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Association reactions at low pressure. III. The C2H2+/C2H2 system.

The association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2 have been examined at pressures between 8 x 10(-8) and 1 x 10(-4) Torr at 298 K in an ion cyclotron resonance mass spectrometer. Association occurred via two different mechanisms. At pressures below approximately 2 x 10(-6) Torr, the association was bimolecular having rate coefficients k2 = 2.7 x 10(-10) cm3 s-1 and 2.0 x 10(-10) cm3 s-1 for C4H2+ and C4H3+, respectively. At pressures above approximately 2 x 10(-6) Torr, termolecular association was observed with rate coefficients, k3 = 5.7 x 10(-23) cm6 s-1 and 1.3 x 10(-23) cm6 s-1 for C4H2+ and C4H3+, respectively, when M = C2H2. The termolecular rate constants with N2, Ar, Ne, and He as the third body, M, are also reported. We propose that the low pressure bimolecular association process was the result of radiative stabilization of the complex and the termolecular association process was the result of collisional stabilization. Elementary rate coefficients were obtained and the lifetime of the collision complex was > or = 57 microseconds for (C6H4+)* and > or = 18 microseconds for (C6H5+)*. At pressures below 1 x 10(-6) Torr, approximately 11% of the (C6H4+)* were stabilized by photon emission and the remaining approximately 89% reverted back to reactants, while approximately 24% of the (C6H5+)* were stabilized by photon emission and the remaining approximately 76% reverted back to reactants. The ionic products of the C2H2(+) + C2H2 reaction, C4H2+ and C4H3+, were found to be formed with enough internal energy that they did not react by the radiative association channel until relaxed by several nonreactive collisions with the bath gas.

Acetylene↗

Comet Sugano-Saigusa-Fujikawa (1983V)--a small, puzzling comet.

Spectroscopic and infrared observations of Comet Sugano-Saigusa-Fujikawa (1983V) were obtained during its close approach to the Earth on 11-14 June 1983. The [O I] production rates of 1.8 +/- 0.9 x 10(26) atoms/s observed on 12.3 June and 7 +/- 3.5 x 10(26) atoms/s on 13.4 June lead to derived water-production rates of 3 x 10(27) mol/s on 12 June and 1.1 x 10(28) mol/s on 13 June. The abundances of the minor species NH2, CN, C2, and C3 are unusually low relative to [O I]. The upper limit to the average nuclear radius from our infrared and visual photometry on 12-13 June (assuming that the entire signal came from the nucleus) is approximately 370 m. The dust/gas mass ratio was <0.01 on June 12 and <0.005 on June 13.

Astronomical Phenomena↗

Radiometry of near-earth asteroids.

We report 10 micrometers infrared photometry for 22 Aten, Apollo, and Amor asteroids. Thermal models are used to derive the corresponding radiometric albedos and diameters. Several of these asteroids appear to have surfaces of relatively high thermal inertia due to the exposure of bare rock or a coarse regolith. The Apollo asteroid 3103, 1982 BB, is recognized as class E. The Jupiter-crossing Amor asteroid 3552, 1983 SA, is confirmed as class D, but low albedos remain rare for near-Earth asteroids.

Astronomical Phenomena↗

The dust coma of Comet P/Giacobini-Zinner in the infrared.

We present 1-20 micrometers photometry of P/Giacobini-Zinner obtained at the NASA Infrared Telescope Facility, during 1985 June-September (r = 1.57-1.03 AU). A broad, weak 10 micrometers silicate emission feature was detected on August 26.6; a similar weak emission feature could have been hidden in the broadband photometry on other dates. The total scattering and emitting cross section of dust in the inner coma was similar to that in other short-period comets, but a factor of 10 (r = 1.56 AU) to 100 (r = 1.03 AU) lower than the amount of dust in Comet Halley. The thermal emission continuum can be fit with models weighted toward either small or large absorbing grains. The dust production rate near perihelion was approximately 10(5) g/s (small-grain model) to approximately 10(6) g/s (large-grain model). The corresponding dust/gas mass ratio on August 26 was approximately 0.1-1. A silicate-rich heterogeneous grain model with an excess of large particles is compatible with the observed spectrum of Giacobini-Zinner on August 26. Thus, weak or absent silicate emission does not necessarily imply an absence of silicates in the dust, although the abundance of silicate particles < or = 1 micrometer radius must have been lower than in Comet Halley.

Astronomy↗

Formaldehyde reactions in dark clouds.

