WorldWideScience

Sample records for copper complexes

  1. Copper complexes as chemical nucleases

    Indian Academy of Sciences (India)

    Akhil R Chakravarty; Pattubala A N Reddy; Bidyut K Santra; Anitha M Thomas

    2002-08-01

    Redox active mononuclear and binuclear copper(II) complexes have been prepared and structurally characterized. The complexes have planar N-donor heterocyclic bases like 1,10-phenanthroline (phen), dipyridoquinoxaline (dpq) and dipyridophenazine (dppz) ligands that are suitable for intercalation to B-DNA. Complexes studied for nuclease activity have the formulations [Cu(dpq)2(H2O)] (ClO4)2.H2O (1), [{CuL(H2O)}2(-ox)](ClO4)2 (L = bpy, 2; phen, 3; dpq, 4; and dppz, 5) and [Cu(L)(salgly)] (L = bpy, 6; phen, 7; dpq, 8; and dppz, 9), where salgly is a tridentate Schiff base obtained from the condensation of glycine and salicylaldehyde. The dpq complexes are efficient DNA binding and cleavage active species. The dppz complexes show good binding ability but poor nuclease activity. The cleavage activity of the bis-dpq complex is significantly higher than the bis-phen complex of copper(II). The nuclease activity is found to be dependent on the intercalating nature of the complex and on the redox potential of the copper(II)/copper(I) couple. The ancillary ligand plays a significant role in binding and cleavage activity.

  2. Copper (II) Complex

    African Journals Online (AJOL)

    CLEMENT O BEWAJI

    Key Words : Histidine, complex compound, acetylacetone, stability constant, ... of a class of chemical compounds called amino acids, which are organic .... Synthesis and techniques in inorganic chemistry W. B. Saunders campany, 2nd Edition.

  3. Electrochemical behaviour of alkaline copper complexes

    Indian Academy of Sciences (India)

    C L Aravinda; S M Mayanna; V R Muralidharan

    2000-10-01

    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 deposition of copper involves the slow formation of a monovalent species. Adsorption of this species obeys Langmuir isotherm. In TEA solutions the deposition involves the formation of monovalent ions obeying the non-activated Temkin isotherm. Conversion of divalent to monovalent copper is also slow. In TEA and TSC alkaline copper solutions, the predominant species that undergo stepwise reduction contain only TEA ligands

  4. Copper complexes as therapeutic agents.

    Science.gov (United States)

    Duncan, Clare; White, Anthony R

    2012-02-01

    The importance of transition metals in biological processes has been well established. Copper (Cu) is a transition metal that can exist in oxidised and reduced states. This allows it to participate in redox and catalytic chemistry, making it a suitable cofactor for a diverse range of enzymes and molecules. Cu deficiency or toxicity is implicated in a variety of pathological conditions; therefore inorganic complexes of Cu have been investigated for their therapeutic and diagnostic potential. These Cu complexes have been shown to be effective in cancer treatment due to their cytotoxic action on tumour cells. Alternatively, Cu complexes can also modulate Cu homeostasis in the brain, resulting in protective effects in several models of neurodegeneration. In other diseases such as coronary heart disease and skin disease, the success of Cu complexes as potential therapeutics will most likely be due to their ability to increase SOD activity, leading to relief of oxidative stress. This review seeks to provide a broad insight into some of the diverse actions of Cu complexes and demonstrate the strong future for these compounds as potential therapeutic agents.

  5. Structure of a copper-isoniazid complex.

    Science.gov (United States)

    Hanson, J C; Camerman, N; Camerman, A

    1981-11-01

    It is well-known that complex formation with copper ions increases the in vitro mycobactericidal action of the antituberculosis agent isoniazid. We report here the preparation and structure of a copper(II)-isoniazid complex. Unit cell parameters are a = 9.575, b = 14.855, and c = 7.056 A and space group P2(1)2(1)2(1). Copper bonding geometry is square planar with the isoniazid carbonyl oxygen and hydrazide amino nitrogen atoms and two chlorines occupying coordination positions. Complexing with copper(II) does not significantly alter the isoniazid molecular conformation.

  6. 21 CFR 73.1125 - Potassium sodium copper chloropyhllin (chlorophyllin-copper complex).

    Science.gov (United States)

    2010-04-01

    ... (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 additive potassium sodium copper chlorophyllin is a green to black powder obtained from chlorophyll...

  7. 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...

  8. A copper vapor laser by using a copper-vapor-complex reaction at a low temperature

    OpenAIRE

    Kano, Toshiyuki; Taniguchi, Hiroshi; Saito, Hiroshi

    1987-01-01

    A copper vapor laser performance by using ametal-vapor-complex reaction (Cu+AlBr3) is reported. The laser operation is obtained at a low temperature without externalheating because of the AlBr3 vapors evaporating at a room temperature. The copper vapor laser using this metal-vapor-complex reaction has an advantage of deposition-free of a metallic copper to the laser tube wall, which is different from the copper halide and the organometallic copper lasers.

  9. Reactivity of copper(II)-alkylperoxo complexes.

    Science.gov (United States)

    Tano, Tetsuro; Ertem, Mehmed Z; Yamaguchi, Satoru; Kunishita, Atsushi; Sugimoto, Hideki; Fujieda, Nobutaka; Ogura, Takashi; Cramer, Christopher J; Itoh, Shinobu

    2011-10-28

    Copper(II) complexes 1a and 1b, supported by tridentate ligand bpa [bis(2-pyridylmethyl)amine] and tetradentate ligand tpa [tris(2-pyridylmethyl)amine], respectively, react with cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH(3)CN to provide the corresponding copper(II) cumylperoxo complexes 2a and 2b, the formation of which has been confirmed by resonance Raman and ESI-MS analyses using (18)O-labeled CmOOH. UV-vis and ESR spectra as well as DFT calculations indicate that 2a has a 5-coordinate square-pyramidal structure involving CmOO(-) at an equatorial position and one solvent molecule at an axial position at low temperature (-90 °C), whereas a 4-coordinate square-planar structure that has lost the axial solvent ligand is predominant at higher temperatures (above 0 °C). Complex 2b, on the other hand, has a typical trigonal bipyramidal structure with the tripodal tetradentate tpa ligand, where the cumylperoxo ligand occupies an axial position. Both cumylperoxo copper(II) complexes 2a and 2b are fairly stable at ambient temperature, but decompose at a higher temperature (60 °C) in CH(3)CN. Detailed product analyses and DFT studies indicate that the self-decomposition involves O-O bond homolytic cleavage of the peroxo moiety; concomitant hydrogen-atom abstraction from the solvent is partially involved. In the presence of 1,4-cyclohexadiene (CHD), the cumylperoxo complexes react smoothly at 30 °C to give benzene as one product. Detailed product analyses and DFT studies indicate that reaction with CHD involves concerted O-O bond homolytic cleavage and hydrogen-atom abstraction from the substrate, with the oxygen atom directly bonded to the copper(II) ion (proximal oxygen) involved in the C-H bond activation step.

  10. Biogenic nanoparticles: copper, copper oxides, copper sulphides, complex copper nanostructures and their applications.

    Science.gov (United States)

    Rubilar, Olga; Rai, Mahendra; Tortella, Gonzalo; Diez, Maria Cristina; Seabra, Amedea B; Durán, Nelson

    2013-09-01

    Copper nanoparticles have been the focus of intensive study due to their potential applications in diverse fields including biomedicine, electronics, and optics. Copper-based nanostructured materials have been used in conductive films, lubrification, nanofluids, catalysis, and also as potent antimicrobial agent. The biogenic synthesis of metallic nanostructured nanoparticles is considered to be a green and eco-friendly technology since neither harmful chemicals nor high temperatures are involved in the process. The present review discusses the synthesis of copper nanostructured nanoparticles by bacteria, fungi, and plant extracts, showing that biogenic synthesis is an economically feasible, simple and non-polluting process. Applications for biogenic copper nanoparticles are also discussed.

  11. Incorporation of copper histidine complexes into a zeolite Y matrix

    NARCIS (Netherlands)

    Mesu, J.G.; Baute, D.; Tromp, H.J.; Faassen, E.E.H. van; Weckhuysen, B.M.

    2003-01-01

    Preformed copper-histidine complexes were loaded into zeolite Y by ion exchange. The zeolite was found to contain a mixture of two different encaged complexes: a mono-histidine complex (A) and a bis-histidine complex (B). The initial copper concentration affects the composition of this mixture, with

  12. Copper(II) complexes with aroylhydrazones

    Indian Academy of Sciences (India)

    Samudranil Pal

    2002-08-01

    The coordination chemistry of copper(II) with tridentate aroylhydrazones is briefly discussed in this article. Two types of aroylhydrazones derived from aroylhydrazines and ortho-hydroxy aldehydes or 2-pyridine-carboxaldehyde have been used. The characterization of the complexes has been performed with the help of various physico-chemical techniques. Solid state structural patterns have been established by X-ray crystallography. In the solid state, structural varieties of these complexes are seen to range from monomeric, dimeric, polymeric and onedimensional self-assembly via hydrogen bonds and - interactions. EPR spectroscopy and variable temperature magnetic susceptibility measurements have been used to reveal the nature of the coordination geometry and magnetic characteristics of these complexes.

  13. Copper complexation in coastal rainwater, southeastern USA

    Science.gov (United States)

    Witt, Melanie; Skrabal, Stephen; Kieber, Robert; Willey, Joan

    Complexation of dissolved copper (Cu) was studied in Atlantic coastal rainwater using adsorptive cathodic stripping voltammetry (ASCV) with salicylaldoxime as a competing ligand at pH 7.8. Detectable concentrations of strong Cu-complexing ligands possessing conditional stability constants of 10 13-10 16 were observed in over 80% of the rain events occurring over the course of 2 year. In 11 of the 23 samples analysed, total dissolved Cu concentrations were higher than those of dissolved ligands, indicating that a significant fraction of the Cu occurred as the free ion and as weaker complexes. In the remaining samples, ligand concentrations were equal to or greater than Cu concentrations, indicating virtually complete (>99%) complexation of the ambient Cu. By varying the analytical detection window, two classes of ligands with differing conditional stability constants were detected in selected rain samples suggesting that the Cu ligands most likely represent a spectrum of organic compounds. Back trajectory analysis indicated that continentally dominated rain samples contained higher concentrations of Cu and organic ligands relative to storms of marine origin, suggesting a strong terrestrial and/or anthropogenic source of both Cu and ligands in rain at this location. Variability in Cu speciation may impact a variety of atmospheric redox reactions because free and complexed forms of the metal have very different reactivities.

  14. Synthesis of aminoarenethiolato-copper(I) complexes

    NARCIS (Netherlands)

    Sperotto, E.; van Klink, G.P.M.; van Koten, G.

    2008-01-01

    Copper(I)-mediated reactions have recently become the choice for large industrial scale applications, since copper is environmentally friendly and cheaper than other transition metals already explored. However, most organocopper compounds still present several limitations including the sensitivity t

  15. Copper(II) complexes encapsulated in human red blood cells.

    Science.gov (United States)

    Bonomo, R P; De Flora, A; Rizzarelli, E; Santoro, A M; Tabbí, G; Tonetti, M

    1995-09-01

    Copper(II) complexes were encapsulated in human red blood cells in order to test their possible use as antioxidant drugs by virtue of their labile character. ESR spectroscopy was used to verify whether encapsulation in red blood cells leads to the modification of such complexes. With copper(II) complexes bound to dipeptides or tripeptides, an interaction with hemoglobin was found to be present, the hemoglobin having a strong coordinative site formed by four nitrogen donor atoms. Instead, with copper(II) complexes with TAD or PheANN3, which have the greatest stability. ESR spectra always showed the original species. Only the copper(II) complex with GHL gave rise to a complicated behavior, which contained signals from iron(III) species probably coming from oxidative processes. Encapsulation of all copper(II) complexes in erythrocytes caused a slight oxidative stress, compared to the unloaded and to the native cells. However, no significant differences were observed in the major metabolic properties (GSH, glycolytic rate, hexose monophosphate shunt, Ca(2+)-ATPase) of erythrocytes loaded with different copper(II) complexes, with the exception of methemoglobin levels, which were markedly increased in the case of [Cu(GHL)H-1] compared to [Cu(TAD)]. This latter finding suggests that methemoglobin formation can be affected by the type of complex used for encapsulation, depending on the direct interaction of the copper(II) complex with hemoglobin.

  16. Copper and conquer: copper complexes of di-2-pyridylketone thiosemicarbazones as novel anti-cancer therapeutics.

    Science.gov (United States)

    Park, Kyung Chan; Fouani, Leyla; Jansson, Patric J; Wooi, Danson; Sahni, Sumit; Lane, Darius J R; Palanimuthu, Duraippandi; Lok, Hiu Chuen; Kovačević, Zaklina; Huang, Michael L H; Kalinowski, Danuta S; Richardson, Des R

    2016-09-01

    Copper is an essential trace metal required by organisms to perform a number of important biological processes. Copper readily cycles between its reduced Cu(i) and oxidised Cu(ii) states, which makes it redox active in biological systems. This redox-cycling propensity is vital for copper to act as a catalytic co-factor in enzymes. While copper is essential for normal physiology, enhanced copper levels in tumours leads to cancer progression. In particular, the stimulatory effect of copper on angiogenesis has been established in the last several decades. Additionally, it has been demonstrated that copper affects tumour growth and promotes metastasis. Based on the effects of copper on cancer progression, chelators that bind copper have been developed as anti-cancer agents. In fact, a novel class of thiosemicarbazone compounds, namely the di-2-pyridylketone thiosemicarbazones that bind copper, have shown great promise in terms of their anti-cancer activity. These agents have a unique mechanism of action, in which they form redox-active complexes with copper in the lysosomes of cancer cells. Furthermore, these agents are able to overcome P-glycoprotein (P-gp) mediated multi-drug resistance (MDR) and act as potent anti-oncogenic agents through their ability to up-regulate the metastasis suppressor protein, N-myc downstream regulated gene-1 (NDRG1). This review provides an overview of the metabolism and regulation of copper in normal physiology, followed by a discussion of the dysregulation of copper homeostasis in cancer and the effects of copper on cancer progression. Finally, recent advances in our understanding of the mechanisms of action of anti-cancer agents targeting copper are discussed.

  17. 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.

  18. 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.

    2010-04-01

    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.

  19. 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.

  20. Asymmetric Intramolecular Cyclopropanation Induced by (β-Diketone)-copper Complex

    Institute of Scientific and Technical Information of China (English)

    Qing Fang CHENG; Xing You XU; Wei Xing MA; Tian Pa YOU

    2005-01-01

    Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.

  1. Coordination geometry around copper in a Schiff-base trinuclear copper complex using EXAFS spectroscopy

    Science.gov (United States)

    Gaur, Abhijeet; Shrivastava, B. D.; Gaur, D. C.; Prasad, J.; Srivastava, K.; Jha, S. N.; Bhattacharyya, D.; Poswal, A.

    2012-05-01

    In the present investigation, we have studied extended X-ray absorption fine structure (EXAFS) spectra of a trinuclear Schiff-base copper complex tetraaqua-di-μ3-(N-salicylidene-DL-glutamato)-tricopper(II)heptahydrate, [Cu3(C12H10NO5)2 (H2O)4]. 7H2O, in which three metal sites are present. One metal site is square-pyramidal (4+1) and other two similar metal sites are tetragonally distorted octahedral (4+2). EXAFS has been recorded at the K-edge of copper in the complex at the dispersive EXAFS beamline at 2 GeV Indus-2 synchrotron source at RRCAT, Indore, India. The analysis of EXAFS spectra of multinuclear metal complexes pose some problems due to the presence of many absorbing atoms, even when the absorbing atoms may be of the same element. Hence, using the available crystal structure of the complex, theoretical models have been generated for the different copper sites separately, which are then fitted to the experimental EXAFS data. The two coordination geometries around the copper sites have been determined. The contributions of the different copper sites to the experimental spectrum have been estimated. The structural parameters, which include bond-lengths, coordination numbers and thermal disorders, for the two types of copper sites have been reported. Further, copper has been found to be in +2 oxidation state at these metal sites.

  2. Copper complexation in marine and terrestrial rain water

    Science.gov (United States)

    Witt, Melanie; Jickells, Tim

    The complexation of copper was studied in rainwater collected in Norwich, UK, and during Atlantic and Indian Ocean cruises. The complexation was measured with Chelex resin, Sep-Pak columns and adsorptive cathodic stripping voltammetry with tropolone as a competing ligand. Strong organic complexation was observed in semi-urban and marine rain samples with conditional stability constants between 10 11 and 10 14. Model solutions of copper and humic matter found organic complexes of a similar strength to those observed in the rain samples suggesting humic material as a potential ligand. A large proportion of the copper in the rains was associated with strong organic complexes over the pH range 4-8 in both filtered and unfiltered rain samples suggesting organic complexation is an important process both in the atmosphere and on arrival to oceans.

  3. Novel oligonuclear copper complexes featuring exciting luminescent characteristics

    Science.gov (United States)

    Zink, Daniel M.; Volz, Daniel; Bergmann, Larissa; Nieger, Martin; Bräse, Stefan; Yersin, Hartmut; Baumann, Thomas

    2013-09-01

    A series of highly luminescent mono-, di-, and trinuclear copper(I) complexes has been synthesized using modular ligand systems of easily accessible N^N, P^P or P^N ligands in order to show the rich structural diversity of copper(I) compounds. Those systems allow for the design of various emitting materials with desired photophysical properties, such as emission colors and high efficiencies. The complexes were characterized with well-established methods such as X-ray crystallographic studies or elemental analysis and, in addition, due to their interesting photoluminescence characteristics, their emission properties were further investigated by means of spectroscopic methods as well as DFT-calculations. In detail, various cationic and neutral mononuclear complexes have been synthesized in order to investigate the photophysical properties of this these different types of emitting compounds. It has been found that neutral copper(I) complexes show superior emission properties (with PLQY up to 89%) compared to their cationic counterparts. Furthermore, a series of dinuclear and trinuclear copper(I) complexes has been synthesized featuring an easy tunable emission maximum from sky blue to deep red (481 nm to 713 nm) with extraordinary high photoluminescence quantum yields up to 99%. In addition, a new crosslinking-technique has been developed to open up the door for a new way to fully solution processed OLED using these promising emitting compounds: Alkyne-substituted emitting complexes crosslink automatically with azide-polymers in a copper-catalyzed alkyne-azide Click reaction.

  4. Unprecedented copper(I) bifluoride complexes: synthesis, characterization and reactivity.

    Science.gov (United States)

    Vergote, Thomas; Nahra, Fady; Welle, Alexandre; Luhmer, Michel; Wouters, Johan; Mager, Nathalie; Riant, Olivier; Leyssens, Tom

    2012-01-16

    To be or not to bifluoride: Two synthetic pathways to unprecedented N-heterocyclic carbene copper(I) bifluoride complexes have been developed. Catalytic tests demonstrated that copper(I) bifluorides are very efficient catalysts, which do not require any additional activating agent. The first Cu-catalyzed diastereoselective allylation of (R)-N-tert-butanesulfinyl aldimines was also established. The method enables efficient, simple and general synthesis of enantiomerically enriched homoallylic amines at room temperature in high yields.

  5. Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I)-copper (II) Complex: {[Bis(ethylenediamine) Copper (II)] Bis[diiodocuprate (I)]}

    OpenAIRE

    Mahboobeh Dashti Ardakani; Majid M. Heravi; Saeed Dehghanpour; Lida Fotouhi

    2007-01-01

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemicaldissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 andtetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure ofthe complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridgi...

  6. Trihydrated Complex of Tetrabenzimidazole Copper(Ⅱ) Sulfate

    Institute of Scientific and Technical Information of China (English)

    JIAN Fang-fang; WANG Huan-xiang; XIAO Hai-lian; JIAO Kui

    2005-01-01

    A Trihydrated complex of benzimidazole copper(Ⅱ) sulfate [(C7H6N2)4CuSO4]·3H2O was synthesized and structurally characterized. The crystal structure of this compound is built up of six solvated water molecules and two dissimilar copper ions identified as Cu1 and Cu2. The coordination geometry of copper(Ⅱ) is a slightly distorted square pyramid. The four equivalent tertiary nitrogen atoms of the benzimidazole ligand form an equatorial plane, while the oxygen atoms of sulfato occupy the axial site. In the solid state, the title compound forms a three dimensional network structure via hydrogen bonds. The benzimidazole, sulfato ion and H2O moieties are connected by the intermolecular hydrogen bonds. The (EPR) spectrum shows axial symmetry with g⊥=2.039 and g∥=2.285. Variable temperature magnetic susceptibility shows that there is a weak antiferromagnetic interaction between the neighboring copper(Ⅱ) ions.

  7. Photocleavage of DNA by copper(II) complexes

    Indian Academy of Sciences (India)

    Akhil R Chakravarty

    2006-11-01

    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 acid like L-methionone or L-lysine and phenanthroline base are efficient photocleavers of DNA. Complexes of formulation [Cu(L)(phen)](ClO4) with NSO-donor Schiff base (HL) and NN-donor heterocyclic base 1,10-phenanthroline (phen) show significant cleavage of supercoiled (SC) DNA on exposure to red light at ≈ 700 nm. The - and CT electronic bands of the copper(II) complexes play important roles in DNA cleavage reactions. The mechanistic pathways are found to be dependent on the types of ligands present in the copper(II) complexes and the photo-excitation energy. While UV exposure generally proceeds via a type-II process forming singlet oxygen as the reactive species, red-light exposure leads to DNA cleavage following different mechanistic pathways, viz. type-I, type-II and photo-redox pathways. Ternary copper(II) complexes with phen as DNA binder and Schiff base with a thiomethyl group as photosensitizer, cleave SC DNA to its nicked circular (NC) form in a type-II process in red-light. The binary complex [Cu(dpq)2(H2O)](ClO4)2 (dpq, dipyridoquinoxaline) cleaves DNA by photo-redox pathway at 694 nm. The binuclear complex [Cu$^{\\text{II}}_{2}$(RSSR)2], where H2RSSR is a Schiff base derived from 2-(thioethyl)salicylaldimine, cleaves SC DNA at 632.8 nm (CW He-Ne laser) and 694 nm (ruby laser) involving sulphide (type-I process) and hydroxyl radicals (photo-redox pathway) as the reactive species.

  8. Antibacterial Activity of Copper and Cobalt Amino Acids Complexes

    Directory of Open Access Journals (Sweden)

    ANDREEA STĂNILĂ

    2011-11-01

    Full Text Available The antibacterial properties of differently copper and cobalt amino acids complexes on agar plates was investigated in the present study. The antibacterial activity of amino acid complexes was evaluated against on three bacteria strains (Escherichia coli, Bacillus cereus, Micrococcus luteus. Generally, the amino acids complexes were mainly active against gram-positive organisms, species like Micrococcus luteus being the most susceptible strain tested. It was registered a moderate antibacterial activity against Bacillus cereus. The microorganisms Escherichia coli, which are already known to be multi-resistant to drugs, were also resistant to the amino acids complexes but also to the free salts tested. Escherichia coli were susceptible only to the CoCl2 and copper complex with phenylalanine. The complexes with leucine and histidine seem to be more active than the parent free ligand against one or more bacterial species. Moderate activity was registered in the case of complexes with methionine and phenylalanine. From the complexes tested less efficient antibacterial activity was noted in the case of complexes with lysine and valine. These results show that cobalt and copper complexes have an antibacterial activity and suggest their potential application as antibacterial agents.

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

    Science.gov (United States)

    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.

  10. The solution structure of the copper clioquinol complex.

    Science.gov (United States)

    Pushie, M Jake; Nienaber, Kurt H; Summers, Kelly L; Cotelesage, Julien J H; Ponomarenko, Olena; Nichol, Helen K; Pickering, Ingrid J; George, Graham N

    2014-04-01

    Clioquinol (5-chloro-7-iodo-8-hydroxyquinoline) recently has shown promising results in the treatment of Alzheimer's disease and in cancer therapy, both of which also are thought to be due to clioquinol's ability as a lipophilic copper chelator. Previously, clioquinol was used as an anti-fungal and anti-protozoal drug that was responsible for an epidemic of subacute myelo-optic neuropathy (SMON) in Japan during the 1960s, probably a myeloneuropathy arising from a clioquinol-induced copper deficiency. Previous X-ray absorption spectroscopy of solutions of copper chelates of clioquinol suggested unusual coordination chemistry. Here we use a combination of electron paramagnetic, UV-visible and X-ray absorption spectroscopies to provide clarification of the chelation chemistry between clioquinol and copper. We find that the solution structures for the copper complexes formed with stoichiometric and excess clioquinol are conventional 8-hydroxyquinolate chelates. Thus, the promise of clioquinol in new treatments for Alzheimer's disease and in cancer therapy is not likely to be due to any novel chelation chemistry, but rather due to other factors including the high lipophilicity of the free ligand and chelate complexes.

  11. Copper complexes as biomimetic models of catechol oxidase : mechanistic studies

    NARCIS (Netherlands)

    Koval, Iryna A.

    2006-01-01

    The research described in this thesis deals with the synthesis of copper(II) complexes with phenol-based or macrocyclic ligands, which can be regarded as model compounds of the active site of catechol oxidase, and with the mechanism of the catalytic oxidation of catechol mediated by these compounds.

  12. Electrocatalytic CO2 conversion to oxalate by a copper complex

    NARCIS (Netherlands)

    Angamuthu, R.; Byers, P.; Lutz, M.; Spek, A.L.; Bouwman, E.

    2010-01-01

    Global warming concern has dramatically increased interest in using CO2 as a feedstock for preparation of value-added compounds, thereby helping to reduce its atmospheric concentration. Here, we describe a dinuclear copper(I) complex that is oxidized in air by CO2 rather than O2; the product is a te

  13. Synthetic, spectral and solution studies on imidazolate-bridged copper(II)-copper(II) and copper(II)-zinc(II) complexes

    Indian Academy of Sciences (India)

    Subodh Kumar; R N Patel; P V Khadikar; K B Pandeya

    2001-02-01

    Synthesis, spectral and solution studies on 2-ethyl imidazolate-bridged (2-EtIm) homo-binuclear copper(II)-copper(II) and hetero-binuclear copper(II)-zinc(II) homologue are described. Magnetic moment values of homo-binuclear complexes indicate that the imidazolate group can mediate antiferromagnetic interactions. Optical spectra of hetero-binuclear complex at varying H values suggest that the imidazolate-bridged complex is stable over the H-range 7 15-10 0.

  14. Study on Polarographic Absorption Wave of Soluble Porphyrin Copper Complex

    Institute of Scientific and Technical Information of China (English)

    HE; YuFeng

    2001-01-01

    The porphyrins is a kind of sensitive color-producing reagent. However, its selectivity is low. If the porphyrin is used in polarographic analysis, the selectivity and sensitivity can be improved. Copper is one of the most important trace element in human and mammalian body. The polarographic method is a kind of important method in determination of metal ion [1]. In this paper, meso-tetra (4-sulfonylphenyl) porphyrin (H2TPPS4) is used as the soluble ligand. The polarographic absorption behavior of meso-tetra (4-sulfonylphenyl) porphyrin complex with copper ion has been studied.  ……

  15. Study on Polarographic Absorption Wave of Soluble Porphyrin Copper Complex

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ The porphyrins is a kind of sensitive color-producing reagent. However, its selectivity is low. If the porphyrin is used in polarographic analysis, the selectivity and sensitivity can be improved. Copper is one of the most important trace element in human and mammalian body. The polarographic method is a kind of important method in determination of metal ion [1]. In this paper, meso-tetra (4-sulfonylphenyl) porphyrin (H2TPPS4) is used as the soluble ligand. The polarographic absorption behavior of meso-tetra (4-sulfonylphenyl) porphyrin complex with copper ion has been studied.

  16. Complex mineral recovery from the copper flotation tailing

    OpenAIRE

    Krstev, Boris; Golomeov, Blagoj

    2005-01-01

    The generally concept of the carried out investigations is discovering an appropriate technological scheme of the possible complex mineral utilisation from the copper flotation tailing. The Bucim - mine laboratory investigations of the flotation tailing are based on the demands of the possible complex recovery from the useful present minerals or mineral components: CuFeS2; FeS2; Fe2O3; Fe3O4; Na-feldspar and K-feldspar; SiO2 etc.

  17. Copper(II) complex of 3-cinnamalideneacetylacetone: Synthesis and characterisation

    Indian Academy of Sciences (India)

    A Veeraraj; P Sami; N Raman

    2000-10-01

    A bidentate ligand derived from cinnamaldehyde and acetylacetone and its copper(II) complex have been synthesized and characterized by elemental analysis, UV-Vis, IR, ESR and magnetic susceptibility measurements. Magnetic susceptibility measurements, ESR and electronic spectral data indicate the presence of six coordinated Cu(II) ion. The ligand and complex are tested for antibacterial activity against Pseudomonas aeroginosa. They are found to show the antibacterial activity

  18. metal complexes of copper(ii)

    African Journals Online (AJOL)

    ABSTRACT. Thermally stable metal complexes based on oligomers were prepared by the reaction ... Besides, coordination compounds of salicylaldehyde Schiff base have proven to be an excellent .... They were insoluble in common organic.

  19. Complex with fullerenol and copper (II

    Directory of Open Access Journals (Sweden)

    Đorđević Aleksandar N.

    2009-01-01

    Full Text Available Polyhydroxy fulleren derivates have significant potential in nanomedical application. Research of polyanion nanoparticle fullerenol C60(OH24 is of high significance for interpretation of biological mechanisms. This paper investigated the properties of polyanion nanoparticle fullerenol C60(OH24 as a potential polydentat ligand. Fullerenol C60(OH24 water solutions were added in solution of [Cu(NH34]2+ in order to form a dark brown complex. Absorbance of [Cu(NH34]2+ solution was decreasing with increasing concentration of polyanion nanoparticle nanoligand fullerenol. This relation was determined in all investigated concentrations of [Cu(NH34]2+. The ratio of Cu2+ complex composer to polyanion polydentat nanoligand fullerenol had an increase from 1.5 to 9, proportional to the increase of the complex composer concentration and decrease of polyanion polydentat nanoligand fullerenol in the alkali medium. The thermogram TGA-DTA of fullerenol and fullerenol and CuSO4 complex, clearly show endothermic effects (which are the result of dehydratation and dehydroxylation and exothermic effects (as the result of degradation of C60(OH24 molecules and processes of oxidation in CO, CO2. At the beginning of TGA-DTA fullerenol thermogram, there is a very well defined endothermic peak of water loss at 100°C, followed by mass decrease as a consequence of lost hydroxyl groups, covalent bounded for C60. The influence of the complex composer is manifested in the moving of thermal stability towards lower temperatures. The complex composer is a catalyst of the process of polyanion polydentat nanoligand fullerenol oxidation to CO and CO2. The temperature peak of fullerenol oxidation is at 490°C and in the case of complex oxidation two peaks were detected at 380 and 410°C.

  20. Copper dynamics in doped metal-bis(histidine) complexes.

    Science.gov (United States)

    Colaneri, Michael J; Vitali, Jacqueline

    2014-07-03

    Electron paramagnetic resonance (EPR) temperature-dependent measurements were undertaken on three Cu(II)-doped metal-histidine complexes to assess copper site dynamic behavior. Previous single-crystal EPR analysis on two of these, zinc d,l-histidine pentahydrate (ZnDLH) and bis(l-histidinato)cadmium dihydrate (CdLH), found that doped Cu(2+) can be modeled as hopping between two neighboring conformational states, with a temperature-dependent rate becoming large enough at room temperature to produce an "averaged" spectrum. By comparing spectra from their powdered form, we show that Cu(2+) doped into a third system, Cd(2+)-d,l-histidine (CdDLH), also exhibits temperature-dependent EPR with features indicating a similar motional-averaging process. In addition, the change of g and copper hyperfine parameters from low to high temperature for CdDLH resembles that in ZnDLH, whereas the change in these parameters for CdLH is like that found in a fourth copper-doped system, zinc l-histidine dihydrate (ZnLH). Taken together, these results suggest that averaging motion between neighboring copper sites is common in metal-bis(histidine) compounds. More detailed studies on biological models are thus warranted, especially because they reveal unique relationships between structure, dynamic processes, and stability and can lead to a better understanding of the role played by site flexibility in copper proteins.

  1. 21 CFR 73.3110 - Chlorophyllin-copper complex, oil soluble.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chlorophyllin-copper complex, oil soluble. 73.3110... GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3110 Chlorophyllin-copper complex, oil soluble. (a) Identity. The color additve is chlorophyllin-copper complex, oil...

  2. 40 CFR 721.2577 - Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine...

    Science.gov (United States)

    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...

  3. Complexes of Lapacholate with Cobalt and Copper

    Directory of Open Access Journals (Sweden)

    R. A. Farfán

    2012-01-01

    Full Text Available The molecular structures of two isostructural complexes of lapacholate (Lap anion and dimethylformamide (DMF, M(Lap2(DMF2 with M: Co Cu, were determined by X-ray diffraction methods. The substances crystallize in the triclinic space group P1¯ with one molecule per unit cell and cell constants a=7.7591(3, b=10.3560(3, c=11.2224(4 Å, α=95.110(2, β=94.310(2, and γ=107.704(2° for the Co complex and a=7.9308(2, b=10.0033(4, c=10.7508(4, α=97.387(2, β=93.621(2, and γ=103.980(2° for the Cu complex. The structures were solved from 2933 (Co and 2888 (Cu reflections with I>2σ (I and refined by full matrix least squares to agreement R1-factors of 0.041 (Co and 0.033 (Cu. The metal M(II ion is sited on a crystallographic inversion center in a MO6 distorted octahedral environment. This ion is coordinated equatorially to two lapacholate anions through their adjacent carbonyl and phenol oxygen atoms [M–O bond distances of 2.134(1 and 2.008(1 Å (Co and 2.301(1 and 1.914(1 Å (Cu] and axially to two DMF molecules through oxygen atoms [M–O bond lengths of 2.143(1 Å (Co and 2.069(1 Å (Cu]. The solid state IR transmittance and solution electronic absorption spectra of both Co and Cu compounds are also reported and compared to each other and to the corresponding spectra of other members of the lapacholate metal family of complexes.

  4. Copper(II) complexes of rat amylin fragments.

    Science.gov (United States)

    Kállay, Csilla; Dávid, Agnes; Timári, Sarolta; Nagy, Eszter Márta; Sanna, Daniele; Garribba, Eugenio; Micera, Giovanni; De Bona, Paolo; Pappalardo, Giuseppe; Rizzarelli, Enrico; Sóvágó, Imre

    2011-10-14

    The fragments of rat amylin rIAPP(17-29) (Ac-VRSSNNLGPVLPP-NH(2)), rIAPP(17-22) (Ac-VRSSNN-NH(2)), rIAPP(19-22) (Ac-SSNN-NH(2)) and rIAPP(17-20) (Ac-VRSS-NH(2)) together with the related mutant peptides (Ac-VASS-NH(2) and Ac-VRAA-NH(2)) have been synthesized and their copper(II) complexes studied by potentiometric, UV-Vis, CD and EPR spectroscopic methods. Despite the lack of any common strongly coordinating donor functions some of these fragments are able to bind copper(II) ions in the physiological pH range. The longest fragment rat amylin(17-29) keeps one equivalent copper(II) ion in solution in the whole pH range, while two other peptides Ac-VRSSNN-NH(2) and Ac-SSNN-NH(2) are also able to interact with copper(II) ions in the slightly alkaline pH range. According to the spectral parameters of the complexes, the peptides can be classified into two different categories: (i) the tetrapeptides Ac-VRSS-NH(2), Ac-VASS-NH(2) and Ac-VRAA-NH(2) can interact with copper(II) only under strongly alkaline conditions (pH > 10.0) and the formation of only one species with four amide nitrogen coordination can be detected; (ii) the peptides Ac-VRSSNNLGPVLPP-NH(2), Ac-VRSSNN-NH(2) and Ac-SSNN-NH(2) can form complexes above pH 6.0 with the major stoichiometries [CuH(-2)L], [CuH(-3)L](-) and [CuH(-4)L](2-). These data support that rIAPP(17-29) can interact with copper(II) ions under physiological conditions and the SSNN tetrapeptide fragment can be considered as the shortest sequence responsible for metal binding. Density functional theory (DFT) calculations provide some information on the possible coordination modes of Ac-SSNN-NH(2) towards the copper(II) ion and suggest that for [CuH(-2)L], [CuH(-3)L](-) and [CuH(-4)L](2-), the binding of two, three and four deprotonated amide nitrogens, with NH(-) of the side chain of asparagine as anchoring group, is probable. Moreover, these data reveal that peptides can be effective metal binding ligands even in the absence of anchoring

  5. Developing mononuclear copper-active-oxygen complexes relevant to reactive intermediates of biological oxidation reactions.

    Science.gov (United States)

    Itoh, Shinobu

    2015-07-21

    Active-oxygen species generated on a copper complex play vital roles in several biological and chemical oxidation reactions. Recent attention has been focused on the reactive intermediates generated at the mononuclear copper active sites of copper monooxygenases such as dopamine β-monooxygenase (DβM), tyramine β-monooxygenase (TβM), peptidylglycine-α-hydroxylating monooxygenase (PHM), and polysaccharide monooxygenases (PMO). In a simple model system, reaction of O2 and a reduced copper(I) complex affords a mononuclear copper(II)-superoxide complex or a copper(III)-peroxide complex, and subsequent H(•) or e(-)/H(+) transfer, which gives a copper(II)-hydroperoxide complex. A more reactive species such as a copper(II)-oxyl radical type species could be generated via O-O bond cleavage of the peroxide complex. However, little had been explored about the chemical properties and reactivity of the mononuclear copper-active-oxygen complexes due to the lack of appropriate model compounds. Thus, a great deal of effort has recently been made to develop efficient ligands that can stabilize such reactive active-oxygen complexes in synthetic modeling studies. In this Account, I describe our recent achievements of the development of a mononuclear copper(II)-(end-on)superoxide complex using a simple tridentate ligand consisting of an eight-membered cyclic diamine with a pyridylethyl donor group. The superoxide complex exhibits a similar structure (four-coordinate tetrahedral geometry) and reactivity (aliphatic hydroxylation) to those of a proposed reactive intermediate of copper monooxygenases. Systematic studies based on the crystal structures of copper(I) and copper(II) complexes of the related tridentate supporting ligands have indicated that the rigid eight-membered cyclic diamine framework is crucial for controlling the geometry and the redox potential, which are prerequisites for the generation of such a unique mononuclear copper(II)-(end-on)superoxide complex

  6. The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

    Science.gov (United States)

    Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

  7. An Efficient (2-Aminoarenethiolato)copper(I) Complex for the Copper-Catalysed Huisgen Reaction (CuAAC)

    NARCIS (Netherlands)

    Fabbrizzi, Pierangelo; Cicchi, Stefano; Brandi, Alberto; Sperotto, E.; van Koten, G.

    2009-01-01

    A (2-aminoarenethiolato)copper(I) complex has been used as an efficient catalyst (1 mol-%) for the copper-catalysedHuisgen reaction (CuAAC) of azides and terminal alkynes in an organic solvent. The reaction was also extremely effective in CH2Cl2 allowing the complete decoration of dendrimeric scaffo

  8. Redox properties of a mononuclear copper(II)-superoxide complex.

    Science.gov (United States)

    Tano, Tetsuro; Okubo, Yuri; Kunishita, Atsushi; Kubo, Minoru; Sugimoto, Hideki; Fujieda, Nobutaka; Ogura, Takashi; Itoh, Shinobu

    2013-09-16

    Redox properties of a mononuclear copper(II) superoxide complex, (L)Cu(II)-OO(•), supported by a tridentate ligand (L = 1-(2-phenethyl)-5-[2-(2-pyridyl)ethyl]-1,5-diazacyclooctane) have been examined as a model compound of the putative reactive intermediate of peptidylglycine α-hydroxylating monooxygenase (PHM) and dopamine β-monooxygenase (DβM) (Kunishita et al. J. Am. Chem. Soc. 2009, 131, 2788-2789; Inorg. Chem. 2012, 51, 9465-9480). On the basis of the reactivity toward a series of one-electron reductants, the reduction potential of (L)Cu(II)-OO(•) was estimated to be 0.19 ± 0.07 V vs SCE in acetone at 298 K (cf. Tahsini et al. Chem.-Eur. J. 2012, 18, 1084-1093). In the reaction of TEMPO-H (2,2,6,6-tetramethylpiperidine-N-hydroxide), a simple HAT (hydrogen atom transfer) reaction took place to give the corresponding hydroperoxide complex LCu(II)-OOH, whereas the reaction with phenol derivatives ((X)ArOH) gave the corresponding phenolate adducts, LCu(II)-O(X)Ar, presumably via an acid-base reaction between the superoxide ligand and the phenols. The reaction of (L)Cu(II)-OO(•) with a series of triphenylphosphine derivatives gave the corresponding triphenylphosphine oxides via an electrophilic ionic substitution mechanism with a Hammett ρ value as -4.3, whereas the reaction with thioanisole (sulfide) only gave a copper(I) complex. These reactivities of (L)Cu(II)-OO(•) are different from those of a similar end-on superoxide copper(II) complex supported by a tetradentate TMG3tren ligand (1,1,1-Tris{2-[N(2)-(1,1,3,3-tetramethylguanidino)]ethyl}amine (Maiti et al. Angew. Chem., Int. Ed. 2008, 47, 82-85).

  9. Characteristics of coated copper wire specimens using high frequency ultrasonic complex vibration welding equipments.

    Science.gov (United States)

    Tsujino, J; Ihara, S; Harada, Y; Kasahara, K; Sakamaki, N

    2004-04-01

    Welding characteristic of thin coated copper wires were studied using 40, 60, 100 kHz ultrasonic complex vibration welding equipments with elliptical to circular vibration locus. The complex vibration systems consisted of a longitudinal-torsional vibration converter and a driving longitudinal vibration system. Polyurethane coated copper wires of 0.036 mm outer diameter and copper plates of 0.3 mm thickness and the other dimension wires were used as welding specimens. The copper wire part is completely welded on the copper substrate and the insulated coating material is driven from welded area to outsides of the wire specimens by high frequency complex vibration.

  10. Neuroprotective copper bis(thiosemicarbazonato) complexes promote neurite elongation.

    Science.gov (United States)

    Bica, Laura; Liddell, Jeffrey R; Donnelly, Paul S; Duncan, Clare; Caragounis, Aphrodite; Volitakis, Irene; Paterson, Brett M; Cappai, Roberto; Grubman, Alexandra; Camakaris, James; Crouch, Peter J; White, Anthony R

    2014-01-01

    Abnormal biometal homeostasis is a central feature of many neurodegenerative disorders including Alzheimer's disease (AD), Parkinson's disease (PD), and motor neuron disease. Recent studies have shown that metal complexing compounds behaving as ionophores such as clioquinol and PBT2 have robust therapeutic activity in animal models of neurodegenerative disease; however, the mechanism of neuroprotective action remains unclear. These neuroprotective or neurogenerative processes may be related to the delivery or redistribution of biometals, such as copper and zinc, by metal ionophores. To investigate this further, we examined the effect of the bis(thiosemicarbazonato)-copper complex, Cu(II)(gtsm) on neuritogenesis and neurite elongation (neurogenerative outcomes) in PC12 neuronal-related cultures. We found that Cu(II)(gtsm) induced robust neurite elongation in PC12 cells when delivered at concentrations of 25 or 50 nM overnight. Analogous effects were observed with an alternative copper bis(thiosemicarbazonato) complex, Cu(II)(atsm), but at a higher concentration. Induction of neurite elongation by Cu(II)(gtsm) was restricted to neurites within the length range of 75-99 µm with a 2.3-fold increase in numbers of neurites in this length range with 50 nM Cu(II)(gtsm) treatment. The mechanism of neurogenerative action was investigated and revealed that Cu(II)(gtsm) inhibited cellular phosphatase activity. Treatment of cultures with 5 nM FK506 (calcineurin phosphatase inhibitor) resulted in analogous elongation of neurites compared to 50 nM Cu(II)(gtsm), suggesting a potential link between Cu(II)(gtsm)-mediated phosphatase inhibition and neurogenerative outcomes.

  11. Neuroprotective copper bis(thiosemicarbazonato complexes promote neurite elongation.

    Directory of Open Access Journals (Sweden)

    Laura Bica

    Full Text Available Abnormal biometal homeostasis is a central feature of many neurodegenerative disorders including Alzheimer's disease (AD, Parkinson's disease (PD, and motor neuron disease. Recent studies have shown that metal complexing compounds behaving as ionophores such as clioquinol and PBT2 have robust therapeutic activity in animal models of neurodegenerative disease; however, the mechanism of neuroprotective action remains unclear. These neuroprotective or neurogenerative processes may be related to the delivery or redistribution of biometals, such as copper and zinc, by metal ionophores. To investigate this further, we examined the effect of the bis(thiosemicarbazonato-copper complex, Cu(II(gtsm on neuritogenesis and neurite elongation (neurogenerative outcomes in PC12 neuronal-related cultures. We found that Cu(II(gtsm induced robust neurite elongation in PC12 cells when delivered at concentrations of 25 or 50 nM overnight. Analogous effects were observed with an alternative copper bis(thiosemicarbazonato complex, Cu(II(atsm, but at a higher concentration. Induction of neurite elongation by Cu(II(gtsm was restricted to neurites within the length range of 75-99 µm with a 2.3-fold increase in numbers of neurites in this length range with 50 nM Cu(II(gtsm treatment. The mechanism of neurogenerative action was investigated and revealed that Cu(II(gtsm inhibited cellular phosphatase activity. Treatment of cultures with 5 nM FK506 (calcineurin phosphatase inhibitor resulted in analogous elongation of neurites compared to 50 nM Cu(II(gtsm, suggesting a potential link between Cu(II(gtsm-mediated phosphatase inhibition and neurogenerative outcomes.

  12. Copper-Mediated Fluorination of Arylboronate Esters. Identification of a Copper(III) Fluoride Complex

    Science.gov (United States)

    Fier, Patrick S.; Luo, Jingwei; Hartwig, John F.

    2013-01-01

    A method for the direct conversion of arylboronate esters to aryl fluorides under mild conditions with readily available reagents is reported. Tandem reactions have also been developed for the fluorination of arenes and aryl bromides through aryl-boronate ester intermediates. Mechanistic studies suggest that this fluorination reaction occurs through facile oxidation of Cu(I) to Cu(III) followed by rate-limiting transmetallation of a bound arylboronate to Cu(III). Fast C-F reductive elimination is proposed to occur from an aryl-copper(III)-fluoride complex. Cu(III) intermediates have been generated independently and identified by NMR spectroscopy and ESI-MS. PMID:23384209

  13. Photo-functional materials based on copper(Ⅰ) complexes

    Institute of Scientific and Technical Information of China (English)

    WANG Yuanmin; TENG Feng; XU Zheng; QIAN Lei; ZHANG Ting; LIU Deang

    2004-01-01

    Copper(Ⅰ) complexes are attractive photo-functional materials due to their rich photochemical and photophysical properties. It has been proved that these new materials have potential application in many fields, such as organic light-emitting diodes, optical sensor, nonlinear optics and dye sensitized solar cells. The goal of this review is to outline the progress in this field. Many aspects, including new ligands, stereochemical control and the construction of supramolecules, design of the excited states, the high-energy emission and low-energy emission, the Cu-Cu bonding interactions and applications, are discussed.

  14. The complexes of multiimidazole with copper (Ⅰ) display tyrosinase activity

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The six multiimidazole copper(Ⅰ) complexes are utilized to mimic tyrosinase. The main product is 3,5-di-t-butylcatechol from o-hydroxylation of the substrate 2,4-di-t-butylphenol. The highest yield of catechol is up to 82.2% and selectivity 94.8% by [Cu(Ⅰ)2(3b)(MeCN)2](ClO4)2 and O2 under mild conditions, which are found to be more efficient than that already reported.

  15. 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.

  16. Inhibition of respiratory complex I by copper(ii)-bis(thiosemicarbazonato) complexes.

    Science.gov (United States)

    Djoko, Karrera Y; Donnelly, Paul S; McEwan, Alastair G

    2014-12-01

    Several copper(ii) complexes of bis(thiosemicarbazones) [Cu(btsc)s] show promise as therapeutics for the treatment of neurological diseases, cancers and bacterial infections. These complexes are thought to act primarily as copper ionophores or "copper boosting" agents, whereby the Cu(II) centre is reduced by cytosolic reductants and Cu(I) is released as "free" or "bioavailable" ion. It is then assumed that the dissociated Cu(I) ion is the species responsible for many of the observed biological effects of Cu(btsc)s. We recently showed that Cu(btsc) complexes inhibited NADH dehydrogenases in the bacterial respiratory chain. In this work, we demonstrate that Cu(btsc) complexes also inhibit mitochondrial respiration and that Complex I in the mitochondrial electron transport chain is a specific target of inhibition. However, bioavailable Cu ions do not appear to contribute to the action of Cu(btsc) as a respiratory inhibitor. Instead, an intact Cu(btsc) molecule may bind reversibly and competitively to the site of ubiquinone binding in Complex I. Our results add to the growing body of evidence that the intact complex may be important in the overall cellular activity of Cu(btsc) complexes and further the understanding of their biological effects as a potential therapeutic.

  17. Mono-nuclear copper complexes mimicking the intermediates for the binuclear copper center of the subunit II of cytochrome oxidase: a peptide based approach.

    Science.gov (United States)

    Dutta Gupta, Dwaipayan; Usharani, Dandamudi; Mazumdar, Shyamalava

    2016-11-28

    Three stable copper complexes of peptides derived from the copper ion binding loop of the subunit II of cytochrome c oxidase have been prepared and characterized by various spectroscopic techniques. These stable copper complexes of peptides were found to exhibit cysteine, histidine and/or methionine ligation, which has predominant σ-contribution in the Cys-Cu charge transfer. The copper(ii) peptide complexes showed type-2 EPR spectra, which is uncommon in copper-cysteinate complexes. UV-visible spectra, Raman and EPR results support a tetragonal structure of the coordination geometry around the copper ion. The copper complex of the 9-amino acid peptide suggested the formation of a 'red' copper center while the copper complexes of the 12- and 11-amino acid peptides showed the formation of a 'green' copper center. The results provide insights on the first stable models of the copper complexes formed in the peptide scaffold that mimic the mono-nuclear copper bound protein intermediates proposed during the formation of the binuclear Cu2S2 core of the enzyme. These three copper complexes of peptides derived from the metal ion binding loop of the CuA center of the subunit II of cytochrome c oxidase showed novel spectroscopic properties which have not so far been reported in any stable small complex.

  18. Copper toxicity to larval stages of three marine invertebrates and copper complexation capacity in San Diego Bay, California.

    Science.gov (United States)

    Rivera-Duarte, Ignacio; Rosen, Gunther; Lapota, David; Chadwick, David B; Kear-Padilla, Lora; Zirino, Alberto

    2005-03-15

    Temporal and spatial measurements of the toxicity (EC50), chemical speciation, and complexation capacity (Cu-CC) of copper in waters from San Diego Bay suggest control of the Cu-CC over copper bioavailability. While spatial distributions of total copper (CuT) indicate an increase in concentration from the mouth toward the head of San Diego Bay, the distribution of aqueous free copper ion (Cu(II)aq) shows the opposite trend. This suggests that the bioavailability of copper to organisms decreases toward the head of the bay, and is corroborated by the increase in the amount of copper needed to reach an EC50, observed for larval stages of three marine invertebrates (Mediterranean mussel, Mytilus galloprovincialis, sand dollar, Dendraster excentricus, and purple sea urchin, Strongylocentrotus purpuratus), and by the increase in Cu-CC heading into the head of the bay. The amount of Cu(II)aq required to produce a 50% reduction in normal larval development (referred to here as pCuTox,) of the mussel, the most sensitive of the three marine invertebrates, was generally at or above approximately 1 x 10(-11) mol L(-1) equivalents of Cu (i.e., pCuTox approximately 11 = -(log [Cu(II)aq])). These results suggest that the copper complexation capacity in San Diego Bay controls copper toxicity by keeping the concentration of Cu(II)aq at nontoxic levels.

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

    Directory of Open Access Journals (Sweden)

    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.

  20. Structures of dioxobipyridil-12-crown-4 and its complexes with silver (I) and copper (II) cations

    Science.gov (United States)

    Starova, Galina L.; Denisova, Anna S.; Dem'yanchuk, Evgeniya M.

    2008-02-01

    The structures of dioxobipyridil-12-crown-4 ( bpy-CO-crown) and its complexes with copper (II) and silver (I) cations have been determined using single crystal X-ray-diffraction. The results have been compared with the literature data on the complexes of dcmbpy and its complex with silver (I) and copper (II) cations.

  1. Electrochemical synthesis and structural characterization of a novel mixed-valence copper(I)-copper(II) complex: {[bis(ethylenediamine)copper(II)] bis[diiodocuprate(I)]}.

    Science.gov (United States)

    Fotouhi, Lida; Dehghanpour, Saeed; Heravi, Majid M; Ardakani, Mahboobeh Dashti

    2007-07-12

    A novel, mixed-valent copper(I)-copper(II) complex, {[bis(ethylene-diamine)copper(II)] bis[diiodocuprate(I)]} (1), has been prepared by electrochemical dissolution of a sacrificial copper anode in a solution of ethylenediamine (en), I2 and tetraethylammoniumperchlorate (TEAP) as supporting electrolyte in acetonitrile (AcN)and characterized by single-crystal X-ray structure determination. The crystal structure of the complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridging Cu(I) ions, with a nearly square planar geometry of bivalent Cu(II) atoms chelated by two ethylenediamine ligands. The results also show that direct electrosynthesis of the complex had high current efficiency, purity and electrolysis yield.

  2. Catalytic nanomedicine technology: copper complexes loaded on titania nanomaterials as cytotoxic agents of cancer cell.

    Science.gov (United States)

    Lopez, Tessy; Ortiz-Islas, Emma; Guevara, Patricia; Gómez, Esteban

    2013-01-01

    The anticancer properties of pure copper (II) acetate and copper (II) acetylacetonate, alone and loaded on functionalized sol-gel titania (TiO(2)), were determined in four different cancer cell lines (C6, RG2, B16, and U373), using increasing concentrations of these compounds. The copper complexes were loaded onto the TiO(2) network during its preparation by the solgel process. Once copper-TiO(2) materials were obtained, these were characterized by several physical-chemical techniques. An in vitro copper complex-release test was developed in an aqueous medium at room temperature and monitored by ultraviolet spectroscopy. The toxic effect of the copper complexes, alone and loaded on TiO(2), was determined using a cell viability 3(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide (MTT) assay, when cancer cells were treated with increasing concentrations (15.75-1000 mg/mL) of these. Characterization studies revealed that the addition of copper complexes to the TiO(2) sol-gel network during its preparation, did not generate changes in the molecular structure of the complexes. The surface area, pore volume, and pore diameter were affected by the copper complex additions and by the crystalline phases obtained. The kinetic profiles of both copper complexes released indicated two different stages of release: The first one was governed by first-order kinetics and the second was governed by zero-order kinetics. The cell viability assay revealed a cytotoxic effect of copper complexes, copper-TiO(2), and cisplatin in a dose-dependent response for all the cell lines; however, the copper complexes exhibited a better cytotoxic effect than the cisplatin compound. TiO(2) alone presented a minor cytotoxicity for C6 and B16 cells; however, it did not cause any toxic effect on the RG2 and U373 cells, which indicates its high biocompatibility with these cells.

  3. [Copper-induced change in the ESR signal of hemoglobin nitrosyl complexes in wound by the action of copper nanoparticles].

    Science.gov (United States)

    Volodina, L A; Baĭder, L M; Rakhmetova, A A; Bogoslovskaia, O A; Ol'khovskaia, I P; Glushchenko, N N

    2013-01-01

    The results concerning changes in the ESR signal of hemoglobin nitrosyl complexes in wound tissues in the course of healing by the action of ointments with copper nanoparticles (patent N2460532, Russia) are presented. It is shown that the wound healing process modified by the influence of copper nanoparticles demonstrates the increase in the ESR signal amplitude for :hemoglobin nitrosyl complexes as compared with controls (the ointment base without nanoparticles). Planimetric measurements of wound area through reparation course indicate an active process of wound healing for injuries treated with copper nanoparticles in the ointment, resulting in lessening half-reparation time up to 5.0 times as compared with controls (treatment with the ointment base). The paper discusses the role of copper nanoparticles, NO and their potential synergistic effect on the skin wound regeneration.

  4. Synthesis and characterization of heteroleptic copper and zinc complexes with saccharinate and aminoacids. Evaluation of SOD-like activity of the copper complexes.

    Science.gov (United States)

    Santi, Eduardo; Viera, Inés; Mombrú, Alvaro; Castiglioni, Jorge; Baran, Enrique J; Torre, María H

    2011-12-01

    Five new copper and zinc heteroleptic complexes with saccharin and aminoacids with general stoichiometry Na(2)[M(sac)(2)(aa)(2)].nH(2)O (M denotes Cu or Zn, sac the saccharinate ion, and aa the aminoacids) were synthesized and characterized by elemental and thermogravimetric analysis, conductimetric measurements and IR, Raman and UV-vis spectroscopies. In all the complexes, copper and zinc ions coordinated with the aminoacids through the terminal amine and carboxylate residues and with saccharin through the heterocyclic nitrogen atom. Besides, the superoxide dismutase-like activity of the heteroleptic copper complexes was evaluated and compared with the homoleptic copper amino acid complexes with the aim to observe the influence of the saccharin coordination.

  5. Luminescent Tetranuclear Copper(I) Phenylacetylide Complex with Cyclohexyl Isocyanide

    Institute of Scientific and Technical Information of China (English)

    施林熙; 张礼仪; 陈忠宁

    2005-01-01

    Depolymerizing copper(I) phenylacetylide [Cu(C(CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡CPh)2. Crystal data: C30H32Cu2N2, Mr = 547.66, space group P1, a = 8.6448(1), b = 11.5772(2), c = 14.6666(4) (A), α = 88.387(2), β = 86.826(2), γ = 68.222(1)°, V = 1360.97(5) (A)3, Z = 2, F(000) = 568, Dc = 1.336 g/cm3, μ = 1.582 mm-1, the final R = 0.0629 and wR = 0.1282 for 3257 observed reflections with I > 2σ(I). The phenylacetylide adopts μ-η1 and μ3-η1,η1,η2 bonding modes. The compound shows intense luminescence in the solid state.

  6. Syntheses of Binuclear Copper(Ⅰ)Complexes Containing Benzimidazole

    Institute of Scientific and Technical Information of China (English)

    LIU Ying-Fan; ZHAO Dong; GUO Li-Bing; ZHENG Xin; SUN Yu-An

    2005-01-01

    A binuclear copper(Ⅰ) complex [Cu2(dppm)2(C7H6N2)2](NO3)2 (C7H6N2 = benzimidazole, dppm = Ph2PCH2PPh2) has been synthesized and characterized by X-ray crystallography.The crystal belongs to monoclinic, space group C2/c with a = 14.167(3), b = 21.209(4), c =20.680(4) A, β = 103.93(3)°, C32H28CuN3O3P2, Mr = 628.05, Z = 8,μ = 0.868 mm-1, V = 6031 (2)(。A)3,F(000) = 2592, Dc= 1.383 g/cm3, R = 0.0593 and wR = 0.1736.A total of 5297 independent reflec tions were collected, of which 3503 were observed with I > 2σ(I).The central copper atom is tri-coordinated by phosphorus atoms from bridging dppm and nitrogen atom from benzimidazole.In the coordination sphere, the bond lengths of Cu-P(1) and Cu-P(2) are 2.2607(17) and 2.2503(16)(。A),respectively and the P-Cu-P bond angle is 127.26(6)°.

  7. 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.

  8. Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Eisenhart, Reed J.; Carlson, Rebecca K.; Clouston, Laura J.; Young, Jr., Victor G.; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C. (UC); (UMM); (MXPL)

    2016-03-04

    Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py3tren)CoCuCl (1-Cl) and (py3tren)CoCu(CH3CN) (2-CH3CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH3CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH3CN with AgOTf generated (py3tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH3CN is reversible at -0.56 and -0.33 V vs Fc+/Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu)+4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu)+3 analogue, and the d-electrons are fully localized at individual metals.

  9. Photocatalysis; IV. Preparation and characterization of a stable copper(I) triflate-trans-cycloheptene complex

    NARCIS (Netherlands)

    Evers, J.T.M.; Mackor, A.

    1979-01-01

    When copper(I) triflate·cis‐cycloheptene is irradiated at 254 nm in n‐hexane solution, cis → trans‐isomerization occurs and the stable complex copper (I) triflate·trans‐cycloheptene precipitates. This complex has been isolated, purified and characterized by elemental analysis and by its 1H and 13C N

  10. Styrene Oxidation by Copper(II) Complexes Salen-Type Encapsulated into Nay Zeolite

    National Research Council Canada - National Science Library

    I. Kuźniarska-Biernacka; M.A. Carvalho; I. Correia Neves; A. M. Fonseca; A. Lisińska-Czekaj; D. Czekaj

    2013-01-01

    The copper(II) complex with a Schiff-base salen-type ligand has been encapsulated in the nanopores of a NaY zeolite by using two different methodologies, the flexible ligand and in situ complex preparation methods...

  11. Investigations on membrane perturbation by chrysin and its copper complex using self-assembled lipid bilayers.

    Science.gov (United States)

    Selvaraj, Stalin; Krishnaswamy, Sridharan; Devashya, Venkappayya; Sethuraman, Swaminathan; Krishnan, Uma Maheswari

    2011-11-01

    The mechanism of membrane interactions of most of the flavonoids in the presence of transition-metal ions is not well-understood. To understand this phenomenon, the present work aims to synthesize a chrysin-copper complex at room temperature and investigate its influence on the electrical characteristics of planar lipid bilayers. The chrysin-copper complex was characterized by various spectroscopic techniques and was found to have a metal/ligand ratio of 1:2 and of cationic nature. Its ability to inhibit 1,1'-diphenyl-2-picrylhydrazyl (DPPH) radicals was not significant at alkaline pH because of the involvement of the 5-hydroxy group in coordination with the copper ion compared to its parent flavonoid, chrysin (p copper complex to lipid bilayers decreases the resistance, indicating a strong surface interaction and partial insertion into the bilayer near the lipid-water interface. The dose-dependent reduction in resistance as a result of the chrysin-copper complex is more pronounced in comparison to chrysin, implying that the bulkier and charged chrysin-copper complex displays greater ability to distort the lipid bilayer architecture. These conclusions were further confirmed by curcumin-loaded liposome permeabilization studies, where both chrysin and its Cu(II) complex increased the fluidity in a dose-dependent manner. However, the extent of fluidization by the chrysin-copper complex was nearly twice that of chrysin alone (p copper complex on cell membranes were studied using a hypotonic hemolysis assay. Our results demonstrate that, at low concentrations (20 μM), the chrysin-copper complex exhibited twice the protection against hypotonic stress-induced membrane disruption when compared to chrysin. However, this stabilizing effect gradually decreased and became comparable to chrysin at higher concentrations. This biphasic behavior of the chrysin-copper complex could further be explored for therapeutic applications.

  12. Aromatic C-nitrosation by a copper(II)-nitrosyl complex.

    Science.gov (United States)

    Rout, Kanhu Charan; Mondal, Biplab

    2015-01-28

    Copper(II) complex of 4-amino-3-hydroxy-1-sulphonic acid was synthesized and characterized. Upon addition of nitric oxide, the copper(II) center of the complex in methanol was found to undergo reduction through an unstable copper(II)-nitrosyl intermediate. The formation of the intermediate was confirmed by UV-visible and FT-IR spectroscopy. The reduction of the copper(II) center was accompanied with a simultaneous C-nitrosation of the aromatic ring of the ligand. The C-nitrosation product was isolated and characterized by various spectroscopic analyses.

  13. Copper complexation in wet precipitation: Impact of different ligand sources

    Science.gov (United States)

    Karavoltsos, Sotirios; Sakellari, Aikaterini; Makarona, Anna; Plavšić, Marta; Ampatzoglou, Dimitrios; Bakeas, Evangelos; Dassenakis, Manos; Scoullos, Michael

    2013-12-01

    Cu complexation in wet precipitation samples was measured by the method of differential pulse anodic stripping voltammetry (DPASV), which presumed the existence of 1:1 Cu ion-ligand complexes. The wet precipitation samples were collected throughout the rainy period (September 2011-May 2012) from four sampling stations of central and southern Greece, two of which were located in urban coastal areas of its mainland (Athens, n = 24; Elefsina, n = 11) and the other two on the island of Crete (Heraklio, n = 26; Ligortynos, n = 12), comprising different features concerning population density, urban/rural/industrial character and influence from the sea. Total Cu (TCu), total organic and inorganic carbon (TOC, IC), pH, conductivity, several inorganic macro-constituents (Cl-, Br-, NO3-, SO42-, Na+, K+, Ca2+, Mg2+), n-alkanes and polycyclic aromatic hydrocarbons (PAHs) were determined for better characterization of the predominant sources and influences. Significant complexation of Cu ions was determined in almost all wet precipitation samples examined, with the apparent complexing capacity of Cu ions in unfiltered samples ranging between 0.07 and 1.9 μM and apparent stability constants (logKapp) in the range 6.5-9.6, which corresponds to values comparable to those deriving from a limited number of studies having a common ‘detection window'. The percentage in the mass of TOC complexed with copper was up to 4%. Among ligands, sources of terrestrial origin appear to be of particular importance. In terrestrial sources, vegetation and anthropogenic emissions seem to have a prominent impact.

  14. Transition metal complexes of neocryptolepine analogues. Part I: Synthesis, spectroscopic characterization, and invitro anticancer activity of copper(II) complexes

    Science.gov (United States)

    Emam, Sanaa Moustafa; El Sayed, Ibrahim El Tantawy; Nassar, Nagla

    2015-03-01

    New generation of copper(II) complexes with aminoalkylaminoneocryptolepine as bidentate ligands has been synthesized and it is characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, 1H NMR and ESR) and thermal studies. The IR data suggest the coordination modes for ligands which behave as a bidentate with copper(II) ion. Based on the elemental analysis, magnetic studies, electronic and ESR data, binuclear square planar geometry was proposed for complexes 7a, 7b, square pyramidal for 9a, 9b and octahedral for 8a, 8b, 10a, 10b. The molar conductance in DMF solution indicates that all complexes are electrolyte except 7a and 7b. The ESR spectra of solid copper(II) complexes in powder form showed an axial symmetry with 2B1g as a ground state and hyperfine structure. The thermal stability and degradation of the ligands and their metal complexes were studied employing DTA and TG methods. The metal-free ligands and their copper(II) complexes were tested for their in vitro anticancer activity against human colon carcinoma (HT-29). The results showed that the synthesized copper(II) complexes exhibited higher anticancer activity than their free ligands. Of all the studied copper(II) complexes, the bromo-substituted complex 9b exhibited high anticancer activity at low micromolar inhibitory concentrations (IC50 = 0.58 μM), compared to the other complexes and the free ligands.

