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At least 19 records

Multidisciplinary research in space sciences and engineering with emphasis on theoretical chemistry

A broad program is reported of research in theoretical chemistry, particularly in molecular quantum and statistical mechanics, directed toward determination of the physical and chemical properties of materials, relation of these macroscopic properties to properties of individual molecules, and determination of the structure and properties of the individual molecules. Abstracts are presented for each research project conducted during the course of the program.

Hirschfelder, J. O.↗

Spectroscopic analysis of solar and cosmic X-ray spectra. 1: The nature of cosmic X-ray spectra and proposed analytical techniques

Techniques for the study of the solar corona are reviewed as an introduction to a discussion of modifications required for the study of cosmic sources. Spectroscopic analysis of individual sources and the interstellar medium is considered. The latter was studied via analysis of its effect on the spectra of selected individual sources. The effects of various characteristics of the ISM, including the presence of grains, molecules, and ionization, are first discussed, and the development of ISM models is described. The expected spectral structure of individual cosmic sources is then reviewed with emphasis on supernovae remnants and binary X-ray sources. The observational and analytical requirements imposed by the characteristics of these sources are identified, and prospects for the analysis of abundances and the study of physical parameters within them are assessed. Prospects for the spectroscopic study of other classes of X-ray sources are also discussed.

Walker, A. B. C., Jr.↗

Lessons from an evolving rRNA: 16S and 23S rRNA structures from a comparative perspective

The 16S and 23S rRNA higher-order structures inferred from comparative analysis are now quite refined. The models presented here differ from their immediate predecessors only in minor detail. Thus, it is safe to assert that all of the standard secondary-structure elements in (prokaryotic) rRNAs have been identified, with approximately 90% of the individual base pairs in each molecule having independent comparative support, and that at least some of the tertiary interactions have been revealed. It is interesting to compare the rRNAs in this respect with tRNA, whose higher-order structure is known in detail from its crystal structure (36) (Table 2). It can be seen that rRNAs have as great a fraction of their sequence in established secondary-structure elements as does tRNA. However, the fact that the former show a much lower fraction of identified tertiary interactions and a greater fraction of unpaired nucleotides than the latter implies that many of the rRNA tertiary interactions remain to be located. (Alternatively, the ribosome might involve protein-rRNA rather than intramolecular rRNA interactions to stabilize three-dimensional structure.) Experimental studies on rRNA are consistent to a first approximation with the structures proposed here, confirming the basic assumption of comparative analysis, i.e., that bases whose compositions strictly covary are physically interacting. In the exhaustive study of Moazed et al. (45) on protection of the bases in the small-subunit rRNA against chemical modification, the vast majority of bases inferred to pair by covariation are found to be protected from chemical modification, both in isolated small-subunit rRNA and in the 30S subunit. The majority of the tertiary interactions are reflected in the chemical protection data as well (45). On the other hand, many of the bases not shown as paired in Fig. 1 are accessible to chemical attack (45). However, in this case a sizeable fraction of them are also protected against chemical modification (in the isolated rRNA), which suggests that considerable higher-order structure remains to be found (although all of it may not involve base-base interactions and so may not be detectable by comparative analysis). The agreement between the higher-order structure of the small-subunit rRNA and protection against chemical modification is not perfect, however; some bases shown to covary canonically are accessible to chemical modification (45).(ABSTRACT TRUNCATED AT 400 WORDS).

Review↗

Aromatic Structure in Simulates Titan Aerosol

Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are demonstrated in the aerosol mass spectra shown in Figure 2. The aromatic aerosol also demonstrates strong chemical reactivity when exposed to laboratory air, indicating substantial stored chemical potential. Oxidatoin and solubility studies wil be presented and implicatoins for prebiotic chemistry o nTitan will be discussed.

Trainer, Melissa G.↗

Chemical evolution and the origin of life; Proceedings of the Third International Conference, Pont-a-Mousson, France, April 19-25, 1970. Volume 1 - Molecular evolution.

