Magnetic coupling in trinuclear partial cubane copper(II) complexes with a hydroxo bridging core and peripheral phenoxo bridges from NNO donor Schiff base ligands

Three new trinuclear copper(II) complexes, [(CuL1)(3)(mu(3)-OH)](ClO4)(2)center dot 3.75H(2)O (1), [(CuL2)(3)(mu(3)-OH)](ClO4)(2) (2) and [(CuL3)(3)(mu(3)-OH)](BF4)(2)center dot 0.5CH(3)CN (3) have been synthesized from three tridentate Schiff bases HL1, HL2, and HL3 (HL1 = 2-[(2-amino-ethylimino)-methyl]-phenol, HL2 = 2-[(2-methylamino-ethylimino)-methyl]-phenol and HL3 = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol). The complexes are characterized by single-crystal X-ray diffraction analyses, IR, UV-vis and EPR spectroscopy, and variable-temperature magnetic measurements. All the compounds contain a partial cubane [Cu3O4] core consisting of the trinuclear unit [(CuL)(3)(mu(3)-OH)](2+) together with perchlorate or fluoroborate anions. In each of the complexes, the three copper atoms are five-coordinated with a distorted square-pyramidal geometry except in complex 1, in which one of the Cu-II ions of the trinuclear unit is six-coordinate being in addition weakly coordinated to one of the perchlorate anions. Variable-temperature magnetic measurements and EPR spectra indicate an antiferromagnetic exchange coupling between the CuII ions of complexes 1 and 2, while this turned out to be ferromagnetic for complex 3. Experimental values have been fitted according to an isotropic exchange Hamiltonian. Calculations based on Density Functional Theory have also been performed in order to estimate the exchange coupling constants in these three complexes. Both sets of values indicate similar trends and specially calculated J values establish a magneto-structural correlation between them and the Cu-O-Cu bond angle, in that the coupling is more ferromagnetic for smaller bond angle values.

Mono-aqua-bridged dinuclear complexes of Cu(II) containing NNO donor Schiff base ligand: Hydrogen-bond-mediated exchange coupling

Two new mono-aqua-bridged dinuclear Cu(II) complexes of tridentate NNO Schiff bases, [Cu-2(mu-H2O)L-2(1)(H2O)(2)](BF4)(2)center dot 2H(2)O (1) and [Cu-2(mu-H2O)L-2(2)(H2O)(2)](BF4)(2)center dot 2H(2)O (2) where HL1 = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol and HL2 =2-[(2-dimethylamino-ethylimino)-methyl]-phenol were synthesized. Both the complexes were characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. For both the complexes each Cu(II) ion is in a square-pyramidal environment being bonded to three atoms from the tridentate NNO Schiff base and a terminal H2O molecule in the equatorial plane; a second H2O ligand acts as a bridge between the two Cu(II) centres through the axial positions. Hydrogen bonds between the terminal H2O ligand and the Schiff base of the adjacent centre complete the intra-dimer linkages. Variable-temperature (4-300 K) magnetic susceptibility measurement shows the presence of significant antiferromagnetic coupling for both the complexes (J = -12.2 and -12.5 cm(-1), respectively, for 1 and 2), mediated mainly through the intra-dimer H-bonds.

Coupling thin layer electrochemistry with epifluorescence microscopy: an expedient way of investigating electrofluorochromism of organic dyes

The first example of thin layer electrochemistry coupled to epifluorescence microscopy in the total internal reflectance mode is described and applied to the investigation of electrochemically modulated fluorescence of an organic dye (chloromethoxytetrazine) in solution. This technique allows to generate full redox switch of fluorescence when converting reversibly the dye into its anion radical, as well as to record the spectral features of the electrogenerated species. Recording simultaneously fluorescence intensity and lifetime along with coulombic charge as a function of the electrode potential will lead to a deep insight into the redox quenching mechanism.

Electromagnetic atmosphere-plasma coupling: the global atmospheric electric circuit

A description is given of the global atmospheric electric circuit operating between the Earth’s surface and the ionosphere. Attention is drawn to the huge range of horizontal and vertical spatial scales, ranging from 10−9 m to 1012 m, concerned with the many important processes at work. A similarly enormous range of time scales is involved from 10−6 s to 109 s, in the physical effects and different phenomena that need to be considered. The current flowing in the global circuit is generated by disturbed weather such as thunderstorms and electrified rain/shower clouds, mostly occurring over the Earth’s land surface. The profile of electrical conductivity up through the atmosphere, determined mainly by galactic cosmic ray ionization, is a crucial parameter of the circuit. Model simulation results on the variation of the ionospheric potential, ∼250 kV positive with respect to the Earth’s potential, following lightning discharges and sprites are summarized. Experimental results comparing global circuit variations with the neutron rate recorded at Climax, Colorado, are then discussed. Within the return (load) part of the circuit in the fair weather regions remote from the generators, charge layers exist on the upper and lower edges of extensive layer clouds; new experimental evidence for these charge layers is also reviewed. Finally, some directions for future research in the subject are suggested.

Parallel pipelined array architectures for real-time histogram computation in consumer devices

The real-time parallel computation of histograms using an array of pipelined cells is proposed and prototyped in this paper with application to consumer imaging products. The array operates in two modes: histogram computation and histogram reading. The proposed parallel computation method does not use any memory blocks. The resulting histogram bins can be stored into an external memory block in a pipelined fashion for subsequent reading or streaming of the results. The array of cells can be tuned to accommodate the required data path width in a VLSI image processing engine as present in many imaging consumer devices. Synthesis of the architectures presented in this paper in FPGA are shown to compute the real-time histogram of images streamed at over 36 megapixels at 30 frames/s by processing in parallel 1, 2 or 4 pixels per clock cycle.

