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Sample records for copperii carboxylate promoted

  1. A one-dimensional carboxylate-bridged helical copper(II) complex containing (quinolin-8-yloxy)acetate.

    Science.gov (United States)

    Wang, Yu-Hong; Lu, Fang

    2004-11-01

    The title compound, catena-poly[[bromocopper(II)]-mu-(quinolin-8-yloxy)acetato-kappa(4)N,O,O':O''], [CuBr(C(11)H(8)NO(3))](n), is a novel carboxylate-bridged one-dimensional helical copper(II) polymer. The metal ion exhibits an approximately square-pyramidal CuBrNO(3) coordination environment, with the three donor atoms of the ligand and the bromide ion occupying the basal positions, and an O atom belonging to the carboxylate group of an adjacent molecule in the apical site. Carboxylate groups are mutually cis oriented, and each anti-anti carboxylate group bridges two copper(II) ions via one apical and one basal position [Cu...Cu = 5.677 (1) A], resulting in the formation of a helical chain along the crystallographic b axis.

  2. Crystal structure, characterization and magnetic properties of a 1D copper(II) polymer incorporating a Schiff base with carboxylate side arm

    Indian Academy of Sciences (India)

    SHYAMAPADA SHIT; MADHUSUDAN NANDY; CORRADO RIZZOLI; CÉDRIC DESPLANCHES; SAMIRAN MITRA

    2016-06-01

    A new 1D polymeric copper(II) complex [{Cu(L)$(CF_{3}COO)}2]_{n}$ has been synthesized using apotentially tetradentate Schiff base ligand, HL, ((E)-2-((pyridin-2-yl)methyleneamino)-5-chlorobenzoic acid)and characterized by different spectroscopic methods. Single crystal X-ray structural characterization revealsthat the side arm carboxylate group of the coordinated Schiff base exhibits a $μ_{1,3}$ -bridging mode and connectsthe neighbouring copper(II) ions leading to a zigzag 1D chain structure where the copper(II) ions displaydistorted square pyramidal geometries. Variable temperature magnetic susceptibility measurement reveals aweak antiferromagnetic exchange (J = −0.47±0.01 $cm_{−1}) prevails between copper(II) ions in the chainmediated by the bridging carboxylate group, is also supported by the room temperature EPR spectral study.Electrochemical property of the complex is also reported.

  3. Antioxidant Promotion of Tyrosine Nitration in the Presence of Copper(II)

    OpenAIRE

    Qiao, Liang; Liu, Baohong; Girault, Hubert

    2013-01-01

    Copper(II) is known to catalyze the generation of reactive nitrogen species in the presence of hydrogen peroxide, nitrite or nitric oxide, leading to tyrosine nitration, a biomarker for free radical species associated diseases. Here, we find that biological antioxidants such as ascorbic acid can promote tyrosine nitration in the presence of copper(II) and nitrite under aerobic and weak acidic conditions. Tyrosine nitration is demonstrated on both β-amyloid peptide and angiotensin I. These stu...

  4. Simultaneous and sensitive analysis of aliphatic carboxylic acids by ion-chromatography using on-line complexation with copper(II) ion.

    Science.gov (United States)

    Kemmei, Tomoko; Kodama, Shuji; Yamamoto, Atsushi; Inoue, Yoshinori; Hayakawa, Kazuichi

    2015-01-02

    A new approach to ion chromatography is proposed to improve the UV detection of aliphatic carboxylic acids separated by anion-exchange chromatography. When copper(II) ion added to the mobile phase, it forms complexes with carboxylic acids that can be detected at 240 nm. The absorbance was found to increase with increasing copper(II) ion concentration. The retention times of α-hydroxy acids were also found to depend on the copper(II) ion concentration. Addition of acetonitrile to the mobile phase improved the separation of aliphatic carboxylic acids. The detection limits of the examined carboxylic acids (formate, glycolate, acetate, lactate, propionate, 3-hydroxypropionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-caproate) calculated at S/N=3 ranged from 0.06 to 3 μM. The detector signal was linear over three orders of magnitude of carboxylic acid concentration. The proposed method was successfully applied to analyze aliphatic carboxylic acids in rainwater and bread.

  5. Antioxidant promotion of tyrosine nitration in the presence of copper(II).

    Science.gov (United States)

    Qiao, Liang; Liu, Baohong; Girault, Hubert H

    2013-06-01

    Copper(II) is known to catalyze the generation of reactive nitrogen species in the presence of hydrogen peroxide, nitrite or nitric oxide, leading to tyrosine nitration, a biomarker for free radical species associated diseases. Here, we find that biological antioxidants such as ascorbic acid can promote tyrosine nitration in the presence of copper(II) and nitrite under aerobic and weak acidic conditions. Tyrosine nitration is demonstrated on both the β-amyloid peptide and angiotensin I. These studies show that (i) ascorbic acid works as a pro-oxidant in the presence of copper(II) to induce oxidation and nitration on peptides, (ii) both free and coordinated copper(II) can catalyze peptide oxidation and nitration, (iii) nitration occurs under mild acidic conditions (pH = 6.0-6.5).

  6. Kinetic resolution of racemic carboxylic acids through asymmetric protolactonization promoted by chiral phosphonous acid diester.

    Science.gov (United States)

    Sakuma, Masayuki; Sakakura, Akira; Ishihara, Kazuaki

    2013-06-07

    Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.

  7. Functionalized adamantane tectons used in the design of mixed-ligand copper(II) 1,2,4-triazolyl/carboxylate metal-organic frameworks.

    Science.gov (United States)

    Senchyk, Ganna A; Lysenko, Andrey B; Krautscheid, Harald; Rusanov, Eduard B; Chernega, Alexander N; Krämer, Karl W; Liu, Shi-Xia; Decurtins, Silvio; Domasevitch, Konstantin V

    2013-01-18

    Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr(2)pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr(2)ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H(4)-adtc) platform for the construction of neutral heteroleptic copper(II) metal-organic frameworks. Two coordination polymers, [{Cu(4)(OH)(2)(H(2)O)(2)}{Cu(4)(OH)(2)}(tr(2)pr)(2)(H-adtc)(4)]·2H(2)O (1) and [Cu(4)(OH)(2)(tr(2)ad)(2)(H-adtc)(2)(H(2)O)(2)]·3H(2)O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N(1),N(2)-1,2,4-triazolyl (tr) and μ(3)-OH(-) groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu(4)(OH)(2)} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu(4)(OH)(2)} secondary building block and trideprotonated carboxylate H-adtc(3-) can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing μ(3)- or μ(4)-binding patterns, introduce additional integrating links between the neighboring {Cu(4)(OH)(2)} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J(1) = -109 cm(-1) and J(2) = -21 cm(-1)), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = -2.5 cm(-1)).

  8. The copper(II) and zinc(II) coordination mode of HExxH and HxxEH motif in small peptides: the role of carboxylate location and hydrogen bonding network.

    Science.gov (United States)

    Grasso, Giuseppe; Magrì, Antonio; Bellia, Francesco; Pietropaolo, Adriana; La Mendola, Diego; Rizzarelli, Enrico

    2014-01-01

    Copper(II) and zinc(II) complexes with two hexapeptides encompassing HExxH and HxxEH motif were characterized by means of a combined experimental and theoretical approach. Parallel tempering and density functional theory (DFT) investigations show the presence of different hydrogen bonding networks between the copper(II) and zinc(II) complexes with the two peptides, suggesting a significant contribution of these non-covalent interactions to the stability constant values. The glutamate carboxylate group has a direct role in metal ion binding. The location of this amino acid along the sequence of the investigated peptides is critical to determine thermodynamic and spectroscopic features of the copper(II) complex species, whereas is less relevant in the zinc(II) complexes formation. Electrospray ionization mass spectrometry (ESI-MS) characterization of the zinc(II) complex species show that in the [ZnH-2L] two deprotonated amide nitrogen atoms are involved in the metal coordination environment, an uncommon behavior in zinc(II) complexes for multi-histidine ligands.

  9. A copper(II) perchlorate-promoted tandem reaction of internal alkynol and salicyl N-tosylhydrazone: direct access to isochromeno[3,4-b]chromene.

    Science.gov (United States)

    Siyang, Hai Xiao; Wu, Xu Rui; Ji, Xiao Yue; Wu, Xin Yan; Liu, Pei Nian

    2014-08-11

    A copper(ii) perchlorate-promoted tandem reaction of internal alkynol and salicyl N-tosylhydrazone provides a novel, concise method for constructing isochromeno[3,4-b]chromene in 35-94% yields. The tandem reaction involves cycloisomerization, formal [4+2] cycloaddition and an elimination process.

  10. Carboxylated N-glycans on RAGE promote S100A12 binding and signaling

    Science.gov (United States)

    Srikrishna, Geetha; Nayak, Jonamani; Weigle, Bernd; Temme, Achim; Foell, Dirk; Hazelwood, Larnele; Olsson, Anna; Volkmann, Niels; Hanein, Dorit; Freeze, Hudson H.

    2010-01-01

    RAGE, the Receptor for Advanced Glycation End Products, is a signaling receptor protein of the immunoglobulin superfamily implicated in multiple pathologies. It binds a diverse repertoire of ligands, but the structural basis for the interaction of different ligands is not well understood. We earlier showed that carboxylated glycans on the V-domain of RAGE promote the binding of HMGB1 and S100A8/A9. Here we study the role of these glycans on the binding and intracellular signaling mediated by another RAGE ligand, S100A12. S100A12 binds carboxylated glycans, and a subpopulation of RAGE enriched for carboxylated glycans shows more than ten fold higher binding potential for S100A12 than total RAGE. When expressed in mammalian cells, RAGE is modified by complex glycans predominantly at the first glycosylation site (N25IT) that retains S100A12 binding. Glycosylation of RAGE and maximum binding sites for S100A12 on RAGE are also cell type dependent. Carboxylated glycan-enriched population of RAGE forms higher order multimeric complexes with S100A12, and this ability to multimerize is reduced upon deglycosylation or by using non-glycosylated sRAGE expressed in E.coli. mAbGB3.1, an antibody against carboxylated glycans, blocks S100A12 mediated NF-κB signaling in HeLa cells expressing full length RAGE. These results demonstrate that carboxylated N-glycans on RAGE enhance binding potential and promote receptor clustering and subsequent signaling events following oligomeric S100A12 binding. PMID:20512925

  11. Hydrolytic activity of -alkoxide/acetato-bridged binuclear Cu(II) complexes towards carboxylic acid ester

    Indian Academy of Sciences (India)

    Weidong Jiang; Bin Xu; Zhen Xiang; Shengtian Huang; Fuan Liu; Ying Wang

    2013-09-01

    Two -alkoxide/acetate-bridged small molecule binuclear copper(II) complexes were synthesized, and used to promote the hydrolysis of a classic carboxylic acid ester, -nitrophenyl picolinate (PNPP). Both binuclear complexes exhibited good hydrolytic reactivity, giving rise to . 15547- and 17462-fold acceleration over background value for PNPP hydrolysis at neutral conditions, respectively. For comparing, activities of the other two mononuclear analogues were evaluated, revealing that binuclear complexes show approximately 150- and 171-fold kinetic advantage over their mononuclear analogues.

  12. In Vitro DNA-Binding, Anti-Oxidant and Anticancer Activity of Indole-2-Carboxylic Acid Dinuclear Copper(II) Complexes

    OpenAIRE

    Xiangcong Wang; Maocai Yan; Qibao Wang; Huannan Wang; Zhengyang Wang; Jiayi Zhao; Jing Li; Zhen Zhang

    2017-01-01

    Indole-2-carboxylic acid copper complex (ICA-Cu) was successfully prepared and characterized through elemental analysis, IR, UV-Vis, 1H-NMR, TG analysis, and molar conductance, and its molecular formula was [Cu2(C9H6O2N)4(H2O)2]·2H2O. The binding ability of ICA-Cu to calf thymus DNA (CT-DNA) was examined by fluorescence spectrometry and the viscosity method. The results indicated that, upon the addition of increasing amounts of CT-DNA, the excitation and emission intensity of ICA-Cu decreased...

  13. Carbon dioxide utilization via carbonate-promoted C-H carboxylation

    Science.gov (United States)

    Banerjee, Aanindeeta; Dick, Graham R.; Yoshino, Tatsuhiko; Kanan, Matthew W.

    2016-03-01

    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO32-) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)—a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO32--promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  14. Carbon dioxide utilization via carbonate-promoted C-H carboxylation.

    Science.gov (United States)

    Banerjee, Aanindeeta; Dick, Graham R; Yoshino, Tatsuhiko; Kanan, Matthew W

    2016-03-10

    Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

  15. Synthesis, crystal structure, spectroscopic investigations and DFT calculations of the copper(II) complex of 4-(Trifluoromethyl)pyridine-2-carboxylic acid

    Science.gov (United States)

    Vural, Hatice; Orbay, Metin

    2017-10-01

    A novel polymeric complex of Cu(II) ion, [Cu(tfpc)2]n [tfpc: 4-(Trifluoromethyl)pyridine-2-carboxylate] has been prepared and characterized spectroscopically (by FT-IR) and structurally (by single-crystal XRD). The geometry around the Cu(II) center can be described as square planar made by tfpc ligand having nitrogen and oxygen atoms. Additionally, the Cu(II) complex has a one-dimensional double-bridged polymeric structure in which Cu(II) ions are bridged by two oxygen atoms of adjacent planes. The crystal packing has been stabilized by Csbnd H⋯O intra and intermolecular hydrogen bonds. The molecular structure of the Cu(II) complex has been optimized using the Density Functional Theory (DFT) B3LYP, B3PW91 and PBEPBE levels with 6-311+G(d,p) basis set. The calculated electronic spectra have been explained using the time dependent DFT (TD-DFT) method by applying the polarized continuum model (PCM). The vibrational spectral data have been calculated and compared with experimental ones. The non-linear optical (NLO) properties of the title compound have been investigated using the DFT method with three different levels. Natural Bond Orbital (NBO) property of the Cu(II) complex has been performed by the B3LYP density functional and the 6-311+G(d,p) basis set.

  16. In Vitro DNA-Binding, Anti-Oxidant and Anticancer Activity of Indole-2-Carboxylic Acid Dinuclear Copper(II) Complexes.

    Science.gov (United States)

    Wang, Xiangcong; Yan, Maocai; Wang, Qibao; Wang, Huannan; Wang, Zhengyang; Zhao, Jiayi; Li, Jing; Zhang, Zhen

    2017-01-20

    Indole-2-carboxylic acid copper complex (ICA-Cu) was successfully prepared and characterized through elemental analysis, IR, UV-Vis, ¹H-NMR, TG analysis, and molar conductance, and its molecular formula was [Cu₂(C₉H₆O₂N)₄(H₂O)₂]·2H₂O. The binding ability of ICA-Cu to calf thymus DNA (CT-DNA) was examined by fluorescence spectrometry and the viscosity method. The results indicated that, upon the addition of increasing amounts of CT-DNA, the excitation and emission intensity of ICA-Cu decreased obviously and the excitation spectra shifted towards a long wavelength. ICA-Cu could displace ethidium bromide (EB) from the EB-DNA system, making the fluorescence intensity of the EB-DNA system decrease sharply; the quenching constant KSV value was 3.99 × 10⁴ M(-1). The emission intensity of the ICA-Cu-DNA system was nearly constant, along with the addition of Na⁺ in a series of concentrations. The fluorescence of the complex could be protected after the complex interacted with DNA. A viscosity measurement further supported the result that the ICA-Cu complex may interact with DNA in an intercalative binding mode. The antioxidant activities of ICA-Cu were evaluated by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, a hydroxyl radical (OH) scavenging assay, and a 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) assay. The ICA-Cu exhibited the highest inhibitory effects on the ABTS radical (94% inhibition at 60 µM), followed by OH and DPPH radicals (the degrees of inhibition being 71% and 56%, respectively). The in vitro cytotoxicity activity of ICA-Cu against two human breast cancer cell lines, MDA-MB-231 and MCF-7, was investigated by 3-[4,5-dimethyltiazol2-yl]-2.5-diphenyl-tetrazolium bromide (MTT) assay and cellular morphological analysis. The results showed that, upon increasing the concentration of ICA-Cu, an increase was observed in growth-inhibitory activity and the inhibition percentage were greater than 90% at 20 µM in both cell

  17. In Vitro DNA-Binding, Anti-Oxidant and Anticancer Activity of Indole-2-Carboxylic Acid Dinuclear Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Xiangcong Wang

    2017-01-01

    Full Text Available Indole-2-carboxylic acid copper complex (ICA-Cu was successfully prepared and characterized through elemental analysis, IR, UV-Vis, 1H-NMR, TG analysis, and molar conductance, and its molecular formula was [Cu2(C9H6O2N4(H2O2]·2H2O. The binding ability of ICA-Cu to calf thymus DNA (CT-DNA was examined by fluorescence spectrometry and the viscosity method. The results indicated that, upon the addition of increasing amounts of CT-DNA, the excitation and emission intensity of ICA-Cu decreased obviously and the excitation spectra shifted towards a long wavelength. ICA-Cu could displace ethidium bromide (EB from the EB-DNA system, making the fluorescence intensity of the EB-DNA system decrease sharply; the quenching constant KSV value was 3.99 × 104 M−1. The emission intensity of the ICA-Cu-DNA system was nearly constant, along with the addition of Na+ in a series of concentrations. The fluorescence of the complex could be protected after the complex interacted with DNA. A viscosity measurement further supported the result that the ICA-Cu complex may interact with DNA in an intercalative binding mode. The antioxidant activities of ICA-Cu were evaluated by a 2,2-diphenyl-1-picrylhydrazyl (DPPH assay, a hydroxyl radical (OH scavenging assay, and a 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS assay. The ICA-Cu exhibited the highest inhibitory effects on the ABTS radical (94% inhibition at 60 µM, followed by OH and DPPH radicals (the degrees of inhibition being 71% and 56%, respectively. The in vitro cytotoxicity activity of ICA-Cu against two human breast cancer cell lines, MDA-MB-231 and MCF-7, was investigated by 3-[4,5-dimethyltiazol2-yl]-2.5-diphenyl-tetrazolium bromide (MTT assay and cellular morphological analysis. The results showed that, upon increasing the concentration of ICA-Cu, an increase was observed in growth-inhibitory activity and the inhibition percentage were greater than 90% at 20 µM in both cell lines. Also

  18. SOYBEAN SEEDLING ROOT GROWTH PROMOTION BY 1-AMINOCYCLOPROPANE-1-CARBOXYLATE DEAMINASE-PRODUCING PSEUDOMONADS

    Directory of Open Access Journals (Sweden)

    Edi Husen

    2016-10-01

    Full Text Available Pseudomonad producing 1-aminocyclopropane-1-carboxylate (ACC deaminase (E.C.4.1.99.4 has been known to promote plant growth by lowering ethylene biosynthesis in higher plants, which can be induced by indole-3-acetic acid (IAA production. The objective of this study was to examine the ability of IAAproducing Pseudomonas isolated from local soil environment (rhizosphere of soybean grown in Plumbon's agricultural areain Cirebon, West Java, Indonesia to promote soybean root growth in relation to their ACC deaminase activities. The experiments were conducted in growth room and Laboratory of Soil Biology Research, Indonesian Soil Research Institute, Bogor, from January to August 2008. Soybean seeds were inoculated by immersing the seeds for 1 hour in bacterial cell suspension containing approximately 108-109 cells ml-1. The seeds were then germinatedfor 2 days before planting in growth pouches containing sterilized distilled water. All treated and untreated seeds were grown for 7 days in growth room at 24°C with 1300 lux of light intensity for 12-hour followed by a 12-hour dark period at 22°C. ACC deaminase activity of the isolates was assayed based on their ability to grow in Dworkin-Foster’s salt minimal medium containing ammonium sulfate or ACC as a source of nitrogen. Thirteen out of 81 isolates tested significantly increased soybean root length and weight, up to 50% from untreated plants. Of 13 isolates, 11 demonstrated ACC deaminase activities. Two isolates that did not show ACC deaminase activities had lower capacity to produce IAA. The results suggest that the effectiveness of IAA producing Pseudomonas in promoting the growth of the soybean seedlings is associated with their ACC deaminase activities or they produce IAA at low levels.

  19. Phosphazene-promoted metal-free ring-opening polymerization of ethylene oxide initiated by carboxylic acid

    KAUST Repository

    Zhao, Junpeng

    2014-03-11

    The effectiveness of carboxylic acid as initiator for the anionic ring-opening polymerization of ethylene oxide was investigated with a strong phosphazene base (t-BuP4) used as promoter. Kinetic study showed an induction period, i.e., transformation of carboxylic acid to hydroxyl ester, followed by slow chain growth together with simultaneous and fast end-group transesterification, which led to poly(ethylene oxide) (PEO) consisting of monoester (monohydroxyl), diester, and dihydroxyl species. An appropriate t-BuP4/acid ratio was proven to be essential to achieve better control over the polymerization and low dispersity of PEO. This work provides important information and enriches the toolbox for macromolecular and biomolecular engineering with protic initiating sites. © 2014 American Chemical Society.

  20. β-Cyclodextrin promoted oxidation of aldehydes to carboxylic acids in water

    Institute of Scientific and Technical Information of China (English)

    Dong Po Shi; Hong Bing Ji

    2009-01-01

    A facile,efficient and substrate-selective oxidation of aldehydes to carboxylic acids with NaC10 catalyzed by β-cyclodextdn in water has been developed.A series of aldehydes which could form inclusion complex with β-cyclodextrin(β-CD)were oxidized selectively with excellent yields.

  1. Phosphate diester hydrolysis and DNA damage promoted by new cis-aqua/hydroxy copper(II) complexes containing tridentate imidazole-rich ligands.

    Science.gov (United States)

    Scarpellini, Marciela; Neves, Ademir; Hörner, Rosmari; Bortoluzzi, Adailton J; Szpoganics, Bruno; Zucco, César; Nome Silva, René A; Drago, Valderes; Mangrich, Antônio S; Ortiz, Wilson A; Passos, Wagner A C; de Oliveira, Maurício C B; Terenzi, Hernán

    2003-12-15

    The tridentate Schiff base [(2-(imidazol-4-yl)ethyl)(1-methylimidazol-2-yl)methyl)imine (HISMIMI) and its reduced form HISMIMA were synthesized and characterized, as well their mononuclear cis-dihalo copper(II) complexes 1 and 2, respectively. In addition, the dinuclear [CuII(mu-OH)2CuII](2+) complexes (3) and (4) obtained from complexes 1 and 2, respectively, were also isolated and characterized by several physicochemical techniques, including magnetochemistry, electrochemistry, and EPR and UV-vis spectroscopies. The crystal structures of 1 and 2 were determined by X-ray crystallography and revealed two neutral complexes with their tridentate chelate ligands meridionally coordinated. Completing the coordination spheres of the square-pyramidal structures, a chloride ion occupies the apical position and another is bonded in the basal plane. In addition, complexes 1 and 2 were investigated by infrared, electronic, and EPR spectroscopies, cyclic voltammetry, and potentiometric equilibrium studies. The hydrolytic activity on phosphate diester cleavage of 1 and 2 was investigated utilizing 2,4-BDNPP as substrate. These experiments were carried out at 50 degrees C, and the data treatment was based on the Michaelis-Menten approach, giving the following kinetic parameters (complex 1/complex 2): vmax (mol L(-1) s(-1))=16.4x10(-9)/7.02x10(-9); KM (mol L(-1))=17.3x10(-3)/3.03x10(-3); kcat (s(-1))=3.28x10(-4)/1.40x10(-4). Complex 1 effectively promoted the hydrolytic cleavage of double-strand plasmid DNA under anaerobic and aerobic conditions, with a rate constant of 0.28 h(-1) for the decrease of form I, which represents about a 10(7) rate increase compared with the estimated uncatalyzed rate of hydrolysis.

  2. Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters.

    Science.gov (United States)

    Li, Yuehui; Topf, Christoph; Cui, Xinjiang; Junge, Kathrin; Beller, Matthias

    2015-04-20

    Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2002-08-01

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

  4. A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions.

    Science.gov (United States)

    Mita, Tsuyoshi; Suga, Kenta; Sato, Kaori; Sato, Yoshihiro

    2015-11-01

    By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.

  5. Crystal structure of a chloride-bridged copper(II) dimer: piperazine-1,4-dium bis-(di-μ-chlorido-bis[(4-carboxypyridine-2-carboxyl-ato-κ(2)N,O(2))chlorido-cuprate(II)].

    Science.gov (United States)

    Inah, Bassey Enyi; Ayi, Ayi Anyama; Adhikary, Amit

    2017-02-01

    Crystals of a new dimeric chloride-bridged cuprate(II) derived from pyridine-2,4-di-carb-oxy-lic acid were obtained solvothermally in the presence of piperazine and hydro-chloric acid. The crystal structure determination of the title salt, (C4H12N2)[Cu2(C7H4NO4)2Cl4], revealed one of the carboxyl groups of the original pyridine-2,4-di-carb-oxy-lic acid ligand to be protonated, whereas the other is deprotonated and binds together with the pyridine N atom to the Cu(II) atom. The coordination environment of the Cu(II) atom is distorted square-pyramidal. One of the chloride ligands bridges two metal cations to form a centrosymmetric dimer with two different Cu-Cl distances of 2.2632 (8) and 2.7853 (8) Å, whereby the longer distance is associated with the apical ligand. The remaining chloride ligand is terminal at one of the basal positions, with a distance of 2.2272 (9) Å. In the crystal, the dimers are linked by inter-molecular O-H⋯O hydrogen bonds, together with N-H⋯O and N-H⋯Cl inter-actions involving the centrosymmetric organic cation, into a three-dimensional supra-molecular network. Further but weaker C-H⋯O and C-H⋯Cl inter-actions consolidate the packing.

  6. Synthesis, crystal structure and investigation of mononuclear copper(II) and zinc(II) complexes of a new carboxylate rich tripodal ligand and their interaction with carbohydrates in alkaline aqueous solution.

    Science.gov (United States)

    Stewart, Christopher D; Pedraza, Mayra; Arman, Hadi; Fan, Hua-Jun; Schilling, Eduardo Luiz; Szpoganicz, Bruno; Musie, Ghezai T

    2015-08-01

    A new carboxylate rich asymmetric tripodal ligand, N-[2-carboxybenzomethyl]-N-[carboxymethyl]-β-alanine (H3camb), and its di-copper(II), (NH4)2[1]2, and di-zinc(II), ((CH3)4N)2[2]2, complexes have been synthesized as carbohydrate binding models in aqueous solutions. The ligand and complexes have been fully characterized using several techniques, including single crystal X-ray diffraction. The interactions of (NH4)2[1]2 and ((CH3)4N)2[2]2 with D-glucose, D-mannose, D-xylose and xylitol in aqueous alkaline media were investigated using UV-Vis and (13)C-NMR spectroscopic techniques, respectively. The molar conductance, NMR and ESI-MS studies indicate that the complexes dissociate in solution to produce the respective complex anions, 1(-) and 2(-). Complexes 1(-) and 2(-) showed chelating ability towards the naturally abundant and biologically relevant sugars, D-glucose, D-mannose, D-xylose, and xylitol. The complex ions bind to one molar equivalent of the sugars, even in the presence of stoichiometric excess of the substrates, in solution. Experimentally obtained spectroscopic data and computational results suggest that the substrates bind to the metal center in a bidentate fashion. Apparent binding constant values, pK(app), between the complexes and the substrates were determined and a specific mode of substrate binding is proposed. The pK(app) and relativistic density functional theory (DFT) calculated Gibbs free energy values indicate that D-mannose displayed the strongest interaction with the complexes. Syntheses, characterizations, detailed substrate binding studies using spectroscopic techniques, single crystal X-ray diffraction and geometry optimizations of the complex-substrates with DFT calculations are also reported.

  7. Biosorption Performance of Encapsulated Candida krusei for the removal of Copper(II).

    Science.gov (United States)

    Luk, Chi Him Jim; Yip, Joanne; Yuen, Chun Wah Marcus; Pang, Siu Kwong; Lam, Kim Hung; Kan, Chi Wai

    2017-05-19

    The use of microorganisms in biosorption is one of the most promising ways to remove trace amounts of heavy metal ions. Nevertheless, the enhancement of the successful removal of heavy metal ions by using different combinations of biosorbents is not generally guaranteed which leaves room to explore the application of the technique. In this study, the performance of free and immobilized forms of a yeast strain, Candida krusei (C. krusei), and calcium alginate (CaAlg) are evaluated for their ability to remove copper(II). Infrared spectroscopy, studies on the effects of pH and temperature, and kinetics and isotherm modelling are carried out to evaluate the biosorption. The infrared spectroscopy shows that the primary biosorption sites on the biosorbents are carboxylate groups. In addition, a higher pH and higher temperatures promote biosorption while a decline in biosorption ability is observed for C. krusei at 50 °C. The kinetics study shows that C. krusei, CaAlg and immobilized C. krusei (MCaAlg) conform with good correlation to pseudo-second order kinetics. MCaAlg and CaAlg fit well to the Langmuir isotherm while C. krusei fits well to the Temkin isotherm. From the experimental data, encapsulating C. krusei showed improved biosoprtion and address clogging in practical applications.

  8. A ubiquitin carboxyl extension protein secreted from a plant-parasitic nematode Globodera rostochiensis is cleaved in planta to promote plant parasitism.

    Science.gov (United States)

    Chronis, Demosthenis; Chen, Shiyan; Lu, Shunwen; Hewezi, Tarek; Carpenter, Sara C D; Loria, Rosemary; Baum, Thomas J; Wang, Xiaohong

    2013-04-01

    Nematode effector proteins originating from esophageal gland cells play central roles in suppressing plant defenses and in formation of the plant feeding cells that are required for growth and development of cyst nematodes. A gene (GrUBCEP12) encoding a unique ubiquitin carboxyl extension protein (UBCEP) that consists of a signal peptide for secretion, a mono-ubiquitin domain, and a 12 amino acid carboxyl extension protein (CEP12) domain was cloned from the potato cyst nematode Globodera rostochiensis. This GrUBCEP12 gene was expressed exclusively within the nematode's dorsal esophageal gland cell, and was up-regulated in the parasitic second-stage juvenile, correlating with the time when feeding cell formation is initiated. We showed that specific GrUBCEP12 knockdown via RNA interference reduced nematode parasitic success, and that over-expression of the secreted Gr(Δ) (SP) UBCEP12 protein in potato resulted in increased nematode susceptibility, providing direct evidence that this secreted effector is involved in plant parasitism. Using transient expression assays in Nicotiana benthamiana, we found that Gr(Δ) (SP) UBCEP12 is processed into free ubiquitin and a CEP12 peptide (GrCEP12) in planta, and that GrCEP12 suppresses resistance gene-mediated cell death. A target search showed that expression of RPN2a, a gene encoding a subunit of the 26S proteasome, was dramatically suppressed in Gr(Δ) (SP) UBCEP12 but not GrCEP12 over-expression plants when compared with control plants. Together, these results suggest that, when delivered into host plant cells, Gr(Δ) (SP) UBCEP12 becomes two functional units, one acting to suppress plant immunity and the other potentially affecting the host 26S proteasome, to promote feeding cell formation. © 2013 The Authors The Plant Journal © 2013 Blackwell Publishing Ltd.

  9. Ubiquitin carboxyl-terminal hydrolase 1 (UCHL1 is a potential tumour suppressor in prostate cancer and is frequently silenced by promoter methylation

    Directory of Open Access Journals (Sweden)

    Meyer-Schwesinger Catherine

    2011-10-01

    Full Text Available Abstract Background We have previously reported significant downregulation of ubiquitin carboxyl-terminal hydrolase 1 (UCHL1 in prostate cancer (PCa compared to the surrounding benign tissue. UCHL1 plays an important role in ubiquitin system and different cellular processes such as cell proliferation and differentiation. We now show that the underlying mechanism of UCHL1 downregulation in PCa is linked to its promoter hypermethylation. Furthermore, we present evidences that UCHL1 expression can affect the behavior of prostate cancer cells in different ways. Results Methylation specific PCR analysis results showed a highly methylated promoter region for UCHL1 in 90% (18/20 of tumor tissue compared to 15% (3/20 of normal tissues from PCa patients. Pyrosequencing results confirmed a mean methylation of 41.4% in PCa whereas only 8.6% in normal tissues. To conduct functional analysis of UCHL1 in PCa, UCHL1 is overexpressed in LNCaP cells whose UCHL1 expression is normally suppressed by promoter methylation and found that UCHL1 has the ability to decrease the rate of cell proliferation and suppresses anchorage-independent growth of these cells. In further analysis, we found evidence that exogenous expression of UCHL1 suppress LNCaP cells growth probably via p53-mediated inhibition of Akt/PKB phosphorylation and also via accumulation of p27kip1 a cyclin dependant kinase inhibitor of cell cycle regulating proteins. Notably, we also observed that exogenous expression of UCHL1 induced a senescent phenotype that was detected by using the SA-ß-gal assay and might be due to increased p14ARF, p53, p27kip1 and decreased MDM2. Conclusion From these results, we propose that UCHL1 downregulation via promoter hypermethylation plays an important role in various molecular aspects of PCa biology, such as morphological diversification and regulation of proliferation.

  10. A phenazine-1-carboxylic acid producing polyextremophilic Pseudomonas chlororaphis (MCC2693) strain, isolated from mountain ecosystem, possesses biocontrol and plant growth promotion abilities.

    Science.gov (United States)

    Jain, Rahul; Pandey, Anita

    2016-09-01

    The genus Pseudomonas is known to comprise a huge diversity of species with the ability to thrive in different habitats, including those considered as extreme environments. In the present study, a psychrotolerant, wide pH tolerant and halotolerant strain of Pseudomonas chlororaphis GBPI_507 (MCC2693), isolated from the wheat rhizosphere growing in a mountain location in Indian Himalayan Region (IHR), has been investigated for its antimicrobial potential with particular reference to phenazine production and plant growth promoting traits. GBPI_507 showed phenazine production at the temperatures ranged from 14 to 25°C. The benzene extracted compound identified as phenazine-1-carboxylic acid (PCA) through GC-MS exhibited antimicrobial properties against Gram positive bacteria and actinomycetes. The inhibition of phytopathogens in diffusible biocontrol assays was recorded in an order: Alternaria alternata>Phytophthora sp.>Fusarium solani>F. oxysporum. In volatile metabolite assays, all the pathogens, except Phytophthora sp. produced distorted colonies, characterized by restricted sporulation. The isolate also possessed other growth promoting and biocontrol traits including phosphate solubilization and production of siderophores, HCN, ammonia, and lytic enzymes (lipase and protease). Molecular studies confirmed production of PCA by the bacterium GBPI_507 through presence of phzCD and phzE genes in its genome. The polyextremophilic bacterial strain possesses various important characters to consider it as a potential agent for field applications, especially in mountain ecosystem, for sustainable and eco-friendly crop production.

  11. Structural analysis of the promoter of tomato 1-aminocyclopropane-1-carboxylate synthase 6 gene(Le-ACS6)

    Institute of Scientific and Technical Information of China (English)

    LIN JingYu; FAN Rong; WAN XiaoRong; CHARNG Yeeyung; WANG NingNing

    2007-01-01

    Ethylene plays an important role in the regulation of many growth and developmental processes of higher plants. In tomato, Le-ACS6, a member of the ACC synthase multigene family involved in system 1 ethylene biosynthesis during fruit ripening, is subject to negative feedback regulation by ethylene. To identify the cis-elements that are responsible for the negative feedback control, we established an in vitro transient assay system employing particle bombardment on mature-green tomato fruit pericarp to examine the expression of a luciferase (LUC) reporter gene driven by a 5'-serially deleted Le-ACS6 promoter. The results localized putative cis-elements required for negative ethylene-response between -347 and -266 upstream from the translational start site ATG. Several lines of stable transformation of the Le-ACS6 promoter and GUS reporter fusion gene containing internal deletion from -347 to -266 were generated. The expression pattern of the GUS reporter showed that removal of the nucleotides from -347 to -266 completely eliminated the response of the Le-ACS6 promoter to exogenous ethylene.

  12. 1-Aminocyclopropane-1-Carboxylic Acid Transported from Roots to Shoots Promotes Leaf Abscission in Cleopatra Mandarin (Citrus reshni Hort. ex Tan.) Seedlings Rehydrated after Water Stress.

    Science.gov (United States)

    Tudela, D; Primo-Millo, E

    1992-09-01

    The effect of water stress and subsequent rehydration on 1-aminocyclopropane-1-carboxylic acid (ACC) content, ACC synthase activity, ethylene production, and leaf abscission was studied in Cleopatra mandarin (Citrus reshni Hort. ex Tan.) seedlings. Leaf abscission occurred when drought-stressed plants were allowed to rehydrate, whereas no abscission was observed in plants under water stress conditions. In roots of water-stressed plants, a high ACC accumulation and an increase in ACC synthase activity were observed. Neither increase in ACC content nor significant ethylene production were detected in leaves of water-stressed plants. After rehydration, a sharp rise in ACC content and ethylene production was observed in leaves of water-stressed plants. Content of ACC in xylem fluid was 10-fold higher in plants rehydrated for 2 h after water stress than in nonstressed plants. Leaf abscission induced by rehydration after drought stress was inhibited when roots or shoots were treated before water stress with aminooxyacetic acid (AOA, inhibitor of ACC synthase) or cobalt ion (inhibitor of ethylene-forming enzyme), respectively. However, AOA treatments to shoots did not suppress leaf abscission. The data indicate that water stress promotes ACC synthesis in roots of Cleopatra mandarin seedlings. Rehydration of plants results in ACC transport to the shoots, where it is oxidized to ethylene. Subsequently, this ethylene induces leaf abscission.

  13. A doppel alpha-helix peptide fragment mimics the copper(II) interactions with the whole protein.

    Science.gov (United States)

    La Mendola, Diego; Magrì, Antonio; Campagna, Tiziana; Campitiello, Maria Anna; Raiola, Luca; Isernia, Carla; Hansson, Orjan; Bonomo, Raffaele P; Rizzarelli, Enrico

    2010-06-01

    The doppel protein (Dpl) is the first homologue of the prion protein (PrP(C)) to be discovered; it is overexpressed in transgenic mice that lack the prion gene, resulting in neurotoxicity. The whole prion protein is able to inhibit Dpl neurotoxicity, and its N-terminal domain is the determinant part of the protein function. This region represents the main copper(II) binding site of PrP(C). Dpl is able to bind at least one copper ion, and the specific metal-binding site has been identified as the histidine residue at the beginning of the third helical region. However, a reliable characterization of copper(II) coordination features has not been reported. In a previous paper, we studied the copper(II) interaction with a peptide that encompasses only the loop region potentially involved in metal binding. Nevertheless, we did not find a complete match between the EPR spectroscopic parameters of the copper(II) complexes formed with the synthesized peptide and those reported for the copper(II) binding sites of the whole protein. Herein, the synthesis of the human Dpl peptide fragment hDpl(122-139) (Ac-KPDNKLHQQVLWRLVQEL-NH(2)) and its copper(II) complex species are reported. This peptide encompasses the third alpha helix and part of the loop linking the second and the third helix of human doppel protein. The single-point-mutated peptide, hDpl(122-139)D124N, in which aspartate 124 replaces an asparagine residue, was also synthesized. This peptide was used to highlight the role of the carboxylate group on both the conformation preference of the Dpl fragment and its copper(II) coordination features. NMR spectroscopic measurements show that the hDpl(122-139) peptide fragment is in the prevailing alpha-helix conformation. It is localized within the 127-137 amino acid residue region that represents a reliable conformational mimic of the related protein domain. A comparison with the single-point-mutated hDpl(122-139)D124N reveals the significant role played by the aspartic

  14. Shielding membrane surface carboxyl groups by covalent-binding graphene oxide to improve anti-fouling property and the simultaneous promotion of flux.

    Science.gov (United States)

    Han, Jing-Long; Xia, Xue; Tao, Yu; Yun, Hui; Hou, Ya-Nan; Zhao, Chang-Wei; Luo, Qin; Cheng, Hao-Yi; Wang, Ai-Jie

    2016-10-01

    Graphene oxide (GO) is an excellent material for membrane surface modification. However, little is known about how and to what extent surface functional groups change after GO modification influence membrane anti-fouling properties. Carboxyl is an inherent functional group on polyamide or other similar membranes. Multivalent cations in wastewater secondary effluent can bridge with carboxyls on membrane surfaces and organic foulants, resulting in serious membrane fouling. In this study, carboxyls of a polydopamine (pDA)/1,3,5-benzenetricarbonyl trichloride (TMC) active layer are shielded by covalently-bound GO. The process is mediated by N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC)/N-hydroxysuccinimide (NHS). For GO containing low quantities of carboxyls, X-ray photoelectron spectroscopy (XPS) and zeta potential analyzer test results reveal that the carboxyl density decreased by 52.3% compare to the pDA/TMC membrane after GO modification. Fouling experiments shows that the flux only slightly declines in the GO functionalized membrane (19.0%), compared with the pDA/TMC membrane (36.0%) after fouling. In addition, during GO modification process the pDA/TMC active layer also become harder and thinner with the aid of EDC/NHS. So the pure water permeability increases from 56.3 ± 18.2 to 103.7 ± 12.0 LMH/MPa. Our results provide new insights for membrane modification work in water treatment and other related fields.

  15. Copper(II) and nickel(II) binding sites of peptide containing adjacent histidyl residues.

    Science.gov (United States)

    Grenács, Ágnes; Sanna, Daniele; Sóvágó, Imre

    2015-10-01

    Copper(II) and nickel(II) complexes of the terminally protected nonapeptide Ac-SGAEGHHQK-NH2 modeling the metal binding sites of the (8-16) domain of amyloid-β have been studied by potentiometric, UV-vis, CD and ESR spectroscopic methods. The studies on the mutants containing only one of the histidyl residues (Ac-SGAEGAHQK-NH2, Ac-SGAEGHAQK-NH2) have also been performed. The formation of imidazole and amide coordinated mononuclear complexes is characteristic of all systems with a preference of nickel(II) binding to the His14 site, while the involvement of both histidines in metal binding is suggested in the corresponding copper(II) complexes. The formation of bis(ligand) and dinuclear complexes has also been observed in the copper(II)-Ac-SGAEGHHQK-NH2 system. The results provide further support for the copper(II) binding ability of the (8-16) domain of amyloid-β and support the previous assumptions that via the bis(ligand) complex formation copper(II) ions may promote the formation of the oligomers of amyloid-β.

  16. Polymeric networks of copper(II) phenylmalonate with heteroaromatic n-donor ligands: synthesis, crystal structure, and magnetic properties.

    Science.gov (United States)

    Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

    2005-10-31

    Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange

  17. Study of Lewis Acid Promoting KBH_4 Reduce Carboxylic Acid Ester%Lewis酸促进KBH_4还原某些羧酸酯的研究

    Institute of Scientific and Technical Information of China (English)

    汪一波; 金召磊; 唐守万; 孙佰申; 潘富友; 高建荣

    2011-01-01

    Potassium borohydride reduction of some carboxylic esters into the corresponding alcohols by the Lewis acid was introduced.The structures were confirmed by 1HNMR,MS and IR,consistent with its structure and the target,and the yield of 37.5~68.5.%在Lewis酸的作用下,研究硼氢化钾将某些羧酸酯还原成相应的醇。其产物经1HNMR、MS和IR表征,其结构与目标物一致,收率在37.5~68.5之间。

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

    Science.gov (United States)

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

    2010-11-28

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

  19. Triphenylphosphine Stabilized Silver Carboxylates

    Institute of Scientific and Technical Information of China (English)

    Jian Lin HAN; Ying Zhong SHEN; Yi PAN

    2005-01-01

    A series of novel triphenylphosphine stabilized silver carboxylates, potential precursors for CVD growth of ultrafast interconnection link in microelectronic devices, have been prepared and characterized.

  20. Photoredox radical conjugate addition of dithiane-2-carboxylate promoted by an iridium(iii) phenyl-tetrazole complex: a formal radical methylation of Michael acceptors.

    Science.gov (United States)

    Gualandi, Andrea; Matteucci, Elia; Monti, Filippo; Baschieri, Andrea; Armaroli, Nicola; Sambri, Letizia; Cozzi, Pier Giorgio

    2017-02-01

    A readily accessible iridium(iii) phenyl-tetrazole complex ([Ir(ptrz)2(tBu-bpy)](+), 2; Hptrz = 2-methyl-5-phenyl-tetrazole; tBu-bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) is shown to be a versatile catalyst for a new photocatalytic Michael reaction. Under light irradiation in the presence of 2, a dithiane 2-carboxylic acid, obtained by simple hydrolysis of a commercially available ethyl ester, generates a 1,3-dithiane radical capable of performing addition to a variety of Michael acceptors (e.g., unsaturated ketones, esters, amides and malonates). This broad scope reaction with high yields is a formal photo-redox addition of the elusive methyl radical and the adducts obtained can be starting materials for a variety of functionalized products. The excited-state oxidation potential of catalyst 2 allows selective formation of radicals only from α-heterosubstituted carboxylates. Chemical modification of this metal complex can tune the electrochemical properties, opening a route to new highly selective catalytic photo-oxidation reactions.

  1. Synthesis, Crystal Structure, and Characterization of Ternary Copper(II Complex Derived from N-(salicylidene-L-valine

    Directory of Open Access Journals (Sweden)

    Sundaramurthy Santha Lakshmi

    2016-01-01

    Full Text Available Ternary Schiff base copper(II complex [CuL(tmpda] (where H2L is N-(salicylidene-L-valine; tmpda is N,N,N′,N′-tetramethyl-1,3-propanediamine has been characterized by UV-Vis., FTIR, and single crystal XRD. The crystal structure displays a distorted square pyramidal geometry in which Schiff base is bonded to the Cu(II ion via phenolate oxygen, imine nitrogen, and an oxygen atom of the carboxylate group through the basal plane and the chelating diamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, displays an axial and equatorial mode of binding via NN-donor atoms.

  2. Biosorption of copper(II) by Marrubium globosum subsp. globosum leaves powder: effect of chemical pretreatment.

    Science.gov (United States)

    Yazici, Hüseyin; Kiliç, Mehmet; Solak, Murat

    2008-03-01

    The study was aimed at determining the effect of chemical pretreatment on copper(II) biosorption by Marrubium globosum subsp. globosum leaves. The uptake capacity of the biomass was increased by chemical pretreatment when compared with the raw biomass. The results of biosorption experiments, carried out at the conditions of 50 mg l(-1) initial metal concentration and pH 5.5, showed that pretreating the biomass with alkali solutions (laundry detergent, sodium hydroxide and sodium bicarbonate, 0.5 M) improved the biosorption capacity of biomass (45.90, 45.78 and 43.91%, respectively) compared with raw biomass. Pretreatment with sulfuric and nitric acid solutions, 0.5 M, increased the biosorption capacity of biomass by 11.82 and 10.18%, respectively, while there was no considerable change in the biosorption capacity of biomass (0.35%) after pretreatment with formic acid solution, 0.5 M. Furthermore, sodium chloride and calcium chloride, 0.5 M, pretreatments resulted in the improvement in biosorption capacity of biomass (31.38 and 26.69%, respectively). FT-IR analysis revealed that hydroxyl and carboxyl functional groups were mainly responsible for copper(II) biosorption.

  3. Crystal structure of a chloride-bridged copper(II) dimer: piperazine-1,4-dium bis­(di-μ-chlorido-bis[(4-carboxypyridine-2-carboxyl­ato-κ2 N,O 2)chlorido­cuprate(II)

    Science.gov (United States)

    Inah, Bassey Enyi; Adhikary, Amit

    2017-01-01

    Crystals of a new dimeric chloride-bridged cuprate(II) derived from pyridine-2,4-di­carb­oxy­lic acid were obtained solvothermally in the presence of piperazine and hydro­chloric acid. The crystal structure determination of the title salt, (C4H12N2)[Cu2(C7H4NO4)2Cl4], revealed one of the carboxyl groups of the original pyridine-2,4-di­carb­oxy­lic acid ligand to be protonated, whereas the other is deprotonated and binds together with the pyridine N atom to the CuII atom. The coordination environment of the CuII atom is distorted square-pyramidal. One of the chloride ligands bridges two metal cations to form a centrosymmetric dimer with two different Cu—Cl distances of 2.2632 (8) and 2.7853 (8) Å, whereby the longer distance is associated with the apical ligand. The remaining chloride ligand is terminal at one of the basal positions, with a distance of 2.2272 (9) Å. In the crystal, the dimers are linked by inter­molecular O—H⋯O hydrogen bonds, together with N—H⋯O and N—H⋯Cl inter­actions involving the centrosymmetric organic cation, into a three-dimensional supra­molecular network. Further but weaker C—H⋯O and C—H⋯Cl inter­actions consolidate the packing. PMID:28217352

  4. Copper(II) complexes with highly water-soluble L- and D-proline-thiosemicarbazone conjugates as potential inhibitors of Topoisomerase IIα.

    Science.gov (United States)

    Bacher, Felix; Enyedy, Éva A; Nagy, Nóra V; Rockenbauer, Antal; Bognár, Gabriella M; Trondl, Robert; Novak, Maria S; Klapproth, Erik; Kiss, Tamás; Arion, Vladimir B

    2013-08-05

    Two proline-thiosemicarbazone bioconjugates with excellent aqueous solubility, namely, 3-methyl-(S)-pyrrolidine-2-carboxylate-2-formylpyridine thiosemicarbazone [L-Pro-FTSC or (S)-H2L] and 3-methyl-(R)-pyrrolidine-2-carboxylate-2-formylpyridine thiosemicarbazone [D-Pro-FTSC or (R)-H2L], have been synthesized and characterized by elemental analysis, one- and two-dimensional (1)H and (13)C NMR spectroscopy, and electrospray ionization mass spectrometry. The complexation behavior of L-Pro-FTSC with copper(II) in an aqueous solution and in a 30% (w/w) dimethyl sulfoxide/water mixture has been studied via pH potentiometry, UV-vis spectrophotometry, electron paramagnetic resonance, (1)H NMR spectroscopy, and spectrofluorimetry. By the reaction of copper(II) acetate with (S)-H2L and (R)-H2L in water, the complexes [Cu(S,R)-L] and [Cu(R,S)-L] have been synthesized and comprehensively characterized. An X-ray diffraction study of [Cu(S,R)-L] showed the formation of a square-pyramidal complex, with the bioconjugate acting as a pentadentate ligand. Both copper(II) complexes displayed antiproliferative activity in CH1 ovarian carcinoma cells and inhibited Topoisomerase IIα activity in a DNA plasmid relaxation assay.

  5. The cloned 1-aminocyclopropane-1-carboxylate (ACC) deaminase gene from Sinorhizobium sp. strain BL3 in Rhizobium sp. strain TAL1145 promotes nodulation and growth of Leucaena leucocephala.

    Science.gov (United States)

    Tittabutr, Panlada; Awaya, Jonathan D; Li, Qing X; Borthakur, Dulal

    2008-06-01

    The objective of this study was to determine the role of 1-aminocyclopropane-1-carboxylate (ACC) deaminase of symbionts in nodulation and growth of Leucaena leucocephala. The acdS genes encoding ACC deaminase were cloned from Rhizobium sp. strain TAL1145 and Sinorhizobium sp. BL3 in multicopy plasmids, and transferred to TAL1145. The BL3-acdS gene greatly enhanced ACC deaminase activity in TAL1145 compared to the native acdS gene. The transconjugants of TAL1145 containing the native or BL3 acdS gene could grow in minimal media containing 1.5mM ACC, whereas BL3 could tolerate up to 3mM ACC. The TAL1145 acdS gene was inducible by mimosine and not by ACC, while the BL3 acdS gene was highly inducible by ACC and not by mimosine. The transconjugants of TAL1145 containing the native- and BL3-acdS genes formed nodules with greater number and sizes, and produced higher root mass on L. leucocephala than by TAL1145. This study shows that the introduction of multiple copies of the acdS gene increased ACC deaminase activities of TAL1145 and enhanced its symbiotic efficiency on L. leucocephala.

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

    Science.gov (United States)

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

    2006-09-01

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

  7. Inoculation of Soil with Plant Growth Promoting Bacteria Producing 1-Aminocyclopropane-1-Carboxylate Deaminase or Expression of the Corresponding acdS Gene in Transgenic Plants Increases Salinity Tolerance in Camelina sativa.

    Science.gov (United States)

    Heydarian, Zohreh; Yu, Min; Gruber, Margaret; Glick, Bernard R; Zhou, Rong; Hegedus, Dwayne D

    2016-01-01

    Camelina sativa (camelina) is an oilseed crop touted for use on marginal lands; however, it is no more tolerant of soil salinity than traditional crops, such as canola. Plant growth-promoting bacteria (PGPB) that produce 1-aminocyclopropane-1-carboxylate deaminase (ACC deaminase) facilitate plant growth in the presence of abiotic stresses by reducing stress ethylene. Rhizospheric and endophytic PGPB and the corresponding acdS- mutants of the latter were examined for their ability to enhance tolerance to salt in camelina. Stimulation of growth and tolerance to salt was correlated with ACC deaminase production. Inoculation of soil with wild-type PGPB led to increased shoot length in the absence of salt, and increased seed production by approximately 30-50% under moderately saline conditions. The effect of ACC deaminase was further examined in transgenic camelina expressing a bacterial gene encoding ACC deaminase (acdS) under the regulation of the CaMV 35S promoter or the root-specific rolD promoter. Lines expressing acdS, in particular those using the rolD promoter, showed less decline in root length and weight, increased seed production, better seed quality and higher levels of seed oil production under salt stress. This study clearly demonstrates the potential benefit of using either PGPB that produce ACC deaminase or transgenic plants expressing the acdS gene under the control of a root-specific promoter to facilitate plant growth, seed production and seed quality on land that is not normally suitable for the majority of crops due to high salt content.

  8. Inoculation of Soil with Plant Growth Promoting Bacteria Producing 1-Aminocyclopropane-1-Carboxylate Deaminase or Expression of the Corresponding acdS Gene in Transgenic Plants Increases Salinity Tolerance in Camelina sativa

    Science.gov (United States)

    Heydarian, Zohreh; Yu, Min; Gruber, Margaret; Glick, Bernard R.; Zhou, Rong; Hegedus, Dwayne D.

    2016-01-01

    Camelina sativa (camelina) is an oilseed crop touted for use on marginal lands; however, it is no more tolerant of soil salinity than traditional crops, such as canola. Plant growth-promoting bacteria (PGPB) that produce 1-aminocyclopropane-1-carboxylate deaminase (ACC deaminase) facilitate plant growth in the presence of abiotic stresses by reducing stress ethylene. Rhizospheric and endophytic PGPB and the corresponding acdS- mutants of the latter were examined for their ability to enhance tolerance to salt in camelina. Stimulation of growth and tolerance to salt was correlated with ACC deaminase production. Inoculation of soil with wild-type PGPB led to increased shoot length in the absence of salt, and increased seed production by approximately 30–50% under moderately saline conditions. The effect of ACC deaminase was further examined in transgenic camelina expressing a bacterial gene encoding ACC deaminase (acdS) under the regulation of the CaMV 35S promoter or the root-specific rolD promoter. Lines expressing acdS, in particular those using the rolD promoter, showed less decline in root length and weight, increased seed production, better seed quality and higher levels of seed oil production under salt stress. This study clearly demonstrates the potential benefit of using either PGPB that produce ACC deaminase or transgenic plants expressing the acdS gene under the control of a root-specific promoter to facilitate plant growth, seed production and seed quality on land that is not normally suitable for the majority of crops due to high salt content. PMID:28018305

  9. Inoculation of soil with plant growth promoting bacteria producing 1-aminocyclopropane-1-carboxylate deaminase or expression the corresponding acdS gene in transgenic plants increases salinity tolerance in Camelina sativa.

    Directory of Open Access Journals (Sweden)

    Zohreh Heydarian

    2016-12-01

    Full Text Available Camelina sativa (camelina is an oilseed crop touted for use on marginal lands; however, it is no more tolerant of soil salinity than traditional crops, such as canola. Plant growth-promoting bacteria (PGPB that produce 1-aminocyclopropane-1-carboxylate deaminase (ACC deaminase facilitate plant growth in the presence of abiotic stresses by reducing stress ethylene. Rhizospheric and endophytic PGPB and the corresponding acdS- mutants of the latter were examined for their ability to enhance tolerance to salt in camelina. Stimulation of growth and tolerance to salt was correlated with ACC deaminase production. Inoculation of soil with wild-type PGPB led to increased shoot length in the absence of salt, and increased seed production by approximately 30-50 percent under moderately saline conditions. The effect of ACC deaminase was further examined in transgenic camelina expressing a bacterial gene encoding ACC deaminase (acdS under the regulation of the CaMV 35S promoter or the root-specific rolD promoter. Lines expressing acdS, in particular those using the rolD promoter, showed less decline in root length and weight, increased seed production, better seed quality and higher levels of seed oil production under salt stress. This study clearly demonstrates the potential benefit of using either PGPB that produce ACC deaminase or transgenic plants expressing the acdS gene under the control of a root-specific promoter to facilitate plant growth, seed production and seed quality on land that is not normally suitable for the majority of crops due to high salt content.

  10. Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis.

    Science.gov (United States)

    Ventre, Sandrine; Petronijevic, Filip R; MacMillan, David W C

    2015-05-06

    The direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides has been achieved via visible light-promoted photoredox catalysis. This operationally simple, redox-neutral fluorination method is amenable to a wide variety of carboxylic acids. Photon-induced oxidation of carboxylates leads to the formation of carboxyl radicals, which upon rapid CO2-extrusion and F(•) transfer from a fluorinating reagent yield the desired fluoroalkanes with high efficiency. Experimental evidence indicates that an oxidative quenching pathway is operable in this broadly applicable fluorination protocol.

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

    Science.gov (United States)

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

    1995-09-01

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

  12. Free carboxylate stretching modes

    NARCIS (Netherlands)

    Oomens, J.; Steill, J. D.

