molecular orbitals energies, dipole moment, isotropic polarizability and the chemical reactivity parameters that arise from Conceptual DFT. PMID:23443107

potentiometric studies of the complexes formed by copper (ii) and zinc

African Journals Online (AJOL)

MBI

, P. M. B. 3011, Kano, Nigeria e-mail: jnaaliya@yahoo.com. ABSTRACT. The overall stability constants of copper (II) and zinc (II) ions with some polar uncharged amino acids including proline, threonine and asparagines were determined by ...

Improvement of the adhesion strength between copper plated layer and resin substrate using a chemically adsorbed monolayer

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Tsuchiya K.

2013-08-01

Full Text Available With reducing the size and weight of electric devices, high-tensile, light and fine copper wire is demanded. So the production technique of a copper wire plated on a super fiber resin (Vectran film was researched for improving the adhesion strength between the copper and the resin. In this study, we used the Cu2+ or Pd2+ complex prepared with a chemically adsorbed monolayer (CAM to improve the adhesion strength between the copper plated layer and the Vectran film. As the result of scotch tape test, it was observed that the adhesion strength between the copper plated layer and Vectran film was improved by the Cu2+ or Pd2+ complex CAM.

Diethylenetriamine/diamines/copper (II complexes [Cu(dien(NN]Br2: Synthesis, solvatochromism, thermal, electrochemistry, single crystal, Hirshfeld surface analysis and antibacterial activity

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Fatima Abu Saleemh

2017-09-01

Full Text Available Two dicationic water soluble mixed triamine/diamine copper (II complexes, of general formula [Cu(dienNN]Br2 (1–2 [dien = diethelenetriamine and NN is en = ethylenediamine or Me4en = N,N′,N,N′-tetramethylethylenediamine] were prepared under ultrasonic mode with a relatively high yield. These complexes were characterized by elemental microanalysis, UV visible IR spectroscopy, and thermal and electrochemical techniques. In addition, complex 2 structure was solved by X-ray single crystal and Hirshfeld surface analysis. The complex exhibits a distorted square pyramidal coordination environment around Cu(II centre. The solvatochromism of the desired complexes was investigated in water and other suitable organic solvents. The results show that the Guttmann’s DN parameter values of the solvents have mainly contributed to the shift of the d–d absorption band towards the linear increase in the wavelength of the absorption maxima of the complexes. The complex 1 showed higher antibacterial activity against the studied microorganisms compared to complex 2. Both complexes revealed promising antibacterial activities.

Synthesis, characterization and antitumour activity of copper(II) 6-(4-chlorobenzylamino)purine complexes. X-ray structure of 6-(4-chloro-benzylamino)purinium perchlorate

Czech Academy of Sciences Publication Activity Database

Maloň, M.; Trávníček, Z.; Maryško, Miroslav; Marek, J.; Doležal, Karel; Rolčík, Jakub; Strnad, Miroslav

2002-01-01

Roč. 27, č. 6 (2002), s. 580-586 ISSN 0340-4285 R&D Projects: GA ČR GA522/01/0275; GA MŠk OC 844.10; GA ČR GA301/02/0475 Institutional research plan: CEZ:AV0Z5038910 Keywords : Copper complexes * human malignant melanoma * purinium perchlorate Subject RIV: CE - Biochemistry Impact factor: 0.949, year: 2002

Sodium diethyldithiocarbamate as accelerator of the rate of copper cementation

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Abeer A. El-Saharty

2015-12-01

Full Text Available The effects of Cu2+ ion concentration and temperature on the cementation rate of copper from copper sulphate on zinc and the effect of additives of the organic compound “sodium diethyldithiocarbamate” (NaDDC were studied. It was noticed that the cementation increases significantly by increasing the concentrations of NaDDC. The rate of cementation increased by 58.58−100.31%. Our data showed that sodium diethyldithiocarbamate reacts with the Cu2+ solution giving a complex of copper diethyldithiocarbamate, which enhances the rate of cementation.

The copper binding properties of metformin - QCM-D, XPS and nanobead agglomeration

DEFF Research Database (Denmark)

Quan, Xueling; Uddin, Rokon; Heiskanen, Arto

2015-01-01

Study of the copper binding properties of metformin is important for revealing its mechanism of action as a first-line type-2 diabetes drug. A quantitative investigation of interactions between metformin and l-cysteine-copper complexes was performed. The results suggest that metformin could...

[Influence of the earthworm Lumbricus terrestris on soil solution complexation capacity].

