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Sample records for soluble cu complexes

  1. Investigation of CuI solubility in potassium metaniobate solution

    International Nuclear Information System (INIS)

    Tanirbergenov, B.

    1980-01-01

    The methods of solubility and potentiometry have been used to established the formation of the iodidometaniobate copper (1) complex [CuINbO 3 ] - in the case of CuI and KNbO 3 interaction. The data of the potentiometric method show the complex dissociation constant to be (0.9+-0.4)x10 -12

  2. Alkane Soluble Transition Metal Complexes.

    Science.gov (United States)

    1983-10-01

    lCam ludoalNm’s W S. has aA F. . Hadley. uppokli *mvahs Capm amAe Hall. 1~i. 6. 08 o.. ILDuataA ulpmr. Cai. 1d. CAM 4. 111aII. lop C Themm. - hftupvtm of...phoahines.3 descrbed previously.’ In this analyuis a series of assumption . isre onadc Our reasons for doing this were twofold. in order to enable a lhoea...nalytical method to be used. It sii be w-me First, pfmospftane complexes have been widely used as be. apparent that the assumptions that must be made

  3. Radioimmunological determination of soluble immune complexes

    Energy Technology Data Exchange (ETDEWEB)

    Falck, P; Meffert, H; Diezel, W; Schmidt, E; Soennichsen, N [Humboldt-Universitaet, Berlin (German Democratic Republic). Bereich Medizin (Charite)

    1979-04-01

    Soluble immune complexes were determined in sera from patients with systemic lupus erythematosus, using /sup 125/I-labelled anti-Ig-antibody and plastics-fixed C1q (component of complement). The detection limit of the method is 0.1 ..mu..g of aggregated human IgG and the range is between 0.1 ..mu..g and 10 ..mu..g per 0.5 ml serum. In 58% of the sera tested an increase of the number of immune complexes was found.

  4. COPPER RESISTANT STRAIN CANDIDA TROPICALIS RomCu5 INTERACTION WITH SOLUBLE AND INSOLUBLE COPPER COMPOUNDS

    Directory of Open Access Journals (Sweden)

    Ie. P. Prekrasna

    2015-10-01

    Full Text Available The focus of the study was interaction of Candida tropicalis RomCu5 isolated from highland Ecuador ecosystem with soluble and insoluble copper compounds. Strain C. tropicalis RomCu5 was cultured in a liquid medium of Hiss in the presence of soluble (copper citrate and CuCl2 and insoluble (CuO and CuCO3 copper compounds. The biomass growth was determined by change in optical density of culture liquid, composition of the gas phase was measured on gas chromatograph, redox potential and pH of the culture fluid was defined potentiometrically. The concentration of soluble copper compounds was determined colorimetrically. Maximal permissible concentration of Cu2+ for C. tropicalis RomCu5 was 30 000 ppm of Cu2+ in form of copper citrate and 500 ppm of Cu2+ in form of CuCl2. C. tropicalis was metabolically active at super high concentrations of Cu2+, despite the inhibitory effect of Cu2+. C. tropicalis immobilized Cu2+ in the form of copper citrate and CuCl2 by it accumulation in the biomass. Due to medium acidification C. tropicalis dissolved CuO and CuCO3. High resistance of C. tropicalis to Cu2+ and ability to interact with soluble and insoluble copper compounds makes it biotechnologically perspective.

  5. Complexation with dissolved organic matter and solubility control of heavy metals in sandy soil

    NARCIS (Netherlands)

    Weng, L.; Temminghoff, E.J.M.; Lofts, S.; Tipping, E.; Riemsdijk, van W.H.

    2002-01-01

    The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The

  6. Effect of cyclodextrin complexation on the aqueous solubility and solubility/dose ratio of praziquantel.

    Science.gov (United States)

    Maragos, Stratos; Archontaki, Helen; Macheras, Panos; Valsami, Georgia

    2009-01-01

    Praziquantel (PZQ), the primary drug of choice in the treatment of schistosomiasis, is a highly lipophilic drug that possesses high permeability and low aqueous solubility and is, therefore, classified as a Class II drug according to the Biopharmaceutics Classification System (BCS). In this work, beta-cyclodextrin (beta-CD) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD) were used in order to determine whether increasing the aqueous solubility of a drug by complexation with CDs, a BCS-Class II compound like PZQ could behave as BCS-Class I (highly soluble/highly permeable) drug. Phase solubility and the kneading and lyophilization techniques were used for inclusion complex preparation; solubility was determined by UV spectroscopy. The ability of the water soluble polymer polyvinylpyrolidone (PVP) to increase the complexation and solubilization efficiency of beta-CD and HP-beta-CD for PZQ was examined. Results showed significant improvement of PZQ solubility in the presence of both cyclodextrins but no additional effect in the presence of PVP. The solubility/dose ratios values of PZQ-cyclodextrin complexes calculated considering the low (150 mg) and the high dose (600 mg) of PZQ, used in practice, indicate that PZQ complexation with CDs may result in drug dosage forms that would behave as a BCS-Class I depending on the administered dose.

  7. Aluminum Solubility in Complex Electrolytes - 13011

    Energy Technology Data Exchange (ETDEWEB)

    Agnew, S.F. [Columbia Energy and Environmental Services, Inc., 1806 Terminal Dr., Richland, WA 99354 (United States); Johnston, C.T. [Dept. of Crop, Soil, and Environmental Sciences, Purdue University, West Lafayette, IN 47907 (United States)

    2013-07-01

    Predicting aluminum solubility for Hanford and Savannah River waste liquids is very important for their disposition. It is a key mission goal at each Site to leach as much aluminum as practical from sludges in order to minimize the amount of vitrified high level waste. And it is correspondingly important to assure that any soluble aluminum does not precipitate during subsequent decontamination of the liquid leachates with ion exchange. This report shows a very simple and yet thermodynamic model for aluminum solubility that is consistent with a wide range of Al liquors, from simple mixtures of hydroxide and aluminate to over 300 Hanford concentrates and to a set of 19 Bayer liquors for temperatures from 20-100 deg. C. This dimer-dS{sub mix} (DDS) model incorporates an ideal entropy of mixing along with previous reports for the Al dimer, water activities, gibbsite, and bayerite thermodynamics. We expect this model will have broad application for nuclear wastes as well as the Bayer gibbsite process industry. (authors)

  8. Effect of Cyclodextrin Complexation on the Aqueous Solubility and Solubility/Dose Ratio of Praziquantel

    OpenAIRE

    Maragos, Stratos; Archontaki, Helen; Macheras, Panos; Valsami, Georgia

    2009-01-01

    Praziquantel (PZQ), the primary drug of choice in the treatment of schistosomiasis, is a highly lipophilic drug that possesses high permeability and low aqueous solubility and is, therefore, classified as a Class II drug according to the Biopharmaceutics Classification System (BCS). In this work, β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HP-β-CD) were used in order to determine whether increasing the aqueous solubility of a drug by complexation with CDs, a BCS-Class II compound ...

  9. Gamma radiolysis of Cu(II) complex of metronidazole

    International Nuclear Information System (INIS)

    Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

    1990-01-01

    Aqueous solutions of Cu(II)Metronidazole (Cu(II)M) at neutral pH were irradiated with 60 Co γ-rays under different conditions of radiolysis. The radiolytic formation of HNO 2 and Cu(I) was followed. The radiolytic yields of chromophore loss of Cu(II)M were also determined under different conditions. The OH radicals attack the metal complex to give the OH adducts of the ligand at C 2 , C 4 , and C 5 either directly or through the formation of Cu(III) species. The C 5 -OH adduct, however, undergoes oxidative denitration and as a result the metal complex is decomposed. The OH adducts also undergo electron transfer to Cu(II) ion to give reduced complex. No denitration was observed due to the reaction of e eq - with the metal complex. On the other hand, the nitro group of the ligand in the complex undergoes successive 4-electron reduction to give hydroxylamino derivative. From the competition kinetics using t-butyl alcohol as the scavenger of OH in N 2 O saturated solution of the metal complex, the rate constant for the reaction of OH with complex was evaluated to be ca. 2.1x10 9 dm 3 mol -1 s -1 which is of the same order as that observed in the case of free metronidazole. (author)

  10. Thermodynamic evaluation of Cu-H-O-S-P system - Phase stabilities and solubilities for OFP-copper

    International Nuclear Information System (INIS)

    Magnusson, Hans; Frisk, Karin

    2013-04-01

    A thermodynamic evaluation for Cu-H-O-S-P has been made, with special focus on the phase stabilities and solubilities for OFP-copper. All binary systems including copper have been reviewed. Gaseous species and stoichiometric crystalline phases have been included for higher systems. Sulphur in OFP-copper will be found in sulphides. The sulphide can take different morphologies but constant stoichiometry Cu 2 S. The solubility of sulphur in FCC-copper reaches ppm levels already at 550 deg C and decreases with lower temperature. No phosphorus-sulphide will be stable, although the copper sulphide can be replaced by copper sulphates at high partial pressure oxygen like in the oxide scale. Phosphorus has a high affinity to oxygen, and phosphorus oxide P 4 O 10 and copper phosphates (Cu 2 P 2 O 7 and Cu 3 (PO 4 ) 2 ) are all more stable than copper oxide Cu 2 O. With hydrogen present at atmospheric pressure, copper phosphates Cu 2 P 2 O 7 and Cu 3 (P 2 O 6 OH) 2 are both more stable than water vapour or aqueous water at temperatures below 400 deg C. At high pressure conditions, the copper phosphates can be reduced giving water. However, the phosphates are still more stable than water vapour. The solubility limit of phosphorus in FCC-copper at 25 deg C is 510 ppm, in equilibrium with copper phosphide Cu 3 P. The major part of phosphorus in OFP-copper will be in solid solution. Oxygen in FCC-copper has a very low solubility. In the presence of a strong oxide forming element such as phosphorus in OFP-copper, the solubility decreases even more. Copper oxides will become stable first when all phosphorus has been consumed, which takes place at twice the phosphorus content, calculated in weight. Hydrogen has a low solubility in copper, calculated as 0.1 ppm at 675 deg C. No crystalline hydrogen phase has been found stable at atmospheric pressures and above 400 deg C. At lower temperatures the hydrogen containing phosphate Cu 3 (P 2 O 6 OH) 2 can become stable. Measured hydrogen

  11. Thermodynamic evaluation of Cu-H-O-S-P system - Phase stabilities and solubilities for OFP-copper

    Energy Technology Data Exchange (ETDEWEB)

    Magnusson, Hans; Frisk, Karin [Swerea KIMAB, Kista (Sweden)

    2013-04-15

    A thermodynamic evaluation for Cu-H-O-S-P has been made, with special focus on the phase stabilities and solubilities for OFP-copper. All binary systems including copper have been reviewed. Gaseous species and stoichiometric crystalline phases have been included for higher systems. Sulphur in OFP-copper will be found in sulphides. The sulphide can take different morphologies but constant stoichiometry Cu{sub 2}S. The solubility of sulphur in FCC-copper reaches ppm levels already at 550 deg C and decreases with lower temperature. No phosphorus-sulphide will be stable, although the copper sulphide can be replaced by copper sulphates at high partial pressure oxygen like in the oxide scale. Phosphorus has a high affinity to oxygen, and phosphorus oxide P{sub 4}O{sub 10} and copper phosphates (Cu{sub 2}P{sub 2}O{sub 7} and Cu{sub 3}(PO{sub 4}){sub 2}) are all more stable than copper oxide Cu{sub 2}O. With hydrogen present at atmospheric pressure, copper phosphates Cu{sub 2}P{sub 2}O{sub 7} and Cu{sub 3}(P{sub 2}O{sub 6}OH){sub 2} are both more stable than water vapour or aqueous water at temperatures below 400 deg C. At high pressure conditions, the copper phosphates can be reduced giving water. However, the phosphates are still more stable than water vapour. The solubility limit of phosphorus in FCC-copper at 25 deg C is 510 ppm, in equilibrium with copper phosphide Cu{sub 3}P. The major part of phosphorus in OFP-copper will be in solid solution. Oxygen in FCC-copper has a very low solubility. In the presence of a strong oxide forming element such as phosphorus in OFP-copper, the solubility decreases even more. Copper oxides will become stable first when all phosphorus has been consumed, which takes place at twice the phosphorus content, calculated in weight. Hydrogen has a low solubility in copper, calculated as 0.1 ppm at 675 deg C. No crystalline hydrogen phase has been found stable at atmospheric pressures and above 400 deg C. At lower temperatures the hydrogen

  12. Complexometric determination: Part I - EDTA and complex formation with the Cu2+ ion

    Directory of Open Access Journals (Sweden)

    Rajković Miloš B.

    2002-01-01

    Full Text Available Compounds forming very stable complexes - chelates, have a wide field of application in analytical chemistry. The most famous group of these compounds are complexons. Complexons represent organic polyaminocarbonic acids as for example ethylenediaminetetraacetic acid (EDTA and its salts. The EDTA molecule has six coordinative sites. It is a hexadentate ligands i.e. it has two binding nitrogen atoms and four oxygen atoms from carboxyl groups and it forms complexes with almost all metal ions. EDTA as a tetraprotonic acid, H4Y disociates through four steps, yielding the ions HsY-, H2Y2-, HY3- and Y4-. Which of the EDTA forms will be encountered in a solution, depends on the pH. Due to the poor solubility of EDTA in pure water, as well as in most organic solvents, the disodium salt of EDTA Na2H2Y-2H2O, under the commercial name complexon III, is utilized for analytical determinations. In water, EDTA forms soluble, stabile chelate complexes with all cations, at the molar ratio 1:1, regardless of the charge of the metal ion. In contrast to other equilibria, which are mainly defined by Le Chatellier's principle, equilibria related to metal-EDTA complex formation are also dependent on the influence of the secondary equilibria of EDTA complex formation. Complexing reactions, which are equilibrium reactions, are simultaneously influenced by the following factors: solution pH and the presence of complexing agents which may also form a stabile complex with metal ions. The secondary reaction influence may be viewed and monitored through conditional stability constants. In the first part of the paper, the reaction of the formation of the Cu2+-ion complex with EDTA is analyzed beginning from the main reaction through various influences of secondary reactions on the complex Cu2+-EDTA: pH effect, complexation effect and hydrolysis effect. The equations are given for conditional stability constants, which include equilibrium reactions under actual conditions.

  13. Synthesis, structure and stability of a chiral imine-based Schiff-based ligand derived from L-glutamic acid and its [Cu4] complex

    Science.gov (United States)

    Muche, Simon; Levacheva, Irina; Samsonova, Olga; Biernasiuk, Anna; Malm, Anna; Lonsdale, Richard; Popiołek, Łukasz; Bakowsky, Udo; Hołyńska, Małgorzata

    2017-01-01

    Studies of the stability of a ligand derived from L-glutamic acid and ortho-vanillin and its new [Cu4] complex are presented. The [Cu4] complex contains a heterocubane [CuII4O4] core and pendant carboxylic groups increasing its solubility in water, also under basic conditions. The stability of the complex in different solvents is confirmed with ESI-MS studies and such experiments as successful recrystallization. The complex is stable also under physiological conditions whereas the ligand is partly decomposed to L-glutamic acid and ortho-vanillin.

  14. Investigation of the solubility and diffusion of Fe atoms in Cu at high temperature using molten salt electrochemistry

    International Nuclear Information System (INIS)

    Wenzl, H.; Sorajic, V.; Bischof, B.

    1977-01-01

    The electrochemical cell CuFesub(n)/KF, LiF, FeF 2 (molten solution)/Fe was used between 800 and 1,000 0 C to produce CuFesub(n) alloys of various copper rich compositions n by electrochemically controlled diffusion. From measurements of cell voltage and current we determined composition, bulk diffusion coefficient D, and atomic solubility limit x 0 of Fe in Cu. The numerical values at the temperature of 950 0 C are D = 0.9 x 10 -9 cm 2 /sec, x 0 = 1.2 at%. (orig.) [de

  15. A new technique for online measurement of total and water-soluble copper (Cu) in coarse particulate matter (PM)

    International Nuclear Information System (INIS)

    Wang, Dongbin; Shafer, Martin M.; Schauer, James J.; Sioutas, Constantinos

    2015-01-01

    This study presents a novel system for online, field measurement of copper (Cu) in ambient coarse (2.5–10 μm) particulate matter (PM). This new system utilizes two virtual impactors combined with a modified liquid impinger (BioSampler) to collect coarse PM directly as concentrated slurry samples. The total and water-soluble Cu concentrations are subsequently measured by a copper Ion Selective Electrode (ISE). Laboratory evaluation results indicated excellent collection efficiency (over 85%) for particles in the coarse PM size ranges. In the field evaluations, very good agreements for both total and water-soluble Cu concentrations were obtained between online ISE-based monitor measurements and those analyzed by means of inductively coupled plasma mass spectrometry (ICP-MS). Moreover, the field tests indicated that the Cu monitor could achieve near-continuous operation for at least 6 consecutive days (a time resolution of 2–4 h) without obvious shortcomings. - Highlights: • A novel only PM sampling and Cu measuring technology is developed. • Very good particle collection efficiency for coarse PM is observed. • Excellent agreement is obtained between Cu ISE and offline ICP-MS measurements. • The new system can be continuously operated for at least 6 consecutive days. - A new technique for online measurements of Cu in coarse PM is described

  16. Nuclease-like activity of some Cu(II) complexes

    International Nuclear Information System (INIS)

    Durackova, Z.; Fenikova, L.; Svorenova, L.; Labudova, O.; Kollarova, M.; Labuda, J.

    1995-01-01

    The nuclease reaction of a copper complex with the macrocyclic Schiff base ligand tetrabenzo[b,f,j,n][a,3,9,13]tetraaza cyclohexadecine (TAAB) at the cleavage of DNA in aerobic conditions and the presence of ascorbic acid has been investigated and compared with that of the copper phenanthroline complex. The AT specifity of the Cu(TAAB) 2+ for both single-stranded and double-stranded DNA templates was observed. (authors), 4 figs., 6 refs

  17. Spectroscopic characterization of some Cu(II) complexes

    International Nuclear Information System (INIS)

    Singh, Puja; Sharma, S.

    2014-01-01

    3-hydroxy-4-methoxy benzaldehyde semicarbazone (HMBS) is a biologically active compound which has several potential donor sites. This compound has been used for complexation with Cu(II) ions to synthesize complexes of general formula [Cu(HMBS) 2 X 2 ] where X is Cl − , NO 3 − and CH 3 COO − . Cu(II) is a d 9 system for which 2 D term is generated. Under O h symmetry, this term splits into 2 E g and 2 T 2g . the ground term 2 Eg is doubly degenerate and hence suffers strong Jahn-Teller effect and accordingly the further splitting of terms occur to lower the symmetry from perfect O h . Here, the ligand occupies four planar positions while the two axial positions have been varied by using different ions like Cl − , NO 3 − and CH 3 COO − . These variations on the axial positions also add to the distortion in O h symmetry. Under strong distortion, the electronic spectral band splits into multiplets exhibiting tetragonal distortion in complexes. The extent of distortion has been derived by the derivation of the two radial parameters D s and D t from electronic spectral bands. The ESR spectra of complexes reveal the real position of the only unpaired electron of the d 9 system in complexes

  18. Modeling Cu{sup 2+}-Aβ complexes from computational approaches

    Energy Technology Data Exchange (ETDEWEB)

    Alí-Torres, Jorge [Departamento de Química, Universidad Nacional de Colombia- Sede Bogotá, 111321 (Colombia); Mirats, Andrea; Maréchal, Jean-Didier; Rodríguez-Santiago, Luis; Sodupe, Mariona, E-mail: Mariona.Sodupe@uab.cat [Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)

    2015-09-15

    Amyloid plaques formation and oxidative stress are two key events in the pathology of the Alzheimer disease (AD), in which metal cations have been shown to play an important role. In particular, the interaction of the redox active Cu{sup 2+} metal cation with Aβ has been found to interfere in amyloid aggregation and to lead to reactive oxygen species (ROS). A detailed knowledge of the electronic and molecular structure of Cu{sup 2+}-Aβ complexes is thus important to get a better understanding of the role of these complexes in the development and progression of the AD disease. The computational treatment of these systems requires a combination of several available computational methodologies, because two fundamental aspects have to be addressed: the metal coordination sphere and the conformation adopted by the peptide upon copper binding. In this paper we review the main computational strategies used to deal with the Cu{sup 2+}-Aβ coordination and build plausible Cu{sup 2+}-Aβ models that will afterwards allow determining physicochemical properties of interest, such as their redox potential.

  19. Modulation of solubility and dissolution of furosemide by preparation of phospholipid complex

    Directory of Open Access Journals (Sweden)

    Mona Semalty

    2014-01-01

    Full Text Available Aim: The aim of this study is to improve the solubility and dissolution of furosemide (a potent high ceiling diuretic used for the treatment of hypertension and a Class IV drug that is low solubility and low permeability drug as per the Biopharmaceutical Classification System by preparing its phospholipid complexes or pharmacosomes. Materials and Methods: Furosemide was complexed with phosphatidylcholine in four different molar ratios (1:1, 1:2, 1:3 and 1:4 by conventional solvent-evaporation technique. The pharmacosomes prepared were evaluated for drug content, solubility, X-ray powder diffraction (XRPD and in-vitro dissolution study. Results: Pharmacosomes of furosemide showed high drug content ranging from 88.30% to 100%. XRPD studies confirmed the formation of phospholipid complex and the amorphization of drug in the complex. The water solubility was found to be increased up to six-fold in the complexes. The octanol solubility also increased in the complexes indicating the probable increase in permeability. The in-vitro dissolution profile of the prepared complexes was found to be much better than furosemide. Conclusion: It was concluded that the phospholipid complexes can be effectively used for improving the solubility, dissolution, permeability and hence the bioavailability of furosemide like Class IV drugs.

  20. A water soluble Cu(I)-NHC for CuAAC ligation of unprotected peptides under open air conditions.

    Science.gov (United States)

    Gaulier, Christelle; Hospital, Audrey; Legeret, Bertrand; Delmas, Agnès F; Aucagne, Vincent; Cisnetti, Federico; Gautier, Arnaud

    2012-04-25

    A reducing agent-free version of CuAAC able to operate under open air conditions is reported. A readily-synthesizable, hydrophilic and highly stable Cu(I)-NHC allows the clean ligations of unprotected peptides comprising sensitive side chains, at millimolar concentrations.

  1. Modulation of solubility and dissolution of furosemide by preparation of phospholipid complex

    OpenAIRE

    Mona Semalty; Prateeksha Badoni; Devendra Singh; Ajay Semalty

    2014-01-01

    Aim: The aim of this study is to improve the solubility and dissolution of furosemide (a potent high ceiling diuretic used for the treatment of hypertension and a Class IV drug that is low solubility and low permeability drug as per the Biopharmaceutical Classification System) by preparing its phospholipid complexes or pharmacosomes. Materials and Methods: Furosemide was complexed with phosphatidylcholine in four different molar ratios (1:1, 1:2, 1:3 and 1:4) by conventional solvent-evaporati...

  2. Increasing solubility of red bell pepper carotenoids by complexation with 2-hydroxypropyl-β-cyclodextrin.

    Science.gov (United States)

    de Lima Petito, Nicolly; da Silva Dias, Daiana; Costa, Valéria Gonçalves; Falcão, Deborah Quintanilha; de Lima Araujo, Kátia Gome

    2016-10-01

    Red bell pepper carotenoids were complexed with 2-hydroxypropyl-β-cyclodextrin (2-HPβCD) in different mass ratios (1:4, 1:6, 1:8 and 1:10) through ultrasonic homogenization in order to increase carotenoid solubility and their use as natural pigment in food. Inclusion complexes, red bell pepper extract and physical mixtures were analyzed by DSC, FT-IR, (1)H NMR and DLS. Solubility assay was performed to identify the effect of complexation on the solubility of carotenoids. From characterization assays, results showed that inclusion process occurred for all tested ratios. Results for water solubility assays demonstrated clear differences between solubility index of inclusion complexes (8.06±2.59-16.55±4.40mg/mL) and physical mixtures (3.53±1.44-7.3±1.88mg/mL), while carotenoid extract was no water soluble, as expected. These results indicated that molecular inclusion of carotenoids in 2-HPβCD was efficient to enhance their solubility in water, enabling application of red bell pepper carotenoid as natural pigment and/or bioactive substances in food. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. ESR studies of heat denaturation in Cu myoglobin complexes

    International Nuclear Information System (INIS)

    Louro, S.R.W.; Ribeiro, S.C.; Bemski, G.

    1975-01-01

    An investigation is made on the behaviour of Cu2 + and Fe3 + in copper doped myoglobin, subjected to heat treatment. ESR is observed at X-band. The amplitude of the g = 5.9 line of the high spin F 3 + in met-myoglobin is studied as a function of the temperature of the heat treatment, the pH and the length of time of exposure to the heat treatment. These experiments are performed for both the pure protein and for the copper-myoglobin complex, at pH between 5 and 8.5. Results concerning the decrease of the amplitude of Fe 3+ high spin signal are discussed in comparison with Hollocher's results in hemoglobin. The Cu spectra obtained are interpreted, with the aid of a computer program, Kivelson and Neiman's results being used to analyse the authors data

  4. Small-angle neutron scattering studies on water soluble complexes ...

    Indian Academy of Sciences (India)

    ... by small-angle neutron scattering. SANS data showed a positive indication of the formation of RCP-SDS complexes. Even though the complete structure of the polyion complexes could not be ascertained, the results obtained give us the information on the local structure in these polymer-surfactant systems. The data were ...

  5. Stabilities of thiomolybdate complexes of iron; implications for retention of essential trace elements (Fe, Cu, Mo) in sulfidic waters.

    Science.gov (United States)

    Helz, George R; Erickson, Britt E; Vorlicek, Trent P

    2014-06-01

    In aquatic ecosystems, availabilities of Fe, Mo and Cu potentially limit rates of critical biological processes, including nitrogen fixation, nitrate assimilation and N2O decomposition. During long periods in Earth's history when large parts of the ocean were sulfidic, what prevented these elements' quantitative loss from marine habitats as insoluble sulfide phases? They must have been retained by formation of soluble complexes. Identities of the key ligands are poorly known but probably include thioanions. Here, the first determinations of stability constants for Fe(2+)-[MoS4](2-) complexes in aqueous solution are reported based on measurements of pyrrhotite (hexagonal FeS) solubility under mildly alkaline conditions. Two linear complexes, [FeO(OH)MoS4](3-) and [(Fe2S2)(MoS4)2](4-), best explain the observed solubility variations. Complexes that would be consistent with cuboid cluster structures were less successful, implying that such clusters probably are minor or absent in aqueous solution under the conditions studied. The new data, together with prior data on stabilities of Cu(+)-[MoS4](2-) complexes, are used to explore computationally how competition of Fe(2+) and Cu(+) for [MoS4](2-), as well as competition of [MoS4](2-) and HS(-) for both metals would be resolved in solutions representative of sulfidic natural waters. Thiomolybdate complexes will be most important at sulfide concentrations near the [MoO4](2-)-[MoS4](2-) equivalence point. At lower sulfide concentrations, thiomolybdates are insufficiently stable to be competitive ligands in natural waters and at higher sulfide concentrations HS(-) ligands out-compete thiomolybdates.

  6. Preparation and characterization of water-soluble ZnSe:Cu/ZnS core/shell quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Lei; Cao, Lixin, E-mail: caolixin@ouc.edu.cn; Su, Ge; Liu, Wei; Xia, Chenghui; Zhou, Huajian

    2013-09-01

    The synthesis and luminescent properties of water-soluble ZnSe:Cu/ZnS core/shell quantum dots (QDs) with different shell thickness are reported in this paper. X-ray powder diffraction (XRD) studies present that the ZnSe:Cu/ZnS core/shell QDs with different shell thickness have a cubic zinc-blende structure. The tests of transmission electron microscope (TEM) pictures exhibit that the QDs obtained are spherical-shaped particles and the average grain size increased from 2.7 to 3.8 nm with the growth of ZnS shell. The emission peak position of QDs has a small redshift from 461 to 475 nm with the growth of ZnS shell within the blue spectral window. The photoluminescence (PL) emission intensity and stability of the ZnSe:Cu core d-dots are both enhanced by coating ZnS shell on the surface of core d-dots. The largest PL intensity of the core/shell QDs is almost 3 times larger than that of Cu doped ZnSe quantum dots (ZnSe:Cu d-dots). The redshift of core/shell QDs compared with the core QDs are observed in both the absorption and the photoluminescence excitation spectra.

  7. Supramolecular Complexation of Carbohydrates for the Bioavailability Enhancement of Poorly Soluble Drugs.

    Science.gov (United States)

    Cho, Eunae; Jung, Seunho

    2015-10-27

    In this review, a comprehensive overview of advances in the supramolecular complexes of carbohydrates and poorly soluble drugs is presented. Through the complexation process, poorly soluble drugs could be efficiently delivered to their desired destinations. Carbohydrates, the most abundant biomolecules, have diverse physicochemical properties owing to their inherent three-dimensional structures, hydrogen bonding, and molecular recognition abilities. In this regard, oligosaccharides and their derivatives have been utilized for the bioavailability enhancement of hydrophobic drugs via increasing the solubility or stability. By extension, polysaccharides and their derivatives can form self-assembled architectures with poorly soluble drugs and have shown increased bioavailability in terms of the sustained or controlled drug release. These supramolecular systems using carbohydrate will be developed consistently in the field of pharmaceutical and medical application.

  8. Study of the formation of soluble complexes of sodium caseinate and xanthan in solution.

    Science.gov (United States)

    Bouhannache, Bouchra; HadjSadok, Abdelkader; Touabet, Abdelkrim

    2017-09-01

    The main objective of this work was to determinate the optimum conditions for the formation of soluble complexes between sodium caseinate and xanthan in solution at neutral pH, in the presence of the NaCl. The study of the influence of the concentrations of these three substances showed that salt was the most influent factor. It worsens the thermodynamic incompatibility of the two biopolymers in solution, when they are present at large amounts. However, it contributes to soluble complexes formation, when sodium caseinate concentration is below 5.5%. In this case, gels with enhanced rheological properties were obtained. Infrared spectroscopy confirmed that the complexes formation within these gels involves hydrophobic interactions. On the other hand, dynamic light scattering revealed that dilution cause their dissociation. These soluble complexes are promising ingredients to ensure new texturing properties.

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

    Science.gov (United States)

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

    2007-07-01

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

  10. Effect of Cyclodextrin Complexation of Curcumin on its Solubility and Antiangiogenic and Anti-inflammatory Activity in Rat Colitis Model

    OpenAIRE

    Yadav, Vivek R.; Suresh, Sarasija; Devi, Kshama; Yadav, Seema

    2009-01-01

    The purpose of the study was to prepare and evaluate the anti-inflammatory activity of cyclodextrin (CD) complex of curcumin for the treatment of inflammatory bowel disease (IBD) in colitis-induced rat model. Inclusion complexes of curcumin were prepared by common solvent and kneading methods. These complexes were further evaluated for increase in solubility of poorly soluble curcumin. The inclusion complexes were characterized for enhancement in solubility, in vitro dissolution, surface morp...

  11. Enhancement of solubility of albendazole by complexation with β-cyclodextrin

    International Nuclear Information System (INIS)

    Moriwaki, C.; Costa, G.L.; Ferracini, C.N.; Matioli, G.; Moraes, F.F. de; Zanin, G.M.; Pineda, E.A.G.

    2008-01-01

    A high dosage of albendazole (ABZ) is required for treating systemic helminth infections because of its low solubility. Aiming at increasing ABZ solubility, complexation with beta-cyclodextrin (β-CD) using aqueous and acetic acid solutions as ABZ solubiliser was studied. In aqueous β-CD, complexation increased solubility 53.4 times, giving a complex equilibrium constant of 1266 L mol -1 with a maximum ABZ concentration of 276 μmol L -1 for 16.3 mmol L -1 β-CD. For complexation in 1.05 mol L -1 acetic acid, UV absorbance spectra and 1 H-NMR analysis confirmed complex formation. The UV absorbance of ABZ/acid acetic/β-CD solutions was modeled by the formation of two complexes with molar ratios 1:1 and 1:2 ABZ:β-CD. When neutralized with NaOH these solutions did not form precipitates only for the ABZ:β-CD molar ratios of 1:8 and 1:10, showing that ABZ solubility could be increased 306 times. Results show that high β-CD molar ratios hold ABZ in solution by complexation enhanced by the acetate anion. (author)

  12. Enhancement of solubility of albendazole by complexation with {beta}-cyclodextrin

    Energy Technology Data Exchange (ETDEWEB)

    Moriwaki, C.; Costa, G.L.; Ferracini, C.N.; Matioli, G. [Universidade Estadual de Maringa (UEM), PR (Brazil). Dept. de Farmacia e Farmacologia]. E-mail: gmatioli@uem.br; Moraes, F.F. de; Zanin, G.M. [Universidade Estadual de Maringa (UEM), PR (Brazil). Dept. de Engenharia Quimica; Pineda, E.A.G. [Universidade Estadual de Maringa (UEM), PR (Brazil). Dept. de Quimica

    2008-04-15

    A high dosage of albendazole (ABZ) is required for treating systemic helminth infections because of its low solubility. Aiming at increasing ABZ solubility, complexation with beta-cyclodextrin ({beta}-CD) using aqueous and acetic acid solutions as ABZ solubiliser was studied. In aqueous {beta}-CD, complexation increased solubility 53.4 times, giving a complex equilibrium constant of 1266 L mol{sup -1} with a maximum ABZ concentration of 276 {mu}mol L{sup -1} for 16.3 mmol L{sup -1} {beta}-CD. For complexation in 1.05 mol L{sup -1} acetic acid, UV absorbance spectra and {sup 1}H-NMR analysis confirmed complex formation. The UV absorbance of ABZ/acid acetic/{beta}-CD solutions was modeled by the formation of two complexes with molar ratios 1:1 and 1:2 ABZ:{beta}-CD. When neutralized with NaOH these solutions did not form precipitates only for the ABZ:{beta}-CD molar ratios of 1:8 and 1:10, showing that ABZ solubility could be increased 306 times. Results show that high {beta}-CD molar ratios hold ABZ in solution by complexation enhanced by the acetate anion. (author)

  13. A contribution to the study of CuSO4.5H2O solubility in aqueous media

    International Nuclear Information System (INIS)

    Juan, D. de; Meseguer, V. F.; Lozano, L. J.

    1999-01-01

    Pentahydrate copper sulphate (Blue vitriol) is a copper salt used in mineralogy as activator reagent in concentration methods by flotation for sulphide ores: In this work, crystallization conditions of copper sulphate solutions have been determined as a function of both temperature and sulphuric acidity. The results obtained showed that Cu 2+ concentration in the solution is mainly a direct function of the logarithm of temperature and the sulfuric acid concentration. The influence of Zn 2+ presence in copper sulphate solubility has been also studied at ambient temperature. Results obtained led to a multiple linear regression between Cu 2+ concentration in the solution and sulphuric acid and Zn 2+ concentrations in the medium. Finally, a comparison between the results obtained and data available in the literature is made. (Author) 5 refs

  14. Pb solubility of the high-temperature superconducting phase Bi2Sr2Ca2Cu3O10+d

    International Nuclear Information System (INIS)

    Kaesche, S.; Majewski, P.; Aldinger, F.

    1994-01-01

    For the nominal composition of Bi 2.27x Pb x Sr 2 Ca 2 Cu 3 O 10+d the lead content was varied from x=0.05 to 0.45. The compositions were examined between 830 degrees C and 890 degrees C which is supposed to be the temperature range over which the so-called 2223 phase (Bi 2 Sr 2 Ca 2 Cu 3 O 10+d ) is stable. Only compositions between x=0.18 to 0.36 could be synthesized in a single phase state. For x>0.36 a lead containing phase with a stoichiometry of Pb 4 (Sr,Ca) 5 CuO d is formed, for x 2 Sr 2 CaCu 2 O 8+d and cuprates are the equilibrium phases. The temperature range for the 2223 phase was found to be 830 degrees C to 890 degrees C but the 2223 phase has extremely varying cation ratios over this temperature range. Former single phase 2223 samples turn to multi phase samples when annealed at slightly higher or lower temperatures. A decrease in the Pb solubility with increasing temperature was found for the 2223 phase

  15. Redox reactions of Cu(II)-amine complexes in aqueous solutions

    International Nuclear Information System (INIS)

    Kumbhar, A.G.; Kishore, Kamal

    2003-01-01

    A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq - with a number of Cu(II)-amine complexes have been determined by following the decay of e aq - absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the λ max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics

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

    Science.gov (United States)

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

    2011-02-01

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

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

    Science.gov (United States)

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

    2011-02-07

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

  18. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    OpenAIRE

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-01-01

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have...

  19. Preparation and characterization of complexes of RE3+ with furfural modified water-soluble chitosan

    Institute of Scientific and Technical Information of China (English)

    WANG Maoyuan; QIU Ligan; MA Guilin

    2008-01-01

    Degraded chitosan, with highly water-solubility, was obtained by the oxidation of chitosan with H2O2, and then reacted with furfural The final product coordinated with the rare earth ions (RE3+ = Sm3+,Eu3+), which led to the formation of the complexes. The prepared complexes were characterized with Inflated Spectroscopy (IR), Ultra Violet (UV), fluorescence, X-Ray Diffraction (XRD), and Thermogravimetric-Differential Scanning Calorimetry (TG-DSC) measurements.

  20. Near-infrared dichroism of a mesogenic transition metal complex and its solubility in nematic hosts

    International Nuclear Information System (INIS)

    Marshall, K.L.; Jacobs, S.D.

    1987-01-01

    A transition metal complex possessing the nematic phase, bis (p-n-butylstyryl-1, 2-dithiolato) nickel, was synthesized and its optical properties and solubility in the nematic hosts K15 and MBBA were investigated. The metal complex displayed a high solubility in both host materials (up to 10% wt/wt) and a strong near-infrared absorption band centered at 860 nm. A blocking extinction of greater than OD = 3 was obtained with a 100 micron pathlength of a 0.5% wt/wt mixture of the nematic metal complex in K15, suggesting its usefulness for passive blocking of near infrared radiation. A 24 micron thick, homogeneously aligned guest-host cell containing a 1% wt/wt mixture of the metal complex in K15 possessed a contrast ratio of nearly 5:1 and a blocking extinction of OD = 3.5 at 860 nm, demonstrating for the first time the existence of near-infrared dichroism in this class of materials. The solubility and blocking extinction of the mesogenic metal complex in K15 was considerably superior to the non-mesogenic near ir laser dye bis(dimethylaminodithiobenzil) nickel in the same host. An interaction of the nematic metal complex in mixtures with MBBA which resulted in the creation of a new absorption band at 1050 nm was also observed. 21 refs., 9 figs

  1. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    Directory of Open Access Journals (Sweden)

    Qing-Xi Wu

    2014-12-01

    Full Text Available Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

  2. Design of chitosan and its water soluble derivatives-based drug carriers with polyelectrolyte complexes.

    Science.gov (United States)

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-12-19

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail.

  3. Design of Chitosan and Its Water Soluble Derivatives-Based Drug Carriers with Polyelectrolyte Complexes

    Science.gov (United States)

    Wu, Qing-Xi; Lin, Dong-Qiang; Yao, Shan-Jing

    2014-01-01

    Chitosan, the cationic polysaccharide derived from the natural polysaccharide chitin, has been studied as a biomaterial for more than two decades. As a polycationic polymer with favorable properties, it has been widely used to form polyelectrolyte complexes with polyanions for various applications in drug delivery fields. In recent years, a growing number of studies have been focused on the preparation of polyelectrolyte complexes based on chitosan and its water soluble derivatives. They have been considered well-suited as biomaterials for a number of vital drug carriers with targeted/controlled release profiles, e.g., films, capsules, microcapsules. In this work, an overview highlights not only the favorable properties of chitosan and its water soluble derivatives but also the good performance of the polyelectrolyte complexes produced based on chitosan. Their various types of applications as drug carriers are reviewed in detail. PMID:25532565

  4. Effect of atmospheric organic complexation on iron-bearing dust solubility

    Directory of Open Access Journals (Sweden)

    R. Paris

    2013-05-01

    Full Text Available Recent studies reported that the effect of organic complexation may be a potentially important process to be considered by models estimating atmospheric iron flux to the ocean. In this study, we investigated this process effect by a series of dissolution experiments on iron-bearing dust in the presence or the absence of various organic compounds (acetate, formate, oxalate, malonate, succinate, glutarate, glycolate, lactate, tartrate and humic acid as an analogue of humic like substances, HULIS typically found in atmospheric waters. Only 4 of tested organic ligands (oxalate, malonate, tartrate and humic acid caused an enhancement of iron solubility which was associated with an increase of dissolved Fe(II concentrations. For all of these organic ligands, a positive linear dependence of iron solubility to organic concentrations was observed and showed that the extent of organic complexation on iron solubility decreased in the following order: oxalate >malonate = tartrate > humic acid. This was attributed to the ability of electron donors of organic ligands and implies a reductive ligand-promoted dissolution. This study confirms that among the known atmospheric organic binding ligands of Fe, oxalate is the most effective ligand promoting dust iron solubility and showed, for the first time, the potential effect of HULIS on iron dissolution under atmospheric conditions.

  5. Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

    Science.gov (United States)

    Novak, Martin; Sipkova, Adela; Chrastny, Vladislav; Stepanova, Marketa; Voldrichova, Petra; Veselovsky, Frantisek; Prechova, Eva; Blaha, Vladimir; Curik, Jan; Farkas, Juraj; Erbanova, Lucie; Bohdalkova, Leona; Pasava, Jan; Mikova, Jitka; Komarek, Arnost; Krachler, Michael

    2016-11-01

    Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ 65 Cu and δ 66 Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ 65 Cu and δ 66 Zn values in snow and rime, extracted by diluted HNO 3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ 65 Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ 65 Cu value of pollution sources (-1.17‰). The variability in δ 65 Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ 66 Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ 66 Zn value of pollution sources (-0.23‰). The variability in δ 66 Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe. Copyright © 2016 Elsevier Ltd. All rights reserved.

  6. Cleaved thioredoxin fusion protein enables the crystallization of poorly soluble ERα in complex with synthetic ligands

    International Nuclear Information System (INIS)

    Cura, Vincent; Gangloff, Monique; Eiler, Sylvia; Moras, Dino; Ruff, Marc

    2007-01-01

    A new crystallization strategy: the presence of cleaved thioredoxin fusion is critical for crystallization of the estrogen nuclear receptor ligand binding domain in complex with synthetic ligands. This novel technique should be regarded as an interesting alternative for crystallization of difficult proteins. The ligand-binding domain (LBD) of human oestrogen receptor α was produced in Escherichia coli as a cleavable thioredoxin (Trx) fusion in order to improve solubility. Crystallization trials with either cleaved and purified LBD or with the purified fusion protein both failed to produce crystals. In another attempt, Trx was not removed from the LBD after endoproteolytic cleavage and its presence promoted nucleation and subsequent crystal growth, which allowed the structure determination of two different LBD–ligand–coactivator peptide complexes at 2.3 Å resolution. This technique is likely to be applicable to other low-solubility proteins

  7. Thermodynamic model of Ni(II) solubility, hydrolysis and complex formation with ISA

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez-Siso, Maria Rosa; Duro, Lara; Bruno, Jordi [Amphos21, Barcelona (Spain); Gaona, Xavier; Altmaier, Marcus [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Inst. for Nuclear Waste Disposal

    2018-04-01

    The solubility of β-Ni(OH){sub 2}(cr) was investigated at T=(22±2) C in the absence and presence of α-isosaccharinic acid (ISA), the main degradation product of cellulose under alkaline pH conditions. Batch solubility experiments were performed from undersaturation conditions under inert gas (Ar) atmosphere. Solubility experiments in the absence of ISA were conducted in 0.5 and 3.0 M NaCl-NaOH solutions at 7.5 ≤ pH{sub m} ≤ 13 (with pH{sub m} = -log{sub 10}[H{sup +}]). XRD analyses of selected solid phases collected after completing the solubility experiments (∼300 days) confirmed that β-Ni(OH){sub 2}(cr) remains as solid phase controlling the solubility of Ni(II) in all investigated conditions. Based on the slope analysis (log{sub 10}[Ni] vs. pH{sub m}) of the solubility data and solid phase characterization, the equilibrium reactions β-Ni(OH){sub 2}(cr)+2 H{sup +} <=> Ni{sup 2+}+2 H{sub 2}O(l) and β-Ni(OH){sub 2}(cr) <=> Ni(OH){sub 2}(aq) were identified as controlling the solubility of Ni(II) within the investigated pH{sub m} region. The conditional equilibrium constants determined from the solubility experiments at different ionic strengths were evaluated with the specific ion interaction theory (SIT). In contrast to the current thermodynamic selection in the NEA-TDB, solubility data collected in the present work does not support the formation of the anionic hydrolysis species Ni(OH){sub 3}{sup -} up to pH{sub m} ≤ 13.0. Solubility experiments in the presence of ISA were conducted in 0.5 M NaCl-NaOH-NaISA solutions with 0.01 M ≤ [NaISA] ≤ 0.2 M and 9 ≤ pH{sub m} ≤ 13. XRD analyses confirmed that β-Ni(OH){sub 2}(cr) is also the solid phase controlling the solubility of Ni(II) in the presence of ISA. Solubility data of all investigated systems can be properly explained with chemical and thermodynamic models including the formation of the complexes NiOHISA(aq), Ni(OH){sub 2}ISA{sup -} and Ni(OH){sub 3}ISA{sup 2-}. The reported data confirm

  8. Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

    International Nuclear Information System (INIS)

    Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gubina, M.Yu.

    1988-01-01

    Stability concetration constants K and solubility of neptunium and plutonium complexes with di- and monobuthylphosphoric acids (APC) and with orthophosphoric and di-2-ethylhexyl-phosphoric acids in 30% TBP solution-n-dodecane system are determined by spectrophotometric titration and radiometry methods. Posibility of forecasting radiation-chemical behaviour of actinids according to data on K and APC radiation-chemical yield values is demonstrated

  9. Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

    International Nuclear Information System (INIS)

    Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gibina, M.Yu.

    1989-01-01

    The concentration stability constants (K s ) and solubility of neptunium and plutonium complexes with di- and monobutylphosphoric acids (APA), as well as with orthophosphoric acid in the system composed of 30% TBP + n-dodecane, have been determined by spectrophotometric titration and radiometry. The feasibility of predicting the radiative chemical behavior of actinides based on their K s values and the radiative chemical yield of APA has been demonstrated

  10. Study of the preparation of Cu-TiC composites by reaction of soluble Ti and ball-milled carbon coating TiC

    Science.gov (United States)

    Xu, Xuexia; Li, Wenbin; Wang, Yong; Dong, Guozhen; Jing, Shangqian; Wang, Qing; Feng, Yanting; Fan, Xiaoliang; Ding, Haimin

    2018-06-01

    In this work, Cu-TiC composites have been successfully prepared by reaction of soluble Ti and carbon coating TiC. Firstly, the ball milling of graphite and TiC mixtures is used to obtain the carbon coating TiC which has fine size and improved reaction activity. After adding the ball milled carbon coating TiC into Cu-Ti melts, the soluble Ti will easily react with the carbon coating to form TiC. This process will also improve the wettability between Cu melts and TiC core. As a result, besides the TiC prepared by reaction of soluble Ti and carbon coating, the ball milled TiC will also be brought into the melts. Some of these ball-milled TiC particles will go on being coated by the formed TiC from the reaction of Ti and the coating carbon and left behind in the composites. However, most of TiC core will be further reacted with the excessive Ti and be transformed into the newly formed TiC with different stoichiometry. The results indicate that it is a feasible method to synthesize TiC in Cu melts by reaction of soluble Ti and ball-milled carbon coating TiC.

  11. Biocompatible Water Soluble Polyacrylic Acid Coated CdSe/Cu Quantum Dot Conjugates for Biomolecule Detection.

    Science.gov (United States)

    Gomaa, Ola M; Okasha, Aly; Hosni, Hany M; El-Hag Ali, Amr

    2018-01-01

    Biocompatible polyacrylic acid functionalized CdSe/Cu quantum dot conjugates were synthesized to be used for biomolecules detection. The study results demonstrate the conjugation of the 2.5-3 nm QD with gram negative bacteria with a low detection limit of 28 cfu/ml. The photoluminescence (PL) intensity was correlated to bacterial count, cellular proteins and exopolysaccharides in the tested samples. Confocal Scanning Laser Microscopy (CSLM) images showed significant QD uptake within the cells, both cytoplasm and DNA were the predominant targeted biomolecules, higher fluorescent uptake was shown in gram negative bacteria than that observed for gram positive bacteria. Moreover, PL showed that there was a distinction between live and dead cells as well as gram negative and gram positive cells. Cell viability was not affected even after 6 days (100% viability) rendering it a non-toxic QD. The method is simple and is performed in a single step within approximately 10 min as compared to multi-step protocols for classical microbial count or fluorescent dye staining. All the above results indicate that the CdSe/Cu-PAA QDs are suitable for biomolecule detection, bio-labeling and bioimaging applications.

  12. Inclusion complex and nanoclusters of cyclodextrin to increase the solubility and efficacy of albendazole.

    Science.gov (United States)

    Pacheco, P A; Rodrigues, L N C; Ferreira, J F S; Gomes, A C P; Veríssimo, C J; Louvandini, H; Costa, R L D; Katiki, L M

    2018-03-01

    Albendazole (ABZ), a benzimidazole widely used to control gastrointestinal parasites, is poorly soluble in water, resulting in variable and incomplete bioavailability. This has favored the appearance ABZ-resistant nematodes and, consequently, an increase in its clinical ineffectiveness. Among the pharmaceutical techniques developed to increase drug efficacy, cyclodextrins (CDs) and other polymers have been extensively used with water-insoluble pharmaceutical drugs to increase their solubility and availability. Our objective was to prepare ABZ formulations, including β-cyclodextrin (βCD) or hydroxypropyl-β-cyclodextrin (HPβCD), associated or not to the water-soluble polymer polyvinylpyrrolidone (PVP). These formulations had their solubility and anthelmintic effect both evaluated in vitro. Also, their anthelmintic efficacy was evaluated in lambs naturally infected with gastrointestinal nematodes (GIN) through the fecal egg count (FEC) reduction test. In vitro, the complex ABZ/HPβCD had higher solubility than ABZ/βCD. The addition of PVP to the complexes increased solubility and dissolution rates more effectively for ABZ/HPβCD than for ABZ/βCD. In vivo, 48 lambs naturally infected with GIN were divided into six experimental groups: control, ABZ, ABZ/βCD, ABZ/βCD-PVP, ABZ/HPβCD, and ABZ/HPβCD-PVP. Each treated animal received 10 mg/kg of body weight (based on the ABZ dose) for three consecutive days. After 10 days of the last administered dose, treatment efficacy was calculated. The efficacy values were as follows: ABZ (70.33%), ABZ/βCD (85.33%), ABZ/βCD-PVP (82.86%), ABZ/HPβCD (78.37%), and ABZ/HPβCD-PVP (43.79%). In vitro, ABZ/HPβCD and ABZ/HPβCD-PVP had high solubility and dissolution rates. In vivo, although the efficacies of ABZ/βCD, ABZ/βCD-PVP, and ABZ/HPβCD increased slightly when compared to pure ABZ, this increase was not significant (P > 0.05).

  13. Soluble dendrimers europium(III) β-diketonate complex for organic memory devices

    International Nuclear Information System (INIS)

    Wang Binbin; Fang Junfeng; Li Bin; You Han; Ma Dongge; Hong Ziruo; Li Wenlian; Su Zhongmin

    2008-01-01

    We report the synthesis of a soluble dendrimers europium(III) complex, tris(dibenzoylmethanato)(1,3,5-tris[2-(2'-pyridyl) benzimidazoly]methylbenzene)-europium(III), and its application in organic electrical bistable memory device. Excellent stability that ensured more than 10 6 write-read-erase-reread cycles has been performed in ambient conditions without current-induced degradation. High-density, low-cost memory, good film-firming property, fascinating thermal and morphological stability allow the application of the dendrimers europium(III) complex as an active medium in non-volatile memory devices

  14. Phase solubility, 1H NMR and molecular modelling studies of bupivacaine hydrochloride complexation with different cyclodextrin derivates

    Science.gov (United States)

    Jug, Mario; Mennini, Natascia; Melani, Fabrizio; Maestrelli, Francesca; Mura, Paola

    2010-11-01

    A novel method, which simultaneously exploits experimental (NMR) and theoretically calculated data obtained by a molecular modelling technique, was proposed, to obtain deeper insight into inclusion geometry and possible stereoselective binding of bupivacaine hydrochloride with selected cyclodextrin derivatives. Sulphobuthylether-β-cyclodextrin and water soluble polymeric β-cyclodextrin demonstrated to be the best complexing agents for the drug, resulting in formation of the most stable inclusion complexes with the highest increase in aqueous drug solubility. The drug-carrier binding modes with these cyclodextrins and phenomena which may be directly related to the higher stability and better aqueous solubility of complexes formed were discussed in details.

  15. Microplasma synthesis on aluminum with additions of iron and nickel soluble complexes in electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Rogov, A.B., E-mail: alex-lab@bk.ru [Nikolaev Institute of Inorganic Chemistry. 3, Acad. Lavrentiev Ave, Novosibirsk, 630090 (Russian Federation); Mironov, I.V.; Terleeva, O.P.; Slonova, A.I. [Nikolaev Institute of Inorganic Chemistry. 3, Acad. Lavrentiev Ave, Novosibirsk, 630090 (Russian Federation)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer Alkaline homogeneous electrolyte with transition metals complexes. Black-Right-Pointing-Pointer Coatings contain metallic iron, nickel and their oxides in alumina-silica matrix. Black-Right-Pointing-Pointer Effect of Fe/Ni ratio on coatings properties and process characteristics. - Abstract: The microplasma synthesis of coatings containing iron and nickel from homogeneous electrolytes has been studied. For stabilization of transition metals in solution, it is proposed to use chelation. It was found that the synthesis of coatings using alternating current leads to the formation of metallic iron and nickel particles in addition to oxide phases. The iron and nickel complexes concentrations ratio in the electrolyte correlates with the coatings composition. Obtained coatings have been studied by scanning electron microscopy with X-ray microanalyser and by X-ray diffraction with Cu and Mo radiation. The metal content in the coating was determined spectrophotometrically from the absorption of iron thiocyanate complexes and nickel dimethylglyoxime complex.

  16. Weak bases and formation of a less soluble lauryl sulfate salt/complex in sodium lauryl sulfate (SLS) containing media.

    Science.gov (United States)

    Bhattachar, Shobha N; Risley, Donald S; Werawatganone, Pornpen; Aburub, Aktham

    2011-06-30

    This work reports on the solubility of two weakly basic model compounds in media containing sodium lauryl sulfate (SLS). Results clearly show that the presence of SLS in the media (e.g. simulated gastric fluid or dissolution media) can result in an underestimation of solubility of some weak bases. We systematically study this phenomenon and provide evidence (chromatography and pXRD) for the first time that the decrease in solubility is likely due to formation of a less soluble salt/complex between the protonated form of the weak base and lauryl sulfate anion. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. In vitro and in vivo studies on the complexes of glipizide with water-soluble β-cyclodextrin-epichlorohydrin polymers.

    Science.gov (United States)

    Nie, Shufang; Zhang, Shu; Pan, Weisan; Liu, Yanli

    2011-05-01

    The purpose of this study was to evaluate the potential of a newly modified cyclodextrin derivative, water-soluble β-cyclodextrin-epichlorohydrin polymer (β-CDP), as an effective drug carrier to enhance the dissolution rate and oral bioavailability of glipizide as a poorly water-soluble model drug. Inclusion complexes of glipizide with β-CDP were prepared by the co-evaporation method and characterized by phase solubility, dissolution, and differential scanning calorimetry. The solubility curve was classified as type A(L), which indicated the formation of 1:1 complex between glipizide and β-CDP. β-CDP had better properties of increasing the aqueous solubility of glipizide compared with HP-β-CD. The dissolution rate of drug from the β-CDP complexes was significantly greater than that of the corresponding physical mixtures indicating that the formation of amorphous complex increased the solubility of glipizide. Moreover, the increment in drug dissolution rate from the glipizide/β-CDP systems was higher than that from the corresponding ones with HP-β-CD, which indicated that β-CDP could provide greater capability of solubilization for poorly soluble drugs. Furthermore, in vivo study revealed that the bioavailability of glipizide was significantly improved by glipizide /β-CDP inclusion complex after oral administration to beagle dogs.

  18. One-Pot Synthesis of Cu(II Complex with Partially Oxidized TTF Moieties

    Directory of Open Access Journals (Sweden)

    Hiroki Oshio

    2012-07-01

    Full Text Available The one-pot synthesis of a Cu(II complex with partially oxidized tetrathiafulvalene (TTF moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF2] [CuICl2] was realized by the simultaneous occurrence of Cu(II complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.

  19. Development and characterization of nanoparticulate formulation of a water soluble prodrug of dexamethasone by HIP complexation.

    Science.gov (United States)

    Gaudana, Ripal; Parenky, Ashwin; Vaishya, Ravi; Samanta, Swapan K; Mitra, Ashim K

    2011-01-01

    The objective of this study was to develop and characterize a nanoparticulate-based sustained release formulation of a water soluble dipeptide prodrug of dexamethasone, valine-valine-dexamethasone (VVD). Being hydrophilic in nature, it readily leaches out in the external aqueous medium and hence partitions poorly into the polymeric matrix resulting in minimal entrapment in nanoparticles. Hence, hydrophobic ion pairing (HIP) complexation of the prodrug was employed with dextran sulphate as a complexing polymer. A novel, solid in oil in water emulsion method was employed to encapsulate the prodrug in HIP complex form in poly(lactic-co-glycolic acid) matrix. Nanoparticles were characterized with respect to size, zeta potential, crystallinity of entrapped drug and surface morphology. A significant enhancement in the entrapment of the prodrug in nanoparticles was achieved. Finally, a simple yet novel method was developed which can also be applicable to encapsulate other charged hydrophilic molecules, such as peptides and proteins.

  20. EPR Study of [Cu(Him)4]·2Br Complex

    International Nuclear Information System (INIS)

    Yıldırım, İ; Karabulut, B

    2016-01-01

    The single crystal of [Cu(Him) 4 ]·2Br (Him: C 3 H 4 N 2 , imidazole) complex has been investigated at ambient temperature in three mutually perpendicular planes by EPR technique. The magnetic environments of [Cu(Him) 4 ]·2Br complex have been identified by EPR technique. The study reveals the existence of two magnetically inequivalent Cu 2+ sites. The principal values of g tensors were obtained. The EPR parameters show that the paramagnetic centers have rhombic symmetry. (paper)

  1. Carboxylate-bridged Cu(II) coordination polymeric complex ...

    Indian Academy of Sciences (India)

    SABITHAKALA THATITURI

    and magnetic materials.10–13 In view of the interest- ing applications, the ... using Cu-Kα λ-radiation (λ = 1.5406Е) at 40 kV and 30. mA. Magnetic moments were ..... netic nature shifts slowly to hard ferromagnetic due to an increase in hopping ...

  2. Solubility enhancement, physicochemical characterization and formulation of fast-dissolving tablet of nifedipine-betacyclodextrin complexes

    Directory of Open Access Journals (Sweden)

    Swati Changdeo Jagdale

    2012-03-01

    Full Text Available The main objective of the study was to enhance the dissolution of nifedipine, a poorly water soluble drug by betacyclodextrin complexation and to study the effect of the preparation method on the in vitro dissolution profile. The stoichiometric ratio determined by phase solubility analysis for inclusion complexation of nifedipine with β-cyclodextrin was 1:1. Binary complex was prepared by different methods and was further characterized using XRD, DSC and FT-IR. A saturation solubility study was carried out to evaluate the increase in solubility of nifedipine. The optimized complex was formulated into fast-dissolving tablets by using the superdisintegrants Doshion P544, pregelatinized starch, crospovidone, sodium starch glycolate and croscarmellose sodium by direct compression. Tablets were evaluated for friability, hardness, weight variation, disintegration and in vitro dissolution. Tablets showed an enhanced dissolution rate compared to pure nifedipine.Este estudo teve por objetivo principal incrementar a dissolução do nifedipino, fármaco pouco solúvel em água, por meio de sua complexação com β-ciclodextrina e estudar o efeito do método de preparação sobre o perfil de dissolução in vitro. A razão estequiométrica, determinada por ensaio de solubilidade de fase, para a complexação de nifedipino por inclusão em β-ciclodextrina foi 1:1. O complexo binário foi preparado por diferentes métodos, sendo caracterizado utilizando-se difratometria de raios X (XRD, calorimetria diferencial de varredura (DSC e espectroscopia no infravermelho com transformada de Fourier (FT-IR. Realizou-se estudo de solubilidade de saturação para avaliar o incremento da solubilidade do nifedipino. O complexo otimizado foi formulado em comprimidos de dissolução rápida preparados por compressão direta, nos quais se utilizaram os superdesintegrantes Doshion P544, amido pré-gelatinizado, crospovidona, amidoglicolato de sódio e croscarmelose s

  3. Electron paramagnetic resonance and density-functional theory studies of Cu(II)-bis(oxamato) complexes.

    Science.gov (United States)

    Bräuer, Björn; Weigend, Florian; Fittipaldi, Maria; Gatteschi, Dante; Reijerse, Edward J; Guerri, Annalisa; Ciattini, Samuele; Salvan, Georgeta; Rüffer, Tobias

    2008-08-04

    In this work we present the investigation of the influence of electronic and structural variations induced by varying the N,N'-bridge on the magnetic properties of Cu(II)- bis(oxamato) complexes. For this study the complexes [Cu(opba)] (2-) ( 1, opba = o-phenylene- bis(oxamato)), [Cu(nabo)] (2-) ( 2, nabo = 2,3-naphthalene- bis(oxamato)), [Cu(acbo)] (2-) ( 3, acbo = 2,3-anthrachinone- bis(oxamato)), [Cu(pba)] (2-) ( 4, pba = propylene- bis(oxamato)), [Cu(obbo)] (2-) ( 5, obbo = o-benzyl- bis(oxamato)), and [Cu(npbo)] (2-) ( 6, npbo = 1,8-naphthalene- bis(oxamato)), and the respective structurally isomorphic Ni(II) complexes ( 8- 13) have been prepared as ( (n)Bu 4N) (+) salts. The new complex ( (n)Bu 4N) 2[Cu(R-bnbo)].2H 2O ( 7, R-bnbo = (R)-1,1'-binaphthalene-2,2'- bis(oxamato)) was synthesized and is the first chiral complex in the series of Cu(II)-bis(oxamato) complexes. The molecular structure of 7 has been determined by single crystal X-ray analysis. The Cu(II) ions of the complexes 1- 7 are eta (4)(kappa (2) N, kappa (2) O) coordinated with a more or less distorted square planar geometry for 1- 6 and a distorted tetrahedral geometry for 7. Using pulsed Electron Nuclear Double Resonance on complex 6, detailed information about the relative orientation of the hyperfine ( A) and nuclear quadrupole tensors ( Q) of the coordinating nitrogens with respect to the g tensor were obtained. Electron Paramagnetic Resonance studies in the X, Q, and W-band at variable temperatures were carried out to extract g and A values of N ligands and Cu ion for 1- 7. The hyperfine values were interpreted in terms of spin population on the corresponding atoms. The obtained trends of the spin population for the monomeric building blocks were shown to correlate to the trends obtained in the dependence of the exchange interaction of the corresponding trinuclear complexes on their geometry.

  4. The electric and thermoelectric properties of Cu(II)-Schiff base nano-complexes

    Science.gov (United States)

    Ibrahim, E. M. M.; Abdel-Rahman, Laila H.; Abu-Dief, Ahmed M.; Elshafaie, A.; Hamdan, Samar Kamel; Ahmed, A. M.

    2018-05-01

    The physical properties, such as electric and optical properties, of metal-Schiff base complexes have been widely investigated. However, their thermoelectric (TE) properties remain unreported. This work presents Cu(II)-Schiff base complexes as promising materials for TE power generation. Therefore, three Cu(II)-Schiff base complexes (namely, [Cu(C32H22N4O2)].3/2H2O, [Cu(C23H17N4O7Br)], and [Cu(C27H22N4O8)].H2O) have been synthesized in nanosized scale. The electric and TE properties have been studied and comprehensive discussions have been presented to promote the nano-complexes (NCs) practical applications in the field of TE power generation. The electrical measurements confirm that the NCs are semiconductors and the electrical conduction process is governed by intermolecular and intramolecular transfer of the charge carriers. The TE measurements reveal that the Cu(II)-Schiff base NCs are nondegenerate P-type semiconductors. The measured Seebeck coefficient values were higher compared to the values reported in previous works for other organic materials indicating that the complexes under study are promising candidates for theremoelectric applications if the electrical conductivity could be enhanced.

  5. New strategies in actinide separation - water-soluble complexing agents for the innovative SANEX process

    International Nuclear Information System (INIS)

    Ruff, Christian M.; Muelllich, Udo; Geist, Andreas; Panak, Petra J.

    2012-01-01

    Reduction of the radiotoxicity and thermal output of radioactive wastes prior to their permanent disposal is a topic of extreme interest for the issue of final nuclear waste disposal. One possibility to this end is a process referred to as actinide separation. This process can be optimised by means of a newly developed water-soluble molecule, as has been shown in studies on the molecule's complex chemistry using ultra-modern laser-based spectroscopy methods under process-relevant reaction conditions. Through the use of curium (III) and europium (III), which as members of the trivalent actinides and lanthanides family have excellent spectroscopic properties, it has been possible to generate spectroscopic and thermodynamic data which will facilitate our understanding of the complex chemistry and extraction chemistry of this molecule family.

  6. Electrospinning fabrication and oxygen sensing properties of Cu(I) complex-polystyrene composite microfibrous membranes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Liyan, E-mail: wanglykmmc@163.co [Department of Orthodontics, School of Stomatology, Fourth Military Medical University, XiAn (China); Xu Yun [Department of Orthodontics, School of Stomatology, KunMing Medical College, Kunming (China); Lin Zhu [Department of Orthodontics, School of Stomatology, Fourth Military Medical University, XiAn (China); Zhao Ning [Department of Orthodontics, School of Stomatology, West China College, SiChuan University, ChengDu (China); Xu Yanhua [Department of Orthodontics, School of Stomatology, KunMing Medical College, Kunming (China)

    2011-07-15

    In this paper, a phosphorescent Cu(I) complex of [Cu(POP)(ECI-Phen)]BF{sub 4}, where POP=bis[2-(diphenylphosphino)phenyl]ether, and ECI-Phen=1-ethyl-2-(N-ethyl-carbazole-yl-4-)imidazo[4,5-f]1,10-phenanthroline, is incorporated into a polystyrene matrix of polystyrene (PS) to form microfibers membranes. The possibility of using the resulted composite microfibrous membranes as an optical oxygen sensor is explored. Good linearity and short response time are obtained with a sensitivity of 9.8. These results suggest that phosphorescent [Cu(POP)(ECI-Phen)]BF{sub 4} is a promising candidate for oxygen-sensors and PS is an excellent matrix for oxygen sensing material because it owns a large surface-area-to-volume ratio and can supply a homogeneous matrix for probe molecules. Further analysis suggests that the molecular structure of diamine ligand in Cu(I) complexes is critical for sensitivity due to the characteristic electronic structure of excited state Cu(I) complexes. - Highlights: {yields} Cu(I) complex is incorporated into polystyrene matrix to form nanofibers. {yields} Resulted sample exhibit good linearity and short response time. {yields} PS is an excellent matrix for oxygen sensing material for probe molecules. {yields} Molecular structure of diamine ligand is critical for sensitivity.

  7. Electrospinning fabrication and oxygen sensing properties of Cu(I) complex-polystyrene composite microfibrous membranes

    International Nuclear Information System (INIS)

    Wang Liyan; Xu Yun; Lin Zhu; Zhao Ning; Xu Yanhua

    2011-01-01

    In this paper, a phosphorescent Cu(I) complex of [Cu(POP)(ECI-Phen)]BF 4 , where POP=bis[2-(diphenylphosphino)phenyl]ether, and ECI-Phen=1-ethyl-2-(N-ethyl-carbazole-yl-4-)imidazo[4,5-f] 1,10-phenanthroline, is incorporated into a polystyrene matrix of polystyrene (PS) to form microfibers membranes. The possibility of using the resulted composite microfibrous membranes as an optical oxygen sensor is explored. Good linearity and short response time are obtained with a sensitivity of 9.8. These results suggest that phosphorescent [Cu(POP)(ECI-Phen)]BF 4 is a promising candidate for oxygen-sensors and PS is an excellent matrix for oxygen sensing material because it owns a large surface-area-to-volume ratio and can supply a homogeneous matrix for probe molecules. Further analysis suggests that the molecular structure of diamine ligand in Cu(I) complexes is critical for sensitivity due to the characteristic electronic structure of excited state Cu(I) complexes. - Highlights: → Cu(I) complex is incorporated into polystyrene matrix to form nanofibers. → Resulted sample exhibit good linearity and short response time. → PS is an excellent matrix for oxygen sensing material for probe molecules. → Molecular structure of diamine ligand is critical for sensitivity.

  8. Soluble/insoluble (dilute-HCl-extractable fractionation of Cd, Pb and Cu in Antarctic snow and its relationship with metal fractionations in the aerosol

    Directory of Open Access Journals (Sweden)

    Annibaldi A.

    2013-04-01

    Full Text Available A chemical fractionation methodology for determination of the (water soluble and the insoluble (dilute-HCl-extractable fractions of Cd, Pb and Cu in Antarctic snow was set-up and verified for the additivity of the two fractions detected. Molten samples were filtrated and the water-insoluble fraction was extracted by dilute ultrapure HCl (pH ~1.5. Metal determinations were carried out in the two fractions by square wave anodic stripping voltammetry. The total metal concentrations in samples collected in the 2000–2001 austral summer in a clean area (Faraglione Camp in the neighbourhood of the Mario Zucchelli Italian Station were of the order of Cd 10-20 pg g−1, Pb 20–40 pg g−1, Cu 60–120 pg g−1 with an approximate equidistribution between soluble and insoluble fractions. These fractionations compare well (and show a quite consistent temporal trend with those observed in the aerosol samples collected in the same area/period and confirm the close relationship between metal distributions in snow/ice and in the aerosol. At the station metal concentrations increase due to anthropic contribution and the distribution changes with Cd predominantly present in the soluble fraction (~80%, while Pb and Cu are more concentrated in the insoluble fraction, 70–80% and ~70%, respectively.

  9. Methyl-β-cyclodextrin quaternary ammonium chitosan conjugate: nanoparticles vs macromolecular soluble complex

    Science.gov (United States)

    Piras, Anna Maria; Fabiano, Angela; Chiellini, Federica; Zambito, Ylenia

    2018-01-01

    Purpose The present study aimed to compare a novel cyclodextrin–polymer–drug complex in solution with a dispersed supramolecular nanosize system, made of the same complex, for ability to carry dexamethasone (DEX) across excised rat intestine. Results Methyl-β-cyclodextrin-quaternary ammonium chitosan conjugate (QA-Ch-MCD) was obtained by covalent grafting through a 10-atom spacer. The conjugate was characterized by 1H-NMR, resulting in 24.4% w/w of MCD content. Phase solubility profile analysis of the QA-Ch-MCD/DEX complex yielded an association constant of 14037 M−1, vs 4428 M−1 for the plain MCD/DEX complex. Nanoparticle (NP) dispersions resulted from ionotropic gelation of the QA-Ch-MCD/DEX complex by sodium tripolyphosphate, leading to 9.9%±1.4% drug loading efficiency. The mean diameter and zeta potential for NP were 299±32 nm (polydispersity index [PI] 0.049) and 11.5±1.1 mV, respectively. Those for QA-Ch-MCD/DEX were 2.7±0.4 nm (PI 0.048) and 6.7±0.6 mV. QA-Ch-MCD/DEX solutions and corresponding NP dispersions were compared in vitro for water-assisted transport through mucus, DEX permeation through excised rat intestine, and ex vivo mucoadhesivity. The complex showed higher mucoadhesion and lower transport rate through mucus; also, it provided faster drug permeation across excised rat intestine. Conclusion Carrier adhesion to mucus surface has played a most important role in favoring transepithelial permeation. Then, within the concerns of the present study, the use of NP seems not to provide any determinant advantage over using the simpler macromolecular complex. PMID:29731628

  10. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  11. Thermodynamic method for obtaining the solubilities of complex medium-sized chemicals in pure and mixed solvents

    DEFF Research Database (Denmark)

    Abildskov, Jens; O'Connell, J.P.

    2005-01-01

    This paper extends our previous simplified approach to using group contribution methods and limited data to determine differences in solubility of sparingly soluble complex chemicals as the solvent is changed. New applications include estimating temperature dependence and the effect of adding cos....... Though we present no new solution theory, the paper shows an especially efficient use of thermodynamic models for solvent and cosolvent selection for product formulations. Examples and discussion of applications are given. (c) 2004 Elsevier B.V. All rights reserved.......This paper extends our previous simplified approach to using group contribution methods and limited data to determine differences in solubility of sparingly soluble complex chemicals as the solvent is changed. New applications include estimating temperature dependence and the effect of adding...