  15. Inhibitory effect of Disulfiram/copper complex on non-small cell lung cancer cells

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Lincan [Department of Thoracic Surgery, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Shen, Hongmei [Cancer Center of Integrative Medicine, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Zhao, Guangqiang [Department of Thoracic Surgery, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Yang, Runxiang [Cancer Chemotherapy Center, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Cai, Xinyi [Colorectal Cancer Center, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Zhang, Lijuan [Department of Pathology, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Jin, Congguo [Cancer Institute, The Third Affiliated Hospital of Kunming Medical University, Kunming (China); Huang, Yunchao, E-mail: daliduanlincan@163.com [Department of Thoracic Surgery, The Third Affiliated Hospital of Kunming Medical University, Kunming (China)

    2014-04-18

    Highlights: • Disulfiram and copper synergistically inhibit lung cancer cell proliferation. • Lung cancer cell colony formation ability is inhibited by Disulfiram/copper. • Disulfiram/copper increases the sensitivity of cisplatin to lung cancer cells. • Lung cancer stem cells are specifically targeted by Disulfiram/copper complex. - Abstract: Non-small cell lung cancer (NSCLC) is the most common cause of cancer-related death in both men and women worldwide. Recently, Disulfiram has been reported to be able to inhibit glioblastoma, prostate, or breast cancer cell proliferation. In this study, the synergistic effect of Disulfiram and copper on NSCLC cell growth was investigated. Inhibition of cancer cell proliferation was detected by 1-(4,5-Dimethylthiazol-2-yl)-3,5-diphenylformazan (MTT) assay and cell cycle analysis. Liquid colony formation and tumor spheroid formation assays were used to evaluate their effect on cancer cell clonogenicity. Real-time PCR was performed to test the mRNA level of cancer stem cell related genes. We found that Disulfiram or copper alone did not potently inhibit NSCLC cell proliferation in vitro. However, the presence of copper significantly enhanced inhibitory effect of Disulfiram on NSCLC cell growth, indicating a synergistic effect between Disulfiram and copper. Cell cycle analysis showed that Disulfiram/copper complex caused NSCLC cell cycle arrest in G2/M phase. Furthermore, Disulfiram/copper significantly increased the sensitivity of cisplatin in NSCLC cells tested by MTT assay. Liquid colony formation assay revealed that copper dramatically increased the inhibitory effect of Disulfiram on NSCLC cell colony forming ability. Disulfiram combined with copper significantly attenuated NSCLC cell spheroid formation and recuded the mRNA expression of lung cancer stem cell related genes. Our data suggest that Disulfiram/copper complex alone or combined with other chemotherapy is a potential therapeutic strategy for NSCLC patients.

  16. Alkynyl triphosphine copper complexes: synthesis and photophysical studies.

    Science.gov (United States)

    Chakkaradhari, Gomathy; Belyaev, Andrey A; Karttunen, Antti J; Sivchik, Vasily; Tunik, Sergey P; Koshevoy, Igor O

    2015-08-07

    A rigid triphosphine PPh2C6H4-PPh-C6H4PPh2 () reacted with Cu(+) and a stoichiometric amount of terminal alkyne under basic conditions to give a family of copper(i) alkynyl compounds [Cu()C[triple bond, length as m-dash]CR]. The number of terminal -C[triple bond, length as m-dash]CH groups in the starting ligand determines the nuclearity of the resulting complexes giving mono- (, R = Ph; , R = C6H4OMe; , R = C6H4NO2; , R = C6H4CF3; , R = 2-pyridyl), di- (R = -(C6H4)n-, n = 1 (), n = 2, (), n = 3 ()) and trinuclear complexes (, R = 1,3,5-(C6H4)3-C6H3; , R = 1,3,5-(C6H4-4-C2C6H4)3-C6H3). In all the complexes the Cu(i) centers are found in a distorted tetrahedral environment that is achieved by tridentate coordination of the ligand and σ-bonding to the alkynyl function. The crystal structures of , and were estimated by single crystal X-ray diffraction analysis. The (31)P, (1)H and (1)H-(1)H COSY NMR spectroscopy confirms that all the molecules remain intact in solution. The photophysical studies carried out in the solid state at 298 and 77 K revealed moderate to weak orange luminescence (Φem up to 19%), tentatively assigned to thermally activated delayed fluorescence for the mononuclear complexes. The quantum yields of emission of demonstrated strong dependence on the nature of the alkynyl ligand, the role of which in the electronic transitions was elucidated by TD-DFT computational studies.

  17. In vitro inhibition of hyaluronidase by sodium copper chlorophyllin complex and chlorophyllin analogs

    Directory of Open Access Journals (Sweden)

    McCook JP

    2015-08-01

    Full Text Available John P McCook,1 Peter L Dorogi,2 David B Vasily,3 Dustin R Cefalo4 1Discovery Partners, LLC, Frisco, TX, 2CHL Industries, LLC, Easton, PA, 3Aesthetica Cosmetic and Laser Surgery Center, Bethlehem, PA, 4Frontier Scientific, Inc., Logan, UT, USA Background: Inhibitors of hyaluronidase are potent agents that maintain hyaluronic acid homeostasis and may serve as anti-aging, anti-inflammatory, and anti-microbial agents. Sodium copper chlorophyllin complex is being used therapeutically as a component in anti-aging cosmeceuticals, and has been shown to have anti-hyaluronidase activity. In this study we evaluated various commercial lots of sodium copper chlorophyllin complex to identify the primary small molecule constituents, and to test various sodium copper chlorophyllin complexes and their small molecule analog compounds for hyaluronidase inhibitory activity in vitro. Ascorbate analogs were tested in combination with copper chlorophyllin complexes for potential additive or synergistic activity. Materials and methods: For hyaluronidase activity assays, dilutions of test materials were evaluated for hydrolytic activity of hyaluronidase by precipitation of non-digested hyaluronate by measuring related turbidity at 595 nm. High-performance liquid chromatography and mass spectroscopy was used to analyze and identify the primary small molecule constituents in various old and new commercial lots of sodium copper chlorophyllin complex. Results: The most active small molecule component of sodium copper chlorophyllin complex was disodium copper isochlorin e4, followed by oxidized disodium copper isochlorin e4. Sodium copper chlorophyllin complex and copper isochlorin e4 disodium salt had hyaluronidase inhibitory activity down to 10 µg/mL. The oxidized form of copper isochlorin e4 disodium salt had substantial hyaluronidase inhibitory activity at 100 µg/mL but not at 10 µg/mL. Ascorbate derivatives did not enhance the hyaluronidase inhibitory activity of

  18. On-line Electrogeneration of Copper-Peptide Complexes in Microspray Mass Spectrometry

    OpenAIRE

    Prudent, M; Girault, H H

    2008-01-01

    The interaction of copper ions with peptides was investigated by electrospray mass spectrometry. Two electrospray micro-emitters were compared, the first one with a platinum electrode using a copper(II) electrolyte solution containing a peptide sample, and the second one with a sacrificial copper anode in a water/methanol solution containing only a peptide (i.e., angiotensin III, bradykinin, or Leu-enkephalin). The former yielded mainly Cu2 complexes either with histidine residues or with th...

  19. Metalloselenonein, the selenium analogue of metallothionein: synthesis and characterization of its complex with copper ions.

    OpenAIRE

    Oikawa, T; Esaki, N; Tanaka, H.; Soda, K

    1991-01-01

    We used an automated peptide synthesizer to produce a peptide, metalloselenonein, that contains selenocysteine residues substituted for all cysteine residues in Neurospora crassa copper metallothionein. Metalloselenonein binds 3 mol of Cu(I) per mol. This adduct shows a broad absorption band between 230 and 400 nm and a fluorescence band at 395 nm, which can be attributed to copper-selenolate coordination. The circular dichroism spectrum of the copper-metalloselenonein complex shows a positiv...

  20. Comparison of copper and zinc in vitro bioaccessibility from cyanobacteria rich in proteins and a synthetic supplement containing gluconate complexes: LC-MS mapping of bioaccessible copper complexes.

    Science.gov (United States)

    Wojcieszek, Justyna; Witkoś, Katarzyna; Ruzik, Lena; Pawlak, Katarzyna

    2016-01-01

    An analytical procedure was proposed to estimate bioaccessibility of copper and zinc in Spirulina Pacifica tablets with respect to that of copper and zinc in gluconate complexes. Spirulina is the common name for diet supplements produced primarily from two species of cyanobacteria, namely Arthrospira platensis and Arthrospira maxima. Spirulina tablets are an excellent source of proteins, vitamins and minerals. To obtain information about the bioavailability of these elements, an in vitro bioaccessibility test was performed by application of a two-step protocol which simulated the gastric (pepsin) and intestinal (pancreatin) digestion. The species obtained were investigated by size exclusion chromatography on a chromatograph coupled to a mass spectrometer with inductively coupled plasma (SEC-ICP-MS) and an on-capillary liquid chromatograph coupled to an electrospray mass spectrometer (μ-HPLC-ESI-MS). Both copper and zinc were found to be highly bioaccessible in Spirulina tablets (90-111%) and those containing gluconate complexes (103% for Cu and 62% for Zn). In Spirulina tablets, copper was found to form two types of complex: (1) polar ones with glycine and aspartic acid and (2) more hydrophobic ones containing amino acids with cyclic hydrocarbons (phenylalanine, histidine, proline and tyrosine). Zinc and copper were also proved to form complexes during the digestion process with products of pepsin digestion, but the stability of these complexes is lower than that of the complexes formed in Spirulina. The results proving the involvement of proteins in the enhancement of copper and zinc bioaccessibility will be useful for the design of new copper and zinc supplements.

  1. Antitumor activity of a 2-pyridinecarboxaldehyde 2-pyridinecarboxylic acid hydrazone copper complex and the related mechanism.

    Science.gov (United States)

    Yang, Yingli; Huang, Tengfei; Zhou, Sufeng; Fu, Yun; Liu, Youxun; Yuan, Yanbin; Zhang, Qiongqing; Li, Shaoshan; Li, Changzheng

    2015-09-01

    In the present study, 2-pyridinecarboxaldehyde 2-pyridinecarboxylic acid hydrazone (PPAH) was prepared and its antitumor activity was evaluated. The inhibition of proliferation of PPAH against the HepG2 and HCT-116 cell lines was less effective, yet in the presence of copper ions, the mixture demonstrated excellent antitumor activity (IC50 at 2.75±0.30 µM for the HepG2 cell line, and 1.90±0.20 µM for the HCT-116 cell line, respectively) and the new active species was confirmed to be a PPAH copper complex with a 1:1 ratio by spectral analysis. The excellent antitumor activity of the copper complex prompted us to investigate the underlying mechanism. RT-PCR was performed to detect the changes in the expression of apoptotic genes induced by PPAH and its copper complex. However, no changes were observed when the cells were treated by the agents for 24 or 48 h, indicating that ROS were unlikely involved. Cell cycle analysis showed that both PPAH and its copper complex led to S phase arrest of the cells. The sDNA relaxation assay revealed that the PPAH-copper complex displayed dual topoisomerase inhibition for type I and II. The data suggest that the inhibition of proliferation exhibited by the PPAH copper complex may stem from its dual topoisomerase inhibition, which is rarely observed for a metal complex.

  2. Copper as an antibacterial agent for human pathogenic multidrug resistant Burkholderia cepacia complex bacteria.

    Science.gov (United States)

    Ibrahim, Muhammad; Wang, Fang; Lou, Miao-miao; Xie, Guan-lin; Li, Bin; Bo, Zhu; Zhang, Gou-qing; Liu, He; Wareth, Abdul

    2011-12-01

    The Burkholderia cepacia complex (Bcc) consists of 17 closely related multidrug resistant bacterial species that are difficult to eradicate. Copper has recently gained attention as an antimicrobial agent because of its inhibitory effects on bacteria, yeast, and viruses. The objective of this study was to evaluate the antibacterial activity of copper surfaces and copper powder against members of the B. cepacia complex. The antibacterial activity of different copper surfaces was evaluated by incubating them with Bcc strain suspensions (5×10(7)cfu/ml). The bacterial survival counts were calculated and the data for various copper surfaces were compared to the data for stainless steel and polyvinylchloride, which were used as control surfaces. The antibacterial activity of copper powder was determined with the diffusimetrical technique and the zone of inhibition was evaluated with paper disks. A single cell gel electrophoresis assay, staining assays, and inductively coupled plasma mass spectroscopy were performed to determine the mechanism responsible for the bactericidal activity. The results showed a significant decrease in the viable bacterial count after exposure to copper surfaces. Moreover, the copper powder produced a large zone of inhibition and there was a significantly higher influx of copper ions into the bacterial cells that were exposed to copper surfaces compared to the controls. The present study demonstrates that metallic copper has an antibacterial effect against Bcc bacteria and that copper adversely affects the bacterial cellular structure, thus resulting in cell death. These findings suggest that copper could be utilized in health care facilities to reduce the bioburden of Bcc species, which may protect susceptible members of the community from bacterial infection.

  3. Photochemistry and Redox Chemistry of an Unsymmetrical Bimetallic Copper(I) Complex.

    Science.gov (United States)

    Back, Oliver; Leppin, Jana; Förster, Christoph; Heinze, Katja

    2016-10-03

    The bimetallic copper(I) complex Cu2L2 (cis-1) is formed with high diasteroselectivity from [Cu(NCCH3)4][BF4] and HL (4-tert-butyl phenyl(pyrrolato-2-yl-methylene)amine) in a kinetically controlled reaction. cis-1 features a rather short Cu···Cu distance of 2.4756(6) Å and is weakly emissive at room temperature in solution. Oxidatively triggered disproportionation of cis-1 yields elemental copper and the mononuclear copper(II) complex CuL2 (trans-2). One-electron reduction of trans-2 gives cuprate [2](-) with a bent bis(pyrrolato) coordinated copper(I) entity. The imine donor atoms of [2](-) can insert an additional copper(I) ion giving exclusively the bimetallic complex cis-1 closing the oxidation-elimination-reduction-insertion cycle.

  4. Electrochemical Synthesis and Structural Characterization of a Novel Mixed-valence Copper (I-copper (II Complex: {[Bis(ethylenediamine Copper (II] Bis[diiodocuprate (I]}

    Directory of Open Access Journals (Sweden)

    Mahboobeh Dashti Ardakani

    2007-07-01

    Full Text Available A novel, mixed-valent copper(I-copper(II complex, {[bis(ethylene-diaminecopper(II] bis[diiodocuprate(I]} (1, has been prepared by electrochemicaldissolution of a sacrificial copper anode in a solution of ethylenediamine (en, I2 andtetraethylammoniumperchlorate (TEAP as supporting electrolyte in acetonitrile (AcNand characterized by single-crystal X-ray structure determination. The crystal structure ofthe complex 1 shows that it consists of a CuI2 polymer formed from I- ligands bridgingCu(I ions, with a nearly square planar geometry of bivalente Cu(II atoms chelated by twoethylenediamine ligands. The results also show that direct electrosynthesis of the complexhad high current efficiency, purity and electrolysis yield.

  5. Effects of dissolved and complexed copper on heterotrophic bacterial production in San Diego bay.

    Science.gov (United States)

    Boyd, Thomas J; Wolgast, David M; Rivera-Duarte, Ignacio; Holm-Hansen, Osmund; Hewes, Christopher D; Zirino, Alberto; Chadwick, D Bart

    2005-04-01

    Bacterial abundance and production, free (uncomplexed) copper ion concentration, total dissolved copper concentration, dissolved organic carbon (DOC), total suspended solids (TSS), and chlorophyll a were measured over the course of 1 year in a series of 27 sample "Boxes" established within San Diego Bay. Water was collected through a trace metal-clean system so that each Box's sample was a composite of all the surface water in that Box. Bacterial production, chlorophyll a, TSS, DOC, and dissolved copper all generally increased from Box 1 at the mouth of the Bay to Box 27 in the South or back Bay. Free copper ion concentration generally decreased from Box 1 to Box 27 presumably due to increasing complexation capacity within natural waters. Based on correlations between TSS, chlorophyll a, bacterial production or DOC and the ratio of dissolved to free Cu ion, both DOC and particulate (bacteria and algae) fractions were potentially responsible for copper complexation, each at different times of the year. CuCl2 was added to bacterial production assays from 0 to 10 microg L(-1) to assess acute copper toxicity to the natural microbial assemblage. Interestingly, copper toxicity appeared to increase with decreases in free copper from the mouth of the Bay to the back Bay. This contrasts the free-ion activity model in which higher complexation capacity should afford greater copper protection. When cell-specific growth rates were calculated, faster growing bacteria (i.e. toward the back Bay) appeared to be more susceptible to free copper toxicity. The protecting effect of natural dissolved organic material (DOM) concentrated by tangential flow ultrafiltration (>1 kDa), illite and kaolinite minerals, and glutathione (a metal chelator excreted by algae under copper stress) was assessed in bacterial production assays. Only DOM concentrate offered any significant protection to bacterial production under increased copper concentrations. Although the potential copper protecting

  6. Copper complexes of bioactive ligands with superoxide dismutase activity.

    Science.gov (United States)

    Khalid, Huma; Hanif, Muhammad; Hashmi, Muhammad Ali; Mahmood, Tariq; Ayub, Khurshid; Monim-Ul-Mehboob, Muhammad

    2013-11-01

    Free radicals or reactive oxygen species (ROS) are highly toxic and their damaging effects result in a variety of detrimental health issues such as neurodegenerative, cardiovascular and age-related diseases. Human body has evolved an effective defense system including superoxide dismutase (SOD) and catalase against the toxicity of these free radicals. SOD is a metalloenzyme and it acts as an excellent antioxidant to protect the body from superoxide radicals that are generated in the biological system. However, the clinical use of SOD is limited due to its short in vivo life span, and its large size that hampered its penetration across the cell membranes. Pharmaceuticals that provide ROS scavenging systems are the most effective when the production of ROS exceeds the scavenging capacity of endogenous SOD as a result of aging or pathological processes. Inspired by the Nature, scientists have designed metal-based mimics of the superoxide dismutase. This review focuses on different copper complexes that are developed from bioactive ligands and mimic the protecting action of the SOD.

  7. Salicylaldimine Copper(II) complex catalyst: Pioneer for ring opening Polymerization of Lactide

    Indian Academy of Sciences (India)

    ANITA ROUTARAY; NIBEDITA NATH; TUNGABIDYA MAHARANA; PRATAP KUMAR SAHOO; JAYA PRAKASH DAS; ALEKHA KUMAR SUTAR

    2016-06-01

    Salicylaldimine copper complex has been synthesized and its reactivity for the ring-opening polymerization(ROP) of lactide has been studied. This monomeric copper complex was prepared by the reaction ofcopper(II) solution with one molar equivalent of salicylaldimine Schiff-base ligand in methanol under nitrogenatmosphere. This copper complex has been characterized by different spectroscopic methods, which showedsquare planar geometry. The molecular structure of the salicylaldimine Schiff-base has been determined byX-ray diffraction studies. The complex was tested as the initiator for the ring-opening polymerization of lactide,with variation in diamine group in ligand. The rate of polymerization is dependent on the diamine groupin the following order: ethylene > propylene > phenyl. The salicylaldimine copper complex allows controlledring-opening polymerization as indicated by the linear relationship between the percentage conversion and thenumber-average molecular weight. On the basis of literature reports, a mechanism for ROP of lactide has beenproposed.

  8. On-line electrogeneration of copper-peptide complexes in microspray mass spectrometry.

    Science.gov (United States)

    Prudent, Michel; Girault, Hubert H

    2008-04-01

    The interaction of copper ions with peptides was investigated by electrospray mass spectrometry. Two electrospray micro-emitters were compared, the first one with a platinum electrode using a copper(II) electrolyte solution containing a peptide sample, and the second one with a sacrificial copper anode in a water/methanol solution containing only a peptide (i.e., angiotensin III, bradykinin, or Leu-enkephalin). The former yielded mainly Cu(2+) complexes either with histidine residues or with the peptide backbone (Cu(+) complexes can be also formed due to gas-phase reactions), whereas the latter can generate a mixture of both Cu(+) and Cu(2+) aqueous complexes that yield different complexation patterns. This study shows that electrospray emitters with soluble copper anodes enable the study of Cu(I)-peptide complexes in solution.

  9. Copper complexes bearing 2-aminobenzothiazole derivatives as potential antioxidant: Synthesis, characterization.

    Science.gov (United States)

    Joseph, J; Janaki, G Boomadevi

    2016-09-01

    Novel copper complexes of Schiff base ligands of 2-aminobenzothiazole derivatives were synthesized by the condensation of Knoevenagel condensate of acetoacetanilide (obtained from substituted benzaldehydes and acetoacetanilide) and 2-aminobenzothiazole. They were characterized by elemental analysis, IR, (1)H NMR, UV-Vis., molar conductance, magnetic susceptibility measurements and electrochemical studies. Based on the magnetic moment and electronic spectral data, square planar geometry has been suggested for all the complexes. Antibacterial and antifungal screening of the ligands and their complexes reveal that all the complexes show higher activities than the ligands. The binding behaviour of the complexes with calf thymus DNA has been investigated by electronic absorption spectra, viscosity measurements and cyclic voltammetry. The DNA binding constants reveal that all these complexes interact with DNA through intercalation binding mode. Superoxide dismutase and antioxidant activities of the copper complexes have also been studied. The antioxidant activities of the complexes showed higher activities. Thermal denaturation studies suggested the nature binding affinity of copper complexes with CT-DNA. All complexes exhibit suitable Cu(II)/Cu(I) redox potential to act as antioxidant enzymes mimic. Further, the copper complexes also showed catalase activity. It is hope that copper complexes were capable of decrease ROS levels or reduce oxidative stress in Alzheimer's patients.

  10. Intensification of luminescence of Europium-EDTA complex in polyvinyl pyrrolidone films by copper nanoparticles

    Science.gov (United States)

    Reisfeld, Renata; Levchenko, Viktoria; Lazarowska, Agata; Mahlik, Sebastian; Grinberg, Marek

    2016-09-01

    Stable copper nanoparticles (CuNPs) were prepared and incorporated into polyvinylpyrrolidone (PVP) films together with pre-prepared complex of europium-ethylenediaminetetraacetic acid (EuEDTA). From the comparison of the excitation spectrum of the complex alone and of the complex in conjunction with CuNPs an increased fluorescence intensity of the complex is observed as the result of interaction of the complex with surface plasmons of copper. This effect is maximal when the extinction band of CuNPs coincides with the absorption maximum of the complex, as much more light reaches the excited state of europium in the complex during the excitation events as the result of light scattered by copper plasmons. An additional band was observed in the excitation spectrum of the complex in co-doped by the CuNPs around 320÷390 nm which we attribute to electron transfer from CuNPs to excited state of europium.

  11. Isotactic rac-Lactide Polymerization with Copper Complexes: The Influence of Complex Nuclearity.

    Science.gov (United States)

    Fortun, Solène; Daneshmand, Pargol; Schaper, Frank

    2015-11-09

    Diiminopyrrolide copper alkoxide complexes, LCuOR (OR(1)=N,N-dimethylamino ethoxide, OR(2)=2-pyridyl methoxide), are active for the polymerization of rac-lactide at ambient temperature in benzene to yield polymers with M(w)/M(n)=1.0-1.2. X-ray diffraction studies showed bridged dinuclear complexes in the solid state for both complexes. While LCuOR(1) provided only atactic polylactide, LCuOR(2) produced partially isotactic polylactide (P(m)=0.7). The difference in stereocontrol is attributed to a dinuclear active species for LCuOR(2) in contrast to a mononuclear species for LCuOR(1).

  12. Copper-chelating azides for efficient click conjugation reactions in complex media.

    Science.gov (United States)

    Bevilacqua, Valentina; King, Mathias; Chaumontet, Manon; Nothisen, Marc; Gabillet, Sandra; Buisson, David; Puente, Céline; Wagner, Alain; Taran, Frédéric

    2014-06-02

    The concept of chelation-assisted copper catalysis was employed for the development of new azides that display unprecedented reactivity in the copper(I)-catalyzed azide-alkyne [3+2] cycloaddition (CuAAC) reaction. Azides that bear strong copper-chelating moieties were synthesized; these functional groups allow the formation of azide copper complexes that react almost instantaneously with alkynes under diluted conditions. Efficient ligation occurred at low concentration and in complex media with only one equivalent of copper, which improves the biocompatibility of the CuAAC reaction. Furthermore, such a click reaction allowed the localization of a bioactive compound inside living cells by fluorescence measurements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Study on copper complexing ligand concentrations in several China's coastal waters

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows: Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer (SSL) in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complexing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China' s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.

  14. Spectral studies of copper(II) complexes of 6-(3-thienyl) pyridine-2-thiosemicarbazone

    Energy Technology Data Exchange (ETDEWEB)

    Mahjoub, Omima Abdalla; Farina, Yang [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor (Malaysia)

    2014-09-03

    Two novel copper(II) complexes [Cu(HL)Cl]Cl.H{sub 2}O (1) and [Cu(L)NO{sub 3}]Ðœ‡H{sub 2}O (2) of the three NNS donor thiosemicarbazone ligand 6-(3-thienyl) pyridine-2-thiosemicarbazone have been synthesized. The ligand and its copper(II) complexes were characterized by elemental analysis (C, H, N, and S), FT-IR, UV-visible, magnetic susceptibility and molar conductance. The thiosemicarbazone is present either as the thione form in complex 1 or as thiol form in complex 2 and is coordinated to copper(II) atom via the pyridine nitrogen atom, the azomethine nitrogen atom and the sulfur atom. The physicochemical and spectral data suggest square planar geometry for copper(II) atoms.

  15. Synthesis, characterization and pharmacological studies of copper complexes of flavone derivatives as potential anti-tuberculosis agents.

    Science.gov (United States)

    Joseph, J; Nagashri, K; Suman, A

    2016-09-01

    Novel series of different hydroxyflavone derivatives and their copper complexes were synthesized. They were characterized using analytical and spectral techniques. The superoxide dismutase (SOD) mimetic activity of the synthesized complexes demonstrated that copper complex of L(10) has promising SOD-mimetic activity than other ligands & complexes. The in vitro antimicrobial activities of the synthesized compounds were tested against the bacterial species and fungal species. The DNA binding properties of copper complexes were studied using cyclic voltametry and electronic absorption techniques. Anti-tuberculosis activity was also performed. The effective complexes was subjected to antimycobacterial activity using MABA method and summarized. The antimycobacterial activity of copper complexes have been evaluated and discussed.

  16. 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.

  17. Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction.

    Science.gov (United States)

    Kügler, Merle; Scholz, Julius; Kronz, Andreas; Siewert, Inke

    2016-04-28

    Herein, we report the synthesis and species distribution of copper(ii) complexes based on two different ligand scaffolds and the application of the two complexes in the electrochemical proton reduction catalysis. The ligands bind to one or two copper(II) ions and the pH-dependent mono/dinuclear equilibrium depends on the steric bulk of the ligands. The two water soluble copper(II) complexes were investigated for their activities in the electrochemical hydrogen evolution reaction (HER). In both complexes the copper(ii) ions have a N4-coordination environment composed of N-heterocycles, although in different coordination geometries (SPY-5 and TBPY-5). The solutions of the complexes were highly active catalysts in water at acidic pH but the complexes decompose under catalytic conditions. They act as precursors for highly active copper(0) and Cu2O deposits at the electrode surface, which are in turn the active catalysts. The absence or presence of the ligands has neither an influence on the catalytic activity of the solutions nor an influence on the activity of the deposit formed during controlled potential electrolysis. Finally, we can draw some conclusions on the stability of copper catalysts in the aqueous electrochemical HER.

  18. Synthesis, spectral, photolysis and electrochemical studies of mononuclear copper(II) complex with a new asymmetric tetradentate ligand: Application as copper nanoparticle precursor

    Science.gov (United States)

    Habibi, Mohammad Hossein; Mikhak, Maryam

    2012-10-01

    A copper(II) complex with asymmetric tetradentate Schiff base ligand, obtained by the single condensation of 1,2-diaminopropane with 2-hydroxy-5-methoxy benzaldehyde was prepared. The ligand and complex were characterized by their IR, UV-Vis, FT-IR, NMR spectra and CV. Crystal structures of the mononuclear copper complex have been obtained by X-ray diffraction studies which revealed to be distorted square planner coordination geometry. The spectral data confirm coordination of ligand to copper ion center. The redox properties of complex at different scan rates exhibit grossly similar features consisting of an electrochemically pseudo-reversible Cu(II)/Cu(I) reduction at ca. -0.97 V and pseudo-reversible Cu(I)/Cu(II) oxidation at ca. -0.81 V. The copper nanoparticles with average size of 73 nm were formed by thermal reduction of copper complex in the presence of triphenylphosphine.

  19. Synthesis, spectral, photolysis and electrochemical studies of mononuclear copper(II) complex with a new asymmetric tetradentate ligand: application as copper nanoparticle precursor.

    Science.gov (United States)

    Habibi, Mohammad Hossein; Mikhak, Maryam

    2012-10-01

    A copper(II) complex with asymmetric tetradentate Schiff base ligand, obtained by the single condensation of 1,2-diaminopropane with 2-hydroxy-5-methoxy benzaldehyde was prepared. The ligand and complex were characterized by their IR, UV-Vis, FT-IR, NMR spectra and CV. Crystal structures of the mononuclear copper complex have been obtained by X-ray diffraction studies which revealed to be distorted square planner coordination geometry. The spectral data confirm coordination of ligand to copper ion center. The redox properties of complex at different scan rates exhibit grossly similar features consisting of an electrochemically pseudo-reversible Cu(II)/Cu(I) reduction at ca. -0.97 V and pseudo-reversible Cu(I)/Cu(II) oxidation at ca. -0.81 V. The copper nanoparticles with average size of 73 nm were formed by thermal reduction of copper complex in the presence of triphenylphosphine.

  20. Synthesis, crystal structures and reactivity of copper(I) amidate complexes with aryl halides: insight into copper(I)-catalyzed Goldberg reaction.

    Science.gov (United States)

    Liu, Xinfang; Zhang, Songlin; Ding, Yuqiang

    2012-05-21

    In this paper, copper(I) amidate complexes (2-3), proposed intermediates in copper-catalyzed Goldberg reaction, have been prepared and characterized by elemental analysis, IR, (1)H NMR and X-ray crystallography. Ancillary ligand bis(diphenylphosphino)ferrocene (dppf) has contributed greatly to the stability of the copper-amidate complexes due to its strong chelating ability and weak intermolecular interactions. Thermal gravimetric analyses are carried out to determine the thermal competency of complexes 2-3 as the intermediates of the high-temperature Goldberg reactions. Reaction of complexes 2 and 3 with aryl halides generates the N-arylation products 5-8, accompanied by the formation of a copper(I) complex Cu(dppf)X (X = I or Br) 4, which has been determined by LC-MS analysis. These results provide new evidence for the mechanism of copper(I)-catalyzed Goldberg reaction.

  1. A novel spectrophotometric determination of trace copper based on charge transfer complex

    Science.gov (United States)

    Di, Junwei; Wu, Ying; Ma, Yun

    2005-03-01

    A new type of colored complex, the charge transfer complex, was used to develop the spectrophotometric determination of copper. The method was based on the formation of a colored product, the charge transfer complex of copper substituted tungstophosphate with 3,3',5,5'-tetramethybenzidine (TMB), which was stabilized and sensitized by the addition of polyvinyl alcohol (PVA) in aqueous solution. The structure of copper substituted tungstophosphate was Keggin-type according to the results of infrared (IR) spectra. The optimum reaction conditions and other important analytic parameters had been investigated. Beer's law was obeyed in the copper(II) concentration range of 0.003-0.1 μg mL -1, and the molar absorptivity at 660 nm is 2.54×10 5 L mol -1 cm -1. The proposed method was simple, selective, and sensitive. It was applied to the analytic samples with satisfactory results.

  2. Supramolecular control of a mononuclear biomimetic copper(II) center: bowl complexes vs funnel complexes.

    Science.gov (United States)

    Gout, Jérôme; Višnjevac, Aleksandar; Rat, Stéphanie; Parrot, Arnaud; Hessani, Assia; Bistri, Olivia; Le Poul, Nicolas; Le Mest, Yves; Reinaud, Olivia

    2014-06-16

    Modeling the mononuclear site of copper enzymes is important for a better understanding of the factors controlling the reactivity of the metal center. A major difficulty stems from the difficult control of the nuclearity while maintaining free sites open to coordination of exogenous ligands. A supramolecular approach consists in associating a hydrophobic cavity to a tripodal ligand that will define the coordination spheres as well as access to the metal ion. Here, we describe the synthesis of a bowl Cu(II) complex based on the resorcinarene scaffold. This study supplements a previous work on Cu(I) coordination. It provides a complete picture of the cavity-copper system in its two oxidation states. The first XRD structure of such a bowl complex was obtained, evidencing a 5-coordinate Cu(II) ion with the three imidazole donors bound to the metal (two in the base of the pyramid, one in the apical position) and with an acetate anion, completing the base of the pyramid, and deeply included in the bowl. Solution studies conducted by EPR and UV-vis absorption spectroscopies as well as cyclic voltammetry highlighted interaction with coordinating solvents, various carboxylates that can sit either in the endo or in the exo position depending on their size as well as possible stabilization of hydroxo species in a mononuclear state. A comparison of the binding and redox properties of the bowl complex with funnel complexes based on the calix[6]arene core further highlights the importance of supramolecular features defining the first, second, and third coordination sphere for control of the metal ion.

  3. Alkynyl functionalized iminopyridine copper(I) phosphine complexes: Synthesis, spectroscopic characterization and photophysical properties

    Energy Technology Data Exchange (ETDEWEB)

    Jadhav, A.N.; Chavan, S.S., E-mail: sanjaycha2@rediffmail.com

    2014-04-15

    Some copper(I) complexes of type [Cu(L{sub 1})(PPh{sub 3}){sub 2}/(dppe)]X (1a–6a) and [Cu(L{sub 2})(PPh{sub 3}){sub 2}/(dppe)]X (1b–6b) [where L{sub 1}=N-(2-pyridylmethylene)-4-(trimethylsilylethynyl)aniline, L{sub 2}=N-(2-pyridylmethylene)-4-(phenylethynyl)aniline, PPh{sub 3}=triphenylphosphine, dppe=1,2-bis(diphenylphosphino)ethane, and X=ClO{sub 4}{sup −}, BF{sub 4}{sup −} and PF{sub 6}{sup −}] have been prepared and characterized on the basis of their elemental analyses and spectroscopic studies (IR, UV–visible, {sup 1}H NMR and {sup 31}P NMR). The representative complex of the series [Cu(L{sub 2})(PPh{sub 3}){sub 2}]ClO{sub 4}{sup −} (1b) has been characterized by single crystal X-ray diffraction which reveals that in the complex the central copper(I) ion assumes highly distorted-tetrahedral geometry. The UV–visible spectra indicate that the ancillary phosphine ligands significantly perturb the MLCT state of copper(I) complexes. Room temperature luminescence is observed for all copper(I) complexes in dichloromethane solution, indicating that alkynyl functionality on iminopyridine ligands enhances the emission property of copper(I) complexes and varies considerably with ancillary phosphine ligands. The thermal behavior of complexes revealed that copper(I) complexes with dppe ligand are thermally more stable than PPh{sub 3} complexes. All the complexes exhibit a quasireversible redox behavior corresponding to Cu(I)/Cu(II) couple and are sensitive to phosphine ligand. -- Highlights: • Synthesis of copper(I) complexes of alkynyl functionalized Schiff base. • Characterization by elemental analyses, IR, {sup 1}H NMR and {sup 31}P NMR spectral studies. • Electrochemical properties indicate a quasireversible redox behavior for all copper(I) complexes • All the copper(I) complexes exhibit intraligand (π→π{sup ⁎}) luminescence in dichloromethane.

  4. 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.

  5. Antitubercular and fluorescence studies of copper(II) complexes with quinolone family member, ciprofloxacin

    Science.gov (United States)

    Kharadi, G. J.

    2011-09-01

    Four new mixed-ligand complexes of Cu(II) with ciprofloxacin (Cip) and uninegative bidentate ligands have been synthesized and characterized. The structure of mixed-ligand complexes was investigated using spectroscopic method, physicochemical and elemental analyses. The fluorescence spectra of complexes show red shift, which may be due to the chelation by the ligands to the metal ion. It enhances ligand ability to accept electrons and decreases the electron transition energy. Antimycobacterial screening of ligand and its copper compound against Mycobacterium tuberculosis shows clear enhancement in the antitubercular activity upon copper complexation.

  6. Magnetic Interactions in the Copper Complex (L-Aspartato)(1,10-phenanthroline)copper(II) Hydrate. An Exchange-Coupled Extended System with Two Dissimilar Copper Ions.

    Science.gov (United States)

    Brondino, Carlos D.; Calvo, Rafael; Atria, Ana María; Spodine, Evgenia; Nascimento, Otaciro R.; Peña, Octavio

    1997-07-02

    We report EPR measurements in single-crystal samples at the microwave frequencies 9.8 and 34.3 GHz and magnetic susceptibility measurements in polycrystalline samples for the ternary complex of copper with aspartic acid and phenanthroline, (L-aspartato)(1,10-phenanthroline)copper(II) hydrate. The crystal lattice of this compound is composed of two dissimilar copper ions identified as Cu(A) and Cu(B), which are in two types of copper chains called A and B, respectively, running parallel to the b crystal axis. The copper ions in the A chains are connected by the aspartic acid molecule, and those in the B chains by a chemical path that involves a carboxylate bridge and a hydrogen bond. Both chains are held together by a complex network of hydrogen bonds and by hydrophobic interactions between aromatic amines. Magnetic susceptibility data indicate a Curie-Weiss behavior in the studied temperature range (2-300 K). The EPR spectra at 9.8 GHz display a single exchange collapsed resonance for any magnetic field orientation, in the so-called strong exchange regime. Those at 34.3 GHz are within the so-called weak exchange regime and display two resonances which belong to each type of copper ion chain. The decoupling of the spectra at 34.3 GHz using a theory based on Anderson's model for the case of two weakly exchange coupled spins S = (1)/(2) allows one to obtain the angular variation of the squares of the g-factor and the peak-to-peak line width of each resonance. This model also allows one to evaluate the exchange parameter |J(AB)/k| = 2.7(6) mK associated with the chemical path connecting dissimilar copper ions. The line width data obtained for each component of the spectra at 34.3 GHz are analyzed in terms of a model based on Kubo and Tomita's theory, to obtain the exchange parameters |J(A)/k| = 0.77(2) K and |J(B)/k| = 1.44(2) K associated with the chemical paths connecting the similar copper ions of types A and B, respectively.

  7. Low-temperature operation of copper-vapor lasers by using vapor-complex reaction of metallic copper and metal halide

    OpenAIRE

    Saito, Hiroshi; Taniguchi, Hiroshi

    1985-01-01

    The first successful use of vapor-complex reactions for a laser is reported. Vapor-complex reactions between metallic copper and metal halides are found effective in reducing the operating temperature in copper-vapor lasers. By using a vapor-complex reaction of Cu+AlBr3, a laser oscillation starts at a reservoir temperature of about 25°C. The results obtained by the mass spectroscopic analysis support the presumption that the copper vapor is generated through a vapor-complex reaction process.

  8. Metalloselenonein, the selenium analogue of metallothionein: synthesis and characterization of its complex with copper ions.

    Science.gov (United States)

    Oikawa, T; Esaki, N; Tanaka, H; Soda, K

    1991-01-01

    We used an automated peptide synthesizer to produce a peptide, metalloselenonein, that contains selenocysteine residues substituted for all cysteine residues in Neurospora crassa copper metallothionein. Metalloselenonein binds 3 mol of Cu(I) per mol. This adduct shows a broad absorption band between 230 and 400 nm and a fluorescence band at 395 nm, which can be attributed to copper-selenolate coordination. The circular dichroism spectrum of the copper-metalloselenonein complex shows a positive band around 245 nm attributable to asymmetry in metal coordination. PMID:1826562

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

    Directory of Open Access Journals (Sweden)

    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.

  10. Thiopyridazine-Based Copper Boratrane Complexes Demonstrating the Z-type Nature of the Ligand.

    Science.gov (United States)

    Holler, Stefan; Tüchler, Michael; Belaj, Ferdinand; Veiros, Luis F; Kirchner, Karl; Mösch-Zanetti, Nadia C

    2016-05-16

    In Z-type ligands the electrons for the coordination bond are formally provided by the metal. They represent an important addition to the much more extensively used L- and X-type σ-donor ligands for the development of transition metal complexes with new reactivities. We report here a new boron Z-type ligand with three tethering thiopyridazinyl donors forming exclusively complexes that feature a metal boron bond. Rational substitution pattern in the backbone of the pyridazinyl heterocycle led to a well-behaved ligand system that allowed preparation of a series of copper boratrane complexes in high yields. They are found to be more soluble in common organic solvents allowing reactivity studies in contrast to previous complexes with this type of ligand. Thus, copper complexes [Cu{B(Pn(Me,tBu))3}X] with X = Cl, OTf, N3, and κN-NCS are reported. Solution behavior was explored, and the molecular structures were determined by single-crystal X-ray diffraction analyses. The thiocyanate ligand is found to coordinate via its nitrogen atom pointing to a high oxidation state of the copper. Density functional theory calculations indicate a high positive charge on copper and a strong copper-boron interaction. Thus, here reported complexes deliver synthetic evidence for the Z-type nature of the ligand. These findings are important for further dissemination of these types of ligands in coordination chemistry.

  11. Intracellular distribution of fluorescent copper and zinc bis(thiosemicarbazonato) complexes measured with fluorescence lifetime spectroscopy.

    Science.gov (United States)

    Hickey, James L; James, Janine L; Henderson, Clare A; Price, Katherine A; Mot, Alexandra I; Buncic, Gojko; Crouch, Peter J; White, Jonathan M; White, Anthony R; Smith, Trevor A; Donnelly, Paul S

    2015-10-05

    The intracellular distribution of fluorescently labeled copper and zinc bis(thiosemicarbazonato) complexes was investigated in M17 neuroblastoma cells and primary cortical neurons with a view to providing insights into the neuroprotective activity of a copper bis(thiosemicarbazonato) complex known as Cu(II)(atsm). Time-resolved fluorescence measurements allowed the identification of the Cu(II) and Zn(II) complexes as well as the free ligand inside the cells by virtue of the distinct fluorescence lifetime of each species. Confocal fluorescent microscopy of cells treated with the fluorescent copper(II)bis(thiosemicarbazonato) complex revealed significant fluorescence associated with cytoplasmic puncta that were identified to be lysosomes in primary cortical neurons and both lipid droplets and lysosomes in M17 neuroblastoma cells. Fluorescence lifetime imaging microscopy confirmed that the fluorescence signal emanating from the lipid droplets could be attributed to the copper(II) complex but also that some degree of loss of the metal ion led to diffuse cytosolic fluorescence that could be attributed to the metal-free ligand. The accumulation of the copper(II) complex in lipid droplets could be relevant to the neuroprotective activity of Cu(II)(atsm) in models of amyotrophic lateral sclerosis and Parkinson's disease.

  12. The crystal and molecular structure of copper(I) trifluoromethanesulphonate cyclohexene complex

    NARCIS (Netherlands)

    Timmermans, P.J.J.A.; Mackor, A.; Spek, A.L.; Kojic-Prodic, B.

    1984-01-01

    The first crystal structure of a copper(I) trifluoromethanesulphonate (cyclo)olefin complex, viz. copper(I) triflate-cyclohexene, CuOSO2CF3 · C6H10, is presented. The compound crystallises in the space group P with a 10.288(1), b 10.412(1), c 11.059(1) Å, α 65.81(1), β 81.25(1), γ 70.45(1)° and Z =

  13. The formation of copper sulphide semiconductors inside Langmuir–Blodgett films of Cu(II) ion complexes

    NARCIS (Netherlands)

    Werkman, P.J.; Wieringa, R.H.; Schouten, A.J.

    1998-01-01

    The fabrication of layers of copper sulphide within multilayers of copper complexes of the amphiphile 4-(10,12-pentacosadiynamido methyl pyridine, by diffusion of H2S into the multilayers, was studied by UV–VIS spectroscopy. XPS measurements revealed that copper sulphides can be synthesised which di

  14. Reaction of beta-diketiminate copper(II) complexes and Na2S2.

    Science.gov (United States)

    Inosako, Masayuki; Kunishita, Atsushi; Shimokawa, Chizu; Teraoka, Junji; Kubo, Minoru; Ogura, Takashi; Sugimoto, Hideki; Itoh, Shinobu

    2008-11-28

    Reaction of beta-diketiminate copper(II) complexes and Na2S2 resulted in formation of (mu-eta2:eta2-disulfido)dicopper(II) complexes (adduct formation) or beta-diketiminate copper(I) complexes (reduction of copper(II)) depending on the substituents of the supporting ligands. In the case of sterically less demanding ligands, adduct formation occurred to provide the (mu-eta2:eta2-disulfido)dicopper(II) complexes, whereas reduction of copper(II) took place to give the corresponding copper(I) complexes with sterically more demanding beta-diketiminate ligands. Spectroscopic examinations of the reactions at low temperature using UV-vis and ESR as well as kinetic analysis have suggested that a 1 : 1 adduct LCuII-S-SNa with an end-on binding mode is initially formed as a common intermediate, from which different reaction pathways exist depending on the steric environment of the metal-coordination sphere provided by the ligands. Thus, with the sterically less demanding ligands, rearrangement of the disulfide adduct from end-on to side-on followed by self-dimerisation occurs to give the (mu-eta2:eta2-disulfido)dicopper(II) complexes, whereas such an intramolecular rearrangement of the disulfide co-ligand does not take place with the sterically more demanding ligands. In this case, homolytic cleavage of the CuII-S bond occurs to give the reduced copper(I) product. The steric effects of the supporting ligands have been discussed on the basis of detailed analysis of the crystal structures of the copper(II) starting materials.

  15. Salt-marsh areas as copper complexing ligand sources to estuarine and coastal systems.

    Science.gov (United States)

    Santos-Echeandía, Juan; Caetano, Miguel; Laglera, Luis M; Vale, Carlos

    2013-01-01

    Dissolved copper levels, copper complexing capacities and conditional stability constants have been determined in the Tagus estuarine waters and one of the saltmarshes located in this estuary, the Rosario saltmarsh. Tagus estuarine waters show a constant and around 20 nM copper concentration during the estuarine mixing. Most of this copper is organically complexed by a strong ligand (L(1)) with a concentration that varies between 19 and 55 nM and a log K' between 14.14 and 15.75. In addition L(1)/Cu ratios are quite constants and close to 1 all through the estuary, indicating the same source. A second and weaker ligand (L(2)) was also detected in these waters in higher concentrations (36-368 nM) but with a lower log K' that varies between 12.06 and 13.13. The present work has demonstrated that salt-marsh areas are important and continuous sources of copper complexing ligands to the Tagus estuary. Noticeable, tidal induced transport continuously feed these waters with copper and ligands, mainly with the stronger one. This continuous input, together with the high residence times of this system results in a quite constant concentration along the salinity gradient. This input represents 95% of the ligand present in the estuary. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Determination of copper(I) and copper(II) ions after complexation with bicinchoninic acid by CE.

    Science.gov (United States)

    Basheer, Chanbasha; Lee, Hian Kee

    2007-10-01

    A facile, sensitive, and selective method was developed for the simultaneous separation and determination of copper(I) [Cu(+)] and copper(II) [Cu(2+)] ions using CE with direct UV detection. The copper ions were complexed with a 1.5 mM bicinchoninic acid disodium salt solution at pH 8.7 prior to analysis. Acetate buffer (2 mM) was used as the CE running buffer. Parameters affecting CE separation such as sample pH, applied voltage, concentration of complexing agent, nature of the buffer solution, and interferences by other metal ions, were evaluated. The LODs for Cu(+) and Cu(2+) were 3.0 and 2.5 microg/mL (S/N = 3), respectively. The developed method allows the simultaneous determination of Cu(+) and Cu(2+) in less than 5 min with RSDs of between 5.3 and 9.5% for migration time and between 3.4 and 9.7% for peak areas, respectively. At optimum conditions, the percentage recoveries of Cu(+) and Cu(2+) were found to be 99.4 and 99.5%.

  17. Reactivity of copper-α-synuclein peptide complexes relevant to Parkinson's disease.

    Science.gov (United States)

    Dell'Acqua, Simone; Pirota, Valentina; Anzani, Cecilia; Rocco, Michela M; Nicolis, Stefania; Valensin, Daniela; Monzani, Enrico; Casella, Luigi

    2015-07-01

    Parkinson's disease (PD) is a neurodegenerative disorder characterized by the presence of abnormal α-synuclein (αSyn) deposits in the brain. Alterations in metal homeostasis and metal-induced oxidative stress may play a crucial role in the aggregation of αSyn and, consequently, in the pathogenesis of PD. We have therefore investigated the capability of copper-αSyn6 and copper-αSyn15 peptide complexes, with the 1-6 and 1-15 terminal fragments of the protein, to promote redox reactions that can be harmful to other cellular components. The pseudo-tyrosinase activity of copper-αSyn complexes against catecholic (di-tert-butylcatechol (DTBCH2), 4-methylcatechol (4-MC)) and phenolic (phenol) substrates is lower compared to that of free copper(II). In particular, the rates (kcat) of DTBCH2 catalytic oxidation are 0.030 s(-1) and 0.009 s(-1) for the reaction promoted by free copper(II) and [Cu(2+)-αSyn15], respectively. On the other hand, HPLC/ESI-MS analysis of solutions of αSyn15 incubated with copper(II) and 4-MC showed that αSyn is competitively oxidized with remarkable formation of sulfoxide at Met1 and Met5 residues. Moreover, the sulfoxidation of methionine residues, which is related to the aggregation of αSyn, also occurs on peptides not directly bound to copper, indicating that external αSyn can also be oxidized by copper. Therefore, this study strengthens the hypothesis that copper plays an important role in oxidative damage of αSyn which is proposed to be strongly related to the etiology of PD.

  18. Inhibitory effect of Disulfiram/copper complex on non-small cell lung cancer cells.

    Science.gov (United States)

    Duan, Lincan; Shen, Hongmei; Zhao, Guangqiang; Yang, Runxiang; Cai, Xinyi; Zhang, Lijuan; Jin, Congguo; Huang, Yunchao

    2014-04-18

    Non-small cell lung cancer (NSCLC) is the most common cause of cancer-related death in both men and women worldwide. Recently, Disulfiram has been reported to be able to inhibit glioblastoma, prostate, or breast cancer cell proliferation. In this study, the synergistic effect of Disulfiram and copper on NSCLC cell growth was investigated. Inhibition of cancer cell proliferation was detected by 1-(4,5-Dimethylthiazol-2-yl)-3,5-diphenylformazan (MTT) assay and cell cycle analysis. Liquid colony formation and tumor spheroid formation assays were used to evaluate their effect on cancer cell clonogenicity. Real-time PCR was performed to test the mRNA level of cancer stem cell related genes. We found that Disulfiram or copper alone did not potently inhibit NSCLC cell proliferation in vitro. However, the presence of copper significantly enhanced inhibitory effect of Disulfiram on NSCLC cell growth, indicating a synergistic effect between Disulfiram and copper. Cell cycle analysis showed that Disulfiram/copper complex caused NSCLC cell cycle arrest in G2/M phase. Furthermore, Disulfiram/copper significantly increased the sensitivity of cisplatin in NSCLC cells tested by MTT assay. Liquid colony formation assay revealed that copper dramatically increased the inhibitory effect of Disulfiram on NSCLC cell colony forming ability. Disulfiram combined with copper significantly attenuated NSCLC cell spheroid formation and recuded the mRNA expression of lung cancer stem cell related genes. Our data suggest that Disulfiram/copper complex alone or combined with other chemotherapy is a potential therapeutic strategy for NSCLC patients.

  19. Effects of copper-aspirin complex on platelet-neutrophil interactions

    Institute of Scientific and Technical Information of China (English)

    Zhi-qiang SHEN; Peng CHEN; Ling LI; Peng CHEN; Wei-ping LIU

    2004-01-01

    AIM: To investigate the effects of copper-aspirin complex on rat thrombosis and the interaction between platelets and neutrophils. METHODS: The model of electrically stimulated carotid artery thrombosis in Sprague Dawley rats was used; the effects of copper-aspirin complex on rat platelet-neutrophil adhesion and platelet aggregation stimulated by activated neutrophils were observed by rosette assay and Born's method, respectively. RESULTS:Intragastric copper-aspirin complex (5, 7, and 10 mg/kg) dose-dependently prolonged the occlusion time; it significantly decreased the rosette number formed between thrombin-activated platelets and neutrophils; the 50 % of inhibitory concentration (IC50) was (54.6±4.3) μmol/L. Copper-aspirin complex markedly inhibited rat platelet aggregation induced by either cell free supernatant of activated neutrophils or by activated neutrophil suspension.The values of IC50 were (224.5±16.2) μmol/L and (820.5±21.4) μmol/L, whereas aspirin had no influence.CONCLUSION: Copper-aspirin complex inhibited platelet-neutrophil interactions through a different property from aspirin and resulted in a more potent antithrombotic activity.

  20. Study on the Crystal Structure of a Macrocycle and Tyrosinase Activity of Its Dinuclear Copper Complexes

    Institute of Scientific and Technical Information of China (English)

    周红; 潘志权; 罗勤慧; 梅光泉; 龙德良; 陈久桐

    2005-01-01

    A ring-contracted form macrocycle, 29,30-dioxo-3,6,9,17,20,23,29,30-octaazapentacyclo[23,3,1,111,15,02,6,016,20]-triacontaneocta- 1 (28),9,11 (12), 13,15(30),23,25(29),26-ene (L) was synthesized by condensation of diethyltriamine with pyridine-1-oxide-2,6-dicarboxaldehyde. A porous three-dimensional layer structure in its crystal was formed by self-assembly through hydrogen bonds and π-π interaction. Its dinuclear copper(I) complex [Cu2L(MeOH)2]-(BF4)2*2H2O and dinuclear-copper(II) complex [Cu2L(MeOH)2](ClO4)4*2H2O were obtained and could oxidize catalytically four phenolic substrates hydroquinone, 2-methyl-hydroquinone, 2,6-di-tert-butylphenol and 2,6-dimethylphenol, in a mixture of methanol and acetonitrile (V : V, 4 : 1). The copper(I) complex reacted with dioxygen to form an oxygenated species as an initial active intermediate for oxidation of the phenols. Oxidation of the substrates by the copper(II) complex produced a copper(I) complex and the oxidation products of the substrates.

  1. 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 m

  2. Characterisation of covalent copper and manganese organometallic complexes with Schiff bases by ionspray mass spectrometry

    NARCIS (Netherlands)

    Raffaelli, A.; Minutolo, F.; Feringa, B.L.; Salvadori, P.

    1998-01-01

    Copper and manganese complexes containing Schiff bases as ligands, having potential interest in homogeneous catalysis, have been characterised by mass spectrometry using ionspray ionisation. Single stage mass spectrometry allowed us to confirm the molecular weight of complexes in all cases, providin

  3. 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 m

  4. Bimetallic Oxidation Catalysts. Oxygen Insertion into an Aryl–Hydrogen Bond of a Binuclear Copper(I) Complex

    NARCIS (Netherlands)

    Gelling, O.J.; Bolhuis, F. van; Meetsma, A.; Feringa, Bernard

    1988-01-01

    The binuclear copper(I) complex of 1,3-bis[N-(2-pyridylethyl)formimidoyl]benzene reacts with molecular oxygen to give a phenoxy- and hydroxy-bridged binuclear copper(II) complex; the structures of both complexes have been determined by X-ray crystallography.

  5. Competitive Complexation of Copper and Zinc by Sequentially Extracted Humic Substances from Manure Compost

    Institute of Scientific and Technical Information of China (English)

    LIU Shuai; WANG Xu-dong; LU Li-lan; DIAO Shi-rong; ZHANG Jun-feng

    2008-01-01

    Chicken manure with similar content of copper and zinc was chosen to conduct a composting experiment to investigate the changes of organic carbon and humus substance complexed copper (HS-Cu) and zinc (HS-Zn), which were extracted by water (H2O), sodium hydroxide (NaOH), and sodium pyrophate-NaOH mixture (Na4P2O7-NaOH), sequentially. Distributions of copper and zinc in fulvic acids (FA) and humic acids (HA) in the three extracts were studied. During manure composting, the concentrations of copper and zinc increased from about 500 mg kg-' in the raw material to 1100 mg kg-1 in the final products. HS-Cu in H2O, NaOH, and Na4P2O7-NaOH extracts occupied 6.7, 26.7, and 19% averagely of total copper and HS-Zn represented 2.7, 13.7, and 17% averagely of total zinc in compost, respectively. In water extracts, both HA and FA mainly complexed with Cu and the mole ratio of Cu to Zn was 2.8 in HA fractions and was 2.6 in FA fractions, respectively. HA mainly complexed with copper, so that the ratios of HA-Cu to HA-Zn averaged 3.4 in NaOH extracts. FA had a similar potential to complex with copper and zinc, so that the ratio of FA-Cu to FA-Zn was close to 1. In Na4P2O7-NaOH extracts, HA or FA had a similar potential to complex with copper and zinc. The ratio of HS-Cu to HS-Zn was close to 1. With manure composting, Na4P2O7-NaOH extractable HS-Zn increased to a level as high as HS-Cu. This indicated that more and more stable complexes of HS-Zn were formed in the late decomposition period. The competition between copper and zinc to be complexed with humic substance became weaker and weaker with the decomposition process.

  6. Copper complexation of methanobactin isolated from Methylosinus trichosporium OB3b: pH-dependent speciation and modeling.

    Science.gov (United States)

    Pesch, Marie-Laure; Christl, Iso; Hoffmann, Martin; Kraemer, Stephan M; Kretzschmar, Ruben

    2012-11-01

    Methanobactins are copper-binding ligands produced by aerobic methanotrophic microorganisms. A quantitative understanding of their potential role in methanotrophic copper acquisition requires the investigation of their copper complexes under relevant pH conditions. In this study, a chemical speciation model describing the pH-dependence of copper binding and the formation of the different complexes by methanobactin (mb) is released by Methylosinus trichosporium OB3b was developed. Potentiometric and spectrophotometric titrations of the free ligand indicated the presence of four protonation sites consistent with the molecular structure of methanobactin. Metal titrations revealed a distinct pH-dependence of copper binding to methanobactin between pH 5 and 8. Based on evidence from size-exclusion chromatography coupled to inductively coupled plasma mass spectrometry (ICP-MS), the copper binding was quantitatively described with three different types of copper-methanobactin complexes which can additionally undergo protonation reactions. The high affinity observed upon initial copper additions resulted from the predominant occurrence of copper-methanobactin dimer complexes, mb(2)H(4)Cu and mb(2)H(3)Cu with log K values of 58 and 52, respectively. With increasing copper to methanobactin ratios, methanobactin bound copper as monomers, mbHCu (log K=25) and mbCu (log K=18), whereas at elevated copper activities methanobactin was able to bind two copper ions (mbHCu(2) and mbCu(2)). Model calculations based on the fitted complexation constants suggest that in natural systems, copper-methanobactin complexes are mostly present as monomers.

  7. Hybrid copper complex-derived conductive patterns printed on polyimide substrates

    Science.gov (United States)

    Lee, Byoungyoon; Jeong, Sooncheol; Kim, Yoonhyun; Jeong, Inbum; Woo, Kyoohee; Moon, Jooho

    2012-06-01

    We synthesized new copper complexes that can be readily converted into highly conductive Cu film. Mechanochemical milling of copper (I) oxide suspended in formic acid resulted in the submicron-sized Cu formate together Cu nanoparticles. The submicrometer-sized Cu formates are reactive toward inter-particle sintering and metallic Cu seeds present in the Cu complexes assist their decomposition and the nucleation of Cu. The hybrid copper complex film printed on polyimide substrate is decomposed into dense and uniform Cu layer after annealing at 250 °C for 30 min under nitrogen atmosphere. The resulting Cu film exhibited a low resistivity of 8.2 μΩ·cm and good adhesion characteristics.

  8. Diethyldithiocarbamate complex with copper: the mechanism of action in cancer cells.

    Science.gov (United States)

    Skrott, Zdenek; Cvek, Boris

    2012-10-01

    The idea of "repurposing" of existing drugs provides an effective way to develop and identify new therapies. Disulfiram (Antabuse), a drug commonly used for the treatment of alcoholism, shows promising anticancer activity in both preclinical and clinical studies. In the human body, disulfiram is rapidly converted to its reduced metabolite, diethyldithiocarbamate. If copper ions are available, a bis(diethyldithiocarbamate)-copper(II) complex is formed. Disulfiram's selective anticancer activity is attributed to the copper(II) complex's ability to inhibit the cellular proteasome. It is assumed that the complex inhibits the proteasome by a mechanism that is distinct to the clinically used drug bortezomib, targeting the 19S rather than the 20S proteasome. This difference could be explained by inhibition of the JAMM domain of the POH1 subunit within the lid of the 19S proteasome.

  9. A tri-copper(II) complex displaying DNA-cleaving properties and antiproliferative activity against cancer cells.

    Science.gov (United States)

    Suntharalingam, Kogularamanan; Hunt, Douglas J; Duarte, Alexandra A; White, Andrew J P; Mann, David J; Vilar, Ramon

    2012-11-19

    A new disubstituted terpyridine ligand and the corresponding tri-copper(II) complex have been prepared and characterised. The binding affinity and binding mode of this tri-copper complex (as well as the previously reported mono- and di-copper analogues) towards duplex DNA were determined by using UV/Vis spectroscopic titrations and fluorescent indicator displacement (FID) assays. These studies showed the three complexes to bind moderately (in the order of 10(4)  M(-1)) to duplex DNA (ct-DNA and a 26-mer sequence). Furthermore, the number of copper centres and the nature of the substituents were found to play a significant role in defining the binding mode (intercalative or groove binding). The nuclease potential of the three complexes was investigated by using circular plasmid DNA as a substrate and analysing the products by agarose-gel electrophoresis. The cleaving activity was found to be dependent on the number of copper centres present (cleaving potency was in the order: tri-copper>di-copper>mono-copper). Interestingly, the tri-copper complex was able to cleave DNA without the need of external co-reductants. As this complex displayed the most promising nuclease properties, cell-based studies were carried out to establish if there was a direct link between DNA cleavage and cellular toxicity. The tri-copper complex displayed high cytotoxicity against four cancer cell lines. Of particular interest was that it displayed high cytotoxicity against the cisplatin-resistant MOLT-4 leukaemia cell line. Cellular uptake studies showed that the tri-copper complex was able to enter the cell and more importantly localise in the nucleus. Immunoblotting analysis (used to monitor changes in protein levels related to the DNA damage response pathway) and DNA-flow cytometric studies suggested that this tri-copper(II) complex is able to induce cellular DNA damage. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis, structural characterization and biological studies of copper complexes with 2-aminobenzothiazole derivatives

    Science.gov (United States)

    Joseph, J.; Boomadevi Janaki, G.

    2014-04-01

    Novel copper complexes of 2-aminobenzothiazole derivatives were synthesized by the condensation of Knoevenagel condensate acetoacetanilide (obtained from substituted benzaldehydes and acetoacetanilide) and 2-aminobenzothiazole. They were thoroughly characterized by elemental analysis, IR, 1H NMR, UV-Vis., MS Spectra, molar conductance, magnetic moment and electrochemical studies. These spectral studies suggested that distorted square planar geometry for all the complexes. Molar conductance data and magnetic susceptibility measurements provide evidence for monomeric and neutral nature of the complexes. The electrochemical behaviour of the ligand and complexes in DMSO at 298 K was studied. The present ligand systems stabilize the unusual oxidation states of copper ion during electrolysis. Antibacterial screening of the ligands and their complexes reveal that all the complexes show higher activities than the free ligands.

  11. 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.

  12. 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.

  13. 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.)

  14. Copper(I)-N-heterocyclic carbene (NHC) complexes : synthesis, characterisation and applications in synthesis and catalysis

    OpenAIRE

    Santoro, Orlando

    2016-01-01

    The work described herein focuses on the synthesis and characterisation of copper(I) complexes bearing N-heterocyclic carbene (NHC) ligands, their use in catalysis as well as organometallic synthesis and related reaction mechanisms. Two classes of complexes were considered: neutral NHC-Cu(I) species and their cationic analogues. Concerning the former, initial efforts were focused on the development of a general and straightforward synthetic methodology towards complexes of the type [Cu(X)(...

  15. Reactivity of mononuclear alkylperoxo copper(II) complex. O-O bond cleavage and C-H bond activation.

    Science.gov (United States)

    Kunishita, Atsushi; Ishimaru, Hirohito; Nakashima, Satoru; Ogura, Takashi; Itoh, Shinobu

    2008-04-02

    A detailed reactivity study has been carried out for the first time on a new mononuclear alkylperoxo copper(II) complex, which is generated by the reaction of copper(II) complex supported by the bis(pyridylmethyl)amine tridentate ligand containing a phenyl group at the 6-position of the pyridine donor groups and cumene hydroperoxide (CmOOH) in CH3CN. The cumylperoxo copper(II) complex thus obtained has been found to undergo homolytic cleavage of the O-O bond and induce C-H bond activation of exogenous substrates, providing important insights into the catalytic mechanism of copper monooxygenases.

  16. Copper(II) complexes of prion protein PEG11-tetraoctarepeat fragment: spectroscopic and voltammetric studies.

    Science.gov (United States)

    Bonomo, Raffaele P; Di Natale, Giuseppe; Rizzarelli, Enrico; Tabbì, Giovanni; Vagliasindi, Laura I

    2009-04-14

    Spectroscopic (UV-Vis and EPR) and voltammetric studies have been carried out on the copper(II) complexes with the Ac-PEG11-(PHGGGWGQ)4-NH2 (L) polypeptide. In the ratios Cu : L 3 : 1 and 4 : 1, the two [Cu3(L)H(-6)] and [Cu4(L)H(-8)] complex species have been characterized at neutral pH values. All the copper atoms occupy similar coordination sites formed by imidazole, peptidic nitrogen atoms and carbonyl oxygen atoms in a square base pyramidal geometry. Voltammetric measurements on these systems point out the cooperativity in the electron transfer processes among the copper(II) sites during their reduction. NO interaction with these polynuclear copper species is characterized by the reduction of the copper sites through the formation of two different intermediate complex species. When an excess of the Ac-PEG11-(PHGGGWGQ)4-NH2 ligand is considered, frozen solution EPR parameters and UV-Vis spectroscopic data identify the [Cu(N(im))4]2+ chromophore, which does not interact with NO.

  17. 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.

    2016-02-01

    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.

  18. 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.

  19. Improving nuclease activity of copper(II)-terpyridine complex through solubilizing and charge effects of glycine.

    Science.gov (United States)

    Zhou, Wen; Wang, Xiaoyong; Hu, Ming; Guo, Zijian

    2013-04-01

    Copper complexes are potential metallonucleases that may find application in biotechnology and molecular biology. In this study, a ternary copper-terpyridine complex [Cu(ttpy)(Gly)(NO3)](NO3)·H2O (1) (ttpy=4'-p-tolyl-2,2':6,2″-terpyridine) is synthesized and characterized by X-ray crystallography and ESI-MS as an artificial nuclease. Glycine (Gly) is introduced into the complex to enhance the water-solubility and electrostatic affinity for the nucleic acid target. The interaction between complex 1 and DNA has been studied by spectroscopy and gel electrophoresis, using a structural analog [Cu(ttpy)(NO3)2] (2) as the reference. Complex 1 demonstrates an increased DNA binding ability and oxidative cleavage activity towards supercoiled pBR322 DNA as compared with complex 2. The enhanced water-solubility and positive charge of complex 1 may facilitate its access to DNA and formation of hydrogen bonds with the sugar-phosphate backbone. The results indicate that carefully positioned auxiliary groups in a copper complex can significantly affect the substrate binding or activation ability and consequently the nuclease efficiency of the complex.

