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At least 487 records · Page 27

Organic Compounds in Carbonaceous Meteorites

Carbonaceous meteorites are relatively enriched in soluble organic compounds. To date, these compounds provide the only record available to study a range of organic chemical processes in the early Solar System chemistry. The Murchison meteorite is the best-characterized carbonaceous meteorite with respect to organic chemistry. The study of its organic compounds has related principally to aqueous meteorite parent body chemistry and compounds of potential importance for the origin of life. Among the classes of organic compounds found in Murchison are amino acids, amides, carboxylic acids, hydroxy acids, sulfonic acids, phosphonic acids, purines and pyrimidines (Table 1). Compounds such as these were quite likely delivered to the early Earth in asteroids and comets. Until now, polyhydroxylated compounds (polyols), including sugars (polyhydroxy aldehydes or ketones), sugar alcohols, sugar acids, etc., had not been identified in Murchison. Ribose and deoxyribose, five-carbon sugars, are central to the role of contemporary nucleic acids, DNA and RNA. Glycerol, a three-carbon sugar alcohol, is a constituent of all known biological membranes. Due to the relative lability of sugars, some researchers have questioned the lifetime of sugars under the presumed conditions on the early Earth and postulated other (more stable) compounds as constituents of the first replicating molecules. The identification of potential sources and/or formation mechanisms of pre-biotic polyols would add to the understanding of what organic compounds were available, and for what length of time, on the ancient Earth.

Cooper, Grorge↗

The Organic Content of the Tagish Lake Meteorite

The Tagish Lake meteorite felt last year on a frozen take in Canada and may provide the most pristine material of its kind. Analyses have now shown this carbonaceous chondrite to contain a suite of soluble organic compounds (approximately 100 parts per million) that includes mono- and dicarboxylic acids, dicarboximides, pyridine carboxylic acids, a sulfonic acid, and both aliphatic and aromatic hydrocarbons. The insoluble carbon exhibits exclusive aromatic character, deuterium enrichment, and fullerenes containing 'planetary' helium and argon. The findings provide insight into an outcome of early solar chemical evolution that differs from any seen so far in meteorites.

Pizzarello, Sandra↗

Novel High Efficient Organic Photovoltaic Materials

In man's mission to the outer space or a remote site, the most abundant, renewable, nonpolluting, and unlimited external energy source is light. Photovoltaic (PV) materials can convert light into electrical power. In order to generate appreciable electrical power in space or on the Earth, it is necessary to collect sunlight from large areas due to the low density of sunlight, and this would be very costly using current commercially available inorganic solar cells. Future organic or polymer based solar cells seemed very attractive due to several reasons. These include lightweight, flexible shape, ultra-fast optoelectronic response time (this also makes organic PV materials attractive for developing ultra-fast photo detectors), tunability of energy band-gaps via molecular design, versatile materials synthesis and device fabrication schemes, and much lower cost on large-scale industrial production. It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks will facilitate the charge separation and migration due to improved electronic ultrastructure and morphology in comparison to current polymer composite photovoltaic system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel donor-bridge-acceptor block copolymer system for potential high-efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene, the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene, and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes the holes, the acceptor block stabilizes the electrons. The bridge block is designed to hinder the electron-hole recombination. Thus, improved charge separation is expected. In addition, charge migration will also be facilitated due to the expected nano-phase separated and highly ordered block copolymer ultrastructural. The combination of all these factors will result in significant overall enhancement of photovoltaic power conversion efficiency.

Sun, Sam↗

Preparation and Preliminary Characterization of Crystallizing Fluorescent Derivatives of Chicken Egg White Lysozyme

Fluorescence is one of the most versatile and powerful tools for the study of macromolecules. While most proteins are intrinsically fluorescent, working at crystallization concentrations require the use of covalently prepared derivatives added as tracers. This approach requires derivatives that do not markedly affect the crystal packing. We have prepared fluorescent derivatives of chicken egg white lysozyme with probes bound to one of two different sites on the protein molecule. Lucifer yellow and 5-(2-aminoethyl)aminonapthalene-i-sulfonic acid (EDANS) have been attached to the side chain carboxyl of Asp(sup 101) using a carbodiimide coupling procedure. Asp(sup 101) lies within the active site cleft, and it is believed that the probes are 'buried' within that cleft. Lucifer yellow and MANS probes with iodoacetamide reactive five groups have been bound to His(sup 15), located on the 'back side' of the molecule relative to the active site. All the derivatives fluoresce in the solution and the crystalline states. Fluorescence characterization has focused on determination of binding effects on the probe quantum yield, lifetime, absorption and emission spectra, and quenching by added solutes. Quenching studies show that, as postulated, the Asp(sup 101)-bound probes are partially sheltered from the bulk solution by their location within the active site cleft. Probes bound to His(sup 15) have quenching constants about equal to those for the free probes, indicating that this site is highly exposed to the bulk solution.

