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PubMed2000

Kinetics of Adsorption and Desorption of Poly(ethylenimine) and Its Complex with Copper(II) on Copper(II) Oxide Powder.

Adsorption of poly(ethylenimine) and complexes of poly(ethylenimine) with copper(II) ions on copper(II) oxide powder has been investigated. The rate of adsorption and reaction between poly(ethylenimine) and CuO is very fast. The desorption rate of the complex of poly(ethylenimine) with copper(II) ions is slower and decreases when the initial polymer concentration is decreased. The desorption rate passes through a minimum when the initial concentration of CuO powder in the mixture increases. A mathematical model of polymer adsorption and desorption is proposed. Copyright 2000 Academic Press.

Journal Article↗
PubMed1996

Unusual trigonal-planar copper configuration revealed in the atomic structure of yeast copper-zinc superoxide dismutase.

The three-dimensional structure of yeast copper-zinc superoxide dismutase (CuZnSOD) has been determined in a new crystal form in space group R32 and refined against X-ray diffraction data using difference Fourier and restrained crystallographic refinement techniques. The unexpected result is that the copper ion has moved approximately 1 angstrom from its position in previously reported CuZnSOD models, the copper-imidazolate bridge is broken, and a roughly trigonal planar ligand geometry characteristic of Cu(I) rather than Cu(II) is revealed. Final R values for the two nearly identical room temperature structures are 18.6% for all 19 149 reflections in the 10.0-1.7 angstrom resolution range and 18. 2% for 17 682 reflections (F > 2 sigma) in the 10.0-1.73 angstrom resolution range. A third structure has been determined using X-ray data collected at -180 degrees C. The final R value for this structure is 19.0% (R(free) = 22.9%) for all 24 356 reflections in the 10.0-1.55 angstrom resolution range. Virtually no change in the positions of the ligands to the zinc center is observed in these models. The origin of the broken bridge and altered Cu-ligand geometry is discussed.

Crystallography, X-Ray↗
PubMed2000

Synthesis, structure, and H2O2-dependent catalytic functions of disulfide-bridged dicopper(I) and related thioether-copper(I) and thioether-copper(II) complexes.

A disulfide-bridged dicopper(I) complex, [Cu2(Py2SSPy2)](ClO4)2 (1) (Py2SSPy2 = bis(2-[N,N-bis(2-pyridylethyl)-amino]-1,1- dimethylethyl)disulfide), a thioether-copper(I) complex, [Cu(iPrSPy2)](ClO4) (2) (iPrSPy2 = N-(2-isopropylthio-2-methyl)propyl-N,N-bis-2-(2-pyridyl)ethylamine, and a thioether-copper(II) complex, [Cu-(PheSPy2)(H2O)](ClO4)2 (3) (PheSPy2 = N-(2-methyl-2-phenethylthio)propyl-N,N-bis-2-(2- pyridyl)ethylamine), were newly synthesized by the reactions of Cu(ClO4)2.6H2O with a thiol ligand of Py2SH (N,N-bis[2-(2-pyridyl)-ethyl]-1,1-dimethyl-2- mercaptoethylamine) and thioether ligands of iPrSPy2 and PheSPy2, respectively. For complexes 1 and 2, X-ray analyses were performed. Complex 1 crystallizes in the triclinic space group P1, and complex 2 crystallizes in the orthorhombic space group Pbca with the following unit cell parameters: for 1, a = 15.165 (3) A, b = 22.185 (4) A, c = 14.989 (3) A, alpha = 105.76 (1) degrees, beta = 90.82 (2) degrees, gamma = 75.23 (1) degrees, and Z = 2; for 2, a = 17.78 (2) A, b = 17.70 (1) A, c = 15.75 (1) A, and Z = 8. Complex 1 is the first structurally characterized example obtained by the redox reaction Cu(II) + RSH-->Cu(I) + RSSR and has two independent structures (1a, 1b) which mainly differ in S-S bond distances, Cu(I)...Cu(I) separations, and C-S-S-C dihedral angles of the disulfide units. The S-S bond distances of 2.088(7) A in 1a and 2.070(7) A in 1b are indicative of significant activation of the S-S bonds by the dicopper centers. Fragment molecular orbital (FMO) analyses and molecular orbital overlap population (MOOP) analyses based on the extended Hückel method clarify the preferable formation of the disulfide S-S bond in 1 rather than the formation of a thiolate-copper(II) complex within the Py2S- ligand framework. Catalytic functions of complexes 1-3 were investigated with peroxides (H2O2 and tBuOOH) as oxidants. Complex 1 catalyzed the selective oxidation of cyclohexane to cyclohexanol and mediated the cyclohexene epoxidation in the presence of H2O2. A transient dark green intermediate observed in the reaction of 1 with H2O2 is characterized by UV-vis, EPR, and resonance Raman spectroscopies, identifying it as a Cu(II)-OOH species, 1(OOH). The resonance Raman features of the nu(O-O) bands at 822 and 836 cm-1, which are red-shifted to 781 and 791 cm-1, respectively, upon introduction of H2(18)O2, are indicative of formation of two kinds of Cu-OOH species rather than the Fermi doublet and the significant weakening of the O-O bonds. These mechanistic studies demonstrate that by virtue of the electron-donating ability of the disulfide unit the Cu-OOH species can be actually activated for one-electron oxidation, which has been reported so far unfavorable for other vibrationally characterized Cu-OOH species.

