Copper Release Research Articles

Effects of ecological restoration on speciation and release of copper in lake sediments

The conclusion about the effect of macrophytes rhizosphere and mollusks bioturbation on morphology and mobility of heavy metals in the sediments is not entirely consistent. It is necessary to study further on influence mechanism of macrophytes growth and macrobenthos bioturbation on speciation and release of heavy metals in natural water body. This study intends to explore the influence mechanism of Bellamya aeruginosa (Bel) bioturbation and Pontederia cordata (Pon) growth on the speciation and release kinetics of Cu in sediment through construction of an aquatic organism-water-sediment system by indoor potted experiment. The results show that the particulate Cu in water of the control group and Pon treatment always maintain in lower level and the particulate Cu concentration in water of Bel treatment and Pon+Bel treatment appeared to a certain level of fluctuations at latter period. There was a significant positive correlation between the content of particulate Cu in water and the water turbidity. Bellamya aeruginosa bioturbation has not significantly affected the different speciation of heavy metals in surface sediments and the concentration of reducible Cu and Zn in the rhizosphere sediment was significantly lower than that in the control group.

Role of estuarine natural flocculation process in removal of Cu, Mn, Ni, Pb and Zn

The flocculation of dissolved heavy metals is a process which has an important effect on decreasing the concentration of the colloidal elements during estuarine mixing of river water and sea or ocean water. During this important process, a large amount of colloidal elements change into particles in the form of flock and the dissolved loads decline. This study is performed to evaluate the mechanism of self-purification of heavy metals in Sardabroud's estuary. For this purpose, the effect of salinity (varying from 1 to 8.5‰) on the removal efficiency of colloidal metals (copper, zinc, lead, nickel and magnesium) by flocculation process during mixing of Sardabroud River water and the Caspian Sea water was explored. The flocculation rate of Ni (25%) > Zn (18.59%) > Cu (16.67%) > Mn(5.83%) > Pb(4.86%) indicates that lead and manganese have relatively conservative behavior but nickel, zinc and copper have non-conservative behavior during Sardabroud River’s estuarine mixing. The highest removal efficiencies were obtained between salinities of 1 to 2.5%. Due to flocculation process, annual discharge of dissolved zinc, copper, lead, manganese and nickel release into the Caspian Sea via Sardabroud River would reduce from 44.30 to 36.06 ton/yr, 3.41 to 2.84 ton/yr, 10.22 to 9.7 ton/yr, 8.52 to 7.8 ton/yr and 3.41 to 2.56 ton/yr, respectively. Statistical analysis shows that the flocculation rate of Nickel is highly controlled by redox potential and dissolved oxygen. Moreover, it is found that total dissolved solid, salinity, electrical conductivity and potential of hydrogen do not have a significant influence in flocculation of studied metals.

A novel XRF method to measure environmental release of copper and zinc from antifouling paints

The release of copper (Cu) and zinc (Zn) from vessels and leisure crafts coated with antifouling paints can pose a threat to water quality in semi-enclosed areas such as harbors and marinas as well as to coastal archipelagos. However, no reliable, practical and low-cost method exists to measure the direct release of metals from antifouling paints. Therefore, the paint industry and regulatory authorities are obliged to use release rate measurements derived from either mathematical models or from laboratory studies. To bridge this gap, we have developed a novel method using a handheld X-Ray Fluorescence spectrometer (XRF) to determine the cumulative release of Cu and Zn from antifouling paints. The results showed a strong linear relationship between XRF Kα net intensities and metal concentrations, as determined by ICP-MS. The release of Cu and Zn were determined for coated panels exposed in harbors located in the Baltic Sea and in Kattegat. The field study showed salinity to have a strong impact on the release of Cu, i.e. the release increased with salinity. Contrary, the effect of salinity on Zn was not as evident. As exemplified in this work, the XRF method also makes it possible to identify the governing parameters to the release of Cu and Zn, e.g. salinity and type of paint formulation. Thus, the XRF method can be used to measure environmentally relevant releases of metallic compounds to design more efficient and optimized antifouling coatings.

