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At least 37 records · Page 2

The effects of ultraviolet light on the degradation of organic compounds - A possible explanation for the absence of organic matter on Mars

The analysis of the top layer of the Martian regolith at the two Viking landing sites did not reveal any indigenous organic compounds. However, the existence of such compounds at deeper layers cannot be ruled out. Cosmochemical considerations indicate various potential sources for organic matter on Mars, such as comets and meteorites. The study tested the stability of a sample of the Murchison meteorite and various organic substances which have been detected in carbonaceous chondrites, such as glycine, adenine and naphthalene, to the action of ultraviolet light. The compounds were adsorbed on powdered quartz and on California desert soil and were irradiated in the presence or absence of oxygen. The organic content, before and after irradiation, was measured by carbon elementary analysis, UV-absorption, amino acid analysis or pyrolysis-gas chromatography-mass spectrometry. In the absence of oxygen, adenine and glycine appear to be stable over the given part of irradiation. A definite degradation was noticed in the case of naphtalene and the Murchison meteorite. In the presence of oxygen in amounts comparable to those on Mars all compounds were degraded. The degree of degradation was influenced by the irradiation time, temperature and oxygen content.

Oro, J.

The fate or organic matter during planetary accretion - Preliminary studies of the organic chemistry of experimentally shocked Murchison meteorite

The fate of organic matter in carbonaceous meteorites during hypervelocity (1-2 km/sec) impacts is investigated using results of experiments in which three samples of the Murchison (CM2) carbonaceous chondrite were shocked to 19, 20, and 36 GPa and analyzed by highly sensitive thermal-desorption photoionization mass spectrometry (SALI). The thermal-desorptive SALI mass spectra of unshocked CM2 material revealed presence of indigenous aliphatic, aromatic, sulfur, and organosulfur compounds, and samples shocked to about 20 GPa showed little or no loss of organic matter. On the other hand, samples shocked to 36 GPa exhibited about 70 percent loss of organic material and a lower alkene/alkane ratio than did the starting material. The results suggest that it is unlikely that the indigenous organic matter in carbonaceous chondritelike planetesimals could have survived the impact on the earth in the later stages of earth's accretion.

Tingle, Tracy N.

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Allamandola, Lou J.

The strength of a calcified tissue depends in part on the molecular structure and organization of its constituent mineral crystals in their organic matrix

High-voltage electron-microscopic tomographic (3D) studies of the ultrastructural interaction between mineral and organic matrix in a variety of calcified tissues reveal different crystal structural and organizational features in association with their respective organic matrices. In brittle or weak pathologic or ectopic calcifications, including examples of osteogenesis imperfecta, calciphylaxis, calcergy, and dermatomyositis, hydroxyapatite crystals occur in various sizes and shapes and are oriented and aligned with respect to collagen in a manner which is distinct from that found in normal calcified tissues. A model of collagen-mineral interaction is proposed which may account for the observed crystal structures and organization. The results indicate that the ultimate strength, support, and other mechanical properties provided by a calcified tissue are dependent in part upon the molecular structure and arrangement of its constituent mineral crystals within their organic matrix.

Non-NASA Center

Formation of Complex Organic Molecules (COMs) from Polycyclic Aromatic Hydrocarbons (PAHs): Top-Down Synthesis of organics in planetary systems

Complex, organic molecules have been found in many solar system objects (i.e., dust, comets, meteorites, moons, etc.); however, their origins and formation remain a mystery. Two chemical evolutionary pathways have been proposed to explain the organic inventory of our solar system. The first pathway, the top-down approach, suggests an interstellar (ISM) heritage whereby the organic material found in the solar system formed from the erosion and functionalization of large pre-solar carbon-bearing species (mainly large Polycyclic Aromatic Hydrocarbons or PAHs). The second pathway suggests that the origin of the Solar System prebiotic matter is the result of bottom-up synthesis from small reactive molecules (e.g., formaldehyde – H2CO, acetylene – H2C2, and similar species). In this second scenario, it is supposed that very few, if any, pre-solar large molecules could have survived due to the proto - solar nebula radiation environment. Polycyclic Aromatic Hydrocarbons or PAHs comprise ~20-30% of all available carbon in the Universe. The PAHs found within our Solar System tend to be smaller than those suspected to be in the ISM, comprised of only 14 to 18 carbon atoms in size whereas ISM PAHs are typically 50 to 100 carbon atoms. The disparity in PAH sizes between the ISM and Solar System environments is not understood, but may point to conversion of large ISM PAHs to Solar System Organics. This presentation details recent experiments regarding the stability of large PAHs to the various types of radiation found within a proto - solar disk and the production of smaller, complex, molecules from the degradation of the larger PAHs. The presentation will highlight differences and similarities in degradation products based on experimental conditions (e.g., radiation type) and discuss future work with a new experimental setup known as ICEE (Institute for Carbon Evolution Experiments).