Science.gov (United States)

el Gharmali, A; Rada, A; el Meray, M; Nejmeddine, A

2001-04-01

Four soil samples highly contaminated with metals of urban and mine origin (SE1, SE2, SM1, SM2) and having different physico-chemical proprieties were selected to study copper complexation capacity (LT) of soil solution. The effect of Lumbricus terrestris on copper complexation capacity of soil solution was investigated on SE1 and SE2. The complexation capacity was estimated by amperometric titration of soil solution by copper. Free hydrated cation and labile complexes of copper were determined by DPASV. The results show that the copper complexation capacity variation depends on the physico-chemical characteristics of soils, particularly pH. Thus, the values of copper complexation capacity are 0; 0.6 x 10(-7); 1.8 x 10(-7) and 5.5 x 10(-7) mol l-1 respectively for SM2; SM1; SE1 and SE2 which are pH 5; 5.4; 6.5 and 7.4. Based on these results, the bioavailability levels of heavy metals show the following pool ranking: SM2 > SM1 > SE1 > SE2. The copper complexation capacity of soil solution increases with the soil disturbance by Lumbricus terrestris. This is more obvious when the time of disturbance by lumbrics is longer. Indeed, average values determined for 1 month and 3 months are 3.8 x 10(-7) and 7.8 x 10(-7) mol l-1 for SE1; 7.7 x 10(-7) and 15.2 x 10(-7) mol l-1 for SE2 respectively. It seems that the action of earthworm on soil can contribute to the decrease of bioavailability of heavy metals, particularly copper.

Copper and copper-nickel-alloys - An overview

Energy Technology Data Exchange (ETDEWEB)

Klassert, Anton; Tikana, Ladji [Deutsches Kupferinstitut e.V. Am Bonneshof 5, 40474 Duesseldorf (Germany)

2004-07-01

With the increasing level of industrialization the demand for and the number of copper alloys rose in an uninterrupted way. Today, the copper alloys take an important position amongst metallic materials due to the large variety of their technological properties and applications. Nowadays there exist over 3.000 standardized alloys. Copper takes the third place of all metals with a worldwide consumption of over 15 millions tons per year, following only to steel and aluminum. In a modern industrial society we meet copper in all ranges of the life (electro-technology, building and construction industry, mechanical engineering, automotive, chemistry, offshore, marine engineering, medical applications and others.). Copper is the first metal customized by humanity. Its name is attributed to the island Cyprus, which supplied in the antiquity copper to Greece, Rome and the other Mediterranean countries. The Romans called it 'ore from Cyprus' (aes cyprium), later cuprum. Copper deposited occasionally also dapper and could be processed in the recent stone age simply by hammering. Already in early historical time copper alloys with 20 to 50 percent tin was used for the production of mirrors because of their high reflecting power. Although the elementary nickel is an element discovered only recently from a historical perspective, its application in alloys - without any knowledge of the alloy composition - occurred at least throughout the last 2.000 years. The oldest copper-nickel coin originates from the time around 235 B.C.. Only around 1800 AD nickel was isolated as a metallic element. In particular in the sea and offshore technology copper nickel alloys found a broad field of applications in piping systems and for valves and armatures. The excellent combination of characteristics like corrosion resistance, erosion stability and bio-fouling resistance with excellent mechanical strength are at the basis of this success. An experience of many decades supports the use

Facilitated transport of diuron and glyphosate in high copper vineyard soils.

Science.gov (United States)

Dousset, Sylvie; Jacobson, Astrid R; Dessogne, Jean-Baptiste; Guichard, Nathalie; Baveye, Philippe C; Andreux, Francis

2007-12-01

The fate of organic herbicides applied to agricultural fields may be affected by other soil amendments, such as copper applied as a fungicide. The effect of copper on the leaching of diuron and glyphosate through a granitic and a calcareous soil was studied in the laboratory using sieved-soil columns. Each soil was enriched with copper sulfate to obtain soil copper concentrations of 125, 250, 500, and 1000 mg kg(-1). Glyphosate leaching was influenced by soil pH and copper concentration, whereas diuron leaching was not. In the calcareous soil, glyphosate leaching decreased as copper levels increased from 17 mg kg(-1) (background) to 500 mg kg(-1). In the granitic soil, glyphosate leaching increased as copper levels increased from 34 mg kg(-1) (background) to 500 mg kg(-1). The shapes of the copper elution curves in presence of glyphosate were similar to shapes of the glyphosate curves, suggesting the formation of Cu-glyphosate complexes that leach through the soil. Soil copper concentration does not influence diuron leaching. In contrast, increasing copper concentrations reduces glyphosate leaching through calcareous soils, and conversely, increases glyphosate leaching through granitic soils. Our findings suggest that the risk of groundwater contamination by glyphosate increases in granitic soils with elevated copper concentrations.

