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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1971

The role of ionizing radiation in primordial organic synthesis.

Attempt to reveal how ionizing radiation may have been effective in producing the molecules necessary for life. In examining the sequence of events leading to the appearance of the first organisms the problem is considered in two parts: the formation of the small molecules such as amino acids, purines, pyrimidines, and carbohydrates; and the condensation of these molecules to give rise to polypeptides and polynucleotides. It is concluded that in the accumulation of organic compounds on the early earth ionizing radiation was not only a substantial part of the available energy, but was also an effective form of energy.

Ponnamperuma, C.↗
NASA NTRS2000

Identification of Gas Phase PAHs in Absorption Towards Protostellar Sources

The infrared emission bands (also known as the UIR bands.) have recently been observed in absorption at 3.25 micrometers in the ices surrounding a few proto-stellar objects at 11.2 micrometers in MonR2, and at 6.2 micrometers towards two sources near the galactic center. The UIR bands have been observed in emission for many years, but identifying these bands has proven to be both difficult and contentious as no one has yet found a single material that provides a good match to the features. However, most investigators agree that some form of carbon-based material with aromatic bonds is the most likely candidate, and many arguments favor free molecules (polycyclic aromatic hydrocarbons, PAHs) as the carriers of at least the narrow emission bands. Since the emission arises not from a single molecule but from a family of molecules, identifying which PAHs are contributing to the infrared emission bands is difficult. The identification is further complicated by the fact that the emission at short wavelengths is dominated by small molecules while at long wavelengths it is dominated by large molecules. Thus, for example, the emission at 3.3 micrometers is from a different mix of molecules than those which produce the 11.2 micrometer band. To complicate matters further, the molecular mix includes both neutral and ionic species. In absorption, the same mixture of molecules contributes at all wavelengths and the molecules should be neutral, potentially simplifying comparisons with lab data. Also, absorption strengths measured in the lab are directly applicable to interstellar absorption bands without the need to model an emission spectrum of an unknown mixture of ionized and neutral PAHs. In this paper we show that a mixture of argon matrix isolated PAH molecules can reproduce the 3.25 micrometers absorption band seen in the ISO SWS spectra of four embedded Infrared sources, S140 IRS1, AFGL 2591, Elias 29, and AFGL 989. In section 2 we describe the ISO SWS data analysis and in section 3 discuss the results.

Bregman, Jesse D.↗
NASA NTRS2015

Nanopore Device for Reversible Ion and Molecule Sensing or Migration

Disclosed are methods and devices for detection of ion migration and binding, utilizing a nanopipette adapted for use in an electrochemical sensing circuit. The nanopipette may be functionalized on its interior bore with metal chelators for binding and sensing metal ions or other specific binding molecules such as boronic acid for binding and sensing glucose. Such a functionalized nanopipette is comprised in an electrical sensor that detects when the nanopipette selectively and reversibly binds ions or small molecules. Also disclosed is a nanoreactor, comprising a nanopipette, for controlling precipitation in aqueous solutions by voltage-directed ion migration, wherein ions may be directed out of the interior bore by a repulsing charge in the bore.

Pourmand, Nader↗
NASA NTRS1978

Molecular rotation and reorientation - Microscopic and hydrodynamic contributions

The relative roles of microscopic and hydrodynamic contributions to molecular rotation and reorientation are examined within the framework of the microscopic boundary layer theory recently proposed by the authors. The theory is applied to rough spheres, for which computer simulation data are available and to experimental results on spherical top molecules. Attention is focused on rotational diffusion constants, the kappa parameter introduced by Kivelson et al., and orientational relaxation times. It is shown that, while collective effects are present and often nonnegligible, the motion of small molecules is dominated by its microscopic aspects. Experimental trends which can incorrectly suggest dominance by hydrodynamic contributions are discussed in some detail. Finally, the transition to the regime where collective effects are dominant is considered.