molecukes

Photooxidation of Organic Sulfide Enhanced by Heavy Atom Effect in Porphyrin Metal–Organic Frameworks with a Sea Topology

The photoactivity of three porphyrin-based metal-organic frameworks (PMOFs) incorporating Al, Ga, and In nodes was systematically evaluated using the photooxidation of an organic sulfide (2-chloroethyl ethyl sulfide, or CEES; a mustard gas simulant). Faster photodegradation of CEES was observed for PMOFs with heavier metal nodes, placing In-PMOF as the most efficient photocatalyst in the series. Guided by this insight, we developed CSLA-10, a MOF integrating In nodes and Sn-doped porphyrin linker to synergistically amplify heavy-atom effects at both the nodes and ligand levels. CSLA-10 exhibited the fastest reported CEES photooxidation to date, achieving a half-life of 38 s in methanol under blue LED irradiation. When grafted onto textiles, CSLA-10 enabled solvent-free CEES degradation in air/O 2 with a half-life of 2.7 min and complete conversion within 7 min, representing the most rapid full degradation reported under solvent-free conditions. Furthermore, this work establishes a dual heavy-atom strategy for enhancing intersystem crossing and singlet oxygen generation in porphyrin MOFs, providing a rational design principle for next-generation photocatalysts for the degradation of toxic organic sulfides.

Metal-organic frameworks

In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds.

ExoMars2018

Laboratory Calibration Studies in Support of ORGANICS on the International Space Station: Evolution of Organic Matter in Space

This paper describes the scientific overview and current status of ORGANICS an exposure experiment performed on the International Space Station (ISS) to study the evolution of organic matter in space (PI: P. Ehrenfreund), with supporting laboratory experiments performed at NASA Ames. ORGANICS investigates the chemical evolution of samples submitted to long-duration exposure to space environment in near-Earth orbit. This experiment will provide information on the nature, evolution, and survival of carbon species in the interstellar medium (ISM) and in solar system targets.

Ruiterkamp, R.

Analysis of the Organic Matter in Interplanetary Dust Particles: Clues to the Organic Matter in Comets, Asteroids, and Interstellar Grains

Reflection spectroscopy suggests the C- , P-, and D-types of asteroids contain abundant carbon, but these Vis-nearIR spectra are featureless, providing no information on the type(s) of carbonaceous matter. Infrared spectroscopy demonstrates that organic carbon is a significant component in comets and as grains or grain coatings in the interstellar medium. Most of the interplanetary dust particles (IDPs) recovered from the Earth s stratosphere are believed to be fragments from asteroids or comets, thus characterization of the carbon in IDPs provides the opportunity to determine the type(s) and abundance of organic matter in asteroids and comets. Some IDPs exhibit isotopic excesses of D and N-15, indicating the presence of interstellar material. The characterization of the carbon in these IDPs, and particularly any carbon spatially associated with the isotopic anomalies, provides the opportunity to characterize interstellar organic matter.

Flynn, G. J.

Racemization and the origin of optically active organic compounds in living organisms

The organic compounds synthesized in prebiotic experiments are racemic mixtures. A number of proposals have been offered to explain how asymmetric organic compounds formed on the Earth before life arose, with the influence of chiral weak nuclear interactions being the most frequent proposal. This and other proposed asymmetric syntheses give only sight enantiomeric excess and any slight excess will be degraded by racemization. This applies particularly to amino acids where half-lives of 10(5)-10(6) years are to be expected at temperatures characteristic of the Earth's surface. Since the generation of chiral molecules could not have been a significant process under geological conditions, the origins of this asymmetry must have occurred at the time of the origin of life or shortly thereafter. It is possible that the compounds in the first living organisms were prochiral rather than chiral; this is unlikely for amino acids, but it is possible for the monomers of RNA-like molecules.

NASA Discipline Exobiology

Organic Globules with Anomalous Nitrogen Isotopic Compositions in the Tagish Lake Meteorite: Products of Primitive Organic Reactions

Interstellar grains in molecular clouds consist primarily of silicate minerals, organic material, and ices. These interstellar materials are heated and partially evaporated during the birth of the protosolar nebula, and the remaining core-mantle grains grow into large aggregates by collision and subsequent sticking to become planetesimals. The chemical diversity of meteoritic material such as chondrules, Ca-Al rich inclusions and amoeboid-olivine aggregates reflects the material distribution in the late stage of the disk evolution before planetesimal formation began. Organic matter in carbonaceous chondrites should also be considered as a sensitive probe for the extent and timing of high temperature processes in the solar nebula. Current models suggest that many of the organic molecules found in the hydrated carbonaceous chondrite meteorites were synthesized by aqueous processing of a suite of precursor molecules, some of which were interstellar with significant isotopic anomalies, such as excesses of deuterium (D), and 15N.

