Analysis of low bit rate image transform coding

Calculations based on high-resolution quantizations prove that the distortion rate D(R¯) of an image transform coding is proportional to 2^-2R when R¯ is large enough. In wavelet and block cosine bases, we show that if R¯<1 bit/pixel, then D(R¯) varies like R¯^1-2γ, where γ remains of the order of 1 for most natural images. The improved performance of embedded codings in wavelet bases is analyzed. At low bit rates, we show that the compression performance of an orthonormal basis depends mostly on its ability to approximate images with a few nonzero vectors     

Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

Audio Denoising by Time-Frequency Block Thresholding

Removing noise from audio signals requires a nondiagonal processing of time-frequency coefficients to avoid producing ldquomusical noise.rdquo State of the art algorithms perform a parameterized filtering of spectrogram coefficients with empirically fixed parameters. A block thresholding estimation procedure is introduced, which adjusts all parameters adaptively to signal property by minimizing a Stein estimation of the risk. Numerical experiments demonstrate the performance and robustness of this procedure through objective and subjective evaluations.     

Antenna phase pattern measurements at millimeter wave frequencies using the differential phase method with only one power meter

The differential phase measurement method has been improved to need the use of only one power meter instead of three power meters. This enables accurate antenna phase pattern measurements with a simplified set-up, accompanied by the reduction in cost. All advantages of the differential phase measurement method are still also available, e.g. there is no need to phase lock oscillators or to use rotary joints. The measurement results for an antenna at 110 GHz are presented. A good agreement with earlier data was obtained.     

Reactant induced restructuring and corrosion of germanium-palladium catalysts during hydrogenation reactions

An anomalous rate enhancement with increasing conversion has been observed during the liquid phase hydrogenation of nitrobenzene and crotonaldehyde over Ge/Pd/C catalysts at ambient temperature and atmospheric pressure. Inductive coupled plasma atomic emission spectroscopy and electrochemical measurement of the oxidation state of catalysts during reaction revealed that the bimetallic particles were partially oxidized by the reactants, which resulted in Ge-dissolution and increased exposure of Pd on the surface. It is proposed that the surface and bulk composition of Ge/Pd catalysts are a function of their oxidation state. This behaviour is due to the unusually high mobility of Ge in the Pd lattice and to the good solubility of GeO₂ in polar solvents. The influence of hydrogen transport on the corrosion process and the stability of other X/Pd type bimetallic catalysts during liquid phase hydrogenation are also discussed.     

EPOXIDATION OF FUNCTIONALIZED OLEFINS OVER SOLID CATALYSTS

Heterogeneous catalytic epoxidation of functionalized olefins in the liquid phase has been reviewed, focusing on catalyst performance and its interrelation with the crucial parameters of the catalytic systems. Efficient catalysts include supported and mixed oxides, framework-substituted (“redox”) molecular sieves, layered-type materials, heterogenized homogeneous catalysts, and some others. Among the various substrates, allylic and homoallylic alcohols, and unsaturated carbonyl compounds have received most attention so far. The great variety of available catalysts enables selective epoxidation of most substituted olefins. The mechanistic understanding of heterogeneous catalytic epoxidation is still underdeveloped, rendering catalyst design rather empirical. A considerable potential for future development lies in the area of “heterogenization” of successful homogeneous catalysts especially for asymmetric epoxidation. Crucial requirements in the development of heterogeneous catalytic epoxidation catalysts are, besides good catalytic performance and cheap oxidant, recyclability and resistance to leaching of the active component. Some of the examples shown in the literature do not fulfill the latter requirement.     

European Minor Constituent Radiometer: A New Millimeter Wave Receiver for Atmospheric Research

EMCOR is a heterodyne receiver for the frequency range of 201 to 210 GHz. It has been designed for ground-based measurements of various minor constituents of the stratosphere involved in ozone chemistry. Since the aim was the detection of faint spectral lines, a superconducting tunnel junction has been chosen as mixer element and special care has been taken in developing the calibration unit of the system. The front-end is completed by a quasi-optical system, a solid state local oscillator with electronic tuning and a HEMT pre-amplifier. In the back-end an acousto-optical spectrometer is employed to analyse the signal. A PC controls the whole system. The instrument has been installed at a high mountain site in the Swiss Alps.     

On the Limited Selectivity of Silica-Based Epoxidation Catalysts

Epoxidation of 2-cyclohexen-1-ol with TBHP and TiO₂–SiO₂, Fe₂O₃–SiO₂ and SiO₂ aerogels has been studied. The influence of surface silanol groups and transition metal impurities in titania–silica on the product distribution has been analyzed. The results, supported by literature data, indicate that high surface area silica cannot generally be regarded as an inert matrix in epoxidation catalysts. Contribution of Ti-free silica limits the selectivity of Ti- and Si-containing catalysts in demanding epoxidation reactions. The activity of silica – together with the background oxidation of the olefin – may lead to overestimated intrinsic activities when the reaction rate is related to the Ti content of the catalyst.     

Product-induced corrosion of Pt/graphite during catalytic oxidation of sorbose studied by in situ STM and cyclic voltammetry

Platinum deposited onto high and low surface area graphites are used as model catalysts in studying the irreversible catalyst deactivation observed previously in the aerobic oxidation of L-sorbose to 2-keto-L-gulonic acid. The corrosion of platinum in the neutral aqueous solution was followed in the liquid cell of a scanning tunnelling microscope. Leaching of platinum was well detectable in the time scale of 1-2 h. Depending on the nature of graphite support and the Pt content, a considerable fraction or even all Pt dissolved during sorbose oxidation, as evidenced by cyclic voltammetry. The strikingly high rate of Pt dissolution into the neutral aqueous medium under ambient conditions is attributed to the excellent chelating properties of the polyhydroxy carboxylic acid product. This revised version was published online in July 2006 with corrections to the Cover Date.