  20. DNA binding and biological studies of some novel water-soluble polymer-copper(II)-phenanthroline complexes.

    Science.gov (United States)

    Kumar, Rajendran Senthil; Arunachalam, Sankaralingam; Periasamy, Vaiyapuri Subbarayan; Preethy, Christo Paul; Riyasdeen, Anvarbatcha; Akbarsha, Mohammad Abdulkader

    2008-10-01

    Some novel water-soluble polymer-copper(II)-phenanthroline complex samples, [Cu(phen)2(BPEI)]Cl(2).4H2O (phen=1,10-phenanthroline, BPEI=branched polyethyleneimine), with different degrees of copper complex content in the polymer chain have been prepared by ligand substitution method in water-ethanol medium and characterized by infrared, UV-visible, EPR spectral and elemental analysis methods. The binding of these complex samples with DNA has been investigated by electronic absorption spectroscopy, emission spectroscopy and gel retardation assay. Electrostatic interactions between DNA molecule and polymer-copper(II) complex molecule containing many high positive charges have been observed. Besides these ionic interactions, van der Waals interactions, hydrogen bonding and other partial intercalation binding modes may also exist in this system. The polymer-copper(II) complex with higher degree of copper complex content was screened for its antimicrobial activity and antitumor activity.

  1. Antiangiogenic activity of mononuclear copper(II) polypyridyl complexes for the treatment of cancers.

    Science.gov (United States)

    Nagababu, Penumaka; Barui, Ayan Kumar; Thulasiram, Bathini; Devi, C Shobha; Satyanarayana, S; Patra, Chitta Ranjan; Sreedhar, Bojja

    2015-07-09

    A series of four new mononuclear copper(II) polypyridyl complexes (1-4) have been designed, developed, and thoroughly characterized by several physicochemical techniques. The CT-DNA binding properties of 1-4 have been investigated by absorption, emission spectroscopy, and viscosity measurements. All the complexes especially 1 and 4 exhibit cytotoxicity toward several cancer cell lines, suggesting their anticancer properties as observed by several in vitro assays. Additionally, the complexes show inhibition of endothelial cell (HUVECs) proliferation, indicating their antiangiogenic nature. In vivo chick embryo angiogenesis assay again confirms the antiangiogenic properties of 1 and 4. The formation of excessive intracellular ROS (H2O2 and O2(•-)) and upregulation of BAX induced by copper(II) complexes may be the plausible mechanisms behind their anticancer activities. The present study may offer a basis for the development of new transition metal complexes through suitable choice of ligands for cancer therapeutics by controlling tumor angiogenesis.

  2. Synthesis, characterisation and biological evaluation of copper and silver complexes based on acetylsalicylic acid.

    Science.gov (United States)

    Rubner, Gerhard; Bensdorf, Kerstin; Wellner, Anja; Bergemann, Silke; Gust, Ronald

    2011-10-01

    Metalcarbonyl complexes with ligands derived from acetylsalicylic acid demonstrated high cytotoxic potential against various tumor cell lines and strong inhibition of the cyclooxygenase enzymes COX-1 and 2. In this study we tried to achieve comparable effects with [alkyne]silver or copper trifluoromethanesulfonate complexes which are more hydrophilic then the uncharged metalcarbonyl derivatives. All compounds were evaluated for growth inhibition against breast (MCF-7, MDA-MB 231) and colon cancer (HT-29) cell lines and for COX-1 and COX-2 inhibitory effects at isolated isoenzymes. Pure ligands showed neither cytotoxic nor COX-inhibitory effects. While the silver complexes of (but-2-ynyl)-2-acetoxybenzoate (But-ASS-Ag) and (but-2-yne-1,4-diyl)-bis(2-acetoxybenzoate) (Di-ASS-But-Ag) were strong cytostatics, only the copper complex Di-ASS-But-Cu was active. At the COX enzymes the complexes were more effective than their ligands and aspirin.

  3. Changes in magnetic properties from solid state to solution in a trinuclear linear copper(II) complex

    NARCIS (Netherlands)

    Koval, I.A.; Akhideno, H.; Tanase, S.; Belle, C.; Duboc, C.; Saint-Aman, E.; Gamez, P.; Tooke, D.M.; Spek, A.L.; Pierre, J.-L.; Reedijk, J.

    2007-01-01

    A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral coor

  4. Interaction of copper (II) complexes by bovine serum albumin: spectroscopic and calorimetric insights.

    Science.gov (United States)

    Singh, Namrata; Pagariya, Darshana; Jain, Surbhi; Naik, Sunil; Kishore, Nand

    2017-07-28

    Serum albumins being the most abundant proteins in the blood and cerebrospinal fluid are significant carriers of essential transition metal ions in the human body. Studies of copper (II) complexes have gained attention because of their potential applications in synthetic, biological, and industrial processes. Study of binding interactions of such bioinorganic complexes with serum albumins improves our understanding of biomolecular recognition process essential for rational drug design. In the present investigation, we have applied quantitative approach to explore interactions of novel synthesized copper (II) complexes viz. [Cu(L(1))(L(2))ClO4] (complex I), [Cu(L(2))(L(3))]ClO4] (complex II) and [Cu(L(4))2(H2O)2] (complex III) with bovine serum albumin (BSA) to evaluate their binding characteristics, site and mode of interaction. The fluorescence quenching of BSA initiated by complexation has been observed to be static in nature. The binding interactions are endothermic driven by entropic factors as confirmed by high sensitivity isothermal titration calorimetry. Changes in secondary and tertiary structure of protein have been studied by circular dichroism and significant reduction in α-helical content of BSA was observed upon binding. Site marking experiments with warfarin and ibuprofen indicated that copper complexes bind at site II of the protein.

  5. Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square-Planar Copper(I) Complex.

    Science.gov (United States)

    Dahl, Eric W; Szymczak, Nathaniel K

    2016-02-24

    6,6''-Bis(2,4,6-trimethylanilido)terpyridine (H2Tpy(NMes)) was prepared as a rigid, tridentate pincer ligand containing pendent anilines as hydrogen bond donor groups in the secondary coordination sphere. The coordination geometry of (H2 Tpy(NMes))copper(I)-halide (Cl, Br and I) complexes is dictated by the strength of the NH-halide hydrogen bond. The Cu(I)Cl and Cu(II)Cl complexes are nearly isostructural, the former presenting a highly unusual square-planar geometry about Cu(I) . The geometric constraints provided by secondary interactions are reminiscent of blue copper proteins where a constrained geometry, or entatic state, allows for extremely rapid Cu(I)/Cu(II) electron-transfer self-exchange rates. Cu(H2 Tpy(NMes))Cl shows similar fast electron transfer (≈10(5)  m(-1)  s(-1)) which is the same order of magnitude as biological systems.

  6. Preparation of ethambutol-copper(II) complex and fabrication of PVC based membrane potentiometric sensor for copper.

    Science.gov (United States)

    Gupta, Vinod K; Prasad, Rajendra; Kumar, Azad

    2003-05-28

    Copper(II) complex of ethambutol (I) was prepared and used in the fabrication of Cu(2+) selective ISE membrane. The membrane having Cu(II)-ethambutol complex (I) as electroactive material, along with sodium tetraphenylborate (NaTPB) as anion discriminator, dioctylphthalate (DOP) as plasticizer in poly(vinyl chloride) (PVC) matrix in the percentage ratio 6:2:190:200 (I:NaTPB:DOP:PVC) (w/w) gave a linear response in the concentration range 7.94x10(-6) to 1.0x10(-1) M of Cu(2+) with a slope of 29.9+/-0.2 mV per decade of activity and a fast response time of 11+/-2 s. The sensor works well in the pH range 2.1-6.3 and could be satisfactorily used in presence of 40% (v/v) methanol, ethanol and acetone and is selective for copper over a large number of cations with slight interference from Na(+) and Co(2+) if present at a level 1.5x10(-5) and 6.5x10(-5) M, respectively. It works well over a period of 6 months and can also be used as indicator electrode for the end point determination in the potentiometric titration of Cu(2+) against EDTA as well as in the determination of Cu(2+) in real samples.

  7. Cyclopentanone thiosemicarbazone, a new complexing agent for copper determination in biological samples by adsorptive stripping voltammetry.

    Science.gov (United States)

    Mahajan, Rakesh Kumar; Walia, T P S; Sumanjit; Lobana, T S

    2006-03-01

    A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with cyclopentanone thiosemicarbazone (CPTSC) is presented. The method is based on the adsorptive accumulation of the resulting copper-CPTSC complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurements at the reduction current of the adsorbed complex at -0.37 V vs. Ag/AgCl. The optimal conditions for the stripping analysis of copper include pH 9.3, deposition time of 120 s, and a deposition potential of -0.1 V (vs. Ag/AgCl). The peak current is linearly proportional to the copper concentration over a range 3.14 x 10(-9) M to 1.57 x 10(-6) M with a limit of detection of 1.57 x 10(-9) M. The technique has been applied to the determination of copper in biological samples, like urine and whole blood.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Taehyung; Kim, Ju Chang [Pukyong National Univ., Busan (Korea, Republic of); Lough, Alan J. [Univ. of Toronto, Toronto (Canada)

    2013-06-15

    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.

  9. Synthesis, structural characterization and thermal properties of copper and silver silyl complexes.

    Science.gov (United States)

    Sgro, Michael J; Piers, Warren E; Romero, Patricio E

    2015-02-28

    The synthesis of copper and silver silyl complexes containing either N-heterocyclic carbenes or nitrogen donors is described. Alterations made to both the neutral donor ligands as well as the silyl group provided access to a number of different compounds. Many of the complexes synthesized were studied in the solid state and the effect of the donor ligand on the final structure of the complexes was examined. The thermal properties of the complexes were explored using thermogravimetric analysis, differential scanning calorimetry and sublimations. Some of the complexes synthesized were demonstrated to be promising volatile metal precursors.

  10. Synthetic, Crystallographic, and Computational Study of Copper(II) Complexes of Ethylenediaminetetracarboxylate Ligands

    NARCIS (Netherlands)

    Matovic, Zoran D.; Miletic, Vesna D.; Cendic, Marina; Meetsma, Auke; van Koningsbruggen, Petra J.; Deeth, Robert J.; Matović, Zoran D.; Miletić, Vesna D.; Ćendić, Marina

    2013-01-01

    Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and Rieddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; ateddadp = ethylenediamine-N,N'-diaceticN,N'-di-3-propionic acid) have been prepared. An octahedral trans(O-6) geometry (two

  11. Synthetic, Crystallographic, and Computational Study of Copper(II) Complexes of Ethylenediaminetetracarboxylate Ligands

    NARCIS (Netherlands)

    Matovic, Zoran D.; Miletic, Vesna D.; Cendic, Marina; Meetsma, Auke; van Koningsbruggen, Petra J.; Deeth, Robert J.; Matović, Zoran D.; Miletić, Vesna D.; Ćendić, Marina

    2013-01-01

    Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and Rieddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; ateddadp = ethylenediamine-N,N'-diaceticN,N'-di-3-propionic acid) have been prepared. An octahedral trans(O-6) geometry (two

  12. Doubly chloro bridged dimeric copper(II) complex: magneto-structural correlation and anticancer activity.

    Science.gov (United States)

    Sikdar, Yeasin; Modak, Ritwik; Bose, Dipayan; Banerjee, Saswati; Bieńko, Dariusz; Zierkiewicz, Wiktor; Bieńko, Alina; Das Saha, Krishna; Goswami, Sanchita

    2015-05-21

    We have synthesized and structurally characterized a new doubly chloro bridged dimeric copper(II) complex, [Cu2(μ-Cl)2(HL)2Cl2] (1) based on a Schiff base ligand, 5-[(pyridin-2-ylmethylene)-amino]-pentan-1-ol). Single crystal X-ray diffraction shows the presence of dinuclear copper(II) centres in a square pyramidal geometry linked by obtuse double chloro bridge. The magnetic study illustrated that weak antiferromagnetic interactions (J = -0.47 cm(-1)) prevail in complex 1 which is well supported by magneto-structural correlation. This compound adds to the library of doubly chloro bridged copper(ii) complexes in the regime of spin state cross over. DFT calculations have been conducted within a broken-symmetry (BS) framework to investigate the exchange interaction further which depicts that the approximate spin projection technique yields the best corroboration of the experimental J value. Spin density plots show the presence of an ∼0.52e charge residing on the copper atom along with a substantial charge on bridging and peripheral chlorine atoms. The potential of complex1 to act as an anticancer agent is thoroughly examined on a series of liver cancer cell lines and screening shows the HepG2 cell line exhibits maximum cytotoxicity by phosphatidyl serine exposure in the outer cell membrane associated with ROS generation and mitochondrial depolarization with increasing time in the in vitro model system.

  13. 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...

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

    Science.gov (United States)

    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.

  15. Copper(i) complexes with phosphine derived from sparfloxacin. Part I - structures, spectroscopic properties and cytotoxicity.

    Science.gov (United States)

    Komarnicka, Urszula K; Starosta, Radosław; Kyzioł, Agnieszka; Jeżowska-Bojczuk, Małgorzata

    2015-07-28

    In this paper we present new copper(i) iodide or copper(i) thiocyanate complexes with hydroxymethyldiphenylphosphine (PPh2(CH2OH)) or phosphine derivatives of sparfloxacin, a 3(rd) generation fluoroquinolone antibiotic agent (PPh2(CH2-Sf)) and 2,9-dimethyl-1,10-phenanthroline (dmp) or 2,2'-biquinoline (bq) auxiliary ligands. The synthesised complexes were fully characterised by NMR and UV-Vis spectroscopy as well as by mass spectrometry. Selected structures were additionally analysed using X-ray and DFT methods. All complexes proved to be stable in solution in the presence of water and atmospheric oxygen for several days. The cytotoxic activity of the complexes was tested against two cancer cell lines (CT26 - mouse colon carcinoma and A549 - human lung adenocarcinoma). Applying two different incubation times, the studies enabled a preliminary estimation of the dependence of the selectivity and the mechanism of action on the type of diimine and phosphine ligands. The results obtained showed that complexes with PPh2(CH2-Sf) are significantly more active than those with PPh2(CH2OH). On the other hand, the relative impact of diimine on cytotoxicity is less pronounced. However, the dmp complexes are characterised by strong inhibitory properties, while the bq ones are rather not. This confirms the interesting and promising biological properties of the investigated group of copper(i) complexes, which undoubtedly are worthy of further biological studies.

  16. Modeling Dinuclear Copper Sites of Biological Relevance : Synthesis, Molecular Structure, Magnetic Properties, and 1H NMR Spectroscopy of a Nonsymmetric Dinuclear Copper(II) Complex. Microcalorimetric Determination of Stepwise Complexation of Copper(II) by

    NARCIS (Netherlands)

    Lubben, Marcel; Hage, Ronald; Meetsma, Auke; Bÿma, Koos; Feringa, Bernard

    1995-01-01

    The new nonsymmetric dinuclear copper(II) complex [Cu2L1(OAc)2](ClO4) (7) was synthesized by complexation of Cu(OAc)2·H2O with a new nonsymmetric dinucleating ligand (5) which is formed in situ by condensation of 2-formyl-6-((4-methylpiperazin-1-yl)methyl)phenol (3a) with 2-(aminoethyl)pyridine. Com

  17. Temperature effects on EPR spectra of a linear chain copper complex-copper calcium acetate hexahydrate

    Science.gov (United States)

    De, D. K.

    1981-03-01

    The observed angular dependence of the electron paramagnetic resonance linewidth in the ab and ac planes of CuCa(AC)2, 6H2O in the temperature interval 77K-12K was explained by considering dipolar interactions along with hyperfine and isotropic exchange interactions in these two planes. It was found that this so called linear-chain copper compound can be better described by a three dimensional paramagnet. The exchange interaction is very nearly isotropic with values Jab = 0.0098 cm-1 and Jc = 0.0103 cm-1. The values of the A⊥ derived from the linewidth fit in the ab plane are 14G at 77K and 60.5G at 1.2K. Due to insufficiency of data in the ac plane, the fit was done with the measured value of A∥. Although the exchange interaction has been found to be temperature independent the hyperfine interaction increases very much at low temperatures. The high temperature (300-460K) EPR spectra are quite different from the low temperature spectra. High temperature differential thermal analyses and thermogravimetric analyses have been carried out and corroborated with the EPR findings.

  18. Tetranuclear Copper complexes with new β—diketone and β—iminoketone—containing ligands

    Institute of Scientific and Technical Information of China (English)

    LuqingYang; XinJu

    1999-01-01

    Novel tetranuclear copper complexes,Cu4(OH)2(ClO4)3 (HA).H2O(1)and Cu4(ClO4)5(H3B).3H2O(2),were synthesized by reacting 1,5-bis(1'-phenyl-3'-methyl-5'-pyrazolone-4')-1,5--pentanedione with 1,3-propanediamine and 2-hydroxyl-1,3-propanediamine in the presence of a template reagent copper ion ,New[2+2] type open cyclic multidentate ligands are also obtained from the reaction(H4A) and H6B stand for new compounds from 1,3-propanediamine and 2-hydroxyl-1,3-propanediamine,respectively),They each contain five C=O ,three C=N and one NH2 group[s,The complexes were characterized by elemental analyses,conductivity,FR-i.r.electronic spectra and extended X-ray absorption fine structure(EXAFS),Copper ions in (1) are basically four coordinate with tetragonal geometry.The average coordination bond distances of Cu-N and Cu-O are 1.91 A and 2.05A .In(2).copper ions are primarily five coordinate with square-based pyramidal geometry.The average coordination bond distances of Cu-N and Cu-O are 1.93 A and 2.08 A.Four copper atoms in molecules may be arranged tetragonally.Both the ligand field and the coordination bonds in complex(1) are stronger than those in(2).Investigations on variable temperature susceptibilities show that some antiferromagnetic exchange interaction exist in the complexes,The plots of x-1 versus T obey the Curie-Weiss law only at low temperature.Preliminary results of a bioassay indicate that the two complexes have some antitumour activity in vitro.

  19. Ergothioneine prevents copper-induced oxidative damage to DNA and protein by forming a redox-inactive ergothioneine-copper complex.

    Science.gov (United States)

    Zhu, Ben-Zhan; Mao, Li; Fan, Rui-Mei; Zhu, Jun-Ge; Zhang, Ying-Nan; Wang, Jing; Kalyanaraman, Balaraman; Frei, Balz

    2011-01-14

    Ergothioneine (2-mercaptohistidine trimethylbetaine) is a naturally occurring amino acid analogue found in up to millimolar concentrations in several tissues and biological fluids. However, the biological functions of ergothioneine remain incompletely understood. In this study, we investigated the role of ergothioneine in copper-induced oxidative damage to DNA and protein, using two copper-containing systems: Cu(II) with ascorbate and Cu(II) with H(2)O(2) [0.1 mM Cu(II), 1 mM ascorbate, and 1 mM H(2)O(2)]. Oxidative damage to DNA and bovine serum albumin was measured as strand breakage and protein carbonyl formation, respectively. Ergothioneine (0.1-1.0 mM) provided strong, dose-dependent protection against oxidation of DNA and protein in both copper-containing systems. In contrast, only limited protection was observed with the purported hydroxyl radical scavengers, dimethyl sulfoxide and mannitol, even at concentrations as high as 100 mM. Ergothioneine also significantly inhibited copper-catalyzed oxidation of ascorbate and competed effectively with histidine and 1,10-phenanthroline for binding of cuprous copper, but not cupric copper, as demonstrated by UV-visible and low-temperature electron spin resonance techniques. We conclude that ergothioneine is a potent, natural sulfur-containing antioxidant that prevents copper-dependent oxidative damage to biological macromolecules by forming a redox-inactive ergothioneine-copper complex.

  20. Inhibition effects of PMA/SbBr3 complex inhibitor on copper and copper-nickel alloy in LiBr solutions

    Institute of Scientific and Technical Information of China (English)

    HU Xian-qi; LIANG Cheng-hao; HUANG Nai-bao

    2005-01-01

    The effects of PMA/SbBr3 inhibitor on copper and copper-nickel alloy in 55%LiBr solution were investigated by chemical immersion and electrochemical measurements. The results indicate that in boiling 55% LiBr solution containing PMA/SbBr3 inhibitor, corrosion rates of copper and copper-nickel alloy are 67.48 μm/a and 38. 14μm/a, respectively. Since both anodic and cathodic electrochemical reactions can be inhibited, PMA/SbBr3 belongs to complex inhibitor. PMA has the effect of inhibiting hydrogen evolution and [PMo12 O40]3- , the anion of PMA,has a strong oxidizing effect. Sb3+ also shows an oxidizing effect. It may exist in LiBr solutions stably with PMA.Because of the synergistic effect of PMA and Sb3+ , a protective film, comprising CuO, Cu2O and Sb, formed on copper and copper-nickel alloy surface may prevent Br- from diffusing to the surface of metals. As a result, the anticorrosion performance of copper and copper-nickel alloy may be improved.

  1. Cytotoxicity of copper(II) complexes of N-salicylidene-L-glutamate: modulation by ascorbic acid.

    Science.gov (United States)

    Paulikova, H; Kadlecikova, E; Suchanova, M; Valkova, Z; Rauko, P; Hudecova, D; Valent, A

    2008-01-01

    Cytotoxic/cytostatic activity of N-salicylidene-L-glutamato diaqua copper(II) complex (CuC) against mice leukemia cells L1210 has been estimated and their bioactivity was enhanced by addition of ascorbic acid. The Cu-complex with isoquinoline ligand (IQ-CuC) had stronger cytostatic effect (IC50 =15.6 microM) than parental complex (CuC) and its cytotoxicity several times increased in the presence of 0.1 mM ascorbic acid (IC50 =1.0 microM). The cytotoxicity has been caused by oxidative stress, enhanced creation of TBARS has been confirmed, and formation of 2',7'-dichlorofluorescein from 2',7'- dichlorodihydrofluorescein has been observed, also. Some hallmarks of apoptotic/necrotic death of L1210 cells have been observed by fluorescent microscopy after dyeing of cell with propidium iodide and Hoechst 33342. In addition, it was confirmed that both complexes in the presence of ascorbic acid cleavaged of pDNA. Although these copper complexes were initially prepared as substances with antioxidant properties we have showed that combined treatment of L1210 cells with IQCuC and ascorbic acid induced strong oxidative stress and death of cells. Our results confirmed that physiological concentration of ascorbic acid increases the cytostatic/cytotoxic efficiency of N-salicylidene-L-glutamato diaqua copper(II) complexes.

  2. Synthesis, structure, DNA binding and cleavage activity of a new copper(Ⅱ) complex of bispyridylpyrrolide

    Institute of Scientific and Technical Information of China (English)

    MIN Rui; HU Xiao-hui; YI Xiao-yi; ZHANG Shou-chun

    2015-01-01

    A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl] (PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space groupPccn,a = 0.9016(3) nm,b = 1.0931(4) nm,c = 2.5319(8) nm, andV = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(Ⅱ) complexwith calf thymus DNA (CT-DNA) was investigated by electronic absorption, circular dichroism (CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled pBR322 DNA in the presence of ascorbate (H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.

  3. Dinuclear copper complexes with imidazole derivative ligands: a theoretical study related to catechol oxidase activity.

    Science.gov (United States)

    Martínez, Ana; Membrillo, Ingrid; Ugalde-Saldívar, Victor M; Gasque, Laura

    2012-07-19

    Catechol oxidase is a very important and interesting metalloprotein. In spite of the efforts to understand the reaction mechanism of this protein, there are important questions that remain unanswered concerning the catalytic mechanism of this enzyme. In this article, dinuclear copper compounds are used as biomimetic models of catechol oxidase to study plausible reaction paths. These dinuclear copper(II) complexes have distant metal centers (of 7.5 Å approximately) and superior catalytic activity to that of many dicopper complexes with shorter Cu-Cu distances. One mononuclear copper(II) complex is also analyzed in this investigation in order to see the influence of the two metal centers in the catalytic activity. Density functional theory calculations were performed to obtain optimized structures, vertical ionization energies, vertical electron affinities, the electrodonating power (ω(-)), the electroaccepting power (ω(+)) and the energy difference of several reaction paths. The K(M) experimental results that were previously reported compare well with the electroaccepting power (ω(+)) of the copper compounds that are included in this article, indicating that this index is useful for the interpretation of the electron transfer capacity and therefore the catalytic activity. The catechol moiety coordinates to only one Cu ion, but two metal atoms are needed in order to have a good electron acceptor capacity of the biomimetic models.

  4. Spectroscopic study of copper(II) complexes with carboxymethyl dextran and dextran sulfate

    Science.gov (United States)

    Glišić, S.; Nikolić, G.; Cakić, M.; Trutić, N.

    2015-07-01

    The copper(II) ion complexes with carboxymethyl dextran (CMD) and dextran sulfate (DS) were studied by different methods. Content of copper was determined by atomic absorption spectroscopy. It was found that copper : ligand mole ratio (Cu : CMD) is 1 : 2, and Cu : DS is 1 : 1 by mole ratio method. Spectrophotometric parameters of synthesized compounds are characteristic for Cu(II) ion in octahedral ( O h ) coordination. Analyzing of FTIR spectra in ν(C=O) vibration region has showed that -COOH group acts as bidentate ligand, while the compounds of Cu(II) with DS copper ions are in the region of four oxygen atoms of two adjacent sulfo groups. The presence of crystalline water was determined by isotopic substitution of H2O molecules with D2O molecules. Comparison of spectra recorded at room (RT) and liquid nitrogen temperature (LNT) has enabled detection bands of water molecules libration indicating that they are coordinated complementing coordination sphere of Cu(II) ions to six. The complexes are of Cu(II) · (CMD)2 · (H2O)2 or Cu(II) · DS · (H2O)2 type. The similarities of the γ(C-H) range in a part of FTIR spectra indicate that there is no difference in the conformation of the 4 C 1 glucopyranose (Glc) unit CMD and DS synthesized Cu(II) complexes.

  5. Nanoscale Reaction Vessels Designed for Synthesis of Copper-Drug Complexes Suitable for Preclinical Development.

    Science.gov (United States)

    Wehbe, Mohamed; Anantha, Malathi; Backstrom, Ian; Leung, Ada; Chen, Kent; Malhotra, Armaan; Edwards, Katarina; Bally, Marcel B

    2016-01-01

    The development of copper-drug complexes (CDCs) is hindered due to their very poor aqueous solubility. Diethyldithiocarbamate (DDC) is the primary metabolite of disulfiram, an approved drug for alcoholism that is being repurposed for cancer. The anticancer activity of DDC is dependent on complexation with copper to form copper bis-diethyldithiocarbamate (Cu(DDC)2), a highly insoluble complex that has not been possible to develop for indications requiring parenteral administration. We have resolved this issue by synthesizing Cu(DDC)2 inside liposomes. DDC crosses the liposomal lipid bilayer, reacting with the entrapped copper; a reaction that can be observed through a colour change as the solution goes from a light blue to dark brown. This method is successfully applied to other CDCs including the anti-parasitic drug clioquinol, the natural product quercetin and the novel targeted agent CX-5461. Our method provides a simple, transformative solution enabling, for the first time, the development of CDCs as viable candidate anticancer drugs; drugs that would represent a brand new class of therapeutics for cancer patients.

  6. Nanoscale Reaction Vessels Designed for Synthesis of Copper-Drug Complexes Suitable for Preclinical Development

    Science.gov (United States)

    Wehbe, Mohamed; Anantha, Malathi; Backstrom, Ian; Leung, Ada; Chen, Kent; Malhotra, Armaan; Edwards, Katarina; Bally, Marcel B.

    2016-01-01

    The development of copper-drug complexes (CDCs) is hindered due to their very poor aqueous solubility. Diethyldithiocarbamate (DDC) is the primary metabolite of disulfiram, an approved drug for alcoholism that is being repurposed for cancer. The anticancer activity of DDC is dependent on complexation with copper to form copper bis-diethyldithiocarbamate (Cu(DDC)2), a highly insoluble complex that has not been possible to develop for indications requiring parenteral administration. We have resolved this issue by synthesizing Cu(DDC)2 inside liposomes. DDC crosses the liposomal lipid bilayer, reacting with the entrapped copper; a reaction that can be observed through a colour change as the solution goes from a light blue to dark brown. This method is successfully applied to other CDCs including the anti-parasitic drug clioquinol, the natural product quercetin and the novel targeted agent CX-5461. Our method provides a simple, transformative solution enabling, for the first time, the development of CDCs as viable candidate anticancer drugs; drugs that would represent a brand new class of therapeutics for cancer patients. PMID:27055237

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

    African Journals Online (AJOL)

    NJD

    Received 14 January 2009, revised 17 October 2009, accepted 23 November 2009. ... powder diffraction, FT-infrared spectroscopy, electron paramagnetic resonance and ... metal complex of a strong ligand and of appropriate dimensions.

  8. Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin.

    Science.gov (United States)

    Sieracki, Nathan A; Tian, Shiliang; Hadt, Ryan G; Zhang, Jun-Long; Woertink, Julia S; Nilges, Mark J; Sun, Furong; Solomon, Edward I; Lu, Yi

    2014-01-21

    Metal-sulfenate centers are known to play important roles in biology and yet only limited examples are known due to their instability and high reactivity. Herein we report a copper-sulfenate complex characterized in a protein environment, formed at the active site of a cavity mutant of an electron transfer protein, type 1 blue copper azurin. Reaction of hydrogen peroxide with Cu(I)-M121G azurin resulted in a species with strong visible absorptions at 350 and 452 nm and a relatively low electron paramagnetic resonance gz value of 2.169 in comparison with other normal type 2 copper centers. The presence of a side-on copper-sulfenate species is supported by resonance Raman spectroscopy, electrospray mass spectrometry using isotopically enriched hydrogen peroxide, and density functional theory calculations correlated to the experimental data. In contrast, the reaction with Cu(II)-M121G or Zn(II)-M121G azurin under the same conditions did not result in Cys oxidation or copper-sulfenate formation. Structural and computational studies strongly suggest that the secondary coordination sphere noncovalent interactions are critical in stabilizing this highly reactive species, which can further react with oxygen to form a sulfinate and then a sulfonate species, as demonstrated by mass spectrometry. Engineering the electron transfer protein azurin into an active copper enzyme that forms a copper-sulfenate center and demonstrating the importance of noncovalent secondary sphere interactions in stabilizing it constitute important contributions toward the understanding of metal-sulfenate species in biological systems.

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

    Directory of Open Access Journals (Sweden)

    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.

  10. Spectroscopic, structural and theoretical studies of copper(II) complexes of tridentate NOS Schiff bases

    Science.gov (United States)

    Olalekan, Temitope E.; Ogunlaja, Adeniyi S.; VanBrecht, Bernardus; Watkins, Gareth M.

    2016-10-01

    Two newly synthesized Schiff bases (L4 and L5) were derived from the condensation reaction of 2-(methylthiomethyl)anilines and 4-methoxysalicylaldehyde. Coordination complexes of these and four previously reported NOS Schiff bases, Cu(L1)2-Cu(L6)2, were synthesized via the reflux reaction of the various Schiff base ligands with CuCl2·2H2O. The compounds were characterized by means of elemental analysis, FTIR and UV-Vis. The crystal structures of Cu(L1)2 and Cu(L2)2 were obtained by X-ray diffraction. The Schiff bases were coordinated to copper ion as monobasic tridentate ligands through the phenolic oxygen, azomethine nitrogen and thioether sulfur. The microanalyses of the coordination complexes were agreeable with bimolar binding of the ligands to the copper metal ion. The crystal structures of the copper complexes confirmed an octahedral geometry around the metal centre and showed they are mononuclear. The magnetic moment values indicated the presence of a lone electron in each copper(II) orbital and confirmed the mononuclearity of the complexes. The electronic spectra of the coordination compounds consist of the intraligand, charge transfer and d→d bands. Molecular modeling studies on the complexes (Cu(L1)2-Cu(L6)2) by employing DFT revealed that complex Cu(L5)2 possessed the smallest optimization energy as well as a small HOMO-LUMO energy gap which may best explain its higher polarizability as well as reactivity in comparison to the other complexes.

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

    Directory of Open Access Journals (Sweden)

    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.

  12. Synthesis, Spectroscopy and Crystal Structure of a New Copper Complex Builtup by Cationic (Dimethylphosphorylmethanaminium Ligands

    Directory of Open Access Journals (Sweden)

    Manuela E. Richert

    2014-05-01

    Full Text Available A new transition metal complex of the mono-protonated ligand (dimethylphosphorylmethanamine (dpmaH+ was obtained by equimolar reaction of copper(II chloride dihydrate and dpma in concentrated hydrochloric acid. The asymmetric unit of the title structure, [CuCl2(C3H11NOP4][CuCl4]2, consists of one half of a fourfold charged trans-dichloridotetrakis[(dimethylphosphorylmethanaminium]copper(II complex with the copper atom located on an inversion centre and one tetrachloridocuprate(II dianion found in a general position. The copper centre in the cationic complex shows a tetragonally distorted octahedral environment composed of four oxygen atoms in a square plane and two trans-coordinated chlorido ligands. This 4+2-coordination causes elongated Cu-Cl distances because of the Jahn-Teller effect. The geometry of the tetrachloridocuprate(II dianion is best described as a seriously distorted tetrahedron. Analysis of the hydrogen bonding scheme by graph-set theory shows three patterns of rings in the title compound. The cationic copper complex reveals intramolecular hydrogen bonds between two aminium groups and the two axial chlorido ligands. Further hydrogen bonding among the cations and anions, more precisely between four aminium groups and the chlorido ligands of four adjacent tetrachloridocuprate(II anions, lead to a chain-type structure. Comparing the coordination chemistry of the title structure with an analogue cobalt(II compound only disclose differences in hydrogen bonding pattern resulting in an unusual chain propagation. Besides the crystal structure received spectroscopic data are in accordance with appropriate literature.

  13. [Development of a therapeutic agent for Menkes disease: solubilization of a copper-disulfiram complex].

    Science.gov (United States)

    Hoshi, Yujiro; Tani, Norihiko; Tabata, Hidetsugu; Wakamatsu, Shintaro; Munakata, Mitsutoshi; Maruyama, Kazuo; Kodama, Hiroko; Oshitari, Tetsuta; Natsugari, Hideaki; Takahashi, Hideyo

    2015-01-01

    Menkes disease (MD) is a neurodegenerative disorder characterized by copper deficiency. It is caused by defective intestinal absorption of copper resulting from a deficiency of a copper-transporting ATPase, ATP7A. We investigated the effects of combination therapy with copper and disulfiram, a known lipophilic chelator. We synthesized a copper-disulfiram complex (Cu-DSF) and determined its crystal structure by X-ray crystallographic analysis. Unfortunately, Cu-DSF was not orally bioavailable due to its lipophilicity. We therefore planned to use cyclodextrin as a solubilizing agent to increase the water solubility of Cu-DSF. After comparisons of the effects of cyclodextrins (α, β, γ), it was found that addition of β-cyclodextrin (β-CyD) increased the solubility of Cu-DSF. Moreover, the modified β-CyD, hydroxypropyl-β-cyclodextrin, was yet more effective as a solubilizing agent. For the development of a convenient method to determine the concentration of Cu-DSF included by β-cyclodextrins, a standard curve based on UV-visible(VIS) absorption was derived.

  14. Effect of decomposition and organic residues on resistivity of copper films fabricated via low-temperature sintering of complex particle mixed dispersions.

    Science.gov (United States)

    Yong, Yingqiong; Nguyen, Mai Thanh; Tsukamoto, Hiroki; Matsubara, Masaki; Liao, Ying-Chih; Yonezawa, Tetsu

    2017-03-24

    Mixtures of a copper complex and copper fine particles as copper-based metal-organic decomposition (MOD) dispersions have been demonstrated to be effective for low-temperature sintering of conductive copper film. However, the copper particle size effect on decomposition process of the dispersion during heating and the effect of organic residues on the resistivity have not been studied. In this study, the decomposition process of dispersions containing mixtures of a copper complex and copper particles with various sizes was studied. The effect of organic residues on the resistivity was also studied using thermogravimetric analysis. In addition, the choice of copper salts in the copper complex was also discussed. In this work, a low-resistivity sintered copper film (7 × 10(-6) Ω·m) at a temperature as low as 100 °C was achieved without using any reductive gas.

  15. Theoretical study, and infrared and Raman spectra of copper(II) chelated complex with dibenzoylmethane

    DEFF Research Database (Denmark)

    Nekoei, A.-R.; Vakili, M.; Hakimi-Tabar, M.

    2014-01-01

    There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational...... assignment for Cu(dbm)2 in the literatures. Density functional theory (DFT) at the B3LYP level and also MP2 calculations using different basis sets, besides Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses, have been employed to investigate the effect of methyl substitution with the phenyl...... group on the stabilities of bis(acetylacetonate) copper (II), Cu(acac)2, and Cu(dbm)2 complexes and the electron delocalization in their chelated rings. Measured solid phase infrared and Raman bands for Cu(dbm)2 complex have been interpreted in terms of the calculated vibrational modes and detailed...

  16. New reagents for the synthesis of a series of ferrocenoyl functionalized copper and silver chalcogenolate complexes.

    Science.gov (United States)

    MacDonald, Daniel G; Corrigan, John F

    2008-10-07

    A series of silylated ferrocenoyl chalcogenide reagents, FcC(O)ESiMe3 (E=S, Se, Te; Fc=ferrocene), can be prepared in very good yield from FcC(O)Cl and LiESiMe3. These reagents are used in the preparation of triphenylphosphine-ligated copper and silver ferrocenoyl thiolate and selenolate complexes, [M4(E{O}CFc)4(PPh3)4], (M=Cu, Ag; E=S, Se) and [Cu2(micro-Se{O}CFc)2(PPh3)3] from solubilized copper(I) and silver(I) acetate. The structures of these complexes have been determined via single-crystal X-ray diffraction. The driving force for these reactions is the thermodynamically favorable formation and elimination of AcOSiMe3. The synthesis and characterization of both starting reagents and cluster complexes are discussed.

  17. Theoretical Studies on the Spin Exchange Interaction in Copper(II) Complexes Coordinated with Nitronyl Nitroxide

    Institute of Scientific and Technical Information of China (English)

    Jie REN; Hai Yan WEI; Qi Hua ZHAO; Zhi Da CHEN

    2003-01-01

    Nitronyl nitroxide radical 1, NIT (4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh=2-phenyl-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) were studied with density functional theory (DFT). The magnetic orbital analysis reveals that the antiferromagnetic coupling for complex 2 is due to the antibonding σ*-orbital overlap between (Cu) and π* (NO) orbitals. Also, spin population and atomic charge distribution analysis suggest that for AFS of complex 2 the antiferromagnetic coupling between the radical ligands and the copper(II) ion originates from the spin delocalization induced by the α electron transfer from π*(NO) to (Cu) orbital.

  18. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

    Science.gov (United States)

    Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

    2008-01-01

    Using a paraffin impregnated graphite electrode (PIGE) and mercury-modified pyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNA purine base solutions have been studied by cyclic (CV) and linear sweep voltammetry (LSV) in connection with elimination voltammetry with linear scan (EVLS). In chloride and bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with two cathodic and two anodic potentially separated signals. According to the elimination function E4, the first cathodic peak corresponds to the reduction Cu(II) + e- → Cu(I) with the possibility of fast disproportionation 2Cu(I) → Cu(II)+ Cu(0). The E4 of the second cathodic peak signalized an electrode process controlled by a surface reaction. The electrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by one cathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodic stripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where the reduction of copper ions took place and Cu(I)-purine complexes were formed. By using ASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complex detection was enhanced relative to either ASV or CSV alone, resulting in higher peak currents of more than one order of magnitude. The statistical treatment of CE data was used to determine the reproducibility of measurements. Our results show that EVLS in connection with the stripping procedure is useful for both qualitative and quantitative microanalysis of purine derivatives and can also reveal details of studied electrode processes. PMID:27879715

  19. Synthesis and Structural Characterization of a Copper Complex with Furaldehyde Salicylylhydrazone

    Institute of Scientific and Technical Information of China (English)

    DU Kang-Kai; LIU Shi-Xiong

    2008-01-01

    The copper complex Cu(C12H9N2O3)2 has been synthesized by the reaction of furaldehyde salicylylhydrazone (Hfs) and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P21/n with a =5.9765(3), b = 15.7196(9), c = 12.0514(6) A, β= 101.618(3)°,V= 1109.0(1) A3,C24H18CuN4O6,M, = 521.96, Z= 2, Dc = 1.563 g/cm3, μ =1.035 mm-1,F(000) = 534, R = 0.0373 and wR =0.1058 for 2283 observed reflections (Ⅰ 20(Ⅰ)). The copper atom has a square-planar CuN2O2 coordination and should be in an oetahedral coordination if considering Cu-O (phenol) with distances of 2.796(2) A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O (phenol) bonds, resulting in an extended 1D chain. The title com-pound exhibits paramagnetie property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.

  20. Properties and ATRP activity of copper complexes with substituted tris(2-pyridylmethyl)amine-based ligands.

    Science.gov (United States)

    Kaur, Aman; Ribelli, Thomas G; Schröder, Kristin; Matyjaszewski, Krzysztof; Pintauer, Tomislav

    2015-02-16

    Synthesis, characterization, electrochemical studies, and ATRP activity of a series of novel copper(I and II) complexes with TPMA-based ligands containing 4-methoxy-3,5-dimethyl-substituted pyridine arms were reported. In the solid state, Cu(I)(TPMA*(1))Br, Cu(I)(TPMA*(2))Br, and Cu(I)(TPMA*(3))Br complexes were found to be distorted tetrahedral in geometry and contained coordinated bromide anions. Pseudo-coordination of the aliphatic nitrogen atom to the copper(I) center was observed in Cu(I)(TPMA*(2))Br and Cu(I)(TPMA*(3))Br complexes, whereas pyridine arm dissociation occurred in Cu(I)(TPMA*(1))Br. All copper(I) complexes with substituted TPMA ligands exhibited a high degree of fluxionality in solution. At low temperature, Cu(I)(TPMA*(1))Br was found to be symmetrical and monomeric, while dissociation of either unsubstituted pyridine and/or 4-methoxy-3,5-dimethyl-substituted pyridine arms was observed in Cu(I)(TPMA*(2))Br and Cu(I)(TPMA*(3))Br. On the other hand, the geometry of the copper(II) complexes in the solid state deviated from ideal trigonal bipyramidal, as confirmed by a decrease in τ values ([Cu(II)(TPMA*(1))Br][Br] (τ = 0.92) > [Cu(II)(TPMA*(3))Br][Br] (τ = 0.77) > [Cu(II)(TPMA*(2))Br][Br] (τ = 0.72)). Furthermore, cyclic voltammetry studies indicated a nearly stepwise decrease (ΔE ≈ 60 mV) of E1/2 values relative to SCE (TPMA (-240 mV) > TPMA*(1) (-310 mV) > TPMA*(2) (-360 mV) > TPMA*(3) (-420 mV)) on going from [Cu(II)(TPMA)Br][Br] to [Cu(II)(TPMA*(3))Br][Br], confirming that the presence of electron-donating groups in the 4 (-OMe) and 3,5 (-Me) positions of the pyridine rings in TPMA increases the reducing ability of the corresponding copper(I) complexes. This increase was mostly the result of a stronger influence of substituted TPMA ligands toward stabilization of the copper(II) oxidation state (log β(I) = 13.4 ± 0.2, log β(II) = 19.3 (TPMA*(1)), 20.5 (TPMA*(2)), and 21.5 (TPMA*(3))). Lastly, ARGET ATRP kinetic studies show that with

  1. Aliphatic C-H bond oxidation of toluene using copper peroxo complexes that are stable at room temperature.

    Science.gov (United States)

    Würtele, Christian; Sander, Ole; Lutz, Volker; Waitz, Thomas; Tuczek, Felix; Schindler, Siegfried

    2009-06-10

    Dinuclear copper peroxo complexes obtained from mononuclear copper(I) complexes showed extremely high stabilities under ambient conditions in the solid state and could be heated above 100 degrees C without decomposition. The increased stability could be explained with regard to their molecular structures. Furthermore, the four complexes investigated showed a high potential for aliphatic C-H bond oxidations: for example, technical-grade toluene was oxidized to benzaldehyde in yields of up to 20%.

  2. Synthesis, characterization and antibacterial studies of a copper(II) levofloxacin ternary complex.

    Science.gov (United States)

    Sousa, Isabel; Claro, Vasco; Pereira, João Lino; Amaral, Ana Luísa; Cunha-Silva, Luís; de Castro, Baltazar; Feio, Maria J; Pereira, Eulália; Gameiro, Paula

    2012-05-01

    Solution behavior of levofloxacin (lvx) complexes with copper(II) in the presence and absence of phen was studied in aqueous solution, by potentiometry. The results obtained show that under physiological conditions (micromolar concentration range and pH 7.4) only copper(II):lvx:phen ternary complexes are stable. Hence, a novel copper(II) ternary complex of fluoroquinolone levofloxacin with nitrogen donor heterocyclic ligand phen was synthesized and characterized by means of UV-Visible and IR spectroscopy, elemental analysis and X-Ray crystallography. In the synthesized complex (1), [Cu(lvx)(phen)(H(2)O)](NO(3)).2H(2)O, levofloxacin acts as a bidentate ligand coordinating to the metal, in its anionic form, through the carbonyl and carboxyl oxygens and phen coordinates through two N-atoms forming the equatorial plane of a distorted square-pyramidal geometry. The fifth ligand of the penta-coordinated Cu(II) centre is occupied axially by an oxygen atom from a water molecule. Minimum inhibitory concentration (MIC) determinations of the complex and comparison with free levofloxacin in various E. coli strains indicated that the Cu-complex is as efficient an antimicrobial as the free antibiotic (both in the case of the dissolved synthesized complex and the complex formed following stoichiometric mixture of the individual components in solution). Moreover, results strongly suggest that the cell intake route of both species is different supporting, therefore, the complex's suitability as a candidate for further biological testing in fluoroquinolone-resistant microorganisms.

  3. N-Arylation of azaheterocycles with aryl and heteroaryl halides catalyzed by iminodiacetic acid resin-chelated copper complex

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Iminodiacetic acid resin-chelated copper(Ⅱ) complex is effective in cross-coupling reactions between azaheterocycles and aryl or heteroaryl halides,providing N-arylated products in good to excellent yields.The copper catalyst is air stable and can be readily recovered and reused with minimal loss of activity for three runs.

  4. The tachykinin peptide neurokinin B binds copper forming an unusual [CuII(NKB)2] complex and inhibits copper uptake into 1321N1 astrocytoma cells.

    Science.gov (United States)

    Russino, Debora; McDonald, Elle; Hejazi, Leila; Hanson, Graeme R; Jones, Christopher E

    2013-10-16

    Neurokinin B (NKB) is a member of the tachykinin family of neuropeptides that have neuroinflammatory, neuroimmunological, and neuroprotective functions. In a neuroprotective role, tachykinins can help protect cells against the neurotoxic processes observed in Alzheimer's disease. A change in copper homeostasis is a clear feature of Alzheimer's disease, and the dysregulation may be a contributory factor in toxicity. Copper has recently been shown to interact with neurokinin A and neuropeptide γ and can lead to generation of reactive oxygen species and peptide degradation, which suggests that copper may have a place in tachykinin function and potentially misfunction. To explore this, we have utilized a range of spectroscopic techniques to show that NKB, but not substance P, can bind Cu(II) in an unusual [Cu(II)(NKB)2] neutral complex that utilizes two N-terminal amine and two imidazole nitrogen ligands (from each molecule of NKB) and the binding substantially alters the structure of the peptide. Using 1321N1 astrocytoma cells, we show that copper can enter the cells and subsequently open plasma membrane calcium channels but when bound to neurokinin B copper ion uptake is inhibited. This data suggests a novel role for neurokinin B in protecting cells against copper-induced calcium changes and implicates the peptide in synaptic copper homeostasis.

  5. Type 1 copper site synthetic model complexes with increased redox potentials.

    Science.gov (United States)

    Yang, Lei; Tolman, William B

    2012-02-01

    Reactions of NaSCPh(3) with (R(3)tacn)Cu(OTf)(2) (R is Me, iPr; tacn is 1,4,7-triazacyclononane; OTf is CF(3)SO(3)(-)) yield blue complexes identified as ((R(3)tacn)CuSCPh(3))(OTf) on the basis of UV-vis, resonance Raman, and electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization mass spectrometry. These complexes exhibit spectroscopic properties typical of type 1 copper sites in proteins, including diagnostic Sπ → Cu(d(x(2)-y(2))) ligand-to-metal charge transfer transitions at approximately 610-630 nm and small A(||) values in EPR spectra of less than 100 × 10(-4) cm(-1). Cyclic voltammetry experiments revealed redox potentials for the complexes similar to those of several low-potential type 1 copper proteins (e.g., azurin, stellacyanin) and approximately 0.5 V higher than those of previously reported model compounds. Thus, the new complexes mimic key aspects of both the structure and the function of type 1 copper sites.

  6. Di- and Trinuclear Mixed-Valence Copper Amidinate Complexes from Reduction of Iodine.

    Science.gov (United States)

    Lane, Andrew C; Barnes, Charles L; Antholine, William E; Wang, Denan; Fiedler, Adam T; Walensky, Justin R

    2015-09-08

    Molecular examples of mixed-valence copper complexes through chemical oxidation are rare but invoked in the mechanism of substrate activation, especially oxygen, in copper-containing enzymes. To examine the cooperative chemistry between two metals in close proximity to each other we began studying the reactivity of a dinuclear Cu(I) amidinate complex. The reaction of [(2,6-Me2C6H3N)2C(H)]2Cu2, 1, with I2 in tetrahydrofuran (THF), CH3CN, and toluene affords three new mixed-valence copper complexes [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I3)(THF)2, 2, [(2,6-Me2C6H3N)2C(H)]2Cu2(μ2-I) (NCMe)2, 3, and [(2,6-Me2C6H3N)2C(H)]3Cu3(μ3-I)2, 4, respectively. The first two compounds were characterized by UV-vis and electron paramagnetic resonance spectroscopies, and their molecular structure was determined by X-ray crystallography. Both di- and trinuclear mixed-valence intermediates were characterized for the reaction of compound 1 to compound 4, and the molecular structure of 4 was determined by X-ray crystallography. The electronic structure of each of these complexes was also investigated using density functional theory.

  7. Redox Activity of Copper(II) Complexes with NSFRY Pentapeptide and Its Analogues

    Science.gov (United States)

    Wiloch, Magdalena Zofia; Wawrzyniak, Urszula Elżbieta; Ufnalska, Iwona; Piotrowski, Grzegorz; Bonna, Arkadiusz; Wróblewski, Wojciech

    2016-01-01

    The influence of cation-π interactions on the electrochemical properties of copper(II) complexes with synthesized pentapeptide C-terminal fragment of Atrial Natriuretic Factor (ANF) hormone was studied in this work. Molecular modeling performed for Cu(II)-NSFRY-NH2 complex indicated that the cation-π interactions between Tyr and Cu(II), and also between Phe-Arg led to specific conformation defined as peptide box, in which the metal cation is isolated from the solvent by peptide ligand. Voltammetry experiments enabled to compare the redox properties and stability of copper(II) complexes with NSFRY-NH2 and its analogues (namely: NSFRA-NH2, NSFRF-NH2, NSAAY-NH2, NSAAA-NH2, AAAAA-NH2) as well as to evaluate the contribution of individual amino acid residues to these properties. The obtained results led to the conclusion, that cation-π interactions play a crucial role in the effective stabilization of copper(II) complexes with the fragments of ANF peptide hormone and therefore could control the redox processes in other metalloproteins. PMID:27517864

  8. Synthesis and Magnetic Studies of Copper ( Ⅱ )-Manganese (Ⅱ)Heterobinuclear Complexes with an Oxamido Bridge

    Institute of Scientific and Technical Information of China (English)

    LI, Yan-Tuan; YAN, Cui-Wei; LIAO, Dai-Zheng

    2001-01-01

    Four new copper ( Ⅱ )-manganese ( Ⅱ ) beterobinuclear complexes bridged by N, N' -bis[ 2- (dimethylamino) ethyl) ] oxamido dianion (dmoxae) and end-capped with 1,10-phenanthroline (phen), 5-methyl-1, l0-phenanthroline (Mephen), diaminoethane (en) or 1,3-di-aminopropane (pn), respectively, namely, [Cu(dmoxae)MnL2](CO4)2 (L= phen, Mephen, en, pn), have been synthesized and characterized by elemental analyses, IR, electronic spectral studies, and molar conductivity measurements. The electronic reflectance spectrum indicates the presence of spin exchange-coupling interaction between bridged copper (Ⅱ) and manganese (Ⅱ) ions.The cryomagnetic measurements (4.2-300 K) of [ Cu(dmoxae)Mn(phen)2](ClO4)2 ( 1 ) and [Cu(dmoxae)Mn(Mephen)2](ClO4)2(2) complexes demonstrated an antiferromagnetic interaction between the adjacent manganese(Ⅱ) and copper (Ⅱ) ions through the oxamido-bridge within each molecule. On the basis of spin Hamiltonian, H^ = - 2JS^1·S^2,the magnetic analysis was carried out for the two complexes and the spin-coupling constant (J) was evaluated as - 35.9cm-1 for 1 and - 32.6 cm-1 for 2. The influence of methyl substitutions in the amine groups of the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.

  9. Ciprofloxacin containing Mannich base and its copper complex induce antitumor activity via different mechanism of action.

    Science.gov (United States)

    Fu, Yun; Yang, Yingli; Zhou, Sufeng; Liu, Youxun; Yuan, Yanbin; Li, Shaoshan; Li, Changzheng

    2014-11-01

    The Mannich base containing ciprofloxacin and kojic acid structural units was prepared and evaluated in antitumor activity. The enhancement in antitumor activity was observed both from the Mannich base (IC(50): 103.3±5.0 µM for HepG2, 87.9±8.0 µM for HCT-116 cell) and its copper complex (IC(50): 11.5±1.8 µM for HepG2, 44.4±2.5 µM for HCT-116 cell) compared to the ciprofloxacin and kojic acid. The mechanistic studies via RT-PCR, cell cycle analysis, mitochondrial membrane potential measurement, inhibition of topoisomerase and molecular docking indicated that there is a different molecular mechanism between the Mannich base and its copper complex. The cytotoxicity of the Mannich base was involved in apoptosis, cell cycle arrest, depolarization of mitochondrial membrane and weaker topoisomerase II inhibition, but the copper complex exerted its cytotoxicity mainly through dual topoisomerase inhibition, especially stabilizing the intermediate of cleavage DNA-topoisomerase complex.

  10. 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.

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

    Science.gov (United States)

    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; Sluis, Bart van de; 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 interacts with the multisubunit WASH complex, an evolutionarily conserved system, which is required for endosomal deposition of F-actin and cargo trafficking in conjunction with the retromer. Interactions between the WASH complex subunit FAM21, and the carboxyl-terminal ends of CCDC22 and CCDC93 are responsible for CCC complex recruitment to endosomes. We show that depletion of CCC complex components leads to lack of copper-dependent movement of the copper transporter ATP7A from endosomes, resulting in intracellular copper accumulation and modest alterations in copper homeostasis in humans with CCDC22 mutations. This work provides a mechanistic explanation for the role of COMMD1 in copper homeostasis and uncovers additional genes involved in the regulation of copper transporter recycling.

  12. Electrocatalytic water oxidation with a copper(II) polypeptide complex.

    Science.gov (United States)

    Zhang, Ming-Tian; Chen, Zuofeng; Kang, Peng; Meyer, Thomas J

    2013-02-13

    A self-assembly-formed triglycylglycine macrocyclic ligand (TGG(4-)) complex of Cu(II), [(TGG(4-))Cu(II)-OH(2)](2-), efficiently catalyzes water oxidation in a phosphate buffer at pH 11 at room temperature by a well-defined mechanism. In the mechanism, initial oxidation to Cu(III) is followed by further oxidation to a formal "Cu(IV)" with formation of a peroxide intermediate, which undergoes further oxidation to release oxygen and close the catalytic cycle. The catalyst exhibits high stability and activity toward water oxidation under these conditions with a high turnover frequency of 33 s(-1).

  13. 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

  14. A new stepped tetranuclear copper(II) complex: synthesis, crystal structure and photoluminescence properties.

    Science.gov (United States)

    Gungor, Elif

    2017-05-01

    Binuclear and tetranuclear copper(II) complexes are of interest because of their structural, magnetic and photoluminescence properties. Of the several important configurations of tetranuclear copper(II) complexes, there are limited reports on the crystal structures and solid-state photoluminescence properties of `stepped' tetranuclear copper(II) complexes. A new Cu(II) complex, namely bis{μ3-3-[(4-methoxy-2-oxidobenzylidene)amino]propanolato}bis{μ2-3-[(4-methoxy-2-oxidobenzylidene)amino]propanolato}tetracopper(II), [Cu4(C11H13NO3)4], has been synthesized and characterized using elemental analysis, FT-IR, solid-state UV-Vis spectroscopy and single-crystal X-ray diffraction. The crystal structure determination shows that the complex is a stepped tetranuclear structure consisting of two dinuclear [Cu2(L)2] units {L is 3-[(4-methoxy-2-oxidobenzylidene)amino]propanolate}. The two terminal Cu(II) atoms are four-coordinated in square-planar environments, while the two central Cu(II) atoms are five-coordinated in square-pyramidal environments. The solid-state photoluminescence properties of both the complex and 3-[(2-hydroxy-4-methoxybenzylidene)amino]propanol (H2L) have been investigated at room temperature in the visible region. When the complex and H2L are excited under UV light at 349 nm, the complex displays a strong blue emission at 469 nm and H2L displays a green emission at 515 nm.

  15. Synthesis, characterization and antibacterial studies of a copper(II) lomefloxacin ternary complex.

    Science.gov (United States)

    Fernandes, Patrícia; Sousa, Isabel; Cunha-Silva, Luís; Ferreira, Mariana; de Castro, Baltazar; Pereira, Eulália F; Feio, Maria J; Gameiro, Paula

    2014-02-01

    Solution behavior of lomefloxacin (lmx) complexes with copper(II) in the presence and absence of 1,10-phenanthroline (phen) was studied in aqueous solution, by potentiometry. The results obtained showed that under physiological conditions (micromolar concentration range and pH7.4) only copper(II):lmx:phen ternary complexes are stable. Hence, a novel copper(II) ternary complex of lomefloxacin with the nitrogen donor heterocyclic ligand phen was synthesized and characterized by means of UV-visible and IR spectroscopy, elemental analysis and X-ray crystallography. In the synthesized complex (1), [Cu(lmx)(phen)(NO3)]·5H2O, lmx acts as a bidentate ligand coordinating the metal cation, in its anionic form, through the carbonyl and carboxyl oxygens and phen coordinates through two N-atoms forming the equatorial plane of a distorted square-pyramidal geometry. The fifth ligand of the penta-coordinated Cu(II) center is occupied axially by an oxygen atom from the nitrate ion. Minimum inhibitory concentration (MIC) determinations of the complex and comparison with free lomefloxacin in various E. coli strains indicated that the Cu-complex is an antimicrobial which is as efficient as the free antibiotic but strongly suggest that the cell intake route of both species is different. Moreover, spectrophotometric stability studies suggest that the solution of the complex synthesized is considerably more photostable than the free fluoroquinolone supporting, therefore, the complex's suitability as a candidate for further biological testing in fluoroquinolone-resistant microorganisms with possible reduced side-effects.

  16. 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.

  17. Catecholase activity investigations using in situ copper complexes continuing Schiff base derivatives with a theoretical calculation

    Directory of Open Access Journals (Sweden)

    A. Djedouani

    2015-03-01

    Full Text Available The study of catecholase activity of a series of Schiff base compounds using in situ copper complexes of 4-hydroxy-6-methyl-3-(1-(phenyliminoethyl-2H-pyran-2-one derivatives has been reported. The reaction rate depends on four parameters: The nature of the substitution in para position to the benzene ring, the nature of counter anion, the concentration of ligand and the nature of solvent. The highest rate activity is given by complex resulting from one equivalent of ligand L2 and two equivalents of copper acetate in methanol, which equal to 62.25 µmol.min-1.L-1.In other part, a theoretical study of such ligands using the semi-empirical method AM1 were also investigated. A good relationship founded between the maximal reaction rate (Vmax and the HOMO energy (Pearson correlation: r=-0.794.

  18. Breast Cancer Stem Cell Potent Copper(II)-Non-Steroidal Anti-Inflammatory Drug Complexes.

    Science.gov (United States)

    Boodram, Janine N; Mcgregor, Iain J; Bruno, Peter M; Cressey, Paul B; Hemann, Michael T; Suntharalingam, Kogularamanan

    2016-02-18

    The breast cancer stem cell (CSC) potency of a series of copper(II)-phenanthroline complexes containing the nonsteroidal anti-inflammatory drug (NSAID), indomethacin, is reported. The most effective copper(II) complex in this series, 4, selectivity kills breast CSC-enriched HMLER-shEcad cells over breast CSC-depleted HMLER cells. Furthermore, 4 reduces the formation, size, and viability of mammospheres, to a greater extent than salinomycin, a potassium ionophore known to selectively inhibit CSCs. Mechanistic studies revealed that the CSC-specificity observed for 4 arises from its ability to generate intracellular reactive oxygen species (ROS) and inhibit cyclooxygenase-2 (COX-2), an enzyme that is overexpressed in breast CSCs. The former induces DNA damage, activates JNK and p38 pathways, and leads to apoptosis.

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

    Directory of Open Access Journals (Sweden)

    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

  20. Synthesis, structural characterization, and magnetic properties of a copper-gadolinium complex derived from a hydroxybenzohydrazide ligand.

    Science.gov (United States)

    Costes, Jean-Pierre; Duhayon, Carine; Vendier, Laure

    2014-02-17

    The reaction of hydroxybenzohydrazide with o-vanillin yields 2-hydroxy-N'-[(2-hydroxy-3-methoxyphenyl)methylidene]benzohydrazide (LH3), a ligand that is able to give mononuclear and tetranuclear copper complexes but also to associate copper and gadolinium ions in a Cu2-Gd2 heterotetranuclear complex. This synthesis is successful if the Gd ions, which are acidic in protic solvents, are introduced in a basic methanol solution of the mononuclear copper complex. In the absence of piperidine, the addition of Gd ions to a methanol solution of the mononuclear copper complex only yields a tetranuclear cubane-type copper complex. This work reports on the first structural characterization of a copper-gadolinium complex involving a benzohydrazide ligand. The resulting complex consists of two Cu-Gd pairs linked by a dihydroxo Gd-Gd bridge, in which the Cu and Gd ions are bridged by a nonsymmetric phenoxo-hydroxo bridge. The magnetostructural correlation between the ferromagnetic coupling constant and the hinge angle observed in symmetrical double-phenoxo Cu-Gd bridges remains valid for dissymmetric Cu-Gd bridges and confirms the preponderance of the structural factor over the nature of the bridge. This tetranuclear complex corresponds to two S = 4 units linked through a dihydroxo bridge introducing a weak antiferromagnetic Gd-Gd interaction and impeding the existence of a S = 8 ground state.

  1. Copper (II) complexes possessing alkyl-substituted polypyridyl ligands: Structural characterization and in vitro antitumor activity.

    Science.gov (United States)

    Angel, Noah R; Khatib, Raneen M; Jenkins, Julia; Smith, Michelle; Rubalcava, Justin M; Le, Brian Khoa; Lussier, Daniel; Chen, Zhuo Georgia; Tham, Fook S; Wilson, Emma H; Eichler, Jack F

    2017-01-01

    In an effort to find alternatives to the antitumor drug cisplatin, a series of copper (II) complexes possessing alkyl-substituted polypyridyl ligands have been synthesized. Eight new complexes are reported herein: μ-dichloro-bis{2,9-di-sec-butyl-1,10-phenanthrolinechlorocopper(II)} {[((di-sec-butyl)phen)ClCu(μ-Cl)2CuCl((di-sec-butyl)phen)]}(1), 2-sec-butyl-1,10-phenanthrolinedichlorocopper(II) {([mono-sec-butyl)phen) CuCl2} (2), 2,9-di-n-butyl-1,10-phenanthrolinedichlorocopper(II) {[(di-n-butyl)phen) CuCl2}(3), 2-n-butyl-1,10-phenanthrolinedichlorocopper(II) {[(mono-n-butyl)phen) CuCl2} (4), 2,9-di-methyl-1,10-phenanthrolineaquadichlorocopper(II) {[(di-methyl)phen) Cu(H2O)Cl2}(5), μ-dichloro-bis{6-sec-butyl-2,2'-bipyridinedichlorocopper(II)} {((mono-sec-butyl)bipy) ClCu(μ-Cl)2CuCl((mono-sec-butyl)bipy)} (6), 6,6'-di-methyl-2,2'-bipyridinedichlorocopper(II) {(6,6'-di-methyl)bipy) CuCl2} (7), and 4,4'-dimethyl-2,2'-bipyridinedichlorocopper(II) {(4,4'-di-methyl)bipy) CuCl2} (8). These complexes have been characterized via elemental analysis, UV-vis spectroscopy, and mass spectrometry. Single crystal X-ray diffraction experiments revealed the complexes synthesized with the (di-sec-butyl)phen ligand (1) and (mono-sec-butyl)bipy ligand (6) crystallized as dimers in which two copper(II) centers are bridged by two chloride ligands. Conversely, complexes 2, 7, and 8 were isolated as monomeric species possessing distorted tetrahedral geometries, and the [((di-methyl)phen)Cu(H2O)Cl2] (5) complex was isolated as a distorted square pyramidal monomer possessing a coordinating aqua ligand. Compounds 1-8 were evaluated for their in vitro antitumor efficacy. Compounds 1, 5, and 7 in particular were found to exhibit remarkable activity against human derived lung cancer cells, yet this class of copper(II) compounds had minimal cytotoxic effect on non-cancerous cells. In vitro control experiments indicate the activity of the copper(II) complexes most likely does not arise from the

  2. Lanthanide-isophthalate cavity frameworks encapsulated copper(I) complexes

    Science.gov (United States)

    Zhou, Youfu; Yuan, Daqiang; Jiang, Feilong; Xu, Yanqing; Hong, Maochun

    2006-08-01

    The hydrothermal reactions of Ln 2O 3, [Cu(2,2'-bpy) 2](ClO 4) and isophthalic acid (H 2ip) yielded a series of heterometallic coordination frameworks with the empirical formula [{Ln 4(ip) 7(H 2O) 2}{Cu(bpy) 2} 2] n [Ln=Nd ( 1), Sm ( 2), Eu ( 3)]. Single-crystal X-ray diffraction analyses reveal that they are isostructural and possess a 3D cavity framework with two complex cations [Cu(2,2'-bpy) 2] + encapsulated in each cavity. TGA curve shows that they are highly thermally stable. Magnetic studies illustrate weakly antiferromagnetic exchange interactions between lanthanide(III) ions at room temperature in 1- 3. Compound 2 has interesting photoluminescent property owing to the coexistence of host and guest photoluminescent units.

  3. Synthesis, Characterization, Molecular Modeling, and DNA Interaction Studies of Copper Complex Containing Food Additive Carmoisine Dye.

    Science.gov (United States)

    Shahabadi, Nahid; Akbari, Alireza; Jamshidbeigi, Mina; Khodarahmi, Reza

    2016-06-02

    A copper complex of carmoisine dye; [Cu(carmoisine)2(H2O)2]; was synthesized and characterized by using physico-chemical and spectroscopic methods. The binding of this complex with calf thymus (ct) DNA was investigated by circular dichroism, absorption studies, emission spectroscopy, and viscosity measurements. UV-vis results confirmed that the Cu complex interacted with DNA to form a ground-state complex and the observed binding constant (2× 10(4) M(-1)) is more in keeping with the groove bindings with DNA. Furthermore, the viscosity measurement result showed that the addition of complex causes no significant change on DNA viscosity and it indicated that the intercalation mode is ruled out. The thermodynamic parameters are calculated by van't Hoff equation, which demonstrated that hydrogen bonds and van der Waals interactions played major roles in the reaction. The results of circular dichroism (CD) suggested that the complex can change the conformation of DNA from B-like form toward A-like conformation. The cytotoxicity studies of the carmoisine dye and its copper complex indicated that both of them had anticancer effects on HT-29 (colon cancer) cell line and they may be new candidates for treatment of the colon cancer.