The low-pressure reactions of formaldehyde (H2CO) with D+, D2+, D3+, and He+ have been studied by the ion cyclotron resonance technique. These reactions are potential loss processes for formaldehyde in cores of dark interstellar clouds. The deuterated reactants, which are easier to study experimentally, represent direct analogs for protons. Rate coefficients and branching ratios of product channels have been measured. Charge transfer is observed to be the dominant reaction of H2CO with D+, D2+, and He+ ions. Only the D3+ reaction exhibits a proton transfer channel. All reactions proceed at rate coefficients near the collision limit. Proton-deuteron exchange reactions were found to be inefficient processes in the formaldehyde system.

Cyclotrons↗

Evolutionary status of the pre-protostellar core L1498.

L1498 is a classic example of a dense cold pre-protostellar core. To study the evolutionary status, the structure, dynamics, and chemical properties of this core we have obtained high spatial and high spectral resolution observations of molecules tracing densities of 10(3)-10(5) cm-3. We observed CCS, NH3, C3H2, and HC7N with NASA's DSN 70 m antennas. We also present large-scale maps of C18O and 13CO observed with the AT&T 7 m antenna. For the high spatial resolution maps of selected regions within the core we used the VLA for CCS at 22 GHz, and the Owens Valley Radio Observatory (OVRO) MMA for CCS at 94 GHz and CS (2-1). The 22 GHz CCS emission marks a high-density [n(H2) > 10(4) cm -3] core, which is elongated with a major axis along the SE-NW direction. NH3 and C3H2 emissions are located inside the boundary of the CCS emission. C18O emission traces a lower density gas extending beyond the CCS boundary. Along the major axis of the dense core, CCS, NH3 and C3H2 emission show evidence of limb brightening. The observations are consistent with a chemically differentiated onion-shell structure for the L1498 core, with NH3 in the inner and CCS in the outer parts of the core. The high angular resolution (9"-12") spectral line maps obtained by combining NASA Goldstone 70 m and VLA data resolve the CCS 22 GHz emission in the southeast and northwest boundaries into arclike enhancements, supporting the picture that CCS emission originates in a shell outside the NH3 emitting region. Interferometric maps of CCS at 94 GHz and CS at 98 GHz show that their emitting regions contain several small-scale dense condensations. We suggest that the differences between the CCS, CS, C3H2, and NH3 emission are caused by a time-dependent effect as the core evolves slowly. We interpret the chemical and physical properties of L1498 in terms of a quasi-static (or slowly contracting) dense core in which the outer envelope is still growing. The growth rate of the core is determined by the density increase in the CCS shell resulting from the accretion of the outer low-density gas traced by C18O. We conclude that L1498 could become unstable to rapid collapse to form a protostar in less than 5 x 10(6) yr.

Ammonia↗

The magnetic field in Lynds 1457: multiband photopolarimetry.

We have performed multiband photopolarimetry toward stars behind the molecular cloud L1457 (MBM 12). This cloud is the nearest known molecular cloud (65 pc) and is thought to be contained within the local "hot bubble." The polarization shows a regular structure, indicating that the cloud is threaded by an ordered magnetic field. The wavelength dependence of the polarization seems to indicate that the grains in L1457 have higher indices of refraction than normal for interstellar clouds. However, the wavelength of maximum polarization indicates that their size distribution is close to normal.

Astronomical Phenomena↗

The IRS 1 circumstellar disk, and the origin of the jet and CO outflow in B5.

We report the discovery of the inner edge of the high velocity CO outflow associated with the bipolar jet originating from IRS 1 in Barnard 5 and the first ever resolution of its circumstellar disk in the 2.6 mm dust continuum and C18O. From high spatial resolution observations made with the Owens Valley Millimeter Array we are able to locate the origin of the outflow to within approximately 500 AU on either side of IRS 1 and apparently at the edge of, or possibly within, its circumstellar disk. The orientation of the continuum disk is perpendicular to the highly collimated jet outflow recently seen in optical emission at much farther distances. The disk has been detected in C18O giving a disk mass approximately 0.16 M (solar). Our HCO+ and HCN maps indicate significant chemical differentiation in the circumstellar region on small scales with HCO+ tracing an extended disk of material. The 12CO interferometer maps of the outflow show two conelike features originating at IRS 1, the blue one fanning open to the northeast and the red one to the southwest. The vertices of the cones are on either side of the circumstellar disk and have a projected opening angle of about 90 degrees. The intrinsic opening angle is in the range of 60 degrees-90 degrees which leads to significant interaction between outflow and infall.

Astronomical Phenomena↗

First astronomical detection of the cumulene carbon chain molecule H2C6 in TMC-1.

