Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

Unambiguous Mono Deuterium Labelling of Alkyl Ethyl Ketones at the α Position of the Ethyl Group by Ruthenium (III) Catalyzed Isomerization of O-Deuterated Allylic Alcohols

Ruthenium (III) tris acetylacetonate is an efficient catalyst for the isomerization of O-deuterated alkylvinyl carbinols allowing thus a facile route to the title compounds.     

Enumerating Perfect Matchings in n-Cubes

The perfect matchings in the n-cube have earlier been enumerated for n?≤?6. A dynamic programming approach is here used to obtain the total number of perfect matchings in the 7-cube, which is 391 689 748 492 473 664 721 077 609 089. The number of equivalence classes of perfect matchings is further shown to be 336 in the 5-cube, 356 788 059 in the 6-cube and 607 158 046 495 120 886 820 621 in the 7-cube. The techniques used can be generalized to arbitrary bipartite and general graphs.     

Wetting effects at a grain boundary

We consider a tier of weakened bonds along the center line of a two-dimensional Ising ferromagnet strip as a model of a grain boundary. When an interface traverses such a strip at an angle, whether or not there is a continuous pinning-depinning transition at subcritical temperature depends on this angle and the degree of bond weakening. We also study the relaxation of such a system to its equilibrium state using continuous time Monte Carlo simulation with Kawasaki dynamics; this reveals a matter transport mechanism confined to the grain boundary.     

Measurement and modeling of diffraction from an edge of a thin panel

The diffraction of sound from an edge of a thin chipboard panel was measured in an anechoic chamber, and compared to simulations based on the diffraction formulation developed by Svensson et al. [Svensson UP, Fred RI, Vanderkooy J. An analytic secondary source model of edge diffraction impulse responses. J Acoust Soc Am 1999;106(5):2331-44]. The measurements and simulations were performed for a line of receiver positions below the panel to include cases for which the direct sound had an unobstructed propagation path to the receivers, as well as cases for which the direct sound was occluded by the panel. Comparison of the measured and simulated responses is provided in both the time and frequency-domains, and shows that the differences between them are small over the entire audible frequency range. This case study verifies that the applied diffraction-modeling method gives accurate results, and that the assumptions of ideal source and wedge characteristics inherent in the method do not preclude its use in simulations of realistic scenarios.     

Wavelet formulation of the polarizable continuum model

The first implementation of a wavelet discretization of the Integral Equation Formalism (IEF) for the Polarizable Continuum Model (PCM) is presented here. The method is based on the application of a general purpose wavelet solver on the cavity boundary to solve the integral equations of the IEF‐PCM problem. Wavelet methods provide attractive properties for the solution of the electrostatic problem at the cavity boundary: the system matrix is highly sparse and iterative solution schemes can be applied efficiently; the accuracy of the solver can be increased systematically and arbitrarily; for a given system, discretization error accuracy is achieved at a computational expense that scales linearly with the number of unknowns. The scaling of the computational time with the number of atoms N is formally quadratic but a N^1.5 scaling has been observed in practice. The current bottleneck is the evaluation of the potential integrals at the cavity boundary which scales linearly with the system size. To reduce this overhead, interpolation of the potential integrals on the cavity surface has been successfully used. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Directional perception of distributed sound sources

The perception of spatially distributed sound sources was investigated by conducting two listening experiments in anechoic conditions with 13 loudspeakers evenly distributed in the frontal horizontal plane emitting incoherent noise signals. In the first experiment, widely distributed sound sources with gaps in their distribution emitted pink noise. The results indicated that the exact loudspeaker distribution could not be perceived accurately and that the width of the distribution was perceived to be narrower than it was in reality. Up to three spatially distributed loudspeakers that were simultaneously emitting sound could be individually perceived. In addition, the number of loudspeakers that were indicated as emitting sound was smaller than the actual number. In the second experiment, a reference with 13 loudspeakers and test cases with fewer loudspeakers were presented and their perceived spatial difference was rated. The effect of the noise bandwidth was of particular interest. Noise with different bandwidths centered around 500 and 4000 Hz was used. The results indicated that when the number of loudspeakers was increased from four to seven, the perceived auditory event was very similar to that perceived with 13 loudspeakers at all bandwidths. The perceived differences were larger in wideband noise than in narrow-band noise.     

The use of Herschel–Quincke tubes to improve the efficiency of lined ducts

The scattering matrix results of Herschel–Quincke (HQ) resonators installed in combination with an acoustic liner (HQ-Liners) are presented in this paper. This approach aims at controlling both tonal and broadband noise to improve the liner efficiency. It uses circumferential arrays of Herschel–Quincke tubes on a main duct in a serial association with a locally reacting liner of known impedance. Results for the scattering matrix of this system are deduced from an analytical model and compared with experimental and numerical data showing a good agreement. Analysis of the scattering matrix coefficients points out the modal conversion properties that depend on the number of HQ tubes along the circumference. Results of the transmission loss show that the choice of an optimal HQ configuration with respect to the liner properties can substantially improve the liner efficiency.