Comparison of three corrosion inhibitors in simulated partial lead service line replacements

Partial lead service line replacements (PLSLR) were simulated using five recirculating pipe loops treated with either zinc orthophosphate (1mg/L as P), orthophosphate (1mg/L as P) or sodium silicate (10mg/L). Two pipe loops served as ⿿inhibitor-free⿿ (Pb-Cu) and ⿿galvanic free⿿ (Pb-PVC) controls. Changes in water quality (CSMR [0.2 or 1], conductivity [⿿330mS/cm or ⿿560mS/cm], chlorine [1.4mg/L]) were not observed to provide a significant impact on lead or copper release, although galvanic corrosion was shown to be a driving factor. Generally, both orthophosphate and zinc orthophosphate provided better corrosion control for both total and dissolved lead (30min, 6h, 65h) and copper (30min, 6h), when compared to either the inhibitor-free control or the sodium silicate treated system. This work highlights the importance of understanding the complex interplay of corrosion inhibitors on particulate and dissolved species when considering both lead and copper.

Mechanical and microbiological properties and drug release modeling of an etch-and-rinse adhesive containing copper nanoparticles

ObjectivesTo evaluate the effect of addition of copper nanoparticles (CN) at different concentrations into a two-step etch-and-rinse (2-ER) adhesive on antimicrobial activity (AMA), copper release (CR), ultimate tensile strength (UTS), degree of conversion (DC), water sorption (WS), solubility (SO), as well as the immediate (IM) and 1-year resin–dentin bond strength (μTBS) and nanoleakage (NL). MethodsSeven adhesives were formulated according to the addition of CN (0, 0.0075, 0.015, 0.06, 0.1, 0.5 and 1wt%) in adhesive. The AMA was evaluated against Streptococcus mutans using agar diffusion assay. For CR, WS and SO, specimens were constructed and tested for 28 days. For UTS, specimens were tested after 24h and 28 days. For DC, specimens were constructed and tested after 24h by FTIR. After enamel removal, the ER was applied to dentin. After composite resin build-ups, specimens were sectioned to obtain resin–dentin sticks. For μTBS and NL, specimens were tested after 24h and 1-year periods. All data were submitted to statistical analysis (α=0.05). ResultsThe addition of CN provided AMA to the adhesives at all concentrations. Higher CR was observed in adhesives with higher concentration of CN. UTS, DC, WS and SO were not influenced. For μTBS an increase was observed in 0.1 and 0.5% copper group. For NL, a significant decrease was observed in all groups in comparison with control group. After 1-year, no significant reductions of μTBS and no significant increases of NL were observed for copper containing adhesives compared to the control group. SignificanceThe addition of CN in concentrations up to 1wt% in the 2-ER adhesive may be an alternative to provide AMA and preserve the bonding to dentin, without reducing adhesives’ mechanical properties evaluated.

Selective cleavage of the polyphosphoester in crosslinked copper based nanogels: enhanced antibacterial performance through controlled release of copper.

Polymeric architectures with controlled and well-defined structural features are required to render a sustainable antibacterial surface - a key requirement in the design of polymeric membranes for water purification. Herein, surface selective crosslinking of copper oxide-polyphosphoester (CuO-PPE) hybrid nanogels on to polyvinylidene fluoride-styrene maleic anhydride (PVDF/SMA) ultrafiltration membranes was developed. The hybrid nanogels, composed of PPE and CuO, with inherent antifouling and antibacterial properties, were crosslinked using a macroinitiator (polyethylene glycol, PEG) and subsequently grafted on to PVDF/SMA by alkyne-anhydride reaction. Partially hydrolysed SMA solubilizes membrane proteins and the phosphatase/phospholipase triggers the cleavage of PPE segments resulting in controlled release of Cu ions. This unique strategy renders the membrane surface antibacterial through sustained and controlled release of Cu ions thereby generating intracellular reactive oxygen species (ROS). In addition, the enhanced antibiofouling performance of these membranes is facilitated by the presence of the hydrophilic macroinitiator (PEG and PPE). The modified membranes designed in this study are durable and possess long-term stability due to strong covalent interaction between CuO-PPE and the PVDF/SMA membrane. Studies on the flux, porosity and protein adsorption of the membranes were performed. An enhanced flux recovery ratio was observed for the modified membrane due to the pendant PPE groups (from CuO-PPE) which prohibit irreversible protein adsorption on the PVDF surface. The cytotoxicity of CuO-PPE is greatly reduced because of an effective coverage of CuO by biocompatible PPEs. This study opens up new avenues of fabricating "smart" inorganic nanoparticles that can be confined in a soft hybrid polymeric gel network with controlled release of Cu ions thereby precluding ubiquitous bacterial treatment in water filtration systems.