    2008-01-01

    We report the first IR spectroscopic observation of carboxylate stretching modes in free space, i.e., in the complete absence of solvent or counterions. Gas-phase spectra of a series of benzoate anions have been recorded and compared to condensed-phase spectra, revealing the profound influence of th

  13. Tetracarboxylate ligands as new chelates supporting copper(II) paddlewheel-like structures.

    Science.gov (United States)

    Gomila, Antoine; Duval, Sylvain; Besnard, Céline; Krämer, Karl W; Liu, Shi-Xia; Decurtins, Silvio; Williams, Alan F

    2014-03-03

    Two new ligands N,N,N',N'-tetrakis(2-methylbenzoic acid)-1,4-diaminomethylbenzene, 5H4, and N,N,N',N'-tetrakis(2-methylbenzoic acid)-4,4'-diaminomethyldiphenyl, 6H4, carrying four carboxylate groups suitable for bridging dinuclear centers have been prepared and their paddlewheel complexes with copper(II) prepared. The phenyl-bridged ligand 5H4 gives a cyclic octanuclear species [(Cu2)4(5)4], while the diphenyl-bridged ligand 6H4 gives a lantern-like tetranuclear species [(Cu2)2(6)2]; both were characterized by X-ray crystallography. If the amine functions of 5 are protonated, intramolecular hydrogen bonds position the four carboxylates in such a way as to allow formation of the unusual compound [Cu4(5H2)2Cl](3+) in which a Cu4 square centered by a chloro ligand is sandwiched between two (5H2)(2-) ligands. The magnetic properties of this compound have been studied and show antiferromagnetic coupling between adjacent coppers (J = -33.7 cm(-1)).

  14. Copper(II) complexes with aroylhydrazones

    Indian Academy of Sciences (India)

    Samudranil Pal

    2002-08-01

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

  15. Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(II) layers.

    Science.gov (United States)

    Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Campo, Javier; Lloret, Francesc; Julve, Miguel

    2006-07-21

    Self-assembly of copper(l) ions, phenylmalonate and pyrimidine yields the layered compound [Cu(pym)(Phmal)n (1) where intralayer ferro- and interlayer antiferromagnetic interactions occur with three-dimensional antiferromagnetic ordering at T(c) = 2.15 K.

  16. CARBOXYLATIONS AND DECARBOXYLATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Calvin, Melvin; Pon, Ning G.

    1959-04-21

    A brief survey of decarboxylation reactions and carboxylation reactions that are known or presumed in biological systems will be presented. While a considerable number of amino acid decarboxylations are known, their mechanisms will not be included in the present discussion but will be reserved for a later paper in the symposium. The remaining decarboxylation reactions may be subdivided into oxidative and nonoxidative decarboxylations. In most cases, these reactions are practically irreversible except when coupled with suitable energy-yielding systems. The carboxylation reactions which are useful in the formation of carbon-carbon bonds in biological systems seem to fall into two or three groups: those which exhibit an apparent ATP requirement, and those which exhibit a reduced pyridine nucleotide requirement, and those which exhibit no apparent ATP requirement. Of the first group at least four cases, and possibly six or seven, are known, and one interpretation of them involves the preliminary formation of 'active' carbon dioxide, generally in the form of a carbonic acid-phosphoric acid anhydride. Those exhibiting no apparent ATP requirement seem to be susceptible to classifications as enol carboxylations in which the energy level of the substrate compound is high, rather than that of the carbon dioxide. There appear to be at least three examples of this latter type known, amongs them being the carboxy-dismutase reaction of ribulose diphosphate with carbon dioxide.

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

    Science.gov (United States)

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

    2015-03-01

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

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

    Science.gov (United States)

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

    2012-05-01

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

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

    Science.gov (United States)

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

    2014-02-01

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

  20. Extraction of copper(II) ions from aqueous solutions with a methimazole-based ionic liquid.

    Science.gov (United States)

    Reyna-González, Juan M; Torriero, Angel A J; Siriwardana, Amal I; Burgar, Iko M; Bond, Alan M

    2010-09-15

    The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf(2)] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf(2)] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV-vis, Raman, and (1)H, (13)C, and (15)N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf(2)] can be recovered from the labile copper-water-IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu(2+) from aqueous media into the [mimSBu][NTf(2)] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf(2)] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction-voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

  1. Proton conduction and long-range ferrimagnetic ordering in two isostructural Copper(II) mesoxalate metal-organic frameworks.

    Science.gov (United States)

    Gil-Hernández, Beatriz; Savvin, Stanislav; Makhloufi, Gamall; Núñez, Pedro; Janiak, Christoph; Sanchiz, Joaquín

    2015-02-16

    Two compounds of formula {(H3O)[Cu7(Hmesox)5(H2O)7]·9H2O}n (1a) and {(NH4)0.6(H3O)0.4[Cu7(Hmesox)5(H2O)7]·11H2O}n (1b) were prepared and structurally characterized by single-crystal X-ray diffraction (H4mesox = mesoxalic acid, 2-dihydroxymalonic acid). The compounds are crystalline functional metal-organic frameworks exhibiting proton conduction and magnetic ordering. Variable-temperature magnetic susceptibility measurements reveal that the copper(II) ions are strongly ferro- and antiferromagnetically coupled by the alkoxide and carboxylate bridges of the mesoxalate linker to yield long-range magnetic ordering with a Tc of 17.6 K, which is reached by a rare mechanism known as topologic ferrimagnetism. Electric conductivity, measured by impedance methods, shows values as high as 6.5 × 10(-5) S cm(-1) and occurs by proton exchange among the hydronium/ammonium and water molecules of crystallization, which fill the voids left by the three-dimensional copper(II) mesoxalate anionic network.

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

    Science.gov (United States)

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

    2014-08-01

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

  3. On the interaction of copper(II) with disulfiram.

    Science.gov (United States)

    Lewis, David J; Deshmukh, Parikshit; Tedstone, Aleksander A; Tuna, Floriana; O'Brien, Paul

    2014-11-11

    In combination with copper(II) ions, disulfiram (DSF) has been reported to be a potentially potent anticancer agent based on in vitro results. The interaction of DSF with copper(II) chloride in solution has been studied using a range of spectroscopic techniques. There is strong evidence for the rapid formation of the bis(N,N-diethyl dithiocarbamato)copper(II) complex in situ. Kinetic experiments were used to determine rate laws for the reaction that give insight into the mechanism of the process which may help to explain the observed in vitro cytotoxicity.

  4. Remarkable inertness of copper(II) chelates of cyclen-based macrobicycles with two trans-N-acetate arms.

    Science.gov (United States)

    Esteves, Catarina V; Lamosa, Pedro; Delgado, Rita; Costa, Judite; Désogère, Pauline; Rousselin, Yoann; Goze, Christine; Denat, Franck

    2013-05-06

    Two cross-bridged cyclen-based macrocycles with two trans-N-acetic acid arms, one having a dibenzofuran (DBF) moiety as the bridge, H2L1, and the other a diphenyl ether (DPE) one, H2L2, were synthesized. Both compounds behave as "proton sponges." The thermodynamic stability constants for the Cu(2+), Zn(2+), Al(3+), and Ga(3+) complexes of both compounds were determined. They exhibit an excellent thermodynamic selectivity for copper(II), ensuring that metal ions largely present in the human body do not interfere with the copper(II) chelates. All complexes are very slow to form, and [CuL2] and [CuL1] are extremely inert to demetallate, especially [CuL2]. The acid-assisted dissociation of [CuL1] led to a half-life of 4.28 h in 5 M HCl at 363.2 K, while [CuL2] needed harsher conditions of 12 M HCl at 363.2 K with a half-life of 30.8 days. To the best of our knowledge, [CuL2] exhibits the highest half-life value for a copper(II) complex of a polyazamacrocycle derivative reported in the literature until now. Single crystal X-ray diffraction determined for [Cu(H2L1)](ClO4)2 showed the copper center in a distorted octahedral environment bound to the N4O donors of the macrobicycle and one oxygen atom from a carboxylic arm, while for [CuL2] it showed the copper center in a trigonal bipyramid geometry only bound to the donors of the macrobicycle and leaving the carboxylate arms away from the coordination sphere. UV-vis-NIR and X-band EPR spectra showed that in [CuL1] the copper center adopts a distorted compressed octahedral environment, which is the only structure found in solution for this complex, while in [CuL2] a similar environment was found in the first stages of its slow formation but reached a square-pyramidal geometry upon stabilization. The acetate arms play therefore an important role during the formation of the complex, as revealed by the comparison of its complexation behavior with the corresponding parent compounds.

  5. Strong effect of copper(II) coordination on antiproliferative activity of thiosemicarbazone-piperazine and thiosemicarbazone-morpholine hybrids.

    Science.gov (United States)

    Bacher, Felix; Dömötör, Orsolya; Chugunova, Anastasia; Nagy, Nóra V; Filipović, Lana; Radulović, Siniša; Enyedy, Éva A; Arion, Vladimir B

    2015-05-21

    In this study, 2-formylpyridine thiosemicarbazones and three different heterocyclic pharmacophores were combined to prepare thiosemicarbazone–piperazine mPip-FTSC (HL1) and mPip-dm-FTSC (HL2), thiosemicarbazone–morpholine Morph-FTSC (HL3) and Morph-dm-FTSC (HL4), thiosemicarbazone–methylpyrrole-2-carboxylate hybrids mPyrr-FTSC (HL5) and mPyrr-dm-FTSC (HL6) as well as their copper(II) complexes [CuCl(mPipH-FTSC-H)]Cl (1 + H)Cl, [CuCl(mPipH-dm-FTSC-H)]Cl (2 + H)Cl, [CuCl(Morph-FTSC-H)] (3), [CuCl(Morph-dm-FTSC-H)] (4), [CuCl(mPyrr-FTSC-H)(H2O)] (5) and [CuCl(mPyrr-dm-FTSC-H)(H2O)] (6). The substances were characterized by elemental analysis, one- and two-dimensional NMR spectroscopy (HL1–HL6), ESI mass spectrometry, IR and UV–vis spectroscopy and single crystal X-ray diffraction (1–5). All compounds were prepared in an effort to generate potential antitumor agents with an improved therapeutic index. In addition, the effect of structural alterations with organic hybrids on aqueous solubility and copper(II) coordination ability was investigated. Complexation of ligands HL2 and HL4 with copper(II) was studied in aqueous solution by pH-potentiometry, UV–vis spectrophotometry and EPR spectroscopy. Proton dissociation processes of HL2 and HL4 were also characterized in detail and microscopic constants for the Z/E isomers were determined. While the hybrids HL5, HL6 and their copper(II) complexes 5 and 6 proved to be insoluble in aqueous solution, precluding antiproliferative activity studies, the thiosemicarbazone–piperazine and thiosemicarbazone–morpholine hybrids HL1–HL4, as well as copper(II) complexes 1–4 were soluble in water enabling cytotoxicity assays. Interestingly, the metal-free hybrids showed very low or even a lack of cytotoxicity (IC50 values > 300 μM) in two human cancer cell lines HeLa (cervical carcinoma) and A549 (alveolar basal adenocarcinoma), whereas their copper(II) complexes were cytotoxic showing IC50 values from 25.5 to 65.1

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

    African Journals Online (AJOL)

    (UV) light. Results: ATR-FTIR confirmed the formation of copper(II) complex with DTT by binding through thiol group based on the .... DNA cleavage detection ... The infrared spectra of pure DTT and its Cu(II) .... and iron complexes. J Phys Conf ...

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

    Science.gov (United States)

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

    2011-10-14

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

  8. Photocleavage of DNA by copper(II) complexes

    Indian Academy of Sciences (India)

    Akhil R Chakravarty

    2006-11-01

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

  9. 1-Azaniumylcyclobutane-1-carboxylate monohydrate

    Directory of Open Access Journals (Sweden)

    Ray J. Butcher

    2014-02-01

    Full Text Available In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7 and 0.118 (7. In the crystal, N—H...O and O—H...O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+ and donor (through a single carboxylate O from two different aminocyclobutane carboxylate moities], resulting in a two-dimensional layered structure lying parallel to (100.

  10. Breaking the Carboxyl Rule

    Science.gov (United States)

    Balashov, Sergei P.; Petrovskaya, Lada E.; Imasheva, Eleonora S.; Lukashev, Evgeniy P.; Dioumaev, Andrei K.; Wang, Jennifer M.; Sychev, Sergey V.; Dolgikh, Dmitriy A.; Rubin, Andrei B.; Kirpichnikov, Mikhail P.; Lanyi, Janos K.

    2013-01-01

    A lysine instead of the usual carboxyl group is in place of the internal proton donor to the retinal Schiff base in the light-driven proton pump of Exiguobacterium sibiricum (ESR). The involvement of this lysine in proton transfer is indicated by the finding that its substitution with alanine or other residues slows reprotonation of the Schiff base (decay of the M intermediate) by more than 2 orders of magnitude. In these mutants, the rate constant of the M decay linearly decreases with a decrease in proton concentration, as expected if reprotonation is limited by the uptake of a proton from the bulk. In wild type ESR, M decay is biphasic, and the rate constants are nearly pH-independent between pH 6 and 9. Proton uptake occurs after M formation but before M decay, which is especially evident in D2O and at high pH. Proton uptake is biphasic; the amplitude of the fast phase decreases with a pKa of 8.5 ± 0.3, which reflects the pKa of the donor during proton uptake. Similarly, the fraction of the faster component of M decay decreases and the slower one increases, with a pKa of 8.1 ± 0.2. The data therefore suggest that the reprotonation of the Schiff base in ESR is preceded by transient protonation of an initially unprotonated donor, which is probably the ϵ-amino group of Lys-96 or a water molecule in its vicinity, and it facilitates proton delivery from the bulk to the reaction center of the protein. PMID:23696649

  11. New Magnetic and Structural Results for Uniformly Spaced, Alternatingly Spaced, and Ladder-Like Copper(II) Linear Chain Compounds.

    Science.gov (United States)

    1980-12-15

    ligands are dig- cussed, including the quasi-linear chain compound bia(dimethyldithio- carbamato )copper(II) in which the copper(II) ions are...sample of the linear chain compound bis(dimethyldithio- adequate to permit a correlation between the magnetic carbamato )copper(II) is plotted as a

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

    Science.gov (United States)

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

    2016-11-21

    Copper(II) complexes have been intensely investigated in a variety of diseases and pathological conditions due to their therapeutic potential. The development of these complexes requires a good knowledge of metal coordination chemistry and ligand design to control species distribution in solution and tailor the copper(II) centers in the right environment for the desired biological activity. Herein we present the synthesis and characterization of two ligands HL1 and H2L2 containing a phenanthroline unit (phen) attached to the amino group of histidine (His). Their copper(II) coordination properties were studied using potentiometry, spectroscopy techniques (UV-vis and EPR), mass spectrometry (ESI-MS) and DFT calculations. The data showed the formation of single copper complexes, [CuL1](+) and [CuL2], with high stability within a large pH range (from 3.0 to 9.0 for [CuL1](+) and from 4.5 to 10.0 for [CuL2]). In both complexes the Cu(2+) ion is bound to the phen unit, the imidazole ring and the deprotonated amide group, and displays a distorted square pyramidal geometry as confirmed by single crystal X-ray crystallography. Interestingly, despite having similar structures, these copper complexes show different redox potentials, DNA cleavage properties and cytotoxic activity against different cancer cell lines (human ovarian (A2780), its cisplatin-resistant variant (A2780cisR) and human breast (MCF7) cancer cell lines). The [CuL2] complex has lower reduction potential (Epc= -0.722 V vs -0.452 V for [CuL1](+)) but higher biological activity. These results highlight the effect of different pendant functional groups (carboxylate vs amide), placed out of the coordination sphere, in the properties of these copper complexes.

  13. Biocatalytic reduction of carboxylic acids.

    Science.gov (United States)

    Napora-Wijata, Kamila; Strohmeier, Gernot A; Winkler, Margit

    2014-06-01

    An increasing demand for non-petroleum-based products is envisaged in the near future. Carboxylic acids such as citric acid, succinic acid, fatty acids, and many others are available in abundance from renewable resources and they could serve as economic precursors for bio-based products such as polymers, aldehyde building blocks, and alcohols. However, we are confronted with the problem that carboxylic acid reduction requires a high level of energy for activation due to the carboxylate's thermodynamic stability. Catalytic processes are scarce and often their chemoselectivity is insufficient. This review points at bio-alternatives: currently known enzyme classes and organisms that catalyze the reduction of carboxylic acids are summarized. Two totally distinct biocatalyst lines have evolved to catalyze the same reaction: aldehyde oxidoreductases from anaerobic bacteria and archea, and carboxylate reductases from aerobic sources such as bacteria, fungi, and plants. The majority of these enzymes remain to be identified and isolated from their natural background in order to evaluate their potential as industrial biocatalysts.

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

    Indian Academy of Sciences (India)

    A Veeraraj; P Sami; N Raman

    2000-10-01

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

  15. Investigation of the interaction of copper(II) oxide and electron beam irradiation crosslinkable polyethylene

    Energy Technology Data Exchange (ETDEWEB)

    Bee, Soo-Tueen, E-mail: direct.beest@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Sin, Lee Tin, E-mail: direct.tinsin@gmail.com [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Ratnam, C.T. [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia); Haraveen, K.J.S.; Tee, Tiam-Ting [Department of Chemical Engineering, Lee Kong Chian Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Sungai Long, Bandar Sungai Long, Cheras, 43000 Kajang, Selangor (Malaysia); Rahmat, A.R. [Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

    2015-10-01

    In this study, the effects of electron beam irradiation on the properties of copper(II) oxide when added to low-density polyethylene (LDPE) blends were investigated. It was found that the addition of low loading level of copper(II) oxide (⩽2 phr) to LDPE results in significantly poorer gel content and hot set results. However, the incorporation of higher loading level of copper(II) oxide (⩾3 phr) could slightly increase the degree of crosslinking in all irradiated LDPE composites. This is due to the fact that higher amounts of copper(II) oxide could slightly induce the formation of free radicals in LDPE matrix. Besides, increasing irradiation doses was also found to gradually increase the gel content of LDPE composites by generating higher amounts of free radicals. As a consequence, these higher amounts of free radicals released in the LDPE matrix could significantly increase the degree of crosslinking. The addition of copper(II) oxide could reduce the tensile strength and fracture strain (elongation at break) of LDPE composites because of poorer interfacial adhesion effect between copper(II) oxide particles and LDPE matrix. Meanwhile, increasing irradiation doses on all copper(II) oxide added LDPE composites could marginally increase the tensile strength. In addition, increasing irradiation dose could enhance the thermal stability of LDPE composites by increasing the decomposition temperature. The oxidation induction time (OIT) analysis showed that, because of the crosslinking network in the copper(II) oxide added LDPE composites, oxidation reaction is much delayed.

  16. Copper(II) enhances membrane-bound α-synuclein helix formation.

    Science.gov (United States)

    Lucas, Heather R; Lee, Jennifer C

    2011-03-01

    Interactions of copper and membranes with α-synuclein have been implicated in pathogenic mechanisms of Parkinson's disease, yet work examining both concurrently is scarce. We have examined the effect of copper(ii) on protein/vesicle binding and found that both the copper(ii) affinity and α-helical content are enhanced for the membrane-bound protein.

  17. Copper(II) enhances membrane-bound α-synuclein helix formation

    OpenAIRE

    Lucas, Heather R.; Lee, Jennifer C.

    2011-01-01

    Interactions of copper and membranes with α-synuclein have been implicated in pathogenic mechanisms of Parkinson’s disease, yet work examining both concurrently is scarce. We have examined the effect of copper(II) on protein/vesicle binding and found that both the copper(II) affinity and α-helical content are enhanced for the membrane-bound protein.

  18. Carboxyl group reactivity in actin

    Energy Technology Data Exchange (ETDEWEB)

    Elzinga, M.

    1986-01-01

    While earlier work showed that the carboxyl groups of proteins could be quantitatively coupled to amino groups at pH 4.75 in the presence of EDC and a denaturing agent, the work presented here indicates that under milder conditions the modification of sidechain carboxyls is limited and somewhat specific. Most of the incorporated glycine ethyl ester (GEE) is apparently bound to five carboxyls. The total GEE incorporated was 3 to 4 moles/mole of protein as measured by an increase in Gly upon acid hydrolysis and amino acid analysis, as well as total radioactivity. 3.55 residues were found in peptides, 2.75 bound to residues 1 to 4, and 0.8 bound to Gly-100. 9 refs., 2 figs., 2 tabs.

  19. Trametes versicolor carboxylate reductase uncovered

    OpenAIRE

    Winkler, Margit; Winkler, Christoph K.

    2016-01-01

    Abstract The first carboxylate reductase from Trametes versicolor was identified, cloned, and expressed in Escherichia coli. The enzyme reduces aromatic acids such as benzoic acid and derivatives, cinnamic acid, and 3-phenylpropanoic acid, but also aliphatic acids such as octanoic acid are reduced. Graphical abstract

  20. Synthesis, crystal structures, spectroscopic characterization and in vitro antidiabetic studies of new Schiff base Copper(II) complexes

    Indian Academy of Sciences (India)

    SUNDARAMURTHY SANTHA LAKSHMI; KANNAPPAN GEETHA; M GAYATHRI; GANESH SHANMUGAM

    2016-07-01

    Two new Schiff base copper(II) complexes, [CuL¹(tmen)] (1) and [Cu₂L₂² (tmen)] (2) {where, H₂L¹ = N-(salicylidene)-L-valine, H₂L² = N-(3,5-dichlorosalicylidene)-L-valine and tmen = N,N,N',N'- tetramethylethylene-1,2-diamine} have been synthesized and characterized by molar conductance, elemental analyses, VSM-RT, UV-Vis, FTIR, EPR, and CD spectra. Both the complexes were structurally characterized by single crystal XRD. The crystal structure of complex 1 displays a distorted square pyramidal geometry in which Schiff base is coordinated to the Cu(II) ion via ONO-donor in the axial mode, whereas, the chelating diamine displays axial and equatorial mode of binding via NN-donor atoms. The crystal structure of the complex 2 reveals a syn-anti mode of carboxylate bridged dinuclear complex, in which, the coordination geometry around Cu(1) is square pyramid and distorted square planar around Cu(2). The target complexes were screened for in vitro antidiabetic activity. Both the complexes showed good inhibitory activity for α-amylase and α-glucosidase.

  1. Carboxylate-bridged Cu(II) coordination polymeric complex: synthesis, crystal structure, magnetic properties, DNA binding and electrochemical studies

    Indian Academy of Sciences (India)

    SABITHAKALA THATITURI; BHARGAVI GOVINDUGARI; VENKATA RAMANA REDDY CHITTIREDDY

    2017-08-01

    A novel water-soluble carboxylate-bridged copper(II) coordination polymer,Cu-BIG was formed by the reaction of Cu(ClO₄)₂ ·6H₂O and tridentate benzimidazole-glycine conjugate ligand, 2-((1H-benzimidazol- 2-yl)methylamino) acetic acid, BIGH and its structure has been determined by IR, UV, powder XRD, VSM, CV, TGA, DTA, EPR and single crystal X-ray diffraction. Crystallographic studies indicate it to be a coordination polymer with P¯ı Space group. The asymmetric unit of complex contains two Cu(II) ions with elongated square pyramid geometry.The axial positions of theCu(II) atoms are occupied by the carbonyl oxygen of the carboxylate group with the bond distances Cu(1)–O(5)axial , 2.28Å, and Cu(2)–O(2)axial , 2.26Å. The two Cu(II) are connected through the carboxylic group present in BIGH, which provides electron mobilisation in the molecule and hence results in the soft ferromagnetic polymer. An in vitro antibacterial activity study of BIGH and Cu-BIG showed moderate activity against Bacillus subtilis. The DNA binding studies showed the interaction of Cu-BIG with CT-DNA.

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

    National Research Council Canada - National Science Library

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

    2013-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-09-03

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

  4. New structural motif for carboxylic acid perhydrolases.

    Science.gov (United States)

    Yin, DeLu Tyler; Purpero, Vince M; Fujii, Ryota; Jing, Qing; Kazlauskas, Romas J

    2013-02-25

    Some serine hydrolases also catalyze a promiscuous reaction--reversible perhydrolysis of carboxylic acids to make peroxycarboxylic acids. Five X-ray crystal structures of these carboxylic acid perhydrolases show a proline in the oxyanion loop. Here, we test whether this proline is essential for high perhydrolysis activity using Pseudomonas fluorescens esterase (PFE). The L29P variant of this esterase catalyzes perhydrolysis 43-fold faster (k(cat) comparison) than the wild type. Surprisingly, saturation mutagenesis at the 29 position of PFE identified six other amino acid substitutions that increase perhydrolysis of acetic acid at least fourfold over the wild type. The best variant, L29I PFE, catalyzed perhydrolysis 83-times faster (k(cat) comparison) than wild-type PFE and twice as fast as L29P PFE. Despite the different amino acid in the oxyanion loop, L29I PFE shows a similar selectivity for hydrogen peroxide over water as L29P PFE (β(0)=170 vs. 160 M(-1)), and a similar fast formation of acetyl-enzyme (140 vs. 62 U mg(-1)). X-ray crystal structures of L29I PFE with and without bound acetate show an unusual mixture of two different oxyanion loop conformations. The type II β-turn conformation resembles the wild-type structure and is unlikely to increase perhydrolysis, but the type I β-turn conformation creates a binding site for a second acetate. Modeling suggests that a previously proposed mechanism for L29P PFE can be extended to include L29I PFE, so that an acetate accepts a hydrogen bond to promote faster formation of the acetyl-enzyme. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Structure Property Relationships of Carboxylic Acid Isosteres.

    Science.gov (United States)

    Lassalas, Pierrik; Gay, Bryant; Lasfargeas, Caroline; James, Michael J; Tran, Van; Vijayendran, Krishna G; Brunden, Kurt R; Kozlowski, Marisa C; Thomas, Craig J; Smith, Amos B; Huryn, Donna M; Ballatore, Carlo

    2016-04-14

    The replacement of a carboxylic acid with a surrogate structure, or (bio)-isostere, is a classical strategy in medicinal chemistry. The general underlying principle is that by maintaining the features of the carboxylic acid critical for biological activity, but appropriately modifying the physicochemical properties, improved analogs may result. In this context, a systematic assessment of the physicochemical properties of carboxylic acid isosteres would be desirable to enable more informed decisions of potential replacements to be used for analog design. Herein we report the structure-property relationships (SPR) of 35 phenylpropionic acid derivatives, in which the carboxylic acid moiety is replaced with a series of known isosteres. The data set generated provides an assessment of the relative impact on the physicochemical properties that these replacements may have compared to the carboxylic acid analog. As such, this study presents a framework for how to rationally apply isosteric replacements of the carboxylic acid functional group.

  6. Samarium(III) as luminescent probe for copper(II)

    Energy Technology Data Exchange (ETDEWEB)

    Jiménez, José A., E-mail: jose.jimenez@unf.edu

    2015-05-15

    Lanthanide-based luminescent sensing of copper(II) is currently an active area of research given the need for determining trace amounts of the analyte in environmental and biological matrices. Moreover, the increasing interest of Cu-doped materials for a variety of applications (e.g. luminescent and plasmonic) calls for appropriate measures for the assessment of residual Cu{sup 2+} in the solid state. In this work, Sm{sup 3+} ions are investigated as luminescent probes for Cu{sup 2+} within a glass matrix as model system based on Sm{sup 3+}→Cu{sup 2+} energy transfer. The Cu{sup 2+} concentration dependence of the Sm{sup 3+} emission quenching and decay rates of the {sup 4}G{sub 5/2} excited state allow for establishing calibration curves useful for determining Cu{sup 2+}. The luminescence-based approaches are employed for estimating residual Cu{sup 2+} in a Cu{sup +}/Sm{sup 3+} co-doped glass as ‘unknown’, the results being compared with the spectrophotometric method based on Cu{sup 2+} absorption in the visible. Remarkably, the approaches appeared in good agreement. Thus, the present work demonstrates the potential of Sm{sup 3+} ions for optical sensing of copper(II), opening research avenues extending from materials to liquid phase systems with relevance to biological and environmental sciences. - Highlights: • Sm{sup 3+}→Cu{sup 2+} energy transfer investigated in glass as model matrix in context of analytical applications. • Sm{sup 3+} photoluminescence and emission decay dynamics correlated with Cu{sup 2+} concentration. • Potential of Sm{sup 3+} ions for optical sensing of Cu{sup 2+} demonstrated.

  7. Recovery of carboxylic acids produced by fermentation.

    Science.gov (United States)

    López-Garzón, Camilo S; Straathof, Adrie J J

    2014-01-01

    Carboxylic acids such as citric, lactic, succinic and itaconic acids are useful products and are obtained on large scale by fermentation. This review describes the options for recovering these and other fermentative carboxylic acids. After cell removal, often a primary recovery step is performed, using liquid-liquid extraction, adsorption, precipitation or conventional electrodialysis. If the carboxylate is formed rather than the carboxylic acid, the recovery process involves a step for removing the cation of the formed carboxylate. Then, bipolar electrodialysis and thermal methods for salt splitting can prevent that waste inorganic salts are co-produced. Final carboxylic acid purification requires either distillation or crystallization, usually involving evaporation of water. Process steps can often be combined synergistically. In-situ removal of carboxylic acid by extraction during fermentation is the most popular approach. Recovery of the extractant can easily lead to waste inorganic salt formation, which counteracts the advantage of the in-situ removal. For industrial production, various recovery principles and configurations are used, because the fermentation conditions and physical properties of specific carboxylic acids differ.

  8. The crystal structure of paramagnetic copper(ii) oxalate (CuC2O4):

    DEFF Research Database (Denmark)

    Christensen, Axel Nørlund; Lebech, Bente; Andersen, Niels Hessel

    2014-01-01

    Synthetic copper(ii) oxalate, CuC2O4, was obtained in a precipitation reaction between a copper(ii) solution and an aqueous solution of oxalic acid. The product was identified from its conventional X-ray powder patterns which match that of the copper mineral Moolooite reported to have the composi...

  9. Utilizing reversible copper(II) peptide coordination in a sequence-selective luminescent receptor.

    Science.gov (United States)

    Stadlbauer, Stefan; Riechers, Alexander; Späth, Andreas; König, Burkhard

    2008-01-01

    Although vast information about the coordination ability of amino acids and peptides to metal ions is available, little use of this has been made in the rational design of selective peptide receptors. We have combined a copper(II) nitrilotriacetato (NTA) complex with an ammonium-ion-sensitive and luminescent benzocrown ether. This compound revealed micromolar affinities and selectivities for glycine- and histidine-containing sequences, which closely resembles those of copper(II) ion peptide binding: the two free coordination sites of the copper(II) NTA complex bind to imidazole and amido nitrogen atoms, replicating the initial coordination steps of non-complexed copper(II) ions. The benzocrown ether recognizes the N-terminal amino moiety intramolecularly, and the significantly increased emission intensity signals the binding event, because only if prior coordination of the peptide has taken place is the intramolecular ammonium ion-benzocrown ether interaction of sufficient strength in water to trigger an emission signal. Intermolecular ammonium ion-benzocrown ether binding is not observed. Isothermal titration calorimetry confirmed the binding constants derived from emission titrations. Thus, as deduced from peptide coordination studies, the combination of a truncated copper(II) coordination sphere and a luminescent benzocrown ether allows for the more rational design of sequence-selective peptide receptors.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-06-15

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

  11. Novel Polymers with Carboxylic Acid Loading

    DEFF Research Database (Denmark)

    Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

    2006-01-01

    Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4-hydroxybenzene......, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conducted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly(4-hydroxystyrene), poly(4...

  12. Activation of carboxylic acids in asymmetric organocatalysis.

    Science.gov (United States)

    Monaco, Mattia Riccardo; Poladura, Belén; Diaz de Los Bernardos, Miriam; Leutzsch, Markus; Goddard, Richard; List, Benjamin

    2014-07-01

    Organocatalysis, catalysis using small organic molecules, has recently evolved into a general approach for asymmetric synthesis, complementing both metal catalysis and biocatalysis. Its success relies to a large extent upon the introduction of novel and generic activation modes. Remarkably though, while carboxylic acids have been used as catalyst directing groups in supramolecular transition-metal catalysis, a general and well-defined activation mode for this useful and abundant substance class is still lacking. Herein we propose the heterodimeric association of carboxylic acids with chiral phosphoric acid catalysts as a new activation principle for organocatalysis. This self-assembly increases both the acidity of the phosphoric acid catalyst and the reactivity of the carboxylic acid. To illustrate this principle, we apply our concept in a general and highly enantioselective catalytic aziridine-opening reaction with carboxylic acids as nucleophiles.

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

    Directory of Open Access Journals (Sweden)

    Akinori Honda

    2016-10-01

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

  14. Carboxylator: incorporating solvent-accessible surface area for identifying protein carboxylation sites

    Science.gov (United States)

    Lu, Cheng-Tsung; Chen, Shu-An; Bretaña, Neil Arvin; Cheng, Tzu-Hsiu; Lee, Tzong-Yi

    2011-10-01

    In proteins, glutamate (Glu) residues are transformed into γ-carboxyglutamate (Gla) residues in a process called carboxylation. The process of protein carboxylation catalyzed by γ-glutamyl carboxylase is deemed to be important due to its involvement in biological processes such as blood clotting cascade and bone growth. There is an increasing interest within the scientific community to identify protein carboxylation sites. However, experimental identification of carboxylation sites via mass spectrometry-based methods is observed to be expensive, time-consuming, and labor-intensive. Thus, we were motivated to design a computational method for identifying protein carboxylation sites. This work aims to investigate the protein carboxylation by considering the composition of amino acids that surround modification sites. With the implication of a modified residue prefers to be accessible on the surface of a protein, the solvent-accessible surface area (ASA) around carboxylation sites is also investigated. Radial basis function network is then employed to build a predictive model using various features for identifying carboxylation sites. Based on a five-fold cross-validation evaluation, a predictive model trained using the combined features of amino acid sequence (AA20D), amino acid composition, and ASA, yields the highest accuracy at 0.874. Furthermore, an independent test done involving data not included in the cross-validation process indicates that in silico identification is a feasible means of preliminary analysis. Additionally, the predictive method presented in this work is implemented as Carboxylator (http://csb.cse.yzu.edu.tw/Carboxylator/), a web-based tool for identifying carboxylated proteins with modification sites in order to help users in investigating γ-glutamyl carboxylation.

  15. New structural motif for carboxylic acid perhydrolases

    OpenAIRE

    Yin, Delu; Purpero, Vince M.; Fujii, Ryota; Jing, Qing; Kazlauskas, Romas J.

    2013-01-01

    Some serine hydrolases also catalyze a promiscuous reaction – reversible perhydrolysis of carboxylic acids to make peroxycarboxylic acids. Five x-ray crystal structures of these carboxylic acid perhydrolases show a proline in the oxyanion loop. Here, we test whether this proline is essential for high perhydrolysis activity using Pseudomonas fluorescens esterase (PFE). The L29P variant of this esterase catalyzes perhydrolysis 43-fold faster (kcat comparison) than wild type. Surprisingly, satur...

  16. New structural motif for carboxylic acid perhydrolases

    OpenAIRE

    Yin, Delu; Purpero, Vince M.; Fujii, Ryota; Jing, Qing; Kazlauskas, Romas J.

    2013-01-01

    Some serine hydrolases also catalyze a promiscuous reaction – reversible perhydrolysis of carboxylic acids to make peroxycarboxylic acids. Five x-ray crystal structures of these carboxylic acid perhydrolases show a proline in the oxyanion loop. Here, we test whether this proline is essential for high perhydrolysis activity using Pseudomonas fluorescens esterase (PFE). The L29P variant of this esterase catalyzes perhydrolysis 43-fold faster (kcat comparison) than wild type. Surprisingly, satur...

  17. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  18. Understanding biocatalyst inhibition by carboxylic acids.

    Science.gov (United States)

    Jarboe, Laura R; Royce, Liam A; Liu, Ping

    2013-09-03

    Carboxylic acids are an attractive biorenewable chemical in terms of their flexibility and usage as precursors for a variety of industrial chemicals. It has been demonstrated that such carboxylic acids can be fermentatively produced using engineered microbes, such as Escherichia coli and Saccharomyces cerevisiae. However, like many other attractive biorenewable fuels and chemicals, carboxylic acids become inhibitory to these microbes at concentrations below the desired yield and titer. In fact, their potency as microbial inhibitors is highlighted by the fact that many of these carboxylic acids are routinely used as food preservatives. This review highlights the current knowledge regarding the impact that saturated, straight-chain carboxylic acids, such as hexanoic, octanoic, decanoic, and lauric acids can have on E. coli and S. cerevisiae, with the goal of identifying metabolic engineering strategies to increase robustness. Key effects of these carboxylic acids include damage to the cell membrane and a decrease of the microbial internal pH. Certain changes in cell membrane properties, such as composition, fluidity, integrity, and hydrophobicity, and intracellular pH are often associated with increased tolerance. The availability of appropriate exporters, such as Pdr12, can also increase tolerance. The effect on metabolic processes, such as maintaining appropriate respiratory function, regulation of Lrp activity and inhibition of production of key metabolites such as methionine, are also considered. Understanding the mechanisms of biocatalyst inhibition by these desirable products can aid in the engineering of robust strains with improved industrial performance.

  19. Understanding biocatalyst inhibition by carboxylic acids

    Directory of Open Access Journals (Sweden)

    Laura R Jarboe

    2013-09-01

    Full Text Available Carboxylic acids are an attractive biorenewable chemical in terms of their flexibility and usage as precursors for a variety of industrial chemicals. It has been demonstrated that such carboxylic acids can be fermentatively produced using engineered microbes, such as Escherichia coli and Saccharomyces cerevisiae. However, like many other attractive biorenewable fuels and chemicals, carboxylic acids become inhibitory to these microbes at concentrations below the desired yield and titer. In fact, their potency as microbial inhibitors is highlighted by the fact that many of these carboxylic acids are routinely used as food preservatives. This review highlights the current knowledge regarding the impact that saturated, straight-chain carboxylic acids, such as hexanoic, octanoic, decanoic and lauric acids can have on E. coli and S. cerevisiae, with the goal of identifying metabolic engineering strategies to increase robustness. Key effects of these carboxylic acids include damage to the cell membrane and a decrease of the microbial internal pH. Certain changes in cell membrane properties, such as composition, fluidity, integrity and hydrophobicity, and intracellular pH are often associated with increased tolerance. The availability of appropriate exporters, such as Pdr12, can also increase tolerance. The effect on metabolic processes, such as maintaining appropriate respiratory function, regulation of Lrp activity and inhibition of production of key metabolites such as methionine, are also considered. Understanding the mechanisms of biocatalyst inhibition by these desirable products can aid in the engineering of robust strains with improved industrial performance.

  20. Carboxylic acids as substrates in homogeneous catalysis.

    Science.gov (United States)

    Goossen, Lukas J; Rodríguez, Nuria; Goossen, Käthe

    2008-01-01

    In organic molecules carboxylic acid groups are among the most common functionalities. Activated derivatives of carboxylic acids have long served as versatile connection points in derivatizations and in the construction of carbon frameworks. In more recent years numerous catalytic transformations have been discovered which have made it possible for carboxylic acids to be used as building blocks without the need for additional activation steps. A large number of different product classes have become accessible from this single functionality along multifaceted reaction pathways. The frontispiece illustrates an important reason for this: In the catalytic cycles carbon monoxide gas can be released from acyl metal complexes, and gaseous carbon dioxide from carboxylate complexes, with different organometallic species being formed in each case. Thus, carboxylic acids can be used as synthetic equivalents of acyl, aryl, or alkyl halides, as well as organometallic reagents. This review provides an overview of interesting catalytic transformations of carboxylic acids and a number of derivatives accessible from them in situ. It serves to provide an invitation to complement, refine, and use these new methods in organic synthesis.

  1. Absorption of copper(II) by creosote bush (Larrea tridentata): use of atomic and x-ray absorption spectroscopy.

    Science.gov (United States)

    Gardea-Torresdey, J L; Arteaga, S; Tiemann, K J; Chianelli, R; Pingitore, N; Mackay, W

    2001-11-01

    Larrea tridentata (creosote bush), a common North American native desert shrub, exhibits the ability to take up copper(II) ions rapidly from solution. Following hydroponic studies, U.S. Environmental Protection Agency method 200.3 was used to digest the plant samples, and flame atomic absorption spectroscopy (FAAS) was used to determine the amount of copper taken up in different parts of the plant. The amount of copper(II) found within the roots, stems, and leaves was 13.8, 1.1, and 0.6 mg/g, respectively, after the creosote bush was exposed to a 63.5-ppm copper(II) solution for 48 h. When the plant was exposed to a 635-ppm copper(II) solution, the roots, stems, and leaves contained 35.0, 10.5, and 3.8 mg/g, respectively. In addition to FAAS analysis, x-ray microfluorescence (XRMF) analysis of the plant samples provided further confirmation of copper absorption by the various plant parts. X-ray absorption spectroscopy (XAS) elucidated the oxidation state of the copper absorbed by the plants. The copper(II) absorbed from solution remained as copper(II) bound to oxygen-containing ligands within the plant samples. The results of this study indicate that creosote bush may provide a useful and novel method of removing copper(II) from contaminated soils in an environmentally friendly manner.

  2. Highly cytotoxic DNA-interacting copper(II) coordination compounds.

    Science.gov (United States)

    Brissos, Rosa F; Torrents, Ester; dos Santos Mello, Francyelli Mariana; Carvalho Pires, Wanessa; Silveira-Lacerda, Elisângela de Paula; Caballero, Ana B; Caubet, Amparo; Massera, Chiara; Roubeau, Olivier; Teat, Simon J; Gamez, Patrick

    2014-10-01

    Four new Schiff-base ligands have been designed and prepared by condensation reaction between hydrazine derivatives (i.e. 2-hydrazinopyridine or 2-hydrazinoquinoline) and mono- or dialdehyde (3-tert-butyl-2-hydroxybenzaldehyde and 5-tert-butyl-2-hydroxyisophthalaldehyde, respectively). Six copper(II) coordination compounds of various nuclearities have been obtained from these ligands, which are formulated as [Cu(L1)Cl](CH3OH) (1), [Cu(L2)NO3] (2), [Cu2(L3)(ClO4)2(CH3O)(CH3OH)](CH3OH) (3), [Cu2(L4)(ClO4)(OH)(CH3OH)](ClO4) (4), [Cu8(L3)4(NO3)4(OH)5](NO3)3(CH3OH)5(H2O)8 (5) and [Cu3(HL2')4Cl6](CH3OH)6 (6), as revealed by single-crystal X-ray studies. Their DNA-interacting abilities have been investigated using different characterization techniques, which suggest that the metal complexes act as efficient DNA binders. Moreover, cytotoxicity assays with several cancer cell lines show that some of them are very active, as evidenced by the sub-micromolar IC50 values achieved in some cases.

  3. Synthesis of first row transition metal carboxylate complexes by ring opening reactions of cyclic anhydrides

    Indian Academy of Sciences (India)

    Jubaraj Bikash Baruah

    2011-03-01

    Hydrolytic and solvolytic ring opening reactions of phthalic anhydride, pyromellitic dianhydride and 2,3-pyridine dicarboxylic anhydride in the presence of various transition metal salts with or without a ancillary ligands were studied. The reactions were found to be dependent on stoichiometry of ligand and types of anhydride used. In the case of pyromellitic dianhydride selective ring opening reaction by cobalt(II) ions gave 1,3-benzene dicarboxylate derivatives, whereas use of copper(II) ions gave 1,4-benzene dicarboxylate derivatives. Preference for methanolysis was seen in the case of copper (II) promoted reactions of pyromellitic dianhydride in the presence of 1:1 metal to 1,10-phenanthroline ratio.

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

    Science.gov (United States)

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

    2008-04-02

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

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

    Science.gov (United States)

    Beyeh, Ngong Kodiah; Puttreddy, Rakesh

    2015-06-07

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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

  8. Two different modes for copper(II ion coordination to quinine-type ligands

    Directory of Open Access Journals (Sweden)

    Rey Nicolás A.

    2006-01-01

    Full Text Available Three new copper(II complexes with the ligands quinuclidine [Cu(C7H13N2(OH2Cl]Cl.2H 2O (1, quinine [Cu(C20H23O2N2(OH 22]ClO4 (2, and hydroquinidine [Cu(C20H27O2N2(OH 2 Cl2]Cl.fraction one-halfH2O (3 have been isolated and characterized. The binding sites were assigned on the basis of vibrational spectroscopy, electron paramagnetic resonance, and thermal analysis results. The possibility of the involvement of the quinuclidinic nitrogen in the coordination was evidenced in complex 1, in which copper(II is coordinated to two quinuclidine molecules. In the case of quinine-type ligands, if the starting material is deprotonated in both nitrogens, copper(II coordination occurs through the quinuclidinic nitrogen, as in complex 2. In contrast, if the starting material is protonated in the quinuclidinic nitrogen the binding site is the quinolinic nitrogen, as in complex 3. Therefore, both nitrogens of quinine-type ligands constitute binding sites for copper(II ions.

  9. Ligand-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Michaels, Heather A; Zhu, Lei

    2011-10-04

    Polytriazole ligands such as the widely used tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), are shown to assist copper(II) acetate-mediated azide-alkyne cycloaddition (AAC) reactions that involve nonchelating azides. Tris(2-{4-[(dimethylamino)methyl]-1H-1,2,3-traizol-1-yl}ethyl)amine (DTEA) outperforms TBTA in a number of reactions. The satisfactory solubility of DTEA in a wide range of polar and nonpolar solvents, including water and toluene, renders it advantageous under copper(II) acetate-mediated conditions. The copper(II) acetate-mediated formation of the three triazolyl groups in a tris(triazolyl)-based ligand occurs sequentially with an inhibitory effect in the last step. The kinetic investigations of the ligand-assisted reactions reveal an interesting mechanistic dependence on the relative affinity of azide and alkyne to copper (II). In addition to expanding the scope of the copper(II) acetate-mediated AAC reactions to include nonchelating azides, this work offers evidence for the mechanistic synergy between the title reaction and the alkyne oxidative homocoupling reaction. The elucidation of the structural details of the polytriazole-ligand-bound reactive species in copper(I/II)-mediated AAC reactions, however, awaits further characterization of the metal coordination chemistry of polytriazole ligands. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Copper(II) complexes with peptides based on the second cell binding site of fibronectin: metal coordination and ligand exchange kinetics.

    Science.gov (United States)

    Pizzanelli, Silvia; Forte, Claudia; Pinzino, Calogero; Magrì, Antonio; La Mendola, Diego

    2016-02-07

    Copper(ii) complexes with short peptides based on the second cell binding site of fibronectin, PHSFN and PHSEN, have been characterized by potentiometric, UV-vis, CD, EPR and NMR spectroscopic methods. The histidine imidazole nitrogen is the anchoring site for the metal ion binding. Thermodynamic and spectroscopic evidence is given that the side chain oxygen donor atom of glutamyl residue in Ac-PHSEN-NH2 is also involved in the binding up to physiological pH. To determine ligand exchange kinetic parameters after the imidazole nitrogen anchoring, proton relaxation enhancement NMR data have been collected for the two hydrogen atoms of the imidazole ring in the temperature range 293-315 K at pH 5.2 and globally treated within different kinetic models for ligand exchange. The best fitting model involves two steps. In the first one, which is slow, a water molecule disengages a carbonyl or a carboxylate group coordinated to the metal ion in the complex formed by PHSFN or PHSEN, respectively. This stage is one order of magnitude slower for PHSEN, due to entropic effects. In the second step, which is fast, the complex just formed exchanges with the ligand. In this step, no appreciable differences are found for the two cases examined.

  11. The ligational behavior of an isatinic quinolyl hydrazone towards copper(II- ions

    Directory of Open Access Journals (Sweden)

    Mousa Marwa A

    2011-04-01

    Full Text Available Abstract Background The importance of the isatinic quinolyl hydrazones arises from incorporating the quinoline ring with the indole ring. Quinoline ring has therapeutic and biological activities whereas, the indole ring occurs in Jasmine flowers and Orange blossoms. As a ligand, the isatin moiety is potentially ambidentate and can coordinate the metal ions either through its lactam or lactim forms. In a previous study, the ligational behavior of a phenolic quinolyl hydrazone towards copper(II- ions has been studied. As continuation of our interest, the present study is planned to check the ligational behavior of an isatinic quinolyl hydrazone. Results New homo- and heteroleptic copper(II- complexes were obtained from the reaction of an isatinic quinolyl hydrazone (HL with several copper(II- salts viz. Clˉ, Brˉ, NO3ˉ, ClO4-, SO42- and AcO-. The obtained complexes have Oh, Td and D4h- symmetry and fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions. Depending on the type of the anion, the ligand coordinates the copper(II- ions either through its lactam (NO3ˉ and ClO4- or lactim (the others forms. Conclusion The effect of anion for the same metal ion is obvious from either the geometry of the isolated complexes (Oh, Td and D4h or the various modes of bonding. Also, the obtained complexes fulfill the strong coordinating ability of Clˉ, Brˉ, NO3ˉ and SO42- anions in consistency with the donor ability of the anions. In case of copper(II- acetate, a unique homoleptic complex (5 was obtained in which the AcO- anion acts as a base enough to quantitatively deprotonate the hydrazone. The isatinic hydrazone uses its lactim form in most complexes.

  12. The Amyloid Precursor Protein of Alzheimer's Disease in the Reduction of Copper(II) to Copper(I)

    Science.gov (United States)

    Multhaup, Gerd; Schlicksupp, Andrea; Hesse, Lars; Beher, Dirk; Ruppert, Thomas; Masters, Colin L.; Beyreuther, Konrad

    1996-03-01

    The transition metal ion copper(II) has a critical role in chronic neurologic diseases. The amyloid precursor protein (APP) of Alzheimer's disease or a synthetic peptide representing its copper-binding site reduced bound copper(II) to copper(I). This copper ion-mediated redox reaction led to disulfide bond formation in APP, which indicated that free sulfhydryl groups of APP were involved. Neither superoxide nor hydrogen peroxide had an effect on the kinetics of copper(II) reduction. The reduction of copper(II) to copper(I) by APP involves an electron-transfer reaction and could enhance the production of hydroxyl radicals, which could then attack nearby sites. Thus, copper-mediated toxicity may contribute to neurodegeneration in Alzheimer's disease.

  13. EPOXY RESINS TOUGHENED WITH CARBOXYL TERMINATED POLYETHERS

    Institute of Scientific and Technical Information of China (English)

    YU Yunchao; LI Yiming

    1983-01-01

    Carboxyl terminated polyethers, the adducts of hydroxyl terminated polytetrahydrofuran and maleic anhydride, were used as toughener for epoxy resins. The morphology of the toughened resins was investigated by means of turbidity measurement, dynamic mechanical testing and scanning electron microscope observation. It turned out that the molecular weight and the carboxyl content of the polyether and the cure conditions are important factors, which affect the particle size of the polyether-rich domains and, in turn, the mechanical properties of the cured resin. Carboxyl terminated polytetrahydrofurans have a low glass transition temperature, and in appropriate amount they do not affect the thermal resistance of the resin. These advantages make them preferable as toughener for epoxy resins.

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

    Science.gov (United States)

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

    2015-03-01

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

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

    Science.gov (United States)

    Haleel, A; Mahendiran, D; Veena, V; Sakthivel, N; Rahiman, A Kalilur

    2016-11-01

    A series of heteroleptic mononuclear copper(II) complexes of the type [Cu(L(1-3))(diimine)]ClO4 (1-6) containing three tetrazolo[1,5-a]pyrimidine core ligands, ethyl 5-methyl-7-(2-hydroxyphenyl)-4,7-dihydrotetrazolo[1,5-a]pyrimidine-6-carboxylate (HL(1)), ethyl 5-methyl-7-(4-diethylamino-2-hydroxyphenyl)-4,7-dihydrotetrazolo[1,5-a]pyrimidine-6-carboxylate (HL(2)) or ethyl 5-methyl-7-(2-hydroxy-4-nitrophenyl)-4,7-dihydrotetrazolo[1,5-a]pyrimidine-6-carboxylate (HL(3)), and two diimine coligands, 2,2'-bipyridyl (bpy) or 1,10-phenanthroline (phen) have been synthesized and characterized by spectral methods. The geometry of complexes have been determined with the help of electronic absorption and EPR splitting patterns, which suggest four coordinated square planar geometry around copper(II) ion. The lowering of HOMO-LUMO band gap value of complex 4 implies its higher biological activity compared to other complexes. Antioxidant studies revealed that the complexes possess considerable radical scavenging potency against DPPH. The binding studies of the complexes with calf thymus DNA (CT-DNA) revealed groove mode of binding, which was further supported by docking simulation. The complexes 3 and 4 strongly inhibit the topoisomerase I, and also strongly interact with VEGFR2 kinase receptor via π-π, σ-π and hydrogen bonding interaction. Gel electrophoresis experiments demonstrated the ability of the complexes to cleave plasmid DNA in the absence of activators. In vitro cytotoxic activities of the complexes were examined on three cancerous cell lines such as human lung (A549), cervical (HeLa) and colon (HCT-15), and two normal cells such as human embryonic kidney (HEK) and peripheral blood mononuclear cells (PBMCs). The live cell and fluorescent imaging of cancer cells were observed with acridine orange/ethidium bromide staining assay. All encouraging chemical and biological findings indicate that the complex 4 is a suitable candidate for drug target.

  16. Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Ames, Richard L. [Colorado School of Mines, Golden, CO (United States)

    2004-09-01

    Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate

  17. Crystal structure of 3-amino-pyridinium 1'-carb-oxy-ferrocene-1-carboxyl-ate.

    Science.gov (United States)

    Medved'ko, Aleksei V; Churakov, Andrei V; Yu, Haojie; Li, Wang; Vatsadze, Sergey Z

    2017-06-01

    The structure of the title salt, (C5H7N2)[Fe(C6H4O2)(C6H5O2)], consists of 3-amino-pyridinium cations and 1'-carb-oxy-ferrocene-1-carboxyl-ate monoanions. The ferrocenyl moiety of the anion adopts a typical sandwich structure, with Fe-C distances in the range 2.0270 (15)-2.0568 (17) Å. The anion possesses an eclipsed conformation, with the torsion angle φ (Csubst-Cpcent-Cpcent- Csubst) equal to 66.0°. The conformations of other 1'-carb-oxy-ferrocene-1-carboxyl-ate monoanions are compared and analyzed on the basis of literature data.

  18. The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

    Science.gov (United States)

    Nicholson, John W.; Wilson, Alan D.

    2004-01-01

    The conversion of carboxylic acids to ketones is a useful chemical transformation with a long history. Several chemists have claimed that they discovered the conversion of carboxylic acids to ketones yet in fact the reaction is actually known for centuries.

  19. Cationic mononuclear ruthenium carboxylates as catalyst prototypes for self-induced hydrogenation of carboxylic acids.

    Science.gov (United States)

    Naruto, Masayuki; Saito, Susumu

    2015-08-28

    Carboxylic acids are ubiquitous in bio-renewable and petrochemical sources of carbon. Hydrogenation of carboxylic acids to yield alcohols produces water as the only byproduct, and thus represents a possible next generation, sustainable method for the production of these alternative energy carriers/platform chemicals on a large scale. Reported herein are molecular insights into cationic mononuclear ruthenium carboxylates ([Ru(OCOR)](+)) as prototypical catalysts for the hydrogenation of carboxylic acids. The substrate-derived coordinated carboxylate was found to function initially as a proton acceptor for the heterolytic cleavage of dihydrogen, and subsequently also as an acceptor for the hydride from [Ru-H](+), which was generated in the first step (self-induced catalysis). The hydrogenation proceeded selectively and at high levels of functional group tolerance, a feature that is challenging to achieve with existing heterogeneous/homogeneous catalyst systems. These fundamental insights are expected to significantly benefit the future development of metal carboxylate-catalysed hydrogenation processes of bio-renewable resources.

  20. 40 CFR 721.2950 - Carboxylic acid glycidyl esters.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Carboxylic acid glycidyl esters. 721... Substances § 721.2950 Carboxylic acid glycidyl esters. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as carboxylic acid glycidyl ester...

  1. Recovery and esterification of aqueous carboxylates by using CO

    NARCIS (Netherlands)

    Cabrera-Rodríguez, Carlos I.; Paltrinieri, Laura; Smet, De Louis C.P.M.; Wielen, Van Der Luuk A.M.; Straathof, Adrie J.J.

    2017-01-01

    The recovery of carboxylic acids from fermentation broth is one of the main bottlenecks for the industrial production of bio-based esters. This paper proposes an alternative for the recovery of carboxylates produced by fermentations at pH values above the pKa of the carboxylic acid. In this

  2. Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2'-Bipyridine, H2pht = o-Phthalic Acid)

    Institute of Scientific and Technical Information of China (English)

    LI Qiang; ZHENG Fa-Kun; CAI Li-Zhen; CHEN Wen-Tong; GUO Guo-Cong; HUANG Jin-Shun

    2005-01-01

    The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2’-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in triclinic, space group P, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) (A), α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) (A)3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2’-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hphtˉand one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

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

    Science.gov (United States)

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

    2015-07-09

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

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

  5. Low-temperature atomic layer deposition of copper(II) oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Iivonen, Tomi, E-mail: tomi.iivonen@helsinki.fi; Hämäläinen, Jani; Mattinen, Miika; Popov, Georgi; Leskelä, Markku [Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, FI-00014 Helsinki (Finland); Marchand, Benoît; Mizohata, Kenichiro [Division of Materials Physics, Department of Physics, University of Helsinki, P.O. Box 43, FI-00014 Helsinki (Finland); Kim, Jiyeon; Fischer, Roland A. [Chair of Inorganic Chemistry II, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum (Germany)

    2016-01-15

    Copper(II) oxide thin films were grown by atomic layer deposition (ALD) using bis-(dimethylamino-2-propoxide)copper [Cu(dmap){sub 2}] and ozone in a temperature window of 80–140 °C. A thorough characterization of the films was performed using x-ray diffraction, x-ray reflectivity, UV‐Vis spectrophotometry, atomic force microscopy, field emission scanning electron microscopy, x-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis techniques. The process was found to produce polycrystalline copper(II) oxide films with a growth rate of 0.2–0.3 Å per cycle. Impurity content in the films was relatively small for a low temperature ALD process.

