Kinetic modeling study of the laser-induced plasma plume of cyclotrimethylenetrinitramine (RDX)

A kinetic model of a laser-induced breakdown spectroscopy (LIBS) plume of cyclotrimethylenetrinitramine (RDX) was developed for the analysis of processes responsible for the LIBS signature of explosives. Air and argon were considered as buffer gases. The model includes a set of processes involving ion chemistry, as well as excitation, ionization, and other processes affecting neutral and ion species. Modeling results show that the overall reaction process can be considered a two-stage process. The first stage corresponds to a fast approach to a quasi-stationary state, while the second stage corresponds to the change of quasi-stationary species concentrations due to the change in temperature. As a result of the two-stage process, the initial mechanism of explosive decomposition is not important in determining its signature in the LIBS measurement time window (1–30 μs). The main processes responsible for generation of excited states for the LIBS emission are electron-excitation impact processes. A mechanism for the appearance of a double peak of the C₂ species concentration in the RDX plasma plume was suggested. Double-peak behavior of the C₂ species was previously experimentally observed during laser ablation of graphite.     

Studies in chemical ionization mass spectrometry:Steroidal ketones

The CH₄ chemical ionization (CI) spectra of several keto-steroids are reported as well as the H₂ and C₃H₈CI spectra of a few keto-steroids. [M + H ? H₂O]⁺ is an abundant ion in the CH₄CI spectrum of 5α-androstane-17-one and the water loss from the [M + H]⁺ ions does not involve the hydrogens on C-18 and only involves the C-16 hydrogens to about 10%. The major loss process has not been determined.3-Keto and 17-Keto steroids are readily distinguished by their CH₄CI spectra. The effectiveness of substituents for directing attack by [CH₅]⁺ and [C₂H₅]⁺ can be estimated:carboxyl > methoxy ? carbonyl > bromo ? chloro > hydroxy. Significant differences are observed in the H₂CI spectra of two 5α-vs. 5β-steroids. Propane CI Spectra are similar to methane CI spectra, but show generally less fragmentation.     

Chemical ionization mass spectra of some 2-norbornyl derivatives

Chemical ionization mass spectra of exo- and endo-2-norbornanols and their phenylurethane derivatives have been obtained with several reactant ions. Small differences are noted in the abundances of norbornyl and [M+H]⁺ ions for the phenylurethane derivatives: more norbornyl ions with the exo compounds. Relative rate constants for decomposition of [M+H]⁺ ions, k_exo/k_endo ? 1-2. No evidence was found for s?-participation in the decomposition of these ions. The i-C₄H₁₀ chemical ionization spectrum of endo-2-norbornanol contains a much greater abundance of [M-H]⁺ ions than the i-C₄H₁₀ chemical ionization spectrum of exo-2-norbornanol. This difference presumably results from steric hindrance toward attack of the endo hydrogen.     

Energy and substituent effects on gaseous ionic decompositions: Electron and charge exchange ionization of benzophenones and benzils

The correlation with substituent constants reported previously for [YØCO]⁺/[ØCO]⁺ ratios in the electron ionization mass spectra of substituted benzophenones and acetophenones has also been observed in the electron ionization spectra of substituted benzils. The [YØCO]⁺/[ØCO]⁺ ratio for the substituted benzils varied with energy of the ionizing electrons according to predictions from a simple kinetic and thermochemical analysis. [YØCO]⁺/[ØCO]⁺ ratios in the charge exchange spectra of benzophenones obtained with Xe, Kr, CO, N₂ and Ar gave good correlations with sub-stituent constants in agreement with the same analysis. Good correlations were also noted for [YØCO]⁺/[ØCO]⁺ ratios with substituent constants for [M]⁺ ions of the benzophenones of the same excess energy (5.5 eV). [YØCO]⁺/[ØCO]⁺ ratios for benzils obtained by charge exchange with [CO]⁺ also showed good correlations with substituent constant. It is suggested that [Ø]⁺ and [YØ]⁺ ions from the benzophenones may be formed primarily by one step decompositions of the molecular ions, but that the [Ø]⁺ and [YØ]⁺ ions from the benzils are formed primarily by decomposition of [ØCO]⁺ and [YØCO]⁺ ions.     