Hynes, J. T.↗
NASA NTRS1989

On the driving force of PAH production

The kinetic factors affecting the production of polycyclic aromatic hydrocarbons (PAH) in high-temperature pyrolysis and combustion environments are analyzed. A lumped kinetic model representing polymerization-type growth by one irreversible step and two reversible steps is considered. It is shown that at high temperatures, PAH growth is controlled by the superequilibrium of hydrogen atoms; at low temperatures and low H2 concentrations, the PAH growth rate is proportional to the rate of the H-abstraction of a hydrogen atom from aromatic molecules; while at low temperatures and high H2 concentrations, it is controlled by the thermodynamics of the H-abstraction and the kinetics of acetylene addition to aromatic radicals. The presence of oxygen mainly affects the small-molecule reactions during the induction period.

Frenklach, Michael↗
NASA NTRS1989

Matrix isolation as a tool for studying interstellar chemical reactions

Since the identification of the OH radical as an interstellar species, over 50 molecular species were identified as interstellar denizens. While identification of new species appears straightforward, an explanation for their mechanisms of formation is not. Most astronomers concede that large bodies like interstellar dust grains are necessary for adsorption of molecules and their energies of reactions, but many of the mechanistic steps are unknown and speculative. It is proposed that data from matrix isolation experiments involving the reactions of refractory materials (especially C, Si, and Fe atoms and clusters) with small molecules (mainly H2, H2O, CO, CO2) are particularly applicable to explaining mechanistic details of likely interstellar chemical reactions. In many cases, matrix isolation techniques are the sole method of studying such reactions; also in many cases, complexations and bond rearrangements yield molecules never before observed. The study of these reactions thus provides a logical basis for the mechanisms of interstellar reactions. A list of reactions is presented that would simulate interstellar chemical reactions. These reactions were studied using FTIR-matrix isolation techniques.

Ball, David W.↗
NASA NTRS1993

Internal vibrations of a molecule consisting of rigid segments. I - Non-interacting internal vibrations

For molecular crystals, a procedure is proposed for interpreting experimentally determined atomic mean square anisotropic displacement parameters (ADPs) in terms of the overall molecular vibration together with internal vibrations with the assumption that the molecule consists of a set of linked rigid segments. The internal librations (molecular torsional or bending modes) are described using the variable internal coordinates of the segmented body. With this procedure, the experimental ADPs obtained from crystal structure determinations involving six small molecules (sym-trinitrobenzene, adenosine, tetra-cyanoquinodimethane, benzamide, alpha-cyanoacetic acid hydrazide and N-acetyl-L-tryptophan methylamide) have been analyzed. As a consequence, vibrational corrections to the bond lengths and angles of the molecule are calculated as well as the frequencies and force constants for each internal torsional or bending vibration.

He, X. M.↗
NASA NTRS1993

An RNA motif that binds ATP

RNAs that contain specific high-affinity binding sites for small molecule ligands immobilized on a solid support are present at a frequency of roughly one in 10(10)-10(11) in pools of random sequence RNA molecules. Here we describe a new in vitro selection procedure designed to ensure the isolation of RNAs that bind the ligand of interest in solution as well as on a solid support. We have used this method to isolate a remarkably small RNA motif that binds ATP, a substrate in numerous biological reactions and the universal biological high-energy intermediate. The selected ATP-binding RNAs contain a consensus sequence, embedded in a common secondary structure. The binding properties of ATP analogues and modified RNAs show that the binding interaction is characterized by a large number of close contacts between the ATP and RNA, and by a change in the conformation of the RNA.

NASA Discipline Exobiology↗
NASA NTRS2015

The Formation of N- and O-Heterocycles from the Irradiation of Benzene and Naphthalene in H2O/NH3- Containing Ices

Aromatic hydrocarbons are an important class of molecules for both astrochemistry and astrobiology (Fig. 1). Within this class of molecules, polycyclic aromatic hydrocarbons (PAHs) are known to be ubiquitous in many astrophysical environments, and are likely present in interstellar clouds and protostellar disks. In dense clouds, PAHs are expected to condense onto grains as part of mixed molecular ice mantles dominated by small molecules like H2O,CH3OH, NH3, CO, and CO2. These ices are exposed to ionizing radiation in the form of cosmic rays and ambient high-energy X-ray and UV photons.

Ice Irradiation↗
NASA NTRS1995

Determination of Quantum Chemistry Based Force Fields for Molecular Dynamics Simulations of Aromatic Polymers

Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).