  4. 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.

  5. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

    Directory of Open Access Journals (Sweden)

    Frantisek Jelen

    2008-01-01

    Full Text Available Using a paraffin impregnated graphite electrode (PIGE and mercury-modifiedpyrolytic graphite electrode with basal orientation (Hg-PGEb copper(II and Cu(II-DNApurine base solutions have been studied by cyclic (CV and linear sweep voltammetry(LSV in connection with elimination voltammetry with linear scan (EVLS. In chlorideand bromide solutions (pH 6, the redox process of Cu(II proceeded on PIGE with twocathodic and two anodic potentially separated signals. According to the eliminationfunction E4, the first cathodic peak corresponds to the reduction Cu(II e- → Cu(I withthe possibility of fast disproportionation 2Cu(I → Cu(II Cu(0. The E4 of the secondcathodic peak signalized an electrode process controlled by a surface reaction. Theelectrode system of Cu(II on Hg-PGEb in borate buffer (pH 9.2 was characterized by onecathodic and one anodic peak. Anodic stripping voltammetry (ASV on PIGE and cathodicstripping voltammetry (CSV on Hg-PGEb were carried out at potentials where thereduction of copper ions took place and Cu(I-purine complexes were formed. By usingASV and CSV in combination with EVLS, the sensitivity of Cu(I-purine complexdetection was enhanced relative to either ASV or CSV alone, resulting in higher peakcurrents of more than one order of magnitude. The statistical treatment of CE data wasused to determine the reproducibility of measurements. Our results show that EVLS inconnection with the stripping procedure is useful for both qualitative and quantitativemicroanalysis of purine derivatives and can also reveal details of studied electrodeprocesses.

  6. Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry.

    Science.gov (United States)

    Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

    2008-01-24

    Using a paraffin impregnated graphite electrode (PIGE) and mercury-modifiedpyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNApurine base solutions have been studied by cyclic (CV) and linear sweep voltammetry(LSV) in connection with elimination voltammetry with linear scan (EVLS). In chlorideand bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with twocathodic and two anodic potentially separated signals. According to the eliminationfunction E4, the first cathodic peak corresponds to the reduction Cu(II) e⁻ → Cu(I) withthe possibility of fast disproportionation 2Cu(I) → Cu(II) Cu(0). The E4 of the secondcathodic peak signalized an electrode process controlled by a surface reaction. Theelectrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by onecathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodicstripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where thereduction of copper ions took place and Cu(I)-purine complexes were formed. By usingASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complexdetection was enhanced relative to either ASV or CSV alone, resulting in higher peakcurrents of more than one order of magnitude. The statistical treatment of CE data wasused to determine the reproducibility of measurements. Our results show that EVLS inconnection with the stripping procedure is useful for both qualitative and quantitativemicroanalysis of purine derivatives and can also reveal details of studied electrodeprocesses.

  7. Synthesis and thermal studies of tetraaza macrocylic ligand and its transition metal complexes. DNA binding affinity of copper complex.

    Science.gov (United States)

    Saif, M; Mashaly, Mahmoud M; Eid, Mohamed F; Fouad, R

    2011-09-01

    A Tetraaza Macrocylic Ligand (H2L) and its complexes, [Cd(H2L)(OH2)2](NO3)(2)·1/2OH2 (I), [Co(H2L)(OH2)](NO3)(2)·1/2OH2 (II), [Cu(H2L)(NO3)2]·3/2OH2 (III) and [Ni(H2L)(NO3)(OH2)]NO3·OH2 (IV), have been synthesized and characterized on the basis of elemental analysis, molar conductivity, 1H NMR, UV-vis, FT-IR and mass spectroscopy. All results confirm that the prepared compounds have 1:1 metal-to-ligand stoichiometry, octahedral configuration and the ligand behaves as a neutral tetradendate towards the metal ions. [CdL(OH2)2] (V), [CoL(OH2)2] (VI), [CuL(OH2)2] (VII) and [Ni(H2L)(NO3)2] (VIII) were synthesized pyrolytically in solid state from corresponding compounds (I-IV). Analytical results of complexes (V-VIII) show that the ligand behaves either as a neutral tetradendate or dianionic tetradentate ligand towards the metal ions. The binding of H2L and its copper complex (III) to DNA has been investigated by ultraviolet absorption spectroscopy. The experiments indicate that H2L and its copper complex (III) can bind to DNA through an intercalative mode. The H2L and its copper complex (III) exhibited anti-tumor activity against Ehrlich Acites Carcinoma (E.A.C) at the concentration of 100 μg/ml.

  8. Synthesis and thermal studies of tetraaza macrocylic ligand and its transition metal complexes. DNA binding affinity of copper complex

    Science.gov (United States)

    Saif, M.; Mashaly, Mahmoud M.; Eid, Mohamed F.; Fouad, R.

    2011-09-01

    A Tetraaza Macrocylic Ligand (H 2L) and its complexes, [Cd(H 2L)(OH 2) 2](NO 3) 2·1/2OH 2 (I), [Co(H 2L)(OH 2)](NO 3) 2·1/2OH 2 (II), [Cu(H 2L)(NO 3) 2]·3/2OH 2 (III) and [Ni(H 2L)(NO 3)(OH 2)]NO 3·OH 2 (IV), have been synthesized and characterized on the basis of elemental analysis, molar conductivity, 1H NMR, UV-vis, FT-IR and mass spectroscopy. All results confirm that the prepared compounds have 1:1 metal-to-ligand stoichiometry, octahedral configuration and the ligand behaves as a neutral tetradendate towards the metal ions. [CdL(OH 2) 2] (V), [CoL(OH 2) 2] (VI), [CuL(OH 2) 2] (VII) and [Ni(H 2L)(NO 3) 2] (VIII) were synthesized pyrolytically in solid state from corresponding compounds (I-IV). Analytical results of complexes (V-VIII) show that the ligand behaves either as a neutral tetradendate or dianionic tetradentate ligand towards the metal ions. The binding of H 2L and its copper complex (III) to DNA has been investigated by ultraviolet absorption spectroscopy. The experiments indicate that H 2L and its copper complex (III) can bind to DNA through an intercalative mode. The H 2L and its copper complex (III) exhibited anti-tumor activity against Ehrlich Acites Carcinoma (E.A.C) at the concentration of 100 μg/ml.

  9. 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.

  10. Synthesis, Characterization and Magnetic Studies of μ-Oxamido Copper(Ⅱ) -Chromium (Ⅲ) Heterodinuclear Complexes

    Institute of Scientific and Technical Information of China (English)

    李延团; 胡春霞; 焉翠蔚; 廖代正

    2001-01-01

    Three new μ-oxamido-bridged heterodinuclear copper (Ⅱ)-chromium(Ⅲ) complexes formulated[Cu(Me2 oxpn)Cr(L)2](NO3)3, where Me2 oxpn denotes N, N'-bis(3-amino-2,2-dimethylpropyl)oxamido dianion and L represents 5-methy1, 10-phenanthroline(Mephen), 4, 7-diphenl-1, 10-phenanthroline (Ph2phen) or 2,2'-bipyridine(bpy), have ben synthesized and characterized by elemental analyses,IR and electronic spectral studies, magnetic moments of room-temperature and molar conductivity measurements.It is proposed that these complexes have oxamido-bridged structures consisting of planar copper(Ⅱ) and octahedral chromium(Ⅲ) ions. The variable temperature magnetic susceptibilities (4.2-300 K)of complexes [Cu(Me2 oxpn)Cr(Ph2phen)2](NO3)3 (1) and [Cu(Me2 ocpn)Cr(Mephen)2] (NO3)3 (2) were further measured and studied, demonstrating the ferromagnetic interaction between the adjacent chromium(Ⅲ)and copper(Ⅱ)ions through the oxamido-bridge in both camplexes 1 and 2.Based on the spin Hamiltonian, H= -2JS1.S2, the exclange integrals J were evaluated as +21.5 cm-1 for 1 and +22.8 cm-1 for 2.

  11. Synthesis and Crystal Structure of a New Mononuclear Copper Complex

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new kind of Cu (Ⅱ) complex [Cu(tpmb)2Cl2]@CH3OH@H2O (tpmb = 1,3,5-tri(2- pyrimidinyl)sulfanylmethyl-2,4,6-trimethylbenzene) was synthesized, and its structure has been determined by X-ray single-crystal diffraction. It crystallizes in the triclinic, space group P ī with a = 8.8397(2), b = 13.327(3), c = 13.926(3) (A), ( = 63.27(3), ( = 86.96(3), ( = 80.68(3)°, V = 1445.6(5) (A)3, C49H51Cl2CuN12O2S6, Mr = 1166.82, Z = 1, F(000) = 604, Dc = 1.340 g/cm3, μ = 0.735 mm-1, R = 0.0545 and wR = 0.1575 for 4521 observed reflections (I > 2σ(I)). X-ray analysis reveals that the Cu (Ⅱ) ion is coordinated by two Cl- anions and two nitrogen atoms from different pyrimidine groups, forming a square structure.

  12. Mixed metal copper(II)-nickel(II) and copper(II)-zinc(II) complexes of multihistidine peptide fragments of human prion protein.

    Science.gov (United States)

    Jószai, Viktória; Turi, Ildikó; Kállay, Csilla; Pappalardo, Giuseppe; Di Natale, Giuseppe; Rizzarelli, Enrico; Sóvágó, Imre

    2012-07-01

    Mixed metal copper(II)-nickel(II) and copper(II)-zinc(II) complexes of four peptide fragments of human prion protein have been studied by potentiometric, UV-vis and circular dichroism spectroscopic techniques. One peptide contained three histidyl residues: HuPrP(84-114) with H85 inside and H96, H111 outside the octarepeat domain. The other three peptides contained two histidyl residues; H96 and H111 for HuPrP(91-115) and HuPrP(84-114)H85A while HuPrP(84-114)H96A contained the histidyl residues at positions 85 and 111. It was found that both histidines of the latter peptides can simultaneously bind copper(II) and nickel(II) ions and dinuclear mixed metal complexes can exist in slightly alkaline solution. One molecule of the peptide with three histidyl residues can bind two copper(II) and one nickel(II) ions. H85 and H111 were identified as the major copper(II) and H96 as the preferred nickel(II) binding sites in mixed metal species. The studies on the zinc(II)-PrP peptide binary systems revealed that zinc(II) ions can coordinate to the 31-mer PrP peptide fragments in the form of macrochelates with two or three coordinated imidazol-nitrogens but the low stability of these complexes cannot prevent the hydrolysis of the metal ion in slightly alkaline solution. These data provide further support for the outstanding affinity of copper(II) ions towards the peptide fragments of prion protein but the binding of nickel(II) can significantly modify the distribution of copper(II) among the available metal binding sites.

  13. Copper N-Heterocyclic Carbene Complexes As Active Catalysts for the Synthesis of 2-Substituted Oxazolines from Nitriles and Aminoalcohols.

    Science.gov (United States)

    Trose, Michael; Lazreg, Faïma; Lesieur, Mathieu; Cazin, Catherine S J

    2015-10-16

    The reaction between nitriles and aminoalcohols to access 2-substituted oxazolines was investigated. Using copper-NHC complexes, various nitriles were successfully converted into the corresponding oxazolines, under milder and less wasteful conditions than those of previously reported methods.

  14. Effect of organic complexation on copper accumulation and toxicity to the estuarine red macroalga Ceramium tenuicorne: a test of the free ion activity model.

    Science.gov (United States)

    Ytreberg, Erik; Karlsson, Jenny; Hoppe, Sabina; Eklund, Britta; Ndungu, Kuria

    2011-04-01

    Current water quality criteria (WQC) regulations on copper toxicity to biota are still based on total dissolved (MINTEQ incorporating the Stockholm Humic Model) show that copper accumulation in C. tenuicorne only correlates linearly well to [Cu2+] at relatively high [Cu2+] and in the absence of fulvic acid. Thus the FIAM fails to describe copper accumulation in C. tenuicorne at copper and DOC concentrations typical of most marine waters. These results seem to indicate that at ambient total dissolved copper concentration in coastal and estuarine waters, C. tenuicorne might be able to access a sizable fraction of organically complexed copper when free copper concentration to the cell membrane is diffusion limited.

  15. Copper-, palladium-, and platinum-containing complexes of an asymmetric dinucleating ligand.

    Science.gov (United States)

    Halvagar, Mohammad Reza; Neisen, Benjamin; Tolman, William B

    2013-01-18

    The coordination chemistry of an asymmetric dinucleating hexadentate ligand LH(2) comprising neutral alkyltriamine and potentially dianionic dicarboxamido-pyridyl donor sets with copper, palladium, and platinum has been explored. Monometallic, dicopper, and heterodinuclear Cu-Pd and -Pt complexes have been prepared and characterized, including by NMR, EPR, UV-vis, and IR spectroscopy and X-ray crystallography. For example, the monometallic complexes [(LH(2))MCl]X (M = Cu, X = OTf; M = Pd or Pt, X = Cl) were prepared, wherein the metal(II) ions are coordinated to the triamine portion and the pyridyldicarboxamide is unperturbed. Treatment of LH(2) with [MesCu](x) (Mes = mesityl) provided a monocopper(I) complex, again with the metal coordinated only to the trialkylamine donor set. Reaction of [(LH(2))CuCl]OTf with NaOMe resulted in an unexpected migration of the copper(II)-chloride fragment to the pyridyldicarboxamide site to yield Na[LCuCl], from which a dicopper complex LCu(2)Cl(2) and mixed-metal complexes LCu(Cl)M(Cl) (M = Pd, Pt) were prepared by addition of CuCl(2) or MCl(2), respectively. The heterodinuclear complexes were also prepared by addition of CuCl(2) to [(LH(2))MCl]Cl.

  16. Antiproliferative effects of copper(II)-polypyridyl complexes in breast cancer cells through inducing apoptosis.

    Science.gov (United States)

    Salimi, Mona; Abdi, Khatereh; Kandelous, Hirsa Mostafapour; Hadadzadeh, Hassan; Azadmanesh, Kayhan; Amanzadeh, Amir; Sanati, Hassan

    2015-04-01

    Although cisplatin has been used for decades to treat human cancer, some toxic side effects and resistance are observed. Previous investigations have suggested copper complexes as a novel class of tumor-cell apoptosis inducers. The present study aimed to evaluate the anti-breast cancer activities of two polypyridyl-based copper(II) complexes, [Cu(tpy)(dppz)](NO3)2 (1) and [Cu(tptz)2](NO3)2 (2) (tpy = 2,2':6',2″-terpyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine, tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine), using human breast adenocarcinoma cell line (MCF-7). The ability of the complexes to cleave supercoiled DNA in the presence and absence of external agents was also examined. The apoptotic activities of the complexes were assessed using flow cytometry, fluorescence microscope and western blotting analysis. Our results indicated the high DNA affinity and nuclease activity of complexes 1 and 2. The cleavage mechanisms between the complexes and plasmid DNA are likely to involve a singlet oxygen or singlet oxygen-like entity as the reactive oxygen species. Complexes 1 and 2 also significantly inhibited the proliferation of MCF-7 cells in a dose-dependent manner (IC50 values = 4.57 and 1.98 μM at 24 h, respectively). Complex 2 remarkably induced MCF-7 cells to undergo apoptosis, which was demonstrated by cell morphology, annexin-V and propidium iodide staining. The caspase cascade was activated as shown by the proteolytic cleavage of caspase-3 after treatment of MCF-7 cells with complex 2. Additionally, complex 2 significantly increased the expression of the Bax-to-Bcl-2 ratio to induce apoptosis. In conclusion, these results revealed that complex 2 may be a potential and promising chemotherapeutic agent to treat breast cancer.

  17. Sulfate-bridged dimeric trinuclear copper(II)-pyrazolate complex with three different terminal ligands.

    Science.gov (United States)

    Mezei, Gellert

    2016-08-01

    The reaction of CuSO4·5H2O, 4-chloro-pyrazole (4-Cl-pzH) and tri-ethyl-amine (Et3N) in di-methyl-formamide (DMF) produced crystals of di-aqua-hexa-kis-(μ-4-chloro-pyrazolato-κ(2) N:N')bis-(N,N-di-methyl-formamide)di-μ3-hydroxido-bis-(μ4-sulfato-κ(4) O:O':O'':O'')hexa-copper(II) N,N-di-methyl-formamide tetra-solvate dihydrate, [Cu3(OH)(SO4)(C3H2ClN2)3(C3H7NO)(H2O)]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper-pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper-pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the Cu(II) atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square-pyramidal coordination geometry around each copper cation. The metal complex and solvent mol-ecules are involved in O-H⋯O hydrogen bonds, leading to a two-dimensional network parallel to (10-1).

  18. Novel copper-based therapeutic agent for anti-inflammatory: synthesis, characterization, and biochemical activities of copper(II) complexes of hydroxyflavone Schiff bases.

    Science.gov (United States)

    Joseph, J; Nagashri, K

    2012-07-01

    Four hydroxyflavone derivatives have been synthesized with the aim of obtaining a good model of superoxide dismutase. Better to mimic the natural metalloenzyme, copper complexes have been designed. The Cu(II) complexes of general formulae, [CuL] where L = 5-hydroxyflavone-o-phenylenediamine (L¹H₂)/m-phenylenediamine (L²H₂) and 3-hydroxyflavone-o-phenylenediamine (L³H₂)/m-phenylenediamine (L⁴H₂) have been synthesized. The structural features have been determined from their analytical and spectral data. All the Cu(II) complexes exhibit square planar geometry. Redox behavior of copper complexes was studied and the present ligand systems stabilize the unusual oxidation state of the copper ion during electrolysis. The in vitro antimicrobial activities of the investigated compounds were tested 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. Superoxide dismutase and anti-inflammatory activities of the copper complexes have also been measured and discussed.

  19. Insight in the transport behavior of copper glycinate complexes through the porcine gastrointestinal membrane using an Ussing chamber assisted by mass spectrometry analysis.

    Science.gov (United States)

    Tastet, Laure; Schaumlöffel, Dirk; Yiannikouris, Alexandros; Power, Ronan; Lobinski, Ryszard

    2010-04-01

    An Ussing chamber study was conducted in order to investigate the transport behavior of copper glycinate complexes through a porcine gastrointestinal membrane. Organic copper complexes such as copper tri- and tetraglycinates (GGG-Cu(II) and GGGG-Cu(II)) were used as model system. In a novel analytical approach the Ussing chamber was combined with mass spectrometry. Therefore, relevant analytical methods based on MALDI-MS and a coupling of capillary electrophoresis to ICP-MS and ESI-MS were developed for the determination of copper complexes in the mucosal and serosal half-chambers. It was found that 86.1+/-8.5% of copper triglycinate but only 20.8+/-9.9% of copper tetraglycinate penetrated the digestive membrane without modification. Furthermore, inorganic copper species were not detected but a new copper complex (m/z 442) was found to be formed in both compartments of the Ussing chamber. 2009 Elsevier GmbH. All rights reserved.

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

    Directory of Open Access Journals (Sweden)

    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

  1. 1,10-Phenanthroline promotes copper complexes into tumor cells and induces apoptosis by inhibiting the proteasome activity.

    Science.gov (United States)

    Zhang, Zhen; Bi, Caifeng; Schmitt, Sara M; Fan, Yuhua; Dong, Lili; Zuo, Jian; Dou, Q Ping

    2012-12-01

    Indole-3-acetic acid and indole-3-propionic acid, two potent natural plant growth hormones, have attracted attention as promising prodrugs in cancer therapy. Copper is known to be a cofactor essential for tumor angiogenesis. We have previously reported that taurine, L-glutamine, and quinoline-2-carboxaldehyde Schiff base copper complexes inhibit cell proliferation and proteasome activity in human cancer cells. In the current study, we synthesized two types of copper complexes, dinuclear complexes and ternary complexes, to investigate whether a certain structure could easily carry copper into cancer cells and consequently inhibit tumor proteasome activity and induce apoptosis. We observed that ternary complexes binding with 1,10-phenanthroline are more potent proteasome inhibitors and apoptosis inducers than dinuclear complexes in PC-3 human prostate cancer cells. Furthermore, the ternary complexes potently inhibit proteasome activity before induction of apoptosis in MDA-MB-231 human breast cancer cells, but not in nontumorigenic MCF-10A cells. Our results suggest that copper complexes binding with 1,10-phenanthroline as the third ligand could serve as potent, selective proteasome inhibitors and apoptosis inducers in tumor cells, and that the ternary complexes may be good potential anticancer drugs.

  2. Complex electronic waste treatment - An effective process to selectively recover copper with solutions containing different ammonium salts.

    Science.gov (United States)

    Sun, Z H I; Xiao, Y; Sietsma, J; Agterhuis, H; Yang, Y

    2016-11-01

    Recovery of valuable metals from electronic waste has been highlighted by the EU directives. The difficulties for recycling are induced by the high complexity of such waste. In this research, copper could be selectively recovered using an ammonia-based process, from industrially processed information and communication technology (ICT) waste with high complexity. A detailed understanding on the role of ammonium salt was focused during both stages of leaching copper into a solution and the subsequent step for copper recovery from the solution. By comparing the reactivity of the leaching solution with different ammonium salts, their physiochemical behaviour as well as the leaching efficiency could be identified. The copper recovery rate could reach 95% with ammonium carbonate as the leaching salt. In the stage of copper recovery from the solution, electrodeposition was introduced without an additional solvent extraction step and the electrochemical behaviour of the solution was figured out. With a careful control of the electrodeposition conditions, the current efficiency could be improved to be 80-90% depending on the ammonia salts and high purity copper (99.9wt.%). This research provides basis for improving the recyclability and efficiency of copper recovery from such electronic waste and the whole process design for copper recycling.

  3. A screened hybrid density functional study on energetic complexes: cobalt, nickel and copper carbohydrazide perchlorates.

    Science.gov (United States)

    Huang, Huisheng; Zhang, Tonglai; Zhang, Jianguo; Wang, Liqiong

    2010-07-15

    The molecular geometry, electronic structure, infrared spectra and thermochemical properties of cobalt and nickel tris(carbohydrazide) perchlorates (CoCP and NiCP) as well as copper bis(carbohydrazide) perchlorate (CuCP) were investigated using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional. The results show that both perchlorate ions coordinate with the copper atom, and the interactions between copper and perchlorate are ionic, whereas all the metal-carbohydrazide interactions are covalent. Due to the delocalization from the sigma(N-H) bond orbital to the n*(M) antibond orbital, the amino stretching vibrations of these complexes show considerable red-shift compared with those of free carbohydrazide ligand. The calculated heats of reaction and formation indicate that the formations of these complexes are exothermic, and the order of their thermal stability is NiCP>CoCP>CuCP. These agree well with the experimental results. Finally, we find that there is a relationship between the energy gap and impact sensitivity.

  4. Preparation and biodistribution of copper-67 complexes with tetradentate Schiff-base ligands.

    Science.gov (United States)

    John, E K; Bott, A J; Green, M A

    1994-04-01

    Uncharged, lipophilic, low molecular weight copper complexes labeled with generator-produced copper-62 are of interest as potential radiopharmaceutials for imaging the brain with positron emission tomography (PET). We report here the synthesis and biodistribution of a series of [67Cu]copper(II) complexes with tetradentate N2O2(2-)Schiff-base ligands. The compounds studied varied in lipophilicity from log P = 1.7 to log P = 3.6, where P is the octanol/water partition coefficient. In rat biodistribution studies the tracers were generally found to penetrate the blood-brain barrier following intravenous injection, but some far better than others. For closely related compounds brain uptake at 1 min postinjection increased with increasing lipophilicity, although log P was clearly not the sole determinant of high brain uptake. Substantial variations were also observed in the rate at which these various compounds are cleared from brain, with a few exhibiting the prolonged cerebral retention of tracer that would be desired for imaging with 62Cu and PET.

  5. Synthesis and structure of copper(II) complexes: Potential cyanide sensor and oxidase model'

    Indian Academy of Sciences (India)

    PALASH MONDAL; SANKAR PRASAD PARUA; POULAMI PATTANAYAK; UTTAM DAS; SURAJIT CHATTOPADHYAY

    2016-05-01

    The new complexes of compositions $[(L_{a})_{2}Cu]$ and $[(L_{b})_{2}Cu]$ were prepared by treating with2-hydroxy-5-methyl-3-(2-aryldiazenyl)phenylimino) methyl) benzaldehyde $(HL_{a})$ and ethyl-2-cyano-3-(2-hydroxy-5-methyl-3-(-(2-aryldiazenyl) phenylimino) methyl) phenyl) acrylate $(HL_{b})$ ligands [where aryl isphenyl for $HL_{a}^{1}$ and $HL_{b}^{1}$ ; p-methyl phenyl for $HL_{a}^{2}$ and $HL_{b}^{2}$ ; and p-chloro phenyl for $HL_{a}^{3}$ and $HL_{b}^{3}$ ] with $Cu(OAc)_{2}.H_{2}O$, respectively. Both the bis copper(II) complexes consist of tridentate (N,N,O) anionic ligands, $L^{-}_a$ or $L^{-}_b$ . X-ray structures of the representative complexes $[(L^{1}_{a})_{2}Cu]$ and $[(L^{2}_{b})_{2}Cu]$ were determined toconfirm the molecular species unequivocally. The molecular structure of copper complexes exhibited tetragonallydistorted (Jahn-Teller) geometry consistent with the $d^{9}$ configuration of Cu(II) metal ion. Oxidation ofbenzyl alcohols using the newly synthesized complexes as catalyst has been studied. Photoluminescence propertiesof $[(L^{2}_{a})_{2}Cu]$ and $[(L^{2}_{b})_{2}Cu]$ were exploited for selective cyanide recognition. The $[(L_{b})_{2}Cu], complexesdisplayed antibacterial activity toward gram positive and gram negative bacteria

  6. 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%.

  7. Potent inhibition of protein tyrosine phosphatases by copper complexes with multi-benzimidazole derivatives.

    Science.gov (United States)

    Li, Ying; Lu, Liping; Zhu, Miaoli; Wang, Qingming; Yuan, Caixia; Xing, Shu; Fu, Xueqi; Mei, Yuhua

    2011-12-01

    A series of copper complexes with multi-benzimidazole derivatives, including mono- and di-nuclear, were synthesized and characterized by Fourier transform IR spectroscopy, UV-Vis spectroscopy, elemental analysis, electrospray ionization mass spectrometry. The speciation of Cu/NTB in aqueous solution was investigated by potentiometric pH titrations. Their inhibitory effects against human protein tyrosine phosphatase 1B (PTP1B), T-cell protein tyrosine phosphatase (TCPTP), megakaryocyte protein tyrosine phosphatase 2 (PTP-MEG2), srchomology phosphatase 1 (SHP-1) and srchomology phosphatase 2 (SHP-2) were evaluated in vitro. The five copper complexes exhibit potent inhibition against PTP1B, TCPTP and PTP-MEG2 with almost same inhibitory effects with IC(50) at submicro molar level and about tenfold weaker inhibition versus SHP-1, but almost no inhibition against SHP-2. Kinetic analysis indicates that they are reversible competitive inhibitors of PTP1B. Fluorescence study on the interaction between PTP1B and complex 2 or 4 suggests that the complexes bind to PTP1B with the formation of a 1:1 complex. The binding constant are about 1.14 × 10(6) and 1.87 × 10(6) M(-1) at 310 K for 2 and 4, respectively.

  8. Two-step flash light sintering process for enhanced adhesion between copper complex ion/silane ink and a flexible substrate

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Eun-Beom; Joo, Sung-Jun [Department of Mechanical Convergence Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Ahn, Heejoon [Department of Organic and Nano Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Kim, Hak-Sung, E-mail: kima@hanyang.ac.kr [Department of Mechanical Convergence Engineering, Hanyang University, Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Institute of Nano Science and Technology, Hanyang University, Seoul 133-791 (Korea, Republic of)

    2016-03-31

    A copper complex ion ink (including copper nanoparticles, a copper precursor and a silane coupling agent) was synthesized to enhance the adhesion between the copper pattern and a polyimide (PI) substrate. Oxygen plasma treatment was performed on the polyimide substrate to initiate a chemical reaction between the complex ion ink and the polyimide. Then, a two-step flash light sintering method (consisting of preheating and main sintering) was used to sinter the copper complex ion ink. The copper complex ion patterns were characterized as a function of the weight fraction of silane coupling agent using scanning electron microscopy (SEM), a four-point probe method and adhesion testing. In addition, a bending fatigue test was performed to evaluate the reliability of the conductive copper pattern under cyclic bending. The copper pattern fabricated with copper complex ion ink containing 3 wt% silane coupling agent exhibited the highest adhesion level (5B), the lowest resistivity (7.6 μΩ·cm) and a low resistance change (18%) after the bending fatigue test. The two-step sintering method used to enhance the adhesion between the copper complex ion ink and polyimide substrate was also studied using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). - Highlights: • The copper complex ion ink with copper nanoparticles and copper precursor was fabricated. • The copper complex ion ink was sintered by two-step flash light sintering method. • The sintered copper pattern exhibited the highest adhesion level (5B). • The resistivity of sintered copper pattern was 7.6 μΩ·cm.

  9. Synthesis,Structure and Magnetic Properties of a Diphenoxobridged Binuclear Copper(Ⅱ) Complex

    Institute of Scientific and Technical Information of China (English)

    XIE,Yong-Shu(解永树); JIANG,Hui(姜晖); XU,Xiao-Long(徐小龙); LIU,Qing-Liang(刘清亮); DU,Chen-Xia(杜晨霞); ZHU,yu(朱玉)

    2002-01-01

    A mixed-ligand copper(Ⅱ) complex [Cu2(phen)2(HL1)2]-(ClO4)2 (1) was synthesized. X-ray analyses reveal that 1has a bis (μ2-phenoxo)-bridged dicopper (Ⅱ) structure. 2D hydrogen-bonded network is formed utilizing the N-H, O-H and C-H groups of the (HL1)- ligands (H2L1 = N-(2-hy-droxybenzyl)ethanolamine), the C-H groups of the phenanthrolines and the perchlorate anions. Variable temperature magnetic properties of 1 have shown comparatively weak antiferromagnetic interactions with respect to the bridge angles,which have been ascribed to the unfavorable overlaps of the magnetic orbitals for the highly distorted copper coordination polyhedra and the pyramidal distortions at the phenoxo oxygen atoms.

  10. Copper-obatoclax derivative complexes mediate DNA cleavage and exhibit anti-cancer effects in hepatocellular carcinoma.

    Science.gov (United States)

    Su, Jung-Chen; Chang, Jung-Hua; Huang, Jui-Wen; Chen, Peter P-Y; Chen, Kuen-Feng; Tseng, Ping-Hui; Shiau, Chung-Wai

    2015-02-25

    Obatoclax is an indole-pyrrole compound that induces cancer cell apoptosis through targeting the anti-apoptotic Bcl-2 protein family. Previously, we developed a series of obatoclax derivatives and studied their STAT3 inhibition-dependent activity against cancer cell lines. The obatoclax analog, prodigiosin, has been reported to mediate DNA cleavage in cancer cells by coordinating with copper complexes. To gain an understanding of copper-obatoclax complex activity, we applied obatoclax derivatives to examine their copper-mediated nuclease activity as a means to establish a basis for structure activity relationship. Replacement of the indole ring of obatoclax with furanyl, thiophenyl or Boc-indolyl rings reduced the DNA cleavage ability. The same effect was achieved through the replacement of the obatoclax pyrrolyl ring with thiazolidinedione and thioacetal. Among the compounds tested, we demonstrated that the complex of obatoclax or compound 7 with copper exhibited potent DNA strand scission which correlated with HCC cell growth inhibition.

  11. The Synthesis and Analysis of Ammine Complexes of Copper and Silver Sulfate: An Undergraduate Laboratory Project

    Science.gov (United States)

    Clareen, Steven S.; Marshall, Shireen R.; Price, Kristin E.; Royall, Margaret B.; Yoder, Claude H.; Schaeffer, Richard W.

    2000-07-01

    An undergraduate chemistry laboratory project involving the synthesis of [Ag(NH3)2]2SO4 and Cu(NH3)4SO4 from the simple sulfate salts is described. Characterization of the stoichiometry of the complexes is accomplished by gravimetric and volumetric analysis. Silver is precipitated as the chloride and copper is precipitated as the hydroxide and converted to the oxide before weighing. The ammonia content of each complex is determined with a back titration using dilute nitric acid and sodium hydroxide. Typical student work gives results for the stoichiometry of the complexes within 1-5% of the theoretical values. The project provides a convenient preparation of two compounds whose identity and formula will not be obvious to the student. The analytical procedures illustrate the fundamentals of gravimetric and volumetric analysis and some basic characteristics of simple coordination complexes. The analytical data allow the student to determine the identity of each product by determining its empirical formula.

  12. Spectroscopic studies on the interaction of DNA with the copper complexes of NSAIDs lornoxicam and isoxicam.

    Science.gov (United States)

    Goswami, Sathi; Ray, Suhita; Sarkar, Munna

    2016-12-01

    Non Steroidal Anti-inflammatory Drugs (NSAIDs) form the most common class of anti-inflammatory and analgesic agents. They also show anticancer properties for which they exert their effects by interacting at the protein but not at the genomic level. This is because most NSAIDs are anions at physiological pH, which prohibit their approach to the polyanionic DNA backbone. Complexing NSAIDs with bioactive metal like copper obliterates this disadvantage. Here, copper complexes of two oxicam NSAIDs, Lornoxicam (Lx) and Isoxicam (Isx) have been chosen to study their interaction with calf thymus (ct) DNA and have been synthesized as per reported protocols. UV-vis absorption showed that DNA binding to Cu(II)-Lx complex alters the absorption spectra indicating changes in the electronic environment of the complex, whereas, for Cu(II)-Isx there was only small changes. Hence, UV-vis absorption was used to determine the binding constant, stoichiometry and thermodynamic parameters of Cu(II)-Lx. However, UV-melting studies and CD difference spectra showed that both Cu(II)-Lx and Cu(II)-Isx can interact with the DNA backbone albeit with different binding modes. The probable binding mode was determined by kinetics of EtBr displacement and viscosity measurements. Our results point to an intercalative mode of binding for Cu(II)-Lx and external groove binding for Cu(II)-Isx.

  13. Synthetic, crystallographic, and computational study of copper(II) complexes of ethylenediaminetetracarboxylate ligands.

    Science.gov (United States)

    Matović, Zoran D; Miletić, Vesna D; Ćendić, Marina; Meetsma, Auke; van Koningsbruggen, Petra J; Deeth, Robert J

    2013-02-04

    Copper(II) complexes of hexadentate ethylenediaminetetracarboxylic acid type ligands H(4)eda3p and H(4)eddadp (H(4)eda3p = ethylenediamine-N-acetic-N,N',N'-tri-3-propionic acid; H(4)eddadp = ethylenediamine-N,N'-diacetic-N,N'-di-3-propionic acid) have been prepared. An octahedral trans(O(6)) geometry (two propionate ligands coordinated in axial positions) has been established crystallographically for the Ba[Cu(eda3p)]·8H(2)O compound, while Ba[Cu(eddadp)]·8H(2)O is proposed to adopt a trans(O(5)) geometry (two axial acetates) on the basis of density functional theory calculations and comparisons of IR and UV-vis spectral data. Experimental and computed structural data correlating similar copper(II) chelate complexes have been used to better understand the isomerism and departure from regular octahedral geometry within the series. The in-plane O-Cu-N chelate angles show the smallest deviation from the ideal octahedral value of 90°, and hence the lowest strain, for the eddadp complex with two equatorial β-propionate rings. A linear dependence between tetragonality and the number of five-membered rings has been established. A natural bonding orbital analysis of the series of complexes is also presented.

  14. Mixed-ligand mononuclear copper(II) complex: crystal structure and anticancer activity.

    Science.gov (United States)

    Qin, Xiu-Ying; Liu, Ya-Nan; Yu, Qian-Qian; Yang, Li-Cong; Liu, Ying; Zhou, Yan-Hui; Liu, Jie

    2014-08-01

    A novel copper(II) complex with mixed ligands including β-[(3-formyl-5-methyl-2-hydroxy-benzylidene)amino]propionic acid anion and 1,10'-phenanthroline was synthesized, and its crystal structure was thoroughly characterized. It exerted excellent inducing apoptosis, anti-angiogenesis and antiproliferative properties in vitro. The complex can bind human serum albumin (HSA) at physiological pH conditions. Remarkably, it can induce formation of the mixed parallel/antiparallel G-quadruplex structures in the G-rich sequence of the proximal vascular endothelial growth factor (VEGF) promoter, and stabilize these G-quadruplex structures, which provide an opportunity for anti-angiogenesis chemotherapeutics. Furthermore, the complex showed a strong uptake, and exhibited multiple anticancer functions by inhibiting the expression of p-Akt and p-Erk1/2 proteins and by upregulating the levels of reactive oxygen species (ROS). Because of the reported results, this new copper(II) complex qualifies itself as a potential anticancer drug candidate.

  15. Theoretical study, and infrared and Raman spectra of copper(II) chelated complex with dibenzoylmethane.

    Science.gov (United States)

    Nekoei, A-R; Vakili, M; Hakimi-Tabar, M; Tayyari, S F; Afzali, R; Kjaergaard, H G

    2014-07-15

    There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational assignment for Cu(dbm)2 in the literatures. Density functional theory (DFT) at the B3LYP level and also MP2 calculations using different basis sets, besides Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses, have been employed to investigate the effect of methyl substitution with the phenyl group on the stabilities of bis(acetylacetonate) copper (II), Cu(acac)2, and Cu(dbm)2 complexes and the electron delocalization in their chelated rings. Measured solid phase infrared and Raman bands for Cu(dbm)2 complex have been interpreted in terms of the calculated vibrational modes and detailed assignment has been presented. We concluded that, theoretically, the results of charge transfer studies, and experimentally, in-phase symmetric O-Cu-O stretching mode of these complexes are very useful measures for M-L bond strength. The electron delocalization in the chelated rings and the M-L bond strength in Cu(dbm)2 are concluded to be higher than those in Cu(acac)2. The calculated geometries and vibrational results are in good agreement with the experimental data.

  16. Structural features and oxidative stress towards plasmid DNA of apramycin copper complex.

    Science.gov (United States)

    Balenci, D; Bonechi, G; D'Amelio, N; Gaggelli, E; Gaggelli, N; Molteni, E; Valensin, G; Szczepanik, W; Dziuba, M; Swiecicki, G; Jezowska-Bojczuk, M

    2009-02-21

    The interaction of apramycin with copper at different pH values was investigated by potentiometric titrations and EPR, UV-vis and CD spectroscopic techniques. The Cu(II)-apramycin complex prevailing at pH 6.5 was further characterized by NMR spectroscopy. Metal-proton distances derived from paramagnetic relaxation enhancements were used as restraints in a conformational search procedure in order to define the structure of the complex. Longitudinal relaxation rates were measured with the IR-COSY pulse sequence, thus solving the problems due to signal overlap. At pH 6.5 apramycin binds copper(II) with a 2 : 1 stoichiometry, through the vicinal hydroxyl and deprotonated amino groups of ring III. Plasmid DNA electrophoresis showed that the Cu(II)-apramycin complex is more active than free Cu(II) in generating strand breakages. Interestingly, this complex in the presence of ascorbic acid damages DNA with a higher yield than in the presence of H(2)O(2).

  17. Synthesis, Spectroscopy, Thermal Analysis, Electrochemistry and Superoxide Scavenging Activity of a New Bimetallic Copper(II Complex

    Directory of Open Access Journals (Sweden)

    Babita Sarma

    2013-01-01

    Full Text Available A new bimetallic copper(II complex has been synthesized with ligand obtained by the condensation of salicylaldehyde and the amine derived from reduction of nitration product of benzil. The ligand was characterized by 1H NMR and mass spectra, and the binuclear Copper(II complex was characterized by vibrational and electronic spectra, EPR spectra, and magnetic moment measurement. Thermogravimetric analysis study and electrochemical study of the complex were also done. The complex was found to show superoxide dismutase activity.

  18. Copper homeostasis in Drosophila by complex interplay of import, storage and behavioral avoidance

    OpenAIRE

    Balamurugan, Kuppusamy; Egli, Dieter; Hua, Haiqing; Rajaram, Rama; Seisenbacher, Gerhard; Georgiev, Oleg; Schaffner, Walter

    2007-01-01

    Copper is an essential but potentially toxic trace element. In Drosophila, the metal-responsive transcription factor (MTF-1) plays a dual role in copper homeostasis: at limiting copper concentrations, it induces the Ctr1B copper importer gene, whereas at high copper concentrations, it mainly induces the metallothionein genes. Here we find that, despite the downregulation of the Ctr1B gene at high copper concentrations, the protein persists on the plasma membrane of intestinal cells for many h...

  19. Comparison of availability of copper(II) complexes with organic ligands to bacterial cells and to chitin

    Energy Technology Data Exchange (ETDEWEB)

    Vasconcelos, M.T.S.D.; Azenha, M.A.O. [Laquipai, Porto (Portugal). Faculdade de Ciencias do Porto; Cabral, J.P.S. [Inst. de Botanica e Centro de Citologia Experimental U.P., Porto (Portugal)

    1997-10-01

    Bacterial cells or chitin were exposed to solutions with 100 {micro}M total but only 5 {micro}M free copper, due to the presence of a proper concentration of proline, lysine, cysteine, or ethylenediamine tetraacetate (EDTA). The influence of the nature and concentration of the particles and soluble ligands, on the sorption and on the desorption of the copper, at pH 6.50 and 25.0 C, was investigated. The metal sorbed by the particles and that left in the solution were measured by atomic absorption spectrometry, after different periods of contact between particles and solution. The interpretation of the results was based on the copper(II) speciation calculated through equilibrium approaches applied to homogeneous or heterogeneous systems. A significant fraction of copper bound to the organic ligands was displaced to the bacteria or chitin, and the extent of chemical reaction depended on the nature of both the soluble (or leaving) ligands and sites on the particle surface (or entering ligands), as expected by the equilibrium theory. But with chitin, the uptake of copper in the presence of cysteine or EDTA was higher than expected, which may be due to the adsorption of the soluble copper complexes on the particle surface. In consequence of a competition between soluble and particulate ligands (cells or chitin), the free copper(II) concentration decreased in the solution, even in the presence of very strong chelators. The results indicate that copper availability is not a simple function of the initial free copper concentration in the solution. Desorption of the previously fixed copper, originated by free soluble ligands indicated that the sorption of copper was quasireversible for both particles, though a larger dismissal of the equilibrium position occurred for the cells, probably due to their biological activity.

  20. Potential links between porphyry copper deposits and exhumed metamorphic basement complexes in northern Chile

    Science.gov (United States)

    Cooper, Frances; Docherty, Alistair; Perkins, Rebecca

    2014-05-01

    Porphyry copper deposits (PCDs) are typically associated with magmatic arcs in compressional subduction zone settings where thickened crust and fractionated calc-alkaline magmas produce favourable conditions for copper mineralisation. A classic example is the Eocene-Oligocene PCD belt of Chile, the world's leading copper producing country. In other parts of the world, older late Cretaceous to early Tertiary PCDs are found in regions of former subduction-related magmatism that have undergone subsequent post-orogenic crustal extension, such as the Basin and Range province of western North America, and the Eurasian Balkan-Carpathian-Dinaride belt. In the Basin and Range there is a striking correlation between the location of many PCDs and exhumed metamorphic core complexes (isolated remnants of the middle to lower crust exhumed during extensional normal faulting). This close spatial relationship raises questions about the links between the two. For example, are their exhumation histories related? Could the presence of impermeable metamorphic rocks at depth affect and localise mineralising fluids? In Chile there appears to be a similar spatial relationship between PCDs and isolated outcrops of exhumed metamorphic basement. In northern Chile, isolated exposures of high-grade metamorphic gneisses and amphibolites are thought to be exhumed remnants of the pre-subduction Proterozoic-Paleozoic continental margin of Gondwana [2], although little is known about when they were exhumed and by what mechanism. For example, the Limón Verde metamorphic complex, exhumed from a depth of ca. 50 km, is situated adjacent to Chuquicamata, the largest open pit copper mine in the world. In northernmost Chile, another metamorphic exposure, the Belén complex, sits close to the Dos Hermanos PCD, a small deposit that is not actively mined. Comprising garnet-bearing gneisses and amphibolites, the Belén is thought to have been exhumed from a depth of ca. 25 km, but when and how is unclear [3

  1. Synthesis and crystal structure of [chlorobis(triphenylphospino) (p-chlorobenzaldehyde thiosemicarbazone)] copper(I) complex

    Indian Academy of Sciences (India)

    Ashiq Khan; Poonam Sharma; Rajnikant; Vivek K Gupta; Naresh Padha; Rekha Sharma

    2016-02-01

    Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H1L) and triphenylphosphine in 1 : 1 : 2 molar ratio yielded complexes of stoichiometry, [CuX(1-S- H1L)(Ph3P)2] (X = I, 1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR, 1H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) Å, b = 13.027(5) Å, c = 16.269(5) Å, = 100.054(5)°, = 99.228(5)° and = 97.234(5)°. This complex has distorted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of complex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemicarbazone, [Cu2Cl2(2-S-Hbtsc)2(Ph3P)2]·2H2O. The intermolecular H-bonding, Cl· · ·HCph, 2.733 Å and interactions, {CHph · · · , 2.796; 2.776 Å} in this complex led to the formation of 1D chain. Two such 1D chains were cross-linked via, Cl· · ·HCph, 2.896 Å H-bonding to form a 2D network.

  2. Syntheses, characterization and properties of silver, copper and palladium complexes from bis(oxazoline)-containing ligands

    Energy Technology Data Exchange (ETDEWEB)

    Kuai, Hai-Wei, E-mail: hyitshy@126.com; Cheng, Xiao-Chun; Li, Deng-Hao; Hu, Tao; Zhu, Xiao-Hong

    2015-08-15

    The reactions of 2,6-di(2-oxazolyl)pyridine (L{sup 1}) and 2,6-bis[(S)-4-phenyl-2-oxazolyl]pyridine (L{sup 2}) with silver, copper and palladium salts to yield six new complexes: ([Ag{sub 5}(L{sup 1}){sub 5}](BF{sub 4}){sub 5}){sub n} (1), ([Ag(L{sup 1})](SbF{sub 6})){sub n} (2), [Cu{sub 4}I{sub 4}(L{sup 1}){sub 2}] (3), [Cu{sub 6}I{sub 6}(L{sup 1}){sub 2}] (4), [Pd(L′{sup 1})(OAc)] (5), [Pd(L′{sup 2})Cl] (6), which were fully characterized by single-crystal and powder X-ray diffraction, IR, elemental and thermogravimetric analyses. 1 and 2 are a pair of Ag-oxazoline helical chain structure complexes. The spiral directions of chains are opposite in 1, while identical in 2; the measurement of CD spectra can further confirm their meso and chiral structures. Complexes 3 and 4 show eight-nuclear and twelve-nuclear iodine–cuprous cluster structure. Their structural diversity is induced by different molar ratios of CuI:L{sup 1}. Complexes 5 and 6 are discrete mononuclear palladium complexes. In situ oxazolyl-ring-opening reactions take place in the syntheses of them and the L{sup 1} and the L{sup 2} were transformed to their oxazolyl-ring opened derivatives L′{sup 1} and L′{sup 2}. Moreover, fluorescence, non-linear optical properties, and ferroelectric properties have been investigated. - Graphical abstract: 2,6-di(2-oxazolyl)pyridine (L{sup 1}) reacts with silver and copper salts to yield helical and cluster structure complexes. - Highlights: • Helical and cluster structure complexes. • In situ oxazolyl-ring-opening reactions. • Fluorescence, non-linear optical properties, and ferroelectric properties.

  3. 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.

  4. Molecular Mechanics (MM) Force Fields for Modelling of Copper(II) Amino Acid Complexes in Different Environments

    Science.gov (United States)

    Sabolović, Jasmina

    2009-03-01

    New MM force field developed for modelling the properties of copper(II) complexes with aliphatic amino acid in vacuo, in crystal, and in aqueous solution was applied to study conformational properties of bis(N,N-diethylglycinato)copper(II). Two hypotheses are examined and confirmed as true: (i) the conformations which do not allow apical coordination to the copper(II) are the most stable in vacuo and in aqueous solution; (ii) MM calculations quantitatively support the supposition that the experimentally observed conformer is better suited for crystal packing than the in vacuo and in solution most stable conformers.

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

    Science.gov (United States)

    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.

  6. Synthesis, Cytotoxic Activity, and DNA Binding Properties of Copper (II Complexes with Hesperetin, Naringenin, and Apigenin

    Directory of Open Access Journals (Sweden)

    Mingxiong Tan

    2009-01-01

    Full Text Available Complexes of copper (II with hesperetin, naringenin, and apigenin of general composition [CuL2(H2O2]⋅nH2O (1–3 have been synthesized and characterized by elemental analysis, UV-Vis, FT-IR, ESI-MS, and TG-DTG thermal analysis. The free ligands and the metal complexes have been tested in vitro against human cancer cell lines hepatocellular carcinoma (HepG-2, gastric carcinomas (SGC-7901, and cervical carcinoma (HeLa. Complexes 1 and 3 were found to exhibit growth inhibition of SGC-7901 and HepG2 cell lines with respect to the free ligands; the inhibitory rate of complex 1 is 43.2% and 43.8%, while complex 3 is 46% and 36%, respectively. The interactions of complex 1 and its ligand Hsp with calf thymus DNA were investigated by UV-Vis, fluorescence, and CD spectra. Both complex 1 and Hsp were found to bind DNA in intercalation modes, and the binding affinity of complex 1 was stronger than that of free ligand.

  7. 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.

  8. Fabrication of Copper(I) Bipyridyl Complex Based Dye Sensitized Solar Cells

    Science.gov (United States)

    Vuong, Son; Nguyen-Dang, Ha-My; Tran, Quang Thinh; Luong, Thi Thu Thuy; Pham, Trang T. T.; Nguyen-Tran, Thuat; Mai, Anh Tuan

    2017-01-01

    This study investigates the performance of dye-sensitized solar cells (DSSC) based on a copper(I) complex. A simple form of copper(I) complex dye was synthesized with a structure of [Cu(L)(CH3CN)], where L is the 6,6'-dimethyl-4,4'-bis(phenylethynyl)-2,2'-bipyridine ligand. The full structure of DSSC investigated in this study is as follows: FTO/TiO2/dye Cu(I) bipyridyl/3I-/I3 - electrolyte/graphite/FTO. The TiO2 photoanodes were deposited from apoly(vinylpyrrolidone)-based paste using a spin coating technique. Different conditions of fabrication, such as paste dispersion time and total TiO2 thickness, were systematically studied in order to optimize the performance of the DSSC. The trigonal planar complex [Cu(L)CH3CN] was revealed to be suitable for applications in DSSC. The highest exhibited short circuit current density was found to be 0.48 mA/cm2, with an open voltage of 477 mV, a form factor of 34% and a power conversion efficiency of 0.08% for the cell with photoanodes thickness of about 2.2 μm. It was shown that the dye and the paste formulation had great potential for applications in DSSC.

  9. Stereochemical Properties of Multidentate Nitrogen Donor Ligands and Their Copper Complexes by Electronic CD and DFT.

    Science.gov (United States)

    Poopari, Mohammad Reza; Dezhahang, Zahra; Xu, Yunjie

    2016-07-01

    UV-Vis and electronic circular dichroism (ECD) spectroscopy, complemented with Density Functional Theory (DFT) calculations, were used to elucidate the structural diversities of three multidentate nitrogen donor ligands and two associated copper complexes in solution directly. The three chiral salen ligands all consist of trans-cyclohexane-1,2-diamine as a chiral scaffold and also of pyridine rings as chromophores, differing only in the linking groups between the two functional groups mentioned above. Very different ECD intensities and somewhat different ECD patterns were observed for these ligands and satisfactorily interpreted theoretically. For the geometry optimization and spectral simulation of the open-shell metal complexes, the LANL2DZ basis set with effective core potential for the Cu and Cl atoms and pure cc-pVTZ for the rest of the atoms was utilized. The performance of the same calculations with the polarization functions (f,g) from the cc-pVTZ basis added to the LANL2DZ basis was compared. While the three ligands exhibit different conformational flexibility, the associated copper complexes show great rigidity imposed by the metal-ligand coordination, taking on a single structure in each case. In addition, dispersion interactions were shown to change the conformational stability ordering of the ligands noticeably and to exert considerable influence on the simulated UV-Vis and ECD spectra. Chirality 28:545-555, 2016. © 2016 Wiley Periodicals, Inc.

  10. 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.

  11. Modeling the bioactive copper(II complex stability by the use of an experimental design

    Directory of Open Access Journals (Sweden)

    Canadi Janos

    2012-01-01

    Full Text Available A new organic-inorganic complex based on copper ions with pullulan polysaccharide can be used for the treatment of copper deficiency in human organism. Therefore, the aim of this paper was to carry out the stress stability study of this potential active substance by the use of mathematical modelling. A full factorial design was successfully applied for the stability studying. The electrical conductivity was taken as the response, while the degradation time, concentration of the oxidative agent, temperature, and pH value were used as the independent variables. All process variables were analyzed at the three levels. On the basis of statistical analysis of data for the thermal stability study, the temperature and degradation time had the main impact on the conductivity of the complex solution. The degradation time had the significant effect in the case of oxidative stability study. In addition to the degradation time, the pH value and the temperature had the significant effect on the complex stability for the hydrolytic stability study.

  12. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes.

    Science.gov (United States)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-26

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1-S3) at neutral pH indicated that the "back-to-back" bisCD complex CuL(1) favoured higher catalytic efficiency and more pronounced enantioselectivity than the "face-to-face" complex CuL(2). The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL(1), which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL(1), even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  13. Enhancing the copper(II) complexes cytotoxicity to cancer cells through bound to human serum albumin.

    Science.gov (United States)

    Gou, Yi; Zhang, Yao; Qi, Jinxu; Zhou, Zuping; Yang, Feng; Liang, Hong

    2015-03-01

    We use Schiff-base salicylaldehyde benzoylhydrazone (HL) as the ligand for copper(II), resulting in the complexes [CuCl(L)]·H2O (C1), [CuNO3(L)]·H2O (C2) and [CuBr(L)]2 (C3). We characterize the Cu(II) compounds' interactions with human serum albumin (HSA) using fluorescence spectroscopy and molecular docking. These studies revealed that Cu(II) compounds propensity bound to IIA subdomain of HSA possible by hydrophobic interactions and hydrogen bond. Cu(II) compounds produce intracellular reactive oxygen species (ROS) in cancer cells. Complexes of HSA and copper(II) compounds enhance about 2-fold cytotoxicity in cancer cells but do not raise cytotoxicity levels in normal cells in vitro. Compared with C3 alone, HSA-C3 complex promotes HepG2 cell apoptosis and has a stronger capacity to promote cell cycle arrest at the G2/M phase of HepG2.

  14. Enantioselective Hydrolysis of Amino Acid Esters Promoted by Bis(β-cyclodextrin) Copper Complexes

    Science.gov (United States)

    Xue, Shan-Shan; Zhao, Meng; Ke, Zhuo-Feng; Cheng, Bei-Chen; Su, Hua; Cao, Qian; Cao, Zhen-Kun; Wang, Jun; Ji, Liang-Nian; Mao, Zong-Wan

    2016-02-01

    It is challenging to create artificial catalysts that approach enzymes with regard to catalytic efficiency and selectivity. The enantioselective catalysis ranks the privileged characteristic of enzymatic transformations. Here, we report two pyridine-linked bis(β-cyclodextrin) (bisCD) copper(II) complexes that enantioselectively hydrolyse chiral esters. Hydrolytic kinetic resolution of three pairs of amino acid ester enantiomers (S1–S3) at neutral pH indicated that the “back-to-back” bisCD complex CuL1 favoured higher catalytic efficiency and more pronounced enantioselectivity than the “face-to-face” complex CuL2. The best enantioselectivity was observed for N-Boc-phenylalanine 4-nitrophenyl ester (S2) enantiomers promoted by CuL1, which exhibited an enantiomer selectivity of 15.7. We observed preferential hydrolysis of L-S2 by CuL1, even in racemic S2, through chiral high-performance liquid chromatography (HPLC). We demonstrated that the enantioselective hydrolysis was related to the cooperative roles of the intramolecular flanking chiral CD cavities with the coordinated copper ion, according to the results of electrospray ionization mass spectrometry (ESI-MS), inhibition experiments, rotating-frame nuclear Overhauser effect spectroscopy (ROESY), and theoretical calculations. Although the catalytic parameters lag behind the level of enzymatic transformation, this study confirms the cooperative effect of the first and second coordination spheres of artificial catalysts in enantioselectivity and provides hints that may guide future explorations of enzyme mimics.

  15. Synthesis and Crystal Structure of Copper(Ⅱ)Complex with N-Acetoxyl-picolinamide

    Institute of Scientific and Technical Information of China (English)

    杜巧云; 曹佃省; 刘志红

    2005-01-01

    Using Cu(Ⅱ) as the template, a complex {[Cu2L2(H2O)2] 4H2O}n (L = N-acetoxyl- picolinamide) has been successfully synthesized and characterized by single-crystal X-ray diffrac tion. The crystal is of monoclinic, space group C2/c, with a = 24.144(5), b = 7.1622(14), c = 17.283(4) (A), C16H24Cu2N4O12, Mr = 591.47, β = 131.73(3)°, V = 2230.3(8) (A)3, Z = 4, Dc= 1.761 g/cm3, F(000) = 1208,μ = 1.978 mm-1, R = 0.0400 and wR = 0.1099. The copper (Ⅱ) ion is five coordinated with a distorted square pyramidal geometry. The complex can be viewed as a one dimensional chain structure by carboxylic bridges among copper atoms. In the complex there exist hydrogen bonding interactions to stabilize the structure.

  16. Assessing the Ultraviolet Exposure Level in Welding Workers of Sar-Cheshmeh Copper Complex

    Directory of Open Access Journals (Sweden)

    Javad Vatani

    2013-04-01

    Full Text Available Background: Because of being exposed to a wide range of ultraviolet radiations, welders are prone to eye and skin diseases. This study aims at determining the ultraviolet exposure level in welding workers of Sar-Cheshmeh Copper Complex.Materials and Methods: This cross-sectional study was conducted in 2010 on all welding workers of the complex using Hagner UV digital radiometer.Results: The mean value for the received ultraviolet radiation level was 0.09±0.045 j2/cm2. The level of UV exposure was significantly different (p=0.001 for the welders working in different units of the complex. The mineworkers received the highest level of radiation (0.14 j2/cm2.Conclusion: In this study, the ultraviolet exposure of welding workers is below the allowable threshold limit for UV radiation.

  17. 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.

  18. Control of size in losartan/copper(II) coordination complex hydrophobic precipitate.

    Science.gov (United States)

    Denadai, Ângelo M L; Da Silva, Jeferson G; Guimarães, Pedro P G; Gomes, Leonardo Bertolini S; Mangrich, Antonio S; de Rezende, Edivaltrys I P; Daniel, Izabela M P; Beraldo, Heloísa; Sinisterra, Rubén D

    2013-10-01

    Reaction of highly soluble orally active, non-peptide antihypertensive drug losartan with copper(II) leads to the spontaneous formation of a very insoluble 2:1 covalent complex, which self assembles in a hydrophobic supramolecular structure of nanometric dimensions. Thermal analysis showed that Los/Cu(II) complex presents intermediate stability in comparison with its precursors KLos and Cu(OAc)2·H2O. Isothermal titration calorimetry indicated complexation to be a stepwise process, driven by enthalpy and entropy. Zeta potential and DLS measurements showed that it is possible to control the size and charge of nanoprecipitates by adjusting the relative concentration of Los(-) and Cu(II). Copyright © 2013 Elsevier B.V. All rights reserved.

  19. In vitro inhibition of hyaluronidase by sodium copper chlorophyllin complex and chlorophyllin analogs

    OpenAIRE

    McCook JP; Dorogi PL; Vasily DB; Cefalo DR

    2015-01-01

    John P McCook,1 Peter L Dorogi,2 David B Vasily,3 Dustin R Cefalo4 1Discovery Partners, LLC, Frisco, TX, 2CHL Industries, LLC, Easton, PA, 3Aesthetica Cosmetic and Laser Surgery Center, Bethlehem, PA, 4Frontier Scientific, Inc., Logan, UT, USA Background: Inhibitors of hyaluronidase are potent agents that maintain hyaluronic acid homeostasis and may serve as anti-aging, anti-inflammatory, and anti-microbial agents. Sodium copper chlorophyllin complex is being used therapeutically as a compon...

  20. Electrochemical and optical characterization of cobalt, copper and zinc phthalocyanine complexes.

    Science.gov (United States)

    Lee, Jaehyun; Kim, Se Hun; Lee, Woosung; Lee, Jiwon; An, Byeong-Kwan; Oh, Se Young; Kim, Jae Pil; Park, Jongwook

    2013-06-01

    New phthalocyanine (Pc) derivatives that include the alkyl group in ligand were synthesized based on three core metals such as zinc (Zn), copper (Cu), and cobalt (Co). Electrochemical behaviors and optical properties of the new phthalocyanine derivatives with ligand and different core metal were investigated by using cyclic voltammetry, UV-Visible (UV-Vis) spectroscopy and photoluminescence (PL) spectroscopy. In UV-Vis data, maximum values of 2H, Co, Cu, and Zn complexes were 708 nm and 677 nm, 686 nm, 684 nm, respectively.

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

    Directory of Open Access Journals (Sweden)

    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.

  2. Methylresorcinarene: a reaction vessel to control the coordination geometry of copper(II) in pyridine N-oxide copper(II) complexes.

    Science.gov (United States)

    Beyeh, Ngong Kodiah; Puttreddy, Rakesh

    2015-06-07

    Pyridine and 2-picolinic acid N-oxides form 2 : 2 and 2 : 1 ligand : metal (L : M) discrete L2M2 and polymeric complexes with CuCl2 and Cu(NO3)2, respectively, with copper(ii) salts. The N-oxides also form 1 : 1 host-guest complexes with methylresorcinarene. In combination, the three components form a unique 2 : 2 : 1 host-ligand-metal complex. The methylresorcinarene acts as a reaction vessel/protecting group to control the coordination of copper(ii) from cis-see-saw to trans-square planar, and from octahedral to square planar coordination geometry. These processes were studied in solution and in the solid state via(1)H NMR spectroscopy and single crystal X-ray diffraction.

  3. Halide impact on emission of mononuclear copper(I) complexes with pyrazolylpyrimidine and triphenylphosphine.

    Science.gov (United States)

    Vinogradova, Katerina A; Plyusnin, Victor F; Kupryakov, Arkady S; Rakhmanova, Marianna I; Pervukhina, Natalia V; Naumov, Dmitrii Yu; Sheludyakova, Lilia A; Nikolaenkova, Elena B; Krivopalov, Viktor P; Bushuev, Mark B

    2014-02-21

    A series of mononuclear heteroleptic copper(I) halide complexes, [CuL(PPh3)X] (X = Cl, Br, I), based on 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(piperidin-1-yl)pyrimidine (L) and triphenylphosphine, have been synthesized by reaction between CuX (X = Cl, Br, I), L and PPh3 in a molar ratio of 1/1/1 in MeCN solutions. The copper atom, showing the distorted tetrahedral environment, is bound by the N,N-chelating ligand L, triphenylphosphine and a halide ion. The complexes [CuL(PPh3)Cl] and [CuL(PPh3)Br] are isostructural. In CH2Cl2 solutions, L and the complexes [CuL(PPh3)X] (X = Cl, Br, I) display a luminescence band with λ(max) = 377 nm and a lifetime of 1.9 ns (ligand-based luminescence (LL*)). However, the complex [CuL(PPh3)I] has an additional weak luminescence band with λ(max) = 681 nm and a lifetime of 96 ns of (3)MLCT origin. In the solid state, L shows the splitting of the luminescence band to λ(max) = 365 and 384 nm and a slight increase of the lifetime to 2.66 ns. Solid samples of the complexes [CuL(PPh3)X] demonstrate (3)MLCT luminescence bands at 620 nm (X = Cl), 605 nm (X = Br) and 559 nm (X = I) with lifetimes in the range 3.6-11.2 μs, whereas the LL* band (377 nm) is absent. Quantum yields and rate constants of radiative and nonradiative processes were determined in CH2Cl2 solutions and in the solid state for all complexes. The luminescence quantum yield and lifetimes for the solid samples increase in the order [CuL(PPh3)Cl] lifetime of 11.2 μs.

  4. Selective anticancer copper(II)-mixed ligand complexes: targeting of ROS and proteasomes.

    Science.gov (United States)

    Ng, Chew Hee; Kong, Siew Ming; Tiong, Yee Lian; Maah, Mohd Jamil; Sukram, Nurhazwani; Ahmad, Munirah; Khoo, Alan Soo Beng

    2014-04-01

    Copper compounds can be alternatives to platinum-based anticancer drugs. This study investigated the effects of a series of ternary copper(II) complexes, [Cu(phen)(aa)(H2O)]NO3·xH2O 1-4 (phen = 1,10-phenanthroline; aa = gly (1), DL-ala (2), sar (3), C-dmg (4)), on metastatic and cisplatin-resistant MDA-MB-231 breast cancer cells and MCF10A non-cancerous breast cells, and some aspects of the mechanisms. These complexes were distinctively more antiproliferative towards and induced greater apoptotic cell death in MDA-MB-231 than in MCF10A cells. 2 and 4 could induce cell cycle arrest only in cancer cells. Further evidence from DCFH-DA assay showed higher induction of reactive oxygen species (ROS) in treated cancer cells but minimal ROS increase in normal cells. DNA double-strand breaks, via a γ-H2AX assay, were only detected in cancer cells treated with 5 μM of the complexes. These complexes poorly inhibited chymotrypsin-like activity in the 20S rabbit proteasome while they did not inhibit the three proteolytic sites of MDA-MB-231 cells at 10 μM. However, the complexes could inhibit degradation of ubiquinated proteins of MDA-MB-231 cells. In addition, compound 4 was found to be effective against cervical (Hela), ovarian (SKOV3), lung (A549, PC9), NPC (Hone1, HK1, C666-1), breast (MCF7, T47D), lymphoma and leukemia (Nalmawa, HL60) and colorectal (SW480, SW48, HCT118) cancer cell lines with IC50 values (24 h) in the 1.7-19.0 μM range. Single dose NCI60 screening of 4 showed the complex to be highly cytotoxic to most cancer cell types and more effective than cisplatin.

  5. Fate of copper complexes in hydrothermally altered deep-sea sediments from the Central Indian Ocean Basin.

    Digital Repository Service at National Institute of Oceanography (India)

    Chakraborty, P.; Sander, S.G.; Jayachandran, S.; Nath, B.N.; Nagaraju, G.; Chennuri, K.; Vudamala, K.; Lathika, N.; Mascarenhas-Pereira, M.B.L.

    version: Environ. Pollut., vol.194; 2014; 138-144 Fate of copper complexes in hydrothermally altered deep-sea sediments from the Central Indian Ocean Basin Parthasarathi Chakraborty*1, Sylvia G. Sander2, Saranya Jayachandran1, B. Nagender Nath1, , G... sulphide deposits on the seafloor. Mining companies are exploring underwater volcanic vents, hoping to extract metals such as gold (Au), copper (Cu), zinc (Zn), rare earth element etc (Birney et al., 2006). The initial stages of exploration are still...