  12. Complex impedance spectra of chip inductor using Li-Zn-Cu-Mn ferrite

    International Nuclear Information System (INIS)

    Nakamura, Tatsuya; Naoe, Masayuki; Yamada, Yoshihiro

    2006-01-01

    A multi-layer chip inductor (MCI) was fabricated using polycrystalline Li-Zn-Cu-Mn ferrite and the green-sheet technique, and its complex impedance spectrum was evaluated with the help of numerical calculations. The complex impedance spectra of the MCI component using Ni-Zn-Cu ferrite, which have been widely used for this application, were very sensitive to the residual stress and deviated much from the calculated values; however, it was found that the complex impedance spectrum of the MCI component using Li-Zn-Cu-Mn ferrite is quite well reproduced by calculation, where the complex permittivity and permeability of the polycrystalline ferrite as well as the MCI dimensions, were used. It implied that the magneto-striction effect was negligible in case of MCI using Li-Zn-Cu-Mn ferrite, and that the difference was related to magneto-strictive coefficient of the polycrystalline ferrite. Consequently, utilization of Li-Zn-Cu-Mn ferrite enabled us to easily design the complex impedance of MCI component

  13. Preparation and characterization of Schiff base Cu(II) complex and its applications on textile materials

    Science.gov (United States)

    Oylumluoglu, G.; Oner, J.

    2017-10-01

    Schiff base ligands are regarded as an important class of organic compounds on account of the fact that their complexation ability with transition metal ions. A new monomeric Schiff base Cu(II) complex, [Cu(HL)2], 1 [H2L = 2-((E)-(2-hydroxypropylimino)methyl)-4-nitrophenol] has been synthesized and characterized by elemental analysis, UV and IR spectroscopy, single crystal X-ray diffraction and photoluminescence study. While the Schiff base ligand and its Cu(II) complex are excited at λex = 349 nm in UV region, the Schiff base ligand shows a blue emission band at λmax = 480 nm whereas its Cu(II) complex shows a strong green emission band at λmax = 520 nm in the solid state at room temperature. The luminescent properties showed that the Schiff base ligand and its Cu(II) complex can be used as novel potential candidates for applications in textile such as UV-protection, antimicrobial, laundry and functional bleaching treatments.

  14. Enhancement of norfloxacin solubility via inclusion complexation with β-cyclodextrin and its derivative hydroxypropyl-β-cyclodextrin

    Directory of Open Access Journals (Sweden)

    Gabriel Onn Kit Loh

    2016-08-01

    Full Text Available The objectives of the study were to investigate the effects of β-cyclodextrin (βCD and hydroxypropyl-β-cyclodextrin (HPβCD on the solubility and dissolution rate of norfloxacin prepared using three different methods, at drug to cyclodextrin weight ratios of 1:1, 1:2, 1:4 and 1:8. All the methods increased the solubility and dissolution rate of norfloxacin via inclusion complexation with βCD and HPβCD. Norfloxacin was converted from crystalline to amorphous form through inclusion complexation. Solvent evaporation method was the most effective method in terms of norfloxacin solubilisation, while inclusion complex of HPβCD has higher solubility than βCD complex when prepared using the same procedure.

  15. Prevention of Acid Mine Drainage Through Complexation of Ferric Iron by Soluble Microbial Growth Products

    Science.gov (United States)

    Pandey, S.; Yacob, T. W.; Silverstein, J.; Rajaram, H.; Minchow, K.; Basta, J.

    2011-12-01

    Acid mine drainage (AMD) is a widespread environmental problem with deleterious impacts on water quality in streams and watersheds. AMD is generated largely by the oxidation of metal sulfides (i.e. pyrite) by ferric iron. This abiotic reaction is catalyzed by conversion of ferrous to ferric iron by iron and sulfur oxidizing microorganisms. Biostimulation is currently being investigated as an attempt to inhibit the oxidation of pyrite and growth of iron oxidizing bacteria through addition of organic carbon. This may stimulate growth of indigenous communities of acidophilic heterotrophic bacteria to compete for oxygen. The goal of this research is to investigate a secondary mechanism associated with carbon addition: complexation of free Fe(III) by soluble microbial growth products (SMPs) produced by microorganisms growing in waste rock. Exploratory research at the laboratory scale examined the effect of soluble microbial products (SMPs) on the kinetics of oxidation of pure pyrite during shaker flask experiments. The results confirmed a decrease in the rate of pyrite oxidation that was dependent upon the concentration of SMPs in solution. We are using these data to verify results from a pyrite oxidation model that accounts for SMPs. This reactor model involves differential-algebraic equations incorporating total component mass balances and mass action laws for equilibrium reactions. Species concentrations determined in each time step are applied to abiotic pyrite oxidation rate expressions from the literature to determine the evolution of total component concentrations. The model was embedded in a parameter estimation algorithm to determine the reactive surface area of pyrite in an abiotic control experiment, yielding an optimized value of 0.0037 m2. The optimized model exhibited similar behavior to the experiment for this case; the root mean squared of residuals for Fe(III) was calculated to be 7.58 x 10-4 M, which is several orders of magnitude less than the actual

  16. Controlled synthesis of titania using water-soluble titanium complexes: A review

    Science.gov (United States)

    Truong, Quang Duc; Dien, Luong Xuan; Vo, Dai-Viet N.; Le, Thanh Son

    2017-07-01

    The development of human society has led to the increase in energy and resources consumption as well as the arising problems of environmental damage and the toxicity to the human health. The development of novel synthesis method which tolerates utilization of toxic solvents and chemicals would fulfill the demand of the society for safer, softer, and environmental friendly technologies. For the past decades, a remarkable progress has been attained in the development of new water-soluble titanium complexes (WSTC) and their use for the synthesis of nanocrystalline titanium dioxide materials by aqueous solution-based approaches. The progress of synthesis of nanocrystalline titanium dioxide using such WSTCs is reviewed in this work. The key structural features responsible for the successfully controlled synthesis of TiO2 are discussed to provide guidelines for the morphology-controlled synthesis. Finally, this review ends with a summary and some perspectives on the challenges as well as new directions in this fascinating research.

  17. Antibacterial, antimalarial and leishmanicidal activities of Cu (II) and nickel (II) complexes of diclofenac sodium

    International Nuclear Information System (INIS)

    Rehman, F.U.; Khan, M.F.; Khan, G.M.; Khan, H.; Khan, I.U.

    2010-01-01

    Metal complexes are famous for a wide array of chemotherapeutic effects. The current study was designed to synthesize and evaluate unexplored chemotherapeutic effects of Cu (II) and Nickel (II) complexes of the non-steroidal anti-inflammatory drug diclofenac. Nickel complex exhibited significant leishmanicidal activity against Lieshmania major, while the copper complex was found to possess low activity against the same pathogen. Both of the complexes revealed low antibacterial activities and were interestingly failed to produce any considerable antimalarial activity against Plasmodium falciparum 3D7. Selective leishmanicidal activities of Nickel (II) complex of diclofenac needs further improvement to be developed as potential new metal-based leishmanicidal agent.(author)

  18. Antibacterial, antimalarial and leishmanicidal activities of Cu (II) and nickel (II) complexes of diclofenac sodium

    Energy Technology Data Exchange (ETDEWEB)

    Rehman, F U; Khan, M F; Khan, G M; Khan, H [Gomal University, D.I. Khan (Pakistan). Dept. of Faculty of Pharmacy; Khan, I U [University of Peshawar (Pakistan). Dept. of Faculty of Pharmacy

    2010-08-15

    Metal complexes are famous for a wide array of chemotherapeutic effects. The current study was designed to synthesize and evaluate unexplored chemotherapeutic effects of Cu (II) and Nickel (II) complexes of the non-steroidal anti-inflammatory drug diclofenac. Nickel complex exhibited significant leishmanicidal activity against Lieshmania major, while the copper complex was found to possess low activity against the same pathogen. Both of the complexes revealed low antibacterial activities and were interestingly failed to produce any considerable antimalarial activity against Plasmodium falciparum 3D7. Selective leishmanicidal activities of Nickel (II) complex of diclofenac needs further improvement to be developed as potential new metal-based leishmanicidal agent.(author)

  19. Diethylenetriamine/diamines/copper (II complexes [Cu(dien(NN]Br2: Synthesis, solvatochromism, thermal, electrochemistry, single crystal, Hirshfeld surface analysis and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Fatima Abu Saleemh

    2017-09-01

    Full Text Available Two dicationic water soluble mixed triamine/diamine copper (II complexes, of general formula [Cu(dienNN]Br2 (1–2 [dien = diethelenetriamine and NN is en = ethylenediamine or Me4en = N,N′,N,N′-tetramethylethylenediamine] were prepared under ultrasonic mode with a relatively high yield. These complexes were characterized by elemental microanalysis, UV visible IR spectroscopy, and thermal and electrochemical techniques. In addition, complex 2 structure was solved by X-ray single crystal and Hirshfeld surface analysis. The complex exhibits a distorted square pyramidal coordination environment around Cu(II centre. The solvatochromism of the desired complexes was investigated in water and other suitable organic solvents. The results show that the Guttmann’s DN parameter values of the solvents have mainly contributed to the shift of the d–d absorption band towards the linear increase in the wavelength of the absorption maxima of the complexes. The complex 1 showed higher antibacterial activity against the studied microorganisms compared to complex 2. Both complexes revealed promising antibacterial activities.

  20. Value of the Debris of Reduction Sculpture: Thiol Etching of Au Nanoclusters for Preparing Water-Soluble and Aggregation-Induced Emission-Active Au(I) Complexes as Phosphorescent Copper Ion Sensor.

    Science.gov (United States)

    Shu, Tong; Su, Lei; Wang, Jianxing; Lu, Xin; Liang, Feng; Li, Chenzhong; Zhang, Xueji

    2016-06-07

    Chemical etching of gold by thiols has been known to be capable of generating nonluminescent gold(I) complexes, e.g., in size-focusing synthesis of atomically precise gold nanoclusters (GNCs). These nonluminescent gold(I) complexes have usually been considered as useless or worthless byproducts. This study shows a promising potential of thiol etching of GNCs to prepare novel water-soluble and phosphorescent gold(I) materials for sensing application. First, cysteamine-induced etching of GNCs is used to produce nonluminescent oligomeric gold(I)-thiolate complexes. Then, cadmium ion induces the aggregation of these oligomeric complexes to produce highly water-soluble ultrasmall intra-aggregates. These intra-aggregates can phosphoresce both in dilute aqueous solutions and in the solid phase. Studies on the effect of pH on their phosphorescent emission reveal the importance of the interaction between the amino groups of the ligands and cadmium ion for their phosphorescent emission property. Furthermore, Cu(2+) ion is found to quickly quench the phosphorescent emission of the intra-aggregates and simultaneously cause a Cu(2+)-concentration-dependent peak wavelength shift, enabling the establishment of a novel colorimetric sensor for sensitive and selective visual sensing of Cu(2+).

  1. Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents

    International Nuclear Information System (INIS)

    Zimmermann, Sonja; Menzel, Christoph M.; Stueben, Doris; Taraschewski, Horst; Sures, Bernd

    2003-01-01

    All complexing agents had a significant influence on octanol solubility of PGM. - Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (P OW ) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (L-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. L-Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility

  2. Lipid solubility of the platinum group metals Pt, Pd and Rh in dependence on the presence of complexing agents

    Energy Technology Data Exchange (ETDEWEB)

    Zimmermann, Sonja; Menzel, Christoph M.; Stueben, Doris; Taraschewski, Horst; Sures, Bernd

    2003-07-01

    All complexing agents had a significant influence on octanol solubility of PGM. - Investigations on the bioaccumulation of the platinum group metals (PGM) Pt, Pd and Rh in aquatic organisms are of growing interest in environmental research due to the increasing emission of these metals by motor vehicles with catalytic converters. Until now, nothing is known about the possible influence of complexing agents on the bioaccumulation capacity of these precious metals. According to the partition coefficient between 1-octanol and water (P{sub OW}) as a measure of bioaccumulation, in this study a simple shaking method was performed in order to investigate the effects of different complexing agents (L-methionine, thio urea, EDTA, humic substances, bile compounds) on the octanol solubility of the PGM. The results demonstrated a significant influence of all agents used. L-Methionine and thio urea decreased the lipid solubility. In contrast, the presence of EDTA, humic substances and especially bile caused a higher transfer of metals in the octanol phase. For most complexing agents tested, the transfer of Pd to the lipid phase was significantly higher compared with Rh and Pt, except for bile acid where the highest octanol solubility was found for Pt. Recent experimental results on PGM accumulation in zebra mussels confirm a high bioaccumulation of Pd which could be predicted from the lipid solubility.

  3. A simple, reversible, colorimetric and water-soluble fluorescent chemosensor for the naked-eye detection of Cu2 + in 100% aqueous media and application to real samples

    Science.gov (United States)

    Sun, Tao; Niu, Qingfen; Li, Tianduo; Guo, Zongrang; Liu, Haixia

    2018-01-01

    A simple, reversible, colorimetric and water-soluble fluorescent chemosensor ADA for the naked-eye detection of Cu2 + was developed. Sensor ADA showed high selectivity and sensitivity toward Cu2 + in 100% aqueous media over wide pH range. Sensor ADA exhibited a red-shift in the absorption spectra from 466 to 480 nm that is accompanied by significant color change from light yellow to yellowish brown instantaneously. The Cu2 + recognition is based on the chelation-enhanced fluorescence quenching (CHEQ) effect of the paramagnetic nature. The lowest detection limit is determined to be 15.8 nM, which is much lower than the allowable level of Cu2 + in drinking water set by U.S. Environmental Protection Agency ( 20 μM) and the World Health Organization ( 30 μM). The 1:1 binding process was confirmed by fluorescence measurements, IR analysis and DFT studies. Moreover, sensor ADA was successfully applied for determination of trace level of Cu2 + with 4 reuse cycles in various water samples, which affords promising potential in ion-detection field.

  4. A simple, reversible, colorimetric and water-soluble fluorescent chemosensor for the naked-eye detection of Cu2+ in ~100% aqueous media and application to real samples.

    Science.gov (United States)

    Sun, Tao; Niu, Qingfen; Li, Tianduo; Guo, Zongrang; Liu, Haixia

    2018-01-05

    A simple, reversible, colorimetric and water-soluble fluorescent chemosensor ADA for the naked-eye detection of Cu 2+ was developed. Sensor ADA showed high selectivity and sensitivity toward Cu 2+ in ~100% aqueous media over wide pH range. Sensor ADA exhibited a red-shift in the absorption spectra from 466 to 480nm that is accompanied by significant color change from light yellow to yellowish brown instantaneously. The Cu 2+ recognition is based on the chelation-enhanced fluorescence quenching (CHEQ) effect of the paramagnetic nature. The lowest detection limit is determined to be 15.8nM, which is much lower than the allowable level of Cu 2+ in drinking water set by U.S. Environmental Protection Agency (~20μM) and the World Health Organization (~30μM). The 1:1 binding process was confirmed by fluorescence measurements, IR analysis and DFT studies. Moreover, sensor ADA was successfully applied for determination of trace level of Cu 2+ with 4 reuse cycles in various water samples, which affords promising potential in ion-detection field. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Syntheses, structures, and properties of imidazolate-bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) dinuclear complexes of a single macrocyclic ligand with two hydroxyethyl pendants.

    Science.gov (United States)

    Li, Dongfeng; Li, Shuan; Yang, Dexi; Yu, Jiuhong; Huang, Jin; Li, Yizhi; Tang, Wenxia

    2003-09-22

    The imidazolate-bridged homodinuclear Cu(II)-Cu(II) complex, [(CuimCu)L]ClO(4).0.5H(2)O (1), and heterodinuclear Cu(II)-Zn(II) complex, [(CuimZnL(-)(2H))(CuimZnL(-)(H))](ClO(4))(3) (2), of a single macrocyclic ligand with two hydroxyethyl pendants, L (L = 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene), have been synthesized as possible models for copper-zinc superoxide dismutase (Cu(2),Zn(2)-SOD). Their crystal structures analyzed by X-ray diffraction methods have shown that the structures of the two complexes are markedly different. Complex 1 crystallizes in the orthorhombic system, containing an imidazolate-bridged dicopper(II) [Cu-im-Cu](3+) core, in which the two copper(II) ions are pentacoordinated by virtue of an N4O environment with a Cu.Cu distance of 5.999(2) A, adopting the geometry of distorted trigonal bipyramid and tetragonal pyramid, respectively. Complex 2 crystallizes in the triclinic system, containing two similar Cu-im-Zn cores in the asymmetric unit, in which both the Cu(II) and Zn(II) ions are pentacoordinated in a distorted trigonal bipyramid geometry, with the Cu.Zn distance of 5.950(1)/5.939(1) A, respectively. Interestingly, the macrocyclic ligand with two arms possesses a chairlike (anti) conformation in complex 1, but a boatlike (syn) conformation in complex 2. Magnetic measurements and ESR spectroscopy of complex 1 have revealed the presence of an antiferromagnetic exchange interaction between the two Cu(II) ions. The ESR spectrum of the Cu(II)-Zn(II) heterodinuclear complex 2 displayed a typical signal for mononuclear trigonal bipyramidal Cu(II) complexes. From pH-dependent ESR and electronic spectroscopic studies, the imidazolate bridges in the two complexes have been found to be stable over broad pH ranges. The cyclic voltammograms of the two complexes have been investigated. Both of the two complexes can catalyze the dismutation of superoxide and show rather high activity.

  6. Molecular complexation of curcumin with pH sensitive cationic copolymer enhances the aqueous solubility, stability and bioavailability of curcumin.

    Science.gov (United States)

    Kumar, Sunny; Kesharwani, Siddharth S; Mathur, Himanshi; Tyagi, Mohit; Bhat, G Jayarama; Tummala, Hemachand

    2016-01-20

    Curcumin is a natural dietary compound with demonstrated potential in preventing/treating several chronic diseases in animal models. However, this success is yet to be translated to humans mainly because of its poor oral bioavailability caused by extremely low water solubility. This manuscript demonstrates that water insoluble curcumin (~1μg/ml) forms highly aqueous soluble complexes (>2mg/ml) with a safe pH sensitive polymer, poly(butyl-methacrylate-co-(2-dimethylaminoethyl) methacrylate-co-methyl-methacrylate) when precipitated together in water. The complexation process was optimized to enhance curcumin loading by varying several formulation factors. Acetone as a solvent and polyvinyl alcohol as a stabilizer with 1:2 ratio of drug to polymer yielded complexes with relatively high loading (~280μg/ml) and enhanced solubility (>2mg/ml). The complexes were amorphous in solid and were soluble only in buffers with pHs less than 5.0. Hydrogen bond formation and hydrophobic interactions between curcumin and the polymer were recorded by infrared spectroscopy and nuclear magnetic resonance spectroscopy, respectively. Molecular complexes of curcumin were more stable at various pHs compared to unformulated curcumin. In mice, these complexes increased peak plasma concentration of curcumin by 6 times and oral bioavailability by ~20 times. This is a simple, economic and safer strategy of enhancing the oral bioavailability of curcumin. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. An azine based sensor for selective detection of Cu2 + ions and its copper complex for sensing of phosphate ions in physiological conditions and in living cells

    Science.gov (United States)

    Tiwari, Karishma; Kumar, Sumit; Kumar, Vipan; Kaur, Jeevanjot; Arora, Saroj; Mahajan, Rakesh Kumar

    2018-02-01

    A simple and cost effective unsymmetrical azine based Schiff base, 5-diethylamino-2-[(2-hydroxy-benzylidene)hydrazonomethyl]-phenol (1) was synthesized which selectively detect Cu2 + ions in the presence of other competitive ions through ;naked eye; in physiological conditions (EtOH-buffer (1:1, v/v, HEPES 10 mM, pH = 7.4)). The presence of Cu2 + induce color change from light yellow green to yellow with the appearance of a new band at 450 nm in UV-Vis spectra of Schiff base 1. The fluorescence of Schiff base 1 (10 μM) was quenched completely in the presence of 2.7 equiv. of Cu2 + ions. Sub-micromolar limit of detection (LOD = 3.4 × 10- 7 M), efficient Stern-Volmer quenching constant (KSV = 1.8 × 105 L mol- 1) and strong binding constant (log Kb = 5.92) has been determined with the help of fluorescence titration profile. Further, 1 - Cu2 + complex was employed for the detection of phosphate ions (PO43 -, HPO42 - and H2PO4-) at micromolar concentrations in EtOH-buffer of pH 7.4 based on fluorescence recovery due to the binding of Cu2 + with phosphate ions. Solubility at low concentration in aqueous medium, longer excitation (406 nm) and emission wavelength (537 nm), and biocompatibility of Schiff base 1 formulates its use in live cell imaging.

  8. Oil-soluble and water-soluble BTPhens and their europium complexes in octanol/water solutions: interface crossing studied by MD and PMF simulations.

    Science.gov (United States)

    Benay, G; Wipff, G

    2013-01-31

    Bistriazinyl-phenantroline "BTPhen" ligands L display the remarkable feature to complex trivalent lanthanide and actinide ions, with a marked selectivity for the latter. We report on molecular dynamics studies of tetrasubstituted X(4)BTPhens: L(4+) (X = (+)Et(3)NCH(2)-), L(4-) (X = (-)SO(3)Ph-), and L(0) (X = CyMe(4)) and their complexes with Eu(III) in binary octanol/water solutions. Changes in free energies upon interface crossing are also calculated for typical solutes by potential of mean force PMF simulations. The ligands and their complexes partition, as expected, to either the aqueous or the oil phase, depending on the "solubilizing" group X. Furthermore, most of them are found to be surface active. The water-soluble L(4+) and L(4-) ligands and their (L)Eu(NO(3))(3) complexes adsorb at the aqueous side of the interface, more with L(4-) than with L(4+). The oil soluble ligand L(0) is not surface active in its endo-endo form but adsorbs on the oil side of the interface in its most polar endo-exo form, as well as in its protonated L(0)H(+) and complexed (L(0))Eu(NO(3))(3) states. Furthermore, comparing PMFs of the Eu(III) complexes with and without nitric acid shows that acidifying the aqueous phase has different effects, depending on the ligand charge. In particular, acid promotes the Eu(III) extraction by L(0) via the (L(0))(2)Eu(NO(3))(2+) complex, as observed experimentally. Overall, the results point to the importance of interfacial adsorption for the liquid-liquid extraction of trivalent lanthanide and actinide cations by BTPhens and analogues.

  9. Ni (II) and Cu(II) complexes of

    African Journals Online (AJOL)

    ADOWIE PERE

    ABSTRACT: The objective of this study is to investigate the antimicrobial activity of novel. Schiff base metal complexes. The resistance of micro-organisms to classical antimicrobial compounds poses a challenge to effective management and treatment of some diseases. In line with this, copper (II), nickel (II) and cobalt (II) ...

  10. Changes in plasma cytokines and their soluble receptors in complex regional pain syndrome.

    Science.gov (United States)

    Alexander, Guillermo M; Peterlin, B Lee; Perreault, Marielle J; Grothusen, John R; Schwartzman, Robert J

    2012-01-01

    Complex Regional Pain Syndrome (CRPS) is a chronic and often disabling pain disorder. There is evidence demonstrating that neurogenic inflammation and activation of the immune system play a significant role in the pathophysiology of CRPS. This study evaluated the plasma levels of cytokines, chemokines, and their soluble receptors in 148 subjects afflicted with CRPS and in 60 gender- and age-matched healthy controls. Significant changes in plasma cytokines, chemokines, and their soluble receptors were found in subjects with CRPS as compared with healthy controls. For most analytes, these changes resulted from a distinct subset of the CRPS subjects. When the plasma data from the CRPS subjects was subjected to cluster analysis, it revealed 2 clusters within the CRPS population. The category identified as most important for cluster separation by the clustering algorithm was TNFα. Cluster 1 consisted of 64% of CRPS subjects and demonstrated analyte values similar to the healthy control individuals. Cluster 2 consisted of 36% of the CRPS subjects and demonstrated significantly elevated levels of most analytes and in addition, it showed that the increased plasma analyte levels in this cluster were correlated with disease duration and severity. The identification of biomarkers that define disease subgroups can be of great value in the design of specific therapies and of great benefit to the design of clinical trials. It may also aid in advancing our understanding of the mechanisms involved in the pathophysiology of CRPS, which may lead to novel treatments for this very severe condition. Copyright © 2012 American Pain Society. Published by Elsevier Inc. All rights reserved.

  11. α-1 Antitrypsin regulates human neutrophil chemotaxis induced by soluble immune complexes and IL-8.

    LENUS (Irish Health Repository)

    Bergin, David A

    2010-12-01

    Hereditary deficiency of the protein α-1 antitrypsin (AAT) causes a chronic lung disease in humans that is characterized by excessive mobilization of neutrophils into the lung. However, the reason for the increased neutrophil burden has not been fully elucidated. In this study we have demonstrated using human neutrophils that serum AAT coordinates both CXCR1- and soluble immune complex (sIC) receptor-mediated chemotaxis by divergent pathways. We demonstrated that glycosylated AAT can bind to IL-8 (a ligand for CXCR1) and that AAT-IL-8 complex formation prevented IL-8 interaction with CXCR1. Second, AAT modulated neutrophil chemotaxis in response to sIC by controlling membrane expression of the glycosylphosphatidylinositol-anchored (GPI-anchored) Fc receptor FcγRIIIb. This process was mediated through inhibition of ADAM-17 enzymatic activity. Neutrophils isolated from clinically stable AAT-deficient patients were characterized by low membrane expression of FcγRIIIb and increased chemotaxis in response to IL-8 and sIC. Treatment of AAT-deficient individuals with AAT augmentation therapy resulted in increased AAT binding to IL-8, increased AAT binding to the neutrophil membrane, decreased FcγRIIIb release from the neutrophil membrane, and normalization of chemotaxis. These results provide new insight into the mechanism underlying the effect of AAT augmentation therapy in the pulmonary disease associated with AAT deficiency.

  12. Surface complexation modeling of Cu(II adsorption on mixtures of hydrous ferric oxide and kaolinite

    Directory of Open Access Journals (Sweden)

    Schaller Melinda S

    2008-09-01

    Full Text Available Abstract Background The application of surface complexation models (SCMs to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO, pure kaolinite (from two sources and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples.

  13. Highly selective detection of glutathione using a NIP/Cu2+ complex fluorescent probe

    International Nuclear Information System (INIS)

    Liang Wenrui; Zhao Zhi; Zhang Yang; Wang Qiusheng; Zhao Xin; Ouyang Jie

    2012-01-01

    A novel fluorescent compound, 4-(trimethyl ammonium chloride)acetamide-2-(1H-naphtho[2,3-d]imidazol-2-yl)phenol (TMACA-NIP), was synthesized and used as a fluorescent probe for detecting glutathione reduced (GSH). The new NIP-based probe exhibited high fluorescence in water, which was quenched during the presence of copper (II) due to the complexation between TMACA-NIP and Cu 2+ . But after adding GSH into the TMACA-NIP and Cu 2+ system, the fluorescence of TMACA-NIP was recovered because the binding force between GSH and Cu 2+ is stronger than that between TMACA-NIP and Cu 2+ , which destroys the equilibrium between NIP and copper (II) ions and releases the fluorescence probe of TMACA-NIP. This three-component competing system of NIP/Cu 2+ /GSH can be used to detect GSH simply and rapidly. - Highlights: ► A novel fluorescence probe was developed to detect GSH that operates in aqueous solution. ► TMACA-NIP was synthesized and employed as “read-out” units of NIP/Cu 2+ /GSH. ► NIP-based probe shows high selectivity over other sulfhydryl compounds.

  14. Mixed-ligand complex formation equilibria of Cu with biguanide in ...

    Indian Academy of Sciences (India)

    Unknown

    by potentiometric investigation on the decomposi- tion of the corresponding complexes with acid.16–18. Literature ... the molecular mechanism of actions of biguanide derivatives as drugs. Results of such investigation .... tems, higher values may be possible. For the ternary. 1 : 1 : 1 CuII : Bg : HG system, p = q = r = 1 and for.

  15. Solubility and superconductivity in RE(Ba2-xREx)Cu3O7+δ (RE = Nd, Sm, Eu, Gd, Dy)

    International Nuclear Information System (INIS)

    Zhang, K.; Dabrowski, B.; Segre, C.U.; Hinks, D.G.; Schuller, I.K.; Jorgensen, J.D.; Slaski, M.

    1987-10-01

    Solid solutions of RE(Ba 2-x RE x )Cu 3 O 7- δ (RE=Nd,Sm,Eu,Gd,Dy) for x=0 to x=0.5 have been investigated. X-ray and resistivity measurements show that there exists a solid solution region, through which, the structure changes from orthorhombic to tetragonal and the superconducting properties are depressed. The solubility limits depend strongly on the size of the rare-earth ion, with the smallest (Dy) showing no appreciable solubility. The superconducting transition temperature versus x for all of the rare-earth ion substitutions falls on a universal curve, indicating that the Ba sites are extremely ionic and magnetically isolated. 20 refs., 4 figs

  16. Porphyry Cu-Au mineralization in the Mirkuh Ali Mirza magmatic complex, NW Iran

    Science.gov (United States)

    Maghsoudi, A.; Yazdi, M.; Mehrpartou, M.; Vosoughi, M.; Younesi, S.

    2014-01-01

    The Mirkuh Ali Mirza Cu-Au porphyry system in East Azerbaijan Province is located on the western part of the Cenozoic Alborz-Azerbaijan volcanic belt. The belt is also an important Cu-Mo-Au metallogenic province in northwestern Iran. The exposed rocks in the study area consist of a volcaniclastic sequence, subvolcanic rocks and intermediate to mafic lava flows of Neogene age. The volcanic rocks show a typical subduction-related magmatic arc geological and geochemical signature, with low concentration of Nb, Ta, and Ti. Mineralization is hosted by Neogene dacitic tuff and porphyritic dacite situated at the intersections of northeast and northwest faults. Field observations, alteration zonation, geochemical haloes and isotopic data of the Mirkuh Ali Mirza magmatic complex show similarities with typical convergent margin Cu-Au porphyry type deposits. The following features confirm the classic model for Cu-Au porphyry systems: (a) close spatial association with high-K calcalkaline to shoshonitic rock related to post-collision extensional setting (b) low grade Cu (0.57%) (c) stockworks as well as disseminated sulfides (c) zonality of the alteration patterns from intense phyllic at the center to outward weak-phyllic, argillic, and propylitic (d) the presence of a pyritic halo (e) accompanied by sheeted veins and low-sulfidation epithermal gold (f) mineralization spatially associated with intersection of structures, (g) genetically related to diorite porphyry stocks at depth (h) geochemical zonation of (Cu ± Au ± Ag ± Bi) → (Cu + Mo ± Bi ± Au ± Pb ± Zn ± As) → (Au + Mo ± Pb ± Zn) → (As + Ag + Sb + Mn + Ba + Pb + Zn + Hg) → Hg from center to outwards (i) The range of sulfur isotopic values is approximately zero (interpreted to have magmatic source) and similar to other subduction-related porphyry Cu deposits.

  17. Effect of cyclodextrin complexation of curcumin on its solubility and antiangiogenic and anti-inflammatory activity in rat colitis model.

    Science.gov (United States)

    Yadav, Vivek R; Suresh, Sarasija; Devi, Kshama; Yadav, Seema

    2009-01-01

    The purpose of the study was to prepare and evaluate the anti-inflammatory activity of cyclodextrin (CD) complex of curcumin for the treatment of inflammatory bowel disease (IBD) in colitis-induced rat model. Inclusion complexes of curcumin were prepared by common solvent and kneading methods. These complexes were further evaluated for increase in solubility of poorly soluble curcumin. The inclusion complexes were characterized for enhancement in solubility, in vitro dissolution, surface morphology, infrared, differential scanning calorimetry, and X-ray studies. Solubility, phase solubility, and in vitro dissolution studies showed that curcumin has higher affinity for hydroxypropyl-beta-CD (HPbetaCD) than other CDs. HPbetaCD complex of curcumin was further investigated for its antiangiogenic and anti-inflammatory activity using chick embryo and rat colitis model. HPbetaCD complex of curcumin proved to be a potent angioinhibitory compound, as demonstrated by inhibition of angiogenesis in chorioallantoic membrane assay. Curcumin- and HPbetaCD-treated rats showed a faster weight gain compared to dextran sulfate solution (DSS) controls. Whole colon length appeared to be significantly longer in HPbetaCD-treated rats than pure curcumin and DSS controls. An additional finding in the DSS-treated rats was the predominance of eosinophils in the chronic cell infiltrate. Decreased mast cell numbers in the mucosa of the colon of CD of curcumin- and pure-curcumin-treated rats was observed. This study concluded that the degree of colitis caused by administration of DSS was significantly attenuated by CD of curcumin. Being a nontoxic natural dietary product, curcumin could be useful in the therapeutic strategy for IBD patients.

  18. In silico properties characterization of water-soluble γ-cyclodextrin bi-capped C60 complex

    DEFF Research Database (Denmark)

    Cao, Ruyin; Wu, Shanshan

    2015-01-01

    Cyclodextrin-related host-guest encapsulation is pivotal to modulate the solubility of C60, thereby promoting its potential therapeutic applications. Here we present a computational study on γ-cyclodextrin bi-capped C60 complex, probing characteristics for all the possible stoichiometry in aqueou...

  19. Emission Properties, Solubility, Thermodynamic Analysis and NMR Studies of Rare-Earth Complexes with Two Different Phosphine Oxides

    Directory of Open Access Journals (Sweden)

    Hiroki Iwanaga

    2010-07-01

    Full Text Available The paper proposes novel molecular designs for rare-earth complexes involving the introduction of two different phosphine oxide structures into one rare-earth ion. These designs are effective for improving solubility and emission intensity. Additionally, the complexes are indispensable for realizing high performances in LEDs and security media. The thermodynamic properties of Eu(III complexes are correlated with the solubility. Correlations between coordination structures and emission intensity were explained by NMR analysis. The luminous flux of red LED devices with Eu(III complexes is very high (20 mA, 870 m lumen. A new white LED has its largest spectra intensity in the red region and a human look much more vividly under this light.

  20. Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

    Science.gov (United States)

    Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

    2008-07-01

    We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

  1. Electron Transfer Mediators for Photoelectrochemical Cells Based on Cu(I Metal Complexes

    Directory of Open Access Journals (Sweden)

    Michele Brugnati

    2007-01-01

    Full Text Available The preparation and the photoelectrochemical characterization of a series of bipyridine and pyridyl-quinoline Cu(I complexes, used as electron transfer mediators in regenerative photoelectrochemical cells, are reported. The best performing mediators produced maximum IPCEs of the order of 35–40%. The J-V curves recorded under monochromatic light showed that the selected Cu(I/(II couples generated higher Vocs and fill factors compared to an equivalent I-/I3- cell, due to a decreased dark current.

  2. Kaempferol-Phospholipid Complex: Formulation, and Evaluation of Improved Solubility, In Vivo Bioavailability, and Antioxidant Potential of Kaempferol

    OpenAIRE

    Darshan R. Telange; Arun T. Patil; Anil M. Pethe; Amol A. Tatode; Sridhar Anand; Vivek S. Dave

    2016-01-01

    The current work describes the formulation and evaluation of a phospholipid complex of kaempferol to enhance the latter’s aqueous solubility, in vitro dissolution rate, in vivo antioxidant and hepatoprotective activities, and oral bioavailability. The kaempferol-phospholipid complex was synthesized using a freeze-drying method with the formulation being optimized using a full factorial design (32) approach. Our results include the validation of the mathematical model in order to ascertain the...

  3. Curcumin-Zn(II) complex for enhanced solubility and stability: an approach for improved delivery and pharmacodynamic effects.

    Science.gov (United States)

    Sareen, Rashmi; Jain, Nitin; Dhar, K L

    2016-08-01

    The aim of present investigation was to prepare Curcumin-Zn(II) complex in a view to enhance solubility, stability and pharmacodynamic effect in experimentally induced ulcerative colitis. Curcumin-Zn(II) complex was prepared by stirring curcumin with anhydrous zinc chloride at a molar ratio of 1:1. The prepared curcumin metallocomplex was characterized by TLC, FTIR, UV spectroscopy and (1)H NMR. In vitro kinetic degradation and solubility of Curcumin and Curcumin-Zn(II) complex was analyzed spectrophotometrically. Pharmacodynamic evaluation of curcumin and its metal complex was assessed in ulcerative colitis in mice. Curcumin showed chelation with zinc ion as confirmed by the TLC, FTIR, UV spectroscopy and (1)H NMR. The results of TLC [Rf value], IR Spectroscopy [shifting of stretching vibrations of υ(C=C) and υ(C=O)], UV spectra [deconvoluted with absorption band at 432-466.4 nm] of Curcumin-Zn(II) complex compared to curcumin confirmed the formation of metallocomplex. (1)HNMR spectra of Curcumin-Zn(II) showed the upfield shift of Ha and Hb. Kinetic stability studies showed metallocomplex with zinc exhibited good stability. In vivo study revealed significant reduction in severity and extent of colonic damage with Curcumin-Zn(II) which were further confirmed by histopathological study. This study recognizes higher solubility and stability of Curcumin-Zn(II) complex and suggested better pharmacodynamic effects.

  4. Spectroscopic, thermal, catalytic and biological studies of Cu(II) azo dye complexes

    Science.gov (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Shoair, A. F.; Hussein, M. A.; El-Boz, R. A.

    2017-08-01

    New complexes of copper(II) with azo compounds of 5-amino-2-(aryl diazenyl)phenol (HLn) are prepared and investigated by elemental analyses, molar conductance, IR, 1H NMR, UV-Visible, mass, ESR spectra, magnetic susceptibility measurements and thermal analyses. The complexes have a square planar structure and general formula [Cu(Ln)(OAc)]H2O. Study the catalytic activities of Cu(II) complexes toward oxidation of benzyl alcohol derivatives to carbonyl compounds were tested using H2O2 as the oxidant. The intrinsic binding constants (Kb) of the ligands (HLn) and Cu(II) complexes (1-4) with CT-DNA are determined. The formed compounds have been tested for biological activity of antioxidants, antibacterial against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria and yeast Candida albicans. Antibiotic (Ampicillin) and antifungal against (Colitrimazole) and cytotoxic compounds HL1, HL2, HL3 and complex (1) showed moderate to good activity against S. aureus, E. coli and Candida albicans, and also to be moderate on antioxidants and toxic substances. Molecular docking is used to predict the binding between the ligands with the receptor of breast cancer (2a91).

  5. The facile synthesis of a chitosan Cu(II) complex by solution plasma process and evaluation of their antioxidant activities.

    Science.gov (United States)

    Ma, Fengming; Li, Pu; Zhang, Baiqing; Wang, Zhenyu

    2017-10-01

    Synthesis of chitosan-Cu(II) complex by solution plasma process (SPP) irradiation was investigated. The effects of the distance between the electrodes, initial Cu(II) concentration, and initial pH on the Cu(II) adsorption capacity were evaluated. The results showed that narrower distance between the electrodes, higher initial Cu(II) concentration and higher initial pH (at pHchitosan-Cu(II) complex by ultraviolet-visible (UV-vis), fourier transform infrared (FT-IR) and electron spin resonance (ESR) spectroscopy revealed that the main structure of chitosan was not changed after irradiation. Thermogravimetry (TG) analysis indicated that Cu(II) ions were well incorporated into the chitosan. The antioxidant activity of the chitosan-Cu(II) complex was evaluated by DPPH, ABTS, and reducing power assays. The chitosan-Cu(II) complex exhibited greater antioxidant activity than the original chitosan. Thus, SPP could be used for preparation of chitosan-Cu(II) complexes. Copyright © 2017. Published by Elsevier B.V.

  6. Superconducting Bi-Sr-Ca-Cu-O thin films from metallo-organic complexes

    International Nuclear Information System (INIS)

    Gruber, H.; Krautz, E.; Fritzer, H.P.; Popitsch, A.

    1991-01-01

    Thin films in the Bi-Sr-Ca-Cu-O system are produced by decomposition of organic precursor compounds containing different metallo-organic complexes. The superconducting phase identified is Bi 2 Sr 2 CaCu 2 O 8+x on (100)-MgO single crystal substrates, polycrystalline Au- and Ag-ribbons and Bi 2 Sr 2 Ca 2 Cu 3 O 10+x on Ag-ribbons. For the 2212-phase a zero resistance temperature of 79 K is found. The 2223-samples on Ag-ribbons show a broad transition at 110 K with a zero resistance at 85 K. SEM and EDX are used for the detection of the microstructure and composition of the prepared films. (orig.)

  7. Synthesis, structure, and magnetic properties of two 1-D helical coordination polymeric Cu(II) complexes

    Science.gov (United States)

    Bian, He-Dong; Yang, Xiao-E.; Yu, Qing; Chen, Zi-Lu; Liang, Hong; Yan, Shi-Ping; Liao, Dai-Zheng

    2008-01-01

    Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL', which are condensed from 2-hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or L-valine, respectively, have been prepared and characterised by X-ray crystallography. In [CuL] n ( 1) the copper(II) atoms are bridged by syn- anti carboxylate groups giving infinite 1-D right-handed helical chains which are further connected by weak C-H⋯Cu interactions to build a 2-D network. While in [CuL'] n ( 2) the carboxylate group acts as a rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic susceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.

  8. Copper(II) oxide solubility behavior in aqueous sodium phosphate solutions at elevated temperatures

    International Nuclear Information System (INIS)

    Ziemniak, S.E.; Jones, M.E.; Combs, K.E.S.

    1990-02-01

    A platinum-lined, flowing autoclave facility is used to investigate the solubility behavior of copper(II) oxide (CuO) in aqueous sodium phosphate solutions at temperatures between 292 and 535 K. Copper solubilities are observed to increase continuously with temperature and phosphate concentration. The measured solubility is examined via a Cu(II) ion hydrolysis/complexing model and thermodynamic functions for the hydrolysis/complexing reactions are obtained from a least- squares analysis of the data. Altogether, thermochemical properties are established for five anionic complexes: Cu(OH) 3 - , Cu(OH) 4 = , Cu(OH) 2 (HPO 4 ) = , Cu(OH) 3 (H 2 PO 4 ) = , and Cu(OH) 2 (PO 4 ) ≡ . Precise thermochemical parameters are also derived for the Cu(OH) + hydroxocomplex based on CuO solubility behavior previously observed in pure water (*) at elevated temperatures. The relative ease of Cu(II) ion hydrolysis is such that Cu(OH) 3 - species become the preferred hydroxocomplex for pH ≥ 9.4. 20 refs., 8 figs., 6 tabs

  9. A water-soluble, mucoadhesive quaternary ammonium chitosan-methyl-β-cyclodextrin conjugate forming inclusion complexes with dexamethasone.

    Science.gov (United States)

    Piras, Anna Maria; Zambito, Ylenia; Burgalassi, Susi; Monti, Daniela; Tampucci, Silvia; Terreni, Eleonora; Fabiano, Angela; Balzano, Federica; Uccello-Barretta, Gloria; Chetoni, Patrizia

    2018-03-30

    The ocular bioavailability of lipophilic drugs, such as dexamethasone, depends on both drug water solubility and mucoadhesion/permeation. Cyclodextrins and chitosan are frequently employed to either improve drug solubility or prolong drug contact onto mucosae, respectively. Although the covalent conjugation of cyclodextrin and chitosan brings to mucoadhesive drug complexes, their water solubility is restricted to acidic pHs. This paper describes a straightforward grafting of methyl-β-cyclodextrin (MCD) on quaternary ammonium chitosan (QA-Ch60), mediated by hexamethylene diisocyanate. The resulting product is a water-soluble chitosan derivative, having a 10-atom long spacer between the quaternized chitosan and the cyclodextrin. The derivative is capable of complexing the model drug dexamethasone and stable complexes were also observed for the lyophilized products. Furthermore, the conjugate preserves the mucoadhesive properties typical of quaternized chitosan and its safety as solubilizing excipient for ophthalmic applications was preliminary assessed by in vitro cytotoxicity evaluations. Taken as a whole, the observed features appear promising for future processing of the developed product into 3D solid forms, such as controlled drug delivery systems, films or drug eluting medical devices.

  10. Synthesis, characterization and biological assay of Salicylaldehyde Schiff base Cu(II) complexes and their precursors

    Science.gov (United States)

    Iftikhar, Bushra; Javed, Kanwal; Khan, Muhammad Saif Ullah; Akhter, Zareen; Mirza, Bushra; Mckee, Vickie

    2018-03-01

    Three new Schiff base ligands were synthesized by the reaction of Salicylaldehyde with semi-aromatic diamines, prepared by the reduction of corresponding dinitro-compounds, and were further used for the formation of complexes with Cu(II) metal ion. The structural features of the synthesized compounds were confirmed by their physical properties and infrared, electronic and NMR spectroscopic techniques. The studies revealed that the synthesized Schiff bases existed as tetradentate ligands and bonded to the metal ion through the phenolic oxygen and azomethine nitrogen. One of the dinitro precursors was also analyzed by single crystal X-ray crystallography, which showed that it crystallizes in monoclinic system with space group P2/n. The thermal behavior of the Cu(II) complexes was determined by thermogravimetric analysis (TGA) and kinetic parameters were evaluated from the data. Schiff base ligands, their precursors and metal complexes were also screened for antibacterial, antifungal, antitumor, Brine shrimp lethality, DPPH free radical scavenging and DNA damage assays. The results of these analyses indicated the substantial potential of the synthesized Schiff bases, their precursors and Cu(II) complexes in biological field as future drugs.

  11. Inclusion complex and nanoclusters of cyclodextrin to increase the solubility and efficacy of albendazole

    Science.gov (United States)

    Albendazole (ABZ), a benzimidazole widely used to control gastrointestinal parasites is poorly soluble in water, resulting in variable and incomplete bioavailability, which has favored the appearance of parasite resistance and, consequently, clinical ineffectiveness. Among the pharmaceutical techniq...

  12. The problem of intermixing of metals possessing no mutual solubility upon explosion welding (Cu-Ta, Fe-Ag, Al-Ta)

    Energy Technology Data Exchange (ETDEWEB)

    Greenberg, B.A., E-mail: bella@imp.uran.ru [Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, S. Kovalevskoi str. 18, Ekaterinburg, 620990 (Russian Federation); Ivanov, M.A. [Kurdyumov Institute of Metal Physics, National Academy of Sciences of Ukraine, Vernadskogo blvd. 36, Kiev, 03680 (Ukraine); Rybin, V.V. [State Polytechnical University, Politekhnicheskaya str. 29, St. Petersburg, 195251 (Russian Federation); Elkina, O.A.; Antonova, O.V.; Patselov, A.M.; Inozemtsev, A.V.; Plotnikov, A.V.; Volkova, A.Yu. [Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, S. Kovalevskoi str. 18, Ekaterinburg, 620990 (Russian Federation); Besshaposhnikov, Yu.P. [OJSC Ural Chemical Machine Building Plant, Khibinogorskii Lane 33, Ekaterinburg, 620010 (Russian Federation)

    2013-01-15

    On the basis of the results obtained for joints of dissimilar metals such as copper-tantalum and iron-silver, the reason of immiscible suspensions mixing upon explosion welding has been cleared out. It has been found that the interface (plain or wavy) is not smooth and contains inhomogeneities, namely, cusps and local melting zones. The role of granulating fragmentation providing partitioning of initial materials as a main channel of input energy dissipation has been revealed. It has been shown that in joints of metals possessing normal solubility the local melting zones are true solutions, but if metals possess no mutual solubility the local melting zones are colloidal solutions. Realization of either emulsion or suspension variant takes place. The results can be used in the development of new joints of metals possessing no mutual solubility. - Highlights: Black-Right-Pointing-Pointer Immiscible pairs Ta/Cu and Fe/Ag are welded successfully by explosive welding. Black-Right-Pointing-Pointer Fragmentation provides for partitioning as the main energy dissipation channel. Black-Right-Pointing-Pointer Immiscible metals form colloidal solid solutions during solidification. Black-Right-Pointing-Pointer Melting and boiling temperatures ratio determines the colloidal solution type. Black-Right-Pointing-Pointer Local melting zones being in suspension form enhance welds hardening.

  13. Effect of anthropogenic organic complexants on the solubility of Ni, Th, U(IV) and U(VI)

    Energy Technology Data Exchange (ETDEWEB)

    Felipe-Sotelo, M., E-mail: m.felipe-sotelo@lboro.ac.uk [Department of Chemistry, Loughborough University, LE11 3TU Loughborough, Leicestershire (United Kingdom); Edgar, M. [Department of Chemistry, Loughborough University, LE11 3TU Loughborough, Leicestershire (United Kingdom); Beattie, T. [MCM Consulting. Täfernstrasse 11, CH 5405 Baden-Dättwil (Switzerland); Warwick, P. [Enviras Ltd., LE11 3TU Loughborough, Leicestershire (United Kingdom); Evans, N.D.M.; Read, D. [Department of Chemistry, Loughborough University, LE11 3TU Loughborough, Leicestershire (United Kingdom)

    2015-12-30

    Highlights: • Citrate increases the solubility of Ni, Th and U between 3 and 4 orders of magnitude. • Theophrastite is the solubility controlling phase of Ni in 95%-saturated Ca(OH){sub 2}. • U(VI) and Ni may form Metal-citrate-OH complexes stabilised by the presence of Ca{sup 2+}. - Abstract: The influence of anthropogenic organic complexants (citrate, EDTA and DTPA from 0.005 to 0.1 M) on the solubility of nickel(II), thorium(IV) and uranium (U(IV) and U(VI)) has been studied. Experiments were carried out in 95%-saturated Ca(OH){sub 2} solutions, representing the high pH conditions anticipated in the near field of a cementitious intermediate level radioactive waste repository. Results showed that Ni(II) solubility increased by 2–4 orders of magnitude in the presence of EDTA and DTPA and from 3 to 4 orders of magnitude in the case of citrate. Citrate had the greatest effect on the solubility of Th(IV) and U(IV)/(VI). XRD and SEM analyses indicate that the precipitates are largely amorphous; only in the case of Ni(II), is there some evidence of incipient crystallinity, in the form of Ni(OH){sub 2} (theophrastite). A study of the effect of calcium suggests that U(VI) and Ni(II) may form metal-citrate-OH complexes stabilised by Ca{sup 2+}. Thermodynamic modelling underestimates the concentrations in solution in the presence of the ligands for all the elements considered here. Further investigation of the behaviour of organic ligands under hyperalkaline conditions is important because of the use of the thermodynamic constants in preparing the safety case for the geological disposal of radioactive wastes.

  14. Spectrophotometric Determination of Metoprolol Tartrate in Pharmaceutical Dosage Forms on Complex Formation with Cu(II

    Directory of Open Access Journals (Sweden)

    Mustafa Cesme

    2011-06-01

    Full Text Available A new, simple, sensitive and accurate spectrophotometric method has been developed for the assay of metoprolol tartrate (MPT, which is based on the complexation of drug with copper(II [Cu(II] at pH 6.0, using Britton-Robinson buffer solution, to produce a blue adduct. The latter has a maximum absorbance at 675 nm and obeys Beer’s law within the concentration range 8.5-70 mg/mL. Regression analysis of the calibration data showed a good correlation coefficient (r = 0.998 with a limit of detection of 5.56 mg/mL. The proposed procedure has been successfully applied to the determination of this drug in its tablets. In addition, the spectral data and stability constant for the binuclear copper(II complex of MPT (Cu2MPT2Cl2 have been reported.

  15. Gallic acid/hydroxypropyl-β-cyclodextrin complex: Improving solubility for application on in vitro/ in vivo Candida albicans biofilms.

    Directory of Open Access Journals (Sweden)

    Guilherme Rodrigues Teodoro

    Full Text Available The aim of this study was to increase the solubility of gallic acid (GA for the treatment of Candida albicans biofilm, which is very difficult to treat and requires high drug concentrations. Cyclodextrins (CDs were used for this purpose. Complexes were evaluated by phase-solubility studies, prepared by spray drying and characterized by drug loading, scanning electron microscopy (SEM and differential scanning calorimetry (DSC. The complexes were tested on C. albicans biofilm using in vitro and in vivo models. HPβCD formed soluble inclusion complexes with GA. The percentage of GA in GA/HPβCD was 10.8 ± 0.01%. The SEM and DSC analyses confirmed the formation of inclusion complexes. GA/HPβCD maintained the antimicrobial activity of the pure GA. GA/HPβCD was effective on C. albicans biofilms of 24 and 48h. The in vivo results showed an anti-inflammatory activity of GA/HPβCD with no difference in invading hypha counting among the groups. This study encourages the development of new antifungal agents.

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

    International Nuclear Information System (INIS)

    Pavelka, Matej; Burda, Jaroslav V.

    2005-01-01

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

  17. Electronic structure of the [MNH2]+ (M = Sc-Cu) complexes.

    Science.gov (United States)

    Hendrickx, Marc F A; Clima, Sergiu

    2006-11-23

    B3LYP geometry optimizations for the [MNH2]+ complexes of the first-row transition metal cations (Sc+-Cu+) were performed. Without any exception the ground states of these unsaturated amide complexes were calculated to possess planar geometries. CASPT2 binding energies that were corrected for zero-point energies and including relativistic effects show a qualitative trend across the series that closely resembles the experimental observations. The electronic structures for the complexes of the early and middle transition metal cations (Sc+-Co+) differ from the electronic structures derived for the complexes of the late transition metal cations (Ni+ and Cu+). For the former complexes the relative higher position of the 3d orbitals above the singly occupied 2p(pi) HOMO of the uncoordinated NH2 induces an electron transfer from the 3d shell to 2p(pi). The stabilization of the 3d orbitals from the left to the right along the first-row transition metal series causes these orbitals to become situated below the HOMO of the NH2 ligand for Ni+ and Cu+, preventing a transfer from occurring in the [MNH2]+ complexes of these metal cations. Analysis of the low-lying states of the amide complexes revealed a rather unique characteristic of their electronic structures that was found across the entire series. Rather exceptionally for the whole of chemistry, pi-type interactions were calculated to be stronger than the corresponding sigma-type interactions. The origin of this extraordinary behavior can be ascribed to the low-lying sp2 lone pair orbital of the NH2 ligand with respect to the 3d level.

  18. Enhancement of Solubility and Antioxidant Activity of Some Flavonoids Based on the Inclusion Complexation with Sulfobutylether β-Cyclodextrin

    International Nuclear Information System (INIS)

    Kwon, Yong Eun; Kim, Hyun Myung; Jung, Seun Ho; Park, Se Yeon

    2010-01-01

    β-CD and SBE-β-CD functioned as a solubilizing agent against three flavonoids. SBE-β-CD is more efficient than native β-CD in solubility enhancement of tested flavonoids. All three tested flavonoids have antioxidant ability. Flavonoid-CD complex positively affected the antioxidant activity comparing with free flavonoids. Throughout this research, SBE-β-CD showed better complexation capacity for the solubility enhancement and bioavailability of tested flavonoids comparing with native β-CD. Flavonoids are polyphenolic photochemicals generally found in plants, foods, and beverages. They contribute to plant colors in fruit, leaves providing a wide spectrum of color from red to blue in flowers. Flavonoids have many good physiological activities such as the antioxidant, antitumor, and antibacterial activities which have been a focus of the attention of many researchers. There are four subgroups of flavonoids, flavone, flavonol, flavanone, and isoflavone, according to their chemical structure

  19. Cu(I)/Cu(II) mixed-valence surface complexes of S-[(2-hydroxyamino)-2-oxoethyl]-N,N-dibutyldithiocarbamate: Hydrophobic mechanism to malachite flotation.

    Science.gov (United States)

    Liu, Sheng; Zhong, Hong; Liu, Guangyi; Xu, Zhenghe

    2018-02-15

    Hydroxamate and sulfhydryl surfactants are effective collectors for flotation of copper minerals. The combination application of hydroxamate and sulfhydryl collectors has been proved to be an effective approach for improving the flotation recovery of non-sulfide copper minerals. A surfactant owing both hydroxamate and dithiocarbamate groups might exhibit strong affinity to non-sulfide copper minerals through double sites adsorption, rendering an enhanced hydrophobization to non-sulfide copper minerals flotation. The flotation performance of S-[(2-hydroxyamino)-2-oxoethyl]- N,N-dibutyldithiocarbamate (HABTC) to malachite, calcite and quartz were first evaluated through systematic micro-flotation experiments. HABTC's hydrophobic mechanism to malachite was further investigated and analyzed by zeta potential, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The micro-flotation results demonstrated HABTC was an excellent collector for malachite flotation and exhibited favorable selectivity for flotation separation of malachite from quartz or calcite under pH 8.5-10.3. Zeta potential and FTIR implied that HABTC might bond with the surface copper atoms of malachite, with releasing the H + ions of its hydroxamate group into pulp. ToF-SIMS provided clear evidences that the Cu-hydroxamate and Cu-dithiocarbamate groups were formed on malachite surfaces after HABTC adsorption. XPS revealed that Cu(I)/Cu(II) mixed-valence surface complexes of HABTC anchored on malachite through formation of Cu(I)S and Cu(II)O bonds, accompanying with reduction of partial surface Cu(II) to Cu(I). The Cu(I)/Cu(II) mixed-valence double chelating character and "chair"-shape N,N-dibutyldithiocarbamate hydrophobic group, resulting in an enhanced affinity and hydrophobization of HABTC to malachite flotation. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Separations on a cellulose exchanger with salicylic acid as functional group. [Fe/sup 3//sup+//Cu/sup 2//sup+/, Cu/sup 2//sup+//Ni/sup 2//sup+//, and Cu/sup 2//sup+//Cu complex separations

    Energy Technology Data Exchange (ETDEWEB)

    Burba, P; Lieser, K H [Technische Hochschule Darmstadt (F.R. Germany). Fachbereich Anorganische Chemie und Kernchemie

    1976-07-01

    The use of a cellulose compound containing salicylic acid as functional group (capacity 0.6 mequ./g) for different problems is described. The seperations Fe/sup 3 +//Cu/sup 2 +/ and Cu/sup 2 +//Ni/sup 2 +/ in aqueous solutions are achieved smoothly at pH 2 and 2.5 resp. In organic solvents (pyridine) copper ions are separated from copper complexes as shown by the examples Cu/sup 2 +//(Cu(mnt)/sub 2/)/sup 2 -/ (mnt = maleonitril-1,2-dithiolate) and Cu/sup 2 +//dibenzo(b.i.)(5.9.14.18)tetraazacyclotetradecene-copper (Cu(chel)). The complex (Cu(mnt)/sub 2/)/sup 2 -/ can be labelled with Cu-64 on a separation column, whereas (Cu-(chel)) is substition inert.

  1. Complex investigation of several silver-less brazed Be/CuCrZr joints

    Energy Technology Data Exchange (ETDEWEB)

    Komarov, A.; Gervash, A.; Komarov, V.; Mazul, I.; Litounovski, N. [Efremov Inst., St Petersburg (Russian Federation); Fedotov, V.; Sevrukov, O. [Moscow Physical Engineering Inst. (Russian Federation); Ganenko, A. [CRISM Prometey, St Petersburg (Russian Federation)

    1998-07-01

    One of the main problems for ITER divertor target technology is to provide a reliable joint between Be as armour material and copper alloy as heat-sink structure. Such joints should satisfy the different requirements. In particular, these joints should successfully withstand cyclic heat fluxes and should have good properties under neutron irradiation. To study such complex of problems several investigation stages were planned in Russia. This paper presents the results of complex investigation of several silver-less brazed Be/CuCrZr joint candidates. (author)

  2. Complex investigation of several silver-less brazed Be/CuCrZr joints

    International Nuclear Information System (INIS)

    Komarov, A.; Gervash, A.; Komarov, V.; Mazul, I.; Litounovski, N.; Fedotov, V.; Sevrukov, O.; Ganenko, A.

    1998-01-01

    One of the main problems for ITER divertor target technology is to provide a reliable joint between Be as armour material and copper alloy as heat-sink structure. Such joints should satisfy the different requirements. In particular, these joints should successfully withstand cyclic heat fluxes and should have good properties under neutron irradiation. To study such complex of problems several investigation stages were planned in Russia. This paper presents the results of complex investigation of several silver-less brazed Be/CuCrZr joint candidates. (author)

  3. The soluble extracellular domain of E-cadherin interferes with EPEC adherence via interaction with the Tir:intimin complex.

    Science.gov (United States)

    Login, Frédéric H; Jensen, Helene H; Pedersen, Gitte A; Amieva, Manuel R; Nejsum, Lene N

    2018-06-19

    Enteropathogenic Escherichia coli (EPEC) causes watery diarrhea when colonizing the surface of enterocytes. The translocated intimin receptor (Tir):intimin receptor complex facilitates tight adherence to epithelial cells and formation of actin pedestals beneath EPEC. We found that the host cell adherens junction protein E-cadherin (Ecad) was recruited to EPEC microcolonies. Live-cell and confocal imaging revealed that Ecad recruitment depends on, and occurs after, formation of the Tir:intimin complex. Combinatorial binding experiments using wild-type EPEC, isogenic mutants lacking Tir or intimin, and E. coli expressing intimin showed that the extracellular domain of Ecad binds the bacterial surface in a Tir:intimin-dependent manner. Finally, addition of the soluble extracellular domain of Ecad to the infection medium or depletion of Ecad extracellular domain from the cell surface reduced EPEC adhesion to host cells. Thus, the soluble extracellular domain of Ecad may be used in the design of intervention strategies targeting EPEC adherence to host cells.-Login, F. H., Jensen, H. H., Pedersen, G. A., Amieva, M. R., Nejsum, L. N. The soluble extracellular domain of E-cadherin interferes with EPEC adherence via interaction with the Tir:intimin complex.

  4. Kaempferol-Phospholipid Complex: Formulation, and Evaluation of Improved Solubility, In Vivo Bioavailability, and Antioxidant Potential of Kaempferol

    Directory of Open Access Journals (Sweden)

    Darshan R. Telange

    2016-12-01

    Full Text Available The current work describes the formulation and evaluation of a phospholipid complex of kaempferol to enhance the latter’s aqueous solubility, in vitro dissolution rate, in vivo antioxidant and hepatoprotective activities, and oral bioavailability. The kaempferol-phospholipid complex was synthesized using a freeze-drying method with the formulation being optimized using a full factorial design (32 approach. Our results include the validation of the mathematical model in order to ascertain the role of specific formulation and process variables that contribute favorably to the formulation’s development. The final product was characterized and confirmed by Differential Scanning Calorimetry (DSC, Fourier Transform Infrared Spectroscopy (FTIR, Proton Nuclear Magnetic Resonance Spectroscopy (1H-NMR, and Powder X-ray Diffraction (PXRD analysis. The aqueous solubility and the in vitro dissolution rate were enhanced compared to that of pure kaempferol. The in vivo antioxidant properties of the kaempferol-phospholipid complex were evaluated by measuring its impact on carbon tetrachloride (CCl4-intoxicated rats. The optimized phospholipid complex improved the liver function test parameters to a significant level by restoration of all elevated liver marker enzymes in CCl4-intoxicated rats. The complex also enhanced the in vivo antioxidant potential by increasing levels of GSH (reduced glutathione, SOD (superoxide dismutase, catalase and decreasing lipid peroxidation, compared to that of pure kaempferol. The final optimized phospholipid complex also demonstrated a significant improvement in oral bioavailability demonstrated by improvements to key pharmacokinetic parameters, compared to that of pure kaempferol.

  5. Complexation of Cu2+, Ni2+ and UO22+ by radiolytic degradation products of bitumen

    International Nuclear Information System (INIS)

    Loon, L.R. Van; Kopajtic, Z.

    1990-05-01

    The radiolytic degradation of bitumen was studied under conditions which reflect those which will exist in the near field of a cementitious radioactive waste repository. The potential complexation capacity of the degradation products was studied and complexation experiments with Cu 2+ , Ni 2+ and UO 2 2+ were performed. In general 1:1 complexes with Cu 2+ , Ni 2+ and UO 2 2+ , with log K values of between 5.7 and 6.0 for Cu 2+ , 4.2 for Ni 2+ and 6.1 for UO 2 2+ , were produced at an ionic strength of 0.1 M. The composition of the bitumen water was analysed by GC-MS and IC. The major proportion of the bitumen degradation products in solution were monocarboxylic acids (acetic acid, formic acid, myric acid, stearic acid ...), dicarboxylic acids (oxalic acid, phthalic acid) and carbonates. The experimentally derived log K data are in good agreement with the literature and suggest that oxalate determines the speciation of Cu 2+ , Ni 2+ and UO 2 2+ in the bitumen water below pH=7. However, under the high pH conditions typical of the near field of a cementitious repository, competition with OH-ligands will be large and oxalate, therefore, will not play a significant role in the speciation of radionuclides. The main conclusion of the study is that the radiolytic degradation products of bitumen will have no influence on radionuclide speciation in a cementitious near field and, as such, need not to be considered in the appropriate safety assessment models. (author) 12 figs., 11 tabs., 31 refs

  6. Solid state luminescence of CuI and CuNCS complexes with phenanthrolines and a new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine

    International Nuclear Information System (INIS)

    Starosta, Radosław; Komarnicka, Urszula K.; Puchalska, Małgorzata

    2014-01-01

    A new tris (aminomethyl) phosphine derived from N-methyl-2-phenylethanamine P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 (1) has been synthesized and characterized by the NMR spectra. Also, three new copper(I) iodide or isothiocyanate complexes with 1 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (dmp) [CuI(phen)P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 ] (1P) CuI(dmp)P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 ] (1I) and [CuNCS(dmp)P(CH 2 N(CH 3 )CH 2 CH 2 Ph) 3 ] (1T), have been synthesized and characterized by elemental analysis as well as studied by NMR, UV–vis, IR and luminescence spectroscopies. An X-ray structure of 1P complex revealed that the geometry around Cu(I) center in this complex is distorted pseudo-tetrahedral. Investigated complexes exhibit orange, rather weak photoluminescence in the solid state. This relatively low intensity may be related to the high flattening deformations of the molecular geometries in the excited triplet states On the basis of TDDFT calculations we confirmed that the absorbance and luminescence bands of (MX,MPR 3 )LCT as well as of (MX)LCT types result mainly from the transitions from the copper–iodine (or isothiocyanate) bonds and a small admixture of copper–phosphine bonds to antibonding orbitals of phen or dmp diimines. -- Highlights: • A novel tris(aminomethyl)phosphine is obtained from N-methyl-2-phenylethanamine. • Three new CuI and CuNCS complexes with phen or dmp and a novel phosphine are presented. • The obtained complexes are luminescent in the solid state. • Main absorbance and luminescence bands are of (MX,MPR 3 )LCT as well as (MX)LCT types

  7. Theoretical Rationalization of the Emission Properties of Prototypical Cu(I)-Phenanthroline Complexes.

    Science.gov (United States)

    Capano, G; Rothlisberger, U; Tavernelli, I; Penfold, T J

    2015-07-09

    The excited state properties of transition metal complexes have become a central focus of research owing to a wide range of possible applications that seek to exploit their luminescence properties. Herein, we use density functional theory (DFT), time-dependent DFT (TDDFT), classical and quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations to provide a full understanding on the role of the geometric and electronic structure, spin-orbit coupling, singlet-triplet gap and the solvent environment on the emission properties of nine prototypical copper(I)-phenanthroline complexes. Our calculations reveal clear trends in the electronic properties that are strongly correlated to the luminescence properties, allowing us to rationalize the role of specific structural modifications. The MD simulations show, in agreement with recent experimental observations, that the lifetime shortening of the excited triplet state in donor solvents (acetonitrile) is not due to the formation of an exciplex. Instead, the solute-solvent interaction is transient and arises from solvent structures that are similar to the ones already present in the ground state. These results based on a subset of the prototypical mononuclear Cu(I) complexes shed general insight into these complexes that may be exploited for development of mononuclear Cu(I) complexes for applications as, for example, emitters in third generation OLEDs.

  8. Enhancement of solubility, dissolution release profile and reduction in ulcerogenicity of piroxicam by inclusion complex with skimmed milk.

    Science.gov (United States)

    Sanka, Krishna; Munjulury, Venkata Saidheeraj; Mohd, Abdul Bari; Diwan, Prakash V

    2014-11-01

    Piroxicam (PXM), a non-steroidal anti-inflammatory drug which is poorly soluble in water and ulcerogenic. Milk has been used against the gastric disturbances caused by non-steroidal anti-inflammatory drugs. In this study, skimmed milk (SKM) is used as the carrier for inclusion complex (IC) due to its surface active agent and amino acid content. To enhance the solubility, dissolution rate and prevent ulcerogenicity of PXM though IC with SKM. IC of PXM were prepared with SKM by solvent evaporation method using rota evaporator and were evaluated for solubility, dissolution, solid state characterization, drug excipient interaction, rat intestinal permeation, ulcerogenicity and histopathological studies. Solubility of PXM was enhanced 2.5 times with IC. The dissolution release and amount of PXM permeated through rat small intestine was enhanced significantly with IC. Decreases in the gastric lesion index values of IC were observed than physical mixture (PM) and free PXM. The histopathological studies revealed significant reduction in ulceration in rat stomach after treatment with IC. It is concluded that SKM is a good carrier to prepare IC of PXM for oral administration.

  9. High-pressure synthesis of CuBa2Ca3Cu4O10+δ superconductor from precursors prepared by a polymerized complex method

    International Nuclear Information System (INIS)

    Aoba, Tomoya; Bizen, Takeshi; Suzuki, Tsuneo; Nakayama, Tadachika; Suematsu, Hisayuki; Niihara, Koichi; Katsumata, Tetsuhiro; Inaguma, Yoshiyuki

    2011-01-01

    Samples of a CuBa 2 Ca 3 Cu 4 O 10+ δ superconductor were synthesized under a high pressure of 5 GPa at 1100-1200degC for 30 min using precursors produced by solid-state reaction and polymerized complex methods. Compared with the precursors prepared by the solid-state reaction method, the precursors produced by the polymerized complex method have low grain sizes. The superconductive transition temperature of the samples prepared using precursors made by the polymerized complex method was found to be 113 K. The volume fractions of the superconducting phase in the samples prepared using precursors made by the solid-state reaction and polymerized complex methods were 49 and 36%, respectively. From these results, precursors made by the polymerized complex method can be used in the high-pressure synthesis of superconductors similarly to those made by the solid-state reaction method. (author)

  10. Cu(II) Complexes of Isoniazid Schiff Bases: DNA/BSA Binding and Cytotoxicity Studies on A549 Cell Line

    OpenAIRE

    Ramadevi, Pulipaka; Singh, Rinky; Prajapati, Akhilesh; Gupta, Sarita; Chakraborty, Debjani

    2014-01-01

    A series of isonicotinoyl hydrazones have been synthesized via template method and were complexed to Cu(II). The ligands are coordinated to Cu(II) ion through the enolic oxygen and azomethine nitrogen resulting in a square planar geometry. The CT-DNA and bovine serum albumin binding propensities of the compounds were determined spectrophotometrically, the results of which indicate good binding propensity of complexes to DNA and BSA with high binding constant values. Furthermore, the compounds...

  11. Redox reactions of the α-synuclein-Cu(2+) complex and their effects on neuronal cell viability.

    Science.gov (United States)

    Wang, Chengshan; Liu, Lin; Zhang, Lin; Peng, Yong; Zhou, Feimeng

    2010-09-21

    α-Synuclein (α-syn), a presynaptic protein believed to play an important role in neuropathology in Parkinson's disease (PD), is known to bind Cu(2+). Cu(2+) has been shown to accelerate the aggregation of α-syn to form various toxic aggregates in vitro. Copper is also a redox-active metal whose complexes with amyloidogenic proteins/peptides have been linked to oxidative stress in major neurodegenerative diseases. In this work, the formation of the Cu(2+) complex with α-syn or with an N-terminal peptide, α-syn(1-19), was confirmed with electrospray-mass spectrometry (ES-MS). The redox potentials of the Cu(2+) complex with α-syn (α-syn-Cu(2+)) and α-syn(1-19) were determined to be 0.018 and 0.053 V, respectively. Furthermore, the Cu(2+) center(s) can be readily reduced to Cu(+), and possible reactions of α-syn-Cu(2+) with cellular species (e.g., O(2), ascorbic acid, and dopamine) were investigated. The occurrence of a redox reaction can be rationalized by comparing the redox potential of the α-syn-Cu(2+) complex to that of the specific cellular species. For example, ascorbic acid can directly reduce α-syn-Cu(2+) to α-syn-Cu(+), setting up a redox cycle in which O(2) is reduced to H(2)O(2) and cellular redox species is continuously exhausted. In addition, the H(2)O(2) generated was demonstrated to reduce viability of the neuroblastoma SY-HY5Y cells. Although our results ruled out the direct oxidation of dopamine by α-syn-Cu(2+), the H(2)O(2) generated in the presence of α-syn-Cu(2+) can oxidize dopamine. Our results suggest that oxidative stress is at least partially responsible for the loss of dopaminergic cells in PD brain and reveal the multifaceted role of the α-syn-Cu(2+) complex in oxidative stress associated with PD symptoms.

  12. Theoretical study of the magnetic behavior of hexanuclear Cu(II) and Ni(II) polysiloxanolato complexes.

    Science.gov (United States)

    Ruiz, Eliseo; Cano, Joan; Alvarez, Santiago; Caneschi, Andrea; Gatteschi, Dante

    2003-06-04

    A theoretical density functional study of the exchange coupling in hexanuclear polysiloxanolato-bridged complexes of Cu(II) and Ni(II) is presented. By calculating the energies of three different spin configurations, we can obtain estimates of the first-, second-, and third-neighbor exchange coupling constants. The study has been carried out for the complete structures of the Cu pristine cluster and of the chloroenclathrated Ni complex as well as for the hypotethical pristine Ni compound and for magnetically dinuclear analogues M(2)Zn(4) (M = Cu, Ni).

  13. Structural characterization and antioxidant properties of Cu(II) and Ni(II) complexes derived from dicyandiamide

    Science.gov (United States)

    Kertmen, Seda Nur; Gonul, Ilyas; Kose, Muhammet

    2018-01-01

    New Cu(II) and Ni(II) complexes derived from dicyandiamide were synthesized and characterised by spectroscopic and analytical methods. Molecular structures of the complexes were determined by single crystal X-ray diffraction studies. In the complexes, the Cu(II) or Ni(II) ions are four-coordinate with a slight distorted square planar geometry. The ligands (L-nPen and L-iPen) derived from dicyandiamide formed via nucleophilic addition of alcohol solvent molecule in the presence Cu(II) or Ni(II) ions. Complexes were stabilised by intricate array of hydrogen bonding interactions. Antioxidant activity of the complexes was evaluated by DPPH radical scavenging and CUPRAC methods. The complexes exhibit antioxidant activity, however, their activities were much lower than standard antioxidants (Vitamin C and trolox).