Jaffe, Richard↗
NASA NTRS2012

Protein Innovations Advance Drug Treatments, Skin Care

Dan Carter carefully layered the sheets of tracing paper on the light box. On each sheet were renderings of the atomic components of an essential human protein, one whose structure had long been a mystery. With each layer Carter laid down, a never-before-seen image became clearer. Carter joined NASA s Marshall Space Flight Center in 1985 and began exploring processes of protein crystal growth in space. By bouncing intense X-rays off the crystals, researchers can determine the electron densities around the thousands of atoms forming the protein molecules, unveiling their atomic structures. Cultivating crystals of sufficient quality on Earth was problematic; the microgravity conditions of space were far more accommodating. At the time, only a few hundred protein structures had been mapped, and the methods were time consuming and tedious. Carter hoped his work would help reveal the structure of human serum albumin, a major protein in the human circulatory system responsible for ferrying numerous small molecules in the blood. More was at stake than scientific curiosity. Albumin has a high affinity for most of the world s pharmaceuticals, Carter explains, and its interaction with drugs can change their safety and efficacy. When a medication enters the bloodstream a cancer chemotherapy drug, for example a majority of it can bind with albumin, leaving only a small percentage active for treatment. How a drug interacts with albumin can influence considerations like the necessary effective dosage, playing a significant role in the design and application of therapeutic measures. In spite of numerous difficulties, including having no access to microgravity following the 1986 Space Shuttle Challenger disaster, the image Carter had hoped to see was finally clarifying. In 1988, his lab had acquired specialized X-ray and detection equipment a tipping point. Carter and his colleagues began to piece together albumin s portrait, the formation of its electron densities coalescing on the sheets of tracing paper he arranged on the light box. While space-grown crystals were ultimately not involved in the achievement, a year later, Carter says, we were on the cover of Science magazine, having determined the atomic structure of albumin.

Source record↗
NASA NTRS2003

Crystallization Physics in Biomacromolecular Systems

The crystals are built of molecules of protein, nucleic acid and their complexes, like viruses, approx. 5x10(exp 3)+ 3x10(exp 6) Da in weight and 2 + 20 nm in effective diameter. This size strongly exceeds action range of molecular forces and makes a big difference with inorganic crystals. Intermolecular contacts form patches on the biomacromolecular surface. Each patch may occupy only a small percent of the whole surface and vary from polymorph to polymorph of the same protein. Thus, under different conditions (pH, solution chemistry, temperature, any area on the macromolecular surface may form a contact. The crystal Young moduli, E approx. equals 0.1 + 0.5 GPa are more than 10 times lower than that of inorganics and the biomolecules themselves. Water within biocrystals (30-70%) is unable to flow unless typical deformation time is longer than approx. 10(exp -5)s. This explains the discrepancy between light scattering and static measurements of E. Nucleation and Growth requires typically concentrations exceeding the equilibrium ones up to 100 times - because of the new size scale results in 10 - 10(exp 3) times lower kinetic coefficients than that needed for inorganic solution growth. All phenomena observed in the latter occur with protein crystallization and are even better studied by AFM. Crystals are typically facetted. Among unexpected findings of general significance are - net molecular exchange flux at kinks is much lower than that expected from supersaturation, steps with low (< approx. 10(exp -2)) kink density at steps follow Gibbs-Thomson law only at very low supersaturations, step segment growth rate may be independent of step energy. Crystal perfection is a must of biocrystallization to achieve the major goal to find 3-D atomic structure of biomacromolecules by x-ray diffraction. Poor diffraction resolution (> 3Angstrom) makes crystallization a bottleneck for structural biology. All defects typical of small molecule crystals are found in biocrystals, but the defects responsible for poor resolution are not identified. Conformational changes are one of them. Biocrystallization in microgravity reportedly results in 20% cases of better crystals. The mechanism of how lack of convection can do this is still not clear. Lower supersaturation, self-purification &om preferentially trapped homologous impurities and step bunching are viable hypotheses.

