Comparison of measurements of phase velocity in human calcaneus to Biot theory

Biot's theory for elastic propagation in porous media has previously been shown to be useful for modeling the dependence of phase velocity on porosity in bovine cancellous bone in vitro. In the present study, Biot's theory is applied to measurements of porosity-dependent phase velocity in 53 human calcanea in vitro. Porosity was measured using microcomputed tomography for some samples (n = 23) and estimated based on bone mineral densitometry for the remaining samples (n = 30). The phase velocity at 500 kHz was measured in a water tank using a through-transmission technique. Biot's theory performed well for the prediction of the dependence of sound speed on porosity. The trend was quasilinear, but both the theory and experiment show similar slight curvature. The root mean square error (RMSE) of predicted versus measured sound speed was 15.8 m/s.     

High fidelity single qubit operations using pulsed electron paramagnetic resonance

Systematic errors in spin rotation operations using simple rf pulses place severe limitations on the usefulness of the pulsed magnetic resonance methods in quantum computing applications. In particular, the fidelity of quantum logic operations performed on electron spin qubits falls well below the threshold for the application of quantum algorithms. Using three independent techniques, we demonstrate the use of composite pulses to improve this fidelity by several orders of magnitude. The observed high-fidelity operations are limited by pulse phase errors, but nevertheless fall within the limits required for the application of quantum error correction.     

Electronic control of chiral quaternary center creation in the intramolecular asymmetric heck reaction

The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.     

Isolation and ring-opening of new 1-sila-3-metallacyclobutanes (eta 5-C5H4Fe)(CO)2CH2SiR2 leading to a new class of organometallic polymer

Treatment of FpCH2SiR2Cl [Fp = (eta5-C5H5)Fe(CO)2] with lithium diisopropylamide leads to the formation of new metallacycle complexes. When R2 = Me2 and MenBu, these ring-open to form a new class of organometallic polymer. When R2 = nBu2, the metallacycle resists ring-opening and may be structurally characterized as the Ph3P-substituted species.     

Dimetallic complexes of acyclic pyridine-armed ligands derived from 3,6-diformylpyridazine

A bis(pyridine-armed) acyclic Schiff base ligand L1 has been synthesised from 3,6-diformylpyridazine and two equivalents of 2-(2-aminoethyl)pyridine. Reduction of this ligand using NaBH(4) resulted in the formation of the amine analogue L2. Complexes of the form [M(2)L1(mu-X)]Y(2)ClO(4)[where: M = Cu(II), X = OH(-) and Y = ClO(4)(-) 1, Cl(-) 2, Br(-) 3 or I(-) 4; M = Co(II), X = OH(-) and Y = ClO(4)(-) 5; M = Ni(II), X = SCN(-) 6 or X = N(3)(-) 7 and Y = ClO(4)(-)], and [Cu(2)L2(mu-OH)](ClO(4))(3) 8 were prepared and characterised. The complexes 1 and 5-7 have been characterised by single-crystal X-ray diffraction. The acyclic L1 ligand provides three nitrogen donor atoms per metal centre, including a pyridazine bridge between the metal centres, and the anion X also bridges the two metal centres. As required, coordinating solvent molecules or additional anions make up the remainder of the coordination sphere. The two copper centres of 1 are very strongly antiferromagnetically coupled (2J=-1146 cm(-1))via the pyridazine and hydroxide ion bridges, whereas the competing antiferromagnetic pyridazine bridging pathway and ferromagnetic 1,1-bridging azide pathway resulted in the observation of weak antiferromagnetic exchange in the dinickel(II) complex 7 (2J=-14 cm(-1)). Electrochemical examination of L1, L2 and complexes 1 and 5-8 revealed multiple redox processes. These have been tentatively assigned to a mixture of metal centred and ligand centred redox processes on the basis of cyclic voltammetry and coulometry results and comparisons with literature examples.     

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.     

