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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRS1990

Laboratory simulation of interstellar grain chemistry and the production of complex organic molecules

During the past 15 years considerable progress in observational techniques has been achieved in the middle infrared (5000 to 500 cm(-1), 2 to 20 microns m), the spectral region most diagnostic of molecular vibrations. Spectra of many different astronomical infrared sources, some deeply embedded in dark molecular clouds, are now available. These spectra provide a powerful probe, not only for the identification of interstellar molecules in both the gas solid phases, but also of the physical and chemical conditions which prevail in these two very different domains. By comparing these astronomical spectra with the spectra of laboratory ices one can determine the composition and abundance of the icy materials frozen on the cold (10K) dust grains present in the interior of molecular clouds. These grains and their ice mantles may well be the building blocks from which comets are made. As an illustration of the processes which can take place as an ice is irradiated and subsequently warmed, researchers present the infrared spectra of the mixture H2O:CH3OH:CO:NH3:C6H14 (100:50:10:10:10). Apart from the last species, the ratio of these compounds is representative of the simplest ices found in interstellar clouds. The last component was incorporated into this particular experiment as a tracer of the behavior of a non-aromatic hydrocarbon. The change in the composition that results from ultraviolet photolysis of this ice mixture using a UV lamp to simulate the interstellar radiation field is shown. Photolysis produces CO, CO2, CH4, HCO, H2CO, as well as a family of moderately volatile hydrocarbons. Less volatile carbonaceous materials are also produced. The evolution of the infrared spectrum of the ice as the sample is warmed up to room temperature is illustrated. Researchers believe that the changes are similar to those which occur as ice is ejected from a comet and warmed up by solar radiation. The warm-up sequence shows that the nitrile or iso-nitrile bearing compound produced during photolysis evaporates between 200 and 250K, suggesting that it is carried by a small molecular species. These molecules could be similar to the source material in Comet Halley that is ejected in grains into the coma, freed by sublimation, and photolyzed by solar radiation to produce the observed jets.

Allamandola, L. J.↗
NASA NTRS2002

The Laboratory Production of Complex Organic Molecules in Simulated Interstellar Ices

Much of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. Their low temperatures preclude most chemical reactions, but ionizing radiation can drive reactions that produce a suite of new species, many of which are complex organics. The Astrochemistry Lab at NASA-Ames studies the UV radiation processing of interstellar ice analogs to better identify the resulting products and establish links between interstellar chemistry, the organics in meteorites, and the origin of life on Earth. Once identified, the spectral properties of the products can be quantified to assist with the search for these species in space. Of particular interest are findings that UV irradiation of interstellar ice analogs produces molecules of importance in current living organisms, including quiriones, amphiphiles, and amino acids. Quinones play a variety of roles including electron transport and are used by all organisms. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are irradiated in interstellar ices (Bernstein et al. 2001). Amphiphiles are also made when mixed molecular ices are irradiated. These amphiphiles self-assemble into membrane-walled vesicles when put in liquid water (Dworkin et al. 2001). Ice irradiation can also produce (Bernstein et al. 2002) and destroy amino acids (Ehrenfreund et al. 2001). Many of the same processes thought to make organics in space should yield products highly enriched in deuterium (D) (Sandford et al. 2001). The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggests that such linkages do exist. By using D as a tracer, we expect to learn more about the different chemical processes occurring in space and their relative importance in the production of different organic compounds and delivery to planetary surfaces.