  6. Spectroscopic studies on Solvatochromism of mixed-chelate copper(II) complexes using MLR technique.

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Fazilati, Hakimeh

    2012-01-01

    Mixed-chelate copper(II) complexes with a general formula [Cu(acac)(diamine)]X where acac=acetylacetonate ion, diamine=N,N-dimethyl,N'-benzyl-1,2-diaminoethane and X=BPh(4)(-), PF(6)(-), ClO(4)(-) and BF(4)(-) have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, UV-vis and IR spectroscopies. The complexes are solvatochromic and their solvatochromism were investigated by visible spectroscopy. All complexes demonstrated the positive solvatochromism and among the complexes [Cu(acac)(diamine)]BPh(4)·H(2)O showed the highest Δν(max) value. To explore the mechanism of interaction between solvent molecules and the complexes, different solvent parameters such as DN, AN, α and β using multiple linear regression (MLR) method were employed. The statistical results suggested that the DN parameter of the solvent plays a dominate contribution to the shift of the d-d absorption band of the complexes.

  7. Copper complexes of 1,10-phenanthroline and related compounds as superoxide dismutase mimetics.

    Science.gov (United States)

    Bijloo, G J; van der Goot, H; Bast, A; Timmerman, H

    1990-11-01

    In a preliminary study we tested CuSO4.5H2O, (Cu(II]2[3,5-diisopropylsalicylate]4.2H2O and a number of copper complexes of substituted 1,10-phenanthrolines for superoxide anion dismutase activity. It appeared that this activity depends on the ligands involved and might be governed by the redox potential of the Cu(I) complex/Cu(II) complex couple. The strong superoxide anion dismutase activity of Cu(II)[DMP]2 complex can be expected considering its high redox potential. Rather surprisingly is the superoxide anion dismutase activity of the Cu(I)[DMP]2 complex since it involves oxidation to Cu(II)[DMP]2 complex. From regression analysis it was established that steric and field effects of the substituents of the investigated phenanthrolines play an important role in SOD activity and therefore it is concluded that complex formation is important for the superoxide dismutase-like activity.

  8. Synthesis, crystal structures and antitumor activities of copper(II) complexes with a 2-acetylpyrazine isonicotinoyl hydrazone ligand

    Science.gov (United States)

    Xu, Jun; Zhou, Tao; Xu, Zhou-Qing; Gu, Xin-Nan; Wu, Wei-Na; Chen, Hong; Wang, Yuan; Jia, Lei; Zhu, Tao-Feng; Chen, Ru-Hua

    2017-01-01

    Five complexes, [Cu(L)2]·4.5H2O (1), [Cu(HL)2](NO3)2·CH3OH (2) {[Cu2(L)2(NO3)(H2O)2]·(NO3)}n (3), [Cu2(HL)2(SO4)2]·2CH3OH (4) and [Cu4(L)4Cl4]·5H2O (5) based on HL (where HL = 2-acetylpyrazine isonicotinoyl hydrazone) have been synthesized and characterized by X-ray diffraction analyses. The counter anion and organic base during the synthesis procedure influence the structures of the complexes efficiently, which generate five complexes as mono-, bi-, tetra-nuclear and one-dimensional structures. The antitumor activities of the complexes 1-5 (except for complex 3 with the poor solubility) against the Patu8988 human pancreatic cancer, ECA109 human esophagus cancer and SGC7901 human gastric cancer cell lines are screened by MTT assay. The results indicate that the chelation of Cu(II) with the ligand is responsible for the observed high cytotoxicity of the copper(II) complexes and the 1:2 copper species 1 and 2 demonstrate lower antitumor activities than that of the 1:1 copper species 4 and 5. In addition, the in vitro apoptosis inducing activity of the copper(II) complex 5 against SGC7901 cell line is determined. And the results show that the complex can bring about apoptosis of the cancerous cells in vitro.

  9. 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

  10. Copper(I) nitro complex with an anionic [HB(3,5-Me2Pz)3]− ligand: a synthetic model for the copper nitrite reductase active site.

    Science.gov (United States)

    Hsu, Sodio C N; Chang, Yu-Lun; Chuang, Wan-Jung; Chen, Hsing-Yin; Lin, I-Jung; Chiang, Michael Y; Kao, Chai-Lin; Chen, Hsuan-Ying

    2012-09-03

    The new copper(I) nitro complex [(Ph(3)P)(2)N][Cu(HB(3,5-Me(2)Pz)(3))(NO(2))] (2), containing the anionic hydrotris(3,5-dimethylpyrazolyl)borate ligand, was synthesized, and its structural features were probed using X-ray crystallography. Complex 2 was found to cocrystallize with a water molecule, and X-ray crystallographic analysis showed that the resulting molecule had the structure [(Ph(3)P)(2)N][Cu(HB(3,5-Me(2)Pz)(3))(NO(2))]·H(2)O (3), containing a water hydrogen bonded to an oxygen of the nitrite moiety. This complex represents the first example in the solid state of an analogue of the nitrous acid intermediate (CuNO(2)H). A comparison of the nitrite reduction reactivity of the electron-rich ligand containing the CuNO(2) complex 2 with that of the known neutral ligand containing the CuNO(2) complex [Cu(HC(3,5-Me(2)Pz)(3))(NO(2))] (1) shows that reactivity is significantly influenced by the electron density around the copper and nitrite centers. The detailed mechanisms of nitrite reduction reactions of 1 and 2 with acetic acid were explored by using density functional theory calculations. Overall, the results of this effort show that synthetic models, based on neutral HC(3,5-Me(2)Pz)(3) and anionic [HB(3,5-Me(2)Pz)(3)](-) ligands, mimic the electronic influence of (His)(3) ligands in the environment of the type II copper center of copper nitrite reductases (Cu-NIRs).

  11. Monopicolinate cross-bridged cyclam combining very fast complexation with very high stability and inertness of its copper(II) complex.

    Science.gov (United States)

    Lima, Luís M P; Halime, Zakaria; Marion, Ronan; Camus, Nathalie; Delgado, Rita; Platas-Iglesias, Carlos; Tripier, Raphaël

    2014-05-19

    The synthesis of a new cross-bridged 1,4,8,11-tetraazacyclotetradecane (cb-cyclam) derivative bearing a picolinate arm (Hcb-te1pa) was achieved by taking advantage of the proton sponge properties of the starting constrained macrocycle. The structure of the reinforced ligand as well as its acid-base properties and coordination properties with Cu(2+) and Zn(2+) was investigated. The X-ray structure of the free ligand showed a completely preorganized conformation that lead to very fast copper(II) complexation under mild conditions (instantaneous at pH 7.4) or even in acidic pH (3 min at pH 5) at room temperature and that demonstrated high thermodynamic stability, which was measured by potentiometry (at 25 °C and 0.10 M in KNO3). The results also revealed that the complex exists as a monopositive copper(II) species in the intermediate pH range. A comparative study highlighted the important selectivity for Cu(2+) over Zn(2+). The copper(II) complex was synthesized and investigated in solution using different spectroscopic techniques and DFT calculations. The kinetic inertness of the copper(II) complex in acidic medium was evaluated by spectrophotometry, revealing the very slow dissociation of the complex. The half-life of 96 days, in 5 M HClO4, and 465 min, in 5 M HCl at 25 °C, show the high kinetic stability of the copper(II) chelate compared to that of the corresponding complexes of other macrocyclic ligands. Additionally, cyclic voltammetry experiments underlined the perfect electrochemical inertness of the complex as well as the quasi-reversible Cu(2+)/Cu(+) redox system. The coordination geometry of the copper center in the complex was established in aqueous solution from UV-vis and EPR spectroscopies.

  12. Synthesis and antibacterial activity of cephradine metal complexes : part II complexes with cobalt, copper, zinc and cadmium.

    Science.gov (United States)

    Sultana, Najma; Arayne, M Saeed; Afzal, M

    2005-01-01

    Cephradine, the first generation cephalosporin, is active against a wide range of Gram-positive and Gram-negative bacteria including penicillinase-producing Staphylococci. Since the presence of complexing ligand may affect the bioavailability of a metal in the blood or tissues, therefore, in order to study the probable interaction of cephradine with essential and trace elements present in human body, cephradine has been reacted with cobalt, copper, zinc and cadmium metal halides in L:M ratio of 2:1 in methanol and the products recrystallized from suitable solvents to pure crystals of consistent melting points. Infrared and ultraviolet studies of these complexes were carried out and compared with ligand. Magnetic susceptibility studies of these complexes were also carried out showing their paramagnetic behavior. From the infra red studies and elemental analysis of the complexes, it has been shown that the drug molecule serves as a bidentate ligand coordinating through both its carboxylate at C-3 and beta-lactam nitrogen and the metal having a square planar or octahedral geometry. To evaluate the changes in microbiological activity of cephradine after complexation, antibacterial studies were carried out by observing the changes in MIC (minimum inhibitory concentration) of the complexes and compared with the parent drug by measuring the zone of inhibition of complexes and compared with the parent cephalosporin against both Gram-positive and Gram-negative organisms. For MIC observation, serial dilution method was employed and zone series were determined by disk diffusion method. Our investigations reveal that formation of complexes results in decrease in antibacterial activity of cephradine and MIC values are increased.

  13. 1D μ-glycine-briged copper (II) chain in complex [Cu(μ-Gly)Im(ClO4)]n and ferromagnetic interactions among copper (II)

    Science.gov (United States)

    Pan, Lu; Lv, Xue-Chuan; Luo, Guan-Hua; Gao, Xiao-Han; Tan, Zhi-Cheng

    2016-12-01

    Complex [Cu(μ-Gly)Im(ClO4)]n(Im = imidazole, and Gly = glycine) with μ-glycine-briged copper (II) chain, containing six-coordination distorted elongated octahedron, was synthesized and characterized. The complex belongs to space group P 21/c measured by X-ray single crystal diffraction. In the cluster, each Cu2+ ion are six-coordination by one nitrogen atom and two oxygen atoms of glycine, one nitrogen atoms of imidazole, and two of oxygen atoms of two perchlorate. Each Cu2+ ion has an N2O4 donor set, which forms the distorted elongated octahedron due to the Jahn-Teller (JT) effect. The magnetic and thermodynamic properties were researched. Magnetic susceptibilities of the complex showed that ferromagnetic interactions occurred between the Cu (II) atoms. The Curie-Weiss constant C = 0.565 cm3 K·mol-1 and the Weiss constant θ = 1.0585 K were given by the Curie-Weiss law The ferromagnetic nature of the interaction could be deduced as the exchange pathway of Cusbnd Osbnd Csbnd Osbnd Cu, which involved an equatorial position at one copper (II) ion and an axial position of the nearest copper (II). The complex decomposed from 511 to 538 K as two steps.

  14. Copper(II) complex formation with a linear peptide encompassing the putative cell binding site of angiogenin.

    Science.gov (United States)

    La Mendola, Diego; Magrì, Antonio; Vagliasindi, Laura I; Hansson, Örjan; Bonomo, Raffaele P; Rizzarelli, Enrico

    2010-11-28

    Angiogenin is one of the more potent angiogenic factors known, whose activity may be affected by the presence of copper ions. Copper(II) complexes with the peptides encompassing the putative endothelial cell binding domain of angiogenin, Ac-KNGNPHREN-NH(2) and Ac-PHREN-NH(2), have been characterized by potentiometric, UV-vis, CD and EPR spectroscopic methods. The coordination features of all the copper complex species derived by both peptides are practically the same, as predictable because of the presence of a proline residue within their aminoacidic sequence. In particular, Ac-PHREN-NH(2) is really the aminoacidic sequence involved in the binding to copper(II). Thermodynamic and spectroscopic evidence are given that side chain oxygen donor atom of glutamyl residue is involved in the copper binding up to physiological pH. EPR parameters suggest that the carboxylate group is still involved also in the predominant species [Cu(L)H(-2)], the metal coordination environment being probably formed by N(Im), 2N(-), H(2)O in equatorial plane and an oxygen atom from COO(-) in apical position, or vice versa, with the carboxylate oxygen atom in the copper coordination plane and the water molecule confined to one of the apical positions. Moreover, the comparison with the thermodynamic and spectroscopic results in the case of the copper(ii) complex species formed by the single point mutated peptide, Ac-PHRQN-NH(2), provides further evidence of the presence of carboxylate oxygen atom in the copper coordination sphere.

  15. Dynamics of reactive oxygen species generation in the presence of copper(II)-histidine complex and cysteine.

    Science.gov (United States)

    Ząbek-Adamska, Anna; Drożdż, Ryszard; Naskalski, Jerzy W

    2013-01-01

    Histidine-copper(II) complex (Cu-His2) is a form of bound copper necessary for cellular copper uptake. Due to the high affinity of histidine to copper(II) ions, the binding of copper(II) by histidine is considered a substantial part of plasma antioxidative defense. Also cysteine plays a role in the antioxidative system. However, we show here that in the presence of oxygen the histidine-copper(II) complex plus cysteine produces reactive oxygen species (ROS). Cysteine concentration was assayed using a thiol specific silver-mercury electrode. Hydrogen peroxide was assayed amperometrically using platinum electrode. ROS formation was followed by chemiluminescence of luminol-fluoresceine-enhanced system. Addition of cysteine to Cu-His2 solution at pH 7.4 in the presence of atmospheric oxygen initiates the synthesis of H2O2 and generation of ROS, which manifests as a burst of chemiluminescence. The reaction has two stages; in the first stage, cysteine is utilized for the synthesis of an unstable intermediary product which becomes a substrate for ROS formation. Anaerobic conditions inhibit ROS formation. Increased cysteine concentration enhances the lag phase of the oxidative burst without influencing the amount of ROS. The synthesis of ROS (measured by chemiluminescence) is proportional to the concentration of Cu-His2 employed. ROS production can be repetitively initiated by further additions of cysteine to the reaction medium. The study suggests that Cu-His2 catalyzes cysteine-dependent reduction of oxygen to superoxide employing an intermediary cysteine-copper(I) complex and enabling Fenton reaction with copper and hydrogen peroxide produced as a secondary product. In effect, Cu-His2 with cysteine may be a source of ROS in biological media.

  16. Formation of Copper-Salivary Component Complexes and Its Effect on Sensory Perception

    OpenAIRE

    Hong, Jae Hee

    2006-01-01

    Copper in drinking water elicits a persisting bitter, metallic, or astringent taste. Characteristics and perception mechanisms of copper sensation have not been fully understood. Saliva is assumed to influence copper sensations via binding of salivary electrolytes or proteins with copper. The interaction between salivary components and copper is thought to influence sensory perception by affecting volatility of aroma compounds, de-lubricating salivary proteins, and by controlling solubil...

  17. Copper (II) diamino acid complexes: Quantum chemical computations regarding diastereomeric effects on the energy of complexation

    NARCIS (Netherlands)

    Zuilhof, H.; Morokuma, K.

    2003-01-01

    Quantum chemical calculations were used to rationalize the observed enantiodifferentiation in the complexation of alpha-amino acids to chiral Cu(II) complexes. Apart from Cu(II)-pi interactions and steric repulsions between the anchoring cholesteryl-Glu moiety and an aromatic amino acid R group, hyd

  18. Studying the Relationship between Managers’ Communicative Styles and Employees’ Counterproductive in Shahrbabak Copper complex

    Directory of Open Access Journals (Sweden)

    Ziaaddini

    2013-09-01

    Full Text Available Communicative style and method among people are of effective factors on their behaviors. Managers’ communication method by which they behave workers can affect on employees’ behavior. This research studies the relationship between managers’ communicative styles and employees’ counterproductive in Shahrbabak copper complex. Statistical society of the research includes formal employed employees in Shahrbabak copper complex containing 746 people from which 186 people were selected as the sample by Cochrane formulation. Data gathering instruments were two questionnaires. Communicative styles standard questionnaire for which validity was obtained 0.92 by Hashemi (2013. Also to measure employees’ counterproductive behaviors a certain questionnaire by validity of 0.93 was used. Every questionnaire’s validity was obtained by Cronbache Alpha method 0.90 and 0.87 respectively. To test hypotheses Pearson & Spearman correlation coefficient was used. All statistical analyses were done by SPSS statistical software. According to obtained results it is determined that there is a positive meaningful relationship between control and avoidance communicative styles; but there is a reverse relationship between equity, dynamic, entrusting and avoidance communicative styles with counterproductive behaviors. By the way there is no relationship between structuralism communicative style and counterproductive behaviors. Regarding the results from research hypotheses managers are suggested to use inclined dynamic communicative styles more to decrease counterproductive behaviors.

  19. Negative ion photoelectron spectroscopy of the copper-aspartic acid anion and its hydrated complexes

    Science.gov (United States)

    Li, Xiang; Wang, Haopeng; Bowen, Kit H.; Martínez, Ana; Salpin, Jean-Yves; Schermann, Jean-Pierre

    2010-08-01

    Negative ions of copper-aspartic acid Cu(Asp)- and its hydrated complexes have been produced in the gas phase and studied by anion photoelectron spectroscopy. The vertical detachment energies (VDE) of Cu(Asp)- and Cu(Asp)-(H2O)1,2 were determined to be 1.6, 1.95, and 2.20 eV, respectively. The spectral profiles of Cu(Asp)-(H2O)1 and Cu(Asp)-(H2O)2 closely resembled that of Cu(Asp)-, indicating that hydration had not changed the structure of Cu(Asp)- significantly. The successive shifts to higher electron binding energies by the spectra of the hydrated species provided measures of their stepwise solvation energies. Density functional calculations were performed on anionic Cu(Asp)- and on its corresponding neutral. The agreement between the calculated and measured VDE values implied that the structure of the Cu(Asp)- complex originated with a zwitterionic form of aspartic acid in which a copper atom had inserted into the N-H bond.

  20. A highly sensitive fluorescence probe for metallothioneins based on tiron-copper complex.

    Science.gov (United States)

    Xiao, Xilin; Xue, Jinhua; Liao, Lifu; Huang, Mingyang; Zhou, Bin; He, Bo

    2015-06-15

    The fabrication of tiron-copper complex as a novel fluorescence probe for the sensitive directly detection of metallothioneins at nanomolar levels was demonstrated. In Britton-Robinson (B-R) buffer (pH 7.50), the interaction of bis(tiron)copper(II) complex cation [Cu(tiron)2](2+) and metallothioneins enhanced the fluorescence intensity of the system. The fluorescence enhancement at 347 nm was proportional to the concentration of metallothioneins. The mechanism was studied and discussed in terms of the fluorescence spectra. Under the optimal experimental conditions, at 347 nm, there was a linear relationship between the fluorescence intensity and the concentration of the metallothioneins in the range of 8.80 × 10(-9)-7.70 × 10(-7)mol L(-1), with a correlation coefficient of r=0.995 and detection limit 2.60 × 10(-9)mol L(-1). The relative standard deviation was 0.77% (n=11), and the average recovery 94.4%. The method proposed was successfully reliable, selective and sensitive in determining of trace metallothioneins in fish visceral organ samples with the results in good agreement with those obtained by HPLC.

  1. Antibacterial, antibiofilm and antioxidant screening of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid

    Science.gov (United States)

    Bukonjić, Andriana M.; Tomović, Dušan Lj.; Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Radojević, Ivana D.; Maksimović, Jovana Z.; Vasić, Sava M.; Čomić, Ljiljana R.; Trifunović, Srećko R.; Radić, Gordana P.

    2017-01-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-propyl derivative of thiosalicylic acid was confirmed by X-ray structural study. The binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid crystallized in two polymorphic forms with main structural difference in the orientation of phenyl rings relative to corresponding carboxylate groups. The antibacterial activity was tested determining the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) by using microdilution method. The influence on bacterial biofilm formation was determined by tissue culture plate method. In general, the copper(II)-complexes manifested a selective and moderate activity. The most sensitive bacteria to the effects of Cu(II)-complexes was a clinical isolate of Pseudomonas aeruginosa. For this bacteria MIC and biofilm inhibitory concentration (BIC) values for all tested complexes were in the range or better than the positive control, doxycycline. Also, for the established biofilm of clinical isolate Staphylococcus aureus, BIC values for the copper(II)-complex with S-ethyl derivative of thiosalicylic acid,[Cu2(S-et-thiosal)4(H2O)2] (C3) and copper(II)-complex with S-butyl derivative of thiosalicylic acid, [Cu2(S-bu-thiosal)4(H2O)2] (C5) were in range or better than the positive control. All the complexes acted better against Gram-positive bacteria (Staphylococcus aureus and Staphylococcus aureus ATCC 25923) than Gram-negative bacteria (Proteus mirabilis ATCC 12453, Pseudomonas aeruginosa, and P. aeruginosa ATCC 27855). The complexes showed weak antioxidative properties tested by two methods (1,1-diphenyl-2-picrylhydrazyl (DPPH) and reducing power assay).

  2. One-dimensional chiral copper (II) complexes with novel nano-structures and superior antitumor activity.

    Science.gov (United States)

    Zhang, Wei Chuan; Tang, Xue; Lu, Xiaoming

    2016-03-01

    Three novel copper(II) compounds of formulas {[Cu(Phen)(Ala)]·NO3·H2O}n (1), {[Cu(Phen)(Ala)]·NO3}n (2) and [Cu(Ala)2]n (3) have been synthesized and determined by X-ray diffraction. 1 and 2 are shown in one dimensional long-chain chiral structures, and 3 is a two dimensional checkerboard-type structure. Both 1 and 2 displayed a higher anticancer activity than 3 against various cancer cells, even higher than the similar mononuclear complexes and clinical anticancer drug 5-fluorouracil. The noncancerous cell lines (CCC-HEL-1) have showed that complexes 1-3 have hardly any cytotoxicity. Transmission electron microscopy was studied to show the nano-structure and π function of two complexes. The ligand 1,10-phenanthroline inserted into its enantiomer lead complex 1 stable, and the π-π interaction outside the chain made complex 2 active, which is easy to crack and pile up together. In addition, the energy gaps, UV-vis, luminescent and cyclic voltammetry were experimented to show the stable one dimensional long-chain chiral structure and the π function of two complexes.

  3. Potential-modulated DNA cleavage by (N-salicylideneglycinato)copper(II) complex.

    Science.gov (United States)

    Yang, Zhou-Sheng; Wang, Yan-Ling; Liu, Yun-Chun; Zhao, Guang-Chao

    2005-11-01

    The interaction of aqua (N-salicylideneglycinato)copper(II) (Cu(salgly)2+) complex with calf thymus DNA has been investigated by cyclic voltammetry. Potential-modulated DNA cleavage in the presence of Cu(salgly)2+ complex was performed at a gold electrode in a thin layer cell. DNA can be efficiently cleaved by electrochemically reducing Cu(salgly)2+ complex to Cu(salgly)+ complex at -0.7 V (vs. Ag/AgCl). When the solution was aerated with a small flow of O2 during electrolysis, the extent of DNA cleavage was dramatically enhanced, and hydroxyl radical scavengers inhibited DNA cleavage. These results suggested that O2 and hydroxyl radical were involved in potential-modulated DNA cleavage reaction. The percentage of DNA cleavage was enhanced as the working potential was shifted to more negative values and the electrolysis time was increased. It was also dependent on the ratio of Cu(salgly)2+ complex to DNA concentration. The cleaved DNA fragments were separated by high performance liquid chromatography (HPLC). The experimental results indicated that the method for potential-modulated DNA cleavage by Cu(salgly)2+ complex was simple and efficient.

  4. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    Science.gov (United States)

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank

    2016-01-01

    Summary A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC) “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  5. Spectroscopic and DFT study of atenolol and metoprolol and their copper complexes

    Science.gov (United States)

    Cozar, O.; Szabó, L.; Cozar, I. B.; Leopold, N.; David, L.; Căinap, C.; Chiş, V.

    2011-05-01

    IR, Raman and surface-enhanced Raman scattering (SERS) spectra of atenolol (ATE) and metoprolol (MET) were recorded and assigned on the basis of density functional theory (DFT) calculations. A reliable assignment of vibrational IR and Raman bands of the two compounds was possible by a proper choice of models used in quantum chemical calculations. Both molecules are adsorbed to the silver surface mainly through the oxygen atoms and π-electrons of the phenyl ring. The coordination mode of the metal ions in Cu(II)-ATE and -MET compounds was also derived from IR and EPR spectra. EPR spectra give evidence for a square-planar arrangement around the copper (II) ion in the case of Cu-ATE complex, with a N 2O 2 chromophore. Only oxygen atoms are involved in the cooper coordination for Cu-MET complex, and two types of local symmetries with d and d as ground states for paramagnetic electron coexist.

  6. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    Directory of Open Access Journals (Sweden)

    Anne L. Schöffler

    2016-07-01

    Full Text Available A dinuclear N-heterocyclic carbene (NHC copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion.

  7. Synthesis, crystallographic characterization and electrochemical property of a copper(II) complex of the anticancer agent elesclomol.

    Science.gov (United States)

    Vo, Nha Huu; Xia, Zhiqiang; Hanko, Jason; Yun, Tong; Bloom, Steve; Shen, Jianhua; Koya, Keizo; Sun, Lijun; Chen, Shoujun

    2014-01-01

    Elesclomol is a novel anticancer agent that has been evaluated in a number of late stage clinical trials. A new and convenient synthesis of elesclomol and its copper complex is described. X-ray crystallographic characterization and the electrochemical properties of the elesclomol copper(II) complex are discussed. The copper(II) cation is coordinated in a highly distorted square-planar geometry to each of the sulphur and amide nitrogen atoms of elesclomol. Electrochemical measurements demonstrate that the complex undergoes a reversible one-electron reduction at biologically accessible potentials. In contrast the free elesclomol is found electrochemically inactive. This evidence is in strong support of the mechanism of action we proposed for the anticancer activity of elesclomol.

  8. Ligand effects on the structures and magnetic properties of tricyanomethanide-containing copper(II) complexes.

    Science.gov (United States)

    Yuste, Consuelo; Bentama, Abdeslem; Stiriba, Salah-Eddine; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel

    2007-11-28

    The preparation, crystal structure and magnetic properties of four heteroleptic copper(II) complexes with the tricyanomethanide (tcm(-)) and the heterocyclic nitrogen donors 3,6-bis(2-pyridyl)pyridazine (dppn), 2,5-bis(2-pyridyl)pyrazine (2,5-dpp), 2,3-bis(2-pyridyl)pyrazine (2,3-dpp) and 2,3-bis(2-pyridyl)quinoxaline (2,3-dpq) are reported, {[Cu(2)(dppn)(OH)(tcm)(2)] x tcm}(n) (1), {[Cu(2,5-dpp)(tcm)] x tcm}(n) (2), {[Cu(2)(2,3-dpp)(2)(tcm)(3)(H(2)O)(0.5)] x tcm x 0.5H(2)O}(n) (3) and [Cu(2,3-dpq)(tcm)(2)](n) (4). 1 has a ladder-like structure with single mu-1,5-tcm ligands forming the sides and a bis-bidentate dppn and a single mu-hydroxo providing the rung. Each copper atom in 1 exhibits a distorted square pyramidal CuN(4)O surrounding: the basal plane is built by the hydroxo-oxygen, a nitrile-nitrogen atom from a tcm group and one pyrazine and a pyridyl nitrogen atoms from the dppn whereas the apical position is filled by a nitrile-nitrogen atom from a symmetry-related tcm ligand. The structures of 2-4 consists of zig-zag (2 and 3)/linear (4) chains of copper(II) ions which are bridged by either bis-bidentate 2,5-dpp (2) and 2,3-dpp (3) molecules or single mu-1,5-tcm (4) groups. The copper atoms in 2 and 4 are five coordinated with distorted trigonal bipyramidal (2) and square pyramidal (4) CuN(5) surroundings. The axial positions in 2 are occupied by two pyridyl-nitrogen atoms from two 2,5-dpp ligands whereas the trigonal plane is built by a nitrile-nitrogen from a terminally bound tcm group and two pyrazine nitrogen atoms from two 2,5-dpp molecules. The basal plane in 4 is defined by a pyridyl and a pyrazine nitrogen atoms from the bidentate 2,3-dpq ligand and two nitrile nitrogen atoms from two tcm groups (one terminal and the other bridging) whereas the apical position is filled by a nitrile nitrogen from another tcm ligand. The crystallographically independent copper atoms in 3 [Cu(1) and Cu(2)] exhibit elongated octahedral geometries being defined by four

  9. Structural characterization of a high affinity mononuclear site in the copper(II)-α-synuclein complex.

    Science.gov (United States)

    Bortolus, Marco; Bisaglia, Marco; Zoleo, Alfonso; Fittipaldi, Maria; Benfatto, Maurizio; Bubacco, Luigi; Maniero, Anna Lisa

    2010-12-29

    Human α-Synuclein (aS), a 140 amino acid protein, is the main constituent of Lewy bodies, the cytoplasmatic deposits found in the brains of Parkinson's disease patients, where it is present in an aggregated, fibrillar form. Recent studies have shown that aS is a metal binding protein. Moreover, heavy metal ions, in particular divalent copper, accelerate the aggregation process of the protein. In this work, we investigated the high affinity binding mode of truncated aS (1-99) (aS99) with Cu(II), in a stoichiometric ratio, to elucidate the residues involved in the binding site and the role of copper ions in the protein oligomerization. We used Electron Paramagnetic Resonance spectroscopy on the Cu(II)-aS99 complex at pH 6.5, performing both multifrequency continuous wave experiments and pulsed experiments at X-band. The comparison of 9.5 and 95 GHz data showed that at this pH only one binding mode is present. To identify the nature of the ligands, we performed Electron Spin Echo Envelope Modulation, Hyperfine Sublevel Correlation Spectroscopy, and pulsed Davies Electron-Nuclear Double Resonance (Davies-ENDOR) experiments. We determined that the EPR parameters are typical of a type-II copper complex, in a slightly distorted square planar geometry. Combining the results from the different pulsed techniques, we obtained that the equatorial coordination is {N(Im), N(-), H(2)O, O}, where N(im) is the imino nitrogen of His50, N(-) a deprotonated amido backbone nitrogen that we attribute to His50, H(2)O an exchangeable water molecule, and O an unidentified oxygen ligand. Moreover, we propose that the free amino terminus (Met1) participates in the complex as an axial ligand. The MXAN analysis of the XAS k-edge absorption data allowed us to independently validate the structural features proposed on the basis of the magnetic parameters of the Cu(II)-aS99 complex and then to further refine the quality of the proposed structural model.

  10. Structural Diversity of Copper(I)-N-Heterocyclic Carbene Complexes; Ligand Tuning Facilitates Isolation of the First Structurally Characterised Copper(I)-NHC Containing a Copper(I)-Alkene Interaction

    OpenAIRE

    Willans, CE; Lake, BRM

    2013-01-01

    The preparation of a series of imidazolium salts bearing N-allyl substituents, and a range of substituents on the second nitrogen atom that have varying electronic and steric properties, is reported. The ligands have been coordinated to a copper(I) centre and the resulting copper(I)–NHC (NHC=N-heterocyclic carbene) complexes have been thoroughly examined, both in solution and in the solid-state. The solid-state structures are highly diverse and exhibit a range of unusual geometries and cuprop...

  11. Synthesis And Third-order Nonlinear Optical Studies of Four-Coordinated Copper(I) Complexes

    Science.gov (United States)

    Kumar, H. C. Sampath; Rudresha, B. J.; Bhat, B. Ramachandra; Philip, Reji; Row, T. N. Guru

    2011-10-01

    Three Cu(I) halide complexes [Cu(L)(PPh3)X] (L = 1,10-phenanthroline, X = Cl (1), Br (2) and I (3), PPh3 = triphenylphosphine) have been synthesised and characterised by spectroscopic techniques. Further structure of the complex 1 was confirmed by single crystal X-ray diffraction analysis. The nonlinear optical properties of the complexes were investigated at 532 nm using single beam Z-scan technique with nanosecond laser pulses. The complexes showed strong optical limiting behavior due to effective three-photon absorption (3PA). The values of 3PA coefficients (γ) for 1, 2 and 3 were found to be 3.2×10-24 m3/W2, 6.0×10-25 m3/W2 and 1.2×10-23 m3/W2 respectively, which are comparable to good optical limiting materials. These studies demonstrate that the Ligand→copper coordinative bonds facilitate the polarization of the electronic π-system which optimizes the third-order NLO response in the reported complexes.

  12. Effect of Counterion on the Solvatochromic Properties of Heteroleptic Chelate Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Hamid Golchoubian

    2013-01-01

    Full Text Available A series of heteroleptic chelate copper(II complexes of the type [Cu(L(acac]X where acac = acetylacetonate; L = N,N′-1,6-bis(2-fluorophenyl-2,5-diazahexane; X=CIO4-, BPh4-, PF6-, and BF4- have been prepared and characterized by elemental analyses, IR and UV-Vis spectroscopies, and molar conductance measurements. The prepared complexes are fairly soluble in a large number of organic solvents and show positive solvatochromism. Among the complexes [Cu(L(acac]ClO4, it is demonstrated the most solvatochromism. A multiparametric equation has been utilized to explain the solvent effect on the d-d transition of the complexes using SPSS/PC software. To explore the mechanism of interaction between solvent molecules and the complexes, different solvent parameters such as DN, AN, α, ET(30, π*, and β using stepwise multiple linear regression (SMLR method were employed. The results demonstrated that the donor power of the solvent plays the most important role in the solvatochromism of the compounds.

  13. 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.

  14. Copper-sulfenate complex from oxidation of a cavity mutant of Pseudomonas aeruginosa azurin

    Energy Technology Data Exchange (ETDEWEB)

    Sieracki, Nathan A.; Tian, Shiliang; Hadt, Ryan G.; Zhang, Jun-Long; Woertink, Julia S.; Nilges, Mark J.; Sun, Furong; Solomon, Edward I.; Lu, Yi [Stanford; (UIUC); (Peking)

    2014-08-25

    Metal–sulfenate centers are known to play important roles in biology and yet only limited examples are known due to their instability and high reactivity. Herein we report a copper–sulfenate complex characterized in a protein environment, formed at the active site of a cavity mutant of an electron transfer protein, type 1 blue copper azurin. Reaction of hydrogen peroxide with Cu(I)–M121G azurin resulted in a species with strong visible absorptions at 350 and 452 nm and a relatively low electron paramagnetic resonance gz value of 2.169 in comparison with other normal type 2 copper centers. The presence of a side-on copper–sulfenate species is supported by resonance Raman spectroscopy, electrospray mass spectrometry using isotopically enriched hydrogen peroxide, and density functional theory calculations correlated to the experimental data. In contrast, the reaction with Cu(II)–M121G or Zn(II)–M121G azurin under the same conditions did not result in Cys oxidation or copper–sulfenate formation. Structural and computational studies strongly suggest that the secondary coordination sphere noncovalent interactions are critical in stabilizing this highly reactive species, which can further react with oxygen to form a sulfinate and then a sulfonate species, as demonstrated by mass spectrometry. Engineering the electron transfer protein azurin into an active copper enzyme that forms a copper–sulfenate center and demonstrating the importance of noncovalent secondary sphere interactions in stabilizing it constitute important contributions toward the understanding of metal–sulfenate species in biological systems.

  15. Oxidative demethylation in monooxygenase model systems. Competing pathways for binuclear and helical multinuclear copper(I) complexes

    NARCIS (Netherlands)

    Gelling, O.J.; Feringa, Bernard

    1990-01-01

    The ligand 2,6-bis[N-(2-pyridylethyl)formimidoyl]-1-methoxybenzene (2,6-BPB-1-OCH3) (4) reacts with Cu(CH3CN)4BF4 to form novel binuclear copper(I) complexes [Cu2(2,6-BPB-1-OCH3)(BF4)2(CH3CN)4] (11) and [Cu2(2,6-BPB-1-OCH3)(BF4)2(CH2Cl2)0.5] (14), or the helical polynuclear copper(1) complex [Cu(2,6

  16. Nanostructured lipid carriers for incorporation of copper(II complexes to be used against Mycobacterium tuberculosis

    Directory of Open Access Journals (Sweden)

    Sato MR

    2017-03-01

    Full Text Available Mariana R Sato,1 João A Oshiro Junior,1 Rachel TA Machado,1 Paula C de Souza,2 Débora L Campos,2 Fernando R Pavan,2 Patricia B da Silva,1,* Marlus Chorilli1,* 1Department of Drugs and Medicines, Faculdade de Ciências Farmacêuticas, UNESP – Univ Estadual Paulista, Campus Araraquara, Araraquara, SP, Brazil; 2Department of Biological Sciences, Faculdade de Ciências Farmacêuticas, UNESP – Univ Estadual Paulista, Campus Araraquara, Araraquara, SP, Brazil *These authors contributed equally to this work Abstract: Tuberculosis (TB is a disease caused by Mycobacterium tuberculosis. Cessation of treatment before the recommended conclusion may lead to the emergence of multidrug-resistant strains. The aim of this study was to develop nanostructured lipid carriers (NLCs for use in the treatment of M. tuberculosis. The NLCs comprised the following lipid phase: 2.07% polyoxyethylene 40 stearate, 2.05% caprylic/capric triglyceride, and 0.88% polyoxyl 40 hydrogenated castor oil; the following aqueous phase: 3.50% poloxamer 407 (F1–F6, and 0.50% cetyltrimethylammonium bromide (F7–F12; and incorporated the copper(II complexes [CuCl2(INH2]·H2O (1, [Cu(NCS2(INH2]·5H2O (2, and [Cu(NCO2(INH2]·4H2O (3 to form compounds F11.1, F11.2, and F11.3, respectively. The mean diameter of F11, F11.1, F11.2, and F11.3 ranged from 111.27±21.86 to 134.25±22.72 nm, 90.27±12.97 to 116.46±9.17 nm, 112.4±10.22 to 149.3±15.82 nm, and 78.65±6.00 to 122.00±8.70 nm, respectively. The polydispersity index values for the NLCs ranged from 0.13±0.01 to 0.30±0.09. The NLCs showed significant changes in zeta potential, except for F11.2, with F11, F11.1, F11.2, and F11.3 ranging from 18.87±4.04 to 23.25±1.13 mV, 17.03±1.77 to 21.42±1.87 mV, 20.51±1.88 to 22.60±3.44 mV, and 17.80±1.96 to 25.25±7.78 mV, respectively. Atomic force microscopy confirmed the formation of nanoscale spherical particle dispersions by the NLCs. Differential scanning calorimetry determined

  17. Novel copper(II) complexes with hydrazides and heterocyclic bases: Synthesis, structure and biological studies.

    Science.gov (United States)

    Paixão, Drielly A; Marzano, Ivana M; Jaimes, Edgar H L; Pivatto, Marcos; Campos, Débora L; Pavan, Fernando R; Deflon, Victor M; Maia, Pedro Ivo da S; Da Costa Ferreira, Ana M; Uehara, Isadora A; Silva, Marcelo J B; Botelho, Françoise V; Pereira-Maia, Elene C; Guilardi, Silvana; Guerra, Wendell

    2017-07-01

    Five new copper(II) complexes of the type [Cu(NO)(NN)(ClO4)2], in which NO=4-fluorophenoxyacetic acid hydrazide (4-FH) or 4-nitrobenzoic hydrazide (4-NH) and NN=1,10-phenanthroline (phen), 4-4'-dimethoxy-2-2'-bipyridine (dmb) or 2,2-bipyridine (bipy) were synthesized and characterized using various spectroscopic methods. The X-ray structural analysis of one representative compound indicates that the geometry around the copper ion is distorted octahedron, in which the ion is coordinated to hydrazide via the terminal nitrogen and the carbonyl oxygen, and to heterocyclic bases via their two nitrogen atoms. Two perchlorate anions occupy the apical positions, completing the coordination sphere. The cytotoxic activity of compounds was investigated in three tumor cell lines (K562, MDA-MB-231 and MCF-7). Concerning K562 cell line, the complexes with 1,10-phenanthroline exhibit high cytotoxic activity and are more active than carboplatin, free ligands and [Cu(phen)2](2+). Considering the cytotoxicity results, further investigations for the compounds [Cu(4-FH)(phen)(ClO4)2] I and [Cu(4-NH)(phen)(ClO4)2]∙H2O III were performed. Flow cytometric analysis revealed that these complexes induce apoptotic cell death in MDA-MB-231 cell line and bind to DNA with K values of 4.38×10(4) and 2.62×10(4), respectively. These compounds were also evaluated against wild type Mycobacterium tuberculosis (ATCC 27294) and exhibited antimycobacterial activity, displayed MIC values lower than those of the corresponding free ligands. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Effects of Cu(II) complexes on photosynthesis in spinach chloroplasts. Aqua(aryloxyacetato)copper(II) complexes.

    Science.gov (United States)

    Král'ová, K; Sersen, F; Blahová, M

    1994-12-01

    The inhibitory effect of 14 aqua(aryloxyacetato) copper(II) complexes on oxygen evolution rate in spinach chloroplasts has been investigated. The inhibitory effect of these effectors on photosynthesis was confirmed by Hill reaction as well as by EPR and fluorescence spectroscopies. The results of the EPR study showed that the sites of action of the studied effectors are Z+ and Y+ intermediates at the donor side of the photosystem (PS) 2. The EPR study also showed that another site of action is the oxygen evolving complex, namely its manganese cluster. The above suggestions were supported by the results of the fluorescence study as well. Based on the restoring of the photosynthetic electron transport to 2,6-dichlorophenol-indophenol in chloroplasts inhibited by the studied Cu(II) complexes using sym-diphenylcarbazide it can be assumed that the own core of PS2 (P680) and a part of the electron transport chain-at least up to plastoquinone-remain intact.

  19. Peculiar reactivity of a di-imine copper(II) complex regarding its binding to albumin protein.

    Science.gov (United States)

    Silveira, Vivian C; Abbott, Mariana P; Cavicchioli, Maurício; Gonçalves, Marcos B; Petrilli, Helena M; de Rezende, Leandro; Amaral, Antonia T; Fonseca, David E P; Caramori, Giovanni F; Ferreira, Ana M da Costa

    2013-05-14

    A set of four di-imine copper(II) complexes containing pyridine, pyrazine and/or imidazole moieties, [Cu(apyhist)H2O](2+) 1 (apyhist = 2-(1H-imidazol-4-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), [Cu(apzhist)OH](+) 2 (apzhist = 2-(1H-imidazol-4-yl)-N-(1-(pyrazin-2-yl)ethylidene)ethanamine), [Cu(apyepy)OH](+) 3 (apyepy = 2-(pyridin-2-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), and [Cu(apzepy)H2O](2+) 4 (apzepy = N-(1-(pyrazin-2-yl)ethylidene)-2-(pyridin-2-yl)ethanamine), were investigated regarding their capability of interacting with serum albumin (human, HSA and bovine, BSA), by using spectroscopic techniques, CD, UV/Vis and EPR. Like other similar di-imine copper(II) complexes, most of them showed an expected preferential insertion of the metal ion at the primary N-terminal site of the protein, very selective for copper and characterized by a CD band at 560 nm. Further insertion of the copper ion at a secondary site is expected when using an excess of the metal. However, one of these studied complexes, [Cu(apyhist)H2O](2+) 1, exhibited anomalous behaviour interacting only at this secondary metal binding site of albumin, characterized by a CD band at 370 nm, and attributed to the coordination of copper at the Cys34 pocket. Analogous experiments with HSA previously treated with N-ethyl-maleimide (NEM), that oxidizes the protein Cys34 residue and obstructs the metal coordination, verified these results. Additional data obtained by EPR spectroscopy complemented those results. DFT calculations, considering some structural and electronic characteristics of such series of di-imine ligands and of the corresponding copper complexes, suggested molecular recognition of the apyhist ligand at the protein cavity as a feasible explanation for this unexpected and peculiar behaviour of complex 1.

  20. Synthesis and Crystal Structure of Bis(barbiturato)triwater Complex of Copper(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    杨文斌; 卢灿忠; 吴传德; 吴鼎铭; 卢绍芳; 庄鸿辉

    2003-01-01

    The crystal structure of the bis(barbiturato)triwater copper( Ⅱ ) complex formulated as Cu(barb)2(HO2)3 (barb = barbiturato) has been determined by single-crystal X-ray diffraction.The analysis was carried out by direct and Fourier methods and the structure was refined by full-matrix least-square computations. The title compound crystallizes in orthorhombic, space group Fdd2 with a = 11.691(1), b = 30.200(4), c = 7.1901(9) (A), V = 2538.7(5) (A)3, Z = 8,C8H12CuN4O9, Mr= 371.76, Dc = 1.945 g/cm3,μ(MoKα) = 1.781 mm-1, F(000) = 1512, the final R = 0.0347 and wR = 0.0766 for 827 observed reflections (Ⅰ> 2o(Ⅰ)). The copper atom is squarepyramidally bonded to the exocyclic oxygen atoms of the barbital anions (Cu-O, 1.976(3)) and the water molecules (Cu-O, 1.926(4) and 2.164(7)(A)). The molecules are held together to form an extensive three-dimensional network via O-H… O and N-H…O hydrogen-bonded contacts.

  1. Genesis of the Precambrian copper-rich Caraiba hypersthenite-norite complex, Brazil

    Science.gov (United States)

    Oliveira, E. P.; Tarney, J.

    1995-08-01

    Caraiba, the largest Brazilian copper deposit under exploitation, consists mostly of disseminated and remobilised bornite and chalcopyrite hosted in early Proterozoic norite and hypersthenite. The mafic igneous complex comprises multiple intrusions of dykes, veins and breccias of norites and hypersthenites, with minor proportions of amphibolised gabbronorite and peridotite xenoliths transported by the magma from deeper levels in the lithosphere. The country rocks are high-grade gneisses, granulites and metasediments. Compositions of plagioclase(An60-40) and orthopyroxene(En70-60) fall in a narrow range similar to the Koperberg Suite from the Okiep copper district, South Africa, and to that in many massif-type anorthosites. Whole-rock major and trace element geochemistry indicate a parental magma enriched in Fe, LREE, P, K, and Cu. Negative Nb anomalies on multi-element plots and fractionated REE patterns, along with sulphide sulphur isotopes in the range δ34S = -1.495 to + 0.643‰, suggest a primary mantle lithosphere source, although a lower crustal source for the gabbronorite and peridotite xenoliths cannot be excluded. Geochronological and field evidence indicate that both norite and hypersthenite are likely to have been emplaced during a major sinistral transcurrent (partly transpressional) shearing event associated with the waning stage of evolution of the early Proterozoic Salvador-Curaçá orogen.

  2. Electron spin relaxation of copper(II) complexes in glassy solution between 10 and 120 K.

    Science.gov (United States)

    Fielding, Alistair J; Fox, Stephen; Millhauser, Glenn L; Chattopadhyay, Madhuri; Kroneck, Peter M H; Fritz, Günter; Eaton, Gareth R; Eaton, Sandra S

    2006-03-01

    The temperature dependence, between 10 and 120 K, of electron spin-lattice relaxation at X-band was analyzed for a series of eight pyrrolate-imine complexes and for ten other copper(II) complexes with varying ligands and geometry including copper-containing prion octarepeat domain and S100 type proteins. The geometry of the CuN4 coordination sphere for pyrrolate-imine complexes with R=H, methyl, n-butyl, diphenylmethyl, benzyl, 2-adamantyl, 1-adamantyl, and tert-butyl has been shown to range from planar to pseudo-tetrahedral. The fit to the recovery curves was better for a distribution of values of T1 than for a single time constant. Distributions of relaxation times may be characteristic of Cu(II) in glassy solution. Long-pulse saturation recovery and inversion recovery measurements were performed. The temperature dependence of spin-lattice relaxation rates was analyzed in terms of contributions from the direct process, the Raman process, and local modes. It was necessary to include more than one process to fit the experimental data. There was a small contribution from the direct process at low temperature. The Raman process was the dominant contribution to relaxation between about 20 and 60 K. Debye temperatures were between 80 and 120 K. For samples with similar Debye temperatures the coefficient of the Raman process tended to increase as gz increased, as expected if modulation of spin-orbit coupling is a major factor in relaxation rates. Above about 60 K local modes with energies in the range of 260-360 K (180-250 cm-1) dominated the relaxation. For molecules with similar geometry, relaxation rates were faster for more flexible molecules than for more rigid ones. Relaxation rates for the copper protein samples were similar to rates for small molecules with comparable coordination spheres. At each temperature studied the range of relaxation rates was less than an order of magnitude. The spread was smaller between 20 and 60 K where the Raman process dominates

  3. 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.

  4. Synthesis, structure, spectroscopic and electrochemical properties of bis(histamine-saccharinate) copper(II) complex

    Science.gov (United States)

    Bulut, İclal; Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet

    2007-05-01

    Crystal structure of [Cu(hsm) 2(sac) 2] (hsm is histamine and sac is saccharinate) complex has been determined by X-ray diffraction analyses and its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystallizes in the monoclinic system, space group P 21/ c with a = 7.4282(4), b = 22.5034(16), c = 8.3300(5) Å, β = 106.227(4)°, V = 1336.98(14) Å 3, and Z = 2. The structure consist of discrete [Cu(hsm) 2(sac) 2] molecules in which the copper ion is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane [Cu-N hsm = 2.024(2) and Cu-N hsm = 2.0338(18) Å]. Two N atoms from the saccharinate ligands coordinate on the elongated axial positions with Cu-N sac being 2.609(5) Å. The complex is also characterized by spectroscopic (IR, UV/Vis) and thermal (TG, and TDA) methods. The cyclic voltammogram of the title complex investigated in DMSO (dimethylsulfoxide) solution exhibits only metal centred electroactivity in the potential range - 1.25-1.5 V versus Ag/AgCl reference electrode. The molecular orbital bond coefficients of Cu(II) ion in d 9 state is also calculated by using EPR and optical absorption parameters.

  5. Synthesis, characterization, DNA binding, cleavage activity and cytotoxicity of copper(II) complexes.

    Science.gov (United States)

    Li, Mei-Jin; Lan, Tao-Yu; Cao, Xiu-Hui; Yang, Huang-Hao; Shi, Yupeng; Yi, Changqing; Chen, Guo-Nan

    2014-02-21

    Three new mononuclear copper(II) complexes, [Cu(L2)](2+) (1), [Cu(acac)(L)](+) (2), and [Cu(acac-Cl)(L)](+) (3) (L = 2-(4-pyridine)oxazo[4,5-f]1,10-phenanthroline (4-PDOP); acac = acetylacetone; acac-Cl = 3-chloroacetylacetone), have been synthesized and characterized by elemental analysis, high resolution mass spectrometry (Q-TOF), and IR spectroscopy. Two of the complexes were structurally characterized by single-crystal X-ray diffraction techniques. Their interactions with DNA were studied by UV-vis absorption and emission spectra, viscosity, thermal melting, DNA unwinding assay and CD spectroscopy. The nucleolytic cleavage activity of the compounds was carried out on double stranded pBR322 circular plasmid DNA by using a gel electrophoresis experiment in the presence and absence of an oxidant (H2O2). Active oxygen intermediates such as hydroxyl radicals and hydrogen peroxide generated in the presence of L and complexes 1-3 may act as active species for the DNA scission. The cytotoxicity of the complexes against HepG2 cancer cells was also studied.

  6. Photocytotoxic ternary copper(II) complexes of histamine Schiff base and pyridyl ligands

    Indian Academy of Sciences (India)

    Samya Banerjee; Akanksha Dixit; K Sesha Maheswaramma; Basudev Maity; Sanjoy Mukherjee; Arun Kumar; Anjali A Karande; Akhil R Chakravarty

    2016-02-01

    Ternary copper(II) complexes of salicylaldehyde-histamine Schiff base (HL) and pyridyl ligands, viz. [Cu(bpy)(L)](ClO4) (1) and [Cu(dppz)(L)](ClO4) (2), where bpy is 2,2′-bipyridine (in 1) and dppz is dipyrido[3,2-a:2′,3′-c]phenazine (in 2), were synthesized, characterized and their DNA binding, photo-activated DNA cleavage activity and photocytotoxicity studied. The 1:1 electrolytic one-electron paramagnetic complexes showed a d-d band near 670 nm in aqueous DMF (1:1 v/v). The crystal structure of complex 1 showed the metal in CuN4O distorted square-pyramidal geometry. Complex 2 intercalatively binds to calf-thymus (ct) DNA with a binding constant (b) of ∼105 M−1. It exhibited moderate chemical nuclease activity but excellent DNA photocleavage activity in red light of 647 nm forming $^{\\bullet}\\text{OH}$ radicals. It showed remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 of 1.6 M in visible light (400-700 nm) with low dark toxicity. The photo-induced cell death is via generation of oxidative stress by reactive oxygen species.

  7. SOD mimetic activity and antiproliferative properties of a novel tetra nuclear copper (II) complex.

    Science.gov (United States)

    Weintraub, Sagiv; Moskovitz, Yoni; Fleker, Ohad; Levy, Ariel R; Meir, Aviv; Ruthstein, Sharon; Benisvy, Laurent; Gruzman, Arie

    2015-12-01

    The search for novel anticancer therapeutic agents is an urgent and important issue in medicinal chemistry. Here, we report on the biological activity of the copper-based bioinorganic complex Cu4 (2,4-di-tert-butyl-6-(1H-imidazo- [1, 10] phenanthrolin-2-yl)phenol)4]·10 CH3CN (2), which was tested in rat L6 myotubes, mouse NSC-34 motor neurone-like cells, and HepG-2 human liver carcinoma. Upon 96 h incubation, 2 exhibited a significant cytotoxic effect on all three types of cells via activation of two cell death mechanisms (apoptosis and necrosis). Complex 2 exhibited better potency and efficacy than the canonical cytotoxic drug cisplatin. Moreover, during shorter incubations, complex 2 demonstrated a significant SOD mimetic activity, and it was more effective and more potent than the well-known SOD mimetic TEMPOL. In addition, complex 2 was able to interact with DNA and, cleave DNA in the presence of sodium ascorbate. This study shows the potential of using polynuclear redox active compounds for developing novel anticancer drugs through SOD-mimetic redox pathways.

  8. Pseudohalide copper(II) complexes derived from polypyridyl ligands: Synthesis and characterization

    Science.gov (United States)

    Mautner, Franz A.; Louka, Febee R.; LeGuet, Thibaut; Massoud, Salah S.

    2009-02-01

    A novel series of pseudohalide- ( N3- NCS -) and perchlorato-Cu(II) complexes possessing a series of ligands with pyridyl-containing donors have been investigated. These include [Cu(pmap)ClO 4)]ClO 4 ( 1), [Cu(pmap)(N 3)]ClO 4 ( 2), [Cu(pmea)(N 3)]ClO 4·H 2O ( 3), [Cu(dp-pa)(N 3)]ClO 4·½H 2O ( 4), [Cu(pzdepy)ClO 4]ClO 4 ( 5), [Cu(pzdepy)(NCS)]ClO 4 ( 6) and [Cu 2(L)(NCS) 4]·2CH 3CN ( 7) where pmap = bis[2-(2-pyridylethyl)]-(2-pyridylmethyl)amine, pmea = bis(2-pyridylmethyl)-2-(2-pyridylethyl)amine, dp-pa = N-propanamide- N, N-bis(2-pyridylmethyl)amine, pzdepy = N, N'-bis[2-(2-pyridylethyl)]piperazine and L = 3,5-bis[bis(2-pyridylmethyl)aminomethyl]-toluene. All complexes were characterized by elemental analyses, IR and UV-Visible spectroscopy. The visible spectra of all complexes reveal the square-pyramidal geometries (SP) around the central Cu 2+ ion. IR spectra confirmed the coordination of the ClO4- group in 1 and 5 and the N-donor thiocyanate group in complexes 6 and 7. The X-ray structure determination of the pseudohalide complexes 2, 6 and 7 confirmed the monodentate coordination nature of N3- and NCS - ions. The structure of 2 or 6 consists of isolated [Cu(pmap)(N 3)] + or [Cu(pzdepy)(NCS)] + cations and perchlorate counter anions. The copper centers are penta-coordinated by the four N atoms of the pmap or pzdepy and N(5) atom of the azide group in 2 and the thiocyanate group in 6. In the dinuclear unit [Cu 2(L)(NCS) 4] of 7, each copper atom forms bonds to three nitrogen atoms of the ligand L, [Cu sbnd N bonds from 2.013(2) to 2.054(2) Å], and to N(4) and N(5) atoms of the two terminal thiocyanato groups [Cu(1) sbnd N(4) = 1.954(2) Å; Cu(1) sbnd N(5) = 2.178(2) Å]. The intradimer Cu(1)...Cu(1A) distance is 5.7010(14) Å. An intramolecular π-π stacking with a ring-ring separation of 3.5991(14) Å is observed between the central benzene ring and the pyridyl rings. In the three complexes ( 2, 6 and 7), the CuN 5 chromophore may be described as an

  9. Synthesis, characterization and DNA interaction of new copper(II) complexes of Schiff base-aroylhydrazones bearing naphthalene ring.

    Science.gov (United States)

    Gökçe, Cansu; Gup, Ramazan

    2013-05-05

    Two new copper(II) complexes with the condensation products of methyl 2-naphthyl ketone with 4-hydroxybenzohydrazide, 4-hydroxy-N'-[(1Z)-1-(naphthalen-2-yl)ethylidene]benzohydrazide [HL(1)] and (Z)-ethyl 2-(4-(2-(1-(naphthalen-2-yl)ethylidene)hydrazinecarbonyl)phenoxy)acetate (HL(2)) were synthesized and characterized by elemental analysis, infrared spectra, UV-Vis electronic absorption spectra, magnetic susceptibility measurements, TGA, powder XRD and SEM-EDS. The binding properties of the copper(II) complexes with calf thymus DNA were studied by using the absorption titration method. DNA cleavage activities of the synthesized copper complexes were examined by using agarose gel electrophoresis. The effect of complex concentration on the DNA cleavage reactions in the absence and presence of H2O2 was also investigated. The experimental results suggest that the copper complexes bind significantly to calf thymus DNA by both groove binding and intercalation modes and cleavage effectively pBR322 DNA. The mechanistic studies demonstrate that a hydrogen peroxide-derived species and singlet oxygen ((1)O2) are the active oxidative species for DNA cleavage.

  10. The Oxidative Coupling of 2,6-Xylenol Catalyzed by Polymeric Complexes of Copper, 1. Kinetic Study of the Catalysis by Copper(II)-Complexes of Partially Aminated Polystyrene

    NARCIS (Netherlands)

    Schouten, Arend Jan; Prak, Nanno; Challa, Ger

    1977-01-01

    The oxidative coupling reaction of 2,6-xylenol catalyzed by copper(II) complexes of chemically modified polystyrene was investigated. Under the applied reaction conditions the main reaction product was 2,6,2',6'-tetramethyl-1,1'-dioxo-4,4'-bicyclohexa-2,5-dienylidene. It was found that the polymeric

  11. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: phenol ring nitration through a putative peroxynitrite intermediate.

    Science.gov (United States)

    Kalita, Apurba; Deka, Ramesh C; Mondal, Biplab

    2013-10-07

    Copper(II) complex, 1, with the histidine-derived ligand L (L = methyl 2-(2-hydroxybenzylamino)-3-(1H-imidazol-5-yl)propanoate) has been synthesized and characterized. Single-crystal structure determination reveals a diphenolato-bridged dicopper(II) core in 1. Addition of (•)NO to an acetonitrile solution of 1 affords the corresponding mononuclear copper(II)-nitrosyl complex, 2. In the presence of H2O2, 2 results in formation of the corresponding copper(I)-peroxynitrite. Formation of peroxynitrite ((-)OONO) intermediate is evident from its characteristic phenol ring nitration reaction which resembles the tyrosine nitration in biological systems. Further, isolation of nitrate (NO3(-)) as the decomposition product from 2 at room temperature also supports the involvement of (-)OONO intermediate.

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

    Directory of Open Access Journals (Sweden)

    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.

  13. Effects of oxidation on redox and cytotoxic properties of copper complex of Aβ1-16 peptide.

    Science.gov (United States)

    Ramteke, S N; Walke, G R; Joshi, B N; Rapole, S; Kulkarni, P P

    2014-12-01

    The effect of oxidation on redox and cytotoxic properties of copper complex of amyloid beta (Aβ) peptide was studied by gamma radiolysis. The oxidation of Aβ1-16 and Aβ1-16/Cu(II) complex was carried out using hydroxyl ((•)OH) radicals produced by gamma radiolysis and the products were analyzed using mass spectrometry. The presence of Cu(II) was found to enhance the oxidation of Aβ1-16 peptide. The oxidation of residues Asp1, His6, and His13 was enhanced due to their involvement in copper binding. The oxidation of His residues of Aβ1-16 peptide, which are chiefly responsible for copper binding, resulted in altered redox properties and subsequently in higher cytotoxicity of the Aβ1-16 peptide in SH-SY5Y cells.

  14. Palladium(II) and copper(I) complexes of wide angle bisphosphine, 1,4-bis((diphenylphosphino)methyl)benzene

    Indian Academy of Sciences (India)

    SAURABH KUMAR; MARAVANJI S BALAKRISHNA

    2017-08-01

    Oxidation reactions and synthesis of copper(I) and palladium(II) complexes of 1,4-bis ((diphenylphosphino) methyl)benzene (1) have been described. Due to the larger separation of phosphorus atoms, bisphosphine exhibits only bridging mode of coordination. The ligand is also ideally suited to form binuclear complexes and 1-D coordination polymers. Reaction of 1 with [Pd(η³−allyl)Cl] ₂ results in dipalladium(II) complex [{Pd(η³−allyl)Cl}₂{μ−Ph₂PCH₂C₆H₄CH₂PPh₂}] (4), whereas with copper halides, dimeric complexes of the type [{CuX}{μ−Ph₂PCH₂C₆H₄CH₂PPh₂}] ₂ (5 X = Cl, 6 X = Br and 7 X = I) were isolated. All the compounds have been fully characterized by spectroscopic and analytical methods. The molecular structures of bisulfide (3), Pd(II) and Cu(I) complexes were confirmed by single crystal X-ray analyses.

  15. Synthesis, characterization, antibacterial activity, SOD mimic and interaction with DNA of drug based copper(II) complexes

    Science.gov (United States)

    Patel, Mohan N.; Dosi, Promise A.; Bhatt, Bhupesh S.; Thakkar, Vasudev R.

    2011-02-01

    Novel metal complexes of the second-generation quinolone antibacterial agent enrofloxacin with copper(II) and neutral bidentate ligands have been prepared and characterized with elemental analysis reflectance, IR and mass spectroscopy. Complexes have been screened for their in-vitro antibacterial activity against two Gram (+ve)Staphylococcus aureus, Bacillus subtilis, and three Gram (-ve)Serratia marcescens, Escherichia coli and Pseudomonas aeruginosa organisms using the double dilution technique. The binding of this complex with CT-DNA has been investigated by absorption titration, salt effect and viscosity measurements. Binding constant is ranging from 1.3 × 10 4-3.7 × 10 4. The cleavage ability of complexes has been assessed by gel electrophoresis using pUC19 DNA. The catalytic activity of the copper(II) complexes towards the superoxide anion (O 2rad -) dismutation was assayed by their ability to inhibit the reduction of nitroblue tetrazolium (NBT).

  16. Magnetic properties of copper(II) complexes containing peptides. Crystal structure of [Cu(phe-leu)

    Science.gov (United States)

    Sanchiz, J.; Kremer, C.; Torre, M. H.; Facchin, G.; Kremer, E.; Castellano, E. E.; Ellena, J.

    2006-09-01

    A novel copper(II) complex containing the peptide phe-leu has been prepared and characterized. The crystal structure of [Cu(phe-leu)] ( 1) was determined by X-ray diffraction. The presence of carboxylate and amido bridges allows the formation of an extended 2D arrangement. This structure is similar to those found in [Cu(gly-val)] · 1/2H 2O ( 2), [Cu(val-gly)] ( 3), [Cu(val-phe)] ( 4), and [Cu(phe-phe)] ( 5). The magnetic properties of compounds 1- 5 were studied and analyzed comparatively. The experimental data show that the magnetic interactions are mainly transmitted through μ 2-COO - bridges, being ferromagnetic for 1 and 3, and antiferromagnetic for 2, 4 and 5.

  17. Computational Molecular Nanoscience Study of the Properties of Copper Complexes for Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Jorge Almaral-Sánchez

    2012-11-01

    Full Text Available 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.

  18. 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

    2012-11-28

    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.

  19. Characterisation of the interactions between substrate, copper(II) complex and DNA and their role in rate acceleration in DNA-based asymmetric catalysis

    NARCIS (Netherlands)

    Draksharapu, Apparao; Boersma, Arnold J; Browne, Wesley R; Roelfes, Gerard

    2015-01-01

    Interactions of the azachalcone derived substrate Aza with copper(II) complexes in the presence and absence of st-DNA were studied in detail by UV/Vis absorption, EPR and Raman and (UV and vis) resonance Raman spectroscopies. The binding of Aza to the Lewis acidic copper(II) complexes, which results

  20. Characterisation of the interactions between substrate, copper(II) complex and DNA and their role in rate acceleration in DNA-based asymmetric catalysis

    NARCIS (Netherlands)

    Draksharapu, Apparao; Boersma, Arnold J; Browne, Wesley R; Roelfes, Gerard

    2015-01-01

    Interactions of the azachalcone derived substrate Aza with copper(II) complexes in the presence and absence of st-DNA were studied in detail by UV/Vis absorption, EPR and Raman and (UV and vis) resonance Raman spectroscopies. The binding of Aza to the Lewis acidic copper(II) complexes, which results

  1. A dual pH/Redox responsive copper-ligand nanoliposome bioactive complex for the treatment of chronic inflammation.

    Science.gov (United States)

    Mavuso, Simphiwe; Choonara, Yahya E; Marimuthu, Thashree; Kumar, Pradeep; du Toit, Lisa C; Kondiah, Pierre P D; Pillay, Viness

    2016-07-25

    A novel dual pH/redox-responsive polymeric nanoliposome system (NLs) loaded with a copper-liganded bioactive complex was prepared and designed as a controlled delivery system for the management of inflammation. The NLs were synthesised after preparation of the copper-glyglycine-prednisolone succinate] ([(Cu(glygly)(PS)]) complex, and the dual pH/redox responsive biopolymer respectively. The methodology undertaken for the development of the drug delivery system involved coordination of the bioactive to Copper (II), preparation of dual pH/redox responsive biopolymer, and the synthesis of dual pH/redox nanoliposomes. Characterisations of the prepared copper-liganded bioactive [Copper-glyglycine-prednisolone succinate] ([(Cu(glygly)(PS)]) complex, dual pH/redox responsive biopolymer (Eudragit E100-cystamine) and [(Cu(glygly)(PS)]-loaded NLs were carried out using spectroscopic and physicochemical techniques. Results indicated a high inflammatory/oxidant inhibitory activity of [Cu(glygly)(PS)] in comparison to the free PS drug. The [Cu(glygly)(PS)] complex exhibited a significant free radical-scavenging activity (60.1±1.2%) and lipoxygenase (LOX-5) inhibitory activity (36.6±1.3%) in comparison to PS which resulted in activity of 4.4±1.4% and inhibition of 6.1±2.6% respectively. The [Cu(glygly)(PS)] loaded NLs demonstrated low release profiles of 22.9±5.4% in 6h at pH 7.4, in comparison to a significant accelerated release at pH 5 in a reducing environment of 75.9±3.7% over 6h duration. Results suggest that the novel copper-liganded bioactive delivery system with controlled drug release mechanism could serve as a potential drug delivery system candidate in the management of inflammation.

