Thermal decomposition of clcn.
Shock tube study of thermal decomposition of cyanogen chloride using specific cyanide absorption spectroscopy
CHEMICAL KINETICS↗
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Importance of impurities on vibrational relaxation measurements in N sub 2.
Range of importance of molecular impurities on nitrogen vibrational relaxation determined, using spectroscopic sodium line reversal techniques
MOLECULAR SPECTROSCOPY↗
The Spacing of the Interstellar 6.2 Microns and 7.7 Microns Emission Features as an Indicator of PAH Size
A database of astrophysically relevant, infrared spectral measurements on a wide variety of neutral as well as positively and negatively charged polycyclic aromatic hydrocarbons ranging in size from C10H8 through C48H20 is now available to extend the interstellar PAH model. Beyond simply indicating general characteristics of the carriers, this collection of data now makes it possible to conduct a more thorough interpretation of the details of the interstellar spectra and thereby derive deeper insights into the nature of the emitting material and conditions in the emission zones. This paper is the first such implementation of this spectral database. The infrared spectra of PAH cations, the main PAH form in the most energetic emission zones, are usually dominated by a few strong features in the 1650 - 1100 per centimeter (6.1 - 9.1 microns) region which tend to cluster in the vicinity of the interstellar emission bands at 1610 per centimeter and 1320 per centimeter (6.2 and 7.6 microns) but with spacings typically somewhat less than that observed in the canonical interstellar spectrum. However, the spectra in the database show that this spacing increases steadily with molecular size. Extrapolation of this trend indicates that PAHS in the 50 to 80 carbon atom size range are entirely consistent with the observed interstellar spacing. Furthermore, the profile of the 1610 per centimeter (6.2 microns) interstellar band indicates that PAHS containing as few as 20 carbon atoms contribute to this feature.
Hudgins, Douglas M.↗
The spacing of the interstellar 6.2 and 7.7 micron emission features as an indicator of polycyclic aromatic hydrocarbon size
A database of astrophysically relevant, infrared spectral measurements on a wide variety of neutral as well as positively and negatively charged polycyclic aromatic hydrocarbons (PAHs), ranging in size from C10H8 through C48H20, is now available to extend the interstellar PAH model. Beyond simply indicating general characteristics of the carriers, this collection of data now makes it possible to conduct a more thorough interpretation of the details of the interstellar spectra and thereby derive deeper insights into the nature of the emitting material and conditions in the emission zones. This Letter is the first such implementation of this spectral database. The infrared spectra of PAH cations, the main PAH form in the most energetic emission zones, are usually dominated by a few strong features in the 1650-1100 cm-1 (6.1-9.1 microns) region that tend to cluster the vicinity of the interstellar emission bands at 1610 and 1320 cm-1 (6.2 and 7.6 microns), but with spacings typically somewhat less than that observed in the canonical interstellar spectrum. However, the spectra in the database show that this spacing increases steadily with molecular size. Extrapolation of this trend indicates that PAHs in the 50-80 carbon atom size range are entirely consistent with the observed interstellar spacing. Furthermore, the profile of the 1610 cm-1 (6.2 microns) interstellar band indicates that PAHs containing as few as 20 carbon atoms contribute to this feature.
Extraterrestrial Environment↗
The calculation of radial dose from heavy ions: predictions of biological action cross sections
The track structure model of heavy ion cross sections was developed by Katz and co-workers in the 1960s. In this model the action cross section is evaluated by mapping the dose-response of a detector to gamma rays (modeled from biological target theory) onto the radial dose distribution from delta rays about the path of the ion. This is taken to yield the radial distribution of probability for a "hit" (an interaction leading to an observable end-point). Radial integration of the probability yields the cross section. When different response from ions of different Z having the same stopping power is observed this model may be indicated. Since the 1960s there have been several developments in the computation of the radial dose distribution, in the measurement of these distributions, and in new radiobiological data against which to test the model. The earliest model, by Butts and Katz made use of simplified delta ray distribution functions, of simplified electron range-energy relations, and neglected angular distributions. Nevertheless it made possible the calculation of cross sections for the inactivation of enzymes and viruses, and allowed extension to tracks in nuclear emulsions and other detectors and to biological cells. It set the pattern for models of observable effects in the matter through which the ion passed. Here we outline subsequent calculations of radial dose which make use of improved knowledge of the electron emission spectrum, the electron range-energy relation, the angular distribution, and some considerations of molecular excitation, of particular interest both close to the path of the ion and the outer limits of electron penetration. These are applied to the modeling of action cross sections for the inactivation of several strains of E-coli and B. subtilis spores where extensive measurements in the "thin-down" region have been made with heavy ion beams. Such calculations serve to test the radial dose calculations at the outer limit of electron penetration. We lack data from which to test these calculations in regions close to the path of the ion aside from our earliest work on latent tracks in plastics, though it appears that the criterion then suggested for the threshold of track formation, of a minimal dose at a minimal distance (of about 20 angstroms, in plastics), remains valid.
