Validation of a thermal decomposition mechanism of formaldehyde by detection of CH2O and HCO behind shock waves

The thermal decomposition of formaldehyde was investigated behind shock waves at temperatures between 1675 and 2080 K. Quantitative concentration time profiles of formaldehyde and formyl radicals were measured by means of sensitive 174 nm VUV absorption (CH₂O) and 614 nm FM spectroscopy (HCO), respectively. The rate constant of the radical forming channel (1a), CH₂O + M → HCO + H + M, of the unimolecular decomposition of formaldehyde in argon was measured at temperatures from 1675 to 2080 K at an average total pressure of 1.2 bar, k_1a = 5.0 × 10¹⁵ exp(‐308 kJ mol^?1/RT) cm³ mol^?1 s^?1. The pressure dependence, the rate of the competing molecular channel (1b), CH₂O + M → H₂ + CO + M, and the branching fraction β = k_1a/(kA_1a + k_1b) was characterized by a two‐channel RRKM/master equation analysis. With channel (1b) being the main channel at low pressures, the branching fraction was found to switch from channel (1b) to channel (1a) at moderate pressures of 1–50 bar. Taking advantage of the results of two preceding publications, a decomposition mechanism with six reactions is recommended, which was validated by measured formyl radical profiles and numerous literature experimental observations. The mechanism is capable of a reliable prediction of almost all formaldehyde pyrolysis literature data, including CH₂O, CO, and H atom measurements at temperatures of 1200–3200 K, with mixtures of 7 ppm to 5% formaldehyde, and pressures up to 15 bar. Some evidence was found for a self‐reaction of two CH₂O molecules. At high initial CH₂O mole fractions the reverse of reaction (6), CH₂OH + HCO ? CH₂O + CH₂O becomes noticeable. The rate of the forward reaction was roughly measured to be k₆ = 1.5 × 10¹³ cm³ mol^?1 s^?1. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 157–169 2004     

A short synthesis of koniamborine, a naturally occurring pyrano[3,2-b]indole

An expedient synthesis of the alkaloid koniamborine, the only to date isolated naturally occurring pyrano[3,2-b]indole is presented. The key pyrano[3,2-b]indole forming step is a palladium-catalyzed reductive N-heteroannulation of 2-(4-methoxy-2-nitrophenyl)-(4H)-pyrane-4-one.     

Dendritic cells: In the forefront of immunopathogenesis and vaccine development – A review

Dendritic cellls (DCs) comprise an essential component of the immune system. These cells, as antigen presenting cells (APCs) to na?ve T cells, are crucial in the initiation of antigen specific immune responses. In the past years, several DC subsets have been identified in different organs which exert different effects in order to elicit adaptive immune responses. Thus, identification of such DC subsets has led to a better understanding of their distribution and function in the body. In this review, several key properties of the immunobiology, immunopathogenesis and vaccine strategies using DCs will be discussed.     

Pulsed-Field-Gradient Measurements of Time-Dependent Gas Diffusion

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O₂, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10⁻⁶m²s⁻¹for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times.     

The location of median paths on grid graphs

In this paper we consider the location of a path shaped facility on a grid graph. In the literature this problem was extensively studied on particular classes of graphs as trees or series-parallel graphs. We consider here the problem of finding a path which minimizes the sum of the (shortest) distances from it to the other vertices of the grid, where the path is also subject to an additional constraint that takes the form either of the length of the path or of the cardinality. We study the complexity of these problems and we find two polynomial time algorithms for two special cases, with time complexity of O(n) and O(nℓ) respectively, where n is the number of vertices of the grid and ℓ is the cardinality of the path to be located. The literature about locating dimensional facilities distinguishes between the location of extensive facilities in continuous spaces and network facility location. We will show that the problems presented here have a close connection with continuous dimensional facility problems, so that the procedures provided can also be useful for solving some open problems of dimensional facilities location in the continuous case.     

Vowel Intelligibility in Classical Singing

Vowel intelligibility during singing is an important aspect of communication during performance. The intelligibility of isolated vowels sung by Western classically trained singers has been found to be relatively low, in fact, decreasing as pitch rises, and it is lower for women than for men. The lack of contextual cues significantly deteriorates vowel intelligibility. It was postulated in this study that the reduced intelligibility of isolated sung vowels may be partly from the vowels used by the singers in their daily vocalises. More specifically, if classically trained singers sang only a few American English vowels during their vocalises, their intelligibility for American English vowels would be less than for those classically trained singers who usually vocalize on most American English vowels. In this study, there were 21 subjects (15 women, 6 men), all Western classically trained performers as well as teachers of classical singing. They sang 11 words containing 11 different American English vowels, singing on two pitches a musical fifth apart. Subjects were divided into two groups, those who normally vocalize on 4, 5, or 6 vowels, and those who sing all 11 vowels during their daily vocalises. The sung words were cropped to isolate the vowels, and listening tapes were created. Two listening groups, four singing teachers and five speech-language pathologists, were asked to identify the vowels intended by the singers. Results suggest that singing fewer vowels during daily vocalises does not decrease intelligibility compared with singing the 11 American English vowels. Also, in general, vowel intelligibility was lower with the higher pitch, and vowels sung by the women were less intelligible than those sung by the men. Identification accuracy was about the same for the singing teacher listeners and the speech-language pathologist listeners except for the lower pitch, where the singing teachers were more accurate.