Copper as an alternative antimicrobial coating for implants - An in vitro study.

AIMTo investigate osteoconductive and antimicrobial properties of a titanium-copper-nitride (TiCuN) film and an additional BONIT® coating on titanium substrates.METHODSFor micro-structuring, the surface of titanium test samples was modified by titanium plasma spray (TPS). On the TPS-coated samples, the TiCuN layer was deposited by physical vapor deposition. The BONIT® layer was coated electrochemically. The concentration of copper ions released from TiCuN films was measured by atomic absorption spectrometry. MG-63 osteoblasts on TiCuN and BONIT® were analyzed for cell adhesion, viability and spreading. In parallel, Staphylococcus epidermidis (S. epidermidis) were cultivated on the samples and planktonic and biofilm-bound bacteria were quantified by counting of the colony-forming units.RESULTSField emission scanning electron microscopy (FESEM) revealed rough surfaces for TPS and TiCuN and a special crystalline surface structure on TiCuN + BONIT®. TiCuN released high amounts of copper quickly within 24 h. These release dynamics were accompanied by complete growth inhibition of bacteria and after 2 d, no planktonic or adherent S. epidermidis were found on these samples. On the other hand viability of MG-63 cells was impaired during direct cultivation on the samples within 24 h. However, high cell colonization could be found after a 24 h pre-incubation step in cell culture medium simulating the in vivo dynamics closer. On pre-incubated TiCuN, the osteoblasts span the ridges and demonstrate a flattened, well-spread phenotype. The additional BONIT®coating reduced the copper release of the TiCuN layer significantly and showed a positive effect on the initial cell adhesion.CONCLUSIONThe TiCuNcoating inhibits the formation of bacterial biofilms on orthopedic implants by influencing the “race for the surface” to the advantage of osteoblasts.

Antibacterial activity of copper salts against microorganisms isolated from chronic infected wounds

The antimicrobial activity of copper (Cu+2) is recognized and used as an antimicrobial agent. To evaluate the antimicrobial activity of copper against microorganisms obtained from chronic cutaneous wound infections. Five chemical products that contained copper particles in their composition were tested (zeolite, silica, acetate, nitrate and nanoparticle of copper). The antimicrobial activity against antibiotic resistant strains usually isolated from chronic cutaneous wound infections was determined for two of the products with better performance in copper release. The minimal inhibitory and minimal bactericidal concentrations of copper acetate and nitrate were similar, fluctuating between 400-2,000 µg/ml. The studied copper salts show great potential to be used to control both gram positive and gram negative, antibiotic resistant bacteria isolated from wound infections.

234 - Investigation into the Oxidation of CuATSM as a Mechanism for Copper Release

Copper delivery to superoxide dismutase (SOD) by copper transport agent CuATSM (diacetyl-bis(N4-methylthiosemi-carbazone) copper(II)) is protective in mouse models of amyotrophic lateral sclerosis (ALS). CuATSM is a neutral, hydrophobic compound, able to cross into the CNS without facilitated transport. Reduction of CuII has frequently been proposed as the mechanism of copper release from the ATSM ligand. However, with a reduction potential of -0.46V, CuII reduction will be difficult to accomplish in a cellular environment. In contrast to reduction, oxidation of the ATSM ligand could serve as a mechanism of copper release in a biological system. We investigated the oxidation of CuATSM ligand in an assay utilizing 10-9M horseradish peroxidase (HRP), 2-10 µM hydrogen peroxide, and 10 to 100 µM 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) as a competitive substrate to test for inhibition by CuATSM. Surprisingly, low micromolar concentrations of CuATSM accelerated the oxidation of ABTS by HRP. Our kinetic results suggest that CuATSM was efficiently oxidized by HRP and the CuATSM radical cation in turn oxidized ABTS, We conclude that oxidative reactions involving CuATSM are likely to occur in vivo and need to be further investigated as clinical trials are now underway in treating human ALS patients. This work is supported by funding from the DoD Congressionally Directed Medical Research Program (AL140108) and by Ice Bucket donations made to the ALSA (Research Award ALSA 320).