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

    Science.gov (United States)

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

    2008-11-28

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

  7. Copper(II tetrafluoroborate as mild and versatile catalyst for the

    Directory of Open Access Journals (Sweden)

    Jihillu. S. Yadav

    2008-12-01

    Full Text Available A variety of -acetamido ketones and ketoesters are readily prepared in high yields under extremelymild conditions via a three component coupling of aromatic aldehydes, enolizable ketones or -ketoesters andnitriles in the presence of 10 mol% of copper(II tetrafluoroborate and a stoichiometric amount of acetylchloride. A solution of 10 mol% of Cu(BF42 in acetonitrile provides a convenient reaction medium to carry out athree component reaction under mild conditions

  8. Copper(II) binding to alpha-synuclein, the Parkinson's protein.

    Science.gov (United States)

    Lee, Jennifer C; Gray, Harry B; Winkler, Jay R

    2008-06-04

    Variations in tryptophan fluorescence intensities confirm that copper(II) interacts with alpha-synuclein, a protein implicated in Parkinson's disease. Trp4 fluorescence decay kinetics measured for the F4W protein show that Cu(II) binds tightly (Kd 100 nM) near the N-terminus at pH 7. Work on a F4W/H50S mutant indicates that a histidine imidazole is not a ligand in this high-affinity site.

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

    NARCIS (Netherlands)

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

    2015-01-01

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

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

    NARCIS (Netherlands)

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

    2015-01-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2015-05-21

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

  13. Carboxylated Polyurethanes Containing Hyperbranched Polyester Soft Segments

    Directory of Open Access Journals (Sweden)

    Žigon, M.

    2006-09-01

    Full Text Available hyperbranched polyester soft segments (HB PU with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylolpropionic acid of the fourth pseudo-generation (Boltorn H40 and hexamethylene (HDI or isophorone diisocyanate (IPDI. The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios rNCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young's modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures.

  14. Borate esters as convenient reagents for direct amidation of carboxylic acids and transamidation of primary amides.

    Science.gov (United States)

    Starkov, Pavel; Sheppard, Tom D

    2011-03-07

    Simple borates serve as effective promoters for amide bond formation with a variety of carboxylic acids and amines. With trimethyl or tris(2,2,2-trifluoroethyl) borate, amides are obtained in good to excellent yield and high purity after a simple work-up procedure. Tris(2,2,2-trifluoroethyl) borate can also be used for the straightforward conversion of primary amides to secondary amides via transamidation.

  15. Heterogeneous and homogeneous catalysis for the hydrogenation of carboxylic acid derivatives: history, advances and future directions.

    Science.gov (United States)

    Pritchard, James; Filonenko, Georgy A; van Putten, Robbert; Hensen, Emiel J M; Pidko, Evgeny A

    2015-06-01

    The catalytic reduction of carboxylic acid derivatives has witnessed a rapid development in recent years. These reactions, involving molecular hydrogen as the reducing agent, can be promoted by heterogeneous and homogeneous catalysts. The milestone achievements and recent results by both approaches are discussed in this Review. In particular, we focus on the mechanistic aspects of the catalytic hydrogenation and highlight the bifunctional nature of the mechanism that is preferred for supported metal catalysts as well as homogeneous transition metal complexes.

  16. Characterization of 1-Aminocyclopropane-1-Carboxylate (ACC) Deaminase-Containing Pseudomonas spp. in the Rhizosphere of Salt-Stressed Canola

    NARCIS (Netherlands)

    Akhgar, A.; Arzanlou, M.; Bakker, Peter; Hamidpour, M.

    2014-01-01

    When exposed to biotic or abiotic stress conditions, plants produce ethylene from its immediate precursor 1-aminocyclopropane-1- carboxylate (ACC), leading to retarded root growth and senescence. Many plant growth-promoting rhizobacteria contain the enzyme ACC deaminase and this enzyme can cleave AC

  17. Methyl 6-Methyl-1-(4-methylphenyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate

    Directory of Open Access Journals (Sweden)

    Haiping Wang

    2012-04-01

    Full Text Available Methyl 6-methyl-1-(4-methylphenyl-2-oxo-4-phenyl-1,2,3,4-tetrahydro-pyrimidine-5-carboxylate has been synthesized via the modified Biginelli reaction from benzaldehyde, p-tolylurea, and methyl acetoacetate, promoted with microwave irradiation and catalyzed by TsOH under solvent-free conditions in high yield.

  18. Formation of a new copper(II) dimer through heterocyclic ligand ring opening reaction: Supramolecular features and magnetic properties

    Science.gov (United States)

    Gonçalves, Bruna Lisboa; Gervini, Vanessa Carratu; Flores, Alex Fabiani Claro; Junior, Jorge Luiz Pimentel; Bortoluzzi, Adailton João; Burrow, Robert Alan; Duarte, Rafael; da Silva, Robson Ricardo; Vicenti, Juliano Rosa de Menezes

    2017-01-01

    Two new compounds were synthesized and characterized in this work: the heterocycle (Z)-1-(4-(hydroxyimino)-3,5-dimethyl-1-(methylcarbamothioyl)-4,5-dihydro-1H-pyrazol-5-yl)-4-methylthiosemicarbazide and a copper(II) thiosemicarbazonato dimeric complex. Green prismatic single crystals of the dimer were obtained by the reaction of the heterocycle with copper(II) chloride dihydrate. Both compounds were essentially characterized by spectroscopic methods and X-ray diffraction crystallography. The crystal structures revealed molecules connected through supramolecular hydrogen bond interactions and copper(II) centers in a slightly distorted square-pyramidal environment. SQUID magnetometry performed for the dimer revealed both ferromagnetic and antiferromagnetic interactions in the studied complex, presenting a critical temperature of 19 K.

  19. Efficient electron-induced removal of oxalate ions and formation of copper nanoparticles from copper(II oxalate precursor layers

    Directory of Open Access Journals (Sweden)

    Kai Rückriem

    2016-06-01

    Full Text Available Copper(II oxalate grown on carboxy-terminated self-assembled monolayers (SAM using a step-by-step approach was used as precursor for the electron-induced synthesis of surface-supported copper nanoparticles. The precursor material was deposited by dipping the surfaces alternately in ethanolic solutions of copper(II acetate and oxalic acid with intermediate thorough rinsing steps. The deposition of copper(II oxalate and the efficient electron-induced removal of the oxalate ions was monitored by reflection absorption infrared spectroscopy (RAIRS. Helium ion microscopy (HIM reveals the formation of spherical nanoparticles with well-defined size and X-ray photoelectron spectroscopy (XPS confirms their metallic nature. Continued irradiation after depletion of oxalate does not lead to further particle growth giving evidence that nanoparticle formation is primarily controlled by the available amount of precursor.

  20. New cyclic tetranuclear copper(II) complexes containing quadrilateral cores: Synthesis, structure, spectroscopy and their interactions with DNA in aqueous solution

    Science.gov (United States)

    Giri, Gopal C.; Haldar, Shobhraj; Ghosh, Aloke Kumar; Chowdhury, Priyanka; Carrella, Luca; Ghosh, Utpal; Bera, Manindranath

    2017-08-01

    Three new cyclic tetranuclear copper(II) complexes, Tetrakis{3-[(2-pyridylmethyl)-amino]-propionato}(tetrachloro)tetracopper(II)methanolhydrate (1·CH3OH·H2O), Tetrakis{3-[(2-pyridylmethyl)-amino]-propionato}(tetrathiocyanato)tetracopper(II) (2) and Tetrakis{3-[(2-pyridylmethyl)-amino]-propionato}(tetraazido)tetracopper(II) (3) have been synthesized by exploiting the chelating ability and bridging potential of a carboxyamine functionalized tridentate ligand, HL (HL = 3-[(2-Pyridylmethyl)-amino]-propionic acid). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand HL with stoichiometric amounts of CuCl2·2H2O, CuCl2·2H2O/NH4SCN, and CuCl2·2H2O/NaN3, respectively, in the presence of NMe4OH at ambient temperature. Various analytical techniques have been employed to characterize the complexes, including single crystal X-ray diffraction study of 1. Structures of complexes 2 and 3 have been optimized by DFT calculation at B3LYP/6-311G level. Analysis of X-ray crystal structure reveals that the metallic core of complex 1 contains four distorted square pyramidal Cu(II) ions. The Cu(II) ions in each complex are arranged at the corners of a quadrilateral showing a μ2:η1:η1syn-anti bidentate bridging mode of four carboxylate groups of L- ligands with each bridging between two Cu(II) ions. These complexes represent a new family of 16-MCCuII-4 metallocoronates with repeating -[CuIIsbnd Osbnd Csbnd O]- units. In aqueous solution (pH∼7.5), the interactions of complexes with DNA have been investigated by UV-Vis and fluorescence titration spectroscopy, and viscosity measurements.

  1. Remote His50 Acts as a Coordination Switch in the High-Affinity N-Terminal Centered Copper(II) Site of α-Synuclein.

    Science.gov (United States)

    De Ricco, Riccardo; Valensin, Daniela; Dell'Acqua, Simone; Casella, Luigi; Dorlet, Pierre; Faller, Peter; Hureau, Christelle

    2015-05-18

    Parkinson's disease (PD) etiology is closely linked to the aggregation of α-synuclein (αS). Copper(II) ions can bind to αS and may impact its aggregation propensity. As a consequence, deciphering the exact mode of Cu(II) binding to αS is important in the PD context. Several previous reports have shown some discrepancies in the description of the main Cu(II) site in αS, which are resolved here by a new scenario. Three Cu(II) species can be encountered, depending on the pH and the Cu:αS ratio. At low pH, Cu(II) is bound to the N-terminal part of the protein by the N-terminal amine, the adjacent deprotonated amide group of the Asp2 residue, and the carboxylate group from the side chain of the same Asp2. At pH 7.4, the imidazole group of remote His50 occupies the fourth labile equatorial position of the previous site. At high Cu(II):αS ratio (>1), His50 leaves the coordination sphere of the first Cu site centered at the N-terminus, because a second weak affinity site centered on His50 is now filled with Cu(II). In this new scheme, the remote His plays the role of a molecular switch and it can be anticipated that the binding of the remote His to the Cu(II) ion can induce different folding of the αS protein, having various aggregation propensity.

  2. Study of the interaction mechanism in the biosorption of copper(II) ions onto posidonia oceanica and peat

    Energy Technology Data Exchange (ETDEWEB)

    Izquierdo, Marta; Marzal, Paula; Gabaldon, Carmen [Departamento de Ingenieria Quimica, Escuela Tecnica Superior de Ingenieria, Universitat de Valencia, Valencia (Spain); Silvetti, Margherita; Castaldi, Paola [Dipartimento di Scienze Ambientali e Agrarie e Biotecnologie Agro-Alimentari, Sez. Chimica Agraria ed Ambientale, University of Sassari, Sassari (Italy)

    2012-04-15

    A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption-desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4-6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q{sub max}) at pH 6 of 85.78 and 49.69 mg g{sup -1}, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO{sub 3}){sub 2}, and EDTA was applied to copper-saturated biosorbents. Around 65-70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH{sub 2}, and CH{sub 3} in aliphatic structures, COO{sup -} and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si-O groups on the surface of peat. The results of SEM-EDX and FTIR analysis of copper-saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption-desorption processes affected the thermal stability of the biosorbents. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Methyl (Sp-2-(diphenylphosphinoferrocene-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Petr Štěpnička

    2009-10-01

    Full Text Available The title compound, [Fe(C5H5(C19H16O2P], obtained serendipitously during recrystallization of 1-hydroxybenzotriazolyl (Sp-2-(diphenylphosphinoferrocene-1-carboxylate from methanol, crystallizes in the chiral space group P212121. Its crystal structure not only confirms the anticipated absolute configuration but also establishes a rather regular geometry for the ferrocene unit, devoid of any significant deformation due to the attached substituents. In the crystal, symmetry-related molecules are linked via weak C—H...O interactions.

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

    Directory of Open Access Journals (Sweden)

    Babita Sarma

    2013-01-01

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

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

    Science.gov (United States)

    Sabolović, Jasmina

    2009-03-01

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

  6. Structure investigations of group 13 organometallic carboxylates.

    Science.gov (United States)

    Justyniak, Iwona; Prochowicz, Daniel; Tulewicz, Adam; Bury, Wojciech; Goś, Piotr; Lewiński, Janusz

    2017-01-17

    The octet-compliant group 13 organometallics with highly polarized bonds in the metal coordination sphere exhibit a significant tendency to maximize their coordination number through the formation of adducts with a wide range of neutral donor ligands or by self-association to give aggregates containing tetrahedral and higher coordinated aluminium centres, and even in some cases molecular complexes equilibrate with ionic species of different coordination numbers of the metal centre. This work provides a comprehensive overview of the structural chemistry landscape of the group 13 carboxylates. Aside from a more systematic approach to the general structural chemistry of the title compounds, the structure investigations of [R2M(μ-O2CPh)]2-type benzoate complexes (where M = B, Al and Ga) and their Lewis acid-base adducts [(R2M)(μ-O2CPh)(py-Me)] are reported. DFT calculations were also performed to obtain a more in-depth understanding of both the changes in the bonding of group 13 organometallic carboxylate adducts with a pyridine ligand.

  7. Short Carboxylic Acid–Carboxylate Hydrogen Bonds Can Have Fully Localized Protons

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Jiusheng; Pozharski, Edwin; Wilson, Mark A.

    2017-01-17

    Short hydrogen bonds (H-bonds) have been proposed to play key functional roles in several proteins. The location of the proton in short H-bonds is of central importance, as proton delocalization is a defining feature of low-barrier hydrogen bonds (LBHBs). Experimentally determining proton location in H-bonds is challenging. Here, bond length analysis of atomic (1.15–0.98 Å) resolution X-ray crystal structures of the human protein DJ-1 and its bacterial homologue, YajL, was used to determine the protonation states of H-bonded carboxylic acids. DJ-1 contains a buried, dimer-spanning 2.49 Å H-bond between Glu15 and Asp24 that satisfies standard donor–acceptor distance criteria for a LBHB. Bond length analysis indicates that the proton is localized on Asp24, excluding a LBHB at this location. However, similar analysis of the Escherichia coli homologue YajL shows both residues may be protonated at the H-bonded oxygen atoms, potentially consistent with a LBHB. A Protein Data Bank-wide screen identifies candidate carboxylic acid H-bonds in approximately 14% of proteins, which are typically short [O–O> = 2.542(2) Å]. Chemically similar H-bonds between hydroxylated residues (Ser/Thr/Tyr) and carboxylates show a trend of lengthening O–O distance with increasing H-bond donor pKa. This trend suggests that conventional electronic effects provide an adequate explanation for short, charge-assisted carboxylic acid–carboxylate H-bonds in proteins, without the need to invoke LBHBs in general. This study demonstrates that bond length analysis of atomic resolution X-ray crystal structures provides a useful experimental test of certain candidate LBHBs.

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

    Science.gov (United States)

    Gungor, Elif

    2017-05-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-06-30

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

  10. Rational design of carboxyl groups perpendicularly attached to a graphene sheet: a platform for enhanced biosensing applications.

    Science.gov (United States)

    Bonanni, Alessandra; Chua, Chun Kiang; Pumera, Martin

    2014-01-01

    Graphene oxide (GO)-based materials offer great potential for biofunctionalization with applications ranging from biosensing to drug delivery. Such biofunctionalization utilizes specific functional groups, typically a carboxyl moiety, as anchoring points for biomolecule. However, due to the fact that the exact chemical structure of GO is still largely unknown and poorly defined (it was postulated to consist of various oxygen-containing groups, such as epoxy, hydroxyl, carboxyl, carbonyl, and peroxy in varying ratios), it is challenging to fabricate highly biofunctionalized GO surfaces. The predominant anchoring sites (i.e., carboxyl groups) are mainly present as terminal groups on the edges of GO sheets and thus account for only a fraction of the oxygen-containing groups on GO. Herein, we suggest a direct solution to the long-standing problem of limited abundance of carboxyl groups on GO; GO was first reduced to graphene and consequently modified with only carboxyl groups grafted perpendicularly to its surface by a rational synthesis using free-radical addition of isobutyronitrile with subsequent hydrolysis. Such grafted graphene oxide can contain a high amount of carboxyl groups for consequent biofunctionalization, at which the extent of grafting is limited only by the number of carbon atoms in the graphene plane; in contrast, the abundance of carboxyl groups on "classical" GO is limited by the amount of terminal carbon atoms. Such a graphene platform embedded with perpendicularly grafted carboxyl groups was characterized in detail by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy, and its application was exemplified with single-nucleotide polymorphism detection. It was found that the removal of oxygen functionalities after the chemical reduction enhanced the electron-transfer rate of the graphene. More importantly, the introduction of carboxyl groups promoted a more efficient immobilization of DNA probes on the

  11. trans-Bis(perchlorato-κOtetrakis(1H-pyrazole-κN2copper(II

    Directory of Open Access Journals (Sweden)

    Viktor Zapol'skii

    2008-10-01

    Full Text Available The title compound, [Cu(ClO42(C3H4N24], was obtained unexpectedly by the reaction of copper(II perchlorate hexahydrate with equimolar amounts of 1-chloro-1-nitro-2,2,2-tripyrazolylethane in methanol solution. The crystal structure comprises octahedrally coordinated Cu2+ ions, located on an inversion centre, with four pyrazole ligands in the equatorial plane. The average Cu—N distance is 2.000 (1 Å. Two perchlorate ions are coordinated to copper in trans positions [Cu—O = 2.4163 (11 Å].

  12. Copper(II) ions and the Alzheimer's amyloid-β peptide: Affinity and stoichiometry of binding

    Science.gov (United States)

    Tõugu, Vello; Friedemann, Merlin; Tiiman, Ann; Palumaa, Peep

    2014-10-01

    Deposition of amyloid beta (Aβ) peptides into amyloid plaques is the hallmark of Alzheimer's disease. According to the amyloid cascade hypothesis this deposition is an early event and primary cause of the disease, however, the mechanisms that cause this deposition remain elusive. An increasing amount of evidence shows that the interactions of biometals can contribute to the fibrillization and amyloid formation by amyloidogenic peptides. From different anions the copper ions deserve the most attention since it can contribute not only toamyloid formation but also to its toxicity due to the generation of ROS. In this thesis we focus on the affinity and stoichiometry of copper(II) binding to the Aβ molecule.

  13. Copper(II) Binding to α-Synuclein, the Parkinson’s Protein

    OpenAIRE

    Lee, Jennifer C.; Gray, Harry B.; Winkler, Jay R.

    2008-01-01

    Variations in tryptophan fluorescence intensities confirm that copper(II) interacts with α-synuclein, a protein implicated in Parkinson’s disease. Trp4 fluorescence decay kinetics measured for the F4W protein show that Cu(II) binds tightly (K d ∼ 100 nM) near the N-terminus at pH 7. Work on a F4W/H50S mutant indicates that a histidine imidazole is not a ligand in this high-affinity site.

  14. Synthesis, characterization, and spectroscopic investigation of new iron(III) and copper(II) complexes of a carboxylate rich ligand and their interaction with carbohydrates in aqueous solution.

    Science.gov (United States)

    Stewart, Christopher D; Arman, Hadi; Bawazir, Huda; Musie, Ghezai T

    2014-10-20

    New tetra-iron(III) (K4[1]·25H2O·(CH3)2CO and K3[2]·3H2O·(OH)) and di-copper(II) (Na3[3]·5H2O) complexes as carbohydrate binding models have been synthesized and fully characterized used several techniques including single crystal X-ray crystallography. Whereas K4[1]·25H2O·(CH3)2CO and Na3[3]·5H2O are completely water-soluble, K3[2]·3H2O·(OH) is less soluble in all common solvents including water. The binding of substrates, such as d-mannose, d-glucose, d-xylose, and xylitol with the water-soluble complexes in different reaction conditions were investigated. In aqueous alkaline media, complexes K4[1]·25H2O·(CH3)2CO and Na3[3]·5H2O showed coordination ability toward the applied substrates. Even in the presence of stoichiometric excess of the substrates, the complexes form only 1:1 (complex/substrate) molar ratio species in solution. Apparent binding constants, pKapp, values between the complexes and the substrates were determined and specific mode of substrate binding is proposed. The pKapp values showed that d-mannose coordinates strongest to K4[1]·25H2O·(CH3)2CO and Na3[3]·5H2O. Syntheses, characterizations and detailed substrate binding study using spectroscopic techniques and single crystal X-ray diffraction are reported.

  15. Selective copper(II acetate and potassium iodide catalyzed oxidation of aminals to dihydroquinazoline and quinazolinone alkaloids

    Directory of Open Access Journals (Sweden)

    Matthew T. Richers

    2013-06-01

    Full Text Available Copper(II acetate/acetic acid/O2 and potassium iodide/tert-butylhydroperoxide systems are shown to affect the selective oxidation of ring-fused aminals to dihydroquinazolines and quinazolinones, respectively. These methods enable the facile preparation of a number of quinazoline alkaloid natural products and their analogues.

  16. Copper(II) coordination properties of the integrin ligand sequence PHSRN and its new β-cyclodextrin conjugates.

    Science.gov (United States)

    Magrì, Antonio; D'Alessandro, Franca; Distefano, Donatella A; Campagna, Tiziana; Pappalardo, Giuseppe; Impellizzeri, Giuseppe; La Mendola, Diego

    2012-08-01

    The peptide sequence PHSRN is the second cell binding site of the human fibronectin protein, a glycoprotein which plays a critical adhesive role during development, tissue repair and angiogenesis. The copper(II) complexes with the peptide fragment PHSRN were characterized by potentiometric and UV-visible, CD, EPR spectroscopic methods. Thermodynamic and spectroscopic evidences indicate that at physiological pH, only one copper(II) complex species, [CuLH(-2)], is present and the metal ion is bound to one imidazole and two amide nitrogen atoms (N(Im), 2N(-)) in a tetrahedral distorted square planar coordination. Two new β-cyclodextrin-ethylendiamino derivatives with the PHSRN covalently attached were synthesized as multitargeting molecules, able to have a site-specific recognition sequence, to interact with copper(II) ions and to be a potential carrier of hydrophobic drugs. Copper(II) complexes with these β-cyclodextrin derivatives were characterized by means of potentiometric and spectroscopic techniques. The comparison of the experimental parameters determined at different pH values with those obtained for the parent peptide complex species, shows that at physiological pH the ethylendiamino-β-CD moiety does not influence the peptide interaction with copper ions and the β-CD hydrophobic cavity is not blocked, being available to host hydrophobic drugs such as naproxen.

  17. Flotation of traces of silver and copper(II) ions with a methyl cellosolve solution of dithizone.

    Science.gov (United States)

    Hiraide, M; Mizuike, A

    1975-06-01

    Microgram quantities of silver and copper(II) ions in aqueous solutions are collected on dithizone precipitates, which are then floated with the aid of small nitrogen bubbles. This separation technique has been successfully applied to the atomic-absorption spectrophotometric determination of down to a tenth ppm of silver and copper in high-purity lead and zinc metals.

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

    Directory of Open Access Journals (Sweden)

    Madhumita Hazra

    2017-01-01

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

  19. Effect of Phosphorylation and Copper(II or Iron(II Ions Enrichment on Some Physicochemical Properties of Spelt Starch

    Directory of Open Access Journals (Sweden)

    Jacek Rożnowski

    Full Text Available ABSTRACT: This paper provides an assessment of the effect of saturation of spelt starch and monostarch phosphate with copper or iron ions on selected physicochemical properties of the resulting modified starches. Native and modified spelt starch samples were analyzed for selected mineral element content using Atomic Absorption Spectroscopy (AAS. Thermodynamic properties were measured using DSC, and pasting properties by RVA. Flow curves of 5% pastes were plotted and described using the Herschel-Bulkley model. The structure recovery ratio was measured. AAS analysis established the presence of iron(II and copper(II ions in the samples of modified starches and that potassium and magnesium ions had leached from them. In comparison to unfortified samples, enriching native starch with copper(II ions decreases value of all temperatures of phase transformation about 1.3-2.7 °C, but in case of monostarch phosphates bigger changes (2.8-3.7 °C were observed. Fortified native spelt starch with copper(II ions caused increasing the final viscosity of paste from 362 to 429 mPa·s. However, presence iron(II ions in samples caused reduced its final viscosity by 170 (spelt starch and 103 mPa·s (monostarch phosphate. Furthermore, enriching monostarch phosphate contributed to reduce degree of structure recovery of pastes from 70.9% to 66.6% in case of copper(II ions and to 59.9% in case of iron(II ions.

  20. Enantioseparation of Amino Acids by Micelle-Enhanced Ultrafiltration : Experimental and Theoretical Studies of Copper(II) Amino Acid Interactions

    NARCIS (Netherlands)

    Bruin, de T.J.M.

    2000-01-01

    A micelle-enhanced ultrafiltration system, which can potentially be used for large scale separations, has been used to investigate the resolution of amino acid enantiomers. For this purpose amino acid derivatives were synthesized, which in combination with copper(II) ions were used as chiral selecto

  1. Copper(II) interaction with peptide fragments of histidine-proline-rich glycoprotein: Speciation, stability and binding details.

    Science.gov (United States)

    La Mendola, Diego; Magrì, Antonio; Santoro, Anna Maria; Nicoletti, Vincenzo G; Rizzarelli, Enrico

    2012-06-01

    GHHPH is the peptide repeat present in histidine-proline rich glycoprotein (HPRG), a plasma glycoprotein involved in angiogenesis process. The copper(II) ions interaction with mono (Ac-GHHPHG-NH(2)) and its bis-repeat (Ac-GHHPHGHHPHG-NH(2)) was investigated by means of potentiometric and spectroscopic techniques. To single out the copper(II) coordination environments of different species formed with Ac-GHHPHG-NH(2), three single point mutated peptides were also synthesized and their ability to coordinate Cu(2+) investigated. Ac-GHHPHG-NH(2) binds Cu(2+) by the imidazole side chain and the amide nitrogen deprotonation that takes place towards the N-terminus. The bis-repeat is able to bind Cu(2+) more efficiently than Ac-GHHPHG-NH(2). This difference is not only due to the number of His residues in the sequence but also to the different binding sites. In fact, the comparison of the potentiometric and spectroscopic data of the copper(II) complexes with a bis-repeatPeg construct Ac-(GHHPHG)-Peg-(GHHPHG)-NH(2) and those of the metal complexes with Ac-HGHH-NH(2), indicates that the central HGHH amino acid sequence is the main copper(II) binding site.

  2. Synthesis and Crystal Structure of Copper(II) Complex with Mixed Bipyridine and 2-Hydroxy-1-naphthaldehyde Ligands

    Institute of Scientific and Technical Information of China (English)

    卜平宇; 程鹏; 赵斌; 阎世平; 瘳代正; 姜宗慧; 刘松岩; 姚心侃; 王宏根

    2002-01-01

    A mononuclear copper(II) complex, [Cu(bipy)(naph)(ClO4)] (where bipy is bipyridine and naph is 2-hydroxy-1-naphthaldehyde), was synthesized and characterized by X-ray single-crystal structure analysis. The crystal is triclinic, space group P ī with a = 9.245(4), b = 9.962(4), c = 10.809(7) A, α = 84.83(5), β =82.35(4), γ = 81.02(4)°, V = 972.1 >3, C21H15ClCuN2O6 Mr = 490.36, Z = 2, F(000) = 498, Dx = 1.68 g/cm3, μ = 13.05 cm-1, R = 0.078, Rw = 0.081 for 2295 observed reflections with I > 3σ(I). The copper(II) ion is coordinated by two nitrogen atoms of bipy and two oxygen atoms of naph in the equatorial plane, with an axial perchlorate oxygen-copper(II) bond to copper(II) ion to form square-pyramidal coordination geometry. The coordination environment of copper(II) is similar to the active site of galactose oxidase and this compound may also be considered as the structural model of galactose oxidase.

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

    NARCIS (Netherlands)

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

    2007-01-01

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

  4. Carboxylates and the uptake of ammonium by excised maize roots

    NARCIS (Netherlands)

    Breteler, H.

    1975-01-01

    The effect of carboxylates (organic acid anions) on NH 4 uptake was studied by changing the carboxylate level of roots prior to uptake experi ments. Succinate was the most effective stimulator of ammonium uptake. The oxocarboxylates (α-oxoglutarate, oxaloacetate and

  5. Critical and distinct roles of amino- and carboxyl-terminal sequences in regulation of the biological activity of the Chp atypical Rho GTPase.

    Science.gov (United States)

    Chenette, Emily J; Abo, Arie; Der, Channing J

    2005-04-08

    Chp (Cdc42 homologous protein) shares significant sequence and functional identity with the human Cdc42 small GTPase, and like Cdc42, promotes formation of filopodia and activates the p21-activated kinase serine/threonine kinase. However, unlike Cdc42, Chp contains unique amino- and carboxyl-terminal extensions. Here we determined whether Chp, like Cdc42, can promote growth transformation and evaluated the role of the amino- and carboxyl-terminal sequences in Chp function. Surprisingly, we found that a GTPase-deficient mutant of Chp exhibited low transforming activity but that deletion of the amino terminus of Chp greatly enhanced its transforming activity. Thus, the amino terminus may serve as a negative regulator of Chp function. The carboxyl terminus of Cdc42 contains a CAAX (where C is cysteine, A is aliphatic amino acid, X is terminal amino acid) tetrapeptide sequence that signals for the posttranslational modification critical for Cdc42 membrane association and biological function. Although Chp lacks aCAAXmotif, we found that Chp showed carboxyl terminus-dependent localization to the plasma membrane and to endosomes. Furthermore, an intact carboxyl terminus was required for Chp transforming activity. However, treatment with inhibitors of protein palmitoylation, but not prenylation, caused Chp to mislocalize to the cytoplasm. Thus, Chp depends on palmitoylation, rather than isoprenylation, for membrane association and function. In summary, Chp is implicated in cell transformation, and the unique amino and carboxyl termini of Chp represent atypical mechanisms of regulation of Rho GTPase function.

  6. Carboxylate-bridged helical chains based on an azo carboxylate oximate ligand

    Institute of Scientific and Technical Information of China (English)

    KOU HuiZhong; ZHANG YanDong; CUI AiLi

    2012-01-01

    Two helical one-dimensional complexes[MnⅡ(MeOH)4][MnⅣ(L·)2]· 2MeOH(1)and[MnⅢ(salen)][MnⅢ(L)2](2)(H2L =HON=C(Ph)N=NC6H4CO2H)contain the noninnocent ligand[Mn(L·)2]2- and innocent low-spin[Mn(L)2]-.Intrachain anfiferromagnetic interaction between adjacent manganese ions via the syn-anti carboxylate bridges in complex 1.Alternate syn-anti and anti-anti carboxylate bridges have been found to transmit ferro- and antiferromagnetic coupling between high-spin and low-spin Mn(Ⅲ)ions in complex 2.

  7. Noncovalent catch and release of carboxylates in water.

    Science.gov (United States)

    Beck, Christie L; Winter, Arthur H

    2014-04-01

    Association constants of a bis-(acetylguanidinium)ferrocene dication to various (di)carboxylates were determined through UV-vis titrations. Association constant values greater than 10(4) M(-1) were determined for both phthalate and maleate carboxylates to the bis-(acetylguanidinium)ferrocene salt in pure water. Density functional theory computations of the binding enthalpy of the rigid carboxylates for these complexes agree well with the experimentally determined association constants. Catch and release competitive binding experiments were done by NMR for the cation-carboxylate ion-pair complexes with cucurbit[7]uril, and they show dissociation of the ion-pair complex upon addition of cucurbit[7]uril and release of the free (di)carboxylate.

  8. Effect of choline carboxylate ionic liquids on biological membranes.

    Science.gov (United States)

    Rengstl, Doris; Kraus, Birgit; Van Vorst, Matthew; Elliott, Gloria D; Kunz, Werner

    2014-11-01

    Choline carboxylates, ChCm, with m=2-10 and choline oleate are known as biocompatible substances, yet their influence on biological membranes is not well-known, and the effect on human skin has not previously been investigated. The short chain choline carboxylates ChCm with m=2, 4, 6 act as hydrotropes, solubilizing hydrophobic compounds in aqueous solution, while the longer chain choline carboxylates ChCm with m=8, 10 and oleate are able to form micelles. In the present study, the cytotoxicity of choline carboxylates was tested using HeLa and SK-MEL-28 cells. The influence of these substances on liposomes prepared from dipalmitoylphosphatidylcholine (DPPC) was also evaluated to provide insights on membrane interactions. It was observed that the choline carboxylates with a chain length of m>8 distinctly influence the bilayer, while the shorter ones had minimal interaction with the liposomes.

  9. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    Science.gov (United States)

    Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

    1998-01-01

    Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

  10. Silver-catalyzed decarboxylative chlorination of aliphatic carboxylic acids.

    Science.gov (United States)

    Wang, Zhentao; Zhu, Lin; Yin, Feng; Su, Zhongquan; Li, Zhaodong; Li, Chaozhong

    2012-03-07

    Decarboxylative halogenation of carboxylic acids, the Hunsdiecker reaction, is one of the fundamental functional group transformations in organic chemistry. As the initial method requires the preparations of strictly anhydrous silver carboxylates, several modifications have been developed to simplify the procedures. However, these methods suffer from the use of highly toxic reagents, harsh reaction conditions, or limited scope of application. In addition, none is catalytic for aliphatic carboxylic acids. In this Article, we report the first catalytic Hunsdiecker reaction of aliphatic carboxylic acids. Thus, with the catalysis of Ag(Phen)(2)OTf, the reactions of carboxylic acids with t-butyl hypochlorite afforded the corresponding chlorodecarboxylation products in high yields under mild conditions. This method is not only efficient and general, but also chemoselective. Moreover, it exhibits remarkable functional group compatibility, making it of more practical value in organic synthesis. The mechanism of single electron transfer followed by chlorine atom transfer is proposed for the catalytic chlorodecarboxylation.

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

    Science.gov (United States)

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

    2008-01-01

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

  12. Highly efficient visual detection of trace copper(II) and protein by the quantum photoelectric effect.

    Science.gov (United States)

    Wang, Peng; Lei, Jianping; Su, Mengqi; Liu, Yueting; Hao, Qing; Ju, Huangxian

    2013-09-17

    This work presented a photocurrent response mechanism of quantum dots (QDs) under illumination with the concept of a quantum photoelectric effect. Upon irradiation, the photoelectron could directly escape from QDs. By using nitro blue tetrazolium (NBT) to capture the photoelectron, a new visual system was proposed due to the formation of an insoluble reduction product, purple formazan, which could be used to visualize the quantum photoelectric effect. The interaction of copper(II) with QDs could form trapping sites to interfere with the quantum confinement and thus blocked the escape of photoelectron, leading to a "signal off" visual method for sensitive copper(II) detection. Meanwhile, by using QDs as a signal tag to label antibody, a "signal on" visual method was also proposed for immunoassay of corresponding protein. With meso-2,3-dimercaptosuccinic-capped CdTe QDs and carcino-embryonic antigen as models, the proposed visual detection methods showed high sensitivity, low detection limit, and wide detectable concentration ranges. The visualization of quantum photoelectric effect could be simply extended for the detection of other targets. This work opens a new visual detection way and provides a highly efficient tool for bioanalysis.

  13. Stabilization of acyclic water tetramer in a copper(II) malonate framework structure.

    Science.gov (United States)

    Deshpande, Megha S; Kumbhar, Avinash S; Näther, Christian

    2010-10-14

    Copper(II) complex [Cu(dpq)(mal)(H(2)O)]·3H(2)O (1) (dpq = dipyrido-[3,2-d:2',3'-f]-quinoxaline, mal = malonato) was synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray crystallography. The single-crystal X-ray structure of 1 reveals a square pyramidal structure, with the dipyrido-[3,2-d:2',3'-f]-quinoxaline and malonato at the equatorial positions and a water molecule at the axial position. The molecule acts as a building block generating a supramolecular three-dimensional metal-organic framework (MOF) encapsulating metal linked acyclic water tetramer. The H-bonding capacity of malonato and the π-π stacking interactions of dipyrido-[3,2-d:2',3'-f]-quinoxaline further reinforce the framework. The copper(II) bound hydroxyl group is demonstrated to mediate hydrolytic cleavage of plasmid pBR322 DNA under dark conditions.

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

    Science.gov (United States)

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

    2009-04-14

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

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

    Science.gov (United States)

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

    2013-02-04

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

  16. A highly selective and sensitive fluorescence assay for determination of copper(II) and cobalt(II) ions in environmental water and toner samples.

    Science.gov (United States)

    Tsai, Chia-Yi; Lin, Yang-Wei

    2013-02-21

    In this study, a highly selective and sensitive fluorescence assay has been proposed for the determination of copper(II) and cobalt(II) ions in environmental water and toner samples. In the presence of hydrogen peroxide, copper(II) reacted with a new fluorescence reagent Amplex® UltraRed (AUR), forming a fluorescence product only at pH 7.0, while the fluorescence product of cobalt(II) with AUR formed only at pH 9.0. The fluorescence signal obtained was linear with respect to the copper(II) concentration over the range of 1.6-12.0 μM (R(2) = 0.988) and was linear with respect to the cobalt(II) concentration over the range of 45.0 nM to 1.0 μM (R(2) = 0.992). The limits of detection (at a signal-to-noise ratio of 3) for copper(II) and cobalt(II) were 0.17 μM and 14.0 nM, respectively. Our present approach is simpler, faster, and more cost-effective than other techniques for the detection of copper(II) and cobalt(II) ions in environmental water samples and that of copper(II) ions in toner samples.

  17. Analysis of Chiral Carboxylic Acids in Meteorites

    Science.gov (United States)

    Burton, A. S.; Elsila, J. E.; Hein, J. E.; Aponte, J. C.; Parker, E. T.; Glavin, D. P.; Dworkin, J. P.

    2015-01-01

    Homochirality of amino acids in proteins and sugars in DNA and RNA is a critical feature of life on Earth. In the absence of a chiral driving force, however, reactions leading to the synthesis of amino acids and sugars result in racemic mixtures. It is currently unknown whether homochirality was necessary for the origins of life or if it was a product of early life. The observation of enantiomeric excesses of certain amino acids of extraterrestrial origins in meteorites provides evidence to support the hypothesis that there was a mechanism for the preferential synthesis or destruction of a particular amino acid enantiomer [e.g., 1-3]. The cause of the observed chiral excesses is un-clear, although at least in the case of the amino acid isovaline, the degree of aqueous alteration that occurred on the meteorite parent body is correlated to the isovaline L-enantiomeric excess [3, 4]. This suggests that chiral symmetry is broken and/or amplified within the meteorite parent bodies. Besides amino acids, there have been only a few reports of other meteoritic compounds found in enantiomeric excess: sugars and sugar acids [5, 6] and the hydroxy acid lactic acid [7]. Determining whether or not additional types of molecules in meteorites are also present in enantiomeric excesses of extraterrestrial information will provide insights into mechanisms for breaking chiral symmetry. Though the previous measurements (e.g., enantiomeric composition of lactic acid [7], and chiral carboxylic acids [8]) were made by gas chromatography-mass spectrometry, the potential for increased sensitivity of liquid chromatography-mass spectrometry (LC-MS) analyses is important because for many meteorite samples, only small sample masses are available for study. Furthermore, at least in the case of amino acids, many of the largest amino acid enantiomeric excesses were observed in samples that contained lower abundances (tens of ppb) of a given amino acid enantiomer. In the present work, we describe

  18. Solvent-controlled synthesis of tetranuclear cage-like copper(II) silsesquioxanes. Remarkable features of the cage structures and their high catalytic activity in oxidation with peroxides.

    Science.gov (United States)

    Dronova, Marina S; Bilyachenko, Alexey N; Yalymov, Alexey I; Kozlov, Yuriy N; Shul'pina, Lidia S; Korlyukov, Alexander A; Arkhipov, Dmitry E; Levitsky, Mikhail M; Shubina, Elena S; Shul'pin, Georgiy B

    2014-01-14

    Two principally different in their molecular architecture isomeric tetranuclear copper(ii) silsesquioxanes, "Globule"-like compound [(PhSiO1.5)12(CuO)4(NaO0.5)4] (1) and "Sandwich"-like derivative [(PhSiO1.5)6(CuO)4(NaO0.5)4(PhSiO1.5)6] (2), were synthesized by the partial cleavage of polymeric copper(ii) silsesquioxane [(PhSiO1.5)2(CuO)]n by tetraphenylcyclotetrasiloxanolate. The route leading to the formation of either 1 or 2 entirely depends on the nature and composition of the solvent used for this reaction. Thus, the process in an ethanol-1-butanol solution gives compound 1. When a 1,4-dioxane-methanol mixture was used, compound 2 was prepared. The structures and unusual crystal packing of the cages were confirmed by the X-ray studies. It has been found that the reaction of benzene with H2O2 in acetonitrile solution at 50 °C catalyzed by 1 requires addition of trifluoroacetic acid (TFA) in low concentration and gives phenol with a turnover number (TON) of 250 after 3 h. The initial reaction rate W0 linearly depends on the concentration of catalyst 2. The oxidation of 1-phenylethanol to acetophenone with hydrogen peroxide catalyzed by complex 1 in the presence of TFA is not efficient. In contrast, 1 exhibited excellent activity in the oxidation with tert-butyl hydroperoxide (TBHP) in the absence of any acid (the yield of acetophenone was close to the quantitative, TON attained 475 after 2 h). A kinetic study of this reaction led to the conclusion that the process occurs with the participation of radicals tert-BuO˙ produced in the Cu-promoted decomposition of TBHP. The mode of dependence of W0 on the initial concentration of TBHP indicates the formation of an intermediate adduct between the catalyst 1 and TBHP (characterized by the equilibrium constant K1≈ 2 M(-1) for the conditions of conducted experiments) followed by subsequent decomposition of the adduct (k2≈ 0.2 s(-1)) to generate an intermediate species tert-BuO˙ which induces the alcohol oxidation.

  19. Developing Anticancer Copper(II) Pro-drugs Based on the Nature of Cancer Cells and the Human Serum Albumin Carrier IIA Subdomain.

    Science.gov (United States)

    Gou, Yi; Qi, Jinxu; Ajayi, Joshua-Paul; Zhang, Yao; Zhou, Zuping; Wu, Xiaoyang; Yang, Feng; Liang, Hong

    2015-10-01

    To synergistically enhance the selectivity and efficiency of anticancer copper drugs, we proposed and built a model to develop anticancer copper pro-drugs based on the nature of human serum albumin (HSA) IIA subdomain and cancer cells. Three copper(II) compounds of a 2-hydroxy-1-naphthaldehyde benzoyl hydrazone Schiff-base ligand in the presence pyridine, imidazole, or indazole ligands were synthesized (C1-C3). The structures of three HSA complexes revealed that the Cu compounds bind to the hydrophobic cavity in the HSA IIA subdomain. Among them, the pyridine and imidazole ligands of C1 and C2 are replaced by Lys199, and His242 directly coordinates with Cu(II). The indazole and Br ligands of C3 are replaced by Lys199 and His242, respectively. Compared with the Cu(II) compounds alone, the HSA complexes enhance cytotoxicity in MCF-7 cells approximately 3-5-fold, but do not raise cytotoxicity levels in normal cells in vitro through selectively accumulating in cancer cells to some extent. We find that the HSA complex has a stronger capacity for cell cycle arrest in the G2/M phase of MCF-7 by targeting cyclin-dependent kinase 1 (CDK1) and down-regulating the expression of CDK1 and cyclin B1. Moreover, the HSA complex promotes MCF-7 cell apoptosis possibly through the intrinsic reactive oxygen species (ROS) mediated mitochondrial pathway, accompanied by the regulation of Bcl-2 family proteins.

  20. Applications of Carboxylic Acid Reductases in Oleaginous Microbes

    Energy Technology Data Exchange (ETDEWEB)

    Resch, Michael G.; Linger, Jeffrey; McGeehan, John; Tyo, Keith; Beckham, Gregg

    2016-04-24

    Carboxylic acid reductases (CARs) are recently emerging reductive enzymes for the direct production of aldehydes from biologically-produced carboxylic acids. Recent work has demonstrated that these powerful enzymes are able to reduce a very broad range of volatile- to long-chain fatty acids as well as aromatic acids. Here, we express four CAR enzymes from different fungal origins to test their activity against fatty acids commonly produced in oleaginous microbes. These in vitro results will inform metabolic engineering strategies to conduct mild biological reduction of carboxylic acids in situ, which is conventionally done via hydrotreating catalysis at high temperatures and hydrogen pressures.

  1. Novel Polymers with a High Carboxylic Acid Loading

    DEFF Research Database (Denmark)

    Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

    2006-01-01

    ABSTRACT: Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4......-hydroxybenzene, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conucted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly (4-hydroxystyrene...

  2. Direct esterification of ammonium salts of carboxylic acids

    Science.gov (United States)

    Halpern, Yuval

    2003-06-24

    A non-catalytic process for producing esters, the process comprising reacting an ammonium salt of a carboxylic acid with an alcohol and removing ammonia from the reaction mixture. Selectivities for the desired ester product can exceed 95 percent.

  3. Carboxylic ester hydrolases in mitochondria from rat skeletal muscle

    DEFF Research Database (Denmark)

    Kirkeby, S; Moe, D; Zelander, T

    1990-01-01

    A mitochondrial pellet, prepared from rat skeletal muscle, contained a number of carboxylic ester hydrolase isoenzymes. The esterases which split alpha-naphthyl acetate were organophosphate sensitive, whereas two out of three indoxyl acetate hydrolysing enzymes were resistant to both organophosph......A mitochondrial pellet, prepared from rat skeletal muscle, contained a number of carboxylic ester hydrolase isoenzymes. The esterases which split alpha-naphthyl acetate were organophosphate sensitive, whereas two out of three indoxyl acetate hydrolysing enzymes were resistant to both...

  4. Ethyl coumarin-3-carboxylate: synthesis and chemical properties

    Directory of Open Access Journals (Sweden)

    Bakr F. Abdel-Wahab

    2014-03-01

    Full Text Available Ethyl coumarin-3-carboxylate occupies an important position in the organic synthesis and is used in production of biologically active compounds. Thus, the data published over the last few years on the methods of synthesis and chemical properties of ethyl coumarin-3-carboxylate are reviewed here for the first time. The reactions were classified as coumarin ring reactions and ester group reactions, and some of these reactions have been applied successfully to the synthesis of biologically and industrially important compounds.

  5. PHOTOLYSIS OF GOETHITE WITH SORBED LOW MOLECULAR WEIGHT CARBOXYLATES.

    Science.gov (United States)

    Goldberg, Marvin C.; Cunningham, Kirkwood M.

    1984-01-01

    Goethite ( alpha -FeOOH) is a common mineral constituent of suspended and bed sediments in aquatic environments. Many types of naturally-occurring organic molecules, including organic carboxylates, are known to sorb to its surface. Carboxylates should be susceptable to photo-oxidation. An experimental program was conducted with systems containing adsorbed films of oxalate, citrate, tartrate, glycolate, formate, maleate, fumarate, butanoate, and benzoate on Goethite, respectively. Photolytic effects were observed at pH 6. 5 and 5. 5.

  6. Corrosion inhibition of steel in concrete by carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Sagoe-Crentsil, K.K.; Glasser, F.P. (Univ. of Aberdeen, Old Aberdeen (United Kingdom). Dept. of Chemistry); Yilmaz, V.T. (Ondokuz Mayis Univ., Samsun (Turkey))

    1993-11-01

    Water soluble carboxylic acids have been used as corrosion inhibitors. They remain largely soluble after curing in cement for up to 90d. Corrosion current measurements are presented showing malonic acid, a dicarboxylic acid, to be a very effective corrosion inhibitor even in the presence of 2.5 wt % chloride. Unfortunately, it has an initial retarding effect on the set of Portland cement. The investigation suggests that corrosion inhibitors based on carboxylic acids remain a fruitful field of investigation.

  7. Selective carboxyl methylation of structurally altered calmodulins in Xenopus oocytes

    Energy Technology Data Exchange (ETDEWEB)

    Desrosiers, R.R.; Romanik, E.A.; O' Connor, C.M. (Worcester Foundation for Experimental Biology, Shrewsbury, MA (USA))

    1990-12-05

    The eucaryotic protein carboxyl methyltransferase specifically modifies atypical D-aspartyl and L-isoaspartyl residues which are generated spontaneously as proteins age. The selectivity of the enzyme for altered proteins in intact cells was explored by co-injecting Xenopus laevis oocytes with S-adenosyl-L-(methyl-3H)methionine and structurally altered calmodulins generated during a 14-day preincubation in vitro. Control experiments indicated that the oocyte protein carboxyl methyltransferase was not saturated with endogenous substrates, since protein carboxyl methylation rates could be stimulated up to 8-fold by increasing concentrations of injected calmodulin. The oocyte protein carboxyl methyltransferase showed strong selectivities for bovine brain and bacterially synthesized calmodulins which had been preincubated in the presence of 1 mM EDTA relative to calmodulins which had been preincubated with 1 mM CaCl2. Radioactive methyl groups were incorporated into base-stable linkages with recombinant calmodulin as well as into carboxyl methyl esters following its microinjection into oocytes. This base-stable radioactivity most likely represents the trimethylation of lysine 115, a highly conserved post-translational modification which is present in bovine and Xenopus but not in bacterially synthesized calmodulin. Endogenous oocyte calmodulin incorporates radioactivity into both carboxyl methyl esters and into base-stable linkages following microinjection of oocytes with S-adenosyl-(methyl-3H)methionine alone. The rate of oocyte calmodulin carboxyl methylation in injected oocytes is calculated to be similar to that of lysine 115 trimethylation, suggesting that the rate of calmodulin carboxyl methylation is similar to that of calmodulin synthesis. At steady state, oocyte calmodulin contains approximately 0.0002 esters/mol of protein, which turn over rapidly.

  8. Electrical conductivity of solutions of copper(II) nitrate crystalohydrate in dimethyl sulfoxide

    Science.gov (United States)

    Mamyrbekova, Aigul K.; Mamitova, A. D.; Mamyrbekova, Aizhan K.

    2016-06-01

    Conductometry is used to investigate the electric conductivity of Cu(NO3)2 ṡ 3H2O solutions in dimethyl sulfoxide in the 0.01-2.82 M range of concentrations and at temperatures of 288-318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu2+ and NO 3 - ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1-0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

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

    Directory of Open Access Journals (Sweden)

    Sato MR

    2017-03-01

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

  10. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Collado, Sergio; Laca, Adriana [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain); Diaz, Mario, E-mail: mariodiaz@uniovi.es [Department of Chemical Engineering and Environmental Technology, University of Oviedo, c/ Julian Claveria s/n, E-33071, Oviedo (Spain)

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10{sup 3} and 1.0 x 10{sup 4} kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu{sup 2+} to Cu{sup +} that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

  11. Biosorption of copper(II) by nonliving lichen biomass of Cladonia rangiformis hoffm

    Energy Technology Data Exchange (ETDEWEB)

    Ekmekyapar, Fatma [Engineering Faculty, Department of Environmental Engineering, Atatuerk University, Erzurum 25240 (Turkey)]. E-mail: fyapar@atauni.edu.tr; Aslan, Ali [Education Faculty, Department of Biology, Atatuerk University, Erzurum 25240 (Turkey); Bayhan, Y. Kemal [Engineering Faculty, Department of Environmental Engineering, Atatuerk University, Erzurum 25240 (Turkey); Cakici, Avni [Engineering Faculty, Department of Environmental Engineering, Atatuerk University, Erzurum 25240 (Turkey)

    2006-09-01

    Biosorption of heavy metals can be an effective process for the removal of heavy metal ions from aqueous solutions. In this study, the adsorption properties of lichen biomass of Cladonia rangiformis hoffm. for copper(II) were investigated by using batch adsorption techniques. The effects of initial metal ion concentration, initial pH, biosorbent concentration, stirring speed and contact time on biosorption efficiency were studied. In the experiments the optimum pH value was found out 5.0 which was the native pH value of solution. The experimental adsorption data were fitted to the Langmuir adsorption model. The highest metal uptake was calculated from Langmuir isotherm and found to be 7.6923 mg Cu(II)/g inactivated lichen at 15 deg. C. The results indicated that the biomass of C. rangiformis is a suitable biosorbent for removing Cu(II) from aqueous solutions.

  12. Voltammetric copper(II) determination with a montmorillonite-modified carbon paste electrode

    Energy Technology Data Exchange (ETDEWEB)

    Kula, P. [Institute of Geonics, Academy of Sciences of Czech Republic, Studertska 1768, 708 00 Ostrava (Czech Republic); Navratilova, Z. [Institute of Geonics, Academy of Sciences of Czech Republic, Studertska 1768, 708 00 Ostrava (Czech Republic)

    1996-03-01

    The clay mineral montmorillonite has been tested as modifier for the carbon paste electrode with a novel electrode modification technique. The differential pulse voltammetric determination of copper(II) by means of this modified carbon paste electrode has been studied. A detection limit of 4 x 10{sup -8} mol/l has been achieved after 10 min preconcentration under open circuit conditions with subsequent anodic stripping voltammetry. The calibration curve for Cu(II) is linear in the range of 4 x 10{sup -8}-8 x 10{sup -7} mol/l. Pb interferes in a 10-fold molar and Cd and Hg in a 100-fold molar excess. The interference by humic ligands is significant. (orig.). With 5 figs., 1 tab.

  13. Catalytic wet oxidation of thiocyanate with homogeneous copper(II) sulphate catalyst.

    Science.gov (United States)

    Collado, Sergio; Laca, Adriana; Díaz, Mario

    2010-05-15

    The wet oxidation of thiocyanate has been investigated in a semi-batch reactor at temperatures between 423 and 473 K and pressures between 6.1 x 10(3) and 1.0 x 10(4)kPa in the presence of copper(II) sulphate as catalyst. The effects of copper concentration, initial thiocyanate concentration, pressure and temperature on the reaction rate were analyzed and the main products of reaction were identified. A kinetic model for the Cu-catalyzed reaction is here proposed, including temperature, oxygen concentration, and the reduction of Cu(2+) to Cu(+) that gives an accurate prediction of the oxidation process under the assayed conditions. A mechanistic model based on the formation of a transition complex between a copper cation and two thiocyanate anions has been proposed for the catalytic wet oxidation.

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

    NARCIS (Netherlands)

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

    1995-01-01

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

  15. Carboxylic acid (bio)isosteres in drug design.

    Science.gov (United States)

    Ballatore, Carlo; Huryn, Donna M; Smith, Amos B

    2013-03-01

    The carboxylic acid functional group can be an important constituent of a pharmacophore, however, the presence of this moiety can also be responsible for significant drawbacks, including metabolic instability, toxicity, as well as limited passive diffusion across biological membranes. To avoid some of these shortcomings while retaining the desired attributes of the carboxylic acid moiety, medicinal chemists often investigate the use of carboxylic acid (bio)isosteres. The same type of strategy can also be effective for a variety other purposes, for example, to increase the selectivity of a biologically active compound or to create new intellectual property. Several carboxylic acid isosteres have been reported, however, the outcome of any isosteric replacement cannot be readily predicted as this strategy is generally found to be dependent upon the particular context (i.e., the characteristic properties of the drug and the drug-target). As a result, screening of a panel of isosteres is typically required. In this context, the discovery and development of novel carboxylic acid surrogates that could complement the existing palette of isosteres remains an important area of research. The goal of this Minireview is to provide an overview of the most commonly employed carboxylic acid (bio)isosteres and to present representative examples demonstrating the use and utility of each isostere in drug design.

  16. Effects of copper(II) and copper oxides on THMs formation in copper pipe.

    Science.gov (United States)

    Li, Bo; Qu, Jiuhui; Liu, Huijuan; Hu, Chengzhi

    2007-08-01

    Little is known about how the growth of trihalomethanes (THMs) in drinking water is affected in copper pipe. The formation of THMs and chlorine consumption in copper pipe under stagnant flow conditions were investigated. Experiments for the same water held in glass bottles were performed for comparison. Results showed that although THMs levels firstly increased in the presence of chlorine in copper pipe, faster decay of chlorine as compared to the glass bottle affected the rate of THMs formation. The analysis of water phase was supplemented by surface analysis of corrosion scales using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDX). The results showed the scales on the pipe surface mainly consisted of Cu(2)O, CuO and Cu(OH)(2) or CuCO(3). Designed experiments confirmed that the fast depletion of chlorine in copper pipe was mainly due to effect of Cu(2)O, CuO in corrosion scales on copper pipe. Although copper(II) and copper oxides showed effect on THMs formation, the rapid consumption of chlorine due to copper oxide made THM levels lower than that in glass bottles after 4h. The transformations of CF, DCBM and CDBM to BF were accelerated in the presence of copper(II), cupric oxide and cuprous oxide. The effect of pH on THMs formation was influenced by effect of pH on corrosion of copper pipe. When pH was below 7, THMs levels in copper pipe was higher as compared to glass bottle, but lower when pH was above 7.

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

    Science.gov (United States)

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

    2011-02-01

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

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

    Science.gov (United States)

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

    2014-01-01

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

  19. Stereocontrol in proline-catalyzed asymmetric amination: a comparative assessment of the role of enamine carboxylic acid and enamine carboxylate.

    Science.gov (United States)

    Sharma, Akhilesh K; Sunoj, Raghavan B

    2011-05-28

    The transition state models in two mechanistically distinct pathways, involving (i) an enamine carboxylic acid (path-A, 4) and (ii) an enamine carboxylate (path-B, 8), in the proline-catalyzed asymmetric α-amination have been examined using DFT methods. The path-A predicts the correct product stereochemistry under base-free conditions while path-B accounts for reversal of configuration in the presence of a base.

  20. Application of Sonication and Microwave Irradiation to Boost Continuous Fabrication of the Copper(II Oxide Sub-Micron Particles

    Directory of Open Access Journals (Sweden)

    Grzegorz Dzido

    2015-03-01

    Full Text Available Viability of the continuous-flow synthesis of rhomboidal copper(II oxide (CuO micro- and nanonoparticles was demonstrated. It has been shown that ultrasonic mixing of reactants, in the stage of Cu(OH2 synthesis, followed by microwave irradiation of the resulting suspension, gives very fine particles of CuO at high yield and within minutes. Near optimal parameters for the synthesis of fine particles in the continuous reactor were determined.

