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At least 307 records · Page 17

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

Maluendes, Sergio A.↗

Houseplants, Indoor Air Pollutants, and Allergic Reactions

The technology of using houseplant leaves for reducing volatile organics inside closed facilities has been demonstrated with formaldehyde and benzene. Philodendrons are among the most effective plants tested to date. Philodendron domesticum had demonstrated the ability to remove formaldehyde from small experimental chambers at a rate of 4.31 micro-g/sq cm leaf surface area with initial starting concentrations of 22 ppm. At initial starting concentrations of 2.3 ppm a formaldehyde removal rate of 0.57 micro-g/sq cm was achieved during a 24 hour test. Aleo vera demonstrated a much higher formaldehyde efficiency removal rate than Philodendron domesticum at low formaldehyde concentrations. During a 24 hour exposure period 5 ppm of formaldehyde were reduced to 0.5 ppm demonstrating a removal efficiency rate of 3.27 micro-g/sq cm. Removal efficiency rates can be expected to decrease with concentration levels because fewer molecules of chemicals come in contact with the leaf surface area. Several centimeters of small washed gravel should be used to cover the surface of pot plants when large numbers of plants are kept in the home. The reason for this is to reduce the exposed area of damp potting soil which encourages the growth of molds (fungi). The leaves of Philodendron domesticum and golden pothos (Scindapsus aureus) have also demonstrated their ability to remove benzene and carbon monoxide from closed chambers. A combination of activated carbon and plant roots have demonstrated the greatest potential for removing large volumes of volatile organics along with smoke and possible radon from closed systems. Although fewer plants are required for this concept a mechanical blower motor must be used to pull or push the air through the carbon-root filter. NASA studies on motor sizes and bioregeneration rates should be completed by 1988.

Wolverton, B. C.↗

Lunar Dust and Lunar Simulant Activation and Monitoring

Prior to returning to the moon, understanding the effects of lunar dust on both human physiology and mechanical equipment is a pressing concern, as problems related to lunar dust during the Apollo missions have been well documented (J.R. Gaier, The Effects of Lunar Dust on EVA Systems During the Apollo Missions. 2005, NASA-Glenn Research Center. p. 65). While efforts were made to remove the dust before reentering the lunar module, via brushing of the suits or vacuuming, a significant amount of dust was returned to the spacecraft, causing various problems. For instance, astronaut Harrison Schmitt complained of hay fever effects caused by the dust, and the abrasive nature of the material was found to cause problems with various joints and seals of the spacecraft and suits. It is clear that, in order to avoid potential health and performance problems while on the lunar surface, the reactive properties of lunar dust must be quenched. It is likely that soil on the lunar surface is in an activated form, i.e. capable of producing oxygen-based radicals in a humidified air environment, due to constant exposure to meteorite impacts, UV radiation, and elements of the solar wind. An activated silica surface serves as a good example. An oxygen-based radical species arises from the breaking of Si-OSi bonds. This system is comparable to that expected for the lunar dust system due to the large amounts of agglutinic glass and silicate vapor deposits present in lunar soil. Unfortunately, exposure to the Earth s atmosphere has passivated the active species on lunar dust, leading to efforts to reactivate the dust in order to understand the true effects that will be experienced by astronauts and equipment on the moon. Electron spin resonance (ESR) spectroscopy is commonly used for the study of radical species, and has been used previously to study silicon- and oxygen-based radicals, as well as the hydroxyl radicals produced by these species in solution (V. Vallyathan, et al., Am. Rev. Respir. Dis. 138 (1988) 1213-1219). The size and cost of these instruments makes them unattractive for the monitoring of lunar dust activity. A more suitable technique is based on the change in fluorescence of a molecule upon reaction with a hydroxyl radical (or other radical species). Fluorescence instruments are much less costly and bulky than ESR spectrometers, and small fluorescence sensors for space missions have already been developed (F. Gao, et al., J. Biomed. Opt. 10 (2005) 054005). For the current fluorescence studies, the terephthalate molecule has been chosen for monitoring the production of hydroxyl radicals in solution. As shown in Scheme 1, the reaction between the non-fluorescent terephthalate molecule and a hydroxyl radical produces the highly-fluorescent 2-hydroxyterephthalate molecule.