Journal Article↗
PubMed2000

Syntheses and crystal structures of "unligated" copper(I) and copper(II) trifluoroacetates.

Two extremely unstable copper trifluoroacetates with no exogenous ligands, namely, Cu(O2CCF3) (1) and Cu(O2CCF3)2 (2), are prepared for the first time and obtained in crystalline form by deposition from the vapor phase. Their structures are determined by X-ray crystallography. The crystallographic parameters are as follows: for 1, monoclinic space group P2(1)/c, with a = 9.7937(6) A, b = 15.322(1) A, c = 12.002(1) A, beta = 106.493(9) degrees, and Z = 4; for 2, orthorhombic space group Pcca, with a = 16.911(1) A, b = 10.5063(9) A, c = 9.0357(6) A, and Z = 4. Both structures are unique among other CuI and CuII carboxylates, as well as among metal carboxylates in general. Compound 1 consists of a planar rhombus of four copper atoms with sides of 2.719(1)-2.833(1) A and trifluoroacetate ligands bridging the pairs of adjacent metal atoms alternately above and below the plane. The tetrameric units are further aggregated in a polymeric zigzag ribbon [Cu4(O2CCF3)4]infinity by virtue of intermolecular Cu...O contacts. The structure of 2 is built on cis bis-bridged dimers in which every metal atom is also connected with two copper atoms of the neighboring units. The stacking planes in this extended chain are almost perpendicular to one another. The Cu...Cu distance inside the dimer is 3.086(2) A, indicating a nonbonding interaction.

Journal Article↗
PubMed2001

Construction of copper halide networks within layered perovskites. Syntheses and characterization of new low-temperature copper oxyhalides.

The construction of two-dimensional (2D) copper halide networks within a variety of perovskite hosts by a low-temperature topochemical method is demonstrated. Ion exchange between some layered perovskite oxides of the type A'[An - 1(M,M')nO3n + 1] (A' = alkali metal, H, NH4; A = alkaline earth, rare earth, or Bi; M,M' = Nb, Ta, Ti; n = 2, 3) with CuX2 (X = Cl, Br) results in the oxyhalides (CuX)[An - 1(M,M')nO3n + 1]. Rietveld refinements from X-ray powder diffraction data show that the structures of these new copper oxyhalides contain edge-sharing CuO2X4 octahedra sandwiched between the M/M'O6 octahedra of the perovskite slabs. The compounds are low-temperature phases that decompose well below 700 degrees C. The copper oxyhalides exhibit antiferromagnetic ordering resulting from the magnetic exchange interactions within the planar Cu-X networks.