Migration of copper from nanocopper/LDPE composite films

ABSTRACTThree nanocopper/low-density polyethylene (LDPE) composite films were tested in food simulants (3% acetic acid and 10% ethanol) and real food matrices (rice vinegar, bottled water and Chinese liquor) to explore the behaviours of copper migration using ICP-OES and GFAAS. The effects of exposure time, temperature, nanocopper concentration and contact media on the release of copper from nanocopper/LDPE composite films were studied. It was shown that the migration of copper into 10% ethanol was much less than that into 3% acetic acid at the same conditions. With the increase of nanocopper concentration, exposure time and temperature, the release of copper increased. Copper migration does not appear to be significant in the case of bottled water and Chinese liquor compared with rice vinegar with a maximum value of 0.54 μg mL−1 for the CF-0.25# bags at 70°C for 2 h. The presence and morphology of copper nanoparticles in the films and the topographical changes of the films were confirmed by field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). In this manner, copper nanoparticles of different morphologies, sizes and distribution were found, and samples with higher nanocopper concentration had a more irregular topography. In the case of Fourier transform infrared spectroscopy (FTIR), no chemical bonds formed between copper nanoparticles and LDPE. Copper nanoparticles were just as physically dispersed in LDPE.

Identification of Two Conserved Residues Involved in Copper Release from Chloroplast PIB-1-ATPases

Copper is an essential transition metal for living organisms. In the plant model Arabidopsis thaliana, half of the copper content is localized in the chloroplast, and as a cofactor of plastocyanin, copper is essential for photosynthesis. Within the chloroplast, copper delivery to plastocyanin involves two transporters of the PIB-1-ATPases subfamily: HMA6 at the chloroplast envelope and HMA8 in the thylakoid membranes. Both proteins are high affinity copper transporters but share distinct enzymatic properties. In the present work, the comparison of 140 sequences of PIB-1-ATPases revealed a conserved region unusually rich in histidine and cysteine residues in the TMA-L1 region of eukaryotic chloroplast copper ATPases. To evaluate the role of these residues, we mutated them in HMA6 and HMA8. Mutants of interest were selected from phenotypic tests in yeast and produced in Lactococcus lactis for further biochemical characterizations using phosphorylation assays from ATP and Pi Combining functional and structural data, we highlight the importance of the cysteine and the first histidine of the CX3HX2H motif in the process of copper release from HMA6 and HMA8 and propose a copper pathway through the membrane domain of these transporters. Finally, our work suggests a more general role of the histidine residue in the transport of copper by PIB-1-ATPases.

Structural and Antibacterial Properties of PP/CuO Composite Filaments Having Different Cross Sectional Shapes

AbstractTextile scientists make researches for producing new types of fibers as well as modifying the existing fibers to provide new raw materials for technical textile applications. The easiest way of modifying fiber physical properties is to change the cross sectional shape of a synthetic fiber. Also, composite fibers loaded with different kinds of additives attracted the attention of researchers in the last decades for functionalizing fibers. Some other methods like coating, exhausting, padding or other novel methods can be used for the same purpose. But in these methods, the functional effect is generally not durable enough against several times of washing and abrasion. Also, these methods usually require higher consumption of water and heat when compared to composite fiber production. As a result, in this work the effect of cross sectional modification and composite fiber production were combined in the same fiber. One of the most important functional properties which can be provided by composite fiber production is antibacterial activity. Only a few research papers were published on antibacterial additive doped polypropylene fibers. In this work cupric oxide (CuO) doped antibacterial composite polypropylene (PP) fibers having different cross sectional shapes (circular, trilobal and triangular) were produced and the effect of cross sectional shape and CuO on the antibacterial activity, structural and mechanical properties of the fibers were investigated for the first time. Cross sectional and longitudinal images of composite fibers were evaluated by using optical microscope and scanning electron microscope (SEM). As the released content of active agent is an important parameter for the activity, durability, environmental and health effect of the product, the copper release from the fibers into the water media was investigated by inductively coupled plasma optical emission spectrometry (ICP-OES). Thermal analysis results showed that PP/CuO composite filaments having three different cross sectional shapes can be produced without any significant changes on thermal behavior of fibers. With the increasing content of cupric oxide, tenacities of fibers slightly decreased. Cupric oxide particles also led to some crystallinity changes. All of the composite fibers showed good antibacterial activity against Gram-negative bacterium Escherichia coli.

