Different reactivity of hydroxylamine with carbamoyl azides and carbamoyl cyanides: synthesis of hydroxyureas and carbamoyl amidoximes

The carbamoylating agents carbamoyl azides and carbamoyl cyanides (aka cyanoformamides) react with hydroxylamine in different ways, leading in the first case to N-hydroxyureas and, in the case of carbamoyl cyanides, to carbamoyl amidoxime derivatives. The synthetic procedure developed for the latter type of compound, which represents an interesting precursor for heterocyclic structures, allowed the highly efficient preparation of a wide selection of examples. The Z configuration of the double bond in the amidoxime moiety was proposed on the basis of comparison between experimental and calculated (13)C and (15)N NMR chemical shift values for the isopropyl and benzyl derivatives.     

Long-distance dominance of the CP asymmetry in B→X(s,d)γ decays

We show that in the standard model the parametrically leading (by a factor 1/α(s)) contribution to the inclusive CP asymmetry in B→X(s,d)γ decays arises from a long-distance effect in the interference of the electromagnetic dipole amplitude with the amplitude for an up-quark penguin transition accompanied by soft gluon emission. Using model estimates for the associated hadronic parameter Λ(17)(u), we predict a value in the range -0.6% < A(X(s)γ)(SM) < 2.8%. In view of current experimental data, a future precision measurement of the flavor-averaged CP asymmetry would signal the presence of new physics only if a value below -2% was found. A cleaner probe of new physics is offered by the difference of the CP asymmetries in charged versus neutral B→X(s,d)γ decays.     

Packing interactions in hydrated and anhydrous forms of the antibiotic Ciprofloxacin: a solid-state NMR, X-ray diffraction, and computer simulation study

We present an experimental NMR, X-ray diffraction (XRD), and computational study of the supramolecular assemblies of two crystalline forms of Ciprofloxacin: one anhydrate and one hydrate forming water wormholes. The resonance assignment of up to 51 and 54 distinct (13)C and (1)H resonances for the hydrate is reported. The effect of crystal packing, identified by XRD, on the (1)H and (13)C chemical shifts including weak interionic H-bonds, is quantified; (1)H chemical shift changes up to ～-3.5 ppm for CH···π contacts and ～+2 ppm (CH···O((-))); ～+4.7 ppm (((+))NH···O((-))) for H-bonds. Water intake induces chemical shift changes up to 2 and 5 ppm for (1)H and (13)C nuclei, respectively. Such chemical shifts are found to be sensitive detectors of hydration/dehydration in highly insoluble hydrates.     

Peculiar field-dependent magnetic behavior of cyano-bridged coordination polymer Er(H2O)4[W(CN)8

The two-dimensional cyano-bridged coordination polymer Er(H(2)O)(4)[W(CN)(8)] exhibits a magnetic transition at 12 K and an unusual field-dependent transition from short-range to ferromagnetic ordering.     

A finite element formulation satisfying the discrete geometric conservation law based on averaged Jacobians

In this article, a new methodology for developing discrete geometric conservation law (DGCL) compliant formulations is presented. It is carried out in the context of the finite element method for general advective–diffusive systems on moving domains using an ALE scheme. There is an extensive literature about the impact of DGCL compliance on the stability and precision of time integration methods. In those articles, it has been proved that satisfying the DGCL is a necessary and sufficient condition for any ALE scheme to maintain on moving grids the nonlinear stability properties of its fixed‐grid counterpart. However, only a few works proposed a methodology for obtaining a compliant scheme. In this work, a DGCL compliant scheme based on an averaged ALE Jacobians formulation is obtained. This new formulation is applied to the θ family of time integration methods. In addition, an extension to the three‐point backward difference formula is given. With the aim to validate the averaged ALE Jacobians formulation, a set of numerical tests are performed. These tests include 2D and 3D diffusion problems with different mesh movements and the 2D compressible Navier–Stokes equations. Copyright © 2011 John Wiley & Sons, Ltd.