Journal Article↗
PubMed2005

A unique cyanide-bridged three-dimensional (3-D) copper(II)-copper(I) mixed-valence polymer containing 1-D water tapes with cyclic pentamer units.

A unique cyano-bridged copper(II)-copper(I) mixed-valence polymer, {[Cu(3)(CN)(4)(H(2)O)(3)](H(2)O)(2)}(n) (1), has been prepared and structurally determined by X-ray diffraction. The cyanide anions with (mu(2),eta(2)) and (mu(3),eta(2)) bridging modes connect the copper centers into a complicated zeolite-like 3-D network. Of further interest, coordinated and lattice water molecules in this structure form 1-D hydrogen-bonded water tapes consisting of linked cyclic pentamer clusters.

Journal Article↗
PubMed2005

Copper hydroxydiphosphate with a one-dimensional arrangement of copper polyhedra: Cu3[P2O6OH]2.

A new copper hydroxydiphosphate Cu3(P2O6OH)2 was synthesized, by soft chemistry. The crystal structure was solved ab initio from X-ray powder diffraction data in the triclinic space group P. The structure is built up from [Cu3O10]infinity zigzag chains linked by P2O6(OH) groups to form a tridimensional framework. The [Cu3O10]infinity chains consist of edge-sharing polyhedra. The structure contains two sorts of copper polyhedra: one CuO6 octahedron and two CuO5 pyramids. Magnetization measurements confirm the presence of divalent copper and suggest antiferromagnetic interactions at low temperature.

Journal Article↗
PubMed2005

Inorganic-metalorganic hybrids based on copper(II)-monosubstituted Keggin polyanions and dinuclear copper(II)-oxalate complexes. Synthesis, X-ray structural characterization, and magnetic properties.

Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-bipyridine-oxalate complexes in the corresponding alkaline acetate buffer led to the formation of hybrid metal organic-inorganic compounds K(2)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)].14H(2)O (1), K(14)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}](2)[SiW(11)O(39)Cu(H(2)O)].55H(2)O (2), (NH(4))(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (3), and Rb(4)[{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}].10H(2)O (4). Their structures have been established by single-crystal X-ray diffraction. The main structural feature of these compounds is the presence of copper(II)-monosubstituted alpha-Keggin polyoxoanions as inorganic building blocks, on which the mu-oxalatodicopper metalorganic blocks are supported. Compound 1contains the discrete hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(H(2)O)(2)(mu-ox)}(2)](2)(-), whereas the polymeric hybrid polyanion [{SiW(11)O(39)Cu(H(2)O)}{Cu(2)(bpy)(2)(mu-ox)}(2)](n)(4)(n)(-) gives a monodimensional character to compounds 2-4. Magnetic and EPR results are discussed with respect to the crystal structure of the compounds. DFT calculations on both the [Cu(2)(bpy)(2)(H(2)O)(4)(mu-ox)](2+) cationic complex and the metalorganic blocks have been performed in order to determine the optimized geometry and the magnetic coupling constants, respectively.

Journal Article↗
PubMed1996

Copper and Bismuth Complexes Containing Dipyridyl gem-Diolato Ligands: Bi(III)(2)[(2-Py)(2)CO(OH)](2)(O(2)CCF(3))(4)(THF)(2), Cu(II)[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), and Cu(II)(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), a Ferromagnetically Coupled Tetranuclear Copper(II) Chain.