The present state of investigations on the origin of life is surveyed together with the current state of molecular paleontology. General and theoretical subjects discussed include an energetic approach to prebiological chemistry, the recognition of description and function in chemical reaction networks, and the origin and development of optical activity of bio-organic compounds on the primordial earth. Other fields considered are the syntheses of small molecules, oligomers and polymers; photochemical processes; the origin of biological structures; primitive biochemistry and biology; and exobiology. Individual items are abstracted in this issue.

Buvet, R.↗

Quantitative Interpretation of Optical Emission Sensors for Microgravity Experiments

Microgravity flight experiments uniquely test our knowledge and understanding of the coupling between chemistry and fluid mechanics. However, compared to ground based laboratory experiments the number of useful diagnostic tools suitable for microgravity environments is severely limited by the space, weight, power consumption, and operator complexity requirements. One of the available tools is the observation of optical emission, and total emission has already proven useful for observations of stable "flame balls" on the space shuttle. Wavelength resolved tomographic measurements of flame emission offer the promise of diagnostics to test our understanding of flame chemistry and structure. Individual emissions from electronically excited radicals, e.g., CH*, OH*, and C2*, can be identified in a methane/air flame. Spatially resolved measurements of the intensity of this resolved optical emission from a specific excited molecule enable chemically resolved flame structure studies. Wavelength resolved emission measurements to determine such structure in diffusion flames are being readied for flight experiments by a group at Yale headed by Profs. Smooke and Long. A quantitative relationship between emission intensity and flame properties, as expressed by a flame model, is needed for species specific optical emission measurements to fulfill its promise. The Yale group compared models and measurements of optical emission in laboratory tests at 1-g. Unfortunately, these experiments show disagreement between measurement and state-of-the-art flame models by over a factor of 50. Therefore, an improved chemical mechanism for optical emission from flames is needed to enable quantitative tests of microgravity flame models. The connection between excited state emission and flame chemistry is not yet adequate.

Jeffries, Jay B.↗

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Leventis, Nicholas↗

Structure of dense molecular gas in TMC 1 from observations of three transitions of HC3N

The Taurus dark cloud complex is a collection of many individual clouds scattered across approximately 50 pc. Within one of these, Heiles Cloud 2, is the dense condensation TMC 1. TMC 1 is one of the few sources in which some of the long carbon chain molecules are found. The present investigation is concerned with a mapping of the density structure in a narrow ridge of the TMC 1 structure. It is shown that the HC3N emission from the J = 5 to 4, J = 9 to 8, and J = 12 to 11 transitions is well matched by a narrow ridge of material at a single density of 50,000-100,000 per cu cm. There is evidence that the HC3N fractional abundance is variable along the ridge. Evidence is also found for the presence of subcondensations within this ridge from maps at individual velocities.

Schloerb, F. P.↗

Spectroscopic analysis of solar and cosmic X-ray spectra. I - The nature of cosmic X-ray spectra and proposed analytical techniques

X-ray spectroscopic techniques developed in the study of the temperature and density structure of the solar corona are reviewed as introduction to a discussion of the modifications in these techniques which will be required for the study of cosmic X-ray sources. The structure of the interstellar medium - the presence of interstellar grains, the presence of molecules, the ionization structure - are considered in relation to the X-ray opacity of the interstellar medium. The expected spectral structure of individual cosmic X-ray sources is reviewed with emphasis on galactic supernova remnants and galactic binary X-ray sources.