  14. Possibilities of application of perfect solution model to calculation of equilibrium composition of complex carbonitrides and their solubility in steels

    International Nuclear Information System (INIS)

    Gol'dshtejn, M.I.; Popov, V.V.; Cheremnykh, V.G.

    1980-01-01

    Using the Fe-Nb-V-C-N and Fe-Ti-V-C-N systems' low carbon steels, the earlier suggested model of perfect solid solutions has been experimentally researched. Also studied has been the feasibility to calculate the composition of carbonitrides in steels by the derived equations, that comprise, as parameters, products of respective compounds' solubility and coefficients of components interaction in iron-based solid solutions. A conclusion is drawn that perfect solutions models may be used adequately for complex carbonitrides like Nbsub(p)Vsub(1-p)Csub(q)Nsub(1-q) and Tisub(p)Vsub(1-p)Csub(q)Nsub(1-q) during the calculations of their equilibrium composition and solubility in steels

  15. Solubility profiles, hydration and desolvation of curcumin complexed with γ-cyclodextrin and hydroxypropyl-γ-cyclodextrin

    Science.gov (United States)

    Shityakov, Sergey; Salmas, Ramin Ekhteiari; Durdagi, Serdar; Roewer, Norbert; Förster, Carola; Broscheit, Jens

    2017-04-01

    In this study, we investigated curcumin (CUR) solubility profiles and hydration/desolvation effects of this substance formulated with γ-cyclodextrin (γ-CD) and hydroxypropyl-γ-cyclodextrin (HP-γ-CD) excipients. The CUR/HP-γ-CD complex was found to be more stable in solution with the highest apparent stability constant for CUR/HP-γ-CD (Kc = 1.58*104 M-1) as the more soluble form in distilled water. The in silico calculations, including molecular docking, Monte Carlo (MC), and molecular dynamics (MD) simulations, indicated that water molecules play an important role in host-guest complexation mediating the CUR binding to cyclodextrins via hydrogen bond formations. The CUR hydration/desolvation effects contributed to the complex formation by elevating the CUR binding affinity to both CDs. The CUR/HP-γ-CD complex after the CUR hydration was determined with a minimal Gibbs free energy of binding (ΔGbind = -9.93 kcal*mol-1) due to the major hydrophobic (vdW) forces. Overall, the results of this study can aid a development of cyclodextrin-based drug delivery vectors, signifying the importance of water molecules during the formulation processes.

  16. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Science.gov (United States)

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Synthesis and spectroscopy of clay intercalated Cu(II) bio-monomer complexes: coordination of Cu(II) with purines and nucleotides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Leeman, H.; Schoonheydt, R.A.

    1999-01-01

    The spectroscopic properties of Cu(bio-monomer)nm+ complexes [BM=bio-monomer (purine, adenine, guanine, hypoxanthine, 5-ADP and 5-GMP)] in saponite clays have been investigated by diffuse reflectance spectroscopy (DRS) in the UV-Vis-NIR region and electron paramagnetic resonance (EPR) at X-band.

  18. Thermal Degradation of Complexes Derived from Cu (II) Groundnut (Arachis hypogaea) and Sesame (Sesamum indicum) Soaps

    Science.gov (United States)

    Joram, Anju; Sharma, Rashmi; Sharma, Arun kumar

    2018-05-01

    The complexes have been synthesized from Cu (II) soaps of groundnut (Arachis hypogaea) and sesame (Sesamum indicum) oils, with ligand containing nitrogen and sulfur atoms like 2-amino-6-methyl benzothiazole. The complexes were greenish brown in color. In order to study TGA, first characterized them by elemental analysis, and spectroscopic technique such as IR, NMR and ESR. From the analytical data, the stoichiometry's of the complexes have been observed to be 1:1 (metal:ligand). These complexes have been thermally analyzed using TGA techniques to determine their energy of activation. These complexes show three step thermal degradation corresponding to fatty acid components of the edible oils and each complex has three decomposition steps in the range of 439-738 K. Various equations like Coats-Redfern (CR), Horowitz-Metzger (HM) and Broido equations (BE) were applied to evaluate the energy of activation. The values of energy of activation are observed to be in the following order for both copper groundnut benzothiazole (CGB) and copper sesame benzothiazole (CSeB) complexes: CGB > CSeB. CGB is observed to be more stable than CSeB due to its higher activation energy. The above studies would provide significant information regarding the applications of synthesized agrochemicals and their safe removal through parameters obtained in degradation curves and its relation with energy.

  19. Magnetotransport of CaCu3Mn4O12 complex perovskite derivatives

    International Nuclear Information System (INIS)

    Sanchez-Benitez, J.; Andres, A. de; Garcia-Hernandez, M.; Alonso, J.A.; Martinez-Lope, M.J.

    2006-01-01

    Neutron powder diffraction, magnetic and magnetotransport studies were carried out on new derivatives of the CaCu 3 Mn 4 O 12 (A'A 3 B 4 O 12 ) complex perovskite. The samples were prepared in polycrystalline form under moderate pressure conditions. Substitutions at A and A' sites of CaCu 3 Mn 4 O 12 , with only Mn 4+ and insulating behavior, imply electron doping that affects the magnetic and transport properties. X-ray Absorption Spectroscopy showed that Mn 3+ /Mn 4+ valence mixing occurs only at B site, progressively filling the e g band and providing the metallic character in these compounds, as we observe in most of these samples. A semiconducting behavior is observed in samples with 50% Mn 3+ at B site. This can be understood by the opening of a gap in the conduction band corresponding to the half filling of the e g states. This is the case of the tetravalent rare earth doped samples (Ce and Th at A' site) and of the appropriate A site doped Ca(CuMn 2 )Mn 4 O 12 sample. At the strongly distorted A positions, Mn 3+ , with localized e g electrons, act as magnetic impurities at very low temperatures (<40 K) giving rise to the observed upturn in the resistivity. The magnetic origin of this scattering is evidenced by its drastic reduction under a magnetic field

  20. Water Soluble Cationic Porphyrin Sensor for Detection of Hg2+, Pb2+, Cd2+, and Cu2+

    Directory of Open Access Journals (Sweden)

    Matibur Zamadar

    2016-01-01

    Full Text Available Here we report the sensing properties of the aqueous solution of meso-tetra(N-methyl-4-pyridylporphine tetrachloride (1 for simultaneous detection of toxic metal ions by using UV-vis spectroscopy. Cationic porphyrin 1 displayed different electronic absorptions in UV-vis region upon interacting with Hg2+, Pb2+, Cd2+, and Cu2+ ions in neutral water solution at room temperature. Quite interestingly, the porphyrin 1 showed that it can function as a single optical chemical sensor and/or metal ion receptor capable of detecting two or more toxic metal ions, particularly Hg2+, Pb2+, and Cd2+ ions coexisting in a water sample. Porphyrin 1 in an aqueous solution provides a unique UV-vis sensing system for the determination of Cd2+ in the presence of larger metal ions such as Hg2+, or Pb2+. Finally, the examination of the sensing properties of 1 demonstrated that it can operate as a Cu2+ ion selective sensor via metal displacement from the 1-Hg2+, 1-Pb2+, and 1-Cd2+.

  1. The complex ac susceptibility of superconducting Y-Ba-CuO thin film and bulk samples

    International Nuclear Information System (INIS)

    Lobotka, P.; Goemoery, F.

    1988-01-01

    Complex ac susceptibility measurements as function of temperature on Y-Ba-CuO superconductors are reported. A strong dependence of the susceptibility curves on the ac field magnitude and little influence of the superimposed dc field are observed on both, thin film and bulk samples. The susceptibilities of these materials are frequency independent in the range 30 to 7200 Hz what demonstrates the negligible role of eddy currents. A second peak in the imaginary part of susceptibility is observed in the bulk sample at higher levels of ac field. This implies the existence of another component in the sample with higher T c and lower losses. (author)

  2. Survey on synthesis and reaction of environmentally benign water-soluble metal complex catalysts; Kankyo chowagata suiyosei sakutai shokubai no gosei hanno no chosa

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    This report describes the research trend survey results on the synthesis and reaction of water-soluble metal complexes which are regarded as environmentally benign catalysts. For the synthesis and catalysis of water-soluble complexes, synthetic methods of water-soluble phosphines, such as sulfonated TPPMS and TPPTS, are described in detail. Synthesis and reactivity of hydroxymethylphosphines are introduced, and the application of electrospray mass spectroscopy is elucidated as a tool for the analysis of them. Changes of the application of transition metal complexes with water-soluble phosphines to catalysis are described. Dual catalysts which have both functions of phase transfer catalysts and homogeneous catalysts are introduced. Concept of counter phase transfer catalysts is also introduced, and some catalytic reactions are described. In addition, this report introduces catalysis of water-soluble polymer-supported metal complexes, immobilization of metal colloids with water-soluble ligands and their analysis, and water-soluble complexes as hybrid catalysts. 144 refs., 94 figs., 10 tabs.

  3. Neuroprotective Effects and Mechanisms of Curcumin–Cu(II and –Zn(II Complexes Systems and Their Pharmacological Implications

    Directory of Open Access Journals (Sweden)

    Fa-Shun Yan

    2017-12-01

    Full Text Available Alzheimer’s disease (AD is the main form of dementia and has a steadily increasing prevalence. As both oxidative stress and metal homeostasis are involved in the pathogenesis of AD, it would be interesting to develop a dual function agent, targeting the two factors. Curcumin, a natural compound isolated from the rhizome of Curcuma longa, is an antioxidant and can also chelate metal ions. Whether the complexes of curcumin with metal ions possess neuroprotective effects has not been evaluated. Therefore, the present study was designed to investigate the protective effects of the complexes of curcumin with Cu(II or Zn(II on hydrogen peroxide (H2O2-induced injury and the underlying molecular mechanisms. The use of rat pheochromocytoma (PC12 cells, a widely used neuronal cell model system, was adopted. It was revealed that curcumin–Cu(II complexes systems possessed enhanced O2·–-scavenging activities compared to unchelated curcumin. In comparison with unchelated curcumin, the protective effects of curcumin–Cu(II complexes systems were stronger than curcumin–Zn(II system. Curcumin–Cu(II or –Zn(II complexes systems significantly enhanced the superoxide dismutase, catalase, and glutathione peroxidase activities and attenuated the increase of malondialdehyde levels and caspase-3 and caspase-9 activities, in a dose-dependent manner. The curcumin–Cu(II complex system with a 2:1 ratio exhibited the most significant effect. Further mechanistic study demonstrated that curcumin–Cu(II or –Zn(II complexes systems inhibited cell apoptosis via downregulating the nuclear factor κB (NF-κB pathway and upregulating Bcl-2/Bax pathway. In summary, the present study found that curcumin–Cu(II or –Zn(II complexes systems, especially the former, possess significant neuroprotective effects, which indicates the potential advantage of curcumin as a promising agent against AD and deserves further study.

  4. Neuroprotective Effects and Mechanisms of Curcumin-Cu(II) and -Zn(II) Complexes Systems and Their Pharmacological Implications.

    Science.gov (United States)

    Yan, Fa-Shun; Sun, Jian-Long; Xie, Wen-Hai; Shen, Liang; Ji, Hong-Fang

    2017-12-28

    Alzheimer's disease (AD) is the main form of dementia and has a steadily increasing prevalence. As both oxidative stress and metal homeostasis are involved in the pathogenesis of AD, it would be interesting to develop a dual function agent, targeting the two factors. Curcumin, a natural compound isolated from the rhizome of Curcuma longa , is an antioxidant and can also chelate metal ions. Whether the complexes of curcumin with metal ions possess neuroprotective effects has not been evaluated. Therefore, the present study was designed to investigate the protective effects of the complexes of curcumin with Cu(II) or Zn(II) on hydrogen peroxide (H₂O₂)-induced injury and the underlying molecular mechanisms. The use of rat pheochromocytoma (PC12) cells, a widely used neuronal cell model system, was adopted. It was revealed that curcumin-Cu(II) complexes systems possessed enhanced O₂ ·- -scavenging activities compared to unchelated curcumin. In comparison with unchelated curcumin, the protective effects of curcumin-Cu(II) complexes systems were stronger than curcumin-Zn(II) system. Curcumin-Cu(II) or -Zn(II) complexes systems significantly enhanced the superoxide dismutase, catalase, and glutathione peroxidase activities and attenuated the increase of malondialdehyde levels and caspase-3 and caspase-9 activities, in a dose-dependent manner. The curcumin-Cu(II) complex system with a 2:1 ratio exhibited the most significant effect. Further mechanistic study demonstrated that curcumin-Cu(II) or -Zn(II) complexes systems inhibited cell apoptosis via downregulating the nuclear factor κB (NF-κB) pathway and upregulating Bcl-2/Bax pathway. In summary, the present study found that curcumin-Cu(II) or -Zn(II) complexes systems, especially the former, possess significant neuroprotective effects, which indicates the potential advantage of curcumin as a promising agent against AD and deserves further study.

  5. EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor.

    Science.gov (United States)

    Das, Kuheli; Patra, Chiranjit; Sen, Chandana; Datta, Amitabha; Massera, Chiara; Garribba, Eugenio; El Fallah, Mohamed Salah; Beyene, Belete B; Hung, Chen-Hsiung; Sinha, Chittaranjan; Askun, Tulin; Celikboyun, Pinar; Escudero, Daniel; Frontera, Antonio

    2017-06-01

    A new Cu(II) dinuclear complex, Cu 2 L 2 (1) was afforded employing the potentially pentatentate Schiff base precursor H 2 L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV-Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H 2 L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H 37 Ra (ATCC 25177) and M. tuberculosis H 37 Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL -1 . A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.

  6. Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

    Directory of Open Access Journals (Sweden)

    Zong-Cheng Chen

    2014-09-01

    Full Text Available In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP to atom transfer self-condensing vinyl polymerization (AT-SCVP through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy in a mixture of styrene (St, 4-vinyl benzyl chloride (VBC, and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC macroinitiator (name as: hbPSt MI with either St or tBA (tert-butyl acrylate. The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98; hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid segments.

  7. Cellular interactions of a water-soluble supramolecular polymer complex of carbon nanotubes with human epithelial colorectal adenocarcinoma cells.

    Science.gov (United States)

    Lee, Yeonju; Geckeler, Kurt E

    2012-08-01

    Water-soluble, PAX-loaded carbon nanotubes are fabricated by employing a synthetic polyampholyte, PDM. To investigate the suitability of the polyampholyte and the nanotubes as drug carriers, different cellular interactions such as the human epithelial Caco-2 cells viability, their effect on the cell growth, and the change in the transepithelial electrical resistance in Caco-2 cells are studied. The resulting complex is found to exhibit an effective anti-cancer effect against colon cancer cells and an increased the reduction of the electrical resistance in the Caco-2 cells when compared to the precursor PAX. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Magnetic exchange couplings from noncollinear perturbation theory: dinuclear CuII complexes.

    Science.gov (United States)

    Phillips, Jordan J; Peralta, Juan E

    2014-08-07

    To benchmark the performance of a new method based on noncollinear coupled-perturbed density functional theory [J. Chem. Phys. 138, 174115 (2013)], we calculate the magnetic exchange couplings in a series of triply bridged ferromagnetic dinuclear Cu(II) complexes that have been recently synthesized [Phys. Chem. Chem. Phys. 15, 1966 (2013)]. We find that for any basis-set the couplings from our noncollinear coupled-perturbed methodology are practically identical to those of spin-projected energy-differences when a hybrid density functional approximation is employed. This demonstrates that our methodology properly recovers a Heisenberg description for these systems, and is robust in its predictive power of magnetic couplings. Furthermore, this indicates that the failure of density functional theory to capture the subtle variation of the exchange couplings in these complexes is not simply an artifact of broken-symmetry methods, but rather a fundamental weakness of current approximate density functionals for the description of magnetic couplings.

  9. Polymer-free nanofibers from vanillin/cyclodextrin inclusion complexes: high thermal stability, enhanced solubility and antioxidant property.

    Science.gov (United States)

    Celebioglu, Asli; Kayaci-Senirmak, Fatma; İpek, Semran; Durgun, Engin; Uyar, Tamer

    2016-07-13

    Vanillin/cyclodextrin inclusion complex nanofibers (vanillin/CD-IC NFs) were successfully obtained from three modified CD types (HPβCD, HPγCD and MβCD) in three different solvent systems (water, DMF and DMAc) via an electrospinning technique without using a carrier polymeric matrix. Vanillin/CD-IC NFs with uniform and bead-free fiber morphology were successfully produced and their free-standing nanofibrous webs were obtained. The polymer-free CD/vanillin-IC-NFs allow us to accomplish a much higher vanillin loading (∼12%, w/w) when compared to electrospun polymeric nanofibers containing CD/vanillin-IC (∼5%, w/w). Vanillin has a volatile nature yet, after electrospinning, a significant amount of vanillin was preserved due to complex formation depending on the CD types. Maximum preservation of vanillin was observed for vanillin/MβCD-IC NFs which is up to ∼85% w/w, besides, a considerable amount of vanillin (∼75% w/w) was also preserved for vanillin/HPβCD-IC NFs and vanillin/HPγCD-IC NFs. Phase solubility studies suggested a 1 : 1 molar complexation tendency between guest vanillin and host CD molecules. Molecular modelling studies and experimental findings revealed that vanillin : CD complexation was strongest for MβCD when compared to HPβCD and HPγCD in vanillin/CD-IC NFs. For vanillin/CD-IC NFs, water solubility and the antioxidant property of vanillin was improved significantly owing to inclusion complexation. In brief, polymer-free vanillin/CD-IC NFs are capable of incorporating a much higher loading of vanillin and effectively preserve volatile vanillin. Hence, encapsulation of volatile active agents such as flavor, fragrance and essential oils in electrospun polymer-free CD-IC NFs may have potential for food related applications by integrating the particularly large surface area of NFs with the non-toxic nature of CD and inclusion complexation benefits, such as high temperature stability, improved water solubility and an enhanced

  10. Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere?

    Directory of Open Access Journals (Sweden)

    Michel Ferreira

    2017-01-01

    Full Text Available The behaviour of platinum(II and palladium(0 complexes coordinated by various hydrosoluble monodentate phosphane ligands has been investigated by 31P{1H} NMR spectroscopy in the presence of randomly methylated β-cyclodextrin (RAME-β-CD. This molecular receptor can have no impact on the organometallic complexes, induce the formation of phosphane low-coordinated complexes or form coordination second sphere species. These three behaviours are under thermodynamic control and are governed not only by the affinity of RAME-β-CD for the phosphane but also by the phosphane stereoelectronic properties. When observed, the low-coordinated complexes may be formed either via a preliminary decoordination of the phosphane followed by a complexation of the free ligand by the CD or via the generation of organometallic species complexed by CD which then lead to expulsion of ligands to decrease their internal steric hindrance.

  11. Amino acid detection using fluoroquinolone–Cu2+ complex as a switch-on fluorescent probe by competitive complexation without derivatization

    International Nuclear Information System (INIS)

    Farokhcheh, Alireza; Alizadeh, Naader

    2014-01-01

    In this work, we describe the use of fluoroquinolone–Cu 2+ complex as a competitive switch-on fluorescence probe for amino acid determination without derivatization. The fluorescence intensity of this probe, which has been reduced due to effective quenching by Cu 2+ ion, increases drastically by an addition of amino acid (glycine, phenylalanine, sarcosine, aspargine, alanine, proline, arginine, aspartic acid, glutamic acid, lysine, leucine and isoleucine). The overall stability constants of Cu 2+ ion complexes with amino acids were determined by fluorometric titration of fluoroquinolone-Cu 2+ complex with the amino acid solution. Furthermore, the probe shows high calibration sensitivity toward aspartic acid. The fluorescence signal depends linearly on the amino acid concentration within the range of concentration from 1.2×10 −7 to 1.1×10 −5 mol L −1 for aspartic acid. The detection limit was found 2.7×10 −8 mol L −1 with the relative standard deviation (RSD%) about 2.1% (five replicate). -- Highlights: • Amino acids are detected by using fluoroquinolone–Cu 2+ complex as fluorescent probe. • Amino acids were detected based on a competitive complexation reaction. • Probe has been able to recognize amino acids through switch-on fluorescence behavior. • Ultra-trace level of aspartic and glutamic acid is determined without derivatization

  12. Amino acid detection using fluoroquinolone–Cu{sup 2+} complex as a switch-on fluorescent probe by competitive complexation without derivatization

    Energy Technology Data Exchange (ETDEWEB)

    Farokhcheh, Alireza; Alizadeh, Naader, E-mail: alizaden@modares.ac.ir

    2014-01-15

    In this work, we describe the use of fluoroquinolone–Cu{sup 2+} complex as a competitive switch-on fluorescence probe for amino acid determination without derivatization. The fluorescence intensity of this probe, which has been reduced due to effective quenching by Cu{sup 2+} ion, increases drastically by an addition of amino acid (glycine, phenylalanine, sarcosine, aspargine, alanine, proline, arginine, aspartic acid, glutamic acid, lysine, leucine and isoleucine). The overall stability constants of Cu{sup 2+} ion complexes with amino acids were determined by fluorometric titration of fluoroquinolone-Cu{sup 2+} complex with the amino acid solution. Furthermore, the probe shows high calibration sensitivity toward aspartic acid. The fluorescence signal depends linearly on the amino acid concentration within the range of concentration from 1.2×10{sup −7} to 1.1×10{sup −5} mol L{sup −1} for aspartic acid. The detection limit was found 2.7×10{sup −8} mol L{sup −1} with the relative standard deviation (RSD%) about 2.1% (five replicate). -- Highlights: • Amino acids are detected by using fluoroquinolone–Cu{sup 2+} complex as fluorescent probe. • Amino acids were detected based on a competitive complexation reaction. • Probe has been able to recognize amino acids through switch-on fluorescence behavior. • Ultra-trace level of aspartic and glutamic acid is determined without derivatization.

  13. Bonding in d9 complexes derived from EPR: Application to CuCl2-4, CuBr2-4, and CdCl2:Cu2+

    Science.gov (United States)

    Aramburu, J. A.; Moreno, M.

    1985-12-01

    In this work are reported the theoretical expressions for the [g], hyperfine, and superhyperfine (shf) tensors of a d9 square-planar complex within a molecular orbital (MO) scheme. These expressions include contributions arising from crystal field and charge transfer excitations calculated up to third and second order perturbations, respectively. This makes the present framework more general than those previously used. Through those expressions we have derived from the experimental EPR and optical data the MO coefficients corresponding to the valence b1g(x2-y2), b2g(xy), and eg(xz,yz) levels and also the core polarization contribution K to the hyperfine tensor for the systems CuCl2-4, CuBr2-4, and CdCl2:Cu2+. The 3d charge obtained for CuCl2-4 is equal to 0.61, 0.83, and 0.85 for the antibonding 3b1g, 2b2g, and 2eg levels, respectively. These figures are much closer to the Xα results by Bencini and Gatteschi [J. Am. Chem. Soc. 105, 5535 (1983)] than to those by Desjardins et al. [J. Am. Chem. Soc. 105, 4590 (1983)]. The σ and π covalency for CuBr2-4 are both higher than for CuCl2-4 in accord to the lower electronegativity for bromine. However, only for the antibonding 3b1g level of CuBr2-4 have we obtained an electronic charge lying mainly on ligands. The covalency of CdCl2:Cu2+ is smaller than that found for CuCl2-4, a fact associated to a higher metal-ligand distance for the former. Evidence of this statement are also given from the analysis of crystal-field spectra and isotropic shf constant. The values of K derived for CuCl2-4 (128.1×10-4 cm-1), CuBr2-4 (103.6×10-4 cm-1), and CdCl2:Cu2+ (123.9×10-4 cm-1) point out the dependence of K on the equatorial covalency but also on the existence of axial ligands. The [g] tensor of CuBr2-4 is dominated by the charge transfer contribution while the crystal field one is negative. Finally an analysis of the importance of each one of the involved contributions to the spin-Hamiltonian parameters is reported for the

  14. A novel multi-tiered experimental approach unfolding the mechanisms behind cyclodextrin-vitamin inclusion complexes for enhanced vitamin solubility and stability.

    Science.gov (United States)

    Braithwaite, Miles C; Kumar, Pradeep; Choonara, Yahya E; du Toit, Lisa C; Tomar, Lomas K; Tyagi, Charu; Pillay, Viness

    2017-10-30

    This study was conducted to provide a mechanistic account for understanding the synthesis, characterization and solubility phenomena of vitamin complexes with cyclodextrins (CD) for enhanced solubility and stability employing experimental and in silico molecular modeling strategies. New geometric, molecular and energetic analyses were pursued to explicate experimentally derived cholecalciferol complexes. Various CD molecules (α-, β-, γ-, and hydroxypropyl β-) were complexed with three vitamins: cholecalciferol, ascorbic acid and α-tocopherol. The Inclusion Efficiency (IE%) was computed for each CD-vitamin complex. The highest IE% achieved for a cholecalciferol complex was for 'βCDD 3 -8', after utilizing a unique CD:cholecalciferol molar synthesis ratio of 2.5:1, never before reported as successful. 2HPβCD-cholecalciferol, γCD-cholecalciferol and α-tocopherol inclusion complexes (IC's) reached maximal IE% with a CD:vitamin molar ratio of 5:1. The results demonstrate that IE%, thermal stability, concentration, carrier solubility, molecular mechanics and intended release profile are key factors to consider when synthesizing vitamin-CD complexes. Phase-solubility data provided insights into the design of formulations with IC's that may provide analogous oral vitamin release profiles even when hydrophobic and hydrophilic vitamins are co-incorporated. Static lattice atomistic simulations were able to validate experimentally derived cholecalciferol IE phenomena and are invaluable parameters when approaching formulation strategies using CD's for improved solubility and efficacy of vitamins. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Study on effect of L-arginine on solubility and dissolution of Zaltoprofen: Preparation and characterization of binary and ternary cyclodextrin inclusion complexes

    Science.gov (United States)

    Sherje, Atul P.; Patel, Forum; Murahari, Manikanta; Suvarna, Vasanti; Patel, Kavitkumar

    2018-02-01

    The present study demonstrated the binary and ternary complexes of Zaltoprofen (ZPF) with β-CD and HP-β-CD. The products were characterized using solubility, in vitro dissolution, and DSC studies. The mode of interaction of guest and host was revealed through 1H NMR and FT-IR studies. A significant increase was noticed in the stability constant (Kc) and complexation efficiency (CE) of β-CD and HP-β-CD due to addition of L-Arg in ternary complexes. The ternary complexes showed greater increase in solubility and dissolution of ZPF than binary complexes. Thus, ternary system of ZPF could be an innovative approach for its solubility and dissolution enhancement.

  16. Hydrophilic olive cake extracts: Characterization by physicochemical properties and Cu(II) complexation

    International Nuclear Information System (INIS)

    Kolokassidou, K.; Szymczak, W.; Wolf, M.; Obermeier, C.; Buckau, G.; Pashalidis, I.

    2009-01-01

    Disposed olive cake generates hydrophilic components that can be mobilized in the aquatic environment. This paper deals with the characterization of such components, isolated by alkaline extraction. It is shown that these substances possess properties very much resembling humic acid, including a substantial inventory of proton exchanging groups. Extraction and purification of the hydrophilic components from the disposed olive cake was performed by the standard approach for isolation of humic acids from solid sources, i.e. alternating alkaline dissolution and acid flocculation, leaving the purified extract in the protonated form. The purified sample was characterized by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Fourier Transform Infra Red Spectroscopy (FTIR), UV-vis, Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Asymmetrical Flow Field-Flow Fractionation (AFFFF). The complex formation properties were investigated by potentiometry using Cu(II) ion selective electrode under atmospheric conditions at I = 0.1 M NaClO 4 (aqueous solution) and pH 6. The formation constant for the CuHA complex is found to be log β = 5.3 ± 0.4 which is close to the corresponding value (log β = 5.2 ± 0.4) obtained from similar investigations with the commercially available Aldrich humic acid (this study) and corresponding published values for various humic acids. Both, structural properties and complex formation data show that the olive cake extract has considerable similarities with humic acids from different sources, pointing towards potential similarities in environmental behavior and impact.

  17. Lateral Fluid Percussion Injury Impairs Hippocampal Synaptic Soluble N-Ethylmaleimide Sensitive Factor Attachment Protein Receptor Complex Formation

    Directory of Open Access Journals (Sweden)

    Shaun W. Carlson

    2017-10-01

    Full Text Available Traumatic brain injury (TBI and the activation of secondary injury mechanisms have been linked to impaired cognitive function, which, as observed in TBI patients and animal models, can persist for months and years following the initial injury. Impairments in neurotransmission have been well documented in experimental models of TBI, but the mechanisms underlying this dysfunction are poorly understood. Formation of the soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE complex facilitates vesicular docking and neurotransmitter release in the synaptic cleft. Published studies highlight a direct link between reduced SNARE complex formation and impairments in neurotransmitter release. While alterations in the SNARE complex have been described following severe focal TBI, it is not known if deficits in SNARE complex formation manifest in a model with reduced severity. We hypothesized that lateral fluid percussion injury (lFPI reduces the abundance of SNARE proteins, impairs SNARE complex formation, and contributes to impaired neurobehavioral function. To this end, rats were subjected to lFPI or sham injury and tested for acute motor performance and cognitive function at 3 weeks post-injury. lFPI resulted in motor impairment between 1 and 5 days post-injury. Spatial acquisition and spatial memory, as assessed by the Morris water maze, were significantly impaired at 3 weeks after lFPI. To examine the effect of lFPI on synaptic SNARE complex formation in the injured hippocampus, a separate cohort of rats was generated and brains processed to evaluate hippocampal synaptosomal-enriched lysates at 1 week post-injury. lFPI resulted in a significant reduction in multiple monomeric SNARE proteins, including VAMP2, and α-synuclein, and SNARE complex abundance. The findings in this study are consistent with our previously published observations suggesting that impairments in hippocampal SNARE complex formation may contribute to

  18. Cu(II AND Zn(II COMPLEX COMPOUNDS WITH BIGUANIDES AROMATIC DERIVATIVES. SYNTHESIS, CHARACTERIZATION, BIOLOGICAL ACTIVITY

    Directory of Open Access Journals (Sweden)

    Ticuţa Negreanu-Pîrjol

    2011-05-01

    Full Text Available In this paper we report the synthesis, physical-chemical characterization and antimicrobial activity of some new complex compounds of hetero-aromatic biguanides ligands, chlorhexidine base (CHX and chlorhexidine diacetate (CHXac2 with metallic ions Cu(II and Zn(II, in different molar ratio. The synthesized complexes were characterized by elemental chemical analysis and differential thermal analysis. The stereochemistry of the metallic ions was determined by infrared spectra, UV-Vis, EPR spectroscopy and magnetic susceptibility in the aim to establish the complexes structures. The biological activity of the new complex compounds was identified in solid technique by measuring minimum inhibition diameter of bacterial and fungal culture, against three standard pathogen strains, Escherichia coli ATCC 25922, Staphilococcus aureus ATCC 25923 and Candida albicans ATCC 10231. The results show an increased specific antimicrobial activity for the complexes chlorhexidine:Cu(II 1:1 and 1:2 compared with the one of the Zn(II complexes.

  19. Magneto-structural correlations in trinuclear Cu(II) complexes: a density functional study

    CERN Document Server

    Rodríguez-Forteá, A; Alvarez, S; Centre-De Recera-En-Quimica-Teorica; Alemany, P A; Centre-De Recera-En-Quimica-Teorica

    2003-01-01

    Density functional theoretical methods have been used to study magneto-structural correlations for linear trinuclear hydroxo-bridged copper(II) complexes. The nearest-neighbor exchange coupling constant shows very similar trends to those found earlier for dinuclear compounds for which the Cu-O-Cu angle and the out of plane displacement of the hydrogen atoms at the bridge are the two key structural factors that determine the nature of their magnetic behavior. Changes in these two parameters can induce variations of over 1000 cm sup - sup 1 in the value of the nearest-neighbor coupling constant. On the contrary, coupling between next-nearest neighbors is found to be practically independent of structural changes with a value for the coupling constant of about -60 cm sup - sup 1. The magnitude calculated for this coupling constant indicates that considering its value to be negligible, as usually done in experimental studies, can lead to considerable errors, especially for compounds in which the nearest-neighbor c...

  20. Cell Permeating Nano-Complexes of Amphiphilic Polyelectrolytes Enhance Solubility, Stability, and Anti-Cancer Efficacy of Curcumin.

    Science.gov (United States)

    Fatima, Munazza T; Chanchal, Abhishek; Yavvari, Prabhu S; Bhagat, Somnath D; Gujrati, Mansi; Mishra, Ram K; Srivastava, Aasheesh

    2016-07-11

    Many hydrophobic drugs encounter severe bioavailability issues owing to their low aqueous solubility and limited cellular uptake. We have designed a series of amphiphilic polyaspartamide polyelectrolytes (PEs) that solubilize such hydrophobic drugs in aqueous medium and enhance their cellular uptake. These PEs were synthesized through controlled (∼20 mol %) derivatization of polysuccinimide (PSI) precursor polymer with hydrophobic amines (of varying alkyl chain lengths, viz. hexyl, octyl, dodecyl, and oleyl), while the remaining succinimide residues of PSI were opened using a protonable and hydrophilic amine, 2-(2-amino-ethyl amino) ethanol (AE). Curcumin (Cur) was employed as a representative hydrophobic drug to explore the drug-delivery potential of the resulting PEs. Unprecedented enhancement in the aqueous solubility of Cur was achieved by employing these PEs through a rather simple protocol. In the case of PEs containing oleyl/dodecyl residues, up to >65000× increment in the solubility of Cur in aqueous medium could be achieved without requiring any organic solvent at all. The resulting suspensions were physically and chemically stable for at least 2 weeks. Stable nanosized polyelectrolyte complexes (PECs) with average hydrodynamic diameters (DH) of 150-170 nm (without Cur) and 220-270 nm (after Cur loading) were obtained by using submolar sodium polyaspartate (SPA) counter polyelectrolyte. The zeta potential of these PECs ranged from +36 to +43 mV. The PEC-formation significantly improved the cytocompatibility of the PEs while affording reconstitutable nanoformulations having up to 40 wt % drug-loading. The Cur-loaded PECs were readily internalized by mammalian cells (HEK-293T, MDA-MB-231, and U2OS), majorly through clathrin-mediated endocytosis (CME). Cellular uptake of Cur was directly correlated with the length of the alkyl chain present in the PECs. Further, the PECs significantly improved nuclear transport of Cur in cancer cells, resulting in their

  1. Synthesis, characterization and antifungal efficacy of C-coordinated O-carboxymethyl chitosan Cu(II) complexes.

    Science.gov (United States)

    Liu, Weixiang; Qin, Yukun; Liu, Song; Xing, Ronge; Yu, Huahua; Chen, Xiaolin; Li, Kecheng; Li, Pengcheng

    2017-03-15

    A novel type of O-carboxymethyl chitosan Schiff bases (O-CSPX) was synthesized via a condensation reaction. After the coordination reaction of cupric ions, Cu(II) complexes (O-CSPX-Cu) were achieved. The theoretical structure of O-CSPX-Cu calculated by Gaussian 09 reveals that the copper ions underwent dsp 2 hybridization, coordinated by the carbon atom in the p-π conjugate group and the oxygen atoms in the acetate ion. Then, the structures were confirmed by FT-IR, 1 H NMR, CP-MAS 13 C NMR, elemental analysis, DSC and XRD. The antifungal properties of O-CSPX-Cu against Phytophthora capsici (P. capsici), Gibberella zeae (G. zeae) and Glomerella cingulata (G. cingulata) were evaluated at concentrations ranging from 0.05mg/mL to 0.20mg/mL. The experiments indicated that the derivatives have significantly enhanced antifungal activity after copper ion complexation compared with the original chitosan. Moreover, it was shown that 0.20mg/mL of O-CSP3-Cu and O-CSP4-Cu can 100% inhibit the growth of P. capsici. The experimental results reveal that the antifungal efficiency is related to the space steric hindrance on the benzene ring, which may provide a novel direction for the development of copper fungicides. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Simultaneous preconcentration of Cu, Fe and Pb as methylthymol blue complexes on naphthalene adsorbent and flame atomic absorption determination

    International Nuclear Information System (INIS)

    Pourreza, Nahid; Hoveizavi, Reza

    2005-01-01

    A simultaneous preconcentration method was developed for determination of trace amounts of Cu, Fe and Pb by atomic absorption spectrometry. The method is based on the retention of their methylthymol blue complexes by naphthalene methyltrioctyl ammonium chloride adsorbent in a column. The adsorbed metal complexes were eluted from the column with nitric acid and Cu, Fe and Pb were determined by flame atomic absorption spectrometry. Several parameters such as pH of the sample solution, ligand concentration, volume of the sample and the amount of methyltrioctyl ammonium chloride loaded on naphthalene were evaluated. The effect of diverse ions on the preconcentration was also investigated. A preconcentration factor of up to 100 or more can easily be achieved depending on the volume of the sample taken. The calibration graphs were obtained in the range of 5-40, 10-100 and 10-200 ng ml -1 for Cu, Fe and Pb in the initial solution, respectively, when using 500 ml of the solution. The detection limit based on three standard deviations of the blank was 0.54, 3.1, and 4.5 ng ml -1 for Cu, Fe and Pb, respectively. The relative standard deviations (R.S.D.) of 0.62-1.4% for Cu, 1.9-3.4% for Fe and 1.0-2.2% for Pb were obtained. The method was applied to the determination of Cu, Fe and Pb in river and wastewater samples

  3. Ab initio study of cubic complex Bi2CrCuO6 perovskite

    International Nuclear Information System (INIS)

    Fajardo, F.; Cardona, R.; Landinez Tellez, D.A.; Arbey Rodriguez M, J.; Roa-Rojas, J.

    2008-01-01

    We report a detailed calculation of the structural and electronic properties for the cubic complex Bi 2 CrCuO 6 perovskite material by density functional theory. The exchange-correlation potential was included through the generalized gradient approximation. From the adjusting of Murnaghan state equation to the energy as a function of volume data, we obtain an ideal lattice parameter of 7.763 A. The density of states study was carried out considering the two spin polarizations. Results reveal that this material behaves as a conductor to the spin-down polarization and evidence a semiconductor tendency to the spin-up configuration. This tendency to the half-metallicity character is corroborated by the integer number of magnetic moment (3.0 μ B ), which is attributed to the Cr-spin-up orbital contribution

  4. Aging of a complex Al-Cu based alloy modified by microalloying

    International Nuclear Information System (INIS)

    Maksimovic, Vesna; Jovanovic, Milan T.; Radmilovic, Velimir; Nikolic, Ruzica

    2003-01-01

    The results of the effect of small addition (0.25 at.%) of Ge on aging kinetics of a complex aluminum alloy containing (wt.%) 5.9% Cu, 0.28% Si and 0.6% (total amount of Fe, Ti, Mn, Zr and V) are presented in this paper. Aging was performed at 190 o C in the interval ranging from 10min to 256h. Hardness measurements, light (LM), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) were used for microstructural characterization during aging. It was shown that the maximum of hardness in alloy containing Ge was achieved three times faster than in the alloy without Ge. TEM results clearly revealed that the accelerated kinetics should be ascribed to heterogeneously nucleated Si-Ge particles serving as sites for dense and fine distribution of θ' strengthening precipitates. Accelerated kinetics of aging was accompanied by increase in hardness. (Original)

  5. Cu(II Complexes of Isoniazid Schiff Bases: DNA/BSA Binding and Cytotoxicity Studies on A549 Cell Line

    Directory of Open Access Journals (Sweden)

    Pulipaka Ramadevi

    2014-01-01

    Full Text Available A series of isonicotinoyl hydrazones have been synthesized via template method and were complexed to Cu(II. The ligands are coordinated to Cu(II ion through the enolic oxygen and azomethine nitrogen resulting in a square planar geometry. The CT-DNA and bovine serum albumin binding propensities of the compounds were determined spectrophotometrically, the results of which indicate good binding propensity of complexes to DNA and BSA with high binding constant values. Furthermore, the compounds have been investigated for their cytotoxicities on A549 human lung cancer cell. Also the mode of cell death was examined employing various staining techniques and was found to be apoptotic.

  6. Coordination Behavior of Ni2+, Cu2+, and Zn2+ in Tetrahedral 1-Methylimidazole Complexes: A DFT/CSD Study

    OpenAIRE

    Tetteh, Samuel

    2018-01-01

    The interaction between nickel (Ni2+), copper (Cu2+), and zinc (Zn2+) ions and 1-methylimidazole has been studied by exploring the geometries of eleven crystal structures in the Cambridge Structural Database (CSD). The coordination behavior of the respective ions was further investigated by means of density functional theory (DFT) methods. The gas-phase complexes were fully optimized using B3LYP/GENECP functionals with 6-31G∗ and LANL2DZ basis sets. The Ni2+ and Cu2+ complexes show distorted ...

  7. A colorimetric and luminescent dual-modal assay for Cu(II ion detection using an iridium(III complex.

    Directory of Open Access Journals (Sweden)

    Dik-Lung Ma

    Full Text Available A novel iridium(III complex-based chemosensor bearing the 5,6-bis(salicylideneimino-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II ions. The interactions of this iridium(III complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration.

  8. The speciation, stability, solubility and biodegradation of organic co-contaminant radionuclide complexes: A review

    International Nuclear Information System (INIS)

    Keith-Roach, Miranda J.

    2008-01-01

    The potential migration of radionuclides is of concern at contaminated land sites and, in the long term, waste repositories. Pathways of migration need to be characterised on a predictive level so that management decisions can be made with confidence. A pathway that is relatively poorly understood at present is radionuclide solubilisation due to complexation by organic complexing agents that are present in mixed radioactive wastes, and at radioactively contaminated land sites. Interactions of the complexing agents with radionuclides and the host environment, and the response to changes in the physicochemical conditions make their role far from simple to elucidate. In addition, chemical and biodegradation of the organic materials may be important. In this paper, key co-contaminant organics are reviewed with emphasis on their environmental fate and impact on radionuclide migration

  9. The speciation, stability, solubility and biodegradation of organic co-contaminant radionuclide complexes: A review

    Energy Technology Data Exchange (ETDEWEB)

    Keith-Roach, Miranda J. [Biogeochemistry and Environmental Analytical Chemistry Group/Consolidated Radio-isotope Facility, School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)], E-mail: mkeith-roach@plymouth.ac.uk

    2008-06-15

    The potential migration of radionuclides is of concern at contaminated land sites and, in the long term, waste repositories. Pathways of migration need to be characterised on a predictive level so that management decisions can be made with confidence. A pathway that is relatively poorly understood at present is radionuclide solubilisation due to complexation by organic complexing agents that are present in mixed radioactive wastes, and at radioactively contaminated land sites. Interactions of the complexing agents with radionuclides and the host environment, and the response to changes in the physicochemical conditions make their role far from simple to elucidate. In addition, chemical and biodegradation of the organic materials may be important. In this paper, key co-contaminant organics are reviewed with emphasis on their environmental fate and impact on radionuclide migration.

  10. Comparison of Aqueous and 1-Octanol Solubility as well as Liquid?Liquid Distribution of Acyclovir Derivatives and Their Complexes with Hydroxypropyl-?-Cyclodextrin

    OpenAIRE

    Ko?bia?, Ma?gorzata; Gierycz, Pawe?

    2013-01-01

    The aim of the presented work is the comparison of aqueous and 1-octanol solubilities of different acyclovir derivatives and their hydroxypropyl-?-cyclodextrin inclusion complexes. The solubility measurements were carried out at different temperatures over the range 25?45??C using water, 1-octanol, water saturated with 1-octanol, 1-octanol saturated with water, buffered aqueous solutions (pH?=?5.5 and 7.0) and buffered aqueous solutions containing cyclodextrin as solvents. The aqueous solubil...

  11. Oxidation of a [Cu2S] complex by N2O and CO2: insights into a role of tetranuclearity in the CuZ site of nitrous oxide reductase.

    Science.gov (United States)

    Bagherzadeh, Sharareh; Mankad, Neal P

    2018-01-25

    Oxidation of a [Cu 2 (μ-S)] complex by N 2 O or CO 2 generated a [Cu 2 (μ-SO 4 )] product. In the presence of a sulfur trap, a [Cu 2 (μ-O)] species also formed from N 2 O. A [Cu 2 (μ-CS 3 )] species derived from CS 2 modeled initial reaction intermediates. These observations indicate that one role of tetranuclearity in the Cu Z catalytic site of nitrous oxide reductase is to protect the crucial S 2- ligand from oxidation.

  12. New soluble functional polymers by free-radical copolymerization of methacrylates and bipyridine ruthenium complexes

    NARCIS (Netherlands)

    Holder, E.; Meier, M.A.R.; Marin, V.N.; Schubert, U.S.

    2003-01-01

    The luminescent complex [4-(3-hydroxypropyl)-4-methyl-2,2-bipyridine]-bis(2,2-bipyridine)-ruthenium(II)-bis(hexafluoroantimonate) and its methacrylate derivative were successfully synthesized and fully characterized by two-dimensional 1H and 13C{1H} NMR techniques [correlation spectroscopy (COSY)

  13. Functional Assembly of Soluble and Membrane Recombinant Proteins of Mammalian NADPH Oxidase Complex.

    Science.gov (United States)

    Souabni, Hajer; Ezzine, Aymen; Bizouarn, Tania; Baciou, Laura

    2017-01-01

    Activation of phagocyte cells from an innate immune system is associated with a massive consumption of molecular oxygen to generate highly reactive oxygen species (ROS) as microbial weapons. This is achieved by a multiprotein complex, the so-called NADPH oxidase. The activity of phagocyte NADPH oxidase relies on an assembly of more than five proteins, among them the membrane heterodimer named flavocytochrome b 558 (Cytb 558 ), constituted by the tight association of the gp91 phox (also named Nox2) and p22 phox proteins. The Cytb 558 is the membrane catalytic core of the NADPH oxidase complex, through which the reducing equivalent provided by NADPH is transferred via the associated prosthetic groups (one flavin and two hemes) to reduce dioxygen into superoxide anion. The other major proteins (p47 phox , p67 phox , p40 phox , Rac) requisite for the complex activity are cytosolic proteins. Thus, the NADPH oxidase functioning relies on a synergic multi-partner assembly that in vivo can be hardly studied at the molecular level due to the cell complexity. Thus, a cell-free assay method has been developed to study the NADPH oxidase activity that allows measuring and eventually quantifying the ROS generation based on optical techniques following reduction of cytochrome c. This setup is a valuable tool for the identification of protein interactions, of crucial components and additives for a functional enzyme. Recently, this method was improved by the engineering and the production of a complete recombinant NADPH oxidase complex using the combination of purified proteins expressed in bacterial and yeast host cells. The reconstitution into artificial membrane leads to a fully controllable system that permits fine functional studies.

  14. Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

    Science.gov (United States)

    Chandra, Sulekh; Kumar, Anil

    2007-12-01

    Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L 1) and semicarbazone (L 2) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L) 2(SO 4) and Cu(L) 2(SO 4) [where L = L 1 and L 2] which are of five coordinated square pyramidal geometry.

  15. Coordination behavior of tetraaza [N4] ligand towards Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes: Synthesis, spectroscopic characterization and anticancer activity

    Science.gov (United States)

    El-Boraey, Hanaa A.

    2012-11-01

    Novel eight Co(II), Ni(II), Cu(II), Cu(I) and Pd(II) complexes with [N4] ligand (L) i.e. 2-amino-N-{2-[(2-aminobenzoyl)amino]ethyl}benzamide have been synthesized and structurally characterized by elemental analysis, spectral, thermal (TG/DTG), magnetic, and molar conductivity measurements. On the basis of IR, mass, electronic and EPR spectral studies an octahedral geometry has been proposed for Co(II), Ni(II) complexes and Cu(II) chloride complex, square-pyramidal for Cu(I) bromide complex. For Cu(II) nitrate complex (6), Pd(II) complex (8) square planar geometry was proposed. The EPR data of Cu(II) complexes in powdered form indicate dx2-y2 ground state of Cu(II) ion. The antitumor activity of the synthesized ligand and some selected metal complexes has been studied. The palladium(II) complex (8) was found to display cytotoxicity (IC50 = 25.6 and 41 μM) against human breast cancer cell line MCF-7 and human hepatocarcinoma HEPG2 cell line.

  16. Effect of atmospheric organic complexation on iron-bearing dust solubility

    OpenAIRE

    Paris , R.; Desboeufs , K. V.

    2013-01-01

    International audience; Recent studies reported that the effect of organic complexation may be a potentially important process to be considered by models estimating atmospheric iron flux to the ocean. In this study, we investigated this process effect by a series of dissolution experiments on iron-bearing dust in the presence or the absence of various organic compounds (acetate, formate, oxalate, malonate, succinate, glutarate, glycolate, lactate, tartrate and humic acid as an analogue of hum...

  17. Solubility of uranovanadates of the series A2+(VUO6)2 · nH2O (A2+ = Mg, Ca, Sr, Ba, Co, Ni, Cu, Pb) in water or aqueous solutions

    International Nuclear Information System (INIS)

    Chernorukov, N.G.; Sulejmanov, E.V.; Nipruk, O.V.; Lizunova, G.M.

    2001-01-01

    Solubility of uranovanadates of the series A 2+ (VUO 6 ) 2 · nH 2 O (A 2+ - Mg, Ca, Sr, Ba, Co, Ni, Cu, Pb) in water and aqueous solutions of inorganic acids at 25 deg C and different pH values was determined experimentally. The data obtained permitted calculation the Gibbs standard functions of formation and consideration of their state under conditions that were not studied experimentally, in the presence of carbon dioxide, in particular [ru

  18. Inclusion complex formation of ternary system: Fluoroscein-p-sulfonato calix[4]arene-Cu(2+) by cooperative binding.

    Science.gov (United States)

    Gawhale, Sharadchandra; Jadhav, Ankita; Rathod, Nilesh; Malkhede, Dipalee; Chaudhari, Gajanan

    2015-09-05

    The aqueous solution of fluorescein-para sulfonato calix[4]arene-metal ion complex has been studied based on absorption, fluorescence, (1)H NMR and FTIR spectroscopic results. It was found that the fluorescence intensity quenched regularly upon addition of pSCX4 and metal ion. The quenching constants and binding constants were determined for pSCX4-FL and pSCX4-FL-Cu(2+) systems. 1:1 stoichiometry is obtained for pSCX4-Cu(2+) system by continuous variation method. The NMR and IR results indicates the interaction among FL, pSCX4 and Cu(2+). The combined results demonstrate the cooperative binding to design the complex for ternary system. The life time for binary and ternary system has been studied. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Synthesis of 3,5-diisopropyl[carboxy-14C]salicylic acid and its 67Cu complex

    International Nuclear Information System (INIS)

    Chidambaram, M.V.; Epperson, C.E.; Williams, S.; Gray, R.A.; Sorenson, J.R.J.

    1991-01-01

    The synthesis of 3,5-diisopropyl[carboxy- 14 C]salicylic acid was achieved via Kolbe-Schmitt carboxylation of potassium 2,4-di-isopropylphenolate. The yield of this acid was 81% based upon the weight of the product and 93% based upon radioactivity incorporated into the labeled acid which contains 98% 14 C in the carboxyl group (specific activity = 5.1 μCi/mg). The labeled acid was characterized by ultraviolet spectrophotometry and purity established by thin-layer chromatography, autoradiography, and liquid scintillation counting. A 90% yield of the double labeled 14 C, 67 Cu-complex (specific activity = 4.6 μCi 67 Cu/mg) was obtained using conditions developed with non-radioactive reactants. The presence of 67 Cu in this complex was established using γ-ray emission spectrophometry. (author)

  20. Improvement of Aripiprazole Solubility by Complexation with (2-Hydroxy)propyl-β-cyclodextrin Using Spray Drying Technique

    OpenAIRE

    Mihajlovic, Tijana; Kachrimanis, Kyriakos; Graovac, Adrijana; Djuric, Zorica; Ibric, Svetlana

    2012-01-01

    Due to the fact that the number of new poorly soluble active pharmaceutical ingredients is increasing, it is important to investigate the possibilities of improvement of their solubility in order to obtain a final pharmaceutical formulation with enhanced bioavailability. One of the strategies to increase drug solubility is the inclusion of the APIs in cyclodextrins. The aim of this study was to investigate the possibility of aripiprazole solubility improvement by inclusion in (2-hydroxy)propy...

  1. Extremely stable soluble high molecular mass multi-protein complex with DNase activity in human placental tissue.

    Directory of Open Access Journals (Sweden)

    Evgeniya E Burkova

    Full Text Available Human placenta is an organ which protects, feeds, and regulates the grooving of the embryo. Therefore, identification and characterization of placental components including proteins and their multi-protein complexes is an important step to understanding the placenta function. We have obtained and analyzed for the first time an extremely stable multi-protein complex (SPC, ∼ 1000 kDa from the soluble fraction of three human placentas. By gel filtration on Sepharose-4B, the SPC was well separated from other proteins of the placenta extract. Light scattering measurements and gel filtration showed that the SPC is stable in the presence of NaCl, MgCl2, acetonitrile, guanidinium chloride, and Triton in high concentrations, but dissociates efficiently in the presence of 8 M urea, 50 mM EDTA, and 0.5 M NaCl. Such a stable complex is unlikely to be a casual associate of different proteins. According to SDS-PAGE and MALDI mass spectrometry data, this complex contains many major glycosylated proteins with low and moderate molecular masses (MMs 4-14 kDa and several moderately abundant (79.3, 68.5, 52.8, and 27.2 kDa as well as minor proteins with higher MMs. The SPC treatment with dithiothreitol led to a disappearance of some protein bands and revealed proteins with lower MMs. The SPCs from three placentas efficiently hydrolyzed plasmid supercoiled DNA with comparable rates and possess at least two DNA-binding sites with different affinities for a 12-mer oligonucleotide. Progress in study of placental protein complexes can promote understanding of their biological functions.

  2. Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

    KAUST Repository

    Kumar, Rajeev Ananda; Zheng, Bin; Huang, Kuo-Wei; Emert, Jack I.; Faust, Rudolf

    2014-01-01

    The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

  3. Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes

    KAUST Repository

    Kumar, Rajeev Ananda

    2014-03-25

    The polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.

  4. Efficient Destruction of Pollutants in Water by a Dual-Reaction-Center Fenton-like Process over Carbon Nitride Compounds-Complexed Cu(II)-CuAlO2.

    Science.gov (United States)

    Lyu, Lai; Yan, Dengbiao; Yu, Guangfei; Cao, Wenrui; Hu, Chun

    2018-04-03

    Carbon nitride compounds (CN) complexed with the in-situ-produced Cu(II) on the surface of CuAlO 2 substrate (CN-Cu(II)-CuAlO 2 ) is prepared via a surface growth process for the first time and exhibits exceptionally high activity and efficiency for the degradation of the refractory pollutants in water through a Fenton-like process in a wide pH range. The reaction rate for bisphenol A removal is ∼25 times higher than that of the CuAlO 2 . According to the characterization, Cu(II) generation on the surface of CuAlO 2 during the surface growth process results in the marked decrease of the surface oxygen vacancies and the formation of the C-O-Cu bridges between CN and Cu(II)-CuAlO 2 in the catalyst. The electron paramagnetic resonance (EPR) analysis and density functional theory (DFT) calculations demonstrate that the dual reaction centers are produced around the Cu and C sites due to the cation-π interactions through the C-O-Cu bridges in CN-Cu(II)-CuAlO 2 . During the Fenton-like reactions, the electron-rich center around Cu is responsible for the efficient reduction of H 2 O 2 to • OH, and the electron-poor center around C captures electrons from H 2 O 2 or pollutants and diverts them to the electron-rich area via the C-O-Cu bridge. Thus, the catalyst exhibits excellent catalytic performance for the refractory pollutant degradation. This study can deepen our understanding on the enhanced Fenton reactivity for water purification through functionalizing with organic solid-phase ligands on the catalyst surface.

  5. New Mononuclear Cu(II Complexes and 1D Chains with 4-Amino-4H-1,2,4-triazole

    Directory of Open Access Journals (Sweden)

    Marinela M. Dîrtu

    2013-12-01

    Full Text Available The crystal structures of two mononuclear Cu(II NH2trz complexes [Cu(NH2trz4(H2O](AsF62 (I and [Cu(NH2trz4(H2O](PF62 (II as well as two coordination polymers [Cu(μ2-NH2trz2Cl]Cl∙H2O (III and [Cu(μ2-NH2trz2Cl] (SiF60.5∙1.5H2O (IV are presented. Cationic 1D chains with bridging bis-monodentate μ2-coordinated NH2trz and bridging μ2-coordinated chloride ligands are present in III and IV. In these coordination polymers, the Cu(II ions are strongly antiferromagnetically coupled with J = −128.4 cm−1 for III and J = −143 cm−1 for IV (H = −JΣSiSi+1, due to the nature of the bridges between spin centers. Inter-chain interactions present in the crystal structures were taken into consideration, as well as g factors, which were determined experimentally, for the quantitative modeling of their magnetic properties.

  6. Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+

    KAUST Repository

    Turias, Francesc; Solà , Miquel; Falivene, Laura; Cavallo, Luigi; Poater, Albert

    2015-01-01

    The present computational study complements the recent experimental efforts by Karlin and coworkers to describe the interconversion of nitrite to nitric oxide by means of an iron porphyrin complex together with a Cu chemical system, i.e., the iron(II) complex (F8TPP)FeII [F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2−)] and a preformed copper(II)–nitrito complex [(tmpa)CuII(NO2)][B(C6F5)4] [tmpa = tris(2-pyridylmethyl)amine], being the latter an oxidized species of [(tmpa)CuI(MeCN)]+. By DFT calculations, we unravel how the reduction of nitrite to nitric oxide takes place through a μ-oxo heme-FeIII–O–CuII complex, following a mimetic path as in the cytochrome c oxidase. Mayer bond order (MBO) and energy decomposition analyses are used to analyze the bonding strength of such nitro derivatives to either copper or iron. © 2015 Springer Science+Business Media New York

  7. The piroxicam complex of copper(II), trans-[Cu(Pir)2(THF)2], and its interaction with DNA

    Science.gov (United States)

    Hadadzadeh, Hassan; Salimi, Mona; Weil, Matthias; Jannesari, Zahra; Darabi, Farivash; Abdi, Khatereh; Khalaji, Aliakbar Dehno; Sardari, Soroush; Ahangari, Reza

    2012-08-01

    The mononuclear Cu(II) complex, trans-[Cu(Pir)2(THF)2], where Pir is 4-hydroxy-2-methyl-N-2-pyridyl-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide (piroxicam), has been prepared and characterized by elemental analysis, spectroscopic methods (UV-Vis, IR, and 1H NMR) and single crystal X-ray structure analysis. The molecular structure of the centrosymmetric complex is made up of two monoanionic bidentate Pir ligands coordinated to the Cu(II) atom through the pyridyl N atom and the carbonyl O atom of the amide group in equatorial positions. The elongated rhombic octahedral (ERO) coordination of the CuNONOO2″ chromophore is completed by the O atoms of two THF molecules in axial positions. A strong intramolecular hydrogen bond between the amide N-H function and the enolate O atom confirms the ZZZ conformation of piroxicam. In addition, CD spectroscopy and gel electrophoresis assays have been used to investigate the interaction of the complex with DNA. The results revealed that the binding of the complex with DNA led to DNA backbone distortion.

  8. Nitrite to nitric oxide interconversion by heme FeII complex assisted by [CuI(tmpa)]+

    KAUST Repository

    Turias, Francesc

    2015-09-09

    The present computational study complements the recent experimental efforts by Karlin and coworkers to describe the interconversion of nitrite to nitric oxide by means of an iron porphyrin complex together with a Cu chemical system, i.e., the iron(II) complex (F8TPP)FeII [F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2−)] and a preformed copper(II)–nitrito complex [(tmpa)CuII(NO2)][B(C6F5)4] [tmpa = tris(2-pyridylmethyl)amine], being the latter an oxidized species of [(tmpa)CuI(MeCN)]+. By DFT calculations, we unravel how the reduction of nitrite to nitric oxide takes place through a μ-oxo heme-FeIII–O–CuII complex, following a mimetic path as in the cytochrome c oxidase. Mayer bond order (MBO) and energy decomposition analyses are used to analyze the bonding strength of such nitro derivatives to either copper or iron. © 2015 Springer Science+Business Media New York

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

    International Nuclear Information System (INIS)

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

    1982-01-01

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

  10. Complex rheological properties of a water-soluble extract from the fronds of the black tree fern, Cyathea medullaris.

    Science.gov (United States)

    Goh, Kelvin K T; Matia-Merino, Lara; Hall, Christopher E; Moughan, Paul J; Singh, Harjinder

    2007-11-01

    A water-soluble extract was obtained from the fronds of a New Zealand native black tree fern (Cyathea medullaris or Mamaku in Māori). The extract exhibited complex rheological behavior. Newtonian, shear-thinning, shear-thickening, thixotropic, antithixotropic, and viscoelastic behaviors were observed depending on polymer concentration, shear rate, and shear history. The extract also displayed rod-climbing and self-siphoning properties typical of viscoelastic fluids. Such complex rheological properties have been reported in synthetic or chemically modified polymers but are less frequent in unmodified biopolymers. Although Mamaku extract obtained from the pith of the fern has been traditionally used by the Māori in New Zealand for treating wounds and diarrhea among other ailments, this material has never been characterized before. This study reports on the chemical composition of the extract and on its viscoelastic properties through rotational and oscillatory rheological measurements. Explanations of the mechanism behind the rheological properties were based on transient network models for associating polymers.

  11. Determination of water-soluble and insoluble (dilute-HCl-extractable) fractions of Cd, Pb and Cu in Antarctic aerosol by square wave anodic stripping voltammetry: distribution and summer seasonal evolution at Terra Nova Bay (Victoria Land)

    Energy Technology Data Exchange (ETDEWEB)

    Annibaldi, A.; Truzzi, C.; Illuminati, S.; Bassotti, E.; Scarponi, G. [Polytechnic University of Marche - Ancona, Department of Marine Science, Ancona (Italy)

    2007-02-15

    Eight PM10 aerosol samples were collected in the vicinity of the ''Mario Zucchelli'' Italian Antarctic Station (formerly Terra Nova Bay Station) during the 2000-2001 austral summer using a high-volume sampler and precleaned cellulose filters. The aerosol mass was determined by differential weighing of filters carried out in a clean chemistry laboratory under controlled temperature and humidity. A two-step sequential extraction procedure was used to separate the water-soluble and the insoluble (dilute-HCl-extractable) fractions. Cd, Pb and Cu were determined in the two fractions using an ultrasensitive square wave anodic stripping voltammetric (SWASV) procedure set up for and applied to aerosol samples for the first time. Total extractable metals showed maxima at midsummer for Cd and Pb and a less clear trend for Cu. In particular, particulate metal concentrations ranged as follows: Cd 0.84-9.2 {mu}g g{sup -1} (average 4.7 {mu}g g{sup -1}), Pb 13.2-81 {mu}g g{sup -1} (average 33 {mu}g g{sup -1}), Cu 126-628 {mu}g g{sup -1} (average 378 {mu}g g{sup -1}). In terms of atmospheric concentration, the values were: Cd 0.55-6.3 pg m{sup -3} (average 3.4 pg m{sup -3}), Pb 8.7-48 pg m{sup -3} (average 24 pg m{sup -3}), Cu 75-365 pg m{sup -3} (average 266 pg m{sup -3}). At the beginning of the season the three metals appear widely distributed in the insoluble (HCl-extractable) fraction (higher proportions for Cd and Pb, 90-100%, and lower for Cu, 70-90%) with maxima in the second half of December. The soluble fraction then increases, and at the end of the season Cd and Pb are approximately equidistributed between the two fractions, while for Cu the soluble fraction reaches its maximum level of 36%. Practically negligible contributions are estimated for crustal and sea-spray sources. Low but significant volcanic contributions are estimated for Cd and Pb ({proportional_to}10% and {proportional_to}5%, respectively), while there is an evident although not

  12. Mechanochemically assisted solid-state and citric acid complex syntheses of Cu-doped sodium cobaltite ceramics

    International Nuclear Information System (INIS)

    Pršić, S.; Savić, S.M.; Branković, Z.; Vrtnik, S.; Dapčević, A.; Branković, G.

    2015-01-01

    Highlights: • Sodium cobaltite was synthesized by mechanochemically assisted solid-state reaction and citric acid complex (CAC) method. • We investigated effect of Cu-doping in NaCo 2−x Cu x O 4 (x = 0, 0.01, 0.03, 0.05). • ICP analysis showed that the controlling of the samples composition is easier by the CAC method. • The Seebeck coefficient in Cu-doped samples was higher compared to the undoped one. • The highest figure of merit was observed in the sample with the lowest Cu concentration. - Abstract: In the last decade, the sodium cobaltite ceramic became a promising candidate for potential thermoelectric applications, because of its large thermopower and low resistivity. In this work, polycrystalline samples of NaCo 2−x Cu x O 4 (x = 0, 0.01, 0.03, 0.05) were prepared using mechanochemically assisted solid-state reaction method (MASSR) and the citric acid complex method (CAC). Bulk samples were prepared by pressing into disc-shaped pellets and subsequently subjected to a thermal treatment at 880 °C in inert argon atmosphere. Changes in structural and microstructural characteristics of the samples, caused by the substitution of Cu for Co, were characterized using X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM), respectively. The results of inductively coupled plasma (ICP) analysis showed that the compositions of the final products correspond to γ-NaCo 2 O 4 and confirmed that desired compound was obtained in both syntheses procedures. The advantages and disadvantages of these two syntheses procedures have been observed and discussed: the CAC method enabled obtaining samples with higher density and fine microstructure compared to the MASSR method, thus better thermoelectric properties. The Cu 2+ substitution led to the increase in Seebeck coefficient in both synthesis routes. The highest figure of merit of 0.022 at 300 K was observed for the sample doped with 1 mol% Cu, obtained by the CAC method, and it was almost twice

  13. Mechanochemically assisted solid-state and citric acid complex syntheses of Cu-doped sodium cobaltite ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Pršić, S., E-mail: sanjaprsic@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia); Savić, S.M., E-mail: slavicas@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia); Branković, Z., E-mail: zorica.brankovic@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia); Vrtnik, S., E-mail: stane.vrtnik@ijs.si [Institute Jožef Stefan, Condensed Matter Physics, Jamova cesta 39, 1000 Ljubljana (Slovenia); Dapčević, A., E-mail: hadzi-tonic@tmf.bg.ac.rs [Department of General and Inorganic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Branković, G., E-mail: goran.brankovic@imsi.bg.ac.rs [Institute for Multidisciplinary Research, University of Belgrade, Kneza Višeslava 1, 11030 Belgrade (Serbia)

    2015-08-15

    Highlights: • Sodium cobaltite was synthesized by mechanochemically assisted solid-state reaction and citric acid complex (CAC) method. • We investigated effect of Cu-doping in NaCo{sub 2−x}Cu{sub x}O{sub 4} (x = 0, 0.01, 0.03, 0.05). • ICP analysis showed that the controlling of the samples composition is easier by the CAC method. • The Seebeck coefficient in Cu-doped samples was higher compared to the undoped one. • The highest figure of merit was observed in the sample with the lowest Cu concentration. - Abstract: In the last decade, the sodium cobaltite ceramic became a promising candidate for potential thermoelectric applications, because of its large thermopower and low resistivity. In this work, polycrystalline samples of NaCo{sub 2−x}Cu{sub x}O{sub 4} (x = 0, 0.01, 0.03, 0.05) were prepared using mechanochemically assisted solid-state reaction method (MASSR) and the citric acid complex method (CAC). Bulk samples were prepared by pressing into disc-shaped pellets and subsequently subjected to a thermal treatment at 880 °C in inert argon atmosphere. Changes in structural and microstructural characteristics of the samples, caused by the substitution of Cu for Co, were characterized using X-ray diffraction (XRD) analysis, and scanning electron microscopy (SEM), respectively. The results of inductively coupled plasma (ICP) analysis showed that the compositions of the final products correspond to γ-NaCo{sub 2}O{sub 4} and confirmed that desired compound was obtained in both syntheses procedures. The advantages and disadvantages of these two syntheses procedures have been observed and discussed: the CAC method enabled obtaining samples with higher density and fine microstructure compared to the MASSR method, thus better thermoelectric properties. The Cu{sup 2+} substitution led to the increase in Seebeck coefficient in both synthesis routes. The highest figure of merit of 0.022 at 300 K was observed for the sample doped with 1 mol% Cu, obtained by

  14. The natural catalytic function of CuGE glucuronoyl esterase in hydrolysis of genuine lignin-carbohydrate complexes from birch

    DEFF Research Database (Denmark)

    Mosbech, Caroline; Holck, Jesper; Meyer, Anne S.

    2018-01-01

    Glucuronoyl esterases belong to carbohydrate esterase family 15 and catalyze de-esterification. Their natural function is presumed to be cleavage of ester linkages in lignin-carbohydrate complexes particularly those linking lignin and glucuronoyl residues in xylans in hardwood. Here, we show...... for the first time a detailed product profile of aldouronic acids released from birchwood lignin by a glucuronoyl esterase from the white-rot fungus Cerrena unicolor (CuGE). CuGE releases substrate for GH10 endo-xylanase which results in significantly increased product release compared to the action of endo......-xylanase alone. CuGE also releases neutral xylo-oligosaccharides that can be ascribed to the enzymes feruloyl esterase side activity as demonstrated by release of ferulic acid from insoluble wheat arabinoxylan. The data verify the enzyme's unique ability to catalyze removal of all glucuronoxylan associated...

  15. Soluble form of membrane attack complex independently predicts mortality and cardiovascular events in patients with ST-elevation myocardial infarction treated with primary percutaneous coronary intervention

    DEFF Research Database (Denmark)

    Lindberg, Søren; Pedersen, Sune H; Mogelvang, Rasmus

    2012-01-01

    The complement system is an important mediator of inflammation, which plays a pivotal role in atherosclerosis and acute myocardial infarction (AMI). Animal studies suggest that activation of the complement cascade resulting in the formation of soluble membrane attack complex (sMAC), contributes...

  16. A comprehensive review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes

    International Nuclear Information System (INIS)

    Caffrey, Martin

    2015-01-01

    A comprehensive and up-to-date review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes is reported. Recent applications of the method for in situ serial crystallography at X-ray free-electron lasers and synchrotrons are described. The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for

  17. A comprehensive review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes

    Energy Technology Data Exchange (ETDEWEB)

    Caffrey, Martin, E-mail: martin.caffrey@tcd.ie [Trinity College Dublin, Dublin (Ireland)

    2015-01-01

    A comprehensive and up-to-date review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes is reported. Recent applications of the method for in situ serial crystallography at X-ray free-electron lasers and synchrotrons are described. The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for

  18. Preparation of YBa2Cu3O7-δ powders by the thermal decomposition of a heteronuclear complex, CuY1/3Ba2/3(dhbaen)(NO3)1/3(H2O)3

    International Nuclear Information System (INIS)

    Hasegawa, E.; Aono, H.; Sadaoka, Y.; Traversa, E.

    1999-01-01

    YBa 2 Cu 3 O 7-δ powders were prepared by the thermal decomposition of a heteronuclear complex, CuY 1/3 Ba 2/3 (dhbaen)(NO 3 ) 1/3 (H 2 O) 3 . The products of the complex thermal decomposition were analyzed by TG-DTA, XRD, SEM-Auger and XPS. The decomposition of the CuY 1/3 Ba 2/3 -complex was obtained at about 500 C and the product was a mixture of oxides and carbonates. The formation of YBa 2 Cu 3 O 7-δ proceeded at 800 C, with a gradual decomposition of the carbonates. A homogeneous distribution of each element, Y, Ba, and Cu, was observed for the decomposed CuY 1/3 Ba 2/3 -complex by SEM-Auger analysis. The binding energy values of Ba3d 5/2 and O1s photolines from Ba and O in the superconductive lattice did not shift during the sputtering period. Furthermore, the formation of Ba rich regions on the surface was depressed by using the complex as a starting material for homogeneous 123-oxide, YBa 2 Cu 3 O 7-δ . (orig.)