The reactions of the singly deprotonated di-2-pyridylmethanediol ligand (dpmdH(-)) with copper(II) and bismuth(III) have been investigated. A new dinuclear bismuth(III) complex Bi(2)(dpmdH)(2)(O(2)CCF(3))(4)(THF)(2), 1, has been obtained by the reaction of BiPh(3) with di-2-pyridyl ketone in the presence of HO(2)CCF(3) in tetrahydrofuran (THF). The reaction of Cu(OCH(3))(2) with di-2-pyridyl ketone, H(2)O, and acetic acid in a 1:2:2:2 ratio yielded a mononuclear complex Cu[(2-Py)(2)CO(OH)](2)(HO(2)CCH(3))(2), 2, while the reaction of Cu(OAC)(2)(H(2)O) with di-2-pyridyl ketone and acetic acid in a 2:1:1 ratio yielded a tetranuclear complex Cu(4)[(2-Py)(2)CO(OH)](2)(O(2)CCH(3))(6)(H(2)O)(2), 3. The structures of these complexes were determined by single-crystal X-ray diffraction analyses. Three different bonding modes of the dpmdH(-) ligand were observed in compounds 1-3. In 2, the dpmdH(-) ligand functions as a tridentate chelate to the copper center and forms a hydrogen bond between the OH group and the noncoordinating HO(2)CCH(3) molecule. In 1 and 3, the dpmdH(-) ligand functions as a bridging ligand to two metal centers through the oxygen atom. The two pyridyl groups of the dpmdH(-) ligand are bound to one bismuth(III) center in 1, while in 3 they are bound two copper(II) centers, respectively. Compound 3 has an unusual one dimensional hydrogen bonded extended structure. The intramolecular magnetic interaction in 3 has been found to be dominated by ferromagnetism. Crystal data: 1, C(38)H(34)N(4)O(14)F(12)Bi(2), triclinic P&onemacr;, a = 11.764(3) Å, b = 11.949(3) Å, c = 9.737(1) Å, alpha =101.36(2) degrees, beta = 105.64(2) degrees, gamma = 63.79(2) degrees, Z = 1; 2, C(26)H(26)N(4)O(8)Cu/CH(2)Cl(2), monoclinic C2/c, a = 25.51(3) Å, b = 7.861(7) Å, c = 16.24(2) Å, beta = 113.08(9) degrees, Z = 4; 3, C(34)H(40)N(4)O(18)Cu(4)/CH(2)Cl(2), triclinic P&onemacr;, a = 10.494(2) Å, b = 13.885(2) Å, c = 7.900(4) Å, alpha =106.52(2) degrees, beta = 90.85(3) degrees, gamma = 94.12(1) degrees, Z = 1.

Journal Article↗
PubMed1999

Copper(I) Complexes with a NS(2)-Macrocyclic Ligand Bearing a Pendant Naphthyl Group: Structures of {N-[2-(1-Naphthyl)ethyl]-1-aza-4,8-dithiacyclodecane}copper(I)-Ligand, where Ligand = eta(2)-Naphthalene, Acetonitrile, or Triphenylphosphine.

