Showing papers on "Copper published in 2009"

The iron-sulfur clusters of dehydratases are primary intracellular targets of copper toxicity.

Abstract: Excess copper is poisonous to all forms of life, and copper overloading is responsible for several human pathologic processes. The primary mechanisms of toxicity are unknown. In this study, mutants of Escherichia coli that lack copper homeostatic systems (copA cueO cus) were used to identify intracellular targets and to test the hypothesis that toxicity involves the action of reactive oxygen species. Low micromolar levels of copper were sufficient to inhibit the growth of both WT and mutant strains. The addition of branched-chain amino acids restored growth, indicating that copper blocks their biosynthesis. Indeed, copper treatment rapidly inactivated isopropylmalate dehydratase, an iron-sulfur cluster enzyme in this pathway. Other enzymes in this iron-sulfur dehydratase family were similarly affected. Inactivation did not require oxygen, in vivo or with purified enzyme. Damage occurred concomitant with the displacement of iron atoms from the solvent-exposed cluster, suggesting that Cu(I) damages these proteins by liganding to the coordinating sulfur atoms. Copper efflux by dedicated export systems, chelation by glutathione, and cluster repair by assembly systems all enhance the resistance of cells to this metal.

Plasmonic Cu2−xS Nanocrystals: Optical and Structural Properties of Copper-Deficient Copper(I) Sulfides

Abstract: Cu2−xS (x = 1, 0.2, 0.03) nanocrystals were synthesized with three different chemical methods: sonoelectrochemical, hydrothermal, and solventless thermolysis methods in order to compare their common optical and structural properties. The compositions of the Cu2−xS nanocrystals were varied from CuS (covellite) to Cu1.97S (djurleite) through adjusting the reduction potential in the sonoelectrochemical method, adjusting the pH value in the hydrothermal method and by choosing different precursor pretreatments in the solventless thermolysis approach, respectively. The crystallinity and morphology of the products were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), which shows that most of them might be of pure stoichiometries but some of them are mixtures. The obtained XRDs were studied in comparison to the XRD patterns of previously reported Cu2−xS. We found consistently that under ambient conditions the copper deficient Cu1.97S (djurleite) is more stable than Cu2S (chalco...

Copper in plants: acquisition, transport and interactions

Abstract: Copper is an essential metal for plants. It plays key roles in photosynthetic and respiratory electron transport chains, in ethylene sensing, cell wall metabolism, oxidative stress protection and biogenesis of molybdenum cofactor. Thus, a deficiency in the copper supply can alter essential functions in plant metabolism. However, copper has traditionally been used in agriculture as an antifungal agent, and it is also extensively released into the environment by human activities that often cause environmental pollution. Accordingly, excess copper is present in certain regions and environments, and exposure to such can be potentially toxic to plants, causing phytotoxicity by the formation of reactive oxygen radicals that damage cells, or by the interaction with proteins impairing key cellular processes, inactivating enzymes and disturbing protein structure. Plants have a complex network of metal trafficking pathways in order to appropriately regulate copper homeostasis in response to environmental copper level variations. Such strategies must prevent accumulation of the metal in the freely reactive form (metal detoxification pathways) and ensure proper delivery of this element to target metalloproteins. The mechanisms involved in the acquisition and the distribution of copper have not been clearly defined, although emerging data in last decade, mainly obtained on copper uptake, and both intra- and intercellular distribution, as well as on long-distance transport, are contributing to the understanding of copper homeostasis in plants and the response to copper stress. This review gives an overview of the current understanding of main features concerning copper function, acquisition and trafficking network as well as interactions between copper and other elements.

Copper in diseases and treatments, and copper-based anticancer strategies.

Abstract: Copper is found in all living organisms and is a crucial trace element in redox chemistry, growth and development. It is important for the function of several enzymes and proteins involved in energy metabolism, respiration, and DNA synthesis, notably cytochrome oxidase, superoxide dismutase, ascorbate oxidase, and tyrosinase. The major functions of copper-biological molecules involve oxidation-reduction reactions in which they react directly with molecular oxygen to produce free radicals. Therefore, copper requires tightly regulated homeostatic mechanisms to ensure adequate supplies without any toxic effects. Overload or deficiency of copper is associated, respectively, with Wilson disease (WD) and Menkes disease (MD), which are of genetic origin. Researches on Menkes and Wilson disorders have provided useful insights in the field of copper homeostasis and in particular into the understanding of intracellular trafficking and distribution of copper at molecular levels. Therapies based on metal supplementation with copper histidine or removal of copper excess by means of specific copper chelators are currently effective in treating MD and WD, respectively. Copper chelation therapy is now attracting much attention for the investigation and treatment of various neurodegenerative disorders such as Alzheimer, Parkinson and CreutzfeldtJakob. An excess of copper appears to be an essential co-factor for angiogenesis. Moreover, elevated levels of copper have been found in many types of human cancers, including prostate, breast, colon, lung, and brain. On these basis, the employment of copper chelators has been reported to be of therapeutic value in the treatment of several types of cancers as anti-angiogenic molecules. More recently, mixtures of copper chelators with copper salts have been found to act as efficient proteasome inhibitors and apoptosis inducers, specifically in cancer cells. Moreover, following the worldwide success of platinum(II) compounds in cancer chemotherapy, several families of individual copper complexes have been studied as potential antitumor agents. These investigations, revealing the occurrence of mechanisms of action quite different from platinum drugs, head toward the development of new anticancer metallodrugs with improved specificity and decreased toxic side effects.