  19. Cellular responses induced by Cu(II quinolinonato complexes in human tumor and hepatic cells

    Directory of Open Access Journals (Sweden)

    Trávníček Zdeněk

    2012-12-01

    Full Text Available Abstract Background Inspired by the unprecedented historical success of cisplatin, one of the most important research directions in bioinorganic and medicinal chemistry is dedicated to the development of new anticancer compounds with the potential to surpass it in antitumor activity, while having lower unwanted side-effects. Therefore, a series of copper(II mixed-ligand complexes of the type [Cu(qui(L]Y · xH2O (1–6, where Hqui = 2-phenyl-3-hydroxy-4(1H-quinolinone, Y = NO3 (1, 3, 5 or BF4 (2, 4, 6, and L = 1,10-phenanthroline (phen (1, 2, 5-methyl-1,10-phenanthroline (mphen (3, 4 and bathophenanthroline (bphen (5, 6, was studied for their in vitro cytotoxicity against several human cancer cell lines (A549 lung carcinoma, HeLa cervix epitheloid carcinoma, G361 melanoma cells, A2780 ovarian carcinoma, A2780cis cisplatin-resistant ovarian carcinoma, LNCaP androgen-sensitive prostate adenocarcinoma and THP-1 monocytic leukemia. Results The tested complexes displayed a stronger cytotoxic effect against all the cancer cells as compared to cisplatin. The highest cytotoxicity was found for the complexes 4 (IC50 = 0.36 ± 0.05 μM and 0.56 ± 0.15 μM, 5 (IC50 = 0.66 ± 0.07 μM and 0.73 ± 0.08 μM and 6 (IC50 = 0.57 ± 0.11 μM and 0.70 ± 0.20 μM against A2780, and A2780cis respectively, as compared with the values of 12.0 ± 0.8 μM and 27.0 ± 4.6 μM determined for cisplatin. Moreover, the tested complexes were much less cytotoxic to primary human hepatocytes than to the cancer cells. The complexes 5 and 6 exhibited significantly high ability to modulate secretion of the pro-inflammatory cytokines TNF-α (2873 ± 238 pg/mL and 3284 ± 139 pg/mL for 5, and 6 respectively and IL-1β (1177 ± 128 pg/mL and 1087 ± 101 pg/mL for 5, and 6 respectively tested on the lipopolysaccharide (LPS-stimulated THP-1 cells as compared with the values of 1173

  20. Bloch Surface Waves Biosensors for High Sensitivity Detection of Soluble ERBB2 in a Complex Biological Environment.

    Science.gov (United States)

    Sinibaldi, Alberto; Sampaoli, Camilla; Danz, Norbert; Munzert, Peter; Sonntag, Frank; Centola, Fabio; Occhicone, Agostino; Tremante, Elisa; Giacomini, Patrizio; Michelotti, Francesco

    2017-08-17

    We report on the use of one-dimensional photonic crystals to detect clinically relevant concentrations of the cancer biomarker ERBB2 in cell lysates. Overexpression of the ERBB2 protein is associated with aggressive breast cancer subtypes. To detect soluble ERBB2, we developed an optical set-up which operates in both label-free and fluorescence modes. The detection approach makes use of a sandwich assay, in which the one-dimensional photonic crystals sustaining Bloch surface waves are modified with monoclonal antibodies, in order to guarantee high specificity during the biological recognition. We present the results of exemplary protein G based label-free assays in complex biological matrices, reaching an estimated limit of detection of 0.5 ng/mL. On-chip and chip-to-chip variability of the results is addressed too, providing repeatability rates. Moreover, results on fluorescence operation demonstrate the capability to perform high sensitive cancer biomarker assays reaching a resolution of 0.6 ng/mL, without protein G assistance. The resolution obtained in both modes meets international guidelines and recommendations (15 ng/mL) for ERBB2 quantification assays, providing an alternative tool to phenotype and diagnose molecular cancer subtypes.

  1. A supramolecular photosensitizer system based on the host-guest complexation between water-soluble pillar[6]arene and methylene blue for durable photodynamic therapy.

    Science.gov (United States)

    Yang, Kui; Wen, Jia; Chao, Shuang; Liu, Jing; Yang, Ke; Pei, Yuxin; Pei, Zhichao

    2018-06-05

    A supramolecular photosensitizer system WP6-MB was synthesized based on water-soluble pillar[6]arene and the photosensitizer methylene blue (MB) via host-guest interaction. MB can complex with WP6 directly with a high complex constant without further modification. In particular, WP6-MB can reduce the dark toxicity of MB remarkably. Furthermore, it can efficiently overcome photobleaching and extend the time for singlet oxygen production of MB upon light irradiation, which is significant for durable photodynamic therapy.

  2. Synthesis and characterization of mixed ligand Cu(II) complexes of salicylic acid derivatives with 2-aminobenzotiyazol derivatives

    OpenAIRE

    İlkimen, Halil; Yenikaya, Cengiz

    2018-01-01

    In thisstudy, mixed ligand transitionmetal complexes of Cu(II)have been prepared between salicylic acid derivatives [salicylic acid (H2sal) or acetylsalicylic acid (Hasal)] and 2-aminobenzothiazole derivatives[2-aminobenzothiazole (abt) or 2-amino-6-chlorobenzothiazole (Clabt) or2-amino-6-methylbenzothiazole (Meabt)]. The structures of amorphous metalcomplexes have been proposed by evaluating the data obtained from elementalanalysis, ICP-OES, FT-IR, UV-Vis, thermal analysis, magnetic suscepti...

  3. Neptunium (IV) oxalate solubility

    International Nuclear Information System (INIS)

    Luerkens, D.W.

    1983-07-01

    The equilibrium solubility of neptunium (IV) oxalate in nitric/oxalic acid solutions was determined at 22 0 C, 45 0 C, and 60 0 C. The concentrations of nitric/oxalic acid solutions represented a wide range of free oxalate ion concentration. A mathematical solubility model was developed which is based on the formation of the known complexes of neptunium (IV) oxalate. the solubility model uses a simplified concentration parameter which is proportional to the free oxalate ion concentration. The solubility model can be used to estimate the equilibrium solubility of neptunium (IV) oxalate over a wide range of oxalic and nitric acid concentrations at each temperature

  4. Synthesis and magnetism of μ-oxamido-bridged Cu2IILnIII - type heterotrinuclear complexes (Ln = Ce, Nd, Sm, Eu, Gd, Tb, Dy, Er)

    International Nuclear Information System (INIS)

    Li, Y.T.; Yan, C.W.

    2001-01-01

    Eight new Cu 2 II Ln III - type (Ln = Ce, Nd, Sm, Eu, Gd, Tb, Dy, Er) heterotrinuclear complexes bridged by N,N'-bis (2-aminopropyl)oxamidocopper(II) [Cu(oxdn)], namely Cu 2 (oxdn)Ln(NO 3 ) 3 , have been synthesized and characterized by elemental analyses, molar conductivity measurements and spectroscopic (IR, UV, ESR) studies. Magnetic susceptibility measurements (4.2 ∼300 K) and studies of Cu 2 (oxdn)Gd(NO 3 ) 3 complex have revealed that the central gadolinium(III) and terminal copper(II) ions are ferromagnetically coupled with the exchange integral J (Cu-Gd) = +2.98 cm -1 , while an antiferromagnetic coupling is detected between the terminal copper(II) metal ions with the exchange integral J' (Cu-Gd) = -0.75 cm -1 , on the basis of the spin Hamiltonian operator [H -2J(S Cu1 -S Gd +S Cu2 +S Gd )-2J'(S Cu1 S Cu2 )]. (author)

  5. The model for solubility of CO2 in saline groundwater with complex ions and the application on Erdos basin

    International Nuclear Information System (INIS)

    Wang Lu; Yu Qingchun

    2014-01-01

    To obtain accurate solubility of CO 2 is one of problems that need solutions urgently in CO 2 sequestration within saline groundwater. However, there are few data published for solubility of CO 2 under geological sequestration conditions. In order to fill the gap of the experimental study, the solubility of CO 2 in five formations of Erdos Basin was explored in this research. Groundwater samples in five reservoirs were carried out through an observation well in the Erdos Basin. The chemical composition was determined and experiments measuring CO 2 solubility were carried out in the synthetic water samples. Krichevsky-Kasarnovsky equation was established to analyze the experimental data. The relationship between concentration of K + , Na + , Ca 2+ , Mg 2+ and the solubility of CO 2 was analyzed and an excellent liner fit was found, which quantifies the impact of ions on the solubility of cO 2 . Solubility data were compared to the model prediction over the temperature and pressure ranges of 318 ∼ 348 K and 8 ∼ 11 MPa. The average absolute deviation is 2.11%. The results can be used as a parameter for the evaluation of the CO 2 storage capacity in deep saline aquifer of Erdos Basin. (authors)

  6. Combined experimental and theoretical approach to understand the reactivity of a mononuclear Cu(II)-hydroperoxo complex in oxygenation reactions.

    Science.gov (United States)

    Kamachi, Takashi; Lee, Yong-Min; Nishimi, Tomonori; Cho, Jaeheung; Yoshizawa, Kazunari; Nam, Wonwoo

    2008-12-18

    A copper(II) complex bearing a pentadentate ligand, [Cu(II)(N4Py)(CF(3)SO(3))(2)] (1) (N4Py = N,N-bis(2-pyridylmethyl)bis(2-pyridyl)methylamine), was synthesized and characterized with various spectroscopic techniques and X-ray crystallography. A mononuclear Cu(II)-hydroperoxo complex, [Cu(II)(N4Py)(OOH)](+) (2), was then generated in the reaction of 1 and H(2)O(2) in the presence of base, and the reactivity of the intermediate was investigated in the oxidation of various substrates at -40 degrees C. In the reactivity studies, 2 showed a low oxidizing power such that 2 reacted only with triethylphosphine but not with other substrates such as thioanisole, benzyl alcohol, 1,4-cyclohexadiene, cyclohexene, and cyclohexane. In theoretical work, we have conducted density functional theory (DFT) calculations on the epoxidation of ethylene by 2 and a [Cu(III)(N4Py)(O)](+) intermediate (3) at the B3LYP level. The activation barrier is calculated to be 39.7 and 26.3 kcal/mol for distal and proximal oxygen attacks by 2, respectively. This result indicates that the direct ethylene epoxidation by 2 is not a plausible pathway, as we have observed in the experimental work. In contrast, the ethylene epoxidation by 3 is a downhill and low-barrier process. We also found that 2 cannot be a precursor to 3, since the homolytic cleavage of the O-O bond of 2 is very endothermic (i.e., 42 kcal/mol). On the basis of the experimental and theoretical results, we conclude that a mononuclear Cu(II)-hydroperoxo species bearing a pentadentate N5 ligand is a sluggish oxidant in oxygenation reactions.

  7. Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

    Science.gov (United States)

    Norkus, E; Vaskelis, A; Zakaite, I

    1996-03-01

    D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

  8. Sulfite induced autoxidation of Cu(II/tetra/ penta and hexaglycine complexes: spectrophotometric and rotating-ring-disk glassy carbon electrode studies and analytical potentialities

    Directory of Open Access Journals (Sweden)

    Alipázaga Maria V.

    2003-01-01

    Full Text Available The oxidation of Cu(II complexes with tetra, penta and hexaglycine in borate buffer aqueous solution, by dissolved oxygen is strongly accelerated by sulfite. The formation of Cu(III complexes with maximum absorbances at 250 nm (e = 9000 mol-1 L cm-1 and 365 nm (e = 7120 mol-1 L cm-1 was also characterized by using rotating ring-disk voltammetry, whose anodic and cathodic components were observed in voltammograms recorded in solutions containing Cu(II. Voltammograms, obtained at various rotation speeds, showed that the Cu(III species electrochemically generated is not stable over the entire time window of the experiment and in solutions containing tetraglycine the overall limiting current is controlled by the kinetics of an equilibrium involving Cu(II species.The calculated first order rate constant of the decomposition was 4.37x10-3 s-1. Electrochemical experiments carried out in Cu(II solutions after the addition of relatively small amounts of sulfite demonstrated that the Cu(III species formed in the chemical reaction is the same as the one collected at the ring electrode when Cu(II is oxidized at the disk electrode in ring-disk voltammetry. The concentration of Cu(III complexes is proportional to the amount of added sulfite and the results indicated that indirect analytical methods for sulfite may be developed by means of spectrophotometric or amperometric detection of the chemically generated product.

  9. Inclusion Complexes of a New Family of Non-Ionic Amphiphilic Dendrocalix[4]arene and Poorly Water-Soluble Drugs Naproxen and Ibuprofen

    Directory of Open Access Journals (Sweden)

    Khalid Khan

    2017-05-01

    Full Text Available The inclusion complexes of a new family of nonionic amphiphilic calix[4]arenes with the anti-inflammatory hydrophobic drugs naproxen (NAP and ibuprofen (IBP were investigated. The effects of the alkyl chain’s length and the inner core of calix[4]arenes on the interaction of the two drugs with the calix[4]arenes were explored. The inclusion complexes of Amphiphiles 1a–c with NAP and IBP increased the solubility of these drugs in aqueous media. The interaction of 1a–c with the drugs in aqueous media was investigated through fluorescence, molecular modeling, and 1H-NMR analysis. TEM studies further supported the formation of inclusion complexes. The length of lipophilic alkyl chains and the intrinsic cyclic nature of cailx[4]arene derivatives 1a–c were found to have a significant impact on the solubility of NAP and IBP in pure water.

  10. Glucose, fructose and sucrose increase the solubility of protein-tannin complexes and at high concentration, glucose and sucrose interfere with bisulphite bleaching of wine pigments.

    Science.gov (United States)

    Harbertson, James F; Yuan, Chunlong; Mireles, Maria S; Hanlin, Rachel L; Downey, Mark O

    2013-05-01

    Wines were modified with increasing sugar concentrations and decreasing tannin concentrations and analysed by a combination of protein precipitation and bisulphite bleaching. Increasing sugar concentration decreased the precipitation of tannin and protein-precipitable polymeric pigments (PPP). The use of a hydrogen bond disruptor (urea) to reduce protein-tannin and protein-pigment complex formation showed that the effect of sugar concentration occurred by increasing the solubility of the tannin-protein complex, not by interfering with protein-tannin complex formation. By increasing the solubility of pigment-protein complexes, non-protein-precipitable polymeric pigments (nPPP) appeared to increase. There was also an increase in total polymeric pigments at each tannin concentration with increasing glucose and sucrose concentration, indicating that sugar concentration might also affect bisulphite bleaching of wine pigments. While a significant effect of sugar concentration on tannin-protein complex solubility was observed, these effects were greatest at sugar concentrations far in excess of normal wine making conditions. Under normal wine making conditions, sugar concentration will have a negligible effect on protein-precipitable tannin, PPP and nPPP concentrations. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Constant Electric and Magnetic Fields Effect on the Structuring and Thermomechanical and Thermophysical Properties of Nanocomposites Formed from Pectin-Cu(2+)-Polyethyleneimine Interpolyelectrolyte-Metal Complexes.

    Science.gov (United States)

    Demchenko, V; Shtompel', V; Riabov, S; Lysenkov, E

    2015-12-01

    Applying wide-angle X-ray scattering method, thermomechanical analysis, and differential scanning calorimetry, the structural organization and properties of nanocomposites formed by chemical reduction of Сu(2+) cations in the interpolyelectrolyte-metal complex (pectin-Cu(2+)-polyethyleneimine) under the influence of a constant magnetic and electric fields have been studied. It has been found that the chemical reduction of Cu(2+) cations in the interpolyelectrolyte-metal complex bulk under constant electric and magnetic fields leads to formation of nanocomposite consisting of interpolyelectrolyte complex, including pectin-polyethyleneimine and nanoparticles of the metal Cu phase, whereas nanocomposite with Cu/Cu2O nanoparticles is formed in original state (without any field). It was observed that, under constant field, nanocomposites obtained have higher structural glass-transition temperatures and thermal stability.

  12. The complex structure of liquid Cu{sub 6}Sn{sub 5} alloy

    Energy Technology Data Exchange (ETDEWEB)

    Qin Jingyu; Gu Tingkun; Bian Xiufang [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Southern Campus, Jinan 250061 (China); Liu Hui [Shandong High Performance Computing Center, Shandong University, Southern Campus, Jinan 250061 (China)

    2009-04-15

    By applying ab initio molecular dynamics simulation to liquid Cu{sub 6}Sn{sub 5} alloy, the hetero-coordination tendency is discovered by Bathia-Thornton partial correlation functions and a chemical short-range parameter. However the local structural environment of Sn in l-Cu{sub 6}Sn{sub 5} alloy resembles that of liquid Sn by Voronoi analysis. A new feature, i.e. a subpeak in between the first and second peaks, is discovered by the present method which implies that topologically disordered {beta}-Sn-type structural units may exist in l-Cu{sub 6}Sn{sub 5} alloy. The local density states of electrons show that both Cu-Sn and Sn-Sn bonding exist in l-Cu{sub 6}Sn{sub 5} alloy. This work suggests that chemical short-range order between unlike atoms and self-coordination between Sn atoms coexists in l-Cu{sub 6}Sn{sub 5} alloy.

  13. Silica functionalized Cu(II) acetylacetonate Schiff base complex: An efficient catalyst for the oxidative condensation reaction of benzyl alcohol with amines

    Science.gov (United States)

    Anbarasu, G.; Malathy, M.; Karthikeyan, P.; Rajavel, R.

    2017-09-01

    Silica functionalized Cu(II) acetylacetonate Schiff base complex via the one pot reaction of silica functionalized 3-aminopropyltriethoxysilane with acetyl acetone and copper acetate has been reported. The synthesized material was well characterized by analytical techniques such as FT-IR, UV-DRS, XRD, SEM-EDX, HR-TEM, EPR, ICP-AES and BET analysis. The characterization results confirmed the grafting of Cu(II) Schiff base complex on the silica surface. The catalytic activity of synthesized silica functionalized Cu(II) acetylacetonate Schiff base complex was evaluated through the oxidative condensation reaction of benzyl alcohol to imine.

  14. Carbonic anhydrase inhibitors. A general approach for the preparation of water-soluble sulfonamides incorporating polyamino-polycarboxylate tails and of their metal complexes possessing long-lasting, topical intraocular pressure-lowering properties.

    Science.gov (United States)

    Scozzafava, Andrea; Menabuoni, Luca; Mincione, Francesco; Supuran, Claudiu T

    2002-03-28

    Reaction of polyamino-polycarboxylic acids or their dianhydrides with aromatic/heterocyclic sulfonamides possessing a free amino/imino/hydrazino/hydroxy group afforded mono- and bis-sulfonamides containing polyamino-polycarboxylic acid moieties in their molecule. The acids/anhydrides used in synthesis included IDA, NTA, EDDA, EDTA and EDTA dianhydride, DTPA and DTPA dianhydride, EGTA and EGTA dianhydride, and EDDHA, among others. All the newly prepared derivatives showed strong affinity toward isozymes I, II, and IV of carbonic anhydrase (CA). Metal complexes of the new compounds have also been prepared. Metal ions used in such preparations included di- and trivalent main-group and transition cations, such as Zn(II), Cu(II), Al(III), etc. Some of the new sulfonamides/disulfonamides obtained in this way, as well as their metal complexes, behaved as nanomolar CA inhibitors against isozymes II and IV, being slightly less effective in inhibiting isozyme I. Some of these sulfonamides as well as their metal complexes strongly lowered intraocular pressure (IOP) when applied topically, directly into the normotensive/glaucomatous rabbit eye, as 1-2% water solutions/suspensions. The good water solubility of these sulfonamide CA inhibitors, correlated with the neutral pH of their water solutions used in the ophthalmologic applications and the long duration of action of the IOP-lowering effect, makes them interesting candidates for developing novel types of antiglaucoma drugs devoid of serious topical side effects.

  15. Core-shell nanofibers of curcumin/cyclodextrin inclusion complex and polylactic acid: Enhanced water solubility and slow release of curcumin.

    Science.gov (United States)

    Aytac, Zeynep; Uyar, Tamer

    2017-02-25

    Core-shell nanofibers were designed via electrospinning using inclusion complex (IC) of model hydrophobic drug (curcumin, CUR) with cyclodextrin (CD) in the core and polymer (polylactic acid, PLA) in the shell (cCUR/HPβCD-IC-sPLA-NF). CD-IC of CUR and HPβCD was formed at 1:2 molar ratio. The successful formation of core-shell nanofibers was revealed by TEM and CLSM images. cCUR/HPβCD-IC-sPLA-NF released CUR slowly but much more in total than PLA-CUR-NF at pH 1 and pH 7.4 due to the restriction of CUR in the core of nanofibers and solubility improvement shown in phase solubility diagram, respectively. Improved antioxidant activity of cCUR/HPβCD-IC-sPLA-NF in methanol:water (1:1) is related with the solubility enhancement achieved in water based system. The slow reaction of cCUR/HPβCD-IC-sPLA-NF in methanol is associated with the shell inhibiting the quick release of CUR. On the other hand, cCUR/HPβCD-IC-sPLA-NF exhibited slightly higher rate of antioxidant activity than PLA-CUR-NF in methanol:water (1:1) owing to the enhanced solubility. To conclude, slow release of CUR was achieved by core-shell nanofiber structure and inclusion complexation of CUR with HPβCD provides high solubility. Briefly, electrospinning of core-shell nanofibers with CD-IC core could offer slow release of drugs as well as solubility enhancement for hydrophobic drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Equilibrium and NMR studies on GdIII, YIII, CuII and ZnII complexes of various DTPA-N,N''-bis(amide) ligands. Kinetic stabilities of the gadolinium(III) complexes.

    Science.gov (United States)

    Jászberényi, Zoltán; Bányai, István; Brücher, Ernö; Király, Róbert; Hideg, Kálmán; Kálai, Tamás

    2006-02-28

    Three DTPA-derivative ligands, the non-substituted DTPA-bis(amide) (L(0)), the mono-substituted DTPA-bis(n-butylamide) (L(1)) and the di-substituted DTPA-bis[bis(n-butylamide)] (L(2)) were synthesized. The stability constants of their Gd3+ complexes (GdL) have been determined by pH-potentiometry with the use of EDTA or DTPA as competing ligands. The endogenous Cu2+ and Zn2+ ions form ML, MHL and M(2)L species. For the complexes CuL(0) and CuL(1) the dissociation of the amide hydrogens (CuLH(-1)) has also been detected. The stability constants of complexes formed with Gd3+, Cu2+ and Zn2+ increase with an increase in the number of butyl substituents in the order ML(0) DTPA)2-, while the complex GdL2 possesses a much higher kinetic stability.

  17. Pb solubility of the high-temperature superconducting phase Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10+d}

    Energy Technology Data Exchange (ETDEWEB)

    Kaesche, S.; Majewski, P.; Aldinger, F. [Max-Planck-Institut fuer Metallforschung, Stuttgart (Germany)] [and others

    1994-12-31

    For the nominal composition of Bi{sub 2.27x}Pb{sub x}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10+d} the lead content was varied from x=0.05 to 0.45. The compositions were examined between 830{degrees}C and 890{degrees}C which is supposed to be the temperature range over which the so-called 2223 phase (Bi{sub 2}Sr{sub 2}Ca{sub 2}Cu{sub 3}O{sub 10+d}) is stable. Only compositions between x=0.18 to 0.36 could be synthesized in a single phase state. For x>0.36 a lead containing phase with a stoichiometry of Pb{sub 4}(Sr,Ca){sub 5}CuO{sub d} is formed, for x<0.18 mainly Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+d} and cuprates are the equilibrium phases. The temperature range for the 2223 phase was found to be 830{degrees}C to 890{degrees}C but the 2223 phase has extremely varying cation ratios over this temperature range. Former single phase 2223 samples turn to multi phase samples when annealed at slightly higher or lower temperatures. A decrease in the Pb solubility with increasing temperature was found for the 2223 phase.

  18. Water-soluble ferrocene complexes (WFCs) functionalized silica nanospheres for WFC delivery in HepG2 tumor therapy.

    Science.gov (United States)

    Yan, Saisai; Hu, Fan; Hong, Xia; Shuai, Qi

    2018-09-01

    Silica-encapsulated nanospheres of water-soluble ferrocene complexes WFCs@SiO 2 and WFCs@SiO 2 @glutaraldehyde (GA) were first synthesized by a facile inverse-microemulsion method. The surface functional groups, particle size, and morphologies of nanospheres were characterized by IR spectra, UV-vis absorption spectra, dynamic light scattering (DLS) and SEM images. Single-crystal X-ray diffraction was used to confirm the molecular structure of free ferrocenyl-pyrazol ligand (L) and three WFCs, namely, [Ni(C 22 H 14 F 6 FeN 4 O 4 )(H 2 O) 4 ] (5a), [Mg(C 22 H 14 F 6 FeN 4 O 4 )(H 2 O) 4 ]·3H 2 O (5b), and [Ba(C 22 H 14 F 6 FeN 4 O 4 )(H 2 O) 3 ] (5c). The electrochemical properties of 5a-5c were explored by cyclic voltammetry. The WFCs-loading capacities of 5a-5c in WFCs@SiO 2 were found to be 38.4, 38.2, and 38.1 μg/mg, respectively. Cell studies under two drug delivery modes (free diffusion and endocytosis) were carried out by MTT cell-survival assays and morphological observation of HepG2 cells. It's interesting that the cytotoxicity of WFCs against HepG2 was increased by applying silica nanocarriers. Compared to WFCs@SiO 2 , the modification of GA on the spherical surface provided not only the better water-dispersity but also additional functional groups for further modification of other pharmacophores. The novel nanocarrier system for WFC delivery present a novel concept-of-proof method to protect varieties of affordable metal-based anticancer agents in physiological conditions and provided experimental basis for future studies focusing on drug delivery of other WFCs. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. A 3D complex containing novel 2D CuII-azido layers: Structure, magnetic properties and effects of “Non-innocent” reagent

    International Nuclear Information System (INIS)

    Gao, Xue-Miao; Guo, Qian; Zhao, Jiong-Peng; Liu, Fu-Chen

    2012-01-01

    A novel copper-azido coordination polymer, [Cu 2 (N 3 ) 3 (L)] n (1, HL=pyrazine-2-carboxylic acid), has been synthesized by hydrothermal reaction with “Non-innocent” reagent in the aqueous solution. In the reaction system, Cu II ions are avoided to reduce to Cu I ions due to the existence of Nd III . It is found that the complex is a 3D structure based on two double EO azido bridged trimmers and octahedron Cu II ions, in which the azide ligands take on EO and μ 1,1,3 mode to form Cu II -azido 2D layers, furthermore L ligands pillar 2D layers into an infinite 3D framework with the Schläfli symbol of {4;6 2 }4{4 2 ;6 12 ;8 10 ;10 4 }{4 2 ;6 4 }. Magnetic studies revealed that the interactions between the Cu II ions in the trimmer are ferromagnetic for the Cu–N–Cu angle nearly 98°, while the interactions between the trimmer and octahedron Cu II ion are antiferromgantic and result in an antiferromagnetic state. - Graphical abstract: A 3D complex containing novel 2D Cu II -azido layers, [Cu 2 (N 3 ) 3 (L)] n (HL=pyrazine-2-carboxylic acid), was synthesized by hydrothermal reaction and exhibit interesting structure and magnetic properties. Highlights: ► “Non-innocent” reagents plays a key role in the process of formation of this complex. ► 2D layer is formed only by Cu II ions and azido ligands. ► Pyrazine-2-carboxylate ligands reinforce 2D layers and pillar them into an infinite 3D framework. ► Magnetic study indicates that alternating FM–AF coupling exists in the complex.

  20. Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

    International Nuclear Information System (INIS)

    Grivé, Mireia; Duro, Lara; Bruno, Jordi

    2014-01-01

    Graphical abstract: - Highlights: • We have determined thermodynamic stabilities of Fe(III)-carbonate species. • We have determined the effect of those species on the solubility of ferrihydrite. • Results. • Highlight the importance of two Fe(III)-carbonate: FeOHCO 3 and Fe(CO 3 ) 3 3− . - Abstract: The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO 2 concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO 2 varying between (0.982–98.154 kPa) at 25 °C. The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO 3 and Fe(CO 3 ) 3 3− , with formation constants log * β° 1,1,1 = 10.76 ± 0.38 and log β° 1,0,3 = 24.24 ± 0.42, respectively. The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO 2 and at T = (25 ± 1) °C, as log * K s,0 = 1.19 ± 0.41. The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO 2 -rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers

  1. Fermentation and complex enzyme hydrolysis for improving the total soluble phenolic contents, flavonoid aglycones contents and bio-activities of guava leaves tea.

    Science.gov (United States)

    Wang, Lu; Luo, You; Wu, Yanan; Liu, Yan; Wu, Zhenqiang

    2018-10-30

    There are both soluble and insoluble-bound forms of phenolics in tea-leaf products. In order to increase total soluble phenolics contents, guava leaves tea (GLT) was first fermented with Monascus anka and Saccharomyces cerevisiae, and then hydrolyzed with complex enzymes. The changes in phenolics profiles, antioxidant activities and inhibitory effect on α-glucosidase in processed GLT were investigated. Compared with the un-fermented GLT, fermentation and complex enzymatic processing (FE) significantly increased the total phenolics, total flavonoids, quercetin and kaempferol contents by 2.1, 2.0, 13.0 and 6.8 times, respectively. After the FE, a major proportion of phenolics existed in the soluble form. Quercetin was released in the highest amount among different phenolics. In addition, soluble phenolic extracts from GLT following FE exhibited a highest antioxidant activity and inhibitory effect on α-glucosidase. The paper suggested an improved method for processing GLT into high-value products rich in phenolics and flavonoids aglycones with enhanced health benefits. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. The Cu2+-nitrilotriacetic acid complex improves loading of α-helical double histidine site for precise distance measurements by pulsed ESR

    Science.gov (United States)

    Ghosh, Shreya; Lawless, Matthew J.; Rule, Gordon S.; Saxena, Sunil

    2018-01-01

    Site-directed spin labeling using two strategically placed natural histidine residues allows for the rigid attachment of paramagnetic Cu2+. This double histidine (dHis) motif enables extremely precise, narrow distance distributions resolved by Cu2+-based pulsed ESR. Furthermore, the distance measurements are easily relatable to the protein backbone-structure. The Cu2+ ion has, till now, been introduced as a complex with the chelating agent iminodiacetic acid (IDA) to prevent unspecific binding. Recently, this method was found to have two limiting concerns that include poor selectivity towards α-helices and incomplete Cu2+-IDA complexation. Herein, we introduce an alternative method of dHis-Cu2+ loading using the nitrilotriacetic acid (NTA)-Cu2+ complex. We find that the Cu2+-NTA complex shows a four-fold increase in selectivity toward α-helical dHis sites. Furthermore, we show that 100% Cu2+-NTA complexation is achievable, enabling precise dHis loading and resulting in no free Cu2+ in solution. We analyze the optimum dHis loading conditions using both continuous wave and pulsed ESR. We implement these findings to show increased sensitivity of the Double Electron-Electron Resonance (DEER) experiment in two different protein systems. The DEER signal is increased within the immunoglobulin binding domain of protein G (called GB1). We measure distances between a dHis site on an α-helix and dHis site either on a mid-strand or a non-hydrogen bonded edge-strand β-sheet. Finally, the DEER signal is increased twofold within two α-helix dHis sites in the enzymatic dimer glutathione S-transferase exemplifying the enhanced α-helical selectivity of Cu2+-NTA.

  3. Design of Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4} nanocomponent photocatalysts for hydrogen evolution under visible light irradiation using water-soluble Erythrosin B dye sensitization

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Piyong; Wang, Tingting; Zeng, Heping, E-mail: hpzeng@scut.edu.cn

    2017-01-01

    Highlights: • A novel photocatalyst Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4} was designed, synthesized and characterized. • Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4} was sensitized by Erythrosin B and a significant enhancement of H{sub 2} evolution rate was achieved. • Electrochemical properties were measured and a possible mechanism of H{sub 2} evolution was proposed. - Abstract: Cu-Cu{sub 2}O nanoparticles (NPs) decorated porous graphitic carbon nitride (g-C{sub 3}N{sub 4}) (Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4}) photocatalysts were prepared. When investment of copper source materials in the experiment increased to 7 wt%, the highest H{sub 2} evolution rate (400 μmol g{sup −1} h{sup −1}) was obtained under visible light irradiation in triethanolamine solution. This is about triple of pure g-C{sub 3}N{sub 4} (140 μmol g{sup −1} h{sup −1}). Moreover, various amount of Erythrosin B dye was added into Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4} photoreaction solution and a significant enhancement of H{sub 2} production rate was achieved. The highest H{sub 2} production rate was 5000 μmol g{sup −1} h{sup −1} with 5 mg Erythrosin B in photoreaction system. Erythrosin B dye sensitized Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4} presented stable photocatalytic H{sub 2} evolution ability and no noticeable degradation or change of photocatalyst were detected after six recycles. A possible photocatalytic mechanism of Erythrosin B dye sensitized Cu-Cu{sub 2}O/g-C{sub 3}N{sub 4} for the enhancement of photocatalytic H{sub 2} evolution is proposed.

  4. How easy is CO2 fixation by M-C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?

    KAUST Repository

    Nolan, Steve; Cavallo, Luigi; Poater, Albert; Vummaleti, Sai V. C.; Talarico, Giovanni

    2015-01-01

    A comparison between different M–C bonds (M = Cu(I), Ni(II), Co(I), Rh(I) and Ir(I)) has been reported by using density functional theory (DFT) calculations to explore the role of the metal in the fixation or incorporation of CO2 into such complexes. The systems investigated are various metal based congeners of the Ir-complex 8 [(cod)(IiPr)Ir-CCPh], with a ligand scaffold based on cod and IiPr ligands (cod = 1,5-cyclooctadiene; IiPr = 1,3-bis(isopropyl)imidazol-2-ylidene). The results of this study show that the calculated CO2 insertion barriers follow the trend: Cu(I) (20.8 kcal mol−1) < Rh(I) (30.0 kcal mol−1) < Co(I) (31.3 kcal mol−1) < Ir(I) (37.5 kcal mol−1) < Ni(II) (45.4 kcal mol−1), indicating that the Cu(I) based analogue is the best CO2 fixer, while Ni(II) is the worst in the studied series.

  5. How easy is CO2 fixation by M-C bond containing complexes (M = Cu, Ni, Co, Rh, Ir)?

    KAUST Repository

    Nolan, Steve

    2015-11-27

    A comparison between different M–C bonds (M = Cu(I), Ni(II), Co(I), Rh(I) and Ir(I)) has been reported by using density functional theory (DFT) calculations to explore the role of the metal in the fixation or incorporation of CO2 into such complexes. The systems investigated are various metal based congeners of the Ir-complex 8 [(cod)(IiPr)Ir-CCPh], with a ligand scaffold based on cod and IiPr ligands (cod = 1,5-cyclooctadiene; IiPr = 1,3-bis(isopropyl)imidazol-2-ylidene). The results of this study show that the calculated CO2 insertion barriers follow the trend: Cu(I) (20.8 kcal mol−1) < Rh(I) (30.0 kcal mol−1) < Co(I) (31.3 kcal mol−1) < Ir(I) (37.5 kcal mol−1) < Ni(II) (45.4 kcal mol−1), indicating that the Cu(I) based analogue is the best CO2 fixer, while Ni(II) is the worst in the studied series.

  6. Surface phase transformations, surface complexation and solubilities of hydroxyapatite in the absence/presence of Cd(II) and EDTA

    International Nuclear Information System (INIS)

    Viipsi, Karin; Sjöberg, Staffan; Shchukarev, Andrey; Tõnsuaadu, Kaia

    2012-01-01

    The removal of Cd from aqueous solutions by hydroxyapatite (HAP) was investigated with and without EDTA being present. Batch experiments were carried out using synthetic hydroxyapatite with Ca/P 1.57 and a specific surface area of 37.5 m 2 /g in the pH range 4–9 (25 °C; 0.1 M KNO 3 ). The surface composition of the solid phases were analysed by X-ray Photoelectron Spectroscopy (XPS). The surface layer of HAP was found to undergo a phase transformation with a (Ca + Cd)/P atomic ratio of 1.4 and the involvement of an ion exchange process (Ca 2+ ↔ Cd 2+ ). The amount of Cd removed from the solution increased with increasing pH, reaching ≈100% at pH 9. In the presence of EDTA Cd removal was reduced due to the formation of [CdEDTA] 2− in solution. The solubility of HAP increases in the presence of EDTA at pH values above 5, mainly due to the formation of [CaEDTA] 2− . In contrast to this, the solubility was found to decrease in the presence of Cd 2+ and CdEDTA 2− . Using XPS the formation of a Cd-enriched HAP surface was found, which was interpreted as the formation of a solid solution of the general composition: Ca 8.4-x Cd x (HPO 4 ) 1.6 (PO 4 ) 4.4 (OH) 0.4 . The information from the chemical analyses and XPS data was used to design an equilibrium model that takes into account dissolution, solution and surface complexation, as well as possible phase transformations. The total concentration of Ca, phosphate, EDTA, and Cd in solution were used in the equilibrium analysis. In the calculations the computer code WinSGW, which is based on the SOLGASWATER algorithm, was used. The following equilibria and compositions of the solid solutions were found to give the best fit to experimental data: logK s (Ca 7.6 Cd 0.8 (HPO 4 ) 1.6 (PO 4 ) 4.4 (OH) 0.4 (s)+4.8H + ⇋7.6Ca 2+ +0.8Cd 2+ +6HPO 4 2- +0.4H 2 O)=-28.03±0.07. The corresponding value for the composition Ca 5.6 Cd 2.8 (HPO 4 ) 1.6 (PO 4 ) 4.4 (OH) 0.4 (s) is −27.39 ± 0.06. The proposed model can be used

  7. Influence of citrate ions as complexing agent for electrodeposition of CuInSe{sub 2} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Chraibi, F. [Universite Libre de Bruxelles (Belgium). Service de Sciences des Materiaux et Electrochimie; Universite Mohammed 5, Rabat (Morocco). Dept. de Physique; Fahoume, M.; Ennaoui, A. [Universite Mohammed 5, Rabat (Morocco). Dept. de Physique; Delplancke, J.L. [Universite Libre de Bruxelles (Belgium). Service de Sciences des Materiaux et Electrochimie

    2001-08-16

    The preparation of CuInSe{sub 2} thin films by electrodeposition is studied. The effect of sodium citrate (Na{sub 3}C{sub 6}H{sub 5}O{sub 7}) as complexing agent on the electrodeposition of pure copper, indium, selenium and of their ternary alloy is emphasized. Cathodic shifts of the copper and selenium electrodeposition potentials with increasing citrate concentration are observed. On the contrary, the presence of citrate in the electrolyte does not change the indium electrodeposition potential but improves its crystallinity. The surface morphology and the composition of the deposited films are characterized by scanning electron microscopy (SEM). The texture of the deposits and their compositions are analyzed by X-ray diffraction. The formation of CuInSe{sub 2} films with a chalcopyrite structure and good stoichiometry is observed. (orig.)

  8. H2S Sensing by Hybrids Based on Nanocrystalline SnO2 Functionalized with Cu(II Organometallic Complexes: The Role of the Ligand Platform

    Directory of Open Access Journals (Sweden)

    Marina Rumyantseva

    2017-11-01

    Full Text Available This paper deals with the functionalization of nanocrystalline SnO2 with Cu(II complexes with organic ligands, aimed at the improvement of sensor selectivity towards gas molecules. For the synthesis of metalorganic/SnO2 hybrid material complexes of Cu(II with phthalocyanine, porphyrinines, bipyridine and azadithiacrown etherwere used. The analysis of gas sensor properties showed the possibility of increasing the sensitivity and selectivity of hybrid materials in H2S detection due to the electron transfer from SnO2 to an adsorbed organic molecule, which changes during the interaction between H2S and Cu(II ions.

  9. Water-Soluble Coenzyme Q10 Inhibits Nuclear Translocation of Apoptosis Inducing Factor and Cell Death Caused by Mitochondrial Complex I Inhibition

    Directory of Open Access Journals (Sweden)

    Haining Li

    2014-07-01

    Full Text Available The objectives of the study were to explore the mechanism of rotenone-induced cell damage and to examine the protective effects of water-soluble Coenzyme Q10 (CoQ10 on the toxic effects of rotenone. Murine hippocampal HT22 cells were cultured with mitochondrial complex I inhibitor rotenone. Water-soluble CoQ10 was added to the culture media 3 h prior to the rotenone incubation. Cell viability was determined by alamar blue, reactive oxygen species (ROS production by dihydroethidine (DHE and mitochondrial membrane potential by tetramethyl rhodamine methyl ester (TMRM. Cytochrome c, caspase-9 and apoptosis-inducing factor (AIF were measured using Western blotting after 24 h rotenone incubation. Rotenone caused more than 50% of cell death, increased ROS production, AIF nuclear translocation and reduction in mitochondrial membrane potential, but failed to cause mitochondrial cytochrome c release and caspase-9 activation. Pretreatment with water-soluble CoQ10 enhanced cell viability, decreased ROS production, maintained mitochondrial membrane potential and prevented AIF nuclear translocation. The results suggest that rotenone activates a mitochondria-initiated, caspase-independent cell death pathway. Water-soluble CoQ10 reduces ROS accumulation, prevents the fall of mitochondrial membrane potential, and inhibits AIF translocation and subsequent cell death.

  10. Synthesis, crystal structures, molecular docking and urease inhibition studies of Ni(II) and Cu(II) Schiff base complexes

    Science.gov (United States)

    Sangeeta, S.; Ahmad, K.; Noorussabah, N.; Bharti, S.; Mishra, M. K.; Sharma, S. R.; Choudhary, M.

    2018-03-01

    [Ni(L)2] 1 and [Cu(L)2] 2 [HL = 2-((E)-(2-methoxyphenylimino)methyl)-4,6-dichlorophenol] Schiff base complexes have been successfully synthesized and were characterized by FT-IR, UV-Vis, fluorescence spectroscopy and thermogravimetric analysis. The crystal structures of the two complexes were determined through X-ray crystallography. Its inhibitory activity against Helicobacter pylori urease was evaluated in vitro and showed strong inhibitory activity against H. pylori urease compared with acetohydroxamic acid (IC50 = 42.12 μmolL-1), which is a positive reference. A docking analysis using the AutoDock 4.0 program could explain the inhibitory activity of the complex against urease.

  11. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases

    OpenAIRE

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-01-01

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the c...

  12. Influence of biochars, compost and iron grit, alone and in combination, on copper solubility and phytotoxicity in a Cu-contaminated soil from a wood preservation site.

    Science.gov (United States)

    Oustriere, Nadège; Marchand, Lilian; Galland, William; Gabbon, Lunel; Lottier, Nathalie; Motelica, Mikael; Mench, Michel

    2016-10-01

    Two biochars, a green waste compost and iron grit were used, alone and in combination, as amendment to improve soil properties and in situ stabilize Cu in a contaminated soil (964mgCukg(-1)) from a wood preservation site. The pot experiment consisted in 9 soil treatments (% w/w): untreated Cu-contaminated soil (Unt); Unt soil amended respectively with compost (5%, C), iron grit (1%, Z), pine bark-derived biochar (1%, PB), poultry-manure-derived biochar (1%, AB), PB or AB+C (5%, PBC and ABC), and PB or AB+Z (1%, PBZ and ABZ). After a 3-month reaction period, the soil pore water (SPW) was sampled in potted soils and dwarf beans were grown for a 2-week period. In the SPW, all amendments decreased the Cu(2+) concentration, but total Cu concentration increased in all AB-amended soils due to high dissolved organic matter (DOM) concentration. No treatment improved root and shoot DW yields, which even decreased in the ABC and ABZ treatments. The PBZ treatment decreased total Cu concentration in the SPW while reducing the gap with common values for root and shoot yields of dwarf bean plants. A field trial is underway before any recommendation for the PB-based treatments. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. A theoretical investigation on the neutral Cu(I) phosphorescent complexes with azole-based and phosphine mixed ligand

    Science.gov (United States)

    Ding, Xiao-Li; Shen, Lu; Zou, Lu-Yi; Ma, Ming-Shuo; Ren, Ai-Min

    2018-04-01

    A theoretical study on a series of neutral heteroleptic Cu(I) complexes with different azole-pyridine-based N^N ligands has been presented to get insight into the effect of various nitrogen atoms in the azole ring on photophysical properties. The results reveal that the highest occupied molecular orbital (HOMO) levels and the emission wavelengths of these complexes are mainly governed by the nitrogen atom number in azole ring. With the increasing number of nitrogen atom , the electron density distribution of HOMO gradually extend from the N^N ligand to the whole molecule, meanwhile, the improved contribution from Cu(d) orbits in HOMO results in an effective mixing of various charge transfermodes, and hence, the fast radiative decay(kr) and the slow non-radiative decay rate(knr) are achieved. The photoluminescence quantum yield (PLQY) show an apparent dependence on the nitrogen atom number in the five-membered nitrogen heterocycles. However, the increasing number of nitrogen atoms is not necessary for increasing PLQY. The complex 3 with 1,2,4-triazole-pyridine-based N^N ligands is considered to be a potential emitter with high phosphorescence efficiency. Finally, we hope that our investigations will contribute to systematical understanding and guiding for material molecular engineering.

  14. Synthesis and studies on Cu(II), Co(II), Ni(II) complexes of Knoevenagel β-diketone ligands

    Science.gov (United States)

    Sumathi, S.; Tharmaraj, P.; Sheela, C. D.; Anitha, C.

    2012-11-01

    Transition metal complexes of various acetylacetone based ligands of the type ML [where M = Cu(II), Ni(II), Co(II); L = 3-(aryl)-pentane-2,4-dione] have been synthesized. The structural features have been derived from their elemental analysis, magnetic susceptibility, molar conductance, IR, UV-Vis, 1H NMR, Mass and ESR spectral studies. Conductivity measurements reveal that all the complexes are non-electrolytic in nature. Spectroscopic and other analytical data of the complexes suggest octahedral geometry for other metal(II) complexes. The redox behavior of the copper(II) complexes have been studied by cyclic voltammetry. The free ligands and their metal complexes have been screened for their in vitro biological activities against the bacteria Pseudomonas aeruginosa, Escherichia coli and Staphylococcus aureus as well as the fungus Candida albicans by well diffusion method. The zone of inhibition value indicates that the most of the metal(II) complexes are found to possess increased activities compared to those of the free ligands. All synthesized compounds may serve as potential photoactive materials as indicated from their characteristic fluorescence properties. The second harmonic generation (SHG) efficiency of the ligands (L1-L3) was found to be considerable effect than that of urea and KDP (potassium dihydrogen phosphate).

  15. Spectroscopic and DFT studies of flurbiprofen as dimer and its Cu(II) and Hg(II) complexes

    Science.gov (United States)

    Sagdinc, Seda; Pir, Hacer

    2009-07-01

    The vibrational study in the solid state of flurbiprofen and its Cu(II) and Hg(II) complexes was performed by IR and Raman spectroscopy. The changes observed between the IR and Raman spectra of the ligand and of the complexes allowed us to establish the coordination mode of the metal in both complexes. The comparative vibrational analysis of the free ligand and its complexes gave evidence that flurbiprofen binds metal (II) through the carboxylate oxygen. The fully optimized equilibrium structure of flurbiprofen and its metal complexes was obtained by density functional B3LYP method by using LanL2DZ and 6-31 G(d,p) basis sets. The harmonic vibrational frequencies, infrared intensities and Raman scattering activities of flurbiprofen were calculated by density functional B3LYP methods by using 6-31G(d,p) basis set. The scaled theoretical wavenumbers showed very good agreement with the experimental values. The electronic properties of the free molecule and its complexes were also performed at B3LYP/6-31G(d,p) level of theory. Detailed interpretations of the infrared and Raman spectra of flurbiprofen are reported. The UV-vis spectra of flurbiprofen and its metal complexes were also investigated in organic solvents.

  16. Dinuclear Cu(II) complexes of isomeric bis-(3-acetylacetonate)benzene ligands: synthesis, structure, and magnetic properties.

    Science.gov (United States)

    Rancan, Marzio; Dolmella, Alessandro; Seraglia, Roberta; Orlandi, Simonetta; Quici, Silvio; Sorace, Lorenzo; Gatteschi, Dante; Armelao, Lidia

    2012-05-07

    Highly versatile coordinating ligands are designed and synthesized with two β-diketonate groups linked at the carbon 3 through a phenyl ring. The rigid aromatic spacer is introduced in the molecules to orient the two acetylacetone units along different angles and coordination vectors. The resulting para, meta, and ortho bis-(3-acetylacetonate)benzene ligands show efficient chelating properties toward Cu(II) ions. In the presence of 2,2'-bipyridine, they promptly react and yield three dimers, 1, 2, and 3, with the bis-acetylacetonate unit in bridging position between two metal centers. X-ray single crystal diffraction shows that the compounds form supramolecular chains in the solid state because of intermolecular interactions. Each of the dinuclear complexes shows a magnetic behavior which is determined by the combination of structural parameters and spin polarization effects. Notably, the para derivative (1) displays a moderate antiferromagnetic coupling (J = -3.3 cm(-1)) along a remarkably long Cu···Cu distance (12.30 Å).

  17. Influence of complexing agent (Na2EDTA on chemical bath deposited Cu4SnS4 thin films

    Directory of Open Access Journals (Sweden)

    Anuar Kassim

    2010-08-01

    Full Text Available The quality of thin film is influenced by the presence of complexing agents such as Na2EDTA. The Cu4SnS4 thin films were deposited onto indium tin oxide glass substrate by chemical bath deposition method. The structural, morphological and optical properties of the deposited films have been studied using X-ray diffraction, atomic force microscopy and UV-Vis spectrophotometer, respectively. The XRD data showed that the films have a polycrystalline and orthorhombic structure. It also indicated that the most intense peak at 2 θ = 30.2° which belongs to (221 plane of Cu4 SnS4. The film deposited with 0.05 M Na2 EDTA showed good uniformity, good surface coverage with bigger grains and produced higher absorbance value. The band gap energy varies with the variation of Na2EDTA concentration which ranging from 1.56-1.60 eV. Deposition at concentration of 0.05 M Na2EDTA proved to offer a reasonably good Cu4SnS4 thin film.

  18. Unsaturated b-ketoesters and their Ni(II, Cu(II and Zn(II complexes

    Directory of Open Access Journals (Sweden)

    MUHAMMED BASHEER UMMATHUR

    2009-03-01

    Full Text Available A new series of b-ketoesters in which the keto group is attached to the olefinic linkage were synthesized by the reaction of methyl acetoacetate and aromatic aldehydes under specified conditions. The existence of these compounds predominantly in the intramolecularly hydrogen bonded enol form was well demonstrated from their IR, 1H-NMR and mass spectral data. Details on the formation of their [ML2] complexes with Ni(II, Cu(II and Zn(II and the nature of the bonding are discussed on the basis of analytical and spectral data.

  19. Complex microwave conductivity of YBa2Cu3O7 in magnetic fields up to 500 T

    International Nuclear Information System (INIS)

    Bykov, A.I.; Dolotenko, M.I.; Fowler, C.M.; Freeman, B.L.; Goettee, J.D.; King, J.C.; Kolokolchikov, N.P.; Kudasov, Yu.B.; Lewis, W.; Marshall, B.R.; Papatheofanis, B.J.; Platonov, V.V.; Rodriguez, P.J.; Tatsenko, O.M.; Veeser, L.R.; Zerwekh, W.D.

    1995-01-01

    The complex microwave conductivity of thin, oriented YBa 2 Cu 3 O 7 films was measured at 94 GHz in pulsed, ultrahigh-magnetic fields up to 500 T. The c-axis of the film was perpendicular to the magnetic field. We estimate the upper critical field of the film at absolute zero as B c2 (0)=340±40 T. Dynamics of the transition into a normal state and connection with previous measurements of the reversibility line are discussed. (orig.)

  20. Complex microwave conductivity of YBa2Cu3O7 in magnetic fields up to 500T

    International Nuclear Information System (INIS)

    Goettee, J.D.; Zerwekh, W.D.; Kudasov, Y.B.

    1994-01-01

    We have measured the complex conductivity of thin films of YBa 2 cu 3 O 7 (YBCO) superconductor down to temperatures of 4K and magnetic fields up to 500T. The highly oriented films were probed by 94 GHz radiation, with the external magnetic field applied perpendicular to the c-axis. These measurements allowed us to assign a value of 340 ± 40 for the upper critical field at T=O. The measurements were recently carried out at the pulsed field facility of the National High Magnetic Field Laboratory at Los Alamos using both Russian and American magnetic flux compression generators

  1. The high water solubility of inclusion complex of taxifolin-γ-CD prepared and characterized by the emulsion solvent evaporation and the freeze drying combination method.

    Science.gov (United States)

    Zu, Yuangang; Wu, Weiwei; Zhao, Xiuhua; Li, Yong; Zhong, Chen; Zhang, Yin

    2014-12-30

    This study selected γ-cyclodextrin (γ-CD) as the inclusion material and prepared inclusion complex of taxifolin-γ-CD by the emulsion solvent evaporation and the freeze drying combination method to achieve the improvement of the solubility and oral bioavailability of taxifolin. We selected ethyl acetate as the oil phase, deionized water as the water phase. The taxifolin emulsion was prepared using adjustable speed homogenate machine in the process of this experiment, whose particle size was related to the concentration of taxifolin solution, the volume ratio of water phase to oil phase, the speed and time of homogenate. We knew through the single-factor test that, the optimum conditions were: the concentration of taxifolin solution was 40 mg/ml, the volume ratio of water phase to oil phase was 1.5, the speed of homogenate was 5,000 rpm, the homogenate time was 11 min. Taxifolin emulsion with a MPS of 142.5 nm was obtained under the optimum conditions, then the high-concentration taxifolin solution (3mg/ml) was obtained by the rotary evaporation process. Finally, the inclusion complex of taxifolin-γ-CD was prepared by vacuum freeze-dry. The characteristics of the inclusion complex of taxifolin-γ-CD were analyzed using SEM, FTIR, XRD, DSC, and TG. The FTIR results analyzed the interaction of taxifolin and γ-CD and determined the molecular structure of the inclusion complex of taxifolin-γ-CD. The analysis results of XRD, DSC and TG indicated that the inclusion complex of taxifolin-γ-CD was obtained and showed significantly different characteristics with taxifolin. In addition, dissolving capability test, antioxidant capacity test, solvent residue test were also carried out. The experimental datas showed that the solubility of inclusion complex of taxifolin-γ-CD at 25°C and 37°C were about 18.5 times and 19.8 times of raw taxifolin, the dissolution rate of inclusion complex of taxifolin-γ-CD were about 2.84 times of raw taxifolin, the bioavailability of

  2. Influence of mechanical activation on the leaching of non-ferrous metals from a CuPbZn complex concentrate

    Directory of Open Access Journals (Sweden)

    Godoèíková Erika

    2000-09-01

    Full Text Available The aim of study was to research the procedures of copper, lead and zinc leaching from CuPbZn complex sulphide concentrate during the intervention of mechanical activation.Mechanical activation belongs to innovative procedures, which intensifies technological processes by means of creation of new surfaces and making defective structure of solid phase. Mechanical impact on the solid phase is a suitable procedure to ensure the mobility of its structure elements and to accumulate the mechanical energy that is later used in following processes of leaching.This paper deals with the intensification of the chloride and thiourea leaching of copper, lead and zinc from a CuPbZn complex concentrate of Hodruša-Hámre (Slovak deposit by using the mechanical activation in an attritor. Ferric chloride and thiourea were used as leaching reagents. The leaching of the concentrate with ferric chloride solution afforded 23 % recovery of Cu, 99 % of Pb and 28 % of Zn. 9 % recovery of Cu, 17 % of Pb and 3 % of Zn were achieved by the leaching with thiourea. Thus results showed that the extraction of Cu, Zn and also Pb in the case of thiourea leaching was low. The use of milling in the attritor as an innovation method of pretreatment leads to the structural degradation and increasing the surface area of the investigated concentrate from the original value of 0.18 m2g-1 to the maximum value of 4.67 m2g-1. This fact manifested itself in the subsequent process of extraction of Cu, Pb and Zn into the chloride and thiourea solutions. Our results indicate more effective leaching of pretreated concentrate in the chloride medium with recoveries of 84 % Zn and 100 % Pb. In thiourea, the recoveries for Zn and Pb were low, however 99 % Cu can be recovered. In regard to the economy, the extraction of Cu, Pb and Zn was studied in this work with the aspect of minimal energy consumption during milling. The maximum recoveries of non-ferrous metals in the solutions of ferric chloride

  3. Aryl-1H-imidazole[4,5f][1,10]phenanthroline Cu(II) complexes: Electrochemical and DNA interaction studies.

    Science.gov (United States)

    Rajebhosale, Bharati S; Dongre, Shivali N; Deshpande, Sameer S; Kate, Anup N; Kumbhar, Anupa A

    2017-10-01

    The reaction of aryl imidazo[4,5f] [1,10]phenanthrolines with Cu(NO 3 ) 2 lead to the formation of Cu(II) complexes of the type [Cu(L)(NO 3 ) 2 ] where L=PIP, 2-(phenyl) [4,5f] imidazo phenanthroline; HPIP=2-(2-hydroxyphenyl)imidazo [4,5f] phenanthroline and NIP=2-(naphthyl) [4,5f] imidazo phenanthroline. The interaction of these complexes with calf thymus DNA has been studied using viscosity measurements, UV-visible and fluorescence spectroscopy. Chemical nuclease activity of these complexes has also been investigated. All complexes cleave DNA via oxidative pathway involving singlet oxygen. Molecular docking studies revealed that these complexes bind to DNA through minor groove. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Investigation of formation constant of complex of a new synthesized tripodal ligand with Cu2+ using rank annihilation factor analysis in surfactant media

    Directory of Open Access Journals (Sweden)

    R. Golbedaghi

    2014-01-01

    Full Text Available The complex formation between a newly synthesized tripodal ligand and the cation Cu2+ in water and surfactant media was studied spectrophotometrically using rank annihilation factor analysis (RAFA. According to molar ratio data the stoichiometry of complexation between the ligand and the cation Cu2+ was 1:1. Formation constant of this complex was derived using RAFA on spectrophotometric data. The performance of the method has been evaluated by using synthetic data. Also concentration and spectral profiles of ligand and complex can be obtained by using the stability constant and appropriate equations. The effect of surfactants such as sodium dodecyl sulfate (SDS, cetyltrimethylammonium bromide (CTAB and Triton X-100 on complex formation constant of Cu2+ with the ligand was investigated.

  5. Cu(II) and Co(II) complexes of benzimidazole derivative: Structures, catecholase like activities and interaction studies with hydrogen peroxide

    Science.gov (United States)

    Kumari, Babli; Adhikari, Sangita; Matalobos, Jesús Sanmartín; Das, Debasis

    2018-01-01

    Present study describes the synthesis and single crystal X-ray structures of two metal complexes of benzimidazole derivative (PBI), viz. the Cu(II) complex, [Cu(PBI)2(NCS)]ClO4 (1) and a Co(II) complex, [Co(PBI)2(NCS)1.75Cl0.25] (2). The Cu(II) complex (1) shows catecholase like activity having Kcat = 1.84 × 104 h-1. Moreover, interactions of the complexes with hydrogen peroxide have been investigated using fluorescence spectroscopy. The interaction constant of 1 and 2 for H2O2 are 6.67 × 102 M-1 and 1.049 × 103 M-1 while their detection limits for H2O2 are 3.37 × 10-7 M and 2.46 × 10-7 M respectively.

  6. Thermodynamic description of Tc(iv) solubility and carbonate complexation in alkaline NaHCO3-Na2CO3-NaCl systems.

    Science.gov (United States)

    Baumann, A; Yalçıntaş, E; Gaona, X; Polly, R; Dardenne, K; Prüßmann, T; Rothe, J; Altmaier, M; Geckeis, H

    2018-03-28

    The solubility of 99 Tc(iv) was investigated in dilute to concentrated carbonate solutions (0.01 M ≤ C tot ≤ 1.0 M, with C tot = [HCO 3 - ] + [CO 3 2- ]) under systematic variation of ionic strength (I = 0.3-5.0 M NaHCO 3 -Na 2 CO 3 -NaCl-NaOH) and pH m (-log[H + ] = 8.5-14.5). Strongly reducing conditions (pe + pH m ≈ 2) were set with Sn(ii). Carbonate enhances the solubility of Tc(iv) in alkaline conditions by up to 3.5 log 10 -units compared to carbonate-free systems. Solvent extraction and XANES confirmed that Tc was kept as +IV during the timeframe of the experiments (≤ 650 days). Solid phase characterization performed by XAFS, XRD, SEM-EDS, chemical analysis and TG-DTA confirmed that TcO 2 ·0.6H 2 O(am) controls the solubility of Tc(iv) under the conditions investigated. Slope analysis of the solubility data in combination with solid/aqueous phase characterization and DFT calculations indicate the predominance of the species Tc(OH) 3 CO 3 - at pH m ≤ 11 and C tot ≥ 0.01 M, for which thermodynamic and activity models are derived. Solubility data obtained above pH m ≈ 11 indicates the formation of previously unreported Tc(iv)-carbonate species, possibly Tc(OH) 4 CO 3 2- , although the likely formation of additional complexes prevents deriving a thermodynamic model valid for this pH m -region. This work provides the most comprehensive thermodynamic dataset available for the system Tc 4+ -Na + -Cl - -OH - -HCO 3 - -CO 3 2- -H 2 O(l) valid under a range of conditions relevant for nuclear waste disposal.

  7. Spectroscopic investigation of new water soluble Mn(II)(2) and Mg(II)(2) complexes for the substrate binding models of xylose/glucose isomerases.

    Science.gov (United States)

    Patra, Ayan; Bera, Manindranath

    2014-01-30

    In methanol, the reaction of stoichiometric amounts of Mn(OAc)(2)·4H(2)O and the ligand H(3)hpnbpda [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in the presence of NaOH, afforded a new water soluble dinuclear manganese(II) complex, [Mn2(hpnbpda)(μ-OAc)] (1). Similarly, the reaction of Mg(OAc)(2)·4H(2)O and the ligand H3hpnbpda in the presence of NaOH, in methanol, yielded a new water soluble dinuclear magnesium(II) complex, [Mg2(hpnbpda)(μ-OAc)(H2O)2] (2). DFT calculations have been performed for the structural optimization of complexes 1 and 2. The DFT optimized structure of complex 1 shows that two manganese(II) centers are in a distorted square pyramidal geometry, whereas the DFT optimized structure of complex 2 reveals that two magnesium(II) centers adopt a six-coordinate distorted octahedral geometry. To understand the mode of substrate binding and the mechanistic details of the active site metals in xylose/glucose isomerases (XGI), we have investigated the binding interactions of biologically important monosaccharides d-glucose and d-xylose with complexes 1 and 2, in aqueous alkaline solution by a combined approach of FTIR, UV-vis, fluorescence, and (13)C NMR spectroscopic techniques. Fluorescence spectra show the binding-induced gradual decrease in emission of complexes 1 and 2 accompanied by a significant blue shift upon increasing the concentration of sugar substrates. The binding modes of d-glucose and d-xylose with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for C1 and C2 carbon atoms. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Synthesis, Structural Characterization and Antimicrobial Activity of Cu(II and Fe(III Complexes Incorporating Azo-Azomethine Ligand

    Directory of Open Access Journals (Sweden)

    Mohammad Azam

    2018-04-01

    Full Text Available We are reporting a novel azo-azomethine ligand, HL and its complexes with Cu(II and Fe(III ions. The ligand and its complexes are characterized by various physico-chemical techniques using C,H,N analyses, FT-IR, 1H-NMR, ESI-MS and UV-Vis studies. TGA analyses reveal complexes are sufficiently stable and undergo two-step degradation processes. The redox behavior of the complexes was evaluated by cyclic voltammetry. Furthermore, the ligand and its complexes were tested for antimicrobial activity against bacterial and fungal strains by determining inhibition zone, minimal inhibitory concentration (MIC and minimal bactericidal concentration (MBC. The complexes showed moderate antimicrobial activity when tested against Gram +ve and Gram −ve bacterial strains. To obtain insights into the structure of ligand, DFT studies are recorded. The results obtained are quite close to the experimental results. In addition, the energy gap, chemical hardness, softness, electronegativity, electrophilic index and chemical potential were calculated using HOMO, LUMO energy value of ligand.

  9. Heterospin systems constructed from [Cu2Ln]3+ and [Ni(mnt)2]1-,2- Tectons: First 3p-3d-4f complexes (mnt = maleonitriledithiolato).

    Science.gov (United States)

    Madalan, Augustin M; Avarvari, Narcis; Fourmigué, Marc; Clérac, Rodolphe; Chibotaru, Liviu F; Clima, Sergiu; Andruh, Marius

    2008-02-04

    New heterospin complexes have been obtained by combining the binuclear complexes [{Cu(H(2)O)L(1)}Ln(O(2)NO)(3)] or [{CuL(2)}Ln(O(2)NO)(3)] (L(1) = N,N'-propylene-di(3-methoxysalicylideneiminato); L(2) = N,N'-ethylene-di(3-methoxysalicylideneiminato); Ln = Gd(3+), Sm(3+), Tb(3+)), with the mononuclear [CuL(1)(2)] and the nickel dithiolene complexes [Ni(mnt)(2)](q)- (q = 1, 2; mnt = maleonitriledithiolate), as follows: (1)infinity[{CuL(1)}(2)Ln(O(2)NO){Ni(mnt)(2)}].Solv.CH(3)CN (Ln = Gd(3+), Solv = CH(3)OH (1), Ln = Sm(3+), Solv = CH(3)CN (2)) and [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)][Ni(mnt)(2)] (3) with [Ni(mnt)2]2-, [{(CH(3)CN)CuL(1)}(2)Ln(H(2)O)][Ni(mnt)(2)]3.2CH(3)CN (Ln = Gd(3+) (4), Sm(3+) (5), Tb(3+) (6)), and [{(CH(3)OH)CuL(2)}{CuL(2)}Gd(O(2)NO){Ni(mnt)(2)}][Ni(mnt)(2)].CH(2)Cl(2) (7) with [Ni(mnt))(2]*-. Trinuclear, almost linear, [CuLnCu] motifs are found in all the compounds. In the isostructural 1 and 2, two trans cyano groups from a [Ni(mnt)2]2- unit bridge two trimetallic nodes through axial coordination to the Cu centers, thus leading to the establishment of infinite chains. 3 is an ionic compound, containing discrete [{(CH(3)OH)CuL(2)}(2)Sm(O(2)NO)](2+) cations and [Ni(mnt)(2)](2-) anions. Within the series 4-6, layers of discrete [CuLnCu](3+) motifs alternate with stacks of interacting [Ni(mnt)(2)](*-) radical anions, for which two overlap modes, providing two different types of stacks, can be disclosed. The strength of the intermolecular interactions between the open-shell species is estimated through extended Hückel calculations. In compound 7, [Ni(mnt)(2)](*-) radical anions coordinate group one of the Cu centers of a trinuclear [Cu(2)Gd] motif through a CN, while discrete [Ni(mnt)(2)](*-) units are also present, overlapping in between, but also with the coordinated ones. Furthermore, the [Cu(2)Gd] moieties dimerize each other upon linkage by two nitrato groups, both acting as chelate toward the gadolinium ion from one unit and monodentate toward a

  10. Cu(II) salen complex with propylene linkage: An efficient catalyst in the formation of Csbnd X bonds (X = N, O, S) and biological investigations

    Science.gov (United States)

    Azam, Mohammad; Dwivedi, Sourabh; Al-Resayes, Saud I.; Adil, S. F.; Islam, Mohammad Shahidul; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Lee, Dong-Ung

    2017-02-01

    The catalytic property of a mononuclear Cu(II) salen complex in Chan-Lam coupling reaction with phenyl boronic acid at room temperature is reported. The studied complex is found to be potential catalyst in the preparation of carbon-heteroatom bonds with excellent yields. The studied Cu(II) salen complex is monoclinic with cell parameters, a = 9.6807(5) (α 90°), (b = 17.2504(8) (β 112.429 (2), c = 11.1403 (6) (γ = 90°), and has distorted square planar environment around Cu(II) ion. Furthermore, there is no π⋯π interactions in the reported complex due to large distance between the centroid of aromatic rings. In addition, DNA binding study of Cu(II) salen complex by fluorescence and absorption spectroscopy is also reported. Moreover, the reported Cu(II) salen complex exhibits significant anticancer activity against MCF-7 cancer cell lines, and displays potential antimicrobial biofilm activity against P. aeruginosa, suggesting antimicrobial biofilm an important tool for suppression of resistant infections caused by P. aeruginosa.

  11. Investigation of the complex structure, comparative DNA-binding and DNA cleavage of two water-soluble mono-nuclear lanthanum(III) complexes and cytotoxic activity of chitosan-coated magnetic nanoparticles as drug delivery for the complexes

    Science.gov (United States)

    Asadi, Zahra; Nasrollahi, Neda; Karbalaei-Heidari, Hamidreza; Eigner, Vaclav; Dusek, Michal; Mobaraki, Nabiallah; Pournejati, Roya

    2017-05-01

    Two water-soluble mono-nuclear macrocyclic lanthanum(III) complexes of 2,6-diformyl-4-methylphenol with 1,3-diamino-2-propanol (C1) or 1,3-propylenediamine (C2) were synthesized and characterized by UV-Vis, FT-IR, 13C and 1H NMR spectroscopy and elemental analysis. C1 complex was structurally characterized by single-crystal X-ray diffraction, which revealed that the complex was mononuclear and ten-coordinated. The coordination sites around lanthanum(III) were occupied with a five-dentate ligand, two bidentate nitrates, and one water molecule. The interaction of complexes with DNA was studied in buffered aqueous solution at pH 7.4. UV-Vis absorption spectroscopy, emission spectroscopy, circular dichroism (CD) and viscometric measurements provided clear evidence of the intercalation mechanism of binding. The obtained intrinsic binding constants (Kb) 9.3 × 103 and 1.2 × 103 M- 1 for C1 and C2, respectively confirmed that C1 is better intercalator than C2. The DNA docking studies suggested that the complexes bind with DNA in a groove binding mode with the binding affinity of C1 > C2. Moreover, agarose gel electrophoresis study of the DNA-complex for both compounds revealed that the C1 intercalation cause ethidium bromide replacement in a competitive manner which confirms the suggested mechanism of binding. Finally, the anticancer experiments for the treated cancerous cell lines with both synthesized compounds show that these hydrophilic molecules need a suitable carrier to pass through the hydrophobic nature of cell membrane efficiently.

  12. The Nucleus 59Cu. Complex Structure, Shape Evolution, Exotic Decay Modes

    International Nuclear Information System (INIS)

    Andreoiu, Corina

    2002-08-01

    High-spin states in the mass A∼60 region were populated using the state-of-art γ-ray spectrometers Gammasphere, Euroball, and GASP in conjunction with dedicated ancillary detectors. In particular, the 59 Cu nucleus was studied in several experiments, and a very extensive level scheme was determined. It comprises more than 320 transitions connecting about 150 excited states. Relative to mass, it is the most extensive level scheme known to date. Next to the spherical states at low excitation energy eight regular sequences of high-energy γ-ray transitions have been observed. They form rotational bands with various degree of deformation, which are interpreted in the light of the shell model and the configuration-dependent Cranked Nilsson-Strutinsky approach. One of the experiments was dedicated to the study of prompt particle decays. It revealed five prompt proton decays connecting five deformed states in three of the rotational bands in 59 Cu with three spherical states in the daughter nucleus 58 Ni. It is the first observation of the fine structure of the newly discovered prompt proton decay mode. The proton decays compete with the γ decay-out from the second minimum of the nuclear potential into the low-spin spherical states in the first minimum of the potential. The discrete γ decay-out mechanism of the yrast superdeformed band is investigated in detail. The nucleus 59 Zn, the mirror partner of 59 Cu, was identified for the first time, and the mirror symmetry of the T=1/2 A=59 pair is discussed

  13. Electrochemical and theoretical complexation studies for Zn and Cu with individual polyphenols

    International Nuclear Information System (INIS)

    Esparza, I.; Salinas, I.; Santamaria, C.; Garcia-Mina, J.M.; Fernandez, J.M.

    2005-01-01

    Zn and Cu interactions with three selected flavonoids (catechin, quercetin and rutin) have been electrochemically monitored. It has been shown that catechin takes one atom of metal per molecule; quercetin takes two atoms, and rutin is able to take up to three atoms. Not all ligands bind metals equally strong, and weakly bonded metals can be distinguished. Zn shows a sluggish kinetics and, at the same time, the highest conditional formation constants. The method could be applied to a real sample. Theoretical models are proposed for the most favourable compounds

  14. Aminoacid N-substituted 1,4,7-triazacyclononane and 1,4,7,10-tetraazacyclododecane Zn2+, Cd2+ and Cu2+ complexes. A preparative, potentiometric titration and NMR spectroscopic study.

    Science.gov (United States)

    Plush, Sally E; Lincoln, Stephen F; Wainwright, Kevin P

    2004-05-07

    The pK(a)s and Zn2+, Cd2+ and Cu2+ complexation constants (K) for 1,4,7-tris[(2''S)-acetamido-2''-(methyl-3''-phenylpropionate)]-1,4,7-triazacyclononane, 1, 1,4,7-tris[(2''S)-acetamido-2''-(1''-carboxy-3''-phenylpropane)]-1,4,7-triazacyclononane, H(3)2, 1,4,7-tris[(2''S)-acetamido-2''-(methyl-3''-(1H-3-indolyl)propionate)]-1,4,7-triazacyclononane, 3, and 1,4,7,10-tetrakis[(2''S)-acetamido-2''-(methyl-3''-phenylpropionate)]-1,4,7,10-tetraazacyclododecane, 4, 1,4,7,10-tetrakis[(2''S)-acetamido-2''-(1''-carboxy-3''-phenylpropane)]-1,4,7,10-tetraazacyclododecane, H(4)5, in 20 : 80 v/v water-methanol solution are reported. The pK(a)s within the potentiometric detection range for H(3)1(3+) = 8.69 and 3.59, for H(6)2(3+) = 9.06, 6.13, 4.93 and 4.52, H(3)3(3+) = 8.79 and 3.67, H(4)4(4+) = 8.50, 5.62 and 3.77 and for H(8)5(4+) = 9.89, 7.06, 5.53, 5.46, 4.44 and 4.26 where each tertiary amine nitrogen is protonated. The complexes of 1: [Zn(1)]2+(9.00), [Cd(1)]2+ (6.49), [Cd(H1)]3+ (4.54) and [Cu(1)]2+ (10.01) are characterized by the log(K/dm3 mol(-1)) values shown in parentheses. Analogous complexes are formed by 3 and 4: [Zn(3)]2+ (10.19), [Cd(3)]2+ (8.54), [Cu(3)]2+ (10.77), [Zn(4)]2+ (11.41) [Cd(4)]2+ (9.16), [Cd(H4)]3+ (6.16) and [Cu(4)]2+ (11.71). The tricarboxylic acid H(3)2 generates a greater variety of complexes as exemplified by: [Zn(2)-] (10.68) [Zn(H2)] (6.60) [Zn(H(2)2)+] (5.15), [Cd(2)](-) (4.99), [Cd(H2)] (4.64), [Cd(H2(2))]+ (3.99), [Cd(H(3)2)]2+ (3.55), [Cu(2)](-) (12.55) [Cu(H2)] (7.66), [Cu(H(2)2)]+ (5.54) and [Cu(2)2](4-) (3.23). The complexes of H(4)5 were insufficiently soluble to study in this way. The 1H and 13C NMR spectra of the ligands are consistent with formation of a predominant Zn2+ and Cd2+ Delta or Lambda diastereomer. The preparations of the new pendant arm macrocycles H(3)2, 3, 4 and H(4)5 are reported.

