Interaction of cobalt(II) and nickel(II) with a gamma-linked, bis-beta-diketone ligand to yield an unusual coordination motif

Discrete cobalt(II) and nickel(II) complexes of type ML (where L is a bis(2,4-pentanedionate) derivative incorporating a -SCH2CH2S- bridge between the gamma-carbons of respective beta-diketone units) have been synthesised and represent the first examples in which a gamma-substituted, thioether-containing beta-diketone ligand coordinates via a sulfur and oxygen donor in preference to the classical coordination mode involving both beta-diketonate oxygens.     

Lanthanide luminescent switches: modulation of the luminescence of bis-macrocyclic based Tb(III) conjugates in water by H+, Na+ and K+

The synthesis of four bis-macrocyclic conjugates made from the coupling of either diaza-15-crown-5 ethers (1 and 3) and diaza-18-crown-6 ethers (2 and 4) to either amide or carboxylate functionalized cyclen (1,4,7,10-tetraazacyclododecane), and their corresponding cationic Tb(III) complexes, Tb-1, Tb-2, and neutral complexes Tb-3 and Tb-4 are described. The effect on the ground, singlet excited states and the Tb(III) emission, was investigated either as a function of pH or the concentration of several Group I and II cations, upon excitation at 300 nm. The ground state and singlet excited states of the Tb(III) complexes were found to be modulated by ions such as H+, Na+ or K+, signifying the recognition of these ions by the crown ether receptors. In acidic media, below pH 4, the Tb(III) emission was highly pH sensitive, gradually increasing with large orders of magnitude of luminescence enhancements. For Tb-1 and Tb-2 complexes, the Tb(III) emission was also "switched on" in alkaline media above pH 8. At pH 7.4, the recognition of Na+ or K+ also gave rise to a significant change in the Tb(III) emission due to the modulation of the antenna-receptor moieties by these ions. For Tb-1 and Tb-3 the largest changes were seen for Na+, whereas for Tb-2 and Tb-4 the largest changes were seen for K+.     

Lamb wave tomography of pipe-like structures

Lamb waves are guided ultrasonic plate waves that can follow the curvature of pipe-like structures. By transmitting and receiving many helically propagating Lamb waves via longitudinal transducers in contact with the surface of a pipe, crosshole tomographic geometries can be mimicked and tomographic reconstructions performed in order to locate and size flaws. We describe here a meridional-array scheme which mimics a single line of transducers along the exterior surface of the pipe in the axial direction, and show proof of concept results on a pipe sample with an internal wall-thinning. We also demonstrate improved reconstructions for the other helical ultrasound tomography geometry where the transmitters and receivers lie along parallel circumferential rings. We find frequency compounding smoothes out some of the noise and artifacts that appear in the reconstructions.     

1+1 dimensional compactifications of string theory

We argue that stable, maximally symmetric compactifications of string theory to 1+1 dimensions are in conflict with holography. In particular, the finite horizon entropies of the Rindler wedge in 1+1 dimensional Minkowski and anti-de Sitter space, and of the de Sitter horizon in any dimension, are inconsistent with the symmetries of these spaces. The argument parallels one made recently by the same authors, in which we demonstrated the incompatibility of the finiteness of the entropy and the symmetries of de Sitter space in any dimension. If the horizon entropy is either infinite or zero, the conflict is resolved.     

Quantitative determination of the selectivities of five different phenyl radicals in hydrogen atom abstraction from ethanol

An experimental method is described for obtaining quantitative selectivity information for H-atom abstraction by organic radicals from different sites of a substrate in the gas phase. The method is used to determine the selectivities of five different phenyl radicals toward the three different types of hydrogen atoms in ethanol. This experimental method involves studying the reactivities and selectivities of derivatives of the radicals that contain a chemically inert, charged group (distonic ions), which allows them to be manipulated in a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer.     

Triangles and tetrahedra: metal directed self-assembly of metallo-supramolecular structures incorporating bis-beta-diketonato ligands

The interaction of six aryl-linked bis-beta-diketones, including a new naphthylene linked species, with copper(II), iron(III) and, in one instance gallium(III), has been investigated with the aim of obtaining metallo-supramolecular assemblies exhibiting different geometries. New examples of two assembly types incorporating the above bis-beta-diketones (L) were generated. The first type is represented by a range of molecular triangles of formula [Cu(3)(L-H(2))(3)](solvent)(n) while the second is given by a corresponding selection of less-common neutral molecular tetrahedra of formula [Fe(4)(L-H(2))(6)](solvent)(n) as well as [Ga(4)(L-H(2))(6)].8.5THF.0.5H(2)O; an example of each type has been characterised by X-ray crystallography. A magnetochemical investigation of [Fe(4)(-H(2))(6)].6THF is reported. The susceptibility is Curie like and consistent with very weak coupling occurring between the iron(III) d(5)(high spin) centres. The X-ray structures of two trinuclear copper(II) as well as a tetranuclear iron(III) and a tetranuclear gallium(III) assembly confirm their discrete triangular and tetrahedral geometries, respectively. The structure of the gallium(III) species is closely related to that of the corresponding iron(III) species. The tetrahedral structures provide rare examples of such assemblies encapsulating guest solvent molecules--in each case tetrahydrofuran is incorporated in the central cavity.     

First principles calculation of anomalous Hall conductivity in ferromagnetic bcc Fe

We perform a first principles calculation of the anomalous Hall effect in ferromagnetic bcc Fe. Our theory identifies an intrinsic contribution to the anomalous Hall conductivity and relates it to the k-space Berry phase of occupied Bloch states. This dc conductivity has the same origin as the well-known magneto-optical effect, and our result accounts for experimental measurement on Fe crystals with no adjustable parameters.     

Guided wave helical ultrasonic tomography of pipes

Ultrasonic guided waves have been used for a wide variety of ultrasonic inspection techniques. We describe here a new variation called helical ultrasound tomography (HUT) that uses guided ultrasonic waves along with tomographic reconstruction algorithms that have been developed by seismologists for what they call "cross borehole" tomography. In HUT, the Lamb-like guided waves travel the various helical criss-cross paths between two parallel circumferential transducer arrays instead of the planar criss-cross seismic paths between two boreholes. Although the measurement itself is fairly complicated, the output of the tomographic reconstruction is a readily interpretable map of a quantity of interest such as pipe wall thickness. In this paper we demonstrate HUT via laboratory scans on steel pipe segments into which controlled thinnings have been introduced.     

pH responsive Eu(III)-phenanthroline supramolecular conjugate: novel "off-on-off" luminescent signaling in the physiological pH range

The formation of luminescent supramolecular ternary complexes in water: delayed luminescence sensing of aromatic carboxylates using coordinated unsaturated cationic heptadenatate lanthanide ion complexes.