Construction of a new functional platform by grafting poly(4-vinylpyridine) in multi-walled carbon nanotubes for complexing copper ions aiming the amperometric detection of L-cysteine

International Nuclear Information System (INIS)

Carvalho Castro e Silva, Cecília de; Breitkreitz, Márcia Cristina; Santhiago, Murilo; Crispilho Corrêa, Cátia; Tatsuo Kubota, Lauro

2012-01-01

Highlights: ► Construction of new nanostructured platform based on MWCNTs–PVP to complex copper(II) ions. ► Development of an amperometric sensor for highly selective determination of Cys in food supplement samples. ► Combination of nanocomposite and the copper(II) ions causes a dramatic enhancement in the sensitivity of Cys quantification at low overpotential. - Abstract: This work describes the preparation of an amperometric sensor for electrocatalytical detection of L-cysteine (Cys). The developed sensor is based on a functional platform to complex copper ions on multi-walled carbon nanotubes (MWCNTs) modified with poly-4-vinylpyridine (PVP) through an in situ polymerization. The obtained values for the kinetic constants of heterogeneous electron transfer rate (k s ) and for chemical reaction (k obs ) between Cu 2+ and cysteine were 5.78 s −1 and 6.96 L mol −1 s −1 , respectively. The analytical curve showed a linear response range for detecting L-cysteine in concentrations from 5 to 60 μmol L −1 . The detection and quantification limits obtained were 1.50 and 5.00 μmol L −1 , respectively with a response time of 0.10 s at an applied potential of 150 mV vs SCE.

Condensed, solution and gas phase behaviour of mono- and dinuclear 2,6-diacetylpyridine (dap) hydrazone copper complexes probed by X-ray, mass spectrometry and theoretical calculations.

Science.gov (United States)

Neto, Brenno A D; Viana, Barbara F L; Rodrigues, Thyago S; Lalli, Priscila M; Eberlin, Marcos N; da Silva, Wender A; de Oliveira, Heibbe C B; Gatto, Claudia C

2013-08-28

We describe the synthesis of novel mononuclear and dinuclear copper complexes and an investigation of their behaviour in solution using mass spectrometry (ESI-MS and ESI-MS/MS) and in the solid state using X-ray crystallography. The complexes were synthesized from two widely used diacetylpryridine (dap) ligands, i.e. 2,6-diacetylpyridinebis(benzoic acid hydrazone) and 2,6-diacetylpyridinebis(2-aminobenzoic acid hydrazone). Theoretical calculations (DFT) were used to predict the complex geometries of these new structures, their equilibrium in solution and energies associated with the transformations.

1D polymeric copper(I) and dinuclear silver(I) complexes of a bidentate Schiff base ligand: synthesis, spectroscopic characterization and thermal studies

Czech Academy of Sciences Publication Activity Database

Khalaji, A.D.; Peyghoun, S.J.; Akbari, A.; Feizi, N.; Dušek, Michal; Eigner, Václav

2016-01-01

Roč. 119, Sep (2016), s. 429-433 ISSN 0277-5387 R&D Projects: GA ČR GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : one-dimensional polymer * copper(I) * di-nuclear complex * silver(I) * crystal structure analysis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.926, year: 2016

A novel dinuclear schiff base copper complex as an efficient and ...

Indian Academy of Sciences (India)

effective catalyst for oxidation of alcohol: Synthesis, crystal structure and theoretical studies .... 0.01 mol dihydrate copper (II) chloride (1.704 g) in 10 mL methanol. .... propyl)imino)methyl)naphthalen-2-ol ligand is coordi- nated to the Cu(II) ion ...

Synthesis, characterization and thermal studies of nickel (II), copper (II), zinc (II) and cadmium (II) complexes with some mixed ligands

International Nuclear Information System (INIS)

Mitra, Samiran; Kundu, Parimal; Singh, Rajkumar Bhubon

1998-01-01

Dichloro-(DCA) and trichloroacetate(TCA) -cyclic ligand morpholine (Morph)/thiomorpholine (Tmorph)/methylmorpholine (Mmorph)/dimethyl-piperazine (DMP) complexes of nickel (II), copper (II), zinc (II) and cadmium (II) with the compositions [Ni(tmorph) 2 (DCA) 2 ], [Ni(tmorph) 2 (TCA) 2 ].2H 2 O, [Cu(DMP) 2 (TCA) 2 ],[ML 2 X 2 ].nH 2 O where M=Zn II or Cd II , L=Morph, DMP or tmorph and X=DCA or TCA and n=O except in case of [Cd (Morph) 2 (TCA) 2 ] where n=1 have been synthesised. Some intermediate complexes have been isolated by temperature arrest technique (pyrolysis) and characterised. Configurational and conformational changes have been studied by elemental analyses, IR and electronic spectra, magnetic moment data (in the case of Ni(II) and Cu(II) complexes) and thermal analysis. E a * , ΔH, and ΔS for the decomposition reaction of these complexes are evaluated and the stability of the complexes with respect to activation energy has also been compared. The linear correlation has been found between E a * and ΔS for the decomposition of the complexes. (author)