NASA Discipline Radiation Health↗
Negative regulators of cell proliferation
Cell proliferation is governed by the influence of both mitogens and inhibitors. Although cell contact has long been thought to play a fundamental role in cell cycling regulation, and negative regulators have long been suspected to exist, their isolation and purification has been complicated by a variety of technical difficulties. Nevertheless, over recent years an ever-expanding list of putative negative regulators have emerged. In many cases, their biological inhibitory activities are consistent with density-dependent growth inhibition. Most likely their interactions with mitogenic agents, at an intracellular level, are responsible for either mitotic arrest or continued cell cycling. A review of naturally occurring cell growth inhibitors is presented with an emphasis on those factors shown to be residents of the cell surface membrane. Particular attention is focused on a cell surface sialoglycopeptide, isolated from intact bovine cerebral cortex cells, which has been shown to inhibit the proliferation of an unusually wide range of target cells. The glycopeptide arrest cells obtained from diverse species, both fibroblasts and epithelial cells, and a broad variety of transformed cells. Signal transduction events and a limited spectrum of cells that are refractory to the sialoglycopeptide have provided insight into the molecular events mediated by this cell surface inhibitor.
Review↗
Frequency Correction for MIRO Chirp Transformation Spectroscopy Spectrum
This software processes the flyby spectra of the Chirp Transform Spectrometer (CTS) of the Microwave Instrument for Rosetta Orbiter (MIRO). The tool corrects the effect of Doppler shift and local-oscillator (LO) frequency shift during the flyby mode of MIRO operations. The frequency correction for CTS flyby spectra is performed and is integrated with multiple spectra into a high signal-to-noise averaged spectrum at the rest-frame RF frequency. This innovation also generates the 8 molecular line spectra by dividing continuous 4,096-channel CTS spectra. The 8 line spectra can then be readily used for scientific investigations. A spectral line that is at its rest frequency in the frame of the Earth or an asteroid will be observed with a time-varying Doppler shift as seen by MIRO. The frequency shift is toward the higher RF frequencies on approach, and toward lower RF frequencies on departure. The magnitude of the shift depends on the flyby velocity. The result of time-varying Doppler shift is that of an observed spectral line will be seen to move from channel to channel in the CTS spectrometer. The direction (higher or lower frequency) in the spectrometer depends on the spectral line frequency under consideration. In order to analyze the flyby spectra, two steps are required. First, individual spectra must be corrected for the Doppler shift so that individual spectra can be superimposed at the same rest frequency for integration purposes. Second, a correction needs to be applied to the CTS spectra to account for the LO frequency shifts that are applied to asteroid mode.
Lee, Seungwon↗
The Temperature and Distribution of Organic Molecules in the Inner Regions of T Tauri Disks
"High-resolution NIR spectroscopic observations of warm molecular gas emission from young circumstellar disks allow us to constrain the temperature and composition of material in the inner planet-forming region. By combining advanced data reduction algorithms with accurate modeling of the terrestrial atmospheric spectrum and a novel double-differencing data analysis technique, we have achieved very high-contrast measurements (S/N approx. 500-1000) of molecular emission at 3 microns. In disks around low-mass stars, we have achieved the first detections of emission from HCN and C2H2 at near-infrared wavelengths from several bright T Tauri stars using the CRIRES spectrograph on the Very Large Telescope and NIRSPEC spectrograph on the Keck Telescope. We spectrally resolve the line shape, showing that the emission has both a Keplerian and non-Keplerian component as observed previously for CO emission. We used a simplified single-temperature local thermal equilibrium (LTE) slab model with a Gaussian line profile to make line identifications and determine a best-fit temperature and initial abundance ratios, and we then compared these values with constraints derived from a detailed disk radiative transfer model assuming LTE excitation but utilizing a realistic temperature and density structure. Abundance ratios from both sets of models are consistent with each other and consistent with expected values from theoretical chemical models, and analysis of the line shapes suggests that the molecular emission originates from within a narrow region in the inner disk (R < 1 AU)."