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

    Science.gov (United States)

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

    2017-07-01

    High carbonate content of the European Kupferschiefer ore deposits is a challenge for acid copper leaching (pH ≤ 2). Therefore investigating the mobility behavior of Cu(II) under conditions related to an alternative, neutrophil biohydrometallurgical Cu(II) leaching approach is of interest. As glutamic acid (Glu) might be present as a component in the growth media, we studied its effects on the adsorption of Cu(II) onto kaolinite. The binary and ternary batch sorption measurements of Cu(II) and Glu onto kaolinite were performed in the presence of 10 mM NaClO4 as background electrolyte and at a pH range from 4 to 9. Sorption experiments were modeled by the charge-distribution multi-site ion complexation (CD-MUSIC) model by using single sorption site (≡SOH) and monodentate surface complexation reactions. Glu sorption on kaolinite is weak (<10%) and independent of pH. Furthermore, Glu slightly enhances the Cu(II) sorption at low pH but strongly hinders (up to 50%) the sorption at higher pH and therewith enhances copper mobility. The results of isotherms show that Cu(II)-Glu sorption onto kaolinite mimics the Freundlich model. The proposed CD-MUSIC model provides a close fit to the experimental data and predicts the sorption of Cu(II), Cu(II)-Glu and Glu onto kaolinite as well as the effect of Glu on Cu(II) mobility. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Cytotoxicity of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-ethyl derivative of thiosalicylic acid

    Science.gov (United States)

    Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Milovanović, Jelena; Arsenijević, Aleksandar; Stojanović, Bojana; Trifunović, Srećko R.; Radić, Gordana P.

    2016-07-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-ethyl derivative of thiosalicylic acid was confirmed by X-ray structural study and compared to previously reported crystal structure of the Cu complex with S-methyl derivative. Single crystals suitable for X-ray measurements were obtained by slow crystallization from a water solution. Cytotoxic effects of S-alkyl (R = benzyl (L1), methyl (L2), ethyl (L3), propyl (L4) and butyl (L5)) derivatives of thiosalicylic acid and the corresponding binuclear copper(II)-complexes on murine colon carcinoma cell lines, CT26 and CT26.CL25 and human colon carcinoma cell line HCT-116 were reported here. The analysis of cancer cell viability showed that all the tested complexes had low cytotoxic effect on murine colon carcinoma cell lines, but several times higher cytotoxicity on normal human colon carcinoma cells.

  4. Efficient white organic light-emitting diodes based on iridium complex sensitized copper complex

    Energy Technology Data Exchange (ETDEWEB)

    Su Zisheng; Li Wenlian; Chu Bei; Xu Maoliang; Che Guangbo; Wang Dan; Han Liangliang; Li Xiao; Zhang Dongyu; Bi Defeng; Chen Yiren [Key Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033 (China)], E-mail: wllioel@yahoo.com.cn

    2008-04-21

    Efficient double emission-layer white organic light-emitting diodes comprising a yellow emission from bis[(4,6-difluorophenyl)-pyridinato-N,C{sup 2}](picolinato)Ir(III) (FIrpic) sensitized [Cu(bis[2-(diphenylphosphino)phenyl]ether) (6,7-Dicyanodipyrido[2,2-d : 2', 3'-f] quinoxaline)]BF{sub 4}(Cu{sup I} complex) and a blue emission from 4, 4'-bis(2,2'-diphenylvinyl)-1, 1'-biphenyl (DPVBi) were demonstrated. The emission spectrum can be fine tuned by effectively controlling the thicknesses of the two emission layers. The optimized device with 18 nm FIrpic and the Cu{sup I} complex codoped 4, 4'-N,N'-dicarbazole-biphenyl layer and 12 nm DPVBi layer shows a maximum current efficiency of 8.5 cd A{sup -1}, a maximum power efficiency of 5.3 lm W{sup -1} and a maximum luminance of 3290 cd m{sup -2}. Moreover, the device exhibits a CIE coordinate of (0.345, 0.357) at a bias of 8 V and a slight colour variation with increased voltage from 6 to 16 V.

  5. Synthesis, characterisation of few N-substituted 1,8-naphthalimide derivatives and their copper(II) complexes

    Indian Academy of Sciences (India)

    Nilotpal Barooah; Chandan Tamuly; Jubaraj B Baruah

    2005-03-01

    A few 1,8-naphthalimide derivatives with phenyl (1), benzyl (2), 3,4-dimethoxyphenyl ethyl (3), 4-pyridyl (4), 2-hydroxy ethyl (5), 4-pyridylmethyl (6) groups attached to the nitrogen atom are synthesized and characterized. Cyclic voltammograms of all these compounds show one-electron reversible redox cycle (-1.24 V to -1.18 V) due to formation of anion radicals. However, in the case of (5), quenching of this redox process occurs when polyhydroxy-aromatic compounds such as 1,3-dihydroxy benzene and 1,3,5-trihydroxybenzene are added. Copper complexes, namely bis-{N-(4-pyridylmethyl)1,8-naphthalimide}copper (II) perchlorate (8), bis-{N-(4-pyridylmethyl)1,8-naphthalimide}copper (II) perchlorate (9) and bis-{N-(4-pyridylmethyl)phthalimide} copper (II) perchlorate (10) are synthesized and characterised. The complexes (8) and (9) show reversible redox couple of the ligand without any significant interaction with the redox active copper (II) centre.

  6. Structural and functional mimic of galactose oxidase by a copper complex of a sterically demanding [N2O2] ligand.

    Science.gov (United States)

    John, Alex; Shaikh, Mobin M; Ghosh, Prasenjit

    2008-06-07

    A structural and functional mimic of the galactose oxidase (GOase) enzyme active-site by a copper complex supported over a sterically demanding ligand having [N2O2] donor sites is reported. Specifically, the binding of the histidine (496 and 581) and tyrosine (272 and 495) residues to the copper center in a square-pyramidal fashion in the active-site of galactose oxidase (GOase) enzyme has been modeled in a copper complex, ([(3-tert-butyl-5-methyl-2-hydoxybenzyl)(3'-tert-butyl-5'-methyl-2'-oxobenzyl)(2-pyridylmethyl)]amine)Cu(OAc)) (1b), stabilized over a sterically demanding ligand in which the two phenolate-O atoms mimicked the tyrosine binding while an amine-N and pyridyl-N atoms emulated the histidine binding to the metal center, similar to that in the enzyme active-site. Furthermore, the copper complex 1b is found to be an effective functional model of the enzyme as it efficiently catalyzed the chemoselective oxidation of primary alcohols to aldehydes in high turnover numbers under ambient conditions. An insight into the nature of the active-species was obtained by EPR and CV studies, which in conjunction with the DFT studies, revealed that the active-species is an anti-ferromagnetically coupled diamagnetic radical cation, (1)1b+, obtained by one electron oxidation at the equatorial phenolate-O atom of the ligand in the 1b complex.

  7. An experimental and theoretical approach of spectroscopic and structural properties of a new chelidamate copper (II) complex.

    Science.gov (United States)

    Vural, Hatice; Uçar, İbrahim; Soylu, M Serkan

    2014-03-25

    The crystal structure of new chelidamate complex of copper (II) ion, [Cu(chel)H2O(pym)]·H2O [chel: chelidamate or 4-hydroxypyridine-2,6-dicarboxylate; pym: 2-Pyridylmethanol] has been determined by single crystal X-ray crystallographic method. The complex was characterized by IR and UV-Vis spectroscopic techniques. The magnetic environment of copper (II) ion has been defined by electron paramagnetic technique (EPR). The central copper (II) ion is six-coordinate with a distorted octahedral geometry, which exhibits Jahn-Teller distortions along one of the O-Cu-O axes with tetragonality of 0.81. Chelidamate behaved as a tridentate ligand was bonded to Cu(II) ion through carboxyl oxygens with nitrogen. The crystal structure is stabilized by O-H⋯O hydrogen bond and π-π interactions. Theoretical calculations have been carried out by using the DFT method. The modeling of copper (II) complex was made by geometric optimization. The geometry optimization and EPR study were carried out using the following unrestricted hybrid density functionals: LSDA, BPV86, B3LYP, B3PW91, MPW1PW91 and HCTH. Frontier molecular orbital energies, absorption wavelengths and excitation energy were computed by time dependent DFT (TD-DFT) method with polarizable continuum model. IR spectra were discussed and compared to other relevant complexes together with theoretical results. The natural charges on the atoms and second-order interaction energies were derived from natural bond orbital analysis (NBO).

  8. Femtomole level photoelectrochemical aptasensing for mercury ions using quercetin-copper(II) complex as the DNA intercalator.

    Science.gov (United States)

    Li, Hongbo; Xue, Yan; Wang, Wei

    2014-04-15

    An ultrasensitive and selective photoelectrochemical (PEC) aptasensor for mercury ions was first fabricated based on perylene-3, 4, 9, 10-tetracarboxylic acid/graphene oxide (PTCA/GO) heterojunction using quercetin-copper(II) complex intercalated into the poly(dT)-poly(dA) duplexes. Both the PTCA/GO heterojunction and the quercetin-copper(II) complex are in favor of the sensitivity for the fabricated PEC aptasensor due to band alignment and strong reduction capability, respectively. And they efficiently promote the separation of photoexcited carriers and enhance the photocurrent. The formation of thymine-Hg(2+)-thymine coordination chemistry resulted in the dehybridization of poly(dT)-poly(dA) duplexes and then the intercalator quercetin-copper(II) complex broke away from the surface of the PEC aptasensor. As the concentration of mercury ions increased, the photocurrent gradually decreased. The electrode response for mercury ions detection was in the linear range from 0.01 pmol L(-1) to 1.00 pmol L(-1) with the detection limit of 3.33 fmol L(-1). The label-free PEC aptasensor has excellent performances with ultrasensitivity and good selectivity besides the advantage of economic and facile fabrication. The strategy of quercetin-copper(II) complex as a novel DNA intercalator paves a new way to improve the performances for PEC sensors. © 2013 Published by Elsevier B.V.

  9. Asymmetric Cyclopropanation Catalyzed by Four Stereoisomers of a Copper-(Schiff-base) Complex with Double Chiral Centers

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Four stereoisomers of a copper-(Schiff-base) complex with double chiral centers were applied to catalyze the asymmetric cyclopropanation. Two of the stereoisomers were also efficient catalysts affording high enantiomeric excess of up to 91.8%. A mechanism that predicts the observed results accurately was proposed.

  10. Copper-peptide complex structure and reactivity when found in conserved His-X(aa)-His sequences.

    Science.gov (United States)

    Park, Ga Young; Lee, Jung Yoon; Himes, Richard A; Thomas, Gnana S; Blackburn, Ninian J; Karlin, Kenneth D

    2014-09-10

    Oxygen-activating copper proteins may possess His-X(aa)-His chelating sequences at their active sites and additionally exhibit imidiazole group δN vs εN tautomeric preferences. As shown here, such variations strongly affect copper ion's coordination geometry, redox behavior, and oxidative reactivity. Copper(I) complexes bound to either δ-HGH or ε-HGH tripeptides were synthesized and characterized. Structural investigations using X-ray absorption spectroscopy, density functional theory calculations, and solution conductivity measurements reveal that δ-HGH forms the Cu(I) dimer complex [{Cu(I)(δ-HGH)}2](2+) (1) while ε-HGH binds Cu(I) to give the monomeric complex [Cu(I)(ε-HGH)](+) (2). Only 2 exhibits any reactivity, forming a strong CO adduct, [Cu(I)(ε-HGH)(CO)](+), with properties closely matching those of the copper monooxygenase PHM. Also, 2 is reactive toward O2 or H2O2, giving a new type of O2-adduct or Cu(II)-OOH complex, respectively.

  11. Quantitative serine protease assays based on formation of copper(II)-oligopeptide complexes.

    Science.gov (United States)

    Ding, Xiaokang; Yang, Kun-Lin

    2015-01-07

    A quantitative protease assay based on the formation of a copper-oligopeptide complex is developed. In this assay, when a tripeptide GGH fragment is cleaved from an oligopeptide chain by serine proteases, the tripeptide quickly forms a pink GGH/Cu(2+) complex whose concentration can be determined quantitatively by using UV-Vis spectroscopy. Therefore, activities of serine proteases can be determined from the formation rate of the GGH/Cu(2+) complex. This principle can be used to detect the presence of serine protease in a real-time manner, or measure proteolytic activities of serine protease cleaving different oligopeptide substrates. For example, by using this assay, we demonstrate that trypsin, a model serine protease, is able to cleave two oligopeptides GGGGKGGH () and GGGGRGGH (). However, the specificity constant (kcat/Km) for is higher than that of (6.4 × 10(3) mM(-1) min(-1)vs. 1.3 × 10(3) mM(-1) min(-1)). This result shows that trypsin is more specific toward arginine (R) than lysine (K) in the oligopeptide sequence.

  12. Synthesis and Characterization of Novel Thiourea Derivatives and Their Nickel and Copper Complexes

    Directory of Open Access Journals (Sweden)

    Gün Binzet

    2013-01-01

    Full Text Available New benzoyl thiourea derivatives and their nickel and copper complexes were synthesized. The structure of the synthesized compounds were confirmed by elemental analysis, FT-IR, and 1H NMR techniques. Four of the synthesized compounds are analyzed by X-ray single crystal diffraction technique. Whereas N,N-dimethyl-N′-(4-fluorobenzoylthiourea, N,N-diethyl-N′-(4-fluorobenzoylthiourea, and N,N-di-n-butyl-N′-(4-fluorobenzoyl thiourea crystallize in the monoclinic system, bis(N,N-di-n-propyl-N′-(4-fluorobenzoylthioureato nickel(II complex crystallizes in the triclinic system. These ligand molecules form dimers through strong intermolecular hydrogen bonds such as N–H⋯S, C–H⋯O, and N–H⋯O. Moreover, there are different types of intramolecular interactions in the crystal structures. Bis(N,N-dimethyl-N′-(4-fluorobenzoylthioureato nickel(II complex has a nearly square-planar coordination. The distance of nickel atom from the best plane through the coordination sphere is 0.029 Å.

  13. Mono- and binuclear copper(I) complexes of thionucleotide analogues and their catalytic activity on the synthesis of dihydrofurans.

    Science.gov (United States)

    Charalampou, D C; Kourkoumelis, N; Karanestora, S; Hadjiarapoglou, L P; Dokorou, V; Skoulika, S; Owczarzak, A; Kubicki, M; Hadjikakou, S K

    2014-08-18

    The reaction of copper(I) halides with 2-thiouracil (TUC), 6-methyl-2-thiouacil (MTUC), and 4-methyl-2-mercaptopyrimidine (MPMTH) in the presence of triphenylphosphine (tpp) in a 1:1:2 molar ratio results in a mixed-ligand copper(I) complex with the formulas [Cu2(tpp)4(TUC)Cl] (1), [Cu2(tpp)4(MTUC)Cl] (2), [Cu(tpp)2(MPMTH)Cl]·(1)/2CH3OH (3), [Cu(tpp)2(MTUC)Br] (4), and [Cu(tpp)2(MTUC)I]·(1)/2CH3CN (5). The complexes have been characterized by FT-IR, (1)H NMR, and UV-vis spectroscopic techniques and single-crystal X-ray crystallography. Complexes 1 and 2 are binuclear copper(I) complexes. Two phosphorus atoms from tpp ligands are coordinated to the copper(I) ions, forming two units that are linked to each other by a deprotonated TUC or MTUC chelating ligand through a sulfur bridge. A linear Cu-S-Cu moiety is formed. The tetrahedral geometry around the metal centers is completed by the nitrogen-donor atom from the TUC or MTUC ligand for the one unit, while for the other one, it is completed by the chloride anion. Two phosphorus atoms from two tpp ligands, one sulfur atom from MPMTH or MTUC ligand, and one halide anion (Cl, Br, and I) form a tetrahedron around the copper ion in 3-5 and two polymorphic forms of 4 (4a and 4b). In all of the complexes, either mono- or binuclear intramolecular O-H···X hydrogen bonds enhance the stability of the structures. On the other hand, in almost all cases of mononuclear complexes (with the exception of a symmetry-independent molecule in 4a), intermolecular NH···O hydrogen-bonding interactions lead to dimerization. Complexes 1-5 were studied for their catalytic activity for the intermolecular cycloaddition of iodonium ylides toward dihydrofuran formation by HPLC, (1)H NMR, and LC-HRMS spectroscopic techniques. The results show that the geometry and halogen and ligand types have a strong effect on the catalytic properties of the complexes. The highest yield of dihydrofurans was obtained when "linear" complexes 1 and 2 were

  14. Physico-chemical characterization and anti- microbial activity of copper(II complexes with 2-amino and 2-methylbenzimidazole derivatives

    Directory of Open Access Journals (Sweden)

    Podunavac-Kuzmanović Sanja O.

    2004-01-01

    Full Text Available Copper(II chloride, in warm ethanolic solution, reacted with 2-amino and 2-methylbenzimidazole derivatives to give complexes of the formula CuL2Cl2·nH2O, where L=1-benzyl-2-aminobenzimidazole 1-(4-methylbenzyl-2-aminobenzimidazole, 1-benzyl-2-methylbenzimidazole and 1-(4-methylbenzyl-2-methylbenzimidazole( n=1 or 2. The complexes were characterized by elemental analysis of the metal, molar conductivity magnetic susceptibility measurements and IR spectra. The molar conductivities of copper(IIcomplexes in dimethyl formamide (DMF corresponding to a 1:1 type of electrolyte indicate that in all the complexes one of the coordinated chloride ions has been replaced by DMF molecule. The room temperature effective magnetic moments and IR data of the complexes suggest that all Cu(II complexes have a tetrahedral configuration, which is realized by participation of the pyridine nitrogen of two organic ligand molecules and two chloride anions. The antimicrobial activity of the ligands and their complexes against Pseudomonas aeruginosa, Bacillus sp. Staphylococcus aureus, Sarcina lutea and Saccharomyces cerevisiae was investigated. The effect of copper complexation on the ligand antimicrobial activity is discussed.

  15. Interaction of a copper(II)-Schiff base complexes with calf thymus DNA and their antimicrobial activity.

    Science.gov (United States)

    Sabolová, D; Kožurková, M; Plichta, T; Ondrušová, Z; Hudecová, D; Simkovič, M; Paulíková, H; Valent, A

    2011-03-01

    The interaction of a copper complexes containing Schiff bases with calf thymus (CT) DNA was investigated by spectroscopic methods. UV-vis, fluorescence and CD spectroscopies were conducted to assess their binding ability with CT DNA. The binding constants K have been estimated from 0.8 to 9.1×10(4) M(-1). The percentage of hypochromism is found to be over 70% (from spectral titrations). The results showed that the copper(II) complexes could bind to DNA with an intercalative mode. Synergic action of Cu(II) complexes with ascorbic acid against Candida albicans induced the generation of free radicals and increased (more than 60 times) antimicrobial effect of these complexes.

  16. 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.

  17. Supramolecular Formation via Hydrogen Bonding in Copper and Nickel Complexes with 2-Hydroxynicotinic Acid

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Two complexes, Cu(HnicO)2 1 and Ni(HnicO)2(H2O)2 2 (H2nicO = 2-hydroxy- nicolinic acid), were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in monoclinic, space group P21/n, with a = 8.314(7), b = 6.275(4), c = 11.283(7) (A), β = 98.32(3)°, V = 582.5(7) (A)3, Z = 2, Mr = 339.74, Dc = 1.937 g/cm3, F(000) = 342, μ = 1.908 mm-1, S = 1.097, the final R = 0.0284 and wR = 0.0781 for 1177 observed reflections with I>2σ(I). Complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.438(5), b = 12.22(1), c = 7.537(5) (A), β = 100.07(3)°, V = 674.3(8) (A)3, Z = 2, Mr = 370.95, Dc = 1.827 g/cm3, F(000) = 380, μ = 1.487 mm-1, S = 1.041, the final R = 0.0335 and wR = 0.0779 for 1202 observed reflections with I>2σ(I). There are extended 3D framework structures in complexes 1 and 2 due to the N-H…O and C-H…O hydrogen bonds. The copper atom in 1 has square planar coordination, while the nickel atom in 2 adopts octahedral coordination geometry. The TG curve shows that complex 2 is stable in solid state to 150 ℃.

  18. Nanostructured lipid carriers for incorporation of copper(II) complexes to be used against Mycobacterium tuberculosis

    Science.gov (United States)

    Sato, Mariana R; Oshiro Junior, João A; Machado, Rachel TA; de Souza, Paula C; Campos, Débora L; Pavan, Fernando R; da Silva, Patricia B; Chorilli, Marlus

    2017-01-01

    Tuberculosis (TB) is a disease caused by Mycobacterium tuberculosis. Cessation of treatment before the recommended conclusion may lead to the emergence of multidrug-resistant strains. The aim of this study was to develop nanostructured lipid carriers (NLCs) for use in the treatment of M. tuberculosis. The NLCs comprised the following lipid phase: 2.07% polyoxyethylene 40 stearate, 2.05% caprylic/capric triglyceride, and 0.88% polyoxyl 40 hydrogenated castor oil; the following aqueous phase: 3.50% poloxamer 407 (F1–F6), and 0.50% cetyltrimethylammonium bromide (F7–F12); and incorporated the copper(II) complexes [CuCl2(INH)2]·H2O (1), [Cu(NCS)2(INH)2]·5H2O (2), and [Cu(NCO)2(INH)2]·4H2O (3) to form compounds F11.1, F11.2, and F11.3, respectively. The mean diameter of F11, F11.1, F11.2, and F11.3 ranged from 111.27±21.86 to 134.25±22.72 nm, 90.27±12.97 to 116.46±9.17 nm, 112.4±10.22 to 149.3±15.82 nm, and 78.65±6.00 to 122.00±8.70 nm, respectively. The polydispersity index values for the NLCs ranged from 0.13±0.01 to 0.30±0.09. The NLCs showed significant changes in zeta potential, except for F11.2, with F11, F11.1, F11.2, and F11.3 ranging from 18.87±4.04 to 23.25±1.13 mV, 17.03±1.77 to 21.42±1.87 mV, 20.51±1.88 to 22.60±3.44 mV, and 17.80±1.96 to 25.25±7.78 mV, respectively. Atomic force microscopy confirmed the formation of nanoscale spherical particle dispersions by the NLCs. Differential scanning calorimetry determined the melting points of the constituents of the NLCs. The in vitro activity of copper(II) complex-loaded NLCs against M. tuberculosis H37Rv showed an improvement in the anti-TB activity of 55.4, 27.1, and 41.1 times the activity for complexes 1, 2, and 3, respectively. An in vivo acute toxicity study of complex-loaded NLCs demonstrated their reduced toxicity. The results suggest that NLCs may be a powerful tool to optimize the activity of copper(II) complexes against M. tuberculosis. PMID:28356717

  19. Synthesis, Crystal Structure, Spectroscopic Properties and Potential Biological Activities of Salicylate‒Neocuproine Ternary Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Lenka Kucková

    2015-01-01

    Full Text Available Mixed ligand copper(II complexes containing derivatives of salicylic acid and heterocyclic ligands with nitrogen donor atoms have been the subject of various studies and reviews. In this paper, synthesis and characterization of the ternary copper(II complexes of neocuproine (2,9-dimethyl-1,10-phenanthroline, Neo and salicylate ligands (Sal are reported. In addition, the crystal structures of ([Cu(H2O(5-Cl-Sal(Neo] (1, [Cu(μ-Sal(Neo]2 (2, Cu2(μ-5-Cl-Sal(5-Cl-HSal2(Neo2]·EtOH (3 were determined. In order to compare structural and biological properties of the prepared complexes, spectroscopic and biological studies were performed. Results of X-ray diffraction show that prepared complexes form three types of crystal structures in a given system: monomeric, dimeric and dinuclear complex. The preliminary study on the DNA cleavage activity has shown that the complexes under study behave as the chemical nucleases in the presence of added hydrogen peroxide with slight differences in the activity (1 > 2 > 3. The complexes 1 and 2 exhibited nuclease activity itself indicating the interaction of complexes with the DNA. It has been proposed that the enhanced destructive effect of the complexes 1 and 2 on the DNA is a result of two possible mechanisms of action: (i the conversion of closed circular DNA (form I to the nicked DNA (form II caused by the copper complex itself and (ii damage of DNA by Reactive Oxygen Species (ROS—products of the interaction of copper with hydrogen peroxide by means of Fenton reaction (hydroxyl radicals. Thus the biological activity of the prepared Cu(II complexes containing derivatives of salicylic acid and phenanthroline molecules is substantiated by two independent mechanisms. While derivatives of salicylic acids in the coordination sphere of copper complexes are responsible for radical-scavenging activity (predominantly towards superoxide radical anion, the presence of chelating ligand 2,9-dimethyl-1,10-phenanthroline

  20. Synthesis, characterization, electrochemical studies and DFT calculations of amino acids ternary complexes of copper (II) with isonitrosoacetophenone. Biological activities

    Science.gov (United States)

    Tidjani-Rahmouni, Nabila; Bensiradj, Nour el Houda; Djebbar, Safia; Benali-Baitich, Ouassini

    2014-10-01

    Three mixed complexes having formula [Cu(INAP)L(H2O)2] where INAP = deprotonated isonitrosoacetophenone and L = deprotonated amino acid such as histidine, phenylalanine and tryptophan have been synthesized. They have also been characterized using elemental analyses, molar conductance, UV-Vis, IR and ESR spectra. The value of molar conductance indicates them to be non-electrolytes. The spectral studies support the binding of the ligands with two N and two O donor sites to the copper (II) ion, giving an arrangement of N2O2 donor groups. Density Functional Theory (DFT) calculations were applied to evaluate the cis and trans coordination modes of the two water molecules. The trans form was shown to be energetically more stable than the cis one. The ESR data indicate that the covalent character of the metal-ligand bonding in the copper (II) complexes increases on going from histidine to phenylalanine to tryptophan. The electrochemical behavior of the copper (II) complexes was determined by cyclic voltammetry which shows that the chelate structure and electron donating effects of the ligands substituent are among the factors influencing the redox potentials of the complexes. The antimicrobial activities of the complexes were evaluated against several pathogenic microorganisms to assess their antimicrobial potentials. The copper complexes were found to be more active against Gram-positive than Gram-negative bacteria. Furthermore, the antioxidant efficiencies of the metal complexes were determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity. The antioxidant activity of the complexes indicates their moderate scavenging activity against the radical DPPH.

  1. Copper-Gold Exploration and Discovery in the Timok Magmatic Complex, Serbia

    Science.gov (United States)

    Banjesević, Miodrag; Ingram, Simon; Large, Duncan

    2014-05-01

    The Timok Magmatic Complex (TMC) comprises the Serbian sector of the Carpathian-Balkan Arc of Late Cretaceous calc-alkaline magmatism that extends for about 1500 km from Romania (Banat), through eastern Serbia (TMC) and into central Bulgaria (Srednogorie). The TMC is lens-shaped, about 85 km long and up to 25 km wide. The complex consists primarily of Turonian to Campanian andesites and trachyandesites (lavas, shallow intrusives and epiclastics), basaltic andesites, volcaniclastics and sediments. There are at least two phases of volcanism, and the volcanic processes were subaerial to submarine eruptive, hypabyssal intrusion, and very rarely explosive. Coupled porphyry and high sulphidation epithermal systems are associated with the first phase of andesite volcanism in the Bor district. The tectonic setting has been described as a back-arc basin, or pull-apart basin, developed on continental crust during subduction related to the convergence of the African plate toward Eurasia, and closure of the Neotethys ocean. The metallogenic endowment of the TMC is a significant contributor to that of the entire Tethyan Metallogenic Province. The world-class Bor and Majdenpek porphyry systems contribute to an estimated historical production of approximately 6 million tonnes of copper and 9.65 million ounces gold. The combined resources and reserves in the TMC are reported by the state-owned RTB Bor mining company to be a cumulative 2.5 billion tonnes, with total copper and gold metal content of 10.5 million tonnes and 11.7 million ounces respectively. Reservoir concluded an agreement in 2010 with Freeport McMoran Exploration Corp. (Freeport) to explore three exploration permits in the TMC for porphyry copper mineralisation. Conceptual studies together with CSAMT geophysics suggested the extension of structures under the Miocene sedimentary cover about 5-7 km south from the Bor porphyry district. The Čukaru Peki discovery was identified from high-grade drill intercepts

  2. Synthesis, structural characterization and cytotoxic activity of ternary copper(II)-dipeptide-phenanthroline complexes. A step towards the development of new copper compounds for the treatment of cancer.

    Science.gov (United States)

    Iglesias, Sebastián; Alvarez, Natalia; Torre, María H; Kremer, Eduardo; Ellena, Javier; Ribeiro, Ronny R; Barroso, Rafael P; Costa-Filho, Antonio J; Kramer, M Gabriela; Facchin, Gianella

    2014-10-01

    In the search for new compounds with antitumor activity, coordination complexes with different metals are being studied by our group. This work presents the synthesis and characterization of six copper complexes with general stoichiometry [Cu(L-dipeptide)(phen)]·nH2O (were phen=1,10-phenanthroline) and their cytotoxic activities against tumor cell lines. To characterize these systems, analytical and spectroscopic studies were performed in solid state (by UV-visible, IR, X-ray diffraction) including the crystal structure of four new complexes (of the six complexes studied): [Cu(Ala-Phe)(phen)]·4H2O, [Cu(Phe-Ala)(phen)]·4H2O, [Cu(Phe-Val)(phen)]·4.5H2O and [Cu(Phe-Phe)(phen)]·3H2O. In all of them, the copper ion is situated in a distorted squared pyramidal environment. The phen ligand is perpendicular to the dipeptide, therefore exposed and potentially available for interaction with biological molecules. In addition, for all the studied complexes, structural information in solution using EPR and UV-visible spectroscopies were obtained, showing that the coordination observed in solid state is maintained. The lipophilicity, DNA binding and albumin interaction were also studied. Biological experiments showed that all the complexes induce cell death in the cell lines: HeLa (human cervical adenocarcinoma), MCF-7 (human metastatic breast adenocarcinoma) and A549 (human lung epithelial carcinoma). Among the six complexes, [Cu(Ala-Phe)(phen)] presents the lowest IC50 values. Taken together all these data we hypothesize that [Cu(Ala-Phe)(phen)] may be a good candidate for further studies in vivo.

  3. Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.

    Science.gov (United States)

    Mereshchenko, Andrey S; Olshin, Pavel K; Karabaeva, Kanykey E; Panov, Maxim S; Wilson, R Marshall; Kochemirovsky, Vladimir A; Skripkin, Mikhail Yu; Tveryanovich, Yury S; Tarnovsky, Alexander N

    2015-07-16

    Copper(II) complexes are extremely labile with typical ligand exchange rate constants on the order of 10(6)-10(9) M(-1) s(-1). As a result, it is often difficult to identify the actual formation mechanism of these complexes. In this work, using UV-vis transient absorption when probing in a broad time range (20 ps to 8 μs) in conjunction with DFT/TDDFT calculations, we studied the dynamics and underlying reaction mechanisms of the formation of extremely labile copper(II) CuCl4(2-) chloro complexes from copper(II) CuCl3(-) trichloro complexes and chloride ions. These two species, produced via photochemical dissociation of CuCl4(2-) upon 420 nm excitation into the ligand-to-metal-charge-transfer electronic state, are found to recombine into parent complexes with bimolecular rate constants of (9.0 ± 0.1) × 10(7) and (5.3 ± 0.4) × 10(8) M(-1) s(-1) in acetonitrile and dichloromethane, respectively. In dichloromethane, recombination occurs via a simple one-step addition. In acetonitrile, where [CuCl3](-) reacts with the solvent to form a [CuCl3CH3CN](-) complex in less than 20 ps, recombination takes place via ligand exchange described by the associative interchange mechanism that involves a [CuCl4CH3CN](2-) intermediate. In both solvents, the recombination reaction is potential energy controlled.

  4. Synthesis and structural investigation of mono- and polynuclear copper complexes of 4-ethyl-1-(pyridin-2-yl) thiosemicarbazide.

    Science.gov (United States)

    Hassanien, M M; Gabr, I M; Abdel-Rhman, M H; El-Asmy, A A

    2008-11-01

    The reaction between 2-hydrazinopyridine and ethylisothiocyanate produced 4-ethyl-1-(pyridin-2-yl) thiosemicarbazide (HEPTS). Its reaction with copper fluoride, chloride, bromide, acetate, nitrate, perchlorate, sulfate, carbonate, hydroxide and copper metal produced 15 Cu(II) complexes. The copper metal is easily oxidized in aqueous-ethanol solution of HEPTS giving [Cu2(EPTS)(H2O)3(OH)3]EtOH. Different complexes for the same anion were synthesized by controlling the heating time. Characterization by elemental, thermal, magnetic and spectral (electronic, IR, mass and ESR) studies showed the formation of mono-, di-, tri- and tetra nuclear complexes. The room temperature solid state ESR spectra of the complexes show an axial spectrum with dx2-y2 ground state, suggesting distorted tetragonal geometry around Cu(II) center. The kinetic and thermodynamic parameters for the different decomposition steps in the complexes were calculated. HEPTS and its Cu(II) complexes showed high activity against gram negative bacteria; [Cu3(EPTS)2(EtOH)2Br4] has more activity.

  5. Hydrometallurgical process for the recycling of copper using anodic oxidation of cuprous ammine complexes and flow-through electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Oishi, T.; Yaguchi, M.; Koyama, K.; Tanaka, M. [Metals Recycling Group, Research Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569 (Japan); Lee, J.-C. [Minerals and Materials Processing Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 30 Gajeong-dong, Yuseong-ku, Daejeon 305-350 (Korea)

    2008-01-01

    Flow-through electrolysis for copper electrowinning from cuprous ammine complex was studied in order to develop a hydrometallurgical copper recycling process using an ammoniacal chloride solution, focusing on the anodic oxidation of cuprous to cupric ammine complexes. The current efficiency of this anodic oxidation was 96% at a current density of 200 A m{sup -2} under a batch condition. In a flow-through electrolysis using a sub-liter cell and a carbon felt anode, the anodic current efficiency increased with the flow rate and was typically higher than 97%. This tendency was explained by the backward flow of the cupric ammine complex, which was formed on the anode, through the diaphragm. The anodic overpotential was lower than 0.3 V even at an apparent current density of 1500 A m{sup -2}. A similar current efficiency and overpotential were also achieved in a liter scale cell, which indicates the scale flexibility of this electrolysis. The power consumption requirements for copper electrowinning in this cell were 460 and 770 kWh t{sup -1} at the current densities of 250 and 500 A m{sup -2}, respectively, which were much lower than that of the conventional copper electrowinning despite the longer interpolar distance. (author)

  6. Diagnosis of abnormal biliary copper excretion by positron emission tomography with targeting of (64)Copper-asialofetuin complex in LEC rat model of Wilson's disease.

    Science.gov (United States)

    Bahde, Ralf; Kapoor, Sorabh; Bhargava, Kuldeep K; Palestro, Christopher J; Gupta, Sanjeev

    2014-01-01

    Identification by molecular imaging of key processes in handling of transition state metals, such as copper (Cu), will be of considerable clinical value. For instance, the ability to diagnose Wilson's disease with molecular imaging by identifying copper excretion in an ATP7B-dependent manner will be very significant. To develop highly effective diagnostic approaches, we hypothesized that targeting of radiocopper via the asialoglycoprotein receptor will be appropriate for positron emission tomography, and examined this approach in a rat model of Wilson's disease. After complexing (64)Cu to asialofetuin we studied handling of this complex compared with (64)Cu in healthy LEA rats and diseased homozygous LEC rats lacking ATP7B and exhibiting hepatic copper toxicosis. We analyzed radiotracer clearance from blood, organ uptake, and biliary excretion, including sixty minute dynamic positron emission tomography recordings. In LEA rats, (64)Cu-asialofetuin was better cleared from blood followed by liver uptake and greater biliary excretion than (64)Cu. In LEC rats, (64)Cu-asialofetuin activity cleared even more rapidly from blood followed by greater uptake in liver, but neither (64)Cu-asialofetuin nor (64)Cu appeared in bile. Image analysis demonstrated rapid visualization of liver after (64)Cu-asialofetuin administration followed by decreased liver activity in LEA rats while liver activity progressively increased in LEC rats. Image analysis resolved this difference in hepatic activity within one hour. We concluded that (64)Cu-asialofetuin complex was successfully targeted to the liver and radiocopper was then excreted into bile in an ATP7B-dependent manner. Therefore, hepatic targeting of radiocopper will be appropriate for improving molecular diagnosis and for developing drug/cell/gene therapies in Wilson's disease.

  7. 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

  8. Solvent effects on the stability of nifuroxazide complexes with cobalt(II), nickel(II) and copper(II) in alcohols.

    Science.gov (United States)

    Khan, Mustayeen A; Ali, S Kauser; Bouet, Gilles M

    2002-05-21

    A spectrophotometric study of the complexation of nifuroxazide with cobalt(II), nickel(II) and copper(II) was carried out in different alcohols. The formation of a complex in each case is reported and their stability constants have been calculated. For a given solvent, the stability of the complexes increases from cobalt to copper. In the case of copper(II), the stability varies as an inverse function of the dielectric constant of the solvent. A possible structure of the complex is proposed.

  9. A Study on Some Copper(Ⅱ) Complexes of Polyaza Cryptandsand Planar Macrocycles-Synthesis, Characterization and Superoxide Dismutase Activity

    Institute of Scientific and Technical Information of China (English)

    GAO, You-Liang; SHEN, Cheng-Yu; TANG, Yin-Yan; LUO, Qin-Hui; YU, Shu-Yan

    2001-01-01

    Two kinds of macrocyclic copper(Ⅱ) complexes were synthesized. One of them is composed of copper(Ⅱ) cryptates of ligands L1-L4 which are condensation products of 5-R-2methoxy-1,3-phenyldialdehyde (R= OCH3, L1) with tris(2-aminoethyl)amine and 5-R-2-methothoxy-1, 3-phenyldialdehyde (R = CH3, L3) with tris(2-aminopropyi)amine as well as their reduced products of L1 and L3 (L2 and L4). The other is composed of two-dimensional macrocyclic copper(Ⅱ) complexcs of ligands L5-L8 of condensation products of diethylene triamine with 4-R-1-methoxy-2, 6-phenyldialdehyde (R = Cl,Br, CH3, OCH3). Therelationship between their structurcs and superoxide dismutase (SOD) activity was investigated.The results can provide some clues to the synthesis of SOD mimics.

  10. Blue copper protein analogue: synthesis and characterization of copper complexes of the N2S2 macrocycle 1,8-dithia-4,11-diazacyclotetradecane.

    Science.gov (United States)

    Walker, Tia L; Mula, Sam; Malasi, Wilhelm; Engle, James T; Ziegler, Christopher J; van der Est, Art; Modarelli, Jody; Taschner, Michael J

    2015-12-14

    To improve understanding of copper at the active site of Type 1 copper proteins, Cu(I) and Cu(II) complexes of 1,8-dithia-4,11-diazacyclotetradecane, shown in , have been successfully isolated and structurally characterized by X-ray crystallography. In these compounds, both Cu(I) and Cu(II) are centered in the plane of the macrocycle containing two sulphur and two nitrogen heteroatoms comprising the distorted tetrahedral/square planar coordination geometry. The UV/VIS spectra, electrochemistry and EPR properties have been obtained for the Cu(II) complex 2. Three absorption bands at 295 nm, 354 nm, and 545 nm are observed in aqueous solution at a pH of 5. These bands have been assigned to the N → Cu(II) and S → Cu(II) charge transfer bands and the d-d transitions respectively. The Cu(I/II) redox midpoint potential of complex 2 in CH3CN is +403 mV versus NHE.

  11. Copper(I)- and copper(0)-promoted homocoupling and homocoupling-hydrodehalogenation reactions of dihalogenoclathrochelate precursors for C-C conjugated iron(II) bis-cage complexes.

    Science.gov (United States)

    Varzatskii, Oleg A; Shul'ga, Sergey V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Vologzhanina, Anna V; Voloshin, Yan Z

    2014-12-28

    Iron(II) dibromo- and diiodoclathrochelates undergo copper(I)-promoted reductive homocoupling in HMPA at 70-80 °C leading to C-C conjugated dibromo- and diiodo-bis-clathrochelates in high yields. Under the same conditions, their dichloroclathrochelate analog does not undergo the same homocoupling reaction, so the target dichloro-bis-cage product was obtained in high yield via dimerization of its heterodihalogenide iodochloromonomacrobicyclic precursor. The use of NMP as a solvent at 120-140 °C gave the mixture of bis-clathrochelates resulting from a tandem homocoupling-hydrodehalogenation reaction: the initial acetonitrile copper(I) solvato-complex at a high temperature underwent re-solvatation and disproportionation leading to Cu(II) ions and nano-copper, which promoted the hydrodehalogenation process even at room temperature. The most probable pathway of this reaction in situ includes hydrodehalogenation of the already formed dihalogeno-bis-clathrochelate via the formation of reduced anion radical intermediates. As a result, chemical transformations of the iron(II) dihalogenoclathrochelates in the presence of an acetonitrile copper(I) solvato-complex were found to depend both on the nature of halogen atoms in their ribbed chelate fragments and on reaction conditions (i.e. solvent and temperature). The C-C conjugated iron(II) dihalogeno-bis-clathrochelates easily undergo nucleophilic substitution with various N,S-nucleophiles giving ribbed-functionalized bis-cage species. These iron(II) complexes were characterized by elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (1)H and (13)C NMR spectroscopy, and by X-ray diffraction; their electrochemical properties were studied by cyclic voltammetry. The isomeric shift values in (57)Fe Mössbauer spectra of such cage compounds allowed identifying them as low-spin iron(II) complexes, while those of the quadrupole splitting are the evidence for a significant TP distortion of their FeN6-coordination polyhedra

  12. Synthesis of copper/nickel nanoparticles using newly synthesized Schiff-base metals complexes and their cytotoxicity/catalytic activities.

    Science.gov (United States)

    Aazam, Elham S; El-Said, Waleed Ahmed

    2014-12-01

    Transition metal complexes compounds with Schiff bases ligand representing an important class of compounds that could be used to develop new metal-based anticancer agents and as precursors of metal NPs. Herein, 2,3-bis-[(3-ethoxy-2-hydroxybenzylidene)amino]but-2-enedinitrile Schiff base ligand and its corresponding copper/nickel complexes were synthesized. Also, we reported a facile and rapid method for synthesis nickel/copper nanoparticles based on thermal reduction of their complexes. Free ligand, its metal complexes and metals nanoparticles have been characterized based on elemental analysis, transmission electron microscopy, powder X-ray diffraction, magnetic measurements and by various spectroscopic (UV-vis, FT-IR, (1)H NMR, GC-MS) techniques. Additionally, the in vitro cytotoxic activity of free ligand and its complexes compounds were assessed against two cancer cell lines (HeLa and MCF-7 cells)and one healthy cell line (HEK293 cell). The copper complex was found to be active against these cancer cell lines at very low LD50 than the free ligand, while nickel complex did not show any anticancer activity against these cell lines. Also, the antibacterial activity of as-prepared copper nanoparticles were screened against Escherichia coli, which demonstrated minimum inhibitory concentration and minimum bactericidal concentration values lower than those values of the commercial Cu NPs as well as the previous reported values. Moreover, the synthesized nickel nanoparticles demonstrated remarkable catalytic performance toward hydrogenation of nitrobenzene that producing clean aniline with high selectivity (98%). This reactivity could be attributed to the high degree of dispersion of Ni nanoparticles. Copyright © 2014 Elsevier Inc. All rights reserved.

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

    Science.gov (United States)

    Tarlani, Aliakbar; Narimani, Khashayar; Mohammadipanah, Fatemeh; Hamedi, Javad; Tahermansouri, Hasan; Amini, Mostafa M.

    2015-06-01

    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 ID/IG 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.

  14. Development and physicochemical characterization of copper complexes-loaded PLGA nanoparticles.

    Science.gov (United States)

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

    2009-09-11

    PLGA nanoparticles were prepared via a modified W/O/W emulsion solvent diffusion process, in which all formulation components were fully biocompatible and biodegradable. Different independent processing parameters were systematically studied. Nanoparticles were characterized by DLS (particle size, polydispersity, zeta-potential) and TEM/AFM (surface morphology). An optimized formulation was used to encapsulate copper complexes of cyclen and DOTA as potential PET imaging agents. Results showed that the predominant formulation factors appeared to be the lactide-to-glycolide (L:G) ratio of PLGA, the nature of the diffusion phase, and the presence of hydroxyl ions in the first-emulsion aqueous phase. By regulating those 3 parameters, PLGA nanoparticles were prepared with very good preparation yields (>95%), a size less than 200 nm and a polydispersity index less than 0.1. TEM pictures showed nanoparticles with a narrow size distribution, a spherical shape and a smooth surface. The optimized formulation allowed to encapsulate Cu-cyclen and Cu-DOTA complexes with an encapsulation efficiency between 20% and 25%.

  15. Synthesis,Structure and Spectral Characterization of a Discrete Binuclear Copper(Ⅱ)Complex

    Institute of Scientific and Technical Information of China (English)

    王瑞虎; 苏伟平; 曹荣; 赵颖隽; 洪茂椿

    2001-01-01

    A discrete bi nuclear copper(Ⅱ)complex containing Cu2 O2 unit has been syntheacterized by X-ray diffraction study and IR spectroscopy.The crystal is monoclinic,space group:P21/n,with unit cell parameters: a=8.2952(2),b=18.4633(3),c=10.5049(2)(A ).β=108.965(1)°,V=1521.56(5)(A)3,Z=2,C22H30N8O10Cl2Cu2,Mr=764.52,Dc=1.669 Mg/m3,F(000)=780,μ(MoKα)=8.60,T=293(2)K,final R=0.0623,wR=0.1536 for 2660 observed reflections with I > 2.0σ(Ⅰ).The centrosymmetric complex Cu2(CH3O)2(C5H6N2)4(ClO4)2 comprises a pair of Cu(Ⅱ)atoms bridged by two methanoxo-and N-coordination 2-aminoppyridine.The Cu(Ⅱ)…Cu(Ⅱ)distance is 3.002(1)(A).

  16. A Pyridine-copper Inclusion Complex of a New Tripodal Ligand

    Institute of Scientific and Technical Information of China (English)

    范承; 马成丙; 陈昌源; 陈锋; 刘秋田

    2003-01-01

    A pyridine-copper inclusion complex with [Cu(py)4Cl]+ core was prepared in the presence of tripodal ligand tbst {tbst = 1,3,5-tris(2-benzimidazol)sulfanylmethyl-2,4,6-trimethyl- benzene}, and its structure has been determined. It crystallizes in triclinic, space group Pī with a = 9.0822(2), b = 17.6026(4), c = 18.7156(4)(A°),α= 93.40,β= 91.2980(1),γ= 91.5560(1)°, V = 2984.81(1)(A°)3, C58H63Cl2CuN11O4S3, Mr = 1208.81, Z = 2, F(000) = 1262, Dc = 1.345 g/cm3,β= 0.615 mm-1, R = 0.0713 and wR = 0.1307 for 7798 observed reflections (I > 2σ(1)). X-ray analysis reveals that the uncoordinated tbst and pyridine as guest molecules are included in the complex with formula {[Cu(py)4Cl]Cl}@(tbst)@(py)@4H2O. The tbst, pyridine, aqua and Cl- anion in the com- plex form extensive hydrogen-bonding interactions, building up a quasi-dinuclear structure.

  17. Electrochemical Studies of Betti Base and Its Copper(II Complex by Cyclic and Elimination Voltammetry

    Directory of Open Access Journals (Sweden)

    Shardul Bhatt

    2013-01-01

    Full Text Available The electrochemical behavior of Betti base 1-(α-amino benzyl-2-naphthol (BB and its copper(II complex by cyclic and elimination voltammetry (EVLS is reported in the present study. The cyclic voltammetric studies carried out at a glassy carbon working electrode, Ag/Ag+ reference electrode (0.01 M AgNO3 in acetonitrile in DCM at 100 mV/sec, 200 mV/sec, and 400 mV/sec scan rates indicated a preceding chemical oxidation of the adsorbed BB species to form an iminium ion followed by formation of a carbanion via two-step quasireversible reduction. The suggested reaction mechanism has been supported by the elimination voltammetry. The CV and EVLS studies revealed Cu(IIBB complex to undergo a chemical or a surface reaction before electron transfer from the electrode at −0.49 V to form Cu(IBB species. The oxidation of Cu(IBB species has been observed to be CV silent.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, J.S.; Dearling, J.L.S.; Blower, P.J. [Research School of Biosciences, University of Kent, Canterbury (United Kingdom); Sosabowski, J.K.; Zweit, J.; Carnochan, P.; Kelland, L.R.; Coley, H.M. [Joint Department of Physics and CRC Centre for Cancer Therapeutics, Institute for Cancer Research, Royal Marsden Hospital, Sutton (United Kingdom)

    2000-06-01

    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.)

  19. Histidine availability is decisive in ROS-mediated cytotoxicity of copper complexes of Aβ1-16 peptide.

    Science.gov (United States)

    Ginotra, Yamini P; Ramteke, Shefali N; Walke, Gulshan R; Rapole, Srikanth; Kulkarni, Prasad P

    2016-01-01

    The binding of metal ions to Aβ peptide plays an important role in the etiology of AD. Copper coordinates chiefly to His residues and produces reactive oxygen species (ROS) upon redox cycling. ROS builds enormous burden on the normal functioning of neuronal cells and results into deleterious effects. Recently, two structurally distinct copper binding sites with contrasting redox properties were characterized. Here, we demonstrate for the first time the effect of binding of two equivalents of Cu(2+) on redox properties and cytotoxicity of Aβ peptide. Our electrochemical data and ascorbate consumption assay suggest that in the presence of two equivalents of copper; Aβ peptide has higher propensity of H2O2 generation. The oxidation of Aβ1-16 peptide due to both gamma radiolysis and metal catalyzed oxidation in the presence of two equivalents of copper is inhibited confirming the binding of both equivalents of copper to peptide. The electrochemical and cytotoxicity study shows that negative shift in the reduction potential is reflected as slightly higher cytotoxicity in SH-SY5Y cell lines for Aβ1-16-Cu(2+) (1:2) complex.

  20. Synthesis and Crystal Structure of Copper(II) Complex with Mixed Bipyridine and 2-Hydroxy-1-naphthaldehyde Ligands

    Institute of Scientific and Technical Information of China (English)

    卜平宇; 程鹏; 赵斌; 阎世平; 瘳代正; 姜宗慧; 刘松岩; 姚心侃; 王宏根

    2002-01-01

    A mononuclear copper(II) complex, [Cu(bipy)(naph)(ClO4)] (where bipy is bipyridine and naph is 2-hydroxy-1-naphthaldehyde), was synthesized and characterized by X-ray single-crystal structure analysis. The crystal is triclinic, space group P ī with a = 9.245(4), b = 9.962(4), c = 10.809(7) A, α = 84.83(5), β =82.35(4), γ = 81.02(4)°, V = 972.1 >3, C21H15ClCuN2O6 Mr = 490.36, Z = 2, F(000) = 498, Dx = 1.68 g/cm3, μ = 13.05 cm-1, R = 0.078, Rw = 0.081 for 2295 observed reflections with I > 3σ(I). The copper(II) ion is coordinated by two nitrogen atoms of bipy and two oxygen atoms of naph in the equatorial plane, with an axial perchlorate oxygen-copper(II) bond to copper(II) ion to form square-pyramidal coordination geometry. The coordination environment of copper(II) is similar to the active site of galactose oxidase and this compound may also be considered as the structural model of galactose oxidase.

  1. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    Science.gov (United States)

    Bera, Manindranath; Patra, Ayan

    2011-10-18

    We have studied the binding interactions of biologically important carbohydrates (D-glucose, D-xylose and D-mannose) with the newly synthesized five-coordinate dinuclear copper(II) complex, [Cu(2)(hpnbpda)(μ-OAc)] (1) and zinc(II) complex, [Zn(2)(hpnbpda)(μ-OAc)] (2) [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in aqueous alkaline solution. The complexes 1 and 2 are fully characterized both in solid and solution using different analytical techniques. A geometrical optimization was made of the ligand H(3)hpnbpda and the complexes 1 and 2 by molecular mechanics (MM+) method in order to establish the stable conformations. All carbohydrates bind to the metal complexes in a 1:1 molar ratio. The binding events have been investigated by a combined approach of FTIR, UV-vis and (13)C NMR spectroscopic techniques. UV-vis spectra indicate a significant blue shift of the absorption maximum of complex 1 during carbohydrate coordination highlighting the sugar binding ability of complex 1. The apparent binding constants of the substrate-bound copper(II) complexes have been determined from the UV-vis titration experiments. The binding ability and mode of binding of these sugar substrates with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for carbon atoms C1, C2, and C3 of sugar substrates.

  2. Sulfate-bridged dimeric trinuclear copper(II–pyrazolate complex with three different terminal ligands

    Directory of Open Access Journals (Sweden)

    Gellert Mezei

    2016-08-01

    Full Text Available The reaction of CuSO4·5H2O, 4-chloropyrazole (4-Cl-pzH and triethylamine (Et3N in dimethylformamide (DMF produced crystals of diaquahexakis(μ-4-chloropyrazolato-κ2N:N′bis(N,N-dimethylformamidedi-μ3-hydroxido-bis(μ4-sulfato-κ4O:O′:O′′:O′′hexacopper(II N,N-dimethylformamide tetrasolvate dihydrate, [Cu3(OH(SO4(C3H2ClN23(C3H7NO(H2O]2·4C3H7NO·2H2O. The centrosymmetric dimeric molecule consists of two trinuclear copper–pyrazolate units bridged by two sulfate ions. The title compound provides the first example of a trinuclear copper–pyrazolate complex with three different terminal ligands on the Cu atoms, and also the first example of such complex with a strongly binding basal sulfate ion. Within each trinuclear unit, the CuII atoms are bridged by μ-pyrazolate groups and a central μ3-OH group, and are coordinated by terminal sulfate, H2O and DMF ligands, respectively. Moreover, the sulfate O atoms coordinate at the apical position to the Cu atoms of the symmetry-related unit, providing square–pyramidal coordination geometry around each copper cation. The metal complex and solvent molecules are involved in O—H...O hydrogen bonds, leading to a two-dimensional network parallel to (10-1.

  3. TThe analysis of air pollution caused by particle matter emission from the copper smelter complex bor (Serbia

    Directory of Open Access Journals (Sweden)

    Nevenka Petrović

    2010-09-01

    Full Text Available The main aim of this paper is to present the analyses of temporal variations of particulate matter in Bor (Serbia influenced by the copper production at the Copper Smelter Complex Bor. Particulate emissions are of concern because the presence of fine particles (PM2.5 – particles with diametar less than 2.5 μm and ultrafine particles (PM0.1 – particles with diametar less than 0.1 μm assume higher risk for human health. Such particles can penetrate deeper into respiratory organs and, at the same time, a probability for such penetration and deposition in the respiratory system is greater. The analysis is based on the comparison of SO2 and PM measurements at several locations in the area of Bor town in the close vicinity of Copper Smelter. PM concentrations were highly correlated with sulfur dioxide and inversely correlated with local wind speed during pollution episodes. The results presented indicate that the dominant source of coarse and fine particles in Bor town is the Copper Smelting Complex Bor. The most significant factors for particulate matter distribution are meteorological parameters of the wind speed and direction. It was found that the daily limit values exceed of concentrations of PM10 (50 μg/m3 usually occurs due to very high concentrations in a period of several hours during the day.

  4. Ability of sodium copper chlorophyllin complex to repair photoaged skin by stimulation of biomarkers in human extracellular matrix

    Directory of Open Access Journals (Sweden)

    McCook JP

    2016-07-01

    Full Text Available John P McCook,1 Thomas J Stephens,2 Lily I Jiang,2 Robert M Law,3 Vincent Gotz4 1Discovery Partners LLC, Frisco, 2Thomas J. Stephens & Associates, Inc., Richardson, 3ProPath, Dallas, TX, 4MDRejuvena, Inc., San Diego, CA, USA Purpose: To examine the effect of sodium copper chlorophyllin complex on the expression of biomarkers of photoaged dermal extracellular matrix indicative of skin repair.Patients and methods: Following a previously published 12-day clinical assessment model, skin biopsy samples from the forearms of four healthy females with signs of photoaged skin were obtained and samples were analyzed by immunohistochemistry for key biomarkers of aging skin after each subject was treated with a test material consisting of a gel containing a liposomal dispersion of sodium copper chlorophyllin complex 0.05%, a positive control of tretinoin cream 0.025%, and an untreated negative control.Results: There was a statistically significantly greater amount of fibrillin/amyloid P and epidermal mucins found for skin treated with the test material containing 0.05% sodium copper chlorophyllin complex and the reference control tretinoin 0.025% cream compared to the negative control (untreated site. Expression of procollagen 1 and dermal mucin also showed a greater presence in the samples treated with the test material and the reference control compared to the negative control, though the differences were not statistically significant. No adverse events were observed or reported by the subjects during the course of the study.Conclusion: The results of this human biopsy study suggest that both retinoids and sodium copper chlorophyllin complex have beneficial effects on biomarkers of photoaged skin. Products containing both sodium copper chlorophyllin complex and retinols may provide a dual approach to reversing age-related decreases in hyaluronic acid (HA in the skin: inhibition of the breakdown of HA via sodium copper chlorophyllin complex by inhibition

  5. Copper(Ⅱ) and Cobalt(Ⅱ) Dinuclear Complexes with Oxime-based Ligand as Catalysts for the Hydrolysis of Phosphate Diester

    Institute of Scientific and Technical Information of China (English)

    DU Juan; MENG Xiang-Guang; ZENG Xian-Cheng

    2008-01-01

    Dinuclear copper(Ⅱ) and cobalt(Ⅱ) complexes were prepared and investigated with respect to their effects on hydrolysis of bis(4-nitrophenyl) phosphate (BNPP). The kinetic data indicated that the mono-deprotonated oxime group could act as an effective intramolecular nucleophile in the reaction. The higher reactivity of dinuclear copper(Ⅱ) complex than that of its mononuclear analogues illustrated the probability of double Lewis acid activation by two metal centers in the former complex.

  6. Synthesis and Structure of the Copper(Ⅰ) Complex [Cu (PPh3) 2 (BH4) ]%Synthesis and Structure of the Copper(Ⅰ) Complex [Cu(PPh3)2(BH4)

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Mononuclear copper( Ⅰ ) complex [Cu(PPh3)2(BH4)] has been synthesized by ligand replacement reaction in methanol and characterized by elemental analyses, molecular weight determination, IR spectra and X-ray single crystal analysis,its conductivity has also been measured. The crystal is monoclinic, space group C2/c, a =24.776(4), b=9.173(7), c=15.564(2)A; β=116.10(1)°, V=3176.73 A3, Z =4, F(000)=1256, μ(MoKα)=8.11 cm-1, Dc=1. 26 g/cm3, M=602.79, R=0. 039, Rw= 0. 050. The results show that PPh3 coordinates as monodentate ligand to the Cu ( Ⅰ ) atoms, and BH4 behaves as a bidentate ligand in the prepared complex.The central copper atom belongs to tetrahedron coordination geometry.

  7. Oxygen binding and activation by the complexes of PY2- and TPA-appended diphenylglycoluril receptors with copper and other metals

    NARCIS (Netherlands)

    Sprakel, VSI; Feiters, MC; Klaucke, WM; Klopstra, M; Brinksma, J; Feringa, BL; Karlin, KD; Nolte, RJM; Sprakel, Vera S.I.; Feiters, Martin C.; Meyer-Klaucke, Wolfram; Karlin, Kenneth D.; Nolte, Roeland J.M.; Feringa, Bernard

    2005-01-01

    The copper( I) complexes of diphenylglycoluril basket receptors 1 and 2, appended with bis(2-ethylpyridine) amine (PY2) and tris(2-methylpyridine) amine (TPA), respectively, and their dioxygen adducts were studied with low-temperature UV-vis and X-ray absorption spectroscopy (XAS). The copper(I) com

  8. Synthesis of isocoumarins through three-component couplings of arynes, terminal alkynes, and carbon dioxide catalyzed by an NHC-copper complex.

    Science.gov (United States)

    Yoo, Woo-Jin; Nguyen, Thanh V Q; Kobayashi, Shū

    2014-09-15

    A copper-catalyzed multicomponent coupling reaction between in situ generated ortho-arynes, terminal alkynes, and carbon dioxide was developed to access isocoumarins in moderate to good yields. The key to this CO2-incorporating reaction was the use of a versatile N-heterocyclic carbene/copper complex that was able to catalyze multiple transformations within the three-component reaction.

  9. 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.

  10. Anticancer activity and computational modeling of ternary copper (II) complexes with 3-indolecarboxylic acid and 1,10-phenanthroline.

    Science.gov (United States)

    Zhang, Zhen; Wang, Huiyun; Wang, Qibao; Yan, Maocai; Wang, Huannan; Bi, Caifeng; Sun, Shanshan; Fan, Yuhua

    2016-08-01

    Metal-containing compounds have been extensively studied for many years as potent proteasome inhibitors. The 20S proteasome, the main component of the ubiquitin proteasome pathway, is one of the excellent targets in anticancer drug development. We recently reported that several copper complexes were able to inhibit cancer-special proteasome and induce cell death in human cancer cells. However, the involved molecular mechanism is not known yet. We therefore synthesized three copper complexes and investigated their abilities on inhibiting proteasome activity and inducting apoptosis in human breast cancer cells. Furthermore, we employed molecular dockings to analyze the possible interaction between the synthetic copper complexes and the β5 subunit of proteasome which only reflects the chymotrypsin-like activity. Our results demonstrate that three Cu(II) complexes possess potent proteasome inhibition capability in a dose-dependent and time-dependent manner in MDA-MB-231 human breast cancer cells. They could bind to the β5 subunit of the 20S proteasome, which consequently cause deactivation of the proteasome and tumor cell death. The present study is significant for providing important theoretical basis for design and synthesis of anticancer drugs with low toxicity, high efficiency and high selectivity.

  11. Multispectroscopic studies on the interaction of a copper(ii) complex of ibuprofen drug with calf thymus DNA.

    Science.gov (United States)

    Shahabadi, Nahid; Shiri, Farshad

    2017-02-01

    The interaction of copper(II)-ibuprofenato complex with calf thymus DNA (ct-DNA) has been explored following, UV-visible spectrophotometry, fluorescence measurement, dynamic viscosity measurements, and circular dichroism spectroscopy. In spectrophotometric studies of ct-DNA it was found that [Cu(ibp)2]2 can form a complex with double-helical DNA. The association constant of [Cu(ibp)2]2 with DNA from UV-Vis study was found to be 6.19 × 10(4) L mol(-1). The values of Kf from fluorescence measurement clearly underscore the high affinity of [Cu(ibp)2]2 to DNA. The experimental results showed that the conformational changes in DNA helix induced by [Cu(ibp)2]2 are the reason for the fluorescence quenching of the DNA-Hoechst system. In addition, the fluorescence emission spectra of intercalated methylene blue (MB) with increasing concentrations of [Cu(ibp)2]2 represented a significant increase of MB intensity as to release MB from MB-DNA system. The results of circular dichroism (CD) suggested that copper(II)-ibuprofenato complex can change the conformation of DNA. In addition, the results of viscosity measurements suggest that copper(II)-ibuprofenato complex may bind with non-classical intercalative mode. From spectroscopic and hydrodynamic studies, it has been found that [Cu(ibp)2]2 interacts with DNA by partial intercalation mode which contains intercalation and groove properties.

  12. Accelerated Hydrolysis of p-Nitrophenyl Picolinate Catalyzed by Metallomicelle Made from a Novel Macrocyclic Polyamine Copper(Ⅱ) Complex

    Institute of Scientific and Technical Information of China (English)

    KOU,Xing-Ming; ZHAO,Guo-Po; HUANG,Zhong; TIAN,Yu-Hua; MENG,Xiang-Guang; ZENG Xian-Cheng

    2007-01-01

    A copper(Ⅱ) complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,ll-bis(hydroxylethyl)-5,7,7,12,14,14-hexamethyl-l,4,8,11-tetraazacyclotetradecane (L) has been synthesized and characterized. Rate enhancement for hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by 1 was studied kinetically under Brij35 micellar condition. For comparision, the catalytic activity of corresponding copper(Ⅱ) complex 2 of non-substituted macrocyclic polyamine ligand, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclote-tradecane (L1) toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic polyamine copper(Ⅱ) complex 1 effectively catalyzed the hydrolysis of PNPP, and the pendant ligand hydroxyl group or deprotonated pendant ligand hydroxyl group can act as catalytically active species in the reaction. A ternary complex kinetic model involving metal ion, ligand and substrate has been proposed, and the results confirmed the reasonability of such kinetic model.

  13. Preparation and Analysis of Complex Barrier Layer of Heterocyclic and Long-Chain Organosilane on Copper Alloy Surface

    Directory of Open Access Journals (Sweden)

    Qian Zhao

    2016-07-01

    Full Text Available A single electrodeposited film of 6-(3-triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol monosodium (TES on a copper alloy surface was prepared by the galvanostatic method, then octyl-triethoxysilane (OTES or hexadecyl-trimethoxysilane (HDTMS was used to modify the electrodeposited film by the self-assembled technique to fabricate the complex film. The electrodeposition process was inferred by cyclic voltammetry. The single and complex films were characterized by means of contact angle, cyclic voltammetry, Fourier transform infrared spectroscopy (FT-IR, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS and scanning electron microscope (SEM. The results showed that the contact angle of the complex film covering the copper alloy surface was up to 118.1° compared with 89.4° of the bare copper alloy. The cyclic voltammogram, polarization curves and EIS indicated that the anti-corrosion performance of complex film was better than that of single electrodeposited TES film, and the protection efficiency was up to 90.2%.

  14. Thermodynamics of the complex formation of copper(II) with L-phenylalanine in aqueous ethanol solutions

    Science.gov (United States)

    Burov, D. M.; Ledenkov, S. F.; Vandyshev, V. N.

    2013-05-01

    Constants of the acid dissociation and complexation of L-phenylalanine (HPhe) with copper(II) ions are determined by potentiometry in aqueous ethanol solutions containing 0 to 0.7 molar fraction of alcohol. Changes in the Gibbs energy for the transfer from water to a binary solvent of L-phenylalanine, Phe- anion, and [CuPhe]+ complex are calculated. It is found that the weakening of solvation of the ligand donor groups in solvents with high ethanol contents is accompanied by an increase in the stability of [CuPhe]+ complex.

  15. SYNTHESIS, SPECTROSCOPIC, THERMAL STUDIES AND BIOLOGICAL ACTIVITY OF A NEW SULFAMETHOXAZOLE SCHIFF BASE AND ITS COPPER COMPLEXES

    Directory of Open Access Journals (Sweden)

    A. M. Abu-Yamin et al.

    2011-12-01

    Full Text Available A new Sulfamethoxazole Schiff base (E-4-(4-methoxybenzylideneamino-N-(5-methylis-oxazol-3-yl benzenesulfonamide (C18H17N3O4S, and its copper complex were synthesized and the structures elucidated on the basis of Physiochemical methods. The studies indicate an octahedral structure for the complexes with the (C22H27N3O10SCu formula. The IR spectra suggest that the ligand act as tridentate (from oxygen and two nitrogen atoms donor. Also the biological activity of the Schiff base and its Cu complex were studied.

  16. Benzaldehyde thiosemicarbazone derived from limonene complexed with copper induced mitochondrial dysfunction in Leishmania amazonensis.