Sumida, John P.↗

Papering Over Corrosion

Kennedy Space Center's battle against corrosion led to a new coating that was licensed to GeoTech and is commercially sold as Catize. The coating uses ligno sulfonic acid doped polyaniline (Ligno-Pani), also known as synthetic metal. Ligno-Pani can be used to extend the operating lives of steel bridges as one example of its applications. future applications include computers, televisions, cellular phones, conductive inks, and stealth technology.

Source record↗

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Sun, Sam-Shajing↗

Synthesis and Characterization of SF-PPV-I

Conjugated electro-active polymers find their potential applications in developing variety inexpensive and flexible shaped electronic and photonic devices, such as photovoltaic or photo/electro light emitting devices. In many of these opto-electronic polymeric materials, certain electron rich donors and electron deficient acceptors are needed in order to fine-tune the electronic or photonic properties of the desired materials and structures. While many donor type of conjugated polymers have been widely studied and developed in the past decades, there are relatively fewer acceptor type of conjugated polymers have been developed. Key acceptor type conjugated polymers developed so far include C60 and CN-PPV, and each has its limitations. Due to the complexity and diversity of variety future electronic materials and structural needs, alternative and synthetically amenable acceptor conjugated polymers need to be developed. In this paper, we present the synthesis and characterization of a new acceptor conjugated polymer, a sulfone derivatized polyphenylenevinylene "SF-PPV".

Wang, Y.↗

Tensile Properties of a Cellulose Ether Hydrogel

Poly(hydroxycellulose) solutions were molded into dumbell-shaped specimens crosslinked with divinyl sulfone. The resulting hydrogels were tested in tension at room temperature and also at a temperature above the 40 C shrinkage transition. In contrast to behavior seen in some other responsive gels, apparent initial tangent moduli were lower in the shrunken state; breaking elongations were significantly higher. Possible molecular mechanisms are suggested, and implications for the design of temperature-responsive actuators ("artificial muscles") from this material are discussed.

Hinkley, Jeffrey A.↗

Novel High Efficient Organic Photovoltaic Materials

Solar energy is a renewable, nonpolluting, and most abundant energy source for human exploration of a remote site or outer space. In order to generate appreciable electrical power in space or on the earth, it is necessary to collect sunlight from large areas and with high efficiency due to the low density of sunlight. Future organic or polymer (plastic) solar cells appear very attractive due to their unique features such as light weight, flexible shape, tunability of energy band-gaps via versatile molecular or supramolecular design, synthesis, processing and device fabrication schemes, and much lower cost on large scale industrial production. It has been predicted that supramolecular and nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration due to improved electronic ultrastructure and morphology in comparison to polymer composite system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel block copolymer system containing donor and acceptor blocks covalently attached. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (RO-PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (SF-PPV). The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block has a strong PL emission at around 560 nm, and acceptor block has a strong PL emission at around 520 nm, the PL emissions of final block copolymers are severely quenched. This verifies the expected electron transfer and charge separation due to interfaces of donor and acceptor nano phase separated blocks. The system therefore has potential for variety light harvesting applications, including high efficient photovoltaic applications.

Sun, Sam↗

Molecular and Enantiomeric Analysis of Organic Compounds in Carbonaceous Meteorites

