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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Poly(N-arylenebenzimidazole)s via aromatic nucleophilic displacement

Novel poly(N-arylenebenzimidazole)s (PNABls) are prepared by the aromatic nucleophilic displacement reaction of novel di(hydroxyphenyl-N-arylene benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl-N-arylenebenzimidazole) monomers are synthesized by reacting phenyl-4-hydroxybenzoate with bis(2-aminoanilino)arylenes in diphenylsulfone. Moderate molecular weight PNABIs of new chemical structures were prepared that exhibit a favorable combination of physical and mechanical properties. The use of the novel di(hydroxyphenyI-N-arylenebenzimidazole)s permits a more economical and easier way to prepare PNABIs than previous routes.

Connell, John W.↗

Purifying Water by Imbibition

Concept for purifying water uses absorbent material to remove organic substances. Entire bulk of material employed, not just surface. Proposed purification process uses inexpensive equipment and low energy. Material is methyl acrylate polymer. Material cheap and regenerated by rinsing with methanol or by allowing absorbed compounds to evaporate from it.

Lawton, E. A.↗

Isotopic composition of Murchison organic compounds: Intramolecular carbon isotope fractionation of acetic acid. Simulation studies of cosmochemical organic syntheses

Recently, in our laboratories, samples of Murchison acetic acid were decarboxylated successfully and the carbon isotopic composition was measured for the methane released by this procedure. These analyses showed significant differences in C-13/C-12 ratios for the methyl and carboxyl carbons of the acetic acid molecule, strongly suggesting that more than one carbon source may be involved in the synthesis of the Murchison organic compounds. On the basis of this finding, laboratory model systems simulating cosmochemical synthesis are being studied, especially those processes capable of involving two or more starting carbon sources.

Yuen, G. U.↗

Vibrational spectra and structure of dimethyl oxalate and dimethyl oxalate-d6

The vibrational spectra of dimethyl oxalate-d6 have been examined in connection with a re-examination of the spectra and structure of dimethyl oxalate. The vibrational spectra of the compound had previously been interpreted as being consistent with a trans C2h structure in the solid phase and a non-planar C2 form in the liquid and gas phases. This behavior is not consistent with that observed in similar compounds and a re-evaluation of the facts suggests that the major spectral changes which are observed may be caused by destroying an intermolecular association in going from the solid to the liquid phase, which allows the methyl groups to assume positions out of the plane. Some modifications and additions have been made in the vibrational assignment and assignments are presented for the deuterated compound.

Durig, J. R.↗

The role of sulfur in osmoregulation and salinity tolerance in cyanobacteria, algae, and plants

Organosulfur compounds are involved in osmoregulation and salinity tolerance in some cyanobacteria and photosynthetic eukaryotes. Glycinebetaine, the osmolyte of the halotolerant cyanobacterium, Aphanothece halophytica, requires the sulfonium compound. S-adenosyl-methionine (SAM) for its synthesis. Glutamate is the nitrogen source, SAM is the methyl carbon and serine the carbon backbone source of this unique osmolyte. Inhibitor studies suggest that photorespiration interacts with sulfur metabolism to control betaine synthesis in cyanobacteria. The limiting factor for SAM synthesis is formate from photorespiration. SAM is, in turn, the methyl donor for betaine synthesis from serine. The nitrogen component of serine is from glutamate. Betaine synthesis is hypothesized to be regulated via potassium. The biosynthesis of dimethyl-B-propiothetin (DMPT, which is the same as beta-dimethyl sulfonioprpionate) and diacylsulfoquinovosylglycerol were elucidated as having their roles in osmoregulation and salinity tolerance. The relation between these sulfolipids and the sulfur cycle was discussed.

Yopp, J. H.↗

Analysis of Organic Molecules Extracted from Mars Analogues and Influence of Their Mineralogy Using N-Methyl-N-(tert-butyldimethylsilyl)Trifluoroacetamide Derivatization Coupled with Gas Chromatography Mass Spectrometry in Preparation for the Sample Analysis at Mars Derivatization Experiment on the Mars Science Laboratory Mission