Walker, A. B. C., Jr.↗

Development of a Linear Ion Trap Mass Spectrometer (LITMS) Investigation for Future Planetary Surface Missions

Future surface missions to Mars and other planetary bodies will benefit from continued advances in miniature sensor and sample handling technologies that enable high-performance chemical analyses of natural samples. Fine-scale (approx.1 mm and below) analyses of rock surfaces and interiors, such as exposed on a drill core, will permit (1) the detection of habitability markers including complex organics in association with their original depositional environment, and (2) the characterization of successive layers and gradients that can reveal the time-evolution of those environments. In particular, if broad-based and highly-sensitive mass spectrometry techniques could be brought to such scales, the resulting planetary science capability would be truly powerful. The Linear Ion Trap Mass Spectrometer (LITMS) investigation is designed to conduct fine-scale organic and inorganic analyses of short (approx.5-10 cm) rock cores such as could be acquired by a planetary lander or rover arm-based drill. LITMS combines both pyrolysis/gas chromatograph mass spectrometry (GCMS) of sub-sampled core fines, and laser desorption mass spectrometry (LDMS) of the intact core surface, using a common mass analyzer, enhanced from the design used in the Mars Organic Molecule Analyzer (MOMA) instrument on the 2018 ExoMars rover. LITMS additionally features developments based on the Sample Analysis at Mars (SAM) investigation on MSL and recent NASA-funded prototype efforts in laser mass spectrometry, pyrolysis, and precision subsampling. LITMS brings these combined capabilities to achieve its four measurement objectives: (1) Organics: Broad Survey Detect organic molecules over a wide range of molecular weight, volatility, electronegativity, concentration, and host mineralogy. (2) Organic: Molecular Structure Characterize internal molecular structure to identify individual compounds, and reveal functionalization and processing. (3) Inorganic Host Environment Assess the local chemical/mineralogical makeup of organic host phases to help determine deposition and preservation factors. (4) Chemical Stratigraphy Analyze the fine spatial distribution and variation of key species with depth.

Mars↗

Novel Materials Containing Single-Wall Carbon Nanotubes Wrapped in Polymer Molecules

In this design, single-wall carbon nanotubes (SWNTs) have been coated in polymer molecules to create a new type of material that has low electrical conductivity, but still contains individual nanotubes, and small ropes of individual nanotubes, which are themselves good electrical conductors and serve as small conducting rods immersed in an electrically insulating matrix. The polymer is attached through weak chemical forces that are primarily non-covalent in nature, caused primarily through polarization rather than the sharing of valence electrons. Therefore, the electronic structure of the SWNT involved is substantially the same as that of free, individual (and small ropes of) SWNT. Their high conductivity makes the individual nanotubes extremely electrically polarizable, and materials containing these individual, highly polarizable molecules exhibit novel electrical properties including a high dielectric constant.

Smalley, Richard E.↗

Sedimentary organic molecules: Origins and information content

To progress in the study of organic geochemistry, we must dissect the processes controlling the composition of sedimentary organic matter. Structurally, this has proven difficult. Individual biomarkers can often be recognized, but their contribution to total organic materials is small, and their presence does not imply that their biochemical cell mates have survived. We are finding, however, that a combination of structural and isotopic lines of evidence provides new information. A starting point is provided by the isotopic compositions of primary products (degradation products of chlorophylls, alkenones derived from coccoliths). We find strong evidence that the isotopic difference between primary carbonate and algal organic material can be interpreted in terms of the concentration of dissolved CO2. Moreover, the isotopic difference between primary and total organic carbon can be interpreted in terms of characteristic isotopic shifts imposed by secondary processes (responsive, for example, to O2 levels in the depositional environment. In favorable cases, isotopic compositions of a variety of secondary products can be interpreted in terms of flows of carbon, and, therefore, in terms of specific processes and environmental conditions within the depositional environment.

