Synthesis of 2-phosphonopyrroles via a one-pot RCM/oxidation sequence

A four-step synthesis of 2-phosphonopyrroles is presented starting from suitable aldehydes. The key step in the synthesis involves a one-pot ring-closing metathesis/oxidation sequence of a functionalized alpha-aminoalkenyl phosphonate. Notwithstanding the presence of a nucleophilic nitrogen atom and high substitution patterns in the substrate, the results of the RCM reaction are excellent using mild reaction conditions. Furthermore, a synergism is observed between the RCM catalyst and the oxidizing agent, causing higher oxidation rates and allowing reaction for substrates that normally fail to ring close under standard RCM conditions.     

Divided powers in Chow rings and integral Fourier transforms

We prove that for any monoid scheme M over a field with proper multiplication maps M×M→M, we have a natural PD-structure on the ideal CH>0(M)⊂CH_∗(M) with regard to the Pontryagin ring structure. Further we investigate to what extent it is possible to define a Fourier transform on the motive with integral coefficients of the Jacobian of a curve. For a hyperelliptic curve of genus g with sufficiently many k-rational Weierstrass points, we construct such an integral Fourier transform with all the usual properties up to N²-torsion, where N=1+⌊log₂(3g)⌋. As a consequence we obtain, over , a PD-structure (for the intersection product) on N²⋅a, where a⊂CH(J) is the augmentation ideal. We show that a factor 2 in the properties of an integral Fourier transform cannot be eliminated even for elliptic curves over an algebraically closed field.     

The effect of multimicrophone noise reduction systems on sound source localization by users of binaural hearing aids

This paper evaluates the influence of three multimicrophone noise reduction algorithms on the ability to localize sound sources. Two recently developed noise reduction techniques for binaural hearing aids were evaluated, namely, the binaural multichannel Wiener filter (MWF) and the binaural multichannel Wiener filter with partial noise estimate (MWF-N), together with a dual-monaural adaptive directional microphone (ADM), which is a widely used noise reduction approach in commercial hearing aids. The influence of the different algorithms on perceived sound source localization and their noise reduction performance was evaluated. It is shown that noise reduction algorithms can have a large influence on localization and that (a) the ADM only preserves localization in the forward direction over azimuths where limited or no noise reduction is obtained; (b) the MWF preserves localization of the target speech component but may distort localization of the noise component. The latter is dependent on signal-to-noise ratio and masking effects; (c) the MWF-N enables correct localization of both the speech and the noise components; (d) the statistical Wiener filter approach introduces a better combination of sound source localization and noise reduction performance than the ADM approach.     

Donor-substituted cyanoethynylethenes: powerful chromophores for opto-electronic applications

Donor-substituted cyanoethynylethenes (CEEs) were synthesised, structurally characterised and investigated for their electronic and two-photon absorption properties, revealing exceptionally strong intramolecular charge-transfer interactions.     

Steric control over arene coordination to beta-diiminate rhodium(I) fragments

The bulky ligands L(X)- (L(X) = (2,6-C6H3X2)NC(Me)CHC(Me)N(2,6-C6H3X2), X =Cl, Me) can be used to generate fluxional mononuclear arene complexes [L(X)Rh(eta4-arene)] (arene = benzene, toluene, m-xylene, mesitylene), which for X = Me disproportionate to fluxional dinuclear complexes [[L(Me)Rh]2(anti-mu-arene)]. For both mononuclear and dinuclear complexes, steric interactions do not stop the fluxionality but govern the preferred orientation of the methyl-substituted arenes, thus allowing indirect determination of the static NMR parameters. For the mu-arene complexes, two distinct types of fluxionality are proposed on the basis of calculations: ring rotation and metal shift. In the solid state, the toluene complex has an eta4(1,2,3,4):eta4(3,4,5,6)-bridged structure; the NMR analysis indicates that the benzene and m-xylene complexes have similar structures. The mesitylene complex, however, has an unprecedented eta3(1,2,3):eta3(3,4,5)-bridged structure, which is proposed to correspond to the transition state for arene rotation in the other cases. Steric factors are thought to be responsible for this reversal of stabilities.     

Determination of the structure factor for concentrated silica dispersions using small angle x-ray scattering. II. Experiment

The structure factor of a number of silica suspensions in cyclohexane, with concentrations ranging from 0.01 to 0.714 gcm^–3, has been determined with small angle x-ray scattering, using a Kratky camera. The experimental structure factor is compared with a theoretical one for which polydispersity effects on the particle scattering factor and on the structure are explicitly taken into account.Analysis of the scattered intensity at a scattering angle=0 shows that the particles in the suspension interact like hard spheres, with a specific hard sphere volume of 0.61 cm³g^–1. A comparison of the experimentally determined structure factor with the structure factor found by a model calculation for a polydisperse system, using the experimental particle size distribution, showed a general agreement. The height of the first maximum agreed well for all concentrations, however its position varied stronger with concentration in the experimental curves. A possible explanation of this effect is given.     

Crystal and molecular deformation in strained high-performance polyethylene fibers studied by wide-angle x-ray scattering and Raman spectroscopy

Wide-angle x-ray scattering (WAXS) and Raman spectroscopic data show that on both the crystal and molecular levels, a bimodal stress distribution exists in strained high-performance polyethylene fibers. In part of the crystalline PE the microscopic strain level is high (ca. 70% of macroscopic strain); in the remainder, the microscopic strain level is low (independent of macroscopic strain, ca. 0.4%). During stress relaxation the fraction of highly strained PE decreases with time. WAXS revealed no indication of a change in the a and b unit-cell dimensions. Furthermore, no indications for stress-induced formation of monoclinic and/or hexagonal PE and for crystal breaking were found. From the latter it can be deduced that all chains within one crystal are equally strained. The WAXS results are used to calibrate the stress-induced frequency shifts of Raman bands.     

Algorithms for some graph theoretical optimization problems

This is a summary of the main results presented in the author’s PhD thesis. This thesis, written in English, was supervised by Frits Spieksma and defended on September 23, 2005 at the Katholieke Universiteit Leuven. A copy of the thesis is available from the authors website (http://www.econ. kuleuven.be/linda.moonen/public/). The thesis can be roughly split into two parts. The first part is dedicated to the problem of partitioning partially ordered sets into chains of limited size. The second part deals with the structure and the connectivity of the Internet.     

Limitations on the use of UV/Vis spectroscopy for the evaluation of conjugation effectiveness

A detailed study on N,N-dimethylanilino donor-substituted cyanoethynylethenes shows that there is no correlation between the effectiveness of the donor-acceptor conjugation pathway and the lowest-energy transition in the UV/Vis absorption spectrum.