Mandell, Avi↗
Determining structure in molecular clouds
We descibe an automatic, objective routine for analyzing the clumpy structure in a spectral line position-position-velocity data cube. The algorithm works by first contouring the data at a multiple of the rms noise of the observations, then searches for peaks of emission which locate the clumps, and then follows them down to lower intensities. No a proiri clump profile is assumed. By creating simulated data, we test the performance of the algorithm and show that a contour map most accurately depicts internal structure at a contouring interval equal to twice the rms noise of the map. Blending of clump emission leads to small errors in mass and size determinations and in severe cases can result in a number of clumps being misidentified as a single unit, flattening the measured clump mass spectrum. The algorithm is applied to two real data sets as an example of its use. The Rosette molecular cloud is a 'typical' star-forming cloud, but in the Maddalena molecular cloud high-mass star formation is completely absent. Comparison of the two clump lists generated by the algorithm show that on a one-to-one basis the clumps in the star-forming cloud have higher peak temperatures, higher average densities, and are more gravitationally bound than in the non-star-forming cloud. Collective properties of the clumps, such as temperature-size-line-width-mass relations appear very similar, however. Contrary to the initial results reported in a previous paper (Williams & Blitz 1993), we find that the current, more thoroughly tes ted analysis finds no significant difference in the clump mass spectrum of the two clouds.
Williams, Jonathan P.↗
Atomic Oxygen Abundance in Molecular Clouds: Absorption Toward Sagittarius B2
We have obtained high-resolution (approximately 35 km/s) spectra toward the molecular cloud Sgr B2 at 63 micrometers, the wavelength of the ground-state fine-structure line of atomic oxygen (O(I)), using the ISO-LWS instrument. Four separate velocity components are seen in the deconvolved spectrum, in absorption against the dust continuum emission of Sgr B2. Three of these components, corresponding to foreground clouds, are used to study the O(I) content of the cool molecular gas along the line of sight. In principle, the atomic oxygen that produces a particular velocity component could exist in any, or all, of three physically distinct regions: inside a dense molecular cloud, in the UV illuminated surface layer (PDR) of a cloud, and in an atomic (H(I)) gas halo. For each of the three foreground clouds, we estimate, and subtract from the observed O(I) column density, the oxygen content of the H(I) halo gas, by scaling from a published high-resolution 21 cm spectrum. We find that the remaining O(I) column density is correlated with the observed (13)CO column density. From the slope of this correlation, an average [O(I)]/[(13)CO] ratio of 270 +/- 120 (3-sigma) is derived, which corresponds to [O(I)]/[(13)CO] = 9 for a CO to (13)CO abundance ratio of 30. Assuming a (13)CO abundance of 1x10(exp -6) with respect to H nuclei, we derive an atomic oxygen abundance of 2.7x10(exp -4) in the dense gas phase, corresponding to a 15% oxygen depletion compared to the diffuse ISM in our Galactic neighborhood. The presence of multiple, spectrally resolved velocity components in the Sgr B2 absorption spectrum allows, for the first time, a direct determination of the PDR contribution to the O(I) column density. The PDR regions should contain O(I) but not (13)CO, and would thus be expected to produce an offset in the O(I)-(13)CO correlation. Our data do not show such an offset, suggesting that within our beam O(I) is spatially coexistent with the molecular gas, as traced by (13)CO. This may be a result of the inhomogeneous nature of the clouds.
Lis, D. C.↗
Evaluation of Raman scattering as a sensor of temperature and molecular density
The performance of the Raman scattering technique for the remote monitoring of temperature and molecular number density in various wind tunnel and engine testing facilities has been experimentally evaluated. Temperature measurements were made by monitoring the pure rotational spectrum of nitrogen and the rotational branch separations of nu2 of CF4 for temperatures in the range 300 to 1000 K. These measurements yielded an average error of 2.6 and 7.6%, respectively, for temperature measurements at pressures near 1 atm. Molecular number density measurements with 20% error could be made at densities as low as 3.5 times 10 to the 22-nd power per cu m by monitoring the 6 to 8 rotational transition of nitrogen, 3.5 times 10 to the 23-rd power per cu m by monitoring the Q-branch of the fundamental vibrational transition of nitrogen, and 7 times 10 to the 22-nd power per cu m by monitoring the nu1 fundamental vibrational transition of CF4.