Hayes, J. M.↗

Paramagnetic Attraction of Impurity-Helium Solids

Impurity-helium solids are formed when a mixture of impurity and helium gases enters a volume of superfluid helium. Typical choices of impurity gas are hydrogen deuteride, deuterium, nitrogen, neon and argon, or a mixture of these. These solids consist of individual impurity atoms and molecules as well as clusters of impurity atoms and molecules covered with layers of solidified helium. The clusters have an imperfect crystalline structure and diameters ranging up to 90 angstroms, depending somewhat on the choice of impurity. Immediately following formation the clusters aggregate into loosely connected porous solids that are submerged in and completely permeated by the liquid helium. Im-He solids are extremely effective at stabilizing high concentrations of free radicals, which can be introduced by applying a high power RF dis- charge to the impurity gas mixture just before it strikes the super fluid helium. Average concentrations of 10(exp 19) nitrogen atoms/cc and 5 x 10(exp 18) deuterium atoms/cc can be achieved this way. It shows a typical sample formed from a mixture of atomic and molecular hydrogen and deuterium. It shows typical sample formed from atomic and molecular nitrogen. Much of the stability of Im-He solids is attributed to their very large surface area to volume ratio and their permeation by super fluid helium. Heat resulting from a chance meeting and recombination of free radicals is quickly dissipated by the super fluid helium instead of thermally promoting the diffusion of other nearby free radicals.

Bernard, E. P.↗

How cells (might) sense microgravity

This article is a summary of a lecture presented at an ESA/NASA Workshop on Cell and Molecular Biology Research in Space that convened in Leuven, Belgium, in June 1998. Recent studies are reviewed which suggest that cells may sense mechanical stresses, including those due to gravity, through changes in the balance of forces that are transmitted across transmembrane adhesion receptors that link the cytoskeleton to the extracellular matrix and to other cells (e.g., integrins, cadherins, selectins). The mechanism by which these mechanical signals are transduced and converted into a biochemical response appears to be based, in part, on the finding that living cells use a tension-dependent form of architecture, known as tensegrity, to organize and stabilize their cytoskeleton. Because of tensegrity, the cellular response to stress differs depending on the level of pre-stress (pre-existing tension) in the cytoskeleton and it involves all three cytoskeletal filament systems as well as nuclear scaffolds. Recent studies confirm that alterations in the cellular force balance can influence intracellular biochemistry within focal adhesion complexes that form at the site of integrin binding as well as gene expression in the nucleus. These results suggest that gravity sensation may not result from direct activation of any single gravioreceptor molecule. Instead, gravitational forces may be experienced by individual cells in the living organism as a result of stress-dependent changes in cell, tissue, or organ structure that, in turn, alter extracellular matrix mechanics, cell shape, cytoskeletal organization, or internal pre-stress in the cell-tissue matrix.--Ingber, D. How cells (might) sense microgravity.

NASA Discipline Cell Biology↗

Microencapsulated Bioactive Agents and Method of Making

Microcapsules prepared by encapsulating an aqueous solution of a protein, drug or other bioactive substance inside a semi-permeable membrane by are disclosed. The microcapsules are formed by interfacial coacervation under conditions where the shear forces are limited to 0- 100 dynes per sq cm at the interface. By placing the microcapsules in a high osmotic watering solution, the protein solution is gradually made saturated and then supersaturated, and the controlled nucleation and crystallization of the protein is achieved. The crystal-filled microcapsules prepared by this method can be conveniently harvested and stored while keeping the encapsulated crystals in essentially pristine condition due to the rugged, protective membrane. Because the membrane components themselves are x-ray transparent, large crystal-containing microcapsules can be individually selected. mounted in x-ray capillary tubes and subjected to high energy x-ray diffraction studies to determine the 3-D structure of the protein molecules. Certain embodiments of the microcapsules of the invention have composite polymeric outer membranes which are somewhat elastic, water insoluble, permeable only to water, salts, and low molecular weight molecules and are structurally stable in fluid shear forces typically encountered in the human vascular system.

Dennis R Morrison↗

Method for determining the three-dimensional structure of a protein

Microcapsules prepared by encapsulating an aqueous solution of a protein, drug or other bioactive substance inside a semi-permeable membrane by are disclosed. The microcapsules are formed by interfacial coacervation under conditions where the shear forces are limited to 0-100 dynes/cm.sup.2 at the interface. By placing the microcapsules in a high osmotic dewatering solution, the protein solution is gradually made saturated and then supersaturated, and the controlled nucleation and crystallization of the protein is achieved. The crystal-filled microcapsules prepared by this method can be conveniently harvested and stored while keeping the encapsulated crystals in essentially pristine condition due to the rugged, protective membrane. Because the membrane components themselves are x-ray transparent, large crystal-containing microcapsules can be individually selected, mounted in x-ray capillary tubes and subjected to high energy x-ray diffraction studies to determine the 3-D structure of the protein molecules. Certain embodiments of the microcapsules of the invention have composite polymeric outer membranes which are somewhat elastic, water insoluble, permeable only to water, salts, and low molecular weight molecules and are structurally stable in fluid shear forces typically encountered in the human vascular system.