Nakamura, K.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Socki, Richard A.

Charge Separation at Organic Interfaces with Near-Zero Energy Offset: A Step toward Designing Inorganic-like Organic Semiconductors

For organic semiconductors, it is often presumed that an energy level offset at the donor–acceptor (D-A) interface is required to provide the driving force for charge separation (CS). This energy level offset unavoidably leads to a voltage loss in organic photovoltaics. In this work, by using zinc phthalocyanine (ZnPc) and fluorinated zinc phthalocyanine (F 4 ZnPc) as a model D/A interface, we found that spontaneous CS, with an enthalpy increase of ∼0.3–0.4 eV, can occur even with an interfacial energy offset as small as ∼0.1 eV. This enthalpy-increase CS process is driven by entropy. The entropic driving force can be enhanced by two factors: (1) a point-like spatial contact between the delocalized electron and hole wave function in the charge transfer exciton; (2) a small band bending near the interface originating from long-range electrostatic interaction. Our work demonstrates that effective CS can occur at interfaces with a near-zero energy level offset, which means that the energy loss at the D/A interface can be avoided.

36 MATERIALS SCIENCE

Probing the External Surface Chemistry of Imine-Based Covalent Organic Frameworks Using Reactive Organic Dyes

The external surfaces of covalent organic frameworks (COFs) are presumably composed of free terminal functional groups from their constituent monomers. These terminal groups have been utilized to immobilize molecules onto COF surfaces for a variety of studies and potential applications. Despite the utility of these latent functional groups for COF functionalization and composite formation, the surface chemistry of the COFs has not been quantitatively investigated and is not well understood. In this work, fluorescent organic dyes bearing reactive amine and aldehyde functional groups are used to probe the surface chemistry of representative two-dimensional (2D) imine-based COFs. Furthermore, systematic dye binding and displacement experiments provide new insights into the characteristics of COF surfaces and the reactivity of different molecules with the surface groups on the COF crystallites.

COFs

Local order, disorder, and everything in between: using 91 Zr solid-state NMR spectroscopy to probe zirconium-based metal–organic frameworks

Characterization of metal centers in metal–organic frameworks (MOFs) is critical for rational design and further understanding of structure–property relationships. The short-range structure about Zr atoms is challenging to properly elucidate in many Zr MOFs, particularly when local disorder is present. Static 91 Zr solid-state NMR spectra of the seven zirconium MOFs UiO-66, UiO-66-NH 2 , UiO-67, MOF-801, MOF-808, DUT-68 and DUT-69 have been acquired at high magnetic fields of 35.2 T and 19.6 T, yielding valuable information on the local structure, site symmetry and order about Zr. 91 Zr NMR is very sensitive to differences in MOF short-range structure caused by guest molecules, linker substitution and post-synthetic treatment. Complementary density functional theory (DFT) calculations assist in the interpretation and assignment of 91 Zr solid-state NMR spectra, lend insight into structural origins of 91 Zr NMR parameters and enable determination of local Zr coordination environments. This approach can be extended to many other materials containing zirconium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

A butterfly-shaped acceptor with rigid skeleton and unique assembly enables both efficient organic photovoltaics and high-speed organic photodetectors

ABSTRACT It remains challenging to design efficient bifunctional semiconductor materials in organic photovoltaic and photodetector devices. Here, we report a butterfly-shaped molecule, named WD-6, which exhibits low energy disorder and small reorganization energy due to its enhanced molecular rigidity and unique assembly with strong intermolecular interaction. The binary photovoltaic device based on PM6:WD-6 achieved an efficiency of 18.41%. Notably, an efficiency of 19.42% was achieved for the ternary device based on PM6:BTP-eC9:WD-6. Moreover, the photodetection device based on WD-6 demonstrated an ultrafast response speed (205 ns response time at λ of 820 nm) and a high cutoff frequency of −3 dB (2.45 MHz), surpassing the values of most commercial Si photodiodes. Based on these findings, we showcased an application of the WD-6-based photodetection device in high-speed optical communication. These results offer valuable insights into the design of organic semiconductor materials capable of simultaneously exhibiting high photovoltaic and photodetective performance.

Science & Technology - Other Topics