Carbonaceous meteorites are relatively enriched in carbon. Much of this carbon is in the form of soluble organic compounds. The Murchison and Murray meteorites are the best-characterized carbonaceous meteorites with respect to organic chemistry. Their content of organic compounds has led to an initial understanding of early solar system organic chemistry as well as what compounds may have played a role in the origin of life (Cronin and Chang, 1993). Reported compounds include: amino acids, amides, carboxylic acids, sulfonic acids, and polyols. This talk will focus on the molecular and enantiomeric analysis of individual meteoritic compounds: polyol acids; and a newly identified class of meteorite compounds, keto acids, i.e., acetoacetic acid, levulinic acid, etc. Keto acids (including pyruvic) are critically important in all contemporary organisms. They are key intermediates in metabolism and processes such as the citric acid cycle. Using gas chromatography-mass spectrometry we identified individual meteoritic keto acids after derivatization to one or more of the following forms: isopropyl ester (ISP), trimethyIsiIy1 (TMS), tert-butyldimethylsilyl (BDMS). Ongoing analyses will determine if, in addition to certain amino acids from Murchison (Cronin and Pizzarello, 1997), other potentially important prebiotic compounds also contain enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life.

Cooper, George↗

Salt modulates the stability and lipid binding affinity of the adipocyte lipid-binding proteins

Adipocyte lipid-binding protein (ALBP or aP2) is an intracellular fatty acid-binding protein that is found in adipocytes and macrophages and binds a large variety of intracellular lipids with high affinity. Although intracellular lipids are frequently charged, biochemical studies of lipid-binding proteins and their interactions often focus most heavily on the hydrophobic aspects of these proteins and their interactions. In this study, we have characterized the effects of KCl on the stability and lipid binding properties of ALBP. We find that added salt dramatically stabilizes ALBP, increasing its Delta G of unfolding by 3-5 kcal/mol. At 37 degrees C salt can more than double the stability of the protein. At the same time, salt inhibits the binding of the fluorescent lipid 1-anilinonaphthalene-8-sulfonate (ANS) to the protein and induces direct displacement of the lipid from the protein. Thermodynamic linkage analysis of the salt inhibition of ANS binding shows a nearly 1:1 reciprocal linkage: i.e. one ion is released from ALBP when ANS binds, and vice versa. Kinetic experiments show that salt reduces the rate of association between ANS and ALBP while simultaneously increasing the dissociation rate of ANS from the protein. We depict and discuss the thermodynamic linkages among stability, lipid binding, and salt effects for ALBP, including the use of these linkages to calculate the affinity of ANS for the denatured state of ALBP and its dependence on salt concentration. We also discuss the potential molecular origins and potential intracellular consequences of the demonstrated salt linkages to stability and lipid binding in ALBP.

NASA Discipline Cell Biology↗

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

Non-NASA Center↗

Chirality Characterization of Dispersed Single Wall Carbon Nanotubes

Raman scattering and optical absorption spectroscopy are used for the chirality characterization of HiPco single wall carbon nanotubes (SWNTs) dispersed in aqueous solution with the surfactant sodium dodecylbenzene sulfonate. Radial breathing mode (RBM) Raman peaks for semiconducting and metallic SWNTs are identified by directly comparing the Raman spectra with the Kataura plot. The SWNT diameters are calculated from these resonant peak positions. Next, a list of (n, m) pairs, yielding the SWNT diameters within a few percent of that obtained from each resonant peak position, is established. The interband transition energies for the list of SWNT (n, m) pairs are calculated based on the tight binding energy expression for each list of the (n, m) pairs, and the pairs yielding the closest values to the corresponding experimental optical absorption peaks are selected. The results reveal that (1, 11), (4, 11), and (0, 11) as the most probable chiralities of the semiconducting nanotubes. The results also reveal that (4, 16), (6, 12) and (8, 8) are the most probable chiralities for the metallic nanotubes. Directly relating the Raman scattering data to the optical absorption spectra, the present method is considered the simplest technique currently available. Another advantage of this technique is the use of the E(sup 8)(sub 11) peaks in the optical absorption spectrum in the analysis to enhance the accuracy in the results.

Namkung, Min↗

New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been produced and which incorporates strongly acidic (proton donating) functional groups into the polymer backbone. Both of these polymer films have demonstrated significantly higher proton conductivity than Nafion at elevated temperatures and low relative humidities. An added advantage is that these polymers are very inexpensive to produce because their starting materials are commodity chemicals that are commercially available in large volumes.