  1. Structures and Magnetic Properties of Monomeric Copper(II) Bromide Complexes with a Pyridine-Containing Tridentate Schiff Base

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Sung Kwon [Chungnam National Univ., Daejeon (Korea, Republic of); Yong, Soon Jung; Song, Young Kwang; Kim, Young Inn [Pusan National Univ., Busan (Korea, Republic of)

    2013-12-15

    Two novel copper(II) bromide complexes with pyridine containing Schiff base ligands, Cu(pmed)Br{sub 2} and Cu(dpmed)Br{sub 2} where pmed = N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (pmed) and dpmed = N,N-diethyl-N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (dpmed) were synthesized and characterized using Xray single crystal structure analysis, optical and magnetic susceptibility measurements. Crystal structural analysis of Cu(pmed)Br{sub 2} showed that the copper(II) ion has a distorted square-pyramidal geometry with the trigonality index of τ = 0.35 and two intermolecular hydrogen bonds, which result in the formation of two dimensional networks in the ab plane. On the other hand, Cu(dpmed)Br{sub 2} displayed a near square-pyramidal geometry with the value of τ = 0.06. In both compounds, the NNN Schiff base and one Br atom occupy the basal plane, whereas the fifth apical position is occupied by the other Br atom at a greater Cu-Br apical distance. The reported complexes show g{sub Π} > g{sub Τ} > 2.0023 with a d{sub x2-y2} ground state and a penta-coordinated square pyramidal geometry. Variable temperature magnetic susceptibility measurements showed that the developed copper(II) complexes follow the Curie-Weiss law, that is there are no magnetic interactions between the copper(II) ions since the Cu--Cu distance is too far for magnetic contact.

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

    Science.gov (United States)

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

    2017-02-01

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

  3. Flocculation of copper(II) and tetracycline from water using a novel pH- and temperature-responsive flocculants.

    Science.gov (United States)

    Yang, Zhen; Jia, Shuying; Zhuo, Ning; Yang, Weiben; Wang, Yuping

    2015-12-01

    Insufficient research is available on flocculation of combined pollutants of heavy metals and antibiotics, which widely exist in livestock wastewaters. Aiming at solving difficulties in flocculation of this sort of combined pollution, a novel pH- and temperature-responsive biomass-based flocculant, carboxymethyl chitosan-graft-poly(N-isoproyl acrylamide-co-diallyl dimethyl ammonium chloride) (denoted as CND) with two responsive switches [lower critical solution temperature (LCST) and isoelectric point (IEP)], was designed and synthesized. Its flocculation performance at different temperatures and pHs was evaluated using copper(II) and tetracycline (TC) as model contaminants. CND exhibited high efficiency for coremoval of both contaminants, whereas two commercial flocculants (polyaluminum chloride and polyacrylamide) did not. Especially, flocculation performance of the dual-responsive flocculant under conditions of temperature>LCST and IEP(contaminants)flocculation mechanism via pH monitoring, zeta potential measurements, floc properties analyses and spectral characterization indicated that, pairwise interactions among CND, copper(II) and TC were present in bridging flocculation, including charge attraction, coordination and hydrophobic effect. Based on these pairwise interactions, copper(II) and TC exerted "aid" roles to each other's removal with the existence of CND, and preferable flocculation performance was thus achieved.

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

    Science.gov (United States)

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

    2015-07-16

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

  5. Cloud point extraction and flame atomic absorption spectrometry combination for copper(II) ion in environmental and biological samples

    Energy Technology Data Exchange (ETDEWEB)

    Shokrollahi, Ardeshir [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of)], E-mail: ashokrollahi@mail.yu.ac.ir; Ghaedi, Mehrorang [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of)], E-mail: m_ghaedi@mail.yu.ac.ir; Hossaini, Omid; Khanjari, Narges [Chemistry Department, Yasouj University, Yasouj 75914-353 (Iran, Islamic Republic of); Soylak, Mustafa [Chemistry Department, University of Erciyes, 38039 Kayseri (Turkey)

    2008-12-30

    A cloud point extraction procedure was presented for the preconcentration of copper(II) ion in various samples. After complexation by 4-(phenyl diazenyl) benzene-1,3-diamine (PDBDM) (chrysoidine), copper(II) ions were quantitatively recovered in Triton X-114 after centrifugation. 0.5 ml of methanol acidified with 1.0 mol L{sup -1} HNO{sub 3} was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). The influence of analytical parameters including ligand, Triton X-114 and HNO{sub 3} concentrations, bath temperature, heating time, centrifuge rate and time were optimized. The effect of the matrix ions on the recovery of copper(II) ions was investigated. The detection limit (3S.D.{sub b}/m, n = 10) of 0.6 ng mL{sup -1} along with preconcentration factor of 30 and enrichment factor of 41.1 with R.S.D. of 1.0% for Cu was achieved. The proposed procedure was applied to the analysis of various environmental and biological samples.

  6. 3-Pyridylmethanol vs. N,N‧-diethylnicotinamide in copper(II) complex formation - A comparative EPR study

    Science.gov (United States)

    Husáriková, L.; Repická, Z.; Valigura, D.; Valko, M.; Mazúr, M.

    2013-10-01

    Copper(II) complexes, formed from 4-chlorosalicylic acid anion A (A = 4-Clsal-), different copper(II) salts (Cu(ac)2 or CuSO4) and different N-donor ligands B (B = 3-pyridylmethanol (ron) or N,N'-diethylnicotinamide (denia)) with varying N-donor ligand-to-metal ratio (x), were studied by EPR spectroscopy in the frozen water/methanol (1:3 v/v) solutions. The number of ligand B molecules coordinated to Cu(II) central ion was determined from the nitrogen perpendicular and parallel superhyperfine splitting multiplets of Cu(II) EPR spectra. It was found for both N-donor ligands: (i) At lower ligand B concentrations (x = 1, 2), [CuB] and/or [CuB2] species having one and/or two molecules of ligands B in equatorial position were dominant. The dominant ternary complex particles were [CuA2B2] species. (ii) At higher ligand B concentrations (x ⩾ 4) the formation of [CuB3] and/or [CuB4] species having three and/or four molecules of ligands B in equatorial position was confirmed. Such information is not possible to get from Cu(II) EPR spectra of powdered samples of given copper(II) complexes.

  7. Determination of copper(II) in the dairy product by an electrochemical sensor based on click chemistry.

    Science.gov (United States)

    Qiu, Suyan; Xie, Lidan; Gao, Sen; Liu, Qida; Lin, Zhenyu; Qiu, Bin; Chen, Guonan

    2011-11-30

    Herein, a novel sensitive electrochemical sensor for copper(II) based on Cu(I) catalyzed alkyne-azide cycloaddition reaction (CuAAC) is described. The catalyst of Cu(I) species is derived from electrochemical reduction of Cu(II) through bulk electrolysis (BE) with coulometry technique. The propargyl-functionalized ferrocene (propargyl-functionalized Fc) is covalently coupled onto the electrode surface via CuAAC reaction and forms propargyl-functionalized Fc modified gold electrode, which allows a good and stable electrochemical signal. The change of current at peak (dI), detected by differential pulse voltammetry (DPV), exhibits a linear response to the logarithm of Cu(II) concentration in the range of 1.0×10(-14)-1.0×10(-9) mol L(-1). It is also found that the proposed sensor has a good selectivity for copper(II) assay even in the presence of other common metal ions. Additionally, the proposed method has been applied to determine copper(II) in the dairy product (yoghurt) with satisfactory results.

  8. Selective esterification of non-conjugated carboxylic acids in the presence of conjugated or aromatic carboxylic acids over active carbon supported methanesulfonic acid

    Institute of Scientific and Technical Information of China (English)

    FENG ZeWang; ZHAO XinQi; BI Hua

    2008-01-01

    Non-conjugated carboxylic acids are selectively esterified in good yields in the presence of conjugated or aromatic carboxylic acids by stirring over active carbon supported methanesulfonic acid in dichloromethane at room temperature.

  9. Selective esterification of non-conjugated carboxylic acids in the presence of conjugated or aromatic carboxylic acids over active carbon supported methanesulfonic acid

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Non-conjugated carboxylic acids are selectively esterified in good yields in the presence of conjugated or aromatic carboxylic acids by stirring over active carbon supported methanesulfonic acid in di-chloromethane at room temperature.

  10. Kinetic and Thermodynamic Parameters for Uncatalyzed Esterification of Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Kehinde S. Bankole

    2014-06-01

    Full Text Available A fundamental study on uncatalyzed esterification of various biomass-derived aliphatic carboxylic acids with stoichiometric amount of ethanol has been investigated in an isothermal batch reactor, with the objective to convert carboxylic acids to corresponding ethyl esters and to determine both the kinetic and thermodynamic parameters. The effects of temperature on the conversion of carboxylic acid, kinetic and thermodynamic parameters have been investigated. Temperature was found to have significant effect on the rate of reaction and conversion of carboxylic acid. A simple second order reversible kinetic model was developed to determine the kinetic and thermodynamic parameters. The thermodynamic and kinetic parameters varied for uncatalyzed esterification reaction of both short-chain and long-chain carboxylic acids considered. The predicted data from the kinetic model were correlated with experimental data and the two sets of data agreed reasonably well for the uncatalyzed esterification systems. It was observed that the Van’t Hoff plot for uncatalyzed esterification of linoleic acid was non-linear curve, whereas for the Arrhenius and Eyring plots, they were linear. Additional experiments to assess the catalytic and corrosion effects of several metallic substances revealed Inconel 625 alloy, nickel wire and stainless steel materials were susceptible to corrosion problem with uncatalyzed esterification reaction at elevated reaction temperatures. However, tantalum and grade-5 titanium materials were corrosion resistance metals, suitable for similar reaction conditions and this can encourage the design of a flow reactor system. Although, uncatalyzed esterification of carboxylic acids at elevated reaction temperature is still at laboratory scale. It is our hope that the estimated kinetic and thermodynamic parameters would be the guiding tools for reactor scale-up, thus providing a new perspective into the conversion of biomass-derived carboxylic

  11. rac-4-Carbamoylpiperidinium cis-2-car-boxy-cyclo-hexane-1-carboxyl-ate.

    Science.gov (United States)

    Smith, Graham; Wermuth, Urs D

    2012-03-01

    In the title racemic salt, C(6)H(13)N(2)O(+)·C(8)H(11)O(4) (-), formed from the reaction of cis-cyclo-hexane-1,2-dicarb-oxy-lic anhydride with isonipecotamide, the cations are linked into duplex chain substructures through both centrosymmetric cyclic head-to-head 'amide motif' hydrogen-bonding associations [graph set R(2) (2)(8)] and 'side-by-side' R(2) (2)(14) associations. The anions are incorporated into the chains through cyclic R(4) (3)(10) inter-actions involving amide and piperidinium N-H⋯O(carbox-yl) hydrogen bonds which, together with inter-anion carb-oxy-lic acid O-H⋯O(carbox-yl) hydrogen bonds, give a two-dimensional layered structure extending along (011).

  12. The coordination structure of the extracted copper(II) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and n-hexyl 3-pyridinecarboxylate ester

    Science.gov (United States)

    Zhu, Shan; Hu, Huiping; Hu, Jiugang; Li, Jiyuan; Hu, Fang; Wang, Yongxi

    2017-09-01

    In continuation of our interest in the coordination structure of the nickel(II) complex with dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC), it was observed that the coordination sphere was completed by the coordination of two N atoms of pyridine rings in ligands 4PC and four water molecules while no direct interaction between Ni(II) and deprotonated HDNNS was observed. To investigate whether the coordination structure of nickel(II) with the synergistic mixture containing HDNNS and 4PC predominates or not in the copper(II) complex with the synergistic mixtures containing HDNNS and pyridinecarboxylate esters, a copper(II) synergist complex with n-hexyl 3-pyridinecarboxylate ester (L) and naphthalene-2-sulfonic acid (HNS, the short chain analogue of HDNNS), was prepared and studied by X-ray single crystal diffraction, elemental analyses and thermo gravimetric analysis (TGA), respectively. It was shown that the composition of the copper(II) synergist complex was [Cu(H2O)2(L)2(NS)2] and formed a trans-form distorted octahedral coordination structure. Two oxygen atoms of the two coordinated water molecules and two N atoms of the pyridine rings in the ligands L defined the basal plane while two O atoms from two sulfonate anions of the deprotonated HNS ligands occupied the apical positions by direct coordination with Cu(II), which was distinguished from the coordination structure of the nickel(II) synergist complex as reported in our previous work. In the crystal lattice, neighboring molecules [Cu(H2O)2L2(NS)2] were linked through the intermolecular hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the sulfonate anions in the copper(II) synergist complex to form a 2D plane. In order to bridge the gap between the solid state structure of the copper(II) synergist complex and the solution structure of the extracted copper(II) complex with the actual synergistic mixture containing

  13. Interaction with DNA and different effect on the nucleus of cancer cells for copper(II) complexes of N-benzyl di(pyridylmethyl)amine.

    Science.gov (United States)

    Chen, Qiu-Yun; Fu, Hai-Jian; Zhu, Wei-Hua; Qi, Yan; Ma, Zheng-Ping; Zhao, Kai-Di; Gao, Jing

    2011-05-01

    Three new copper(II) complexes of N-benzyl di(pyridylmethyl)amine (phdpa) were synthesized and characterized by spectroscopic methods. The interaction between CT-DNA and the complexes was studied by UV and fluorescence titration methods. It was found that the complex [(phdpa)Cu(H(2)O)Ac)](Ac), with the non-planar aromatic heterocyclic ring ligand (phdpa), showed good anticancer properties and could cause the fragmentation of the nucleus, although its interaction with CT-DNA was weaker than that of 1,10-phenanthroline (phen)-based copper(II) complexes. The anticancer activities of copper(II) complexes with phdpa and phen based ligands are correlated to their binding constants with DNA, but phen-based copper(II) complexes did not cause the nucleus fragmentation of HeLa cells. [(phdpa)Cu(H(2)O)Ac)](Ac) can noticeably decrease the oxygen content of a culture solution and of HeLa cells, which make it a new nucleus and oxygen related anticancer copper(II) complex. Information obtained here would be helpful in the design of new antitumor complexes in oxidative therapy.

  14. RAGE, carboxylated glycans and S100A8/A9 play essential roles in colitis-associated carcinogenesis.

    Science.gov (United States)

    Turovskaya, Olga; Foell, Dirk; Sinha, Pratima; Vogl, Thomas; Newlin, Robbin; Nayak, Jonamani; Nguyen, Mien; Olsson, Anna; Nawroth, Peter P; Bierhaus, Angelika; Varki, Nissi; Kronenberg, Mitchell; Freeze, Hudson H; Srikrishna, Geetha

    2008-10-01

    Patients with inflammatory bowel diseases are at increased risk for colorectal cancer, but the molecular mechanisms linking inflammation and cancer are not well defined. We earlier showed that carboxylated N-glycans expressed on receptor for advanced glycation end products (RAGE) and other glycoproteins mediate colitis through activation of nuclear factor kappa B (NF-kappaB). Because NF-kappaB signaling plays a critical role in the molecular pathogenesis of colitis-associated cancer (CAC), we reasoned that carboxylated glycans, RAGE and its ligands might promote CAC. Carboxylated glycans are expressed on a subpopulation of RAGE on colon cancer cells and mediate S100A8/A9 binding to RAGE. Colon tumor cells express binding sites for S100A8/A9 and binding leads to activation of NF-kappaB and tumor cell proliferation. Binding, downstream signaling and tumor cell proliferation are blocked by mAbGB3.1, an anti-carboxylate glycan antibody, and by anti-RAGE. In human colon tumor tissues and in a mouse model of CAC, we found that myeloid progenitors expressing S100A8 and S100A9 infiltrate regions of dysplasia and adenoma. mAbGB3.1 administration markedly reduces chronic inflammation and tumorigenesis in the mouse model of CAC and RAGE-deficient mice are resistant to the onset of CAC. These findings show that RAGE, carboxylated glycans and S100A8/A9 play essential roles in tumor-stromal interactions, leading to inflammation-associated colon carcinogenesis.

  15. Novel Polymers with a High Carboxylic Acid Loading

    DEFF Research Database (Denmark)

    Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

    2006-01-01

    ABSTRACT: Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4......-hydroxybenzene, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conucted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly (4-hydroxystyrene...... investigations of ali the polymers in general exhibit [when poly(4-hydroxystyrene) is a subetantial parti significant changes in the glass-transition temperature from the polar poly(4-hydroxystyr- ene) (120—130 “C) to the much less polar alkyne polymers (46—60 DC). A direct correlation between the nature...

  16. Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

    Science.gov (United States)

    Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

    2015-01-01

    N-hydroxysuccinimide (NHS) esters have been used for gas-phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ɛ-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas phase, where they are shown to be reactive, and the solution phase, where they are not regarded as reactive with NHS esters.

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

    Science.gov (United States)

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

    2017-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Sandipan Sarkar

    2014-12-01

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

  19. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying [ETH Zurich, Institute of Environmental Engineering (Switzerland); Kim, Nayoung [EMPA, Building Energy Materials and Components (Switzerland); Wang, Jing, E-mail: jing.wang@ifu.baug.ethz.ch [ETH Zurich, Institute of Environmental Engineering (Switzerland)

    2015-10-15

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH{sub 3}CO{sub 2}NH{sub 4}) and sodium acetate (CH{sub 3}CO{sub 2}Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example.

  20. Biotin Carboxyl Carrier Protein in Barley Chloroplast Membranes

    DEFF Research Database (Denmark)

    Kannangara, C. G.; Jense, C J

    1975-01-01

    Biotin localized in barley chloroplast lamellae is covalently bound to a single protein with an approximate molecular weight of 21000. It contains one mole of biotin per mole of protein and functions as a carboxyl carrier in the acetyl-CoA carboxylase reaction. The protein was obtained by solubil......Biotin localized in barley chloroplast lamellae is covalently bound to a single protein with an approximate molecular weight of 21000. It contains one mole of biotin per mole of protein and functions as a carboxyl carrier in the acetyl-CoA carboxylase reaction. The protein was obtained...

  1. Silver-Catalyzed Decarboxylative Azidation of Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Zhu, Yuchao; Li, Xinyao; Wang, Xiaoyang; Huang, Xiaoqiang; Shen, Tao; Zhang, Yiqun; Sun, Xiang; Zou, Miancheng; Song, Song; Jiao, Ning

    2015-10-02

    The catalytic decarboxylative nitrogenation of aliphatic carboxylic acids for the synthesis of alkyl azides is reported. A series of tertiary, secondary, and primary organoazides were prepared from easily available aliphatic carboxylic acids by using K2S2O8 as the oxidant and PhSO2N3 as the nitrogen source. The EPR experiment sufficiently proved that an alkyl radical process was generated in the process, and DFT calculations further supported the SET process followed by a stepwise SH2 reaction to afford azide product.

  2. Guanine-containing copper(II) complexes: synthesis, X-ray structures and magnetic properties.

    Science.gov (United States)

    Mastropietro, Teresa F; Armentano, Donatella; Grisolia, Ettore; Zanchini, Claudia; Lloret, Francesc; Julve, Miguel; De Munno, Giovanni

    2008-01-28

    Three new compounds of formula {[Cu(gua)(H(2)O)(3)](BF(4))(SiF(6))(1/2)}(n) (1), {[Cu(gua)(H(2)O)(3)](CF(3)SO(3))(2).H(2)O}(n) (2) and [Cu(gua)(2)(H(2)O)(HCOO)]ClO(4).H(2)O.1/2HCOOH] (3) [gua = 2-amino-1H-purin-6(9H)-one] showing the unprecedented coordination of neutral guanine, have been synthesised and structurally characterized. The structures of the compounds 1 and 2 contain uniform copper(II) chains of formula [Cu(gua)(H(2)O)(3)](n)(2n+), where the copper atoms are bridged by guanine ligands coordinated via N(3) and N(7). The electroneutrality is achieved by uncoordinated tetrafluoroborate and hexafluorosilicate (1) and triflate (2). Each copper atom in 1 and 2 is five-coordinated in a distorted square pyramidal environment: two water molecules in trans positions and the N(3) and N(7a) nitrogen atoms of two guanine ligands build the basal plane whereas a water molecule fills the axial position. The values of the copper-copper separation across the bridging guanine ligand are 7.183(1) (1) and 7.123(1) A (2). is an ionic salt whose structure is made up of mononuclear [Cu(gua)(2)(H(2)O)(HCOO)](+) cations and perchlorate anions plus water and formic acid as crystallization molecules. The two guanine ligands in the cation are coordinated to the copper centre through the N(9) atom. The copper atom in 3 is four-coordinated with two monodentate guanine molecules in the trans position, a water molecule and a monodenate formate ligand building a quasi square planar surrounding. Magnetic susceptibility measurements for 1 and 2 in the temperature range 1.9-300 K show the occurrence of significant intrachain antiferromagnetic interactions between the copper(ii) ions across the guanine bridge [J = -9.6(1) (1) and -10.3(1) cm(-1) (2) with H = -J summation operator(i)S(i).S(i+1)].

  3. Mixed-ligand binuclear copper(II) complex of 5-methylsalicylaldehyde and 2,2'-bipyridyl: Synthesis, crystal structure, DNA binding and nuclease activity

    Indian Academy of Sciences (India)

    Perumal Gurumoorthy; Jayaram Ravichandran; Aziz Kalilur Rahiman

    2014-05-01

    A new mixed-ligand binuclear copper(II) complex [Cu(MS)(bpy)]2.(ClO4)2, built of 5-methylsalicylaldehyde and 2,2'-bipyridyl has been synthesized and characterized by using elemental analysis, IR and UV-Vis spectroscopy. Crystal structure of the complex shows that copper(II) ion lies in a square pyramidal coordination environment. The structure consists of two symmetrical half units in which the copper(II) ion of one half unit connected with the phenolate oxygen atom of other half unit along with one perchlorate anion in the crystal lattice as free molecule. Presence of uncoordinated perchlorate anion was also confirmed by IR spectroscopy. Absorption spectroscopy exhibits d-d transition at 628 nm, which further supports the square pyramidal geometry around the copper(II) ions. EPR spectrum of the copper(II) complex at room temperature shows a broad signal without any splitting pattern at ∥ = 2.26, ⊥ = 2.03 and the magnetic moment (eff = 1.31 BM) obtained at room temperature indicate an antiferromagnetic interaction between the two copper(II) ions through phenoxide-bridge. Binding studies reveal that the complex possesses good binding propensity (b = 5.2 ± 1.7 × 104 M-1) and bind to nitrogenous bases of DNA through intercalation. Nuclease activity of the complex with pBR322 DNA shows that the effect of hydrolytic cleavage is dose-dependent and the oxidative cleavage indicates the involvement of hydroxyl radical and singlet-oxygen as reactive oxygen species.

  4. N,N,O and N,O,N Meridional cis Coordination of Two Guanines to Copper(II) by d(CGCGCG)2.

    Science.gov (United States)

    Rohner, Melanie; Medina-Molner, Alfredo; Spingler, Bernhard

    2016-06-20

    Many research groups study the generation of supramolecular n-dimensional arrays by combining metals with DNA building blocks. Most of the time, the natural nucleobases are modified to obtain higher-affinity metal binding sites. Using unmodified nucleobases avoids a potentially difficult synthesis; however, they have the possible disadvantage of a less defined and/or weaker coordination mode of the metal. Structural studies on the behavior of copper(II) as a linking metal and guanine as the natural ligand for metals in unmodified DNA are reported. Previously, the ability of mono- and dinuclear metal complexes to induce Z-DNA has been explored [Medina-Molner, A.; Spingler, B. Chem. Commun. 2012, 48, 1961; Medina-Molner, A.; Rohner, M.; Pandiarajan, D.; Spingler, B. Dalton Trans. 2015, 44, 3664]. Herein, X-ray crystallographic studies of the structures resulting from the combination of copper(II) ions with DNA hexamers of the general sequence d(CG)3 are presented. Three different packing motifs were observed in three crystal structures with resolutions ranging from 2.15 to 1.45 Å. The motifs are dependent upon other cations being present and/or the crystallization conditions. The first examples of intramolecular O6,N7-chelates of a neutral purine nucleobase to copper(II) were obtained as well as the first meridional N,N,O and N,O,N coordination modes of two guanines to copper(II). The fascinating coordination chemistry of copper(II) complexes generated by the Z-DNA oligonucleotides and the differences to simple nucleobases complexes with copper(II) are discussed in detail.

  5. Antimicrobial Activity and Urease Inhibition of Schiff Bases Derived from Isoniazid and Fluorinated Benzaldehydes and of Their Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Ladislav Habala

    2016-12-01

    Full Text Available In order to evaluate the influence of substitution on biological properties of Schiff bases and their metal complexes, a series of differently substituted fluorine-containing Schiff bases starting from the drug isoniazid (isonicotinylhydrazide were prepared and their structures were established by single-crystal X-ray diffraction. Also, four copper(II complexes of these Schiff bases were synthesized. The prepared compounds were evaluated for their antimicrobial activity and urease inhibition. Two of the Schiff bases exerted activity against C. albicans. All copper(II complexes showed excellent inhibitory properties against jack bean urease, considerably better than that of the standard inhibitor acetohydroxamic acid.

  6. Antimicrobial Activity and Urease Inhibition of Schiff Bases Derived from Isoniazid and Fluorinated Benzaldehydes and of Their Copper(II) Complexes.

    Science.gov (United States)

    Habala, Ladislav; Varényi, Samuel; Bilková, Andrea; Herich, Peter; Valentová, Jindra; Kožíšek, Jozef; Devínsky, Ferdinand

    2016-12-17

    In order to evaluate the influence of substitution on biological properties of Schiff bases and their metal complexes, a series of differently substituted fluorine-containing Schiff bases starting from the drug isoniazid (isonicotinylhydrazide) were prepared and their structures were established by single-crystal X-ray diffraction. Also, four copper(II) complexes of these Schiff bases were synthesized. The prepared compounds were evaluated for their antimicrobial activity and urease inhibition. Two of the Schiff bases exerted activity against C. albicans. All copper(II) complexes showed excellent inhibitory properties against jack bean urease, considerably better than that of the standard inhibitor acetohydroxamic acid.

  7. Solvent effects on the stability of nifuroxazide complexes with cobalt(II), nickel(II) and copper(II) in alcohols.

    Science.gov (United States)

    Khan, Mustayeen A; Ali, S Kauser; Bouet, Gilles M

    2002-05-21

    A spectrophotometric study of the complexation of nifuroxazide with cobalt(II), nickel(II) and copper(II) was carried out in different alcohols. The formation of a complex in each case is reported and their stability constants have been calculated. For a given solvent, the stability of the complexes increases from cobalt to copper. In the case of copper(II), the stability varies as an inverse function of the dielectric constant of the solvent. A possible structure of the complex is proposed.

  8. Thermodynamics of the formation of complexes of copper(II) ions and glycylglycine in aqueous solutions at 298 K according to calorimetry data

    Science.gov (United States)

    Kochergina, L. A.; Emel'yanov, A. V.

    2015-04-01

    Heat effects of the interaction between glycylglycine and copper(II) nitrate solutions are measured by direct calorimetry at a [metal] : [ligand] ratio of 1 : 5 and at different pH values of the solution. The measurements are made at a temperature of 298.15 K and ionic strengths of 0.25, 0.50, and 0.75. KNO3 is used as a background electrolyte. The thermodynamic characteristics of complex formation by the peptide and copper(II) ions in aqueous solutions are determined. Standard enthalpies of the formation of complex particles in aqueous solutions are calculated.

  9. Mono-, di- and polynuclear copper(II) compounds derived from N-butyldiethanolamine: structural features, magnetism and catalytic activity for the mild peroxidative oxidation of cyclohexane.

    Science.gov (United States)

    Gruenwald, Katrin R; Kirillov, Alexander M; Haukka, Matti; Sanchiz, Joaquin; Pombeiro, Armando J L

    2009-03-28

    The new mononuclear [Cu(Hbdea)(2)].2Hdnba (), dinuclear [Cu(2)(mu-Hbdea)(2)(N(3))(2)] () and [Cu(2)(mu-Hbdea)(2)(pta)(2)].2H(2)O (), and 1D polymeric [Cu(2)(mu-Hbdea)(2)(mu-tpa)](n).2nH(2)O () copper(II) compounds have been prepared by self-assembly, in aqueous alkali medium and at ambient conditions, from Cu(II) acetate, N-butyldiethanolamine (H(2)bdea) and the corresponding auxiliary reagents, 3,5-dinitrobenzoic acid (Hdnba), sodium azide, p-toluic acid (Hpta) and terephthalic acid (H(2)tpa), respectively. They have been fully characterized by IR spectroscopy, FAB-MS(+), elemental and single-crystal X-ray diffraction analyses, the latter also revealing intensive intermolecular hydrogen bonding in , resulting in the extension of the structural motifs and generation of tetrameric aggregates (in ) and 1D (in ) or 2D (in ) supramolecular networks. All compounds constitute the first examples of Cu complexes derived from N-butyldiethanolamine, while represents also the first coordination polymer bearing this ligand. Magnetic susceptibility measurements reveal that compound follows the Curie-Weiss law, whereas follow the Bleaney-Bowers dinuclear model displaying antiferromagnetic coupling. Compounds act as valuable catalyst precursors for the mild peroxidative oxidation of cyclohexane, by aqueous H(2)O(2) in acidic MeCN medium, to cyclohexanol and cyclohexanone with overall yields up to 38%. The effects of various acid additives (promoters) have been studied, showing the preferable use of trifluoroacetic (TFA), nitric and hydrochloric acids.

  10. Synthesis, Crystal and Molecular Structure Studies and DFT Calculations of Phenyl Quinoline-2-Carboxylate and 2-Methoxyphenyl Quinoline-2-Carboxylate; Two New Quinoline-2 Carboxylic Derivatives

    Directory of Open Access Journals (Sweden)

    Edakot Fazal

    2015-02-01

    Full Text Available The crystal and molecular structures of the title compounds, phenyl quinoline-2-carboxylate and 2-methoxyphenyl quinoline-2-carboxylate, two new derivatives of quinolone-2-carboxylic acid, are reported and confirmed by single crystal X-ray diffraction and spectroscopic data. Compound (I, C16H11NO2, crystallizes in the monoclinic space group P21/c, with 8 molecules in the unit cell. The unit cell parameters are a = 14.7910(3 Å; b = 5.76446(12 Å; c = 28.4012(6 Å; β = 99.043(2°; V = 2391.45(9 Å3. Compound (II, C17H13NO5, crystallizes in the monoclinic space group P21/n with 4 molecules in the unit cell. The unit cell parameters are a = 9.6095(3 Å; b = 10.8040(3 Å; c = 13.2427(4 Å; β = 102.012(3°; V = 1344.76(7 Å3. Density functional theory (DFT geometry optimized molecular orbital calculations were performed and frontier molecular orbitals of each compound are displayed. Correlation between the calculated molecular orbital energies (eV for the surfaces of the frontier molecular orbitals to the electronic excitation transitions from the absorption spectra of each compound has been proposed. Additionally, similar correlations observed among six closely related compounds examining small structural differences to their frontier molecular orbital surfaces and from their DFT molecular orbital energies, provide further support for the suggested assignments of the title compounds.

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

    Science.gov (United States)

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

    2013-11-01

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

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

    Indian Academy of Sciences (India)

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

    2016-05-01

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

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

    Science.gov (United States)

    Tarlani, Aliakbar; Narimani, Khashayar; Mohammadipanah, Fatemeh; Hamedi, Javad; Tahermansouri, Hasan; Amini, Mostafa M.

    2015-06-01

    In a new approach, a copper(II) tetraaza macrocyclic complex (CuTAM) was covalently bonded on modified multi-walled carbon nanotubes (MWCNTs). To achieve this purpose, MWCNTs were converted to MWCNT-COCl and then reacted to NH groups of TAM ligand. The prepared material was characterized by Fourier Transform Infrared (FT-IR), X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), and FESEM (field emission scanning electron microscopy). FT-IR and TGA demonstrated the presence of the organic moieties, and XRD proved that the structure of MWCNTs remained intact during the three modification steps. An increase in the ID/IG ratio in Raman spectra confirmed the surface modifications. Finally, the samples were subjected to an antibacterial assessment to compare their biological activity. The antibacterial test showed that the grafted complex on the surface of the nanotube (MWCNT-CO-CuTAM) has higher antibacterial activity against Bacillus subtilis ATCC 6633 than the MWCNT-COOH and CuTAM with 1000 and 2000 μg/mL.

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

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Fazilati, Hakimeh

    2012-01-01

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

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

    Science.gov (United States)

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

    2014-02-21

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

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

    Directory of Open Access Journals (Sweden)

    Hamid Golchoubian

    2013-01-01

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

  17. Biosorption of copper(II) and cobalt(II) from aqueous solutions by crab shell particles.

    Science.gov (United States)

    Vijayaraghavan, K; Palanivelu, K; Velan, M

    2006-08-01

    Biosorption of each of the heavy metals, copper(II) and cobalt(II) by crab shell was investigated in this study. The biosorption capacities of crab shell for copper and cobalt were studied at different particle sizes (0.456-1.117 mm), biosorbent dosages (1-10 g/l), initial metal concentrations (500-2000 mg/l) and solution pH values (3.5-6) in batch mode. At optimum particle size (0.767 mm), biosorbent dosage (5 g/l) and initial solution pH (pH 6); crab shell recorded maximum copper and cobalt uptakes of 243.9 and 322.6 mg/g, respectively, according to Langmuir model. The kinetic data obtained at different initial metal concentrations indicated that biosorption rate was fast and most of the process was completed within 2h, followed by slow attainment of equilibrium. Pseudo-second order model fitted the data well with very high correlation coefficients (>0.998). The presence of light and heavy metal ions influenced the copper and cobalt uptake potential of crab shell. Among several eluting agents, EDTA (pH 3.5, in HCl) performed well and also caused low biosorbent damage. The biosorbent was successfully regenerated and reused for five cycles.

  18. A kinetic study of copper(II) oxide powder reduction with hydrogen, based on thermogravimetry

    Energy Technology Data Exchange (ETDEWEB)

    Jelic, Dijana [Faculty of Medicine, Departmet of Pharmacy - Chair of Physical Chemistry, University of Banja Luka, Banja Luka, Bosnia and Herzegovina (Bosnia and Herzegowina); Tomic-Tucakovic, Biljana [Institute of General and Physical Chemistry, Studentski trg 12, 11158 Belgrade (Serbia); Mentus, Slavko, E-mail: slavko@ffh.bg.ac.rs [University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12, 11185 Belgrade (Serbia)

    2011-07-10

    Highlights: {yields} The reduction of CuO by hydrogen was studied by thermogravimetry. {yields} The particle size of the samples varied inside the submicron range. {yields} The experimental data were fitted by means of a nucleation-growth model. {yields} The particle size influenced the kinetic parameters but not the reaction model. - Abstract: The reduction of powdery copper(II) oxide was carried out in a stream of gaseous mixture 25% H{sub 2} + Ar, and followed by thermogravimetry. The two samples of different history were studied: the commercial one, and that synthesized by citrate gel combustion method. The characterization of the starting materials, based on X-ray diffractometry and scanning electron microscopy, indicated equal crystal structure, but different particle size and morphology. The particle size and shape of the metallic particles obtained upon the reduction were observed by means of electron microscope. By a nonlinear regression analysis by means of a software Kinetics05, the experimental data were fitted with the nucleation-growth kinetic model, and the corresponding kinetic parameters were determined.

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

    Science.gov (United States)

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

    2015-07-01

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

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

    Indian Academy of Sciences (India)

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

    2016-02-01

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

  1. New masking procedure for selective complexometric determination of copper(II).

    Science.gov (United States)

    Singh, R P

    1972-11-01

    A study has been made of a new masking procedure for highly selective complexometric determination of copper(II), based on decomposition of the copper-EDTA complex at pH 5-6. Among the various combinations of masking agents tried, ternary masking mixtures comprising a main complexing agent (thiourea), a reducing agent (ascorbic acid) and an auxiliary complexing agent (thiosemicarbazide or a small amount of 1,10-phenanthroline or 2,2'-dipyridyl) have been found most suitable. An excess of EDTA is added and the surplus EDTA is back-titrated with lead (or zinc) nitrate with Xylenol Orange as indicator (pH 5-6). A masking mixture is then added to decompose the copper-EDTA complex and the liberated EDTA is again back-titrated with lead (or zinc) nitrate. The following cations do not interfere: Ag(+), Hg(2+), Pb(2+), Ni(2+), Bi(3+), As(3+), Al(3+), Sb(3+), Sn(4+), Cd(2+), Co(2+), Cr(3+) and moderate amounts of Fe(3+) and Mn(2+). The notable feature is that consecutive determination of Hg(2+) and Cu(2+) can be conveniently carried out in the presence of other cations.

  2. Amine nitrosation via NO reduction of the polyamine copper(II) complex Cu(DAC)2+.

    Science.gov (United States)

    Khin, Chosu; Lim, Mark D; Tsuge, Kiyoshi; Iretskii, Alexei; Wu, Guang; Ford, Peter C

    2007-10-29

    The reaction of the fluorescent macrocyclic ligand 1,8-bis(anthracen-9-ylmethyl)-1,4,8,11-tetraazacyclotetradecane with copper(II) salts leads to formation of the Cu(DAC)2+ cation (I), which is not luminescent. However, when aqueous methanol solutions of I are allowed to react with NO, fluorescence again develops, owing to the formation of the strongly luminescent N-nitrosated ligand DAC-NO (II), which is released from the copper center. This reaction is relatively slow in neutral media, and kinetics studies show it to be first order in the concentrations of NO and base. In these contexts, it is proposed that the amine nitrosation occurs via NO attack at a coordinated amine that has been deprotonated and that this step occurs with concomitant reduction of the Cu(II) to Cu(I). DFT computations at the BP/LACVP* level support these mechanistic arguments. It is further proposed that such nitrosation of electron-rich ligands coordinated to redox-active metal centers is a mechanistic pathway that may find greater generality in the biochemical formation of nitrosothiols and nitrosoamines.

  3. Electrochemical Studies of Betti Base and Its Copper(II Complex by Cyclic and Elimination Voltammetry

    Directory of Open Access Journals (Sweden)

    Shardul Bhatt

    2013-01-01

    Full Text Available The electrochemical behavior of Betti base 1-(α-amino benzyl-2-naphthol (BB and its copper(II complex by cyclic and elimination voltammetry (EVLS is reported in the present study. The cyclic voltammetric studies carried out at a glassy carbon working electrode, Ag/Ag+ reference electrode (0.01 M AgNO3 in acetonitrile in DCM at 100 mV/sec, 200 mV/sec, and 400 mV/sec scan rates indicated a preceding chemical oxidation of the adsorbed BB species to form an iminium ion followed by formation of a carbanion via two-step quasireversible reduction. The suggested reaction mechanism has been supported by the elimination voltammetry. The CV and EVLS studies revealed Cu(IIBB complex to undergo a chemical or a surface reaction before electron transfer from the electrode at −0.49 V to form Cu(IBB species. The oxidation of Cu(IBB species has been observed to be CV silent.

  4. Improvement of ruthenium based decarboxylation of carboxylic acids

    Science.gov (United States)

    The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

  5. Dissolving Carboxylic Acids and Primary Amines on the Overhead Projector

    Science.gov (United States)

    Solomon, Sally D.; Rutkowsky, Susan A.

    2010-01-01

    Liquid carboxylic acids (or primary amines) with limited solubility in water are dissolved by addition of aqueous sodium hydroxide (or hydrochloric acid) on the stage of an overhead projector using simple glassware and very small quantities of chemicals. This effective and colorful demonstration can be used to accompany discussions of the…

  6. Carboxylic Acids Plasma Membrane Transporters in Saccharomyces cerevisiae.

    Science.gov (United States)

    Casal, Margarida; Queirós, Odília; Talaia, Gabriel; Ribas, David; Paiva, Sandra

    2016-01-01

    This chapter covers the functionally characterized plasma membrane carboxylic acids transporters Jen1, Ady2, Fps1 and Pdr12 in the yeast Saccharomyces cerevisiae, addressing also their homologues in other microorganisms, as filamentous fungi and bacteria. Carboxylic acids can either be transported into the cells, to be used as nutrients, or extruded in response to acid stress conditions. The secondary active transporters Jen1 and Ady2 can mediate the uptake of the anionic form of these substrates by a H(+)-symport mechanism. The undissociated form of carboxylic acids is lipid-soluble, crossing the plasma membrane by simple diffusion. Furthermore, acetic acid can also be transported by facilitated diffusion via Fps1 channel. At the cytoplasmic physiological pH, the anionic form of the acid prevails and it can be exported by the Pdr12 pump. This review will highlight the mechanisms involving carboxylic acids transporters, and the way they operate according to the yeast cell response to environmental changes, as carbon source availability, extracellular pH and acid stress conditions.

  7. Light dependence of carboxylation capacity for C3 photosynthesis models

    Science.gov (United States)

    Photosynthesis at high light is often modelled by assuming limitation by the maximum capacity of Rubisco carboxylation at low carbon dioxide concentrations, by electron transport capacity at higher concentrations, and sometimes by triose-phosphate utilization rate at the highest concentrations. Pho...

  8. Palladium-Catalyzed Carboxylation of Activated Vinylcyclopropanes with CO2.

    Science.gov (United States)

    Mita, Tsuyoshi; Tanaka, Hiroyuki; Higuchi, Yuki; Sato, Yoshihiro

    2016-06-01

    By using a palladium catalyst with ZnEt2, activated vinylcyclopropanes were successfully converted into the corresponding β,γ-unsaturated carboxylic acids in high yields under a CO2 atmosphere (1 atm). The intermediate in this reaction is thought to be a nucleophilic η(1)-allylethylpalladium species, which would be produced from π-allylpalladium and ZnEt2 (umpolung reactivity).

  9. Dimerization of Carboxylic Acids: An Equation of State Approach

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios; Panayiotou, Costas

    2017-01-01

    . Consequently, the observed endothermic dissolution process is mainly attributed to the hindering of polar interactions. Furthermore, upon mixing of two carboxylic acids, the rearrangement of hydrogen bonds due to the formation of cross associating species results in an insignificant contribution to the heats...

  10. Cyclodextrin derivatives with cyanohydrin and carboxylate groups as artificial glycosidases

    DEFF Research Database (Denmark)

    Bols, Mikael; Ortega-Caballero, Fernando

    2006-01-01

    Two cyclodextrin derivatives (1 and 2) were prepared in an attempt to create glycosidase mimics with a general acid catalyst and a nucleophilic carboxylate group. The catalysts 1 and 2 were found to catalyse the hydrolysis of 4-nitrophenyl beta-D-glucopyranoside at pH 8.0, but rapidly underwent...

  11. 21 CFR 177.1600 - Polyethylene resins, carboxyl modified.

    Science.gov (United States)

    2010-04-01

    ... (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as... resins used in food-packaging adhesives complying with § 175.105 of this chapter. ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyethylene resins, carboxyl modified....

  12. Synthon preferences in cocrystals of cis-carboxamides:carboxylic acids

    NARCIS (Netherlands)

    Moragues-Bartolome, A.M.; Jones, W.; Cruz-Cabeza, A.J.

    2012-01-01

    We study synthon preferences in cocrystals of cis-carboxamides with carboxylic acids using a combination of database analyses, cocrystallisation experiments and theoretical calculations. We classify the cis-carboxamides into three families: primary amides, cyclic amides (lactams) and cyclic imides.

  13. Novel Lactate Transporters from Carboxylic Acid-Producing Rhizopus

    Science.gov (United States)

    The fungus Rhizopus is frequently used for fermentative production of lactic acid, but little is known about the mechanisms or proteins for transporting this carboxylic acid. Since transport of the lactate anion across the plasma membrane is critical to prevent acidification of the cytoplasm, we ev...

  14. Carboxylate shifts steer interquinone electron transfer in photosynthesis.

    Science.gov (United States)

    Chernev, Petko; Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2011-02-18

    Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolution x-ray absorption spectroscopy after laser-flash excitation of PSII. After formation of the reduced primary quinone, Q(A)(-), the x-ray spectral changes revealed a transition (t½ ≈ 150 μs) from a bidentate to a monodentate coordination of the bicarbonate at the Fe(II) (carboxylate shift), which reverted concomitantly with the slower ET to the secondary quinone Q(B). A redox change of the iron during the ET was excluded. Density-functional theory calculations corroborated the carboxylate shift both in PSII and bacterial RCs and disclosed underlying changes in electronic configuration. We propose that the iron-carboxyl complex facilitates the first interquinone ET by optimizing charge distribution and hydrogen bonding within the Q(A)FeQ(B) triad for high yield Q(B) reduction. Formation of a specific priming intermediate by nuclear rearrangements, setting the stage for subsequent ET, may be a common motif in reactions of biological redox cofactors.

  15. Conformation of some carboxylic acids and their derivatives

    NARCIS (Netherlands)

    Kanters, J.A.; Kroon, Jan; Peerdeman, A.F.; Schoone, J.C.

    1967-01-01

    The conformation in the crystalline state of some aliphatic carboxylic acids and their derivatives has been analysed. This analysis, based upon the results of structure determinations by means of X-ray diffraction, seems to support the concept that the conformation of a molecule is governed chiefly

  16. Wind tunnel investigations on the retention of carboxylic acids during riming

    Science.gov (United States)

    Jost, Alexander; Szakáll, Miklós; Diehl, Karoline; Mitra, Subir K.; Borrmann, Stephan

    2015-04-01

    In mid-latitudes, precipitation is mainly initiated via the ice phase in mixed phase clouds. In such clouds the ice particles grow to precipitation sizes at the expense of liquid drops through riming which means that supercooled droplets collide with ice particles and subsequently freeze. Water-soluble trace substances present in the liquid phase might remain only fractionally in the ice phase after freezing. This fractionation is called retention and is an important ratio which quantifies the partitioning of atmospheric trace substances between the phases. Laboratory experiments were carried out at the Mainz vertical wind tunnel to determine the retention of lower mono- and di-carboxylic acids during riming. Due to their low molecular weight and their polarity these acids are water-soluble. In the atmosphere formic acid and acetic acid are the most abundant mono-carboxylic acids in the gas and aqueous phase, thus, they represent the major fraction of carboxylic acids in cloud water. Oxalic and malonic acid are common coatings on aerosol particles because of their relatively low saturation vapor pressure. These di-carboxylic acids might therefore promote the aerosol particles to act as cloud condensation nuclei and additionally contribute to the aqueous phase chemistry in cloud droplets. The conditions during the riming experiments in the wind tunnel were similar to those in atmospheric mixed phase clouds, i.e. temperatures from -18°C to -6 °C, liquid water contents between 0.5 and 1.5 g/m3, and liquid drop radii between 10 and 20 μm. The liquid phase concentrations ranged from 3 to 5 mg/l (4.1 water was analyzed by ion chromatography and the retention coefficients, i.e. the fractions of the species which remained in the ice phase were determined. Average retention coefficients of formic acid and acetic acid were 0.73 ± 0.07 and 0.62 ± 0.12, respectively; both oxalic and malonic acids had average retention coefficients of 0.98 ± 0.04. These variations can be

  17. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Science.gov (United States)

    Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

    2011-02-01

    Clouds are multiphasic atmospheric systems in which the dissolved organic compounds, dominated by carboxylic acids, are subject to multiple chemical transformations in the aqueous phase. Among them, solar radiation, by generating hydroxyl radicals (•OH), is considered as the main catalyzer of the reactivity of organic species in clouds. We investigated to which extent the active biomass existing in cloud water represents an alternative route to the chemical reactivity of carboxylic acids. Pure cultures of seventeen bacterial strains (Arthrobacter, Bacillus, Clavibacter, Frigoribacterium, Pseudomonas, Sphingomonas and Rhodococcus), previously isolated from cloud water and representative of the viable community of clouds were first individually incubated in two artificial bulk cloud water solutions at 17 °C and 5 °C. These solutions mimicked the chemical composition of cloud water from "marine" and "continental" air masses, and contained the major carboxylic acids existing in the cloud water (i.e. acetate, formate, succinate and oxalate). The concentrations of these carboxylic compounds were monitored over time and biodegradation rates were determined. In average, they ranged from 2 ×10-19 for succinate to 1 × 10-18 mol cell-1 s-1 for formate at 17 °C and from 4 × 10-20 for succinate to 6 × 10-19 mol cell-1 s-1 for formate at 5 °C, with no significant difference between "marine" and "continental" media. In parallel, irradiation experiments were also conducted in these two artificial media to compare biodegradation and photodegradation of carboxylic compounds. To complete this comparison, the photodegradation rates of carboxylic acids by •OH radicals were calculated from literature data. Inferred estimations suggested a significant participation of microbes to the transformation of carboxylic acids in cloud water, particularly for acetate and succinate (up to 90%). Furthermore, a natural cloud water sample was incubated (including its indigenous microflora

  18. Unusual conformation of a dinuclear paddle wheel copper(II) complex. Synthesis, structural characterization and EPR studies.

    Science.gov (United States)

    Paredes-García, Verónica; Santana, Ricardo C; Madrid, Rosa; Vega, Andrés; Spodine, Evgenia; Venegas-Yazigi, Diego

    2013-08-05

    An unusual and unique conformation of a paddle wheel type binuclear copper(II) complex containing acetate and acetamido ligands, {Cu2(μ2-O2CCH3)4}(OCNH2CH3) (1), was obtained by solvothermal synthesis. The structural characterization of this compound shows that the apical (acetamido) ligands are disposed at a 62° dihedral angle, generating a special conformation as a consequence of the synthetic method used. This conformation has not been reported in other paddle wheel copper(II) tetraacetate compounds. Electron paramagnetic resonance (EPR) spectra of powder samples of (1) were obtained at 9.5 and 33.8 GHz, while single crystal spectra were obtained at 33.8 GHz with a B0 applied in three orthogonal planes. The fit of the single crystal experimental data allowed gave g∥ = 2.345 ± 0.003, and g⊥ = 2.057 ± 0.005. The angular variation of the EPR line allows evaluation of the fine structure of (1), giving D = -0.337 ± 0.002 cm(-1) and E = -0.005 ± 0.001 cm(-1). The line width angular dependence, used together with the Anderson model and Kubo-Tomita theory, permitted the interdimer interaction to be evaluated as |J'| = (0.051 ± 0.002) cm(-1). Using the powder spectral temperature dependence it was possible to evaluate the intradinuclear exchange coupling constan J0 as -101 ± 2 cm(-1), which is considerably lower than that reported for other analogous copper(II) tetraacetate paddle wheel compounds (Cu(II)-PW), showing the remarkable effect of the conformation of the terminal ligands on the magnetic interaction.

  19. Synthesis of Stereoisomers of 3-Aminocyclohexanecarboxylic Acid and cis-3-Aminocyclohexene-5-carboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    HU Yu; YU Sheng-Liang; YANG Yu-Jin; ZHU Jin; DENG Jin-Gen

    2006-01-01

    A practical synthesis of stereoisomers of 3-aminocyclohexanecarboxylic acid and cis-3-aminocyclohexene-5-carboxylic acid was achieved from cyclohexene-4-carboxylic acid via a key resolving approach with chiral 1-phenylethylamine.

  20. Controlled clustering of carboxylated SPIONs through polyethylenimine

    Energy Technology Data Exchange (ETDEWEB)

    Nesztor, Dániel; Bali, Krisztina; Tóth, Ildikó Y.; Szekeres, Márta; Tombácz, Etelka, E-mail: tombacz@chem.u-szeged.hu

    2015-04-15

    Clusters of magnetite nanoparticles (MNPs) were synthesized using poly(acrylic acid-co-maleic acid) coated MNPs (PAM@MNP) and branched polyethylenimine (PEI). Materials were characterized by potentiometric titration, zeta potential and dynamic light scattering (DLS) measurements. PEI and PAM@MNP are oppositely charged as characterized by zeta potential measurements (+8, −34 mV respectively) and titration (10.30 mmol −NH{sub 3}{sup +}/g PEI; 0.175 mmol −COO{sup −}/g PAM@MNP) at pH 6.5±0.2; therefore magnetic clusters are formed by electrostatic adhesion. Two different preparation methods and the effect of PEI and electrolyte (NaCl) concentration on the cluster formation was studied. Choosing an optimal concentration of PEI (charge ratio of PEI to PAM@MNP: 0.17) and electrolyte (10 mM), a concentrated (10 g MNP/L) product containing PEI–PAM@MNP nanoclusters with size of 165±10 nm was prepared. Its specific absorption rate (SAR) measured in AC magnetic field (110 kHz, 25 mT) is 12 W/g Fe. The clustered product is expected to have enhanced contrast efficiency in MRI. - Highlights: • SPION clusters of controlled size were prepared by means of electrostatic adhesion. • Nanocluster formation optimum was at 0.17 charge ratio of PEI to PAM@MNP. • Huge aggregates form at higher PEI to PAM@MNP charge ratio. • Higher ionic strength promotes the formation of clusters at lower PEI concentrations.

  1. Thermodynamics of the complex formation of copper(II) with L-phenylalanine in aqueous ethanol solutions

    Science.gov (United States)

    Burov, D. M.; Ledenkov, S. F.; Vandyshev, V. N.

    2013-05-01

    Constants of the acid dissociation and complexation of L-phenylalanine (HPhe) with copper(II) ions are determined by potentiometry in aqueous ethanol solutions containing 0 to 0.7 molar fraction of alcohol. Changes in the Gibbs energy for the transfer from water to a binary solvent of L-phenylalanine, Phe- anion, and [CuPhe]+ complex are calculated. It is found that the weakening of solvation of the ligand donor groups in solvents with high ethanol contents is accompanied by an increase in the stability of [CuPhe]+ complex.

  2. Green and selective synthesis of N-substituted amides using water soluble porphyrazinato copper(II) catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ghodsinia, Sara S.E.; Akhlaghinia, Batool; Eshghi, Hossein, E-mail: akhlaghinia@um.ac.ir [Ferdowsi University of Mashhad (Iran, Islamic Republic of). Faculty of Sciences. Department of Chemistry; Safaei, Elham [Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of). Department of Chemistry

    2013-06-15

    N, N',N{sup ,} N{sup '}-Tetramethyl tetra-2,3-pyridinoporphyrazinato copper(II) methyl sulfate ([Cu(2,3-tmtppa)](MeSO{sub 4}){sub 4}) efficiently catalyzed the direct conversion of nitriles to N-substituted amides. The one pot selective synthesis of the N-substituted amides from nitriles and primary amines was performed in refluxing H{sub 2}O. The catalyst was recovered and reused at least four times, maintaining its efficiency. (author)

  3. Photolithographically patterned enzyme membranes for the detection of pesticides and copper(II) based on enzyme inhibition

    Energy Technology Data Exchange (ETDEWEB)

    Zuern, A. (Inst. fuer Analytik und Umweltchemie, Univ. Halle, FB Chemie, Merseburg (Germany)); Mueller, H. (Inst. fuer Analytik und Umweltchemie, Univ. Halle, FB Chemie, Merseburg (Germany))

    A non-aqueous and an aqueous photopolymer system with an enzyme are used to prepare photolithographically patterned enzyme membranes for amperometric (thinfilm platinum electrode) and potentiometric (ISFET) sensors based on enzyme inhibition. Flow methods for enzyme inhibition tests are described. The decrease in enzyme (AChE) activity after incubation in a solution of dichlorvos as inhibitor is detected amperometrically. The enzyme urease is immobilized onto the pH-sensitive gate area of an ISFET. Such a biosensor is able to detect copper(II) in water in the ppm-range without preconcentration. (orig.)

  4. Preparation and thermal decomposition of copper(II, zinc(II and cadmium(II chelates with 8-hydroxyquinoline

    Directory of Open Access Journals (Sweden)

    Crespi Marisa S.

    1999-01-01

    Full Text Available When the compounds are heated in an inert atmosphere it can be verified the consecutive partial sublimation, fusion, partial volatilization and partial thermal decomposition of the anhydrous complexes. When in an oxidating atmosphere the above process is only verified to Cu(II chelates. Anhydrous copper(II complexes present a monoclinic structure in the b form and the volatilized compound in a a form. Zinc(II and cadmium(II hydrated complexes are isomorphous and they present different cell dimensions from those reported previously.

  5. Spectrophotometric determination of copper(II) in pharmaceutical, biological and water samples by 4-(2'-benzothiazolylazo)-salicylic acid

    Science.gov (United States)

    Hashem, E. Y.; Seleim, M. M.; El-Zohry, A. M.

    2011-09-01

    A highly sensitive method is proposed to determine copper(II) ions by forming a stable complex through their interaction with 4-(2'-benzothiazolylazo)-salicylic acid (BTAS) at room temperature and pH of about 5.0. The complex gave a maximum absorption at λ = 485 nm with a molar absorptivity coefficient of 2.35·104 l/(mol·cm). The linear range for the copper determination is 0.63-5.04 mg/l. The method can be applied to determine copper ions in different biological specimens like some drugs and water samples.

  6. Structural characterization of a metal-based perfusion tracer: copper(II) pyruvaldehyde bis(N4-methylthiosemicarbazone).

    Science.gov (United States)

    John, E; Fanwick, P E; McKenzie, A T; Stowell, J G; Green, M A

    1989-01-01

    Copper(II) pyruvaldehyde bis(N4-methylthiosemicarbazone), Cu(PTSM), has been obtained as a dark red crystalline solid from EtOH-DMSO solvent mixture and structurally characterized by x-ray crystallography. The molecule possesses the expected pseudo-square planar N2S2 metal coordination sphere; however, the copper center also interacts through its axial coordination site with the sulfur atom of an adjacent Cu(PTSM) molecule in the crystal lattice. The structure of this compound is compared with the structures of other metal complexes that have been proposed in the nuclear medicine literature as perfusion tracers.

  7. Experimental and theoretical study on a new copper(II) complex derived from pyridoxal hydrochloride and 1,2-diaminocyclohexane

    Science.gov (United States)

    Mandal, Senjuti; Sikdar, Yeasin; Sanyal, Ria; Goswami, Sanchita

    2017-01-01

    In this work, guided by a pyridoxal derived Schiff base ligand, H2PydChda [5-Hydroxymethyl-4-({2-[5-hydroxymethyl-2-methylpyridin-3-hydroxy-4-ylethylene)-amino]-cyclohexylimino}-methyl)-2-methylpyridin-3-ol], a new copper(II) complex, [Cu(PydChda-2H+)]2·4ClO4·2H2O was constructed and structurally characterized by single crystal X-ray diffraction study. DFT calculations further substantiate the experimental features. Additionally, experiments were performed to demonstrate the accessibility to any enzymatic activity and the complex provides positive response for phosphatase activity towards 4-NPP substrate.

  8. Highly Regioselective Palladium-Catalyzed Carboxylation of Allylic Alcohols with CO2.

    Science.gov (United States)

    Mita, Tsuyoshi; Higuchi, Yuki; Sato, Yoshihiro

    2015-11-01

    Various allylic alcohols were carboxylated in the presence of a catalytic amount of PdCl2 and PPh3 using ZnEt2 as a stoichiometric transmetalation agent under a CO2 atmosphere (1 atm). This carboxylation proceeded in a highly regioselective manner to afford branched carboxylic acids predominantly. The β,γ-unsaturated carboxylic acid thus obtained was successfully converted into an optically active γ-butyrolactone, a known intermediate of (R)-baclofen.

