Orientational properties of stretched polystyrene gels in organic solvents and the suppression of their residual 1H NMR signals

While residual dipolar couplings (RDCs) are an established method in high-resolution biomolecular NMR, their use for structure determination of small molecules in organic solvents is limited by the alignment media available. Only recently stretched polystyrene (PS) gels were introduced for the measurement of RDCs on small compounds that allowed urgently needed free scalability of the induced anisotropy. Here, the properties of such stretched PS gels in different organic solvents as well as for different magnetic field strengths and temperatures are studied and practical NMR-spectroscopic aspects are discussed.     

Sigma-delocalization versus pi-resonance in alpha-aryl-substituted vinyl cations

The synthesis and isolation of 12 alpha-aryl, beta, beta'-disilyl-substituted vinyl cations 1b-l, 7, and 8 with the tetrakis(pentafluorophenyl)borate counteranion is reported. The vinyl cations are characterized by NMR spectroscopy and are identified by their specific NMR chemical shifts (delta13C(C(+)) = 178.1-194.5; delta13C (Cbeta) = 83.3-89.9; delta13C (Cipso)) = 113.6-115.2; delta (29)Si = 25.0-12.0), supported by density functional calculations at the B3LYP/6-311G(2d,p)//B3LYP/6-31G(d) level. All cations are found to be stable at room temperature in solution and in the solid state. The NMR chemical shifts as well as J-coupling data indicate for vinyl cations, 1b-l, 7, and 8, the occurrence of substantial stabilization through pi-resonance via the aryl substituents and through sigma-delocalization via the beta-silyl groups. For vinyl cation 8, the free enthalpy of stabilization via pi-resonance by the alpha-ferrocenyl substituent is determined by temperature-dependent (29)Si NMR spectroscopy to be DeltaG++ = (48.9 +/- 4.2) kJ mol(-1). A Hammett-type analysis, which relates the (1)J(SiC(beta)) coupling constant and the low-field shift of the (29)Si NMR signal upon ionization, Deltadelta (29)Si, with the electron-donating ability of the aryl group, indicates an inverse relation between the extent of Si-C hyperconjugation and pi-donation. The computed structures (at B3LYP/6-31G(d)) of the vinyl cations 1a-l, 7, and 8 reveal the consequences of Si-C hyperconjugation and of pi-resonance interactions with the aryl groups. The structures, however, fail to express the interplay between sigma-delocalization and pi-conjugation in that the calculated Si-C bond lengths and the C+-C(ipso) bond lengths do not vary as a function of the substituent.     

Optimal a priori error estimates for the -version of the local discontinuous Galerkin method for convection-diffusion problems

We study the convergence properties of the -version of the local discontinuous Galerkin finite element method for convection-diffusion problems; we consider a model problem in a one-dimensional space domain. We allow arbitrary meshes and polynomial degree distributions and obtain upper bounds for the energy norm of the error which are explicit in the mesh-width , in the polynomial degree , and in the regularity of the exact solution. We identify a special numerical flux for which the estimates are optimal in both and . The theoretical results are confirmed in a series of numerical examples.

     

Fast anomalous diffusion of small hydrophobic species in water

Using Car-Parrinello molecular dynamics a structural diffusion mechanism for the simplest hydrophobic species in water, an H atom, is proposed. The hydrophobic solvation cavity is a highly dynamical aggregate that actually drives, by its own hydrogen-bond fluctuations, the diffusion of the enclosed solute. This makes possible an anomalously fast diffusion that falls only short of that of "Grotthuss structural diffusion" of H+ in water. Here, the picture of a static, i.e., "iceberglike," clathrate cage is a misleading concept. The uncovered scenario is similar to the "dynamical hole mechanism" found in a very different context, that is, large molecules moving in hot polymeric melts.     

A tuneable 600 GHz bandpass-filter with large free-spectral-range

Considering recent ozon problems in the upper atmosphere the measuring technique in the spectral range of about some hundred GHz gains in importance increasingly. Ozon concentration is measured by high sensitive radiometers consisting of several quasioptical components. A tunable bandpass filter represents a versatile component in such a test assembly. The bandpass filter is realized as interferometer and can be adapted to its respective application by individual tuning of its coupling links. Metallic meshes of different aperture size are used for injection and feedback of the electromagnetic wave. A stepper motor control serves for the integration in an automatic measurement setup. The construction principles of the interferometer are summarized. An analysis of the component by means of plane wave theory is extended to a theory of diffraction. Finally the theoretical approach is verified on an application as single-sideband filter comparing the measured results with the computed values of the simulation.     

Amphotericin B as a potential probe of the physical state of vesicle membranes

[structure: see text] The investigations described introduce a new role for a natural product such as amphotericin B as a potential biophysical reporter group to probe the physical state of a membrane. Specifically, we demonstrated that the K(+) efflux pattern reveals an interesting sterol dependence. This is suggested to be correlated to the physical state of the membrane showing high efflux in a vesicle membrane of intermediate fluidity.     

Structurally diverse Rh(I) and Mn(I) complexes derived from the new ambidentate indene ligand, (1-[iPr2P(S)]-2-[NMe2])C9H6

A new indene-based ligand featuring pendant phosphine sulfide and amine donor fragments has been developed; Rh(I) coordinates to the neutral form of the ligand in a kappa2-[N,S] fashion, while the anionic form of the ligand binds Rh(I) and Mn(I) in kappa2-[C,S] and eta5 modes, respectively.     

A locally conservative LDG method for the incompressible Navier-Stokes equations

In this paper a new local discontinuous Galerkin method for the incompressible stationary Navier-Stokes equations is proposed and analyzed. Four important features render this method unique: its stability, its local conservativity, its high-order accuracy, and the exact satisfaction of the incompressibility constraint. Although the method uses completely discontinuous approximations, a globally divergence-free approximate velocity in is obtained by simple, element-by-element post-processing. Optimal error estimates are proven and an iterative procedure used to compute the approximate solution is shown to converge. This procedure is nothing but a discrete version of the classical fixed point iteration used to obtain existence and uniqueness of solutions to the incompressible Navier-Stokes equations by solving a sequence of Oseen problems. Numerical results are shown which verify the theoretical rates of convergence. They also confirm the independence of the number of fixed point iterations with respect to the discretization parameters. Finally, they show that the method works well for a wide range of Reynolds numbers.