Wallace, W. T.↗

Coherent fiber optic sensor for early detection of cataractogenesis in a human eye lens

A lensless backscatter fiber optic probe is used to measure the size distribution of protein molecules inside an excised, but intact, human eye lens. The fiber optic probe, about 5 mm in diameter, can be positioned arbitrarily close to the anterior surface of the eye; it is a trans-receiver, which delivers a Gaussian laser beam into a small region inside the lens and provides a coherent detection of the laser light scattered by the protein molecules in the backward direction. Protein sizes determined from the fast and slow diffusion coefficients show good correlation with the age of the lens and cataractogenesis.

Dhadwal, Harbans S.↗

Diffuse interstellar band formation in dense clouds

Data are presented which show that the strengths of the diffuse interstellar bands at 4430, 5780, and 5797 A tend to be deficient with respect to color excess in the lines of sight to stars lying behind dense interstellar clouds. In addition, diffuse-band data for ten stars in the well-studied rho Ophiuchi cloud complex are presented, and systematic variations of band strengths with optical depth are discussed. It is found that the band strength per grain in the line of sight apparently decreases with increasing grain size, taking the ratio of total-to-selective absorption and the wavelength of maximum polarization as indicators of the latter. It is concluded that diffuse-band formation probably takes place most efficiently in the outer regions of interstellar clouds. This may be consistent with a diffuse-band origin in small grains which are coated by mantles in cloud interiors; or in some molecule or molecules which are most abundant in the outer portions of interstellar clouds.

Snow, T. P., Jr.↗

Polytetrafluoroethylene transfer film studied with X-ray photoelectron spectroscopy

Polytetrafluoroethylene (PTFE) was rubbed against nickel in ultrahigh vacuum at loads up to 3.9 N and speeds up to 94 mm/sec. The transfer film formed on the nickel was analyzed using X-ray phototectron spectroscopy. The film was indistinguishable from bulk PTFE except for the possible presence of a small amount of NiF2. The transfer film was found to be about 1 molecule (0.5 nm) thick under all conditions; but at speeds above 10 mm/sec, there was evidence of bulk transfer in the form of fragments as well. The thickness measurements required a choice among conflicting published values of the inelastic mean free path for electrons in polymers. The values chosen gave internally consistent results.

Wheeler, D. R.↗

An airborne sensor for the avoidance of clear air turbulence

This paper describes an airborne microwave radiometer that may be able to provide altitude guidance away from layers containing clear air turbulence, CAT. The sensor may also be able to predict upper limits for the severity of upcoming CAT. The 55 GHz radiometer is passive, not radar, and it measures the temperature of oxygen molecules in the viewing direction (averaged along a several-kilometer path). A small computer directs the viewing direction through elevation angle scans, and converts observed quantities to an 'altitude temperature profile'. The principle for CAT avoidance is that CAT is found statistically more often within inversion layers and at the tropopause, both of which are easily located from sensor-generated altitude temperature profiles.

Gary, B. L.↗

Ab initio calculation of the X 1 Sigma + state of CsH

Stevens et al. (1981) considered CsH as a two electron problem, but simulated the Cs core electrons by an empirical pseudopotential following the work by Bardsley (1970). These potentials, since they are derived empirically, include the relativistic effects and the atomic core-valence interactions. However, molecular core-core interactions are not accounted for. Stevens et al. obtained an R(e) value which is too small. This result was attributed to uncorrected core (proton)-core interactions in the molecule. The present investigation is concerned with a resolution of the discrepancies between the results of earlier studies. The X 1 Sigma + ground state of CsH is recalculated. The calculation employs a nine valence electron relativistic effective core potential (RECP) for Cs. The bonding in CsH is found to involve a Cs(6s)-H(1s) bond but with a significant ionic (Cs+H-) component.