Precursors for formation of copper selenide, indium selenide, copper indium diselenide, and/or copper indium gallium diselenide films

Science.gov (United States)

Curtis, Calvin J; Miedaner, Alexander; Van Hest, Maikel; Ginley, David S

2014-11-04

Liquid-based precursors for formation of Copper Selenide, Indium Selenide, Copper Indium Diselenide, and/or copper Indium Galium Diselenide include copper-organoselenides, particulate copper selenide suspensions, copper selenide ethylene diamine in liquid solvent, nanoparticulate indium selenide suspensions, and indium selenide ethylene diamine coordination compounds in solvent. These liquid-based precursors can be deposited in liquid form onto substrates and treated by rapid thermal processing to form crystalline copper selenide and indium selenide films.

Accumulation and hyperaccumulation of copper in plants

Science.gov (United States)

Adam, V.; Trnkova, L.; Huska, D.; Babula, P.; Kizek, R.

2009-04-01

Copper is natural component of our environment. Flow of copper(II) ions in the environment depends on solubility of compounds containing this metal. Mobile ion coming from soil and rocks due to volcanic activity, rains and others are then distributed to water. Bio-availability of copper is substantially lower than its concentration in the aquatic environment. Copper present in the water reacts with other compounds and creates a complex, not available for organisms. The availability of copper varies depending on the environment, but moving around within the range from 5 to 25 % of total copper. Thus copper is stored in the sediments and the rest is transported to the seas and oceans. It is common knowledge that copper is essential element for most living organisms. For this reason this element is actively accumulated in the tissues. The total quantity of copper in soil ranges from 2 to 250 mg / kg, the average concentration is 30 mg / kg. Certain activities related to agriculture (the use of fungicides), possibly with the metallurgical industry and mining, tend to increase the total quantity of copper in the soil. This amount of copper in the soil is a problem particularly for agricultural production of food. The lack of copper causes a decrease in revenue and reduction in quality of production. In Europe, shows the low level of copper in total 18 million hectares of farmland. To remedy this adverse situation is the increasing use of copper fertilizers in agricultural soils. It is known that copper compounds are used in plant protection against various illnesses and pests. Mining of minerals is for the development of human society a key economic activity. An important site where the copper is mined in the Slovakia is nearby Smolníka. Due to long time mining in his area (more than 700 years) there are places with extremely high concentrations of various metals including copper. Besides copper, there are also detected iron, zinc and arsenic. Various plant species

Advanced Copper Composites Against Copper-Tolerant Xanthomonas perforans and Tomato Bacterial Spot.

Science.gov (United States)

Strayer-Scherer, A; Liao, Y Y; Young, M; Ritchie, L; Vallad, G E; Santra, S; Freeman, J H; Clark, D; Jones, J B; Paret, M L

2018-02-01

Bacterial spot, caused by Xanthomonas spp., is a widespread and damaging bacterial disease of tomato (Solanum lycopersicum). For disease management, growers rely on copper bactericides, which are often ineffective due to the presence of copper-tolerant Xanthomonas strains. This study evaluated the antibacterial activity of the new copper composites core-shell copper (CS-Cu), multivalent copper (MV-Cu), and fixed quaternary ammonium copper (FQ-Cu) as potential alternatives to commercially available micron-sized copper bactericides for controlling copper-tolerant Xanthomonas perforans. In vitro, metallic copper from CS-Cu and FQ-Cu at 100 μg/ml killed the copper-tolerant X. perforans strain within 1 h of exposure. In contrast, none of the micron-sized copper rates (100 to 1,000 μg/ml) from Kocide 3000 significantly reduced copper-tolerant X. perforans populations after 48 h of exposure compared with the water control (P copper-based treatments killed the copper-sensitive X. perforans strain within 1 h. Greenhouse studies demonstrated that all copper composites significantly reduced bacterial spot disease severity when compared with copper-mancozeb and water controls (P copper composites significantly reduced disease severity when compared with water controls, using 80% less metallic copper in comparison with copper-mancozeb in field studies (P copper composites have the potential to manage copper-tolerant X. perforans and tomato bacterial spot.