    Directory of Open Access Journals (Sweden)

    Elizandra Aparecida Britta

    Full Text Available BACKGROUND: Leishmaniasis is a major health problem that affects more than 12 million people. Treatment presents several problems, including high toxicity and many adverse effects, leading to the discontinuation of treatment and emergence of resistant strains. METHODOLOGY/PRINCIPAL FINDINGS: We evaluated the in vitro antileishmanial activity of benzaldehyde thiosemicarbazone derived from limonene complexed with copper, termed BenzCo, against Leishmania amazonensis. BenzCo inhibited the growth of the promastigote and axenic amastigote forms, with IC(50 concentrations of 3.8 and 9.5 µM, respectively, with 72 h of incubation. Intracellular amastigotes were inhibited by the compound, with an IC(50 of 10.7 µM. BenzCo altered the shape, size, and ultrastructure of the parasites. Mitochondrial membrane depolarization was observed in protozoa treated with BenzCo but caused no alterations in the plasma membrane. Additionally, BenzCo induced lipoperoxidation and the production of mitochondrial superoxide anion radicals in promastigotes and axenic amastigotes of Leishmania amazonensis. CONCLUSION/SIGNIFICANCE: Our studies indicated that the antileishmania activity of BenzCo might be associated with mitochondrial dysfunction and oxidative damage, leading to parasite death.

  17. First insights on the molybdenum-copper Bled M'Dena complex (Eglab massif, Algeria)

    Science.gov (United States)

    Lagraa, Karima; Salvi, Stefano; Béziat, Didier; Debat, Pierre; Kolli, Omar

    2017-03-01

    Molybdenum-Copper showings in the Eglab massif (eastern part of the Reguibat rise of Algeria), are found in quartz-monzodiorite and granodiorite of the Bled M'Dena complex, a Paleoproterozoic circular structure of ∼5 km in diameter, comprising volcanic and intrusive suites. The latter consist of quartz-diorite, quartz-monzodiorite and granodiorite with a metaluminous normative composition. They display an "adakitic character" with moderate light rare-earth element (LREE) enrichment, minor Eu anomalies, high Sr/Y ratio and low Yb concentration, suggestive of a hydrous, arc magma of volcanic-arc affinity. The mineralization occurs mostly in quartz + molybdenite + chalcopyrite stockwork veins marked by widespread propylitic alteration along the selvages. Molybdenite and chalcopyrite are commonly associated with calcite, which precipitated at relatively late stages of the hydrothermal alteration. Fluid inclusions related to the mineralization stage, range from aqueous to aqueous-carbonic to solid bearing. The latter inclusions have the highest homogenization temperature (up to ∼400 °C), are salt saturated, and commonly contain molybdenite and/or chalcopyrite crystals. The petrology and geochemistry of the host rocks, the style of the hydrothermal alteration, the ore mineral associations, and the characteristics of the fluid inclusions, are all coherent in indicating that the Bled M'Dena represents a Paleoproterozoic porphyry style Mo mineralization, which is far unreported in the African continent.

  18. Synthesis and Structure of the Copper(I) Complex Containing Bis(diphenylphosphino)ethane

    Institute of Scientific and Technical Information of China (English)

    林宽华; 谢青; 杨瑞娜; 邝爱燕; 金斗满

    2002-01-01

    The mononuclear copper(I) complex, [Cu(dppe)2](PF6)(CH3COCH3) [dppe = bis-(diphenylphosphino)ethane] has been synthesized and characterized by X-ray crystallography. The crystal belongs to monoclinic, Mr=1062.3, space group P21/n with cell parameters a =14.741(2), b =19.354(8), c =18.587(3) A, β = 91.41(1)°, V = 5301.5 A3, Z = 4, Dc=1.302 g/cm3, F(000)= 2200, μ = 6.16cm-1, R=0.062, Rw = 0.068. A total of 9679 independent reflections were collected, of which 4574 reflections with I >3σ(I) were observed. The central Cu atom is coordinated by four P atoms from dppe to form a distorted tetrahedral environment. In the coordination sphere the bond lengths of Cu-P(1), Cu-P(2), Cu-P(3) and Cu-P(4) are 2.298(2), 2.305(2), 2.311(2) and 2.295?, respectively; and the P-Cu-P bond angles vary from 87.52(9) to 120.12(9)°.

  19. Modeling dinuclear copper sites of biological relevance - synthesis, molecular-structure, magnetic-properties, and h-1- nmr spectroscopy of a nonsymmetric dinuclear copper(ii) complex - microcalorimetric determination of stepwise complexation of copper(ii) by a nonsymmetric dinucleating ligand

    NARCIS (Netherlands)

    Lubben, M; Hage, R.; Meetsma, A.; Bijma, Koos; Feringa, B.L.

    1995-01-01

    The new nonsymmetric dinuclear copper(II) complex [Cu(2)L(1)(OAcW(ClO4) (7) was synthesized by complexation of Cu(OAc). H2O with a new nonsymmetric dinucleating ligand (5) which' is formed in situ by condensation of 2-formyl-6-((4-methylpiperazin-1-yl)methyl)phenol (3a) with 2-(aminoethyl)pyridine.

  20. The copper-nickel concentration log: A tool for stratigraphic interpretation within the ultramafic and basal zones of the stillwater complex, Montana

    Science.gov (United States)

    Drew, L.J.; Bawiec, W.J.; Page, N.J.; Schuenemeyer, J.H.

    1985-01-01

    An analogue to the electric well log was devised for copper-nickel concentration drill-hole data from the Basal and lower part of the Ultramafic zones of the Stillwater Complex using automated data processing. The copper-nickel concentration logs graphically represent intensity (concentration) values that reflect the distribution of the elements in sulfide and silicate minerals. Four major patterns are recognized by their characteristic variations in copper and nickel intensity: (1) relatively flat, low-level copper-intensity signatures associated with arcuate nickel-intensity patterns that correlate with rocks in the Peridotite member of the Ultramafic zone; (2) arcuate or bulb-like patterns of copper and nickel intensity that correlate closely with the Basal bronzite cumulate member of the Basal zone; (3) complex patterns consisting of intervals of low-intensity copper and moderate-intensity nickel, spikes of high nickel and copper intensity, and high copper intensity associated with low nickel intensity that correlate respectively with cordierite-pyroxene hornfels, massive sulfide, norites and mineralized diabase dikes in the Basal norite member; and (4) large intervals of extremely low copper and nickel intensity that correlate with quartz-orthopyroxene hornfels. The recognition and interpretation of these patterns allow two- and three-dimensional stratigraphic and lithologic reconstructions to be done by means of concentration-log correlations instead of variable quality lithologic logging. ?? 1985.

  1. Direct observation of intersystem crossing in a thermally activated delayed fluorescence copper complex in the solid state.

    Science.gov (United States)

    Bergmann, Larissa; Hedley, Gordon J; Baumann, Thomas; Bräse, Stefan; Samuel, Ifor D W

    2016-01-01

    Intersystem crossing in thermally activated delayed fluorescence (TADF) materials is an important process that controls the rate at which singlet states convert to triplets; however, measuring this directly in TADF materials is difficult. TADF is a significant emerging technology that enables the harvesting of triplets as well as singlet excited states for emission in organic light emitting diodes. We have observed the picosecond time-resolved photoluminescence of a highly luminescent, neutral copper(I) complex in the solid state that shows TADF. The time constant of intersystem crossing is measured to be 27 picoseconds. Subsequent overall reverse intersystem crossing is slow, leading to population equilibration and TADF with an average lifetime of 11.5 microseconds. These first measurements of intersystem crossing in the solid state in this class of mononuclear copper(I) complexes give a better understanding of the excited-state processes and mechanisms that ensure efficient TADF.

  2. Machining characteristics of complex prism pattern on electroplated roll by copper

    Institute of Scientific and Technical Information of China (English)

    Tae-Jin JE; Sang-Cheon PARK; Kang-Won LEE; Yeong-Eun YOO; Doo-Sun CHOI; Kyung-Hyun WHANG; Myung-Chang KANG

    2009-01-01

    The BLU (back light unit)is the core component of the LCD for notebook, mobile-phone, navigation, as well as large sized TV, PID (public information display), etc. In order to enhance optical efficiency of LCD, optical films with the uniform prism patterns have been used for BLU by stacking two films up orthogonally. In this case, light interference-phenomenon occurred such as Morie, wet-out, u-turning, etc. It caused several problems such as low brightness, spots and stripes in LCD. Recently, the high-luminance micro complex prism patterns are actively studied to avoid the light interference-phenomenon and enhance the optical efficiency. In this study, the roll master to manufacture complex micro prism pattern film was machined by using the high precision lathe. The machined patterns on the roll master were 50, 45, 40, 35, 30, 25, 20, 15, 10 and 5μm in the pitch with 25.0, 22.5, 20.0, 17.5, 15.0, 12.5, 10.0, 7.5, 5.0 and 2.5 μm in the peak height, respectively. The roll was 2 000 mm in length and 320 mm in diameter. The electroplated roll by copper and the natural single crystal diamond tool was used for machining the patterns. The cutting force was measured and analyzed for each cutting condition by using the dynamometer. The chips and the surfaces after being machined were analyzed by SEM and microscope.

  3. Coordination modes, spectral, thermal and biological evaluation of hetero-metal copper containing 2-thiouracil complexes.

    Science.gov (United States)

    Masoud, Mamdouh S; Soayed, Amina A; El-Husseiny, Amel F

    2012-12-01

    Mononuclear copper complex [CuL(NH(3))(4)]Cl(2)·0.5H(2)O and three new hetero-metallic complexes: [Cu(2)Ni(L)(2)(NH(3))(2)Cl(2)·6H(2)O] 2H(2)O(,) [Cu(3)Co(L)(4)·8H2O]Cl·4(·)5H(2)O, and [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2)O]4H(2)O where L is 2-thiouracil, were prepared and characterized by elemental analyses, molar conductance, room-temperature magnetic susceptibility, spectral (IR, UV-Vis and ESR) studies and thermal analyses techniques (TG, DTG and DTA). The molar conductance data revealed that [CuL(NH(3))(4)]Cl(2)·0.5H(2)O and [Cu(3)Co(L)(4)·8H2O]Cl·4.5H(2)O are electrolytes, while, [Cu(2)Ni(L)(2)(NH(3))(2)Cl(2·)6H(2)O]·2H(2)O and [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2)O]4H(2)O are non-electrolytes. IR spectra showed, that 2-thiouracil ligand behaves as a bidentate or tetradentate ligand. The geometry around the metal atoms is octahedral in all the prepared complexes except in [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2)O]4H(2)O complex where square planar environment around Co(II), Ni(II) and Cu(II) were suggested. Thermal decomposition study of the prepared complexes was monitored by TG, DTG and DTA analyses under N(2) atmosphere. The decomposition course and steps were analyzed. The order of chemical reactions (n) was calculated via the peak symmetry method and the activation parameters of the non- isothermal decomposition were computed from the thermal decomposition data. The negative values of ΔS(∗) deduced the ordered structures of the prepared complexes compared to their starting reactants. The antimicrobial activity of the prepared complexes were screened in vitro against a Gram positive, a Gram negative bacteria, a filamentous fungi and a yeast. The antimicrobial screening data showed that the studied compounds exhibited a good level of activity against Escherichia coli, Staphylococcus aureus and Candida albicans but have no efficacy against Aspergillus flavus. It was observed that [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2

  4. A photoreducible copper(II)-tren complex of practical value: generation of a highly reactive click catalyst.

    Science.gov (United States)

    Harmand, Lydie; Lambert, Romain; Scarpantonio, Luca; McClenaghan, Nathan D; Lastécouères, Dominique; Vincent, Jean-Marc

    2013-11-25

    A detailed study on the photoreduction of the copper(II) precatalyst 1 to generate a highly reactive cuprous species for the copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click reaction is presented. For the photoactive catalyst described herein, the activation is driven by a photoinduced electron transfer (PET) process harnessing a benzophenone-like ketoprofenate chromophore as a photosensitizer, which is equally the counterion. The solvent is shown to play a major role in the Cu(II) to Cu(I) reduction process as the final electron source, and the influence of the solvent nature on the photoreduction efficiency has been studied. Particular attention was paid to the use of water as a potential solvent, aqueous media being particularly appealing for CuAAC processes. The ability to solubilize the copper-tren complexes in water through the formation of inclusion complexes with β-CDs is demonstrated. Data is also provided on the fate of the copper(I)-tren catalytic species when reacting with O2, O2 being used to switch off the catalysis. These data show that partial oxidation of the secondary benzylamine groups of the ligand to benzylimines occurs. Preliminary results show that when prolonged irradiation times are employed a Cu(I) to Cu(0) over-reduction process takes place, leading to the formation of copper nanoparticles (NPs). Finally, the main objective of this work being the development of photoactivable catalysts of practical value for the CuAAC, the catalytic, photolatent, and recycling properties of 1 in water and organic solvents are reported.

  5. Spectral studies of dimeric copper(II) complexes of acid amide derivatives as models for type III copper enzymes

    Science.gov (United States)

    Garg, Bhagwan S.; Nandan Kumar, Deo; Sarbhai, Meenu; Reddy, Malladi J.

    2003-10-01

    Dimeric (hydrated and anhydrated) complexes of Cu(II) with N, N'-bis(3-carboxy-1-oxo-2-prop-2-enyl)ethylenediamine(BCOPENH 2, A) and N, N'-bis(2-carboxy-1-oxo-phenylenyl)ethylenediamine(BCOPHENH 2, B) have been prepared and characterised by elemental analysis, magnetic susceptibility measurements, EPR, thermal and spectral (IR, UV/Vis) studies. EPR parameters and magnetic behaviour indicates that the complexes are antiferromagnetic in nature and most likely adopt the typical carboxylate cage structure. Interesting amide bonding patterns have been observed and various EPR parameters have been evaluated on the basis of these studies, tentative probable structures of the complexes have been proposed.

  6. Bio-inspired multinuclear copper complexes covalently immobilized on reduced graphene oxide as efficient electrocatalysts for the oxygen reduction reaction.

    Science.gov (United States)

    Xi, Yue-Ting; Wei, Ping-Jie; Wang, Ru-Chun; Liu, Jin-Gang

    2015-05-01

    Inspired by the multicopper active site of laccase, which efficiently catalyzes the oxygen reduction reaction (ORR), herein we report a novel bio-inspired ORR catalyst composed of a multinuclear copper complex that was immobilized on the surface of reduced graphene oxide (rGO) via the covalently grafted triazole-dipyridine (TADPy) dinucleating ligand. This rGO-TADPyCu catalyst exhibited high ORR activity and superior long-term stability compared to Pt/C in alkaline media.

  7. Electrocatalytic O2 Reduction at a Bio-inspired Mononuclear Copper Phenolato Complex Immobilized on a Carbon Nanotube Electrode.

    Science.gov (United States)

    Gentil, Solène; Serre, Doti; Philouze, Christian; Holzinger, Michael; Thomas, Fabrice; Le Goff, Alan

    2016-02-12

    An original copper-phenolate complex, mimicking the active center of galactose oxidase, featuring a pyrene group was synthesized. Supramolecular pi-stacking allows its efficient and soft immobilization at the surface of a Multi-Walled Carbon Nanotube (MWCNT) electrode. This MWCNT-supported galactose oxidase model exhibits a 4 H(+)/4 e(-) electrocatalytic activity towards oxygen reduction at a redox potential of 0.60 V vs. RHE at pH 5.

  8. New Copper(Ⅱ) and Nickel(Ⅱ) Complexes of 4-Morpholinoacetophenone Thiosemicarbazone: Structural, Electrochemical and Antimicrobial Studies

    Institute of Scientific and Technical Information of China (English)

    BINGOL Haluk; COSKUN Ahmet; AKGEMCI Emine Guler; KAYA Basturk; ATALAY Tevfik

    2007-01-01

    4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel(Ⅱ) and copper(Ⅱ) complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods (FT-IR, 1H NMR) and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu(MAPT)2]Cl2 complex shows Cu(Ⅱ)/Cu(I) couple and quasi-reversible wave associated with the Cu(Ⅲ)/Cu(Ⅱ) process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.

  9. Spectroscopic, solvent influence and thermal studies of ternary copper(II) complexes of diester and dinitrogen base ligands.

    Science.gov (United States)

    Emara, Adel A A; Abu-Hussein, Azza A A; Taha, Ahmed A; Mahmoud, Nelly H

    2010-10-15

    New mixed-ligand copper(II) complexes containing the bidentate dinitrogen ligands [N,N,N',N'-tetramethylethylenediamine (tmen), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)] and the bidentate dioxygen ligands [diethylmalonate (DEM), ethylacetoacetate (EAA) and ethylbenzoylacetate (EBA)] were prepared. The complexes were characterized by elemental analysis, infrared, mass and ESR spectral data, magnetic and molar conductance measurements and thermal gravimetric analysis. From the investigation, the geometries of the complexes are square planar for perchlorate complexes and a square pyramid or octahedral for the nitrate complexes. Solvatochromic behavior of the Cu(II) complexes indicates strong solvatochromism of their solutions in polar and non-polar solvents. The observed solvatochromism is due to the solute-solvent interaction between the chelate cation and the solvent molecules.

  10. 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.

  11. An in-vivo study for targeted delivery of copper-organic complex to breast cancer using chitosan polymer nanoparticles.

    Science.gov (United States)

    Pramanik, Arindam; Laha, Dipranjan; Dash, Sandeep Kumar; Chattopadhyay, Sourav; Roy, Somenath; Das, Dipak Kumar; Pramanik, Panchanan; Karmakar, Parimal

    2016-11-01

    We have developed a strategy for targeted delivery of metal-diketo complex, "bis(2,4-pentanedionato) copper(II)" to breast cancer cells both in-vitro and in-vivo. This metal-organic complex induced ROS and subsequently DNA damage as well as mitochondrial membrane depolarization was observed. The mitochondria rupture further triggered apoptosis. For in-vitro targeting strategies, two different approaches were employed, folic acid or her-2 specific peptide (KCCYSL) was attached to stearic acid-modified polymeric Chitosan nanoparticles loaded with metal-organic complex "bis(2,4-pentanedionato)copper(II)". This was tested on two pairs of isogenic cells (FR+/FR- MCf-7 and her2+ /her2- MCF-7) and it was observed that cells expressing the receptor were susceptible to the drug whereas non-expressing isogenic cells were almost un-affected. During in-vivo studies, mice receiving targeted delivery of bis(2,4-pentanedionato) copper (II) had increased survivability and reduced tumor volume compared to non-targeted drug delivery. During toxicity studies for liver enzymes it was also found that the mice receiving targeted drug did not show any sign of liver damage as well as other histology changes. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Magnetic, catalytic, EPR and electrochemical studies on binuclear copper(II) complexes derived from 3,4-disubstituted phenol

    Indian Academy of Sciences (India)

    R Kannappan; R Mahalakshmy; T M Rajendiran; R Venkatesan; P Sambasiva Rao

    2003-02-01

    New symmetrical compartmental binucleating ligands 2,6-bis[N-(2-{dimethylamino}ethyl)-N-methyl)aminomethyl]-3,4-dimethylphenol [HL1] and 2,6-bis[N-(2-{diethylamino}ethyl)-N-ethyl)aminomethyl]-3,4-dimethylphenol [HL2], and their copper(II) complexes [Cu2L1-2(X)]ClO4, (X = NO$_{2}^{-}$, OAc- and OH-) have been prepared. Spectral, catalytic, magnetic, EPR and electrochemical studies have been carried out. A catecholase activity study indicates that only HL1 complexes have efficient catalytic activity due to a less sterically hindered methyl group and enhanced planarity (larger -2 values) with respect to the oxidation of 3,5-di--butylcatechol to the corresponding quinone. Variable temperature magnetic susceptibility studies of the complexes show antiferromagnetic interaction between the copper atoms. X-band EPR signals could not be observed for polycrystalline samples both at room temperatures and liquid nitrogen, consistent with two antiferrromagnetically coupled copper centres in the solid state. EPR spectral studies in methanol solvent show welldefined four hyperfine signals at room temperature due to decomposition of the dimer into monomers. This however is not seen in frozen methanol glass, may be owing to restructuring of the monomers into dimers due to an increase in viscosity of the solvent. Electrochemical studies revealed chemically irreversible behaviour due to chemical or/and stereochemical changes subsequent to electron transfer.

  13. Structural, spectroscopic, magnetic and electrochemical studies of monomer N-substituted-sulfanilamide copper (II) complex with 2,2'-bipyridine.

    Science.gov (United States)

    Öztürk, Filiz; Bulut, İclal; Bulut, Ahmet

    2015-03-05

    A novel copper (II) complex of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl] benzene sulfonamide, Hsmz) ([Cu(smz)2bipy]⋅0.8H2O; bipy: 2,2'-bipyridine) has been synthesized and characterized by single crystal X-ray diffraction, EPR, IR, UV-vis and electrochemical methods. The single crystal X-ray analysis indicated that the compound crystallizes in the monoclinic space group P21/c with Z=4. The central copper (II) ion is coordinated by two bidentate sulfamethazine anions through the nitrogen atoms together with one bidentate 2,2'-bipyridine ligand forming the octahedral geometry. The characteristic vibration bands support the X-ray analysis results. The EPR spectral analysis has led to that the ground state wave function of the unpaired electron of copper ion is [Formula: see text] ((2)B1g state) and also indicated that the metal ions are located in distorted octahedral sites (D4h) elongated along the z-axis. The electrochemical studies of the complex were also carried out to determine the active sites of the ligands. The cyclic and square wave voltammetric techniques have been used to determine the complex.

  14. 3-Pyridylmethanol vs. N,N‧-diethylnicotinamide in copper(II) complex formation - A comparative EPR study

    Science.gov (United States)

    Husáriková, L.; Repická, Z.; Valigura, D.; Valko, M.; Mazúr, M.

    2013-10-01

    Copper(II) complexes, formed from 4-chlorosalicylic acid anion A (A = 4-Clsal-), different copper(II) salts (Cu(ac)2 or CuSO4) and different N-donor ligands B (B = 3-pyridylmethanol (ron) or N,N'-diethylnicotinamide (denia)) with varying N-donor ligand-to-metal ratio (x), were studied by EPR spectroscopy in the frozen water/methanol (1:3 v/v) solutions. The number of ligand B molecules coordinated to Cu(II) central ion was determined from the nitrogen perpendicular and parallel superhyperfine splitting multiplets of Cu(II) EPR spectra. It was found for both N-donor ligands: (i) At lower ligand B concentrations (x = 1, 2), [CuB] and/or [CuB2] species having one and/or two molecules of ligands B in equatorial position were dominant. The dominant ternary complex particles were [CuA2B2] species. (ii) At higher ligand B concentrations (x ⩾ 4) the formation of [CuB3] and/or [CuB4] species having three and/or four molecules of ligands B in equatorial position was confirmed. Such information is not possible to get from Cu(II) EPR spectra of powdered samples of given copper(II) complexes.

  15. Syntheses, characterization, crystal structure and manetic properties of copper(Ⅱ) a, b-unsaturated carboxylate complexes with trimethyl phosphate

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2== CH-COO- and CH2==C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu2[CH2== C(CH3)-COO]4[OP(OCH3)3]2 is triclinic, with space group P, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α = 91.263(14)°, β = 102.559(6)°, γ = 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four a-methacrylate groups, and each copper(Ⅱ) atom is coordi-nated with a trimethyl phosphate molecule in the axial posi-tion, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist an-tiferromagnetic interactions between the two copper(Ⅱ) atoms.

  16. Synthesis and Structures of Oxyanion Encapsulated Copper(I)-dppm Complexes (dppm = Bis(diphenylphosphino)methane).

    Science.gov (United States)

    Bera, Jitendra K.; Nethaji, Munirathnam; Samuelson, Ashoka G.

    1999-04-19

    Copper(I)-dppm complexes encapsulating the oxyanions ClO(4)(-), NO(3)(-), CH(3)C(6)H(4)CO(2)(-), SO(4)(2-), and WO(4)(2-) have been synthesized either by reduction of the corresponding Cu(II) salts and treatment with dppm, or by treating the complex [Cu(2)(dppm)(2)(dmcn)(3)](BF(4))(2) (1) (dmcn = dimethyl cyanamide) with the respective anion. The isolated complexes [Cu(2)(dppm)(2)(dmcn)(2)(ClO(4))] (ClO(4)) (2), [Cu(2)(dppm)(2)(dmcn)(2)(NO(3))] (NO(3)) (3), Cu(2)(dppm)(2)(NO(3))(2) (4), [Cu(2)(dppm)(2)(CH(3)C(6)H(4)CO(2))(2)]dmcn.2THF (5), Cu(2)(dppm)(2)(SO(4)) (6), and [Cu(3)(dppm)(3)(Cl)(WO(4))] 0.5H(2)O (7) have been characterized by IR, (1)H and (31)P{(1)H} NMR, UV-vis, and emission spectroscopy. The solid-state molecular structure of complexes 1, 2, 4, and 7 were determined by single-crystal X-ray diffraction. Pertinent crystal data are as follows: for 1, monoclinic P2(1)/c, a = 11.376(10) Å, b = 42.503(7) Å, c = 13.530(6) Å, beta = 108.08(2) degrees, V = 6219(3) Å(3), Z = 4; for 2, monoclinic P2(1)/n, a = 21.600(3) Å, b = 12.968(3) Å, c = 23.050(3) Å, beta = 115.97(2) degrees, V = 5804(17) Å(3), Z = 4; for 4, triclinic P&onemacr;, a = 10.560(4) Å, b = 10.553(3) Å, c = 22.698(3) Å, alpha = 96.08(2) degrees, beta = 96.03(2) degrees, gamma = 108.31(2) degrees, V = 2362(12) Å(3), Z = 2; and for 7, orthorhombic P2(1)2(1)2(1), a = 14.407(4) Å, b = 20.573(7) Å, c = 24.176(6) Å, V = 7166(4) Å(3), Z = 4. Analyses of the crystallographic and spectroscopic data of these complexes reveal the nature of interactions between the Cu(I)-dppm core and oxyanion. The anchoring of the oxyanion to the Cu(n)()(dppm)(n)() unit is primarily through coordination to the metal, but the noncovalent C-H.O interactions between the methylene and phenyl protons of the dppm and oxygen atoms of the oxyanion play a significant role. The solid-state emission spectra for complexes 1-6 are very similar but different from 7. In CDCl(3) solution, addition of ClO(4)(-) or NO(3)(-) (as

  17. Copper(II) complexes with 4-hydroxyacetophenone-derived acylhydrazones: Synthesis, characterization, DNA binding and cleavage properties

    Science.gov (United States)

    Gup, Ramazan; Gökçe, Cansu; Aktürk, Selçuk

    2015-01-01

    Two new Cu(II) complexes of Schiff base-hydrazone ligands, hydroxy-N‧-[(1Z)-1-(4-hydroxyphenyl)ethylidene]benzohydrazide [H3L1] and ethyl 2-(4-(1-(2-(4-(2-ethoxy-2-oxoethoxy)benzoyl)hydrazono)ethyl)phenoxy)acetate (HL2) have been synthesized and then characterized by microcopy and spectral studies. X-ray powder diffraction illustrates that [Cu(L2)2] complex is crystalline in nature whereas [Cu(H2L1)2]·2H2O has an amorphous structure. Binding of the copper complexes with Calf thymus DNA (CT-DNA) has been investigated by UV-visible spectra, exhibiting non-covalent binding to CT-DNA. DNA cleavage experiments have been also investigated by agarose gel electrophoresis in the presence and absence of an oxidative agent (H2O2). The effect of complex concentration on the DNA cleavage reaction has been also studied. Both copper complexes show nuclease activity, which significantly depends on concentrations of the complexes, in the presence of H2O2 through oxidative mechanism whereas they slightly cleavage DNA in the absence an oxidative agent.

  18. Systematic coordination chemistry and cytotoxicity of copper(II) complexes with methyl substituted 4-nitropyridine N-oxides.

    Science.gov (United States)

    Puszko, Aniela; Brzuszkiewicz, Anna; Jezierska, Julia; Adach, Anna; Wietrzyk, Joanna; Filip, Beata; Pełczynska, Marzena; Cieslak-Golonka, Maria

    2011-08-01

    Three new nitrato copper(II) complexes of dimethyl substituted 4-nitropyridine N-oxide were synthesized and characterized by elemental analysis, magnetic, spectroscopic, thermal and X-ray methods, respectively. They were isolated as trans isomers, mononuclear (μ=1.70-1.88 BM), five (1-2) and four (3) coordinate species of general formula [Cu(NO3)2(H2O)L2] where L=2,3-dimethyl-, 2,5-dimethyl-4-nitropyridine N-oxide and [Cu (NO3)2L2], L=3,5-dimethyl-4-nitropyridine N-oxide, respectively. The X-ray crystal structure of (1) (L=2,3-dimethyl-4-nitropyridine N-oxide) was determined. The organic ligands, the complexes and copper hexaqua ion as a reference were tested in vitro on the cytotoxic activity against human cancer cell lines: MCF-7 (breast), SW-707 (colon) and P-388 (murine leukemia). The complexes are relatively strong cytotoxic agents towards P-388 cell line. Comparative analysis was performed for all known copper(II) complexes containing methyl derivatives of the 4-nitropyridine N-oxide on the basis of their composition, structure and cytotoxic activities. To obtain the typical structure for these species (i.e., 4-coordinate mononuclear of the type trans-[Cu(inorganic anion)2L2]), two methyl groups must be situated on both sides of nitrogen atom(s) (i.e., NO and NO2) in the ligand. The biological activity was found to be strongly dependent upon the number of the methyl groups and the type of cell line. The best cytotoxic results were found for the complexes without substituents or with one methyl group. Generally, for all cell lines, the complexation increased cytotoxicity when compared with the free ligands.

  19. Anti-cancer activity and mutagenic potential of novel copper(II) quinolinone Schiff base complexes in hepatocarcinoma cells.

    Science.gov (United States)

    Duff, Brian; Thangella, Venkat Reddy; Creaven, Bernadette S; Walsh, Maureen; Egan, Denise A

    2012-08-15

    This study determined the cytotoxic, cyto-selective and mutagenic potential of novel quinolinone Schiff base ligands and their corresponding copper(II) complexes in human-derived hepatic carcinoma cells (Hep-G2) and non-malignant human-derived hepatic cells (Chang). Results indicated that complexation of quinolinone Schiff bases with copper served to significantly enhance cytotoxicity. Here, the complex of (7E)-7-(3-ethoxy-2-hydroxybenzylideamino)-4-methylquinolin-2(1H)-one (TV117-FM) exhibited the lowest IC(50) value (17.9 μM) following 96 h continuous exposure, which was comparable to cisplatin (15.0 μM). However, results revealed that TV117-FM lacked cytoselectivity over non-malignant cells. Additionally, the complex was minimally effluxed from cells via Pglycoprotein (P-gp) and was shown to be non-mutagenic in the Standard Ames test. Furthermore, BrdU incorporation assays showed that it was capable of inhibiting DNA synthesis in a concentrationand time-dependent manner. However, inhibition was not as a consequence of DNA intercalation, as illustrated in electrophoretic mobility shift assays. Interestingly, it was shown that the ligand was capable of inhibiting the action of topoisomerase II, but this was lost following complexation. This indicated that the mechanism of action of the novel copper(II) complex was different from that of the parent ligand and suggests that TV117-FM may have a therapeutic role to play in the treatment of hepatocellular carcinoma. Studies are currently underway to elucidate the exact in vitro mechanism of action of this novel, metal-based anti-cancer agent.

  20. Synthesis and DNA cleavage activities of mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes which linked with uracil.

    Science.gov (United States)

    Wang, Xiao-Yan; Zhang, Ji; Li, Kun; Jiang, Ning; Chen, Shan-Yong; Lin, Hong-Hui; Huang, Yu; Ma, Li-Jian; Yu, Xiao-Qi

    2006-10-01

    Mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes, which could attach to peptide nucleic acid (PNA), were synthesized as DNA cleavage agents. The structures of these new mononuclear complexes were identified by MS and (1)H NMR spectroscopy. The catalytic activities on DNA cleavage of these mononuclear complexes with different central metals were subsequently studied, which showed that copper complex was better catalyst in the DNA cleavage process than zinc and cobalt complexes. The effects of reaction time, concentration of complexes were also investigated. The results indicated that the copper(II) complexes could catalyze the cleavage of supercoiled DNA (pUC 19 plasmid DNA) (Form I) under physiological conditions to produce selectively nicked DNA (Form II, no Form III produced) with high yields. The mechanism of the cleavage process was also studied.

  1. Structures and Magnetic Properties of Monomeric Copper(II) Bromide Complexes with a Pyridine-Containing Tridentate Schiff Base

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Sung Kwon [Chungnam National Univ., Daejeon (Korea, Republic of); Yong, Soon Jung; Song, Young Kwang; Kim, Young Inn [Pusan National Univ., Busan (Korea, Republic of)

    2013-12-15

    Two novel copper(II) bromide complexes with pyridine containing Schiff base ligands, Cu(pmed)Br{sub 2} and Cu(dpmed)Br{sub 2} where pmed = N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (pmed) and dpmed = N,N-diethyl-N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (dpmed) were synthesized and characterized using Xray single crystal structure analysis, optical and magnetic susceptibility measurements. Crystal structural analysis of Cu(pmed)Br{sub 2} showed that the copper(II) ion has a distorted square-pyramidal geometry with the trigonality index of τ = 0.35 and two intermolecular hydrogen bonds, which result in the formation of two dimensional networks in the ab plane. On the other hand, Cu(dpmed)Br{sub 2} displayed a near square-pyramidal geometry with the value of τ = 0.06. In both compounds, the NNN Schiff base and one Br atom occupy the basal plane, whereas the fifth apical position is occupied by the other Br atom at a greater Cu-Br apical distance. The reported complexes show g{sub Π} > g{sub Τ} > 2.0023 with a d{sub x2-y2} ground state and a penta-coordinated square pyramidal geometry. Variable temperature magnetic susceptibility measurements showed that the developed copper(II) complexes follow the Curie-Weiss law, that is there are no magnetic interactions between the copper(II) ions since the Cu--Cu distance is too far for magnetic contact.

  2. Synthesis, micellization behavior, antimicrobial and intercalative DNA binding of some novel surfactant copper(II) complexes containing modified phenanthroline ligands.

    Science.gov (United States)

    Nagaraj, Karuppiah; Ambika, Subramanian; Rajasri, Shanmugasundaram; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

    2014-10-01

    The novel surfactant copper(II) complexes, [Cu(ip)2DA](ClO4)21, [Cu(dpqc)2DA](ClO4)22, [Cu(dppn)2DA](ClO4)23, where ip=imidazo[4,5-f][1,10]phenanthroline, dpqc=dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine, dppn=benzo[1]dipyrido[3,2-a':2',3'-c]phenazine and DA-dodecylamine, were synthesized and characterized by physico-chemical and spectroscopic methods. In these complexes 1-3, the geometry of copper metal ions was described as square pyramidal. The critical micelle concentration (CMC) value of these surfactant copper(II) complexes in aqueous solution was found out from conductance measurements. Specific conductivity data at different temperatures served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔGm°, ΔHm° and ΔSm°). The binding interaction of these complexes with DNA (calf thymus DNA) in Tris buffer was studied by physico-chemical techniques. In the presence of the DNA UV-vis spectrum of complexes showed red shift of the absorption band along with significant hypochromicity indicating intercalation of our complexes with nucleic acids. Competitive binding study with ethidium bromide (EB) shows that the complexes exhibit the ability to displace the nucleic acid-bound EB indicating that the complexes bind to nucleic acids in strong competition with EB for the intercalative binding site. Observed changes in the circular dichoric spectra of DNA in the presence of surfactant complexes support the strong binding of complexes with DNA. CV results also confirm this mode of binding. Some significant thermodynamic parameters of the binding of the titled complexes to DNA have also been determined. The results reveal that the extent of DNA binding of 3 was greater than that of 1 and 2. The antibacterial and antifungal screening tests of these complexes have shown good results compared to its precursor chloride complexes.

  3. 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)......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)...

  4. Effect of copper-sulphur bond on the DNA photo-cleavage activity of 2-(methylthio)ethylpyridine-2-carbaldimine copper(II) complexes

    Indian Academy of Sciences (India)

    Tarkeshwar Gupta; Ashis K Patra; Shanta Dhar; Munirathinam Nethaji; Akhil R Chakravarty

    2005-03-01

    The binding and photo-induced DNA cleavage activity of a binary complex [CuL2](ClO4)2 (1) and the in situ generated ternary complexes [CuLB](ClO4)2 from 1 (B: 1,10-phenanthroline, phen, 2; dipyrido[3,2-: 2',3'-]quinoxaline, dpq, 3) are studied, where L is a N2S-donor tridentate Schiff base 2-(methylthio)ethylpyridine-2-carbaldimine. Complex 1, structurally characterized by X-ray diffraction study, has six-coordinate meridional geometry showing CuN4S2 coordination. The Cu-N bond lengths are in the range of 1.968(3) to 2.158(4) Å. The Cu-S bond lengths of 2.599(2) and 2.705(2) Å are significantly long indicating weak covalent interaction between copper and sulphur atoms. The thiomethyl groups are cis to each other giving S-Cu-S angle of 75.82(5)°. The Cu-N(pyridyl) bond distances are longer than the Cu-N(imine) bonds. The complexes are redox active and display a quasi-reversible cyclic voltammetric response assignable to the Cu(II)/Cu(I) couple near 0.0 V vs SCE in DMF-Tris buffer (1 : 4 /) using 0.1 M KCl as supporting electrolyte. Electronic spectra of the complexes show a - band in the range 630 to 700 nm in DMF along with higher energy charge transfer bands. While complex 1 is a poor binder to DNA, the ternary complexes show good DNA binding propensity. The photo-nuclease activity of 1-3 is studied using UV and visible wavelengths. The DNA cleavage activity at 365 nm follows the order: 3 > 2 > 1. The cleavage reaction involves the formation of singlet oxygen as the reactive species in a type-II process.

  5. A copper complex supported by an N2S-tridentate ligand inducing efficient heterolytic O-O bond cleavage of alkylhydroperoxide.

    Science.gov (United States)

    Tano, Tetsuro; Mieda, Kaoru; Sugimoto, Hideki; Ogura, Takashi; Itoh, Shinobu

    2014-03-28

    We have recently reported a copper(II)-superoxide complex supported by an N3-tridentate ligand (L(N3)), which exhibits a similar structure and reactivity to those of a putative reactive intermediate involved in the catalytic reactions of copper monooxygenases such as peptidylglycine α-hydroxylating monooxygenase (PHM) and dopamine β-monooxygenase (DβM). In this study, we have synthesised and characterised copper complexes supported by a related sulphur-containing ligand (L(N2S)) to get insight into the notable electronic effect of the sulphur donor atom in the reaction with cumene hydroperoxide, inducing efficient heterolytic O-O bond cleavage.

  6. Redox cycling of copper-amyloid β 1-16 peptide complexes is highly dependent on the coordination mode.

    Science.gov (United States)

    Trujano-Ortiz, Lidia G; González, Felipe J; Quintanar, Liliana

    2015-01-05

    Copper (Cu)-amyloid β (Aβ) interactions play a role in the etiology of Alzheimer's disease. This work presents a spectroscopic and electrochemical study of two physiologically relevant Aβ-Cu(II) complexes, as a function of pH and relative Cu-Aβ(1-16) concentrations. Our results reveal that these coordination modes display distinct redox behaviors and provide experimental evidence for the existence of an intermediate Cu(I) species. A mechanism for the redox cycling of these complexes is proposed, providing further insight into the redox relevance of Aβ-Cu interactions.

  7. Experimental and theoretical study on a new copper(II) complex derived from pyridoxal hydrochloride and 1,2-diaminocyclohexane

    Science.gov (United States)

    Mandal, Senjuti; Sikdar, Yeasin; Sanyal, Ria; Goswami, Sanchita

    2017-01-01

    In this work, guided by a pyridoxal derived Schiff base ligand, H2PydChda [5-Hydroxymethyl-4-({2-[5-hydroxymethyl-2-methylpyridin-3-hydroxy-4-ylethylene)-amino]-cyclohexylimino}-methyl)-2-methylpyridin-3-ol], a new copper(II) complex, [Cu(PydChda-2H+)]2·4ClO4·2H2O was constructed and structurally characterized by single crystal X-ray diffraction study. DFT calculations further substantiate the experimental features. Additionally, experiments were performed to demonstrate the accessibility to any enzymatic activity and the complex provides positive response for phosphatase activity towards 4-NPP substrate.

  8. Mixed-ligand copper(II) phenolate complexes: Synthesis, spectral characterization, phosphate-hydrolysis, antioxidant, DNA interaction and cytotoxic studies

    Science.gov (United States)

    Gurumoorthy, Perumal; Mahendiran, Dharmasivam; Prabhu, Durai; Arulvasu, Chinnasamy; Rahiman, Aziz Kalilur

    2015-01-01

    A series of phenol-based mixed-ligand copper(II) complexes of the type [CuL1-4(diimine)] (1-8), where L1-4 = N1,N2-bis(5-substituted-2-hydroxybenzylidene)-1,2-ethylene/phenylenediimine and diimine = 2,2‧-bipyridyl (bpy) or 1,10-phenanthroline (phen), have been isolated and fully characterized by analytical and spectral techniques. Electronic spectra of complexes suggest Cu(II) cation has a d9 electronic configuration, adopting distorted octahedral geometry with axial elongation, due to Jahn-Teller effect. Electrochemical studies of complexes evidenced one-electron irreversible reduction wave in the cathodic region. The observed rate constant (k) values for the hydrolysis of 4-nitrophenylphosphate (4-NPP) are in the range of 0.25-3.82 × 10-2 min-1. The obtained room temperature magnetic moment values (1.79-1.90 BM) lies within the range observed for octahedral copper(II) complexes. Antioxidant studies revealed that these complexes possess considerable radical scavenging potency against DPPH. The binding studies of complexes with calf thymus DNA (CT-DNA) revealed intercalation with minor-groove binding, and the complex 4 exhibits highest binding activity than the other complexes. The cleavage activity on supercoiled pBR322 DNA revealed the involvement of hydroxyl radical and singlet-oxygen as reactive oxygen species, and complexes encourage binding to minor-groove. Further, the cytotoxicity of complex 4 on human hepatocellular liver carcinoma HepG2 cell line implies the cell death through apoptosis.

  9. DNA cleavage, structural elucidation and anti-microbial studies of three novel mixed ligand Schiff base complexes of copper(II

    Directory of Open Access Journals (Sweden)

    N. RAMAN

    2007-10-01

    Full Text Available Three new copper complexes of mixed ligands derived from Schiff bases (condensation of p-aminoacetanilide and substituted benzaldehydes with 1,10-phenanthroline have been synthesized and characterized by elemental analysis, IR, UV–Vis, magnetic moments, conductivity and electrochemical measurements. The spectral techniques suggest that all the copper complexes exhibit octahedral geometry. The low electrical conductance of the complexes supports their neutral nature. The monomeric nature of the complexes was assessed from their magnetic susceptibility values. The in vitro biological screening effects of the investigated compounds were tested against the bacteria Escherichia coli, Staphylococcus aureus, and Salmonella typhi and the fungi Rhizopus stolonifer and Candida albicans by the serial dilution method. A comparative study of the MIC values of the Schiff bases and their copper complexes indicates that the metal complexes exhibited higher antibacterial activity than the free ligands. The DNA cleavage ability of the complexes was monitored by the gel electrophoresis technique. It was found that electron withdrawing group substituted copper complex had higher DNA cleavage activity than the other copper complexes.

  10. 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.

  11. Can Dynamics Be Responsible for the Complex Multipeak Infrared Spectra of NO Adsorbed to Copper(II) Sites in Zeolites?

    Science.gov (United States)

    Göltl, Florian; Sautet, Philippe; Hermans, Ive

    2015-06-26

    Copper-exchanged SSZ-13 is a very efficient material in the selective catalytic reduction of NO(x) using ammonia (deNO(x)-SCR) and characterizing the underlying distribution of copper sites in the material is of prime importance to understand its activity. The IR spectrum of NO adsorbed to divalent copper sites are modeled using ab initio molecular dynamics simulations. For most sites, complex multi-peak spectra induced by the thermal motion of the cation as well as the adsorbate are found. A finite temperature spectrum for a specific catalyst was constructed, which shows excellent agreement with previously reported data. Additionally these findings allow active and inactive species in deNO(x)-SCR to be identified. To the best of our knowledge, this is the first time such complex spectra for single molecules adsorbed to single active centers have been reported in heterogeneous catalysis, and we expect similar effects to be important in a large number of systems with mobile active centers.

  12. Bioelectrochemical recovery of ammonia-copper(II) complexes from wastewater using a dual chamber microbial fuel cell.

    Science.gov (United States)

    Zhang, Li-Juan; Tao, Hu-Chun; Wei, Xue-Yan; Lei, Tao; Li, Jin-Bo; Wang, Ai-Jie; Wu, Wei-Min

    2012-11-01

    The cathodic reduction of complex-state copper(II) was investigated in a dual chamber microbial fuel cell (MFC). The inner resistance of MFC system could be reduced in the presence of ionizing NH(4)(+), however, mass transfer was hindered at higher ammonia concentration. Thermodynamic and electrochemical analyses indicated that the processes of complex dissociation and copper reduction were governed by the ratio of T[Cu]:T[NH(3)] and the pH of solution. The reduction of Cu(NH(3))(4)(2+) could be achieved via two possible pathways: (1) releasing Cu(2+) from Cu(NH(3))(4)(2+), then reducing Cu(2+) to Cu or Cu(2)O and (2) Cu(NH(3))(4)(2+) accepting an electron and forming Cu(NH(3))(2)(+), and depositing as Cu or Cu(2)O consequently. At initial concentration of 350 mg T[Cu] L(-1), copper removal efficiency of 96% was obtained at pH=9.0 within 12 h (with △Cu/△COD=1.24), 84% was obtained at pH=3.0 within 8 h (with △Cu/△COD=1.72). Cu(NH(3))(4)(2+) was reduced as polyhedral deposits on the cathode. Copyright © 2012 Elsevier Ltd. All rights reserved.

  13. The Synthesis of a Coumarin Carbohydrazide Dinuclear Copper Complex Based Fluorescence Probe and Its Detection of Thiols.

    Science.gov (United States)

    He, Guangjie; Li, Jing; Yang, Lu; Hou, Chunhua; Ni, Tianjun; Yang, Zhijun; Qian, Xinlai; Li, Changzheng

    2016-01-01

    Small-molecule thiols, such as cysteine (CYS) and glutathione (GSH), are essential for maintaining the cellular redox environment and play important roles in regulating various cellular physiological functions. A fluorescence probe (compound 1-Cu2+) for thiols based on coumarin carbohydrazide dinuclear copper complex was developed. Compound 1 was synthesized from the reaction of 7-(diethylamino)-2-oxo-2H-chromene-3-carbohydrazide with 4-tert-butyl-2,6- diformylphenol. Accordingly, the copper complex (compound 1-Cu2+) was prepared by mixing compound 1 with 2 equivalents copper ions. Compound 1 had strong fluorescence while compound 1-Cu2+ hardly possessed fluorescence owing to the quenching nature of paramagnetism Cu2+ to the fluorescence molecule excited state. However, the fluorescence intensity of compound 1-Cu2+ was increased dramatically after the addition of thiol-containing amino acids, but not the other non-sulfhydryl amino acids. UV-vis absorption and fluorescence spectra indicated that compound 1-Cu2+ had good selectivity and sensitivity for thiols such as glutathione in CH3CN:H2O (3:2, v/v) PBS solution. The fluorescence imaging experiments implied that compound 1-Cu2+ has potential application in thiol-containing amino acids detection in living cells.

  14. Complexation and Toxicity of Copper in Higher Plants. I. Characterization of Copper Accumulation, Speciation, and Toxicity in Crassula helmsii as a New Copper Accumulator1[W][OA

    Science.gov (United States)

    Küpper, Hendrik; Götz, Birgit; Mijovilovich, Ana; Küpper, Frithjof C.; Meyer-Klaucke, Wolfram

    2009-01-01

    The amphibious water plant Crassula helmsii is an invasive copper (Cu)-tolerant neophyte in Europe. It now turned out to accumulate Cu up to more than 9,000 ppm in its shoots at 10 μm (=0.6 ppm) Cu2+ in the nutrient solution, indicating that it is a Cu hyperaccumulator. We investigated uptake, binding environment, and toxicity of Cu in this plant under emerged and submerged conditions. Extended x-ray absorption fine structure measurements on frozen-hydrated samples revealed that Cu was bound almost exclusively by oxygen ligands, likely organic acids, and not any sulfur ligands. Despite significant differences in photosynthesis biochemistry and biophysics between emerged and submerged plants, no differences in Cu ligands were found. While measurements of tissue pH confirmed the diurnal acid cycle typical for Crassulacean acid metabolism, Δ13C measurements showed values typical for regular C3 photosynthesis. Cu-induced inhibition of photosynthesis mainly affected the photosystem II (PSII) reaction center, but with some unusual features. Most obviously, the degree of light saturation of electron transport increased during Cu stress, while maximal dark-adapted PSII quantum yield did not change and light-adapted quantum yield of PSII photochemistry decreased particularly in the first 50 s after onset of actinic irradiance. This combination of changes, which were strongest in submerged cultures, shows a decreasing number of functional reaction centers relative to the antenna in a system with high antenna connectivity. Nonphotochemical quenching, in contrast, was modified by Cu mainly in emerged cultures. Pigment concentrations in stressed plants strongly decreased, but no changes in their ratios occurred, indicating that cells either survived intact or died and bleached quickly. PMID:19641032

  15. Complexation and toxicity of copper in higher plants. I. Characterization of copper accumulation, speciation, and toxicity in Crassula helmsii as a new copper accumulator.

    Science.gov (United States)

    Küpper, Hendrik; Götz, Birgit; Mijovilovich, Ana; Küpper, Frithjof C; Meyer-Klaucke, Wolfram

    2009-10-01

    The amphibious water plant Crassula helmsii is an invasive copper (Cu)-tolerant neophyte in Europe. It now turned out to accumulate Cu up to more than 9,000 ppm in its shoots at 10 microm (=0.6 ppm) Cu(2+) in the nutrient solution, indicating that it is a Cu hyperaccumulator. We investigated uptake, binding environment, and toxicity of Cu in this plant under emerged and submerged conditions. Extended x-ray absorption fine structure measurements on frozen-hydrated samples revealed that Cu was bound almost exclusively by oxygen ligands, likely organic acids, and not any sulfur ligands. Despite significant differences in photosynthesis biochemistry and biophysics between emerged and submerged plants, no differences in Cu ligands were found. While measurements of tissue pH confirmed the diurnal acid cycle typical for Crassulacean acid metabolism, Delta(13)C measurements showed values typical for regular C3 photosynthesis. Cu-induced inhibition of photosynthesis mainly affected the photosystem II (PSII) reaction center, but with some unusual features. Most obviously, the degree of light saturation of electron transport increased during Cu stress, while maximal dark-adapted PSII quantum yield did not change and light-adapted quantum yield of PSII photochemistry decreased particularly in the first 50 s after onset of actinic irradiance. This combination of changes, which were strongest in submerged cultures, shows a decreasing number of functional reaction centers relative to the antenna in a system with high antenna connectivity. Nonphotochemical quenching, in contrast, was modified by Cu mainly in emerged cultures. Pigment concentrations in stressed plants strongly decreased, but no changes in their ratios occurred, indicating that cells either survived intact or died and bleached quickly.

  16. Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine.

    Science.gov (United States)

    Barreto, Wagner J; Barreto, Sônia R G; Ando, Rômulo A; Santos, Paulo S; DiMauro, Eduardo; Jorge, Thiago

    2008-12-15

    The anionic complexes [Cu(L(1-))3](1-), L(-)=dopasemiquinone or L-dopasemiquinone, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the nuCC+nuCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g=2.0005 and g=2.0923, and for Cu(II) with g=2.008 and g=2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease.

  17. Synthesis, characterization, plasmid cleavage and cytotoxicity of cancer cells by a copper(II) complex of anthracenyl-terpyridine.

    Science.gov (United States)

    Kumar, Amit; Chinta, Jugun Prakash; Ajay, Amrendra Kumar; Bhat, Manoj Kumar; Rao, Chebrolu P

    2011-11-01

    Metallo-organic compounds are interesting to study for their antitumor activity and related applications. This paper deals with the syntheses, characterization, structure determination of a copper complex of anthracenyl terpyridine (1) and its plasmid cleavage and cytotoxicity towards different cancer cell lines. The complex binds CT-DNA through partial intercalation mode. The plasmid cleavage studies carried out using pBR322 and pUC18 resulted in the formation of all the three forms of the plasmid DNA. Plasmid cleavage studies carried out with a non-redoxable Zn(2+) complex (2) supported the role of the redox activity of copper in 1. The complex 1 showed remarkable antiproliferative activity against cancer cell lines, viz., cervical (HeLa, SiHa, CaSki), breast (MCF-7), liver (HepG2) and lung (H1299). A considerable lowering was observed in the IC(50) values of HPV-infected (viz., HeLa, SiHa, CaSki) vs. non-HPV-infected cell lines (MCF-7, HepG2, H1299). Antiproliferative activity of 1 was found to be much higher than the carboplatin when treated with the same cell lines. Incubation of the cells with 1 results in granular structures only with the HPV-infected cells and not with others as studied by phase contrast and fluorescence microscopy. The lower IC(50) value observed in case of 1 with HPV-infected cell lines may be correlated with the involvement of HPV oncoprotein. The role of HPV has been further augmented by transfecting the MCF-7 cells (originally not possessing HPV copy) with e6 oncoprotein cDNA. To our knowledge this is the first copper complex that causes cell death by interacting with HPV oncoprotein followed by exhibition of remarkable antiproliferative activity.

  18. Synthesis and Crystal Structure of a Copper(Ⅱ) Complex with Benzilic Acid and 1,10-Phenanthroline

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A new complex [Cu(phen)3][(C6H5)2C(OH)COO]2·6H2O was prepared by self-assembly of benzilic acid, 1,10-phenanthroline (phen), and copper perchlorate.It crystallizes in triclinic, space group P1-, with a = 1.14661(17), b = 1.6455(2), c = 1.6457(2) nm, α = 74.779(2),β= 74.904(3), γ= 84.424(3)°,V= 2.8914(7) nm3, Dc = 1.340 g/cm3, Z = 2, F(000) = 1218, GOOF= 1.018, the final R = 0.0643 and wR= 0.1633.The crystal structure shows that the copper ion is coordinated with six nitrogen atoms from six 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry.

  19. 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.

  20. Interaction with DNA and different effect on the nucleus of cancer cells for copper(II) complexes of N-benzyl di(pyridylmethyl)amine.

    Science.gov (United States)

    Chen, Qiu-Yun; Fu, Hai-Jian; Zhu, Wei-Hua; Qi, Yan; Ma, Zheng-Ping; Zhao, Kai-Di; Gao, Jing

    2011-05-01

    Three new copper(II) complexes of N-benzyl di(pyridylmethyl)amine (phdpa) were synthesized and characterized by spectroscopic methods. The interaction between CT-DNA and the complexes was studied by UV and fluorescence titration methods. It was found that the complex [(phdpa)Cu(H(2)O)Ac)](Ac), with the non-planar aromatic heterocyclic ring ligand (phdpa), showed good anticancer properties and could cause the fragmentation of the nucleus, although its interaction with CT-DNA was weaker than that of 1,10-phenanthroline (phen)-based copper(II) complexes. The anticancer activities of copper(II) complexes with phdpa and phen based ligands are correlated to their binding constants with DNA, but phen-based copper(II) complexes did not cause the nucleus fragmentation of HeLa cells. [(phdpa)Cu(H(2)O)Ac)](Ac) can noticeably decrease the oxygen content of a culture solution and of HeLa cells, which make it a new nucleus and oxygen related anticancer copper(II) complex. Information obtained here would be helpful in the design of new antitumor complexes in oxidative therapy.

  1. Reaction of a copper(II)-nitrosyl complex with hydrogen peroxide: putative formation of a copper(I)-peroxynitrite intermediate.

    Science.gov (United States)

    Kalita, Apurba; Kumar, Pankaj; Mondal, Biplab

    2012-05-14

    The reaction of a Cu(II)-nitrosyl complex (1) with hydrogen peroxide at -20 °C in acetonitrile results in the formation of the corresponding Cu(I)-peroxynitrite intermediate. The reduction of the Cu(II) center was monitored by UV-visible spectroscopic studies. Formation of the peroxynitrite intermediate has been confirmed by its characteristic phenol ring nitration reaction as well as isolation of corresponding Cu(I)-nitrate (2). On air oxidation, 2 resulted in the corresponding Cu(II)-nitrate (3). Thus, these results demonstrate a possible decomposition pathway for H(2)O(2) and NO through the formation of a peroxynitrite intermediate in biological systems.

  2. Copper(II) complexes of bis(amino amide) ligands: effect of changes in the amino acid residue.

    Science.gov (United States)

    Martí, Inés; Ferrer, Armando; Escorihuela, Jorge; Burguete, M Isabel; Luis, Santiago V

    2012-06-14

    A family of ligands derived from bis(amino amides) containing aliphatic spacers has been prepared, and their protonation and stability constants for the formation of Cu(2+) complexes have been determined potentiometrically. Important differences are associated to both the length of the aliphatic spacer and the nature of the side chains derived from the amino acid. In general, ligands containing aliphatic side chains display higher basicities as well as stability constants with Cu(2+). In the same way, basicities and stability constants tend to increase when decreasing the steric hindrance caused by the corresponding side-chain. FT-IR, UV-vis and ESI-MS were used for analyzing the complex species detected in the speciation diagram. UV-vis studies showed the presence of different coordination environments for the copper(II) complexes. Complexes with different stoichiometries can be formed in some instances. This was clearly highlighted with the help of ESI-MS experiments.

  3. Superoxide dismutase activity of the naturally occurring human serum albumin-copper complex without hydroxyl radical formation.

    Science.gov (United States)

    Kato, Ryunosuke; Akiyama, Matofusa; Kawakami, Hiroyoshi; Komatsu, Teruyuki

    2014-01-01

    The superoxide radical anion (O2(.-)) is biologically toxic and contributes to the pathogenesis of various diseases. Here we describe the superoxide dismutase (SOD) activity of human serum albumin (HSA) complexed with a single Cu(II) ion at the N-terminal end (HSA-Cu complex). The structure of this naturally occurring copper-coordinated blood serum protein has been characterized by several physicochemical measurements. The O2(.-) dismutation ability of the HSA-Cu (1:1) complex is almost the same as that of the well-known SOD mimics, such as Mn(III) -tetrakis(N-methylpyridinium)porphyrin. Interestingly, the HSA-Cu complex does not induce a subsequent Fenton reaction to produce the hydroxyl radical (OH(.)), which is one of the most harmful reactive oxygen species.

  4. Structural characterization and biological evaluation of a clioquinol-ruthenium complex with copper-independent antileukaemic activity.

    Science.gov (United States)

    Gobec, Martina; Kljun, Jakob; Sosič, Izidor; Mlinarič-Raščan, Irena; Uršič, Matija; Gobec, Stanislav; Turel, Iztok

    2014-06-28

    In this study, we present the synthesis, biological characterization, and first crystal structure of an organometallic-clioquinol complex. Combining ruthenium with the established apoptotic agent and 8-hydroxyquinoline derivative, clioquinol, resulted in a complex that induces caspase-dependent cell death in leukaemia cells. This activity is copper independent and is improved compared to the parent compound, clioquinol. The study of the mode of action reveals that this clioquinol-ruthenium complex does not intercalate between DNA base pairs. Additionally, this clioquinol-ruthenium complex shows proteasome-independent inhibition of the NFκB signalling pathway, with no effects on cell-cycle distribution. These data suggest a mechanism of action that involves a target profile that is different from that for clioquinol alone.

  5. Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process.

    Science.gov (United States)

    Molinari, Raffaele; Poerio, Teresa; Argurio, Pietro

    2008-01-01

    The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.

  6. Different types of copper complexes with the quinolone antimicrobial drugs ofloxacin and norfloxacin: structure, DNA- and albumin-binding.

    Science.gov (United States)

    Živec, Petra; Perdih, Franc; Turel, Iztok; Giester, Gerald; Psomas, George

    2012-12-01

    Three novel copper(II) complexes with the second-generation quinolone antibacterial agents norfloxacin (nfH) and ofloxacin (ofloH) have been synthesized resulting in the complexes [Cu(nfH)(phen)Cl]Cl·5H(2)O (1·5H(2)O), [Cu(nfH)(2)]Cl(2)·6H(2)O (2·6H(2)O) and [Cu(II)(ofloH)(2)][(Cu(I)Cl(2))(2)] (3), respectively. The crystal structures of the complexes have been determined by X-ray crystallography revealing that the quinolones act as bidentate ligands coordinated to Cu(II) atom through the pyridone oxygen and a carboxylato oxygen. UV study of the interaction of the quinolones and the complexes with calf-thymus DNA (CT DNA) has shown that they can bind to CT DNA with [Cu(II)(ofloxacin)(2)][(Cu(I)Cl(2))(2)] exhibiting the highest binding constant to CT DNA. The cyclic voltammograms of the complexes in the presence of CT DNA solution have shown that the interaction of the complexes with CT DNA is mainly through electrostatic binding. DNA solution viscosity measurements have shown that the interaction of the compounds with CT DNA by classical intercalation may be ruled out. Competitive studies with ethidium bromide (EB) indicate that the complexes can partially displace the DNA-bound EB suggesting low to moderate competition with EB. Norfloxacin, ofloxacin and their copper complexes exhibit good binding propensity to human or bovine serum albumin protein having relatively high binding constant values. Copyright © 2012 Elsevier Inc. All rights reserved.

  7. One-dimensional Copper(Ⅱ) Complex Constructed with Nitrate Counter-anion as Bitopic Connector

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Coordination polymer {[Cu(NPPCA)3(NO3)(H2O)]·NO3·H2O}n 1 ( NPPCA = N-(4′-nitrophenyl)-4-pyridinecarboxamide) has been synthesized by the reaction of NPPCA with copper(Ⅱ) nitrate in ethanol-water solution and characterized by X-ray diffraction. 1 crystallizes in the monoclinic space, group P21/n, a = 17.341(6)A, b = 6.744(2) (A), c = 34.555(12)(A), β =100.493(6)°, V = 3974(2) (A)3, Z = 4. Each copper(Ⅱ) ion has a distorted octahedral coordination geometry. Nitrate anion adopts the unusual coordination mode linking two adjacent copper(Ⅱ)ions to form a one-dimensional coordination polymer and these chains are further linked by noncovalent interactions.

  8. Copper(II) complexes with 2-pyridineformamide-derived thiosemicarbazones: Spectral studies and toxicity against Artemia salina

    Science.gov (United States)

    Ferraz, Karina O.; Wardell, Solange M. S. V.; Wardell, James L.; Louro, Sonia R. W.; Beraldo, Heloisa

    2009-07-01

    The copper(II) complexes [Cu(H2Am4DH)Cl 2] ( 1), [Cu(H2Am4Me)Cl 2] ( 2), [Cu(H2Am4Et)Cl 2] ( 3) and [Cu(2Am4Ph)Cl] ( 4) with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives were studied by means of infrared and EPR spectral techniques. The crystal structure of 4 was determined. The studied compounds proved to be toxic to Artemia salina, suggesting that they could present cytotoxic activity against solid tumors. Among the free thiosemicarbazones H2Am4Ph presented higher toxicity than all other compounds, which showed comparable effects. In the case of complexes 2 and 3 toxicity is probably attributable to the complex as an entity or to a synergistic effect involving the thiosemicarbazone and copper. H2Am4Ph and complexes 2 and 3 revealed to be the most promising compounds as potential antineoplasic agents.

  9. Hydrolytic protein cleavage mediated by unusual mononuclear copper(II) complexes: X-ray structures and solution studies.

    Science.gov (United States)

    de Oliveira, Mauricio C B; Scarpellini, Marciela; Neves, Ademir; Terenzi, Hernán; Bortoluzzi, Adailton J; Szpoganics, Bruno; Greatti, Alessandra; Mangrich, Antônio S; de Souza, Emanuel M; Fernandez, Pablo M; Soares, Marcia R

    2005-02-21

    The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes.

  10. Preparation and Standard Formation Enthalpy of 2-Amino-4,6-dimethylpyrimidine and Its Related Complexes of Copper

    Institute of Scientific and Technical Information of China (English)

    CHEN San-ping; WEI Qing; JIAO Bao-juan; GAO Sheng-li

    2003-01-01

    The complexes of hydrous copper chloride and copper nitrate with 2-amino-4,6-dimethylpyrimidine(ADMP) were prepared via reflux in alcohol. The compositions of the complexes were identified as Cu(ADMP)2Cl2*2H2O(b) and Cu(ADMP)(NO3)2*H2O(c) by chemical and elemental analyses. The complexes were characterized by IR, XPS, 1H NMR and TG-DTG techniques. The constant-volume combustion energies of ADMP and the complexes, ΔcE, were determined by a precise rotating-bomb calorimeter at 298.15 K. They were (-3664.53±1.18), (-4978.47±2.72) and (-1696.70±1.36) Kj/mol, respectively. Their standard enthalpies of combustion, ΔcH0m, and standard enthalpies of formation, ΔfH0m, were calculated to be (-3666.39±1.18), (-4977.23±2.72), (-1691.12±1.36) Kj/mol and (19.09±1.43), (-2041.80±3.29), (-2397.24±1.65) Kj/mol, respectively.

  11. Guanine-containing copper(II) complexes: synthesis, X-ray structures and magnetic properties.

    Science.gov (United States)

    Mastropietro, Teresa F; Armentano, Donatella; Grisolia, Ettore; Zanchini, Claudia; Lloret, Francesc; Julve, Miguel; De Munno, Giovanni

    2008-01-28

    Three new compounds of formula {[Cu(gua)(H(2)O)(3)](BF(4))(SiF(6))(1/2)}(n) (1), {[Cu(gua)(H(2)O)(3)](CF(3)SO(3))(2).H(2)O}(n) (2) and [Cu(gua)(2)(H(2)O)(HCOO)]ClO(4).H(2)O.1/2HCOOH] (3) [gua = 2-amino-1H-purin-6(9H)-one] showing the unprecedented coordination of neutral guanine, have been synthesised and structurally characterized. The structures of the compounds 1 and 2 contain uniform copper(II) chains of formula [Cu(gua)(H(2)O)(3)](n)(2n+), where the copper atoms are bridged by guanine ligands coordinated via N(3) and N(7). The electroneutrality is achieved by uncoordinated tetrafluoroborate and hexafluorosilicate (1) and triflate (2). Each copper atom in 1 and 2 is five-coordinated in a distorted square pyramidal environment: two water molecules in trans positions and the N(3) and N(7a) nitrogen atoms of two guanine ligands build the basal plane whereas a water molecule fills the axial position. The values of the copper-copper separation across the bridging guanine ligand are 7.183(1) (1) and 7.123(1) A (2). is an ionic salt whose structure is made up of mononuclear [Cu(gua)(2)(H(2)O)(HCOO)](+) cations and perchlorate anions plus water and formic acid as crystallization molecules. The two guanine ligands in the cation are coordinated to the copper centre through the N(9) atom. The copper atom in 3 is four-coordinated with two monodentate guanine molecules in the trans position, a water molecule and a monodenate formate ligand building a quasi square planar surrounding. Magnetic susceptibility measurements for 1 and 2 in the temperature range 1.9-300 K show the occurrence of significant intrachain antiferromagnetic interactions between the copper(ii) ions across the guanine bridge [J = -9.6(1) (1) and -10.3(1) cm(-1) (2) with H = -J summation operator(i)S(i).S(i+1)].