Biological Effects of Drug-Free Alginate Beads Cross-Linked by Copper Ions Prepared Using External Ionotropic Gelation.

External ionotropic gelation offers a unique possibility to entrap multivalent ions in a polymer structure. The aim of this experimental study was to prepare new drug-free sodium alginate (ALG) particles cross-linked by Cu2+ ions and to investigate their technological parameters (particle size, sphericity, surface topology, swelling capacity, copper content, release of Cu2+ ions, mucoadhesivity) and biological activity (cytotoxicity and efficiency against the most common vaginal pathogens-Herpes simplex, Escherichia coli, Candida albicans) with respect to potential vaginal administration. Beads prepared from NaALG dispersions (3 or 4%) were cross-linked by Cu2+ ions (0.5 or 1.0M CuCl2) using external ionotropic gelation. Prepared mucoadhesive beads with particle size over 1000μm exhibited sufficient sphericity (all ˃0.89) and copper content (214.8-249.07g/kg), which increased with concentration of polymer and hardening solution. Dissolution behaviour was characterized by extended burst effect, followed by 2h of copper release. The efficiency of all samples against the most common vaginal pathogens was observed at cytotoxic Cu2+ concentrations. Anti-HSV activity was demonstrated at a Cu2+ concentration of 546mg/L. Antibacterial activity of beads (expressed as minimum inhibition concentration, MIC) was influenced mainly by the rate of Cu2+ release which was controlled by the extent of swelling capacity. Lower MIC values were found for E. coli in comparison with C. albicans. Sample ALG-3_1.0 exhibited the fastest copper release and was proved to be the most effective against both bacteria. This could be a result of its lower polymer concentration in combination with smaller particle size and thus larger surface area.

Investigation of Structural, Compositional and Anti-Microbial Properties of Copper Thin Film Using Direct Current Magnetron Sputtering for Surgical Instruments

Surgical instruments and other bioimplant devices, owing to their importance in the biomedical industry require high biocompatibility to be used in the human body. Nevertheless, issues of compatibility, bacterial infections are quite common in such devices. Hence development of surface coatings on various substrates for implant applications is a promising technique to combat the issues arising in these implant materials. The present investigation aims at coating copper on stainless steel substrate using DC Magnetron sputtering which is used to achieve film of required thickness (0.5–8[Formula: see text][Formula: see text]m). The deposition pressure, substrate temperature, power supply, distance between the specimen and target are optimized and maintained constant, while the sputtering time (30–110[Formula: see text]min) is varied. The sputtered copper thin film’s morphology, composition are characterized by SEM and EDAX. X-ray diffraction analysis shows copper oriented on (111) and (002) and copper oxide on (111) planes. The contact angle of copper thin film is 92[Formula: see text] while AISI 316L shows 73[Formula: see text]. The antimicrobial studies carried in Staphylococcus aureus, Escherichia Coli, Klebsiella pneumonia and Candida albicans show that the maximum reduction was seen upto 35, 26, 54, 39[Formula: see text]CFU/mL, respectively after 24[Formula: see text]h. The cell viability is studied by MTT assay test on Vero cell line for 24[Formula: see text]h, 48[Formula: see text]h and 72[Formula: see text]h and average cell viability is 43.85%. The copper release from the thin film to the culture medium is 6691[Formula: see text][Formula: see text]g/L (maximum) is estimated from AAS studies. The copper coated substrate does not show much reaction with living Vero cells whereas the bacteria and fungi are found to be destroyed.

Water-Stable Metal-Organic Framework/Polymer Composites Compatible with Human Hepatocytes.