Dworkin, Jason P.↗
NASA NTRS2016

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗
NASA NTRS2003

Complex Organics from Laboratory Simulated Interstellar Ices

Many of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. The low temperatures of these ices (T < 50 K) preclude most chemical reactions, but photolysis can drive reactions that produce a suite of new species, many of which are complex organics. We study the UV and proton radiation processing of interstellar ice analogs to explore links between interstellar chemistry, the organics in comets and meteorites, and the origin of life on Earth. The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggest that such links are plausible. Once identified, these species may serve as markers of interstellar heritage of cometary dust and meteorites. Of particular interest are our findings that UV photolysis of interstellar ice analogs produce molecules of importance in current living organisms, including quinones, amphiphiles, and amino acids. Quinones are essential in vital metabolic roles such as electron transport. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are photolyzed in interstellar ices. In the case of anthracene-containing ices, we have observed the production of 9-anthrone and 9,10 anthraquinone, both of which have been observed in the Murchison meteorite. Amphiphiles are also made when mixed molecular ices are photolyzed. These amphiphiles self-assemble into fluorescent vesicles when placed in liquid water, as do Murchison extracts. Both have the ability to trap an ionic dye. Photolysis of plausible ices can also produce alanine, serine, and glycine as well as a number of small alcohols and amines. Flash heating of the room temperature residue generated by such experiments generates mass spectral distributions similar to those of IDPs. The detection of high D/H ratios in some interstellar molecular species, and the knowledge that many of the organics, such as hydroxy and amino acids, in primitive meteorites are D-enriched provides evidence for a connection between intact organic material in the interstellar medium and in meteorites. Thus, some of the oxidized aromatics, amphiphiles, amino acids, hydroxy acids, and other compounds found in meteorites may have had an interstellar ancestry and not solely a product of parent body aqueous alteration. Such compounds should also be targeted for searches of organics in cometary dust.

Dworkin, J. P.↗
NASA NTRS1999

A Study of Direct and Cloud-Mediated Radiative Forcing of Climate Due to Aerosols