The search for complex organic molecules on Mars, including important biomolecules such as amino acids and carboxylic acids will require a chemical extraction and derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). We have developed, a one-pot extraction and chemical derivatization protocol using N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF) for the Sample Analysis at Mars (SAM) experiment on the Mars Science Laboratory (MSL). The temperature and duration the derivatization reaction, pre-concentration of chemical derivatives, and gas chromatographic separation parameters have been optimized under SAM instrument design constraints. MTBSTFA/DMF extraction and derivatization at 300 C for several minutes of a variety of terrestrial Mars analogue materials facilitated the detection of amino acids and carboxylic acids in a surface soil sample collected from the Atacama Desert and a carbonate-rich stromatolite sample from Svalbard. However, the rapid reaction of MTBSTFA with water in several analogue materials that contained high abundances of hydrated minerals and the possible deactivation of derivatized compounds by iron oxides, as detected by XRD/XRF using the CheMin field unit Terra, proved to be highly problematic for the direct extraction of organics using MTBSTFA, The combination of pyrolysis and two different chemical derivatization methods employed by SAM should enable a wide range of organic compounds to be detected by GCMS if present on Mars,

Stalport, F.↗

Molecular modeling of interactions in electronic nose sensors for environmental monitoring

We report a study aimed at understanding analyte interactions with sensors made from polymer-carbon black composite films. The sensors are used in an Electronic Nose (ENose) which is used for monitoring the breathing air quality in human habitats. The model mimics the experimental conditions of the composite film deposition and formation and was developed using molecular modeling and simulation tools. The Dreiding 2.21 Force Field was used for the polymer and analyte molecules while graphite parameters were assigned to the carbon black atoms. The polymer considered for this work is methyl vinyl ether / maleic acid copolymer. The target analytes include both inorganic (NH3) and organic (methanol) types of compound. Results indicate different composite-analyte interaction behavior.

electronic noise polymer-carbon composite molecula↗

Fire-Resistant Polyamides Containing Phosphorus

Flammability and weight loss reduced. Fire-resistant polymers obtained from 1-{(dialkoxyphosphonyl) methyl}-2, 4- and -2, 6-diaminobenzenes by reaction with acyl or diacyl halides of higher functionality. Incorporation of compounds containing phosphorus into certain polymers shown previously to increase fire retardance. Discovery adds new class of polyamides to group of such polymers.

Kourtides, Demetrius A.↗

Soluble Organic Molecules in Samples of the Carbonaceous Asteroid (162173) Ryugu

The Hayabusa2 spacecraft collected samples from the surface of the carbonaceous near-Earth asteroid (162173) Ryugu, and brought them to Earth. The samples were expected to contain organic molecules, which record processes that occurred in the early Solar System. We analyzed organic molecules extracted from the Ryugu surface samples. We identify a variety of molecules containing the atoms CHNOS, formed by methylation, hydration, hydroxylation, and sulfurization reactions. Amino acids, aliphatic amines, carboxylic acids, polycyclic aromatic hydrocarbons, and nitrogen-heterocyclic compounds were detected, with properties consistent with an abiotic origin. These compounds likely arose from aqueous reaction on Ryugu’s parent body and are similar to organics in Ivuna-type meteorites. These molecules can survive on the surfaces of asteroids and be transported throughout the Solar System.

Hiroshi Naraoka↗

Searching for Reduced Carbon on the Surface of Mars: The SAM Combustion Experiment

The search for reduced carbon has been a major focus of past and present missions to Mars. Thermal evolved gas analysis was used by the Viking and Phoenix landers and is currently in use by the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to characterize volatiles evolved from solid samples, including those associated with reduced organic species. SAM has the additional capability to perform a combustion experiment, in which a sample of Mars regolith is heated in the presence of oxygen and the composition of the evolved gases is measured using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS) [1]. Organics detection on the Martian surface has been complicated by oxidation and destruction during heating by soil oxidants [2], including oxychlorine compounds, and terrestrial organics in the SAM background contributed by one of the SAM wet chemistry reagents MTBSTFA (N-Methyl-N-tertbutyldimethylsilyl- trifluoroacetamide) [3,4]. Thermal Evolved Gas Analysis (TEGA) results from Phoenix show a mid temperature CO2 release between 400 C - 680 C speculated to be carbonate, CO2 adsorbed to grains, or combustion of organics by soil oxidants [5]. Low temperature CO2 evolutions (approx. 200 C - 400 C) were also present at all three sites in Gale Crater where SAM Evolved Gas Analysis (EGA) was performed, and potential sources include combustion of terrestrial organics from SAM, as well as combustion and/or decarboxylation either indigenous martian or exogenous organic carbon [4,6]. By performing an experiment to intentionally combust all reduced materials in the sample, we hope to compare the bulk abundance of CO2 and other oxidized species evolved by combustion to that evolved during an EGA experiment to estimate how much CO2 could be contributed by reduced carbon sources. In addition, C, O, and H isotopic compositions of CO2 and H2O measured by TLS can contribute information regarding the potential sources of these volatiles.