The cumulene carbenes are important components of hydrocarbon chemistry in low-mass star-forming cores. Here we report the first astronomical detection of the long-chain cumulene carbene H2C6 in the interstellar cloud TMC-1, from observations of two of its rotational transitions: J(K,K') = 7(1,7) --> 6(1,6) at 18.8 GHz and 8(1,8) --> 7(1,7) at 21.5 GHz, using NASA's Deep Space Network 70 m antenna at Goldstone, California. In addition we also observed the shorter cumulene carbene H2C4 at the same position. The fractional abundance of H2C6 relative to H2 is about 4.7 x 10(-11) and that of H2C4 is about 4.1 x 10(-9). The abundance of H2C6 is in fairly good agreement with gas-phase chemical models for young molecular cloud cores, but the abundance of H2C4 is significantly larger than predicted.

Astronomy↗

Dielectric constant of liquid alkanes and hydrocarbon mixtures.

The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

Alkanes↗

Life: past, present and future.

Molecular methods of taxonomy and phylogeny have changed the way in which life on earth is viewed; they have allowed us to transition from a eukaryote-centric (five-kingdoms) view of the planet to one that is peculiarly prokarote-centric, containing three kingdoms, two of which are prokaryotic unicells. These prokaryotes are distinguished from their eukaryotic counterparts by their toughness, tenacity and metabolic diversity. Realization of these features has, in many ways, changed the way we feel about life on earth, about the nature of life past and about the possibility of finding life elsewhere. In essence, the limits of life on this planet have expanded to such a degree that our thoughts of both past and future life have been altered. The abilities of prokaryotes to withstand many extreme conditions has led to the term extremophiles, used to describe the organisms that thrive under conditions thought just a few years ago, to be inconsistent with life. Perhaps the most extensive adaptation to extreme conditions, however, is represented by the ability of many bacteria to survive nutrient conditions not compatible with eukaryotic life. Prokaryotes have evolved to use nearly every redox couple that is in abundance on earth, filling the metabolic niches left behind by the oxygen-using, carbon-eating eukaryotes. This metabolic plasticity leads to a common feature in physically stratified environments of layered microbial communities, chemical indicators of the metabolic diversity of the prokaryotes. Such 'metabolic extremophily' forms a backdrop by which we can view the energy flow of life on this planet, think about what the evolutionary past of the planet might have been, and plan ways to look for life elsewhere, using the knowledge of energy flow on earth.

Adaptation, Physiological↗

Bacillus odysseyi sp. nov., a round-spore-forming bacillus isolated from the Mars Odyssey spacecraft.

A round-spore-forming Bacillus species that produces an exosporium was isolated from the surface of the Mars Odyssey spacecraft. This novel species has been characterized on the basis of phenotypic traits, 16S rDNA sequence analysis and DNA-DNA hybridization. According to the results of these analyses, this strain belongs to the genus Bacillus and is a Gram-positive, aerobic, rod-shaped, endospore-forming eubacterium. Ultrathin sections of the spores showed the presence of an exosporium, spore coat, cortex and core. 16S rDNA sequence similarities between this strain, Bacillus fusiformis and Bacillus silvestris were approximately 96% and DNA-DNA reassociation values with these two bacilli were 23 and 17%, respectively. Spores of the novel species were resistant to desiccation, H2O2 and UV and gamma radiation. Of all strains tested, the spores of this strain were the most consistently resistant and survived all of the challenges posed, i.e. exposure to conditions of desiccation (100% survival), H2O2 (26% survival), UV radiation (10% survival at 660 J m(-2)) and gamma radiation (0.4% survival). The name proposed for this novel bacterium is Bacillus odysseyi sp. nov.; the type strain is 34hs-1T (=ATCC PTA-4993T=NRRL B-30641T=NBRC 100172T).

Bacillus↗

VLSI architectures for computing multiplications and inverses in GF(2m).

Finite field arithmetic logic is central in the implementation of Reed-Solomon coders and in some cryptographic algorithms. There is a need for good multiplication and inversion algorithms that can be easily realized on VLSI chips. Massey and Omura recently developed a new multiplication algorithm for Galois fields based on a normal basis representation. In this paper, a pipeline structure is developed to realize the Massey-Omura multiplier in the finite field GF(2m). With the simple squaring property of the normal basis representation used together with this multiplier, a pipeline architecture is developed for computing inverse elements in GF(2m). The designs developed for the Massey-Omura multiplier and the computation of inverse elements are regular, simple, expandable, and therefore, naturally suitable for VLSI implementation.

Algorithms↗

Ulysses dust measurements near Jupiter.

Submicrometer- to micrometer-sized particles were recorded by the Ulysses dust detector within 40 days of the Jupiter flyby. Nine impacts were recorded within 50 Jupiter radii with most of them recorded after closest approach. Three of these impacts are consistent with particles on prograde orbits around Jupiter and the rest are believed to have resulted from gravitationally focused interplanetary dust. From the ratio of the impact rate before the Jupiter flyby to the impact rate after the Jupiter flyby it is concluded that interplanetary dust particles at the distance of Jupiter move on mostly retrograde orbits. On 10 March 1992, Ulysses passed through an intense dust stream. The dust detector recorded 126 impacts within 26 hours. The stream particles were moving on highly inclined and apparently hyperbolic orbits with perihelion distances of >5 astronomical units. Interplanetary dust is lost rather quickly from the solar system through collisions and other mechanisms and must be almost continuously replenished to maintain observed abundances. Dust flux measurements, therefore, give evidence of the recent rates of production from sources such as comets, asteroids, and moons, as well as the possible presence of interstellar grains.