Laskowski, B. C.↗

Ejection of sodium from sodium sulfide by the sputtering of the surface of Io

The mechanism by which Na is removed from the surface of Io prior to its injection into the plasma torus is investigated experimentally. Na2S films of thickness 3-8 microns were produced by spray coating an Ni substrate in a dry N2 atmosphere and subjected to sputtering by 34-keV Ar(+), Ne(+), Kr(+), or Xe(+) ions up to total doses of about 5 x 10 to the 18th ions/sq cm. The sputtering yields and mass spectra are found to be consistent with ejection of only small amounts of atomic Na and somewhat larger amounts of Na-containing molecules. It is concluded that the amount of Na ejected by magnetospheric-ion sputtering of Na2S would be insufficient to account for the amounts observed in the Io neutral cloud. A scenario involving sputtering of larger polysulfide molecules is considered.

Chrisey, D. B.↗

Phoretic and Radiometric Force Measurements on Microparticles in Microgravity Conditions

Thermophoretic, diffusiophoretic and radiometric forces on microparticles are being measured over a wide range of gas phase and particle conditions using electrodynamic levitation of single particles to simulate microgravity conditions. The thermophoretic force, which arises when a particle exists in a gas having a temperature gradient, is measured by levitating an electrically charged particle between heated and cooled plates mounted in a vacuum chamber. The diffusiophoretic force arising from a concentration gradient in the gas phase is measured in a similar manner except that the heat exchangers are coated with liquids to establish a vapor concentration gradient. These phoretic forces and the radiation pressure force acting on a particle are measured directly in terms of the change in the dc field required to levitate the particle with and without the force applied. The apparatus developed for the research and the experimental techniques are discussed, and results obtained by thermophoresis experiments are presented. The determination of the momentum and energy accommodation coefficients associated with molecular collisions between gases molecules and particles and the measurement of the interaction between electromagnetic radiation and small particles are of particular interest.

Davis, E. James↗

The origin of intermediary metabolism

The core of intermediary metabolism in autotrophs is the citric acid cycle. In a certain group of chemoautotrophs, the reductive citric acid cycle is an engine of synthesis, taking in CO(2) and synthesizing the molecules of the cycle. We have examined the chemistry of a model system of C, H, and O that starts with carbon dioxide and reductants and uses redox couples as the energy source. To inquire into the reaction networks that might emerge, we start with the largest available database of organic molecules, Beilstein on-line, and prune by a set of physical and chemical constraints applicable to the model system. From the 3.5 million entries in Beilstein we emerge with 153 molecules that contain all 11 members of the reductive citric acid cycle. A small number of selection rules generates a very constrained subset, suggesting that this is the type of reaction model that will prove useful in the study of biogenesis. The model indicates that the metabolism shown in the universal chart of pathways may be central to the origin of life, is emergent from organic chemistry, and may be unique.

Non-NASA Center↗

Does formate reduce alpha-ketoglutarate and ammonia to glutamate?

The reported reduction of alpha-ketoglutarate and ammonia by formate is much slower than described (Morowitz et al., 1995). The formate reduction if any is small under these conditions. Glutamate is produced from a reduction by a second molecule of alpha-ketoglutarate involving an oxidative decarboxylation.

NASA Discipline Exobiology↗

First Global Observations of Atmospheric COClF from the Atmospheric Chemistry Experiment Mission

Carbonyl chlorofluoride (COClF) is an important reservoir of chlorine and fluorine in the Earth's atmosphere. Satellite-based remote sensing measurements of COClF, obtained by the Atmospheric Chemistry Experiment (ACE) for a time period spanning February 2004 through April 2007, have been used in a global distribution study. There is a strong source region for COClF in the tropical stratosphere near 27 km. A layer of enhanced COClF spans the low- to mid-stratosphere over all latitudes, with volume mixing ratios of 40-100 parts per trillion by volume, largest in the tropics and decreasing toward the poles. The COClF volume mixing ratio profiles are nearly zonally symmetric, but they exhibit a small hemispheric asymmetry that likely arises from a hemispheric asymmetry in the parent molecule CCl3F. Comparisons are made with a set of in situ stratospheric measurements from the mid-1980s and with predictions from a 2-D model.

