Dimetallic complexes of macrocycles with two rigid dibenzofuran units as receptors for detection of anionic substrates

The hexaazamacrocycles [28](DBF)2N6 {cyclo[bis(4,6-dimethyldibenzo[b,d]furaniminoethyleneiminoethylene]} and [32](DBF)2N6 {cyclo[bis(4,6-dimethyldibenzo[b,d]furaniminopropyleneiminopropylene]} form stable dinuclear copper(II) complexes suitable to behave as receptors for several anionic substrates. These two receptors were used to study the binding interactions with several substrates, such as imidazole (Him) and some carboxylates [benzoate (bz−), oxalate (ox2−), malonate (mal2−), phthalate (ph2−), isophthalate (iph2−), and terephthalate (tph2−)] by spectrophotometric titrations and EPR spectroscopy in MeOH (or H2O):DMSO (1:1 v/v) solution. The largest association constant was found for ox2− with Cu2[32](DBF)2N64+, whereas for the aromatic dicarboxylate anions the binding constants follow the trend ph2− > iph2− > tph2−, i.e. decrease with the increase of the distance of the two binding sites of the substrate. On the other hand, the large blue shift of 68 nm observed by addition of Him to Cu2[32](DBF)2N64+ points out for the formation of the bridged CuimCu cascade complex, indicating this receptor as a potential sensor for the detection and determination of imidazole in solution. The X-band EPR spectra of the Cu2[28](DBF)2N64+ and Cu2[32](DBF)2N6]4+ complexes and the cascade complexes with the substrates, performed in H2O:DMSO (1:1 v/v) at 5 to 15 K, showed that the CuCu distance is slightly larger than the one found in crystal state and that this distance increases when the substrate is accommodated between the two copper centres. The crystal structure of [Cu2[28](DBF)2N6(ph)2]·CH3OH was determined by X-ray diffraction and revealed the two copper centres bridged by two ph2− anions at a Cu···Cu distance of 5.419(1) Å. Each copper centre is surrounded by three carboxylate oxygen atoms from two phthalate anions and three contiguous nitrogen atoms of the macrocycle in a pseudo octahedral coordination environment.

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.

From CAD to virtual reality: modelling approaches, data exchange and interactive 3D building design tools

Virtual reality has the potential to improve visualisation of building design and construction, but its implementation in the industry has yet to reach maturity. Present day translation of building data to virtual reality is often unidirectional and unsatisfactory. Three different approaches to the creation of models are identified and described in this paper. Consideration is given to the potential of both advances in computer-aided design and the emerging standards for data exchange to facilitate an integrated use of virtual reality. Commonalities and differences between computer-aided design and virtual reality packages are reviewed, and trials of current system, are described. The trials have been conducted to explore the technical issues related to the integrated use of CAD and virtual environments within the house building sector of the construction industry and to investigate the practical use of the new technology.

Detecting intraday periodicities with application to high frequency exchange rates

Many recent papers have documented periodicities in returns, return volatility, bid–ask spreads and trading volume, in both equity and foreign exchange markets. We propose and employ a new test for detecting subtle periodicities in time series data based on a signal coherence function. The technique is applied to a set of seven half-hourly exchange rate series. Overall, we find the signal coherence to be maximal at the 8-h and 12-h frequencies. Retaining only the most coherent frequencies for each series, we implement a trading rule that is based on these observed periodicities. Our results demonstrate in all cases except one that, in gross terms, the rules can generate returns that are considerably greater than those of a buy-and-hold strategy, although they cannot retain their profitability net of transactions costs. We conjecture that this methodology could constitute an important tool for financial market researchers which will enable them to detect, quantify and rank the various periodic components in financial data better.

Rational speculative bubbles: an empirical investigation of the London Stock Exchange

In recent years, a sharp divergence of London Stock Exchange equity prices from dividends has been noted. In this paper, we examine whether this divergence can be explained by reference to the existence of a speculative bubble. Three different empirical methodologies are used: variance bounds tests, bubble specification tests, and cointegration tests based on both ex post and ex ante data. We find that, stock prices diverged significantly from their fundamental values during the late 1990's, and that this divergence has all the characteristics of a bubble.