Dust↗

Iron isotope biosignatures.

The (56)Fe/(54)Fe of Fe-bearing phases precipitated in sedimentary environments varies by 2.5 per mil (delta(56)Fe values of +0.9 to -1. 6 per mil). In contrast, the (56)Fe/(54)Fe of Fe-bearing phases in igneous rocks from Earth and the moon does not vary measurably (delta(56)Fe = 0.0 +/- 0.3 per mil). Experiments with dissimilatory Fe-reducing bacteria of the genus Shewanella algae grown on a ferrihydrite substrate indicate that the delta(56)Fe of ferrous Fe in solution is isotopically lighter than the ferrihydrite substrate by 1.3 per mil. Therefore, the range in delta(56)Fe values of sedimentary rocks may reflect biogenic fractionation, and the isotopic composition of Fe may be used to trace the distribution of microorganisms in modern and ancient Earth.

Earth, Planet↗

Expression of a tetraheme protein, Desulfovibrio vulgaris Miyazaki F cytochrome c(3), in Shewanella oneidensis MR-1.

Cytochrome c(3) from Desulfovibrio vulgaris Miyazaki F was successfully expressed in the facultative aerobe Shewanella oneidensis MR-1 under anaerobic, microaerophilic, and aerobic conditions, with yields of 0.3 to 0.5 mg of cytochrome/g of cells. A derivative of the broad-host-range plasmid pRK415 containing the cytochrome c(3) gene from D. vulgaris Miyazaki F was used for transformation of S. oneidensis MR-1, resulting in the production of protein product that was indistinguishable from that produced by D. vulgaris Miyazaki F, except for the presence of one extra alanine residue at the N terminus.

Aerobiosis↗

Quantum dots as strain- and metabolism-specific microbiological labels.

Biologically conjugated quantum dots (QDs) have shown great promise as multiwavelength fluorescent labels for on-chip bioassays and eukaryotic cells. However, use of these photoluminescent nanocrystals in bacteria has not previously been reported, and their large size (3 to 10 nm) makes it unclear whether they inhibit bacterial recognition of attached molecules and whether they are able to pass through bacterial cell walls. Here we describe the use of conjugated CdSe QDs for strain- and metabolism-specific microbial labeling in a wide variety of bacteria and fungi, and our analysis was geared toward using receptors for a conjugated biomolecule that are present and active on the organism's surface. While cell surface molecules, such as glycoproteins, make excellent targets for conjugated QDs, internal labeling is inconsistent and leads to large spectral shifts compared with the original fluorescence, suggesting that there is breakup or dissolution of the QDs. Transmission electron microscopy of whole mounts and thin sections confirmed that bacteria are able to extract Cd and Se from QDs in a fashion dependent upon the QD surface conjugate.

Bacteria↗

Comparison of computer- and human-derived coronary angiographic end-point measures for controlled therapy trials.

The Cholesterol Lowering Atherosclerosis Study, a randomized angiographic clinical trial, demonstrated the beneficial effect of niacin/colestipol plus diet therapy on coronary atherosclerosis. Outcome was determined by panel-based estimates (viewed in both still and cine modes) of percent stenosis severity and change in native artery and bypass graft lesions. Computer-based quantitative coronary angiography (QCA) was also used to measure lesion and bypass graft stenosis severity and change in individual frames closely matched in orientation, opacification, and cardiac phase. Both methods jointly evaluated 350 nonoccluded lesions. The correlation between QCA and panel estimates of lesion size was 0.70 (p less than 0.0001) and for change in lesion size was 0.28 (p = 0.002). Agreement between the two methods in classifying lesion changes (i.e., regression, unchanged, or progression) occurred for 60% (210 of 350) of the lesions kappa +/- SEM = 0.20 +/- 0.05, p less than 0.001). The panel identified 442 nonoccluded lesions for which QCA stenosis measurements could not be obtained. Lesions not measurable by QCA included those with stenosis greater than 85% that could not be reliably edge tracked, segments with diffuse or ecstatic disease that had no reliable reference diameter, and segments for which matched frames could not be located. Seventy-nine lesions, the majority between 21% and 40% stenosis, were identified and measured by QCA but were not identified by the panel. This comparison study demonstrates the need to consider available angiographic measurement methods in relation to the goals of their use.

Adult↗