  9. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  10. 40 CFR 721.2088 - Carboxylic acids, (C6-C9) branched and linear.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Carboxylic acids, (C6-C9) branched and... Specific Chemical Substances § 721.2088 Carboxylic acids, (C6-C9) branched and linear. (a) Chemical... as carboxylic acids, (C6-C9) branched and linear (PMNs P-93-313, 314, 315, and 316) are subject...

  11. Carboxyl-terminal multi-site phosphorylation regulates internalization and desensitization of the human sst2 somatostatin receptor.

    Science.gov (United States)

    Lehmann, Andreas; Kliewer, Andrea; Schütz, Dagmar; Nagel, Falko; Stumm, Ralf; Schulz, Stefan

    2014-04-25

    The somatostatin receptor 2 (sst2) is the pharmacological target of somatostatin analogs that are widely used in the diagnosis and treatment of human neuroendocrine tumors. We have recently shown that the stable somatostatin analogs octreotide and pasireotide (SOM230) stimulate distinct patterns of sst2 receptor phosphorylation and internalization. Like somatostatin, octreotide promotes the phosphorylation of at least six carboxyl-terminal serine and threonine residues namely S341, S343, T353, T354, T356 and T359, which in turn leads to a robust receptor endocytosis. Unlike somatostatin, pasireotide stimulates a selective phosphorylation of S341 and S343 of the human sst2 receptor followed by a partial receptor internalization. Here, we show that exchange of S341 and S343 by alanine is sufficient to block pasireotide-driven internalization, whereas mutation of T353, T354, T356 and T359 to alanine is required to strongly inhibited both octreotide- and somatostatin-induced internalization. Yet, combined mutation of T353, T354, T356 and T359 is not sufficient to prevent somatostatin-driven β-arrestin mobilization and receptor desensitization. Replacement of all fourteen carboxyl-terminal serine and threonine residues by alanine completely abrogates sst2 receptor internalization and β-arrestin mobilization in HEK293 cells. Together, our findings demonstrate for the first time that agonist-selective sst2 receptor internalization is regulated by multi-site phosphorylation of its carboxyl-terminal tail.

  12. Density functional theory study of the oligomerization of carboxylic acids.

    Science.gov (United States)

    Di Tommaso, Devis; Watson, Ken L

    2014-11-20

    We present a density functional theory [M06-2X/6-31+G(d,p)] study of the structures and free energies of formation of oligomers of four carboxylic acids (formic acid, acetic acid, tetrolic acid, and benzoic acid) in water, chloroform, and carbon tetrachloride. Solvation effects were treated using the SMD continuum solvation model. The low-lying energy structures of molecular complexes were located by adopting an efficient search procedure to probe the potential energy surfaces of the oligomers of carboxylic acids (CA)n (n = 2-6). The free energies of the isomers of (CA)n in solution were determined as the sum of the electronic energy, vibrational-rotational-translational gas-phase contribution, and solvation free energy. The assessment of the computational protocol adopted in this study with respect to the dimerization of acetic acid, (AA)2, and formic acid, (FA)2, located new isomers of (AA)2 and (FA)2 and gave dimerization constants in good agreement with the experimental values. The calculation of the self-association of acetic acid, tetrolic acid, and benzoic acid shows the following: (i) Classic carboxylic dimers are the most stable isomer of (CA)2 in both the gas phase and solution. (ii) Trimers of carboxylic acid are stable in apolar aprotic solvents. (iii) Molecular clusters consisting of two interacting classic carboxylic dimers (CA)4,(D+D) are the most stable type of tetramers, but their formation from the self-association of classic carboxylic dimers is highly unfavorable. (iv) For acetic acid and tetrolic acid the reactions (CA)2 + 2CA → (CA)4,(D+D) and (CA)3 + CA → (CA)4,(D+D) are exoergonic, but these aggregation pathways go through unstable clusters that could hinder the formation of tetrameric species. (v) For tetrolic acid the prenucleation species that are more likely to form in solution are dimeric and trimeric structures that have encoded structural motifs resembling the α and β solid forms of tetrolic acid. (vi) Stable tetramers of

  13. Carboxyl-terminal truncated HBx regulates a distinct microRNA transcription program in hepatocellular carcinoma development.

    Directory of Open Access Journals (Sweden)

    Wing-Kit Yip

    Full Text Available BACKGROUND: The biological pathways and functional properties by which misexpressed microRNAs (miRNAs contribute to liver carcinogenesis have been intensively investigated. However, little is known about the upstream mechanisms that deregulate miRNA expressions in this process. In hepatocellular carcinoma (HCC, hepatitis B virus (HBV X protein (HBx, a transcriptional trans-activator, is frequently expressed in truncated form without carboxyl-terminus but its role in miRNA expression and HCC development is unclear. METHODS: Human non-tumorigenic hepatocytes were infected with lentivirus-expressing full-length and carboxyl-terminal truncated HBx (Ct-HBx for cell growth assay and miRNA profiling. Chromatin immunoprecipitation microarray was performed to identify the miRNA promoters directly associated with HBx. Direct transcriptional control was verified by luciferase reporter assay. The differential miRNA expressions were further validated in a cohort of HBV-associated HCC tissues using real-time PCR. RESULTS: Hepatocytes expressing Ct-HBx grew significantly faster than the full-length HBx counterparts. Ct-HBx decreased while full-length HBx increased the expression of a set of miRNAs with growth-suppressive functions. Interestingly, Ct-HBx bound to and inhibited the transcriptional activity of some of these miRNA promoters. Notably, some of the examined repressed-miRNAs (miR-26a, -29c, -146a and -190 were also significantly down-regulated in a subset of HCC tissues with carboxyl-terminal HBx truncation compared to their matching non-tumor tissues, highlighting the clinical relevance of our data. CONCLUSION: Our results suggest that Ct-HBx directly regulates miRNA transcription and in turn promotes hepatocellular proliferation, thus revealing a viral contribution of miRNA deregulation during hepatocarcinogenesis.

  14. Aqueous aerobic oxidation of alkyl arenes and alcohols catalyzed by copper(II) phthalocyanine supported on three-dimensional nitrogen-doped graphene at room temperature.

    Science.gov (United States)

    Mahyari, Mojtaba; Laeini, Mohammad Sadegh; Shaabani, Ahmad

    2014-07-25

    Copper(ii) tetrasulfophthalocyanine supported on three-dimensional nitrogen-doped graphene-based frameworks was synthesized and introduced as a bifunctional catalyst for selective aerobic oxidation of alkyl arenes and alcohols to the corresponding carbonyl compounds. The ease of catalyst separation, high turnover, low catalyst loading and recyclability could potentially render it applicable in industrial setting.

  15. Biological Role of Cobalt(II), Copper(II) and Nickel(II) Metal Ions on the Antibacterial Properties of Some Nicotinoyl-Hydrazine Derived Compounds

    OpenAIRE

    Chohan, Zahid H.; Sherazi, Syed K. A.

    1997-01-01

    Several cobalt(II), copper(II) and nickel(II) complexes of nicotinoylhydrazine-derived compounds were prepared and characterised by physical, spectral and analytical data. These compounds and their complexes have proven to be antibacterial. The screening data show the metal complexes to be more potential/bactericidal than the uncomplexed compounds against one or more bacterial species.

  16. Characterisation of spin-waves in copper(II) deuteroformate tetradeuterate: A square ¤S¤=1/2 Heisenberg antiferromagnet

    DEFF Research Database (Denmark)

    Clarke, S.J.; Harrison, A.; Mason, T.E.;

    1999-01-01

    Copper(II) formate tetrahydrate (CFTH) is a model square S = 1/2 Heisenberg antiferromagnet with T-N = 16.54 +/- 0.05 K. The dispersion of spin-waves in the magnetic layers of a fully deuterated sample of this material has been mapped at 4.3 K by inelastic neutron scattering from the zone centre...

  17. Self-assembly of a chiral carbonate- and cytidine-containing dodecanuclear copper(II) complex: a multiarm-supplied globular capsule.

    Science.gov (United States)

    Armentano, Donatella; Marino, Nadia; Mastropietro, Teresa F; Martínez-Lillo, José; Cano, Joan; Julve, Miguel; Lloret, Francesc; De Munno, Giovanni

    2008-11-17

    A dodecanuclear copper(II) globular-shaped structure has been obtained with the cytidine nucleoside and the templating carbonate anion. It shows receptor properties through anion-cation and multiple anion-pi interactions toward ClO 4 (-) as well as an overall antiferromagnetic coupling.

  18. Probing the copper(II) binding features of angiogenin. Similarities and differences between a N-terminus peptide fragment and the recombinant human protein.

    Science.gov (United States)

    La Mendola, Diego; Farkas, Daniel; Bellia, Francesco; Magrì, Antonio; Travaglia, Alessio; Hansson, Örjan; Rizzarelli, Enrico

    2012-01-02

    The angiogenin protein (hAng) is a potent angiogenic factor and its cellular activities may be affected by copper ions even if it is yet unknown how this metal ion is able to produce this effect. Among the different regions of hAng potentially able to bind copper ions, the N-terminal domain appears to be an ideal candidate. Copper(II) complexes of the peptide fragments encompassing the amino acid residues 4-17 of hAng protein were characterized by potentiometric, UV-vis, CD, and EPR spectroscopic methods. The results show that these fragments have an unusual copper(II) binding ability. At physiological pH, the prevailing complex species formed by the peptide encompassing the protein sequence 4-17 is [CuHL], in which the metal ion is bound to two imidazole and two deprotonated amide nitrogen atoms disposed in a planar equatorial arrangement. Preliminary spectroscopic (UV-vis, CD, and EPR) data obtained on the copper(II) complexes formed by the whole recombinant hAng protein, show a great similarity with those obtained for the N-terminal peptide fragments. These findings indicate that within the N-terminal domain there is one of the preferred copper(II) ions anchoring site of the whole recombinant hAng protein.

  19. Synthesis and Structure of a Ternary Copper(II) Complex with Mixed Ligands of Diethylenetriamine and Picrate: DNA/Protein-Binding Property and In Vitro Anticancer Activity Studies.

    Science.gov (United States)

    Shi, Ya-Ning; Zheng, Kang; Zhu, Ling; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei

    2015-05-01

    Based on the importance of the design and synthesis of transition metal complexes with noncovalent DNA/protein-binding abilities in the field of metallo pharmaceuticals, a new mononuclear ternary copper(II) complex with mixed ligands of diethylenetriamine (dien) and picrate anion (pic), identified as [Cu(dien)(pic)](pic), was synthesized and characterized by elemental analysis, molar conductivity measurement, infrared spectrum, electronic spectral studies, and single-crystal X-ray diffractometry. The structure analysis reveals that the copper(II) complex crystallizes in the monoclinic space group P21 /c, and the copper(II) ion has a distorted square pyramidal coordination geometry. A two-dimensional supramolecular structure is formed through hydrogen bonds. The DNA/bovine serum albumin (BSA)-binding properties of the complex are explored, indicating that the complex can interact with herring sperm DNA via intercalation mode and bind to BSA responsible for quenching of tryptophan fluorescence by static quenching mechanism. The in vitro anticancer activity shows that the copper(II) complex is active against the selected tumor cell lines.

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

    Science.gov (United States)

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

    2015-02-28

    Interactions of the azachalcone derived substrate Aza with copper(II) complexes in the presence and absence of st-DNA were studied in detail by UV/Vis absorption, EPR and Raman and (UV and vis) resonance Raman spectroscopies. The binding of Aza to the Lewis acidic copper(II) complexes, which results in activation of the substrate, was established spectroscopically. It was shown that the binding of Aza differs between Cu(II)dmbpy and Cu(II)terpy, consistent with the observed differences in catalytic asymmetric Diels-Alder reactions with regard to both the rate and enantiomeric preference. Finally, it was shown that DNA has a major beneficial effect on the binding of Aza to the copper(II) complex due to the fact that both bind to the DNA. The result is a high effective molarity of both the copper complexes and the Aza substrate, which leads to a significant increase in binding of Aza to the copper(II) complex. This effect is a key reason for the observed rate acceleration in the catalyzed reactions brought about by the presence of DNA.

  1. Synthesis of mononuclear copper(II) complexes of acyclic Schiff's base ligands: Spectral, structural, electrochemical, antibacterial, DNA binding and cleavage activity

    Science.gov (United States)

    Jayamani, Arumugam; Thamilarasan, Vijayan; Sengottuvelan, Nallathambi; Manisankar, Paramasivam; Kang, Sung Kwon; Kim, Young-Inn; Ganesan, Vengatesan

    2014-03-01

    The mononuclear copper(II) complexes (1&2) of ligands L1 [N,N";-bis(2-hydroxy-5-methylbenzyl)-1,4-bis(3-iminopropyl)piperazine] or L2 [N,N";-bis(2-hydroxy-5-bromobenzyl)-1,4-bis(3-iminopropyl) piperazine] have been synthesized and characterised. The single crystal X-ray study had shown that ligands L1 and L2 crystallize in a monoclinic crystal system with P21/c space group. The mononuclear copper(II) complexes show one quasireversible cyclic voltammetric response near cathodic region (-0.77 to -0.85 V) in DMF assignable to the Cu(II)/Cu(I) couple. Binding interaction of the complexes with calf thymus DNA (CT DNA) investigated by absorption studies and fluorescence spectral studies show good binding affinity to CT DNA, which imply both the copper(II) complexes can strongly interact with DNA efficiently. The copper(II) complexes showed efficient oxidative cleavage of plasmid pBR322 DNA in the presence of 3-mercaptopropionic acid as reducing agent through a mechanistic pathway involving formation of singlet oxygen as the reactive species. The Schiff bases and their Cu(II) complexes have been screened for antibacterial activities which indicates that the complexes exhibited higher antimicrobial activity than the free ligands.

  2. Novel homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff bases: Synthesis, characterization, solvent-extraction and catalase-like activity studies

    Energy Technology Data Exchange (ETDEWEB)

    Dede, Buelent [Sueleyman Demirel University, Department of Chemistry, Isparta, 32260 (Turkey)], E-mail: dbulent@fef.sdu.edu.tr; Karipcin, Fatma; Cengiz, Mustafa [Sueleyman Demirel University, Department of Chemistry, Isparta, 32260 (Turkey)

    2009-04-30

    Twelve homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff base ligands containing N{sub 4} donor sets have been prepared by employing several steps. The characterization and nature of bonding of the complexes have been deduced from elemental analysis, FT-IR, molar conductivity, magnetic moment measurements and thermal analysis. The three Schiff base ligands were further identified using {sup 1}H and {sup 13}C NMR spectra. All copper(II) complexes are 1:2 electrolytes as shown by their molar conductivities ({lambda}{sub M}) in DMF and paramagnetic. The subnormal magnetic moment values of the di- and tri-nuclear complexes explained by a very strong anti-ferromagnetic interaction. The extraction ability of the ligands has been examined by the liquid-liquid extraction of selected transition metal (Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cu{sup 2+}, Zn{sup 2+}, Pb{sup 2+}, Cd{sup 2+}, Hg{sup 2+}) cations. The ligands show strong binding ability toward copper(II) ion. Furthermore the homo- and hetero-nuclear copper(II) complexes were each tested for their ability to catalyse the disproportionation of hydrogen peroxide in the presence of the added base imidazole.

  3. Rh(III)-catalyzed decarboxylative ortho-heteroarylation of aromatic carboxylic acids by using the carboxylic acid as a traceless directing group.

    Science.gov (United States)

    Qin, Xurong; Sun, Denan; You, Qiulin; Cheng, Yangyang; Lan, Jingbo; You, Jingsong

    2015-04-03

    Highly selective decarboxylative ortho-heteroarylation of aromatic carboxylic acids with various heteroarenes has been developed through Rh(III)-catalyzed two-fold C-H activation, which exhibits a wide substrate scope of both aromatic carboxylic acids and heteroarenes. The use of naturally occurring carboxylic acid as the directing group avoids troublesome extra steps for installation and removal of an external directing group.

  4. Surface modification of silicone tubes by functional carboxyl and amine, but not peroxide groups followed by collagen immobilization improves endothelial cell stability and functionality.

    Science.gov (United States)

    Salehi-Nik, Nasim; Amoabediny, Ghassem; Shokrgozar, Mohammad Ali; Mottaghy, Khosrow; Klein-Nulend, Jenneke; Zandieh-Doulabi, Behrouz

    2015-03-02

    Surface modification by functional groups promotes endothelialization in biohybrid artificial lungs, but whether it affects endothelial cell stability under fluid shear stress, and the release of anti-thrombotic factors, e.g. nitric oxide (NO), is unknown. We aimed to test whether surface-modified silicone tubes containing different functional groups, but similar wettability, improve collagen immobilization, endothelialization, cell stability and cell-mediated NO-release. Peroxide, carboxyl, and amine-groups increased collagen immobilization (41-76%). Only amine-groups increased ultimate tensile strength (2-fold). Peroxide and amine enhanced (1.5-2.5 fold), but carboxyl-groups decreased (2.9-fold) endothelial cell number after 6 d. After collagen immobilization, cell numbers were enhanced by all group-modifications (2.8-3.8 fold). Cells were stable under 1 h-fluid shear stress on amine, but not carboxyl or peroxide-group-modified silicone (>50% cell detachment), while cells were also stable on carboxyl-group-modified silicone with immobilized collagen. NO-release was increased by peroxide and amine (1.1-1.7 fold), but decreased by carboxyl-group-modification (9.8-fold), while it increased by all group-modifications after collagen immobilization (1.8-2.8 fold). Only the amine-group-modification changed silicone stiffness and transparency. In conclusion, silicone-surface modification of blood-contacting parts of artificial lungs with carboxyl and amine, but not peroxide-groups followed by collagen immobilization allows the formation of a stable functional endothelial cell layer. Amine-group-modification seems undesirable since it affected silicone's physical properties.

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

    Science.gov (United States)

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

    2007-11-28

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

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

    Science.gov (United States)

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

    2016-10-01

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

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

    Science.gov (United States)

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

    2017-07-01

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

  8. Influences of Carboxyl Methyl Cellulose on Performances of Mortar

    Institute of Scientific and Technical Information of China (English)

    WANG Yuli; ZHOU Mingkai; SHAN Junhong; XU Fang; YANG Yuhui

    2007-01-01

    Carboxyl methyl cellulose (CMC) was mixed into mortar to improve the waterretention performance of mortar, the quality of floated coat of aerated concrete became better. The consistency and compression strength of mortar with CMC were studied. The water absorption was studied with the method of filter paper. The micro mechanism was researched with X-ray diffraction and scanning electron microscopy(SEM). The experimental results show the water-holding performance of mortar with CMC is largely improved and it is better when the mixed amount is about 1.5%; the compression strength had a descending trend with the increase of CMC; CMC reacted with calcium hydroxide(CH) into the deposition of calcium carboxyl methyl cellulose.

  9. Quinoline based receptor in fluorometric discrimination of carboxylic acids

    Directory of Open Access Journals (Sweden)

    2008-12-01

    Full Text Available Quinoline and naphthalene-based fluororeceptors 1 and 2 have been designed and synthesized for detection of hydroxy carboxylic acids in less polar solvents. The receptor 1 shows monomer emission quenching followed by excimer emission upon hydrogen bond-mediated complexation of carboxylic acids. The excimer emission distinguishes aromatic dicarboxylic acids from aliphatic dicarboxylic acids and even long chain aliphatic dicarboxylic acids from short chain aliphatic dicarboxylic acids. The receptor 1 is found to be selective for citric acid with a strong excimer emission in CHCl3. On the contrary, the receptor 2 exhibited less binding constant value and did not form any excimer upon complexation with the same acids under similar conditions. This established the role of quinoline ring nitrogen in binding with the acids.

  10. Propensity of salicylamide and ethenzamide cocrystallization with aromatic carboxylic acids.

    Science.gov (United States)

    Przybyłek, Maciej; Ziółkowska, Dorota; Mroczyńska, Karina; Cysewski, Piotr

    2016-03-31

    The cocrystallization of salicylamide (2-hydroxybenzamide, SMD) and ethenzamide (2-ethoxybenzamide, EMD) with aromatic carboxylic acids was examined both experimentally and theoretically. The supramolecular synthesis taking advantage of the droplet evaporative crystallization (DEC) technique was combined with powder diffraction and vibrational spectroscopy as the analytical tools. This led to identification of eleven new cocrystals including pharmaceutically relevant coformers such as mono- and dihydroxybenzoic acids. The cocrystallization abilities of SMD and EMD with aromatic carboxylic acids were found to be unexpectedly divers despite high formal similarities of these two benzamides and ability of the R2,2(8) heterosynthon formation. The source of diversities of the cocrystallization landscapes is the difference in the stabilization of possible conformers by adopting alternative intramolecular hydrogen boding patterns. The stronger intramolecular hydrogen bonding the weaker affinity toward intermolecular complexation potential. The substituent effects on R2,2(8) heterosynthon properties are also discussed.

  11. Carboxylic Acids as Indicators of Parent Body Conditions

    Science.gov (United States)

    Lerner N. R.; Chang, Sherwood (Technical Monitor)

    1995-01-01

    Alpha-hydroxy and alpha-amino carboxylic acids found on the Murchison meteorite are deuterium enriched. It is postulated that they arose from a common interstellar scurce: the reaction of carbonyl compounds in an aqueous mixture containing HCN and NH3. Carbonyl compounds react with HCN to form alpha-hydroxy nitriles, RR'CO + HCN right and left arrow RR'C(OH)CN. If ammonia is also present, the alpha-hydroxy nitriles will exist in equilibrium with the alpha-amino nitriles, RR'C(OH)CN + NH3 right and left arrow - RRCNH2CN + H2O. Both nitrites are hydrolyzed by water to form carboxylic acids: RR'C(OH)CN + H2O yields RR'C(OH)CO2H and RR'C(NH2)CN + H2O yields RR'C(NH2)CO2H.

  12. CARBOXYLIC ACIDS OF HERB OF THYMUS CRETACEUS KLOK. ET SCHOST

    Directory of Open Access Journals (Sweden)

    V. N. Bubenchikova

    2014-01-01

    Full Text Available We have studied carboxylic acids of the herb of Thymus cretaceus Klok. et Schost which is widespread on a territory of some regions (Belgorod, Voronezh. The study was carried out using gas-liquid chromatography at Agilent Technologies 6890 chromatographer with massspectrometric detector 5973 N. Acids concentration was calculated by means of inner standard.We have established that carboxylic acids of Thymus cretaceus are represented by 34 compounds. Palmitic (1779.02 mg/kg, behenic (1084.15 mg/kg, levulinic (986.24 mg/kg and linoleic acids (678.82 mg/kg predominate among fatty acids; citric (9835.14 mg/kg, malonic (447.91 mg/kg and oxalic acids (388.32 mg/kg predominate among organic acids; andferulic acid predominate amongphenolcarbonic acids.

  13. Soluble, High Molecular Weight Polysilsesquioxanes with Carboxylate Functionalities

    Energy Technology Data Exchange (ETDEWEB)

    RAHIMIAN,KAMYAR; LOY,DOUGLAS A.; WHEELER,DAVID R.

    2000-07-14

    Trialkoxysilyl-containing monomers of the type (RO){sub 3}Si(CH{sub 2}){sub 3}C(O)OtBu (R = Me, Et) were prepared by hydrosilation of the corresponding vinylic tert-butyl esters CH{sub 3}CHCH{sub 2}C(O)OtBu. Acid- or base-catalyzed polymerization of the monomers leads to very high molecular weight polymers with relatively narrow polydispersities. The polymerization results in complete condensation of the alkoxy groups while the tert-butyl ester functionality remains fully intact. Partial or full deprotection of the tert-butyl group can easily be achieved to yield the corresponding carboxylic acid polymers. The ester and carboxylic acid functionalities of these new materials allow for their potential use in a variety of applications such as scavenging of heavy metals.

  14. Substrate specificity within a family of outer membrane carboxylate channels.

    Directory of Open Access Journals (Sweden)

    Elif Eren

    2012-01-01

    Full Text Available Many Gram-negative bacteria, including human pathogens such as Pseudomonas aeruginosa, do not have large-channel porins. This results in an outer membrane (OM that is highly impermeable to small polar molecules, making the bacteria intrinsically resistant towards many antibiotics. In such microorganisms, the majority of small molecules are taken up by members of the OprD outer membrane protein family. Here we show that OprD channels require a carboxyl group in the substrate for efficient transport, and based on this we have renamed the family Occ, for outer membrane carboxylate channels. We further show that Occ channels can be divided into two subfamilies, based on their very different substrate specificities. Our results rationalize how certain bacteria can efficiently take up a variety of substrates under nutrient-poor conditions without compromising membrane permeability. In addition, they explain how channel inactivation in response to antibiotics can cause resistance but does not lead to decreased fitness.

  15. Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids.

    Science.gov (United States)

    Kan, Jian; Huang, Shijun; Lin, Jin; Zhang, Min; Su, Weiping

    2015-02-09

    A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.

  16. Fluorescently tuned nitrogen-doped carbon dots from carbon source with different content of carboxyl groups

    Directory of Open Access Journals (Sweden)

    Hao Wang

    2015-08-01

    Full Text Available In this study, fluorescent nitrogen-doped carbon dots (NCDs were tuned via varying the sources with different number of carboxyl groups. Owing to the interaction between amino and carboxyl, more amino groups conjugate the surface of the NCDs by the source with more carboxyl groups. Fluorescent NCDs were tuned via varying the sources with different content of carboxyl groups. Correspondingly, the nitrogen content, fluorescence quantum yields and lifetime of NCDs increases with the content of carboxyl groups from the source. Furthermore, cytotoxicity assay and cell imaging test indicate that the resultant NCDs possess low cytotoxicity and excellent biocompatibility.

  17. Fluorescently tuned nitrogen-doped carbon dots from carbon source with different content of carboxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Wang, Yun; Dai, Xiao; Zou, Guifu, E-mail: kqzhang@suda.edu.cn, E-mail: zouguifu@suda.edu.cn [College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Gao, Peng; Zhang, Ke-Qin, E-mail: kqzhang@suda.edu.cn, E-mail: zouguifu@suda.edu.cn; Du, Dezhuang [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou 215123 (China); Guo, Jun [Testing and Analysis Center, Soochow University, Suzhou 215123 (China)

    2015-08-01

    In this study, fluorescent nitrogen-doped carbon dots (NCDs) were tuned via varying the sources with different number of carboxyl groups. Owing to the interaction between amino and carboxyl, more amino groups conjugate the surface of the NCDs by the source with more carboxyl groups. Fluorescent NCDs were tuned via varying the sources with different content of carboxyl groups. Correspondingly, the nitrogen content, fluorescence quantum yields and lifetime of NCDs increases with the content of carboxyl groups from the source. Furthermore, cytotoxicity assay and cell imaging test indicate that the resultant NCDs possess low cytotoxicity and excellent biocompatibility.

  18. X-ray and DFT studies of a mono- and binuclear copper(II) ionic compound containing a Schiff base.

    Science.gov (United States)

    Langer, Vratislav; Mach, Pavol; Gyepesová, Dalma; Andrezálová, Lucia; Kohútová, Mária

    2012-11-01

    In the structure of trans-bis(ethanol-κO)tetrakis(1H-imidazole-κN(3))copper(II) bis[μ-N-(2-oxidobenzylidene)-D,L-glutamato]-κ(4)O(1),N,O(2'):O(2');κ(4)O(2'):O(1),N,O(2')-bis[(1H-imidazole-κN(3))cuprate(II)], [Cu(C(3)H(4)N(2))(4)(C(2)H(6)O)(2)][Cu(2)(C(15)H(14)N(3)O(5))(2)], both ions are located on centres of inversion. The cation is mononuclear, showing a distorted octahedral coordination, while the anion is a binuclear centrosymmetric dimer with a square-pyramidal copper(II) coordination. An extensive three-dimensional hydrogen-bonding network is formed between the ions. According to B3LYP/6-31G* calculations, the two equivalent components of the anion are in doublet states (spin density located mostly on Cu(II) ions) and are coupled as a triplet, with only marginal preference over an open-shell singlet.

  19. Thermal, Structural and Morphological Characterisation of Freeze-dried Copper(II Acetate Monohydrate and its Solid Decomposition Products

    Directory of Open Access Journals (Sweden)

    Bellini J.V.

    2002-01-01

    Full Text Available In the present study the thermal decomposition of a freeze-dried copper(II acetate monohydrate powder, (CH3COO2Cu.H2O, (FDCuAcH2O, was analysed by a combination of high-temperature X-ray diffractometry; differential scanning calorimetry and thermogravimetry, up to 700 degreesC. The structure and morphology of the calcined freeze-dried powders were analysed by scanning electron microscopy and X-ray diffractometry. The results showed that FDAcCuH2O decomposes during heating in two stages: I (25-225 degreesC FDCuAcH2O dehydrates giving rise to copper(II acetate, (CH3COO2Cu, (AcCu, and II (225-525 degreesC AcCu decomposes to CuO through complex oxidation reactions of Cu and Cu2O, simultaneously. SEM showed that FDCuAcH2O powder has a scale-like morphology, which is created in the freezing stage and retained after freeze-drying. After calcination at 125 and 225 degreesC, clusters of elongated tubes (or filaments compose the resulting powder (AcCu. Subsequent calcination at temperatures above 325 degreesC resulted in hard clusters of spheroid-like CuO particles.

  20. Synthesis, Immobilization and Catalytic Activity of a Copper(II Complex with a Chiral Bis(oxazoline

    Directory of Open Access Journals (Sweden)

    Liliana Carneiro

    2014-08-01

    Full Text Available A chiral bis(oxazoline bearing CH2OH groups was synthesized from a commercial bis(oxazoline and characterized by 1H- and 13C-NMR, high resolution ESI-mass spectrometry and FTIR. The corresponding copper(II complex was immobilized onto the surface of a mesoporous carbonaceous material (Starbon® 700 in which the double bonds had been activated via conventional bromination. The materials were characterized by elemental analysis, ICP-OES, XPS, thermogravimetry and nitrogen adsorption at 77 K. The new copper(II bis(oxazoline was tested both in the homogeneous phase and once immobilized onto a carbonaceous support for the kinetic resolution of hydrobenzoin. Both were active, enantioselective and selective in the mono-benzoylation of hydrobenzoin, but better enantioselectivities were obtained in the homogeneous phase. The heterogeneous catalyst could be separated from the reaction media at the end of the reaction and reused in another catalytic cycle, but with loss of product yield and enantioselectivity.

  1. Removal of Copper(II and Zinc(II Ions From Aqueous Solution by Chemical Treatment of Coal Fly Ash

    Directory of Open Access Journals (Sweden)

    Eleonora Sočo

    2015-12-01

    Full Text Available The aim of this study was to investigate the chemical modifications of coal fly ash (CFA treated with HNO3 or ammonium acetate (AcNH4 or NaOH or sodium diethyldithiocarbamate (NaDDTC as an adsorbent for the removal of copper(II and zinc(II ions from aqueous solution. The morphology of fly ash grains before and after modification was examined via X-ray diffraction (XRD and images of scanning electron microscope (SEM. Adsorption of copper(II and zinc(II ions was conducted under batch process at different duration, concentrations and temperature of the suspension. Equilibrium experiments shows that the selectivity of CFA-NaOH nanoparticles towards Cu(II ions is greater than that of Zn(II ions, which is related to their hydrated ionic radius and first hydrolysis equilibrium constant. The adsorption isotherms were described by Langmuir and Freundlich models. Kinetic data revealed that the adsorption fits well by the pseudo-second-order rate model with high regression coefficients. Thermodynamic parameters suggested that the immobilization Cu(II and Zn(II ions onto CFA-NaOH is a spontaneous process. Results demonstrated that the treating coal fly ash with alkaline solution was a promising way to enhance Cu(II and Zn(II ions adsorption.

  2. New tridentate azo-azomethines and their copper(II) complexes: Synthesis, solvent effect on tautomerism, electrochemical and biological studies

    Science.gov (United States)

    Sarigul, Munire; Deveci, Pervin; Kose, Muhammet; Arslan, Ugur; Türk Dagi, Hatice; Kurtoglu, Mukerrem

    2015-09-01

    In this study, three azo-azomethines and their copper(II) complexes were prepared and characterized by analytical and spectroscopic methods. The complexes prepared were found to be mononuclear and the chelation of the ligands to the copper(II) ions occurs through two phenolic oxygens and a nitrogen atom of the azomethine group of the ligand. The tautomeric behaviors of the azo-azomethines in solution were studied by UV-Vis. spectra in three organic solvents with different polarity (CHCl3, DMSO and DMF) at room temperature. The redox behaviors of the azo-azomethines and their Cu(II) complexes were investigated by cyclic voltammetry (CV) in DMSO solution containing 0.1 M tetrabutylammonium tetrafluoroborate (TBATFB) as supporting electrolyte. Additionally, the antibacterial activity was also evaluated by the broth microdilution methods against Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa. The compounds were found to be less effective against all bacteria tested than two reference antibiotics (ampicillin and gentamicin).

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

    Science.gov (United States)

    Gökçe, Cansu; Gup, Ramazan

    2013-05-05

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

  4. New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions.

    Science.gov (United States)

    Bera, Manindranath; Patra, Ayan

    2011-10-18

    We have studied the binding interactions of biologically important carbohydrates (D-glucose, D-xylose and D-mannose) with the newly synthesized five-coordinate dinuclear copper(II) complex, [Cu(2)(hpnbpda)(μ-OAc)] (1) and zinc(II) complex, [Zn(2)(hpnbpda)(μ-OAc)] (2) [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in aqueous alkaline solution. The complexes 1 and 2 are fully characterized both in solid and solution using different analytical techniques. A geometrical optimization was made of the ligand H(3)hpnbpda and the complexes 1 and 2 by molecular mechanics (MM+) method in order to establish the stable conformations. All carbohydrates bind to the metal complexes in a 1:1 molar ratio. The binding events have been investigated by a combined approach of FTIR, UV-vis and (13)C NMR spectroscopic techniques. UV-vis spectra indicate a significant blue shift of the absorption maximum of complex 1 during carbohydrate coordination highlighting the sugar binding ability of complex 1. The apparent binding constants of the substrate-bound copper(II) complexes have been determined from the UV-vis titration experiments. The binding ability and mode of binding of these sugar substrates with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for carbon atoms C1, C2, and C3 of sugar substrates.

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

    Science.gov (United States)

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

    2017-01-01

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

  6. Hydrolytic protein cleavage mediated by unusual mononuclear copper(II) complexes: X-ray structures and solution studies.

    Science.gov (United States)

    de Oliveira, Mauricio C B; Scarpellini, Marciela; Neves, Ademir; Terenzi, Hernán; Bortoluzzi, Adailton J; Szpoganics, Bruno; Greatti, Alessandra; Mangrich, Antônio S; de Souza, Emanuel M; Fernandez, Pablo M; Soares, Marcia R

    2005-02-21

    The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes.

  7. Crystal structure of ethyl 2,4-dichloroquinoline-3-carboxylate

    Directory of Open Access Journals (Sweden)

    Alberto Cabrera

    2015-12-01

    Full Text Available In the crystal structure of the title compound, C12H9Cl2NO2, the mean planes through the quinoline and carboxylate groups have r.m.s. deviations of 0.006 and 0.021 Å, respectively, and form a dihedral angle of 87.06 (19°. In the crystal, molecules are linked via very weak C—H...O hydrogen bonds, forming chains, which propagate along the c-axis direction.

  8. STUDY OF CARBOXYL METHYL STARCH ON PAPER STRENGTH

    Institute of Scientific and Technical Information of China (English)

    Li Xinping; Liu Ye; Lin Youfeng

    2004-01-01

    A novel starch derivative--carboxyl methyl starch (CMS) was investigated in this paper. Through a series of experiments, the results showed that CMS has considerable effect on paper strength as internal additive, and the better technology conditions are as follows: pH=7.0, CMS dosage is 1.0% (on o.d. pulp),mixing time is 45min and drying temperature is 105℃.

  9. STUDY OF CARBOXYL METHYL STARCH ON PAPER STRENGTH

    Institute of Scientific and Technical Information of China (English)

    LiXinping; LiuYe; LinYoufeng

    2004-01-01

    A novel starch derivative--carboxyl methyl starch(CMS) was investigated in this paper. Through aseries of experiments, the results showed that CMShas considerable effect on paper strength as internaladditive, and the better technology conditions are asfollows: pH=7.0, CMS dosage is 1.0% (on o.d. pulp),mixing time is 45min and drying temperature is105~C.

  10. 2-Oxo-1,2-dihydroquinoline-4-carboxylic acid monohydrate

    Directory of Open Access Journals (Sweden)

    Yassir Filali Baba

    2016-06-01

    Full Text Available In the title compound, C10H7NO3·H2O, O—H...O hydrogen bonds involving the carboxyl groups, the keto groups and the lattice water molecules form stepped sheets approximately parallel to {010} which are tied together by pairwise N—H...O interactions. The asymmetric unit contains two independent quinolone derivatives and two water molecules, one of which is disordered over two positions, of equal occupancy.

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

    Science.gov (United States)

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

    2014-05-19

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

  12. N-benzoylated 1,4,8,11-tetraazacyclotetradecane and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, crystal structure, catalytic and antimicrobial studies

    Science.gov (United States)

    Nirmala, G.; Rahiman, A. Kalilur; Sreedaran, S.; Jegadeesh, R.; Raaman, N.; Narayanan, V.

    2010-09-01

    A series of N-benzoylated cyclam ligands incorporating three different benzoyl groups 1,4,8,11-tetra-(benzoyl)-1,4,8,11-tetraazacyclotetradecane (L 1), 1,4,8,11-tetra-(2-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 2) and 1,4,8,11-tetra-(4-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 3) and their nickel(II) and copper(II) complexes are described. Crystal structure of L 1 is also reported. The ligands and complexes were characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. N-benzoylation causes red shift in the λmax values of the complexes. The cyclic voltammogram of the complexes of ligand L 1 show one-electron, quasi-reversible reduction wave in the region -1.00 to -1.04 V, whereas that of L 2 and L 3 show two quasi-reversible reduction peaks. Nickel complexes show one-electron quasi-reversible oxidation wave at a positive potential in the range +1.05 to +1.15 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment values μeff 1.70-1.73 BM which is close to the spin-only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. All the ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.

  13. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    Energy Technology Data Exchange (ETDEWEB)

    Bahrami, Zohreh; Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [University of Tehran, School of Chemistry, College of Science (Iran, Islamic Republic of); Ziarani, Ghodsi Mohammadi [Alzahra University, Research Laboratory of Pharmaceutical (Iran, Islamic Republic of)

    2015-03-15

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N{sub 2} adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples.

  14. Behavior of carboxylic acids upon complexation with beryllium compounds.

    Science.gov (United States)

    Mykolayivna-Lemishko, Kateryna; Montero-Campillo, M Merced; Mó, Otilia; Yáñez, Manuel

    2014-07-31

    A significant acidity enhancement and changes on aromaticity were previously observed in squaric acid and its derivatives when beryllium bonds are present in those systems. In order to know if these changes on the chemical properties could be considered a general behavior of carboxylic acids upon complexation with beryllium compounds, complexes between a set of representative carboxylic acids RCOOH (formic acid, acetic acid, propanoic acid, benzoic acid, and oxalic acid) and beryllium compounds BeX2 (X = H, F, Cl) were studied by means of density functional theory calculations. Complexes that contain a dihydrogen bond or a OH···X interaction are the most stable in comparison with other possible BeX2 complexation patterns in which no other weak interactions are involved apart from the beryllium bond. Formic, acetic, propanoic, benzoic, and oxalic acid complexes with BeX2 are much stronger acids than their related free forms. The analysis of the topology of the electron density helps to clarify the reasons behind this acidity enhancement. Importantly, when the halogen atom is replaced by hydrogen in the beryllium compound, the dihydrogen bond complex spontaneously generates a new neutral complex [RCOO:BeH] in which a hydrogen molecule is lost. This seems to be a trend for carboxylic acids on complexing BeX2 compounds.

  15. ELECTROANALYTICAL APPLICATIONS OF CARBOXYL-MODIFIED CARBON NANOTUBE FILM ELECTRODES

    Institute of Scientific and Technical Information of China (English)

    C.G. Hu; W.L. Wang; K.J. Liao; W. Zhu

    2003-01-01

    The electrochemical behavior of a carboxyl-modified carbon nanotube films was investigated to explore its possibility in electroanalytical applicaton. Cyclic voltammetry of quinone was conducted in 1mol/L Na2SO4, which showed a stable, quasi-reversible voltammetric response for quinone / hydroquinone, and the anodic and the cathodic peak potentials were 0.657V and -0.029V (vs. SCE) at a scan rate of 0.1V.s-1, respectively. Both anodic and cathodic peak currents depended linearly on the square root of the scan rate over the range of 0.01-0. 5 V.s-1, which suggested that the process of the electrode reactions was diffusion-controlled. Carboxyl-modified carbon nanotube electrodes made it possible to determine low level of dopamine selectively in the presence of a large excess of ascorbic acid in acidic media using derivative voltammetry.The results obtained were discussed in details. This work demonstrates the potential of carboxyl-modified carbon nanotube electrodes for electroanalytical applications.

  16. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    Science.gov (United States)

    Bahrami, Zohreh; Badiei, Alireza; Ziarani, Ghodsi Mohammadi

    2015-03-01

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N2 adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples.

  17. Oxidation of Alpha-Ketoglutarate Is Required for Reductive Carboxylation in Cancer Cells with Mitochondrial Defects

    Directory of Open Access Journals (Sweden)

    Andrew R. Mullen

    2014-06-01

    Full Text Available Mammalian cells generate citrate by decarboxylating pyruvate in the mitochondria to supply the tricarboxylic acid (TCA cycle. In contrast, hypoxia and other impairments of mitochondrial function induce an alternative pathway that produces citrate by reductively carboxylating α-ketoglutarate (AKG via NADPH-dependent isocitrate dehydrogenase (IDH. It is unknown how cells generate reducing equivalents necessary to supply reductive carboxylation in the setting of mitochondrial impairment. Here, we identified shared metabolic features in cells using reductive carboxylation. Paradoxically, reductive carboxylation was accompanied by concomitant AKG oxidation in the TCA cycle. Inhibiting AKG oxidation decreased reducing equivalent availability and suppressed reductive carboxylation. Interrupting transfer of reducing equivalents from NADH to NADPH by nicotinamide nucleotide transhydrogenase increased NADH abundance and decreased NADPH abundance while suppressing reductive carboxylation. The data demonstrate that reductive carboxylation requires bidirectional AKG metabolism along oxidative and reductive pathways, with the oxidative pathway producing reducing equivalents used to operate IDH in reverse.

  18. "S" shaped organotin(IV) carboxylates based on amide carboxylic acids: Syntheses, crystal structures and antitumor activities

    Science.gov (United States)

    Xiao, Xiao; Li, Yan; Dong, Yuan; Li, Wenliang; Xu, Kun; Shi, Nianqiu; Liu, Xin; Xie, Jingyi; Liu, Peigen

    2017-02-01

    Three organotin carboxylates based on amide carboxylic acids: (Ph3Sn)2(L1) (1) (L1 = 3,3‧-(1,3,5,7-tetraoxo-5,7-dihydropyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)dipropionic acid), (Ph3Sn)2(L2)·C7H8 (2) (L2 = 3,3‧-(1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo [lmn][3,8]phenanthroline-2,7-diyl)dipropionic acid), [(Ph3Sn)(CH3CH2O)]2(L3) (3) (L3 = 2,2‧-(1,3,5,7-tetraoxo-5,7-dihydropyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl) dibenzoic acid) were synthesized and characterized by elemental analysis, IR, 1H, 13C, 119Sn NMR spectroscopy and X-ray crystallography diffraction analyses. Complexes 1-3 are di-nuclear triphenlytin carboxylates owning "S" shaped monomer structures. Ligands in 1-3 adopt unidentate coordination. Intermolecular hydrogen bonds and Sn···O interactions help complexes 1-3 build their supramolecular structures which are discussed in detail. The preliminary antitumor activities of 1-3 against HepG2 cell lines have also been studied.

  19. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    Directory of Open Access Journals (Sweden)

    H. F. Xie

    2012-09-01

    Full Text Available Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN. The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg, mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOHs nanocomposites were investigated by differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, universal test machine, thermogravimetric analysis and scanning electron microscopy (SEM. DSC kinetic studies showed that the addition of MWCNT–COOHs accelerated the curing reaction of the rubber-toughened epoxy resin. DMA results revealed that Tg of rubber-toughened epoxy nanocomposites lowered with MWCNT–COOH contents. The tensile strength, elongation at break, flexural strength and flexural modulus of DGEBA/CTBN/MWCNT-COOHs nanocomposites were increased at lower MWCNT-COOH concentration. A homogenous dispersion of nanocomposites at lower MWCNT–COOH concentration was observed by SEM.

  20. Cu(I)-catalyzed (11)C carboxylation of boronic acid esters: a rapid and convenient entry to (11)C-labeled carboxylic acids, esters, and amides.

    Science.gov (United States)

    Riss, Patrick J; Lu, Shuiyu; Telu, Sanjay; Aigbirhio, Franklin I; Pike, Victor W

    2012-03-12

    Rapid and direct: the carboxylation of boronic acid esters with (11)CO(2) provides [(11)C]carboxylic acids as a convenient entry into [(11)C]esters and [(11)C]amides. This conversion of boronates is tolerant to diverse functional groups (e.g., halo, nitro, or carbonyl).

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

    Directory of Open Access Journals (Sweden)

    Patricia B. da Silva

    2015-12-01

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

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

    Science.gov (United States)

    Silva, Patricia B da; Bonifácio, Bruna V; Frem, Regina C G; Godoy Netto, Adelino V; Mauro, Antonio E; Ferreira, Ana M da Costa; Lopes, Erica de O; Raddi, Maria S G; Bauab, Tais M; Pavan, Fernando R; Chorilli, Marlus

    2015-12-16

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

  3. Self-assembled copper(II) coordination polymers derived from aminopolyalcohols and benzenepolycarboxylates: structural and magnetic properties.

    Science.gov (United States)

    Kirillov, Alexander M; Karabach, Yauhen Y; Haukka, Matti; Guedes da Silva, M Fatima C; Sanchiz, Joaquin; Kopylovich, Maximilian N; Pombeiro, Armando J L

    2008-01-07

    The new copper(II) or copper(II)/sodium(I) 1D coordination polymers [Cu2(Hmdea)2(mu-H2O)(mu2-tpa)]n.2nH2O (1), [Cu2(H2tipa)2(mu2-ipa)]n.4nH2O (2), [Cu2(H2tea)2Na(H2O)2(mu2-tma)]n.6nH2O (3), [Cu2(H2tea)2(mu2-ipa)]n.nH2O (4a), and [Cu2(H2tea)2{mu3-Na(H2O)3}(mu3-ipa)]n(NO3)n.0.5nH2O (4b) have been prepared in aqueous medium by self-assembly from copper(II) nitrate, aminopolyalcohols [methyldiethanolamine (H2mdea), triisopropanolamine (H3tipa), and triethanolamine (H3tea)] as main chelating ligands and benzenepolycarboxylic acids [terephthalic (H2tpa), isophthalic (H2ipa), and trimesic (H3tma) acid] as spacers. They have been characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses, the latter indicating the formation of unusual multinuclear metal cores interconnected by various benzenepolycarboxylate spacers, leading to distinct wavelike, zigzag, or linear 1D polymeric metal-organic chains. These are further extended to 2D or 3D hydrogen-bonded supramolecular networks via extensive interactions with the intercalated crystallization water molecules. The latter are associated, also with aqua ligands, by hydrogen bonds resulting in acyclic (H2O)3 clusters in 1, (H2O)8 clusters in 2, infinite 1D water chains in 3, and disordered water-nitrate associates in 4b, all playing a key role in the structure stabilization and its extension to further dimensions. Variable-temperature magnetic susceptibility measurements have shown that 1-4 exhibit a moderately strong ferromagnetic coupling through the alkoxo bridge. The small Cu-O-Cu bridging angle and the large out-of-plane displacement of the carbon atom of the alkoxo group accounts for this behavior. The magnetic data have been analyzed by means of a dinuclear and a 1D chain model, and the magnetic parameters have been determined. The magnetic exchange coupling in 3, to our knowledge, is the highest found in alkoxo-bridged copper(II) complexes.

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

    Science.gov (United States)

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

    2006-03-01

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

  5. Physicochemical model of detonation synthesis of nanoparticles from metal carboxylates

    Science.gov (United States)

    Tolochko, B. P.; Chernyshev, A. P.; Ten, K. A.; Pruuel, E. R.; Zhogin, I. L.; Zubkov, P. I.; Lyakhov, N. Z.; Luk'yanchikov, L. A.; Sheromov, M. A.

    2008-02-01

    We have shown previously that when metal carboxylates are subjected to a shock-wave action, diamond nanoparticles and nanoparticles of metals (Ag, Bi, Co, Fe, Pb) are formed and their characteristic size is about 30-200 Å. The metal nanoparticles formed are covered by an amorphous-carbon layer up to 20 Å thick. In this work we put forward a physicochemical model of the formation of diamond and metal nanoparticles from metal carboxylates upon shock-wave action. The energy released upon detonation inside the precursor is lower than in regions not occupied by the stearates. The characteristic time of temperature equalization has been estimated to be on the order of ˜10-3 s, which is greater by a factor of ˜103 than the characteristic reaction time. Due to the adiabatic nature of the processes occurring, the typical temperature of a "particle" will be lower than the temperature of the surrounding medium. In the framework of the model suggested, it has been assumed that the growth of metal clusters should occur by the diffusion mechanism; i.e., the "building material" is supplied through diffusion. The calculation using our previous experimental data on the reaction time and average size of metal particles has shown that the diffusion properties of the medium in which the metal nanoparticles are formed are close to those of the liquid state of the substance. The temperature and pressure under detonation conditions markedly exceed the analogous parameters characteristic of experiments on the thermodestruction of metal carboxylates. The small time of existence of the reaction mixture is compensated by the high mobility and concentration of reagents.

  6. Study on Copolymerization of Rare Earth-Carboxylic Acid Complex

    Institute of Scientific and Technical Information of China (English)

    Qiu Guanmin(邱关明); Zhang Ming(张明); Yan Chang hao(严长浩); Zhou Lanxiang(周兰香); Dai Shaojun(戴少俊); Okamo to Hiroshi

    2003-01-01

    Complex of rare earth with carboxylic acid was prepared by precipita tion and direct method. It was copolymerized with such monomers as acrylic acid and other ones to synthesize ionomer of rare earth and organic polymer with different rare earth contents. Its glass-transition temperature and heat stability were analyzed by TG and DTA. Infra-red detector was used to show its structure. The effect of rare earth complex prepared by different methods on copolymerization and properties of copolymers was also discussed.

  7. Sodium borohydride reduction of aromatic carboxylic acids via methyl esters

    Indian Academy of Sciences (India)

    Aamer Saeed; Zaman Ashraf

    2006-09-01

    A number of important aromatic carboxylic acids precursors, or intermediates in the syntheses of natural products, are converted into methyl esters and reduced to the corresponding primary alcohols using a sodium borohydride-THF-methanol system. The alcohols are obtained in 70-92% yields in 2-5 hours, in a pure state. This two-step procedure not only provides a better alternative to aluminum hydride reduction of acids but also allows the selective reduction of esters in presence of acids, amides, nitriles or nitro functions which are not affected under these conditions.

  8. 1H-Imidazol-3-ium-4-carboxylate

    Directory of Open Access Journals (Sweden)

    Qiang Cao

    2012-01-01

    Full Text Available In the title compound, C4H4N2O2, both imidazole N atoms are protonated and carboxylate group is deprotonated, resulting in a zwitterion. The molecule is essentially planar, with an r.m.s. deviation of 0.012 (1 Å. In the crystal, N—H...O hydrogen bonds and π–π stacking interactions [centroid–centroid distance = 3.674 (2 Å] between the imidazole rings link the molecules into a three-dimensional supramolecular network.

  9. Azetidine-2-carboxylic acid in garden beets (Beta vulgaris).

    Science.gov (United States)

    Rubenstein, Edward; Zhou, Haihong; Krasinska, Karolina M; Chien, Allis; Becker, Christopher H

    2006-05-01

    Azetidine-2-carboxylic acid (L-Aze) is a toxic and teratogenic non-protein amino acid. In many species, including man, L-Aze is misincorporated into protein in place of proline, altering collagen, keratin, hemoglobin, and protein folding. In animal models of teratogenesis, it causes a wide range of malformations. The role of L-Aze in human disease has been unexplored, probably because the compound has not been associated with foods consumed by humans. Herein we report the presence of L-Aze in the garden or table beet (Beta vulgaris).

  10. Bacterial conversion of phenylalanine and aromatic carboxylic acids into dihydrodiols.

    Science.gov (United States)

    Wegst, W; Tittmann, U; Eberspächer, J; Lingens, F

    1981-03-15

    Strain E of chloridazon-degrading bacteria, when grown on L-phenylalanine accumulates cis-2,3-dihydro-2,3-dihydroxyphenylalanine. In experiments with resting cells and during growth the bacterium converts the aromatic carboxylic acids phenylacetate, phenylpropionate, phenylbutyrate and phenyl-lactate into the corresponding cis-2,3-dihydrodiol compounds. The amino acids L-phenylalanine, N-acetyl-L-phenylalanine and t-butyloxycarbonyl-L-phenylalanine were also transformed into dihydrodiols. All seven dihydrodiols, thus obtained, were characterized both by conventional analytical techniques and by the ability to serve as substrates for a cis-dihydrodiol dehydrogenase.

  11. Uncatalysed Production of Coumarin-3-carboxylic Acids: A Green Approach

    Directory of Open Access Journals (Sweden)

    Joel Martínez

    2016-01-01

    Full Text Available A green contribution in short reaction times with moderate yields to produce coumarin-3-carboxylic acids is offered. Five different modes to activate the reactions (microwave, near-infrared, mechanical milling, and ultrasound were compared with mantle heating in the presence or absence of ethanol, a green solvent. Near-infrared and microwave irradiations deliver the best yields in contrast to ultrasound and mechanical milling; moreover, these four processes offered shorter reaction times in comparison with the conventional mantle heating method. It is also important to highlight that the obtained molecules were produced without the requirement of a catalyst and two nonconventional energies forms are presented as new processes.

  12. Separation and determination of some carboxylic acids by capillary electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Sladkov, V.; Fourest, B

    2006-07-01

    Separation and determination of some organic acids, mono-carboxylic (formic and acetic), dicarboxylic (oxalic and tartaric), tricarboxylic (citric) acids and aromatic acids (phtalic, benzoic, mellitic and trimellitic), by capillary electrophoresis are reviewed. The method development parameters, such as separation and injection mode, are discussed. Special attention is paid to the comparison of different detection types (spectroscopic and electrochemical). The optimisation of the carrier electrolyte composition (choice of carrier electrolyte, effect of pH, ionic strength, electro-osmotic flow modifier) is treated. Different additives (alkali-earth and transition metal ions, cyclodextrins and alcohol), which are often used for improving organic acid separation, are also considered. (authors)

  13. 2-Amino-4-methylpyridinium 6-carboxypyridine-2-carboxylate methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Behrouz Notash

    2011-01-01

    Full Text Available In the title solvated molecular salt, C6H9N2+·C7H4NO4−·CH4O, the pyridine N atom of 2-amino-4-methylpyridine is protonated and one carboxyl group of pyridine-2,6-dicarboxylic acid is deprotonated. The dihedral angles between the –CO2 and –COH groups and the pyridine ring are 0.65 (13 and 7.4°. The crystal packing is stabilized by intermolecular N—H...O, O—H...O and weak C—H...O hydrogen bonds.

  14. Induction of apoptosis in leukemia cell lines by new copper(II) complexes containing naphthyl groups via interaction with death receptors.

    Science.gov (United States)

    Fernandes, Christiane; Horn, Adolfo; Lopes, Bruna F; Bull, Erika S; Azeredo, Nathália F B; Kanashiro, Milton M; Borges, Franz V; Bortoluzzi, Adailton J; Szpoganicz, Bruno; Pires, Anderson B; Franco, Roberto W A; Almeida, João Carlos de A; Maciel, Leide L F; Resende, Jackson A L C; Schenk, Gerhard

    2015-12-01

    The synthesis, physico-chemical characterization and cytotoxicity of four new ligands and their respective copper(II) complexes toward two human leukemia cell lines (THP-1 and U937) are reported (i.e. [(HL1)Cu(μ-Cl)2Cu(HL1)]Cl2·H2O (1), [(H2L2)Cu(μ-Cl)2Cu(H2L2)]Cl2·5H2O (2), [(HL3)Cu(μ-Cl)2Cu(HL3)]Cl2·4H2O (3), [(H2L4)Cu(μ-Cl)2Cu(H2L4)]Cl2·6H2O (4)). Ligands HL1 and HL3 contain two pyridines, amine and alcohol moieties with a naphthyl pendant unit yielding a N3O coordination metal environment. Ligands H2L2 and H2L4 have pyridine, phenol, amine and alcohol groups with a naphthyl pendant unit providing a N2O2 coordination metal environment. These compounds are likely to be dinuclear in the solid state but form mononuclear species in solution. The complexes have an antiproliferative effect against both leukemia cell lines; complex (2) exhibits higher activity than cisplatin against U937 (8.20 vs 16.25μmoldm(-3)) and a comparable one against THP-1. These human neoplastic cells are also more susceptible than peripheral blood mononuclear cells (PBMCs) toward the tested compounds. Using C57BL/6 mice an LD50 of 55mgkg(-1) was determined for complex (2), suggesting that this compound is almost four times less toxic than cisplatin (LD50=14.5mgkg(-1)). The mechanism of cell death promoted by ligand H2L2 and by complexes (2) and (4) was investigated by a range of techniques demonstrating that the apoptosis signal triggered at least by complex (2) starts from an extrinsic pathway involving the activation of caspases 4 and 8. This signal is amplified by mitochondria with the concomitant release of cytochrome c and the activation of caspase 9.

  15. Modeling dinuclear copper sites of biological relevance - synthesis, molecular-structure, magnetic-properties, and h-1- nmr spectroscopy of a nonsymmetric dinuclear copper(ii) complex - microcalorimetric determination of stepwise complexation of copper(ii) by a nonsymmetric dinucleating ligand

    NARCIS (Netherlands)

    Lubben, M; Hage, R.; Meetsma, A.; Bijma, Koos; Feringa, B.L.