Kinder, James D.↗

Nonhumidified High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

Fuel cells are being considered for a wide variety of aerospace applications. One of the most versatile types of fuel cells is the proton-exchange-membrane (PEM) fuel cell. PEM fuel cells can be easily scaled to meet the power and space requirements of a specific application. For example, small 100-W PEM fuel cells are being considered for personal power for extravehicular activity suit applications, whereas larger PEM fuel cells are being designed for primary power in airplanes and in uninhabited air vehicles. Typically, PEM fuel cells operate at temperatures up to 80 C. To increase the efficiency and power density of the fuel cell system, researchers are pursuing methods to extend the operating temperature of the PEM fuel cell to 180 C. The most widely used membranes in PEM fuel cells are Nafion 112 and Nafion 117--sulfonated perfluorinated polyethers that were developed by DuPont. In addition to their relatively high cost, the properties of these membranes limit their use in a PEM fuel cell to around 80 C. The proton conductivity of Nafion membranes significantly decreases above 80 C because the membrane dehydrates. The useful operating range of Nafion-based PEM fuel cells can be extended to over 100 C if ancillary equipment, such as compressors and humidifiers, is added to maintain moisture levels within the membrane. However, the addition of these components reduces the power density and increases the complexity of the fuel cell system.

Kinder, James D.↗

Magnetic particles

Metal oxide containing polymers and particularly styrene, acrylic or protein polymers containing fine, magnetic iron oxide particles are formed by combining a NO.sub.2 -substituted polymer with an acid such as hydrochloric acid in the presence of metal, particularly iron particles. The iron is oxidized to fine, black Fe.sub.3 O.sub.4 particles which deposit selectively on the polymer particles. Nitrated polymers are formed by reacting functionally substituted, nitrated organic compounds such as trinitrobenzene sulfonate or dinitrofluoro benzene with a functionally coreactive polymer such as an amine modified acrylic polymer or a protein. Other transition metals such as cobalt can also be incorporated into polymers using this method.

Chang, Manchium↗

Ethynyl terminated imidothioethers and resins therefrom

Ethynyl terminated imidothioethers (ETIs) are prepared by the reaction of a dimercaptan, such as 4,4'-dimercaptodiphenyl ether, and an ethynyl containing maleimide, such as N-(3-ethynylphenyl)maleimide. Blends of thse ETIs and ethynyl terminated polymeric materials, such as ethynyl terminated sulfones and ethynyl terminated arylene ethers, are also prepared. These resin blends exhibit excellent processability, and the cured blends show excellent fracture toughness and solvent resistance, as well as excellent adhesive and composite properties.

Hergenrother, Paul M.↗

Development of a Compact Efficient Cooling Pump for Space Suit Life Support Systems

With the increasing demands placed on extravehicular activity (EVA) for the International Space Station (ISS) assembly and maintenance, along with planned lunar and Martian missions, the need for increased human productivity and capability becomes ever more critical. This is most readily achieved by reduction in space suit weight and volume, and increased hardware reliability, durability, and operating lifetime. Considerable progress has been made with each successive generation of space suit design; from the Apollo A7L suit, to the current Shuttle Extravehicular Mobile Unit (EMU) suit, and the next generation Constellation Space Suit Element (CSSE). However, one area of space suit design which has continued to lag is the fluid pump used to drive the water cooling loop of the Primary Life Support System (PLSS). The two main types of fluid pumps typically used in space applications are rotodynamic pumps (pumping is achieved through a rotary vaned impeller) and displacement pumps (which includes rotary and diaphragm pumps). The rotating and moving parts found in the pumps and electric motor add significantly to the susceptibility to wear and friction, thermal mismatch, and complexity of the pumps. Electric motor-driven pumps capable of achieving high operational reliability are necessarily large, heavy, and energy inefficient. This report describes a development effort conducted for NASA by Lynntech, Inc., who recently demonstrated the feasibility of an electrochemically-driven fluid cooling pump. With no electric motor and minimal lightweight components, an electrochemically-driven pump is expected to be significantly smaller, lighter and achieve a longer life time than conventional rotodynamic and displacement pumps. By employing sulfonated polystyrene-based proton exchange membranes, rather than conventional Nafion membranes, a significant reduction in the actuator power consumption was demonstrated. It was also demonstrated that these membranes possess the necessary mechanical strength, durability, and temperature range for long life space operation. The preliminary design for a Phase II prototype pump compares very favorably to the fluid cooling pumps currently used in space suit portable life support systems (PLSS). Characteristics of the electrochemically-driven pump are described and the benefits of the technology as a replacement for electric motor pumps in mechanically pumped single-phase fluid loops (MPFLs) is discussed.

vanBoeyen, Roger W.↗