A new macrocyclic ligand with a pendant naphthalene group, N-[2-(1-naphthyl)ethyl]-1-aza-4,8-dithiacyclodecane (L), has been synthesized and characterized. The copper(I)-acetonitrile complex [LCu(CH(3)CN)](PF(6)) (1) was synthesized from L and [Cu(CH(3)CN)(4)](PF(6)). The acetonitrile ligand from 1 was easily removed to give [LCu](PF(6)) (2). Complexes 1 and 2 have been crystallographically characterized. 1: C(21)H(28)N(2)CuF(6)PS(2), triclinic, P&onemacr;, a = 11.1901(10) Å, b = 11.2735(12) Å, c = 12.1350(10) Å, alpha = 98.996(8) degrees, beta = 117.188(6) degrees, gamma = 105.354(7) degrees, Z = 2, R1 = 0.0505 (wR2 = 0.1418). 2.0.5hexane: C(22)H(31)NCuF(6)PS(2), monoclinic, P2(1)/c, a = 15.7318(15) Å, b = 8.9164(10) Å, c = 17.205(5) Å, beta = 102.431(6) degrees, Z = 4, R1 = 0.0587 (wR2 = 0.1545). In addition, a cocrystallized mixture of both complexes was crystallographically characterized. 1&2.hexane: C(46)H(61)N(3)Cu(2)F(12)P(2)S(4), triclinic, P&onemacr;, a = 10.8308(9) Å, b = 12.6320(8) Å, c = 19.9412(13) Å, alpha = 80.445(5) degrees, beta = 76.405(6) degrees, gamma = 78.825(5) degrees, Z = 2, R1 = 0.0661 (wR2 = 0.1871). The solid-state structure of 2 features the pendant naphthalene group bound in an eta(2)-fashion, which is highly unusual for copper complexes. In CDCl(3), 2 exhibits fluxional behavior with the barrier to the process estimated, DeltaG() = 12-13 kcal. Variable temperature NMR spectroscopy gave compelling evidence for solution binding of the naphthalene group in 2, apparently the first example for copper(I). The fluxional process seen for 1 is best described as interconversion of the two enantiomers via a species with an unbound naphthalene group. Consistent with the weak binding of the naphthalene group, it is readily replaced with other ligands, such as triphenylphosphine to form [LCu(PPh(3))](PF(6)) (3). Complex 3 has also been structurally characterized: C(37)H(40)NCuF(6)P(2)S(2), monoclinic, P2(1)/c, a = 11.462(2) Å, b = 15.972(2) Å, c = 19.835(9) Å, beta = 94.50(3) degrees, Z = 4, R1 = 0.0906 (wR2 = 0.1889).

Journal Article↗
PubMed2000

Synthesis, characterization, and polymerization activity of [bis(4,4'-bis(neophyldimethylsilylmethyl)-2,2'-bipyridyl)copper(I)]+CuBr2- and Implications for copper(I) catalyst structures in atom transfer radical polymerization.

A series of 4,4'-disilyl-substituted-2,2'-bipyridine ligands were prepared using a metathesis reaction of the dianion of 4,4'-dimethyl-2,2'-bipyridine with several trialkylsilyl chlorides: 4,4'bis(tert-butyldimethylsilylmethyl)-2,2'-bipyridine (dTBDMSbipy), 4,4'-bis(dimethylthexylsilylmethyl)-2,2'-bipyridine (dTHEXbipy), and 4,4'-bis(neophyldimethylsilylmethyl)-2-2'-bipyridine (dNEObipy). It was observed that the side chain length correlated with the ability of the ligand to form hydrocarbon soluble complexes of copper(I) bromide, with dNEObipy forming the most soluble and easily crystallized complexes. The atom transfer radical polymerization (ATRP) of styrene using dNEObipy as the ligand displayed molecular weight control equivalent to other ATRP systems in which solubilizing ligands, such as 4,4'-di-5-nonyl-2,2'-bipyridine or 4,4'-di-n-heptyl-2,2'-bipyridine, were used. The one-to-one complex of dNEObipy with CuBr was prepared and its crystal structure was determined. The resulting complex had the ionic formulation [(dNEObipy)2Cu]+[CuBr2]- and displayed similar activities in styrene ATRP as the standard 2 dNEObipy/CuBr catalyst system. These and other polymerization results in addition to NMR experiments suggest that the predominant copper(I) species formed in ATRP solutions is the 2-to-1 ligand-to-copper(I) cation, [(dNEObipy)2Cu]+, with either a dihalocuprate or halide counteranion, depending upon the conditions.

Journal Article↗
PubMed2002

Gas-phase structure of (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(eta(2)-1,5-cyclooctadiene)copper(I), Cu(1,5-cod)(hfac), an important precursor for vapor deposition of copper.

