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NASA NTRS1999

Exotic Molecules in Space: A Coordinated Astronomical Laboratory and Theoretical Study

The past three years have been a period of great progress in our laboratory investigation of molecules of astrophysical interest-the most productive by far in the 20-year history of a research program which has led to the discovery of over 20% of the 123 known interstellar and circumstellar molecules. Most of the discoveries made during this period have been the result of the construction in late 1995 and early 1996 of a Fourier transform microwave spectrometer working in the centimeter-wave band. The sensitivity of this instrument from the moment that it was turned on has exceeded our expectations by an order of magnitude. The Table below shows the 46 new molecules which have been discovered. Most are carbon chains, the dominant type of molecule which has been found in space. Several comments with respect to these molecules should be made: 1. There are probably no mistakes in any of the identifications, since these have been confirmed by the standard, powerful assays and tests used to check spectroscopic identifications: isotopic substitution, quantum calculations of the expected molecular structures, detection of hyperfine structure, Zeeman effect, etc. 2. The radio laboratory astrophysics of the entire set is complete for the time being, in the sense that essentially all the astronomically interesting radio transitions (including hfs when present) are either directly measured or can now be calculated from the derived spectroscopic constants to better than 1 part per million (or 0.3 km s-1 in radial velocity, and often much better than that). 3. Six of the forty six new molecules have already been identified in space, in every case but one on the basis of our laboratory measurements. 4. Sensitive as they are, our laboratory techniques are far from fundamental limits on sensitivity, and 5. One of the principal motivations of our research is to close the fairly small mass and size gap, now only a factor of a few, between the smallest postulated interstellar grains and the largest identified interstellar molecules.

Thaddeus, Patrick↗

NASA NTRS2009

Enhancing SERS by Means of Supramolecular Charge Transfer

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Wong, Eric↗

NASA NTRS1984

Oxygen isotopes in deep sea spherules

The determination of the genetic relationships between the dust and small particles in the solar system, and the meteorites and larger bodies are examined. Oxygen isotopes proved useful in the identification of such relationships between one meteorite group and another. Of the various samples of submillimeter extraterrestrial particles available for laboratory study, only the deep sea spherules are abundant enough for precise oxygen isotope analysis using existing techniques. Complications arise in interpretation of the isotopic data, since these particles were melted during passage through the Earth's atmosphere, and have been in contact with seawater for prolonged periods. Spherules that were originally silicates are considered with the originally metallic ones to deduce their preterrestrial isotopic compositions. The type 1 spherules which enter the atmosphere as metallic particles, contain only atmospheric oxygen. The type S spherules contain a mixture of atmospheric oxygen and their original extraterrestrial oxygen. It is suggested that the Earth's mesosphere is strongly enriched in heavy isotopes of oxygen at altitudes near 90 km at which the iron particles are oxidized. Fractionation due to the combined diffusion of O atoms and O2 molecules may be responsible.

Mayeda, T. K.↗

NASA NTRS1995

Identification And Survival Of Bacteriohopanepolyol In A Hot Spring Microbial Mat

The polar lipids of a hot spring microbial mat located in Yellowstone National Park were examined for the presence of bacteriohopanepolvols (BHP). BHP are a group of molecules consisting of a hopanoid (peotacyclic triterpene) linked via a n-alkyl polyhydroxylated chain to a variety of polar end groups. BHP have been isolated in varying amounts from phylogenetically diverse eubacterial groups including cyanobacteria, methanotrophs and the Rhodospirillaceae. The hopanoids are excellent biomarkers and have been detected in sedimentary rocks as old as 1.7 bya. In order to interpret the ancient organic record, it is important to understand the abundance, source and fate of such biomarker compounds in microbial mats. A 40 sq cm mat section was taken from a 52 to 55 C site in the effluent channel of Octopus Spring and was sampled vertically over approximately 16 mm. The first 5-6 mm was sectioned into a top green layer (310 mg dry weight) and several subjacent, deep orange layers (240 and 250 mg, respectively). The lower 10 mm of the mat was sectioned into two gelatinous orange layers containing a siliceous gritty material (260 and 440 mg) which increased with depth, and a bottom layer composed almost exclusively of siliceous sinter (4.1 g). The progressive decrease in total organic carbon from 45% in the top green layer to only 4% in the bottom layer reflects the observed increase in siliceous deposition. GC-MS analysis of the phospholipid and glycolipid fatty acids yielded predominantly saturated normal chain acids, n-15 to n-18, and iso-branched acids, i-15 to i-17. Small amounts of unsaturated fatty acids (16:1, two positional isomers of 18:1, and two cyclopropyl acids, C(sub 17) and C(sub 19)) were present mainly in the top layer. Esterified fatty acid which is a good index for intact cellular membrane, i.e. viable organisms, was highest in the top two layers (203 and 231 micro g/mg total lipid, respectively) and gradually decreased to 66 micro g/mg total lipid in the bottom layer. Small amounts of BHP were present in all six layers, however in this case, BHP was lowest in the top green and subjacent deep-orange layers (118 and 172 micro g/mg total lipid, respectively) and increased with depth reaching almost 400 micro g/mg in the bottom two layers. This data suggest that BHP are survivina the initial phase of mat degradation and may be preferentially enriched in any organic record of such thermal environments. The relatively low level of BHP in the top layer also suggests that cyanobacteria may not be the major source of BHP in this mat. Since Chloroflexus a major component of the deep-orange layer has been reported to lack BHP, this material may prove a valuable biomarker for some other mat inhabitant. Further isotopic characterization of this BHP should help resolve this finding.