Importance of copper for nitrification in biological rapid sand filters for drinking water production

DEFF Research Database (Denmark)

Wagner, Florian Benedikt

nitrification during drinking water production provided the motivation to investigate if a lack of copper could be responsible for the problems in nitrifying biofilters. Copper is believed to be an essential cofactor in the enzyme ammonia monooxygenase (AMO), which catalyzes the first essential step...... be supplied in a controlled fashion, and that little maintenance and no chemicals are required. Copper dosing through the novel electrolysis method, as well as through passive dosing from solid copper and active dosing of copper solution, was studied at nine more DWTPs, which all shared a long history...... and chemical speciation modelling were carried out for Nærum DWTP. Results showed that substantial amounts of copper were bound to iron oxide-hydroxides in the filter and that bicarbonate heavily complexed copper in the water phase. Only total copper...

Copper as a target for prostate cancer therapeutics: copper-ionophore pharmacology and altering systemic copper distribution

Science.gov (United States)

Denoyer, Delphine; Pearson, Helen B.; Clatworthy, Sharnel A.S.; Smith, Zoe M.; Francis, Paul S.; Llanos, Roxana M.; Volitakis, Irene; Phillips, Wayne A.; Meggyesy, Peter M.; Masaldan, Shashank; Cater, Michael A.

2016-01-01

Copper-ionophores that elevate intracellular bioavailable copper display significant therapeutic utility against prostate cancer cells in vitro and in TRAMP (Transgenic Adenocarcinoma of Mouse Prostate) mice. However, the pharmacological basis for their anticancer activity remains unclear, despite impending clinical trails. Herein we show that intracellular copper levels in prostate cancer, evaluated in vitro and across disease progression in TRAMP mice, were not correlative with copper-ionophore activity and mirrored the normal levels observed in patient prostatectomy tissues (Gleason Score 7 & 9). TRAMP adenocarcinoma cells harbored markedly elevated oxidative stress and diminished glutathione (GSH)-mediated antioxidant capacity, which together conferred selective sensitivity to prooxidant ionophoric copper. Copper-ionophore treatments [CuII(gtsm), disulfiram & clioquinol] generated toxic levels of reactive oxygen species (ROS) in TRAMP adenocarcinoma cells, but not in normal mouse prostate epithelial cells (PrECs). Our results provide a basis for the pharmacological activity of copper-ionophores and suggest they are amendable for treatment of patients with prostate cancer. Additionally, recent in vitro and mouse xenograft studies have suggested an increased copper requirement by prostate cancer cells. We demonstrated that prostate adenocarcinoma development in TRAMP mice requires a functional supply of copper and is significantly impeded by altered systemic copper distribution. The presence of a mutant copper-transporting Atp7b protein (tx mutation: A4066G/Met1356Val) in TRAMP mice changed copper-integration into serum and caused a remarkable reduction in prostate cancer burden (64% reduction) and disease severity (grade), abrogating adenocarcinoma development. Implications for current clinical trials are discussed. PMID:27175597

Copper toxicity and organic matter: Resiliency of watersheds in the Duluth Complex, Minnesota, USA

Science.gov (United States)

Piatak, Nadine; Seal, Robert; Jones, Perry M.; Woodruff, Laurel G.

2015-01-01

We estimated copper (Cu) toxicity in surface water with high dissolved organic matter (DOM) for unmined mineralized watersheds of the Duluth Complex using the Biotic Ligand Model (BLM), which evaluates the effect of DOM, cation competition for biologic binding sites, and metal speciation. A sediment-based BLM was used to estimate stream-sediment toxicity; this approach factors in the cumulative effects of multiple metals, incorporation of metals into less bioavailable sulfides, and complexation of metals with organic carbon. For surface water, the formation of Cu-DOM complexes significantly reduces the amount of Cu available to aquatic organisms. The protective effects of cations, such as calcium (Ca) and magnesium (Mg), competing with Cu to complex with the biotic ligand is likely not as important as DOM in water with high DOM and low hardness. Standard hardness-based water quality criteria (WQC) are probably inadequate for describing Cu toxicity in such waters and a BLM approach may yield more accurate results. Nevertheless, assumptions about relative proportions of humic acid (HA) and fulvic acid (FA) in DOM significantly influence BLM results; the higher the HA fraction, the higher calculated resiliency of the water to Cu toxicity. Another important factor is seasonal variation in water chemistry, with greater resiliency to Cu toxicity during low flow compared to high flow.Based on generally low total organic carbon and sulfur content, and equivalent metal ratios from total and weak partial extractions, much of the total metal concentration in clastic streambedsediments may be in bioavailable forms, sorbed on clays or hydroxide phases. However, organicrich fine-grained sediment in the numerous wetlands may sequester significant amount of metals, limiting their bioavailability. A high proportion of organic matter in waters and some sediments will play a key role in the resiliency of these watersheds to potential additional metal loads associated with future

Development of pyridine-containing macrocyclic copper(II) complexes: potential role in the redox modulation of oxaliplatin toxicity in human breast cells.