Fu, Dejian↗

Appendix C: First Global Observations of Atmospheric COClF from the Atmospheric Chemistry Experiment Mission

Carbonyl chlorofluoride (COCIF) is an important reservoir of chlorine and Fluorine in the Earth's atmosphere. Satellite-based remote sensing measurements of COCIF, obtained by Received in revised form the Atmospheric Chemistry Experiment (ACE) for a time period spanning February 2004 through April 2007, have been used in a global distribution study. There is a strong Accepted 18 February 2009 source region for COCIF in the tropical stratosphere near 27 km. A layer of enhanced COCIF spans the low- to mid-stratosphere over all latitudes, with volume mixing ratios of 40-100 parts Per trillion by volume, largest in the tropics and decreasing toward the poles. The COCIF volume mixing ratio profiles are nearly zonally symmetric, but they exhibit a small hemispheric asymmetry that likely arises from a hemispheric asymmetry in the parent molecule CCl3F. Comparisons are made with a set of in situ stratospheric measurements from the mid-1980s and with predictions from a 2-D model.

Fu, Djian↗

First Global Observations of Atmospheric COCIF from the Atmospheric Chemistry Experiment Mission

Carbonyl chlorofluoride (COCIF) is an important reservoir of chlorine and fluorine in the Earth's atmosphere. Satellite-based remote sensing measurements of COCIF, obtained by the Atmospheric Chemistry Experiment (ACE) for a time period spanning February 2004 through April 2007, have been used in a global distribution study. There is a strong source region for COCIF in the tropical stratosphere near 27 km. A layer of enhanced COCIF spans the low- to mid-stratosphere over all latitudes, with volume mixing ratios of 40-100 parts per trillion by volume, largest in the tropics and decreasing toward the poles. The COCIF volume mixing ratio profiles are nearly zonally symmetric, but they exhibit a small hemispheric asymmetry that likely arises from a hemispheric asymmetry in the parent molecule CCl3 F. Comparisons are made with a set of in situ stratospheric measurements from the mid-1980s and with predictions from a 2-D model.

Fu, Dejian↗

New Material for Surface-Enhanced Raman Spectroscopy

A chemical method of synthesis and application of coating materials that are especially suitable for surface-enhanced Raman spectroscopy (SERS) has been developed. The purpose of this development is to facilitate the utilization of the inherently high sensitivity of SERS to detect chemicals of interest (analytes) in trace amounts, without need for lengthy sample preparation. Up to now, the use of SERS has not become routine because the methods available have not been able to reproduce sampling conditions and provide quantitative measurements. In contrast, the coating materials of the present method enable analysis with minimum preparation of samples, and SERS measurements made using these materials are reproducible and reversible. Moreover, unlike in methods investigated in prior efforts to implement SERS, sampling is not restricted to such specific environments as electrolytes or specific solvents. The coating materials of this method are porous glasses, formed in sol-gel processes, that contain small particles of gold or silver metal. Materials of this type can be applied to the sample-contact surfaces of a variety of sampling and sensing devices, including glass slides, glass vials, fiber-optic probes, and glass tubes. Glass vials with their insides coated according to this method are particularly convenient for SERS to detect trace chemicals in solutions: One simply puts a sample solution containing the analyte(s) into a vial, then puts the vial into a Raman spectrometer for analysis. The chemical ingredients and the physical conditions of the sol-gel process have been selected so that the porous glass formed incorporates particles of the desired metal with size(s) to match the wavelength(s) of the SERS excitation laser in order to optimize the generation of surface plasmons. The ingredients and processing conditions have further been chosen to tailor the porosity and polarity of the glass to optimize the sample flow and the interaction between the analyte(s) and the plasmon field that generates Raman photons. The porous silica network of a sol-gel glass creates a unique environment for stabilizing SERS-active metal particles. Relative to other material structures that could be considered for SERS, the porous silica network offers higher specific surface area and thus greater interaction between analyte molecules and metal particles. Efforts to perform SERS measurements with the help of sampling devices coated by this method have been successful. In tests, numerous organic and inorganic chemicals were analyzed in several solvents, including water. The results of the tests indicate that the SERS measurements were reproducible within 10 percent and linear over five orders of magnitude. One measure of the limits of detectability of chemicals in these tests was found to be a concentration of 300 parts per billion. Further development may eventually make it possible to realize the full potential sensitivity of SERS for detecting some analytes in quantities as small as a single molecule.