    1995-01-01

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

  16. Kinetics of the oxidative hydroxylation of tetraphosphorus in the presence of copper(II chloride modified by humic (fulvo- acid

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available It was established that in mild conditions (50-70 oC, РО2= 1 atm white phosphorus effectively is oxidized by oxygen in water-toluene solutions of copper(II chloride modified by humic (fulvo- acid to give mainly phosphoric acid. Humic (fulvo- acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, intermediate and final products, optimum conditions of new catalytic reaction of P4 oxidation by oxygen in water medium were defined by kinetics, volumometry, redox-potentiometry, 31Р{1Н} NMR spectroscopy and  titration. 

  17. Copper(II) complexes of bis(amino amide) ligands: effect of changes in the amino acid residue.

    Science.gov (United States)

    Martí, Inés; Ferrer, Armando; Escorihuela, Jorge; Burguete, M Isabel; Luis, Santiago V

    2012-06-14

    A family of ligands derived from bis(amino amides) containing aliphatic spacers has been prepared, and their protonation and stability constants for the formation of Cu(2+) complexes have been determined potentiometrically. Important differences are associated to both the length of the aliphatic spacer and the nature of the side chains derived from the amino acid. In general, ligands containing aliphatic side chains display higher basicities as well as stability constants with Cu(2+). In the same way, basicities and stability constants tend to increase when decreasing the steric hindrance caused by the corresponding side-chain. FT-IR, UV-vis and ESI-MS were used for analyzing the complex species detected in the speciation diagram. UV-vis studies showed the presence of different coordination environments for the copper(II) complexes. Complexes with different stoichiometries can be formed in some instances. This was clearly highlighted with the help of ESI-MS experiments.

  18. Spectroscopic, solvent influence and thermal studies of ternary copper(II) complexes of diester and dinitrogen base ligands.

    Science.gov (United States)

    Emara, Adel A A; Abu-Hussein, Azza A A; Taha, Ahmed A; Mahmoud, Nelly H

    2010-10-15

    New mixed-ligand copper(II) complexes containing the bidentate dinitrogen ligands [N,N,N',N'-tetramethylethylenediamine (tmen), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)] and the bidentate dioxygen ligands [diethylmalonate (DEM), ethylacetoacetate (EAA) and ethylbenzoylacetate (EBA)] were prepared. The complexes were characterized by elemental analysis, infrared, mass and ESR spectral data, magnetic and molar conductance measurements and thermal gravimetric analysis. From the investigation, the geometries of the complexes are square planar for perchlorate complexes and a square pyramid or octahedral for the nitrate complexes. Solvatochromic behavior of the Cu(II) complexes indicates strong solvatochromism of their solutions in polar and non-polar solvents. The observed solvatochromism is due to the solute-solvent interaction between the chelate cation and the solvent molecules.

  19. Bis[(E-4-bromo-2-(methoxyiminomethylphenolato-κ2N,O1]copper(II

    Directory of Open Access Journals (Sweden)

    Shang-Sheng Gong

    2009-12-01

    Full Text Available In the title centrosymmetric mononuclear copper(II complex, [Cu(C8H7BrNO22], the CuII atom, lying on an inversion centre, is four-coordinated in a trans-CuN2O2 square-planar geometry by two phenolate O atoms and two oxime N atoms from two symmetry-related N,O-bidentate oxime-type ligands. Intermolecular C—H...O hydrogen bonds link neighbouring molecules into a one-dimensional supramolecular structure with an R22(14 ring motif. This structure is further stabilized by π–π stacking interactions between adjacent benzene rings [centroid–centroid distance = 3.862 (1 Å].

  20. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    OpenAIRE

    Ban, van den, A.W.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interesting reactions, since the generated products, aldehydes and alcohols, are potentially applicable in the fine-chemical industry. However, the reduction of carboxylic acids to the corresponding aldehydes is a thermodynamicall...

  1. A synthetic approach to carbon-14 labeled anti-bacterial naphthyridine and quinolone carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Ekhato, I.V.; Huang, C.C. (Parke, Davis and Co., Ann Arbor, MI (United States))

    1993-09-01

    Labeled versions of (S)-clinafloxacin (1) and two napththyridine carboxylic acid anti-bacterial compounds 2 and 3 which are currently in development were synthesized. Preparations started from hitherto unknown bromo compounds 22 and 10, from which the corresponding [sup 14]C-labeled aromatic carboxylic acids 23 and 12 were generated by metal-halogen exchange followed by carboxylation reaction. Details of these preparations are given. (author).

  2. (Quinoline-2-carboxyl-ato-κO)(quinoline-2-carb-oxy-lic acid-κO)bis-(quinoline-2-carb-oxy-lic acid-κN,O)potassium.

    Science.gov (United States)

    Ng, Seik Weng

    2010-07-17

    The K atom in the title complex, [K(C(10)H(6)NO(2))(C(10)H(7)NO(2))(3)], lies on a twofold rotation axis that relates one N,O-chelating quinoline-2-carb-oxy-lic acid to the other; their N and O atoms are cis to each other in the distorted octa-hedral coordination geometry. The K atom is also coordinated by another monodentate quinoline-2-carb-oxy-lic acid; the acid is disordered with respect to a monodentate quinoline-2-carboxyl-ate anion; the acid and anion are linked by an O-H⋯O hydrogen bond. An O-H⋯N hydrogen bond links adjacent mol-ecules into a linear chain structure along the a axis.

  3. Systematic coordination chemistry and cytotoxicity of copper(II) complexes with methyl substituted 4-nitropyridine N-oxides.

    Science.gov (United States)

    Puszko, Aniela; Brzuszkiewicz, Anna; Jezierska, Julia; Adach, Anna; Wietrzyk, Joanna; Filip, Beata; Pełczynska, Marzena; Cieslak-Golonka, Maria

    2011-08-01

    Three new nitrato copper(II) complexes of dimethyl substituted 4-nitropyridine N-oxide were synthesized and characterized by elemental analysis, magnetic, spectroscopic, thermal and X-ray methods, respectively. They were isolated as trans isomers, mononuclear (μ=1.70-1.88 BM), five (1-2) and four (3) coordinate species of general formula [Cu(NO3)2(H2O)L2] where L=2,3-dimethyl-, 2,5-dimethyl-4-nitropyridine N-oxide and [Cu (NO3)2L2], L=3,5-dimethyl-4-nitropyridine N-oxide, respectively. The X-ray crystal structure of (1) (L=2,3-dimethyl-4-nitropyridine N-oxide) was determined. The organic ligands, the complexes and copper hexaqua ion as a reference were tested in vitro on the cytotoxic activity against human cancer cell lines: MCF-7 (breast), SW-707 (colon) and P-388 (murine leukemia). The complexes are relatively strong cytotoxic agents towards P-388 cell line. Comparative analysis was performed for all known copper(II) complexes containing methyl derivatives of the 4-nitropyridine N-oxide on the basis of their composition, structure and cytotoxic activities. To obtain the typical structure for these species (i.e., 4-coordinate mononuclear of the type trans-[Cu(inorganic anion)2L2]), two methyl groups must be situated on both sides of nitrogen atom(s) (i.e., NO and NO2) in the ligand. The biological activity was found to be strongly dependent upon the number of the methyl groups and the type of cell line. The best cytotoxic results were found for the complexes without substituents or with one methyl group. Generally, for all cell lines, the complexation increased cytotoxicity when compared with the free ligands.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-10-01

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

  5. A new approach for crystallization of copper(ii) oxide hollow nanostructures with superior catalytic and magnetic response

    Science.gov (United States)

    Singh, Inderjeet; Landfester, Katharina; Chandra, Amreesh; Muñoz-Espí, Rafael

    2015-11-01

    We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism.We report the synthesis of copper(ii) oxide hollow nanostructures at ambient pressure and close to room temperature by applying the soft templating effect provided by the confinement of droplets in miniemulsion systems. Particle growth can be explained by considering a mechanism that involves both diffusion and reaction control. The catalytic reduction of p-nitrophenol in aqueous media is used as a model reaction to prove the catalytic activity of the materials: the synthesized hollow structures show nearly 100 times higher rate constants than solid CuO microspheres. The kinetic behavior and the order of the reduction reaction change due to the increase of the surface area of the hollow structures. The synthesis also leads to modification of physical properties such as magnetism. Electronic supplementary information (ESI) available: Associated structural and morphological analysis, XPS characterization, BET surface area, catalytic measurements, recycle tests of the catalyst, and magnetic characterizations. See DOI: 10.1039/c5nr05579b

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

    Science.gov (United States)

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

    2013-05-14

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

  7. Dinuclear cobalt(II) and copper(II) complexes with a Py2N4S2 macrocyclic ligand.

    Science.gov (United States)

    Núñez, Cristina; Bastida, Rufina; Lezama, Luis; Macías, Alejandro; Pérez-Lourido, Paulo; Valencia, Laura

    2011-06-20

    The interaction between Co(II) and Cu(II) ions with a Py(2)N(4)S(2)-coordinating octadentate macrocyclic ligand (L) to afford dinuclear compounds has been investigated. The complexes were characterized by microanalysis, conductivity measurements, IR spectroscopy and liquid secondary ion mass spectrometry. The crystal structure of the compounds [H(4)L](NO(3))(4), [Cu(2)LCl(2)](NO(3))(2) (5), [Cu(2)L(NO(3))(2)](NO(3))(2) (6), and [Cu(2)L(μ-OH)](ClO(4))(3)·H(2)O (7) was also determined by single-crystal X-ray diffraction. The [H(4)L](4+) cation crystal structure presents two different conformations, planar and step, with intermolecular face-to-face π,π-stacking interactions between the pyridinic rings. Complexes 5 and 6 show the metal ions in a slightly distorted square-pyramidal coordination geometry. In the case of complex 7, the crystal structure presents the two metal ions joined by a μ-hydroxo bridge and the Cu(II) centers in a slightly distorted square plane or a tetragonally distorted octahedral geometry, taking into account weak interactions in axial positions. Electron paramagnetic resonance spectroscopy is in accordance with the dinuclear nature of the complexes, with an octahedral environment for the cobalt(II) compounds and square-pyramidal or tetragonally elongated octahedral geometries for the copper(II) compounds. The magnetic behavior is consistent with the existence of antiferromagnetic interactions between the ions for cobalt(II) and copper(II) complexes, while for the Co(II) ones, this behavior could also be explained by spin-orbit coupling.

  8. Anti-cancer activity and mutagenic potential of novel copper(II) quinolinone Schiff base complexes in hepatocarcinoma cells.

    Science.gov (United States)

    Duff, Brian; Thangella, Venkat Reddy; Creaven, Bernadette S; Walsh, Maureen; Egan, Denise A

    2012-08-15

    This study determined the cytotoxic, cyto-selective and mutagenic potential of novel quinolinone Schiff base ligands and their corresponding copper(II) complexes in human-derived hepatic carcinoma cells (Hep-G2) and non-malignant human-derived hepatic cells (Chang). Results indicated that complexation of quinolinone Schiff bases with copper served to significantly enhance cytotoxicity. Here, the complex of (7E)-7-(3-ethoxy-2-hydroxybenzylideamino)-4-methylquinolin-2(1H)-one (TV117-FM) exhibited the lowest IC(50) value (17.9 μM) following 96 h continuous exposure, which was comparable to cisplatin (15.0 μM). However, results revealed that TV117-FM lacked cytoselectivity over non-malignant cells. Additionally, the complex was minimally effluxed from cells via Pglycoprotein (P-gp) and was shown to be non-mutagenic in the Standard Ames test. Furthermore, BrdU incorporation assays showed that it was capable of inhibiting DNA synthesis in a concentrationand time-dependent manner. However, inhibition was not as a consequence of DNA intercalation, as illustrated in electrophoretic mobility shift assays. Interestingly, it was shown that the ligand was capable of inhibiting the action of topoisomerase II, but this was lost following complexation. This indicated that the mechanism of action of the novel copper(II) complex was different from that of the parent ligand and suggests that TV117-FM may have a therapeutic role to play in the treatment of hepatocellular carcinoma. Studies are currently underway to elucidate the exact in vitro mechanism of action of this novel, metal-based anti-cancer agent.

  9. Mixed-ligand copper(II) phenolate complexes: Synthesis, spectral characterization, phosphate-hydrolysis, antioxidant, DNA interaction and cytotoxic studies

    Science.gov (United States)

    Gurumoorthy, Perumal; Mahendiran, Dharmasivam; Prabhu, Durai; Arulvasu, Chinnasamy; Rahiman, Aziz Kalilur

    2015-01-01

    A series of phenol-based mixed-ligand copper(II) complexes of the type [CuL1-4(diimine)] (1-8), where L1-4 = N1,N2-bis(5-substituted-2-hydroxybenzylidene)-1,2-ethylene/phenylenediimine and diimine = 2,2‧-bipyridyl (bpy) or 1,10-phenanthroline (phen), have been isolated and fully characterized by analytical and spectral techniques. Electronic spectra of complexes suggest Cu(II) cation has a d9 electronic configuration, adopting distorted octahedral geometry with axial elongation, due to Jahn-Teller effect. Electrochemical studies of complexes evidenced one-electron irreversible reduction wave in the cathodic region. The observed rate constant (k) values for the hydrolysis of 4-nitrophenylphosphate (4-NPP) are in the range of 0.25-3.82 × 10-2 min-1. The obtained room temperature magnetic moment values (1.79-1.90 BM) lies within the range observed for octahedral copper(II) complexes. Antioxidant studies revealed that these complexes possess considerable radical scavenging potency against DPPH. The binding studies of complexes with calf thymus DNA (CT-DNA) revealed intercalation with minor-groove binding, and the complex 4 exhibits highest binding activity than the other complexes. The cleavage activity on supercoiled pBR322 DNA revealed the involvement of hydroxyl radical and singlet-oxygen as reactive oxygen species, and complexes encourage binding to minor-groove. Further, the cytotoxicity of complex 4 on human hepatocellular liver carcinoma HepG2 cell line implies the cell death through apoptosis.

  10. Do carboximide–carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

    Directory of Open Access Journals (Sweden)

    Ramanpreet Kaur

    2015-05-01

    Full Text Available Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular interactions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations.

  11. Do carboximide-carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics.

    Science.gov (United States)

    Kaur, Ramanpreet; Gautam, Raj; Cherukuvada, Suryanarayan; Guru Row, Tayur N

    2015-05-01

    Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular inter-actions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations.

  12. Metazoan promoters

    DEFF Research Database (Denmark)

    Lenhard, Boris; Sandelin, Albin Gustav; Carninci, Piero

    2012-01-01

    Promoters are crucial for gene regulation. They vary greatly in terms of associated regulatory elements, sequence motifs, the choice of transcription start sites and other features. Several technologies that harness next-generation sequencing have enabled recent advances in identifying promoters...... and their features, helping researchers who are investigating functional categories of promoters and their modes of regulation. Additional features of promoters that are being characterized include types of histone modifications, nucleosome positioning, RNA polymerase pausing and novel small RNAs. In this Review, we...... discuss recent findings relating to metazoan promoters and how these findings are leading to a revised picture of what a gene promoter is and how it works....

  13. Substituent effects on hydrogen bonding of aromatic amide-carboxylate

    Science.gov (United States)

    Sen, Ibrahim; Kara, Hulya; Azizoglu, Akın

    2016-10-01

    N-(p-benzoyl)-anthranilic acid (BAA) derivatives have been synthesized with different substituents (X: Br, Cl, OCH3, CH3), and their crystal structures have been analyzed in order to understand the variations in their molecular geometries with respect to the substituents by using 1H NMR, 13C NMR, IR and X-ray single-crystal diffraction. The carboxylic acid group forms classic Osbnd H ⋯ O hydrogen bonded dimers in a centrosymmetric R22(8) ring motifs for BAA-Br and BAA-Cl. However, no carboxylic acid group forms classic Osbnd H ⋯ O hydrogen bonded dimers in BAA-OCH3 and BAA-CH3. The asymmetric unit consists of two crystallographically independent molecules in BAA-OCH3. DFT computations show that the interaction energies between monomer and dimer are in the range of 0.5-3.8 kcal/mol with the B3LYP/6-31 + G*, B3LYP/6-31 ++G*, B3LYP/6-31 ++G**, and B3LYP/AUG-cc-pVDZ levels of theory. The presence of different hydrogen bond patterns is also governed by the substrate. For monomeric compounds studied herein, theoretical calculations lead to two low-energy conformers; trans (a) and cis (b). Former one is more stable than latter by about 4 kcal/mol.

  14. Integrated process for preparing a carboxylic acid from an alkane

    Science.gov (United States)

    Benderly, Abraham; Chadda, Nitin; Sevon, Douglass

    2011-12-20

    The present invention relates to an integrated process for producing unsaturated carboxylic acids from the corresponding C.sub.2-C.sub.4 alkane. The process begins with performance of thermally integrated dehydrogenation reactions which convert a C.sub.2-C.sub.4 alkane to its corresponding C.sub.2-C.sub.4 alkene, and which involve exothermically converting a portion of an alkane to its corresponding alkene by oxidative dehydrogenation in an exothermic reaction zone, in the presence of oxygen and a suitable catalyst, and then feeding the products of the exothermic reaction zone to an endothermic reaction zone wherein at least a portion of the remaining unconverted alkane is endothermically dehydrogenated to form an additional quantity of the same corresponding alkene, in the presence of carbon dioxide and an other suitable catalyst. The alkene products of the thermally integrated dehydrogenation reactions are then provided to a catalytic vapor phase partial oxidation process for conversion of the alkene to the corresponding unsaturated carboxylic acid or nitrile. Unreacted alkene and carbon dioxide are recovered from the oxidation product stream and recycled back to the thermally integrated dehydrogenation reactions.

  15. Biocompatibility studies of polyacrylonitrile membranes modified with carboxylated polyetherimide

    Energy Technology Data Exchange (ETDEWEB)

    Senthilkumar, S.; Rajesh, S.; Jayalakshmi, A.; Mohan, D., E-mail: mohantarun@gmail.com

    2013-10-15

    Poly (ether-imide) (PEI) was carboxylated and used as the hydrophilic modification agent for the preparation of polyacrylonitrile (PAN) membranes. Membranes were prepared with different blend compositions of PAN and CPEI by diffusion induced precipitation. The modified membranes were characterized by thermo gravimetric analysis (TGA), mechanical analysis, scanning electron microscopy (SEM) and contact angle measurement to understand the influence of CPEI on the properties of the membranes. The biocompatibility studies exhibited reduced plasma protein adsorption, platelet adhesion and thrombus formation on the modified membrane surface. The complete blood count (CBC) results of CPEI incorporated membranes showed stable CBC values and significant decrease in the complement activation were also observed. In addition to good cytocompatibility, monocytes cultured on these modified membranes exhibited improved functional profiles in 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay. Thus it could be concluded that PAN/CPEI membranes with excellent biocompatibility can be useful for hemodialysis. Highlights: • Carboxylated PEI was prepared and utilized as hydrophilic modification agent. • CPEI incorporated into PAN to improved biocompatibility and cyto compatibility • Biocompatibility of membranes was correlated with morphology and hydrophilicity. • Antifouling studies of the PAN/CPEI membranes was studied by BSA as model foulant.

  16. The connexin43 carboxyl terminus and cardiac gap junction organization.

    Science.gov (United States)

    Palatinus, Joseph A; Rhett, J Matthew; Gourdie, Robert G

    2012-08-01

    The precise spatial order of gap junctions at intercalated disks in adult ventricular myocardium is thought vital for maintaining cardiac synchrony. Breakdown or remodeling of this order is a hallmark of arrhythmic disease of the heart. The principal component of gap junction channels between ventricular cardiomyocytes is connexin43 (Cx43). Protein-protein interactions and modifications of the carboxyl-terminus of Cx43 are key determinants of gap junction function, size, distribution and organization during normal development and in disease processes. Here, we review data on the role of proteins interacting with the Cx43 carboxyl-terminus in the regulation of cardiac gap junction organization, with particular emphasis on Zonula Occludens-1. The rapid progress in this area suggests that in coming years we are likely to develop a fuller understanding of the molecular mechanisms causing pathologic remodeling of gap junctions. With these advances come the promise of novel approach to the treatment of arrhythmia and the prevention of sudden cardiac death. This article is part of a Special Issue entitled: The Communicating junctions, composition, structure and characteristics. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. [Carboxyl nanodiamond as intracellular transporters of anticancer drug--podophyllotoxin].

    Science.gov (United States)

    Sun, Tao-Li; Wang, Bin; Peng, Yan; Ni, Jing-Man

    2013-01-01

    The purpose of this study is to investigate the intracellular transporters effect and the cytotoxicity of carboxyl nanodiamond (CND) - podophyllotoxin (PPT). Nanodiamond (ND) was treated with mixed carboxylic acid and finally got 64 nm CND by centrifugation, and then it was reacted with PPT to form CND-PPT. UV spectrophotometry was used to calculate the content of PPT in CND-PPT, the particle size distribution and zeta potential were measured by Dynamic laser scattering instrument. CND, PPT, CND-PPT and CND + PPT (physical mixture of CND and PPT) were characterized by Fourier transform infrared spectroscopy, at the same time, thermal analysis and element analysis were used to estimate the content of the PPT in CND-PPT. The affect of CND, PPT, CND-PPT on HeLa cell was measured with MTT assay. The results showed that content of PPT combined with CND accounted for about 10%. MTT assay showed that CND has low cytotoxicity and CND-PPT can increase the water soluble of PPT. As a conclusion, CND as a hydrophilic pharmaceutical carrier combined with PPT is able to increase the water solubility of PPT, at low concentration, CND-PPT can enhance the antitumor activity in comparison with PPT, so CND can be used as a potential anticancer drug carrier.

  18. Enhance decarboxylation reaction of carboxylic acids in clay minerals

    Energy Technology Data Exchange (ETDEWEB)

    Negron-Mendoza, A.; Ramos, S.; Albarran, G. [Instituto de Ciencias y Artes, Chiapas (Mexico). Escuela de Biologia

    1995-10-01

    Clay minerals are important constituents of the Earth`s crust. These minerals catalyze reactions in several ways: by energy transfer processes, redox reactions, stabilization of intermediates and by Broensted or Lewis acidity behavior. Important set of organic reactions can be improved in the precedence of clay minerals. Besides the properties of clays to catalyze chemical reactions, it is possible to enhance some of its reactions by using ionizing radiation. The phenomenon of radiation-induced catalysis may be connected with ionizing process in the solid and with the trapped non-equilibrium charge carriers. In this paper we are reporting the decarboxylation reaction of carboxylic acids catalyzed by clay and by irradiation of the system acid-clay. We studied the behaviour of several carboxylic acids and analyzed them by gas chromatography, X-ray and infrared spectroscopy. The results showed that decarboxylation of the target compound is the dominating pathway. The reaction is enhanced by gamma radiation in several orders of magnitude. (author).

  19. Dispersion of Co-poly Carboxylate Superplasticizer Containing Polyether Side Chain

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Free radical co-polymerization was employed to synthesize co-poly carboxylate (PC) superplasticizers with different amount of carboxyl and methyl polyethylene glycol (MPEG) side chain.Dispersion ability and retention of PC were compared with one another. The results show that increase of side chain is advantageous to dispersion, but it decreases when amount of MPEG is beyond a certain value which is different with the proportion of carboxyl. If the amount of carboxyl increases, the influence of side chain in copolymer on dispersion diminishes. Polyether side chain is advantageous to retention. And the author explained the mechanism of PC using the theory of steric repulsive force.

  20. Topologically unique heterometallic Cu(II)/Li coordination polymers self-assembled from N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid biobuffer: versatile catalyst precursors for mild hydrocarboxylation of alkanes to carboxylic acids.

    Science.gov (United States)

    Kirillova, Marina V; Kirillov, Alexander M; Martins, André N C; Graiff, Claudia; Tiripicchio, Antonio; Pombeiro, Armando J L

    2012-05-07

    The facile aqueous medium reactions of copper(II) nitrate with BES biobuffer [(HOCH(2)CH(2))(2)N(CH(2)CH(2)SO(3)H), hereinafter referred as H(3)bes] in the presence of various benzenecarboxylic acids [benzoic (Hba), 3-hydroxybenzoic (Hhba), and 3,5-dihydroxybenzoic (Hdhba) acid] and lithium hydroxide gave rise to the self-assembly generation of three new heterometallic Cu(II)/Li materials, [Li(H(2)O)(4)][Cu(4)(μ(2)-Hbes)(4)(μ(2)-ba)]·H(2)O (1) and [Cu(4)(μ(3)-Hbes)(4)(L){Li(H(2)O)(2)}](n)·3nH(2)O {L = μ(2)-hba (2) and μ(2)-dhba (3)}. They were isolated as air-stable crystalline solids and fully characterized by infrared (IR) and UV-vis spectroscopy and electrospray ionization (ESI)-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses. The latter revealed that 1-3 have comparable packing patterns and unit cell parameters, being composed of similar [Cu(4)(μ-Hbes)(4)(μ-carboxylate)](-) cores and [Li(H(2)O)(4)](+) cations (in 1) or [μ-Li(H(2)O)(2)](+) groups (in 2 and 3), which are arranged into discrete 0D aggregates in 1 or infinite 3D noninterpenetrating metal-organic networks in 2 and 3. The topological analysis of the coordination polymers 2 and 3 disclosed the trinodal 3,3,4-connected underlying nets with an unprecedented topology defined by the point symbol of (4.6.8)(4)(4(2).6)(2)(6(2).16(2).18(2)), further simplification of which resulted in the binodal 4,4-connected nets with the pts (PtS) topology. Apart from representing very rare examples of coordination compounds derived from H(3)bes, 1-3 feature solubility in water and were applied as efficient and versatile catalyst precursors for the mild (60 °C) single-pot hydrocarboxylation, by CO and H(2)O, of various gaseous, linear, and cyclic C(n) (n = 2-9) alkanes into the corresponding C(n+1) carboxylic acids, in H(2)O/MeCN medium under homogeneous conditions and in the presence of potassium peroxodisulfate. Total yields (based on alkane) of carboxylic acids up to 78% were

  1. Copper(II)-8-hydroxquinoline coprecipitation system for preconcentration and separation of cobalt(II) and manganese(II) in real samples.

    Science.gov (United States)

    Soylak, Mustafa; Kaya, Betul; Tuzen, Mustafa

    2007-08-25

    A separation-preconcentration procedure based on the coprecipitation of cobalt(II) and manganese(II) ions with copper(II)-8-hydroxquinoline system has been developed. The analytical parameters including pH, amount of copper(II) as carrier element, amount of 8-hydroxquinoline, sample volume, etc., was investigated for the quantitative recoveries of Co(II) and Mn(II). No interferic effects were observed from the concomitant ions which are present in real samples. The detection limits for analyte ions by three sigma criteria were 0.86microgL(-1) for cobalt and 0.98microgL(-1) for manganese. The validation of the presented preconcentration procedure was performed by the analysis of NIST SRM 2711 Montana soil and GBW 07605 Tea certified reference materials. The procedure presented was applied to the analyte contents of real samples including natural waters and some food samples with successfully analytical results.

  2. Synthesis and DNA cleavage activities of mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes which linked with uracil.

    Science.gov (United States)

    Wang, Xiao-Yan; Zhang, Ji; Li, Kun; Jiang, Ning; Chen, Shan-Yong; Lin, Hong-Hui; Huang, Yu; Ma, Li-Jian; Yu, Xiao-Qi

    2006-10-01

    Mononuclear macrocyclic polyamine zinc(II), copper(II), cobalt(II) complexes, which could attach to peptide nucleic acid (PNA), were synthesized as DNA cleavage agents. The structures of these new mononuclear complexes were identified by MS and (1)H NMR spectroscopy. The catalytic activities on DNA cleavage of these mononuclear complexes with different central metals were subsequently studied, which showed that copper complex was better catalyst in the DNA cleavage process than zinc and cobalt complexes. The effects of reaction time, concentration of complexes were also investigated. The results indicated that the copper(II) complexes could catalyze the cleavage of supercoiled DNA (pUC 19 plasmid DNA) (Form I) under physiological conditions to produce selectively nicked DNA (Form II, no Form III produced) with high yields. The mechanism of the cleavage process was also studied.

  3. Cloning of phenazine carboxylic acid genes of Fusarium fujikuroi ...

    African Journals Online (AJOL)

    STORAGESEVER

    2010-03-08

    Mar 8, 2010 ... 2Department of Plant Pathology, Faculty of Agriculture, Islamic Azad University, Rasht, Iran. Accepted ..... promotion and biocontrol by rhizobacteria. Curr. ... Jetiyanon K, Kloepper JW (2002) Mixtures of plant growth promoting.

  4. SYNTHESIS, CRYSTAL STRUCTURE, AND PROPERTIES OF COPPER(II COMPLEXES WITH 1,4,7-TRIS(2-AMINOETHYL-1,4,7-TRIAZACYCLONONANE

    Directory of Open Access Journals (Sweden)

    Masahiro Mikuriya

    2015-12-01

    Full Text Available Three kinds of copper(II complexes with 1,4,7-tris(2-aminoethyl-1,4,7-triazacyclononane (taetacn, [Cu(taetacn](ClO42 (1, [Cu(Htaetacn](ClO43 (2, and [Cu(Htaetacn](BF43 (3 were synthesized and characterized by elemental analyses, IR and UV-Vis spectroscopies. The spectral features are in harmony with an octahedral geometry for 1 and a square-pyramidal coordination for 2 and 3.

  5. Reagents for selective extraction of nickel(II), cobalt(II) and copper(II) from highly acidic sulfate feeds containing iron

    OpenAIRE

    Roebuck, James William

    2015-01-01

    This thesis focuses on development of new regents which are suitable for recovering nickel, cobalt and copper from laterite leach solutions, specifically focusing on reagent requirements for novel base metal flowsheets developed by Anglo American. The work aims to design reagents which can extract nickel(II), cobalt(II) and copper(II) from a highly acidic aqueous sulfate solutions whilst showing selectivity over iron(II) and iron(III). Chapter 1 reviews current extractive metallur...

  6. Visible-light-induced water oxidation by a hybrid photocatalyst consisting of bismuth vanadate and copper(II) meso-tetra(4-carboxyphenyl)porphyrin.

    Science.gov (United States)

    Nakashima, Shu; Negishi, Ryo; Tada, Hiroaki

    2016-03-04

    Copper(II) meso-tetra(4-carboxyphenyl)porphyrin surface-modified monoclinic scheelite bismuth vanadate (CuTCPP/BiVO4) has been synthesized via a two-step route involving chemisorption of TCPP on BiVO4 and successive Cu(II) ion incorporation into the TCPP, and the surface modification drastically enhances the water oxidation to oxygen (O2) under visible-light irradiation (λ > 430 nm).

  7. Magnetic Exchange in a Chloride- and Adeninium-Bridged Linear Trimer of Copper(II) -Octachlorobis(Adeninium)- Tricopper(II) Tetrahydrate

    Science.gov (United States)

    1976-09-28

    temperature. This result implies a value of IJI>300 cm" 1. Several Schiff base copper(II) trimers have been synthesized and examined magnetically,15-19...Although crystal structures have not been determined, chemical and physical evidence indicates these Schiff base complexes to be oxygen-bridged...The magnitude of J iii these corn- pounds is comparable to that observed in analogous dimeric Schiff base complexes.2 The exceptional case is bis N,N

  8. Structural diversity of copper(II) complexes with N-(2-pyridyl)imidazolidin-2-ones(thiones) and their in vitro antitumor activity.

    Science.gov (United States)

    Balewski, Łukasz; Sączewski, Franciszek; Bednarski, Patrick J; Gdaniec, Maria; Borys, Ewa; Makowska, Anna

    2014-10-23

    Six series of structurally different mono- and binuclear copper(II) complexes 5-10 were obtained by reacting N-(2-pyridyl)imidazolidin-2-ones (1a-l), N,N'-bis(2-pyridyl)imidazolidin-2-ones (2a,b), N-acyl-N'(2-pyridyl)imidazolodin-2-ones (3a-j) and N-(2-pyridyl)imidazolidine-2-thiones (4a-g) with copper(II) chloride at an ambient temperature. The coordination modes of the complexes obtained were established by elemental analysis, IR spectroscopic data and single crystal X-ray diffraction studies. The in vitro cytotoxic activities of both the free ligands and copper(II) complexes were evaluated using a crystal violet microtiter plate assay on five human tumor cell lines: LCLC-103H, A-427, SISO, RT-4 and DAN-G. The free ligands 1-4 at concentration attainable in cancer cells of 20 μM showed no meaningful cytotoxic effect with cell viability in the range of 88%-100%. The most potent copper(II) complex of 1-(6-ethoxy-2-pyridyl)imidazolidin-2-one (6b) exhibited selective cytotoxicity against A-427 lung cancer cell line, while the complexes of 1-(5-methyl-2-pyridyl)imidazolidine-2-thione (5h) and 1-(4-tert-butyl-2-pyridyl)imidazolidine-2-thione (5j) showed cytostatic effect against a whole panel of five human tumor cell lines. In conclusion, the only complexes that showed remarkably increased activity in comparison to the free ligands were those obtained from N-(2-pyridyl)imidazolidine-2-thiones 4c and 4e substituted with alkyl group at position 4 or 5 of pyridine ring.

  9. Structural Diversity of Copper(II Complexes with N-(2-PyridylImidazolidin-2-Ones(Thiones and Their in Vitro Antitumor Activity

    Directory of Open Access Journals (Sweden)

    Łukasz Balewski

    2014-10-01

    Full Text Available Six series of structurally different mono- and binuclear copper(II complexes 5–10 were obtained by reacting N-(2-pyridylimidazolidin-2-ones (1a–l, N,N'-bis(2-pyridylimidazolidin-2-ones (2a,b, N-acyl-N'(2-pyridylimidazolodin-2-ones (3a–j and N-(2-pyridylimidazolidine-2-thiones (4a–g with copper(II chloride at an ambient temperature. The coordination modes of the complexes obtained were established by elemental analysis, IR spectroscopic data and single crystal X-ray diffraction studies. The in vitro cytotoxic activities of both the free ligands and copper(II complexes were evaluated using a crystal violet microtiter plate assay on five human tumor cell lines: LCLC-103H, A-427, SISO, RT-4 and DAN-G. The free ligands 1–4 at concentration attainable in cancer cells of 20 μM showed no meaningful cytotoxic effect with cell viability in the range of 88%–100%. The most potent copper(II complex of 1-(6-ethoxy-2-pyridylimidazolidin-2-one (6b exhibited selective cytotoxicity against A-427 lung cancer cell line, while the complexes of 1-(5-methyl-2-pyridylimidazolidine-2-thione (5h and 1-(4-tert-butyl-2-pyridylimidazolidine-2-thione (5j showed cytostatic effect against a whole panel of five human tumor cell lines. In conclusion, the only complexes that showed remarkably increased activity in comparison to the free ligands were those obtained from N-(2-pyridylimidazolidine-2-thiones 4c and 4e substituted with alkyl group at position 4 or 5 of pyridine ring.

  10. Ternary complexes of copper(II) and cobalt(II) involving nitrite/pyrazole and tetradentate N4-coordinate ligand: Synthesis, characterization, structures and antimicrobial activity

    Science.gov (United States)

    Solanki, Ankita; Sadhu, Mehul H.; Kumar, Sujit Baran

    2015-12-01

    Five new mononuclear mixed ligand complexes of the type [Cu(NCCH3)(dbdmp)](ClO4)2, [M(ONO)(dbdmp)]ClO4, [M(pz) (dbdmp)](ClO4)2 where M = Cu(II) and Co(II), pz = 3,5-dimethylpyrazole and dbdmp = N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine have been synthesized and characterized by physico-chemical and spectroscopy studies. The crystal structures of three copper(II) complexes [Cu(NCCH3)(dbdmp)](ClO4)2, [Cu(ONO)(dbdmp)]ClO4 and [Cu(pz)(dbdmp)](ClO4)2 have been determined by single crystal X-ray diffraction studies. Structural analyses reveal the geometry of [Cu(pz)(dbdmp)](ClO4)2 is distorted square pyramidal and other two copper(II) complexes have distorted trigonal bipyramidal geometry. Molecular composition of cobalt(II) complexes have been determined by mass spectral data. The EPR spectra of copper(II) complexes in frozen acetonitrile solution exhibit axial spectra, characteristic of dx2-y2 ground state. Electrochemical studies of copper(II) complexes using glassy carbon as working electrode in acetonitrile solution show Cu(II)/Cu(I) couple with quasi reversible electron transfer versus Ag/Ag+ reference electrode. Antimicrobial activity of all the synthesized complexes were investigated against two Gram positive and two Gram negative bacterial strains.

  11. Formation of a dinuclear copper(II) complex through the cleavage of CN bond of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole

    Science.gov (United States)

    Shardin, Rosidah; Pui, Law Kung; Yamin, Bohari M.; Kassim, Mohammad B.

    2014-09-01

    A simple mononuclear octahedral copper(II) complex was attempted from the reaction of three moles of 1-benzoyl-3-(pyridin-2-yl)-1H-pyrazole and one mole of copper(II) perchlorate hexahydrate in methanol. However, the product of the reaction was confirmed to be a dinuclear copper(II) complex with μ-{3-(pyridin-2-yl)-pyrazolato} and 3-(pyridin-2-yl)-1H-pyrazole ligands attached to each of the Cu(II) centre atom. The copper(II) ion assisted the cleavage of the CbenzoylN bond afforded a 3-(pyridin-2-yl)-1H-pyrazole molecule. Deprotonation of the 3-(pyridin-2-yl)-1H-pyrazole gave a 3-(pyridin-2-yl)-pyrazolato, which subsequently reacted with the Cu(II) ion to give the {3-(pyridin-2-yl)-pyrazolato}{3-(pyridin-2-yl)-1H-pyrazole}Cu(II) product moiety. The structure of the dinuclear complex was confirmed by x-ray crystallography. The complex crystallized in a monoclinic crystal system with P2(1)/n space group and cell dimensions of a = 12.2029(8) Å, b = 11.4010(7) Å, c = 14.4052(9) Å and β = 102.414(2)°. The compound was further characterized by mass spectrometry, CHN elemental analysis, infrared and UV-visible spectroscopy and the results concurred with the x-ray structure. The presence of d-d transition at 671 nm (ɛ = 116 dm3 mol-1 cm-1) supports the presence of Cu(II) centres.

  12. Synthesis, spectral characterization, DNA binding ability and antibacterial screening of copper(II) complexes of symmetrical NOON tetradentate Schiff bases bearing different bridges

    Science.gov (United States)

    Bahaffi, Saleh O.; Abdel Aziz, Ayman A.; El-Naggar, Maher M.

    2012-08-01

    A novel series of four copper(II) complexes were synthesized by thermal reaction of copper acetate salt with symmetrical tetradentate Schiff bases, N,N'bis(o-vanillin)4,5-dimethyl-l,2-phenylenediamine (H2L1), N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H2L2), N,N'bis(o-vanillin)4,5-dichloro-1,2-phenylenediamine (H2L3) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H2L4), respectively. All the new synthesized complexes were characterized by using of microanalysis, FT-IR, UV-Vis, magnetic measurements, ESR, and conductance measurements, respectively. The data revealed that all the Schiff bases (H2L1-4) coordinate in their deprotonated forms and behave as tetradentate NOON coordinated ligands. Moreover, their copper(II) complexes have square planar geometry with general formula [CuL1-4]. The binding of the complexes with calf thymus DNA (CT-DNA) was investigated by UV-Vis spectrophotometry, fluorescence quenching and viscosity measurements. The results indicated that the complexes bind to CT-DNA through an intercalative mode. From the biological activity view, the copper(II) complexes and their parent ligands were screened for their in vitro antibacterial activity against the bacterial species Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli and Pseudomonas aeruginosai by well diffusion method. The complexes showed an increased activity in comparison to some standard drugs.

  13. Insight into the gas-phase structure of a copper(II) L-histidine complex, the agent used to treat Menkes disease.

    Science.gov (United States)

    Ziegler, Blake E; Marta, Richard A; Burt, Michael B; McMahon, Terry B

    2014-03-03

    Copper(II) L-histidine is used in the treatment of a rare neurological disease called Menkes disease. An infrared multiple photon dissociation (IRMPD) vibrational spectrum of the gas-phase copper(II) L-histidine complex has been obtained. This spectrum was compared to lowest-energy computational spectra obtained at the B3LYP/6-311+G** level of theory. Two species, CuHis1 and CuHis2, are very close in Gibbs free energy, and both have computed vibrational spectra in good agreement with the experimentally observed IRMPD spectrum. The first structure exhibits four histidine-copper interactions in the same plane and a fifth out-of-plane interaction. The second structure exhibits four histidine-copper interactions in the same plane. The fact that the experimental and computational spectra are found to be in good agreement adds considerable insight into the gas-phase structure of the copper(II) L-histidine complex.

  14. Development of an extractive spectrophotometric method for the determination of copper(II) in leafy vegetable and pharmaceutical samples using pyridoxal-4-phenyl-3-thiosemicarbazone (PPT).

    Science.gov (United States)

    Sarma, L Subramanyam; Kumar, J Rajesh; Reddy, K Janardhan; Reddy, A Varada

    2005-07-13

    A highly sensitive extractive spectrophotometric method has been developed for the determination of copper(II) using pyridoxal-4-phenyl-3-thiosemicarbazone(PPT) as an analytical reagent. The PPT forms reddish brown species of copper(II) at a pH range of 3.0-5.5, and the complex was extracted into n-butanol. The Cu(II)-PPT complex shows maximum absorbance at 440 nm, with molar absorptivity and Sandell's sensitivity being 2.16 x 10(4) L mol(-1) cm(-1) and 2.94 x 10(-3) microg cm(-2), respectively. The system obeys Beer's law in the range of 0.2-5.0 mg/L. The regression coefficient of the Beer's law straight line is 0.338, and the correlation coefficient is 0.96. The detection limit of the method is 0.0065 microg mL(-1). Most of the common metal ions generally found associated with copper do not interfere. The repeatability of the method was checked by finding the relative standard deviation. The developed method has been successfully employed for the determination of copper(II) in leafy vegetable and pharmaceutical samples. The method is evaluated by analyzing samples from the Bureau of Analyzed Samples (BCS 233, 266, 216/1, 207, and 179) and by intercomparison of experimental values using AAS.

  15. Geometrical and optical benchmarking of copper(II) guanidine-quinoline complexes: insights from TD-DFT and many-body perturbation theory (part II).

    Science.gov (United States)

    Hoffmann, Alexander; Rohrmüller, Martin; Jesser, Anton; dos Santos Vieira, Ines; Schmidt, Wolf Gero; Herres-Pawlis, Sonja

    2014-11-05

    Ground- and excited-state properties of copper(II) charge-transfer systems have been investigated starting from density-functional calculations with particular emphasis on the role of (i) the exchange and correlation functional, (ii) the basis set, (iii) solvent effects, and (iv) the treatment of dispersive interactions. Furthermore (v), the applicability of TD-DFT to excitations of copper(II) bis(chelate) charge-transfer systems is explored by performing many-body perturbation theory (GW + BSE), independent-particle approximation and ΔSCF calculations for a small model system that contains simple guanidine and imine groups. These results show that DFT and TD-DFT in particular in combination with hybrid functionals are well suited for the description of the structural and optical properties, respectively, of copper(II) bis(chelate) complexes. Furthermore, it is found an accurate theoretical geometrical description requires the use of dispersion correction with Becke-Johnson damping and triple-zeta basis sets while solvent effects are small. The hybrid functionals B3LYP and TPSSh yielded best performance. The optical description is best with B3LYP, whereby heavily mixed molecular transitions of MLCT and LLCT character are obtained which can be more easily understood using natural transition orbitals. An natural bond orbital analysis sheds light on the donor properties of the different donor functions and the intraguanidine stabilization during coordination to copper(I) and (II).

  16. Cytotoxic activity, X-ray crystal structures and spectroscopic characterization of cobalt(II), copper(II) and zinc(II) coordination compounds with 2-substituted benzimidazoles.

    Science.gov (United States)

    Sánchez-Guadarrama, Obdulia; López-Sandoval, Horacio; Sánchez-Bartéz, Francisco; Gracia-Mora, Isabel; Höpfl, Herbert; Barba-Behrens, Noráh

    2009-09-01

    Herein we present the synthesis, structural and spectroscopic characterization of coordination compounds of cobalt(II), copper(II) and zinc(II) with 2-methylbenzimidazole (2mbz), 2-phenylbenzimidazole (2phbz), 2-chlorobenzimidazole (2cbz), 2-benzimidazolecarbamate (2cmbz) and 2-guanidinobenzimidazole (2gbz). Their cytotoxic activity was evaluated using human cancer cell lines, PC3 (prostate), MCF-7 (breast), HCT-15 (colon), HeLa (cervic-uterine), SKLU-1 (lung) and U373 (glioblastoma), showing that the zinc(II) and copper(II) compounds [Zn(2mbz)(2)Cl(2)].0.5H(2)O, [Zn(2cmbz)(2)Cl(2)].EtOH, [Cu(2cmbz)Br(2)].0.7H(2)O and [Cu(2gbz)Br(2)] had significant cytotoxic activity. The isostructural cobalt(II) complexes showed not significant activity. The cytotoxic activity is related to the presence of halides in the coordination sphere of the metal ion. Recuperation experiments with HeLa cells, showed that the cells recuperated after removing the copper(II) compounds and, on the contrary, the cells treated with the zinc(II) compounds did not. These results indicate that the mode of action of the coordination compounds is different.

  17. Improved preparation of halopropyl bridged carboxylic ortho esters

    Directory of Open Access Journals (Sweden)

    Richard J. Petroski

    2008-10-01

    Full Text Available Bridged ortho esters of 3-halopropyl carboxylic acids were prepared by esterification of 3-methyl-3-hydroxymethyloxetane with 3-bromopropionyl chloride and pyridine in dry THF, followed by rearrangement with boron trifluoroetherate, to afford 1-(2-bromoethyl-4-methyl-2,6,7-trioxabicyclo[2,2,2]-octane. The 1-(2-iodoethyl-4-methyl-2,6,7-trioxabicyclo[2,2,2]-octane analogue could not be prepared directly by halogen exchange of 1-(2-bromoethyl-4-methyl-2,6,7-trioxabicyclo[2,2,2]-octane but could be prepared by halogen exchange of the (3-methyloxetan-3-ylmethyl 3-bromopropanoate with a mixture of sodium iodide and anhydrous sodium sulfate in acetone, followed by rearrangement with boron trifluoroetherate.

  18. Biohydrogen and carboxylic acids production from wheat straw hydrolysate.

    Science.gov (United States)

    Chandolias, Konstantinos; Pardaev, Sindor; Taherzadeh, Mohammad J

    2016-09-01

    Hydrolyzed wheat straw was converted into carboxylic acids and biohydrogen using digesting bacteria. The fermentations were carried out using both free and membrane-encased thermophilic bacteria (55°C) at various OLRs (4.42-17.95g COD/L.d), in semi-continuous conditions using one or two bioreactors in a series. The highest production of biohydrogen and acetic acid was achieved at an OLR of 4.42g COD/L.d, whilst the highest lactic acid production occurred at an OLR of 9.33g COD/L.d. Furthermore, the bioreactor with both free and membrane-encased cells produced 60% more lactic acid compared to the conventional, free-cell bioreactor. In addition, an increase of 121% and 100% in the production of acetic and isobutyric acid, respectively, was achieved in the 2nd-stage bioreactor compared to the 1st-stage bioreactor.

  19. Spectrofluorimetric determination of gallium with calon-carboxylic acid

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A simple and sensitive spectrofluorimetric procedure for the analysis of microquantities of gallium in alloy wasdescribed. The method is based on the formation of Ga(Ⅲ)-CCA (calon-carboxylic acid) complex. The emission of thefluorescent complex was measured at λ = 620 nm with excitation at λ = 584 nm. A good linearity was found in the galliumrange of 0.7-280 ng/mL. The precision of the method is good and the relative standard deviation is 1.9% for a gallium stan-dard solution of 70 ng/mL. The procedure was proved to be suitable in terms of accuracy and selectivity for the mi-croamount of gallium in alloy.

  20. Microarray of DNA probes on carboxylate functional beads surface

    Institute of Scientific and Technical Information of China (English)

    黄承志; 李原芳; 黄新华; 范美坤

    2000-01-01

    The microarray of DNA probes with 5’ -NH2 and 5’ -Tex/3’ -NH2 modified terminus on 10 um carboxylate functional beads surface in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) is characterized in the preseni paper. it was found that the microarray capacity of DNA probes on the beads surface depends on the pH of the aqueous solution, the concentra-tion of DNA probe and the total surface area of the beads. On optimal conditions, the minimum distance of 20 mer single-stranded DNA probe microarrayed on beads surface is about 14 nm, while that of 20 mer double-stranded DNA probes is about 27 nm. If the probe length increases from 20 mer to 35 mer, its microarray density decreases correspondingly. Mechanism study shows that the binding mode of DNA probes on the beads surface is nearly parallel to the beads surface.

  1. Microarray of DNA probes on carboxylate functional beads surface

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The microarray of DNA probes with 5′-NH2 and 5′-Tex/3′-NH2 modified terminus on 10 m m carboxylate functional beads surface in the presence of 1-ethyl-3-(3-dimethylaminopropyl)- carbodiimide (EDC) is characterized in the present paper. It was found that the microarray capacity of DNA probes on the beads surface depends on the pH of the aqueous solution, the concentration of DNA probe and the total surface area of the beads. On optimal conditions, the minimum distance of 20 mer single-stranded DNA probe microarrayed on beads surface is about 14 nm, while that of 20 mer double-stranded DNA probes is about 27 nm. If the probe length increases from 20 mer to 35 mer, its microarray density decreases correspondingly. Mechanism study shows that the binding mode of DNA probes on the beads surface is nearly parallel to the beads surface.

  2. Carboxylated nitrile butadiene rubber/hybrid filler composites

    Directory of Open Access Journals (Sweden)

    Ahmad Mousa

    2012-08-01

    Full Text Available The surface properties of the OSW and NLS are measured with the dynamic contact-angle technique. The x-ray photoelectron spectroscopy (XPS of the OSW reveals that the OSW possesses various reactive functional groups namely hydroxyl groups (OH. Hybrid filler from NLS and OSW were incorporated into carboxylated nitrile rubber (XNBR to produce XNBR hybrid composites. The reaction of OH groups from the OSW with COOH of the XNBR is checked by attenuated total reflectance spectra (ATR-IR of the composites. The degree of curing ΔM (maximum torque-minimum torque as a function of hybrid filler as derived from moving die rheometer (MDR is reported. The stress-strain behavior of the hybrid composites as well as the dynamic mechanical thermal analysis (DMTA is studied. Bonding quality and dispersion of the hybrid filler with and in XNBR are examined using scanning-transmission electron microscopy (STEM in SEM.

  3. Carboxyl-modified single-walled carbon nanotubes negatively affect bacterial growth and denitrification activity

    Science.gov (United States)

    Zheng, Xiong; Su, Yinglong; Chen, Yinguang; Wan, Rui; Li, Mu; Wei, Yuanyuan; Huang, Haining

    2014-07-01

    Single-walled carbon nanotubes (SWNTs) have been used in a wide range of fields, and the surface modification via carboxyl functionalization can further improve their physicochemical properties. However, whether carboxyl-modified SWNT poses potential risks to microbial denitrification after its release into the environment remains unknown. Here we present the possible effects of carboxyl-modified SWNT on the growth and denitrification activity of Paracoccus denitrificans (a model denitrifying bacterium). It was found that carboxyl-modified SWNT were present both outside and inside the bacteria, and thus induced bacterial growth inhibition at the concentrations of 10 and 50 mg/L. After 24 h of exposure, the final nitrate concentration in the presence of 50 mg/L carboxyl-modified SWNT was 21-fold higher than that in its absence, indicating that nitrate reduction was substantially suppressed by carboxyl-modified SWNT. The transcriptional profiling revealed that carboxyl-modified SWNT led to the transcriptional activation of the genes encoding ribonucleotide reductase in response to DNA damage and also decreased the gene expressions involved in glucose metabolism and energy production, which was an important reason for bacterial growth inhibition. Moreover, carboxyl-modified SWNT caused the significant down-regulation and lower activity of nitrate reductase, which was consistent with the decreased efficiency of nitrate reduction.

  4. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    NARCIS (Netherlands)

    Ban, van den E.C.D.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interes

  5. 3-Methyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Rajendiran Nagappan

    2010-01-01

    Full Text Available 3-Methyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic acid was synthesized chemoselectively from 3-formyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic acid, using Et3SiH/I2 as a reducing agent. The title compound was characterized by IR, 1H NMR, 13C NMR and LCMS.

  6. Plastic scintillators with high loading of one or more metal carboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Cherepy, Nerine; Sanner, Robert Dean

    2016-09-20

    According to one embodiment, a method includes incorporating a metal carboxylate complex into a polymeric matrix to form an optically transparent material. According to another embodiment, a material includes at least one metal carboxylate complex incorporated into a polymeric matrix, where the material is optically transparent.

  7. Development of technology for fabrication of lithium CPS on basis of CNT-reinforced carboxylic fabric

    Energy Technology Data Exchange (ETDEWEB)

    Tazhibayeva, Irina, E-mail: tazhibayeva@ntsc.kz [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan); Baklanov, Viktor; Ponkratov, Yuriy [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan); Abdullin, Khabibulla [Institute of Experimental and Theoretical Physics of Kazakh National University, Almaty (Kazakhstan); Kulsartov, Timur; Gordienko, Yuriy; Zaurbekova, Zhanna [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan); Lyublinski, Igor [JSC «Red Star», Moscow (Russian Federation); NRNU «MEPhI», Moscow (Russian Federation); Vertkov, Alexey [JSC «Red Star», Moscow (Russian Federation); Skakov, Mazhyn [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan)

    2017-04-15

    Highlights: • Preliminary study of carboxylic fabric wettability with liquid lithium is presented. • Preliminary studies of carboxylic fabric wettability with liquid lithium consist in carrying out of experiments at temperatures 673,773 and 873 К in vacuum during long time. • A scheme of experimental device for manufacturing of lithium CPS and matrix filling procedure with liquid lithium are presented. • The concept of lithium limiter with CPS on basis of CNT-reinforced carboxylic fabric is proposed. - Abstract: The paper describes the analysis of liquid lithium interaction with materials based on carbon, the manufacture technology of capillary-porous system (CPS) matrix on basis of CNT-reinforced carboxylic fabric. Preliminary study of carboxylic fabric wettability with liquid lithium is presented. The development of technology includes: microstructural studies of carboxylic fabric before its CNT-reinforcing; validation of CNT-reinforcing technology; mode validation of CVD-method for CNT synthesize; study of synthesized carbon structures. Preliminary studies of carboxylic fabric wettability with liquid lithium consist in carrying out of experiments at temperatures 673, 773 and 873 К in vacuum during long time. The scheme of experimental device for manufacturing of lithium CPS and matrix filling procedure with liquid lithium are presented. The concept of lithium limiter with CPS on basis of CNT-reinforced carboxylic fabric is proposed.

  8. Facile synthesis of α-hydroxy carboxylic acids from the corresponding α-amino acids

    DEFF Research Database (Denmark)

    Stuhr-Hansen, Nicolai; Padrah, Shahrokh; Strømgaard, Kristian

    2014-01-01

    An effective and improved procedure is developed for the synthesis of α-hydroxy carboxylic acids by treatment of the corresponding protonated α-amino acid with tert-butyl nitrite in 1,4-dioxane-water. The amino moiety must be protonated and located α to a carboxylic acid function in order...

  9. Vitamin K-dependent carboxylation of matrix gla protein influences the risk of calciphylaxis

    Science.gov (United States)

    Matrix Gla protein (MGP) is a potent inhibitor of vascular calcification. The ability of MGP to inhibit calcification requires the activity of a vitamin K-dependent enzyme, which mediates MGP carboxylation. We investigated how MGP carboxylation influences the risk of calciphylaxis in adult patients ...

  10. Olfactory sensitivity and odor structure-activity relationships for aliphatic carboxylic acids in CD-1 mice.

    Science.gov (United States)

    Can Güven, Selçuk; Laska, Matthias

    2012-01-01

    Using a conditioning paradigm, the olfactory sensitivity of CD-1 mice for a homologous series of aliphatic n-carboxylic acids (ethanoic acid to n-octanoic acid) and several of their isomeric forms was investigated. With all 14 odorants, the animals significantly discriminated concentrations as low as 0.03 ppm (parts per million) from the solvent, and with four odorants the best-scoring animals even detected concentrations as low as 3 ppt (parts per trillion). Analysis of odor structure-activity relationships showed that the correlation between olfactory detection thresholds of the mice for the unbranched carboxylic acids and carbon chain length can best be described as a U-shaped function with the lowest threshold values at n-butanoic acid. A significant positive correlation between olfactory detection thresholds and carbon chain length of the carboxylic acids with their branching next to the functional carboxyl group was found. In contrast, no such correlation was found for carboxylic acids with their branching at the distal end of the carbon chain relative to the functional carboxyl group. Finally, a significant correlation was found between olfactory detection thresholds and the position of the branching of the carboxylic acids. Across-species comparisons suggest that mice are more sensitive for short-chained (C(2) to C(4)) aliphatic n-carboxylic acids than other mammalian species, but not for longer-chained ones (C(5) to C(8)). Further comparisons suggest that odor structure-activity relationships are both substance class- and species-specific.

  11. Catalyst for the carboxylation of carbonylated compounds in the gas phase

    DEFF Research Database (Denmark)

    2013-01-01

    The invention relates to a catalyst for the carboxylation of carbonylated compounds in the gas phase. Said catalyst consists of a metal complex which is active when the carboxylation is under reaction conditions and an organic salt, which is solid under normal conditions and liquid under reaction...

  12. H2O2-reactivity of copper(II) complexes supported by tris[(pyridin-2-yl)methyl]amine ligands with 6-phenyl substituents.