  15. Complexes of Cu(II), Ni(II), Co(II), oxovanadium(IV) and dioxouranium(VI) with N,N'-ethylenebis (2-hydroxy-4-methylpropiophenoneimine)

    International Nuclear Information System (INIS)

    Patel, M.M.; Patel, M.R.; Patel, M.N.; Patel, R.P.

    1982-01-01

    Complexes of Cu(II), Ni(II), Co(II), oxovanadium(IV) and dioxouranium(VI) with the schiff base, N,N'-ethylenebis(2-hydroxy-4-methylpropiophenoneimine)(4-MeOHPEN), have been synthesised and characterised on the basis of elemental analyses, conductivity, magnetic moment, electronic and infrared spectral data. Square-planar structures are suggested for Cu(II), Ni(II) and Co(II) complexes while a distorted square-pyramidal structure is suggested for the oxovanadium(IV) complex. (author)

  16. Selective C–C Coupling Reaction of Dimethylphenol to Tetramethyldiphenoquinone Using Molecular Oxygen Catalyzed by Cu Complexes Immobilized in Nanospaces of Structurally-Ordered Materials

    Directory of Open Access Journals (Sweden)

    Zen Maeno

    2015-02-01

    Full Text Available Two high-performance Cu catalysts were successfully developed by immobilization of Cu ions in the nanospaces of poly(propylene imine (PPI dendrimer and magadiite for the selective C–C coupling of 2,6-dimethylphenol (DMP to 3,3',5,5'-tetramethyldiphenoquinone (DPQ with O2 as a green oxidant. The PPI dendrimer encapsulated Cu ions in the internal nanovoids to form adjacent Cu species, which exhibited significantly high catalytic activity for the regioselective coupling reaction of DMP compared to previously reported enzyme and metal complex catalysts. The magadiite-immobilized Cu complex acted as a selective heterogeneous catalyst for the oxidative C–C coupling of DMP to DPQ. This heterogeneous catalyst was recoverable from the reaction mixture by simple filtration, reusable without loss of efficiency, and applicable to a continuous flow reactor system. Detailed characterization using ultraviolet-visible (UV-vis, Fourier transform infrared (FTIR, electronic spin resonance (ESR, and X-ray absorption fine structure (XAFS spectroscopies and the reaction mechanism investigation revealed that the high catalytic performances of these Cu catalysts were ascribed to the adjacent Cu species generated within the nanospaces of the PPI dendrimer and magadiite.

  17. Magnetic behavior in heterometallic one-dimensional chains or octanuclear complex regularly aligned with metal-metal bonds as -Rh-Rh-Pt-Cu-Pt

    Science.gov (United States)

    Uemura, Kazuhiro

    2018-06-01

    Heterometallic one-dimensional chains, [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}]n(PF6)2n (1 and 2, piam = pivalamidate) and [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}2](CF3CO2)2(ClO4)2·2H2O (3), are paramagnetic one-dimensional chains or octanuclear complexes that are either aligned as -Rh-Rh-Pt-Cu-Pt- (1 and 2) or as Pt-Cu-Pt-Rh-Rh-Pt-Cu-Pt (3) with metal-metal bonds. Compounds 1-3 have rare structures, from the standpoint of that the paramagnetic species of Cu atoms are linked by direct metal-metal bonds. Magnetic susceptibility measurements for 1-3 performed at temperatures of 2 K-300 K indicated that the unpaired electrons localize in the Cu 3dx2-y2 orbitals, where S = 1/2 Cu(II) atoms are weakly antiferromagnetically coupled with J = -0.35 cm-1 (1), -0.47 cm-1 (2), and -0.45 cm-1 (3).

  18. The guanidinium group as a key part of water-soluble polymer carriers for siRNA complexation and protection against degradation.

    Science.gov (United States)

    Tabujew, Ilja; Freidel, Christoph; Krieg, Bettina; Helm, Mark; Koynov, Kaloian; Müllen, Klaus; Peneva, Kalina

    2014-07-01

    Here, the preparation of a novel block copolymer consisting of a statistical copolymer N-(2-hydroxypropyl) methacrylamide-s-N-(3-aminopropyl) methacrylamide and a short terminal 3-guanidinopropyl methacrylamide block is reported. This polymer structure forms neutral but water-soluble nanosized complexes with siRNA. The siRNA block copolymer complexes are first analyzed using agarose gel electrophoresis and their size is determined with fluorescence correlation spectroscopy. The protective properties of the polymer against RNA degradation are investigated by treating the siRNA block copolymer complexes with RNase V1. Heparin competition assays confirm the efficient release of the cargo in vitro. In addition, the utilization of microscale thermophoresis is demonstrated for the determination of the binding strength between a fluorescently labeled polyanion and a polymer molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. New investigation of phase equilibria in the system Al-Cu-Si.

    Science.gov (United States)

    Ponweiser, Norbert; Richter, Klaus W

    2012-01-25

    The phase equilibria and invariant reactions in the system Al-Cu-Si were investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and electron probe micro analysis (EPMA). Isothermal phase equilibria were investigated within two isothermal sections. The isothermal section at 500 °C covers the whole ternary composition range and largely confirms the findings of previous phase diagram investigations. The isothermal section at 700 °C describes phase equilibria only in the complex Cu-rich part of the phase diagram. A new ternary compound τ was found in the region between (Al,Cu)-γ(1) and (Cu,Si)-γ and its solubility range was determined. The solubility of Al in κ-CuSi was found to be extremely high at 700 °C. In contrast, no ternary solubility in the β-phase of Cu-Al was found, although this phase is supposed to form a complete solid solution according to previous phase diagram assessments. Two isopleths, at 10 and 40 at.% Si, were investigated by means of DTA and a partial ternary reaction scheme (Scheil diagram) was constructed, based on the current work and the latest findings in the binary systems Al-Cu and Cu-Si. The current study shows that the high temperature equilibria in the Cu-rich corner are still poorly understood and additional studies in this area would be favorable.

  20. A Study on Solubilization of Poorly Soluble Drugs by Cyclodextrins and Micelles: Complexation and Binding Characteristics of Sulfamethoxazole and Trimethoprim

    Directory of Open Access Journals (Sweden)

    Sinem Göktürk

    2012-01-01

    > α-CD. With taking into consideration of solubilization capacity of SDS micelles, it has been found that the solubility enhancement of TMP is much higher than that of SMX in the presence of SDS micelles. The binding constants of SMX and TMP obtained from the Benesi-Hildebrand equation are also confirmed by the estimated surface properties of SDS, employing the surface tension measurements. In order to elucidate the solubilization characteristics the surface tension measurements were also performed for nonionic surfactant Triton X-100. Polarity of the microenvironment and probable location of SMX and TMP were also discussed in the presence of various organic solvents.

  1. Copper, nickel and zinc complexes of a new water-soluble thiosemicarbazone ligand: Synthesis, characterization, stability and biological evaluation

    Czech Academy of Sciences Publication Activity Database

    Hosseini-Yazdi, S.A.; Mirzaahmadi, A.; Khandar, A.A.; Mahdavi, M.; Rahimian, A.; Eigner, Václav; Dušek, Michal; Zarrini, G.

    2017-01-01

    Roč. 248, Dec (2017), s. 658-667 ISSN 0167-7322 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk(CZ) LO1603 EU Projects: European Commission(CZ) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : cytotoxicity * thiosemicarbazone * water-soluble Schiff base * stability * antioxidant * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.648, year: 2016

  2. DNA binding and biological activity of mixed ligand complexes of Cu(II, Ni(II and Co(II with quinolones and N donor ligand

    Directory of Open Access Journals (Sweden)

    S.M M Akram

    2015-10-01

    Full Text Available  AbstractMixed ligand complexes of  Cu(II, Ni(II and Co(II have been synthesized by using levofloxacin and bipyridyl and characterized using spectral and analytical techniques. The binding behavior of the Ni(II and Cu(II complexes with herring sperm DNA(Hs-DNA were determined using electronic absorption titration, viscometric measurements and cyclic voltammetry measurements. The binding constant calculated  for Cu(II and Ni(II complexes are 2.0 x 104 and 4.0 x 104 M-1 respectively. Detailed analysis reveals that these metal complexes interact with DNA through intercalative binding mode. The nuclease activity of  Cu(II and Ni(II complexes with ct-DNA was carried out using agarose gel electrophoresis technique. The antioxidant activities for the synthesized complexes have been tested and the antibacterial activity for Ni(II complex was also checked.Key words: Intercalation, hypochromism, red shift and  peak potential.

  3. Quantum chemical calculations and experimental investigations on 2-aminobenzoic acid-cyclodiphosph(V)azane derivative and its homo-binuclear Cu(II) complex

    Science.gov (United States)

    El-Gogary, Tarek M.; Alaghaz, Abdel-Nasser M. A.; Ammar, Reda A. A.

    2012-03-01

    A novel 2-aminobenzoic acid-cyclodiphosph(V)azane ligand H4L and its homo-binuclear Cu(II) complex of the type [Cu2L(H2O)2].2.5 H2O in which L is 1,3-di(-o-pyridyl)-2,4-(dioxo)-2',4'-bis-(2-iminobenzoic acid) cyclodiphosph(V)azane, were synthesized and characterized by different physical techniques. Infrared spectra of the complex indicate deprotonation and coordination of the imine NH and carboxyl COOH groups. It also confirms that nitrogen atom of the pyridine ring contribute to the complexation. Electronic spectra and magnetic susceptibility measurements reveal square-planar geometry for the Cu(II) complex. The elemental analyses and thermogravimetric results have justified the [Cu2L(H2O)2]·2.5H2O composition of the complex. Quantum chemical calculations were utilized to explore the electronic structure and stability of the H4L as well as the binuclear Cu(II) complex. Computational studies have been carried out at the DFT-B3LYP/6-31G(d) level of theory on the structural and spectroscopic properties of H4L and its binuclear Cu(II) complex. Different tautomers and geometrical isomers of the ligand were optimized at the ab initio DFT level. Simulated IR frequencies were scaled and compared with that experimentally measured. TD-DFT method was used to compute the UV-VIS spectra which show good agreement with measured electronic spectra.

  4. Modeling the adsorption of metal ions (Cu 2+, Ni 2+, Pb 2+) onto ACCs using surface complexation models

    Science.gov (United States)

    Faur-Brasquet, Catherine; Reddad, Zacaria; Kadirvelu, Krishna; Le Cloirec, Pierre

    2002-08-01

    Activated carbon cloths (ACCs), whose efficiency has been demonstrated for microorganics adsorption from water, were here studied in the removal of metal ions from aqueous solution. Two ACCs are investigated, they are characterized in terms of porosity parameters (BET specific surface area, percentage of microporosity) and chemical characteristics (acidic surface groups, acidity constants, point of zero charge). A first part consists in the experimental study of three metal ions removal (Cu 2+, Ni 2+ and Pb 2+) in a batch reactor. Isotherms modeling by Freundlich and Brunauer-Emmett-Teller (BET) equations enables the following adsorption order: Cu 2+>Ni 2+>Pb 2+ to be determined for adsorption capacities on a molar basis. It may be related to adsorbates characteristics in terms of electronegativity and ionic radius. The influence of adsorbent's microporosity is also shown. Adsorption experiments carried out for pH values ranging from 2 to 10 demonstrate: (i) an adsorption occurring below the precipitation pH; (ii) the strong influence of pH, with a decrease of electrostatic repulsion due to the formation of less charged hydrolyzed species coupled with a decrease of activated carbon surface charge as pH increases. The second part focuses on the modeling of adsorption versus the pH experimental data by the diffuse layer model (DLM) using Fiteql software. The model is efficient to describe the system behavior in the pH range considered. Regarding complexation constants, they show the following affinity for ACC: Pb 2+>Cu 2+>Ni 2+. They are related to initial concentrations used for the three metal ions.

  5. Exchange coupling transformations in Cu (II) heterospin complexes of “breathing crystals” under structural phase transitions

    Energy Technology Data Exchange (ETDEWEB)

    Morozov, Vitaly A.; Petrova, Marina V.; Lukzen, Nikita N., E-mail: luk@tomo.nsc.ru [International Tomography Center SB RUS, Institutskaya Str. 3a, Novosibirsk, 630090 (Russian Federation); Novosibirsk State University, Pirogova Str. 2, Novosibirsk 630090 (Russian Federation)

    2015-08-15

    Family of “breathing crystals” is the polymer-chain complexes of Cu(hfac){sub 2} with nitroxides. The polymer chains consist of one-, two- or three-spin clusters. The “breathing crystals” experience simultaneous magnetic and Jahn-Teller type structural phase transitions with change of total cluster spin and drastic change of bond lengths (ca. 10-12%). For the first time the intra-cluster magnetic couplings in ”breathing crystals” have been calculated both by band structure methods GGA + U and hybrid DFT (B3LYP and PBE0) for the isolated exchange clusters. The temperature dependence of the magnetic coupling constant was calculated for two polymer-chain compounds of the “breathing crystal” family - C{sub 21}H{sub 19}CuF{sub 12}N{sub 4}O{sub 6} with the chains containing two-spin clusters and C{sub 22}H{sub 21}CuF{sub 12}N{sub 4}O{sub 6} with the chains of alternating three-spin clusters and one-spin sites. It was found that adding a Hubbard-like parameter not only to the copper 3d electrons but also to the oxygen 2p electrons (GGA + U{sub d} + U{sub p} approach) results in an improved description of exchange coupling in the “breathing crystal” compounds. At the same time treatment of the isolated clusters by a large basis hybrid DFT with high computational cost provides a similar quality fit of the experimental magneto-chemical data as that for the GGA + U{sub d} + U{sub p} band structure calculation scheme. Our calculations also showed that in spite of the abrupt transformation of the magnetic coupling constant under the phase transition, the band gap in the “breathing crystals” remains about the same value with temperature decrease.

  6. Cu(II) complexes of glyco-imino-aromatic conjugates in DNA binding ...

    Indian Academy of Sciences (India)

    Abstract. Binding of metal complexes of C2-glucosyl conjugates with DNA has been established by absorp- ... Metal complexes have shown toxicity to the HeLa and MCF–7 .... ber with 5% CO2. ..... ing/reducing agent or laser/UV–visible light.

  7. Water-Soluble Dinitrosyl Iron Complex (DNIC): a Nitric Oxide Vehicle Triggering Cancer Cell Death via Apoptosis.

    Science.gov (United States)

    Wu, Shou-Cheng; Lu, Chung-Yen; Chen, Yi-Lin; Lo, Feng-Chun; Wang, Ting-Yin; Chen, Yu-Jen; Yuan, Shyng-Shiou; Liaw, Wen-Feng; Wang, Yun-Ming

    2016-09-19

    Nitric oxide (NO) is an important cellular signaling molecule that modulates various physiological activities. Angiogenesis-promoting activities of NO-donor drugs have been explored in both experimental and clinical studies. In this study, a structurally well characterized and water-soluble neutral {Fe(NO)2}(9) DNIC [(S(CH2)2OH)(S(CH2)2NH3)Fe(NO)2] (DNIC 2) was synthesized to serve as a NO-donor species. The antitumor activity of DNIC 2 was determined by MTT assay, confocal imaging, and Annexin-V/PI staining. The IC50 values of DNIC 2 were 18.8, 42.9, and 38.6 μM for PC-3, SKBR-3, and CRL5866 tumor cells, respectively. Moreover, DNIC 2 promoted apoptotic cell death via activation of apoptosis-associated proteins and inhibition of survival associated proteins. In particular, DNIC 2 treatment suppressed PC-3 tumor growth by 2.34- and 19.3-fold at 7 and 21 days, in comparison with the control group. These results indicate that water-soluble DNIC 2 may serve as a promising drug for cancer therapy.

  8. Preparation and Characterization of Water-Soluble Chitosan Microparticles Loaded with Insulin Using the Polyelectrolyte Complexation Method

    International Nuclear Information System (INIS)

    Wu, S.; Tao, Y.; Zhang, H.; Su, Z.

    2011-01-01

    Polymeric delivery systems based on microparticles have emerged as a promising approach for peroral insulin delivery. The amount of insulin was quantified by the improved Bradford method. It was shown that water-soluble chitosan/insulin/tripolyphosphate (TPP) mass ratio played an important role in microparticles formation. Stable, uniform, and spherical water-soluble chitosan microparticles (WSC-MPs) with high insulin association efficiency were formed at or close to optimized WSC/insulin/TPP mass ratio. WSC-MPs had higher association efficiency in the ph 4.0 and ph 9.7 of TPP solution. The results showed that association efficiency and loading capacity of insulin-loaded WSC-MPs prepared in 0.01 mol/L HCl of insulin were 48.28 ± 0.90% and 9.52 ± 1.34%. The average size of insulin-loaded WSC-MPs was 292 nm. The presented WSC microparticulate system has promising properties towards the development of an oral delivery system for insulin

  9. Soil solution dynamics of Cu and Zn in a Cu- and Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction.

    Science.gov (United States)

    Luo, Y M; Yan, W D; Christie, P

    2001-01-01

    A pot experiment was conducted to study soil solution dynamics of Cu and Zn in a Cu/Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction. A slightly acid sandy loam was amended with Cu and Zn (as nitrates) either singly or in combination (100 mg Cu and 150 mg Zn kg(-1) soil) and was then gamma-irradiated (10 kGy). Unamended and unirradiated controls were included, and spring barley (Hordeum vulgare L. cv. Forrester) was grown for 50 days. Soil solution samples obtained using soil moisture samplers immediately before transplantation and every ten days thereafter were used directly for determination of Cu, Zn, pH and absorbance at 360 nm (A360). Cu and Zn concentrations in the solution of metal-polluted soil changed with time and were affected by gamma-irradiation and metal interaction. gamma-Irradiation raised soil solution Cu substantially but generally decreased soil solution Zn. These trends were consistent with increased dissolved organic matter (A360) and solution pH after gamma-irradiation. Combined addition of Cu and Zn usually gave higher soil solution concentrations of Cu or Zn compared with single addition of Cu or Zn in gamma-irradiated and non-irradiated soils, indicating an interaction between Cu and Zn. Cu would have been organically complexed and consequently maintained a relatively high concentration in the soil solution under higher pH conditions. Zn tends to occur mainly as free ion forms in the soil solution and is therefore sensitive to changes in pH. The extent to which gamma-irradiation and metal interaction affected solubility and bioavailability of Cu and Zn was a function of time during plant growth. Studies on soil solution metal dynamics provide very useful information for understanding metal mobility and bioavailability.

  10. Curcumin-β-cyclodextrin inclusion complex: stability, solubility, characterisation by FT-IR, FT-Raman, X-ray diffraction and photoacoustic spectroscopy, and food application.

    Science.gov (United States)

    Mangolim, Camila Sampaio; Moriwaki, Cristiane; Nogueira, Ana Claudia; Sato, Francielle; Baesso, Mauro Luciano; Neto, Antônio Medina; Matioli, Graciette

    2014-06-15

    Curcumin was complexed with β-CD using co-precipitation, freeze-drying and solvent evaporation methods. Co-precipitation enabled complex formation, as indicated by the FT-IR and FT-Raman techniques via the shifts in the peaks that were assigned to the aromatic rings of curcumin. In addition, photoacoustic spectroscopy and X-ray diffraction, with the disappearance of the band related to aromatic rings, by Gaussian fitting, and modifications in the spectral lines, respectively, also suggested complex formation. The possible complexation had an efficiency of 74% and increased the solubility of the pure colourant 31-fold. Curcumin-β-CD complex exhibited a sunlight stability 18% higher than the pure colourant. This material was stable to pH variations and storage at -15 and 4°C. With an isothermal heating at 100 and 150°C for 2h, the material exhibited a colour retention of approximately 99%. The application of curcumin-β-CD complex in vanilla ice creams intensified the colour of the products and produced a great sensorial acceptance. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Analysis of a Soluble (UreD:UreF:UreG)2 Accessory Protein Complex and its Interactions with Klebsiella aerogenes Urease by Mass Spectrometry

    Science.gov (United States)

    Farrugia, Mark A.; Han, Linjie; Zhong, Yueyang; Boer, Jodi L.; Ruotolo, Brandon T.; Hausinger, Robert P.

    2013-01-01

    Maturation of the nickel-containing urease of Klebsiella aerogenes is facilitated by the UreD, UreF, and UreG accessory proteins along with the UreE metallo-chaperone. A fusion of the maltose binding protein and UreD (MBP-UreD) was co-isolated with UreF and UreG in a soluble complex possessing a (MBP-UreD:UreF:UreG)2 quaternary structure. Within this complex a UreF:UreF interaction was identified by chemical cross-linking of the amino termini of its two UreF protomers, as shown by mass spectrometry of tryptic peptides. A pre-activation complex was formed by the interaction of (MBP-UreD:UreF:UreG)2 and urease. Mass spectrometry of intact protein species revealed a pathway for synthesis of the urease pre-activation complex in which individual hetero-trimer units of the (MBP-UreD:UreF:UreG)2 complex bind to urease. Together, these data provide important new insights into the structures of protein complexes associated with urease activation. PMID:23797863

  12. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    Science.gov (United States)

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

  13. Ensayo de arcillas modificadas con materia orgánica soluble para la eliminación de Cu y Zn

    OpenAIRE

    Durán, Esperanza; Gámiz, B.; Cox, L.; Hermosín, M.C.

    2015-01-01

    La contaminación por metales pesados es un tema de gran preocupación. Entre las diversas actividades que contribuyen a aumentar la presencia de metales pesados en el medio ambiente, se encuentra la agricultura. Por ejemplo, el uso de fertilizantes de tipo fosforados y algunos fungicidas incrementan la aparición Cu y Zn en aguas de zonas agrícolas e incluso residuales de la industria agroalimentaria. La eliminación de metales pesados mediante el uso de minerales de la arcilla tipo montmorillon...

  14. Transition metal complexes with thiosemicarbazide-based ligands. Part 60. Reactions of copper(II bromide with pyridoxal S-methylisothiosemicarbazone (PLITSC. Crystal structure of [Cu(PLITSC−HH2O]Br•H2O

    Directory of Open Access Journals (Sweden)

    Leovac Vukadin M.

    2014-01-01

    Full Text Available The synthesis and structural characterization of a square-planar copper(II complex with pyridoxal S-methylisothiosemicarbazone (PLITSC of the formula [Cu(PLITSC−HH2O]Br•H2O (1 as the first Cu(II complex with monoanionic form of this ligand were described. Complex 1 together with two previously synthesized complexes [Cu(PLITSCBr2] (2 and [Cu(PLITSCBr(MeOH]Br (3 were characterized by elemental analysis, IR and electronic spectra and also by the methods of thermal analysis, conductometry and magnetochemistry. [Projekat Pokrajisnkog sekretarijata za nauku i tehnoloski razvoj Vojvodine i Ministarstva nauke Republike Srbije, br. 172014

  15. Vibrational spectroscopic and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and the complexes Co2L2Cl4, Cu2L2Cl4 and Cu2L2Br2

    International Nuclear Information System (INIS)

    Nemcsok, Denes; Kovacs, Attila; Szecsenyi, Katalin Meszaros; Leovac, Vukadin M.

    2006-01-01

    In the present paper we report a joint experimental and theoretical study of 3,5-dimethyl-1-thiocarboxamide pyrazole (L) and its complexes Co 2 L 2 Cl 4 , Cu 2 L 2 Cl 4 and Cu 2 L 2 Br 2 . DFT computations were used to model the structural and bonding properties of the title compounds as well as to derive a reliable force field for the normal coordinate analysis of L. The computations indicated the importance of hydrogen bonding interactions in stabilising the global minimum structures on the potential energy surfaces. In contrast to the S-bridged binuclear Cu 2 L 2 Br 2 complex found in the crystal, our computations predicted the formation of (CuLBr) 2 dimers in the isolated state stabilized by very strong (53 kJ/mol) N-H...Br hydrogen bonding interactions. On the basis of FT-IR and FT-Raman experiments and the DFT-derived scaled quantum mechanical force field we carried out a complete normal coordinate analysis of L. The FT-IR spectra of the three complexes were interpreted using the present assignment of L, literature data and computed results

  16. Stabilization of the soluble, cleaved, trimeric form of the envelope glycoprotein complex of human immunodeficiency virus type 1

    NARCIS (Netherlands)

    Sanders, Rogier W.; Vesanen, Mika; Schuelke, Norbert; Master, Aditi; Schiffner, Linnea; Kalyanaraman, Roopa; Paluch, Maciej; Berkhout, Ben; Maddon, Paul J.; Olson, William C.; Lu, Min; Moore, John P.

    2002-01-01

    The envelope glycoprotein (Env) complex of human immunodeficiency virus type I has evolved a structure that is minimally immunogenic while retaining its natural function of receptor-mediated virus-cell fusion. The Env complex is trimeric; its six individual subunits (three gp120 and three gp41

  17. Water soluble (Eta sup (6) - arene) ruthenium (II) complexes incorporating marine derived bioligand: Synthesis, spectral and structural studies

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Svitlyk, V.; PrabhaDevi; Mozharivskyj, Y.

    by the reaction of [{(eta sup(6)-arene) RuCl sub(2)}sub(2)] with HMP. The complexes 1 and 2 react with NaN sub(3) to give in excellent yield tetra-azido complexes [{(Eta sup(6)-arene)Ru(Mu N sub(3))N sub(3)}sub(2)] (arene = cymene 4, HMB = 5) but similar reaction...

  18. Interaction between water-soluble rhodium complex RhCl(CO)(TPPTS)₂ and surfactants probed by spectroscopic methods.

    Science.gov (United States)

    Zhou, Li-Mei; Guo, Cai-Hong; Fu, Hai-Yan; Jiang, Xiao-Hui; Chen, Hua; Li, Rui-Xiang; Li, Xian-Jun

    2012-07-01

    The interactions of rhodium complex RhCl(CO)(TPPTS)(2) [TPPTS=P(m-C(6)H(4)SO(3)Na)(3)] with cationic, nonionic, and anionic surfactants have been investigated by UV-vis, fluorescence and (1)H NMR measurements. The presence of four different species of RhCl(CO)(TPPTS)(2) in cationic cetyltrimethylammonium (CTAB) solution has been demonstrated: free rhodium complex, rhodium complex bound to CTAB monomer, rhodium complex bound to CTAB premicelles, rhodium complex bound to CTAB micelles. The spectroscopy data show that RhCl(CO)(TPPTS)(2) can adsorb on the interface of cationic CTAB micelles by strong electrostatic attraction, weakly bind to the nonionic polyoxyethylene (20) sorbitan monolaurate (Tween 20) micelles by hydrophobic interaction, and does not interact with anion sodium dodecyl sulfate (SDS) micelles due to the strong electrostatic repulsion. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. Solubility diagrams in ternary aqueous-salt systems with yttrium, barium and copper nitrates at 25 deg C

    International Nuclear Information System (INIS)

    Petrenko, S.V.; Lyashchenko, A.K.; Karataeva, I.M.; Mozhaev, A.P.

    1990-01-01

    Solubility diagrams in Cu(NO 3 ) 2 -Y(NO 3 ) 3 -H 2 O, Y(NO 3 ) 3 -Ba(NO 3 ) 2 -H 2 O and Cu(NO 3 ) 2 -Ba(NO 3 ) 2 -H 2 O systems are studied at 25 deg C based on experimental determinations of salt solubility, isopiestic measurements and data of the calculation-experimental method in the framework of the Pitzer model. Binary and ternary parameters of interionic interactions are calculated; applicability of the method to the given systems is shown. Salts of complex composition and structure are absent in them; mutual salting out of components is also observed

  20. Determination of adenine based on the fluorescence recovery of the L-Tryptophan-Cu(2+) complex.

    Science.gov (United States)

    Duan, Ruilin; Li, Chunyan; Liu, Shaopu; Liu, Zhongfang; Li, Yuanfang; Yuan, Yusheng; Hu, Xiaoli

    2016-01-05

    A simple and sensitive method for determination of adenine was developed based on fluorescence quenching and recovery of L-Tryptophan (L-Trp). The fluorescence of L-Trp could efficiently quenched by copper ion compared with other common metal ions. Upon addition of adenine (Ade) in L-Trp-Cu(II) system, the fluorescence was reoccurred. Under the optimum conditions, the recovery fluorescence intensity was linearly correlated with the concentration of adenine in the range from 0.34 to 25.0μmolL(-1), with a correlation coefficient (R(2)) of 0.9994. The detection limit (3σ/k) was 0.046μmolL(-1), indicating that this method could applied to detect trace adenine. In this study, amino acids including L-Trp, D-Trp, L-Tyr, D-Tyr, L-Phe, D-Phe were investigated and only L-Trp could well chelated copper ion. Additionally, the mechanism of quench and recovery also were discussed and the method was successfully applied to detect the adenine in DNA with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Synthesis, Characterization and Antimicrobial Activity of Cu(II, Co(II and Ni(II Complexes with O, N, and S Donor Ligands

    Directory of Open Access Journals (Sweden)

    Vidyavati Reddy

    2008-01-01

    Full Text Available The complexes of the type ML2 [where M = Cu(II, Co(II, and Ni(II] L = 1-phenyl-1-ene-3-(2-hydroxyphenyl-prop-2-ene with 3- substituted-5-mercapto-4-amino-1,2,4-triazoles. Schiff base ligands have been prepared by reacting 3-(2-hydroxyphenyl-1-phenylprop-2-en-1-one and 3-phenyl/pyridyl-4-amino-5-mercapto-1,2,4-triazoles in an alcoholic medium. The complexes are non-electrolytes in DMF. The resulting complexes were characterized by elemental analysis, magnetic measurements, conductivity measurements and spectral studies. The Schiff base acts as a tridentate dibasic and coordinating through the deprotonated oxygen, thioenolic sulphur and azomethine nitrogen atoms. It is found that Cu(II, Co(II, and Ni(II complexes exhibited octahedral geometry. The antimicrobial activities of ligands and its complexes were screened by cup plate method.

  2. Kinetic studies of the impact of thiocyanate moiety on the catalytic properties of Cu(II) and Fe(III) complexes of a new Mannich base

    Science.gov (United States)

    Ayeni, Ayowole O.; Watkins, Gareth M.

    2018-04-01

    Four new metal complexes of a novel Mannich base 5-methyl-2-((4-(pyridin-2-yl)piperazin-1-yl)methyl)phenol (HL) have been prepared. The compounds were characterized by an array of analytical and spectroscopic methods including Nuclear Magnetic Resonance, Infra-red and UV-Visible spectroscopy. Compounds 1-4 behaved as effective catalysts towards the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to its corresponding quinone in the presence of molecular oxygen in DMF solution while compound 4 proved to be the best catalyst with a turnover rate of 17.93 ± 1.10 h-1 as other complexes showed lower rates of oxidation. Also with the exception of dinuclear iron complex (4); thiocyanate containing Cu(II) complex exhibited lower catecholase activity compared to the Cu(II) complex without it.

  3. Spectrophotometric analysis of vitamin E using Cu(I)-Bathocuproine or/and Fe(II)-2,4,6-tris-(2'-pyridyl)-s-triazine complexes

    International Nuclear Information System (INIS)

    Devi, I.; Memon, S. A.; Khuhawar, M.Y.

    2004-01-01

    Vitamin E (tocopherols and tocotrienols) antioxidants are determined by reducing Cu(II) to Cu(I) or Fe(III) to Fe(II) in presence of vitamin E and subsequent complexation of Cu(I) with bathocuproine and/or Fe(II) with 2,4,6-tris-(2'-pyridyl)-s-triazine (TPTZ). Both the reactions are monitored separately, Cu(I)-bathocuproine at 479 nm where as, Fe(II)-(TPTZ) at 595 nm spectrophotometrically. Linear calibration curves are achieved for both complexes between I to 5mu g ml-1 for vitamin E. The methods were applied for the determination of vitamin E in pharmaceutical preparations and edible oils. Vitamin E, from edible oils, was solvent extracted into n-hexane prior to saponification. Furthermore, a single lined flow was also examined. A larger excess of Cu(II) or Fe =(II) with different concentrations of vitamin E in buffer pH 4 was run on the line and constant amounts of reagent bathocuproine or TPTZ in each case was injected through the injector. The peak height shows a linear relationship for vitamin E between 0.5 to 2.5 mu g ml-1 for both complexes. (author)

  4. Two-dimensional layer architecture assembled by Keggin polyoxotungstate, Cu(II)-EDTA complex and sodium linker: Synthesis, crystal structures, and magnetic properties

    International Nuclear Information System (INIS)

    Liu Hong; Xu Lin; Gao Guanggang; Li Fengyan; Yang Yanyan; Li Zhikui; Sun Yu

    2007-01-01

    Reaction of Keggin polyoxotungstate with copper(II)-EDTA (EDTA=ethylenediamine tetraacetate) complex under mild conditions led to the formation of hybrid inorganic-organic compounds Na 4 (OH)[(Cu 2 EDTA)PW 12 O 40 ].17H 2 O (1) and Na 4 [(Cu 2 EDTA)SiW 12 O 40 ].19H 2 O (2). The single-crystal X-ray diffraction analyses reveal their two structural features: (1) one-dimensional chain structure consisting of Keggin polyoxotungstate and copper(II)-EDTA complex; (2) Two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker. The results of magnetic measurements in the temperature range 300-2 K indicated the existence of ferromagnetic exchange interactions between the Cu II ions for both compounds. In addition, TGA analysis, IR spectra, and electrochemical properties were also investigated to well characterize these two compounds. - Graphical abstract: Two new polyoxometalate-based hybrids, Na 4 (OH)[Cu 2 (EDTA)PW 12 O 40 ].17H 2 O (1) and Na 4 [Cu 2 (EDTA)SiW 12 O 40 ].19H 2 O (2), have been synthesized and structurally characterized, which consist of one-dimensional chain structure assembled by Keggin polyoxotungstate and copper(II)-EDTA complex. The chains are further connected to form two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker

  5. Synthesis and characterization of heterobimetallic complexes of the type [Cu(pn2][MCl4] where M = Co(II, Ni(II, Cu(II, Zn(II, Cd(II, and Hg(II

    Directory of Open Access Journals (Sweden)

    Seema Yadav

    2016-11-01

    Full Text Available A series of new bimetallic transition metal complexes of the type [Cu(pn2] [MCl4] have been synthesized (where M = Co(II, Ni(II, Cu(II, Zn(II, Cd(II and Hg(II, pn = 1,3-diaminopropane and characterized by elemental analysis, molar conductance, TGA, IR and electronic spectra. All the compounds are 1:1 electrolyte in DMF. The Cu(II ion is square-planar while metal ions in the anionic moiety acquire their usual tetrahedral arrangement. On the basis of these studies it is concluded that anionic moiety is electrically stabilized by its cationic counterpart.

  6. Synthesis of 2D polymeric dicyanamide bridged hexa-coordinated Cu(II) complex: Structural characterization, spectral studies and TDDFT calculation

    Science.gov (United States)

    Konar, Saugata; Saha, Urmila; Dolai, Malay; Chatterjee, Sudipta

    2014-10-01

    A rare 2D polymeric dicyanamide bridged hexa-coordinated copper(II) complex [Cu(L1‧)(μ1,5-dca)2]n (1) (L1‧ = 2-carboxypyrazine) has been synthesized from the reaction of Cu(NO3)2ṡ6H2O, 2-pyrazinecarbonitrile (L1) and sodium dicyanamide (Nadca) in methanolic medium. Single crystal X-ray analysis reveals that the complex has a 2D infinite zigzag chain structure in which copper(II) ions are bridged by single dicyanamide ligand in an end-to-end fashion. Such 2-carboxypyrazine can be obtained on the way of metal-assisted nitrile hydrolysis which well connected with Cu(NO3)2ṡ6H2O and dicyanamide (dca) to give rare 2D Cu(II) polymeric complex due to the flexibility in the coordination ability of the copper(II) ions within the polymeric chain. The geometry of the asymmetric unit of the complex was optimized in singlet state by DFT method with multilayer ONIOM model at doublet spin state accordance with repeating asymmetric unit only. The electronic spectrum of the complex is explained using TDDFT calculation.

  7. trans-Methylpyridine cyclen versus cross-bridged trans-methylpyridine cyclen. Synthesis, acid-base and metal complexation studies (metal = Co2+, Cu2+, and Zn2+).

    Science.gov (United States)

    Bernier, Nicolas; Costa, Judite; Delgado, Rita; Félix, Vítor; Royal, Guy; Tripier, Raphaël

    2011-05-07

    The synthesis of the cross-bridged cyclen CRpy(2) {4,10-bis((pyridin-2-yl)methyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane}, a constrained analogue of the previously described trans-methylpyridine cyclen Cpy(2) is reported. The additional ethylene bridge confers to CRpy(2) proton-sponge type behaviour which was explored by NMR and potentiometric studies. Transition metal complexes have been synthesized (by complexation of both ligands with Co(2+), Cu(2+) and Zn(2+)) and characterized in solution and in the solid state. The single crystal X-ray structures of [CoCpy(2)](2+), [CuCpy(2)](2+) and [ZnCpy(2)](2+) complexes were determined. Stability constants of the complexes, including those of the cross-bridged derivative, were determined using potentiometric titration data and the kinetic inertness of the [CuCRpy(2)](2+) complex in an acidic medium (half-life values) was evaluated by spectrophotometry. The pre-organized structure of the cross-bridged ligand imposes an additional strain for the complexation leading to complexes with smaller thermodynamic stability in comparison with the related non-bridged ligand. The electrochemical study involving cyclic voltammetry underlines the importance of the ethylene cross-bridge on the redox properties of the transition metal complexes.

  8. Chitosan-based Schiff base-metal complexes (Mn, Cu, Co) as ...

    Indian Academy of Sciences (India)

    and A C PISE. Chemistry Research ... Data obtained by thermal analysis revealed that these complexes showed good thermal ... vents along with its inherent chirality makes chitosan .... resulting Schiff base IC was cooled, filtered and washed with ethanol ..... experiments with homogeneous Mn-salen catalyst at different ...

  9. The synthesis of N-Zn, N-Cu complexes involving 2-amino pyridine ...

    Indian Academy of Sciences (India)

    amino pyridine and ethylenediamine ligands (1a-b and 2a-b) have been described. They were synthesized with a simple, one-pot method, and the crystal structures of 1a, 1b, 2a and 2b were determined by X-ray crystallography. The complexes ...

  10. Pyrone-based Cu(II) complexes, their characterization, DFT based ...

    Indian Academy of Sciences (India)

    ... of P. G. Studies and. Research in Chemistry and Pharmacy, R. D. University, Jabalpur 482 001, India ... fascination.2,3 Such type of metal complexes are quite interesting due to .... in the ground state were optimized by the DFT method using B3LYP ..... Vogel A I 1996 In A Text Book of Qualitative Inorganic. Analysis (7th ...

  11. The synthesis of N–Zn, N–Cu complexes involving 2-amino pyridine ...

    Indian Academy of Sciences (India)

    Administrator

    alcohol, and the reaction mixture was refluxed for. 14 h. The mixture was filtered to furnish white cry- .... benzaldehyde to 2-nitro-1-phenylethanol was esta- blished according to the content ratio of the remin- ... Zn(OAc)2 ·2 H2O in ethanol, THF or acetonitrile, the corresponding complexes were obtained after reflux- ing for 14 ...

  12. Theoretical studies on BTA-Metal (M=Ni, Cu) Complexes as High ...

    Indian Academy of Sciences (India)

    Density Functional Theory (DFT) was used to predict the optimized geometry of the complexes at TPSS/. 6-311G(d,p) ..... the molecules using Monte Carlo integration method as ..... age value that reflects the 50% probability of detona- tion.

  13. Mixed metal complexes of isoniazid and ascorbic acid: chelation ...

    African Journals Online (AJOL)

    Novel mixed complexes of isoniazid and ascorbic acid have been synthesized and characterized using infrared, electronic absorption data, elemental analysis, molar conductivity, melting point, thin layer chromatography and solubility. The metal ions involved in the complex formation are Cu2+, Zn2+ and Cd2+. The melting ...

  14. Plutonium solubilities

    International Nuclear Information System (INIS)

    Puigdomnech, I.; Bruno, J.

    1991-02-01

    Thermochemical data has been selected for plutonium oxide, hydroxide, carbonate and phosphate equilibria. Equilibrium constants have been evaluated in the temperature range 0 to 300 degrees C at a pressure of 1 bar to T≤100 degrees C and at the steam saturated pressure at higher temperatures. Measured solubilities of plutonium that are reported in the literature for laboratory experiments have been collected. Solubility data on oxides, hydroxides, carbonates and phosphates have been selected. No solubility data were found at temperatures higher than 60 degrees C. The literature solubility data have been compared with plutonium solubilities calculated with the EQ3/6 geochemical modelling programs, using the selected thermodynamic data for plutonium. (authors)

  15. Synthesis, characterization, X-ray crystal structure and conductometry studying of a number of new Schiff base complexes; a new example of binuclear square pyramidal geometry of Cu(II) complex bridged with an oxo group

    Science.gov (United States)

    Golbedaghi, Reza; Alavipour, Ehsan

    2015-11-01

    Three new binuclear Cu(II), Mn(II), Co(II) complexes [Cu2(L) (ClO4)](ClO4)2 (1), [Mn2(L) (ClO4)](ClO4)2 (2), and [Co2(L) (ClO4)](ClO4)2 (3), {L = 1,3-bis(2-((Z)-(2-aminopropylimino)methyl)phenoxy)propan-2-ol} have been synthesized. Single crystal X-ray structure analysis of complex 1 showed that the complex is binuclear and all nitrogen and oxygen atoms of ligand (N4O3) are coordinated to two Cu(II) center ions. In addition, the crystal structure studying shows, a perchlorate ion has been bridged to the Cu(II) metal centers. However, two distorted square pyramidal Cu(II) ions are bridged asymmetrically by a perchlorate ion and oxygen of hydroxyl group of Schiff base ligand. In addition, the conductometry behaviors of all complexes were studied in acetonitrile solution.

  16. Production of bioactive soluble interleukin-15 in complex with interleukin-15 receptor alpha from a conditionally-replicating oncolytic HSV-1.

    Directory of Open Access Journals (Sweden)

    David C Gaston

    Full Text Available Oncolytic type-1 herpes simplex viruses (oHSVs lacking the γ134.5 neurovirulence gene are being evaluated for treatment of a variety of malignancies. oHSVs replicate within and directly kill permissive cancer cells. To augment their anti-tumor activity, oHSVs have been engineered to express immunostimulatory molecules, including cytokines, to elicit tumor-specific immune responses. Interleukin-15 (IL-15 holds potential as an immunotherapeutic cytokine because it has been demonstrated to promote both natural killer (NK cell-mediated and CD8(+ T cell-mediated cytotoxicity against cancer cells. The purpose of these studies was to engineer an oHSV producing bioactive IL-15. Two oHSVs were constructed encoding murine (mIL-15 alone (J100 or with the mIL-15 receptor α (mIL-15Rα, J100D to determine whether co-expression of these proteins is required for production of bioactive mIL-15 from oHSV. The following were demonstrated: i both oHSVs retain replication competence and cytotoxicity in permissive tumor cell lines. ii Enhanced production of mIL-15 was detected in cell lysates of neuro-2a cells following J100D infection as compared to J100 infection, suggesting that mIL-15Rα improved mIL-15 production. iii Soluble mIL-15 in complex with mIL-15Rα was detected in supernates from J100D-infected, but not J100-infected, neuro-2a, GL261, and CT-2A cells. These cell lines vary in permissiveness to oHSV replication and cytotoxicity, demonstrating soluble mIL-15/IL-15Rα complex production from J100D was independent of direct oHSV effects. iv The soluble mIL-15/IL-15Rα complex produced by J100D was bioactive, stimulating NK cells to proliferate and reduce the viability of syngeneic GL261 and CT-2A cells. v J100 and J100D were aneurovirulent inasmuch as no neuropathologic effects were documented following direct inoculation into brains of CBA/J mice at up to 1x10(7 plaque forming units. The production of mIL-15/mIL-15Rα from multiple tumor lines, as well

  17. Demetalation of Fe, Mn, and Cu chelates and complexes: application to the NMR analysis of micronutrient fertilizers.

    Science.gov (United States)

    López-Rayo, Sandra; Lucena, Juan J; Laghi, Luca; Cremonini, Mauro A

    2011-12-28

    The application of nuclear magnetic resonance (NMR) for the quality control of fertilizers based on Fe(3+), Mn(2+), and Cu(2+) chelates and complexes is precluded by the strong paramagnetism of metals. Recently, a method based on the use of ferrocyanide has been described to remove iron from commercial iron chelates based on the o,o-EDDHA [ethylenediamine-N,N'bis(2-hydroxyphenylacetic)acid] chelating agent for their analysis and quantification by NMR. The present work extended that procedure to other paramagnetic ions, manganese and copper, and other chelating, EDTA (ethylenediaminetetraacetic acid), IDHA [N-(1,2-dicarboxyethyl)-d,l-aspartic acid], and complexing agents, gluconate and heptagluconate. Results showed that the removal of the paramagnetic ions was complete, allowing us to obtain (1)H NMR spectra characterized by narrow peaks. The quantification of the ligands by NMR and high-performance liquid chromatography showed that their complete recovery was granted. The NMR analysis enabled detection and quantification of unknown impurities without the need of pure compounds as internal standards.

  18. Water-soluble tetrapodal N, O ligands incorporating soft N-heterocycles for the selective complexation of Am(III) over Ln(III)

    Energy Technology Data Exchange (ETDEWEB)

    Heitzmann, M.; Gateau, Ch.; Delangle, P. [CEA Grenoble, Inac, Service de Chimie Inorganique et Biologique, UMR E 3 CEA UJF, FRE CNRS 3200, F-38054 Grenoble (France); Chareyre, L.; Miguirditchian, M.; Charbonnel, M.Ch. [CEA Marcoule, DEN, DRCP, SCPS, F-30207, Bagnols-sur-Ceze (France)

    2010-07-01

    A series of four water-soluble N, O-tetrapodal ligands derived from ethylenediamine, bearing hard acetate groups and soft N-heterocycles, either pyridine or pyrazine, was developed to study the impact of the softness of N-donors on the complexation properties with trivalent f ions. Two novel ligands of enhanced soft character, bearing three pyridines (L{sup 3py}) or three pyrazines (L{sup 3pz}), were synthesized and the related lanthanide complexes were studied in solution. The ligand containing three pyridyl-methyl moieties L{sup 3py} gives complexes with a coordination similar to EDTA, i.e. a hexa-dentate coordination mode as indicated by NMR and luminescence decays (q = 3) and stability constants in the range log {beta}{sub 110} = 6.99-9.3 (La-Lu). On the other hand, the softest molecule L{sup 3pz} forms much less stable complexes with log {beta}{sub 110} = 4.0-4.4 (La-Eu). The selective back-extraction of Am(III) from organic solutions containing 4f and 5f elements was tested with the four water-soluble complexing agents. The ligand L{sup 3pz} demonstrates poor stripping ability and selectivity. In contrast, the three ligands L{sup py}, L{sup pz} and L{sup 3py} give interesting back-extraction results with Eu/Am separation factors ranging from 36 to 46, which are significantly higher than with HEDTA. This exemplifies the role of the N-hetero-cycle softness in enhancing the separation between Am(III) and Eu(III). Interestingly, the pyrazine-based ligand, L{sup pz}, demonstrates the best stripping properties, with a distribution factor that approaches that of HEDTA in the same conditions (D{sub Am{approx}}0.3). This molecule is a good compromise between softness and hardness and forms complexes still stable at pH 3 due to its low basicity. (authors)

  19. Thermally-activated vortex dynamics in bismuth calcium strontium copper oxide (Bi2CaSr2Cu2O8+δ) studied by complex susceptibility measurements

    NARCIS (Netherlands)

    Emmen, J.H.P.M.; Brabers, V.A.M.; Jonge, de W.J.M.

    1991-01-01

    Complex AC magnetic susceptibility has been measured on Bi2CaSr2Cu2O8+d single crystals with hnc, Hdc|c-axis. It will be shown that field, frequency and temperature dependence of both ¿' and ¿¿ in a constant but sufficiently large DC magnetic field can quantitatively be described by

  20. Resolution of D- and L-glucoses by chiral N-octyl-beta-D-glycoside-Cu(II) complex adsorbed at the gas/liquid interface of small bubbles

    NARCIS (Netherlands)

    Sakai, M.; Miyazawa, K.; Jitsumatsu, H.; Kamio, K.; Mitsuiki, S.; Toh, N.; Sugihara, G.; Norde, W.

    2010-01-01

    A new technique of the jet drop method (JDM) was applied to a chiral molecular discrimination of optically active D- or L-glucose (guest) by chiral N-octyl-beta-D-glycoside (O beta DG)-Cu(II) complex (host) at the gas/liquid interface of small bubbles. The discrimination of glucoses as the guests is

  1. The Formation of Metal (M=Co(II), Ni(II), and Cu(II)) Complexes by Aminosilanes Immobilized within Mesoporous Molecular Sieves

    International Nuclear Information System (INIS)

    Park, Dong Ho; Park, Sung Soo; Choe, Sang Joon

    1999-01-01

    The immobilization of APTMS(3-(2-aminoethylamino)propyltrimethoxysilane) and AAPTMS(3-(2-(2-aminoethyl) aminoethylamino)propyltrimethoxysilane) on the surface of high quality mesoporous molecular sieves MCM-41 and MCM-48 have been confirmed by F.T.-IR spectroscopy, Raman spectroscopy, 29 Si solid state NMR, and a surface polarity measurement using Reichardt's dye. The formation of metal (Co(II), Ni(II), and Cu(II)) complexes by immobilized aminosilanes have been investigated by photoacoustic spectroscopy(PAS). The assignment of UV-Vis. PAS bands makes it possible to identify the structure of metal complexes within mesoporous molecular sieves. Co(II) ion may be coordinated mainly in a tetrahedral symmetry by two APTMS onto MCM-41, and in an octahedral one by two AAPTMS. Both Ni(II) and Cu(II) coordinated by aminosilanes within MCM-41 form possibly the octahedral complexes such as [Ni(APTMS) 2 (H 2 O) 2 ] 2+ , [Ni(AAPTMS) 2 ] 2+ , [Cu(APTMS) 2 (H 2 O) 2 ] 2+ , and [Cu(AAPTMS)(H 2 O) 3 ] 2+ , respectively. The PAS band shapes of complexes onto MCM-48 are similar to those of corresponding MCM-41 with the variation of PAS intensity. Most of metal ion(II) within MCM-41 and MCM-48 are coordinated by aminosilanes without the impregnation on the surface

  2. Grafting of [(64)Cu]-TPPF20 porphyrin complex on Functionalized nano-porous MCM-41 silica as a potential cancer imaging agent.

    Science.gov (United States)

    Fazaeli, Yousef; Feizi, Shahzad; Jalilian, Amir R; Hejrani, Ali

    2016-06-01

    Mesoporous silica, MCM-41, functionalized with 3-aminopropyltriethoxysilane (APTES) was investigated as a potential drug delivery system, using [(64)Cu]-5, 10, 15, 20-tetrakis penta fluorophenyl porphyrin complex. [(64)Cu]-TPPF20 complex was grafted on functionalized MCM-41. The product was characterized by paper chromatography, FTIR spectroscopy, low angle X-ray diffraction, CHN and TGA/DTA analyses and atomic force microscopy. The biological evaluations of the grafted complex, [(64)Cu]-TPPF20@NH2-MCM-41, were done in Fibrosarcoma tumor-bearing Sprague-Dawley rats using scarification studies and Sopha DST-XL Dual-Head SPECT system. The actual loading amount of aminopropyl groups was found about 1.6mmol per gram of final silica. The specific activity of the final compound was found to be 3Ci/g. Amine functionalized MCM-41 was found to be a good platform for theranostic radiopharmaceuticals such as copper-64 complexes. Considering the accumulation of the tracer in tumor cells, fast wash-out from normal tissues, the short half-life copper-64 and less imposed radiation doses to patients, [(64)Cu]-TPPF20@NH2-MCM-41 can potentially be a suitable candidate for tumor imaging applications and future PET studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Microscale Syntheses, Reactions, and 1H NMR Spectroscopic Investigations of Square Planar Macrocyclic Tetraamido-N Cu(III) Complexes Relevant to Green Chemistry

    Science.gov (United States)

    Uffelman, Erich S.; Doherty, Jonathan R.; Schulze, Carl; Burke, Amy L.; Bonnema, Kristen R.; Watson, Tanya T.; Lee, Daniel W., III

    2004-01-01

    Microscale fusions, description, and spectroscopic analysis of the reactivity of a square planar Cu(III) complex significant to green chemistry, are presented. The experiment also includes nine focal points on which pre-lab and post-lab questions are based, and the final exams reflect the students' comprehension of these and other features of…

  4. The complexity of non-Schmid behavior in the CuZnAl shape memory alloy

    Science.gov (United States)

    Alkan, S.; Ojha, A.; Sehitoglu, H.

    2018-05-01

    The paper addresses one of the most important yet overlooked phenomenon in shape memory research- the plastic slip response. We show that the slip response is highly crystal orientation dependent and we demonstrate the precise reasons behind such complex response. The fractional dislocations on {112} or {011} systems can be activated depending on the sample orientation and solutions are derived for the variations in disregistries and dislocation core spreadings. This leads to the calculation of critical resolved shear stress in close agreement with experimental trends. The results show considerable dependence of the flow behavior on the non-Schmid stress components and the proposed yield criterion captures the role of stress tensor components.

  5. Anthracyclines as radiosensitizers. A Cu(II) complex of a simpler analogue modifies DNA in Chinese Hamster V79 cells under low-dose γ radiation

    International Nuclear Information System (INIS)

    Saurabh Das; Mandal, P.C.

    2014-01-01

    Hydroxy-9,10-anthraquinones are structural analogues of anthracycline anticancer drugs showing similarity in physicochemical attributes, electrochemical behavior and biophysical interactions. 1,2-dihydroxy-9,10-anthraquinone (Q) and its complexes with Cu(II)/Ni(II) were studied for γ radiation induced modification of DNA in Chinese Hamster V79 cells. The amount of double stranded DNA remaining was ascertained by fluorometric analysis of DNA unwinding using ethidium bromide. Modification of double stranded DNA increased in the presence of Q and Cu(II)-Q when cells were irradiated (0-4.2 Gray). Ni(II)-Q was not that effective. Changing incubation time before recovery of DNA from cells there was evidence for DNA repair that was least for Cu(II)-Q treated cells. Minimum repair in case of Cu(II)-Q treated cells suggest the compound either assists radiation induced damage of agents responsible for repair or interacts with species like H 2 O 2 that assist in repair. Since a hydroxy-9,10-anthraquinone and its Cu(II) complex show radiosensitizing property, anthracyclines that contain a hydroxy-9,10-anthraquinone as the core moiety could also be tried as radiosensitizers in treating cancer. (author)

  6. Surface-driven, one-step chemical vapor deposition of γ-Al{sub 4}Cu{sub 9} complex metallic alloy film

    Energy Technology Data Exchange (ETDEWEB)

    Prud’homme, Nathalie [CIRIMAT, Université de Toulouse - CNRS, 4 allée Emile Monso, BP-44362, 31432 Toulouse Cedex 4 (France); Université Paris-Sud 11, LEMHE/ICMMO, Bat 410, 91405 Orsay Cedex (France); Duguet, Thomas, E-mail: thomas.duguet@ensiacet.fr [CIRIMAT, Université de Toulouse - CNRS, 4 allée Emile Monso, BP-44362, 31432 Toulouse Cedex 4 (France); Samélor, Diane; Senocq, François; Vahlas, Constantin [CIRIMAT, Université de Toulouse - CNRS, 4 allée Emile Monso, BP-44362, 31432 Toulouse Cedex 4 (France)

    2013-10-15

    The present paper is a paradigm for the one-step formation of complex intermetallic coatings by chemical vapor deposition. It genuinely addresses the challenge of depositing an intermetallic coating with comparable contents of Cu and Al. Depending on processing conditions, a pure γ-Al{sub 4}Cu{sub 9} and multi-phase Al-Cu films are grown with wetting properties of the former being similar to its bulk counterpart. The deposition process and its parametric investigation are detailed. Two metalorganic precursors are used taking into account their transport and chemical properties, and deposition temperature ranges. On line and ex situ characterizations enlighten the competition which occurs at the growing surface between molecular fragments, and which limits growth rates. Notably, introducing a partial pressure of hydrogen gas during deposition reduces Al growth rate from dimethylethylamine alane (DMEAA), by displacing the hydrogen desorption equilibrium. This Al partial growth rate decrease is not sufficient to achieve a Cu/Al atomic ratio that is high enough for the formation of intermetallics with close Al and Cu compositions. A fivefold increase of the flux of the gaseous copper(I) cyclopentadienyl triethylphosphine CpCuPEt{sub 3}, whereas the DMEAA flux remains constant, results in the targeted Al/Cu atomic ratio equal to 44/56. Nevertheless, the global growth rate is rendered extremely low by the deposition inhibition caused by a massive phosphine adsorption (-PEt{sub 3}). Despite these limitations, the results pave the way towards the conformal coating of complex surface geometries by such intermetallic compounds.

  7. Electrospray ionization mass spectrometric investigations of the complexation behavior of macrocyclic thiacrown ethers with bivalent transitional metals (Cu, Co, Ni and Zn).

    Science.gov (United States)

    Tsybizova, Alexandra; Tarábek, Ján; Buchta, Michal; Holý, Petr; Schröder, Detlef

    2012-10-15

    Heavy metals are both a problem for the environment and an important resource for industry. Their selective extraction by means of organic ligands therefore is an attractive topic. The coordination of three thiacrown ethers to late 3d-metal ions was investigated by a combination of electrospray ionization mass spectrometry (ESI-MS) and electron paramagnetic resonance (EPR). The mass spectrometric experiments were carried out in an ion trap mass spectrometer with an ESI source. Absolute binding constants were estimated by comparison with data for 18-crown-6/Na(+). EPR spectroscopy was used as a complementary method for investigating the Cu(I) /Cu(II) redox couple. The study found that thiacrown ethers preferentially bind traces of copper even at an excess of other metal ions (Co(II), Ni(II), and Zn(II)). The absolute association constants of the Cu(I) complexes were about 10(8) M(-1), and about two orders of magnitude lower for the other 3d-metal cations. The EPR spectra demonstrated that the reduction from Cu(II) to Cu(I) upon formation of the [(thiacrown)Cu](+) species takes place in solution. ESI-MS demonstrated that the three thiacrown ligands examined had high binding constants as well as good selectivities for copper(I) at low concentrations, and in the presence of other metal ions. By a combination of ESI-MS and EPR spectrometry it was shown that the reduction from Cu(II) to Cu(I) occurred in solution. Copyright © 2012 John Wiley & Sons, Ltd.

  8. Fe- and Cu-complex formation with artificial ligands investigated by ultra-high resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS: Implications for natural metal-organic complex studies

    Directory of Open Access Journals (Sweden)

    Hannelore Waska

    2016-07-01

    Full Text Available In recent years, electrospray-ionization mass spectrometry (ESI-MS has been increasingly used to complement the bulk determination of metal-ligand equilibria, for example via competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV. However, ESI-MS speciation analyses may be impacted by instrumental artefacts such as reduction reactions, fragmentation, and adduct formation at the ESI source, changes in the ionization efficiencies of the detected species in relation to sample matrix, and peak overlaps in response to increasing sample complexity. In our study, equilibria of the known artificial ligands citrate, ethylenediaminetetraacetic acid (EDTA, 1-nitroso-2-naphthol (NN, and salicylaldoxime (SA with iron (Fe and copper (Cu were investigated by ultra-high resolution ESI-MS, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS, under a variety of sample matrix and ionization settings. The acquired mass spectra were compared with metal-ligand equilibrium data from the literature as well as an adapted speciation model. Overall, the mass spectra produced representative species mentioned in previous reports and predicted by the speciation calculations, such as Fe(Cit, Cu(Cit2, Fe(EDTA, Cu(EDTA, Fe(NN3, and Cu(SA2. The analyses furthermore revealed new species which had been hypothesized but not measured directly using other methods, for example ternary complexes of citrate with Fe and Cu, Cu(SA monomers, and the dimer Fe(SA2. Finally, parallel measurements of a Cu+SA calibration series and a Cu+SA+EDTA competition series indicated that FT-ICR-MS can produce linear responses and low detection limits analogous to those of ACSV. We propose that ultra-high resolution FT-ICR-MS can be used as a representative tool to study interactions of trace metals with artificial as well as natural, unknown ligands at the molecular level.

  9. Spray deposition of water-soluble multiwall carbon nanotube and Cu2ZnSnSe4 nanoparticle composites as highly efficient counter electrodes in a quantum dot-sensitized solar cell system

    Science.gov (United States)

    Zeng, Xianwei; Xiong, Dehua; Zhang, Wenjun; Ming, Liqun; Xu, Zhen; Huang, Zhanfeng; Wang, Mingkui; Chen, Wei; Cheng, Yi-Bing

    2013-07-01

    In this paper, low-cost counter electrodes (CEs) based on water-soluble multiwall carbon nanotube (MWCNT) and Cu2ZnSnSe4 nanoparticle (CZTSe NP) composites have been successfully introduced into a quantum dot-sensitized solar cell (QDSC) system. Suitable surface modification allows the MWCNTs and CZTSe NPs to be homogeneously dispersed in water, facilitating the subsequent low-temperature spray deposition of high quality composite films with different composite ratios. The electrochemical catalytic activity of the composite CEs has been critically compared by electrochemical impedance spectroscopy and Tafel-polarization analysis. It is found that the composite CE at the MWCNT : CZTSe ratio of 0.1 offers the best performance, leading to an optimal solar cell efficiency of 4.60%, which is 50.8% higher than that of the Pt reference CE. The as-demonstrated higher catalytic activity of the composite CEs compared to their single components could be ascribed to the combination of the fast electron transport of the MWCNTs and the high catalytic activity of CZTSe NPs.In this paper, low-cost counter electrodes (CEs) based on water-soluble multiwall carbon nanotube (MWCNT) and Cu2ZnSnSe4 nanoparticle (CZTSe NP) composites have been successfully introduced into a quantum dot-sensitized solar cell (QDSC) system. Suitable surface modification allows the MWCNTs and CZTSe NPs to be homogeneously dispersed in water, facilitating the subsequent low-temperature spray deposition of high quality composite films with different composite ratios. The electrochemical catalytic activity of the composite CEs has been critically compared by electrochemical impedance spectroscopy and Tafel-polarization analysis. It is found that the composite CE at the MWCNT : CZTSe ratio of 0.1 offers the best performance, leading to an optimal solar cell efficiency of 4.60%, which is 50.8% higher than that of the Pt reference CE. The as-demonstrated higher catalytic activity of the composite CEs compared to

  10. Toxicity assessment using Lactuca sativa L. bioassay of the metal(loid)s As, Cu, Mn, Pb and Zn in soluble-in-water saturated soil extracts from an abandoned mining site

    Energy Technology Data Exchange (ETDEWEB)

    Bagur-Gonzalez, Maria Gracia [Univ. of Granada, Faculty of Sciences, Dept. of Analytical Chemistry, Granada (Spain); Univ. of Granada-CSIC, Inst. Andaluz de Ciencias de la Tierra, Faculty of Sciences, Granada (Spain); Estepa-Molina, Carmen [Univ. of Granada, Faculty of Sciences, Dept. of Mineralogy and Petrology, Granada (Spain); Martin-Peinado, Francisco [Univ. of Granada, Faculty of Sciences, Dept. of Soil Science, Granada (Spain); Morales-Ruano, Salvador [Univ. of Granada-CSIC, Inst. Andaluz de Ciencias de la Tierra, Faculty of Sciences, Granada (Spain); Univ. of Granada, Faculty of Sciences, Dept. of Mineralogy and Petrology, Granada (Spain)

    2011-02-15

    We used the different soluble-in-water concentrations of As, Cu, Mn, Pb and Zn from contaminated soils in an abandoned mining area (anthropogenic origin) to assess the phytotoxicity of the abandoned site using the results obtained with a Lactuca sativa L. bioassay. Material and methods The study has been carried out on potentially polluted samples from the Rodalquilar mining district (southern Spain). The area was sampled according to the different metallurgical treatments for gold extraction used in each one: dynamic cyanidation and heap leaching. The saturation extracts were obtained by filtering each saturated paste with a vacuum-extraction pump, in which measurements of metal(loid) concentrations, pH and electrical conductivity were made. The variables evaluated in the bioassay, defined as toxicity indices ranging from -1 (maximum phytotoxicity) to >0 (hormesis), were seed germination (SG) and root elongation (RE) of lettuce seeds. Results and discussion In areas with a low degree of contamination, the most sensitive toxicity index is RE, whereas in highly contaminated areas, both RE and SG are good estimators of soil toxicity. According to these results, samples from the western area showed moderate to low toxicity, which was closely related to water-soluble As concentrations. Samples from the eastern area had a high degree of toxicity in 40% of the soils. Conclusions The comparison of the two indices (SG and RE) defined using the L. sativa L. bioassay indicates that, for areas with a low degree of contamination, the most sensitive toxicity index is RE, whereas in highly contaminated areas, both RE and SG are good estimators of soil phytotoxicity. Unsupervised pattern recognition methods such as HCA and PCA enabled us to conclude that the low/moderate phytotoxicity of the soils is related to the extraction process used for the recovery of gold (mainly dynamic cyanidation in tanks located in the eastern area) and to the As and Pb contents. (orig.)

  11. Synthesis and characterization of Ni(II, Cu(II and Co(III complexes with polyamine-containing macrocycles bearing an aminoethyl pendant arm

    Directory of Open Access Journals (Sweden)

    K. S. SIDDIQI

    2004-09-01

    Full Text Available Reaction of [M(ppn2]X2 (where M = Cu(II, Ni(II, Co(II and ppn = 1,3-diaminopropane with formaldehyde and ethylenediamine in methanol results in the ready formation of a 16-membered macrocyclic complex. The complexes were characterized by elemental anlysis, IR, EPR, electronic spectral data, magnetic moments and conductance measurements. The Cu(II, Ni(II and Co(III complexes are coordinated axially with both pendant groups of the hexadentate macrocycle. These pendant donors are attached to the macrocycle by a carbon chain. The electrical conductivities of the Cu(II and Ni(II chelates indicated them to be 1:2 electrolytes whilst those of Co(III is a 1:3 electrolyte in DMSO. The EPR spectrum of the copper complex exhibited G at 3.66, which indicates a considerable exchange interaction in the complex. Spectroscopic evidence suggests that in all of the complexes the metal ion is in an octahedral environment.

  12. Dichloro (bis[diphenylthiourea] cadmium complex as a precursor for HDA-capped CdS nanoparticles and their solubility in water

    Directory of Open Access Journals (Sweden)

    Tshinyadzo R. Tshikhudo

    2010-07-01

    Full Text Available A single-source precursor route has been explored by using the diphenylthiourea cadmium complex as the source of cadmium sulphide (CdS nanoparticles. The reaction was carried out using hexadecylamine (HDA as the solvent and stabilising agent for the particles. The phenylthiourea complex was synthesised and characterised by means of a combination of spectroscopic techniques, microanalysis and X-ray crystal structural analysis. The diphenylthiourea complex was thermolysed in HDA at 120 °C for 1 h to produce CdS nanoparticles. The CdS nanoparticles prepared were made water-soluble via a ligand exchange reaction involving the use of pyridine to displace HDA. The pyridine was, in turn, replaced by glucose and glucuronic acid. The absorption and emission spectra showed the typical features of quantum confinement for the nanoparticles for both HDA-capped and glucose- or glucuronic acid-capped CdS nanoparticles. The change in the capping groups, from HDA to glucose and glucuronic acid, resulted in absorption and emission features that were almost similar, with only slight red-shifting and tailing.

  13. Aqueous solubility of calcium citrate and interconversion between the tetrahydrate and the hexahydrate as a balance between endothermic dissolution and exothermic complex formation

    DEFF Research Database (Denmark)

    Hedegaard, Martina Vavrusova; Skibsted, Leif Horsfelt

    2016-01-01

    Aqueous solubility of calcium citrate tetrahydrate was found to decrease with increasing temperature, while solubility of hexahydrate increased with a transition temperature at 51.6 °C. Excess citrate increased calcium citrate solubility but decreased the calcium ion activity of the saturated sol...

  14. Solubility Products of M(II) - Carbonates

    International Nuclear Information System (INIS)

    Grauer, Rolf; Berner, Urs

    1999-01-01

    Many solubility data for M(II) carbonates commonly compiled in tables are contradictory and sometimes obviously wrong. The quality of such data has been evaluated based on the original publications and reliable solubility constants have been selected for the carbonates of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb with the help of cross-comparisons. (author)

  15. Separation of americium by liquid-liquid extraction using diglycol-amides water-soluble complexing agents

    Energy Technology Data Exchange (ETDEWEB)

    Chapron, S.; Marie, C.; Pacary, V.; Duchesne, M.T.; Miguirditchian, M. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Processses Departement, 30207 Bagnols-sur-Ceze (France); Arrachart, G.; Pellet-Rostaing, S. [Institut de Chimie Separative de Marcoule, LTSM, Bat 426, F-30207 Bagnols-sur- Ceze (France)

    2016-07-01

    Recycling americium (Am) alone from spent nuclear fuels is an important option studied for the future nuclear cycle (Generation IV systems) since Am belongs to the main contributors of the long-term radiotoxicity and heat power of final waste. Since 2008, a liquid-liquid extraction process called EXAm has been developed by the CEA to allow the recovery of Am alone from a PUREX raffinate (a dissolution solution already cleared from U, Np and Pu). A mixture of DMDOHEMA (N,N'-dimethyl-N,N'-dioctyl-2-(2-(hexyloxy)ethyl)-malonamide) and HDEHP (di-2-ethylhexylphosphoric acid) in TPH is used as the solvent and the Am/Cm selectivity is improved using TEDGA (N,N,N',N'-tetraethyl-diglycolamide) as a selective complexing agent to maintain Cm and heavier lanthanides in the acidic aqueous phase (5 M HNO{sub 3}). Americium is then stripped selectively from light lanthanides at low acidity (pH=3) with a poly-aminocarboxylic acid. The feasibility of sole Am recovery was already demonstrated during hot tests in ATALANTE facility and the EXAm process was adapted to a concentrated raffinate to optimize the process compactness. The speciation of TEDGA complexes formed in the aqueous phase with Am, Cm and lanthanides was studied to better understand and model the behavior of TEDGA in the process. Some Ln-TEDGA species are extracted into the organic phase and this specific chemistry might play a role in the Am/Cm selectivity improvement. Hence the hydrophilicity-lipophilicity balance of the complexing agent is an important parameter. In this comprehensive study, new analogues of TEDGA were synthesized and tested in the EXAm process conditions to understand the relationship between their structure and selectivity. New derivatives of TEDGA with different N-alkyl chain lengths and ramifications were synthesized. The impact of lipophilicity on ligand partitioning and Am/Cm selectivity was investigated. (authors)

  16. Polymerization of Methyl Methacrylate Catalyzed by Co(II), Cu(II), and Zn(II) Complexes Bearing N-Methyl-N-((pyridin-2-yl)methyl) cyclohexanamine

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Seoung Hyun; Lee, Hyosun [Kyungpook National University, Daegu (Korea, Republic of); Shin, Jongwon [POSTECH, Pohang (Korea, Republic of); Nayab, Saira [Shaheed Benazir Bhutto University, Sheringal (Pakistan)

    2016-05-15

    We demonstrated the synthesis and characterization of Co(II), Cu(II), and Zn(II) complexes ligated to N-methyl-N-((pyridin-2-yl)methyl)cyclohexanamine. The complex [Co(nmpc)Cl{sub 2}] in the presence of MMAO showed the highest catalytic activity for MMA polymerization at 60 °C compared with its Zn(II) and Cu(II) analogs. The metal center showed an obvious influence on the catalytic activity, although this appeared to have no effect on the stereo-regularity of the resultant PMMA. X-ray diffraction analysis revealed that [Co(nmpc)Cl{sub 2}] and [Zn(nmpc)Cl{sub 2}] crystallized in the monoclinic system with space group P2{sub 1}/c and existed as monomeric and solvent-free complexes.

  17. DFT predictions, synthesis, stoichiometric structures and anti-diabetic activity of Cu (II) and Fe (III) complexes of quercetin, morin, and primuletin

    Science.gov (United States)

    Jabeen, Erum; Janjua, Naveed Kausar; Ahmed, Safeer; Murtaza, Iram; Ali, Tahir; Masood, Nosheen; Rizvi, Aysha Sarfraz; Murtaza, Gulam

    2017-12-01

    The current study is aimed at the synthesis of Cu (II) and Fe (III) complexes of three flavonoids {morin (mor), quercetin (quer) and primuletin (prim)} and characterization through UV-Vis spectroscopy, cyclic voltammetry, FTIR, and thermal analysis. Structure prediction through DFT calculation was supported by experimental data. Benesi-Hildebrand equation was modified to function for 1:2 Cu-flavonoid and 1:3 Fe-flavonoid complexes. DFT predictions revealed that out of poly chelation sites present in morin and quercetin, 3-OH site was utilized as preferable chelation site while primuletin chelated through 5-OH position. In-vivo trials revealed the complexes to have better anti-diabetic potential than respective flavonoid. Fls/M-Fls proved as antagonistic to Alloxan induced diabetes and also retained anti-diabetic activity even in the presence of (2-hydroxypropyl)-β-cyclodextrin (HPβCD).