Studies in chemical ionization mass spectrometry: 17-hydroxy steroids

The chemical ionization mass spectra of several hydroxy steroids were obtained using methane as the reactant gas. The spectra are much less complex than the electron ionization spectra and little fragmentation of the steroid nucleus is observed. The major fragment ions involve the loss of water from [M + H]⁺. A 3-keto group in the steroids was characterized by an abundant [M + C₂H₅]⁺ ion. 5α- and 5β-Dihydrotestosterone could be distinguished by their spectra, with H₂ as the reactant gas by marked differences in amounts of [M + H]⁺, [M + H ? H₂O]⁺ and [M + H ? 2H₂O]⁺. Substituted 3α-X-, 17 β-ol compounds, (X = Cl, Br) were also studied to obtain relative amounts of protonation at these sites.     

Die Temperaturkorrektur beim Zeiss'schen Butterrefraktometer

Ohne Zusammenfassung     

Modeling languages and Condor: metacomputing for optimization

A generic framework is postulated for utilizing the computational resources provided by a metacomputer to concurrently solve a large number of optimization problems generated by a modeling language. An example of the framework using the Condor resource manager and the AMPL and GAMS modeling languages is provided. A mixed integer programming formulation of a feature selection problem from machine learning is used to test the mechanism developed. Due to this application’s computational requirements, the ability to perform optimizations in parallel is necessary in order to obtain results within a reasonable amount of time. Details about the simple and easy to use tool and implementation are presented so that other modelers with applications generating many independent mathematical programs can take advantage of it to significantly reduce solution times. Received: October 28, 1998 / Accepted: December 01, 1999?Published online June 8, 2000     

Phonetic identification in quiet and in noise by listeners with cochlear implants

This study examined the effect of noise on the identification of four synthetic speech continua (/ra/-/la/, /wa/-/ja/, /i/-/u/, and say-stay) by adults with cochlea implants (CIs) and adults with normal-hearing (NH) sensitivity in quiet and noise. Significant group-by-SNR interactions were found for endpoint identification accuracy for all continua except /i/-/u/. The CI listeners showed the least NH-like identification functions for the /ra/-/la/ and /wa/-/ja/ continua. In a second experiment, NH adults identified four- and eight-band cochlear implant stimulations of the four continua, to examine whether group differences in frequency selectivity could account for the group differences in the first experiment. Number of bands and SNR interacted significantly for /ra/-/la/, /wa/-/ja/, and say-stay endpoint identification; strongest effects were found for the /ra/-/la/ and say-stay continua. Results suggest that the speech features that are most vulnerable to misperception in noise by listeners with CIs are those whose acoustic cues are rapidly changing spectral patterns, like the formant transitions in the /wa/-/ja/ and /ra/-/la/ continua. However, the group differences in the first experiment cannot be wholly attributable to frequency selectivity differences, as the number of bands in the second experiment affected performance differently than suggested by group differences in the first experiment.     

Patterns of phoneme perception errors by listeners with cochlear implants as a function of overall speech perception ability

Many studies have noted great variability in speech perception ability among postlingually deafened adults with cochlear implants. This study examined phoneme misperceptions for 30 cochlear implant listeners using either the Nucleus-22 or Clarion version 1.2 device to examine whether listeners with better overall speech perception differed qualitatively from poorer listeners in their perception of vowel and consonant features. In the first analysis, simple regressions were used to predict the mean percent-correct scores for consonants and vowels for the better group of listeners from those of the poorer group. A strong relationship between the two groups was found for consonant identification, and a weak, nonsignificant relationship was found for vowel identification. In the second analysis, it was found that less information was transmitted for consonant and vowel features to the poorer listeners than to the better listeners; however, the pattern of information transmission was similar across groups. Taken together, results suggest that the performance difference between the two groups is primarily quantitative. The results underscore the importance of examining individuals' perception of individual phoneme features when attempting to relate speech perception to other predictor variables.