Application of NMR Spectroscopy and Mass Spectrometry to the Structural Elucidation of Modified Flavan‐3‐ols and Their Coupling Reaction Products*

NMR and MS techniques were used for the unambiguous structural elucidation of synthesized modified monomeric and dimeric flavan‐3‐ols presenting different substituents on the A‐ring C8 position. The full characterization of the synthesized compounds was achieved by concerted use of NMR and ESI‐MS techniques. Assignments of proton and carbon atoms was achieved through analysis of the 1D ¹H and ¹³C NMR spectra combined with homo‐ and heteronuclear 2D NMR experiments. In each case, HMBC correlation between proton H2 and carbon C8a was observed allowing assignment of this carbon, which represents the key for attribution of the A‐ring carbon atoms. The synthesis and structural characterization of activated monomeric and dimeric flavanols were also achieved and used as precursors for preparation of natural and modified dimeric procyanidin derivatives. The preparation of various dimeric species involving modified flavanols was explored through different coupling reactions. The structures of the compounds formed were characterized on the basis of their MS and NMR spectral analysis. Dimeric species were characterized through proton–proton and proton–carbon correlations, which distinguished between the different flavanol moieties and established their sequences.     

Towards a General Theory of Quantized Fields on the Anti-de Sitter Space-Time

 We propose a general framework for studying quantum field theory on the anti-de-Sitter space-time, based on the assumption of positivity of the spectrum of the possible energy operators. In this framework we show that the n-point functions are analytic in suitable domains of the complex AdS manifold, that it is possible to Wick rotate to the Euclidean manifold and come back, and that it is meaningful to restrict AdS quantum fields to Poincaré branes. We give also a complete characterization of two-point functions which are the simplest example of our theory. Finally we prove the existence of the AdS-Unruh effect for uniformly accelerated observers on trajectories crossing the boundary of AdS at infinity, while that effect does not exist for all the other uniformly accelerated trajectories. Received: 3 December 2001 / Accepted: 26 July 2002 Published online: 21 October 2002     

A nilregular element property

An element a of a commutative ring R is nilregular if and only if x is nilpotent whenever ax is nilpotent. More generally, an ideal I of R is nilregular if and only if x is nilpotent whenever ax is nilpotent for all a ∈ I . We give a direct proof that if R is Noetherian, then every nilregular ideal contains a nilregular element. In constructive mathematics, this proof can then be seen as an algorithm to produce nilregular elements of nilregular ideals whenever R is coherent, Noetherian, and discrete. As an application, we give a constructive proof of the Eisenbud-Evans-Storch theorem that every algebraic set in n-dimensional affine space is the intersection of n hypersurfaces.Received: 6 September 2004     

Response of plane viscous jet to entrance flow rate perturbation

A two‐dimensional numerical simulation solving unsteady incompressible Navier–Stokes equations is used to study the natural varicose instability of a plane jet in the Reynolds number range of 100–900. A transient train of vortices is observed at the beginning of the computation. It disappears yielding a steady flow. This flow is then used at the basis for forced excitation in order to study the space time development of instability. A Reynolds number dependant behaviour is observed which implies that viscosity directly affects the vortex dynamics. Copyright © 2001 John Wiley & Sons, Ltd.     

Nonorganic Habitual Dysphonia and Autonomic Dysfunction

The present study was designed to test the hypothesis that there is a relation between nonorganic habitual dysphonia and subjective experience of dysfunction of the autonomic nervous system (neurovegetative lability). Eighty-three patients (65 women and 18 men) with a nonorganic voice disorder and a matched control group answered a questionnaire of 46 questions. One question replicated in different terms and six nonrelevant questions point out that the inquiry forms were answered in a consistent way. It appears that female patients in all age categories with a nonorganic habitual dysphonia report significantly more autonomic symptoms and complaints than healthy controls. This hypothesis cannot be confirmed for the male subgroup.     

Theoretical and Experimental Study on Boron β‐Diketonate Complexes with Intense Two‐Photon‐Induced Fluorescence in Solution and in the Solid State

Three boron diketonate chromophores with extended π‐conjugated backbone were prepared and their spectroscopic features were investigated through a combined theoretical/experimental study. It was shown that these complexes, which undergo very large electronic reorganization upon photoexcitation, combine large two‐photon absorption cross section with an emission energy and quantum efficiency in solution that is strongly dependent on solvent polarity. The strong positive influence of boron complexation on the magnitude of the two‐photon absorption was clearly established, and it was shown that the two‐photon absorption properties were dominated by the quadrupolar term. For one of the synthesized compounds, intense one‐ and two‐photon‐induced solid‐state emission (fluorescence quantum yield of 0.65 with maximum wavelength of 610 nm) was obtained as a result of antiparallel J‐aggregate crystal packing.     

Image analysis of oil film interferometry — a method of measuring wall shear stress distributions

A method is described of measuring a wall shear stress distribution that varies in the direction of the flow. Variations in the height of a very thin oil film moving under the boundary layer generate interference fringes, which are recorded and digitised using image processing equipment.The evolution of the film surface in space and time can be reconstructed from the interference fringe patterns and used to calculate the shear stress field. This reconstruction is achieved by comparing the picture data with images that were calculated for prescribed heights that are adjusted iteratively, until the calculated intensities match the data.The method is applied to a flow approaching a step, and the results are compared with pulsed-wire measurements.     

Discrete charge patterns in a Holstein‐SSH DNA lattice

DNA nonlinear charge transport is addressed in a combined Holstein–Su–Schrieffer–Heeger (HSSH) model. In the adiabatic approximation the dynamics of the system is shown to be governed by a modified discrete nonlinear Schrödinger (MDNLS) equation, where charge‐lattice coupling parameters are obvious. Attention is paid to the effective coupling parameter, , between charge and internal molecular vibrations, which importantly influences the stability/instability features of the plane wave, solution to the MDNLS equation. Region of instability are remarkably reduced, therefore predicting that increasing could progressively quench charge transport. This is confirmed by numerical simulations on the generic HSSH model, where only the charge density is excited and drives the dynamics of the global system. Polarons, as well as longitudinal and transversal nonlinear waves, are obtained and the dependence of charge transport on DNA conformation is discussed. Accordingly, the longtime evolution of the found polarons is studied and we observe a progressive extinction of its temporal evolution as increases. © 2014 Wiley Periodicals, Inc.