Farquharson, Stuart↗

Behavior of Molecules on Interstellar Grains: Application of the Langevin Equation and Iterative Extended Huckel

The Langevin equation was used to explore an adsorbate desorption mechanism. Calculations were performed using iterative extended Huckel on a silica model site with various small adsorbates, e.g., H, CH, OH, NO, CO. It was found that barriers to free traversal from one site to another are substantial (approximately 3 - 10 eV). A bootstrap desorption mechanism for some molecules in the process of forming at a site also became apparent from the calculations. The desorption mechanisms appear to be somewhat balanced by a counterforce--the attraction of sites for the newly desorbed molecule. The order of attraction to a silica grain site for the diatomic molecules considered was OH > CH > CO > NO, when these entities were sufficiently distant. The nature of the silica grain and that of the "cold" desorption mechanism, when considered together, suggest that the abundance of very small grains might be less common than anticipated.

Aronowitz. Sheldon↗

Negative-ion formation in the explosives RDX, PETN, and TNT using the Reversal Electron Attachment Detection (READ) technique

In the search for high sensitivity and direct atmospheric sampling of trace species, techniques have been developed such as atmospheric-sampling, glow-discharge ionization (ASGDI), corona discharge, atmospheric pressure ionization (API), electron-capture detection (ECD), and negative-ion chemical ionization (NICI) that are capable of detecting parts-per-billion to parts-per-trillion concentrations of trace species. These techniques are based on positive- or negative-ion formation via charge-transfer to the target, or electron capture under multiple-collision conditions in a Maxwellian distribution of electron energies at the source temperature. One drawback of the high-pressure, corona- or glow-discharge devices is that they are susceptible to interferences either through indistinguishable product masses, or through undesired ion-molecule reactions. The ASGDI technique is relatively immune from such interferences, since at target concentrations of less than 1 ppm the majority of negative ions arises via electron capture rather than through ion-molecule chemistry. A drawback of the conventional ECD, and possibly of the ASGDI, is that they exhibit vanishingly small densities of electrons with energies in the range 0-10 millielectron volts (meV), as can be seen from a typical Maxwellian electron energy distribution function at T = 300 K. Slowing the electrons to these subthermal (less than 10 meV) energies is crucial, since the cross section for attachment of several large classes of molecules is known to increase to values larger than 10(exp -12) sq cm at near-zero electron energies. In the limit of zero energy these cross sections are predicted to diverge as epsilon(exp -1/2), where epsilon is the electron energy. In order to provide a better 'match' between the electron energy distribution function and attachment cross section, a new concept of attachment in an electrostatic mirror was developed. In this scheme, electrons are brought to a momentary halt by reversing their direction with electrostatic fields. At this turning point the electrons have zero or near-zero energy. A beam of target molecules is introduced, and the resultant negative ions extracted. This basic idea has been recently improved to allow for better reversal geometry, higher electron currents, lower backgrounds, and increased negative-ion extraction efficiency. We present herein application of the so-called reversal electron attachment detector (READ) to the study of negative-ion formation in the explosives molecules RDX, PETN, and TNT under single-collision conditions.

Chutijian, Ara↗