The Intergovernmental Panel on Climate Change (IPCC) has reported that in the southeastern US and eastern China, the general greenhouse warming due to anthropogenic gaseous emissions is dominated by the cooling effect of anthropogenic aerosols. To verify this model prediction in eastern China and southeastern US, we analyzed regional patterns of climate changes at 72 stations in eastern China during 1951- 94 (44 years), and at 52 stations in the southeastern US during 1949-94 (46 years) to detect the fingerprint of aerosol radiative forcing. It was found that the mean rates of change of annual mean daily, maximum, minimum temperatures and diurnal temperature range (DTR) in eastern China were 0.8, -0.2, 1.8, and -2.0 C/100 years respectively, while the mean rates of change of annual mean daily, maximum, minimum temperatures and DTR in the southeastern US were -0.2, -0.6, 0.2, and -0.8 C/100 years, respectively. This indicates that the high rate of increase in annual mean minimum temperature in eastern China results in a slightly warming trend of daily temperature, while the high rate of decrease in annual mean maximum temperature and low rate of increase in annual mean minimum temperature lead to the cooling trend of daily temperature in the southeastern US. We found that the warming from the longwave forcing due to both greenhouse gases and aerosols was completely counteracted by the shortwave aerosol forcing in the southeastern US in the past 46 years. A slightly overall warming trend in eastern China is evident; winters have become milder. This finding is explained by hypothesizing that increasing energy usage during the past 44 years has resulted in more coal and biomass burning, thus increasing the emission of absorbing soot and organic aerosols in eastern China. Such emissions, in addition to well-known Asia dust and greenhouse gases, may be responsible for the winter warming trend in eastern China that we have reported here. The sensitivity of aerosol radiative properties to aerosol composition, size distribution, relative humidity (RH) is examined for the following aerosol systems: inorganic and organic ions (Cl-, Br-, NO3 -, SO4 2-, Na+, NH4 +, K+, Ca2+, Mg2+, HCOO-, CH3COO-, CH3CH2COO-, CH3COCOO-, OOCCOO2-, MSA-1); water-insoluble inorganic and organic compounds (elemental carbon, n-alkanes, SiO2, Al2O3, Fe2O3 and other organic compounds). The partial molar refraction method was used to calculate the real part of the refractive index. It was found that the asymmetry factor increased by approximately 48% with the real part varying from 1.40 to 1.65, and the single scattering albedo decreased by 24% with the imaginary part varying from -0.005 to -0.1. The asymmetry factor increased by 5.4 times with the geometric standard deviation varying from 1.2 to 3.0. The radiation transmission is very sensitive to the change in size distribution; other factors are not as significant. To determine the aerosol direct radiative forcing (ADRF), the aerosol optical depth (AOD) values at the three operational wavelengths (415, 500 and 673 nm) were determined at a regionally representative site, namely, Mt. Gibbs (35.78 deg N, 82.29 deg W, elevation 2006 m) in Mt. Mitchell State Park, NC, and a site located in an adjacent valley (Black Mountain, 35.66 deg N, 82.38 deg W, elevation 951 m) in the southeastern US. The two sites are separated horizontally by 10 km and vertically by 1 km. It was found that the representative total AOD values at 500 nm at the valley site for highly polluted (HP), marine (M) and continental (C) air masses were 0.68 +/- 0.33, 0.29 +/- 0.19 and 0.10 +/- 0.04, respectively. A search-graph method was used to retrieve the columnar size distribution (number concentration N, effective radius reff and geometric standard deviation=?g) from the optical depth observations at three operational wavelengths. The ground albedo, single scattering albedo and imaginary part of the refractive index were calculated using a mathematically unique procedure involving a Mie code and a radiative transfer code in conjunction with the retrieved aerosol size distribution, AOD, and diffuse-direct irradiance ratio. It was found that N, r(eff) and sigma(g) were in the ranges of 10 to 1.7 x 10(exp 4)/cubic cm, 0.09 to 0.68 micrometers and 1.12 to 2.95, respectively. The asymmetry factor and single scattering albedo were in the ranges of 0.63 to 0.75 and 0.74 to 0.97 respectively. The ground albedo for the forested terrain and imaginary part of refractive index were found to be in the ranges of 0.06 to 0.29 and 0.005 to 0.051 respectively. On the basis of these aerosol radiative properties obtained at the research sites and computations using the Column Radiation Model (CRM) of National Center of Atmospheric Research (NCAR) Community Climate Model (CCM3), it was found that the average cloud-free 24-hour ADRF values were -13 +/- 8, -8 +/- 3, -33 +/- 16 W/square m for marine, continental, and polluted air masses, respectively. On the assumption that the fractional coverage of clouds is 0.61, it was estimated that the annual mean ADRF was 7 +/- 2 W/square m in the southeastern US. The review with respect to the current knowledge of organic acids shows that aerosol formate and acetate concentrations range from 0.02 to 5.3 nmol/cubic m and from 0.03 to 12.4 nmol/cubic m respectively, and that between 34% to 77% of formate and between 21% to 66% of acetate are present in the fine fraction of aerosols. It was found that although most (98-99%) of these volatile organic acids were present in the gas phase, their concentrations in the aerosol particles were sufficient to make them a good candidate for cloud condensation nuclei (CCN). It is hypothesized that organic acids are at least one of the primary sources of CCN in the atmosphere due to their ubiquitous presence in the troposphere, especially over the continental forested areas. The results of our measurements at Palmer Station, Antarctica show that the daily average CCN concentrations at 0.3% and 1% supersaturations ranged from 0.3 to 160/cubic cm and from 4 to 168/cubic cm, respectively, during the period from 17 January to 26 February, 1994. New evidence for substantial and definitive CCN enhancement near and within cloud has been observed at Mt. Mitchell, North Carolina. The results show that the average monthly CCN concentrations were 460 +/- 217, 386 +/- 286, 429 +/- 228 and 238 +/- 134/cubic cm for in-cloud, overcast, clear and rainy conditions, respectively. The typical CCN spectra show that there were a lot of small CCN produced and the ion concentrations (especially H+ and SO4 2-) were very high during the CCN enhancement period. The significantly positive correlation between black carbon (BC) and CCN at 1% supersaturation indicates that a percentage of the BC measured at the site may be in the form of an internal mixture and participated in the formation of CCN.

Yu, Shao-Cai↗