Science.gov (United States)

Fernandes, Ana S; Costa, Judite; Gaspar, Jorge; Rueff, José; Cabral, M Fátima; Cipriano, Madalena; Castro, Matilde; Oliveira, Nuno G

2012-09-01

The unique redox and catalytic chemistry of Cu has justified the development of novel Cu complexes for different therapeutic uses including cancer therapy. In this work, four pyridine-containing aza-macrocyclic copper(II) complexes were prepared (CuL1-CuL4) varying in ring size and/or substituents and their superoxide scavenging activity evaluated. CuL3, the most active superoxide scavenger, was further studied as a modulator of the cytotoxicity of oxaliplatin in epithelial breast MCF10A cells and in MCF7 breast cancer cells. Our results show that CuL3 enhances the therapeutic window of oxaliplatin, by both protecting non-tumour cells and increasing its cytotoxic effect in breast carcinoma cells. CuL3 is thus a promising complex to be further studied and to be used as a lead compound for the optimization of novel chemotherapy sensitizers.

A natural analogue for copper waste canisters: The copper-uranium mineralised concretions in the Permian mudrocks of south Devon, United Kingdom

International Nuclear Information System (INIS)

Milodowski, A.E.; Styles, M.T.; Hards, V.L.

2000-08-01

This report presents the results of a small-scale pilot study of the mineralogy and alteration characteristics of unusual sheet-like native copper occurring together with uraniferous and vanadiferous concretions in mudstones and siltstones of the Permian Littleham Mudstone Formation, at Littleham Cove, south Devon, England. The host mudstones and siltstones are smectitic and have been compacted through deep Mesozoic burial. The occurrence of native copper within these rocks represents a natural analogue for the long-term behaviour of copper canisters, sealed in a compacted clay (bentonite) backfill, that will be used for the deep geological disposal of high-level radioactive waste by the SKB. The study was undertaken by the British Geological Survey (BGS) on behalf of SKB between November 1999 and June 2000. The study was based primarily on archived reference material collected by the BGS during regional geological and mineralogical surveys of the area in the 1970's and 1980's. However, a brief visit was made to Littleham Cove in January 2000 to try to examine the native copper in situ and to collect additional material. Unfortunately, recent landslips and mudflows obscured much of the outcrop, and only one new sample of native copper could be collected. The native copper occurs as thin plates, up to 160 mm in diameter, which occur parallel to bedding in the Permian Littleham Mudstone Formation at Littleham Cove (near Budleigh Salterton) in south Devon. Each plate is made up of composite stacks of individual thin copper sheets each 1-2 mm thick. The copper is very pure (>99.4% Cu) but is accompanied by minor amounts of native silver (also pure - >99%) which occurs as small inclusions within the native copper. Detailed mineralogical and petrological studies of the native copper sheets, using optical petrography, backscattered scanning electron microscopy, X-ray diffraction analysis and electron probe microanalytical techniques, reveal a complex history of

A natural analogue for copper waste canisters: The copper-uranium mineralised concretions in the Permian mudrocks of south Devon, United Kingdom

Energy Technology Data Exchange (ETDEWEB)

Milodowski, A.E.; Styles, M.T.; Hards, V.L. [Natural Environment Research Council (United Kingdom). British Geological Survey

2000-08-01

This report presents the results of a small-scale pilot study of the mineralogy and alteration characteristics of unusual sheet-like native copper occurring together with uraniferous and vanadiferous concretions in mudstones and siltstones of the Permian Littleham Mudstone Formation, at Littleham Cove, south Devon, England. The host mudstones and siltstones are smectitic and have been compacted through deep Mesozoic burial. The occurrence of native copper within these rocks represents a natural analogue for the long-term behaviour of copper canisters, sealed in a compacted clay (bentonite) backfill, that will be used for the deep geological disposal of high-level radioactive waste by the SKB. The study was undertaken by the British Geological Survey (BGS) on behalf of SKB between November 1999 and June 2000. The study was based primarily on archived reference material collected by the BGS during regional geological and mineralogical surveys of the area in the 1970's and 1980's. However, a brief visit was made to Littleham Cove in January 2000 to try to examine the native copper in situ and to collect additional material. Unfortunately, recent landslips and mudflows obscured much of the outcrop, and only one new sample of native copper could be collected. The native copper occurs as thin plates, up to 160 mm in diameter, which occur parallel to bedding in the Permian Littleham Mudstone Formation at Littleham Cove (near Budleigh Salterton) in south Devon. Each plate is made up of composite stacks of individual thin copper sheets each 1-2 mm thick. The copper is very pure (>99.4% Cu) but is accompanied by minor amounts of native silver (also pure - >99%) which occurs as small inclusions within the native copper. Detailed mineralogical and petrological studies of the native copper sheets, using optical petrography, backscattered scanning electron microscopy, X-ray diffraction analysis and electron probe microanalytical techniques, reveal a complex history of

