Covalent linkage of the type-2 and type-3 structural mimics to model the active site structure of multicopper oxidases: synthesis and magneto- structural properties of two angular trinuclear copper(II) complexes

Two new angular trinuclear copper(II) complexes of formulation [Cu(3)(HL)LL'](ClO(4)), where L' is imidazole (Him, 1) or 1-methylimidazole (1-MeIm, 2) and H(3)L is a Schiff base obtained from the condensation of salicylaldehyde and 1,3-diaminopropan-2-ol (2:1 mole ratio), are prepared from a reaction of [Cu(2)L(mu-Br)] and [Cu(HL)] in the presence of L' and isolated as perchlorate salts. The crystal structures of 1 and 2 consist of a trinuclear copper(II) unit formed by the covalent linkage of monomeric type-2 mimic and dimeric type-3 mimic precursor complexes to give an angular arrangement of the metal atoms in the core which is a model for the active site structure of blue multicopper oxidases. In 1 and 2, the coordination geometry of two terminal copper atoms is distorted square-planar. The central copper has a distorted square-pyramidal (4 + 1) geometry. The mean Cu...Cu distance is approximately 3.3 A. The complex has a diphenoxo-bridged dicopper(II) unit with the phenoxo oxygen atoms showing a planar geometry. In addition, the complex has an endogenous alkoxo-bridged dicopper(II) unit showing a pyramidal geometry for the oxygen atom. The 1:1 electrolytic complexes show a d-d band at 607 nm. Cyclic voltammetry of the complexes in MeCN containing 0.1 M TBAP using a glassy carbon working electrode displays a Cu(3)(II)/Cu(2)(II)Cu(I) couple near -1.0 V (vs SCE). The variable temperature magnetic susceptibility measurements in the range 300-18 K show antiferromagnetic coupling in the complexes giving magnetic moments of approximately 3.0 mu(B) at 300 K and approximately 2.1 mu(B) at 18 K for the tricopper(II) unit. The experimental susceptibility data are theoretically fitted using a model with Heisenberg spin-(1)/(2) Hamiltonian for a trimer of spin-(1)/(2) copper(II) ions having two exchange parameters involving the alkoxo-bridged dicopper(II) (J1) and the diphenoxo-bridged dicopper(II) (J2) units, giving J1 and J2 values of -82.7, -73 cm(-1) for 1 and -98.3, -46.1 cm(-1) for 2, respectively. The structural features indicate a higher magnitude of anitiferromagnetic coupling in the alkoxo-bridged unit based on the greater value of the Cu-O-Cu angle in comparison to the diphenoxo-bridged unit. The core structures of 1 and 2 compare well with the first generation model complexes for the active site structure of multicopper oxidases in the oxidized form. The crystal structure of 1 exhibits a lamellar structure with a gap of approximately 7 A containing water molecules in the interlamellar space. Complex 2 forms a hexanuclear species due to intermolecular hydrogen bonding interactions involving two trimeric units. The crystal packing diagram of 2 displays formation of a three-dimensional framework with cavities containing the perchlorate anions.     

The Performance of an Electrorheological Fluid in Dynamic Squeeze Flow: The Influence of Solid Phase Size

This paper is concerned with an experimental investigation of a comparison of the rheological performance of an ER fluid, consisting of a carrier with a range of solid phase sizes, in oscillatory squeeze-flow under DC conditions. The fluid is sandwiched between two parallel plane electrodes, the upper one stationary and the lower one oscillating normal to its plane. It is seen that the dynamic performance of the fluid, in terms of the capacity for the transmission of imposed forces across the fluid, is highly dependent on the size of the dispersed solid phase and has an optimum value which is dependent on the mean value of the interelectrode gap. In addition the paper includes some measurements of the current through the fluid which may help to shed some further light on the mechanism of the ER effect. Finally the implications of the results to vibration control are discussed. Copyright 1999 Academic Press.     