Chernov, A. A.↗
NASA NTRSDate not supplied

Bioreactor Development for CO2-Based In Situ Resource Utilization Manufacturing

Sustainable long-duration manned missions on both the Moon and Mars will require in situ resource utilization (ISRU). Carbon dioxide (CO2) has great potential as a harvestable resource, making up 95% of the atmosphere on Mars and being produced as respiratory waste in spacecraft and future planetary habitats. Through ISRU, biomanufacturing has the capability to produce a near limitless array of products from local space resources, which include pharmaceuticals, bioplastics, chemical feedstocks, and industrial enzymes. Here, a CO2-based ISRU recombinant protein bioreactor and associated biomanufacturing organisms were designed to produce a highly stable carbonic anhydrase (CA). Initial work characterized candidate organisms for growth on acetate and formic acid, carbon substrates that can be synthesized via electrochemical conversion of CO2. To improve growth on the CO2 producing substrate formic acid and for direct integration of ISRU CO2, a synthetic Calvin-Benson-Bassam cycle was designed for use in Cyberlindnera jadinii and Escherichia coli. Genetic modifications in E. coli will be facilitated by a tailored CRISPR/Cas9 and λ red recombineering two-vector system. For expression of CA, a blue light regulated T7 promoter was employed for dynamic and small molecule free induction. Efficient bioproduction through a fed-batch exponential feeding strategy was determined via mass balance calculations from ISRU substrates to biomass and CA yield. Flux balance analysis was used to model ISRU substrate metabolism and metabolic pathway engineering in candidate organisms under cultivation strategy conditions for both metabolism reconstruction and pathway design optimization. Finally, a small-scale, disposable bag bioreactor concept for use in the NASA Bioculture System infrastructure was designed to enable CO2-based CA production in reduced-gravity environments.

Biomanufacturing, Pathway Engineering, Flux Balanc↗
NASA NTRSDate not supplied

Bioreactor Development for CO2-Based In Situ Resource Utilization Manufacturing

Sustainable long-duration manned missions on both the Moon and Mars will require in situ resource utilization (ISRU). Carbon dioxide (CO2) has great potential as a harvestable resource, making up 95% of the atmosphere on Mars and being produced as respiratory waste in spacecraft and future planetary habitats. Through ISRU, biomanufacturing has the capability to produce a near limitless array of products from local space resources. Here, a CO2-based ISRU recombinant protein producing bioreactor and associated biomanufacturing organisms were designed to produce a highly stable carbonic anhydrase (CA). Candidate organisms were selected by growth characterization on acetate and formic acid, carbon substrates that are synthesized via electrochemical conversion of CO2. To improve growth on the CO2 producing substrate formic acid and for direct integration of ISRU CO2, a synthetic Calvin-Benson-Bassam cycle was designed for use in Escherichia coli. Multiplex genetic modification in E. coli was facilitated by a tailored CRISPR/Cas9 and λ red recombineering two-vector system. For expression of CA, a blue light regulated T7 promoter was employed for dynamic and small molecule free induction. Efficient bioproduction through a fed-batch exponential feeding strategy was determined via mass balance analysis from ISRU substrates to biomass and CA yield. Flux balance analysis was used to model ISRU substrate metabolism and metabolic pathway engineering in candidate organisms under cultivation strategy conditions for both metabolism reconstruction and pathway design optimization. Finally, a small-scale, disposable bag bioreactor for use in the NASA Bioculture System infrastructure was designed to enable CO2-based CA biomanufacturing in reduced-gravity environments.

biomanufacturing↗
NASA NTRS1982

Determination of accurate dissociation limits and interatomic interactions at large internuclear distances

This paper illustrates (using the molecules LiH, Li2 and Na2) how laser-induced fluorescence can be used to greatly expand the range of observed vibrational levels in ground electronic states. This expanded vibrational range leads to the determination of virtually the full well of the potential energy curve. This also leads to improved determination of the dissociation limit and serves as a severe test for highly accurate ab initio calculations now available for many small molecules.

