Kinetics and mechanism of the thermal reactions of endo- and exo-5-cyanobicyclo[2.2.2]oct-2-ene and methyl-substituted derivatives in the gas phase

The thermal reactions of endo- and exo-5-cyanobicyclo-[2.2.2]oct-2-ene and their trans- and cis-6-methyl-substituted derivatives have been investigated in the gas phase between 518 and 630 K. Each product decomposes by two parallel first-order retro-Diels-Alder reactions, a main one with formation of cyclohexa-1,3-diene and a minor one with elimination of ethene. Slight isomerizations are also observed. The kinetic results can be explained in terms of a biradical mechanism. The rate-determining step is shown to depend on the amount of resonance energy in the biradical. Heats of formation and entropies of the bicyclo[2.2.2]oct-2-enes studied are estimated.     

Conformational analysis of 1,2-difluoroethane, an ab-initio investigation

Contrary to expectation, the gauche conformer of 1,2-difluoroethane is more stable than the trans conformer in the gas phase. In order to understand the underlying causes of the “gauche effect”, a complete geometry relaxation was performed for the gauche and trans conformers of 1,2-difluoroethane with the 4-21G, 4-31G and 4-31G** basis sets. The 4-31G** optimized geometry of the gauche conformer compares well with the experimental values obtained from a number of electron-diffraction studies. A correction for the correlation energy, calculated by means of second-order Møller—Plesset perturbation theory with the 6-31G** basis set, proves to be essential to obtain a correct estimate of the energy difference between the gauche and trans conformers 1,2-difluoroethane.     

Tone detection and synthetic speech discrimination in band-reject noise by hearing-impaired listeners

Frequency resolution was evaluated for two normal-hearing and seven hearing-impaired subjects with moderate, flat sensorineural hearing loss by measuring percent correct detection of a 2000-Hz tone as the width of a notch in band-reject noise increased. The level of the tone was fixed for each subject at a criterion performance level in broadband noise. Discrimination of synthetic speech syllables that differed in spectral content in the 2000-Hz region was evaluated as a function of the notch width in the same band-reject noise. Recognition of natural speech consonant/vowel syllables in quiet was also tested; results were analyzed for percent correct performance and relative information transmitted for voicing and place features. In the hearing-impaired subjects, frequency resolution at 2000 Hz was significantly correlated with the discrimination of synthetic speech information in the 2000-Hz region and was not related to the recognition of natural speech nonsense syllables unless (a) the speech stimuli contained the vowel /i/ rather than /a/, and (b) the score reflected information transmitted for place of articulation rather than percent correct.     

Synthesis of 20-deoxoluteone

20-Deoxoluteone has been synthesized from sclareol. Sclareol was brominated with phosphorus tribromide to form a mixture of primary allyl bromides, from which, by the malonic synthesis, a mixture of bicyclogeranylgeranylacetic acids was obtained which was cyclized with fluorosulfonic acid to form a mixture of two diastereomeric δ-lactones. The predominating lactone was converted by successive reduction with lithium tetrahydroaluminate, oxidation with oxalyl chloride in dimethyl sulfoxide, reaction with methylmagnesium iodide, and oxidation by the chromium trioxide/pyridine complex into 20-deoxyluteone. Institute of Chemistry, Moldavian SSR Academy of Science, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 346–353, May–June, 1990.     

Lattice displacement waves in AuTe2

¹²⁵Te and¹²⁹I Mössbauer spectra were studied of AuTe₂, AuAgTe₄, and AuCuTe₄. A distribution in hyperfine parameters is needed to obtain a satisfactory fit of the¹²⁹I spectra, and is interpreted in favor of lattice displacement waves recently observed in these compounds.     

Pitch perception by cochlear implant subjects

Direct electrical stimulation of the auditory nerve can be used to restore some degree of hearing to the profoundly deaf. Percepts due to electrical stimulation have characteristics corresponding approximately to the acoustic percepts of loudness, pitch, and timbre. To encode speech as a pattern of electrical stimulation, it is necessary to determine the effects of the stimulus parameters on these percepts. The effects of the three basic stimulus parameters of level, repetition rate, and stimulation location on subjects' percepts were examined. Pitch difference limens arising from changes in rate of stimulation increase as the stimulating rate increases, up to a saturation point of between 200 and 1000 pulses per second. Changes in pitch due to electrode selection depend upon the subject, but generally agree with a tonotopic organization of the human cochlea. Further, the discriminability of such place-pitch percepts seems to be dependent on the degree of current spread in the cochlea. The effect of stimulus level on perceived pitch is significant but is highly dependent on the individual tested. The results of these experiments are discussed in terms of their impact on speech-processing strategies and their relevance to acoustic pitch perception.     

Proactive heuristic procedures for robust project scheduling: An experimental analysis

Solution-robust project scheduling is a growing research field aiming at constructing proactive schedules to cope with multiple disruptions during project execution. When stochastic activity durations are considered, including time buffers between activities is a proven method to improve the stability of a baseline schedule.     

Apparent inhibition by arginine of macrocyclic <Emphasis Type="Italic">b</Emphasis> ion formation from singly charged protonated peptides

There is now strong evidence for the existence of macrocyclic isomers of b_n⁺ ions, the formation and subsequent opening of which can lead to loss of sequence information from protonated peptides in multiple-stage tandem mass spectrometry experiments. In this study, the fragmentation patterns of protonated YARFLG and permuted isomers of the model peptide were investigated by collision-induced dissociation. Of interest was the potential influence of the arginine residue, and its position in the peptide sequence, on formation of the presumed macrocyclic b₅ ion isomer and potential loss of sequence information. We find that regardless of the sequence position (either internal or at the N- or C-terminus), only direct sequence ions or ions directly related to fragmentation of the arginine side chain are observed.