The first total synthesis of (R)-convolutamydine A

The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic.     

Using graphs for some discrete tomography problems

Given a rectangular array whose entries represent the pixels of a digitalized image, we consider the problem of reconstructing an image from the number of occurrences of each color in every column and in every row. The complexity of this problem is still open when there are just three colors in the image. We study some special cases where the number of occurrences of each color is limited to small values. Formulations in terms of edge coloring in graphs and as timetabling problems are used; complexity results are derived from the model.     

The Role of a Specific Response of Media in the Vavilov-Cherenkov Effect

It is shown that the condition υ > υ_p (ω), which is necessary in order to trigger the Vavilov-Cherenkov effect, determines the interval of radiated frequencies and it alone cannot establish a strong restriction to the velocity of the particle. It is exhibited that it is possible to define a general lower bound for the velocity of the particle, which does not depend on the frequency when both, a specific response of the medium is taken into account and the mentioned condition is considered. The minimum value of the phase velocity of light in the medium determines the existence of such general lower bound.     

The effect of linguistic entropy on speech perception in noise in young and elderly listeners.

The rationale for a method to quantify the information content of linguistic stimuli, i.e., the linguistic entropy, is developed. The method is an adapted version of the letter-guessing procedure originally devised by Shannon [Bell Syst. Tech. J. 30, 50-64 (1951)]. It is applied to sentences included in a widely used test to measure speech-reception thresholds and originally selected to be approximately equally redundant. Results of a first experiment reveal that this method enables one to detect subtle differences between sentences and sentence lists with respect to linguistic entropy. Results of a second experiment show that (1) in young listeners and with the sentences employed, manipulating linguistic entropy can result in an effect on SRT of approximately 4 dB in terms of signal-to-noise ratio; (2) the range of this effect is approximately the same in elderly listeners.     

A proof of Parrott's theorem on quotient norms

We prove, as an application of our positive extension argument, a theorem of Parrott concerning the quotient norm with respect to spaces of Hilbert space operators.     

Stochastic Visual Interactive Simulation Models

Many writers and practitioners have mentioned the difficulties that result from randomness in visual interactive simulation or animated simulation modelling. This paper discusses the use of VIS to model transient system behaviour, and proposes some approaches to stochastic VIS modelling which may be helpful in overcoming the difficulties.     

The six-vertex model eigenvectors as critical limit of the eight-vertex model bethe ansatz

The critical limit of the eight-vertex model eigenvectors obtained by means of the generalized Bethe Ansatz is shown to give the six-vertex eigenvectors as constructed in a previous paper by two of the authors. Furthermore, an explicit mapping is established between these eigenvectors and the usual Bethe Ansatz eigenvectors of the six-vertex model. This allows one to show that the indexv labeling the eight-vertex eigenstates becomes exactly the third component of the total spin in the critical limit.     

FT-EPR and HPLC study of the mechanism of 4-chlorophenol photolysis

The mechanism of 4-chlorophenol (4CP) photolysis was investigated with the aid of Fourier Transform Electron Paramagnetic Resonance (FT-EPR) and pulsed-laser photolysis combined with High Performance Liquid Chromatography (HPLC) detection-of stable (diamagnetic) products. With FT-EPR transient free radicals produced by pulsed-laser excitation of solutions of 4CP in alcohols could be identified. Time profiles of the FT-EPR spectra provided information on reaction kinetics and Chemically Induced Dynamic, Electron Polarization (CIDEP) effects. It was found that 4CP photolysis in alcohols leads to the simultaneous formation of the phenoxyl radical and radicals produced by hydrogen abstraction from the solvent. CIDEP patterns establish that these radicals are formed in a reaction sequence involving a triplet state precursor and radical pair intermediate. Results of earlier transient optical absorption measurements indicate that the triplet precursor must be the carbene 4-oxocyclohexa-2,5-dienylidene. This assignment is supported by the finding that photolysis of quinone diazide in a hydrogen-donating solvent gives the same free radical products as those obtained from 4CP. The formation of the phenoxyl radical intermediate accounts for the finding that photolysis of deoxygenated solutions of 4CP in alcohols gives phenol as stable diamagnetic product. By contrast, photolysis of aerated and deoxygenated aqueous solutions of 4CP produces benzoquinone and hydroquinone as primary products, respectively.     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002