Bandy, A. R.↗
The bird: A pressure-confined explosion in the interstellar medium
The non-thermal radio continuum source G5.3-1.0, mapped at 20 cm with the Very Large Array (VLA) by Becker and Helfand, has an unusual bird-like shape. In order to determine possible interaction of this source with adjacent cold gas, we have mapped this region in the J=1-0 line of CO using the AT and T Bell Laboratories 7m antenna and the FCRAO 14m antenna. The map shown contains 1859 spectra sampled on a 1.5 arcminute grid; each spectrum has an rms noise of 0.2 K in 1 MHz channels. There are several molecular clouds at different velocities along the line of sight. The outer regions of a previously unknown Giant Molecular Cloud (GMC) at l=4.7 deg., b=-0.85 deg., v=200 km s(-1) appears to be interacting with G5.3-10: the molecular cloud has a bird-shaped hole at the position of the continuum source, except that the brightest continuum point (the bird's head) appears to be embedded in the cloud. The velocity of this GMC indicates it is within 2 kpc of the galactic center. The morphology suggests that a supernova or other explosive event occurred near the outside of the GMC, in a region where (n) is approximately 300 cm(-3), and expanded into a region of lower density and pressure. The pressures, densities, and velocity gradients of molecular clouds near the galactic center are on average higher than those of clouds near the Sun. We therefore expect that Type II supernovae near the galactic center would be distorted by their interactions with their parent molecular clouds.
Lane, A. P.↗
Moderate-Resolution Spitzer Infrared Spectrograph Observations of M, L, and T Dwarfs
We present 10-19 micrometers moderate-resolution spectra of 10 M dwarfs, one L dwarf, and two T dwarf systems obtained with the Infrared Spectrograph (IRS) on board the Spitzer Space Telescope. The IRS allows us to examine molecular spectroscopic features/lines at moderate spectral resolution in a heretofore untapped wavelength regime. These R = (lamda)/(Delta)(lamda) approximately equal to 600 spectra allow for a more detailed examination of clouds and nonequilibrium chemistry, as well as the molecular features of H2O, NH3, and other trace molecular species that are the hallmarks of these objects. A cloud-free model best fits our mid-infrared spectrum of the T1 dwarf (Sigma) Indi Ba, and we find that the NH3 feature in (Sigma) Indi Bb is best explained by a nonequilibrium abundance due to vertical transport in its atmosphere.We examined a set of objects (mostly M dwarfs) in multiple systems to look for evidence of emission features, which might indicate an atmospheric temperature inversion, as well as trace molecular species; however, we found no evidence of either.
low mass brown dwarfs↗
The X-ray Emitting Components towards l = 111 deg: The Local Hot Bubble and Beyond
We have obtained an XMM-Newton spectrum of the diffuse X-ray emission towards (l, b) = (111.14,1.11), a line of sight with a relatively simple distribution of absorbing clouds; > 9 x 10(exp 19)/sq cm at R>170 pc, a 6 x 10(exp 21)/sq cm molecular cloud at 2.5-3.3 kpc, and a total column of 1.2 x 10(exp 22)/sq cm. We find that the analysis of the XMM-Newton spectrum in conjunction with the RASS spectral energy distribution for the same direction requires three thermal components to be well fit: a "standard" Local Hot Bubble component with kT = 0.089, a component beyond the molecular cloud with kT = 0.59, and a component before the molecular cloud with kT = 0.21. The strength of the O VII 0.56 keV line from the Local Hot Bubble, 2.1+/-0.7 photons/sq cm/s/sr, is consistent with other recent measures. The 0.21 keV component has an emission measure of 0.0022+/-0.0006 pc and is not localized save as diffuse emission within the Galactic plane; it is the best candidate for a pervasive hot medium. The spatial separation of the approx. 0.2 keV component from the approx. 0.6 keV component suggests that the spectral decompositions of the emission from late-type spiral disks found in the literature do represent real temperature components rather than reflecting more complex temperature distributions.