Metal-organic frameworks (MOFs) have demonstrated promise in biomedical applications as vehicles for drug delivery, as well as for the ability of copper-based MOFs to generate nitric oxide (NO) from endogenous S-nitrosothiols (RSNOs). Because NO is a participant in biological processes where it exhibits anti-inflammatory, antibacterial, and antiplatelet activation properties, it has received significant attention for therapeutic purposes. Previous work has shown that the water-stable MOF H3[(Cu4Cl)3-(BTTri)8] (H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), or CuBTTri, produces NO from RSNOs and can be included within a polymeric matrix to form NO-generating materials. While such materials demonstrate potential, the possibility of MOF degradation leading to copper-related toxicity is a concern that must be addressed prior to adapting these materials for biomedical applications. Herein, we present the first cytotoxicity evaluation of an NO-generating CuBTTri/polymer composite material using 3T3-J2 murine embryonic fibroblasts and primary human hepatocytes (PHHs). CuBTTri/polymer films were prepared from plasticized poly(vinyl chloride) (PVC) and characterized via PXRD, ATR-FTIR, and SEM-EDX. Additionally, the ability of the CuBTTri/polymer films to enhance NO generation from S-nitroso-N-acetylpenicillamine (SNAP) was evaluated. Enhanced NO generation in the presence of the CuBTTri/polymer films was observed, with an average NO flux (0.90 ± 0.13 nmol cm(-2) min(-1)) within the range associated with antithrombogenic surfaces. The CuBTTri/polymer films were analyzed for stability in phosphate buffered saline (PBS) and cell culture media under physiological conditions for a 4 week duration. Cumulative copper release in both cell media (0.84 ± 0.21%) and PBS (0.18 ± 0.01%) accounted for less than 1% of theoretical copper present in the films. In vitro cell studies performed with 3T3-J2 fibroblasts and PHHs did not indicate significant toxicity, providing further support for the potential implementation of CuBTTri-based materials in biomedical applications.

Level of Copper in Human Split Ejaculate

The purpose of this study was to understand the details of splits of an ejaculate and to locate the origin of release of copper into semen. Laboratory methods routinely followed for semen analysis were carried out. Copper was estimated by employing atomic absorption spectrophotometry. First split of ejaculate showed the highest number of motile sperm, the quality of which decreased from first to third. Copper level in splits 1, 2 and 3 was 29, 23 and 22 µg%, respectively. This study concluded that copper was released from throughout the genital tract.

Slow‐release Coated Copper Sulfate as an Algicide for Aquaculture

AbstractA coated copper sulfate algicide designed for controlled release of copper was evaluated for its effectiveness in controlling phytoplankton in hybrid catfish, ♀Ictalurus punctatus × ♂Ictalurus furcatus, ponds. Copper concentrations were greater in ponds receiving weekly treatments with copper sulfate crystals than in ponds in which the coated copper sulfate was suspended in porous bags and left in ponds during the study. However, the coated copper sulfate treatment provided a similar degree of phytoplankton control for a period of about 4 mo. Copper additions did not negatively affect catfish survival, production, or feed conversion in either the copper sulfate crystal treatment or in the coated copper sulfate treatment as compared with the control (P > 0.05). Flavor scores for fish did not differ between control and treatments (P > 0.05). The coated copper sulfate appeared to be a potentially effective method for controlling phytoplankton in aquaculture ponds. It would be easier to apply and require fewer applications, and the coated copper algicide would not present a fish toxicity issue that can arise from high copper concentration immediately following copper sulfate crystal treatment.

Effect of copper-doped silicate 13–93 bioactive glass scaffolds on the response of MC3T3-E1 cells in vitro and on bone regeneration and angiogenesis in rat calvarial defects in vivo

