Copper(II) complexes of mono- and di-nucleating hexaamines

The potentially hexadentate polyamines N,N,N',N'-tetrakis(2-aminoethyl)ethane-1,2-diamine (L-1) and the octamethylated analogue N,N,N',N'-tetrakis(2-dimethylaminoethyl)ethane 1,2-diamine (L-2) have been complexed with copper(II) and the crystal structures of their complexes determined. A trigonal-bipyramidal co-ordination geometry for [Cu(HL1)][ClO4](3) was found where one aminoethyl arm is not co-ordinated. By contrast, a dinuclear structure of formula [(H2O)Cu(L-2)Cu(OH)](3+) was determined for the N-methylated analogue, where the hexaamine acts as a bridging ligand between the two square-pyramidal metal centres. Electronic and EPR spectroscopy are both consistent with these structures being maintained in solution.

The metal directed assembly of a trinuclear macrocyclic copper(II) complex

A trinuclear macrocyclic complex is reported from the metal directed condensation between melamine, formaldehyde and the Cu-II complex of a linear tetraamine.

The chemistry of copper patination

The chemistry of copper patination was investigated by two series of experiments. The chemistry of an aqueous copper-sulphate solution was studied at concentrations and pH values near those predicted in an electrolyte on copper exposed to the atmosphere. The electrochemical reactions in an electrolyte in contact with cuprite were investigated in a reaction vessel which used cuprite powder in artificial rainwater to study the electrochemistry of the atmospheric corrosion and patination of copper. Typical sulphate concentrations in rainwater are sufficient to precipitate posnjakite (Cu4SO4(OH)(6)2H(2)O)), a possible precursor to brochantite, within an hour of wetting a cuprite surface. Brochantite (Cu4SO4(OH)(6)), the most commonly found copper salt in natural patinas is responsible for their green appearance. Precipitation of brochantite from the electrolyte resulted from an increase in pH due to the cathodic reduction of oxygen and an increase in cupric ion concentrations by cuprite oxidation. (C) 1998 Elsevier Science Ltd. All rights reserved.

The solution structure of a copper(II) compound of a new cyclic octapeptide by EPR spectroscopy and force field calculations

A new cyclic octapeptide, cyclo(Ile-Ser-(Gly)Thz-Ile-Thr-(Gly)Thz) (PatN), related to patellamide A, has been synthesized and reacted with copper(II) and base to form mono- and dinuclear complexes. The coordination environments around copper(TI) have been characterized by EPR spectroscopy. The solution structure of the thermodynamically most stable product, a purple dicopper(TI) compound, has been examined by simulating weakly dipole-dipole coupled EPR spectra based upon structural parameters obtained from force field (MM and MD) calculations. The MM-EPR method produces a saddle-shaped structure for [Cu-2(PatN)(OH2)(6)] that is similar to the known solution structure of patellamide A and the known solid-state structure of [Cu-2(AscidH(2))CO3(OH2)(2)]. Compared with the latter, [Cu-2(PatN)] has no carbonate bridge and a significantly flatter topology. The MM-EPR approach to solution-structure determination for paramagnetic metallopeptides may find wide applications to other metallopeptides and metalloproteins.

Metal-centred versus ligand-centred luminescence quenching of a macrocyclic copper(II) complex

The new macrocyclic ligand trans-6-(9-anthracenylmethylamino)-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecan-13-amine has been synthesized and characterised as its copper(II) complex and the crystal structure of this complex has been determined. Fluorescence of the anthracenyl group of the macrocycle is quenched in its free base form and when complexed with Cu-II. Fluorescence returns when Lewis acids such as H+ and Zn-II are added to solutions of the ligand, indicating that photoinduced electron transfer from the amine lone pairs is responsible for fluorescence quenching in the free base form. By contrast, fluorescence of the complex is quenched by intramolecular electronic energy transfer.

Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).