Coherence function and mean field of plane and spherical sound waves propagating through inhomogeneous anisotropic turbulence

Inhomogeneity and anisotropy are intrinsic characteristics of daytime and nighttime atmospheric turbulence. For example, turbulent eddies are often stretched in the direction of the mean wind, and the turbulence statistics depends on the height above the ground. Recent studies have shown that the log-amplitude and phase fluctuations of plane and spherical sound waves are significantly affected by turbulence inhomogeneity and anisotropy. The present paper is devoted to studies of the mean sound field and the coherence functions of plane and spherical sound waves propagating through inhomogeneous anisotropic turbulence with temperature and velocity fluctuations. These statistical moments of a sound field are important in many practical applications, e.g., for source detection, ranging, and recognition. Formulas are derived for the mean sound field and coherence function of initially arbitrary waveform. Using the latter formula, we also obtained formulas for the coherence functions of plane and spherical sound waves. All these formulas coincide with those known in the literature for two limiting cases: homogeneous isotropic turbulence with temperature and wind velocity fluctuations, and inhomogeneous anisotropic turbulence with temperature fluctuations only. Using the formulas obtained, we have numerically shown that turbulence inhomogeneity significantly affects the coherence functions of plane and spherical sound waves.     

Genetic integrity of cryopreserved plant cells: a review

Cryopreservation techniques exist for some 100-plant species. Cryopreservation for the long-term conservation of in vitro germplasm results in the exposure of tissues to physical, chemical and physiological stresses causing cryoinjury. Although, the effects of cryoinjury upon the genome are often unknown, any accumulative DNA polymorphisms may not be induced by cryopreservation per se but are the result of the whole culture-cryoprotection-regeneration process. It is desirable to assess the genetic integrity of plants surviving cryogenic storage to determine if they are true to type after cryopreservation. This can be done at the phenotypic, histological, cytological, biochemical and molecular levels. The relevance of these approaches to stability investigations is discussed with their limitations. This review provides a definition for Cryobionomics - a novel term describing the re-modelled concept of genetic stability and the re-introduction of cryopreserved plants into the environment.     

Absorption and scattering imaging of tissue with steady-state second-differential spectral-analysis tomography

A novel approach to reconstructing both the absorption and the scattering properties of a turbid medium simultaneously from steady-state broadband spectral measurements is presented that utilizes second-differential fitting to the water spectrum to estimate the optical path length in tissue. Theoretical and experimental evidence is provided to demonstrate the robust accuracy of the spectroscopy approach and reconstructed absorption images. The steady-state broadband CCD system has the potential to provide accurate chromophore imaging without the technological complexity of time- or frequency-domain systems.     

Theory of the Greenspan viscometer

We present a detailed acoustic model of the Greenspan acoustic viscometer, a practical instrument for accurately measuring the viscosity eta of gases. As conceived by Greenspan, the viscometer is a Helmholtz resonator composed of two chambers coupled by a duct of radius rd. In the lowest order, eta=pi f rho(rd/Q)2, where f and Q are the frequency and quality factor of the isolated Greenspan mode, and rho is the gas density. In this level of approximation, the viscosity can be determined by measuring the duct radius and frequency response of the resonator. In the full acoustic model of the resonator, the duct is represented by a T-equivalent circuit, the chambers as lumped impedances, and the effects of the diverging fields at the duct ends by lumped end impedances with inertial and resistive components. The model accounts for contributions to 1/Q from thermal dissipation (primarily localized in the chambers) and from a capillary used for filling and evacuating the resonator. A robust, prototype instrument is being used for measuring the viscosity of reactive gases used in semiconductor processing. For well-characterized surrogate gases, the prototype viscometer generated values of eta that were within +/-0.8% of published reference values throughout the pressure range 0.2-3.2 MPa. Remarkably, we achieved this level of agreement by only slight adjustment of the numerically calculated inertial and resistive end effect parameters to improve the agreement with helium reference values. No other parameters were adjusted.