    Science.gov (United States)

    Kunishita, Atsushi; Kubo, Minoru; Ishimaru, Hirohito; Ogura, Takashi; Sugimoto, Hideki; Itoh, Shinobu

    2008-12-15

    The structure and H(2)O(2)-reactivity of a series of copper(II) complexes supported by tris[(pyridin-2-yl)methyl]amine (TPA) derivatives having a phenyl group at the 6-position of pyridine donor group(s) [(6-phenylpyridin-2-yl)methyl]bis[(pyridin-2-yl)methyl]amine (Ph(1)TPA), bis[(6-phenylpyridin-2-yl)methyl][(pyridin-2-yl)methyl]amine (Ph(2)TPA), and tris[(6-phenylpyridin-2-yl)methyl]amine (Ph(3)TPA) have systematically been examined to get insights into the aromatic substituent (6-Ph) effects on the coordination chemistry of TPA ligand system. The X-ray crystallographic analyses have revealed that [Cu(II)(TPA)(CH(3)CN)](ClO(4))(2) (CuTPA) and [Cu(II)(Ph(3)TPA)(CH(3)CN)](ClO(4))(2) (3) exhibit a trigonal bipyramidal structure, whereas [Cu(II)(Ph(1)TPA)(CH(3)CN)](ClO(4))(2) (1) shows a slightly distorted square pyramidal structure and [Cu(II)(Ph(2)TPA)(CH(3)CN)](ClO(4))(2) (2) has an intermediate structure between trigonal bipyramidal and square pyramidal. On the other hand, the UV-vis and ESR data have suggested that all the copper(II) complexes have a similar trigonal bipyramidal structure in solution. The redox potentials of CuTPA, 1, 2, and 3 have been determined as E(1/2) = -0.34, -0.28, -0.16, and -0.04 mV vs Ag/AgNO(3), respectively, demonstrating that introduction of each 6-Ph group causes positive shift of E(1/2) about 0.1 V. Notable difference in H(2)O(2)-reactivity has been found among the copper(II) complexes. Namely, CuTPA and 1 afforded mononuclear copper(II)-hydroperoxo complexes CuTPA-OOH and 1-OOH, respectively, whereas complex 2 provided bis(mu-oxo)dicopper(III) complex 2-oxo. On the other hand, copper(II) complex 3 was reduced to the corresponding copper(I) complex 3(red). On the basis of the H(2)O(2)-reactivity together with the X-ray structures and the redox potentials of the copper(II) complexes, the substituent effects of 6-Ph are discussed in detail.

  13. Novel Polycarbo-Substituted Alkyl (Thieno[3,2-c]quinoline-2-Carboxylates: Synthesis and Cytotoxicity Studies

    Directory of Open Access Journals (Sweden)

    Malose Jack Mphahlele

    2014-11-01

    Full Text Available Direct one-pot base-promoted conjugate addition–elimination of 6,8-dibromo-4-chloroquinoline-3-carbaldehyde with methyl mercaptoacetate and subsequent cyclization afforded methyl [(6,8-dibromothieno[3,2-c]quinoline]-2-carboxylate. The latter undergoes Suzuki-Miyaura cross-coupling with arylboronic acids to yield exclusively the corresponding alkyl [(6,8-diarylthieno[3,2-c]quinoline]-2-carboxylates,. The cytotoxicity of the prepared compounds was evaluated against the human breast cancer cell line MCF-7 using the MTT assay. The effects of compounds 2, 3c and 4d on cell kinetics were further determined using the xCELLigence Real Time Cell Analysis (RTCA system. In both the MTT assay and Real Time Cell Analysis, the compounds inhibited cancer cell growth in a dose- and time-dependent manner. Furthermore, on the basis of the calculated LC50 values, the compounds compared favourably with nocodazole, a well-established anticancer drug.

  14. The structure-anticoagulant activity relationships of sulfated lacquer polysaccharide: effect of carboxyl group and position of sulfation.

    Science.gov (United States)

    Yang, Jianhong; Du, Yumin; Huang, Ronghua; Wan, Yunyang; Wen, Yan

    2005-07-01

    Regiospecific oxidation of the primary hydroxyl groups in lacquer polysaccharide (LPL, Mw 6.85 x 10(4)) and its NaIO4 oxidation derivatives (LPLde) to C-6 carboxy groups was achieved with NaOCl in the presence of Tempo and NaBr. Sulfate groups were incorporated into the oxidated polysaccharides using Py.SO3 complex as a reagent. Reactivity of polysaccharide hydroxyl group was C-6 > C-2 > C-4. Sulfate groups were mainly linked to the second hydroxy at C-2 in the products. The results of APTT assay showed after incorporation of carboxyl groups into lacquer polysaccharides, the intrinsic coagulation pathway was promoted, and all sulfated polysaccharides had very weak anticoagulant activity within the scope of studied DS (0.39-1.11). These indicated that carboxyl groups and sulfate groups had the synergistic action. At the same time, the anticoagulant activity increased very slowly with the DS in the second hydroxy. This indicated that 6-O-SO3- in the side chains took an important role in the anticoagulant activity.

  15. [Screening and identification of an endophytic bacterium with 1-aminocyclopropane-1-carboxylate deaminase activity from Panax ginseng and its effect on host growth].

    Science.gov (United States)

    Tian, Lei; Jiang, Yun; Chen, Changqing; Zhang, Guanjun; Li, Tong; Tong, Bin; Xu, Peng

    2014-07-04

    This study aimed to screen endophytic bacteria with 1-aminocyclopropane-1-carboxylate deaminase activity from Panax ginseng and test the capability of growth promotion to its host. In total 120 endophytic bacterial strains isolated from Panax ginseng were screened for 1-aminocyclopropane-1-carboxylate deaminase activity using the qualitative and quantitative methods. The obtained strain was also tested for its ability of nitrogen fixation using the Ashby agar plates and the gene of nifH, for its ability of phosphate solubilization using the Pikovaskaia's plates and quantitative analysis of Mo-Sb-Ascrobiology acid colorimetry, for its ability of producing siderophores using the method of Chrome azurol S detecting, and its effect on promoting growth of Panax ginseng by laboratory and field experiments. The bacterial strain with ACC deaminase was identified based on morphology, physiological and biochemical traits, and 16S rRNA sequence analysis. The bacterial stain JJ8-3 with the ability of producing ACC deaminase activity was obtained through screening, which its ACC deaminase activity was alpha-ketobutyric acid 6.7 micromol/(mg x h). Strain JJ8-3 had other traits of phosphate solubilizing, nitrogen fixation, producing siderophores, and the ability of promoting growth of Panax ginseng. Strain JJ8-3 was identified as Pseudomonas fluorescens. Strain JJ8-3 of endophytic bacterium with ACC deaminase activity from Panax ginseng was obtained and would lay the foundation for its further study and application on plant growth promotion.

  16. Efficient Fixation of Carbon Dioxide by Electrolysis - Facile Synthesis of Useful Carboxylic Acids -

    Institute of Scientific and Technical Information of China (English)

    Masao Tokuda

    2006-01-01

    Electrochemical fixation of atmospheric pressure of carbon dioxide to organic compounds is a useful and attractive method for synthesizing of various carboxylic acids. Electrochemical fixation of carbon dioxide, electrochemical carboxylation, organic halides, organic triflates, alkenes, aromatic compounds, and carbonyl compounds can readily occur in the presence of an atmospheric pressure of carbon dioxide to form the corresponding carboxylic acids with high yields, when a sacrificial anode such as magnesium or aluminum is used in the electrolysis. The electrochemical carboxylation of vinyl bromides was successfully applied for the synthesis of the precursor of nonsteroidal anti-inflammatory agents such as ibuprofen and naproxen. On the other hand, supercritical carbon dioxide (scCO2) has significant potential as an environmentally benign solvent in organic synthesis and it could be used both as a solvent and as a reagent in these electrochemical carboxylations by using a small amount of cosolvent.

  17. A novel ubiquitin carboxyl terminal hydrolase is involved in toad oocyte maturation

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    p28, a 28kD protein from toad (Bufo bufo gargarizans) oocytes, was identified by using p13suc1-agaroseaffinity chromatography. Sequence homology analysis of the full-length cDNA of p28 (Gene Bank accessionnumber: AF 314091) indicated that it encodes a protein containing 224 amino-acids with about 55% iden-tities and more than 70% positives to human, rat or mouse UCH-L1, and contains homological functionaldomains of UCH family. Anti-p28 monoclonal antibody, on injecting into the oocytes, could inhibit theprogesterone-induced resumption of meiotic division in a dose-dependent manner. The recombinant proteinp28 showed similar SDS/PAGE behaviors to the native one, and promoted ubiquitin ethyl ester hydrolysis,a classical catalytic reaction for ubiquitin carboxyl terminai hydrolases (UCHs). The results in this paperreveal that a novel protein, p28, exists in the toad oocytes, is a UCH L1 homolog, was engaged in theprocess of progesterone-induced oocyte maturation possibly through an involvement in protein turnover anddegradation.

  18. Study of kinetics of degradation of cyclohexane carboxylic acid by acclimated activated sludge.

    Science.gov (United States)

    Wang, Chunhua; Shi, Shuian; Chen, Hongyan

    2016-01-01

    Activated sludge contains complex microorganisms, which are highly effective biodegrading agents. In this study, the kinetics of biodegradation of cyclohexane carboxylic acid (CHCA) by an acclimated aerobic activated sludge were investigated. The results showed that after 180 days of acclimation, the activated sludge could steadily degrade >90% of the CHCA in 120 h. The degradation of CHCA by the acclimated activated sludge could be modeled using a first-order kinetics equation. The equations for the degradation kinetics for different initial CHCA concentrations were also obtained. The kinetics constant, kd, decreased with an increase in the CHCA concentration, indicating that, at high concentrations, CHCA had an inhibiting effect on the microorganisms in the activated sludge. The effects of pH on the degradation kinetics of CHCA were also investigated. The results showed that a pH of 10 afforded the highest degradation rate, indicating that basic conditions significantly promoted the degradation of CHCA. Moreover, it was found that the degradation efficiency for CHCA increased with an increase in temperature and concentration of dissolved oxygen under the experimental conditions.

  19. Diaquabis(4-bromobenzoato-κObis(nicotinamide-κN1copper(II

    Directory of Open Access Journals (Sweden)

    Hacali Necefoğlu

    2011-07-01

    Full Text Available The asymmetric unit of the title mononuclear CuII complex, [Cu(C7H4BrO22(C6H6N2O2(H2O2], contains one half-molecule, the CuII atom being located on an inversion center. The unit cell contains two nicotinamide (NA, two 4-bromobenzoate (PBB ligands and two coordinated water molecules. The four O atoms in the equatorial plane around the CuII ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 22.17 (16°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.80 (6°. In the crystal, N—H...O, O—H...O and C—H...O hydrogen bonds link the molecules into a three-dimensional network. A weak C—H...π interaction is also observed.

  20. Radiation-induced grafting of sweet sorghum stalk for copper(II) removal from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Jing; Hu, Jun [Laboratory of Environmental Technology, INET, Tsinghua University, Beijing 100084 (China); Wang, Jianlong, E-mail: wangjl@mail.tsinghua.edu.cn [Laboratory of Environmental Technology, INET, Tsinghua University, Beijing 100084 (China); Key Laboratory of Advanced Reactor Engineering and Safety, Ministry of Education, Tsinghua University, Beijing 100084 (China)

    2013-11-15

    Highlights: • Radiation-induced grafting was used to modify the stalk. • Cellulose, hemicellulose and lignin participated in grafting reaction. • Both the structure and composition of stalk had influence on grafting. • The sorption capacity of the grafted stalk increased about five times. -- Abstract: The influence of main components (cellulose, hemicellulose and lignin) of the sweet sorghum stalk on radiation-induced grafting reaction and adsorption of copper from aqueous solution was investigated. Sweet sorghum stalk was grafted with acrylic acid induced by γ-irradiation. The results showed that the grafted stalk contained 1.6 mmol/g carboxyl groups, and its maximal adsorption capacity was 13.32 mg/g. The cellulose, hemicellulose and lignin of the raw materials were confirmed to involve in grafting reaction through comparing the grafting yield and the structure of the grafted materials. Both the structure and the composition of the sweet sorghum stalk had influence on the grafting reaction and adsorption capacity. The adsorption capacity of the grafted sweet sorghum stalk increased about five times, and the adsorption isotherm of the grafted materials conformed to the Langmuir model. The main mechanism for copper adsorption involved in ion exchange.

  1. New insights into 1-aminocyclopropane-1-carboxylate (ACC deaminase phylogeny, evolution and ecological significance.

    Directory of Open Access Journals (Sweden)

    Francisco X Nascimento

    Full Text Available The main objective of this work is the study of the phylogeny, evolution and ecological importance of the enzyme 1-aminocyclopropane-1-carboxylate (ACC deaminase, the activity of which represents one of the most important and studied mechanisms used by plant growth-promoting microorganisms. The ACC deaminase gene and its regulatory elements presence in completely sequenced organisms was verified by multiple searches in diverse databases, and based on the data obtained a comprehensive analysis was conducted. Strain habitat, origin and ACC deaminase activity were taken into account when analyzing the results. In order to unveil ACC deaminase origin, evolution and relationships with other closely related pyridoxal phosphate (PLP dependent enzymes a phylogenetic analysis was also performed. The data obtained show that ACC deaminase is mostly prevalent in some Bacteria, Fungi and members of Stramenopiles. Contrary to previous reports, we show that ACC deaminase genes are predominantly vertically inherited in various bacterial and fungal classes. Still, results suggest a considerable degree of horizontal gene transfer events, including interkingdom transfer events. A model for ACC deaminase origin and evolution is also proposed. This study also confirms the previous reports suggesting that the Lrp-like regulatory protein AcdR is a common mechanism regulating ACC deaminase expression in Proteobacteria, however, we also show that other regulatory mechanisms may be present in some Proteobacteria and other bacterial phyla. In this study we provide a more complete view of the role for ACC deaminase than was previously available. The results show that ACC deaminase may not only be related to plant growth promotion abilities, but may also play multiple roles in microorganism's developmental processes. Hence, exploring the origin and functioning of this enzyme may be the key in a variety of important agricultural and biotechnological applications.

  2. Synthesis, micellization behavior, antimicrobial and intercalative DNA binding of some novel surfactant copper(II) complexes containing modified phenanthroline ligands.

    Science.gov (United States)

    Nagaraj, Karuppiah; Ambika, Subramanian; Rajasri, Shanmugasundaram; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

    2014-10-01

    The novel surfactant copper(II) complexes, [Cu(ip)2DA](ClO4)21, [Cu(dpqc)2DA](ClO4)22, [Cu(dppn)2DA](ClO4)23, where ip=imidazo[4,5-f][1,10]phenanthroline, dpqc=dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine, dppn=benzo[1]dipyrido[3,2-a':2',3'-c]phenazine and DA-dodecylamine, were synthesized and characterized by physico-chemical and spectroscopic methods. In these complexes 1-3, the geometry of copper metal ions was described as square pyramidal. The critical micelle concentration (CMC) value of these surfactant copper(II) complexes in aqueous solution was found out from conductance measurements. Specific conductivity data at different temperatures served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔGm°, ΔHm° and ΔSm°). The binding interaction of these complexes with DNA (calf thymus DNA) in Tris buffer was studied by physico-chemical techniques. In the presence of the DNA UV-vis spectrum of complexes showed red shift of the absorption band along with significant hypochromicity indicating intercalation of our complexes with nucleic acids. Competitive binding study with ethidium bromide (EB) shows that the complexes exhibit the ability to displace the nucleic acid-bound EB indicating that the complexes bind to nucleic acids in strong competition with EB for the intercalative binding site. Observed changes in the circular dichoric spectra of DNA in the presence of surfactant complexes support the strong binding of complexes with DNA. CV results also confirm this mode of binding. Some significant thermodynamic parameters of the binding of the titled complexes to DNA have also been determined. The results reveal that the extent of DNA binding of 3 was greater than that of 1 and 2. The antibacterial and antifungal screening tests of these complexes have shown good results compared to its precursor chloride complexes.

  3. Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition.

    Science.gov (United States)

    Kuang, Gui-Chao; Guha, Pampa M; Brotherton, Wendy S; Simmons, J Tyler; Stankee, Lisa A; Nguyen, Brian T; Clark, Ronald J; Zhu, Lei

    2011-09-07

    A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)(2)) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)(2) suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)(2) in

  4. Copper(II) complexes of terminally free alloferon mutants containing two histidyl binding sites inside peptide chain structure and stability.

    Science.gov (United States)

    Kadej, Agnieszka; Kuczer, Mariola; Kowalik-Jankowska, Teresa

    2015-12-21

    Mononuclear and polynuclear copper(II) complexes of alloferon 1 with point mutations, H1A/H12A H2N-A(1)GVSGH(6)GQH(9)GVA(12)G-COOH, H1A/H9A H2N-A(1)GVSGH(6)GQA(9)GVH(12)G-COOH, and H1A/H6A H2N-A(1)GVSGA(6)GQH(9)GVH(12)G-COOH, have been studied by potentiometric, UV-visible, CD, and EPR spectroscopy, and mass spectrometry (MS) methods. Complete complex speciation at different metal-to-ligand molar ratios ranging from 1 : 1 to 3 : 1 was obtained. Over a wide 6-8 pH range, including physiological pH 7.4, and a 1 : 1 metal-to-ligand molar ratio, the peptides studied formed a CuH-1L complex with the 4N{NH2,N(-),2NIm} coordination mode. The presence of the 4N binding site for the CuH-1L complexes prevented the deprotonation and coordination of the second amide nitrogen atom to copper(II) ions (pK-1/-2 7.83-8.07) compared to that of pentaGly (6.81). The amine nitrogen donor and two imidazole nitrogen atoms (H(6)H(9), H(6)H(12) and H(9)H(12)) can be considered to be independent metal-binding sites in the species formed. As a consequence, di- and trinuclear complexes for the metal-to-ligand 2 : 1 and 3 : 1 molar ratios dominate in the solution, respectively. For the Cu(II)-H1A/H9A and Cu(II)-H1A/H12A systems, the Cu3H-9L complexes are likely formed by the coordination of amide nitrogen atoms towards C-termini with ring sizes (7,5,5).

  5. Effect of the Peptidic Scaffold in Copper(II) Coordination and the Redox Properties of Short Histidine-Containing Peptides.

    Science.gov (United States)

    Fragoso, Ana; Carvalho, Tiago; Rousselot-Pailley, Pierre; Correia Dos Santos, Margarida M; Delgado, Rita; Iranzo, Olga

    2015-09-07

    A linear decapeptide containing three His and one Asp residues and a β-turn-inducing dProPro unit was synthesised. A detailed potentiometric, mass spectrometric and spectroscopic study showed that at a 1:1 ratio of CCu /Cpeptide this peptide formed a major [CuH(O(dPro)-Asp)](2+) species (pH range 5.5-7.0), in which the Cu(2+) ion was bound to the His and Asp residues in square-planar or square-pyramidal geometries. The stability constant corrected for protonated species (log K* CuH(O dPro-Asp)=9.33) is almost equal to the value obtained for the parent [CuH(OAsp)](2+) species (log K*CuH(O-Asp) =9.28), but lower than that obtained for the cyclic [CuH(C-Asp)](2+) complex (log K*CuH(C-Asp) =10.79) previously published. Thus, the replacement of the ProGly unit by the stronger β-turn-inducing dProPro unit did not generate a more stable copper(II) species, although the O(dPro)-Asp peptide was structured in solution, as shown by circular dichroism (CD) spectroscopy. Interestingly, the calculated value of Keff showed that this peptide behaved similarly to the O-Asp or C-Asp counterparts, depending on the pH value. The cyclic voltammetry data indicated that the most easily reducible species were [CuH(O-Asp)](2+) (E'(0) =262 mV versus a normal hydrogen electrode (NHE)) and [CuH(O(dPro)-Asp)](2+) (E'(0) =294 mV versus NHE) complexes, the peptidic scaffolds of which are open. A lower value was obtained for [CuH(C-Asp)](2+) (E'(0) =24 mV versus NHE). A different degree of non-reversibility was observed for the three copper(II) complexes; this could reflect a different degree of flexibility in their respective peptidic scaffolds.

  6. Halogen-bonded network of trinuclear copper(II 4-iodopyrazolate complexes formed by mutual breakdown of chloroform and nanojars

    Directory of Open Access Journals (Sweden)

    Stuart A. Surmann

    2016-11-01

    Full Text Available Crystals of bis(tetrabutylammonium di-μ3-chlorido-tris(μ2-4-iodopyrazolato-κ2N:N′tris[chloridocuprate(II] 1,4-dioxane hemisolvate, (C16H36N2[Cu3(C3H2IN23Cl5]·0.5C4H8O or (Bu4N2[CuII3(μ3-Cl2(μ-4-I-pz3Cl3]·0.5C4H8O, were obtained by evaporating a solution of (Bu4N2[{CuII(μ-OH(μ-4-I-pz}nCO3] (n = 27–31 nanojars in chloroform/1,4-dioxane. The decomposition of chloroform in the presence of oxygen and moisture provides HCl, which leads to the breakdown of nanojars to the title trinuclear copper(II pyrazolate complex, and possibly CuII ions and free 4-iodopyrazole. CuII ions, in turn, act as catalyst for the accelerated decomposition of chloroform, ultimately leading to the complete breakdown of nanojars. The crystal structure presented here provides the first structural description of a trinuclear copper(II pyrazolate complex with iodine-substituted pyrazoles. In contrast to related trinuclear complexes based on differently substituted 4-R-pyrazoles (R = H, Cl, Br, Me, the [Cu3(μ-4-I-pz3Cl3] core in the title complex is nearly planar. This difference is likely a result of the presence of the iodine substituent, which provides a unique, novel feature in copper pyrazolate chemistry. Thus, the iodine atoms form halogen bonds with the terminal chlorido ligands of the surrounding complexes [mean length of I...Cl contacts = 3.48 (1 Å], leading to an extended two-dimensional, halogen-bonded network along (-110. The cavities within this framework are filled by centrosymmetric 1,4-dioxane solvent molecules, which create further bridges via C—H...Cl hydrogen bonds with terminal chlorido ligands of the trinuclear complex not involved in halogen bonding.

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

    Directory of Open Access Journals (Sweden)

    Lenka Kucková

    2015-01-01

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

  8. Health Promotion

    DEFF Research Database (Denmark)

    Povlsen, Lene; Borup, I.

    2015-01-01

    In 1953 when the Nordic School of Public Health was founded, the aim of public health programmes was disease prevention more than health promotion. This was not unusual, since at this time health usually was seen as the opposite of disease and illness. However, with the Ottawa Charter of 1986......, the World Health Organization made a crucial change to view health not as a goal in itself but as the means to a full life. In this way, health promotion became a first priority and fundamental action for the modern society. This insight eventually reached NHV and in 2002 - 50 years after the foundation...... - an associate professorship was established with a focus on health promotion. Nevertheless, the concept of health promotion had been integrated with or mentioned in courses run prior to the new post. Subsequently, a wide spectrum of courses in health promotion was introduced, such as Empowerment for Child...

  9. [Determination of the carboxyl content of oxidized starch by fourier transform infrared (FTIR) spectroscopy].

    Science.gov (United States)

    Ding, Long-Long; Zhang, Yan-Hua; Gu, Ji-You; Tan, Hai-Yan; Zhu, Li-Bin

    2014-02-01

    In the present study, the carboxyl content of oxidized starch was determined by FTIR spectroscopy. Standard curve was drawn in which the ordinate was carboxyl content determined by national standard method with the ratio of carbonyl absorbance to the key of C-H absorbance in FTIR spectroscopy as the abscissa. The ratio of absorbance of unknown oxidized starch tested by FTIR spectroscopy was obtained, The carboxyl content was calculated by standard curve, and then compared with the carboxyl content determined by national standard method, and the deviation is between 2% and 4%. In order to improve the accuracy of the experiment, standard sample was selected to draw standard curve to better ensure that the carboxyl content of the unknown oxidized starch is in the range of standard curve calculation limit, and deviates from the limit of standard curve. Compared with the carboxyl content determined by national standard method, testing with FTIR spectroscopy is simple, easy to operate, and of high efficiency and better accuracy. So, it is significant to forecast the carboxyl content of oxidized starch by FTIR spectroscopy.

  10. Thermal stability of carboxylic acid functionality in coal; Sekitanchu ni sonzaisuru karubokishiruki no netsubunkai kyodo

    Energy Technology Data Exchange (ETDEWEB)

    Tsutsumi, Y.; Aida, T. [Kinki University, Osaka (Japan). Faculty of Engineering

    1996-10-28

    Carboxyl in coal was focused in discussing its pyrolytic behavior while tracking change of its absolute amount relative to the heating temperatures. A total of four kinds of coals, consisting of two kinds brown coals, sub-bituminous coal and bituminous coal were used. Change in the absolute amount of carboxyl due to heating varies with coalification degree. Decomposition starts in the bituminous coal from around 300{degree}C, and is rapidly accelerated when 400{degree}C is exceeded. Carboxyls in brown coals exist two to three times as much as those in bituminous and sub-bituminous coals, of which 40% is decomposed at a temperature as low as about 300{degree}C. Their pyrolytic behavior at temperatures higher than 400{degree}C resembles that of the bituminous coal. Carboxyls consist of those easy to decompose and difficult to decompose. Aromatic and aliphatic carboxylic acids with simple structure are stable at temperatures lower than 300{degree}C, and decompose abruptly from about 400{degree}C, hence their behavior resembles that of carboxyls in bituminous and sub-bituminous coals. Structure of low-temperature decomposing carboxyls in brown coals is not known, but it is assumed that humic acid originated from natural materials remains in the structure. 4 refs., 3 figs., 1 tab.

  11. Characterization and diagenesis of strong-acid carboxyl groups in humic substances

    Science.gov (United States)

    Leenheer, J.A.; Wershaw, R. L.; Brown, G.K.; Reddy, M.M.

    2003-01-01

    A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

  12. Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

    Science.gov (United States)

    Uznanski, Pawel; Zakrzewska, Joanna; Favier, Frederic; Kazmierski, Slawomir; Bryszewska, Ewa

    2017-03-01

    A comparative study of amine and silver carboxylate adducts [R1COOAg-2(R2NH2)] (R1 = 1, 7, 11; R2 = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, 13C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies (1H and 13C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.

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

    Science.gov (United States)

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

    2014-06-16

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

  14. Copper(II) and lead(II) removal from aqueous solution by water treatment residues.

    Science.gov (United States)

    Castaldi, Paola; Silvetti, Margherita; Garau, Giovanni; Demurtas, Daniela; Deiana, Salvatore

    2015-01-01

    In this study, we investigated the ability of Fe- and Al-based water treatment residues (Fe- and Al-WTR) to accumulate Pb(II) and Cu(II) at pH 4.5. The role of the inorganic and organic fractions of WTRs in metals sorption was also assessed. Sorption isotherms showed a higher sorption of Pb(II) by both WTRs with respect to Cu(II) (e.g. 0.105 and 0.089 mmol g(-1) of Pb(II) and Cu(II) respectively sorbed by Fe-WTR). Fe-WTR revealed a stronger sorbent for both metals than Al-WTR. The amount of Pb(II) and Cu(II) sorbed by Fe-WTR was about the 69% and 63% higher than that sorbed by the Al-WTR. The organic matter of Fe- and Al-WTR contributed to about 26% and 8.5% respectively in the sorption of both metals. The sequential extraction procedure showed that the greatest amount of metals sorbed by both WTRs were tightly bound and not extractable, and this was particularly apparent for Cu(II). The FT-IR spectra indicated the formation of inner-sphere complexes between the Fe(Al)-O nucleus and Pb(II) and Cu(II). Moreover, the FT-IR spectra also suggested that the humic fraction of WTRs interacted, through the carboxylate groups, with Cu(II) and Pb(II) by forming mainly monodentate and bidentate complexes, respectively.

  15. Influence of cyclic dimer formation on the phase behavior of carboxylic acids.

    Science.gov (United States)

    Janecek, Jiri; Paricaud, Patrice

    2012-07-12

    A new thermodynamic approach based on the Sear and Jackson association theory for doubly bonded dimers [Mol. Phys.1994, 82, 1033] is proposed to describe the thermodynamic properties of carboxylic acids. The new model is able to simultaneously represent the vapor pressures, saturated densities, and vaporization enthalpies of the shortest acids and is in a much better agreement with experimental data than other approaches that do no consider the formation of cyclic dimers. The new model is applied to mixtures of carboxylic acids with nonassociating compounds, and a very good description of the vapor-liquid equilibria in mixtures of alkanes + carboxylic acids is obtained.

  16. Chiral discrimination of secondary alcohols and carboxylic acids by NMR spectroscopy.

    Science.gov (United States)

    Pal, Indrani; Chaudhari, Sachin R; Suryaprakash, Nagaraja Rao

    2015-02-01

    The manuscript reports two novel ternary ion-pair complexes, which serve as chiral solvating agents, for enantiodiscrimination of secondary alcohols and carboxylic acids. The protocol for discrimination of secondary alcohols is designed by using one equivalent mixture each of enantiopure mandelic acid, 4-dimethylaminopyridine (DMAP) and a chiral alcohol. For discrimination of carboxylic acids, the ternary complex is obtained by one equivalent mixture each of enantiopure chiral alcohol, DMAP and a carboxylic acid. The designed protocols also permit accurate measurement of enantiomeric composition.

  17. Carboxylated Capped Carbon Nanotubes Interacting with Nimesulide Molecules: Applied Electric Fields Effects

    Directory of Open Access Journals (Sweden)

    Vivian Machado de Menezes

    2015-01-01

    Full Text Available Interactions of carboxylated capped carbon nanotubes with nimesulide molecules under electric fields were investigated by ab initio simulations. Repulsive forces between the nimesulide molecules and the carboxyl group of the carbon nanotubes, except for the nimesulide radical configuration, were observed. To keep the original molecule in the pristine form, electric fields with different intensities were applied, where changes in the behavior of the interactions between the molecules were noticed. It was shown that the intensity of the interaction between the nimesulide and the hydrophilic carboxylated capped carbon nanotube can be modulated by the action of the external electric fields making promising systems for drug delivery applications.

  18. Chromone-2- and -3-carboxylic acids inhibit differently monoamine oxidases A and B.

    Science.gov (United States)

    Alcaro, Stefano; Gaspar, Alexandra; Ortuso, Francesco; Milhazes, Nuno; Orallo, Francisco; Uriarte, Eugenio; Yáñez, Matilde; Borges, Fernanda

    2010-05-01

    Chromone carboxylic acids were evaluated as human monoamine oxidase A and B (hMAO-A and hMAO-B) inhibitors. The biological data indicated that only chromone-3-carboxylic acid is a potent hMAO-B inhibitor, with a high degree of selectivity for hMAO-B compared to hMAO-A. Conversely the chromone-2-carboxylic acid resulted almost inactive against both MAO isoforms. Docking experiments were performed to elucidate the reasons of the different MAO IC(50) data and to explain the absence of activity versus selectivity, respectively. 2010 Elsevier Ltd. All rights reserved.

  19. Nano-sized carboxylates as anode materials for rechargeable lithium-ion batteries

    Institute of Scientific and Technical Information of China (English)

    Xiaoyan Wu; Jie Ma; Yong-Sheng Hu; Hong Li; Liquan Chen

    2014-01-01

    Nano-sized carboxylates Na2C7H3NO4 and Na2C6H2N2O4 were prepared and investigated as anode materials for lithium-ion batteries. Both carboxylates exhibit high reversible capacities around 190 mAh/g above a cut-off voltage of 0.8 V vs. Li+/Li, potentially improving the safety of the batteries. In addition, good rate performance and long cycle life of these carboxylates make them promising candidates as anode materials for lithium-ion batteries.

  20. A novel synthesis of carbon-labelled quinolone-3-carboxylic acid antibacterials

    Energy Technology Data Exchange (ETDEWEB)

    Carr, R.M.; Sutherland, D.R. (Glaxo Research and Development Ltd., Greenford (United Kingdom). Isotope Chemistry Group)

    1994-10-01

    3-Iodoquinolones were prepared from the corresponding quinolone-3-carboxylic acids by Hunsdiecker-type iododecarboxylation reactions with lead tetraacetate and iodine. Cyanation of the iodo compounds with mixtures of potassium [[sup 13]C]cyanide and copper (1) iodide, gave [3-[sup 13]C]cyanoquinolones which on acidic hydrolysis afforded quinolone-[3-[sup 13]C]carboxylic acids. In this way, nalidixic acid, an immediate precursor of norfloxacin, and quinolone WIN57273 were labelled with carbon-13 in the metabolically stable carboxylic acid fragment. (author).

  1. The crystalline structures of carboxylic acid monolayers adsorbed on graphite.

    Science.gov (United States)

    Bickerstaffe, A K; Cheah, N P; Clarke, S M; Parker, J E; Perdigon, A; Messe, L; Inaba, A

    2006-03-23

    X-ray and neutron diffraction have been used to investigate the formation of solid crystalline monolayers of all of the linear carboxylic acids from C(6) to C(14) at submonolayer coverage and from C(8) to C(14) at multilayer coverages, and to characterize their structures. X-rays and neutrons highlight different aspects of the monolayer structures, and their combination is therefore important in structural determination. For all of the acids with an odd number of carbon atoms, the unit cell is rectangular of plane group pgg containing four molecules. The members of the homologous series with an even number of carbon atoms have an oblique unit cell with two molecules per unit cell and plane group p2. This odd-even variation in crystal structure provides an explanation for the odd-even variation observed in monolayer melting points and mixing behavior. In all cases, the molecules are arranged in strongly hydrogen-bonded dimers with their extended axes parallel to the surface and the plane of the carbon skeleton essentially parallel to the graphite surface. The monolayer crystal structures have unit cell dimensions similar to certain close-packed planes of the bulk crystals, but the molecular arrangements are different. There is a 1-3% compression on increasing the coverage over a monolayer.

  2. Coordination Polymers of Palladium Bridged by Carboxylate and Dimethylaminoalkylselenolate Ligands.

    Science.gov (United States)

    Paluru, Dilip K; Dey, Sandip; Wadawale, Amey P; Bhuvanesh, Nattamai; Grupp, Anita; Kaim, Wolfgang; Jain, Vimal K

    2016-02-04

    Coordination polymers of palladium stabilized by dimethylaminoalkylselenolate and carboxylate ligands are reported. The reaction of [PdCl(SeCH2 CH2 NMe2 )]3 with AgOTf followed by treatment with sodium acetate afforded [Pd(0) Pd(II) 4 (SeCH2 CH2 NMe2 )3 (OAc)3 ](OTf)2 (1) in which one of the Pd atoms is in the zero oxidation state. In the absence of NaOAc, a tetranuclear complex, [Pd(II) 4 (SeCH2 CH2 NMe2 )4 (OTf)](OTf)3 (2), is isolated from the same reaction. Subsequent treatment with NaO2 CR afforded [Pd4 (SeCH2 CH2 NMe2 )4 (O2 CR)4 ] (R=tBu (3) and Ph (4)). The reaction of [PdCl(SeCH2 CH2 CH2 NMe2 )]2 with AgOTf and NaOAc yielded an ionic binuclear complex, [Pd(II) 2 (SeCH2 CH2 CH2 NMe2 )2 (OAc)](OTf) (5). These complexes have been characterized by NMR spectroscopy, crystal structures, and in some cases by X-ray photoelectron spectroscopy, cyclic voltammetry and mass spectrometry. Complexes 1 and 5 are associated through secondary interactions and coordinate bonds, respectively, to generate polymeric structures in the solid state. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Role of phosphate and carboxylate ions in maillard browning.

    Science.gov (United States)

    Rizzi, George P

    2004-02-25

    The Maillard reaction of carbohydrates and amino acids is the underlying chemical basis for flavor and color formation in many processed foods. Phosphate and other polyatomic anions will accelerate the rate of Maillard browning, and this effect has been explained by invoking enhanced proton abstraction from intermediate Amadori compounds. In this work, the effect of phosphate and carboxylate ions on browning was measured for a series of reducing sugars with and without the presence of beta-alanine. Significant browning was observed for sugars alone suggesting that polyatomic anions contribute to Maillard browning by providing reactive intermediates directly from sugars. A mechanism is proposed for decomposition of sugars by polyatomic anions and efforts to trap reactive species using o-phenylenediamine (OPD) are described. The results of this study suggest how complications may arise from the popular usage of phosphate buffers in the study of Maillard reaction kinetics. In addition, the results imply how phosphates may be useful for enhancing browning during food processing.

  4. Isoprenyl carboxyl methyltransferase inhibitors: a brief review including recent patents.

    Science.gov (United States)

    Yang, Woo Seok; Yeo, Seung-Gu; Yang, Sungjae; Kim, Kyung-Hee; Yoo, Byong Chul; Cho, Jae Youl

    2017-06-19

    Among the enzymes involved in the post-translational modification of Ras, isoprenyl carboxyl methyltransferase (ICMT) has been explored by a number of researchers as a significant enzyme controlling the activation of Ras. Indeed, inhibition of ICMT exhibited promising anti-cancer activity against various cancer cell lines. This paper reviews patents and research articles published between 2009 and 2016 that reported inhibitors of ICMT as potential chemotherapeutic agents targeting Ras-induced growth factor signaling. Since ICMT inhibitors can modulate Ras signaling pathway, it might be possible to develop a new class of anti-cancer drugs targeting Ras-related cancers. Researchers have discovered indole-based small-molecular ICMT inhibitors through high-throughput screening. Researchers at Duke University identified a prototypical inhibitor, cysmethynil. At Singapore University, Ramanujulu and his colleagues patented more potent compounds by optimizing cysmethynil. In addition, Rodriguez and Stevenson at Universidad Complutense De Madrid and Cancer Therapeutics CRC PTY Ltd., respectively, have developed inhibitors based on formulas other than the indole base. However, further optimization of chemicals targeted to functional groups is needed to improve the characteristics of ICMT inhibitors related to their application as drugs, such as solubility, effectiveness, and safety, to facilitate clinical use.

  5. Nasal pungency and odor of homologous aldehydes and carboxylic acids.

    Science.gov (United States)

    Cometto-Muñiz, J E; Cain, W S; Abraham, M H

    1998-01-01

    Airborne substances can stimulate both the olfactory and the trigeminal nerve in the nose, giving rise to odor and pungent (irritant) sensations, respectively. Nose, eye, and throat irritation constitute common adverse effects in indoor environments. We measured odor and nasal pungency thresholds for homologous aliphatic aldehydes (butanal through octanal) and carboxylic acids (formic, acetic, butanoic, hexanoic, and octanoic). Nasal pungency was measured in subjects lacking olfaction (i.e., anosmics) to avoid odor biases. Similar to other homologous series, odor and pungency thresholds declined (i.e., sensory potency increased) with increasing carbon chain length. A previously derived quantitative structure-activity relationship (QSAR) based on solvation energies predicted all nasal pungency thresholds, except for acetic acid, implying that a key step in the mechanism for threshold pungency involves transfer of the inhaled substance from the vapor phase to the receptive biological phase. In contrast, acetic acid - with a pungency threshold lower than predicted - is likely to produce threshold pungency through direct chemical reaction with the mucosa. Both in the series studied here and in those studied previously, we reach a member at longer chain-lengths beyond which pungency fades. The evidence suggests a biological cut-off, presumably based upon molecular size, across the various series.

  6. Preparation and evaluation of some amide ether carboxylate surfactants

    Directory of Open Access Journals (Sweden)

    M.M.A. El-Sukkary

    2012-06-01

    Full Text Available A homologous series of new mild surfactants, namely: Alkyl amide ether carboxylates surfactants (AEC RCO–NHCH2CH2O (CH2CH2O6CH2COONa, were synthesized by esterification, amidation, ethoxylation and carboxymethylation reaction steps of fatty acids (Lauric, Myristic, palmitic, stearic, oleic or linoleic. The chemical structures of the prepared compounds were confirmed using different spectroscopic techniques, FTIR spectroscopy, mass spectra and HNMR. The surface properties including surface and interfacial tensions, foaming height, emulsification power, calcium ion stability, stability to hydrolysis and critical micelle concentration (cmc were determined. The study of their surface properties showed their stability in hard water and in acidic and alkaline media. These compounds have high calcium ion stability. The low foaming power could have an application in the dyeing auxiliary industry. The lower values of the interfacial tension values indicate the ability of using these surfactants in several applications as corrosion inhibitors and biocides. The data revealed various advantages and potentials as a main surfactant as well as co- surfactants.

  7. Structural and thermal properties of carboxylic acid functionalized polythiophenes

    Directory of Open Access Journals (Sweden)

    Ariane de França Mescoloto

    2014-01-01

    Full Text Available Polythiophenes functionalized with polar groups at the end of side-chain have emerged as an alternative method to obtain good compatibility between this class of conjugated polymers and electron acceptor compounds. The aim is to prevent phase segregation and to improve the efficiency of the polythiophene technological devices. However, homopolymers synthesized from thiophene rings with high polar groups at the end of the side-chain, such as hydroxyl and carboxylic acid groups, are poorly soluble in common volatile organic solvents. We report on a systematic preparation of copolymers of 3-hexylthiophene (HT and thiophene-3-acetic acid (TAA, using different feed ratios. The chemical structures of the copolymers were confirmed by FTIR and ¹H-NMR. The TAA content in these copolymers were 33, 38 and 54 mol %. HPSEC results did not show any remarkable correlation with TAA contents in the copolymers. In contrast, the thermal analyses showed a decrease in the thermal stability and an increase in rigidity of their backbones, for the copolymers with high amounts of TAA. The solubility and optical property of copolymers were also related to the TAA contents. Thus, the properties of these copolymers can be modulated by a simple control of feed ratio of TAA in the copolymerization.

  8. Expression of the 1-Aminocyclopropane-1-Carboxylic Acid Deaminase Gene Requires Symbiotic Nitrogen-Fixing Regulator Gene nifA2 in Mesorhizobium loti MAFF303099

    OpenAIRE

    Nukui, Noriyuki; MINAMISAWA, KIWAMU; Ayabe, Shin-Ichi; Aoki, Toshio

    2006-01-01

    Many soil bacteria contain 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase, which degrades ACC, a precursor of the phytohormone ethylene. In order to examine the regulation of the acdS gene encoding ACC deaminase in Mesorhizobium loti MAFF303099 during symbiosis with the host legume Lotus japonicus, we introduced the β-glucuronidase (GUS) gene into acdS so that GUS was expressed under control of the acdS promoter, and we also generated disruption mutants with mutations in a nitrogen fix...

  9. Synthesis, structure and electrochemical behavior of a 3D crystalline copper(II) metal-organic framework

    Science.gov (United States)

    Bai, Hong-Ye; Fan, Wei-Qiang; Liu, Chun-Bo; Shi, Wei-Dong; Yan, Yong-Sheng

    2014-05-01

    Using an flexible amide-type tripodal ligand N,N‧,N″-tris(3-pyridyl)-1,3,5-benzenetricarboxamide (L) and 1,4-benzenedicarboxylic acid (H2bdc), a three-dimensional copper(II) metal-organic framework (MOF) formulated as [Cu(bdc)(L)]n has been hydrothermally synthesized and structurally characterized by IR, elemental, X-ray single-crystal diffraction and thermal analysis. The complex crystallizes in the triclinic, space group P - 1, a = 8.891(2) Å, b = 11.760(2) Å, c = 15.348(3) Å, α = 96.73(3)°, β = 105.96(3)°, γ = 106.47(3)°, V = 1446.2(5) Å3, Mr = 666.10, Dc = 1.530 g/cm3, Z = 2, F(000) = 682, GOOF = 1.0560, μ(MoKα) = 0.817 mm-1, R = 0.0366 and wR = 0.0885. The structural analyses reveal that the title compound consists of one Cu(II) atom, two halves of bdc, and one L ligand. Each Cu(II) atom is linked by two bdc ligands and three L ligands to form a three-dimensional network. In addition, the electrochemical behavior of title compound has been studied. CCDC No. 990526.

  10. Theoretical investigation of the magnetic exchange interactions in copper(II) oxides under chemical and physical pressures.

    Science.gov (United States)

    Rocquefelte, Xavier; Schwarz, Karlheinz; Blaha, Peter

    2012-01-01

    It remains a challenge to understand the unconventional mechanisms that cause high-T(C) superconductivity in cuprate superconductors, high-T(C) multiferroicity in CuO, or low-dimensional magnetism in the spin-Peierls transition compounds such as CuGeO(3). A common feature of all these copper oxide compounds (containing Cu(2+) ions) is the presence of large magnetic superexchange interactions J. It is a general strategy to apply chemical and/or physical pressure in order to tune these exotic properties. Here we show theoretically, for the first time, the impact of physical pressure on J on CuO, for which we predict a strong enhancement of the low-dimensionality of the magnetic interactions and the spin-frustration at high-pressures. Such modifications are expected to strongly influence the multiferroic properties of CuO. We finally demonstrate that PBE0 hybrid DFT calculations provide reliable J values for a wide range of copper(II) oxides compounds, i.e. CuGeO(3), BaCu(2)Si(2)O(7), BaCu(2)Ge(2)O(7), and La(2)CuO(4).

  11. Selective determination of trace copper(II) by cathodic adsorptive stripping voltammetry with a naphthol-derivative Schiff's base.

    Science.gov (United States)

    Shamsipur, Mojtaba; Saeidi, Mahboubeh; Sharghi, Hashem; Naeimi, Hossein

    2003-01-01

    A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with a recently synthesized naphthol-derivative Schiff's base (2,2'-[1,2-ethanediylbis(nitriloethylidyne)]bis(1-naphthalene)) is presented. The method is based on adsorptive accumulation of the resulting copper-Schiff's base complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurement at the reduction current of adsorbed complex at -0.15 V (vs. Ag/AgCl). The optimal conditions for the stripping analysis of copper include pH 5.5 to 6.5, 8 microM Schiff's base and an accumulation potential of -0.05 V (vs. Ag/AgCI). The peak current is linearly proportional to the copper concentration over a range 2.3-50.8 ng ml(-1) with a limit of detection of 1.9 ng ml(-1). The accumulation time and RSD are 90 s and (3.2-3.5)%, respectively. The method was applied to the determination of copper in some analytical grade salts, tap water, human serum and sheep's liver.

  12. Trapping of muscle relaxant methocarbamol degradation product by complexation with copper(II) ion: Spectroscopic and quantum chemical studies

    Science.gov (United States)

    Mansour, Ahmed M.; Shehab, Ola R.

    2014-07-01

    Structural properties of methocarbamol (Mcm) were extensively studied both experimentally and theoretically using FT IR, 1H NMR, UV-Vis., geometry optimization, Mulliken charge, and molecular electrostatic potential. Stability arises from hyper-conjugative interactions, charge delocalization and H-bonding was analyzed using natural bond orbital (NBO) analysis. Mcm was decomposed in ethanol/water mixture at 80 °C to guaifenesin [(RS)-3-(2-methoxyphenoxy)propane-1,2-diol] and carbamate ion [NH2COO-], where the degradation mechanism was explained by trapping the carbamate ion via the complexation with copper(II) ion. The structure of the isolated complex ([Cu(NH2COO)2(H2O)]ṡ4H2O) was elucidated by spectral, thermal, and magnetic tools. Electronic spectra were discussed by TD-DFT and the descriptions of frontier molecular orbitals and the relocations of the electron density were determined. Calculated g-tensor values showed best agreement with experimental values from EPR when carried out using both the B3LYP and B3PW91 functional.

  13. Study on the interaction of a copper(II) complex containing the artificial sweetener aspartame with human serum albumin.

    Science.gov (United States)

    Shahabadi, Nahid; Khodaei, Mohammad Mehdi; Kashanian, Soheila; Kheirdoosh, Fahimeh; Filli, Soraya Moradi

    2014-05-01

    A copper(II) complex containing aspartame (APM) as ligand, Cu(APM)2Cl2·2H2O, was synthesized and characterized. In vitro binding interaction of this complex with human serum albumin (HSA) was studied at physiological pH. Binding studies of this complex with HSA are useful for understanding the Cu(APM)2Cl2·2H2O-HSA interaction mechanism and providing guidance for the application and design of new and more efficient artificial sweeteners drive. The interaction was investigated by spectrophotometric, spectrofluorometric, competition experiment and circular dichroism. Hyperchromicity observed in UV absorption band of Cu(APM)2Cl2·2H2O. A strong fluorescence quenching reaction of HSA to Cu(APM)2Cl2·2H2O was observed and the binding constant (Kf) and corresponding numbers of binding sites (n) were calculated at different temperatures. Thermodynamic parameters, enthalpy change (∆H) and entropy change (∆S) were calculated to be -458.67 kJ mol(-1) and -1,339 J mol(-1 )K(-1) respectively. According to the van't Hoff equation, the reaction is predominantly enthalpically driven. In conformity with experimental results, we suggest that Cu(APM)2Cl2·2H2O interacts with HSA. In comparison with previous study, it is found that the Cu(II) complex binds stronger than aspartame.

  14. Bioinspired, direct synthesis of aqueous CdSe quantum dots for high-sensitive copper(II) ion detection.

    Science.gov (United States)

    Bu, Xiaohai; Zhou, Yuming; He, Man; Chen, Zhenjie; Zhang, Tao

    2013-11-21

    Luminescent CdSe semiconductor quantum dots (QDs), which are coated with a denatured bovine serum albumin (dBSA) shell, have been directly synthesized via a bioinspired approach. The dBSA coated CdSe QDs are ultrasmall (d CdSe QDs. The luminescent QDs are used for copper(II) ion detection due to their highly sensitive and selective fluorescence quenching response to Cu(2+). The concentration dependence of the quenching effect can be best described by the typical Stern-Volmer equation in a linearly proportional concentration of Cu(2+) ranging from 10 nM to 7.5 μM with a detection limit of 5 nM. As confirmed by various characterization results, a possible quenching mechanism is given: Cu(2+) ions are first reduced to Cu(+) by the dBSA shell and then chemical displacement between Cu(+) and Cd(2+) is performed at the surface of the ultrasmall metallic core to impact the fluorescence performance.

  15. Electrochemicla Behavior of Ascorbic Acid on Hexaaza Macrocyclic Copper(II) Complex Modified Au Electrode and Its Analytical Application

    Institute of Scientific and Technical Information of China (English)

    WU,Hai-Xia; DONG,Shu-Qing; KANG,Jing-Wan; LU,Xiao-Quan

    2008-01-01

    A novel hexaaza macrocyclic copper(II) complex modified Au electrode was developed and used for the measurement of ascorbic acid. Its electrochemical behavior was investigated by cyclic voltammetry and scanning electrochemical microscopy. This modified electrode exhibited electrocatalytic response to the oxidation of ascorbic acid. Compared with a bare gold electrode, the modified electrode exhibited a 250 mV shift of the oxidation potential of ascorbic acid in the cathodic direction and a marked enhancement of the current response. The response current revealed a good linear relationship with the concentration of ascorbic acid in the range of 5.0×10-7 to 4.0× 10-5 mol/L and the detection limit of 4.8× 10-8 mol/L (S/N=3) in the pH 4.0 Tris-HCl buffer of ascorbic acid in fruits without any other pretreatment. The concentrations of ascorbic acid measured by this method were in good agreement with the literature values. It is very promising for the modified electrode to be used as an electrochemical sensor for the detection of ascorbic acid.

  16. Magnetic, catalytic, EPR and electrochemical studies on binuclear copper(II) complexes derived from 3,4-disubstituted phenol

    Indian Academy of Sciences (India)

    R Kannappan; R Mahalakshmy; T M Rajendiran; R Venkatesan; P Sambasiva Rao

    2003-02-01

    New symmetrical compartmental binucleating ligands 2,6-bis[N-(2-{dimethylamino}ethyl)-N-methyl)aminomethyl]-3,4-dimethylphenol [HL1] and 2,6-bis[N-(2-{diethylamino}ethyl)-N-ethyl)aminomethyl]-3,4-dimethylphenol [HL2], and their copper(II) complexes [Cu2L1-2(X)]ClO4, (X = NO$_{2}^{-}$, OAc- and OH-) have been prepared. Spectral, catalytic, magnetic, EPR and electrochemical studies have been carried out. A catecholase activity study indicates that only HL1 complexes have efficient catalytic activity due to a less sterically hindered methyl group and enhanced planarity (larger -2 values) with respect to the oxidation of 3,5-di--butylcatechol to the corresponding quinone. Variable temperature magnetic susceptibility studies of the complexes show antiferromagnetic interaction between the copper atoms. X-band EPR signals could not be observed for polycrystalline samples both at room temperatures and liquid nitrogen, consistent with two antiferrromagnetically coupled copper centres in the solid state. EPR spectral studies in methanol solvent show welldefined four hyperfine signals at room temperature due to decomposition of the dimer into monomers. This however is not seen in frozen methanol glass, may be owing to restructuring of the monomers into dimers due to an increase in viscosity of the solvent. Electrochemical studies revealed chemically irreversible behaviour due to chemical or/and stereochemical changes subsequent to electron transfer.

  17. Dinuclear Silver(I) and Copper(II) Complexes of Hexadentate Macrocyclic Ligands Containing p-Xylyl Spacers

    DEFF Research Database (Denmark)

    McKenzie, Christine J.; Nielsen, Lars Preuss; Søtofte, Inger

    1998-01-01

    The cyclocondensation of terephthalic aldehyde with N,N-bis(3-aminopropyl)-methylamine in the presence of silver(I) gives the dinuclear tetramine Schiff base macrocyclic complex, [Ag2L1](NO3)2 (L1=7,22-N,N'-dimethyl-3,7,11,18, 22,26-hexaazatricyclo[26.2.21.18.213.16]-tetratricosa-2,11,13,15,1 7......,26,28,30,31,33-decaene). [Ag2L1](NO3)2 crystallizes in the monoclinic space group P21/c, with a=14.153(6), b=12.263(4), c=9.220(2) Å, beta=97.52(3) Å and Z=2. The silver ions are strongly coordinated at each end of the macrocycle by the two imine nitrogen atoms [2.177(3) and 2.182(3) Å] with close interatomic......,7,11,18,22,26-hexaazatricyclo[26.2.21.18.213. 16]tetratricosa-13,15,28,30,31,33-decane, L2, was prepared by reduction of Ag2L1](NO3)2 with NaBH4. The copper(II) complexes of the reduced ligand, [Cu2Cl2L2]Cl2xCH3OH, [CU2Cl2L2](PF6)2 and [Cu2(CH3CO2)2L2](PF6)2x4H2O, have been prepared and characterized....

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

    Directory of Open Access Journals (Sweden)

    Podunavac-Kuzmanović Sanja O.

    2004-01-01

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

  19. Copper(II) complexes with 2-pyridineformamide-derived thiosemicarbazones: Spectral studies and toxicity against Artemia salina

    Science.gov (United States)

    Ferraz, Karina O.; Wardell, Solange M. S. V.; Wardell, James L.; Louro, Sonia R. W.; Beraldo, Heloisa

    2009-07-01

    The copper(II) complexes [Cu(H2Am4DH)Cl 2] ( 1), [Cu(H2Am4Me)Cl 2] ( 2), [Cu(H2Am4Et)Cl 2] ( 3) and [Cu(2Am4Ph)Cl] ( 4) with 2-pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-methyl (H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph) derivatives were studied by means of infrared and EPR spectral techniques. The crystal structure of 4 was determined. The studied compounds proved to be toxic to Artemia salina, suggesting that they could present cytotoxic activity against solid tumors. Among the free thiosemicarbazones H2Am4Ph presented higher toxicity than all other compounds, which showed comparable effects. In the case of complexes 2 and 3 toxicity is probably attributable to the complex as an entity or to a synergistic effect involving the thiosemicarbazone and copper. H2Am4Ph and complexes 2 and 3 revealed to be the most promising compounds as potential antineoplasic agents.

  20. Joint toxicity of tetracycline with copper(II) and cadmium(II) to Vibrio fischeri: effect of complexation reaction.

    Science.gov (United States)

    Tong, Fei; Zhao, Yanping; Gu, Xueyuan; Gu, Cheng; Lee, Charles C C

    2015-03-01

    Co-contamination of antibiotic and heavy metals commonly occurs in the environment. Tetracycline (TC), a common antibiotic, can behave as an efficient organic ligand to complex with cations. In this paper, the joint toxicity of TC with two commonly existing metals, copper(II) and cadmium(II), towards a luminescent bacteria, Vibrio fischeri, are investigated. Results showed that coexistence of TC and Cu(II) showed a significant antagonistic effect, while TC and Cd(II) showed a synergistic effect. The aqueous speciation of TC with two metal cations was calculated using a chemical equilibrium software Visual MINTEQ and results indicated that a strong complexation exist between TC and Cu(II), while much weaker interaction between TC and Cd(II). Traditional joint toxicity prediction model based on independent action failed to predict the combined toxicity of TC with metals. A new method based on speciation calculation was used to evaluate the joint toxicity of ligands and cations. It is assumed that the metal-ligand complexes are non-toxic to V. fischeri and the joint toxicity is determined by the sum of toxic unit of free metal-ions and free organic ligands. It explained the joint toxicity of the mixed systems reasonably well. Meanwhile, citric acid (CA) and fulvic acid (FA) were also introduced in this study to provide a benchmark comparison with TC. Results showed it is also valid for mixed systems of CA and FA with metals except for the Cd-CA mixture.

  1. Acid-base characterization, coordination properties towards copper(II) ions and DNA interaction studies of ribavirin, an antiviral drug.

    Science.gov (United States)

    Nagaj, Justyna; Starosta, Radosław; Jeżowska-Bojczuk, Małgorzata

    2015-01-01

    We have studied processes of copper(II) ion binding by ribavirin, an antiviral agent used in treating hepatitis C, which is accompanied usually by an increased copper level in the serum and liver tissue. Protonation equilibria and Cu(II) binding were investigated using the UV-visible, EPR and NMR spectroscopic techniques as well as the DFT (density functional theory) calculations. The spectroscopic data suggest that the first complex is formed in the water solution at pH as low as 0.5. In this compound Cu(II) ion is bound to one of the nitrogen atoms from the triazole ring. Above pH6.0, the metal ion is surrounded by two nitrogen and two oxygen atoms from two ligand molecules. The DFT calculations allowed to determine the exact structure of this complex. We found that in the lowest energy isomer two molecules of the ligand coordinate via O and N4 atoms in trans positions. The hypothetical oxidative properties of the investigated system were also examined. It proved not to generate plasmid DNA scission products. However, the calf thymus (CT)-DNA binding studies showed that it reacts with ribavirin and its cupric complex. Moreover, the interaction with the complex is much more efficient.

  2. 4-nitroacetophenone-derived thiosemicarbazones and their copper(II) complexes with significant in vitro anti-trypanosomal activity.