Efficient visible light induced nuclease activity of a ternary mono-1,10-phenanthroline copper(II) complex containing 2-(methylthio)ethylsalicylaldimine

Ternary Schiff base copper(II) complex [CuL(phen)](ClO(4)), where HL is 2-(methylthio)ethylsalicylaldimine and phen is 1,10-phenanthroline, has been prepared and structurally characterized by X-ray crystallography. The complex shows a CuN(3)OS coordination in a square-pyramidal (4 + 1) geometry with the sulfur as an equatorial ligand. The complex is an avid binder to double-stranded DNA in the minor groove and exhibits both photonuclease and chemical nuclease activity. When exposed to UV light of 312 nm (96 W) or visible light of 532 nm (125 W) under aerobic conditions, the complex causes significant cleavage of supercoiled pUC19 DNA in the absence of any externally added reducing agent or H(2)O(2).     

Excellent electromagnetic interference shielding effectiveness of chemically reduced graphitic oxide paper at 101 GHz*

Graphitic oxide (GO) was synthesized by oxidation of graphite powder using Hummer’s method and the formed GO is solution processed into paper-like macroscopic form. Subsequently, chemically reduced graphitic oxide paper (CRGOP) is prepared by hydrazine vapours induced reduction of formed GO precursor based paper. The formation of GO and its successful reduction to RGO phase is confirmed by FTIR, Raman Spectroscopy and X-ray diffraction. It has been observed that due to high electrical conductivity ~200 micron thick CRGOP display excellent EMI shielding performance at very high frequency of 101 GHz frequency with total shielding effectiveness (SE) value of ?35.49 dB (i.e. >99.97% blocking of incident EM radiation) which is much higher compared to pristine GO paper (?1.55 dB) or comparable to expanded graphite (EG) sheet (?35.61 dB). Due to their lightweight nature, these freestanding CRGOPs display average specific SE value of ?221.8 dB cm³/g. Besides, their excellent flexibility and makes them potential candidate for lightweight EMI gasketing material compared to other forms of flexible carbons like EG.     

Dissipation and criticality in the lowest Landau level of graphene

The lowest Landau level of graphene is studied numerically by considering a tight-binding Hamiltonian with disorder. The Hall conductance sigma_{xy} and the longitudinal conductance sigma_{xx} are computed. We demonstrate that bond disorder can produce a plateaulike feature centered at nu=0, while the longitudinal conductance is nonzero in the same region, reflecting a band of extended states between +/-E_{c}, whose magnitude depends on the disorder strength. The critical exponent corresponding to the localization length at the edges of this band is found to be 2.47+/-0.04. When both bond disorder and a finite mass term exist the localization length exponent varies continuously between approximately 1.0 and approximately 7/3.     

Molecularly nonstoichiometric crystals in phosphorus compounds

Molecularly nonstoichiometric crystals obtained as a result of differential occupation of sites with oxygen atom/phosphorus lone pair of electrons or with sulfur/selenium in three sets of phosphorus compounds are described. These are formed by a combination of (a) [CH2(6-t-Bu-4-MeC6H2O)2]PNMe2 (11) and [CH2(6-t-Bu-4-MeC6H2O)2]P(O)NMe2 (13), (b) [CH2(6-t-Bu-4-MeC6H2O)2]P(S)NMe2 (14) and [CH2(6-t-Bu-4-MeC6H2O)2]P(Se)NMe2 (15), and (c) [(2,6-Me2C6H3O)(O)P-micro-N-t-Bu]2 (16) and (2,6-Me2C6H3O)(O)P(micro-N-t-Bu)2P(O-2,6-Me2C6H3) (17). In the case of c, three different types of crystals with varying stoichiometry of 16 and 17 (1:9, 1:1.5, and 1:0.43) are obtained. The results are substantiated by the combined use of 31P NMR spectroscopy and X-ray crystallography. These observations suggest that we should be cautious with regards to the purity of samples when syntheses involving the oxidation of P(III) systems are reported. It is also emphasized that the apparent P-X distances in some of these crystals cannot actually be taken as true bond lengths.     

Photosensitizer in a molecular bowl: steric protection enhancing the photonuclease activity of copper(II) scorpionates

Steric encumbrance caused by the tripodal ligand in the ternary tris(3-phenylpyrazolyl)borate copper(II) heterocyclic base complexes [Cu(B)(Tp(Ph))](ClO(4)) (B = dipyridoquinoxaline, dipyridophenazine) leads to efficient cleavage of supercoiled DNA to its relaxed form upon exposure to red light at 632.8 and 694 nm as a result of protection of the photosensitizer in the molecular bowl of the {Cu(Tp(Ph))} moiety, which generates singlet oxygen as the reactive species in a type-II process.