The molecular structure of Cu(1,5-cod)(hfac) in the gas phase has been determined by electron diffraction, restrained by parameters calculated ab initio (MP2/AE1 level) or using Density Functional Theory (BP86/AE1 level). The most stable structure is one in which one olefinic group of the cyclooctadiene ligand is coordinated to the square-planar copper atom [refined Cu-C distances 194.0(13) and 194.4(9) pm]. The second C=C double bond is weakly associated with the copper atom [Cu...C distances 267.2(23) and 276.9(25) pm], and the cyclooctadiene ligand has a twist-boat conformation, so that the complex has C(1) symmetry. The nature of the bonding between copper and each of the two olefin moieties has been assessed by topological analysis of the BP86/AE1 total electron density. A form with C(2) symmetry, lying between 2 and 7 kJ mol(-1) above the ground state, is a transition state for exchange of the two olefinic groups. There are also two higher energy conformers, both 10 kJ mol(-1) or more above the ground state. In one of these the cyclooctadiene ligand retains the twist-boat conformation, but the Cu(hfac) moiety is coordinated in the exo position with respect to the noncoordinated olefin, instead of endo, as in the most stable conformer. The molecular symmetry is C(1) in this isomer. In the remaining form the ligand has the chair conformation, and the molecular symmetry is C(s).

Journal Article↗
PubMed2004

Identification and characterization of monoanionic tripodal tetradentate ligand complexes of copper(I) and copper(II) involved in halogen atom transfer reactions.

The copper(I) complex of bis-(2-(2-pyridyl)-ethyl)-(2-(N-p-toluenesulfonamido)-ethyl)amine (PETAEA), a monoanionic, tripodal tetradentate ligand, was prepared, characterized, and shown to be an effective catalyst for atom transfer radical polymerization (ATRP). A model atom transfer reaction of Cu(PETAEA) with 1-phenylethyl bromide and TEMPO radical trapping agent was studied. The copper(II) complex formed in this reaction was identified by comparison of its spectroscopic data with that of Cu(PETAEA)Br prepared by an independent synthesis. Kinetic and spectroscopic data indicated that the reaction mechanism involved simple atom transfer from the alkyl halide to the Cu(PETAEA) to form the Cu(PETAEA)Br, and no other intermediates were involved. The solid-state structures of the copper(I) and (II) complexes appeared to be maintained in solution, so this system is an atom transfer reaction in which all of the reactive species are identified and characterized.

Journal Article↗
PubMed2004

Unidirectionally aligned copper hydroxide crystalline nanorods from two-dimensional copper hydroxy nitrate.

We were able to synthesize unidirectionally aligned copper hydroxide nanorods from two-dimensional copper hydroxide nitrate by anion exchange reaction using NaOH without any membrane or template. The structural conversion from Cu2(OH)3NO3 to Cu(OH)2 was confirmed by XRD and FT-IR data. The synthesized copper hydroxide nanorods showed unidirectionally aligned and tightly bound arrays on a hexagonal plate, leading to giant nanorod bundles.

Journal Article↗
PubMed1981

Extended x-ray absorption fine structure of copper in cytochrome c oxidase: Direct evidence for copper-sulfur ligation.

The copper x-ray fluorescence excitation spectrum of cytochrome c oxidase (ferrocytochrome c:oxygen oxidoreductase, EC 1.9.3.1) has been recorded in the 245-270 K range. The beat pattern observed in the extended x-ray absorption fine structure can be accounted for only by postulating a combination of sulfur and nitrogen (or oxygen) ligands to the copper. The average Cu-S distance is 2.27 +/- 0.02 A and the average Cu-N (or Cu-O) distance is 1.97 +/- 0.02 A. The amplitudes require ca, 1-1.5 sulfurs and 2 nitrogens (or oxygens) per copper. The distribution of sulfur ligands between Cu(A) and Cu(B) sites is not known, although there is some evidence that two sulfur atoms are bound to Cu(A).

Journal Article↗
PubMed2006

Bis(1-ferrocenylbutane-1,3-dionato-kappa2O,O')copper(II) and bis(1,3-diferrocenylpropane-1,3-dionato-kappa2O,O')copper(II).