    Science.gov (United States)

    Pérez-Rebolledo, Anayive; Teixeira, Letícia R; Batista, Alzir A; Mangrich, Antonio S; Aguirre, Gabriela; Cerecetto, Hugo; González, Mercedes; Hernández, Paola; Ferreira, Ana M; Speziali, Nivaldo L; Beraldo, Heloisa

    2008-05-01

    N(4)-methyl-4-nitroacetophenone thiosemicarbazone (H4NO(2)Ac4M, 1), N(4),N(4)-dimethyl-4-nitroacetophenone thiosemicarbazone (H4NO(2)Ac4DM, 2) and N(4)-piperidyl-4-nitroacetophenone thiosemicarbazone (H4NO(2)Ac4Pip, 3) and their copper(II) complexes [Cu(4NO(2)Ac4M)(2)] (4), [Cu(4NO(2)Ac4DM)(2)] (5) and [Cu(4NO(2)Ac4Pip)(2)] (6) were tested for their in vitro ability to inhibit the growth of Trypanosoma cruzi epimastigote forms. H4NO(2)Ac4DM (2), [Cu(4NO(2)Ac4M)(2)] (4) and [Cu(4NO(2)Ac4DM)(2)] (5) proved to be as active as the clinical reference drugs nifurtimox and benznidazol. Taking into consideration the serious side effects and the poor efficacy of the reference drugs, as well as the appearance of resistance during treatment, the studied compounds could constitute a new class of anti-trypanosomal drug candidates.

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

    Science.gov (United States)

    Basheer, Chanbasha; Lee, Hian Kee

    2007-10-01

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

  4. One-Dimensional Hydrogen-bonded Double Chain Composed of a Copper(II) Complex with Chelidamic Acid

    Institute of Scientific and Technical Information of China (English)

    ZHOU Guo-Wei; GUO Guo-Cong; CAI Li-Zhen; LIU Bing; HUANG Jin-Shun

    2006-01-01

    Complex [Cu(C7H3NO5)(DMF)(H2O)] was crystallized from the reaction of Cu(CH3COO)2·H2O with 2,6-dicarboxy-4-hydroxypyridine (chelidamic acid) in DMF solution and its structure was characterized by X-ray crystallography. The crystal is of triclinic, space group (P1)with a = 7.835(2), b = 8.594(2), c = 10.309(2)(A),α = 84.16(3), β= 77.94(3), γ= 69.22(3)°, V = 634.4(2) (A)3, Mr = 335.76, Z = 2, Dc = 1.758 g/cm3, λ = 0.71073(A), μ(MoKα) = 1.756 mm-1 and F(000) = 342. The structure was refined to R = 0.0367 and wR = 0.0805 for 2191 observed reflections with I > 2σ(I). The crystal structure shows a distorted square pyramidal geometry around the copper(II) ion, which is chelated by one nitrogen atom and two oxygen atoms of the chelidamic acid, one water molecule and one DMF molecule. The title complex displays 1-D hydrogen-bonded double chains.

  5. Determination of ultra trace amount of enrofloxacin by adsorptive cathodic stripping voltammetry using copper(II) as an intermediate.

    Science.gov (United States)

    Ensaifi, Ali A; Khayamian, T; Taei, M

    2009-05-15

    In this work, a simple and sensitive electroanalytical method was developed for the determination of enrofloxacin (ENRO) by adsorptive cathodic stripping voltammetry (ADSV) using Cu(II) as a suitable probe. The complex of copper(II) with ENRO was accumulated at the surface of a hanging mercury drop electrode at -0.10 V for 40 s. Then, the preconcentrated complex was reduced and the peak current was measured using square wave voltammetry (SWV). The optimization of experimental variables was conducted by experimental design and support vector machine (SVM) modeling. The model was used to find optimized values for the factors such as pH, Cu(II) concentration and accumulation potential. Under the optimized conditions, the peak current at -0.30 V is proportional to the concentration of ENRO over the range of 10.0-80.0 nmol L(-1) with a detection limit of 0.33 nmol L(-1). The influence of potential interfering substances on the determination of ENRO was examined. The method was successfully applied to determination of ENRO in plasma and pharmaceutical samples.

  6. Synthesis, crystal structures and properties of two novel macrocyclic nickel(II) and copper(II) complexes

    Science.gov (United States)

    Su, Yan-Hui; Liu, Jie; Li, Jia; Si, Xue-Zhi

    2007-06-01

    Two new 14-membered hexaaza macrocyclic complexes with the formulae [NiL](ClO 4) 2·CH 3COCH 3 ( 1) and [CuL](ClO 4) 2·CH 3COCH 3 ( 2), where L = 3,10-bis(2-thiophenemethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, have been synthesized and characterized by elemental analyses, single-crystal X-ray diffraction analyses, electronic spectra, IR and TG-DTA. In 1, the nickel(II) ion is four-coordinated with four nitrogen atoms from the macrocycle and forms a square-planar coordination geometry. In 2, the copper(II) ion is six-coordinated with four nitrogen atoms from the macrocyclic ligand in the equatorial plane and two oxygen atoms from the perchlorate anions in the axial position exhibiting an elongated octahedron coordination geometry. The two complexes present two different molecular arrangements in which the [ML] 2+ (M = Ni, Cu) cation arrays in the manner of M(1)M(2)M(1)… in sequence. The pendant thiophene groups of the neighboring macrocycles have no π⋯π interactions. All the ClO4- anions and acetone molecules are involved in hydrogen-bonding interactions with the macrocyclic ligand.

  7. Can copper(II) mediate Hoogsteen base-pairing in a left-handed DNA duplex? A pulse EPR study.

    Science.gov (United States)

    Santangelo, Maria Grazia; Antoni, Philipp M; Spingler, Bernhard; Jeschke, Gunnar

    2010-02-22

    Pulse EPR spectroscopy is used to investigate possible structural features of the copper(II) ion coordinated to poly(dG-dC).poly(dG-dC) in a frozen aqueous solution, and the structural changes of the polynucleotide induced by the presence of the metal ion. Two different copper species were identified and their geometry explained by a molecular model. According to this model, one species is exclusively coordinated to a single guanine with the N7 nitrogen atom forming a coordinative bond with the copper. In the other species, a guanine and a cytosine form a ternary complex together with the copper ion. A copper crosslink between the N7 of guanine and N3 of cytosine is proposed as the most probable coordination site. Moreover, no evidence was found for an interaction of either copper species with a phosphate group or equatorial water molecules. In addition, circular dichroism (CD) spectroscopy showed that the DNA of the Cu(II)-poly(dG-dC).poly(dG-dC) adducts resembles the left-handed Z-form. These results suggest that metal-mediated Hoogsteen base pairing, as previously proposed for a right-handed DNA duplex, can also occur in a double-stranded left-handed DNA.

  8. Induction of cell death by ternary copper(II) complexes of L-tyrosine and diimines: role of coligands on DNA binding and cleavage and anticancer activity.

    Science.gov (United States)

    Ramakrishnan, Sethu; Rajendiran, Venugopal; Palaniandavar, Mallayan; Periasamy, Vaiyapuri Subbarayan; Srinag, Bangalore Suresh; Krishnamurthy, Hanumanthappa; Akbarsha, Mohammad Abdulkader

    2009-02-16

    The mononuclear mixed ligand copper(II) complexes of the type [Cu(L-tyr)(diimine)](ClO(4)), where tyr is L-tyrosine and diimine is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), 5,6-dimethyl-1,10-phenanthroline (5,6-dmp) (3), and dipyrido[3,2-d:2',3'-f]quinoxaline (dpq) (4), have been isolated and characterized by analytical and spectral methods. In the X-ray crystal structure 3 Cu(II) possesses a distorted square pyramidal coordination geometry with the two nitrogen atoms of 5,6-dmp ligand and the amine nitrogen and carboxylate oxygen atoms of L-tyrosine located at the equatorial sites and the coordinated water molecule present in the apical position. The electronic absorption and electron paramagnetic resonance (EPR) spectral parameters reveal that the complexes retain their square-based geometries even in solution. All of the complexes display a ligand field band in the visible region (600-700 nm) in Tris-HCl/NaCl buffer (5:50 mM) at pH 7.2 and also axial EPR spectra in acetonitrile at 77 K with g(parallel) > g(perpendicular) indicating a d(x(2)-y(2)) ground state. The g(parallel) and A(parallel) values of 2.230 and (170-180) x 10(-4) cm(-1), respectively, conform to a square-based CuN(3)O coordination chromophore, which is consistent with the X-ray crystal structure of 3. The interaction of the complexes with calf thymus DNA (CT DNA) has been explored by using physical methods to propose modes of DNA binding of the complexes. Absorption (K(b)) and emission spectral studies and viscosity measurements indicate that 4 interacts with DNA more strongly than all of the other complexes through partial intercalation of the extended planar ring of dpq with DNA base stack. Interestingly, complex 3 exhibits a DNA binding affinity that is higher than that of 2, which suggests the involvement of 5,6-dimethyl groups on the phen ring in hydrophobic interaction with DNA surface. In contrast with the increase in relative viscosities of DNA bound to 2-4, the

  9. The first salen-type ligands derived from 3',5'-diamino-3',5'-dideoxythymidine and -dideoxyxylothymidine and their corresponding copper(II complexes

    Directory of Open Access Journals (Sweden)

    Koth Daniel

    2006-08-01

    Full Text Available Abstract Background There are many nucleoside metal complexes known. According to observations made, only very few of them reveal their central ion to be co-ordinated by the sugar part of their molecules. The regio- and stereospecific exchange of the hydroxyl groups at the sugar moiety by chelating units improves its complexation ability and should give access to a new class of chiral ligands. Results In this paper we present the synthesis of 3',5'-diamino substituted thymidines with ribo- as well as xylo-configuration and the preparation of copper(II complexes derived from their corresponding Schiff bases. Starting from thymidine, the amino derivatives were prepared in a three and four step reaction sequence respectively. The absolute configuration of the ligands was proved by the three-bond 1H-1H spin spin coupling constants 3J obtained by NMR-studies. Condensation of the amino derivatives with salicylic aldehydes resulted in the corresponding diimines, which represent a new class of chiral salen-type ligands. All ligands formed uncharged stable copper(II complexes. The structure of 3',5'-bis(3,5-di-tert-butylsalicylaldiminato-3',5'-dideoxyxylothymidine-copper(II could be determined by single crystal X-ray structure analysis. The copper centre in this complex has distorted tetrahedral coordination geometry. Conclusion For the synthesis of 3',5'-diamino-3',5'-dideoxy thymidines with xylo- as well as ribo-configuration an effective synthesis pathway has been developed. Their corresponding salicylidene imines form stable coordination compounds with copper(II ions. They represent the first salen type complexes of nucleosides with this substitution pattern.

  10. Studies of 1-Amino-2,2-difluorocyclopropane-1-carboxylic Acid: Mechanism of Decomposition and Inhibition of 1-Aminocyclopropane-1-carboxylic Acid Deaminase.

    Science.gov (United States)

    Liu, Cheng-Hao; Wang, Shao-An; Ruszczycky, Mark W; Chen, Huawei; Li, Keqiang; Murakami, Kazuo; Liu, Hung-wen

    2015-07-02

    1-Amino-2,2-difluorocyclopropane-1-carboxylic acid (DFACC) is of interest in the study of 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase due to the increased reactivity of its cyclopropyl functionality. It is shown that DFACC is unstable under near-physiological conditions where it primarily decomposes via specific-base catalysis to 3-fluoro-2-oxobut-3-enoic acid with a rate constant of 0.18 ± 0.01 min(-1). Upon incubation with ACC deaminase, DFACC is found to be a slow-dissociating inhibitor of ACC deaminase with submicromolar affinity.

  11. Synthesis and Anti-influenza Virus Activity of Ethyl 6-Bromo-5-hydroxyindole-3-carboxylate Derivatives

    Institute of Scientific and Technical Information of China (English)

    Yan Fang ZHAO; Jin Hua DONG; Ping GONG

    2004-01-01

    A series of ethyl 6-bromo-5-hydroxyindole-3-carboxylate derivatives were synthesized and their in vitro anti-influenza virus activity was evaluated. All the compounds were characterized by 1H NMR and MS.

  12. Preferential Interaction of Na+ over K+ to Carboxylate-functionalized Silver Nanoparticles

    Science.gov (United States)

    Elucidating mechanistic interactions between specific ions (Na+/ K+) and nanoparticle surfaces to alter particle stability in polar media has received little attention. We investigated relative preferential binding of Na+ and K+ to carboxylate-functionalized silver nanoparticles ...

  13. Layered transition metal carboxylates: efficient reusable heterogeneous catalyst for epoxidation of olefins.

    Science.gov (United States)

    Sen, Rupam; Bhunia, Susmita; Mal, Dasarath; Koner, Subratanath; Miyashita, Yoshitaro; Okamoto, Ken-Ichi

    2009-12-01

    Layered metal carboxylates [M(malonato)(H(2)O)(2)](n) (M = Ni(II) and Mn(II)) that have a claylike structure have been synthesized hydrothermally and characterized. The interlayer separation in these layered carboxylates is comparable to that of the intercalation distance of the naturally occurring clay materials or layered double hydroxides (LDHs). In this study, we have demonstrated that, instead of intercalating the metal complex into layers of the clay or LDH, layered transition metal carboxylates, [M(malonato)(H(2)O)(2)](n), as such can be used as a recyclable heterogeneous catalyst in olefin epoxidation reaction. Metal carboxylates [M(malonato)(H(2)O)(2)](n) exhibit excellent catalytic performance in olefin epoxidation reaction.

  14. Amino Acids, Aromatic Compounds, and Carboxylic Acids: How Did They Get Their Common Names?

    Science.gov (United States)

    Leung, Sam H.

    2000-01-01

    Surveys the roots of the common names of organic compounds most likely to be encountered by undergraduate organic chemistry students. Includes information for 19 amino acids, 17 aromatic compounds, and 21 carboxylic acids. (WRM)

  15. Efficient Debromination of Vicinal (, (-Dibromo Carboxylic Acid Derivatives with the Sm/HOAc System

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The α, β vicinal dibromo carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.

  16. ANALYSIS OF PERFLUORINATED CARBOXYLIC ACIDS IN SOILS II: OPTIMIZATION OF CHROMATOGRAPHY AND EXTRACTION

    Science.gov (United States)

    With the objective of detecting and quantitating low concentrations of perfluorinated carboxylic acids (PFCAs), including perfluorinated octanoic acid (PFOA), in soils, we compared the analytical suitability of liquid chromatography columns containing three different stationary p...

  17. Characterizing and predicting carboxylic acid reductase activity for diversifying bioaldehyde production.

    Science.gov (United States)

    Moura, Matthew; Pertusi, Dante; Lenzini, Stephen; Bhan, Namita; Broadbelt, Linda J; Tyo, Keith E J

    2016-05-01

    Chemicals with aldehyde moieties are useful in the synthesis of polymerization reagents, pharmaceuticals, pesticides, flavors, and fragrances because of their high reactivity. However, chemical synthesis of aldehydes from carboxylic acids has unfavorable thermodynamics and limited specificity. Enzymatically catalyzed reductive bioaldehyde synthesis is an attractive route that overcomes unfavorable thermodynamics by ATP hydrolysis in ambient, aqueous conditions. Carboxylic acid reductases (Cars) are particularly attractive, as only one enzyme is required. We sought to increase the knowledge base of permitted substrates for four Cars. Additionally, the Lys2 enzyme family was found to be mechanistically the same as Cars and two isozymes were also tested. Our results show that Cars prefer molecules where the carboxylic acid is the only polar/charged group. Using this data and other published data, we develop a support vector classifier (SVC) for predicting Car reactivity and make predictions on all carboxylic acid metabolites in iAF1260 and Model SEED.

  18. Controlled Electrochemical Carboxylation of Graphene To Create a Versatile Chemical Platform for Further Functionalization

    DEFF Research Database (Denmark)

    Bjerglund Pedersen, Emil; Kongsfelt, Mikkel S.; Shimizu, Kyoko

    graphene is allowed to react with added CO2 in an addition reaction, introducing carboxylate groups stabilized by the Bu4N+ already present. This procedure may be carried out repetitively to further increase the carboxylation degree under controlled conditions. We observe an equal functionalization degree...... in a multi-layered but expanded structure accessible for functionalization. On a more general level, this approach will provide a versatile way of forming new hybrid materials based on intimate bond coupling to graphene via carboxylate groups.......An electrochemical approach is introduced for the versatile carboxylation of multilayered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate is negatively charged at −1.9 V vs. Ag/AgI to allow for intercalation of Bu4N+. In the second step, the strongly activated and nucleophilic...

  19. Enrichment of Nanodiamond Surfaces with Carboxyl Groups for Doxorubicin Loading and Release

    Science.gov (United States)

    Astuti, Y.; Saputra, F. D.; Wuning, S.; Arnelli; Bhaduri, G.

    2017-02-01

    In their pristine state, nanodiamond crystals produced via detonation techniques containing several functional groups present on the surface including amine, amide, alcohol, carbonyl, and carboxyl. These functional groups facilitate nanodiamond to interact drugs so as to nanodiamond is potential for medical application such as drug delivery. Even though research on t he use of nanodiamond for this application has been conducted widely, research on the effect of enrichment of nanodiamond surface with carboxyl functional groups for drug loading and release has not been explored extensively. Therefore, in this paper, the effect of carboxyl-terminated nanodiamond (ND-COOH) on drug loading and release will be presented. The enrichment of nanodiamond with carboxyl groups was undertaken by treating nanodiamond with sulphuric acid and nitric acid. The results show that the doxorubicin (DOX) loading and release efficiencies of ND pristine are higher than that of ND-COOH.

  20. Pyrazole carboxamides and carboxylic acids as protein kinase inhibitors in aberrant eukaryotic signal transduction

    DEFF Research Database (Denmark)

    Persson, Tobias; Yde, Christina W.; Rasmussen, Jakob Ewald

    2007-01-01

    Densely functionalised pyrazole carboxamides and carboxylic acids were synthesised in an expedient manner through saponification and transamidation, respectively, of ester-functionalised pyrazoles. This synthetic protocol allowed for three diversifying steps in which appendages on the pyrazole...

  1. Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

    Science.gov (United States)

    Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

    2012-11-01

    Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction.

  2. Theoretical study of structure and stability of small gadolinium carboxylate complexes in liquid scintillator solvents.

    Science.gov (United States)

    Huang, Pin-Wen

    2014-09-01

    The structural properties of three small gadolinium carboxylate complexes in three liquid scintillator solvents (pseudocumene, linear alkylbenzene, and phenyl xylylethane) were theoretically investigated using density functional theory (B3LYP/LC-RECP) and polarizable continuum model (PCM). The average interaction energy between gadolinium atom and carboxylate ligand (E(int)) and the energy difference of the highest singly occupied molecular orbital and lowest unoccupied molecular orbital (Δ(SL)) were calculated to evaluate and compare the relative stability of these complexes in solvents. The calculation results show that the larger (with a longer alkyl chain) gadolinium carboxylate complex has greater stability than the smaller one, while these gadolinium carboxylates in linear alkylbenzene were found to have greater stability than those in the other two solvents.

  3. Facile and efficient synthesis of quinoline-4-carboxylic acids under microwave irradiation

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A facile and efficient method for the preparation of 2-non-substituted quinoline-4-carboxylic acids is described via the Pfitzinger reaction of isatins with sodium pyruvate following consequent decarboxylation under microwave irradiation.

  4. ANALYSIS OF PERFLUORINATED CARBOXYLIC ACIDS IN SOILS II: OPTIMIZATION OF CHROMATOGRAPHY AND EXTRACTION

    Science.gov (United States)

    With the objective of detecting and quantitating low concentrations of perfluorinated carboxylic acids (PFCAs), including perfluorinated octanoic acid (PFOA), in soils, we compared the analytical suitability of liquid chromatography columns containing three different stationary p...

  5. Effect of thermal stabilizers (Ba/Cd/Zn metal salts carboxylate and ...

    African Journals Online (AJOL)

    The IR spectroscopic analysis has shown that during processing (to produce the films), the Ba/Cd/Zn carboxylate salt reacts almost completely with PVC while the dibasic lead stearate ... complex growing absorption band centered around.

  6. Cyclam Derivatives with a Bis(phosphinate) or a Phosphinato-Phosphonate Pendant Arm: Ligands for Fast and Efficient Copper(II) Complexation for Nuclear Medical Applications.

    Science.gov (United States)

    David, Tomáš; Kubíček, Vojtěch; Gutten, Ondrej; Lubal, Přemysl; Kotek, Jan; Pietzsch, Hans-Jürgen; Rulíšek, Lubomír; Hermann, Petr

    2015-12-21

    Cyclam derivatives bearing one geminal bis(phosphinic acid), -CH2PO2HCH2PO2H2 (H2L(1)), or phosphinic-phosphonic acid, -CH2PO2HCH2PO3H2 (H3L(2)), pendant arm were synthesized and studied as potential copper(II) chelators for nuclear medical applications. The ligands showed good selectivity for copper(II) over zinc(II) and nickel(II) ions (log KCuL = 25.8 and 27.7 for H2L(1) and H3L(2), respectively). Kinetic study revealed an unusual three-step complex formation mechanism. The initial equilibrium step leads to out-of-cage complexes with Cu(2+) bound by the phosphorus-containing pendant arm. These species quickly rearrange to an in-cage complex with cyclam conformation II, which isomerizes to another in-cage complex with cyclam conformation I. The first in-cage complex is quantitatively formed in seconds (pH ≈5, 25 °C, Cu:L = 1:1, cM ≈ 1 mM). At pH >12, I isomers undergo nitrogen atom inversion, leading to III isomers; the structure of the III-[Cu(HL(2))] complex in the solid state was confirmed by X-ray diffraction analysis. In an alkaline solution, interconversion of the I and III isomers is mutual, leading to the same equilibrium isomeric mixture; such behavior has been observed here for the first time for copper(II) complexes of cyclam derivatives. Quantum-chemical calculations showed small energetic differences between the isomeric complexes of H3L(2) compared with analogous data for isomeric complexes of cyclam derivatives with one or two methylphosphonic acid pendant arm(s). Acid-assisted dissociation proved the kinetic inertness of the complexes. Preliminary radiolabeling of H2L(1) and H3L(2) with (64)Cu was fast and efficient, even at room temperature, giving specific activities of around 70 GBq of (64)Cu per 1 μmol of the ligand (pH 6.2, 10 min, ca. 90 equiv of the ligand). These specific activities were much higher than those of H3nota and H4dota complexes prepared under identical conditions. The rare combination of simple ligand synthesis, very

  7. Light-Induced Copper(II) Coordination by a Bicyclic Tetraaza Chelator through a Ligand-to-Metal Charge-Transfer Reaction

    DEFF Research Database (Denmark)

    Holm-Jørgensen, Jacob Rørdam; Jensen, Mikael; Bjerrum, Morten

    2011-01-01

    To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values...... and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu2+ and [24.31]adz in water show the existence of a longlived two-coordinated copper(II) intermediate (only counting...

  8. Synthesis, Spectroscopy, and Magnetic Characterization of Copper(II) and Cobalt(II) Complexes with 2-Amino-5-bromopyridine as Ligand

    OpenAIRE

    Arab Ahmadi, Raziyeh; Hasanvand, Farshideh; Bruno, Giuseppe; Amiri Rudbari, Hadi; Amani,Saeid

    2013-01-01

    The synthesis, spectroscopic, and magnetic characterization of two new copper(II) and cobalt(II) complexes are described. Both two compounds have the general formula [M(L)2(Cl)2], in which L= 2-amino-5-bromopyridine. These complexes were prepared in one-step synthesis and characterized by elemental analysis, FTIR, UV-Vis, and EPR spectroscopy. Moreover, the single crystal structure of complex (1) was studied by the X-ray diffraction method. This compound consists of mononuclear units consisti...

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

    Directory of Open Access Journals (Sweden)

    S. O. PODUNAVAC-KUZMANOVIC

    1999-05-01

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

  10. The crucial role of chelate-chelate stacking interactions in the crystal structure of a square planar copper(II) complex

    Science.gov (United States)

    Jana, Subrata; Khan, Samim; Bauzá, Antonio; Frontera, Antonio; Chattopadhyay, Shouvik

    2017-01-01

    A square planar copper(II) complex has been synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction study. The X-ray structure of the complex is used to analyze the crucial role of the π-interactions in the solid state. The complex also shows significant hydrogen-bonding interactions. Moreover, we have evaluated energetically both interactions by means of high level DFT calculations (BP86-D3/def2-TZVP) and characterized them using the Bader's theory of "atoms-in-molecules".

  11. Synthesis, crystal structure and Thermogravimetry of ortho-phthalic acid bridged coordination polymer of Copper(II)

    Indian Academy of Sciences (India)

    BABITA SARMA; SAURAV BHARALI; DIGANTA KUMAR DAS

    2016-06-01

    Coordination polymer of Cu(II) bridged by o-phthalic acid alone is not known. The reaction of$CuCl_{2}.2H_{2}O$ with (2-butoxycarbonyl)benzoic acid yielded three dimensional coordination polymer bridged byo-phthalic acid. X-ray crystal structure shows structure with monoclinic P21/c space group. o-Phthalic acidmolecules act as bridge between two Cu(II), one carboxylate binds to one Cu(II) as bidentate while the othercarboxylate binds to another Cu(II) as monodentate. The four planar co-ordination positions of Cu(II) aresatisfied by two chelated carboxylates while fifth and sixth co-ordination positions are satisfied by monodentatecarboxylates. EPR and TGA of the coordination polymer are also reported.

  12. Effect of the cement type on compatibility with carboxylate superplasticisers

    Directory of Open Access Journals (Sweden)

    Bundyra-Oracz, G.

    2011-06-01

    Full Text Available An empirical study was conducted to gain a fuller understanding of the interactions taking place in cementsuperplasticiser systems. To this end, two clinkers of known chemical and phase composition were prepared in this study to gain insight into such interactions. One contained no tricalcium aluminate (C1, while the other had a 9% C3A content (C2. These clinkers were ground to approximately 340 m2/kg and blended with gypsum only or gypsum and Klein compound (3CaO·3Al2O3·CaSO4 (1, 2. Sufficient compound was added to C1 to ensure the formation of about the same amount of ettringite after 0.5 and 1 h of hydration as found in cement C2 + gypsum. The admixture used was a carboxylate superplasticiser. Rheology measurements showed that while paste yield stress was correlated to ettringite formation, no such simple relationship was observed for plastic viscosity. Plastic viscosity depended on the total hydrates formed, i.e., not only as ettringite but also as C-S-H gel. The findings revealed that in clinkers with very low sulfate and potassium contents, the rheology of carboxylate-containing cement paste is primarily controlled by ettringite formation.

    En el presente trabajo se ha realizado un estudio empírico con el objetivo de profundizar en el conocimiento de las interacciones del sistema cemento-superplastificante. Con este fin, se prepararon dos clínkeres con una composición química y de fases conocida: el primero (C1 sin aluminato tricálcico y el segundo (C2 con un contenido en C3A del 9%. Ambos se molieron hasta obtener una superficie específica aproximada de 340 m2/kg y se emplearon con dos adiciones: yeso y el compuesto de Klein (3CaO·3Al2O3·CaSO4 (1, 2. Se añadió la cantidad necesaria del compuesto de Klein a C1 para garantizar la formación, tras 0,5 y 1ª h. de hidratación, de aproximadamente la misma cantidad de etringita en dicho

  13. Silver(I) and copper(II)-imidazolium carboxylates: Efficient catalysts in Ullmann coupling reactions

    Indian Academy of Sciences (India)

    GANESAN PRABUSANKAR; CHATLA NAGA BABU; GEMBALI RAJU; NATARAJAN SAMPATH

    2017-05-01

    The silver(I) and copper(II)-imidazolium carboxylate coordination assemblies were derived from the reaction between corresponding carboxylic acid ligands and metal salts. These new metal derivatives depict a novel structural motif with variable chemical and thermal properties. These metal complexes act as potentialcatalysts in Ullmann coupling reactions. The imidazolium linker present in these complexes plays a role as both ligand and counter ion to balance the metal charge.

  14. Lung carcinoma progression and survival versus amino- and carboxyl-parathyroid hormone-related protein expression.

    Science.gov (United States)

    Hastings, Randolph H; Montgrain, Philippe R; Quintana, Rick A; Chobrutskiy, Boris; Davani, Ashkhan; Miyanohara, Atsushi; Mahooti, Sepi

    2017-08-01

    Expression of the carboxyl PTHrP region of parathyroid hormone-related protein (PTHrP) is a positive prognostic indicator in women with lung cancer, but amino PTHrP is a negative indicator in other lung cancer patients. This project investigated whether PTHrP could be expressed as predominantly amino PTHrP or carboxyl PTHrP in individual lung carcinomas. It also assessed domain-specific effects on cancer progression and patient survival. PTHrP immunoreactivities were analyzed versus survival in a human lung cancer tissue microarray (TMA). Growth was compared in athymic mice for isogenic lung carcinoma xenografts differing in expression of amino and carboxyl PTHrP domains. In the TMA, 33 of 99 patient tumors expressed only one PTHrP domain, while 54 expressed both. By Cox regression, the hazard ratio for cancer-specific mortality (95% confidence interval) was 2.6 (1.28-5.44) for amino PTHrP (P = 0.008) and 0.6 (0-2.58) for carboxyl PTHrP (P = 0.092). Xenografts of H358 lung adenocarcinoma cells that overexpressed amino PTHrP grew twice as fast as isogenic low PTHrP tumors in athymic mice, but growth of tumors expressing amino plus carboxyl PTHrP was not significantly different than growth of the control tumors. In summary, the presence of amino PTHrP signifies worse prognosis in lung cancer patients. In mouse xenografts, this effect was abrogated if carboxyl PTHrP was also present. Amino PTHrP and carboxyl PTHrP can vary independently in different lung carcinomas. Carboxyl PTHrP may temper the stimulatory effect of amino PTHrP on cancer progression.

  15. Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

    Directory of Open Access Journals (Sweden)

    Brett N. Hemric

    2016-01-01

    Full Text Available This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates.

  16. Silver-Catalyzed Decarboxylative Allylation of Aliphatic Carboxylic Acids in Aqueous Solution.

    Science.gov (United States)

    Cui, Lei; Chen, He; Liu, Chao; Li, Chaozhong

    2016-05-06

    Direct decarboxylative radical allylation of aliphatic carboxylic acids is described. With K2S2O8 as the oxidant and AgNO3 as the catalyst, the reactions of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in satisfactory yields under mild conditions. This site-specific allylation method is applicable to all primary, secondary, and tertiary alkyl acids and exhibits wide functional group compatibility.

  17. Reductive carboxylation supports redox homeostasis during anchorage-independent growth.

    Science.gov (United States)

    Jiang, Lei; Shestov, Alexander A; Swain, Pamela; Yang, Chendong; Parker, Seth J; Wang, Qiong A; Terada, Lance S; Adams, Nicholas D; McCabe, Michael T; Pietrak, Beth; Schmidt, Stan; Metallo, Christian M; Dranka, Brian P; Schwartz, Benjamin; DeBerardinis, Ralph J

    2016-04-14

    Cells receive growth and survival stimuli through their attachment to an extracellular matrix (ECM). Overcoming the addiction to ECM-induced signals is required for anchorage-independent growth, a property of most malignant cells. Detachment from ECM is associated with enhanced production of reactive oxygen species (ROS) owing to altered glucose metabolism. Here we identify an unconventional pathway that supports redox homeostasis and growth during adaptation to anchorage independence. We observed that detachment from monolayer culture and growth as anchorage-independent tumour spheroids was accompanied by changes in both glucose and glutamine metabolism. Specifically, oxidation of both nutrients was suppressed in spheroids, whereas reductive formation of citrate from glutamine was enhanced. Reductive glutamine metabolism was highly dependent on cytosolic isocitrate dehydrogenase-1 (IDH1), because the activity was suppressed in cells homozygous null for IDH1 or treated with an IDH1 inhibitor. This activity occurred in absence of hypoxia, a well-known inducer of reductive metabolism. Rather, IDH1 mitigated mitochondrial ROS in spheroids, and suppressing IDH1 reduced spheroid growth through a mechanism requiring mitochondrial ROS. Isotope tracing revealed that in spheroids, isocitrate/citrate produced reductively in the cytosol could enter the mitochondria and participate in oxidative metabolism, including oxidation by IDH2. This generates NADPH in the mitochondria, enabling cells to mitigate mitochondrial ROS and maximize growth. Neither IDH1 nor IDH2 was necessary for monolayer growth, but deleting either one enhanced mitochondrial ROS and reduced spheroid size, as did deletion of the mitochondrial citrate transporter protein. Together, the data indicate that adaptation to anchorage independence requires a fundamental change in citrate metabolism, initiated by IDH1-dependent reductive carboxylation and culminating in suppression of mitochondrial ROS.

  18. Aerosol volatility and enthalpy of sublimation of carboxylic acids.

    Science.gov (United States)

    Salo, Kent; Jonsson, Asa M; Andersson, Patrik U; Hallquist, Mattias

    2010-04-08

    The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.

  19. Carbon isotope fractionation during photorespiration and carboxylation in Senecio.

    Science.gov (United States)

    Lanigan, Gary J; Betson, Nicholas; Griffiths, Howard; Seibt, Ulli

    2008-12-01

    The magnitude of fractionation during photorespiration and the effect on net photosynthetic (13)C discrimination (Delta) were investigated for three Senecio species, S. squalidus, S. cineraria, and S. greyii. We determined the contributions of different processes during photosynthesis to Delta by comparing observations (Delta(obs)) with discrimination predicted from gas-exchange measurements (Delta(pred)). Photorespiration rates were manipulated by altering the O(2) partial pressure (pO(2)) in the air surrounding the leaves. Contributions from (13)C-depleted photorespiratory CO(2) were largest at high pO(2). The parameters for photorespiratory fractionation (f), net fractionation during carboxylation by Rubisco and phosphoenolpyruvate carboxylase (b), and mesophyll conductance (g(i)) were determined simultaneously for all measurements. Instead of using Delta(obs) data to obtain g(i) and f successively, which requires that b is known, we treated b, f, and g(i) as unknowns. We propose this as an alternative approach to analyze measurements under field conditions when b and g(i) are not known or cannot be determined in separate experiments. Good agreement between modeled and observed Delta was achieved with f = 11.6 per thousand +/- 1.5 per thousand, b = 26.0 per thousand +/- 0.3 per thousand, and g(i) of 0.27 +/- 0.01, 0.25 +/- 0.01, and 0.22 +/- 0.01 mol m(-2) s(-1) for S. squalidus, S. cineraria, and S. greyii, respectively. We estimate that photorespiratory fractionation decreases Delta by about 1.2 per thousand on average under field conditions. In addition, diurnal changes in Delta are likely to reflect variations in photorespiration even at the canopy level. Our results emphasize that the effects of photorespiration must be taken into account when partitioning net CO(2) exchange of ecosystems into gross fluxes of photosynthesis and respiration.

  20. Structure-activity relationship between carboxylic acids and T cell cycle blockade.

    Science.gov (United States)

    Gilbert, Kathleen M; DeLoose, Annick; Valentine, Jimmie L; Fifer, E Kim

    2006-04-04

    This study was designed to examine the potential structure-activity relationship between carboxylic acids, histone acetylation and T cell cycle blockade. Toward this goal a series of structural homologues of the short-chain carboxylic acid n-butyrate were studied for their ability to block the IL-2-stimulated proliferation of cloned CD4+ T cells. The carboxylic acids were also tested for their ability to inhibit histone deacetylation. In addition, Western blotting was used to examine the relative capacity of the carboxlic acids to upregulate the cyclin kinase-dependent inhibitor p21cip1 in T cells. As shown earlier n-butyrate effectively inhibited histone deacetylation. The increased acetylation induced by n-butyrate was associated with the upregulation of the cyclin-dependent kinase inhibitor p21cip1 and the cell cycle blockade of CD4+ T cells. Of the other carboxylic acids studied, the short chain acids, C3-C5, without branching were the best inhibitors of histone deacetylase. This inhibition correlated with increased expression of the cell cycle blocker p21cip1, and the associated suppression of CD4+ T cell proliferation. The branched-chain carboxylic acids tested were ineffective in all the assays. These results underline the relationship between the ability of a carboxylic acid to inhibit histone deacetylation, and their ability to block T cell proliferation, and suggests that branching inhibits these effects.

  1. How many carboxyl groups does an average molecule of humic-like substances contain?

    Directory of Open Access Journals (Sweden)

    I. Salma

    2008-05-01

    Full Text Available The carboxyl groups of atmospheric humic-like substances (HULIS are of special interest because they influence the solubility in water, affect the water activity and surface tension of droplets in the air, and allow formation of chelates with biologically active elements. Experimentally determined abundances of the carboxyl group within HULIS by functional group analysis are consistent with our knowledge on the average molecular mass of HULIS if the number of dissociable carboxyl groups is assumed to be rather small. The best agreement between the average molecular mass derived from the existing abundance data and the average molecular mass published earlier occurs for assuming approximately one dissociable carboxyl group only. This implies that HULIS can not be regarded as polycarboxilic acid. The average molecular mass of HULIS derived from our electrochemical measurements with the assumption of one dissociable carboxyl group per molecule ranges from 248 to 305 Da. It was concluded that HULIS are a moderately strong/weak acid with a dissociation constant of about pK=3.4, which fits well into the interval represented by fulvic and humic acids. The mean number of dissociable carboxyl groups in HULIS molecules was refined to be between 1.1 and 1.4.

  2. How many carboxyl groups does an average molecule of humic-like substances contain?

    Directory of Open Access Journals (Sweden)

    I. Salma

    2008-10-01

    Full Text Available The carboxyl groups of atmospheric humic-like substances (HULIS are of special interest because they influence the solubility in water, affect the water activity and surface tension of droplets in the air, and allow formation of chelates with biologically active elements. Experimentally determined abundances of the carboxyl group within HULIS by functional group analysis are consistent with our knowledge on the average molecular mass of HULIS if the number of dissociable carboxyl groups is assumed to be rather small. The best agreement between the average molecular mass derived from the existing abundance data and the average molecular mass published earlier occurs for assuming approximately one dissociable carboxyl group only. This implies that HULIS can not be regarded as polycarboxilic acid in diluted solutions. The average molecular mass of HULIS derived from our electrochemical measurements with the assumption of one dissociable carboxyl group or equivalently, one dissociable sulphate ester per molecule ranges from 250 to 310 Da. It was concluded that HULIS are a moderately strong/weak acid with a dissociation constant of about pK=3.4, which fits well into the interval represented by fulvic and humic acids. The mean number of dissociable hydrogen (i.e. of carboxyl groups and sulphate esters jointly in HULIS molecules was refined to be between 1.1 and 1.4 in acidic solutions.

  3. The significant role of carboxylated carbonaceous fragments in the electrochemistry of carbon nanotubes.

    Science.gov (United States)

    Ma, Xiao; Jia, Li; Zhang, Lu; Zhu, Liande

    2014-04-01

    Carbon nanotubes (CNTs) have been widely employed as electrode materials in diverse branches of electrochemistry, which are claimed to display dramatically improved electrochemical behaviour compared to the conventional carbon materials. But a series of recent publications have demonstrated that the electrocatalysis of CNTs might be due to the presence of some impurities, such as metallic catalysts, nanographitic particles and amorphous carbon. For this reason, CNTs are usually purified or treated with nitric acid or nitric and sulphuric acid prior to their versatile applications. However, the strong acidic and oxidative conditions are so aggressive that serious erosion of the tube structures has inevitably taken place, which creates defects on the sidewalls and gives rise to numerous molecular byproducts, commonly referred as carboxylated carbonaceous fragments (CCFs). The adsorption of CCFs on CNTs greatly alters the surface conditions of CNTs which may significantly impact on their electrochemical properties. To this end, we wish to disclose whether the electrocatalysis of the nitric acid purified CNTs is affected by the adsorption of the CCFs. Ascorbic acid (AA) and β-nicotinamide adenine dinucleotide (NADH) as selected as the targeting benchmarks that are known to be insensitive to the presence of metallic impurities, which may guarantee the preclusion of the promoting contributions from the metallic catalysts resident in CNTs. We have demonstrated that the electrocatalytic activities of the CNTs are actually dominated by the adsorbed CCFs generated during the acidic pre-treatment. After removal of the CCFs by base rinse, the electrocatalytic properties of CNTs are greatly deteriorated and degraded to the level similar to the conventional graphite powder. We believe this finding is particularly meaningful to uncover the mysterious electrocatalysis of CNTs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Copper-promoted methylene C-H oxidation to a ketone derivative by O2

    DEFF Research Database (Denmark)

    Deville, Claire; McKee, Vickie; McKenzie, Christine J.

    2017-01-01

    ) was characterized in the heteroleptic copper(ii) complex [Cu(bpca)(hidpe)](ClO4). The co-ligand in this complex, N-(2′-pyridylcarbonyl)pyridine-2-carboximidate (bpca−), is derived from a copper-promoted Beckmann rearrangement of hidpe. In the presence of bromide only [Cu(bpca)Br] is isolated. When significant water...... of C-H activation are produced from the dpeo-Cu/Mn systems and specifically O2. The metastable copper complexes [Cu(dpeo)2](ClO4)2 and [Cu(bpca)(hidpe)](ClO4), along with [NiX2(dpeo)2] (X = Cl, Br), [Ni(dpeo)3](ClO4)2, [Co(dpeo)3](ClO4)3 and the mixed valence complex [FeIIIFeII2(dpeo-H)3(dpeo)3](PF6...

  5. Promoting Models

    Science.gov (United States)

    Li, Qin; Zhao, Yongxin; Wu, Xiaofeng; Liu, Si

    There can be multitudinous models specifying aspects of the same system. Each model has a bias towards one aspect. These models often override in specific aspects though they have different expressions. A specification written in one model can be refined by introducing additional information from other models. The paper proposes a concept of promoting models which is a methodology to obtain refinements with support from cooperating models. It refines a primary model by integrating the information from a secondary model. The promotion principle is not merely an academic point, but also a reliable and robust engineering technique which can be used to develop software and hardware systems. It can also check the consistency between two specifications from different models. A case of modeling a simple online shopping system with the cooperation of the guarded design model and CSP model illustrates the practicability of the promotion principle.

  6. Electrostatic immobilisation of copper(I) and copper(II) bis(oxazolinyl)pyridine catalysts on silica: application to the synthesis of propargylamines via direct addition of terminal alkynes to imines

    NARCIS (Netherlands)

    McDonagh, C.; O'Conghaile, P.; Klein Gebbink, R.J.M.; O'Leary, P.F.

    2007-01-01

    Copper(I) and copper(II) complexes of two bis(oxazolinyl)pyridines were immobilized on silica via electrostatic interactions. The catalytic activity of the immobilized catalysts in the direct addition of terminal alkynes to imines leading to propargylamines was investigated under a variety of reacti

  7. Solvent-free microwave-assisted peroxidative oxidation of secondary alcohols to the corresponding ketones catalyzed by copper(ii) 2,4-alkoxy-1,3,5-triazapentadienato complexes.

    Science.gov (United States)

    Figiel, Paweł J; Kopylovich, Maximilian N; Lasri, Jamal; da Silva, M Fátima C Guedes; da Silva, João J R Fraústo; Pombeiro, Armando J L

    2010-04-28

    A facile, efficient and selective solvent-free synthesis of ketones from secondary alcohols with tert-butylhydroperoxide (TBHP) as the oxidant under microwave irradiation is achieved, where the copper(ii) 2,4-alkoxy-1,3,5-triazapentadienato complexes are efficient catalysts providing high yields (up to 100%), TONs (up to 890) and TOFs (up to 1780 h(-1)).

  8. Spectrophotometric tool for the determination of the total carboxylate content in proteins; molar extinction coefficient of the enol ester from Woodward's reagent K reacted with protein carboxylates

    NARCIS (Netherlands)

    Kosters, H.A.; Jongh, H.H.J.de

    2003-01-01

    A number of relevant properties of Woodward's reagent K have been determined, such as the stability of the reactant and the optimal reaction conditions of the reactant with protein carboxylates. A Woodward's reagent K stock solution was stable at 4°C for prolonged time, whereas upon storage at 22°C,

  9. Genome Sequence of the Banana Plant Growth-Promoting Rhizobacterium Pseudomonas fluorescens PS006.

    Science.gov (United States)

    Gamez, Rocío M; Rodríguez, Fernando; Ramírez, Sandra; Gómez, Yolanda; Agarwala, Richa; Landsman, David; Mariño-Ramírez, Leonardo

    2016-05-05

    Pseudomonas fluorescens is a well-known plant growth-promoting rhizobacterium (PGPR). We report here the first whole-genome sequence of PGPR P. fluorescens evaluated in Colombian banana plants. The genome sequences contains genes involved in plant growth and defense, including bacteriocins, 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase, and genes that provide resistance to toxic compounds.

  10. Copper(II) complexes with new fluoroquinolones: Synthesis, structure, spectroscopic and theoretical study, DNA damage, cytotoxicity and antiviral activity.

    Science.gov (United States)

    Dorotíková, Sandra; Kožíšková, Júlia; Malček, Michal; Jomová, Klaudia; Herich, Peter; Plevová, Kristína; Briestenská, Katarína; Chalupková, Anna; Mistríková, Jela; Milata, Viktor; Dvoranová, Dana; Bučinský, Lukáš

    2015-09-01

    Copper(II) complexes with fluoroquinolones in the presence of the nitrogen donor heterocyclic ligands 1,10-phenanthroline have been considered in detail. The phenanthroline moiety was introduced into the ligand environment with the aim to determine whether the nuclease activity is feasible. All suitable X-ray structures of the complexes under study reveal a distorted square pyramidal coordination geometry for Cu(II) atom. The conformational and spectroscopic (FT-IR and UV-visible) behavior has been analyzed and has been interpreted with respect to B3LYP/6-311G* calculations including molecular dynamics. The ability of the complexes to cleave DNA was studied by agarose gel electrophoresis with plasmid DNA pBSK+. The results have confirmed that the complexes under study behave as the chemical nucleases. Nuclease like activity in the absence of hydrogen peroxide allows us to deduce an interaction of the complexes with the DNA resulting in the conversion of supercoiled circular DNA to the nicked form. The DNA cleavage activity enhanced by the presence of hydrogen peroxide demonstrates the participation of reactive oxygen species, such as superoxide radical anions and hydroxyl radicals which presence was confirmed independently using the standard radical scavenging agents. It has been suggested that the radical formation through the Fenton/Haber-Weiss reaction is mediated by the redox cycling mechanisms with the participation of cupric/cuprous ions. Cytotoxic activity was evaluated as the 50% cytotoxic concentration (CC50). The potential effects of tested compounds on replication of murine gammaherpesvirus 68 (MHV-68) under in vitro conditions were also evaluated. However, no antiviral activity against MHV-68 was observed. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. Electrochemical assay for the determination of nitric oxide metabolites using copper(II) chlorophyllin modified screen printed electrodes.

    Science.gov (United States)

    Balamurugan, Murugesan; Madasamy, Thangamuthu; Pandiaraj, Manickam; Bhargava, Kalpana; Sethy, Niroj Kumar; Karunakaran, Chandran

    2015-06-01

    This work presents a novel electrochemical assay for the collective measurement of nitric oxide (NO) and its metabolites nitrite (NO2(-)) and nitrate (NO3(-)) in volume miniaturized sample at low cost using copper(II) chlorophyllin (CuCP) modified sensor electrode. Zinc oxide (ZnO) incorporated screen printed carbon electrode (SPCE) was used as a host matrix for the immobilization of CuCP. The morphological changes of the ZnO and CuCP modified electrodes were investigated using scanning electron microscopy. The electrochemical characterization of CuCP-ZnO-SPCE exhibited the characteristic quasi-reversible redox peaks at the potential +0.06 V versus Ag/AgCl. This biosensor electrode showed a wide linear range of response over NO concentrations from 200 nM to 500 μM with a detection limit of 100 nM and sensitivity of 85.4 nA μM(-1). Furthermore, NO2(-) measurement showed linearity of 100 nM to 1mM with a detection limit of 100 nM for NO2(-) and sensitivity of 96.4 nA μM(-1). Then, the concentration of NO3(-) was measured after its enzymatic conversion into NO2(-). Using this assay, the concentrations of NO, NO2(-), and NO3(-) present in human plasma samples before and after beetroot supplement were estimated using suitable membrane coated CuCP-ZnO-SPCE and validated with the standard Griess method.

  12. Halochromism, ionochromism, solvatochromism and density functional study of a synthesized copper(II) complex containing hemilabile amide derivative ligand

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Reisi, Neda

    2015-03-01

    This study investigates chromotropism of newly synthesized 3,3‧-(ethane-1,2-diylbis(benzylazanediyl))dipropanamide copper(II) perchlorate complex. The compound was structurally characterized by physico-chemical and spectroscopic methods. X-ray crystallography of the complex showed that the copper atom achieved a distorted square pyramidal environment through coordination of two amine N atoms and two O atoms of the amide moieties. The pH effect on the visible absorption spectrum of the complex was studied which functions as pH-induced "off-on-off" switches through protonation and deprotonation of amide moieties along with the Cusbnd O to Cusbnd N bond rearrangement at room temperature. The complex was also observed to show solvatochromism and ionochromism. The distinct solution color changes mainly associated with hemilability of the amide groups. The solvatochromism of the complex was investigated with different solvent parameter models using stepwise multiple linear regression method. The results suggested that the basicity power of the solvent has a dominant contribution to the shift of the d-d absorption band of the complex. Density functional theory, DFT calculations were performed in order to study the electronic structure of the complex, the relative stabilities of the Cusbnd N/Cusbnd O isomers, and to understand the nature of the halochromism processes taking place. DFT computational results buttressed the experimental observations indicating that in the natural pH (5.8) the Cusbnd O isomer is more stable than its linkage isomer and conversely in alkaline aqueous solution.

  13. Reactive oxygen species generation by copper(II) oxide nanoparticles determined by DNA damage assays and EPR spectroscopy.

    Science.gov (United States)

    Angelé-Martínez, Carlos; Nguyen, Khanh Van T; Ameer, Fathima S; Anker, Jeffrey N; Brumaghim, Julia L

    2017-03-01

    Copper(II) oxide nanoparticles ((NP)CuO) have many industrial applications, but are highly cytotoxic because they generate reactive oxygen species (ROS). It is unknown whether the damaging ROS are generated primarily from copper leached from the nanoparticles, or whether the nanoparticle surface plays a significant role. To address this question, we separated nanoparticles from the supernatant containing dissolved copper, and measured their ability to damage plasmid DNA with addition of hydrogen peroxide, ascorbate, or both. While DNA damage from the supernatant (measured using an electrophoresis assay) can be explained solely by dissolved copper ions, damage by the nanoparticles in the presence of ascorbate is an order of magnitude higher than can be explained by dissolved copper and must, therefore, depend primarily upon the nanoparticle surface. DNA damage is time-dependent, with shorter incubation times resulting in higher EC50 values. Hydroxyl radical ((•)OH) is the main ROS generated by (NP)CuO/hydrogen peroxide as determined by EPR measurements; (NP)CuO/hydrogen peroxide/ascorbate conditions generate ascorbyl, hydroxyl, and superoxide radicals. Thus, (NP)CuO generate ROS through several mechanisms, likely including Fenton-like and Haber-Weiss reactions from the surface or dissolved copper ions. The same radical species were observed when (NP)CuO suspensions were replaced with the supernatant containing leached copper, washed (NP)CuO, or dissolved copper solutions. Overall, (NP)CuO generate significantly more ROS and DNA damage in the presence of ascorbate than can be explained simply from dissolved copper, and the (NP)CuO surface must play a large role.

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

    Science.gov (United States)

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

    2016-05-01

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

  15. Halochromism, ionochromism, solvatochromism and density functional study of a synthesized copper(II) complex containing hemilabile amide derivative ligand.

    Science.gov (United States)

    Golchoubian, Hamid; Moayyedi, Golasa; Reisi, Neda

    2015-03-05

    This study investigates chromotropism of newly synthesized 3,3'-(ethane-1,2-diylbis(benzylazanediyl))dipropanamide copper(II) perchlorate complex. The compound was structurally characterized by physico-chemical and spectroscopic methods. X-ray crystallography of the complex showed that the copper atom achieved a distorted square pyramidal environment through coordination of two amine N atoms and two O atoms of the amide moieties. The pH effect on the visible absorption spectrum of the complex was studied which functions as pH-induced "off-on-off" switches through protonation and deprotonation of amide moieties along with the CuO to CuN bond rearrangement at room temperature. The complex was also observed to show solvatochromism and ionochromism. The distinct solution color changes mainly associated with hemilability of the amide groups. The solvatochromism of the complex was investigated with different solvent parameter models using stepwise multiple linear regression method. The results suggested that the basicity power of the solvent has a dominant contribution to the shift of the d-d absorption band of the complex. Density functional theory, DFT calculations were performed in order to study the electronic structure of the complex, the relative stabilities of the CuN/CuO isomers, and to understand the nature of the halochromism processes taking place. DFT computational results buttressed the experimental observations indicating that in the natural pH (5.8) the CuO isomer is more stable than its linkage isomer and conversely in alkaline aqueous solution.

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

    Science.gov (United States)

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

    2014-07-01

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

  17. Synthesis and characterization of mononuclear copper(II) complexes of pyridine 2-carboxamide: Their application as catalyst in peroxidative oxidation and antimicrobial agents

    Indian Academy of Sciences (India)

    Suvendu Samanta; Shounak Ray; Sutapa Joardar; Supriya Dutta

    2015-08-01

    Four water soluble copper(II) complexes, [Cu(HL)2 (H2O)2]Cl2 (1), [Cu(HL) 2 (ClO4)2 ] (2), [Cu(HL)2 (SCN)2] (3) and [CuL 2 ]·8H 2 O (4), where HL is pyridine 2–carboxamide, have been synthesized and characterized by various spectroscopic techniques. Structures have been determined by single crystal X-ray crystallography. The pH induced inter-conversion of Cu(HL)2 (H2O)2 ]Cl2 (1) and [CuL2]·8H2O (4) through co-ordination mode switching was investigated thoroughly with the help of absorption spectroscopy. Complexes 1–3 were found to be active catalysts for the oxidation of toluene, ethyl benzene and cyclohexane in the presence of hydrogen peroxide as the oxidant under mild conditions. Toluene was oxidized to benzyl alcohol and benzaldehyde, ethyl benzene was oxidized to 1-phenylethanol and acetophenone and cyclohexane was oxidized to yield cyclohexanol and cyclohexanone Antimicrobial activities have been investigated with these copper(II) complexes against gram + ve bacteria, gram − ve bacterial and fungal species.

  18. Synthesis and Characterisation of Copper(II Complexes with Tridentate NNO Functionalized Ligand: Density Function Theory Study, DNA Binding Mechanism, Optical Properties, and Biological Application

    Directory of Open Access Journals (Sweden)

    Madhumita Hazra

    2014-01-01

    Full Text Available The photo physical properties of two mononuclear pentacoordinated copper(II complexes formulated as [Cu(L(Cl(H2O] (1 and [Cu(L(Br(H2O] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized and characterized by elemental, physicochemical, and spectroscopic methods. The density function theory calculations are used to investigate the electronic structures and the electronic properties of ligand and complex. The interactions of copper(II complexes towards calf thymus DNA were examined with the help of absorption, viscosity, and fluorescence spectroscopic techniques at pH 7.40. All spectroscopy's result indicates that complexes show good binding activity to calf thymus DNA through groove binding. The optical absorption and fluorescence emission properties of microwires were characterized by fluorescence microscope. From a spectroscopic viewpoint, all compounds strongly emit green light in the solid state. The microscopy investigation suggested that microwires exhibited optical waveguide behaviour which are applicable as fluorescent nanomaterials and can be used as building blocks for miniaturized photonic devices. Antibacterial study reveals that complexes are better antimicrobial agents than free Schiff base due to bacterial cell penetration by chelation. Moreover, the antioxidant study of the ligand and complexes is evaluated by using 1,1-diphenyl-2-picrylhydrazyl (DPPH free-radical assays, which demonstrate that the complexes are of higher antioxidant activity than free ligand.

  19. Structural studies of copper(II) complexes with 2-(2-aminoethyl)pyridine derived Schiff bases and application as precursors of thin organic-inorganic layers.

    Science.gov (United States)

    Barwiolek, Magdalena; Szlyk, Edward; Berg, Andrzej; Wojtczak, Andrzej; Muziol, Tadeusz; Jezierska, Julia

    2014-07-14

    Cu(ii) complexes with Schiff bases derived from 2-pyridin-2-ylethanamine were obtained and characterized by UV-Vis, fluorescence, and IR spectra. The X-ray crystal structures determined for [Cu(ii)(epy(di-t-Buba))Cl] × 0.042H2O and [Cu(ii)(epy(di-t-Buba))O2CCH3] revealed tetrahedral distortion of the Cu(ii) coordination sphere in the solid phase. For both molecules the Cu(ii) ions were found in tetragonal environments, as was confirmed by the values of EPR g-matrix diagonal components. The thermal properties of the complexes and the gas phase composition were studied by TG/IR techniques. Thin layers of the studied copper(ii) complexes were deposited on Si(111) by a spin coating method and characterized by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM) and fluorescence spectra. For copper(ii) layers the most intensive fluorescence band from intra-ligand transition was observed between 498 and 588 nm. The layers' fluorescence intensity was related to the rotation speed and deposition time.

  20. Coumarin-Based Fluorescent Probes for Dual Recognition of Copper(II and Iron(III Ions and Their Application in Bio-Imaging

    Directory of Open Access Journals (Sweden)

    Olimpo García-Beltrán

    2014-01-01

    Full Text Available Two new coumarin-based “turn-off” fluorescent probes, (E-3-((3,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS1 and (E-3-((2,4-dihydroxybenzylideneamino-7-hydroxy-2H-chromen-2-one (BS2, were synthesized and their detection of copper(II and iron(III ions was studied. Results show that both compounds are highly selective for Cu2+ and Fe3+ ions over other metal ions. However, BS2 is detected directly, while detection of BS1 involves a hydrolysis reaction to regenerate 3-amino-7-hydroxycoumarin (3 and 3,4-dihydroxybenzaldehyde, of which 3 is able to react with copper(II or iron(III ions. The interaction between the tested compounds and copper or iron ions is associated with a large fluorescence decrease, showing detection limits of ca. 10−5 M. Preliminary studies employing epifluorescence microscopy demonstrate that Cu2+ and Fe3+ ions can be imaged in human neuroblastoma SH-SY5Y cells treated with the tested probes.