  18. New Cu (II), Co(II) and Ni(II) complexes of chalcone derivatives: Synthesis, X-ray crystal structure, electrochemical properties and DFT computational studies

    Science.gov (United States)

    Tabti, Salima; Djedouani, Amel; Aggoun, Djouhra; Warad, Ismail; Rahmouni, Samra; Romdhane, Samir; Fouzi, Hosni

    2018-03-01

    The reaction of nickel(II), copper(II) and cobalt(II) with 4-hydroxy-3-[(2E)-3-(1H-indol-3-yl)prop-2-enoyl]-6-methyl-2H-pyran-2-one (HL) leads to a series of new complexes: Ni(L)2(NH3), Cu(L)2(DMF)2 and Co(L)2(H2O). The crystal structure of the Cu(L)2(DMF)2 complex have been determined by X-ray diffraction methods. The Cu(II) lying on an inversion centre is coordinated to six oxygen atoms forming an octahedral elongated. Additionally, the electrochemical behavior of the metal complexes were investigated by cyclic voltammetry at a glassy carbon electrode (GC) in CH3CN solutions, showing the quasi-reversible redox process ascribed to the reduction of the MII/MI couples. The X-ray single crystal structure data of the complex was matched excellently with the optimized monomer structure of the desired compound; Hirschfeld surface analysis supported the packed crystal lattice 3D network intermolecular forces. HOMO/LUMO energy level and the global reactivity descriptors quantum parameters are also calculated. The electrophilic and nucleophilic potions in the complex surface are theoretically evaluated by molecular electrostatic potential and Mulliken atomic charges analysis.

  19. Synthesis, Spectral and Antimicrobial Studies of Some Co(II, Ni(II and Cu(II Complexes Containing 2-Thiophenecarboxaldehyde Moiety

    Directory of Open Access Journals (Sweden)

    A. P. Mishra

    2012-01-01

    Full Text Available Some new Schiff base metal complexes of Co(II, Ni(II and Cu(II derived from 3-chloro-4-fluoroaniline (HL1 and 4-fluoroaniline (HL2 with 2-thiophenecarboxaldehyde have been synthesized and characterized by elemental analysis, FT-IR, FAB-mass, molar conductance, electronic spectra, ESR and magnetic susceptibility. The complexes exhibit coordination number 4 or 6. The complexes are colored and stable in air. Analytical data revealed that all the complexes exhibited 1:2 (metal: ligand ratio. FAB-mass data show degradation pattern of the complexes. The Schiff base and metal complexes show a good activity against the bacteria; B. subtilis, E. coli and S. aureus and fungi A. niger, A. flavus and C. albicans. The antimicrobial results also indicate that the metal complexes are better antimicrobial agents as compared to the Schiff bases.

  20. A sensor for acetaminophen in a blood medium using a Cu(II)-conducting polymer complex modified electrode

    International Nuclear Information System (INIS)

    Boopathi, Mannan; Won, Mi-Sook; Shim, Yoon-Bo

    2004-01-01

    Complexation of Cu ions in a terthiophene carboxylic acid (TTCA) polymer film resulted an enhanced anodic current for acetaminophen oxidation when compared to polymer coated and bare glassy carbon electrodes in human blood and buffer media. Scanning electron microscopy (SEM) and ESCA experiments indicate the involvement of copper in the electrocatalytic oxidation of acetaminophen. No interference was observed from other biologically important and phenolic compounds used with this modified electrode. Especially, the non-interference from N-acetylcysteine, an antidote for the treatment of acetaminophen poisoning, reveals the proposed method's superiority in medicinal applications. In addition, the present modified electrode avoids surface fouling at higher concentrations of acetaminophen. The calibration range obtained with CV was based between 2.0x10 -5 and 5.0x10 -3 M [r 2 =0.997 (n=5, R.S.D.=2.5%); DL=5.0x10 -6 M (S/N=3)]. The analytical utility of the modified electrode was achieved by analyzing the content of acetaminophen in different drugs without pretreatment using CV and amperometric techniques

  1. Spray deposition of water-soluble multiwall carbon nanotube and Cu2ZnSnSe4 nanoparticle composites as highly efficient counter electrodes in a quantum dot-sensitized solar cell system.

    Science.gov (United States)

    Zeng, Xianwei; Xiong, Dehua; Zhang, Wenjun; Ming, Liqun; Xu, Zhen; Huang, Zhanfeng; Wang, Mingkui; Chen, Wei; Cheng, Yi-Bing

    2013-08-07

    In this paper, low-cost counter electrodes (CEs) based on water-soluble multiwall carbon nanotube (MWCNT) and Cu2ZnSnSe4 nanoparticle (CZTSe NP) composites have been successfully introduced into a quantum dot-sensitized solar cell (QDSC) system. Suitable surface modification allows the MWCNTs and CZTSe NPs to be homogeneously dispersed in water, facilitating the subsequent low-temperature spray deposition of high quality composite films with different composite ratios. The electrochemical catalytic activity of the composite CEs has been critically compared by electrochemical impedance spectroscopy and Tafel-polarization analysis. It is found that the composite CE at the MWCNT : CZTSe ratio of 0.1 offers the best performance, leading to an optimal solar cell efficiency of 4.60%, which is 50.8% higher than that of the Pt reference CE. The as-demonstrated higher catalytic activity of the composite CEs compared to their single components could be ascribed to the combination of the fast electron transport of the MWCNTs and the high catalytic activity of CZTSe NPs.

  2. Standardization and application of the solid phase C1q radioimmunoassay using soluble tetanus toxoid-antitetanus immune complexes in sera of patients with chronic polyarthritis and Lupus erythematodes

    International Nuclear Information System (INIS)

    Menzel, E.J.; Steffen, C.; Smolen, J.

    1982-01-01

    Soluble tetanus-antitetanus immune complexes were prepared with affinity-chromatography and gel chromatography. Serial dilutions of these immune complex preparations were tested in a solid phase C1q radioimmunoassay. Soluble immune complexes as well as aggregated human gamma globulin of identical protein concentrations were comparatively investigated. Soluble immune complexes rendered a more sensitive standardization of RIA. According to these observations a relation between μg/ml equivalents of defined tetanus-antitetanus complexes and ng second antibody obtained in C1q-RIA was calculated. Upper limit of mean values and two standard deviations of ng second antibody obtained in investigations of 55 normal sera was designated as 1 unit immune complexes and regarded as border line of negative results. Multiplication of μg/ml immune complex equivalents of 1 unit led to a scale of 1 to 15 units, showing the area of positive results. According to these values a standardization curve was constructed allowing a conversion of ng-second antibody obtained in serum investigations into immune complex units equivalent to defined standard immune complexes. With this curve investigation results of 56 RA sera and 21 SLE sera were expressed in the range of units, making a distinct gradation of positive results and a clear cut separation of positive and negative results possible. SLE sera of patients in acute stage showed highly positive results. (orig.) [de

  3. Standardization and application of the solid phase C1q radioimmunoassay using soluble tetanus toxoid-antitetanus immune complexes in sera of patients with chronic polyarthritis and Lupus erythematodes

    Energy Technology Data Exchange (ETDEWEB)

    Menzel, E J; Steffen, C; Smolen, J

    1982-11-22

    Soluble tetanus-antitetanus immune complexes were prepared with affinity-chromatography and gel chromatography. Serial dilutions of these immune complex preparations were tested in a solid phase C1q radioimmunoassay. Soluble immune complexes as well as aggregated human gamma globulin of identical protein concentrations were comparatively investigated. Soluble immune complexes rendered a more sensitive standardization of RIA. According to these observations a relation between ..mu..g/ml equivalents of defined tetanus-antitetanus complexes and ng second antibody obtained in C1q-RIA was calculated. Upper limit of mean values and two standard deviations of ng second antibody obtained in investigations of 55 normal sera was designated as 1 unit immune complexes and regarded as border line of negative results. Multiplication of ..mu..g/ml immune complex equivalents of 1 unit led to a scale of 1 to 15 units, showing the area of positive results. According to these values a standardization curve was constructed allowing a conversion of ng-second antibody obtained in serum investigations into immune complex units equivalent to defined standard immune complexes. With this curve investigation results of 56 RA sera and 21 SLE sera were expressed in the range of units, making a distinct gradation of positive results and a clear cut separation of positive and negative results possible. SLE sera of patients in acute stage showed highly positive results.

  4. Zeolite-encapsulated Co(II), Mn(II), Cu(II) and Cr(III) salen complexes as catalysts for efficient selective oxidation of benzyl alcohol

    Science.gov (United States)

    Li, F. H.; Bi, H.; Huang, D. X.; Zhang, M.; Song, Y. B.

    2018-01-01

    Co(II), Mn(II), Cu(II) and Cr(III) salen type complexes were synthesized in situ in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. Data of characterization indicates the formation of metal salen complexes in the pores without affecting the zeolite framework structure, the absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activity results show that Cosalcyen Y exhibited higher catalytic activity in the water phase selective oxidation of benzyl alcohol, which could be attributed to their geometry and the steric environment of the metal actives sites.

  5. Polynuclear water-soluble dinitrosyl iron complexes with cysteine or glutathione ligands: electron paramagnetic resonance and optical studies.

    Science.gov (United States)

    Vanin, Anatoly F; Poltorakov, Alexander P; Mikoyan, Vasak D; Kubrina, Lyudmila N; Burbaev, Dosymzhan S

    2010-09-15

    Electron paramagnetic resonance and optical spectrophotometric studies have demonstrated that low-molecular dinitrosyl iron complexes (DNICs) with cysteine or glutathione exist in aqueous solutions in the form of paramagnetic mononuclear (capital EM, Cyrillic-DNICs) and diamagnetic binuclear complexes (B-DNICs). The latter represent Roussin's red salt esters and can be prepared by treatment of aqueous solutions of Fe(2+) and thiols (small er, Cyrilliccapital EN, Cyrillic 7.4) with gaseous nitric oxide (NO) at the thiol:Fe(2+) ratio 1:1. capital EM, Cyrillic-DNICs are synthesized under identical conditions at the thiol:Fe(2+) ratios above 20 and produce an EPR signal with an electronic configuration {Fe(NO)(2)}(7) at g(aver.)=2.03. At neutral pH, aqueous solutions contain both M-DNICs and B-DNICs (the content of the latter makes up to 50% of the total DNIC pool). The concentration of B-DNICs decreases with a rise in pH; at small er, Cyrilliccapital EN, Cyrillic 9-10, the solutions contain predominantly M-DNICs. The addition of thiol excess to aqueous solutions of B-DNICs synthesized at the thiol:Fe(2+) ratio 1:2 results in their conversion into capital EM, Cyrillic-DNICs, the total amount of iron incorporated into M-DNICs not exceeding 50% of the total iron pool in B-DNICs. Air bubbling of cys-capital EM, Cyrillic-DNIC solutions results in cysteine oxidation-controlled conversion of capital EM, Cyrillic-DNICs first into cys-B-DNICs and then into the EPR-silent compound capital HA, Cyrillic able to generate a strong absorption band at 278 nm. In the presence of glutathione or cysteine excess, compound capital HA, Cyrillic is converted into B-DNIC/M-DNIC and is completely decomposed under effect of the Fe(2+) chelator small o, Cyrillic-phenanthroline or N-methyl-d-glucamine dithiocarbamate (MGD). Moreover, MGD initiates the synthesis of paramagnetic mononitrosyl iron complexes with MGD. It is hypothesized that compound capital HA, Cyrillic represents a polynuclear

  6. Accomplishing simple, solubility-based separations of rare earth elements with complexes bearing size-sensitive molecular apertures.

    Science.gov (United States)

    Bogart, Justin A; Cole, Bren E; Boreen, Michael A; Lippincott, Connor A; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-12-27

    Rare earth (RE) metals are critical components of electronic materials and permanent magnets. Recycling of consumer materials is a promising new source of rare REs. To incentivize recycling, there is a clear need for the development of simple methods for targeted separations of mixtures of RE metal salts. Metal complexes of a tripodal hydroxylaminato ligand, TriNOx 3- , featured a size-sensitive aperture formed of its three η 2 -(N,O) ligand arms. Exposure of cations in the aperture induced a self-associative equilibrium comprising RE(TriNOx)THF and [RE(TriNOx)] 2 species. Differences in the equilibrium constants K dimer for early and late metals enabled simple separations through leaching. Separations were performed on RE1/RE2 mixtures, where RE1 = La-Sm and RE2 = Gd-Lu, with emphasis on Eu/Y separations for potential applications in the recycling of phosphor waste from compact fluorescent light bulbs. Using the leaching method, separations factors approaching 2,000 were obtained for early-late RE combinations. Following solvent optimization, >95% pure samples of Eu were obtained with a 67% recovery for the technologically relevant Eu/Y separation.

  7. Soluble CD163

    DEFF Research Database (Denmark)

    Møller, Holger J

    2012-01-01

    CD163 is an endocytic receptor for haptoglobin-hemoglobin complexes and is expressed solely on macrophages and monocytes. As a result of ectodomain shedding, the extracellular portion of CD163 circulates in blood as a soluble protein (sCD163) at 0.7-3.9 mg/l in healthy individuals. The function o...

  8. The Nokomis Cu-Ni-PGE Deposit, Duluth Complex: A sulfide-bearing, crystal-laden magmatic slurry

    Science.gov (United States)

    Peterson, D. M.

    2009-12-01

    Duluth Metals Limited’s Nokomis deposit is the most recently discovered Cu-Ni-PGE deposit in the 1.1 Ga. Duluth Complex, Minnesota. The deposit was discovered utilizing a genetic ore deposit model that identified and back-tracked channelized magma flow within the basal zone of the South Kawishiwi intrusion (SKI). The model led to exploratory drilling in 2006, deposit discovery and initial resource estimation in 2007, and significant resource expansion in 2008, all in a period of 18 months. The deposit’s updated 2008 NI 43-101 compliant Resource Estimate, based on 108 holes drilled by Duluth Metals and 52 historic drill holes on and off the property, contains 449 million tonnes of Indicated Resources grading 0.624% copper, 0.199% nickel, and 0.600 grams per tonne of total precious metals (TPM = Platinum+Palladium+Gold), and an additional 284 million tonnes of Inferred Resources grading 0.627% copper, 0.194% nickel, and 0.718 grams per tonne of TPM. The combined Indicated and Inferred Resources contain approximately 10 billion lbs Cu, 3.1 billion lbs Ni, 165 million lbs Co, 4 million ounces Pt, 9 million ounces Pd, and 2 million ounces of Au. Within these NI 43-101 resources are large tonnages of higher grade material, and the company has commenced an internal research program to identify the geologic controls on the formation nickel-rich and PGE-rich mineralization in the SKI, as well as copper-PGE rich mineralization in the footwall Archean rocks. To date, Duluth Metals has drilled more than 500,000 Ft. (~155,000 m) of core in 155 holes into the deposit, and has only drilled about half of the property. The ore deposit model was developed in cooperation with researchers from the Natural Resources Research Institute of the University of Minnesota, Duluth. As well, research and collaboration with faculty and students at Johns Hopkins University on the Ferrar Dolerites of the Antarctic Dry Valleys has played a key role in developing the magmatic model for the

  9. Soluble immune complexes shift the TLR-induced cytokine production of distinct polarized human macrophage subsets towards IL-10.

    Directory of Open Access Journals (Sweden)

    Carmen A Ambarus

    Full Text Available BACKGROUND: Costimulation of murine macrophages with immune complexes (ICs and TLR ligands leads to alternative activation. Studies on human myeloid cells, however, indicate that ICs induce an increased pro-inflammatory cytokine production. This study aimed to clarify the effect of ICs on the pro- versus anti-inflammatory profile of human polarized macrophages. MATERIALS AND METHODS: Monocytes isolated from peripheral blood of healthy donors were polarized for four days with IFN-γ, IL-4, IL-10, GM-CSF, M-CSF, or LPS, in the presence or absence of heat aggregated gamma-globulins (HAGGs. Phenotypic polarization markers were measured by flow cytometry. Polarized macrophages were stimulated with HAGGs or immobilized IgG alone or in combination with TLR ligands. TNF, IL-6, IL-10, IL-12, and IL-23 were measured by Luminex and/or RT-qPCR. RESULTS: HAGGs did not modulate the phenotypic polarization and the cytokine production of macrophages. However, HAGGs significantly altered the TLR-induced cytokine production of all polarized macrophage subsets, with the exception of MΦ(IL-4. In particular, HAGGs consistently enhanced the TLR-induced IL-10 production in both classically and alternatively polarized macrophages (M1 and M2. The effect of HAGGs on TNF and IL-6 production was less pronounced and depended on the polarization status, while IL-23p19 and IL-12p35 expression was not affected. In contrast with HAGGs, immobilized IgG induced a strong upregulation of not only IL-10, but also TNF and IL-6. CONCLUSION: HAGGs alone do not alter the phenotype and cytokine production of in vitro polarized human macrophages. In combination with TLR-ligands, however, HAGGs but not immobilized IgG shift the cytokine production of distinct macrophage subsets toward IL-10.

  10. Synthesis, characterization and anti-fungal evaluation of Ni(II and Cu(II complexes with a derivative of 4-aminoantipyrine

    Directory of Open Access Journals (Sweden)

    Monika Tyagi

    2017-01-01

    Full Text Available Transition metal complexes of Ni(II and Cu(II metal ions with the general stoichiometry [M(LX]X and [M(LSO4], where M = Ni(II and Cu(II, L = (1E-N-((5-((E-(2,3-dimethyl-1-phenyl-4-pyrazolineiminomethylthiophen-2-ylmethylene-2,3-dimethyl-1-phenyl-4-pyrazolineamine and X = Cl−, NO3− and SO42−, have been synthesized and characterized. The synthesized ligand and metal complexes were characterized by 1H NMR, IR, mass spectrometry, UV–Vis spectra and EPR. In molecular modelling, the geometries of the Schiff's base and metal complexes were fully optimized with respect to the energy using the 6-31g(d,p basis set. The nickel(II complexes were found to have octahedral geometry, whereas the copper(II complexes were of tetragonal geometry. The covalency factor (β and orbital reduction factor (k suggest the covalent nature of the complexes. To develop broad spectrum new molecules against seed-borne fungi, the minimum inhibitory concentration (MIC of the ligand and its metal complexes was evaluated by the serial dilution method.

  11. Synthesis, characterization, DNA/protein interaction and cytotoxicity studies of Cu(II) and Co(II) complexes derived from dipyridyl triazole ligands

    Science.gov (United States)

    Zhang, Wei; Yao, Di; Wei, Yi; Tang, Jie; Bian, He-Dong; Huang, Fu-Ping; Liang, Hong

    2016-06-01

    Four different transition metal complexes containing dipyridyl triazole ligands, namely [Cu(abpt)2Cl2]·2H2O (1), [Cu(abpt)2(ClO4)2] (2), [Co2(abpt)2(H2O)2Cl2]·Cl2·4H2O (3) and [Co2(Hbpt)2(CH3OH)2(NO3)2] (4) have been designed, synthesized and further structurally characterized by X-ray crystallography, ESI-MS, elemental analysis, IR and Raman spectroscopy. In these complexes, the both ligands act as bidentate ligands with N, N donors. DNA binding interactions with calf thymus DNA (ct-DNA) of the ligand and its complexes 1 ~ 4 were investigated via electronic absorption, fluorescence quenching, circular dichroism and viscosity measurements as well as confocal Laser Raman spectroscopy. The results show these complexes are able to bind to DNA via the non-covalent mode i.e. intercalation and groove binding or electrostatic interactions. The interactions with bovine serum albumin (BSA) were also studied using UV-Vis and fluorescence spectroscopic methods which indicated that fluorescence quenching of BSA by these compounds was the presence of both static and dynamic quenching. Moreover, the in vitro cytotoxic effects of the complexes against four cell lines SK-OV-3, HL-7702, BEL7404 and NCI-H460 showed the necessity of the coordination action on the biological properties on the respective complex and that all four complexes exhibited substantial cytotoxic activity.

  12. Abnormalities in soluble CD147 / MMPs / TIMPs axis in Ankylosing Spondylitis patients with and without a history of Acute Anterior Uveitis / Anomalii ale axei CD147 solubil / MMPs / TIMPs la pacienții cu spondilită anchilozantă cu sau fără uveită acută anterioară

    Directory of Open Access Journals (Sweden)

    Mitulescu Traian Costin

    2014-12-01

    Full Text Available Spondilita Anchilozantă (SA este prototipul formei axiale a spondiloartritelor. În pofida studiilor extinse, sunt încă incomplet înțelese mecansimele complexe legate de procesele celulare și moleculare anormale din SA. Printre mediatorii inflamației, cum ar fi citokinele proinflamatoare, NOS-2, chemokinele, care conduc la inflamație, metaloproteinazele de matrice (MMPs joacă un rol important în procesele inflamatoare care caracterizează SA. De aceea, ne-am propus să evaluăm dacă perturbări ale homeostaziei inductorului extracelular de MMPs (EMMPRIN/CD147, MMPs și inhibitorilor tisulari ai MMPs (TIMPs joacă un rol în evoluția SA în special la pacienții care au în istoricul lor Uveită Acută Anterioară (UAA. În acest scop seruri de la pacienți cu SA și de la donatori sănătoși (DS au fost analizate pentru nivelurile de CD147 solubil (sCD147, MMP-3 și TIMP-1 prin tehnica imunoenzimatica ELISA și pentru activitatea gelatinazelor MMP-2 si MMP-9 folosind gelatin zimografia. Rezultatele experimentale au arătat că nivelurile de sCD147, MMP-3 si TIMP-1 sunt semnificativ crescute la pacienții cu SA comparativ cu DS. sCD147 ca și raportul MMP-2/sCD147 a diferențiat pacienții cu UAA de cei fără UAA în istoricul lor. La pacienții cu SA rapoartele MMP-2/sCD147, MMP-3/sCD147 și MMP-3/TIMP-1 au sugerat dezechilibrul dintre MMPs și reglatorii lor. Aceste rezultate sugerează că rapoartele MMPs/sCD147 pot deveni biomarkeri potențiali pentru întărirea caracterizării pacienților cu SA și pentru a prognoza evoluția bolii. Corelațiile pozitive și negative dintre anumite caracteristici experimentale și/sau clinice ale pacienților cu SA și terapie subliniază de asemenea utilitatea evaluării acestor biomarkeri pentru a identifica o terapie individualizată și eficientă.

  13. Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu4 core structural changes.

    Science.gov (United States)

    Kato, Merii; Sah, Ajay Kumar; Tanase, Tomoaki; Mikuriya, Masahiro

    2006-08-21

    Tetranuclear copper(II) complexes containing alpha-D-glucose-1-phosphate (alpha-D-Glc-1P), [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(bpy)4(H2O)2]X3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(phen)4(H2O)2](NO3)3 (2) were prepared by reacting the copper(II) salt with Na2[alpha-D-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}2+ fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu4-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-D-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-CA)2(bpy)4](NO3)2 [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)2] also gave the discrete tetracopper(II) cationic complex [Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)(CH2COOH))2(bpy)4](NO3)2 (5a) as well as the cluster polymer formulated as {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)2)(bpy)4](NO3)2}n (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu(II) ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta

  14. Development of a Novel Cu(II Complex Modified Electrode and a Portable Electrochemical Analyzer for the Determination of Dissolved Oxygen (DO in Water

    Directory of Open Access Journals (Sweden)

    Salvatore Gianluca Leonardi

    2016-04-01

    Full Text Available The development of an electrochemical dissolved oxygen (DO sensor based on a novel Cu(II complex-modified screen printed carbon electrode is reported. The voltammetric behavior of the modified electrode was investigated at different scan rates and oxygen concentrations in PBS (pH = 7. An increase of cathodic current (at about −0.4 vs. Ag/AgCl with the addition of oxygen was observed. The modified Cu(II complex electrode was demonstrated for the determination of DO in water using chronoamperometry. A small size and low power consumption home-made portable electrochemical analyzer based on custom electronics for sensor interfacing and operating in voltammetry and amperometry modes has been also designed and fabricated. Its performances in the monitoring of DO in water were compared with a commercial one.

  15. Preparation of detergent-lipase complexes utilizing water-soluble amphiphiles in single aqueous phase and catalysis of transesterifications in homogeneous organic solvents.

    Science.gov (United States)

    Mine, Y; Fukunaga, K; Maruoka, N; Nakao, K; Sugimura, Y

    2000-01-01

    A novel method of preparing detergent-enzyme complexes that can be employed in organic media was developed utilizing newly synthesized water-soluble nonionic gemini-type detergents, N,N-bis(3-D-gluconamidopropyl)-3-(dialkyl-L-glutamatecarbonyl)propanamides (BIG2CnCA: n = 10,12,14,16,18) and N,N-bis(3-D-lactonamidopropyl)-3-(dialkyl-L-glutamatecarbonyl)propanamides (BIL2CnCA: n = 16,18), and nonionic twin-headed detergents, N,N-bis(3-D-gluconamidopropyl)alkanamides (BIG1Cn: n = 12,14,16,18,delta9). This method simply entails mixing a selected enzyme with an appropriate detergent in an aqueous solution followed by lyophilization, and it offers the advantages of enhanced enzymatic activity in organic solvents and eliminates both enzyme loss and the necessity for an organic solvent in the preparation stage. Using various modified lipases originating from Aspergillus niger (Lipase A), Candida rugosa (Lipase C), Pseudomonas cepacia (Lipase P), and porcine pancreas (PPL), prepared using the novel method and detergents, including conventional synthesized nonionic detergents such as dialkyl N-D-glucona-L-glutamates (2CnGE: n = 12,18delta9) and octanoyl-N-methylglucamide (MEGA-8), enantioselective transesterifications of 6-methyl-5-hepten-2-ol (sulcatol) and 2,2-dimethyl-1,3-dioxolane-4-methanol (solketal) with a vinyl or isopropenyl carboxylate were carried out in an organic solvent. The modified lipase activity was influenced by both the lipases and the structure of the detergents. The value for the hydrophile-lipophile balance (HLB) of the detergent provided a means of correlating the structure and the obtained modified lipase activity. For detergents of the same class with a HLB value of approximately 9 and 12, the highest activity was obtained for Lipase A and Lipase P, and Lipase C and PPL, respectively. Among detergents of the same HLB value tested, the gemini-type detergents possessing the most bulky head and tail were most effective as a modifier for lipases of all

  16. Nonempirical investigations of the structure and stability of complex boro- and alumohydrides of K, Ca, Cu and Zn

    International Nuclear Information System (INIS)

    Musaev, D.G.; Charkin, O.P.

    1991-01-01

    Using nonempirical MO LCAO SCF method the structural and relative energy characteristics of boro- and alumohydrides of alternative configurations, CuAlH 4 , ZnBH 4 + , ZnAlH 4 + and HZnAlH 4 , were calculated. Differences and similarities in the properties of identical boro- and alumohydrides, as well as L 1 MH 4 , HL 2 MH 4 and L 2 MH 4 + molecules with the change of cation in the series K + -HCa + -Ca 2+ and Cu + -HZn + -Zn 2+ on the one hand, and with Cu and Zn substitution for K and Ca on the other hand, were considered. It was shown that alumohydrides of electropositive alkali and alkaline-earth cations K and Ca are less, and those of transition metals Cu and Zn are more hard to cation migration around AlH 4 - and BH 4 - anions than borohydrides

  17. Synthesis, structures, nuclease activity, cytotoxicity, DFT and molecular docking studies of two nitrato bridged homodinuclear (Cu-Cu, Zn-Zn) complexes containing 2,2'-bipyridine and a chalcone derivative.

    Science.gov (United States)

    Gaur, Ruchi; Choubey, Diksha Kumari; Usman, Mohammad; Ward, Benzamin D; Roy, Jagat Kumar; Mishra, Lallan

    2017-08-01

    Nitrato briged dinuclear complexes of type [Cu 2 (L) 2 (bpy) 2 (NO 3 )](NO 3 )·4H 2 O, 1 and [Zn 2 (L) 2 (bpy) 2 (NO 3 )](NO 3 )·4H 2 O, 2 (L=deprotonated form of free ligand LH, [1-(2-hydroxyphenyl)-3-(9-anthracenyl) propenone; bpy=2,2'bipyridine] are synthesized and characterized using a battery of physicochemical techniques and X-ray crystallography. A distorted square pyramidal geometry is assigned to them with N 2 O 3 coordination core around the metal ion. The co-ligand L binds the metal ions through its O,O' atoms in anti-syn mode. The metal centers in complexes 1 and 2 are separated via bridging nitrato group at a distance of 6.073Å and 5.635Å respectively. Their structures and absorption spectra are supported by the computational studies using density functional theory (DFT) and TD-DFT. Both complexes exhibit nuclease activity and cleave supercoiled (form I) DNA. The complex 1 preferentially binds major groove of DNA and follows an oxidative pathway whereas complex 2 binds with minor groove of DNA via hydrolytic pathway. Both complexes inhibit topoisomerase I relaxation activity with IC 50 values of 7 and 35μM. Molecular docking studies support the groove binding and topoisomerase I binding of the complexes. The complex 1 showed a significant cytotoxicity against HeLa cell lines (a cervical cancer cell lines) in vitro with IC 50 value calculated as 2.9±0.021μM as compared to 28.2±0. 044μΜ for complex 2. Complex 2 induces the cell apoptosis at a later-stage as compared to complex 1. The cell apoptosis and topoisomerase inhibition by complexes enable them to be potential candidates as future anticancer drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Biologically active new Fe(II, Co(II, Ni(II, Cu(II, Zn(II and Cd(II complexes of N-(2-thienylmethylenemethanamine

    Directory of Open Access Journals (Sweden)

    C. SPÎNU

    2008-04-01

    Full Text Available Iron(II, cobalt(II, nickel (II, copper (II, zinc(II and cadmium(II complexes of the type ML2Cl2, where M is a metal and L is the Schiff base N-(2-thienylmethylenemethanamine (TNAM formed by the condensation of 2-thiophenecarboxaldehyde and methylamine, were prepared and characterized by elemental analysis as well as magnetic and spectroscopic measurements. The elemental analyses suggest the stoichiometry to be 1:2 (metal:ligand. Magnetic susceptibility data coupled with electronic, ESR and Mössbauer spectra suggest a distorted octahedral structure for the Fe(II, Co(II and Ni(II complexes, a square-planar geometry for the Cu(II compound and a tetrahedral geometry for the Zn(II and Cd(II complexes. The infrared and NMR spectra of the complexes agree with co-ordination to the central metal atom through nitrogen and sulphur atoms. Conductance measurements suggest the non-electrolytic nature of the complexes, except for the Cu(II, Zn(II and Cd(II complexes, which are 1:2 electrolytes. The Schiff base and its metal chelates were screened for their biological activity against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the metal chelates were found to possess better antibacterial activity than that of the uncomplexed Schiff base.

  19. A new tridentate Schiff base Cu(II) complex: synthesis, experimental and theoretical studies on its crystal structure, FT-IR and UV-Visible spectra.

    Science.gov (United States)

    Saheb, Vahid; Sheikhshoaie, Iran; Setoodeh, Nasim; Rudbari, Hadi Amiri; Bruno, Giuseppe

    2013-06-01

    A new Cu(II) complex [Cu(L)(NCS)] has been synthesized, using 1-(N-salicylideneimino)-2-(N,N-methyl)-aminoethane as tridentate ONN donor Schiff base ligand (HL). The dark green crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FT-IR) and UV-Visible spectra. Electronic structure calculations at the B3LYP and MP2 levels of theory are performed to optimize the molecular geometry and to calculate the UV-Visible and FT-IR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TD-DFT) method is used to calculate the electronic transitions of the complex. A scaling factor of 1.015 is obtained for vibrational frequencies computed at the B3LYP level using basis sets 6-311G(d,p). It is found that solvent has a profound effect on the electronic absorption spectrum. The UV-Visible spectrum of the complex recorded in DMSO and DMF solution can be correctly predicted by a model in which DMSO and DMF molecules are coordinated to the central Cu atom via their oxygen atoms. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Composition and solubility of precipitated copper(II) arsenates

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, Hanna; Shchukarev, Andrey; Sjoeberg, Staffan [Department of Chemistry, Umea University, SE-901 87 Umea (Sweden); Loevgren, Lars, E-mail: lars.lovgren@chem.umu.se [Department of Chemistry, Umea University, SE-901 87 Umea (Sweden)

    2011-05-15

    Research Highlights: > By mixing solutions of Cu{sup 2+} and HAsO{sub 4}{sup 2-} solid phases are formed in a wide pH range. > Five different stoichiometric compositions were found. > Two of the solid phases formed in 0.1 M NaCl contained Na{sup +}. > Stability constants for all solid phases have been determined. > Aqueous complexes containing Cu{sup 2+} and AsO{sub 4}{sup 3-} ions could not be detected. - Abstract: Equilibrium reactions involving Cu(II) and As(V) have been studied with respect to formation of complexes in aqueous solutions as well as formation of solid phases. Potentiometric titrations performed at 25 deg. C (I = 0.1 M Na(Cl)) and at different Cu to As ratios gave no evidence for the existence of Cu(II) arsenate complexes in solution below the pH of the precipitation boundaries (pH {approx} 4), irrespective of the Cu to As ratio and pH. Mixing of solutions of Cu(II) and As(V) at different proportions and adjusting pH to values ranging from 4 to 9 resulted in precipitation of five different solid phases. The elemental composition of the solids was determined using X-ray Photoelectron Spectroscopy, and Environmental Scanning Microscopy-Field Emission Gun equipped with an energy dispersive spectroscopy detector. The average Cu/As ratio was determined by dissolving the solids. Total soluble concentrations of the components Cu(II) and As(V), as well as the basicity of the solid phases were determined by analysis of aqueous solutions. Based upon these experimental data the stoichiometric composition of the solid phases and their stability were determined. The resulting equilibrium model includes the solid phases Cu{sub 3}(AsO{sub 4}){sub 2}, Cu{sub 3}(AsO{sub 4})(OH){sub 3}, Cu{sub 2}(AsO{sub 4})(OH), Cu{sub 5}Na(HAsO{sub 4})(AsO{sub 4}){sub 3} and Cu{sub 5}Na{sub 2}AsO{sub 4}){sub 4}, where Cu{sub 5}Na(HAsO{sub 4})(AsO{sub 4}){sub 3} and Cu{sub 5}Na{sub 2}(AsO{sub 4}){sub 4} have not been reported previously. In 0.1 M Na(Cl), Na{sup +} was found to be

  1. Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N-Heterocyclic Carbene Complexes of Late Transition Metals.

    Science.gov (United States)

    Jantke, Dominik; Pardatscher, Lorenz; Drees, Markus; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

    2016-10-06

    The synthesis and characterization of two water-soluble bis-N-heterocyclic carbene (NHC) complexes of rhodium and iridium is presented. Both compounds are active in H 2 generation from formic acid and in hydrogenation of bicarbonate to formate. The rhodium derivative is most active in both reactions, reaching a TOF of 39 000 h -1 and a TON of 449 000 for H 2 production. The catalytic hydrogenation reactions were carried out in an autoclave system and analyzed using the integrated peak areas in the 1 H NMR spectra. Decomposition of formic acid was investigated using a Fisher-Porter bottle equipped with a pressure transducer. Long-term stability for hydrogen evolution was tested by surveillance of the gas flow rate. The procedure does not require any additives like amines or inert gas conditions. Density functional theory calculations in agreement with experimental results suggest a bicarbonate reduction mechanism involving a second catalyst molecule, which provides an external hydride acting as reducing agent. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Expression and clinical value of the soluble major histocompatibility complex class I-related chain A molecule in the serum of patients with renal tumors.

    Science.gov (United States)

    Zhao, Y-K; Jia, C-M; Yuan, G-J; Liu, W; Qiu, Y; Zhu, Q-G

    2015-06-29

    We investigated the expression and clinical value of the soluble major histocompatibility complex class I-related chain A (sMICA) molecule in the serum of patients with renal tumors. Sixty patients diagnosed with renal tumors were enrolled in the experimental group, whereas 20 healthy volunteers served as the control group. The sMICA levels were measured via enzyme-linked immunosorbent assay, and the results were analyzed in combination with data from pathol-ogy examination. The experimental group had a statistically significant higher sMICA level (P < 0.05) than the control group. The sMICA level was higher in patients with malignant tumors than in those with be-nign tumors. We also observed a positive relationship among different tumor-node-metastasis (TNM) pathological stages with more advanced diseases exhibiting higher sMICA levels. As a tumor-associated antigen, MICA has a close relationship with renal tumorigenesis and immune es-cape. Our results indicated that sMICA levels were related to tumor pathol-ogy, TNM stage, and metastasis. Therefore, sMICA might be a potential marker for tumor characteristics, prognosis, and recurrence prediction.

  3. Effects of organic complexed or inorganic Co, Cu, Mn and Zn supplementation during a 45-day preconditioning period on productive and health responses of feeder cattle.

    Science.gov (United States)

    Lippolis, K D; Cooke, R F; Silva, L G T; Schubach, K M; Brandao, A P; Marques, R S; Larson, C K; Russell, J R; Arispe, S A; DelCurto, T; Bohnert, D W

    2017-11-01

    This experiment evaluated production and health parameters among cattle offered concentrates containing inorganic or organic complexed sources of supplemental Cu, Co, Mn and Zn during a 45-day preconditioning period. In total, 90 Angus×Hereford calves were weaned at 7 months (day -1), sorted by sex, weaning BW and age (261±2 kg; 224±2 days), and allocated to 18 drylot pens (one heifer and four steers per pen) on day 0; thus, all pens had equivalent initial BW and age. Pens were randomly assigned to receive a corn-based preconditioning concentrate containing: (1) Cu, Co, Mn and Zn sulfate sources (INR), (2) Cu, Mn, Co and Zn complexed organic source (AAC) or (3) no Cu, Co, Mn and Zn supplementation (CON). From day 0 to 45, cattle received concentrate treatments (2.7 kg/animal daily, as-fed basis) and had free-choice access to orchardgrass (Dactylis glomerata L.), long-stem hay and water. The INR and AAC treatments were formulated to provide the same daily amount of Co, Cu, Mn and Zn at a 50-, 16-, 8- and ninefold increase, respectively, compared with the CON treatment. On day 46, cattle were transported to a commercial feedlot, maintained as a single pen, and offered a free-choice receiving diet until day 103. Calf full BW was recorded on days -1 and 0, 45 and 46, and 102 and 103 for average daily gain (ADG) calculation. Liver biopsy was performed on days 0 (used as covariate), 22 and 45. Cattle were vaccinated against respiratory pathogens on days 15, 29 and 46. Blood samples were collected on days 15, 29, 45, 47, 49, 53 and 60. During preconditioning, mean liver concentrations of Co, Zn and Cu were greater (P⩽0.03) in AAC and INR compared with CON. No treatment effects were detected (P⩾0.17) for preconditioning feed intake, ADG or feed efficiency. No treatment effects were detected (P⩾0.48) for plasma concentrations of antibodies against Mannheimia haemolytica, bovine viral diarrhea types 1 and 2 viruses. Plasma haptoglobin concentrations were similar

  4. Re-Os isotope systematics of the Radio Hill Ni-Cu-PGE complex, West Pilbara Craton, Western Australia

    International Nuclear Information System (INIS)

    Frick, L.R.; McBride, J.S.

    1999-01-01

    Full text: The Radio Hill Complex is one of several layered mafic-ultramafic intrusions that were emplaced into the west Pilbara Craton at ca. 2.9 Ga. It is believed to be genetically related to other similar intrusions in the area which include the Munni Munni, Andover, Dingo and Maitland Complexes (Hoatson et al. 1999). The Radio Hill Complex is the only one of these intrusions to contain economic quantities of Ni and Cu at the present time. This relatively small intrusion (∼1200 m stratigraphic thickness) is divided into two zones, an upper gabbroic zone and a lower ultramafic zone, the base of which possesses massive magmatic sulfide mineralisation (pyrrhotite, pentlandite, chalcopyrite, magnetite). Re-Os isotopic data have been obtained for a suite of samples from underground, outcrop (gabbroic zone samples) and drill core. Os concentrations in the mineralised zone are very high, ranging from 19 to 191 ppb Os, with low Re/Os ratios ( 10,000), where R-factor is defined as the mass ratio of silicate magma to sulfide magma that it has equilibrated with. However, modelling of the Radio Hill ore system using Re, Os and PGE (Hoatson et al. 1992) concentrations suggest that the R-factor in the Radio Hill ore was low (100-900). Therefore, the initial Os isotopic composition of the ore should be radiogenic (high gOs >+500) if local crustal contamination triggered sulfide saturation. The slightly radiogenic initial Os isotopic composition suggests that the bulk parental magma was a crustally-contaminated magma. R-factor modelling further suggests that the parental magma to this intrusion was neither a basalt nor a pure komatiite, but more likely a contaminated komatiite (with a relatively high Os concentration). This agrees with the previous findings of Hoatson et al. (1992) who proposed a parental magma of siliceous high-magnesium basalt (SHMB) composition. Our Re-Os isotope modelling agrees with the trace elements, Nd and Sr isotope modelling of Hoatson et al. (1992

  5. Synthesis and characterization of monomeric and polymeric Cu(II) complexes of 3,4-ethylenedioxythiophene-functionalized with cyclam ligand

    International Nuclear Information System (INIS)

    Velauthamurty, Kuhamoorthy; Higgins, Simon J.; Rajapakse, R.M. Gamini; Bandara, H.M.N.; Shimomura, Masaru

    2010-01-01

    A functionalized EDOT derivative with 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand pendant to the ethylene bridge (4) and its complexes [M(4)(BF 4 ) 2 ], where M(II) = Cu(II), was prepared and characterized. Their electrochemical copolymerization with EDOT was studied. The electro-co-polymerized films were characterized by electrochemical methods, X-ray photoelectron spectroscopy and by X-ray fluorescence spectroscopy. The co-polymerization method was found to afford a good control of the metal concentration in the polymer matrix and represents a good technique for preparing electronically conductive polymers containing redox-active metal complexes.

  6. The Pathogenic A2V Mutant Exhibits Distinct Aggregation Kinetics, Metal Site Structure, and Metal Exchange of the Cu2+ -Aβ Complex

    DEFF Research Database (Denmark)

    Somavarapu, Arun Kumar; Shen, Fei; Teilum, Kaare

    2017-01-01

    2V. 1H NMR relaxation exhibits the same trend for the non-coordinating aromatic residues (A2T2V), and implies markedly faster inter-peptide Cu2+exchange for the A2V variant than for WT and A2T. We therefore hypothesize that component I of the Cu–Aβ complex is related to pathogenicity......A prominent current hypothesis is that impaired metal ion homeostasis may contribute to Alzheimer's disease (AD). We elucidate the interaction of Cu2+ with wild-type (WT) Aβ1–40 and the genetic variants A2T and A2V which display increasing pathogenicity as A2T2V. Cu2+ significantly extends...... the lag phase in aggregation kinetics, in particular for the pathogenic A2V variant. Additionally, a rapid, initial, low intensity ThT response is observed, possibly reflecting formation of Cu2+ induced amorphous aggregates, as supported by atomic force microscopy (AFM) and circular dichroism (CD...

  7. Conjugate additions of a simple monosilylcopper reagent with use of the CuI.DMS complex: stereoselectivities and a dramatic impact by DMS.

    Science.gov (United States)

    Dambacher, Jesse; Bergdahl, Mikael

    2005-01-21

    Conjugate additions utilizing the simple monosilylcuprate reagent Li[PhMe2SiCuI] to alpha,beta-unsaturated carbonyl compounds are described. The presence of dimethyl sulfide (DMS), either as a component originating from the (CuI)4(DMS)3 complex or as a solvent added, has an amazing influence on both chemical yield and the level of diastereomeric ratio (dr) of the products. Gilman-type silylcyanocuprates {Li(Ph2MeSi)2Cu/LiCN} have previously been used to guarantee good results in conjugate addition reactions. External additives such as HMPA, tributylphosphine, or dialkylzinc are not necessary in conjunction with the simple Li[PhMe2SiCuI] reagent. It is demonstrated that the monosilylcuprate reagent with DMS as the solvent is very useful with sterically hindered (beta,beta-disubstituted) enones, and provides very high yields of the beta-silylated 1,4-addition products. Since there is no oligomerization problem associated with the simple monosilylcuprate reagent, this reagent should be considered as a very useful 1,4-silyl donor to enals, enones, and enoates in conjugate addition reactions.

  8. Metal complexes of salicylhydroxamic acid (H2Sha), anthranilic hydroxamic acid and benzohydroxamic acid. Crystal and molecular structure of [Cu(phen)2(Cl)]Cl x H2Sha, a model for a peroxidase-inhibitor complex.

    Science.gov (United States)

    O'Brien, E C; Farkas, E; Gil, M J; Fitzgerald, D; Castineras, A; Nolan, K B

    2000-04-01

    Stability constants of iron(III), copper(II), nickel(II) and zinc(II) complexes of salicylhydroxamic acid (H2Sha), anthranilic hydroxamic acid (HAha) and benzohydroxamic acid (HBha) have been determined at 25.0 degrees C, I=0.2 mol dm(-3) KCl in aqueous solution. The complex stability order, iron(III) > copper(II) > nickel(II) approximately = zinc(II) was observed whilst complexes of H2Sha were found to be more stable than those of the other two ligands. In the preparation of ternary metal ion complexes of these ligands and 1,10-phenanthroline (phen) the crystalline complex [Cu(phen)2(Cl)]Cl x H2Sha was obtained and its crystal structure determined. This complex is a model for hydroxamate-peroxidase inhibitor interactions.

  9. Mechanism of Exciplex Formation Between Cu-Porphyrin and Calf-thymus DNA as Revealed by Saturation Resonance Raman Spectroscopy

    NARCIS (Netherlands)

    Shvedko, A.G.; Kruglik, S.; Kruglik, S.G.; Ermolenkov, V.V.; Turpin, P.Y.; Greve, Jan; Otto, Cornelis

    1999-01-01

    The excited-state complex (exciplex) formation that results from the photoinduced interaction of water-soluble cationic copper(II) 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin [Cu(TMpy-P4)] with calf-thymus DNA has been studied in detail by resonance Raman (RR) spectroscopy using both ~10 ns

  10. Process of preparing superconductive oxide complexes containing L, Ba, Cu and O and method of using the same

    International Nuclear Information System (INIS)

    Salama, K.; Selvamanickam, V.

    1995-01-01

    A superconductor material having a current density, J, of from about 30,000 to about 85,000 amps/cm 2 at zero magnetic field and 77 K is disclosed. The 123 superconductor, of the formula L 1 Ba 2 Cu 3 O 6+δ wherein L is preferably yttrium, is capable of entrapping sufficiently high magnetic fields and exhibits a low microwave surface resistance. The process of preparing the superconductor comprises compacting the bulk product, L 1 Ba 2 Cu 3 O, and then sintering the reaction product at a temperature between about 40 C to about 90 C below its melting point, i.e., for Y 1 Ba 2 Cu 3 O 6+δ at a temperature of approximately 940 C. The composition is then heated in a preheated chamber maintained at approximately 1090 C to about 1,200 C (approximately 1,100 C for Y 1 Ba 2 Cu 3 O 6+δ ) until it has been decomposed, and is then rapidly cooled to a temperature between about 10 C to about 30 C above its melting point, i.e. for Y 1 Ba 2 Cu 3 O 6+δ a temperature of 1,030 C, and then is controlled cooled at a rate of 1 C/hr until it reaches a temperature of about 20 C to about 40 C below its melting point, i.e., for Y 1 Ba 2 Cu 3 O 6+δ a temperature of 980 C. The composition is steadily held at this temperature for at least eight hours, and then cooled to a temperature of approximately 400 C below its melting point (for Y 1 Ba 2 Cu 3 O 6+δ approximately a temperature of 600 C). The material is then slowly cooled by another 200 C and is then annealed in oxygen. 5 figs

  11. Synthesis, characterization, DNA interaction and antimicrobial screening of isatin-based polypyridyl mixed-ligand Cu(II and Zn(II complexes

    Directory of Open Access Journals (Sweden)

    NATARAJAN RAMAN

    2010-06-01

    Full Text Available Several mixed ligand Cu(II/Zn(II complexes using 3-(phenyl-imino-1,3-dihydro-2H-indol-2-one (obtained by the condensation of isatin and aniline as the primary ligand and 1,10-phenanthroline (phen/2,2’-bipyridine (bpy as an additional ligand were synthesized and characterized analytically and spectroscopically by elemental analyses, magnetic susceptibility and molar conductance measurements, as well as by UV–Vis, IR, NMR and FAB mass spectroscopy. The interaction of the complexes with calf thymus (CT DNA was studied using absorption spectra, cyclic voltammetric and viscosity measurements. They exhibit absorption hypochromicity, and the specific viscosity increased during the binding of the complexes to calf thymus DNA. The shifts in the oxidation–reduction potential and changes in peak current on addition of DNA were shown by CV measurements. The Cu(II/Zn(II complexes were found to promote cleavage of pUC19 DNA from the supercoiled form I to the open circular form II and linear form III. The complexes show enhanced antifungal and antibacterial activities compared with the free ligand.

  12. Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

    Science.gov (United States)

    Paul, Aparup; Bertolasi, Valerio; Figuerola, Albert; Manna, Subal Chandra

    2017-05-01

    Three novel tetranuclear copper(II) complexes namely [Cu4(L1)4]•2(dmf) (1), [Cu4(L1)4] (2) and [Cu4(L2)2(HL2)2(H2O)2]•2(ClO4)·6(H2O) (3) (H2L1, (E)-2-((1-hydroxybutan-2-ylimino)methyl)phenol; H2L2, (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)) were synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that complex 1 crystallizes in the monoclinic system with space group C2/c, whereas both the complexes 2 and 3 crystallize in the triclinic system with space group P-1. Complexes 1 and 2 possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π…π and C-H…π interactions lead to formation of a 2D supramolecular architecture for complexes 1 and 2. At room temperature complexes 1, 2 and 3, exhibit fluorescence with a quantum yield (Φs) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2-300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H =- J1(S1S2+S1S2'+S1'S2+S1'S2') - J2S1S1', where S1 = S1' = S2 = S2' = SCu =1/2, was used for studying complexes 1 and 2. Simulations performed suggest magnetic exchange constants with values close to J1 =-20 cm-1 and J2 =0 cm-1 for these complexes. On the other hand, the spin Hamiltonian H =- J1(S1S4+S2S3) - J2(S1S3+S2S4) - J3S1S2, where S1 = S2 = S3 = S4 = SCu =1/2, was used to study the magnetic behaviour of the double open cubane core of complex 3 and a good agreement between the experimental and simulated results was found by using the parameters g1 = g2 =2.20, g3 = g4 =2.18, J1 =-36 cm-1, J2 =-44 cm-1 and J3 =0 cm-1.

  13. A stochastic model for the synthesis and degradation of natural organic matter. Part III: Modeling Cu(II) complexation

    Energy Technology Data Exchange (ETDEWEB)

    Cabaniss, Stephen E. [Department of Chemistry, University of New Mexico, Albuquerque, NM 87131 (United States)], E-mail: cabaniss@unm.edu; Maurice, Patricia A. [Department of Geology and Civil Engineering, University of Notre Dame (United States); Madey, Greg [Department of Computer Science, University of Notre Dame (United States)

    2007-08-15

    An agent-based biogeochemical model has been developed which begins with biochemical precursor molecules and simulates the transformation and degradation of natural organic matter (NOM). This manuscript presents an empirical quantitative structure activity relationship (QSAR) which uses the numbers of ligand groups, charge density and heteroatom density of a molecule to estimate Cu-binding affinity (K{sub Cu}{sup '}) at pH 7.0 and ionic strength 0.10 for the molecules in this model. Calibration of this QSAR on a set of 41 model compounds gives a root mean square error of 0.88 log units and r{sup 2} 0.93. Two simulated NOM assemblages, one beginning with small molecules (tannins, terpenoids, flavonoids) and one with biopolymers (protein, lignin), give markedly different distributions of logK{sub Cu}{sup '}. However, calculations based on these logK{sub Cu}{sup '} distributions agree qualitatively with published experimental Cu(II) titration data from river and lake NOM samples.

  14. Effect on the Inhibitory Activity of Potential Microbes on the Complexation of Methyl Anthranilate Derived Hydrazide with Cu, Ni and Zn (II) Metal Ions

    International Nuclear Information System (INIS)

    Ikram, M.; Rehman, S.; Khan, K.

    2013-01-01

    The hydrazide ligand 2-amino-(N-aminobezoyl)benzohydrazide (ABH) have been synthesized and characterized by 1H-NMR, 13C-NMR, ES+-MS, elemental analyses and infrared studies. The ligand was complexed with Ni(II), Cu(II) and Zn(II) metal ions and were characterized by analytical and spectroscopic methods including elemental analyses, ES+-MS, conductance, infrared, UV-Visible and magnetic susceptibilities studies. Infrared spectra show that the ligand form complexes through -NH2 and carbonyl moieties, the elemental studies suggested the M(ABH)X2 composition of the coordination compounds. The synthesized complexes were studied for their biological activities against gram negative bacteria including Escherichia coli, Salmonella typhi, Enterobacter aerogenes, Proteus vulgaris, Pseudomonas aeruginosa, Gram positive bacterial strains like Staphylococcus aureus and fungus like Candida albican. These activities show that the metal complexes are more active to the tested microbes as compared to neat ligand. (author)

  15. Radical scavenging propensity of Cu2 +, Fe3 + complexes of flavonoids and in-vivo radical scavenging by Fe3 +-primuletin

    Science.gov (United States)

    Jabeen, Erum; Janjua, Naveed Kausar; Ahmed, Safeer; Murtaza, Iram; Ali, Tahir; Hameed, Shahid

    2017-01-01

    Cu2 + and Fe3 + complexes of three flavonoids (morin or mo, quercetin or quer and primuletin or prim) were synthesized with the objective of improving antioxidant capacities of flavonoids. The radical scavenging activities of pure flavonoids and their metal complexes were assayed to monitor their tendencies towards sequestering of radicals at physiological conditions. The scavenger potencies of metal-flavonoid complexes were significantly higher than those of the parent flavonoids. Further, influence of the solvent polarity on the radical capturing by flavonoids and their metal complexes was in favor for the polar solvent. Fe3 +-prim displayed its radical scavenging ability via up gradation of CAT and SOD activities in in-vivo antioxidant assays.

  16. Indigo Carmine-Cu complex probe exhibiting dual colorimetric/fluorimetric sensing for selective determination of mono hydrogen phosphate ion and its logic behavior

    Science.gov (United States)

    Tavallali, Hossein; Deilamy-Rad, Gohar; Moaddeli, Ali; Asghari, Khadijeh

    2017-08-01

    A new selective probe based on copper complex of Indigo Carmine (IC-Cu2) for colorimetric, naked-eye, and fluorimetric recognition of mono hydrogen phosphate (MHP) ion in H2O/DMSO (4:1 v/v, 1.0 mmol L- 1 HEPES buffer solution pH 7.5) was developed. Detection limit of HPO42 - determination, achieved by fluorimetric and 3lorimetric method, are 0.071 and 1.46 μmol L- 1, respectively. Potential, therefore is clearly available in IC-Cu2 complex to detect HPO42 - in micromolar range via dual visible color change and fluorescence response. Present method shows high selectivity toward HPO42 - over other phosphate species and other anions and was successfully utilized for analysis of P2O5 content of a fertilizer sample. The results obtained by proposed chemosensor presented good agreement with those obtained the colorimetric reference method. INHIBIT and IMPLICATION logic gates operating at molecular level have been achieved using Cu2 + and HPO42 - as chemical inputs and UV-Vis absorbance signal as output.

  17. Indigo Carmine-Cu complex probe exhibiting dual colorimetric/fluorimetric sensing for selective determination of mono hydrogen phosphate ion and its logic behavior.

    Science.gov (United States)

    Tavallali, Hossein; Deilamy-Rad, Gohar; Moaddeli, Ali; Asghari, Khadijeh

    2017-08-05

    A new selective probe based on copper complex of Indigo Carmine (IC-Cu 2 ) for colorimetric, naked-eye, and fluorimetric recognition of mono hydrogen phosphate (MHP) ion in H 2 O/DMSO (4:1v/v, 1.0mmolL -1 HEPES buffer solution pH7.5) was developed. Detection limit of HPO 4 2- determination, achieved by fluorimetric and 3 lorimetric method, are 0.071 and 1.46μmolL -1 , respectively. Potential, therefore is clearly available in IC-Cu 2 complex to detect HPO 4 2- in micromolar range via dual visible color change and fluorescence response. Present method shows high selectivity toward HPO 4 2- over other phosphate species and other anions and was successfully utilized for analysis of P 2 O 5 content of a fertilizer sample. The results obtained by proposed chemosensor presented good agreement with those obtained the colorimetric reference method. INHIBIT and IMPLICATION logic gates operating at molecular level have been achieved using Cu 2+ and HPO 4 2- as chemical inputs and UV-Vis absorbance signal as output. Copyright © 2017. Published by Elsevier B.V.

  18. Synthesis, structures and properties of Cu(II) and Mn(II) complexes with 1,10-phenanthroline-2-carboxylic acid and 2,2'-bipyridine ligands.

    Science.gov (United States)

    Sun, Jingya; Xu, Huanzhi

    2010-11-15

    Four new 2,2'-bipyridine and 1,10-phenanthroline complexes, namely [Mn(phenca)(2)]·(H(2)O)(2) (1), [Cu(4)(phen)(4)(OH-)(4)(H(2)O)(2)](DMF)(4)(ClO(4)-)(4)(H(2)O) (2), [Cu(2)(2,2-bipy)(2)(C(2)O(4)2-)(H(2)O)(2)(NO(3))(2)] (3) and [Cu(2,2-bipy)(2)(ClO(4)-)](ClO(4)-) (4) (2,2'-bpy = 2,2'-bipyridine, Hphenca = 1,10-phenanthroline-2-carboxylic acid) have been synthesized by a hydrothermal reaction. The products were characterized by elemental analysis, infrared spectroscopy and X-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as π···π interactions is also evident in the structures. A preliminary investigation on the ion exchange properties of the complexes is presented.

  19. A CU-Level Rate and Distortion Estimation Scheme for RDO of Hardware-Friendly HEVC Encoders Using Low-Complexity Integer DCTs.

    Science.gov (United States)

    Lee, Bumshik; Kim, Munchurl

    2016-08-01

    In this paper, a low complexity coding unit (CU)-level rate and distortion estimation scheme is proposed for High Efficiency Video Coding (HEVC) hardware-friendly implementation where a Walsh-Hadamard transform (WHT)-based low-complexity integer discrete cosine transform (DCT) is employed for distortion estimation. Since HEVC adopts quadtree structures of coding blocks with hierarchical coding depths, it becomes more difficult to estimate accurate rate and distortion values without actually performing transform, quantization, inverse transform, de-quantization, and entropy coding. Furthermore, DCT for rate-distortion optimization (RDO) is computationally high, because it requires a number of multiplication and addition operations for various transform block sizes of 4-, 8-, 16-, and 32-orders and requires recursive computations to decide the optimal depths of CU or transform unit. Therefore, full RDO-based encoding is highly complex, especially for low-power implementation of HEVC encoders. In this paper, a rate and distortion estimation scheme is proposed in CU levels based on a low-complexity integer DCT that can be computed in terms of WHT whose coefficients are produced in prediction stages. For rate and distortion estimation in CU levels, two orthogonal matrices of 4×4 and 8×8 , which are applied to WHT that are newly designed in a butterfly structure only with addition and shift operations. By applying the integer DCT based on the WHT and newly designed transforms in each CU block, the texture rate can precisely be estimated after quantization using the number of non-zero quantized coefficients and the distortion can also be precisely estimated in transform domain without de-quantization and inverse transform required. In addition, a non-texture rate estimation is proposed by using a pseudoentropy code to obtain accurate total rate estimates. The proposed rate and the distortion estimation scheme can effectively be used for HW-friendly implementation of

  20. DNA incision evaluation, binding investigation and biocidal screening of Cu(II), Ni(II) and Co(II) complexes with isoxazole Schiff bases.

    Science.gov (United States)

    Ganji, Nirmala; Chityala, Vijay Kumar; Marri, Pradeep Kumar; Aveli, Rambabu; Narendrula, Vamsikrishna; Daravath, Sreenu; Shivaraj

    2017-10-01

    Two new series of binary metal complexes [M(L 1 ) 2 ] and [M(L 2 ) 2 ] where, M=Cu(II), Ni(II) & Co(II) and L 1 =4-((3,4-dimethylisoxazol-5-ylimino)methyl)benzene-1,3-diol; L 2 =2-((3,4-dimethylisoxazol-5-ylimino)methyl)-5-methoxyphenol were synthesized and characterized by elemental analysis, 1 H NMR, 13 C NMR, FT-IR, ESI mass, UV-Visible, magnetic moment, ESR, SEM and powder XRD studies. Based on these results, a square planar geometry is assigned for all the metal complexes where the Schiff base acts as uninegatively charged bidentate chelating agent via the hydroxyl oxygen and azomethine nitrogen atoms. DNA binding studies of all the complexes with calf thymus DNA have been comprehensively investigated using electronic absorption spectroscopy, fluorescence quenching and viscosity studies. The oxidative and photo cleavage affinity of metal complexes towards supercoiled pBR322 DNA has been ascertained by agarose gel electrophoresis assay. From the results, it is observed that all the metal complexes bind effectively to CT-DNA via an intercalative mode of binding and also cleave pBR322 DNA in a promising manner. Further the Cu(II) complexes have shown better binding and cleavage properties towards DNA. The antimicrobial activities of the Schiff bases and their metal complexes were studied on bacterial and fungal strains and the results denoted that the complexes are more potent than their Schiff base ligands. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Cu(II complexes of an ionic liquid-based Schiff base [1-{2-(2-hydroxy benzylidene amino ethyl}-3-methyl­imidazolium]Pf6: Synthesis, characterization and biological activities

    Directory of Open Access Journals (Sweden)

    Saha Sanjoy

    2015-01-01

    Full Text Available Two Cu(II complexes of an ionic liquid based Schiff base 1-{2-(2-hydroxybenzylideneamino ethyl}-3-methylimidazolium hexaflurophosphate, were prepared and characterized by different analytical and spectroscopic methods such as elemental analysis, magnetic susceptibility, UV-Vis, IR, NMR and mass spectroscopy. The Schiff base ligand was found to act as a potential bidentate chelating ligand with N, O donor sites and formed 1:2 metal chelates with Cu(II salts. The synthesized Cu(II complexes were tested for biological activity.

  2. Preparation of Water-soluble Polyion Complex (PIC Micelles Covered with Amphoteric Random Copolymer Shells with Pendant Sulfonate and Quaternary Amino Groups

    Directory of Open Access Journals (Sweden)

    Rina Nakahata

    2018-02-01

    Full Text Available An amphoteric random copolymer (P(SA91 composed of anionic sodium 2-acrylamido-2-methylpropanesulfonate (AMPS, S and cationic 3-acrylamidopropyl trimethylammonium chloride (APTAC, A was prepared via reversible addition-fragmentation chain transfer (RAFT radical polymerization. The subscripts in the abbreviations indicate the degree of polymerization (DP. Furthermore, AMPS and APTAC were polymerized using a P(SA91 macro-chain transfer agent to prepare an anionic diblock copolymer (P(SA91S67 and a cationic diblock copolymer (P(SA91A88, respectively. The DP was estimated from quantitative 13C NMR measurements. A stoichiometrically charge neutralized mixture of the aqueous P(SA91S67 and P(SA91A88 formed water-soluble polyion complex (PIC micelles comprising PIC cores and amphoteric random copolymer shells. The PIC micelles were in a dynamic equilibrium state between PIC micelles and charge neutralized small aggregates composed of a P(SA91S67/P(SA91A88 pair. Interactions between PIC micelles and fetal bovine serum (FBS in phosphate buffered saline (PBS were evaluated by changing the hydrodynamic radius (Rh and light scattering intensity (LSI. Increases in Rh and LSI were not observed for the mixture of PIC micelles and FBS in PBS for one day. This observation suggests that there is no interaction between PIC micelles and proteins, because the PIC micelle surfaces were covered with amphoteric random copolymer shells. However, with increasing time, the diblock copolymer chains that were dissociated from PIC micelles interacted with proteins.

  3. High Resolution X-ray Diffraction Dataset for Bacillus licheniformis Gamma Glutamyl Transpeptidase-acivicin complex: SUMO-Tag Renders High Expression and Solubility.

    Science.gov (United States)

    Kumari, Shobha; Pal, Ravi Kant; Gupta, Rani; Goel, Manisha

    2017-02-01

    Gamma glutamyl transpeptidase, (GGT) is a ubiquitous protein which plays a central role in glutathione metabolism and has myriad clinical implications. It has been shown to be a virulence factor for pathogenic bacteria, inhibition of which results in reduced colonization potential. However, existing inhibitors are effective but toxic and therefore search is on for novel inhibitors, which makes it imperative to understand the interactions of various inhibitors with the protein in substantial detail. High resolution structures of protein bound to different inhibitors can serve this purpose. Gamma glutamyl transpeptidase from Bacillus licheniformis is one of the model systems that have been used to understand the structure-function correlation of the protein. The structures of the native protein (PDB code 4OTT), of its complex with glutamate (PDB code 4OTU) and that of its precursor mimic (PDB code 4Y23) are available, although at moderate/low resolution. In the present study, we are reporting the preliminary analysis of, high resolution X-ray diffraction data collected for the co-crystals of B. licheniformis, Gamma glutamyl transpeptidase, with its inhibitor, Acivicin. Crystals belong to the orthorhombic space group P2 1 2 1 2 1 and diffract X-ray to 1.45 Å resolution. This is the highest resolution data reported for all GGT structures available till now. The use of SUMO fused expression system enhanced yield of the target protein in the soluble fraction, facilitating recovery of protein with high purity. The preliminary analysis of this data set shows clear density for the inhibitor, acivicin, in the protein active site.

  4. Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

    International Nuclear Information System (INIS)

    Paul, Aparup; Bertolasi, Valerio; Figuerola, Albert; Manna, Subal Chandra

    2017-01-01

    Three novel tetranuclear copper(II) complexes namely [Cu 4 (L 1 ) 4 ]∙2(dmf) (1), [Cu 4 (L 1 ) 4 ] (2) and [Cu 4 (L 2 ) 2 (HL 2 ) 2 (H 2 O) 2 ]∙2(ClO 4 )·6(H 2 O) (3) (H 2 L 1 , (E)−2-((1-hydroxybutan-2-ylimino)methyl)phenol; H 2 L 2 , (E)−2-((1-hydroxybutan-2-ylimino)methyl)−6-methoxyphenol)) were synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that crystallizes in the monoclinic system with space group C2/c, whereas both the and crystallize in the triclinic system with space group P-1. and possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π…π and C–H…π interactions lead to formation of a 2D supramolecular architecture for and . At room temperature and , exhibit fluorescence with a quantum yield (Φ s ) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2–300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H =– J 1 (S 1 S 2 +S 1 S 2’ +S 1' S 2 +S 1' S 2’ ) – J 2 S 1 S 1’ , where S 1 = S 1’ = S 2 = S 2’ = S Cu =1/2, was used for studying and . Simulations performed suggest magnetic exchange constants with values close to J 1 =−20 cm −1 and J 2 =0 cm -1 for these complexes. On the other hand, the spin Hamiltonian H =– J 1 (S 1 S 4 +S 2 S 3 ) – J 2 (S 1 S 3 +S 2 S 4 ) – J 3 S 1 S 2 , where S 1 = S 2 = S 3 = S 4 = S Cu =1/2, was used to study the magnetic behaviour of the double open cubane core of and a good agreement between the experimental and simulated results was found by using the parameters g 1 = g 2 =2.20, g 3 = g 4 =2.18, J 1 =−36 cm -1 , J 2

  5. Geochronology and characteristics of Ni-Cu-(PGE) mineralization at Rožany, Lusatian Granitoid Complex, Czech Republic

    Czech Academy of Sciences Publication Activity Database

    Haluzová, Eva; Ackerman, Lukáš; Pašava, J.; Jonášová, Šárka; Svojtka, Martin; Hrstka, Tomáš; Veselovský, F.

    2015-01-01

    Roč. 60, č. 4 (2015), s. 219-236 ISSN 1802-6222 R&D Projects: GA ČR GA13-15390S Institutional support: RVO:67985831 Keywords : Ni-Cu-(PGE) * Lusatia * Re-Os * Bohemian Massif * sulphur Subject RIV: DD - Geochemistry Impact factor: 1.326, year: 2015

  6. Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils

    Energy Technology Data Exchange (ETDEWEB)

    Ylivainio, Kari, E-mail: kari.ylivainio@mtt.f [Department of Applied Chemistry and Microbiology, FIN-00014 University of Helsinki (Finland)

    2010-10-15

    In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg{sup -1}). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching. - When correcting Fe chlorosis Fe-EDDS causes lower environmental concern than Fe-EDTA.

  7. Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils

    International Nuclear Information System (INIS)

    Ylivainio, Kari

    2010-01-01

    In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg -1 ). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching. - When correcting Fe chlorosis Fe-EDDS causes lower environmental concern than Fe-EDTA.

  8. Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils.

    Science.gov (United States)

    Ylivainio, Kari

    2010-10-01

    In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg(-1)). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  9. Density functional studies on the exchange interaction of a dinuclear Gd(iii)-Cu(ii) complex: method assessment, magnetic coupling mechanism and magneto-structural correlations.

    Science.gov (United States)

    Rajaraman, Gopalan; Totti, Federico; Bencini, Alessandro; Caneschi, Andrea; Sessoli, Roberta; Gatteschi, Dante

    2009-05-07

    Density functional calculations have been performed on a [Gd(iii)Cu(ii)] complex [L(1)CuGd(O(2)CCF(3))(3)(C(2)H(5)OH)(2)] () (where L(1) is N,N'-bis(3-ethoxy-salicylidene)-1,2-diamino-2-methylpropanato) with an aim of assessing a suitable functional within the DFT formalism to understand the mechanism of magnetic coupling and also to develop magneto-structural correlations. Encouraging results have been obtained in our studies where the application of B3LYP on the crystal structure of yields a ferromagnetic J value of -5.8 cm(-1) which is in excellent agreement with the experimental value of -4.42 cm(-1) (H = JS(Gd).S(Cu)). After testing varieties of functional for the method assessment we recommend the use of B3LYP with a combination of an effective core potential basis set. For all electron basis sets the relativistic effects should be incorporated either via the Douglas-Kroll-Hess (DKH) or zeroth-order regular approximation (ZORA) methods. A breakdown approach has been adopted where the calculations on several model complexes of have been performed. Their wave functions have been analysed thereafter (MO and NBO analysis) in order to gain some insight into the coupling mechanism. The results suggest, unambiguously, that the empty Gd(iii) 5d orbitals have a prominent role on the magnetic coupling. These 5d orbitals gain partial occupancy via Cu(ii) charge transfer as well as from the Gd(iii) 4f orbitals. A competing 4f-3d interaction associated with the symmetry of the complex has also been observed. The general mechanism hence incorporates both contributions and sets forth rather a prevailing mechanism for the 3d-4f coupling. The magneto-structural correlations reveal that there is no unique parameter which the J values are strongly correlated with, but an exponential relation to the J value found for the O-Cu-O-Gd dihedral angle parameter is the most credible correlation.

  10. Mass-spectrometric study of phosphorous amides and their Co(O), Mo(O), Ni(II), and Cu(I) complexes

    International Nuclear Information System (INIS)

    Nifant'ev, E.E.; Blokhin, Y.I.; Chikishev, Y.G.; Rozynov, B.V.; Teleshev, A.T.

    1985-01-01

    This article examines the performance of the mass-spectroscopic method in investigating allied comounds and original kigands. Apart from Cu(I) complexes, Co(O), Mo(O), and Ni(II) derivatives. The nature of the organophosphorus ligand is shown as having a substantial indluence on the structure of the cobalt complexes formed. The breakdown of the original ligands is accompanied by the initial breakage of the P-N bond. In the halide complexes first the metal is eliminated with the formation of the XhaL fragment, and the halogen is eliminated subsequently, but in the carbonyl derivatives the stagewise elimination of CO groups occurs with the subsequent elimination of the metal

  11. Synthesis and Characterization of Some New Cu(II, Ni(II and Zn(II Complexes with Salicylidene Thiosemicarbazones: Antibacterial, Antifungal and in Vitro Antileukemia Activity

    Directory of Open Access Journals (Sweden)

    Tudor Rosu

    2013-07-01

    Full Text Available Thirty two new Cu(II, Ni(II and Zn(II complexes (1–32 with salicylidene thiosemicarbazones (H2L1–H2L10 were synthesized. Salicylidene thiosemicarbazones, of general formula (XN-NH-C(S-NH(Y, were prepared through the condensation reaction of 2-hydroxybenzaldehyde and its derivatives (X with thiosemicarbazide or 4-phenylthiosemicarbazide (Y = H, C6H5. The characterization of the new formed compounds was done by 1H-NMR, 13C-NMR, IR spectroscopy, elemental analysis, magnetochemical, thermoanalytical and molar conductance measurements. In addition, the structure of the complex 5 has been determined by X-ray diffraction method. All ligands and metal complexes were tested as inhibitors of human leukemia (HL-60 cells growth and antibacterial and antifungal activities.

  12. On the americium oxalate solubility

    International Nuclear Information System (INIS)

    Zakolupin, S.A.; Korablin, Eh.V.