"Twin copper source" growth of metal-organic framework membrane: Cu(3)(BTC)(2) with high permeability and selectivity for recycling H(2).

Abstract: In this communication, the copper net supported Cu(3)(BTC)(2) membranes have been successfully synthesized by means of a "twin copper source" technique. Separation studies on gaseous mixtures (H(2)/CO(2), H(2)/CH(4), and H(2)/N(2)) using the membrane revealed that the membrane possesses high permeability and selectivity for H(2) over CO(2), N(2), and CH(4). Compared with the conventional zeolite membranes, the copper net supported Cu(3)(BTC)(2) membrane exhibited high permeation flux in gas separation. Such highly efficient copper net supported Cu(3)(BTC)(2) membranes could be used to separate, recycle, and reuse H(2) exhausted from steam reforming natural gas.

SQUAMOSA Promoter Binding Protein–Like7 Is a Central Regulator for Copper Homeostasis in Arabidopsis

Abstract: Expression of miR398 is induced in response to copper deficiency and is involved in the degradation of mRNAs encoding copper/zinc superoxide dismutase in Arabidopsis thaliana. We found that SPL7 (for SQUAMOSA promoter binding protein–like7) is essential for this response of miR398. SPL7 is homologous to Copper response regulator1, the transcription factor that is required for switching between plastocyanin and cytochrome c6 in response to copper deficiency in Chlamydomonas reinhardtii. SPL7 bound directly to GTAC motifs in the miR398 promoter in vitro, and these motifs were essential and sufficient for the response to copper deficiency in vivo. SPL7 is also required for the expression of multiple microRNAs, miR397, miR408, and miR857, involved in copper homeostasis and of genes encoding several copper transporters and a copper chaperone, indicating its central role in response to copper deficiency. Consistent with this idea, the growth of spl7 plants was severely impaired under low-copper conditions.

Intense pulsed light sintering of copper nanoink for printed electronics

Abstract: An intense pulsed light (IPL) from a xenon flash lamp was used to sinter copper nanoink printed on low-temperature polymer substrates at room temperature in ambient condition. The IPL can sinter the copper nanoink without damaging the polymer substrates in extremely short time (2 ms). The microstructure of the sintered copper film was investigated using X-ray powder diffraction (XRD), optical microscopy, scanning electron microscopy (SEM), X-ray micro tomography, and atomic force microscopy (AFM). The sintered copper film has a grainy structure with neck-like junctions. The resulting resistivity was 5 μΩ cm of electrical resistivity which is only 3 times as high as that of bulk copper. The IPL sintering technique allows copper nanoparticles to be used in inkjet printing on low-temperature substrates such as polymers in ambient conditions.

Surface characteristics, copper release, and toxicity of nano- and micrometer-sized copper and copper(II) oxide particles: a cross-disciplinary study.

Abstract: An interdisciplinary and multianalytical research effort is undertaken to assess the toxic aspects of thoroughly characterized nano- and micrometer-sized particles of oxidized metallic copper and copper(II) oxide in contact with cultivated lung cells, as well as copper release in relevant media. All particles, except micrometer-sized Cu, release more copper in serum-containing cell medium (supplemented Dulbecco's minimal essential medium) compared to identical exposures in phosphate-buffered saline. Sonication of particles for dispersion prior to exposure has a large effect on the initial copper release from Cu nanoparticles. A clear size-dependent effect is observed from both a copper release and a toxicity perspective. In agreement with greater released amounts of copper per quantity of particles from the nanometer-sized particles compared to the micrometer-sized particles, the nanometer particles cause a higher degree of DNA damage (single-strand breaks) and cause a significantly higher percentage of cell death compared to cytotoxicity induced by micrometer-sized particles. Cytotoxic effects related to the released copper fraction are found to be significantly lower than the effects related to particles. No DNA damage is induced by the released copper fraction.