A mutual friend: poems for Charles Dickens

An anthology of poems by contemporary poets celebrating Charles Dickens' bicentenary

The effect of the spacer length on the nature of coupling in side chain liquid crystals polymers and elastomers

Side chain liquid crystal polymers and elastomers exhibit a rich phase behaviour which arises from the antagonistic influences of the entropically disordered polymer chain configuration and the long range orientational ordering of the mesogenic units. This competition arises since the natural macroscopic phase separation is inhibited by the inherent chemical connectivity of the system. At the heart of this connectivity is the spacer link and we consider here its influence on the phase behaviour. In particular we consider a series of elastomers in which the number of alkyl units in the spacer is systematically varied from 2 to 6. The lengthening of the coupling spacer is accompanied by an alternation of the sign of coupling between the polymer chain and the mesogenic unit. These results demonstrate the dominating influence of the so-called hinge effect in determining the phase behaviour. In addition to the alternation of the sign there is some decrease in the magnitude of the coupling with increasing spacer length.

Coupling between mesogenic units and polymer backbone in side-chain liquid crystal polymers and elastomers

The levels of alignment of the mesogenic units and of the polymer backbone trajectory for polyacrylate based nematic side-chain liquid crystal polymers and elastomers were evaluated by using wide angle X-ray and small angle neutron scattering procedures. The X-ray scattering measurements show that substantial levels of preferred orientation of the mesogenic units may be introduced through magnetic fields for uncrosslinked polymers and through mechanical extension for liquid crystal elastomers. Small angle neutron scattering measurements show that for highly aligned samples an anisotropic polymer backbone trajectory is observed in which the envelope is slightly extended by ∼ 10% in the direction parallel to the axis of alignment of the mesogenic units. The sense of this coupling differs from that recorded for other uncrosslinked side-chain liquid crystal polymers. Possible mechanisms to account for this anisotropy and its relationship to the properties of liquid crystal elastomers are discussed. The observed deformation behaviour of the liquid crystal elastomer is non-affine and this appears to confirm the dominating influence of the liquid crystal order of the side chains on the mechanical properties of these novel networks.

Coupling and memory in liquid crystal elastomers

The polymer backbone of a side-chain liquid crystal polymer exhibits an anisotropic shape due to the coupling of the liquid crystal orientational order of the mesogenic side-chains to the backbone. The magnitude and sign of this coupling may be controlled by chemical design. The introduction of chemical cross-links in to such a system provides both a memory of the anisotropic organisation and a mechanism by which the microscopic anisotropy can be realised at a macroscopic level. We show how this anisotropic network structure yields new phenomena when electric or mechanical fields are applied.

Side-chain liquid crystalline elastomers: the relationship between the orientational ordering of the polymer backbone and the length of the coupling chain

The influence of cross-linking on the phase behaviour of a series of side-chain liquid crystalline elastomers has been studied. For samples cross-linked in the temperature range corresponding to the nematic phase, the phase transition was shifted compared to that observed when an identical sample was cross-linked in the isotropic phase. This shift represented a stabilisation of the nematic phase in the former case, in line with theoretical expectations. By utilising a novel, slow cross-linking method, which allows the polymer backbone to take up an equilibrium conformation prior to network formation, it proved possible to monitor the shifts in phase transition temperature as a function of the length of the methylene chain coupling the mesogenic units to the polymer backbone. The results obtained are related to the backbone anisotropy and indicate that the level of orientational order of the polymer in the nematic phase backbone increases with a reduction in the length of the coupling chain.

Separating skill from luck in REIT mutual funds

This study uses a bootstrap methodology to explicitly distinguish between skill and luck for 80 Real Estate Investment Trust Mutual Funds in the period January 1995 to May 2008. The methodology successfully captures non-normality in the idiosyncratic risk of the funds. Using unconditional, beta conditional and alpha-beta conditional estimation models, the results indicate that all but one fund demonstrates poor skill. Tests of robustness show that this finding is largely invariant to REIT market conditions and maturity.

Dispersion of a point-source release of a passive scalar through an urban-like array for different wind directions

The dispersion of a point-source release of a passive scalar in a regular array of cubical, urban-like, obstacles is investigated by means of direct numerical simulations. The simulations are conducted under conditions of neutral stability and fully rough turbulent flow, at a roughness Reynolds number of Reτ = 500. The Navier–Stokes and scalar equations are integrated assuming a constant rate release from a point source close to the ground within the array. We focus on short-range dispersion, when most of the material is still within the building canopy. Mean and fluctuating concentrations are computed for three different pressure gradient directions (0◦ , 30◦ , 45◦). The results agree well with available experimental data measured in a water channel for a flow angle of 0◦ . Profiles of mean concentration and the three-dimensional structure of the dispersion pattern are compared for the different forcing angles. A number of processes affecting the plume structure are identified and discussed, including: (i) advection or channelling of scalar down ‘streets’, (ii) lateral dispersion by turbulent fluctuations and topological dispersion induced by dividing streamlines around buildings, (iii) skewing of the plume due to flow turning with height, (iv) detrainment by turbulent dispersion or mean recirculation, (v) entrainment and release of scalar in building wakes, giving rise to ‘secondary sources’, (vi) plume meandering due to unsteady turbulent fluctuations. Finally, results on relative concentration fluctuations are presented and compared with the literature for point source dispersion over flat terrain and urban arrays. Keywords Direct numerical simulation · Dispersion modelling · Urban array