    1977-01-01

    The americium oxalate solubility at different nitric (0.0-1 M) and oxalic (0.0-0.4 M) acid concentrations was investigated in the temperature range from 14 to 60 deg C. The dependence of americium oxalate solubility on the oxalic acid concentration was determined. Increasing oxalic acid concentration was found to reduce the americium oxalate solubility. The dependence of americium oxalate solubility on the oxalic acid concentration was noted to be a minimum at low acidity (0.1-0.3 M nitric acid). This is most likely due to Am(C 2 O 4 ) + , Am(C 2 O 4 ) 2 - and Am(C 2 O 4 ) 3 3- complex ion formation which have different unstability constants. On the basis of the data obtained, a preliminary estimate was carried out for the product of americium oxalate solubility in nitric acid medium (10 -29 -10 -31 ) and of the one in water (6.4x10 -20 )

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

    Directory of Open Access Journals (Sweden)

    Aliakbar Dehno Khalaji

    2015-12-01

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

  14. CuX2络合物催化甲基丙烯酸甲酯的氧化聚合%CuX2 COMPLEX-CATALYZED OXIDATIVE POLYMERIZATIONS OF METHYL METHACRYLATE

    Institute of Scientific and Technical Information of China (English)

    孙燕; 孙晋; 宋瑾; 黄文艳; 蒋必彪; 翟光群

    2011-01-01

    Oxidative polymerizations of methyl methacrylate ( MMA) catalyzed by complexes of transition metal halides in high oxidation states were investigated. First, CuBr2/2, 2'-bipyridine ( bPy)-catalyzed oxidative polymerizations of MMA in the presence of poly (2-( N, iV-dimethylamino) ethyl methacrylate) were performed in different solvents. When cyclohexanone was used as a solvent, only poly ( methyl methacrylate) ( PMMA) was obtained, suggesting redox initiation between CuBr2/bPy and tertiary amines in cyclohexanone is negligible. Second, oxidative polymerizations of MMA catalyzed by different complexes were carried out. Complexes of CuCl2 ,CuBr2 or FeCl3 with bPy,N,N,/V',N",/V"-pentamethyldiethylenetriamine or N,N,N',N'-tetramethylethylenediamine can catalyze oxidative polymerizations of MMA, and polymerization rates increased with the increase of the catalyst concentration. Molecular weight of PMMA increases with monomer conversions initially and maintains constant later. Last,atom transfer radical polymerization ( ATRP) chain extension using PMMA from the oxidative polymerizations at different conversions was performed. The results show the C-X functionality of PMMA chains at low conversion was also 100% ,and it decreased sharply with conversions. Two different mechanisms were conceived to contribute to the oxidative polymerization of MMA: (1) the complexes form ATRP initiators and catalysts with MMA via monomer addition, and then ATRP proceeds to give rise to PMMA chains with C-X terminal groups; (2) the complexes catalyze/initiate conventional free radical polymerizations of MMA.%研究了高氧化态过渡金属卤化物络合物催化甲基丙烯酸甲酯(MMA)的氧化聚合.首先在叔胺类聚合物存在条件下以CuBr2/2,2′-联吡啶(bPy)络合物催化MMA在不同溶剂中的氧化聚合,结果在环己酮中得到PMMA均聚物,CuBr2/bPy同叔胺的氧化还原引发可以忽略.随后在环己酮中分别以不同络合物催化MMA的氧化聚合.结果发现,Cu

  15. Studies on some VO(IV, Ni(II and Cu(II complexes of non-symmetrical tetradentate Schiff-bases

    Directory of Open Access Journals (Sweden)

    Aderoju A. Osowole

    2008-08-01

    Full Text Available The coordination chemistry of VO(IV, Ni(II and Cu(II with unsymmetrical Schiff base ligands, [HO(OCH3C6H3C(CH3:N(CH2CH2N:C(CH3CH:C(C6H5OH], H2L and [HO(OCH3C6H3C(CH3:N(CH2CH2N:C(CH3CH:C(CH3OH], H2L1 (derived from condensation of 1-phenyl-1,3-butanedione/2,4-pentanedione, ethylenediamine and 5-methoxy-2-hydroxy acetophenone is discussed. The metal complexes were characterized by elemental analysis, molar conductance, magnetic susceptibility, infrared and electronic spectral measurements. They are magnetically dilute, non-electrolytes in nitromethane. The ligands are tetradentately coordinating via the imine N and enolic O atoms, resulting in 5-coordinate square-pyramidal geometry for the VO(IV complexes and 4-coordinate square-planar geometry for the Ni(II and Cu(II complexes. The assignment of geometry is supported by magnetic and spectral measurements.

  16. Detection of Maillard reaction products by a coupled HPLC-Fraction collector technique and FTIR characterization of Cu(II)-complexation with the isolated species

    Science.gov (United States)

    Ioannou, Aristos; Daskalakis, Vangelis; Varotsis, Constantinos

    2017-08-01

    The isolation of reaction products of asparagine with reducing sugars at alkaline pH and high temperature has been probed by a combination of high performance liquid chromatography (HPLC) coupled with a Fraction Collector. The UV-vis and FTIR spectra of the isolated Maillard reaction products showed structure-sensitive changes as depicted by deamination events and formation of asparagine-saccharide conjugates. The initial reaction species of the Asn-Gluc reaction were also characterized by Density Functional Theory (DFT) methods. Evidence for Cu (II) metal ion complexation with the Maillard reaction products is supported by UV-vis and FTIR spectroscopy.

  17. Solubility Products of M(II) - Carbonates

    Energy Technology Data Exchange (ETDEWEB)

    Grauer, Rolf; Berner, Urs [ed.

    1999-01-01

    Many solubility data for M(II) carbonates commonly compiled in tables are contradictory and sometimes obviously wrong. The quality of such data has been evaluated based on the original publications and reliable solubility constants have been selected for the carbonates of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb with the help of cross-comparisons. (author) translated from a PSI internal report written in German in 1994 (TM-44-94-05). 5 figs., 1 tab., 68 refs.

  18. Synthesis, characterization and biological studies of metal complexes of Co (II), Ni (II), Cu (II), Zn (II) with sulphadimidine-benzylidene

    International Nuclear Information System (INIS)

    Tahira, F.; Imran, M.; Iqbal, J.

    2009-01-01

    Some novel complexes of Co (II), Ni (II), Cu (II), and Zn (II) have been synthesized with a Schiff base ligand derived from sulphadimidine and benzaldehyde. The structural features of the complexes have been determined by elemental analysis, magnetic susceptibility, conductance measurement, UV/ Vis. and infrared spectroscopy. IR studies revealed that the Schiff base ligand Sulphadimidine-benzylidene has monoanionic bidendate nature and coordinate with metal ions through nitrogen atom of azomethine (>C = N) and deprotonated -NH group. All the complexes were assigned octahedral geometry on the basis of magnetic moment and electronic spectroscopic data. Low value of conductance supports their non-electrolytic nature. The ligand, as well as its complexes were checked for their in vitro antimicrobial activities against two gram positive bacterial strains, Bacillus subtillus. Staphylococcus aureus and one gram negative Salmonella typhae and five fungal strains, Nigrospora oryzae, Curvularia lunata, Drechslera rostrata, Aspergillus niger and Candida olbicans by disc diffusion method and agar plate technique, respectively. Both the antibacterial and antitungal activities of the synthesized metal complexes were found to be more as compared to parent drug and uncomplexed ligand. All the complexes contain coordinated water, which is lost at 141-160 degree C. (author)

  19. Inorganic anion-dependent assembly of zero-, one-, two- and three-dimensional Cu(II)/Ag(I) complexes under the guidance of the HSAB theory: Synthesis, structure, and magnetic property

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yaru; Xing, Zhiyan [School of Science, North University of China, Taiyuan, Shanxi 030051 (China); Zhang, Xiao [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150080 (China); Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080 PR China (China); Liang, Guorui [School of Science, North University of China, Taiyuan, Shanxi 030051 (China)

    2017-02-15

    To systematically explore the influence of inorganic anions on building coordination complexes, five novel complexes based on 1-(benzotriazole-1-methyl)−2-propylimidazole (bpmi), [Cu(bpmi){sub 2}(Ac){sub 2}]·H{sub 2}O (1), [Cu(bpmi){sub 2}(H{sub 2}O){sub 2}]·2NO{sub 3}·2H{sub 2}O (2), [Cu(bpmi)(N{sub 3}){sub 2}] (3), [Ag(bpmi)(NO{sub 3})] (4) and [Cu{sub 3}(bpmi){sub 2}(SCN){sub 4}(DMF)] (5) (Ac{sup −}=CH{sub 3}COO{sup −}, DMF=N,N-Dimethylformamide) are synthesized through rationally introducing Cu(II) salts and Ag(I) salt with different inorganic anions. X-ray single-crystal analyses reveal that these complexes show interesting structural features from mononuclear (1), one-dimensional (2 and 3), two-dimensional (4) to three-dimensional (5) under the influence of inorganic anions with different basicities. The structural variation can be explained by the hard-soft-acid-base (HSAB) theory. Magnetic susceptibility measurement indicates that complex 3 exhibits an antiferromagnetic coupling between adjacent Cu(II) ions. - Graphical abstract: Five new Cu(II)/Ag(I) complexes show interesting structural features from mononuclear, one-dimension, two-dimension to three-dimension under the influence of inorganic anions. The structural variation can be explained by the HSAB theory. - Highlights: • Five inorganic anion-dependent complexes are synthesized. • Structural variation can be explained by the hard-soft-acid-base (HSAB) theory. • The magnetic property of complex has been studied.

  20. An experimental and theoretical study on the interaction of DNA and BSA with novel Ni2 +, Cu2 + and VO2 + complexes derived from vanillin bidentate Schiff base ligand

    Science.gov (United States)

    Dostani, Morteza; Kianfar, Ali Hossein; Mahmood, Wan Ahmad Kamil; Dinari, Mohammad; Farrokhpour, Hossein; Sabzalian, Mohammad R.; Abyar, Fatemeh; Azarian, Mohammad Hossein

    2017-06-01

    In this investigation, the structure of bidentate N,N-Schiff base ligand of vanillin, (E)-4-(((2-amino-5-nitrophenyl)imino)methyl)-2-methoxyphenol (HL) was determined by single crystal X-ray diffraction. The interaction of new [CuL2], [NiL2] and [VOL2] complexes with DNA and BSA was explored through UV-Vis and fluorescence spectroscopy. The electronic spectra changes displayed an isosbestic point for the complexes upon titration with DNA. The Kb values for the complexes [CuL2], [NiL2] and [VOL2] were 2.4 × 105, 1.9 × 105 and 4.2 × 104, respectively. [CuL2] complex was bound more toughly than [NiL2] and [VOL2] complexes. These complexes had a significant interaction with Bovine Serum Albumin (BSA) and the results demonstrated that the quenching mechanism was a static procedure. Also, the complexes interacted with BSA by more than one binding site (n > 1). Finally, the theoretical studies were performed using the docking method to calculate the binding constants and recognize the binding site of the DNA and BSA with the complexes. The ligand and complexes including Ni2 +, Cu2 + and VO2 + ions were colonized by fungal growth.

  1. Aminoalcohols and benzoates-friends or foes? Tuning nuclearity of Cu(ii) complexes, studies of their structures, magnetism, and catecholase-like activities as well as performing DFT and TDDFT studies.

    Science.gov (United States)

    Sama, Farasha; Dhara, Ashish Kumar; Akhtar, Muhammad Nadeem; Chen, Yan-Cong; Tong, Ming-Liang; Ansari, Istikhar A; Raizada, Mukul; Ahmad, Musheer; Shahid, M; Siddiqi, Zafar A

    2017-08-14

    Herein, the coordination chemistry of a series of Cu(ii) complexes of various aminoalcohol and benzoate ligands was explored. The pH-dependent reactions of copper(ii) salts with propanolamine (Hpa), N-methyl diethanolamine (H 2 mdea), triethanolamine (H 3 tea), and n butyl-diethanolamine (H 2 budea) were carried out in the presence of various benzoates (benzoic acid, 2-hydroxy benzoic acid, 4-hydroxy benzoic acid, 3-methoxy benzoic acid, and 4-methoxy benzoic acid). The resulting complexes [Cu 2 (pa) 2 (benzoate) 2 ] (1), [Cu 2 (pa) 2 (3-methoxybenzoate) 2 ] (2), [Cu 2 (pa) 2 (4-methoxybenzoate) 2 ] (3), [Cu 2 (H 2 tea) 2 (benzoate) 2 ]·2H 2 O (4), [Cu 2 (H 2 tea) 2 (2-hydroxybenzoate) 2 ]·2H 2 O (5), [Cu 2 (H 3 tea) 2 (4-hydroxybenzoate) 2 ][Cu(Htea) 2 ]·2H 2 O (6), [Cu(H 2 mdea) 2 ][benzoate] 2 (7), [Cu(H 2 mdea) 2 ][4-methoxybenzoate] 2 (8), [Cu(H 2 bdea) 2 ][2-hydroxybenzoate] 2 (9), [Cu 2 (benzoate) 4 (benzoic acid) 2 ] (10), [Cu 2 (4-methoxybenzoate) 4 (CH 3 CN) 2 ]·4CH 3 CN (11) and [Cu 3 (H 2 tea) 2 (benzoate) 2 (NO 3 ) 2 ] (12) were formed as mono-, di- or trinuclear entities depending upon the pH conditions of the reaction. The complexes were characterized employing spectral, magnetic, single-crystal X-ray and DFT/TDDFT studies. 7 and 8 exhibited emission peaks at 510 and 460 nm, respectively, in the solid-state photoluminescence (PL) spectra. The temperature variable magnetic properties of 1-12 revealed the presence of antiferromagnetic (in 1-3 and 7-11) or ferromagnetic interactions (in 4-6 and 12) with Curie constants C = 0.24 (7), 0.28 (8) or 0.35 cm 3 K mol -1 (9) and Weiss constants θ = -0.34 (7), -0.32 (8) or -0.40 (9) K for the mononuclear complexes. The dinuclear complexes demonstrated J values of -89.2(2) (1), -71.1(3) (2), -59.6(1) (3), 98(1) (4), 79.1(2) (5), -85.4(2) (10) and -89.5(2) (11) cm -1 . Strong ferromagnetic interactions were observed in the case of 6 (J = 172(3) cm -1 and zJ' = 2.3(2) cm -1 ), which were comparable with those

  2. Synthesis of a new ONNO donor tetradentate schiff base ligand and binuclear Cu(II) complex: Quantum chemical, spectroscopic and photoluminescence investigations

    International Nuclear Information System (INIS)

    Sarıoğlu, Ahmet Oral; Ceylan, Ümit; Yalçın, Şerife Pınar; Sönmez, Mehmet; Ceyhan, Gökhan; Aygün, Muhittin

    2016-01-01

    The Schiff base compound 3,3′-(1,4-phenylimino)-bis-[1,3-bis-(4-methoxyphenyl) propan-1-one)], formulated as C 40 H 36 N 2 O 6, and its Cu(II) complex were synthesized and characterized by analytical analysis, various spectral techniques such as FT-IR, NMR, UV–vis, magnetic measurements and molar conductivity. Thermo gravimetric analysis (TGA and DTA) carried out to obtain information about its thermal stability. The molecular structure and spectroscopic properties of the ligand were obtained with FT-IR, 1 H and 13 C NMR, UV–vis investigations as experimentally and compared with theoretical results obtained from DFT/B3LYP/6-311++G(d,p) basis set. In addition to molecular calculations of the title compound, molecular electrostatic potential (MEP), dipole moments, atomic charges, HOMO–LUMO, NLO and NBO analysis were computed. The calculated results show that the optimized geometry can well reproduce the crystal structure parameters, and the theoretical vibrational frequencies, 1 H and 13 C NMR chemical shifts show good agreement with experimental values. Photoluminescence properties of the ligand and its Cu(II) complex were examined. - Highlights: • FT-IR and 1 H– 13 C NMR spectra were recorded and compared with the theoretical results. • The photoluminescence properties were studied. • NLO, NBO analysis of the molecule were studied. • HOMO and LUMO energies, MEP distribution of the molecule were calculated.

  3. Uranyl Oxalate Solubility

    Energy Technology Data Exchange (ETDEWEB)

    Leturcq, G.; Costenoble, S.; Grandjean, S. [CEA Marcoule DEN/DRCP/SCPS/LCA - BP17171 - 30207 Bagnols sur Ceze cedex (France)

    2008-07-01

    The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO{sub 2}C{sub 2}O{sub 4}, 3H{sub 2}O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO{sub 2}C{sub 2}O{sub 4} (log {beta}1), for ionic strengths varying between 1 and 3 mol/L. Ks and log {beta}1 values were found to vary from 1.9 10{sup -8} to 9.2 10{sup -9} and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H{sup +}] at 3 M. The Ks value would then be 1.3 10{sup -8}. (authors)

  4. Water-soluble building blocks for terpyridine-containing supramolecular polymers : synthesis, complexation, and pH stability studies of poly(ethylene oxide) moieties

    NARCIS (Netherlands)

    Lohmeijer, B.G.G.; Schubert, U.S.

    2003-01-01

    Poly(ethylene oxide) of various molecular weights ([bar M ]n = 3 000, 5 200, 10 000, 16 500 g · mol-1) has been modified with terpyridine end groups as building blocks for water-soluble metallo-supramolecular polymers. Metallo-supramolecular A-A homopolymers have been prepared and characterized by

  5. Dinuclear copper(II) complexes with {Cu2(mu-hydroxo)bis(mu-carboxylato)}+ cores and their reactions with sugar phosphate esters: A substrate binding model of fructose-1,6-bisphosphatase.

    Science.gov (United States)

    Kato, Merii; Tanase, Tomoaki; Mikuriya, Masahiro

    2006-04-03

    Reactions of CuX2.nH2O with the biscarboxylate ligand XDK (H2XDK = m-xylenediamine bis(Kemp's triacid imide)) in the presence of N-donor auxiliary ligands yielded a series of dicopper(II) complexes, [Cu2(mu-OH)(XDK)(L)2]X (L = N,N,N',N'-tetramethylethylenediamine (tetmen), X = NO3 (1a), Cl (1b); L = N,N,N'-trimethylethylenediamine (tmen), X = NO3 (2a), Cl (2b); L =2,2'-bipyridine (bpy), X = NO3 (3); L = 1,10-phenanthroline (phen), X = NO3 (4); L = 4,4'-dimethyl-2,2'-bipyridine (Me2bpy), X = NO3 (5); L = 4-methyl-1,10-phenanthroline (Mephen), X = NO3 (6)). Complexes 1-6 were characterized by X-ray crystallography (Cu...Cu = 3.1624(6)-3.2910(4) A), and the electrochemical and magnetic properties were also examined. Complexes 3 and 4 readily reacted with diphenyl phosphoric acid (HDPP) or bis(4-nitrophenyl) phosphoric acid (HBNPP) to give [Cu2(mu-phosphate)(XDK)(L)2]NO3 (L = bpy, phosphate = DPP (11); L = phen, phosphate = DPP (12), BNPP (13)), where the phsophate diester bridges the two copper ions in a mu-1,3-O,O' bidentate fashion (Cu...Cu = 4.268(3)-4.315(1) A). Complexes 4 and 6 with phen and Mephen have proven to be good precursors to accommodate a series of sugar monophosphate esters (Sugar-P) onto the biscarboxylate-bridged dicopper centers, yielding [Cu2(mu-Sugar-P)(XDK)(L)2] (Sugar-P = alpha-D-Glc-1-P (23a and b), D-Glc-6-P (24a and b), D-Man-6-P (25a), D-Fru-6-P (26a and b); L = phen (a), Mephen (b)) and [Cu2(mu-Gly-n-P)(XDK)(Mephen)2] (Gly-n-P = glycerol n-phosphate; n = 2 (21), 3 (22)), where Glc, Man, and Fru are glucose, mannose, and fructose, respectively. The structure of [Cu2(mu-MNPP)(XDK)(phen)2(CH3OH)] (20) was characterized as a reference compound (H2MNPP = 4-nitrophenyl phosphoric acid). Complexes 4 and 6 also reacted with d-fructose 1,6-bisphosphate (D-Fru-1,6-P2) to afford the tetranuclear copper(II) complexes formulated as [Cu4(mu-D-Fru-1,6-P2)(XDK)2(L)4] (L = phen (27a), Mephen (27b)). The detailed structure of 27a was determined by X

  6. The preparation and characterization of Cu(II complexes with N,N’,N”,N’”-tetrakis(2-pyridylmethyl-1,4,8,11-tetraazacyclotetradecane and 2,6-diacetylpyridine bis(semi/thiosemicarbazones

    Directory of Open Access Journals (Sweden)

    GORDANA VUCKOVIC

    2004-03-01

    Full Text Available Two new Cu(II mixed-ligand complexes with octadentate N,N’,N”,N’”-tetrakis(2-pyridylmethyl-1,4,8,11-tetraazacyclotetradecane (tpmc and potentially pentadentate ligands 2,6-diacetylpyridine bis(semicarbazone (DAPsc2 or 2,6-diacetylpyridine bis(thiosemicarbazone (DAPtsc2 were prepared. The general formulas: [Cu4 DAPsc2(tpmc2]ClO48·5CH3COCH3·H2O and [Cu2 DAPtsc2(tpmc](ClO44·7C2H5OH were proposed on the basis of elemental analyses and conductometric measurements. The complexes were characterized by magnetic measurement, electronic absorption and IR spectroscopy. For the dinuclear complex, an exo coordination of Cu(II with four nitrogens from tpmc and m-bonded DAPtsc2 through sulfurs and possibly terminal hydrazinic (azomethine nitrogens is assumed. For the tetranuclear complex, it is supposed that one DAPsc2 bridges two [Cu2 tpmc]4+ units using oxygens and terminal hydrazinic nitrogens as ligators. Finally, some antibacterial activity of the complexes was found.

  7. A non-aqueous all-copper redox flow battery with highly soluble active species

    International Nuclear Information System (INIS)

    Li, Yun; Sniekers, Jeroen; Malaquias, João; Li, Xianfeng; Schaltin, Stijn; Stappers, Linda; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F.J.

    2017-01-01

    A metal-based redox pair with acetonitrile as ligand [Cu(MeCN)_4][Tf_2N] is described for use in non-aqueous redox flow battery (RFB). The electrode kinetics of the anode and cathode are studied using cyclic voltammetry. The Cu"2"+/Cu"+ and Cu"+/Cu couples in this system yield a cell potential of 1.24 V. The diffusion coefficient for [Cu(MeCN)_4][Tf_2N] in acetonitrile is estimated to be 6.8 × 10"−"6 cm"2 s"−"1 at room temperature. The copper-acetonitrile complex has a very high solubility of 1.68 M in acetonitrile, the most widely used organic solvent for non-aqueous electrochemical applications. Hence, a maximum theoretical energy density around 28 Wh L"−"1 can be reached with the reported system. The RFB with this electrolyte shows a promising performance, with coulombic efficiencies of 87% and energy efficiencies of 44% (5 mA cm"−"2).

  8. Model studies of the Cu(B) site of cytochrome c oxidase utilizing a Zn(II) complex containing an imidazole-phenol cross-linked ligand.

    Science.gov (United States)

    Pesavento, Russell P; Pratt, Derek A; Jeffers, Jerry; van der Donk, Wilfred A

    2006-07-21

    Cytochrome c oxidase, the enzyme complex responsible for the four-electron reduction of O2 to H2O, contains an unusual histidine-tyrosine cross-link in its bimetallic heme a3-CuB active site. We have synthesised an unhindered, tripodal chelating ligand, BPAIP, containing the unusual ortho-imidazole-phenol linkage, which mimics the coordination environment of the CuB center. The ligand was used to investigate the physicochemical (pKa, oxidation potential) and coordination properties of the imidazole-phenol linkage when bound to a dication. Zn(II) coordination lowers the pKa of the phenol by 0.6 log units, and increases the potential of the phenolate/phenoxyl radical couple by approximately 50 mV. These results are consistent with inductive withdrawal of electron density from the phenolic ring. Spectroscopic data and theoretical calculations (DFT) were used to establish that the cationic complex [Zn(BPAIP)Br]+ has an axially distorted trigonal bipyramidal structure, with three coordinating nitrogen ligands (two pyridine and one imidazole) occupying the equatorial plane and the bromide and the tertiary amine nitrogen of the tripod in the axial positions. Interestingly, the Zn-Namine bonding interaction is weak or absent in [Zn(BPAIP)Br]+ and the complex gains stability in basic solutions, as indicated by 1H NMR spectroscopy. These observations are supported by theoretical calculations (DFT), which suggest that the electron-donating capacity of the equatorial imidazole ligand can be varied by modulation of the protonation and/or redox state of the cross-linked phenol. Deprotonation of the phenol makes the equatorial imidazole a stronger sigma-donor, resulting in an increased Zn-Nimd interaction and thereby leading to distortion of the axial ligand axis toward a more tetrahedral geometry.

  9. Controlled synthesis, formation mechanism, and carbon oxidation properties of Ho{sub 2}Cu{sub 2}O{sub 5} nanoplates prepared with a coordination-complex method

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Rui [School of Resources and Materials, Northeastern University at Qinhuangdao 066004 (China); School of Metallurgy, Northeastern University, Shenyang 110004 (China); You, Junhua [School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870 (China); Han, Fei; Li, Chaoyang; Zheng, Guiyuan; Xiao, Weicheng [School of Resources and Materials, Northeastern University at Qinhuangdao 066004 (China); Liu, Xuanwen, E-mail: lxw@mail.neuq.edu.cn [School of Resources and Materials, Northeastern University at Qinhuangdao 066004 (China); School of Metallurgy, Northeastern University, Shenyang 110004 (China)

    2017-02-28

    Highlights: • The crystallization mechanism relies on Ho{sup 3+} and Cu{sup 2+} diffusion. • The Ho{sub 2}Cu{sub 2}O{sub 5} particles are refined by the coordination complex method under N{sub 2} environment. • The catalytic oxidation activity of Ho{sub 2}Cu{sub 2}O{sub 5} samples for carbon is enhanced. - Abstract: Ho{sub 2}Cu{sub 2}O{sub 5} nanoplates with perovskite structures were synthesized via a simple solution method (SSM) and a coordination-complex method (CCM) using [HoCu(3,4-pdc){sub 2}(OAc)(H{sub 2}O){sub 3}]·8H{sub 2}O (L = 3,4-pyridinedicarboxylic acid) as a precursor. The CCM was also performed in an N{sub 2} environment (CCMN) under various calcination conditions. The crystallization processes were characterized using X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. Ho{sub 2}Cu{sub 2}O{sub 5} formed through the diffusion of CuO into Ho{sub 2}O{sub 3} particles. Cu{sup 2+} diffused faster than Ho{sup 3+} during this process. The initial products of CCMN (along with the thermal decomposition products) were initially laminarized in the N{sub 2} atmosphere, which prevented the growth of CuO particles and decreased the size of the Ho{sub 2}Cu{sub 2}O{sub 5} particles. The final Ho{sub 2}Cu{sub 2}O{sub 5} particles from CCMN had a nanoplate morphology with an average thickness of 75 nm. The decomposition of organic molecules and protection from N{sub 2} played important roles in determining the morphology of the resulting Ho{sub 2}Cu{sub 2}O{sub 5}. The catalytic oxidation activity of Ho{sub 2}Cu{sub 2}O{sub 5} samples for carbon was characterized using a specific surface area measurement and thermogravimetric analysis, which revealed that the samples produced by CCMN had the highest catalytic activity.

  10. Synthesis and characterization of 5-amino-2-((3-hydroxy-4-((3-hydroxyphenyl phenyl diazenyl phenol and its Cu(II complex – a strategy toward developing azo complexes for reduction of cytotoxicity

    Directory of Open Access Journals (Sweden)

    Durba Ganguly

    2014-12-01

    Full Text Available A major drawback of azo compounds is their associated toxicity, often carcinogenic, which is related to the reduction of the azo bond. This study intends to re-investigate this behavior by studying 5-amino-2-((3-hydroxy-4-((3-hydroxyphenyl phenyl diazenyl phenol (AHPD, a compound containing two azo bonds. Interaction of AHPD and its dimeric Cu(II complex with bacterial strains Escherichia coli and Staphylococcus aureus revealed the complex was less toxic. Reductive cleavage of the azo bond in AHPD and the complex followed using cytochrome c reductase (a model azo-reductase as well as azo-reductase enzymes obtained from bacterial cell extracts. Degradation of the azo bond was less in the complex allowing us to correlate the observed cytotoxicity. Cyclic voltammetry on AHPD and the complex support observations of enzyme assay experiments. These were particularly useful in realizing the formation of amines as an outcome of the reductive cleavage of azo bonds in AHPD that could not be identified through an enzyme assay. Results suggest that complex formation of azo compounds could be a means to control the formation of amines responsible for cytotoxicity. Studies carried out on bacterial cells for mere simplicity bear significance for multicellular organisms and could be important for human beings involved with the preparation and utilization of azo dyes.

  11. Microwave synthesis, spectral, thermal and antimicrobial studies of some Ni(II) and Cu(II) Schiff base complexes

    OpenAIRE

    Mishra, A. P.; Sharma, Neha; Jain, Rajendra K.

    2012-01-01

    Se sintetizaron bases de Schiff bidentadas y tridentadas (NO), (ONO) a través de la reacción de condensación entre la metil-isobutilcetona y el 2-amino-4clorofonol y 2-hidroxiacetofenona con la hidracina del ácido isonicotínico. Los complejos metálicos 1:1 o 1:2 han sido preparados mediante la interacción de estas bases de Schiff y los iones Ni(II) y Cu(II). La síntesis fue realizada empleando el método convencional y el de microondas, y los productos fueron caracterizados por análisis elemen...

  12. Complexing power of hydro-soluble degradation products from γ-irradiated polyvinylchloride. Influence on Eu(OH)_3(s) solubility and Eu(III) speciation in neutral to alkaline environment

    International Nuclear Information System (INIS)

    Reiller, Pascal E.; Badji, Hawa; Tabarant, Michel; Vercouter, Thomas; Fromentin, Elodie; Ferry, Muriel; Dannoux-Papin, Adeline

    2017-01-01

    The complexing power of hydrosoluble degradation products (HDPs) from an alkaline hydrolysis of a 10 MGy γ-irradiated polyvinylchloride is studied. The complexation of Eu(III), as an analogue of lanthanide and actinide radionuclides at their +III oxidation state for oxygen containing functions, is evidenced both from the increasing of Eu(OH)_3(s) dissolution, and from a complexometric titration by time-resolved luminescence spectroscopy. The dissolution of Eu(OH)_3(s) in a simplified alkaline solution (0.3 M KOH/0.1 M NaOH) increases moderately, but significantly, with the HDPs concentration. The luminescence signal of the supernatant clearly indicates the presence of several complexed Eu(III) species. Performing a complexometric titration of Eu(III) from pH 6 by alkaline HDPs shows the formation of two different species with increasing HDPs' concentration and pH. Operational complexation constants - based on dissolved carbon concentration - are proposed. The analyses of the spectra and luminescence decays seem to confirm the presence of two different species.

  13. Complexing power of hydro-soluble degradation products from γ-irradiated polyvinylchloride. Influence on Eu(OH){sub 3}(s) solubility and Eu(III) speciation in neutral to alkaline environment

    Energy Technology Data Exchange (ETDEWEB)

    Reiller, Pascal E.; Badji, Hawa; Tabarant, Michel; Vercouter, Thomas [CEA, Paris-Saclay Univ., Gif-sur-Yvette (France). Service d' Etudes Analytiques et de Reactivite des Surfaces (SEARS); Fromentin, Elodie; Ferry, Muriel [CEA, Paris-Saclay Univ., Gif-sur-Yvette (France). Service d' Etudes du Comportement des Radionucleides (SECR); Dannoux-Papin, Adeline [CEA, Bagnols-sur-Ceze (France). Service des Procedes de Decontamination et d' Enrobage

    2017-10-01

    The complexing power of hydrosoluble degradation products (HDPs) from an alkaline hydrolysis of a 10 MGy γ-irradiated polyvinylchloride is studied. The complexation of Eu(III), as an analogue of lanthanide and actinide radionuclides at their +III oxidation state for oxygen containing functions, is evidenced both from the increasing of Eu(OH){sub 3}(s) dissolution, and from a complexometric titration by time-resolved luminescence spectroscopy. The dissolution of Eu(OH){sub 3}(s) in a simplified alkaline solution (0.3 M KOH/0.1 M NaOH) increases moderately, but significantly, with the HDPs concentration. The luminescence signal of the supernatant clearly indicates the presence of several complexed Eu(III) species. Performing a complexometric titration of Eu(III) from pH 6 by alkaline HDPs shows the formation of two different species with increasing HDPs' concentration and pH. Operational complexation constants - based on dissolved carbon concentration - are proposed. The analyses of the spectra and luminescence decays seem to confirm the presence of two different species.

  14. Usage of a statistical method of designing factorial experiments in the mechanical activation of a complex CuPbZn sulphide concentrate

    Directory of Open Access Journals (Sweden)

    BalហPeter

    2003-09-01

    Full Text Available Mechanical activation belongs to innovative procedures which intensify technological processes by creating new surfaces and making a defective structure of solid phase. Mechanical impact on the solid phase is a suitable procedure to ensure the mobility of its structure elements and to accumulate the mechanical energy that is later used in the processes of leaching.The aim of this study was to realize the mechanical activation of a complex CuPbZn sulphide concentrate (Slovak deposit in an attritor by using of statistical methods for the design of factorial experiments and to determine the conditions for preparing the optimum mechanically activated sample of studied concentrate.The following parameters of the attritor were studied as variables:the weight of sample/steel balls (degree of mill filling, the number of revolutions of the milling shaft and the time of mechanical activation. Interpretation of the chosen variables inducing the mechanical activation of the complex CuPbZn concentrate was also carried out by using statistical methods of factorial design experiments. The presented linear model (23 factorial experiment does not support directly the optimum search, therefore this model was extended to the nonlinear model by the utilization of second order ortogonal polynom. This nonlinear model does not describe adequately the process of new surface formation by the mechanical activation of the studied concentrate. It would be necessary to extend the presented nonlinear model to the nonlinear model of the third order or choose another model. In regard to the economy with the aspect of minimal energy input consumption, the sample with the value of 524 kWht-1 and with the maximum value of specific surface area 8.59 m2g-1 (as a response of the factorial experiment was chosen as the optimum mechanically activated sample of the studied concentrate. The optimum mechanically activated sample of the complex CuPbZn sulphide concentrate was prepared

  15. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    Science.gov (United States)

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  16. New complexes of Co(II, Ni(II, Cu(II with Schiff base N,N’-bis-(3-methoxy-saliciliden-3,3’-dimethylbenzidine

    Directory of Open Access Journals (Sweden)

    Alan Ionela

    2013-01-01

    Full Text Available The new N,N’-bis-(3-methoxy-saliciliden-3,3’-dimetilbenzidine (H2L Schiff base and complexes with Co(II, Ni(II and Cu(II of type [M(HLCl(H2O] (M=Co(II, Cu(II [M2L(H2O4]X2 (M=Co(II, X=ClO4 and M=Cu(II, X=NO3 and [M2L(CH3COO2] (M=Co(II, Ni(II, Cu(II were synthesised. The ligand and complexes were characterized by elemental analysis, conductibility measurements, magnetic moments at room temperature, IR, NMR, UV-VIS-NIR, EPR spectra and thermogravimetric analysis. A molar ratio of 1:1 or 1:2 between ligand and metal was determined from the elemental analysis. Except for perchlorate complex that behave as electrolyte, the rest of complexes are non-electrolytes. The spectral data suggest a tetrahedral, pseudo-tetrahedral or square-planar stereochemistry respectively, data confirmed by magnetic behaviour of complexes. The antimicrobial tests indicate a fungicide effect both for ligand and complexes.

  17. Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Aparup [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721102, West Bengal (India); Bertolasi, Valerio [Dipartimento di Scienze Chimiche e Farmaceutiche, Centro di Strutturistica Diffrattometrica, Università di Ferrara, Via L. Borsari, 46, 44100 Ferrara (Italy); Figuerola, Albert [Departament de Química Inorgànica i Orgànica (Secció de Química Inorgànica) and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain); Manna, Subal Chandra, E-mail: scmanna@mail.vidyasagar.ac.in [Department of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721102, West Bengal (India)

    2017-05-15

    Three novel tetranuclear copper(II) complexes namely [Cu{sub 4}(L{sup 1}){sub 4}]∙2(dmf) (1), [Cu{sub 4}(L{sup 1}){sub 4}] (2) and [Cu{sub 4}(L{sup 2}){sub 2}(HL{sup 2}){sub 2}(H{sub 2}O){sub 2}]∙2(ClO{sub 4})·6(H{sub 2}O) (3) (H{sub 2}L{sup 1}, (E)−2-((1-hydroxybutan-2-ylimino)methyl)phenol; H{sub 2}L{sup 2}, (E)−2-((1-hydroxybutan-2-ylimino)methyl)−6-methoxyphenol)) were synthesized from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that crystallizes in the monoclinic system with space group C2/c, whereas both the and crystallize in the triclinic system with space group P-1. and possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π…π and C–H…π interactions lead to formation of a 2D supramolecular architecture for and . At room temperature and , exhibit fluorescence with a quantum yield (Φ{sub s}) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2–300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H =– J{sub 1}(S{sub 1}S{sub 2}+S{sub 1}S{sub 2’}+S{sub 1'}S{sub 2}+S{sub 1'}S{sub 2’}) – J{sub 2}S{sub 1}S{sub 1’}, where S{sub 1} = S{sub 1’} = S{sub 2} = S{sub 2’} = S{sub Cu} =1/2, was used for studying and . Simulations performed suggest magnetic exchange constants with values close to J{sub 1} =−20 cm{sup −1} and J{sub 2} =0 cm{sup -1} for these complexes. On the other hand, the spin Hamiltonian H =– J{sub 1}(S{sub 1}S{sub 4}+S{sub 2}S{sub 3}) – J{sub 2}(S{sub 1}S{sub 3}+S{sub 2}S{sub 4}) – J{sub 3}S{sub 1}S{sub 2}, where S{sub 1} = S{sub 2} = S{sub 3} = S{sub 4

  18. The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal

    Science.gov (United States)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua

    2017-10-01

    Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

  19. Effect of Dietary Phytase Supplementation on Bone and Hyaline Cartilage Development of Broilers Fed with Organically Complexed Copper in a Cu-Deficient Diet.

    Science.gov (United States)

    Muszyński, Siemowit; Tomaszewska, Ewa; Kwiecień, Małgorzata; Dobrowolski, Piotr; Tomczyk, Agnieszka

    2018-04-01

    Tibial mechanical, chemical, and histomorphometrical traits were investigated for growing male Ross 308 broiler chickens fed diets that had copper (Cu) from organic source at a lowered level of 25% of the daily requirement (4 mg kg -1 of a premix) with or without phytase. Dietary treatments were control non-copper, non-phytase group (0 Suppl); 4 mg kg -1 Cu non-phytase group (25%Cu); and 4 mg kg -1 Cu + 500 FTU kg -1 phytase group (25%Cu + phyt). The results show that birds fed with the addition of phytase exhibited improved weight gain and final body weight and had increased serum IGF-1 and osteocalcin concentrations. The serum concentration of Cu and P did not differ between groups; however, Ca concentration decreased in the 25%Cu + phyt group when compared to the 25%Cu group. Added Cu increased bone Ca, P, Cu, and ash content in Cu-supplemented groups, but bone weight and length increased only by the addition of phytase. Bone geometry, yield, and ultimate strengths were affected by Cu and phytase addition. A decrease of the elastic stress and ultimate stress of the tibia in Cu-supplemented groups was observed. The histomorphometric analysis showed a positive effect of Cu supplementation on real bone volume and trabecular thickness in the tibia metaphyseal trabeculae; additionally, phytase increased the trabeculea number. The supplementation with Cu significantly increased the total articular cartilage and growth plate cartilage thickness; however, the changes in thickness of particular zones were dependent upon phytase addition. In summary, dietary Cu supplements given to growing broilers with Cu in their diet restricted to 25% of the daily requirement had a positive effect on bone metabolism, and phytase supplementation additionally improved cartilage development.

  20. Immobilization of [Cu(bpy)2]Br2 complex onto a glassy carbon electrode modified with alpha-SiMo12O40(4-) and single walled carbon nanotubes: application to nanomolar detection of hydrogen peroxide and bromate.

    Science.gov (United States)

    Salimi, Abdollah; Korani, Aazam; Hallaj, Rahman; Khoshnavazi, Roshan; Hadadzadeh, Hasan

    2009-03-02

    A simple procedure has been used for preparation of modified glassy carbon electrode with carbon nanotubes and copper complex. Copper complex [Cu(bpy)(2)]Br(2) was immobilized onto glassy carbon (GC) electrode modified with silicomolybdate, alpha-SiMo(12)O(40)(4-) and single walled carbon nanotubes (SWCNTs). Copper complex and silicomolybdate irreversibly and strongly adsorbed onto GC electrode modified with CNTs. Electrostatic interactions between polyoxometalates (POMs) anions and Cu-complex, cations mentioned as an effective method for fabrication of three-dimensional structures. The modified electrode shows three reversible redox couples for polyoxometalate and one redox couple for Cu-complex at wide range of pH values. The electrochemical behavior, stability and electron transfer kinetics of the adsorbed redox couples were investigated using cyclic voltammetry. Due to electrostatic interaction, copper complex immobilized onto GC/CNTs/alpha-SiMo(12)O(40)(4-) electrode shows more stable voltammetric response compared to GC/CNTs/Cu-complex modified electrode. In comparison to GC/CNTs/Cu-complex the GC/CNTs/alpha-SiMo(12)O(40)(4-) modified electrodes shows excellent electrocatalytic activity toward reduction H(2)O(2) and BrO(3)(-) at more reduced overpotential. The catalytic rate constants for catalytic reduction hydrogen peroxide and bromate were 4.5(+/-0.2)x10(3) M(-1) s(-1) and 3.0(+/-0.10)x10(3) M(-1) s(-1), respectively. The hydrodynamic amperommetry technique at 0.08 V was used for detection of nanomolar concentration of hydrogen peroxide and bromate. Detection limit, sensitivity and linear concentration range proposed sensor for bromate and hydrogen peroxide detection were 1.1 nM and 6.7 nA nM(-1), 10 nM-20 microM, 1 nM, 5.5 nA nM(-1) and 10 nM-18 microM, respectively.

  1. Compounds Containing Tetragonal Cu2+ Complexes: Is the dx2–y2–d3z2–r2 Gap a Direct Reflection of the Distortion?

    DEFF Research Database (Denmark)

    García-Fernández, Pablo; Barriuso, María Teresa; García Lastra, Juan Maria

    2013-01-01

    complex. This internal field, especially important for layered compounds, is shown to explain all puzzling experimental facts on the d–d transitions of the studied systems and is of interest in the search of new Cu2+ and Ag2+ superconducting materials where a strong correlation between Δ...... to be not correct through the study of pure K2CuF4-, KCuF3-, and Cu2+-doped KZnF3 and K2ZnF4 model compounds. Indeed, ab initio calculations prove that Δ in these insulating materials also depends on the internal electric field created by the rest of lattice ions on active electrons confined in a given CuF64...

  2. Antibacterial Co(II, Ni(II, Cu(II and Zn(II complexes with biacetyl-derived Schiff bases

    Directory of Open Access Journals (Sweden)

    MUHAMMAD IMRAN

    2010-08-01

    Full Text Available The condensation reactions of biacetyl with ortho-hydroxyaniline and 2-aminobenzoic acid to form bidendate NO donor Schiff bases were studied. The prepared Schiff base ligands were further utilized for the formation of metal chelates having the general formula [ML2(H2O2] where M = Co(II, Ni(II, Cu(II and Zn(II and L = HL1 and HL2. These new compounds were characterized by conductance measurements, magnetic susceptibility measurements, elemental analysis, and IR, 1H-NMR, 13C-NMR and electronic spectroscopy. Both Schiff base ligands were found to have a mono-anionic bidentate nature and octahedral geometry was assigned to all metal complexes. All the complexes contained coordinated water which was lost at 141–160 °C. These compounds were also screened for their in vitro antibacterial activity against four bacterial species, namely: Escherichia coli, Staphylococcus aureus, Salmonella typhi and Bacillus subtilis. The metal complexes were found to have greater antibacterial activity than the uncomplexed Schiff base ligands.

  3. Carbonate binding to copper(II) in solution: mixed-ligand complex formation and its application to the isolation and separation of the three isomers of [Cu(bpp)(H2O)][ClO4]2 [bpp = 2,6-bis(pyrrolidin-2-yl)pyridine

    OpenAIRE

    Bernauer, Klaus; Godefroy, Isabelle; Cabort, Amel; Guicher, Nathalie; Stoeckli-Evans, Helen; Süss-Fink, Georg

    2006-01-01

    The binding of the carbonate anion to [Cu(meso-bpp)(H2O)]2+ and rac-[Cu(bpp)(H2O)]2+ [bpp = 2,6-bis(pyrrolidin-2-yl)pyridine] in aqueous solution has been investigated. Formation constants of the carbonato complexes [Cu(meso-bpp)(CO3)] and rac-[Cu(bpp)(CO3)] (1.02 × 103 M–1 and 1.77 × 103 M–1, respectively, µ= 0.70 M) have been calculated from spectrophotometric measurements. The formation of these Cu2+ complexes can also be used for an improved synthesis and an easy isolation of the three di...

  4. Thermodynamics and kinetics insight into reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} nanoink based on binary metal-amine complexes in polyetheramine-synthesized process

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chi-Jie [Institute of Microelectronics and Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China); Shei, Shih-Chang, E-mail: scshei@mail.nutn.edu.tw [Department of Electrical Engineering, National University of Tainan, 700, Taiwan, ROC (China); Chang, Shoou-Jinn [Institute of Microelectronics and Department of Electrical Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China)

    2016-08-15

    This paper reports on the reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) nanoink via a solvent-thermal reflux method using copper (Cu), zinc (Zn), tin (Sn), and selenium (Se) powders as precursors and polyetheramine as a reaction solvent. The formation of CZTSe nanoparticles in polyetheramine began with the formation of binary phase CuSe and CuSe{sub 2} due to the strong catalysis provided by polyetheramine. Finally, ternary crystals of Cu{sub 2}SnSe{sub 3} transformed into well-dispersed nanocrystals of Cu{sub 2}ZnSnSe{sub 4}. The size of the crystals was shown to decrease with reaction time due to the emulsification effect of the polyetheramine epoxy group. The PH value-reaction time curves for single Cu, Zn elements and CZTSe from all participants elements reacted together have a relationship just reversed each other and both multistage feature were observed, which indicates that the CZTSe reaction was dominated by copper and zinc elements. The PH-temperature mechanism demonstrates that the reaction was controlled by the formation of metal-amine complexes, especially, after heating the PH-time variation manner is the same for pure element and all four elements reacted together. To the best of our knowledge, this is the first study on the mechanism underlying CZTSe formation based on the reactivity and stability of reaction species. - Highlights: • Reaction mechanism of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) nanoink via a solvent-thermal reflux method using polyetheramine was developed. • PH effect on thermal dynamics and characteristics of reagents and solvents in the CZTSe nanoink has been realized. • PH-temperature mechanism demonstrates that the reaction controlled by the formation of metal-amine complexes.

  5. Cofortification of ferric pyrophosphate and citric acid/trisodium citrate into extruded rice grains doubles iron bioavailability through in situ generation of soluble ferric pyrophosphate citrate complexes.

    Science.gov (United States)

    Hackl, Laura; Cercamondi, Colin I; Zeder, Christophe; Wild, Daniela; Adelmann, Horst; Zimmermann, Michael B; Moretti, Diego

    2016-05-01

    Iron fortification of rice is a promising strategy for improving iron nutrition. However, it is technically challenging because rice is consumed as intact grains, and ferric pyrophosphate (FePP), which is usually used for rice fortification, has low bioavailability. We investigated whether the addition of a citric acid/trisodium citrate (CA/TSC) mixture before extrusion increases iron absorption in humans from FePP-fortified extruded rice grains. We conducted an iron absorption study in iron-sufficient young women (n = 20), in which each participant consumed 4 different meals (4 mg Fe/meal): 1) extruded FePP-fortified rice (No CA/TSC); 2) extruded FePP-fortified rice with CA/TSC added before extrusion (CA/TSC extruded); 3) extruded FePP-fortified rice with CA/TSC solution added after cooking and before consumption (CA/TSC solution); and 4) nonextruded rice fortified with a FeSO4 solution added after cooking and before consumption (reference). Iron absorption was calculated from erythrocyte incorporation of stable iron isotopes 14 d after administration. In in vitro experiments, we assessed the soluble and dialyzable iron from rice meals in which CA/TSC was added at different preparation stages and from meals with different iron:CA:TSC ratios. Fractional iron absorption was significantly higher from CA/TSC-extruded meals (3.2%) than from No CA/TSC (1.7%) and CA/TSC solution (1.7%; all P solubility and dialyzability were higher in CA/TSC-extruded rice than in rice with No CA/TSC and CA/TSC solution, and solubility increased with higher amounts of added CA and TSC in extruded rice. Iron bioavailability nearly doubled when CA/TSC was extruded with FePP into fortified rice, resulting in iron bioavailability comparable to that of FeSO4 We attribute this effect to an in situ generation of soluble FePP citrate moieties during extrusion and/or cooking because of the close physical proximity of FePP and CA/TSC in the extruded rice matrix. This trial was registered at

  6. Selective and Sensitive Detection of Cyanide Based on the Displacement Strategy Using a Water-Soluble Fluorescent Probe

    Science.gov (United States)

    La, Ming; Hao, Yuanqiang; Wang, Zhaoyang; Han, Guo-Cheng; Qu, Lingbo

    2016-01-01

    A water-soluble fluorescent probe (C-GGH) was used for the highly sensitive and selective detection of cyanide (CN−) in aqueous media based on the displacement strategy. Due to the presence of the recognition unit GGH (Gly-Gly-His), the probe C-GGH can coordinate with Cu2+ and consequently display ON-OFF type fluorescence response. Furthermore, the in situ formed nonfluorescent C-GGH-Cu2+ complex can act as an effective OFF-ON type fluorescent probe for sensing CN− anion. Due to the strong binding affinity of CN− to Cu2+, CN− can extract Cu2+ from C-GGH-Cu2+ complex, leading to the release of C-GGH and the recovery of fluorescent emission of the system. The probe C-GGH-Cu2+ allowed detection of CN− in aqueous solution with a LOD (limit of detection) of 0.017 μmol/L which is much lower than the maximum contaminant level (1.9 μmol/L) for CN− in drinking water set by the WHO (World Health Organization). The probe also displayed excellent specificity for CN− towards other anions, including F−, Cl−, Br−, I−, SCN−, PO4 3−, N3 −, NO3 −, AcO−, SO4 2−, and CO3 2−. PMID:26881185

  7. Selective and Sensitive Detection of Cyanide Based on the Displacement Strategy Using a Water-Soluble Fluorescent Probe

    Directory of Open Access Journals (Sweden)

    Ming La

    2016-01-01

    Full Text Available A water-soluble fluorescent probe (C-GGH was used for the highly sensitive and selective detection of cyanide (CN− in aqueous media based on the displacement strategy. Due to the presence of the recognition unit GGH (Gly-Gly-His, the probe C-GGH can coordinate with Cu2+ and consequently display ON-OFF type fluorescence response. Furthermore, the in situ formed nonfluorescent C-GGH-Cu2+ complex can act as an effective OFF-ON type fluorescent probe for sensing CN− anion. Due to the strong binding affinity of CN− to Cu2+, CN− can extract Cu2+ from C-GGH-Cu2+ complex, leading to the release of C-GGH and the recovery of fluorescent emission of the system. The probe C-GGH-Cu2+ allowed detection of CN− in aqueous solution with a LOD (limit of detection of 0.017 μmol/L which is much lower than the maximum contaminant level (1.9 μmol/L for CN− in drinking water set by the WHO (World Health Organization. The probe also displayed excellent specificity for CN− towards other anions, including F−, Cl−, Br−, I−, SCN−, PO43-, N3-, NO3-, AcO−, SO42-, and CO32-.

  8. Crystal structure, DNA binding, cleavage, antioxidant and antibacterial studies of Cu(II), Ni(II) and Co(III) complexes with 2-((furan-2-yl)methylimino)methyl)-6-ethoxyphenol Schiff base

    Science.gov (United States)

    Venkateswarlu, Kadtala; Kumar, Marri Pradeep; Rambabu, Aveli; Vamsikrishna, Narendrula; Daravath, Sreenu; Rangan, Krishnan; Shivaraj

    2018-05-01

    Three novel binary metal complexes; 1 [Cu(L)2], 2 [Ni(L)2] and 3 [Co(L)3] where, L (2-(((furan-2-yl) methylimino)methyl)-6-ethoxyphenol, C14H15NO3), were synthesized and characterized by various spectral techniques. Based on spectral studies square planar geometry is assigned for Cu(II) and Ni(II) complexes, whereas Co(III) owned octahedral geometry. Ligand, [Cu(L)2] and [Ni(L)2] are crystallized and found to be monoclinic crystal systems. CT-DNA absorption binding studies revealed that the complexes show good binding propensity (Kb = 5.02 × 103 M-1, 2.77 × 103 M-1, 1.63 × 104 M-1 for 1, 2 and 3 respectively). The role of these complexes in the oxidative and photolytic cleavage of supercoiled pBR322 DNA was studied and found that the complexes cleave the pBR322 DNA effectively. The catalytic ability of 1, 2 and 3 follows the order: 3 > 1 >2. Antioxidant studies of the new complexes revealed that they exhibit significant antioxidant activity against DPPH radical. The Schiff base and its metal complexes have been screened for antibacterial studies by Minimum Inhibitory Concentration method. It is observed that all metal complexes showed more activity than free ligand.

  9. Synthesis, characterization, structure and properties of heterobimetallic complexes [CuNi(μ-OAc) (μ-OH) (μ-OH2) (bpy)2] (BF4)2 and [CuNi(bz)3(bpy)2] ClO4 from 2,2‧ bipyridine

    Science.gov (United States)

    Kurbah, Sunshine D.; Kumar, A.; Syiemlieh, I.; Dey, A. K.; Lal, R. A.

    2018-02-01

    Heterobimetallic complexes of the composition [CuNi(bpy)2 (μ-OAc) (μ-OH) (μ-OH2)](BF4)2 (1) and [CuNi(bz)3 (bpy)2]ClO4 (2) were synthesized in moderate yield through solid state reaction and have been characterized by elemental analyses, molar conductance, mass spectra, magnetic moment, EPR, UV-Vis, IR spectroscopies and cyclic voltammetry. The ground state in complex (1) is doublet while that in complex (2), the ground state is a mixture of doublet and quartet, respectively. The structure of the complexes has been established by X-ray crystallography. The electron transfer reactions of the complexes have been investigated by cyclic voltammetry.

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

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

  11. Application of SGT1-Hsp90 chaperone complex for soluble expression of NOD1 LRR domain in E. coli

    International Nuclear Information System (INIS)

    Hong, Tae-Joon; Hahn, Ji-Sook

    2016-01-01

    NOD1 is an intracellular sensor of innate immunity which is related to a number of inflammatory diseases. NOD1 is known to be difficult to express and purify for structural and biochemical studies. Based on the fact that Hsp90 and its cochaperone SGT1 are necessary for the stabilization and activation of NOD1 in mammals, SGT1 was chosen as a fusion partner of the leucine-rich repeat (LRR) domain of NOD1 for its soluble expression in Escherichia coli. Fusion of human SGT1 (hSGT1) to NOD1 LRR significantly enhanced the solubility, and the fusion protein was stabilized by coexpression of mouse Hsp90α. The expression level of hSGT1-NOD1 LRR was further enhanced by supplementation of rare codon tRNAs and exchange of antibiotic marker genes. - Highlights: • The NOD1 LRR domain was solubilized by SGT1 fusion in E. coli. • The coexpression of HSP90 stabilized the SGT1-NOD1 LRR fusion protein. • Several optimizations could enhance the expression level of the fusion protein.

  12. Microscopy and microanalysis of complex nanosized strengthening precipitates in new generation commercial Al-Cu-Li alloys.

    Science.gov (United States)

    Guinel, M J-F; Brodusch, N; Sha, G; Shandiz, M A; Demers, H; Trudeau, M; Ringer, S P; Gauvin, R

    2014-09-01

    Precipitates (ppts) in new generation aluminum-lithium alloys (AA2099 and AA2199) were characterised using scanning and transmission electron microscopy and atom probe tomography. Results obtained on the following ppts are reported: Guinier-Preston zones, T1 (Al2 CuLi), β' (Al3 Zr) and δ' (Al3 Li). The focus was placed on their composition and the presence of minor elements. X-ray energy-dispersive spectrometry in the electron microscopes and mass spectrometry in the atom probe microscope showed that T1 ppts were enriched in zinc (Zn) and magnesium up to about 1.9 and 3.5 at.%, respectively. A concentration of 2.5 at.% Zn in the δ' ppts was also measured. Unlike Li and copper, Zn in the T1 ppts could not be detected using electron energy-loss spectroscopy in the transmission electron microscope because of its too low concentration and the small sizes of these ppts. Indeed, Monte Carlo simulations of EEL spectra for the Zn L2,3 edge showed that the signal-to-noise ratio was not high enough and that the detection limit was at least 2.5 at.%, depending on the probe current. Also, the simulation of X-ray spectra confirmed that the detection limit was exceeded for the Zn Kα X-ray line because the signal-to-noise ratio was high enough in that case, which is in agreement with our observations. © 2014 The Authors Journal of Microscopy © 2014 Royal Microscopical Society.

  13. Purity of targets prepared on Cu substrates

    Science.gov (United States)

    Méens, A.; Rossini, I.; Sens, J. C.

    1993-09-01

    The purity of several elemental self-supporting targets usually prepared by evaporation onto soluble Cu substrates has been studied. The targets were analysed by Rutherford backscattering and instrumental neutron activation analysis. Because of the high percentage of Cu observed in some Si targets, further measurements, including transmission electron microscopy, have been performed on Si targets deposited by e-gun bombardment onto Cu and ion-beam sputtering onto betaine.

  14. Solubility database for TILA-99

    Energy Technology Data Exchange (ETDEWEB)

    Vuorinen, U.; Carlsson, T. [VTT Chemical Technology, Espoo (Finland); Kulmala, S.; Hakanen, M. [Helsinki Univ. (Finland). Lab. of Radiochemistry; Ahonen, L. [Geological Survey of Finland, Espoo (Finland)

    1998-11-01

    The safety assessment of spent fuel disposal requires solubility values for several elements estimated in Finnish disposal conditions. In Finland four sites (Haestholmen, Kivetty, Olkiluoto and Romuvaara) are investigated for the disposal of spent fuel. Haestholmen and OLkiluoto are onshore sites, while Kivetty and Romuvaara are inland sites. Based on groundwater analysis and classification according to salinity at the planned disposal depth mainly fresh groundwater is encountered at Kivetty and Romuvaara, while brackish and saline water-types are met at Haestholmen and Olkiluoto. Very saline, almost brine-type water ({approx}70 g/l) has been found in the deepest parts of the investigated bedrock at one of the sites (Olkiluoto). The reference waters and conditions were chosen according to the water-types. The considered reference conditions incorporated both the near- and far-field, and both oxidizing and reducing conditions were considered. In the reference conditions, the changes in solubilities were also estimated as caused by possible variations in the pH, carbonate content and redox conditions. Uranium, which is the main component of spent fuel is dealt with in a separate report presenting the solubility of uranium and spent fuel dissolution. In this work the solubilities of all the other elements of concern (Am, Cu, Nb, Np, Pa, Pd, Pu, Ra, Se, Sn, Tc, Zr, Cm, Ni, Sr, Th, C, Cl, Cs, Fe, Ho, I, and Sm) in the safety assessment are considered. Some discussion on the corrosion of the spent fuel canister is also presented. For the estimation of solubilities of the elements in question, literature data was collected that mainly comprised experimentally measured concentrations. The sources used were spent fuel experiments, concentrations measured in solubility measurements, natural concentrations and concentrations from natural analogue sites (especially Palmottu and Hyrkkoelae in Finland) as well as the concentrations measured at the Finnish investigation sites

  15. Solubility database for TILA-99

    International Nuclear Information System (INIS)

    Vuorinen, U.; Carlsson, T.; Kulmala, S.; Hakanen, M.

    1998-11-01

    The safety assessment of spent fuel disposal requires solubility values for several elements estimated in Finnish disposal conditions. In Finland four sites (Haestholmen, Kivetty, Olkiluoto and Romuvaara) are investigated for the disposal of spent fuel. Haestholmen and OLkiluoto are onshore sites, while Kivetty and Romuvaara are inland sites. Based on groundwater analysis and classification according to salinity at the planned disposal depth mainly fresh groundwater is encountered at Kivetty and Romuvaara, while brackish and saline water-types are met at Haestholmen and Olkiluoto. Very saline, almost brine-type water (∼70 g/l) has been found in the deepest parts of the investigated bedrock at one of the sites (Olkiluoto). The reference waters and conditions were chosen according to the water-types. The considered reference conditions incorporated both the near- and far-field, and both oxidizing and reducing conditions were considered. In the reference conditions, the changes in solubilities were also estimated as caused by possible variations in the pH, carbonate content and redox conditions. Uranium, which is the main component of spent fuel is dealt with in a separate report presenting the solubility of uranium and spent fuel dissolution. In this work the solubilities of all the other elements of concern (Am, Cu, Nb, Np, Pa, Pd, Pu, Ra, Se, Sn, Tc, Zr, Cm, Ni, Sr, Th, C, Cl, Cs, Fe, Ho, I, and Sm) in the safety assessment are considered. Some discussion on the corrosion of the spent fuel canister is also presented. For the estimation of solubilities of the elements in question, literature data was collected that mainly comprised experimentally measured concentrations. The sources used were spent fuel experiments, concentrations measured in solubility measurements, natural concentrations and concentrations from natural analogue sites (especially Palmottu and Hyrkkoelae in Finland) as well as the concentrations measured at the Finnish investigation sites. The

  16. Spectroscopic Studies of a Three-dimensional, Five-coordinated Copper(Ⅱ) Complex via Hydrogen Bonds: [Cu(PDA)(H2O)2](H2PDA=Pyridine-2,6-dicarboxylic Acid)

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new copper(Ⅱ) complex [Cu(PDA)(H2O)2] was synthesized and its structure was determined. Cu(Ⅱ) is five-coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02 nm. The whole crystal is linked to form a three-dimensional network by means of hydrogen bonds. The X-band ESR spectrum shows three different g tensors with a well-resolved hyperfine structure in the gz signal, giving the ESR parameters gx=2.05, gy=2.065 and gz=2.29. The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.

  17. Pure Phase Solubility Limits: LANL

    International Nuclear Information System (INIS)

    C. Stockman

    2001-01-01

    The natural and engineered system at Yucca Mountain (YM) defines the site-specific conditions under which one must determine to what extent the engineered and the natural geochemical barriers will prevent the release of radioactive material from the repository. Most important mechanisms for retention or enhancement of radionuclide transport include precipitation or co-precipitation of radionuclide-bearing solid phases (solubility limits), complexation in solution, sorption onto surfaces, colloid formation, and diffusion. There may be many scenarios that could affect the near-field environment, creating chemical conditions more aggressive than the conditions presented by the unperturbed system (such as pH changes beyond the range of 6 to 9 or significant changes in the ionic strength of infiltrated waters). For an extended period of time, the near-field water composition may be quite different and more extreme in pH, ionic strength, and CO 2 partial pressure (or carbonate concentration) than waters at some distance from the repository. Reducing conditions, high pH (up to 11), and low carbonate concentration may be present in the near-field after reaction of infiltrating groundwater with engineered barrier systems, such as cementitious materials. In the far-field, conditions are controlled by the rock-mass buffer providing a near-neutral, oxidizing, low-ionic-strength environment that controls radionuclide solubility limits and sorption capacities. There is the need for characterization of variable chemical conditions that affect solubility, speciation, and sorption reactions. Modeling of the groundwater chemistry is required and leads to an understanding of solubility and speciation of the important radionuclides. Because experimental studies cannot be performed under the numerous potential chemical conditions, solubility limitations must rely on geochemical modeling of the radionuclide's chemistry. Fundamental thermodynamic properties, such as solubility products

  18. Pure Phase Solubility Limits: LANL

    Energy Technology Data Exchange (ETDEWEB)

    C. Stockman

    2001-01-26

    The natural and engineered system at Yucca Mountain (YM) defines the site-specific conditions under which one must determine to what extent the engineered and the natural geochemical barriers will prevent the release of radioactive material from the repository. Most important mechanisms for retention or enhancement of radionuclide transport include precipitation or co-precipitation of radionuclide-bearing solid phases (solubility limits), complexation in solution, sorption onto surfaces, colloid formation, and diffusion. There may be many scenarios that could affect the near-field environment, creating chemical conditions more aggressive than the conditions presented by the unperturbed system (such as pH changes beyond the range of 6 to 9 or significant changes in the ionic strength of infiltrated waters). For an extended period of time, the near-field water composition may be quite different and more extreme in pH, ionic strength, and CO{sub 2} partial pressure (or carbonate concentration) than waters at some distance from the repository. Reducing conditions, high pH (up to 11), and low carbonate concentration may be present in the near-field after reaction of infiltrating groundwater with engineered barrier systems, such as cementitious materials. In the far-field, conditions are controlled by the rock-mass buffer providing a near-neutral, oxidizing, low-ionic-strength environment that controls radionuclide solubility limits and sorption capacities. There is the need for characterization of variable chemical conditions that affect solubility, speciation, and sorption reactions. Modeling of the groundwater chemistry is required and leads to an understanding of solubility and speciation of the important radionuclides. Because experimental studies cannot be performed under the numerous potential chemical conditions, solubility limitations must rely on geochemical modeling of the radionuclide's chemistry. Fundamental thermodynamic properties, such as solubility

  19. Dichloro (bis[diphenylthiourea]) cadmium complex as a precursor for HDA-capped CdS nanoparticles and their solubility in water

    OpenAIRE

    Tshinyadzo R. Tshikhudo; Manuel Fernandes; Makwena J. Moloto; Poslet M. Shumbula

    2010-01-01

    A single-source precursor route has been explored by using the diphenylthiourea cadmium complex as the source of cadmium sulphide (CdS) nanoparticles. The reaction was carried out using hexadecylamine (HDA) as the solvent and stabilising agent for the particles. The phenylthiourea complex was synthesised and characterised by means of a combination of spectroscopic techniques, microanalysis and X-ray crystal structural analysis. The diphenylthiourea complex was thermolysed in HDA at 120 ºC for...

  20. Neuroprotective Effects and Mechanisms of Curcumin–Cu(II) and –Zn(II) Complexes Systems and Their Pharmacological Implications

    OpenAIRE

    Yan, Fa-Shun; Sun, Jian-Long; Xie, Wen-Hai; Shen, Liang; Ji, Hong-Fang

    2017-01-01

    Alzheimer’s disease (AD) is the main form of dementia and has a steadily increasing prevalence. As both oxidative stress and metal homeostasis are involved in the pathogenesis of AD, it would be interesting to develop a dual function agent, targeting the two factors. Curcumin, a natural compound isolated from the rhizome of Curcuma longa, is an antioxidant and can also chelate metal ions. Whether the complexes of curcumin with metal ions possess neuroprotective effects has not been evaluated....

  1. Synthesis, NMR characterization, X-ray crystal structure of Co(II) Ni(II) and Cu(II) complexes of a pyridine containing self-assembling

    International Nuclear Information System (INIS)

    Ranjbar, M.; Taghavipour, M.; Moghimi, A.; Aghabozorg, H.

    2002-01-01

    In the recent years, the self-assembling systems have been attracted chemists. The intermolecular bond in such systems mainly consists of ion pairing and hydrogen bonding [1,2]. The reaction between self-assembling system liquid LH 2 (py dc=2,6-pyridinedicarboxylic acid and py da=2,6- pyridine diamin) with cobalt (II) nitrate, nickel (II) chloride, and copper (II) acetate in water leads to the formation of self- assemble coordination complexes, [py da.H] 2 [M(py dc) 2 ]. H 2 O, M=Co(II),Ni(II), and Cu(II). The characterization was performed using elemental analysis, ESI mass spectroscopy, 1 H and 13 C NMR and X-ray crystallography. The crystal systems are monoclinic with space group P2 1 /n and four molecules per unit cell. These complexes shows 13 C NMR resonances of cationic counter ion [(py dc,H)] + in DMSO- d 6 but no signal corresponding to the two coordinated ligands [py dc] 2- The metal atoms are six-coordinated with a distorted octahedral geometry. The two [py de] 2- units are almost perpendicular to each other

  2. Histidine, lysine, and arginine radical cations: isomer control via the choice of auxiliary ligand (L) in the dissociation of [CuII(L)amino acid]*2+ complexes.

    Science.gov (United States)

    Ke, Yuyong; Zhao, Junfang; Verkerk, Udo H; Hopkinson, Alan C; Siu, K W Michael

    2007-12-27

    Histidine, lysine, and arginine radical cations have been generated through collision-induced dissociation (CID) of complexes [CuII(auxiliary ligand)namino acid]*2+, using tri-, bi-, as well as monodentate auxiliary ligands. On the basis of the observed CID products, the existence of two isomeric amino-acid populations is postulated. The Type 1 radical cations of histidine and lysine, stable on the mass spectrometer time scale, were found to lose water, followed by the loss of carbon monoxide under more energetic CID conditions. The arginine Type 1 radical cation behaved differently, losing dehydroalanine. The Type 2 radical cations were metastable and easily fragmented by the loss of carbon dioxide, effectively preventing direct observation. Type 1 radical cations are proposed to result from neutral (canonical) amino-acid coordination, whereas Type 2 radical cations are from zwitterionic amino-acid coordination to copper in the complex. The ratio of Type 1/Type 2 ions was found to be dependent on the auxiliary ligand, providing a method of controlling which radical cation would be formed primarily. Density functional calculations at B3LYP/6-311++G(d,p) have been used to determine the relative energies of five His*+ isomers. Barriers against interconversion between the isomers and against fragmentation have been calculated, giving insight as to why the Type 1 ions are stable, while only fragmentation products of the Type 2 ions are observable under CID conditions.

  3. Humic acids and their interactions with metallic elements: Cu II, Eu III, Th IV, U VI: contribution of size exclusion chromatography method and research of complexation models

    International Nuclear Information System (INIS)

    Lesourd-Moulin, V.

    1986-04-01

    The interest given to natural organic matter (humic and fulvic acids) as complexing agents of metallic ions in soils and natural waters becomes more and more important in environmental area. Cation - humic matter interactions have a great importance, a better understanding of the contribution of these substances in natural media specially towards radioactive elements with long life time. Interactions are studied by a chromatographic technique of gel filtration: the dynamic equilibrium method is based on the separation of the formed complex humic macromolecule - metallic ion and the free metallic ion, which due to its size penetrates totally in the pores of the gel. Separation mechanisms of the chromatographic support and the contribution of each parameter, are studied as a function of the buffer nature, its concentration, the PH, the gel porosity and the valence of the metallic cation. This study led to the determination of the appropriate experimental conditions for each cation. A study of metallic binding with humic acid has been undertaken with Cu 2+ , Eu 3+ , Th 4+ , Uo 2 2+ . These elements, except copper, have been chosen for their properties similar to the transuranic elements. Different samples of humic acids (commercial, podzolic soil, rendzine soil) are also studied. A deeper research of europium - humic acid interactions by means of different treatment models (discrete or gaussian models) has been undertaken in order to determine the number, the binding site strength and the global interaction constants [fr

  4. Synthesis and characterization of novel Cu(II) complex coated Fe3O4@SiO2 nanoparticles for catalytic performance

    Science.gov (United States)

    Nasrollahzadeh, Mahmoud; Sajjadi, Mohaddeseh; Khonakdar, Hossein Ali

    2018-06-01

    In this study, a convenient method for the synthesis of arylaminotetrazoles has been developed using a copper (II)-aminotetrazole complex immobilized on silica-coated Fe3O4 (Fe3O4@SiO2) nanoparticles (Fe3O4@SiO2-aminotet-Cu(II)) as a novel and efficient magnetically catalyst. The constructed superparamagnetic core-shell nanoparticles were successfully prepared, as proven using different spectroscopic techniques such as fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscope (TEM), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), thermogravimetry and differential thermogravimetry (TG-DTG) and vibrating sample magnetometer (VSM) analysis. The applicability of Fe3O4@SiO2-aminotet-Cu(II) magnetic catalyst allows the efficient synthesis of a variety of arylaminotetrazoles from the reaction between various arylcyanamides with sodium azide in high yields. The effect of catalyst loading was investigated. In addition, the reaction mechanism for the synthesis of arylaminotetrazoles was reasonably proposed. Results show that the 1-aryl-5-amino-1H-tetrazole (B isomer) and 5-arylamino-1H-tetrazole (A isomer) can be obtained from the arylcyanamides carrying electron-donating and electron-withdrawing substituents, respectively. This procedure offers a simple methodology, relatively short reaction times, easy work-up, high yields of the products and a cleaner reaction with elimination of hydrazoic acid (HN3). Moreover, catalyst can be conveniently recovered through the use of external magnet and reused for at least 6 times without any significant loss of its activity.

  5. Synthesis and vibrational spectra of cooper(II) and erbium(III) complexes with 2-diazo[2'-(oxymethyldiphenylphosphinyl)phenyl]-4-tert-butylphenol (HL) - [CuL2]·2H2O and Er(NO3)3·2HL·2H2O. Crystal structure of [CuL2]·2H2O

    International Nuclear Information System (INIS)

    Tsivadze, A.Yu.; Minacheva, L.Kh.; Ivanova, I.S.; Pyatova, E.N.; Sergienko, V.S.; Baulin, V.E.