Morrison, Dennis R.↗

Making Macroscopic Assemblies of Aligned Carbon Nanotubes

A method of aligning and assembling single-wall carbon nanotubes (SWNTs) to fabricate macroscopic structures has been invented. The method entails suspending SWNTs in a fluid, orienting the SWNTs by use of a magnetic and/or electric field, and then removing the aligned SWNTs from suspension in such a way as to assemble them while maintaining the alignment. SWNTs are essentially tubular extensions of fullerene molecules. It is desirable to assemble aligned SWNTs into macroscopic structures because the common alignment of the SWNTs in such a structure makes it possible to exploit, on a macroscopic scale, the unique mechanical, chemical, and electrical properties that individual oriented SWNTs exhibit at the molecular level. Because of their small size and high electrical conductivity, carbon nanotubes, and especially SWNTs, are useful for making electrical connectors in integrated circuits. Carbon nanotubes can be used as antennas at optical frequencies, and as probes in scanning tunneling microscopes, atomic-force microscopes, and the like. Carbon nanotubes can be used with or instead of carbon black in tires. Carbon nanotubes are useful as supports for catalysts. Ropes of SWNTs are metallic and, as such, are potentially useful in some applications in which electrical conductors are needed - for example, they could be used as additives in formulating electrically conductive paints. Finally, macroscopic assemblies of aligned SWNTs can serve as templates for the growth of more and larger structures of the same type. The great variety of tubular fullerene molecules and of the structures that could be formed by assembling them in various ways precludes a complete description of the present method within the limits of this article. It must suffice to present a typical example of the use of one of many possible variants of the method to form a membrane comprising SWNTs aligned substantially parallel to each other in the membrane plane. The apparatus used in this variant of the method (see figure) includes a reservoir containing SWNTs dispersed in a suspending agent (for example, dimethylformamide) and a reservoir containing a suitable solvent (for example, water mixed with a surfactant). By use of either pressurized gas supplied from upstream or suction from downstream, the suspension of SWNTs and the solvent are forced to mix and flow into a tank. A filter inside the tank contains pores small enough to prevent the passage of most SWNTs, but large enough to allow the passage of molecules of the solvent and suspending agent. The filter is oriented perpendicular to the flow path. A magnetic field parallel to the plane of the filter is applied. The success of the method is based on the tendency of SWNTs to become aligned with their longitudinal axes parallel to an applied magnetic field. The alignment energy of an SWNT increases with the length of the SWNT and the magnetic-field strength. In order to obtain an acceptably small degree of statistical deviation of SWNTs of a given length from alignment with a magnetic field, one must make the field strong enough so that the thermal energy associated with rotation of an SWNT away from alignment is less than the alignment energy.

Smalley, Richard E.↗

A definition of the domains Archaea, Bacteria and Eucarya in terms of small subunit ribosomal RNA characteristics

The number of small subunit rRNA sequences is now great enough that the three domains Archaea, Bacteria and Eucarya (Woese et al., 1990) can be reliably defined in terms of their sequence "signatures". Approximately 50 homologous positions (or nucleotide pairs) in the small subunit rRNA characterize and distinguish among the three. In addition, the three can be recognized by a variety of nonhomologous rRNA characters, either individual positions and/or higher-order structural features. The Crenarchaeota and the Euryarchaeota, the two archaeal kingdoms, can also be defined and distinguished by their characteristic compositions at approximately fifteen positions in the small subunit rRNA molecule.

NASA Program Exobiology↗