Asymmetric MRI magnet design using a hybrid numerical method

This paper describes a hybrid numerical method for the design of asymmetric magnetic resonance imaging magnet systems. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. A new type of asymmetric magnet is proposed in this work. The asymmetric MRI magnet allows the diameter spherical imaging volume to be positioned close to one end of the magnet. The main advantages of making the magnet asymmetric include the potential to reduce the perception of claustrophobia for the patient, better access to the patient by attending physicians, and the potential for reduced peripheral nerve stimulation due to the gradient coil configuration. The results highlight that the method can be used to obtain an asymmetric MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1.2 m in length. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries. (C) 1999 Academic Press.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

A hybrid, inverse approach to the design of magnetic resonance imaging magnets

This paper describes a hybrid numerical method of an inverse approach to the design of compact magnetic resonance imaging magnets. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first, kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. The emphasis of this work is on the optimal design of short MRI magnets. Details of the hybrid numerical model are presented, and the model is used to investigate compact, symmetric MRI magnets as well as asymmetric magnets. The results highlight that the method can be used to obtain a compact MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1 m in length, significantly shorter than current designs. Viable asymmetric magnet designs, in which the edge of the homogeneous region is very close to one end of the magnet system are also presented. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries. (C) 2000 American Association of Physicists in Medicine. [S0094-2405(00)00303-5].

Hybrid modelling of coupled pore fluid-solid deformation problems

A hybrid formulation for coupled pore fluid-solid deformation problems is proposed. The scheme is a hybrid in the sense that we use a vertex centered finite volume formulation for the analysis of the pore fluid and a particle method for the solid in our model. The pore fluid formally occupies the same space as the solid particles. The size of the particles is not necessarily equal to the physical size of materials. A finite volume mesh for the pore fluid flow is generated by Delaunay triangulation. Each triangle possesses an initial porosity. Changes of the porosity are specified by the translations of the mass centers of particles. Net pore pressure gradients are applied to the particle centers and are considered in the particle momentum balance. The potential of our model is illustrated by means of a simulation of coupled fracture and fluid flow developed in porous rock under biaxial compression condition.

Copper/MCM-41 as catalyst for the wet oxidation of phenol

A heterogeneous copper catalyst supported on mesoporous MCM-41 was developed. The parent MCM-41 has a large pore area of over 1400 m(2)/g. Copper was chosen as the active element of catalyst and loaded into MCM-41 by adsorption at ambient temperature. The prepared catalysts were evaluated in the catalytic wet oxidation of phenol solution with an initial concentration of 1,300 ppm at 150 and 200 degreesC. The catalyst was found to be of high catalytic activity. It is also shown that the catalyst with a higher copper loading exhibits higher ability of accelerating the catalytic reaction to certain extent but reaches its constant level afterwards. (C) 2001 Elsevier Science B.V. All rights reserved.

Copper/MCM-41 as catalyst for photochemically enhanced oxidation of phenol by hydrogen peroxide

Heterogeneous copper catalyst was developed using the mesoporous molecular sieve MCM-41 as the catalyst support. Copper was impregnated onto the support. Catalysts with different copper loadings were obtained. The performance of the developed catalysts was evaluated in photochemically enhanced oxidation of phenol using hydrogen peroxide as the oxidant. The catalyst was found to significantly increase the oxidation rate and enhance the removal level of phenol with UV light present. The effects of copper loading on the catalyst, photo (UV), H2O2 concentration, and catalyst dosage on the photo-oxidation of phenol were studied. (C) 2001 Elsevier Science B.V. All rights reserved.

Hybrid auctions

In this paper we analyze a hybrid auction that combines a first-price and a Vickrey auction. We show that this auction may generate more expected revenue than a standard first-price auction. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis and characterization of ternary hybrid material based on poly-o-methoxyaniline and poly(ethylene oxide) in mesostructured V(2)O(5)

New hybrid composites based on mesostructured V(2)O(5) containing intercalated poly(ethylene oxide), poly-o-methoxyaniline and poly(ethylene oxide)/poly-o-methoxyaniline were prepared. The results suggest that the polymers were intercalated into the layers of the mesostructured V(2)O(5). Electrochemical studies showed that the presence of both polymers in the mesostructured V(2)O(5) (ternary hybrid) leads to an increase in total charge and stability after several cycles compared with binary hybrid composites. This fact makes this material a potential component as cathode for lithium ion intercalation and further, a promising candidate for applications in batteries.