The title compounds, [CuFe2(C5H5)2(C9H8O2)2], (I), and [CuFe4(C5H5)4(C13H9O2)2], (II), are four-coordinate square-planar copper(II) complexes with two bidentate 1-ferrocenylbutane-1,3-dionate or 1,3-diferrocenylpropane-1,3-dionate ligands, respectively. The copper ion in (I) lies on an inversion centre, with one-half of the molecule in the asymmetric unit, while in (II), there are two independent half molecules in the asymmetric unit, with the copper ions also situated on inversion centres. The ferrocene substituents in (I) are in an anti arrangement. The molecules assemble in the crystal structure in layers with ferrocene groups at the surface. The pairs of ferrocene substituents on each ligand in complex (II) are syn and these adopt an anti arrangement with respect to the pair on the other diketonate ligand. As found in (I), complexes assemble in a layered structure with ferrocene-coated surfaces.

Journal Article↗
PubMed2004

Cyanide as a copper and quinone-directed inhibitor of amine oxidases from pea seedlings ( Pisum sativum) and Arthrobacter globiformis: evidence for both copper coordination and cyanohydrin derivatization of the quinone cofactor.

The interactions of cyanide with two copper-containing amine oxidases (CuAOs) from pea seedlings (PSAO) and the soil bacterium Arthrobacter globiformis (AGAO) have been investigated by spectroscopic and kinetic techniques. Previously, we rationalized the effects of azide and cyanide for several CuAOs in terms of copper coordination by these exogenous ligands and their effects on the internal redox equilibrium TPQ(amr)-Cu(II) right harpoon over left harpoon TPQ(sq)-Cu(I). The mechanism of cyanide inhibition was proposed to occur through complexation to Cu(I), thereby directly competing with O(2) for reoxidation of TPQ. Although cyanide readily and reversibly reacts with quinones, no direct spectroscopic evidence for cyanohydrin derivatization of TPQ has been previously documented for CuAOs. This work describes the first direct spectroscopic evidence, using both model and enzyme systems, for cyanohydrin derivatization of TPQ. K(d) values for Cu(II)-CN(-) and Cu(I)-CN(-), as well as the K(i) for cyanide inhibition versus substrate amine, are reported for PSAO and AGAO. In spite of cyanohydrin derivatization of the TPQ cofactor in these enzymes, the uncompetitive inhibition of amine oxidation is determined to arise almost exclusively through CN(-) complexation of Cu(I).

Amine Oxidase (Copper-Containing)↗
PubMed1994

Contraceptive efficacy of the Copper T 380A and Copper T 200 intrauterine devices: results from a comparative clinical trial in six developing countries.

The clinical performance of the Copper T 380A (TCu 380A) and the Copper T 200 (TCu 200) intrauterine devices (IUDs) was evaluated for 12 months in a group of women who had one of the two IUDs inserted. Results are from a multicenter randomized clinical trial at one site in each of six developing countries. The pregnancy rate with the TCu 380A IUD was significantly lower than the pregnancy rate with the TCu 200 IUD at 12 months (0.5 and 2.6 per 100 women, respectively, p < 0.01). No statistically significant differences between the two study IUDs were found with regards to expulsion or removals due to bleeding/pain, personal, medical, or planned pregnancy. The TCu 380A IUD did not have a disproportionately higher incidence of side effects such as intermenstrual bleeding or pain, inflammations or infections, or insertion-related events compared to the TCu 200 IUD. TCu 380A IUD users, however, were significantly more likely to report increased dysmenorrhea than were TCu 200 IUD users. The performance of the TCu 380A IUD in preventing pregnancy during this trial indicates that this IUD may be a better option than the TCu 200 IUD for women wishing to practice effective, long-term, reversible birth control without having to resort to hormonal methods.

Contraception↗