Structural biology of copper trafficking.

Abstract: 1.1. Background The use of copper in biological systems coincides with the advent of an oxygen atmosphere about 1.7 billion years ago. The presence of O2 both allowed the oxidation of insoluble Cu(I) to the more soluble and bioavailable Cu(II) and led to the requirement for a redox active metal with potentials in the 0-800 mV range. Not only did copper meet this need, but the oxidation of Fe(II) to the insoluble Fe(III) form rendered the use of iron more energetically expensive.1-5 As a result, copper plays a key role in many proteins that react with O2. Generally, O2-reactive centers are mononuclear (type 2), dinuclear (type 3), or trinuclear (type 2 and type 3). Well studied mononuclear copper enzymes include the monooxygenases dopamine-β-hydroxylase and peptidylglycine α-hydroxylating monooxygenase as well as oxidases that also contain organic cofactors, such as amine, galactose, and lysyl oxidases.6 Dinuclear copper proteins include the O2 carrier hemocyanin and enzymes like tyrosinase and catechol oxidase.7 Copper also plays a key role in numerous electron transfer proteins. Mononuclear type 1 (blue copper) centers are found in proteins such as plastocyanin and azurin.8 The multicopper oxidases like laccase, ascorbate oxidase, and ceruloplasmin contain both a catalytic trinuclear type 2/type 3 site and an electron transfer type 1 site.9,10 The classification of copper centers into types is derived from optical and electron paramagnetic resonance (EPR) spectroscopic properties, and there are some notable exceptions, including the cysteine-bridged dinuclear CuA electron transfer site in cytochrome c oxidase11 and nitrous oxide reductase, the tetranuclear catalytic CuZ center in nitrous oxide reductase,12 and the proposed catalytic copper center in particulate methane monooxygenase.13-15 The same redox properties that render copper useful in all these metalloproteins can lead to oxidative damage in cells. Reaction of Cu(I) with hydrogen peroxide and re-reduction of Cu(II) by superoxide via Fenton and Haber-Weiss chemistry yields hydroxyl radicals that can damage proteins, lipids, and nucleic acids.16 Thus, intracellular copper concentrations must be controlled such that copper ions are provided to essential enzymes, but do not accumulate to deleterious levels. In humans, deficiencies in copper metabolism are linked to diseases such as Menkes syndrome, Wilson disease, prion diseases, and Alzheimer’s disease.17 Several classes of proteins, including membrane transporters,18-20 metallochaperones,21,22 and metalloregulatory proteins,23,24 are implicated in copper homeostasis. These proteins have two functions. First, they ensure that copper is provided to the correct proteins and cellular compartments for necessary activities. Second, these proteins detoxify excess copper. Just as copper-containing proteins and enzymes are found in all kingdoms of life, members of these groups of homeostatic proteins are also widespread,5 and have been structurally and biochemically characterized from eukaryotes and prokaryotes.

Formation of air-stable copper–silver core–shell nanoparticles for inkjet printing

Abstract: Copper nanoparticles can be utilized as a low-cost replacement for silver and gold nanoparticles which are currently used in inkjet printing of conductive patterns. However, the main obstacle for using copper nanoparticles is their spontaneous oxidation at ambient conditions. Here we describe the synthesis of nonoxidizable copper nanoparticles by coating them with a silver shell, and inkjet printing of these particles. The formation of these core–shell nanoparticles is driven by a transmetalation reaction on the surface of copper nanoparticles, where the copper atoms present on the particles' surface are used as the reducing agent for the silver. This process results in formation of solely copper–silver core–shell nanoparticles, with no individual silver particles. It was found that coating 40 nm copper nanoparticles with a 2 nm layer of silver prevents oxidation of the copper core and preserves its metallic characteristic. Characterization of these nanoparticles by HR-TEM, SEM, EDS, XRD, spectrophotometry and XPS confirm the core–shell structure and their stability to oxidation. Inkjet printing of concentrated aqueous dispersions of these copper–silver nanoparticles was done on various substrates, and it was found that conductive and decorative patterns with metallic appearance, stable to oxidation (up to 150 °C) are formed.