Stern, J. C.↗

Certain problems of space biotechnology

Experiments in the field of biotechnology conducted by the USA Apollo and Skylab space probes are described, as well as the joint Soviet-American Apollo-Soyuz Test Project (ASTP). Experiments in electrophoretic separation in space of biological compounds in a liquid medium are detailed. Space processing of vaccines and separation of human and animal cells are described. Methyl-cellulose, a coating for use in electrophoresis was developed. Erythropoietin, which stimulates the formation of red blood corpuscles in bone marrow, was obtained in pure form.

Gilyarov, V. N.↗

Spectra and structure of organophosphorus compounds. XII - Infrared and Raman spectra of /CH3/2PH and /CD3/2PH

The vibrational spectra of (CH3)2PH and (CD3)2PH have been studied and assignments made. In the infrared, the region between 4000 and 33 wavelength/cm was recorded for the gaseous and solid states, while Raman spectra from 3500 to 10 wavelength/cm in the gaseous, liquid and solid states were observed. There is some evidence of weak hydrogen bonding, based on the behavior of the phosphorus-hydrogen stretching and bending modes. There also appears to be considerable interaction between the methyl rocking and phosphorus-carbon stretching modes. The a double prime and a prime torsional modes appear to be accidentally degenerate at 182 and 142 wavelength/cm for the 'light' and 'heavy' compounds, respectively. This gives barriers of 2.14 and 2.30 kcal/mole, respectively.

Durig, J. R.↗

Some 1-(diorganooxyphosphonyl)methyl-2,4- and -2,6-dinitro-benzenes

1-(Diorgano oxyphosphonyl) methyl) 2,4- and 2,6-dinitro- and diamino benzenes are prepared by nitrating an (organophosphonyl)methly benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo group (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids, (HO)2P(double bond O) single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

Mikroyannidis, John A.↗

Polybenzimidazoles via aromatic nucleophilic displacement

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl benzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl) benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl) benzimidazoles are synthesizedby reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Connell, John W.↗

Polybenzimidazoles Via Aromatic Nucleophilic Displacement

Novel molecular weight controlled and endcapped polybenzimidazoles (PBI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenylbenzimidazole) monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The PBI are endcapped with mono(hydroxyphenyl)benzimidazoles. The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. Mono(hydroxyphenyl)benzimidazoles are synthesized by reacting phenyl-4-hydroxybenzoate with aromatic (o-diamine)s in diphenylsulfone. Molecular weight controlled and endcapped PBI of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Connell, John W.↗

Fluoroester Co-Solvents for Low-Temperature Li+ Cells

Electrolytes comprising LiPF6 dissolved in alkyl carbonate/fluoroester mixtures have been found to afford improved low-temperature performance and greater high-temperature resilience in rechargeable lithium-ion electrochemical cells. These and other electrolytes comprising lithium salts dissolved mixtures of esters have been studied in continuing research directed toward extending the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. The purpose of the present focus on high-temperature resilience in addition to low-temperature performance is to address issues posed by the flammability of the esters and, at temperatures near the upper end (about 55 C) of their intended operating temperature range, by their high chemical reactivity. As used here, high-temperature resilience signifies, loosely, a desired combination of low flammability of an electrolyte mixture and the ability of a cell that contains the mixture to sustain a relatively small loss of reversible charge/discharge capacity during storage in the fully charged condition at high temperature. The selection of fluoroesters for study as candidate electrolyte solvent components to increase high-temperature resilience was prompted in part by the observation that like other halogenated compounds, fluoroesters have low flammability. The fluoroesters investigated in this study include trifluoroethyl butyrate (TFEB), ethyl trifluoroacetate (ETFA), trifluoroethyl acetate (TFEA), and methyl pentafluoropropionate (MPFP). Solvent mixtures were prepared by mixing these fluoroesters with two other esters: ethylene carbonate (EC) and ethyl methyl carbonate (EMC).

Smart, Marshall↗