Stwalley, W. C.↗
NASA NTRS1993

SALI chemical analysis of provided samples

SRI has completed the chemical analysis of all the samples supplied by NASA. The final batch of four samples consisted of: one inch diameter MgF2 mirror, control 1200-ID-FL3; one inch diameter neat resin, PMR-15, AO171-IV-55, half exposed and half unexposed; one inch diameter chromic acid anodized, EOIM-3 120-47 aluminum disc; and AO-exposed and unexposed samples of fullerene extract material in powdered form, pressed into In foil for analysis. Chemical analyses of the surfaces were performed by the surface analysis by laser ionization (SALI) method. The analyses emphasize surface contamination or general organic composition. SALI uses nonselective photoionization of sputtered or desorbed atoms and molecules above but close (approximately one mm) to the surface, followed by time-of-flight (TOF) mass spectrometry. In these studies, we used laser-induced desorption by 5-ns pulse-width 355-nm light (10-100 mJ/sq cm) and single-photon ionization (SPI) by coherent 118-nm radiation (at approximately 5 x 10(exp 5) W/sq cm). SPI was chosen primarily for its ability to obtain molecular information, whereas multiphoton ionization (not used in the present studies) is intended primarily for elemental and small molecule information. In addition to these four samples, the Au mirror (EOIM-3 200-11, sample four) was depth profiled again. Argon ion sputtering was used together with photoionization with intense 355-nm radiation (35-ps pulsewidths). Depth profiles are similar to those reported earlier, showing reproducibility. No chromium was found in the sample above noise level; its presence could at most be at the trace level. Somewhat more Ni appears to be present in the Au layer in the unexposed side, indicating thermal diffusion without chemical enhancement. The result of the presence of oxygen is apparently to tie-up/draw out the Ni as an oxide at the surface. The exposed region has a brownish tint appearance to the naked eye.

Becker, Christopher H.↗
NASA NTRS2010

Distinct Distribution of Purines in CM and CR Carbonaceous Chondrites

Carbonaceous meteorites contain a diverse suite of organic molecules and delivered pre biotic organic compounds, including purines and pyrimidines, to the early Earth (and other planetary bodies), seeding it with the ingredients likely required for the first genetic material. We have investigated the distribution of nucleobases in six different CM and CR type carbonaceous chondrites, including fivc Antarctic meteorites never before analyzed for nucleobases. We employed a traditional formic acid extraction protocol and a recently developed solid phase extraction method to isolate nucleobases. We analyzed these extracts by high performance liquid chromatography with UV absorbance detection and tandem mass spectrometry (HPLC-UV -MS/MS) targeting the five canonical RNAIDNA bases and hypoxanthine and xanthine. We detected parts-per-billion levels of nucleobases in both CM and CR meteorites. The relative abundances of the purines found in Antarctic CM and CR meteorites were clearly distinct from each other suggesting that these compounds are not terrestrial contaminants. One likely source of these purines is formation by HCN oligomerization (with other small molecules) during aqueous alteration inside the meteorite parent body. The detection of the purines adenine (A), guanine (0), hypoxanthine (HX), and xanthine (X) in carbonaceous meteorites indicates that these compounds should have been available on the early Earth prior to the origin of the first genetic material.

Callahan, Michael P.↗
NASA NTRS1990

Analysis of pressure-broadened ozone spectra in the 3 micron region

The Molecular Spectroscopy Lab at NASA-Langley has been involved in a long term effort to carefully characterize the infrared spectra of small molecules of atmospheric interest, including methane, water vapor, ozone, and their isotopic counterparts. High resolution gas phase infrared spectra are obtained using both a tunable diode laser system, and the McMath Fourier transform spectrometer at the Kitt Peak Solar Observatory. Spectra are obtained at various pressures and temperatures for pure gas samples, and for samples containing mixtures of the species of interest in nitrogen, oxygen, or air. From these spectra, using a nonlinear least squares fitting technique, spectral parameters of position, intensity, and half-width were determined for varying laboratory conditions that approximate atmospheric conditions experienced in remote sensing situations. These parameters are of interest in theoretical studies of these species, as well as in allowing more accurate interpretation of remote sensing data. The current work involves the analysis of a series of McMath FTIR spectra of ozone broadened by mixing with air, nitrogen, or oxygen. Each spectrum covers the region from 2396 to 4057/cm. Each vibrational band is analyzed by first diving its region into small intervals containing a few well isolated absorption lines of reasonable intensity. Each of these small intervals is fit by multiple iterations of the nonlinear least square program until residuals are minimized to a reasonable value which corresponds to the noise level of the measured spectrum. Intervals for the 3 nu(sub 3) ozone band in the region from 3000 to 3060 wavenumbers are being examined.

Prochaska, Eleanor S.↗