Synthesis and Structure Characterization of Copper Terephthalate Metal–Organic Frameworks

Abstract: In this paper, we report on a high-throughput (gram quantities) solvothermal method for the synthesis of copper terephthalate metal–organic frameworks in dmf. While the structure of MOF-2 and some of the associated polymorphs are well known, we know of no equivalent structural studies for the isostructural copper terephthalate (Cu–tpa). The material we have made crystallizes in the C2/m space group. Cu–tpa also exhibits reversible solvent-exchange properties. These properties make this material useful for potential applications in gas storage and catalysis applications. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Electrical and mechanical properties of carbon nanotube reinforced copper nanocomposites fabricated by electroless deposition process

Abstract: Multiwalled carbon nanotube/copper (CNT/Cu) nanocomposite powders with different CNTs volume fractions were prepared by electroless Cu deposition on the CNTs. The CNTs underwent acid treatment, sensitization and electroless copper deposition on their surface respectively. The microstructure of the prepared CNT/Cu nanocomposites was investigated by SEM and HRTEM as well as by XRD analysis. Copper was deposited in a form of a layer on the CNTs surface. The CNT/Cu nanocomposite powders were sintered by spark plasma sintering. The microstructure of the sintered materials were investigated by SEM indicating that the CNTs were homogenous distributed in the copper matrix with good sinterability and porosity content lower than unity in case of 5 and 10 vol.% of CNT/Cu nanocomposites and 2.9 and 3.5% respectively for 15 and 20 vol.% CNT/Cu nanocomposites. The electrical conductivity, hardness and the tensile properties were measured for evaluating the sintered CNT/Cu nanocomposites. The electrical conductivity decreased by increasing CNTs volume fraction in copper matrix, but the hardness was increased by increasing CNTs volume fraction. The Young's modulus was increased and the elongation was decreased by increasing the volume fraction of CNTs in copper matrix. In addition, the yield strength of the sintered materials was increased by increasing CNTs volume fraction except in case of 20 vol.% CNT/Cu composite the material was fractured before yielding.

Electrodeposition of copper composites from deep eutectic solvents based on choline chloride.

Abstract: Here we describe for the first time the electrolytic deposition of copper and copper composites from a solution of the metal chloride salt in either urea–choline chloride, or ethylene glycol–choline chloride based eutectics. We show that the deposition kinetics and thermodynamics are quite unlike those in aqueous solution under comparable conditions and that the copper ion complexation is also different. The mechanism of copper nucleation is studied using chronoamperometry and it is shown that progressive nucleation leads to a bright nano-structured deposit. In contrast, instantaneous nucleation, at lower concentrations of copper ions, leads to a dull deposit. This work also pioneers the use of the electrochemical quartz crystal microbalance (EQCM) to monitor both current efficiency and the inclusion of inert particulates into the copper coatings. This technique allows the first in situ quantification or particulate inclusion. It was found that the composition of composite material was strongly dependent on the amount of species suspended in solution. It was also shown that the majority of material was dragged onto the surface rather than settling on to it. The distribution of the composite material was found to be even throughout the coating. This technology is important because it facilitates deposition of bright copper coatings without co-ligands such as cyanide. The incorporation of micron-sized particulates into ionic liquids has resulted, in one case, in a decrease in viscosity. This observation is both unusual and surprising; we explain this here in terms of an increase in the free volume of the liquid and local solvent perturbation.

Copper-catalyzed C-C bond formation through C-H functionalization: synthesis of multisubstituted indoles from N-aryl enaminones.

Abstract: Because of the economic attractiveness and good functional tolerance of copper-catalyzed methods and hence their potential in large-scale applications, during the past few years there have been remarkable advances in the use of copper catalysis in organic synthesis. An impressive number of Ullmann coupling reactions have been described starting from aryl halides and suitable reagents. Recent reports have shown that copper catalysis can also be used in the formation of C heteroatom and C C bonds through selective catalytic activation of aryl C H bonds, a topic of intense current interest that, for the most part, has witnessed the use of palladium-, rhodium-, and ruthenium-based catalysts. In particular, intramolecular copper-catalyzed ortho C H functionalizations through C N and C O bond-forming reactions have been shown to form benzimidazoles and benzoxazoles from amidines and anilides, respectively. Herein, we disclose a new synthesis of multisubstituted indoles from N-aryl enaminones that involves an intramolecular coppercatalyzed aryl C H functionalization through C C bond formation. The indole moiety is prevalent in a vast array of biologically active natural and nonnatural compounds. Consequently, despite the existence of numerous methods for the synthesis of indole derivatives, the development of new, more efficient procedures is a subject of great importance. N-Aryl enaminones 1 were readily prepared through Sonogashira cross-coupling of terminal alkynes with aroyl chlorides, followed by the conjugate addition of anilines with the resultant a,b-ynones. We initiated our study by examining whether the enaminone 1a could be converted into the corresponding indole 2a. Reactions were usually carried out under an atmosphere of air. After an initial screen of copper catalysts (CuSO4, CuCl2, CuI), we found that 2 a could be isolated in 63 % yield by using CuI, Li2CO3, and 1,10-phenanthroline (phen) in dimethyl acetamide (DMA) after 48 h (Table 1, entry 1). Optimization studies were then performed that varied the