Janke, Linda L.↗

NASA NTRS2011

Polymer Electrolyte-Based Ambient Temperature Oxygen Microsensors for Environmental Monitoring

An ambient temperature oxygen microsensor, based on a Nafion polymer electrolyte, has been developed and was microfabricated using thin-film technologies. A challenge in the operation of Nafion-based sensor systems is that the conductivity of Nafion film depends on the humidity in the film. Nafion film loses conductivity when the moisture content in the film is too low, which can affect sensor operation. The advancement here is the identification of a method to retain the operation of the Nafion films in lower humidity environments. Certain salts can hold water molecules in the Nafion film structure at room temperature. By mixing salts with the Nafion solution, water molecules can be homogeneously distributed in the Nafion film increasing the film s hydration to prevent Nafion film from being dried out in low-humidity environment. The presence of organics provides extra sites in the Nafion film to promote proton (H+) mobility and thus improving Nafion film conductivity and sensor performance. The fabrication of ambient temperature oxygen microsensors includes depositing basic electrodes using noble metals, and metal oxides layer on one of the electrode as a reference electrode. The use of noble metals for electrodes is due to their strong catalytic properties for oxygen reduction. A conducting polymer Nafion, doped with water-retaining components and extra sites facilitating proton movement, was used as the electrolyte material, making the design adequate for low humidity environment applications. The Nafion solution was coated on the electrodes and air-dried. The sensor operates at room temperature in potentiometric mode, which measures voltage differences between working and reference electrodes in different gases. Repeat able responses to 21-percent oxygen in nitrogen were achieved using nitrogen as a baseline gas. Detection of oxygen from 7 to 21 percent has also been demonstrated. The room-temperature oxygen micro sensor developed has extremely low power consumption (no heating for operation, no voltage applied to the sensor, only a voltmeter is needed to measure the output), is small in size, is simple to batch-fabricate, and is high in sensor yield. It is applicable in a wide humidity range, with improved operation in low humidity after the additives were added to the Nafion film. Through further improvement and development, the sensor can be used for aerospace applications such as fuel leak detection, fire detection, and environmental monitoring.

Hunter, Gary W.↗

NASA NTRS2019

The unexpected surface of asteroid (101955) Bennu

NASA’S Origins, Spectral Interpretation, Resource Identification and Security-Regolith Explorer (OSIRIS-REx) spacecraft recently arrived at the near-Earth asteroid (101955) Bennu, a primitive body that represents the objects that may have brought prebiotic molecules and volatiles such as water to Earth1. Bennu is a low-albedo B-type asteroid2 that has been linked to organic-rich hydrated carbonaceous chondrites3. Such meteorites are altered by ejection from their parent body and contaminated by atmospheric entry and terrestrial microbes. Therefore, the primary mission objective is to return a sample of Bennu to Earth that is pristine—that is, not affected by these processes4. The OSIRIS-REx spacecraft carries a sophisticated suite of instruments to characterize Bennu’s global properties, support the selection of a sampling site and document that site at a sub-centimetre scale5,6,7,8,9,10,11. Here we consider early OSIRIS-REx observations of Bennu to understand how the asteroid’s properties compare to pre-encounter expectations and to assess the prospects for sample return. The bulk composition of Bennu appears to be hydrated and volatile-rich, as expected. However, in contrast to pre-encounter modelling of Bennu’s thermal inertia12 and radar polarization ratios13—which indicated a generally smooth surface covered by centimetre-scale particles—resolved imaging reveals an unexpected surficial diversity. The albedo, texture, particle size and roughness are beyond the spacecraft design specifications. On the basis of our pre-encounter knowledge, we developed a sampling strategy to target 50-metre-diameter patches of loose regolith with grain sizes smaller than two centimetres4. We observe only a small number of apparently hazard-free regions, of the order of 5 to 20 metres in extent, the sampling of which poses a substantial challenge to mission success.

D. S. Lauretta↗

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.↗