Role of the Bridging Arylethynyl Ligand in Bi- and Trinuclear Ruthenium and Iron Complexes

Czech Academy of Sciences Publication Activity Database

Klein, A.; Lavastre, O.; Fiedler, Jan

2006-01-01

Roč. 25, č. 3 (2006), s. 635-643 ISSN 0276-7333 R&D Projects: GA MŠk 1P05OC068; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503 Keywords : X-ray crystal * nonlinear optical properties * sigma-acetylide complexes Subject RIV: CG - Electrochemistry Impact factor: 3.632, year: 2006

Native copper as a natural analogue for copper canisters

International Nuclear Information System (INIS)

Marcos, N.

1989-12-01

This paper discusses the occurrence of native copper as found in geological formations as a stability analogue of copper canisters that are planned to be used for the disposal of spent nuclear fuel in the Finnish bedrock. A summary of several publications on native copper occurrences is presented. The present geochemical and geohydrological conditions in which copper is met with in its metallic state show that metallic copper is stable in a wide range of temperatures. At low temperatures native copper is found to be stable where groundwater has moderate pH (about 7), low Eh (< +100 mV), and low total dissolved solids, especially chloride. Microscopical and microanalytical studies were carried out on a dozen of rock samples containing native copper. The results reveal that the metal shows no significant alteration. Only the surface of copper grains is locally coated. In the oldest samples there exist small corrosion cracks; the age of the oldest samples is over 1,000 million years. A review of several Finnish groundwater studies suggests that there are places in Finland where the geohydrological conditions are favourable for native copper stability. (orig.)

Synthesis, Characterization and DNA Cleavage of Copper(II ...

African Journals Online (AJOL)

Keywords: DNA shearing, Copper(II) complex, Dithiothreitol, Attenuated total reflectance-Fourier transform .... confirm the fragmentation of DNA by the newly .... sperm. Biochem Biophys Acta 1986; 884: 124-134. 7. Cornell NW, Crivaro KE.

Formation of copper-indium-selenide and/or copper-indium-gallium-selenide films from indium selenide and copper selenide precursors

Science.gov (United States)

Curtis, Calvin J [Lakewood, CO; Miedaner, Alexander [Boulder, CO; Van Hest, Maikel [Lakewood, CO; Ginley, David S [Evergreen, CO; Nekuda, Jennifer A [Lakewood, CO

2011-11-15

Liquid-based indium selenide and copper selenide precursors, including copper-organoselenides, particulate copper selenide suspensions, copper selenide ethylene diamine in liquid solvent, nanoparticulate indium selenide suspensions, and indium selenide ethylene diamine coordination compounds in solvent, are used to form crystalline copper-indium-selenide, and/or copper indium gallium selenide films (66) on substrates (52).

Cyanide and Copper Recovery from Barren Solution of the Merrill Crowe Process

Science.gov (United States)

Parga, José R.; Valenzuela, Jesús L.; Díaz, J. A.

This paper is a brief overview of the role of inducing the nucleated precipitation of copper and cyanide in a flashtube serpentine reactor, using sodium sulfide as the precipitate and sulfuric acid as pH control. The results showed that pH had a great effect on copper cyanide removal efficiency and the optimum pH was about 3 to 3.5. At this pH value copper cyanide removal efficiency could be achieved above 97 and 99 %, when influent copper concentration ions were 650 and 900 ppm respectively. In this process the cyanide associated with the copper, zinc, iron cyanide complexes are released as HCN gas under strong acidic conditions, allowing it to be recycled back to the cyanidation process as free cyanide.

Uptake and internalisation of copper by three marine microalgae: comparison of copper-sensitive and copper-tolerant species.