The Nature of Active Copper Species in Cu-HMS Catalyst for Hydrogenation of Dimethyl Oxalate to Ethylene Glycol: New Insights on the Synergetic Effect between Cu0 and Cu+

Abstract: Copper-containing mesoporous HMS catalysts prepared via a one-pot synthesis method based on sol−gel chemistry have been systematically characterized focusing on the effect of copper loading. Structural characterization of a series of different copper loading samples was performed by means of N2 adsorption, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, temperature programmed reduction, N2O titration, and X-ray photoelectron spectroscopy. It is concluded that the copper loading has a great influence on the pore structure of the catalyst. On the basis of the characterizations, the copper species on calcined CuO/HMS samples and reduced Cu/HMS samples were assigned. The synergetic effect between the Cu0 and Cu+ is considered to be responsible for the enhanced catalytic performance in the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG). The maximum ratio of Cu0/Cu+ obtained via tuning the copper loading can result in the highest DMO hydrogenation a...

Copper‐Catalyzed Cross‐Couplings with Part‐per‐Million Catalyst Loadings

Abstract: Due to the importance of functionalized arenes as scaffolds in applied organic materials and biologically relevant molecules, metal-catalyzed cross-couplings have gained significant attention in recent years. 2] Among them Ullmann type C X bond formations are particularly attractive because they often allow the use of low-cost starting materials in combination with readily available copper salts. Whereas the initial protocols required high temperatures and over-stoichiometric quantities of metal, recent approaches involving wellchosen and optimized metal–ligand combinations allow for milder reaction conditions and catalytic turnover. Despite these significant advances it has to be noted that commonly in these catalytic Ullmann type reactions both TONs (turnover numbers) as well as TOFs (turnover frequencies) remain rather limited resulting in the requirement of metal salt amounts in the range of 5 to 10 mol%. Lowering the catalyst loading leads to extended reaction times and decreased product yields. Here, we report on Ullmann type reactions with “homeopathic amounts” of copper salts. During investigations of iron-catalyzed cross-coupling reactions 8] it was noted that for some substrate combinations the catalyst activity depended on the metal salt source and its purity. Those observations suggested a closer look into the effects of metal traces under the applied reaction conditions. Taking into account the results by Taillefer and others on Fe/Cu co-catalyses, copper became the prime metal of choice. To our surprise we found that even with catalyst loadings in the 0.01 mol% range of copper(II) salts N-, O-, and S-arylations were possible to provide the corresponding products in yields > 90%. As a representative example, the coupling between pyrazole (1) and phenyliodide (2, 1.5 equiv) to provide N-arylated product 3 [Eq. (1)] was studied in detail. Further reaction components were N,N’dimethylethylenediamine (DMEDA) as (potential) ligand (20 mol %), K3PO4·H2O as base (2 equiv) [12] and toluene as solvent. The reaction mixture was kept under inert atmosphere at 135 8C in a sealed microwave tube for 24 h.

Copper Compounds in Anticancer Strategies

Abstract: The chemical properties of copper allow it to take part in many biological functions such as electron transfer, catalysis, and structural shaping. The ability to cycle between +1 and +2 oxidation state is one of the features that has been exploited by organisms throughout the evolutionary process. Since copper is potentially toxic to cells also a finely controlled mechanism for copper handling has evolved. On the other side, many copper complexes were synthesized and tested for their anticancer activity in vitro and in vivo. Their ability to kill cancer cells is mainly related to the induction of an oxidative stress, but recently it emerged their ability to inhibit the proteasome, a protein complex whose proteolitic activity is needed by several cellular process. It has generally been described that the toxic effects of copper complexes leads to cell death either by necrosis or through the activation of the apoptotic process. Evidences are rising about the ability of some copper compounds to induce alternative non-apoptotic form of programmed cell death. Since copper is indispensable for the formation of new blood vessels, angiogenesis, a different antitumor approach based on the administration of copper sequestering agents has been attempted and its effectiveness is currently under evaluation by clinical trials. The proven essentiality of copper for angiogenesis, together with the marked sensitivity shown by several cancer cell lines to the copper toxicity, open a new perspective in the anticancer strategy: exploiting the tumor need of copper to accumulate toxic amount of the metal inside its cells.