Kuntz, K. D.↗
A Fluorinated Lewis Acidic Organoboron Tunes Polysulfide Complex Structure for High–Performance Lithium–Sulfur Batteries
Many challenges in lithium-sulfur (Li–S) batteries are associated with the radical change in lithium polysulfide (LPS) solubility during cycling, but chemical approaches to address such inconsistency are still lacking. Here, the use of a strong Lewis acidic fluorinated organoboron, tri(2,2,2-trifluoroethyl) borate (TFEB), is reported as a multi-functional mediator to simultaneously overcome multiple technical barriers in practical Li–S batteries. TFEB acts as an anion acceptor and forms strong molecular complexes with Lewis basic LPS. The TFEB-LPS complexes have consistent solubility across the full polysulfide spectrum and deliver several times improved better redox kinetics, unlocking a true redox catalytic mechanism that covers the majority of redox events in thick sulfur cathodes. As a result, Li–S batteries evaluated under practical conditions exhibit significantly improved discharge capacity, rate capability, and cycling stability with the addition of the TFEB additive. More importantly, TFEB also contributes to the stabilization of lithium anode in the presence of polysulfides by generating strong interfacial film. These attributes significantly improve the cycling stability of practical Li–S pouch cells, which are assembled with a unit energy density of 219 Wh kg –1 . Finally, the results provide new molecular insights on the design of unlocking solvation networks of practical Li–S systems.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
A balloon-borne 102-cm telescope for far-infrared astronomy
In the early 1970's, the Smithsonian Astrophysical Observatory and the University of Arizona engaged in a cooperative program to develop a balloon-borne 102-cm telescope capable of carrying out far infrared (40 to 250 micron) observations of astronomical interest above the earth's atmosphere. Since 1972, the telescope has flown and successfully recovered a total of nineteen times. Thirteen of the flights produced high-quality astronomical data, resulting in more than 92.5 hours of photometric and spectroscopic observations of numerous objects, such as H 2 regions, dark clouds, molecular clouds, a planetary nebula, a galaxy, the galactic center, the planets, and an asteroid. From the launch site in Palestine, Texas, sources as far south as -50 degrees declination were observed. The balloon-borne telescope was one of the most sensitive instruments ever used for observation in the far infrared region of the spectrum. It was most productive in producing high resolution maps of large areas (typically square degrees) centered on known H 2 regions, molecular clouds, and dark cloud complexes. In many cases, these scans produced the first far infrared maps of these regions, and many new sources were discovered. The results have led to a better understanding of the distribution of gas and dust in these regions, the evolution of H 2 regions, and the processes of star formation in giant molecular clouds. The following topics are presented: (1) the focal plane instrumentation; (2) the history and flight record; (3) scientific results and publications; (4) eduational aspects; and (5) future planes.
Fazio, Giovanni G.↗
Low Mutation Rate and Atypical Mutation Spectrum in Prasinoderma coloniale : Insights From an Early Diverging Green Lineage
Mutations are the ultimate source of genetic diversity on which natural selection and genetic drift act, playing a crucial role in evolution and long-term adaptation. At the molecular level, the spontaneous mutation rate (µ), defined as the number of mutations per base per generation, thus determines the adaptive potential of a species. Through a mutation accumulation experiment, we estimate the mutation rate and spectrum in Prasinoderma coloniale, a phytoplankton species from an early-branching lineage within the Archaeplastida, characterized by an unusually high genomic guanine-cytosine (GC) content (69.8%). We find that P. coloniale has a very low total mutation rate of µ = 2.00 × 10 -10 . The insertion–deletion mutation rate is almost 5 times lesser than the single nucleotide mutation rate with µ ID = 3.40 × 10 -11 and µ SNM = 1.62 × 10 -10 . Prasinoderma coloniale also exhibits an atypical mutational spectrum: While essentially all other eukaryotes show a bias toward GC to AT mutations, no evidence of this AT-bias is observed in P. coloniale. Since cytosine methylation is known to be mutagenic, we hypothesized that this may result from an absence of C-methylation. Surprisingly, we found high levels of C-methylation (14% in 5mC, 25% in 5mCG contexts). Methylated cytosines did not show increased mutation rates compared with unmethylated ones, not supporting the prevailing notion that C-methylation universally leads to higher mutation rates. Overall, P. coloniale combines a GC-rich genome with a low mutation rate and original mutation spectrum, suggesting the almost universal AT-bias may not have been present in the ancestor of the green lineage.
59 BASIC BIOLOGICAL SCIENCES↗
Modeling the Conformer-Dependent Electronic Absorption Spectra and Photolysis Rates of Methyl Vinyl Ketone Oxide and Methacrolein Oxide
Criegee intermediates are important atmospheric oxidants, formed via the reaction of ozone with volatile alkenes emitted into the troposphere. Small Criegee intermediates (e.g., CH 2 OO and CH 3 CHOO) are highly reactive, and their removal via unimolecular decay or bimolecular chemistry dominates their atmospheric lifetimes. As the molecular complexity of Criegee intermediates increases, their electronic absorption spectra show a bathochromic shift within the solar spectrum relevant to the troposphere. In such cases, solar photolysis may become a competitive contributor to their atmospheric removal. In this article, we report the conformer-dependent simulated electronic absorption spectra of two four-carbon-centered Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). Both MVK-oxide and MACR-oxide contain four low-energy conformers, which are convoluted in the experimentally measured spectra. Here, we deconvolute each conformer and estimate contributions from each of the four conformers to the experimentally measured spectra. We also estimate the photolysis rates and predict that solar photolysis should be a more competitive removal process for MVK-oxide and MACR-oxide (cf. CH 2 OO and CH 3 CHOO).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