The release of inorganic ions from biomaterials could provide an alternative approach to the use of growth factors for improving tissue healing. In the present study, the release of copper (Cu) ions from bioactive silicate (13–93) glass scaffolds on the response of cells in vitro and on bone regeneration and angiogenesis in vivo was studied. Scaffolds doped with varying concentrations of Cu (0–2.0wt.% CuO) were created with a grid-like microstructure by robotic deposition. When immersed in simulated body fluid in vitro, the Cu-doped scaffolds released Cu ions into the medium in a dose-dependent manner and converted partially to hydroxyapatite. The proliferation and alkaline phosphatase activity of pre-osteoblastic MC3T3-E1 cells cultured on the scaffolds were not affected by 0.4 and 0.8wt.% CuO in the glass but they were significantly reduced by 2.0wt.% CuO. The percent new bone that infiltrated the scaffolds implanted for 6weeks in rat calvarial defects (46±8%) was not significantly affected by 0.4 or 0.8wt.% CuO in the glass whereas it was significantly inhibited (0.8±0.7%) in the scaffolds doped with 2.0wt.% CuO. The area of new blood vessels in the fibrous tissue that infiltrated the scaffolds increased with CuO content of the glass and was significantly higher for the scaffolds doped with 2.0wt.% CuO. Loading the scaffolds with bone morphogenetic protein-2 (1μg/defect) significantly enhanced bone infiltration and reduced fibrous tissue in the scaffolds. These results showed that doping the 13–93 glass scaffolds with up to 0.8wt.% CuO did not affect their biocompatibility whereas 2.0wt.% CuO was toxic to cells and detrimental to bone regeneration.

Cleavage of carbon–nitrogen bond in 1,3,5-tri-tert-butyl-1,3,5-triazacyclohexane by copper(I) bromide

Reactions of CuCl, CuCl2 and CuBr2 with 1,3,5-tri-tert-butyl-1,3,5-triazacyclohexane (tBu3tach) resulted in the formation of [(tBu3tach-H)+(CuCl2)] (1), [(tBu3tach)(CuCl2)] (2) and [(tBu3tach-H)+(CuBr2)] (3) respectively. Interestingly, CuBr was found to mediate the cleavage of the C–N bonds of tBu3tach in a vast range of solvents, namely, chloroform, dichloromethane, tetrahydrofuran, acetonitrile and methanol to yield [Cu4Br4(tBuNCH2)4] (4) and stands as an example of C–N bond cleavage of 1,3,5-triazacyclohexane rings by copper salts. Compounds 1 and 3 contains amidinium cations and are unstable in solution towards the release of copper. The release of copper from 3 in solution was confirmed by the isolation of the compound, [CuBr(MeCN)] (5). Formation of the amidinium cations [(tBu3tach-H)+] in 1 and 3 may be avoided by the use of PPh3 to yield [(tBu3tach)Cu(PPh3)](PF6) (6), while the coordinated N-tert-butylmethanimine (tBuNCH2) in 4 could be replaced by PPh3 to yield [Cu4Br4(PPh3)4] (7). Complexes 1–7 are characterized by a combination of single crystal X-ray structure determination and/or elemental analysis, NMR, IR, and UV–Vis spectroscopy, and Mass spectrometry.

KINETIC OF COPPER ADSORPTION IN CALCAREOUS SOIL

Laboratory experiment was carried out to study kinetic of copper adsorption using silt clay loam calcareous Iraqi soil. 5ml of copper nitrate solutions (0,25,100 and500 mg Cu L-1)that were prepared from Cu(NO3)2.3H2O Added to (soil) and (soil+compost) treatments. Compost (0.05gm) was added to (soil+compost) treatment that equal 10g kg-1 soil. The soil samples were incubated at 293±2 K for four incubation periods 24,168,336 and 672 h using Batch equilibrium technique. At each incubation period the soluble copper was determined and kinetic equations were tested. The results showed that the soil had high fixation capacity to copper at all concentrations and treatment. The percentage of copper adsorption was 99.72% at first incubation period followed by gradual increase till the pseudo equilibrium at 336h at all concentration (25,100 and 500 mg Cu L-1 solution). Compost application increased the copper fixation capacity and the copper adsorption curves showed the continuation of adsorption from 24 h. to 336 h. incubation period followed by little release of copper at 672 h. at all concentration and treatments. The power function equation was best described the adsorption of copper and copper adsorption constant (Ka) ranged from 3x10-4 to 5.5x10-3 mg Cu kg-1 h-1, which indicate to the high adsorption capacity of such alkaline soil to adsorb Cu and this will be related to Cu fertilizer management.