  12. The development of copper(Ⅱ) complexes matter anticancer activity%铜(Ⅱ)配合物抗癌活性研究进展

    Institute of Scientific and Technical Information of China (English)

    葛蓓蕾; 徐霞; 陈小让

    2013-01-01

    金属配合物抗癌药物的研究已经成为抗肿瘤药物研究的热点之一。越来越多的研究表明铜(Ⅱ)配合物具有较好的抗癌活性。本文在参阅大量文献的基础上,对铜(Ⅱ)配合物的结构特征﹑和铂(Ⅱ)配合物的活性对比、与DNA的作用﹑与氨基酸的共价作用及对癌细胞的诱导凋亡作用等方面作了介绍。%Metal complexes matter anticancer drugs has become one hotspot of studies on anticancer drugs. The growing number of studies show that the copper(Ⅱ) complexes with good anti-cancer activity. On the basis of the extensive literature,This paper mainly introduced the structural characteristics of the copper( Ⅱ ) complexes,the activity contrast between copper( Ⅱ ) complexes and platinum( Ⅱ ) complexes,the role of copper( Ⅱ ) complexes with DNA,copper( Ⅱ ) complexes with the covalent interaction of matter with amino acids and the induction of apoptosis in the cancer cells.

  13. Syntheses and Crystal Structures of Mono- and Binuclear Copper( Ⅱ ) Mixed-ligand Complexes Involving Schiff Base

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    The mononuclear copper(Ⅱ) complex [Cu(L)(2-AP)] 1 and binuclear copper(Ⅱ)complex [Cu(L)(py)]2 2 (L = C1oH1 1O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine)with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1: orthorhombic, space group Pbca with a = 11.921(4), b = 15.816(6), c = 17.076(6) (A), V=3219.7(19) (A)3, C15H17CuN3O5S, Z = 8, Mr = 414.92, Dc = 1.712 g/cm3,μ(MoKα) = 1.520 mm-1,F(000) = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I > 2σ(I);and crystal data for 2: monoclinic, space group P21/c with a = 7.929(3), b = 17.038(5), c = 11.734(4)(A), β = 98.162(6)°, V = 1569.1 (9) (A)3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm3, F(000)= 820,μ(MoKα) = 1.554 mm-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections (I > 2o(I)). The molecular structure of complex 1 consists of one tetra-coordinated Cu(Ⅱ) atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper(Ⅱ) structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.

  14. Synthesis and structural studies of copper(II) complex supported by -ONNO- tetradentate ligand:Efficient catalyst for the ring-opening polymerization of lactide

    Institute of Scientific and Technical Information of China (English)

    Anita Routaray; Nibedita Nath; Somanath Mantri; Tungabidya Maharan; Alekha Kumar Sutar

    2015-01-01

    The –ONNO– tetradentate Schiff base ligandN,N’-bis(2-hydroxy-3-methoxybenzaldehyde)benzene-1,2-diamine (HMBBD) has been synthesized. The ligand was attached to copper (Cu-HMBBD) in methanol under N2 atmosphere to give a mononuclear complex. The reactivity of this complex in the ring-opening polymerization (ROP) of lactide has been studied. The complex has a square planner geometry, as determined by X-ray diffraction studies. The copper complex is highly active towards the ring-opening polymerization of lactide, and the rate of polymerization is heavily dependent on the initiator used. The copper complex allows controlled ring-opening polymerization, as shown by the linear relationship between the percentage conversion and the number average molecular weight. Based on the literature, a mechanism for the ROP of lactide has been proposed.

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

    Directory of Open Access Journals (Sweden)

    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.

  16. Halochromism, ionochromism, solvatochromism and density functional study of a synthesized copper(II) complex containing hemilabile amide derivative ligand

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Reisi, Neda

    2015-03-01

    This study investigates chromotropism of newly synthesized 3,3‧-(ethane-1,2-diylbis(benzylazanediyl))dipropanamide copper(II) perchlorate complex. The compound was structurally characterized by physico-chemical and spectroscopic methods. X-ray crystallography of the complex showed that the copper atom achieved a distorted square pyramidal environment through coordination of two amine N atoms and two O atoms of the amide moieties. The pH effect on the visible absorption spectrum of the complex was studied which functions as pH-induced "off-on-off" switches through protonation and deprotonation of amide moieties along with the Cusbnd O to Cusbnd N bond rearrangement at room temperature. The complex was also observed to show solvatochromism and ionochromism. The distinct solution color changes mainly associated with hemilability of the amide groups. The solvatochromism of the complex was investigated with different solvent parameter models using stepwise multiple linear regression method. The results suggested that the basicity power of the solvent has a dominant contribution to the shift of the d-d absorption band of the complex. Density functional theory, DFT calculations were performed in order to study the electronic structure of the complex, the relative stabilities of the Cusbnd N/Cusbnd O isomers, and to understand the nature of the halochromism processes taking place. DFT computational results buttressed the experimental observations indicating that in the natural pH (5.8) the Cusbnd O isomer is more stable than its linkage isomer and conversely in alkaline aqueous solution.

  17. Halochromism, ionochromism, solvatochromism and density functional study of a synthesized copper(II) complex containing hemilabile amide derivative ligand.

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Reisi, Neda

    2015-03-05

    This study investigates chromotropism of newly synthesized 3,3'-(ethane-1,2-diylbis(benzylazanediyl))dipropanamide copper(II) perchlorate complex. The compound was structurally characterized by physico-chemical and spectroscopic methods. X-ray crystallography of the complex showed that the copper atom achieved a distorted square pyramidal environment through coordination of two amine N atoms and two O atoms of the amide moieties. The pH effect on the visible absorption spectrum of the complex was studied which functions as pH-induced "off-on-off" switches through protonation and deprotonation of amide moieties along with the CuO to CuN bond rearrangement at room temperature. The complex was also observed to show solvatochromism and ionochromism. The distinct solution color changes mainly associated with hemilability of the amide groups. The solvatochromism of the complex was investigated with different solvent parameter models using stepwise multiple linear regression method. The results suggested that the basicity power of the solvent has a dominant contribution to the shift of the d-d absorption band of the complex. Density functional theory, DFT calculations were performed in order to study the electronic structure of the complex, the relative stabilities of the CuN/CuO isomers, and to understand the nature of the halochromism processes taking place. DFT computational results buttressed the experimental observations indicating that in the natural pH (5.8) the CuO isomer is more stable than its linkage isomer and conversely in alkaline aqueous solution.

  18. A Novel Catenarian Cyano(triphenyl phosphite) Copper(Ⅰ) Complex: Synthesis, Crystal Structure, Thermal, Voltammetric and Spectral Properties

    Institute of Scientific and Technical Information of China (English)

    QIAO,Yuan-Biao; WANG,Ke-Fei; HU,Li-Hong; JIAN,Fang-Fang

    2006-01-01

    Quantitative reaction between copper(Ⅰ) cyanide and triphenyl phosphite forms copper(Ⅰ) complex [(P(OPh)3)4Cu4(CN)4] (1). X-Ray crystal structure shows a catenarian polymer of tandem interconnected copper cyanide, with C and N connecting to proximal Cu atoms. The Cu atoms adopt two different conformations: one exhibits linear construction, while the other exhibits distorted tetrahedral geometry through coordinating to two cyano groups and the P donors of triphenyl phosphite molecules. The feature of 1 is the propagation pattern of two- and four-coordination along with the chain. IR and electronic absorption spectra also confirm the established single crystal structure. Thermal analysis indicates that 1 has a high thermal stability. 3-D fluorescence result shows the middle absorption peaks with the maximum excitement and emission wavelength 342 and 350 nm, respectively.Cyclic voltammogram in DMSO, DMF and MeCN gives a midpoint voltage of -0.003, 0.061 and 0.137 V versus SCE, respectively, showing the different solvent virtue on reduction potential.

  19. The coordination structure of the extracted copper(II) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and n-hexyl 3-pyridinecarboxylate ester

    Science.gov (United States)

    Zhu, Shan; Hu, Huiping; Hu, Jiugang; Li, Jiyuan; Hu, Fang; Wang, Yongxi

    2017-09-01

    In continuation of our interest in the coordination structure of the nickel(II) complex with dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC), it was observed that the coordination sphere was completed by the coordination of two N atoms of pyridine rings in ligands 4PC and four water molecules while no direct interaction between Ni(II) and deprotonated HDNNS was observed. To investigate whether the coordination structure of nickel(II) with the synergistic mixture containing HDNNS and 4PC predominates or not in the copper(II) complex with the synergistic mixtures containing HDNNS and pyridinecarboxylate esters, a copper(II) synergist complex with n-hexyl 3-pyridinecarboxylate ester (L) and naphthalene-2-sulfonic acid (HNS, the short chain analogue of HDNNS), was prepared and studied by X-ray single crystal diffraction, elemental analyses and thermo gravimetric analysis (TGA), respectively. It was shown that the composition of the copper(II) synergist complex was [Cu(H2O)2(L)2(NS)2] and formed a trans-form distorted octahedral coordination structure. Two oxygen atoms of the two coordinated water molecules and two N atoms of the pyridine rings in the ligands L defined the basal plane while two O atoms from two sulfonate anions of the deprotonated HNS ligands occupied the apical positions by direct coordination with Cu(II), which was distinguished from the coordination structure of the nickel(II) synergist complex as reported in our previous work. In the crystal lattice, neighboring molecules [Cu(H2O)2L2(NS)2] were linked through the intermolecular hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the sulfonate anions in the copper(II) synergist complex to form a 2D plane. In order to bridge the gap between the solid state structure of the copper(II) synergist complex and the solution structure of the extracted copper(II) complex with the actual synergistic mixture containing

  20. Photobehavior of copper(I) compounds. 4. Role of the triplet state of (arylphosphine)copper(I) complexes in the photosensitized isomerization dienes

    Energy Technology Data Exchange (ETDEWEB)

    Liaw, B.; Orchard, S.W.; Kutal, C.

    1988-04-20

    Photoisomerization of cis- and trans-piperylene can be sensitized with high quantum efficiency by Cu(diphos)BH/sub 4/ (diphos is 1,2-bis(diphenylphosphino)ethane) and Cu(prophos)BH/sub 4/ (prophos is 1,3-bis(diphenylphosphino)propane). Sensitization is accompanied by quenching of the emissive /sup 3/(/sigma/-a/sub /pi//) excited state in each copper(I) complex, and the two processes occur with identical Stern-Volmer kinetics. Measurements of the trans/cis diene ratio at the photostationary state can be used to estimate the triplet-state energy as 60-61 kcal for Cu(diphos)BH/sub 4/ and > 61 kcal for Cu(prophos)BH/sub 4/; additional evidence suggests that 66-67 kcal is a reasonable value for the latter complex. Collectively, the results support the assignment of triplet-triplet energy transfer as the primary mechanism for sensitization and quenching in these systems. This mechanism also can accommodate earlier reports that Cu(diphos)BH/sub 4/ and Cu(prophos)BH/sub 4/ sensitize the valence isomerization of norbornadiene to quadricyclene with markedly different quantum efficiencies. 17 refs., 6 figs., 2 tabs.

  1. Improvement of copper FAAS determination conditions via preconcentration procedure with the use of salicylaldoxime complex trapped in polymer matrix.

    Science.gov (United States)

    Tobiasz, Anna; Walas, Stanisław; Landowska, Lucyna; Konefał-Góral, Jadwiga

    2012-07-15

    The paper presents application of a new resin dedicated to copper(II) flow-injection on-line preconcentration prior its flame atomic absorption spectrometric (FAAS) determination. The new sorbent, obtained by suspension polymerization technique, was styrene-divinylbenzene copolymer modified with 5-dodecylsalicylaldoxime-copper(II) complex. In flow mode leaching of initially imprinted Cu(II) ions from polymer beads was effective with 1% (v/v) nitric acid, however for elution of ions retained on the sorbent during the loading process sufficient efficiency was obtained for 0.5% (v/v) nitric acid. The most effective copper(II) sorption was observed within sample pH ca. 6.3 at flow rate 7.5mLmin(-1). Furthermore, preconcentration studies of Cu(II) ions realized in the presence of popular foreign ions like Cd(II), Pb(II), Zn(II), Ni(II), Mn(II), Co(II) did not reveal significant interference. The expected effect of Cu(II)-imprinting was confirmed by higher tolerance level for interferents ions concentration for the new sorbent than for the control polymer. It was found that alkaline metals ions and humic acid had the most relevant influence on copper(II) uptake. Accuracy of the evaluated method was assessed for analysis of water samples (tap and mineral water, river water, artesian water) and certified water reference materials compare them to results obtained by inductively plasma mass spectrometry. The satisfactory relative error values obtained with use of standard addition calibration method, confirms the feasibility of this method for Cu(II) determination in water samples. Application of 120s sorption time enabled to obtain 74-fold enrichment factor and limit of detection (3σ) equal to 0.4μgL(-1). Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Synthesis, characterization, biological studies (DNA binding, cleavage, antibacterial and topoisomerase I) and molecular docking of copper(II) benzimidazole complexes.

    Science.gov (United States)

    Arjmand, Farukh; Parveen, Shazia; Afzal, Mohd; Shahid, Mohd

    2012-09-03

    To explore the therapeutic potential of copper-based benzimidazole complexes, tetranuclear Cu(II) complex 1 and dinuclear ternary amino acid complexes 2 and 3 {L-trp and L-val, respectively} were synthesized and thoroughly characterized. In vitro DNA binding studies of complexes 1-3 were carried out employing UV-vis titrations, fluorescence, circular dichroic and viscosity measurements which revealed that the complexes 1-3 bind to CT DNA preferably via groove binding. Complex 1 cleaved pBR322 DNA via hydrolytic pathway (validated by T4 DNA ligase assay), accessible to major groove while 2 followed oxidative mechanism, binding to minor groove of DNA double helix; binding events were further validated by molecular docking studies. Additionally, the complexes 1 and 2 exhibit high Topo-I inhibitory activity at different concentrations. The complexes 1-3 were evaluated for antibacterial activity against Escherichia coli and Staphylococcus aureus, and 2 was found to be most effective against Gram-positive bacteria.

  3. New tridentate azo-azomethines and their copper(II) complexes: Synthesis, solvent effect on tautomerism, electrochemical and biological studies

    Science.gov (United States)

    Sarigul, Munire; Deveci, Pervin; Kose, Muhammet; Arslan, Ugur; Türk Dagi, Hatice; Kurtoglu, Mukerrem

    2015-09-01

    In this study, three azo-azomethines and their copper(II) complexes were prepared and characterized by analytical and spectroscopic methods. The complexes prepared were found to be mononuclear and the chelation of the ligands to the copper(II) ions occurs through two phenolic oxygens and a nitrogen atom of the azomethine group of the ligand. The tautomeric behaviors of the azo-azomethines in solution were studied by UV-Vis. spectra in three organic solvents with different polarity (CHCl3, DMSO and DMF) at room temperature. The redox behaviors of the azo-azomethines and their Cu(II) complexes were investigated by cyclic voltammetry (CV) in DMSO solution containing 0.1 M tetrabutylammonium tetrafluoroborate (TBATFB) as supporting electrolyte. Additionally, the antibacterial activity was also evaluated by the broth microdilution methods against Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa. The compounds were found to be less effective against all bacteria tested than two reference antibiotics (ampicillin and gentamicin).

  4. Studies of EXAFSSpectra using Copper (II) Schiff Base complexes and Determination of Bond lengths Using Synchrotron Radiation

    Science.gov (United States)

    Mishra, A.; Vibhute, V.; Ninama, S.; Parsai, N.; Jha, S. N.; Sharma, P.

    2016-10-01

    X-ray absorption fine structure (XAFS) at the K-edge of copper has been studied in some copper (II) complexes with substituted anilines like (2Cl, 4Br, 2NO2, 4NO2 and pure aniline) with o-PDA (orthophenylenediamine) as ligand. The X-ray absorption measurements have been performed at the recently developed BL-8 dispersive EXAFS beam line at 2.5 GeV Indus-2 Synchrotron Source at RRCAT, Indore, India. The data obtained has been processed using EXAFS data analysis program Athena.The graphical method gives the useful information about bond length and also the environment of the absorbing atom. The theoretical bond lengths of the complexes were calculated by using interactive fitting of EXAFS using fast Fourier inverse transformation (IFEFFIT) method. This method is also called as Fourier transform method. The Lytle, Sayers and Stern method and Levy's method have been used for determination of bond lengths experimentally of the studied complexes. The results of both methods have been compared with theoretical IFEFFIT method.

  5. Effect of pH and chemical mechanical planarization process conditions on the copper-benzotriazole complex formation

    Science.gov (United States)

    Cho, Byoung-Jun; Kim, Jin-Yong; Hamada, Satomi; Shima, Shohei; Park, Jin-Goo

    2016-06-01

    Benzotriazole (BTA) has been used to protect copper (Cu) from corrosion during Cu chemical mechanical planarization (CMP) processes. However, an undesirable Cu-BTA complex is deposited after Cu CMP processes and it should be completely removed at post-Cu CMP cleaning for next fabrication process. Therefore, it is very important to understand of Cu-BTA complex formation behavior for its applications such as Cu CMP and post-Cu CMP cleaning. The present study investigated the effect of pH and polisher conditions on the formation of Cu-BTA complex layers using electrochemical techniques (potentiodynamic polarization and electrochemical impedance spectroscopy) and the surface contact angle. The wettability was not a significant factor for the polishing interface, as no difference in the contact angles was observed for these processes. Both electrochemical techniques revealed that BTA had a unique advantage of long-term protection for Cu corrosion in an acidic condition (pH 3).

  6. Preparation and antibacterial activity of copper and cobalt complexes of 4-chloro-3-nitrobenzoate with a nitrogen donor ligand.

    Science.gov (United States)

    Kabbani, Ahmad Toufic; Hammud, Hassan Hasan; Ghannoum, Amer Mohammed

    2007-03-01

    Copper and cobalt complexes with 4-chloro-3-nitrobenzoate (ClNBz) and the nitrogen ligands 1,3-diaminopropane (1,3-DAP) or o-phenylenediamine (o-PDA), were prepared and characterized. The complexes [Cu(ClNBz)2(1,3-DAP)] (1), [Cu(ClNBz)(o-PDA)]Cl (2), [Co(ClNBz)2(1,3-DAP)] (3) and [Co(ClNBz)2(o-PDA)2] (4) were characterized by FTIR, UV-Visible absorption, elemental analysis and thermal analysis. Complex [Cu(ClNBz)(o-PDA)]Cl (2) shows high antibacterial activity as indicated by its ability to inhibit the growth of Staphylococcus aureus, Enterococcus faecalis.

  7. Matrix isolation infrared spectroscopic and theoretical study of the copper (I) and silver (I) nitrous oxide complexes

    Science.gov (United States)

    Wang, Guanjun; Jin, Xi; Chen, Mohua; Zhou, Mingfei

    2006-03-01

    Copper and silver chloride-nitrous oxide complexes: ClCuNNO and ClAgNNO have been produced and trapped in solid argon by co-deposition of laser-evaporated metal chlorides with nitrous oxide in excess argon. On the basis of isotopic substituted experiments as well as theoretical calculations, infrared absorptions at 2305.8 and 1318.4 cm -1, and 2291.2 and 1325.4 cm -1 are assigned to the N-N and N-O stretching modes of the linear ClCuNNO and ClAgNNO complexes, respectively. The binding energies for the complexes with respect to MCl (M = Cu, Ag) and N 2O were computationally estimated to be 27.9 and 13.1 kcal/mol.

  8. Highly active and selective catalysis of copper diphosphine complexes for the transformation of carbon dioxide into silyl formate.

    Science.gov (United States)

    Motokura, Ken; Kashiwame, Daiki; Takahashi, Naoki; Miyaji, Akimitsu; Baba, Toshihide

    2013-07-22

    Copper diphosphine complexes have been found to be highly active and selective homogeneous catalysts for the hydrosilylation of CO2. The structure of the phosphine ligands strongly affects their catalytic activity. Turnover number (TON) reaches 70,000 after 24 hours with 1,2-bis(diisopropylphosphino)benzene as a ligand under 1 atmosphere of CO2. (1)H and (13)C NMR spectra, carried out under the reaction conditions, showed the reaction mechanism through insertion of CO2 into Cu-H to afford Cu/formate species.

  9. Synthesis of Azoxy Dyes and Their Copper Complexes and Their Application on Polyvinyl Alcohol (PVA) Polarizing Film

    Institute of Scientific and Technical Information of China (English)

    LI Ke-bin; HE Jin-xin

    2008-01-01

    Azoxy dyes and their copper complexes with maximum dichroism in the spectrum range from 550 nm to 700 nm were synthesized and used to prepare polyvinyl alcohol (PVA) polarizing films.These films showed excellent polarizing ability.In addition, a neutral gray polarizing film was prepared by mixing synthesized dichromatic dyes with other dyes.The obtained polarizable film for gray shade was little pervious to light over the visible radiation wavelength region, ranging from 400 nm to 700 nm at cross state, and excellent in the polarizing activities and stable to moisture and heat.

  10. Synthesis, Crystal Structure, and Characterization of Ternary Copper(II Complex Derived from N-(salicylidene-L-valine

    Directory of Open Access Journals (Sweden)

    Sundaramurthy Santha Lakshmi

    2016-01-01

    Full Text Available Ternary Schiff base copper(II complex [CuL(tmpda] (where H2L is N-(salicylidene-L-valine; tmpda is N,N,N′,N′-tetramethyl-1,3-propanediamine has been characterized by UV-Vis., FTIR, and single crystal XRD. The crystal structure displays a distorted square pyramidal geometry in which Schiff base is bonded to the Cu(II ion via phenolate oxygen, imine nitrogen, and an oxygen atom of the carboxylate group through the basal plane and the chelating diamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, displays an axial and equatorial mode of binding via NN-donor atoms.

  11. Copper Tetrahydrosalen Complex Encapsulated in Zeolite Y:an Effective Heterogeneous Catalyst for the Oxidation of Cycloalkanes

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A new heterogeneous catalyst, copper tetrahydrosalen complex encapsulated in zeolite Y (denoted as Cu[H4]salen/Y) has been developed with flexible ligand method, and characterized by FTIR, DR UV-Vis spectroscopy, N2 adsorption/desorption at -196℃. This catalyst behaved like a bio-mimic enzyme, and exhibited much higher activity for the oxidation of cycloalkanes than Cusalen/Y prepared with the same method. The effects of the reaction conditions on the catalytic performance were investigated.

  12. Synthesis of New Azo Dyes and Copper(II) Complexes Derived from Barbituric Acid and 4-Aminobenzoylhydrazone

    OpenAIRE

    GUP, Bülent KIRKAN and Ramazan

    2008-01-01

    Four new azo dyes, L1, L2, L3, and L4, were prepared by linking benzaldehyde p-aminobenzoylhydrazone (3) and p-hydroxybenzaldehyede p--aminobenzoylhydrazone (4) to barbituric acid and 1,3-dimethylbarbituric acid through diazo-coupling reactions. Reactions of the azo-dyes with copper chloride and bidentate ligand, 1,10-phenanthroline, produced mixed-ligand dinuclear complexes with general stoichiometry [Cu2L(phen)2]Cl2 (7, 8, 9, and 10). The structures of both azo dyes and their compl...

  13. Multiphase enantioselective Kharasch-Sosnovsky allylic oxidation based on neoteric solvents and copper complexes of ditopic ligands.

    Science.gov (United States)

    Aldea, Luis; García, José I; Mayoral, José A

    2012-07-21

    Recoverable multiphase enantioselective catalytic systems for the Kharasch-Sosnovsky oxidation of cycloalkenes with tert-butyl peroxybenzoate are described, based on the use of [BMIM][PF(6)] and a new solvent derived from glycerol as the catalyst reservoir phases, and chiral copper complexes with different ligands from the bis(oxazoline) family. The best results are obtained with the glycerol-derived solvent and a recently described azabisoxazoline-based ditopic ligand, allowing up to four uses of the catalytic phase with good results.

  14. Effect of the Schiff base complex diaqua-(N-salicylidene-l-glutamato)copper(II) monohydrate on human tumor cells.

    Science.gov (United States)

    Konarikova, Katarina; Andrezalova, Lucia; Rapta, Peter; Slovakova, Marianna; Durackova, Zdenka; Laubertova, Lucia; Gbelcova, Helena; Danisovic, Lubomir; Bohmer, Daniel; Ruml, Tomas; Sveda, Martin; Zitnanova, Ingrid

    2013-12-05

    The aim of our study was to estimate cytostatic/cytotoxic activity of the copper(II) Schiff base complex of the composition [Cu(N-salicylidene-l-glutamato)(H2O)2]·H2O, further Cu(SG-L)H2O, against human colon carcinoma cell line HT-29, as well as to determine type of cell death and to find out the molecular mechanism of apoptosis induced by this complex. Two highest concentrations (50, 100 µmol/l) of the complex showed a strong cytotoxic activity against human colon carcinoma cells HT-29 after 72 h of influence. Other concentrations had a cytostatic activity. Unchelated copper(II) ions and free ligands had no effect on the cell growth. Cu(SG-L)H2O preferentially reduced cancer cell viability compared to healthy cells (NIH-3T3). Cu(SG-L)H2O induced apoptosis of cells HT-29 at all concentrations used (1-100 µmol/l) after 48 h of influence. Apoptosis was carried out by the mitochondrial pathway with active caspases 3 and 9. By the spin-trapping technique combined with electron paramagnetic resonance we found that our complex is photochemically stable in aqueous systems and does not exhibit radical-scavenging activity when 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) cation radical was used as an oxidant. The complex exhibits a strong prooxidant property in the initial stages of thermal decomposition of K2S2O8 in water solutions leading to the massive production of (·)OH radicals. Therefore, this complex could strongly participate in anticancer action via a free radical mechanism.

  15. Antimicrobial Activity and Urease Inhibition of Schiff Bases Derived from Isoniazid and Fluorinated Benzaldehydes and of Their Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Ladislav Habala

    2016-12-01

    Full Text Available In order to evaluate the influence of substitution on biological properties of Schiff bases and their metal complexes, a series of differently substituted fluorine-containing Schiff bases starting from the drug isoniazid (isonicotinylhydrazide were prepared and their structures were established by single-crystal X-ray diffraction. Also, four copper(II complexes of these Schiff bases were synthesized. The prepared compounds were evaluated for their antimicrobial activity and urease inhibition. Two of the Schiff bases exerted activity against C. albicans. All copper(II complexes showed excellent inhibitory properties against jack bean urease, considerably better than that of the standard inhibitor acetohydroxamic acid.

  16. Antimicrobial Activity and Urease Inhibition of Schiff Bases Derived from Isoniazid and Fluorinated Benzaldehydes and of Their Copper(II) Complexes.

    Science.gov (United States)

    Habala, Ladislav; Varényi, Samuel; Bilková, Andrea; Herich, Peter; Valentová, Jindra; Kožíšek, Jozef; Devínsky, Ferdinand

    2016-12-17

    In order to evaluate the influence of substitution on biological properties of Schiff bases and their metal complexes, a series of differently substituted fluorine-containing Schiff bases starting from the drug isoniazid (isonicotinylhydrazide) were prepared and their structures were established by single-crystal X-ray diffraction. Also, four copper(II) complexes of these Schiff bases were synthesized. The prepared compounds were evaluated for their antimicrobial activity and urease inhibition. Two of the Schiff bases exerted activity against C. albicans. All copper(II) complexes showed excellent inhibitory properties against jack bean urease, considerably better than that of the standard inhibitor acetohydroxamic acid.

  17. XRD and xanes studies of copper complexes using (diethyl 4-amino-1-phenyl-1H-pyrazole-3,5 dicarboxylate) as ligand

    Science.gov (United States)

    Mishra, Ashutosh; Jain, Garima

    2013-06-01

    X-ray diffraction (XRD) and X-ray absorption spectroscopic (XAS) studies have been done on three copper complexes using (diethyl 4-amino-1-phenyl-1H-pyrazole-3,5 dicarboxylate) as ligand. The X-ray diffraction studies of copper complexes have been recorded using Rigaku RINT-2000 X-ray diffractometer equipped with a rotating anode with tube voltage of 40 kV and current of 100 mA. The X-ray absorption spectra of the complexes have been recorded at Raja Ramanna Centre for Advanced Technology (RRCAT), Indore and is called beamline.

  18. Experimental and molecular modeling studies on the DNA-binding of diazacyclam-based acrocyclic copper complex.

    Science.gov (United States)

    Shahabadi, Nahid; Hakimi, Mohammad; Morovati, Teimoor; Falsafi, Monireh; Fili, Soraya Moradi

    2017-02-01

    The interaction of a new macrocyclic copper complex, [CuL(NO3)2] in which L is 1,3,6,10,12,15-hexaaza tricyclo[13.3.1.1(6,10)] eicosane was investigated in vitro under simulated physiological conditions by multi-spectroscopic techniques and molecular modeling study. The fluorescence spectroscopy and UV absorption spectroscopy indicated the complex interacted with ct-DNA in a groove binding mode while the binding constant of UV-vis and the number of binding sites were 1.0±0.2×10(4)Lmol(-1) and 1.01, respectively. The fluorometric studies showed that the reaction between the complex with ct-DNA is exothermic (ΔH=14.85kJmol(-1); ΔS=109.54Jmol(-1)K(-1)). Circular dichroism spectroscopy (CD) was employed to measure the conformational change of DNA in the presence of [CuL(NO3)2] complex. Furthermore, the complex induces detectable changes in the viscosity of DNA. The molecular modeling results illustrated that the complex strongly binds to groove of DNA. Experimental and molecular modeling results showed that Cu(II) complex bound to DNA by a groove binding mode.

  19. Synthesis, crystal structures, spectroscopic characterization and in vitro antidiabetic studies of new Schiff base Copper(II) complexes

    Indian Academy of Sciences (India)

    SUNDARAMURTHY SANTHA LAKSHMI; KANNAPPAN GEETHA; M GAYATHRI; GANESH SHANMUGAM

    2016-07-01

    Two new Schiff base copper(II) complexes, [CuL¹(tmen)] (1) and [Cu₂L₂² (tmen)] (2) {where, H₂L¹ = N-(salicylidene)-L-valine, H₂L² = N-(3,5-dichlorosalicylidene)-L-valine and tmen = N,N,N',N'- tetramethylethylene-1,2-diamine} have been synthesized and characterized by molar conductance, elemental analyses, VSM-RT, UV-Vis, FTIR, EPR, and CD spectra. Both the complexes were structurally characterized by single crystal XRD. The crystal structure of complex 1 displays a distorted square pyramidal geometry in which Schiff base is coordinated to the Cu(II) ion via ONO-donor in the axial mode, whereas, the chelating diamine displays axial and equatorial mode of binding via NN-donor atoms. The crystal structure of the complex 2 reveals a syn-anti mode of carboxylate bridged dinuclear complex, in which, the coordination geometry around Cu(1) is square pyramid and distorted square planar around Cu(2). The target complexes were screened for in vitro antidiabetic activity. Both the complexes showed good inhibitory activity for α-amylase and α-glucosidase.

  20. Halogen-bonded network of trinuclear copper(II 4-iodopyrazolate complexes formed by mutual breakdown of chloroform and nanojars

    Directory of Open Access Journals (Sweden)

    Stuart A. Surmann

    2016-11-01

    Full Text Available Crystals of bis(tetrabutylammonium di-μ3-chlorido-tris(μ2-4-iodopyrazolato-κ2N:N′tris[chloridocuprate(II] 1,4-dioxane hemisolvate, (C16H36N2[Cu3(C3H2IN23Cl5]·0.5C4H8O or (Bu4N2[CuII3(μ3-Cl2(μ-4-I-pz3Cl3]·0.5C4H8O, were obtained by evaporating a solution of (Bu4N2[{CuII(μ-OH(μ-4-I-pz}nCO3] (n = 27–31 nanojars in chloroform/1,4-dioxane. The decomposition of chloroform in the presence of oxygen and moisture provides HCl, which leads to the breakdown of nanojars to the title trinuclear copper(II pyrazolate complex, and possibly CuII ions and free 4-iodopyrazole. CuII ions, in turn, act as catalyst for the accelerated decomposition of chloroform, ultimately leading to the complete breakdown of nanojars. The crystal structure presented here provides the first structural description of a trinuclear copper(II pyrazolate complex with iodine-substituted pyrazoles. In contrast to related trinuclear complexes based on differently substituted 4-R-pyrazoles (R = H, Cl, Br, Me, the [Cu3(μ-4-I-pz3Cl3] core in the title complex is nearly planar. This difference is likely a result of the presence of the iodine substituent, which provides a unique, novel feature in copper pyrazolate chemistry. Thus, the iodine atoms form halogen bonds with the terminal chlorido ligands of the surrounding complexes [mean length of I...Cl contacts = 3.48 (1 Å], leading to an extended two-dimensional, halogen-bonded network along (-110. The cavities within this framework are filled by centrosymmetric 1,4-dioxane solvent molecules, which create further bridges via C—H...Cl hydrogen bonds with terminal chlorido ligands of the trinuclear complex not involved in halogen bonding.

  1. Characterisation of the interactions between substrate, copper(II) complex and DNA and their role in rate acceleration in DNA-based asymmetric catalysis.

    Science.gov (United States)

    Draksharapu, Apparao; Boersma, Arnold J; Browne, Wesley R; Roelfes, Gerard

    2015-02-28

    Interactions of the azachalcone derived substrate Aza with copper(II) complexes in the presence and absence of st-DNA were studied in detail by UV/Vis absorption, EPR and Raman and (UV and vis) resonance Raman spectroscopies. The binding of Aza to the Lewis acidic copper(II) complexes, which results in activation of the substrate, was established spectroscopically. It was shown that the binding of Aza differs between Cu(II)dmbpy and Cu(II)terpy, consistent with the observed differences in catalytic asymmetric Diels-Alder reactions with regard to both the rate and enantiomeric preference. Finally, it was shown that DNA has a major beneficial effect on the binding of Aza to the copper(II) complex due to the fact that both bind to the DNA. The result is a high effective molarity of both the copper complexes and the Aza substrate, which leads to a significant increase in binding of Aza to the copper(II) complex. This effect is a key reason for the observed rate acceleration in the catalyzed reactions brought about by the presence of DNA.

  2. 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)].

  3. Dinuclear cobalt(II) and copper(II) complexes with a Py2N4S2 macrocyclic ligand.

    Science.gov (United States)

    Núñez, Cristina; Bastida, Rufina; Lezama, Luis; Macías, Alejandro; Pérez-Lourido, Paulo; Valencia, Laura

    2011-06-20

    The interaction between Co(II) and Cu(II) ions with a Py(2)N(4)S(2)-coordinating octadentate macrocyclic ligand (L) to afford dinuclear compounds has been investigated. The complexes were characterized by microanalysis, conductivity measurements, IR spectroscopy and liquid secondary ion mass spectrometry. The crystal structure of the compounds [H(4)L](NO(3))(4), [Cu(2)LCl(2)](NO(3))(2) (5), [Cu(2)L(NO(3))(2)](NO(3))(2) (6), and [Cu(2)L(μ-OH)](ClO(4))(3)·H(2)O (7) was also determined by single-crystal X-ray diffraction. The [H(4)L](4+) cation crystal structure presents two different conformations, planar and step, with intermolecular face-to-face π,π-stacking interactions between the pyridinic rings. Complexes 5 and 6 show the metal ions in a slightly distorted square-pyramidal coordination geometry. In the case of complex 7, the crystal structure presents the two metal ions joined by a μ-hydroxo bridge and the Cu(II) centers in a slightly distorted square plane or a tetragonally distorted octahedral geometry, taking into account weak interactions in axial positions. Electron paramagnetic resonance spectroscopy is in accordance with the dinuclear nature of the complexes, with an octahedral environment for the cobalt(II) compounds and square-pyramidal or tetragonally elongated octahedral geometries for the copper(II) compounds. The magnetic behavior is consistent with the existence of antiferromagnetic interactions between the ions for cobalt(II) and copper(II) complexes, while for the Co(II) ones, this behavior could also be explained by spin-orbit coupling.

  4. 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.

  5. Synthesis, Crystal Structure, Stacking Effect and Antibacterial Studies of a Novel Quaternary Copper (II Complex with Quinolone

    Directory of Open Access Journals (Sweden)

    Longguan Zhu

    2003-02-01

    Full Text Available The structural properties of a new copper (II complex [Cu2(cip2(bpy2(pip]·6H2O (bpy=2,2’-bipyridyl, cip=1-cyclopropyl-6-4-oxo-1,4-dihydroquinoline-3-carboxylic acid, pip= piperazinyl anion, obtained during the synthesis of the copper complex with ciprofloxacin (cpf, has been investigated. The complex crystallizes in the triclinic system, space group P-1. The cell dimensions are: a=6.874(2 Å, b= 10.761(3 Å, c= 17.969(5 Å, α =80.071(6°, β= 85.253(6°, γ=79.109(6°,V=1284.5(6 Å3, and Z=2. The Cu (II ion displays a five-coordinate square pyramidal coordination with two nitrogen donors from bpy, the 4-keto and 3-carboxylate oxygen donors of cip, and the third nitrogen atom of the pip anion occupying the fifth site. There is a stack effect between cip ring and bpy ring from another molecule, where the stacking distance is about 3.5 Å. The results of elemental analysis and FT-IR measurement are also included. Both ligand and complex were assayed against gram-positive and gram-negative bacteria by the doubling dilutions method. The complex shows the same minimal inhibitory concentration (MIC against S. Aureus and E. Coli bacteria as the corresponding ligand.

  6. Observation of contrast variations of a copper (Ⅱ) complex by scanning tunneling microscopy

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    This report presents experimental observations of dramatic variations in STM images of bis [1,3- di(p-n-tetradecyloxyphenyl)propane-1,3-dionato] copper(Ⅱ) (abbreviated to C14O-Cu) physisorbed on HOPG as the bias voltage is changed. Several representative image patterns were obtained for the rich changes of the internal contrast of the molecule. Submolecular features of the molecular cores and the interdigitated alkyl parts are clearly visible.

  7. Synthesis and Characterization of an Unexpected Asymmetric Binuclear Copper(Ⅰ) Complex Containing 4-Vinyl-pyridine

    Institute of Scientific and Technical Information of China (English)

    JIANG, Kai(蒋凯); ZHAO, Dong(赵东); GUO, Li-Bing(郭利兵); ZHANG, Chuan-Jian(张传建); YANG, Rui-Na(杨瑞娜)

    2004-01-01

    The asymmetric binuclear copper(Ⅰ) complex [Cu2(dppm)2(C7H7N)(μ-HCOO)](NO3) (dppm=Ph2PCH2PPh2, C7H7N=4-vinyl-pyridine) has been prepared and characterized by physicochemical and spectroscopic methods. The complex is photoluminescent at room temperature. It crystallizes in triclinic system, space group P-1 with a= 1.2719(3) nm, b= 1.8637(4) nm, c= 1.1656(2) nm, α=97.16(3)°, β= 104.94(3)°, γ=89.39(3)°, V=2.648.1(9) nm3, Dc= 1.390 gbcm-3, Z=2, μ=0.974 mm-1, R=0.0483 for 5716 independently observed reflections with I>2σ(I).The structure consists of [Cu2(dppm)2(C7H7N)(μ-HCOO)]+cations and nitrate anions. The copper atoms show different coordination modes: Cu(1) displays a distorted trigonal and Cu(2) a tetrahedred geometry.

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

    Directory of Open Access Journals (Sweden)

    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

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

    Science.gov (United States)

    Silva, Patricia B da; Bonifácio, Bruna V; Frem, Regina C G; Godoy Netto, Adelino V; Mauro, Antonio E; Ferreira, Ana M da Costa; Lopes, Erica de O; Raddi, Maria S G; Bauab, Tais M; Pavan, Fernando R; Chorilli, Marlus

    2015-12-16

    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(INH)₂]·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-diyldinitrilo)tetraacetic 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-81(TM)) 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

  10. Tyrosinase and catechol oxidase activity of copper(I) complexes supported by imidazole-based ligands: structure-reactivity correlations.

    Science.gov (United States)

    Wendt, Franziska; Näther, Christian; Tuczek, Felix

    2016-09-01

    Four new imidazole-based ligands, 4-((1H-imidazol-4-yl)methyl)-2-phenyl-4,5-dihydrooxyzole (L OL 1), 4-((1H-imidazol-4-yl)methyl)-2-(tert-butyl)-4,5-dihydrooxyzole (L OL 2), 4-((1H-imidazol-4-yl)methyl)-2-methyl-4,5-dihydrooxyzole (L OL 3), and N-(2,2-dimethylpropylidene)-2-(1-trityl-1H-imidazol-4-yl-)ethyl amine (L imz 1), have been synthesized. The corresponding copper(I) complexes [Cu(I)(L OL 1)(CH3CN)]PF6 (CuL OL 1), [Cu(I)(L OL 2)(CH3CN)]PF6 (CuL OL 2), [Cu(I)(L OL 3)(CH3CN)]PF6 (CuL OL 3), [Cu(I)(L imz 1)(CH3CN)2]PF6 (CuL imz 1) as well as the Cu(I) complex derived from the known ligand bis(1-methylimidazol-2-yl)methane (BIMZ), [Cu(I)(BIMZ)(CH3CN)]PF6 (CuBIMZ), are screened as catalysts for the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC-H2) to 3,5-di-tert-butylquinone (3,5-DTBQ). The primary reaction product of these oxidations is 3,5-di-tert-butylsemiquinone (3,5-DTBSQ) which slowly converts to 3,5-DTBQ. Saturation kinetic studies reveal a trend of catalytic activity in the order CuL OL 3 ≈ CuL OL 1 > CuBIMZ > CuL OL 2 > CuL imz 1. Additionally, the catalytic activity of the copper(I) complexes towards the oxygenation of monophenols is investigated. As substrates 2,4-di-tert-butylphenol (2,4-DTBP-H), 3-tert-butylphenol (3-TBP-H), 4-methoxyphenol (4-MeOP-H), N-acetyl-L-tyrosine ethyl ester monohydrate (NATEE) and 8-hydroxyquinoline are employed. The oxygenation products are identified and characterized with the help of UV/Vis and NMR spectroscopy, mass spectrometry, and fluorescence measurements. Whereas the copper complexes with ligands containing combinations of imidazole and imine functions or two imidazole units (CuL imz 1 and CuBIMZ) are found to exhibit catalytic tyrosinase activity, the systems with ligands containing oxazoline just mediate a stoichiometric conversion. Correlations between the structures of the complexes and their reactivities are discussed.

  11. 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 H2L2 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 (Epc= -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.

  12. Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes.

    Science.gov (United States)

    Shebl, Magdy

    2014-01-03

    The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H and (13)C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M=Co, Ni or Cu, m=4, 0 and n=2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34×10(4) and 2.5×10(4) M(-1), respectively.

  13. 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.

  14. N-benzoylated 1,4,8,11-tetraazacyclotetradecane and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, crystal structure, catalytic and antimicrobial studies

    Science.gov (United States)

    Nirmala, G.; Rahiman, A. Kalilur; Sreedaran, S.; Jegadeesh, R.; Raaman, N.; Narayanan, V.

    2010-09-01

    A series of N-benzoylated cyclam ligands incorporating three different benzoyl groups 1,4,8,11-tetra-(benzoyl)-1,4,8,11-tetraazacyclotetradecane (L 1), 1,4,8,11-tetra-(2-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 2) and 1,4,8,11-tetra-(4-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 3) and their nickel(II) and copper(II) complexes are described. Crystal structure of L 1 is also reported. The ligands and complexes were characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. N-benzoylation causes red shift in the λmax values of the complexes. The cyclic voltammogram of the complexes of ligand L 1 show one-electron, quasi-reversible reduction wave in the region -1.00 to -1.04 V, whereas that of L 2 and L 3 show two quasi-reversible reduction peaks. Nickel complexes show one-electron quasi-reversible oxidation wave at a positive potential in the range +1.05 to +1.15 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment values μeff 1.70-1.73 BM which is close to the spin-only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. All the ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.

  15. 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 undeveloped

  16. Bi- and trinuclear copper(I) complexes of 1,2,3-triazole-tethered NHC ligands: synthesis, structure, and catalytic properties

    Science.gov (United States)

    Du, Jiehao; Huang, Jingjing; Xia, Huan; Yang, Ling; Xu, Weilin

    2016-01-01

    Summary A series of copper complexes (3–6) stabilized by 1,2,3-triazole-tethered N-heterocyclic carbene ligands have been prepared via simple reaction of imidazolium salts with copper powder in good yields. The structures of bi- and trinuclear copper complexes were fully characterized by NMR, elemental analysis (EA), and X-ray crystallography. In particular, [Cu2(L2)2](PF6)2 (3) and [Cu2(L3)2](PF6)2 (4) were dinuclear copper complexes. Complexes [Cu3(L4)2](PF6)3 (5) and [Cu3(L5)2](PF6)3 (6) consist of a triangular Cu3 core. These structures vary depending on the imidazolium backbone and N substituents. The copper–NHC complexes tested are highly active for the Cu-catalyzed azide–alkyne cycloaddition (CuAAC) reaction in an air atmosphere at room temperature in a CH3CN solution. Complex 4 is the most efficient catalyst among these polynuclear complexes in an air atmosphere at room temperature. PMID:27340477

  17. Synthesis, spectral characterization, DNA binding ability and antibacterial screening of copper(II) complexes of symmetrical NOON tetradentate Schiff bases bearing different bridges

    Science.gov (United States)

    Bahaffi, Saleh O.; Abdel Aziz, Ayman A.; El-Naggar, Maher M.

    2012-08-01

    A novel series of four copper(II) complexes were synthesized by thermal reaction of copper acetate salt with symmetrical tetradentate Schiff bases, N,N'bis(o-vanillin)4,5-dimethyl-l,2-phenylenediamine (H2L1), N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L2), N,N'bis(o-vanillin)4,5-dichloro-1,2-phenylenediamine (H2L3) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L4), respectively. All the new synthesized complexes were characterized by using of microanalysis, FT-IR, UV-Vis, magnetic measurements, ESR, and conductance measurements, respectively. The data revealed that all the Schiff bases (H2L1-4) coordinate in their deprotonated forms and behave as tetradentate NOON coordinated ligands. Moreover, their copper(II) complexes have square planar geometry with general formula [CuL1-4]. The binding of the complexes with calf thymus DNA (CT-DNA) was investigated by UV-Vis spectrophotometry, fluorescence quenching and viscosity measurements. The results indicated that the complexes bind to CT-DNA through an intercalative mode. From the biological activity view, the copper(II) complexes and their parent ligands were screened for their in vitro antibacterial activity against the bacterial species Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli and Pseudomonas aeruginosai by well diffusion method. The complexes showed an increased activity in comparison to some standard drugs.

  18. Synthesis, structure analysis, anti-bacterial and in vitro anti-cancer activity of new Schiff base and its copper complex derived from sulfamethoxazole

    Indian Academy of Sciences (India)

    I Rama; R Selvameena

    2015-04-01

    A new bidentate Schiff base ligand (HL1), containing O,N donors was prepared by the reaction of sulfamethoxazole with 5-nitrosalicylaldehyde and characterized by elemental analysis, FT-IR, 1H and 13C NMR. The copper complex of this ligand was synthesised by treating DMF-ethanolic mixture solution of the ligand of two equivalents with one equivalent of copper acetate. The complex was characterized on the basis of UV, FT-IR, molar conductance, EPR, magnetic moment and single crystal X-ray diffraction. Interestingly, the crystal structure of the octahedral complex showed two solvent molecules (DMF) as ligands at their axial positions. The molar conductance data revealed that the complex is a non-electrolyte. The Schiff base and its copper complex have been investigated as anti-bacterial and anti-fungal agents against various microorganisms. The in vitro cytotoxicity tests of the ligand and its copper complex were carried out in two different human tumour cell lines, HCT-116 and MDA – MB - 231. The cytotoxicity studies showed that the complex exhibited higher activity than cisplatin and carboplatin towards MDA – MB – 231.

  19. Bi- and trinuclear copper(I complexes of 1,2,3-triazole-tethered NHC ligands: synthesis, structure, and catalytic properties

    Directory of Open Access Journals (Sweden)

    Shaojin Gu

    2016-05-01

    Full Text Available A series of copper complexes (3–6 stabilized by 1,2,3-triazole-tethered N-heterocyclic carbene ligands have been prepared via simple reaction of imidazolium salts with copper powder in good yields. The structures of bi- and trinuclear copper complexes were fully characterized by NMR, elemental analysis (EA, and X-ray crystallography. In particular, [Cu2(L22](PF62 (3 and [Cu2(L32](PF62 (4 were dinuclear copper complexes. Complexes [Cu3(L42](PF63 (5 and [Cu3(L52](PF63 (6 consist of a triangular Cu3 core. These structures vary depending on the imidazolium backbone and N substituents. The copper–NHC complexes tested are highly active for the Cu-catalyzed azide–alkyne cycloaddition (CuAAC reaction in an air atmosphere at room temperature in a CH3CN solution. Complex 4 is the most efficient catalyst among these polynuclear complexes in an air atmosphere at room temperature.

  20. Synthesis of mononuclear copper(II) complexes of acyclic Schiff's base ligands: Spectral, structural, electrochemical, antibacterial, DNA binding and cleavage activity

    Science.gov (United States)

    Jayamani, Arumugam; Thamilarasan, Vijayan; Sengottuvelan, Nallathambi; Manisankar, Paramasivam; Kang, Sung Kwon; Kim, Young-Inn; Ganesan, Vengatesan

    2014-03-01

    The mononuclear copper(II) complexes (1&2) of ligands L1 [N,N";-bis(2-hydroxy-5-methylbenzyl)-1,4-bis(3-iminopropyl)piperazine] or L2 [N,N";-bis(2-hydroxy-5-bromobenzyl)-1,4-bis(3-iminopropyl) piperazine] have been synthesized and characterised. The single crystal X-ray study had shown that ligands L1 and L2 crystallize in a monoclinic crystal system with P21/c space group. The mononuclear copper(II) complexes show one quasireversible cyclic voltammetric response near cathodic region (-0.77 to -0.85 V) in DMF assignable to the Cu(II)/Cu(I) couple. Binding interaction of the complexes with calf thymus DNA (CT DNA) investigated by absorption studies and fluorescence spectral studies show good binding affinity to CT DNA, which imply both the copper(II) complexes can strongly interact with DNA efficiently. The copper(II) complexes showed efficient oxidative cleavage of plasmid pBR322 DNA in the presence of 3-mercaptopropionic acid as reducing agent through a mechanistic pathway involving formation of singlet oxygen as the reactive species. The Schiff bases and their Cu(II) complexes have been screened for antibacterial activities which indicates that the complexes exhibited higher antimicrobial activity than the free ligands.

  1. Ionic liquids as a key medium for efficient extraction of copper complexes from chia seeds (Salvia hispanica L.).

    Science.gov (United States)

    Wojcieszek, Justyna; Popowski, Dominik; Ruzik, Lena

    2016-05-15

    Due to insufficient information, the aim of study was to concern on the optimization of extraction procedure of selected metal complexes with flavonoids from chia seeds. Evaluation of the amount of elements in compound, not only their total concentration content, is highly important due to the fact, that only a part from total content of metal is absorbed by human body. At the beginning the total amount of elements in chia seeds was established as 14.51±0.42 µg g(-1) for copper, 57.44±1.23 µg g(-1) for manganese, 81.12±1.89 µg g(-1) for zinc and 0.35±0.13 µg g(-1) for cobalt. After the most suitable solvent was established, effects of several parameters on the efficiency of metal extraction were studied. Solvent concentration, solid-solvent ratio, extraction method, extraction time and temperature have been investigated as independent variables. The optimal extraction conditions included vortexing during 20 min in 50°C, using an ionic liquid (1-butyl-3-methylimidazolium bromide) as an extractant, with solid-solvent ratio of 1:20. The determination of total and extractable amount of metals in chia seeds was carried out by standalone ICP MS. In addition, a complementary analysis of extracted metal complexes was performed using SEC-ICP MS method. It was confirmed that the ionic liquid is able to extract different copper complexes in comparison with commonly used solvents. The study indicated that extraction by using an ionic liquid has been successfully applied for determination of metals and metal complexes in chia seeds. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. A new copper(II) complex with 2-thenoyltrifluoroacetone and 2,2-bipyridine: Crystal structure, spectral properties and cytotoxic activity

    Science.gov (United States)

    Lopes, P. S.; Paixão, D. A.; de Paula, F. C. S.; Ferreira, A. M. D. C.; Ellena, J.; Guilardi, S.; Pereira-Maia, E. C.; Guerra, W.

    2013-02-01

    This work reports the synthesis and characterization of a new copper(II) complex with 2-thenoyltrifluoroacetone (HTTA) and 2,2-bipyridine (bipy). The complex was characterized by elemental analysis, UV-Vis, IR and EPR. The crystal structure was determined by single-crystal X-ray diffraction. The copper ion has a distorted square-pyramidal geometry and is coordinated to two bidentate ligands (HTTA and bipy) and a perchlorate ion weakly bonded in the apical position. The crystal packing is stabilized by non-classical hydrogen bonds and weak interactions π-π stacking. In the copper complex, the metal ion binds to HTTA via the oxygen atoms of the β-diketone group and to bipy via its two heterocyclic nitrogens. The title compound inhibits the growth of K562 cells with an IC50 value equal to 28.2 μmol L-1.

  3. Mixed-ligand copper(II) complexes of dipicolylamine and 1,10-phenanthrolines: The role of diimines in the interaction of the complexes with DNA

    Indian Academy of Sciences (India)

    S Ramakrishnan; M Palaniandavar

    2005-03-01

    Mixed-ligand copper(II) complexes of the type [Cu(dipica)(diimine)](ClO4)2, where dipica is di(2-picolyl)amine and diimine is 1,10-phenanthroline (phen), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp), 2,9-dimethyl-1,10-phenanthroline (2,9-dmp) or dipyridoquinoxaline (dpq), have been isolated and characterized by analytical and spectral methods. The copper(II) complexes exhibit a broad band in the visible region around 675 nm and axial EPR spectra in acetonitrile glass (77 K) with ∥ and ∥ values of ~2.22 and 185 × 10-4 cm-1 respectively, suggesting the presence of a square-based coordination geometry for the CuN5 chromophore involving strong axial interaction. The interaction of the complexes with CT DNA has been studied using absorption, emission and circular dichroic spectral methods and viscosity measurements. Absorption spectral titrations reveal that the intrinsic DNA binding affinities are dependent upon the nature of the diimine ligand: dpq > 5,6-dmp > phen > 2,9-dmp. This suggests the involvement of the diimine rather than the dipica `face’ of the complexes in DNA binding. An intercalative mode of DNA interaction, which involves the insertion of dpq and to a lesser extent the phen ring of the complexes in between the DNA base pairs, is proposed. However, interestingly, the 5,6-dmp complex is involved in hydrophobic interaction of the 5,6-dmp ring in the grooves of DNA. The large enhancement in the relative viscosity of DNA on binding to the dpq and 5,6-dmp complexes supports the proposed DNA binding modes. Further, remarkably, the 5,6-dmp complex is selective in exhibiting a positive-induced CD band on binding to DNA suggesting the transition of the B form of CT DNA to A-like conformation. The variation in relative emission intensities of DNA-bound ethidium bromide observed upon treatment with the complexes parallels the trend in DNA binding affinities.

  4. Antitumoral, antihypertensive, antimicrobial, and antioxidant effects of an octanuclear copper(II)-telmisartan complex with an hydrophobic nanometer hole.

    Science.gov (United States)

    Islas, María S; Martínez Medina, Juan J; López Tévez, Libertad L; Rojo, Teófilo; Lezama, Luis; Griera Merino, Mercedes; Calleros, Laura; Cortes, María A; Rodriguez Puyol, Manuel; Echeverría, Gustavo A; Piro, Oscar E; Ferrer, Evelina G; Williams, Patricia A M

    2014-06-02

    A new Cu(II) complex with the antihypertensive drug telmisartan, [Cu8Tlm16]·24H2O (CuTlm), was synthesized and characterized by elemental analysis and electronic, FTIR, Raman and electron paramagnetic resonance spectroscopy. The crystal structure (at 120 K) was solved by X-ray diffraction methods. The octanuclear complex is a hydrate of but otherwise isostructural to the previously reported [Cu8Tlm16] complex. [Cu8Tlm16]·24H2O crystallizes in the tetragonal P4/ncc space group with a = b = 47.335(1), c = 30.894(3) Å, Z = 4 molecules per unit cell giving a macrocyclic ring with a double helical structure. The Cu(II) ions are in a distorted bipyramidal environment with a somewhat twisted square basis, cis-coordinated at their core N2O2 basis to two carboxylate oxygen and two terminal benzimidazole nitrogen atoms. Cu8Tlm16 has a toroidal-like shape with a hydrophobic nanometer hole, and their crystal packing defines nanochannels that extend along the crystal c-axis. Several biological activities of the complex and the parent ligand were examined in vitro. The antioxidant measurements indicate that the complex behaves as a superoxide dismutase mimic with improved superoxide scavenger power as compared with native sartan. The capacity of telmisartan and its copper complex to expand human mesangial cells (previously contracted by angiotensin II treatment) is similar to each other. The antihypertensive effect of the compounds is attributed to the strongest binding affinity to angiotensin II type 1 receptor and not to the antioxidant effects. The cytotoxic activity of the complex and that of its components was determined against lung cancer cell line A549 and three prostate cancer cell lines (LNCaP, PC-3, and DU 145). The complex displays some inhibitory effect on the A549 line and a high viability decrease on the LNCaP (androgen-sensitive) line. From flow cytometric analysis, an apoptotic mechanism was established for the latter cell line. Telmisartan and CuTlm show

  5. Copper Complex in Poly(vinyl chloride) as a Nitric Oxide-Generating Catalyst for the Control of Nitrifying Bacterial Biofilms.

    Science.gov (United States)

    Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

    2015-10-14

    In this study, catalytic generation of nitric oxide by a copper(II) complex embedded within a poly(vinyl chloride) matrix in the presence of nitrite (source of nitric oxide) and ascorbic acid (reducing agent) was shown to effectively control the formation and dispersion of nitrifying bacteria biofilms. Amperometric measurements indicated increased and prolonged generation of nitric oxide with the addition of the copper complex when compared to that with nitrite and ascorbic acid alone. The effectiveness of the copper complex-nitrite-ascorbic acid system for biofilm control was quantified using protein analysis, which showed enhanced biofilm suppression when the copper complex was used in comparison to that with nitrite and ascorbic acid treatment alone. Confocal laser scanning microscopy (CLSM) and LIVE/DEAD staining revealed a reduction in cell surface coverage without a loss of viability with the copper complex and up to 5 mM of nitrite and ascorbic acid, suggesting that the nitric oxide generated from the system inhibits proliferation of the cells on surfaces. Induction of nitric oxide production by the copper complex system also triggered the dispersal of pre-established biofilms. However, the addition of a high concentration of nitrite and ascorbic acid to a pre-established biofilm induced bacterial membrane damage and strongly decreased the metabolic activity of planktonic and biofilm cells, as revealed by CLSM with LIVE/DEAD staining and intracellular adenosine triphosphate measurements, respectively. This study highlights the utility of the catalytic generation of nitric oxide for the long-term suppression and removal of nitrifying bacterial biofilms.

  6. Cationic copper (I) complexes with bulky 1,4-diaza-1,3-butadiene ligands - Synthesis, solid state structure and catalysis

    Science.gov (United States)

    Anga, Srinivas; Kottalanka, Ravi K.; Pal, Tigmansu; Panda, Tarun K.

    2013-05-01

    We report the full characterization of two glyoxal-based ligands N,N bis(diphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh2, 1) and more bulky N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh3, 2) by the condensation reaction of glyoxal and diphenylmethanamine and triphenyl-methanamine respectively. The copper (I) complex of composition [Cu(DADPh2)2]PF6 (3) having two neutral bidentate N,N bis(diphenyl-methyl)-1,4-diaza-1,3-butadiene ligand was prepared by the reaction of [Cu(CH3CN)4]PF6 and 1 in 1:2 ratio in dichloromethane. In a similar reaction with N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (2) and [Cu(CH3CN)4]PF6 in dichloromethane yielded corresponding heteroleptic copper (I) complex [Cu(DADPh3)(CH3CN)2]PF6 (4). Another copper (I) complex [Cu(DADPh2)(PPh3)]PF6 (5) can also be obtained by the one pot reaction involving ligand 1, [Cu(CH3CN)4]PF6 and triphenylphosphine. Solid state structures of all the five compounds were established by single crystal X-ray diffraction analysis. The solid state structures of the copper complexes 3-5 reveal a distorted tetrahedral geometry around the copper (I) centers. The copper complexes 3-5 were tested as catalysts for the coupling reaction of o-iodophenol and phenyl acetylene and it was observed that complex 4 exhibits the highest catalytic activity.

  7. Synthesis, characterization, cytotoxicity and antiangiogenic activity of copper(II) complexes with 1-adamantoyl hydrazone bearing pyridine rings.

    Science.gov (United States)

    Rodić, Marko V; Leovac, Vukadin M; Jovanović, Ljiljana S; Spasojević, Vojislav; Joksović, Milan D; Stanojković, Tatjana; Matić, Ivana Z; Vojinović-Ješić, Ljiljana S; Marković, Violeta

    2016-06-10

    Three novel copper complexes with tridentate N2O ligand di(2-pyridil) ketone 1-adamantoyl hydrazone (Addpy) of the formula [Cu(II)2Cu(I)2(Addpy)2Br2(μ-Br4)] (1), catena-poly[CuCl(μ-Addpy)(μ-Cl)CuCl2]n (2) and [Cu(Addpy)(NCS)2] (3) were synthesized. Complexes are characterized by X-ray crystallography, spectral (UV-Vis, FTIR), electrochemical (CV) analyses, and magnetochemical measurements. Investigation of anticancer potential of Cu(II) complexes, mode of cell death, apoptosis, and inhibition of angiogenesis were performed. All tested malignant cell lines (HeLa, LS174, A549, K562, and MDA-MB-231) showed high sensitivity to the examined Cu(II) complexes. It has been shown that the complexes induce apoptosis in the caspase 3-dependent manner, whereas the anti-angiogenic effects of 1, 2, and 3 have been confirmed in EA.hy926 cells using a tube formation assay.

  8. Unusual conformation of a dinuclear paddle wheel copper(II) complex. Synthesis, structural characterization and EPR studies.

    Science.gov (United States)

    Paredes-García, Verónica; Santana, Ricardo C; Madrid, Rosa; Vega, Andrés; Spodine, Evgenia; Venegas-Yazigi, Diego

    2013-08-05

    An unusual and unique conformation of a paddle wheel type binuclear copper(II) complex containing acetate and acetamido ligands, {Cu2(μ2-O2CCH3)4}(OCNH2CH3) (1), was obtained by solvothermal synthesis. The structural characterization of this compound shows that the apical (acetamido) ligands are disposed at a 62° dihedral angle, generating a special conformation as a consequence of the synthetic method used. This conformation has not been reported in other paddle wheel copper(II) tetraacetate compounds. Electron paramagnetic resonance (EPR) spectra of powder samples of (1) were obtained at 9.5 and 33.8 GHz, while single crystal spectra were obtained at 33.8 GHz with a B0 applied in three orthogonal planes. The fit of the single crystal experimental data allowed gave g∥ = 2.345 ± 0.003, and g⊥ = 2.057 ± 0.005. The angular variation of the EPR line allows evaluation of the fine structure of (1), giving D = -0.337 ± 0.002 cm(-1) and E = -0.005 ± 0.001 cm(-1). The line width angular dependence, used together with the Anderson model and Kubo-Tomita theory, permitted the interdimer interaction to be evaluated as |J'| = (0.051 ± 0.002) cm(-1). Using the powder spectral temperature dependence it was possible to evaluate the intradinuclear exchange coupling constan J0 as -101 ± 2 cm(-1), which is considerably lower than that reported for other analogous copper(II) tetraacetate paddle wheel compounds (Cu(II)-PW), showing the remarkable effect of the conformation of the terminal ligands on the magnetic interaction.

  9. Crystal structures of two mixed-valence copper cyanide complexes with N-methyl-ethylenedi-amine.

    Science.gov (United States)

    Corfield, Peter W R; Sabatino, Alexander

    2017-02-01

    The crystal structures of two mixed-valence copper cyanide compounds involving N-methyl-ethylenedi-amine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3C:C:N)tris(μ2-cyanido-κ2C:N)bis(N-methylethane-1,2-di-amine-κ2N,N')tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link Cu(I) atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra-hedrally bound Cu(I) atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound Cu(I) atoms link these units together to form the network. The Cu(II) atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol-ecular compound (II), [(N-methylethylenediamine-κ(2)N,N')copper(II)]-μ(2)-cyanido-κ(2)C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a Cu(II) atom coordinated by two meen groups with a trigonal-planar Cu(I) atom coordinated by CN groups. The mol-ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol-ecules. In both compounds, the bridging cyanide between the Cu(II) and Cu(I) atoms has the N atom bonded to Cu(II) and the C atom bonded to Cu(I), and the Cu(II) atoms are in a square-pyramidal coordination.

  10. Synthesis, Spectral, Thermal Analysis, Biological Activity and Kinetic Studies of Copper(II)-Pyridine-2,5-dicarboxylate Complexes with 2-Aminomethylpyridine and 8-Hydroxyquinoline.

    Science.gov (United States)

    Colak, Alper Tolga; Colak, Ferdağ; Atar, Necip; Olgun, Asım

    2010-03-01

    In this work we report the synthesis of two novel square-planar copper(II) complexes, namely, (2-aminomethylpyridinium-pyridinedicarboxylato)copper(II) dihydrate, [Cu(pydc)(2-amp)] • 2H2O (1) and (8-hydroxyquinolinum-pyridinedicarboxylato)copper(II) hydrate, [Cu(pydc)(8-HQ)] • H2O (2) (2-amp = 2-aminomethylpyridine, 8-HQ = 8-hydroxyquinoline, H2pydc = pyridine-2,5-dicarboxylic acid or isocinchomeronic acid) and present the first preliminary study on kinetics and biological activities of copper complexes. The synthesized complexes have been characterized by elemental, spectroscopic (FT-IR, UV and mass spectra), thermal analysis, magnetic and conductivity measurements techniques. Kinetic parameters were obtained for each stage of thermal degradation of the complexes using Coats-Redfern and Horowitz-Metzger methods. Antimicrobial activities of two complexes and two ligands were evaluated using agar diffusion method. Antimicrobial activity of complex 2 was determined with the agar dilution methods. The results were compared with two well known antibiotics, namely, tetracycline and nystatin.

  11. Synthesis and Structure of a Ternary Copper(II) Complex with Mixed Ligands of Diethylenetriamine and Picrate: DNA/Protein-Binding Property and In Vitro Anticancer Activity Studies.

    Science.gov (United States)

    Shi, Ya-Ning; Zheng, Kang; Zhu, Ling; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei

    2015-05-01

    Based on the importance of the design and synthesis of transition metal complexes with noncovalent DNA/protein-binding abilities in the field of metallo pharmaceuticals, a new mononuclear ternary copper(II) complex with mixed ligands of diethylenetriamine (dien) and picrate anion (pic), identified as [Cu(dien)(pic)](pic), was synthesized and characterized by elemental analysis, molar conductivity measurement, infrared spectrum, electronic spectral studies, and single-crystal X-ray diffractometry. The structure analysis reveals that the copper(II) complex crystallizes in the monoclinic space group P21 /c, and the copper(II) ion has a distorted square pyramidal coordination geometry. A two-dimensional supramolecular structure is formed through hydrogen bonds. The DNA/bovine serum albumin (BSA)-binding properties of the complex are explored, indicating that the complex can interact with herring sperm DNA via intercalation mode and bind to BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. The in vitro anticancer activity shows that the copper(II) complex is active against the selected tumor cell lines.

  12. Topical Treatment With Liposomal Sodium Copper Chlorophyllin Complex in Subjects With Facial Redness and Erythematotelangiectatic Rosacea: Case Studies.

    Science.gov (United States)

    Vasily, David B

    2015-10-01

    Physicians are often presented with patients complaining of facial redness and difficult to control rosacea. The water soluble so