Nuclear hyperfine coupling interactions in the rotational spectra of the linear and bent isomers of HF-N2O

The rotational spectra of six isotopomers of the linear and bent isomers of HF-N₂O have been collected in the 7-18 GHz region with a Fourier transform microwave spectrometer. The nuclear hyperfine structure in the spectra produced by HF spin-spin coupling interaction and nuclear quadrupole coupling interactions due to the D nucleus of DF and the nuclei of N₂O have been resolved and analyzed. In the linear isomer, H in HF is bonded to the terminal N in N₂O. The NF bond lengths are 2.9808(2) Å for the HF-containing isotopomers and 2.9732(2) Å for the DF-containing isotopomers. The zero point angles are 23.1° for HF and 31-34° for N₂O. The hyperfine constants suggest that the HF bond is lengthened by 0.0105 Å upon complexation and that the electric field gradients of the two nitrogen nuclei in N₂O are perturbed differently in the complex. In the bent isomer, the hydrogen bond is formed between HF and O in N₂O. The intermolecular distances are 3.4942(2) Å for the HF-containing isotopomers and 3.4436(2) Å for the DF-containing isotopomers, with HF and N₂O forming angles of 34° and 46°, respectively, with the intermolecular axis. The nuclear quadrupole coupling constants of the two nitrogen nuclei do not indicate electric field gradient perturbation in this isomer.     

Multiphonon vibrations at high angular momentum in 182 Os

Evidence is presented for multiphonon excitations based on a high-spin (25 Planck) intrinsic state in the deformed nucleus 182 Os. Angular momentum generation by this mode competes with collective rotation. The experimental data are compared with tilted-axis cranking calculations, supporting the vibrational interpretation. However, the lower experimental energies provide evidence that more complex interactions of states are playing a role.     

A definitive synthesis of D-myo-inositol 1,4,5,6-tetrakisphosphate and its enantiomer D-myo-inositol 3,4,5,6-tetrakisphosphate from a novel butane-2,3-diacetal-protected inositol

New and rapid syntheses of the enantiomeric intracellular signalling molecules d-myo-inositol 1,4,5,6-tetrakisphosphate (1 a) and D-myo-inositol 3,4,5,6-tetrakisphosphate (1 b) are described. The synthetic strategy employs the novel butane-2,3-diacetal-protected (BDA-protected) myo-inositol (+/-)-3 ab, directly accessible from myo-inositol on a large scale, and an optical resolution with diastereoisomeric (R)-(-)-acetylmandelate esters. The X-ray crystal structure of (+/-)-4, an unusual side product of acid-catalysed reaction of myo-inositol with butanedione is also presented, and the absolute configurations of 1 a and 1 b are definitively assigned by conversion of key precursors into (+)-bornesitol and L-iditol hexaacetate, respectively. Biological activity of synthetic 1 b was confirmed in comparison with the natural polyphosphate.     

Electrical currents and liquid flow rates in micro-reactors

For micro-reactor devices in which liquids are pumped by electro-osmotic flow (EOF), in situ monitoring of the electrical currents in the channel networks provides a valuable diagnostic tool. We demonstrate here that the voltage-current characteristics of a micro-reactor channel network can be accurately modelled using measurements of the full 3-D geometry of the channel network, the liquid conductivity and the channel wall-liquid surface conductivity. It is shown that surface conductivity provides a significant contribution to the overall measured electrical currents in channel networks for which the ratio of surface area to volume is high. Following correction for surface conductivity, the electrical currents are proportional to the liquid volumetric flow rates measured in the different branches of the channel network. The constant of proportionality is related to the zeta potential of the channel wall-liquid surface. Measurements of the variation of electrical currents and volumetric flow rates as a function of the applied voltages allows the determination of the surface conductivity and zeta potential within the micro-reactor which enables the prediction of the voltages required to produce the desired flow rates in any channel section. In situ logging of the electrical currents, incorporated within the control system, allows continuous monitoring of the liquid flow rates during micro-reactor operation.     

Discontinuous Galerkin finite element methods for linear elasticity and quasistatic linear viscoelasticity

Summary. We consider a finite-element-in-space, and quadrature-in-time-discretization of a compressible linear quasistatic viscoelasticity problem. The spatial discretization uses a discontinous Galerkin finite element method based on polynomials of degree r—termed DG(r)—and the time discretization uses a trapezoidal-rectangle rule approximation to the Volterra (history) integral. Both semi- and fully-discrete a priori error estimates are derived without recourse to Gronwall's inequality, and therefore the error bounds do not show exponential growth in time. Moreover, the convergence rates are optimal in both h and r providing that the finite element space contains a globally continuous interpolant to the exact solution (e.g. when using the standard ^k polynomial basis on simplicies, or tensor product polynomials, ^k, on quadrilaterals). When this is not the case (e.g. using ^k on quadri-laterals) the convergence rate is suboptimal in r but remains optimal in h. We also consider a reduction of the problem to standard linear elasticity where similarly optimal a priori error estimates are derived for the DG(r) approximation. Mathematics Subject Classification (2000):65N36Shaw and Whiteman would like to acknowledge the support of the US Army Research Office, Grant #DAAD19-00-1-0421, and the UK EPSRC, Grant #GR/R10844/01. Whiteman would also like to acknowledge support from TICAM in the form of Visiting Research Fellowships.