Science.gov (United States)

Levy, Jacqueline L; Angel, Brad M; Stauber, Jennifer L; Poon, Wing L; Simpson, Stuart L; Cheng, Shuk Han; Jolley, Dianne F

2008-08-29

Although it has been well established that different species of marine algae have different sensitivities to metals, our understanding of the physiological and biochemical basis for these differences is limited. This study investigated copper adsorption and internalisation in three algal species with differing sensitivities to copper. The diatom Phaeodactylum tricornutum was particularly sensitive to copper, with a 72-h IC50 (concentration of copper to inhibit growth rate by 50%) of 8.0 microg Cu L(-1), compared to the green algae Tetraselmis sp. (72-h IC50 47 microg Cu L(-1)) and Dunaliella tertiolecta (72-h IC50 530 microg Cu L(-1)). At these IC50 concentrations, Tetraselmis sp. had much higher intracellular copper (1.97+/-0.01 x 10(-13)g Cu cell(-1)) than P. tricornutum (0.23+/-0.19 x 10(-13)g Cu cell(-1)) and D. tertiolecta (0.59+/-0.05 x 10(-13)g Cu cell(-1)), suggesting that Tetraselmis sp. effectively detoxifies copper within the cell. By contrast, at the same external copper concentration (50 microg L(-1)), D. tertiolecta appears to better exclude copper than Tetraselmis sp. by having a slower copper internalisation rate and lower internal copper concentrations at equivalent extracellular concentrations. The results suggest that the use of internal copper concentrations and net uptake rates alone cannot explain differences in species-sensitivity for different algal species. Model prediction of copper toxicity to marine biota and understanding fundamental differences in species-sensitivity will require, not just an understanding of water quality parameters and copper-cell binding, but also further knowledge of cellular detoxification mechanisms.

Towards a thermally regenerative all-copper redox flow battery

OpenAIRE

Peljo, Pekka; Lloyd, David; Nguyet, Doan; Majaneva, Marko; Kontturi, Kyosti

2014-01-01

An all-copper redox flow battery based on strong complexation of Cu+ with acetonitrile is demonstrated, exhibiting reasonable battery performance. More interestingly, the battery can be charged by heat sources of 100 degrees C, by distilling off the acetonitrile. This destabilizes the Cu+ complex, leading to recovery of the starting materials.

Towards a thermally regenerative all-copper redox flow battery.

Science.gov (United States)

Peljo, Pekka; Lloyd, David; Doan, Nguyet; Majaneva, Marko; Kontturi, Kyösti

2014-02-21

An all-copper redox flow battery based on strong complexation of Cu(+) with acetonitrile is demonstrated, exhibiting reasonable battery performance. More interestingly, the battery can be charged by heat sources of 100 °C, by distilling off the acetonitrile. This destabilizes the Cu(+) complex, leading to recovery of the starting materials.

The mineralogical characterization of tellurium in copper anodes

Science.gov (United States)

Chen, T. T.; Dutrizac, J. E.

1993-12-01

A mineralogical study of a «normal» commercial copper anode and six tellurium-rich copper anodes from the CCR Refinery of the Noranda Copper Smelting and Refining Company was carried out to identify the tellurium carriers and their relative abundances. In all the anodes, the major tellurium carrier is the Cu2Se-Cu2Te phase which occurs as a constituent of complex inclusions at the copper grain boundaries. In tellurium-rich anodes, the molar tellurium content of the Cu2Se-Cu2Te phase can exceed that of selenium. Although >85 pct of the tellurium occurs as the Cu2Se-Cu2Te phase, minor amounts are present in Cu-Pb-As-Bi-Sb oxide, Cu-Bi-As oxide, and Cu-Te-As oxide phases which form part of the grain-boundary inclusions. About 1 pct of the tellurium content of silver-rich anodes occurs in various silver alloys, but gold tellurides were never detected. Surprising is the fact that 2 to 8 pct of the total tellurium content of the anodes occurs in solid solution in the copper-metal matrix, and presumably, this form of tellurium dissolves at the anode interface during electrorefining.

Preparation of Conductive Organometallic Complexes and Their Pastes or Inks Using the Electron Beam Apparatus

International Nuclear Information System (INIS)

Gu, Ja Min; Lee, Hyosun; Lee, Byung Cheol; Park, Ji Hyun

2011-01-01

We have synthesized the silver and copper complexes using the ligands, amine derivatives Ν-methylhydantoin amine, Ν-triethanol amine, the copper complexes are prepared depending on the equivalents of starting materials, however the silver complexes failed. In case of terephthalic acid, glutaric acid, we have synthesized silver and copper complexes successfully. We have measured conductivity of silver and copper complexes paste and ink themselves by thermal reduction using PULSE UV method. A couple of synthesized copper complex's paste have shown some resistance which is not enough for the conductive materials. Commercially silver pastes composed of silver oxide and silver salt of carboxylic acid, applied to the printed transistor circuits with suitable process, i. e. thermal reduction. This process substituted for electron beam brings a simplification of process, economical, environmental friendly process and a development of in the application of flexible substrate