    2008-01-01

    Paper describes synthesis of CuL 2 ·2H 2 O (I) complex cupric salt and of Er(NO 3 ) 3 ·2HL·2H 2 O (II) erbium nitrate complex (HL=2-diazo-[2'(oxymethyl-diphenyl-phosphinyl)phenyl]-4-tert-butylphenol). One interprets the fundamental frequencies within the IR-spectra of (I) and (II) compounds. One has performed X-ray diffraction analysis of I compound. The crystals are monoclinic ones, a=15.157(3), b=17.080(2), c=22.451(9) A, β=106.09(3) Deg, V=5584(3) A 3 , Z=4, C2/c sp.gr., R=0.0546 as to 1152 reflections with I>2σ(I). The copper atom coordination polyhedron (C 2 symmetry) may be described as a symmetrically-prolonged square bipyramid (4+2). Cu polyhedron central square is formed by substituted phenol oxygen atom and by one of diazo-group nitrogen atoms of either of two deprotonated ligands, namely: L - (Cu-N 1.969(6), Cu-O 1.899(5) A). The angles between lying opposite O and N atoms constitute 157.6 Deg, while the rest equatorial angles range within 90.6 Deg-95.9 Deg. The axial positions are occupied by O(2) and O(2A) anisole atoms (Cu-O 2.737(6) A, O(2)Cu(1)O(2A) angle constitutes 132.3 Deg). Within crystal I the complex molecules and the crystallization molecules of water are combined by by the hydrogen bond system. According to the IR-spectra data, within complex II in contrast to compound I erbium atom coordination by HL ligand involves oxygen phosphoryl atom [ru

  6. Synthesis, spectral and structural studies of water soluble arene ruthenium (II) complexes containing 2,2′-dipyridyl-N-alkylimine ligand

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Kaminsky, W.

    of the complexes. A similar downfield of chemical shifts was also observed for the alkyl protons attached to the nitrogen. For instant, the methyl proton of dpNmei was observed as a singlet at around δ 4.05 in the complexes [1]PF 6 , [3]PF 6 and [5]PF 6 as 9...

  7. Coordination chemistry of two heavy metals: I, Ligand preferences in lead(II) complexation, toward the development of therapeutic agents for lead poisoning: II, Plutonium solubility and speciation relevant to the environment

    Energy Technology Data Exchange (ETDEWEB)

    Neu, Mary Patricia [Univ. of California, Berkeley, CA (United States)

    1993-11-01

    The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pKas and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pKa = 5.94, logβ120 = 10.92; acetohydroxamic acid, pKa = 9.34, logβ120 = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinate geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is logβ120 = 41.7. The solubility limited speciation of 242Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods.

  8. Coordination chemistry of two heavy metals: I, Ligand preferences in lead(II) complexation, toward the development of therapeutic agents for lead poisoning: II, Plutonium solubility and speciation relevant to the environment

    International Nuclear Information System (INIS)

    Neu, M.P.

    1993-11-01

    The coordination chemistry and solution behavior of the toxic ions lead(II) and plutonium(IV, V, VI) have been investigated. The ligand pK a s and ligand-lead(II) stability constants of one hydroxamic acid and four thiohydroaxamic acids were determined. Solution thermodynamic results indicate that thiohydroxamic acids are more acidic and slightly better lead chelators than hydroxamates, e.g., N-methylthioaceto-hydroxamic acid, pK a = 5.94, logβ 120 = 10.92; acetohydroxamic acid, pK a = 9.34, logβ l20 = 9.52. The syntheses of lead complexes of two bulky hydroxamate ligands are presented. The X-ray crystal structures show the lead hydroxamates are di-bridged dimers with irregular five-coordinate geometry about the metal atom and a stereochemically active lone pair of electrons. Molecular orbital calculations of a lead hydroxamate and a highly symmetric pseudo octahedral lead complex were performed. The thermodynamic stability of plutonium(IV) complexes of the siderophore, desferrioxamine B (DFO), and two octadentate derivatives of DFO were investigated using competition spectrophotometric titrations. The stability constant measured for the plutonium(IV) complex of DFO-methylterephthalamide is logβ 110 = 41.7. The solubility limited speciation of 242 Pu as a function of time in near neutral carbonate solution was measured. Individual solutions of plutonium in a single oxidation state were added to individual solutions at pH = 6.0, T = 30.0, 1.93 mM dissolved carbonate, and sampled over intervals up to 150 days. Plutonium solubility was measured, and speciation was investigated using laser photoacoustic spectroscopy and chemical methods

  9. Solubility and Potential Mobility of Heavy Metals in Two Contaminated Urban Soils from Stockholm, Sweden

    International Nuclear Information System (INIS)

    Oborn, Ingrid; Linde, Mats

    2001-01-01

    The solubility and potential mobility of heavy metals (Cd, Cu,Hg, Pb and Zn) in two urban soils were studied by sequential and leaching extractions (rainwater). Compared to rural (arable) soils on similar parent material, the urban soils were highly contaminated with Hg and Pb and to a lesser extent also with Cd,Cu and Zn. Metal concentrations in rainwater leachates were related to sequential extractions and metal levels reported from Stockholm groundwater. Cadmium and Zn in the soils were mainly recovered in easily extractable fractions, whereas Cu and Pb were complex bound. Concentrations of Pb in the residual fraction were between two- and eightfold those in arable soils, indicating that the sequential extraction scheme did not reflect the solid phases affected by anthropogenic inputs. Cadmium and Zn conc. in the rainwater leachates were within the range detected in Stockholm groundwater, while Cu and Pb conc. were higher, which suggests that Cu and Pb released from the surface soil were immobilised in deeper soil layers. In a soil highly contaminated with Hg, the Hg conc. in the leachate was above the median concentration, but still 50 times lower than the max concentration found in groundwater, indicating the possibility of other sources. In conclusion, it proved difficult to quantitatively predict the mobility of metals in soils by sequential extractions

  10. Effect of the competition of Cu(II) and Ni(II) on the kinetic and thermodynamic stabilities of Cr(III)-organic ligand complexes using competitive ligand exchange (EDTA).

    Science.gov (United States)

    Cunha, Graziele da Costa; Goveia, Danielle; Romão, Luciane Pimenta Cruz; de Oliveira, Luciana Camargo

    2015-05-01

    The effect of competition of Cu(II) and Ni(II) on the kinetic stability of Cr(III) complexed with natural organic matter (NOM) was characterized using EDTA exchange with single-stage tangential-flow ultrafiltration. For a water sample from Serra de Itabaiana, 3% of spiked Cr(III) was exchanged, while for a sample from the Itapanhaú River, 7, 10, 10, and 21% was exchanged in experiments using Cr(III) alone and in combination with Cu(II), Ni(II), or Cu(II) + Ni(II), respectively. Times required to reach exchange equilibrium with EDTA were less than 360 min. The influence of competition from Ni(II) and Cu(II) on the availability of complexed Cr(III) was low, demonstrating preference of the ligand sites for Cr(III). This was correlated with sample humification, as confirmed by EPR and (13)C NMR analyses. Exchange efficiency was in the order Cu > Ni > Cr, and the process could be readily described by first order kinetics, with average rate constants of 0.35-0.37 h(-1). Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Chelating water-soluble polymers for waste minimization

    International Nuclear Information System (INIS)

    Smith, B.; Cournoyer, M.; Duran, B.; Ford, D.; Gibson, R.; Lin, M.; Meck, A.; Robinson, P.; Robison, T.

    1996-01-01

    Within the DOE complex and in industry there is a tremendous need for advanced metal ion recovery and waste minimization techniques. This project sought to employ capabilities for ligand-design and separations chemistry in which one can develop and evaluate water- soluble chelating polymers for recovering actinides and toxic metals from various process streams. Focus of this work was (1) to develop and select a set of water-soluble polymers suitable for a selected waste stream and (2) demonstrate this technology in 2 areas: removal of (a) actinides and toxic RCRA metals from waste water and (b) recovery of Cu and other precious metals from industrial process streams including from solid catalysts and aqueous waste streams. The R ampersand D was done in 4 phases for each of the 2 target areas: polymer synthesis for scaleup, equipment assembly, process demonstration at a DOE or industrial site, and advanced ligand/polymer synthesis. The TA- 50 site at Los Alamos was thought to be appropriate due to logistics and to its being representative of similar problems throughout the DOE complex

  12. Gas solubilities widespread applications

    CERN Document Server

    Gerrard, William

    1980-01-01

    Gas Solubilities: Widespread Applications discusses several topics concerning the various applications of gas solubilities. The first chapter of the book reviews Henr's law, while the second chapter covers the effect of temperature on gas solubility. The third chapter discusses the various gases used by Horiuti, and the following chapters evaluate the data on sulfur dioxide, chlorine data, and solubility data for hydrogen sulfide. Chapter 7 concerns itself with solubility of radon, thoron, and actinon. Chapter 8 tackles the solubilities of diborane and the gaseous hydrides of groups IV, V, and

  13. In vitro Solubility of Copper(II) Sulfate and Dicopper Chloride Trihydroxide for Pigs.

    Science.gov (United States)

    Park, C S; Kim, B G

    2016-11-01

    This study was conducted to determine the solubility of copper (Cu) in two sources of copper(II) sulfate (CuSO 4 ) including monohydrate and pentahydrate and three sources of dicopper chloride trihydroxide (dCCTH) including α-form (dCCTH-α), β-form (dCCTH-β), and a mixture of α- and β-form (dCCTH-αβ) at different pH and a 3-step in vitro digestion assay for pigs. In Exp. 1, Cu sources were incubated in water-based buffers at pH 2.0, 3.0, 4.8, and 6.8 for 4 h using a shaking incubator at 39°C. The CuSO 4 sources were completely dissolved within 15 min except at pH 6.8. The solubility of Cu in dCCTH-α was greater (pCopper in dCCTH sources were non-soluble at pH 6.8. In Exp. 2, the solubility of Cu was determined during the 3-step in vitro digestion assay for pigs. All sources of Cu were completely dissolved in step 1 which simulated digestion in the stomach. In Exp. 3, the solubility of Cu in experimental diets including a control diet and diets containing 250 mg/kg of additional Cu from five Cu sources was determined during the in vitro digestion assay. The solubility of Cu in diets containing additional Cu sources were greater (p<0.05) than the control diet in step 1. In conclusion, the solubility of Cu was influenced by pH of digesta but was not different among sources based on the in vitro digestion assay.

  14. Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

    Energy Technology Data Exchange (ETDEWEB)

    Sizmur, Tom, E-mail: t.p.sizmur@reading.ac.uk [Soil Research Centre, Dept. Geography and Environmental Science, School of Human and Environmental Sciences, University of Reading, Whiteknights, Reading, RG6 6DW (United Kingdom); Palumbo-Roe, Barbara [British Geological Survey, Kingsley Dunham Centre, Keyworth, Nottingham, NG12 5GG (United Kingdom); Hodson, Mark E. [Soil Research Centre, Dept. Geography and Environmental Science, School of Human and Environmental Sciences, University of Reading, Whiteknights, Reading, RG6 6DW (United Kingdom)

    2011-07-15

    The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg{sup -1} and 362 mgCu kg{sup -1}) and Pb/Zn mine (4550 mgPb kg{sup -1} and 908 mgZn kg{sup -1}) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element. - Graphical abstract: Display Omitted Highlights: > Compost reduced the mobility of Cu, Pb and Zn. > Compost increased the mobility of As. > Earthworms decreased water soluble As and Cu but increased Pb and Zn in porewater. > These effects are explained by the impact of the earthworms and compost on pH and DOC. - The effect of earthworms on metal solubility was due to changes in dissolved organic carbon and pH but was reduced with increasing compost amendments.

  15. Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

    International Nuclear Information System (INIS)

    Sizmur, Tom; Palumbo-Roe, Barbara; Hodson, Mark E.

    2011-01-01

    The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg -1 and 362 mgCu kg -1 ) and Pb/Zn mine (4550 mgPb kg -1 and 908 mgZn kg -1 ) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element. - Graphical abstract: Display Omitted Highlights: → Compost reduced the mobility of Cu, Pb and Zn. → Compost increased the mobility of As. → Earthworms decreased water soluble As and Cu but increased Pb and Zn in porewater. → These effects are explained by the impact of the earthworms and compost on pH and DOC. - The effect of earthworms on metal solubility was due to changes in dissolved organic carbon and pH but was reduced with increasing compost amendments.

  16. Synthesis, spectral, antitumor, antioxidant and antimicrobial studies on Cu(II), Ni(II) and Co(II) complexes of 4-[(1H-Benzoimidazol-2-ylimino)-methyl]-benzene-1,3-diol.

    Science.gov (United States)

    El-wakiel, Nadia; El-keiy, Mai; Gaber, Mohamed

    2015-08-05

    A new Schiff base of 2-aminobenzimidazole with 2,4-dihydroybezaldehyde (H₃L), and its Cu(II), Ni(II) and Co(II) complexes have been synthesized and characterized by elemental analyses, molar conductance, thermal analysis (TGA), inductive coupled plasma (ICP), magnetic moment measurements, IR, EI-mass, UV-Vis. and ESR spectral studies. On the basis of spectral studies and analytical data, it is evident that the Schiff base acts as dibasic tridentate ligand coordinating via deprotonated OH, NH and azomethine nitrogen atom. The results showed that Co(II) and Ni(II) complexes have tetrahedral structure while Cu(II) complexes has octahedral geometry. The kinetic and thermodynamic parameters of the thermal decomposition stages have been evaluated. The studied complexes were tested for their in vitro antimicrobial activities against some bacterial strains. The anticancer activity of the ligand and its metal complexes is evaluated against human liver Carcinoma (HEPG2) cell. These compounds exhibited a moderate and weak activity against the tested HEPG2 cell lines with IC₅₀ of 9.08, 18.2 and 19.7 μg/ml for ligand, Cu(II) and Ni(II) complexes, respectively. In vitro antioxidant activity of the newly synthesized compounds has also been evaluated. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Stress-induced reorientation of hydride precipitates in Zr-2.5Nb-0.5Cu garter springs under complex loading

    International Nuclear Information System (INIS)

    De, P.K.; John, J.T.; Raman, V.V.; Banerjee, S.

    1991-01-01

    Zr-2.5Nb-0.5Cu garter springs which are placed between coolant and calandria tubes in PHWRs experience complex loading due to simultaneous application of tension, compression and torus bending moment due to coolant tubes. The gradual pick up of hydrogen by the garter springs during service is likely to have hydride platelets reoriented under the applied stresses. In the present paper, the magnitudes and the directions of the principal stresses under the complex loading condition obtained have been calculated and the extent of hydride reorientation predicted. Simulation experiments consisting of simulated loading of hydrogen (upto 400 ppm) precharged springs at the service temperature (300degC) and also in-situ hydrogen charging of the springs under simulated loading conditions have been carried out. In addition, hydrogen precharged springs have been subjected to temperature cycling between 50 and 300degC under complex loading conditions, to evaluate the influence of temperature variation on hydride reorientation. Metallographic examination of the hydride platelets in the above springs has shown an excellent agreement with the analytical prediction. Torus bending moment values appear to play a significant role in reorienting the hydride platelets. It has been observed that under normal torus bending moment corresponding to 90 mm dia coolant tubes hydrogen platelets close to the outer rim of the spiral get reoriented in the radial direction. However, on application a torus bending moment corresponding to 30 mm dia tubes, hydride platelets get reoriented along the radial direction, irrespective of the magnitude of tensile and compression loading. (author). 9 refs., 15 figs., 1 appendix

  18. Synthesis and structural characterization of ternary Cu (II) complexes of glycine with 2,2'-bipyridine and 2,2'-dipyridylamine. The DNA-binding studies and biological activity.

    Science.gov (United States)

    Mohamed, Mervat S; Shoukry, Azza A; Ali, Ayat G

    2012-02-01

    In this study two new complexes [Cu(bpy)(Gly)Cl]·2H(2)O (1) and [Cu(dpa)(Gly)Cl]·2H(2)O (2) (bpy=2,2'-bipyridine; dpa=2,2'-dipyridylamine, Gly=glycine) have been synthesized and characterized by elemental analysis, IR, TGA, UV-vis and magnetic susceptibility measurements. The binding properties of the complexes with CT-DNA were investigated by electronic absorption spectra. The intrinsic binding constants (K(b)) calculated from UV-vis absorption studies were 1.84 × 10(3) M(-1) and 3.1 × 10(3) M(-1) for complexes 1 and 2 respectively. Thermal denaturation has been systematically studied by spectrophotometric method and the calculated ΔT(m) was nearly 5 °C for each complex. All the results suggest that the interaction modes between the complexes and CT-DNA were electrostatic and/or groove binding. The redox behavior of the two complexes was investigated by cyclic voltammetry. Both complexes, in presence and absence of CT-DNA show a quasi-reversible wave corresponding to Cu(II)/Cu(I) redox couple. The change in E(1/2), ΔE and I(pc)/I(pa) ascertain the interaction of complexes 1 and 2 with CT-DNA. Further insight into the binding of complexes with CT-DNA has been made by gel electrophoresis, where the binding of complexes is confirmed through decreasing the mobility and intensity of DNA bands. In addition, the antitumor activity of the complexes was tested on two cancer cell lines; the breast cancer (MCF7) and the human hepatocellular carcinoma (HEPG2), as well as one normal cell line; the human normal melanocytes (HFB4). The results showed that complex 1 was more potent antitumor agent than complex 2. The in-vitro antimicrobial activity of the two complexes was carried out using the disc diffusion method against different species of pathogenic bacteria and fungi. The activity data showed that complex 2 was more active in inhibiting the growth of the tested organisms. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Theoretical insight into electronic structure and optoelectronic properties of heteroleptic Cu(I)-based complexes for dye-sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Shuxian; Li, Ke; Lu, Xiaoqing, E-mail: luxq@upc.edu.cn; Zhao, Zigang; Shao, Yang; Dang, Yong; Li, Shaoren; Guo, Wenyue, E-mail: wyguo@upc.edu.cn

    2016-04-15

    A series of heteroleptic Cu(I)-based dyes were investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT). Results showed that Cu(I)-based dyes were inclined to form distorted pseudo-trigonal pyramidal configurations with four-coordinated geometry index τ{sub 4} ranging from 0.905 to 0.914. The absorption spectra of Cu(I)-based dyes covered ∼300.0–600.0 nm region, and the lowest excitation states were crucial for efficient electron excitation and separation. Suitable energy levels of Cu(I)-based dyes rendered them thermodynamically favorable for efficient electron injection into semiconductor and regeneration from electrolyte. Relative to π-conjugation, heteroaromatic groups introduced into ancillary ligands could significantly improve the property of Cu(I)-based dyes by decreasing HOMO-LUMO gaps, red-shifting spectral range, strengthening absorption intensity, boosting light-harvesting efficiency, and promoting interfacial electron injection. Specifically, Cu(I)-based dye with dithiole-functionalized group exhibited outstanding optoelectronic property. - Highlights: • Assessment of heteroleptic Cu(I) dyes for dye-sensitized solar cells. • Suitable energy levels render Cu(I) dyes ideal candidates for electron injection. • Heteroaromatic groups efficiently improve Cu(I) dyes light-harvesting properties. • Dye with dithiole group exhibits ideal photoelectronic property.

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

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  1. A ruthenium(II) complex as turn-on Cu(II) luminescent sensor based on oxidative cyclization mechanism and its application in vivo

    Science.gov (United States)

    Zhang, Yunfei; Liu, Zonglun; Yang, Kui; Zhang, Yi; Xu, Yongqian; Li, Hongjuan; Wang, Chaoxia; Lu, Aiping; Sun, Shiguo

    2015-02-01

    Copper ions play a vital role in a variety of fundamental physiological processes not only in human beings and plants, but also for extensive insects and microorganisms. In this paper, a novel water-soluble ruthenium(II) complex as a turn-on copper(II) ions luminescent sensor based on o-(phenylazo)aniline was designed and synthesized. The azo group would undergo a specific oxidative cyclization reaction with copper(II) ions and turn into high luminescent benzotriazole, triggering significant luminescent increasements which were linear to the concentrations of copper(II) ions. The sensor distinguished by its high sensitivity (over 80-fold luminescent switch-on response), good selectivity (the changes of the emission intensity in the presence of other metal ions or amino acids were negligible) and low detection limit (4.42 nM) in water. Moreover, the copper(II) luminescent sensor exhibited good photostability under light irradiation. Furthermore, the applicability of the proposed sensor in biological samples assay was also studied and imaged copper(II) ions in living pea aphids successfully.

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

    Science.gov (United States)

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

    2017-01-01

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

  3. Synthesis, spectral characterization thermal stability, antimicrobial studies and biodegradation of starch–thiourea based biodegradable polymeric ligand and its coordination complexes with [Mn(II, Co(II, Ni(II, Cu(II, and Zn(II] metals

    Directory of Open Access Journals (Sweden)

    Nahid Nishat

    2016-09-01

    Full Text Available A biodegradable polymer was synthesized by the modification reaction of polymeric starch with thiourea which is further modified by transition metals, Mn(II, Co(II, Ni(II, Cu(II and Zn(II. All the polymeric compounds were characterized by (FT-IR spectroscopy, 1H NMR spectroscopy, 13C NMR spectroscopy, UV–visible spectra, magnetic moment measurements, thermogravimetric analysis (TGA and antibacterial activities. Polymer complexes of Mn(II, Co(II and Ni(II show octahedral geometry, while polymer complexes of Cu(II and Zn(II show square planar and tetrahedral geometry, respectively. The TGA revealed that all the polymer metal complexes are more thermally stable than their parental ligand. In addition, biodegradable studies of all the polymeric compounds were also carried out through ASTM-D-5338-93 standards of biodegradable polymers by CO2 evolution method which says that coordination decreases biodegradability. The antibacterial activity was screened with the agar well diffusion method against some selected microorganisms. Among all the complexes, the antibacterial activity of the Cu(II polymer–metal complex showed the highest zone of inhibition because of its higher stability constant.

  4. Synthesis, Characterization, and Biological Activity of Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II Complexes of N-Thiophenoyl-N′-Phenylthiocarbohydrazide

    Directory of Open Access Journals (Sweden)

    M. Yadav

    2013-01-01

    Full Text Available Mn(II, Fe(II, Co(II, Ni(II, Cu(II, Zn(II, and Cd(II complex of N-thiophenoyl -N′-phenylthiocarbohydrazide (H2 TPTH have been synthesized and characterized by elemental analysis, magnetic susceptibility measurements, infrared, NMR, electronic, and ESR spectral studies. The complexes were found to have compositions [Mn(H TPTH2], [Co(TPTH (H2O2], [Ni(TPTH (H2O2], [Cu(TPTH], [Zn(H TPTH], [Cd(H TPTH2], and [Fe(H TPTH2(EtOH]. The magnetic and electronic spectral studies suggest square planar geometry for [Cu(TPTH], tetrahedral geometry for [Zn(TPTH] and [Cd(H TPTH2], and octahedral geometry for rest of the complexes. The infrared spectral studies of the 1 : 1 deprotonated complexes suggest bonding through enolic oxygen, thiolato sulfur, and both the hydrazinic nitrogens. Thus, H2TPTH acts as a binegative tetradentate ligand. H2 TPTH and its metal complexes have been screened against several bacteria and fungi.

  5. Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability.

    Science.gov (United States)

    Turner, Andrew; Mawji, Edward

    2005-05-01

    The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.

  6. Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

    Energy Technology Data Exchange (ETDEWEB)

    Turner, Andrew [School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)]. E-mail: aturner@plymouth.ac.uk; Mawji, Edward [School of Earth, Ocean and Environmental Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)

    2005-05-01

    The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D{sub ow}, ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10{sup 3.3}-10{sup 5.3} ml g{sup -1}. The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision. - New approaches are presented for fractionating

  7. Micellar effect on metal-ligand complexes of Co(II, Ni(II, Cu(II and Zn(II with citric acid

    Directory of Open Access Journals (Sweden)

    Nageswara Rao Gollapalli

    2009-12-01

    Full Text Available Chemical speciation of citric acid complexes of Co(II, Ni(II, Cu(II and Zn(II was investigated pH-metrically in 0.0-2.5% anionic, cationic and neutral micellar media. The primary alkalimetric data were pruned with SCPHD program. The existence of different binary species was established from modeling studies using the computer program MINIQUAD75. Alkalimetric titrations were carried out in different relative concentrations (M:L:X = 1:2:5, 1:3:5, 1:5:3 of metal (M to citric acid. The selection of best chemical models was based on statistical parameters and residual analysis. The species detected were MLH, ML2, ML2H and ML2H2. The trend in variation of stability constants with change in mole fraction of the medium is explained on the basis of electrostatic and non-electrostatic forces. Distributions of the species with pH at different compositions of micellar media are also presented.

  8. Spanish normative studies in young adults (NEURONORMA young adults project): norms for the Rey-Osterrieth Complex Figure (copy and memory) and Free and Cued Selective Reminding Test.

    Science.gov (United States)

    Palomo, R; Casals-Coll, M; Sánchez-Benavides, G; Quintana, M; Manero, R M; Rognoni, T; Calvo, L; Aranciva, F; Tamayo, F; Peña-Casanova, J

    2013-05-01

    The Rey-Osterrieth Complex Figure (ROCF) and the Free and Cued Selective Reminding Test (FCSRT) are widely used in clinical practice. The ROCF assesses visual perception, constructional praxis, and visuo-spatial memory. The FCSRT assesses verbal learning and memory. In this study, as part of the Spanish normative studies project in young adults (NEURONORMA young adults), we present age- and education-adjusted normative data for both tests obtained by using linear regression techniques. The sample consisted of 179 healthy participants ranging in age from 18 to 49 years. We provide tables for converting raw scores to scaled scores in addition to tables with scores adjusted by socio-demographic factors. The results showed that education affects scores for some of the memory tests and the figure-copying task. Age was only found to have an effect on the performance of visuo-spatial memory tests, and the effect of sex was negligible. The normative data obtained will be extremely useful in the clinical neuropsychological evaluation of young Spanish adults. Copyright © 2011 Sociedad Española de Neurología. Published by Elsevier Espana. All rights reserved.

  9. Synthesis, spectra and X-ray crystallography of dipyridin-2-ylmethanone oxime and its CuX2(oxime)2 complexes: Thermal, Hirshfeld surface and DFT analysis

    Science.gov (United States)

    Warad, Ismail; Abdoh, Muneer; Al Ali, Anas; Shivalingegowda, Naveen; Kumara, Karthik; Zarrouk, Abdelkader; Lokanath, Neartur Krishnappagowda

    2018-02-01

    Dipyridin-2-ylmethanone oxime (C11H9N3O), was prepared using di-2-pyridyl ketone. The oxime ligand and its neutral CuX2 (oxime)2 (X = Cl or Br) complexes have been identified with the aid of several spectroscopic techniques such as: IR, EI-MS, EA, UV-visible, TG, 1H-NMR and finally the structure of the free oxime ligand was confirmed by X-ray diffraction studies. The oxime crystallizes in the monoclinic space group P21/c, with cell parameters a = 8.8811 (8) Å, b = 10.6362 (8) Å, c = 11.2050 (8) Å, β = 109.085 (4) º, V = 1000.26 (14) Å3 and Z = 4. The molecular conformation is stabilized by a strong intramolecular Osbnd H⋯N hydrogen bonding between the hydroxyl group of the oxime moiety and the nitrogen of the pyridine ring. Since the oxime structure was solved by XRD, the ligand structure parameters like bond length and angles were compared to the DFT computed one, the UV-visible to TD-SCF and Hirshfeld surface to MEP analysis.

  10. Co(II), Ni(II) and Cu(II) complexes of methyl-5-(Phenylthio) benzimidazole-2-carbamate: Molecular structures, spectral and DFT calculations

    Science.gov (United States)

    Mansour, Ahmed M.; El Bakry, Eslam M.; Abdel-Ghani, Nour T.

    2016-05-01

    [Co(FBZ)2(H2O)]·2NO3·0.5H2O (1), [Ni(FBZ)2X2]·zH2O (X = Cl​-, z = 0.5 (2) and X = CH3COO-, z = 1 (3)) and [Cu(FBZ)2(H2O) (NO3)]·NO3·1.5H2O (4) (FBZ = methyl-5-(Phenylthio) benzimidazole-2-carbamate; Fenbendazole) complexes were synthesized and characterized by elemental analysis, thermal, IR, EPR, UV-Vis, magnetic and conductance measurements. Geometry optimization, molecular electrostatic potential maps and natural bond orbital analysis were carried out at DFT/B3LYP/6-31G∗ level of theory. FBZ behaves as a neutral bidentate ligand via the pyridine-type nitrogen of the benzimidazole moiety and the carbamate group. Three-step ionization with pKa values of 3.38, 4.06 and 10.07 were reported for FBZ. The coordination of FBZ to the metal ions led to an increase in the antibacterial activity against the tested Staphylococcus aureus and Escherichia coli bacteria.

  11. Structure and thermodynamic properties of (C5H12N)CuBr3: a new weakly coupled antiferromagnetic spin-1/2 chain complex lying in the 1D-3D dimensional cross-over regime.

    Science.gov (United States)

    Pan, Bingying; Wang, Yang; Zhang, Lijuan; Li, Shiyan

    2014-04-07

    Single crystals of a metal organic complex (C5H12N)CuBr3 (C5H12N = piperidinium, pipH for short) have been synthesized, and the structure was determined by single-crystal X-ray diffraction. (pipH)CuBr3 crystallizes in the monoclinic group C2/c. Edging-sharing CuBr5 units link to form zigzag chains along the c axis, and the neighboring Cu(II) ions with spin-1/2 are bridged by bibromide ions. Magnetic susceptibility data down to 1.8 K can be well fitted by the Bonner-Fisher formula for the antiferromagnetic spin-1/2 chain, giving the intrachain magnetic coupling constant J ≈ -17 K. At zero field, (pipH)CuBr3 shows three-dimensional (3D) order below TN = 1.68 K. Calculated by the mean-field theory, the interchain coupling constant J' = -0.91 K is obtained and the ordered magnetic moment m0 is about 0.23 μB. This value of m0 makes (pipH)CuBr3 a rare compound suitable to study the 1D-3D dimensional cross-over problem in magnetism, since both 3D order and one-dimensional (1D) quantum fluctuations are prominent. In addition, specific heat measurements reveal two successive magnetic transitions with lowering temperature when external field μ0H ≥ 3 T is applied along the a' axis. The μ0H-T phase diagram of (pipH)CuBr3 is roughly constructed.

  12. Deuterium transport in Cu, CuCrZr, and Cu/Be

    Science.gov (United States)

    Anderl, R. A.; Hankins, M. R.; Longhurst, G. R.; Pawelko, R. J.

    This paper presents the results of deuterium implantation/permeation experiments and TMAP4 simulations for a CuCrZr alloy, for OFHC-Cu and for a Cu/Be bi-layered structure at temperatures from 700 to 800 K. Experiments used a mass-analyzed, 3-keV D 3+ ion beam with particle flux densities of 5 × 10 19 to 7 × 10 19 D/m 2 s. Effective diffusivities and surface molecular recombination coefficients were derived giving Arrhenius pre-exponentials and activation energies for each material: CuCrZr alloy, (2.0 × 10 -2 m 2/s, 1.2 eV) for diffusivity and (2.9 × x10 -14 m 4/s, 1.92 eV) for surface molecular recombination coefficients; OFHC Cu, (2.1 × 10 -6 m 2/s, 0.52 eV) for diffusivity and (9.1 × 10 -18 m 4/s, 0.99 eV) for surface molecular recombination coefficients. TMAP4 simulation of permeation data measured for a Cu/Be bi-layer sample was achieved using a four-layer structure (Cu/BeO interface/Be/BeO back surface) and recommended values for diffusivity and solubility in Be, BeO and Cu.

  13. Copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone - ({sup 64}Cu)(H2Ac4oT)Cl - internal dosimetry: animal model and human extrapolation

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Josianne L.; Silva, Paulo R.O.; Santos, Raquel G.; Ferreira, Andrea V., E-mail: jlr@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil)

    2011-07-01

    Thiosemicarbazones have attracted great pharmacological interest because of their biological properties, such as cytotoxic activity against multiple strains of human tumors. Due to the excellent properties of {sup 64}Cu, the copper complex N(4)-ortho-toluyl-2-acetylpyridine thiosemicarbazone (({sup 64}Cu)(H2Ac4oT)Cl) was developed for tumor detection by positron emission tomography. The radiopharmaceuticals were produced in the nuclear reactor TRIGA-IPR-R1 from CDTN. At the present work, ({sup 64}Cu)(H2Ac4oT)Cl biokinetic data (evaluated in mice bearing Ehrlich tumor) were treated by MIRD formalism to perform Internal Dosimetry studies. Doses in several organs of mice were determinate, as well as in implanted tumor, for ({sup 64}Cu)(H2Ac4oT)Cl. Doses results obtained for animal model were extrapolated to humans assuming a similar concentration ratio among various tissues between mouse and human. In the extrapolation, it was used human organ masses from Cristy/Eckerman phantom. Both penetrating and non-penetrating radiation from {sup 64}Cu in the tissue were considered in dose calculations. (author)

  14. Thermal, spectral, magnetic and biological studies of thiosemicarbazones complexes with metal ions: Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO2(VI)

    International Nuclear Information System (INIS)

    Mashaly, M.M.; Seleem, H.S.; El-Behairy, M.A.; Habib, H.A.

    2004-01-01

    Thiosemicarbazones ligands, isatin-3-thiosemicarbazone(HIT) and N-acetylisatin-3-thiosemicarbazone (HAIT), which have tridentate ONN coordinating sites were prepared. The complexes of both ligands with Cu(II), Co(II), Ni(II), Fe(III), Zn(II), Mn(II) and UO 2 (VI) ions were isolated. The ligands and their metal complexes were characterized by elemental analysis, IR, UV-Vis and mass spectra, also by conductance, magnetic moment and TG-DSC measurements. All the transition metal complexes have octahedral configurations, except Cu-complexes which have planar geometry and the UO 2 (VI) complexes which have coordination number 8 and may acquire the distorted dodecahedral geometry. Thermal studies explored the possibility of obtaining new complexes. Inversion from octahedral to square-planar configuration occurred upon heating the parent Ni-HIAT complex to form the corresponding pyrolytic product. The antifungal activity against the tested organisms showed that some metal complexes enhanced the activity with respect to the parent ligands. (author)

  15. Study on positron annihilation spectroscopy of methanol synthesis catalyst CuO/ZnO

    International Nuclear Information System (INIS)

    Liu Qisheng; Dai Guohuan; Sun Jiying; Ding Yingru; Yao Jianhua

    1989-01-01

    A new method was developed for determining the solid solubility of a metal oxide series prepared by precipitation using the positron lifetime parameters. The positron lifetime spectra of a series of CuO/ZnO catalysts prepared by precipitation were measured, in which the CuO at % contents were different before and after reducing. The relations between the solid solubility of the catalysts and the positron lifetime parameters were obtained, from which a result of solid solubility of 12 CuO at% after reducing had been found. The viewpoint that the Cu + ion acted as the active centre in the CuO/ZnO catalyst was supported

  16. A quinoline-based Cu2 + ion complex fluorescence probe for selective detection of inorganic phosphate anion in aqueous solution and its application to living cells

    Science.gov (United States)

    Dai, Yanpeng; Wang, Peng; Fu, Jiaxin; Yao, Kun; Xu, Kuoxi; Pang, Xiaobin

    2017-08-01

    A quinaldine functionalized probe QP has been designed and synthesized. It exhibited selective turn-off fluorescence response toward Cu2 + ion over most of the biologically important ions at physiological pH. The binding ratio of the probe QP and Cu2 + ion was determined to be 1:1 through fluorescence titration, Job's plot and ESI-MS. The binding constant (K) of Cu2 + to probe QP was found to be 2.12 × 104 M- 1. Further, the Cu2 + ensemble of probe QP was found to respond H2PO4- and HPO42 - among other important biological anions via fluorescence turn-on response at physiological pH. Fluorescence microscopy imaging using living Hela cells showed that probe QP could be used as an effective fluorescent probe for detecting Cu2 + cation and H2PO4- and HPO42 - anions in living cells.

  17. Reaction of cyanide with cytochrome ba3 from Thermus thermophilus: spectroscopic characterization of the Fe(II)a3-CN.Cu(II)B-CN complex suggests four 14N atoms are coordinated to CuB.

    Science.gov (United States)

    Surerus, K K; Oertling, W A; Fan, C; Gurbiel, R J; Einarsdóttir, O; Antholine, W E; Dyer, R B; Hoffman, B M; Woodruff, W H; Fee, J A

    1992-01-01

    Cytochrome ba3 from Thermus thermophilus reacts slowly with excess HCN at pH 7.4 to create a form of the enzyme in which CuA, cytochrome b, and CuB remain oxidized, while cytochrome a3 is reduced by one electron, presumably with the formation of cyanogen. We have examined this form of the enzyme by UV-visible, resonance Raman, EPR, and electron nuclear double resonance spectroscopies in conjunction with permutations of 13C- and 15N-labeled cyanide. The results support a model in which one CN- binds through the carbon atom to ferrous a3, supporting a low-spin (S = 0) configuration on the Fe; bridging by this cyanide to the CuB is weak or absent. Four 14N atoms, presumably donated by histidine residues of the protein, provide a strong equatorial ligand field about CuB; a second CN- is coordinated through the carbon atom to CuB in an axial position. PMID:1314380

  18. The Dovyren Intrusive Complex (Southern Siberia, Russia): Insights into dynamics of an open magma chamber with implications for parental magma origin, composition, and Cu-Ni-PGE fertility

    Science.gov (United States)

    Ariskin, Alexey; Danyushevsky, Leonid; Nikolaev, Georgy; Kislov, Evgeny; Fiorentini, Marco; McNeill, Andrew; Kostitsyn, Yuri; Goemann, Karsten; Feig, Sandrin T.; Malyshev, Alexey

    2018-03-01

    The Dovyren Intrusive Complex (DIC, Northern Baikal region, 728 Ma) includes the layered dunite-troctolite-gabbronorite Yoko-Dovyren massif (YDM), associated mafic-ultramafic sills, and dykes of olivine-rich to olivine-free gabbronorite. Major rock types of the DIC are presented, including a diversity of olivine orthocumulates to olivine-plagioclase and gabbroic adcumulates, carbonate-contaminated ultramafics and Cu-Ni-PGE mineralisation. Detailed comparisons of complete cross-sections of the YDM in its centre and at the NE and SW margins demonstrate differences in the cumulate succession, mineral chemistry, and geochemical structure that likely reflect variations in parental magma compositions. Combining petrochemical reconstructions for most primitive rocks and calculations using the COMAGMAT-5 model, it is shown that the central and peripheral parts of the intrusion formed by olivine-laden parental magmas ranged in their temperatures by 100 °C, approximately from 1290 °C ( 11 wt% MgO, olivine Fo88) to 1190 °C ( 8 wt% MgO, olivine Fo86). Thermodynamic modelling suggests that the most primitive high-Mg magma was S-undersaturated, whereas its derivatives became S-saturated at T piles to generate poorly-mineralised plagiodunite. In the troctolite and gabbroic parts of the Dovyren chamber, sulphide immiscibility likely occurred at lower temperatures, producing Cu-rich sulphide precursors, which gave rise to the 'platinum group mineral' (PGM-containing) troctolite and low-mineralised PGE-rich anorthosite in the Main Reef. The geochemical structure of the YDM demonstrates C-shaped distributions of TiO2, K2O, P2O5, and incompatible trace elements, which are 3-5 fold depleted in the cumulate rocks from the inner horizons of the intrusion with respect to the relatively thin lower and upper contact zones. In addition, a marked misbalance between estimates of the average composition of the YDM and that of the proposed olivine-laden parental magmas is established. This

  19. Improvement of Meloxicam Solubility Using a β-Cyclodextrin Complex Prepared via the Kneading Method and Incorporated into an Orally Disintegrating Tablet

    Directory of Open Access Journals (Sweden)

    Ahmad Ainurofiq

    2016-09-01

    Conclusion: Incorporation of the MEL/β-CD complex during ODT formulation using the QbD approach serves as a model for ODT product development, with optimal product performance based on the specification of quality target product profiles. To understand more specific phenomena, one point in the middle of the design for each factor should be added to more powerfully estimate this effect and avoid the lack of estimate due to an inadequate equation.

  20. Fe (III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of schiff bases based-on glycine and phenylalanine: Synthesis, magnetic/thermal properties and antimicrobial activity

    Science.gov (United States)

    Sevgi, Fatih; Bagkesici, Ugur; Kursunlu, Ahmed Nuri; Guler, Ersin

    2018-02-01

    Zinc (II), copper (II), nickel (II), cobalt (II) and iron (III) complexes of Schiff bases (LG, LP) derived from 2-hydroxynaphthaldehyde with glycine and phenylalanine were reported and characterized by 1H NMR, 13C NMR, elemental analyses, melting point, FT-IR, magnetic susceptibility and thermal analyses (TGA). TGA data show that iron and cobalt include to the coordinated water and metal:ligand ratio is 1:2 while the complex stoichiometry for Ni (II), Cu (II) and Zn (II) complexes is 1:1. As expected, Ni (II) and Zn (II) complexes are diamagnetic; Cu (II), Co (II) and Fe (III) complexes are paramagnetic character due to a strong ligand of LG and LP. The LG, LP and their metal complexes were screened for their antimicrobial activities against five Gram-positive (Staphylococcus aureus, Methicillin resistant Staphylococcus aureus (MRSA), Bacillus cereus, Streptococcus mutans and Enterococcus faecalis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa) and one fungi (Candida albicans) by using broth microdilution techniques. The activity data show that ligands and their metal complexes exhibited moderate to good activity against Gram-positive bacteria and fungi.

  1. The use of a water-soluble formazan complex to quantitate the cell number and mitochondrial function of Leishmania major promastigotes

    DEFF Research Database (Denmark)

    Berg, K; Zhai, L; Chen, M

    1994-01-01

    in that the formazan complex precipitates inside the parasites and has to be extracted by denaturants before measurements can be performed. By using a new synthetic substrate, 3-(4,5-dimethylthiazol-2-yl)-5- (3-carboxymethoxyphenyl)-2-(4-sulfonyl)-2H-tetrazolium (MTS), the extraction procedure is eliminated...... as the formazan-like dye is released spontaneously into the medium, making it possible to perform several measurements on the same parasite culture without disturbing or killing the parasites. The measurements were shown to reflect the numbers of parasites as confirmed via comparative experiments using...

  2. Thermochemical properties of oxides in Y-Ba-Cu-O, Sr-Bi-O, Cu-Nb-O, Sr-Cu-O, Ca-Cu-O, Cu-O and Hg-Ba-Ca-Cu-O systems

    International Nuclear Information System (INIS)

    Moiseev, G.K.; Vatolin, N.A.; Il'inykh, N.I.

    2000-01-01

    Thermochemical properties (ΔH 0 298 , S 0 298 , H 0 298 -H 0 0 , C p (T), C p at T>T melt ) of complex oxides in Y-Ba-Cu-O, Sr-Bi-O, Cu-Nb-O, Sr-Cu-O, Ca-Cu-O, Cu-O and Hg-Ba-Ca-Cu-O systems obtained with application of calculation methods are presented. Nonexperimental methods of estimation, revision and correction of standard formation enthalpies of inorganic compounds are described [ru

  3. Solvated copper(I) hexafluorosilicate π-complexes based on [Cu2(amtd)2]2+ (amtd = 2-allylamino-5-methyl-1,3,4-thiadiazole) dimer

    OpenAIRE

    Goreshnik, E.A.; Veryasov, G.; Morozov, Dmitry; Slyvka, Yu.; Ardan, B.; Mys'kiv, M.G.

    2016-01-01

    [Cu2(amdt)2]SiF6·C6H6 and [Cu2(amdt)2(H2O)2]SiF6·CH3CN·2H2O (amdt = 2-allylamino-5- methyl-1,3,4-thiadiazole) were obtained by alternating-current electrochemical synthesis, starting from water–acetonitrile–benzene mixtures containing 2-allylamino-5-methyl-1,3,4- thiadiazole and CuSiF6·4H2O. The electrochemical reduction of the saturated copper hexafluorosilicate water solution beneath the neatly poured layer of acetonitrile-benzene amdt solution resulted in the formation of cr...

  4. Cu-Cr Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Need, Ryan F. [Los Alamos National Laboratory

    2012-08-09

    Cu-Cr alloys are part of a class of face-centered cubic (FCC)-body-centered cubic (BCC) composites that includes similar alloys, such as Cu-Nb and Cu-Ta. When heavily deformed, these FCC-BCC materials create 'in situ' composites with a characteristic structure-nanoscale BCC filaments in a ductile FCC matrix. The strength of these composites is vastly greater than predicted by the rule of mixtures, and has been shown to be inversely proportional to the filament spacing. Lower raw materials costs suggest that Cu-Cr alloys may offer more economical solution to high-strength, high-conductivity wire than either their Nb or Ta counterparts. However, Cr is also more brittle and soluble in Cu than Nb or Ta. These qualities necessitate thermal treatments to remove solute atoms from the Cu matrix, improve conductivity, and maintain the ductility of the Cr filaments. Through the use of different thermomechanical processing routes or the addition of select dopants, alloys with strength in excess of 1 GPa at 70% IACS have been achieved. To date, previous research on Cu-Cr alloys has focused on a relatively small number of alloy compositions and processing methods while the effects of dopants and ageing treatments have only been studied independently. Consequently, there remains considerable opportunity for the development and optimization of these alloys as a leading high-strength, high-conductivity material.

  5. Crystal chemical substitutions and doping of YBa2Cu3Ox and related superconductors

    International Nuclear Information System (INIS)

    Skakle, J.M.S.

    1998-01-01

    This review covers the literature on cationic and anionic substitutions and their effect on the properties of YBCO. Reported solubility limits are given, together with crystal symmetry and trends in unit cell parameters with dopant concentration. The dopant site is considered; this is additionally complex in the case of copper substitution because of the two distinct copper sites in the crystal structure. The effect of the dopant on the critical temperature, T c , is reviewed; the literature is often contradictory due to the dual effects of variable oxygen content and the nature of the dopant. Preparation methods appear to have an effect on solubility limits, crystal symmetry and T c . Also, the methods used to determine solubility limits are often imprecise which can lead to contradictions. The magnetic properties of doped materials are reviewed; for some dopants, particularly the magnetic lanthanides, antiferromagnetism and superconductivity co-exist. The related RBa 2 Cu 3 O δ phases (R=lanthanide), their structure, properties and behaviour on doping are reviewed in a similar way. For the larger rare earths, the related systems R 1+x Ba 2-x Cu 3 O δ are reviewed; as x increases, the transition temperature decreases and compositions R 1.5 Ba 1.5 Cu 3 O δ are semiconducting. The upper and lower solubility limit changes with R, and for R=Dy, the upper limit is 2 Cu 3 O δ , cannot be prepared in air since substitution of La onto the Ba site occurs, forming the Ba-deficient solid solutions. (orig.)

  6. He-Ne laser protection barrier by means of poly (Tetrafluoroethylene-Perfluoro vinyl Ether) grafted by acrylic acid complexed with Cu(II)

    International Nuclear Information System (INIS)

    El-Ahdal, M.A.; Fayek, S.A.; El-Sawy, N.M.

    2006-01-01

    Appropriate eye and skin protection is a prerequisite for the safe operation of He-Ne laser in industrial and laboratory environments. In the present paper, measurement of the optical parameters of poly (tetrafluoroethylene-perfluorovinyl ether) grafted by acrylic acid and complexed with Cu(II) are reported. He-Ne laser beam radiation on wavelength of 632.8 nm and power 12.5mW was used. Transmittance and reflectance spectra and refractive index dispersion are presented. The study showed that the material has a protective level 4. Environmental conditions like thermal and fading processes were tested. This suggested that the material preserves its protective features as a protective eye and skin barriers of protective level 4. This was applied for occupational working time up to 8 h, temperature up to 50 degree C and for a time equal 74 days after laser irradiation. Radiation protection from laser sources has attracted a great deal of attention for long time because of their importance for human body. Intensive progress in lasers, optical communications, and data storage has challenged scientists to achieve perfection in optical components. These challenges have resulted in an active development of a wide variety of unconventional optical elements (Hariharan, 1996 and Efimov et al., 2002). Alexandrite solid state lasers with a wavelength of about 755 nm are frequently used in the field of medicine (Schirmarcher and Sutter, 2001). For removing tattoos, the Q-switched versions with impulse widths of several ten nanoseconds are an ideal instrument to keep the thermal stress of the patient's skin at low level. He-Ne laser is one of the most commonly used visible light lasers

  7. THE DYNAMICS SORPTION FEATURES OF A COMPLEX 1,5- DIPHENILCARBAZONATE CHROMIUM(III BY USING ION-EXCHANGE RESINS CU-2-8 AND CB-4P-2 FROM DIFFERENT CATEGORIES OF WATER

    Directory of Open Access Journals (Sweden)

    Н. M. Guzenko

    2014-12-01

    Full Text Available The formation mechanism features of adsorption layers are established on a surface ionexchange resins CU-2-8 and CB-4p-2 in the presence of the inorganic ions amount, that are typical for natural and sewage water by using the dynamic and kinetic graphs considering change of complex 1,5-diphenylcarbazonate of chromium(III quantity, and also factor of sorption process speed.

  8. Auto-assembly of nanometer thick, water soluble layers of plasmid DNA complexed with diamines and basic amino acids on graphite: Greatest DNA protection is obtained with arginine

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, T.T.; Boulanouar, O. [Université de Bourgogne Franche-Comté, UMR CNRS 6249 Chrono-Environnement, 16, Route de Gray, 25030 Besançon Cedex (France); Heintz, O. [Université de Bourgogne Franche-Comté, UMR CNRS 6303Laboratoire Interdisciplinaire Carnot de Bourgogne, DTAI/Centre de micro/nano caractérisation, 9 Av. A. Savary, BP 47870, F-21078 DIJON Cedex (France); Fromm, M., E-mail: michel.fromm@univ-fcomte.fr [Université de Bourgogne Franche-Comté, UMR CNRS 6249 Chrono-Environnement, 16, Route de Gray, 25030 Besançon Cedex (France)

    2017-02-01

    We have investigated the ability of diamines as well as basic amino acids to condense DNA onto highly ordered pyrolytic graphite with minimum damage after re-dissolution in water. Based on a bibliographic survey we briefly summarize DNA binding properties with diamines as compared to basic amino acids. Thus, solutions of DNA complexed with these linkers were drop-cast in order to deposit ultra-thin layers on the surface of HOPG in the absence or presence of Tris buffer. Atomic Force Microscopy analyses showed that, at a fixed ligand-DNA mixing ratio of 16, the mean thickness of the layers can be statistically predicted to lie in the range 0–50 nm with a maximum standard deviation ± 6 nm, using a simple linear law depending on the DNA concentration. The morphology of the layers appears to be ligand-dependent. While the layers containing diamines present holes, those formed in the presence of basic amino acids, except for lysine, are much more compact and dense. X-ray Photoelectron Spectroscopy measurements provide compositional information indicating that, compared to the maximum number of DNA sites to which the ligands may bind, the basic amino acids Arg and His are present in large excess. Conservation of the supercoiled topology of the DNA plasmids was studied after recovery of the complex layers in water. Remarkably, arginine has the best protection capabilities whether Tris was present or not in the initial solution. - Highlights: • Characterization of nanometer scaled layers composed of pUC21 plasmid DNA • Relation between nature of the ligand and structure of the layers • Capacities of the ligands to protect plasmids from strand break depending on their nature.

  9. Estudo das interações entre o complexo polieletrolítico trimetilquitosana/carboximetilcelulose e Cu+2, ácido húmico e atrazina em solução aquosa Study of the interactions between the polyelectrolyte complex trimethylchitosan/carboxymethylcellulose and Cu+2, humic acid and atrazine in aqueous solution

    Directory of Open Access Journals (Sweden)

    Sergio P. Campana-Filho

    2009-01-01

    Full Text Available The polyelectrolyte complex (PEC resulting from the reaction of sodium carboxymethylcellulose (CMC and N,N,N-trimethylchitosan hydrochloride (TMQ was prepared and then characterized by infrared spectroscopy and energy dispersive X rays analysis. The interactions involving the PEC and Cu2+ ions, humic acid and atrazine in aqueous medium were studied. From the adsorption isotherms the maximum amount adsorbed (Xmax was determined as 61 mg Cu2+/g PEC, 171 mg humic acid/g PEC and 5 mg atrazine/g PEC. The results show that the CMC/TMQ complex has a high affinity for the studied species, indicating its potential application to remove them from aqueous media.

  10. New modulated design, docking and synthesis of carbohydrate-conjugate heterobimetallic CuII-SnIV complex as potential topoisomerase II inhibitor: in vitro DNA binding, cleavage and cytotoxicity against human cancer cell lines.

    Science.gov (United States)

    Tabassum, Sartaj; Afzal, Mohd; Arjmand, Farukh

    2014-03-03

    New carbohydrate-conjugate heterobimetallic complexes [C₂₂H₅₀N₆O₁₃CuSnCl₂] (3) and [C₂₂H₅₈N₆O₁₇NiSnCl₂] (4) were synthesized from their monometallic analogs [C₂₂H₅₂N₆O₁₃Cu] (1) and [C₂₂H₆₀N₆O₁₇Ni] (2) containing N-glycoside ligand (L). In vitro DNA binding studies of L and complexes (1-4) with CT DNA were carried out by employing various biophysical and molecular docking techniques which revealed that heterobimetallic complex 3 strongly binds to DNA in comparison to 4, monometallic complexes (1 and 2) and the free ligand. Complex 3 cleaves pBR322 DNA via hydrolytic pathway (confirmed by T4 DNA ligase assay) and inhibited Topo-II activity in a dose-dependent manner. Furthermore, complex 3 was docked into the ATPase domain of human-Topo-II in order to probe the possible mechanism of inhibition. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  11. Supramolecular assemblies in [Cu(L-Arg){sub 2}(H{sub 2}O)]C{sub 2}O{sub 4}·6H{sub 2}O complex – Structural, spectroscopic, magnetic and thermal behavior

    Energy Technology Data Exchange (ETDEWEB)

    Wojciechowska, Agnieszka, E-mail: agnieszka.wojciechowska@pwr.edu.pl [Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspiańskiego 27, 50-370, Wrocław (Poland); Kochel, Andrzej [Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wrocław (Poland); Duczmal, Marek [Faculty of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspiańskiego 27, 50-370, Wrocław (Poland)

    2016-10-01

    The reaction of L-arginine and oxalate ions with copper(II) salts yields a new complex with formula of [Cu(L-Arg){sub 2}(H{sub 2}O)]·C{sub 2}O{sub 4}·6H{sub 2}O (1) (where L-Arg = L-arginine). Single crystals of 1 were synthesized by crystallization from aqueous solution. The complex properties were characterized by X-ray diffraction, spectroscopy (FT-IR, FT-Raman, NIR-Vis-UV and EPR) as well as thermal and magnetic methods. The square pyramidal (SP) geometry around Cu(II) ions in [Cu(L-Arg){sub 2}(H{sub 2}O)]{sup 2+} cation complex is formed by two cis-chelated L-arginine zwitterions and a water molecule coordinated in the apex of square pyramid. The trigonality distortion of SP geometry is relatively small, τ = 0.0087. The solid state EPR spectrum showed broad hyperfine splitting with g{sub ⊥} = 2.061 at 77 K. The copper centres distanced at 7.558(5) Å are joined in a single zig-zag structure via a chain based on the combination of Cu−O(5)−H(29)⋯O(2)−C1−O1−Cu hydrogen bonds along the b axis (d (O2⋯O5) = 2.812 Å). Taking into account the structural features, the magnetic susceptibility data were best-fitted, giving the exchange parameter J = −0.16 cm{sup −1}. Complex 1 is thermally stable up to 66 °C, where it was observed to lose the crystallization water molecules with an 11.7% mass loss (calc. 11.5%). - Highlights: • Crystal and molecular structure of [Cu(L-Arg){sub 2}(H{sub 2}O)]C{sub 2}O{sub 4}·6H{sub 2}O crystals have been studied. • The magnetic interactions of Cu(II) centres are assisted by the formation of single zig-zag chain. • Role of oxalate ions in completed relatively small square pyramid distortion is described. • The cis-fashioned L-arginine created the stronger ligand field than trans-configuration.

  12. Synthesis, solvatochromism and crystal structure of trans-[Cu(Et2NCH2CH2NH2)2.H2O](NO3)2 complex: Experimental with DFT combination

    Science.gov (United States)

    Warad, Ismail; Musameh, Sharif; Badran, Ismail; Nassar, Nashaat N.; Brandao, Paula; Tavares, Carlos Jose; Barakat, Assem

    2017-11-01

    In this study, two dicationic asymmetrical diamine/copper(II) nitrate salt complexes of the general formula trans-[CuII(NN‧)2.H2O](NO3)2 were successfully synthesized using N,N-dimethylethylenediamine and N,N-diethylethylenediamine as asymmetrical diamine ligands. The structure of complex 2 was identified by X-ray single crystal diffraction analysis confirming that the bidentate ligand N,N-dimethylethylenediamine forms a penta-coordinated complex with an H2O molecule located around the copper(II) ion in a trans configuration. It was found that the metal centre is coordinated in a distorted square pyramidal fashion with a τ value of 0.274. The desired complexes were fully characterized using, MS, UV-Vis, CV, FTIR, TG/DTA, and Hirshfeld surface computational analysis. High level theoretical calculations were also performed in order to investigate the complexes structure, conformers, vibrational frequencies, and their excited states.

  13. Synthesis, characterization and biological studies of 2-(4-nitrophenylamino-carbonyl)benzoic acid and its complexes with Cr(III), Co(II), Ni(II), Cu(II) and Zn(II)

    International Nuclear Information System (INIS)

    Imran, M; Nazir, S.; Latif, S.; Mahmood, Z.

    2010-01-01

    Cr(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of 2-(4-Nitrophenyl aminocarbonyl)benzoic acid were synthesized and characterized on the basis of physical, analytical and spectroscopic data. The ligands, as well as its metal complexes were checked for their in-vitro antimicrobial activity against three bacterial strains, Mycobacterium smegmatis, Escherichia coli, Pseudomonas aeuroginosa, and three fungal strains, Nigrospora oryzae, Aspergillus niger and Candida albicans. Disc diffusion method and Tube diffusion test were used for antibacterial and antifungal activities, respectively. The synthesized complexes only show significant antifungal activity but inactive for antibacterial, however, in general, the metal complexes were found to be more active against antimicrobial activities as compared to their un complexed ligand. (author)

  14. Lecithin Complex

    African Journals Online (AJOL)

    1Department of Food Science and Engineering, Xinyang College of Agriculture and ... Results: The UV and IR spectra of the complex showed an additive effect of polydatin-lecithin, in which .... Monochromatic Cu Ka radiation (wavelength =.

  15. Water Soluble Polymers for Pharmaceutical Applications

    Directory of Open Access Journals (Sweden)

    Veeran Gowda Kadajji

    2011-11-01

    Full Text Available Advances in polymer science have led to the development of novel drug delivery systems. Some polymers are obtained from natural resources and then chemically modified for various applications, while others are chemically synthesized and used. A large number of natural and synthetic polymers are available. In the present paper, only water soluble polymers are described. They have been explained in two categories (1 synthetic and (2 natural. Drug polymer conjugates, block copolymers, hydrogels and other water soluble drug polymer complexes have also been explained. The general properties and applications of different water soluble polymers in the formulation of different dosage forms, novel delivery systems and biomedical applications will be discussed.

  16. Time evolution of morphology in mechanically alloyed Fe-Cu

    KAUST Repository

    Wille, Catharina Gabriele; Al-Kassab, Talaá t; Kirchheim, Reiner

    2011-01-01

    Being widely accessible as well as already utilised in many applications, Fe-Cu acts as an ideal binary model alloy to elaborate the enforced nonequilibrium enhanced solubility in such a solution system that shows a limited regime of miscibility

  17. Spectrophotometric studies, synthesis and magnetic properties of Co(2), Cu(2), Ni(2) and UO2(6) complexes of 1,2-O-iso-propylidene-4-aza-7-aminoheptane

    International Nuclear Information System (INIS)

    Memet Sekerci

    2000-01-01

    1,2-O-iso-propylidene-4-aza-7-aminoheptane (L) is synthesized from 1-chloro-2,3-O-iso-propylidenepropane. In turn the last is prepared from the epichlorhydrine and acetone. Then the complexes of this ligand with Co(2), Cu(2), Ni(2) and UO 2 (6) salts are obtained. The structure of the ligand and its complexes is proposed according to the data of 1 H and 13 C NMR method, IR spectroscopy, element, thermogravimetric and differential thermal analyses and magnetic susceptibility measurements [ru

  18. Synergistic effect of signaling from receptors of soluble platelet agonists and outside-in signaling in formation of a stable fibrinogen-integrin αIIbβ3-actin cytoskeleton complex.

    Science.gov (United States)

    Budnik, Ivan; Shenkman, Boris; Savion, Naphtali

    2015-01-01

    Thrombus formation in the injured vessel wall is a highly complex process involving various blood-born components that go through specific temporal and spatial changes as observed by intravital videomicroscopy. Platelets bind transiently to the developing thrombus and may either become stably incorporated into or disengage from the thrombus. The aim of the present study was to reveal the processes involved in the formation of a stable thrombus. Platelet-rich plasma and washed platelets were studied by the aggregometer. The aggregate stability was challenged by eptifibatide. Platelet Triton-insoluble fraction was prepared and the actin and αIIb content in the cytoskeleton was analyzed by western blot. Maximal actin polymerization is achieved 1min after platelet activation while maximal αIIbβ3-actin cytoskeleton association requires 5 to 10min of activation and fibrinogen-mediated platelet-to-platelet bridging. Thus, actin polymerization is dependent on platelet activation and requires neither αIIbβ3 integrin occupation nor platelet aggregation. Formation of a stable aggregate requires platelet activation for more than 1min, complete increase in actin cytoskeleton fraction and partial association of αIIbβ3 with the actin cytoskeleton. However, direct αIIbβ3 activation is not sufficient for cytoskeleton complex formation. Thus, stable αIIbβ3-fibrinogen interaction, representing stable aggregate, is achieved after more than 1min agonist activation, involving inside-out and outside-in signaling but not after direct integrin activation, involving only outside-in signaling. Formation of a stable fibrinogen-αIIbβ3-actin cytoskeleton complex is the result of the combined effect of platelet stimulation by soluble agonists, activation of αIIbβ3, fibrinogen binding and platelet-to-platelet bridging. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Solubility of lead and copper in biochar-amended small arms range soils: influence of soil organic carbon and pH.

    Science.gov (United States)

    Uchimiya, Minori; Bannon, Desmond I

    2013-08-14

    Biochar is often considered a strong heavy metal stabilizing agent. However, biochar in some cases had no effects on, or increased the soluble concentrations of, heavy metals in soil. The objective of this study was to determine the factors causing some biochars to stabilize and others to dissolve heavy metals in soil. Seven small arms range soils with known total organic carbon (TOC), cation exchange capacity, pH, and total Pb and Cu contents were first screened for soluble Pb and Cu concentrations. Over 2 weeks successive equilibrations using weak acid (pH 4.5 sulfuric acid) and acetate buffer (0.1 M at pH 4.9), Alaska soil containing disproportionately high (31.6%) TOC had nearly 100% residual (insoluble) Pb and Cu. This soil was then compared with sandy soils from Maryland containing significantly lower (0.5-2.0%) TOC in the presence of 10 wt % (i) plant biochar activated to increase the surface-bound carboxyl and phosphate ligands (PS450A), (ii) manure biochar enriched with soluble P (BL700), and (iii) unactivated plant biochars produced at 350 °C (CH350) and 700 °C (CH500) and by flash carbonization (corn). In weak acid, the pH was set by soil and biochar, and the biochars increasingly stabilized Pb with repeated extractions. In pH 4.9 acetate buffer, PS450A and BL700 stabilized Pb, and only PS450A stabilized Cu. Surface ligands of PS450A likely complexed and stabilized Pb and Cu even under acidic pH in the presence of competing acetate ligand. Oppositely, unactivated plant biochars (CH350, CH500, and corn) mobilized Pb and Cu in sandy soils; the putative mechanism is the formation of soluble complexes with biochar-borne dissolved organic carbon. In summary, unactivated plant biochars can inadvertently increase dissolved Pb and Cu concentrations of sandy, low TOC soils when used to stabilize other contaminants.

  20. Preparation of Schiff s base complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) and their spectroscopic, magnetic, thermal, and antifungal studies

    International Nuclear Information System (INIS)

    Parekh, H.M.; Patel, M.N.

    2006-01-01

    The potassium salt of salicylidene-DL-alanine (KHL), bis(benzylidene)ethylenediamine (A 1 ), thiophene-o-carboxaldene-p-toluidine (A 2 ), and its metal complexes of the formula [(M II (L)(A)(H 2 O)] (M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II); A = A 1 or A 2 ) are prepared. They are characterized by elemental analysis, magnetic susceptibility measurements, thermogravimetric analysis, and infrared and electronic spectral studies. The electronic spectral and magnetic moment data suggest an octahedral geometry for the complexes. All of these complexes, metal nitrates, fungicides (bavistin and emcarb), and ligands are screened for their antifungal activity against Aspergillus niger, Fusarium oxysporum, and Aspergillus flavus using a plate poison technique. The complexes show higher activity than those of the free ligands, metal nitrate, and the control (DMSO) and moderate activity against bavistin and emcarb [ru

  1. Synthesis, Structures and Properties of Cu(II and Mn(II Complexes with 1,10-Phenanthroline-2-carboxylic acid and 2,2’-Bipyridine Ligands

    Directory of Open Access Journals (Sweden)

    Huanzhi Xu

    2010-11-01

    Full Text Available Four new 2,2’-bipyridine and 1,10-phenanthroline complexes, namely [Mn(phenca2]·(H2O2 (1, [Cu4(phen4(OH-4(H2O2](DMF4(ClO4-4(H2O (2, [Cu2(2,2-bipy2(C2O42-(H2O2(NO32] (3 and [Cu(2,2-bipy2(ClO4-](ClO4- (4 (2,2’-bpy = 2,2’-bipyridine, Hphenca = 1,10-phenanthroline-2-carboxylic acid have been synthesized by a hydrothermal reaction. The products were characterized by elemental analysis, infrared spectroscopy and X-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as π···π interactions is also evident in the structures. A preliminary investigation on the ion exchange properties of the complexes is presented.

  2. Solar photocatalytic removal of Cu(II), Ni(II), Zn(II) and Pb(II): Speciation modeling of metal-citric acid complexes

    International Nuclear Information System (INIS)

    Kabra, Kavita; Chaudhary, Rubina; Sawhney, R.L.

    2008-01-01

    The present study is targeted on solar photocatalytic removal of metal ions from wastewater. Photoreductive deposition and dark adsorption of metal ions Cu(II), Ni(II), Pb(II) and Zn(II), using solar energy irradiated TiO 2 , has been investigated. Citric acid has been used as a hole scavenger. Modeling of metal species has been performed and speciation is used as a tool for discussing the photodeposition trends. Ninety-seven percent reductive deposition was obtained for copper. The deposition values of other metals were significantly low [nickel (36.4%), zinc (22.2%) and lead (41.4%)], indicating that the photocatalytic treatment process, using solar energy, was more suitable for wastewater containing Cu(II) ions. In absence of citric acid, the decreasing order deposition was Cu(II) > Ni(II) > Pb(II) > Zn(II), which proves the theoretical thermodynamic predictions about the metals

  3. Solubility of AnO{sub 2}.xH{sub 2}O(am) in carbonate solution and formation of ternary An(IV) hydroxide-carbonate complexes

    Energy Technology Data Exchange (ETDEWEB)

    Neck, V.; Altmaier, M. [Institut fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Postfach 3640, D-76021 Karlsruhe (Germany); Fanghaenel, Th. [Institut fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Postfach 3640, D-76021 Karlsruhe (Germany); Physikalisch-Chemisches Institut, Ruprecht-Karls-Universitaet, Im Neuenheimer Feld 253, D-69120 Heidelberg (Germany)

    2005-07-01

    Full text of publication follows: The solubility of amorphous An(IV) hydroxides or hydrous oxides is studied with Th(IV) as a redox-stable surrogate for the other tetravalent actinides at I = 0.1 - 4 M (NaHCO{sub 3}-Na{sub 2}CO{sub 3}-NaOHNaCl) and 22 deg. C. Several series of closed system experiments at total carbonate concentrations of C{sub tot} = [HCO{sub 3}{sup -}] + [CO{sub 3}{sup 2-}] = 0.02 and 0.1 M in the range pH{sub c} = 8 - 13 and in Na{sub 2}CO{sub 3}-NaOH mixtures are performed with Th(IV) and additionally with Pu(IV). In our recent study with Th(IV) at I = 0.5 M [1], the simultaneous evaluation of solubility data at widely varied pH and carbonate concentrations has shown that Th(OH)(CO{sub 3}){sub 4}{sup 5-}, Th(OH){sub 2}(CO{sub 3}){sub 2}{sup 2-} and Th(OH){sub 4}(CO{sub 3}){sup 2-} are the most important ternary complexes. The present results at I = 0.1 - 4 M are used to describe the ionic strength dependence of the equilibrium constants log K{sub s,1yz} = log K{sub sp} + log {beta}{sub 1yz} for the reactions An(OH){sub 4}(am) + z CO{sub 3}{sup 2-} {r_reversible} An(OH){sub y}(CO{sub 3}){sub z}{sup 4-y-2z} + (4-y) OH{sup -}. Using the evaluated ion interaction (SIT) coefficients, available solubility data for U(IV), Np(IV) and Pu(IV) in wide ranges of pH, carbonate concentration and ionic strength, in particular apparently conflicting literature data for Np(IV) [2, 3] and Pu(IV) [2, 4], can be described with a consistent set of equilibrium constants. The predominant complexes An(OH){sub y}(CO{sub 3}){sub z}{sup 4-y-2z} and their formation constants log {beta}{sup 0}{sub 1yz} show pronounced analogies and systematic tendencies in the series Th(IV)-U(IV)-Np(IV)-Pu(IV). [1] Altmaier, M., Neck, V., Mueller, R., Fanghaenel, Th., Radiochim. Acta 93 (2005), in press.; [2] Rai, D., Hess, N.J., Felmy, A.R., Moore, D.A., Yui, M., Vitorge, P., a) Radiochim. Acta 84 (1999), 159, b) Radiochim. Acta 86 (1999), 89.; [3] Kitamura, A., Kohara, Y., J. Nucl

  4. Binuclear Copper(I Borohydride Complex Containing Bridging Bis(diphenylphosphino Methane Ligands: Polymorphic Structures of [(µ2-dppm2Cu2(η2-BH42] Dichloromethane Solvate

    Directory of Open Access Journals (Sweden)

    Natalia V. Belkova

    2017-10-01

    Full Text Available Bis(diphenylphosphinomethane copper(I tetrahydroborate was synthesized by ligands exchange in bis(triphenylphosphine copper(I tetrahydroborate, and characterized by XRD, FTIR, NMR spectroscopy. According to XRD the title compound has dimeric structure, [(μ2-dppm2Cu2(η2-BH42], and crystallizes as CH2Cl2 solvate in two polymorphic forms (orthorhombic, 1, and monoclinic, 2 The details of molecular geometry and the crystal-packing pattern in polymorphs were studied. The rare Twisted Boat-Boat conformation of the core Cu2P4C2 cycle in 1 is found being more stable than Boat-Boat conformation in 2.

  5. Raman spectroscopy of DNA-metal complexes. I. Interactions and conformational effects of the divalent cations: Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Pd, and Cd

    OpenAIRE

    Duguid, J.; Bloomfield, V.A.; Benevides, J.; Thomas Jr, G.J.

    1993-01-01

    Interactions of divalent metal cations (Mg2+, Ca2+, Ba2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) with DNA have been investigated by laser Raman spectroscopy. Both genomic calf-thymus DNA (> 23 kilobase pairs) and mononucleosomal fragments (160 base pairs) were employed as targets of metal interaction in solutions containing 5 weight-% DNA and metal:phosphate molar ratios of 0.6:1. Raman difference spectra reveal that transition metal cations (Mn2+, Co2+, Ni2+, Cu2+, Pd2+, and Cd2+) ind...

  6. Leaching of copper concentrates using NaCl and soluble copper contributed by the own concentrate; Lixiviacion de concentrados de cobre utilizando NaCl y el cobre soluble aportado por el propio concentrado

    Energy Technology Data Exchange (ETDEWEB)

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

    2005-07-01

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

  7. Studies on coordination chemistry and bioactivity of metal complexes of some nitrogen-sulfur donor ligands: Section A: hydraziniumdithiocarbazate and its complexes. Section B: complexes of Ni2+ and Cu2+ ions with s-picolyldithiocarbazate

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Liza bt Abdullah; Crouse, Karen A.; Ali, A.M.

    2003-08-01

    Two new nitrogen - sulphur donor ligands, hydraziniumdithiocarbazate(HzDTC) and S-picolyldithiocarbazate(SPDTC), along with three novel Schiff bases were prepared. Complexes of some of HzDTC with nickel(II), zinc(II), and those of SPDTC with nickel(II) and copper(II) were prepared and characterized by a variety of physico- chemical techniques. The ligand, HzDTC, was a potential bidentate and uninegatively charged providing terminal amino and thiolate bindings with the metal ions, while SPDTC coordinates via the pyridine nitrogen and the thiolate anion. All of the compounds were tested against four pathogenic bacteria and fungi. HzDTC was found to be very effective antimicrobial than its complexes. The complexes of SPDTC and the Schiff bases of HzDTC were more antifungal. None of the compounds were effective anti- cancer agents except for [Ni(HzDTCA)Cl.H 2 O], which was moderately active against CEM- SS (Human cell T- lymphoblastic) leukemic cells. (author)

  8. Solubility of Copper(II Sulfate and Dicopper Chloride Trihydroxide for Pigs

    Directory of Open Access Journals (Sweden)

    C. S. Park

    2016-11-01