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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Reactions of Ethylidene on a Model Chromia Surface: 1 1-Dichloroethane on Stoichiometric alpha-Cr2O3 (1012)

The reaction of CH{sub 3}CHCl{sub 2} over the nearly-stoichiometric {alpha}-Cr{sub 2}O{sub 3} (10{sub {bar 1}} > 2) surface produces an ethylidene intermediate that yields primarily gas phase CH{sub 2}{double_bond}CH{sub 2} and surface chlorine adatoms; however, trace amounts of HC{triple_bond}CH, CH{sub 3}CH{sub 3}, H{sub 2} and CH{sub 3}CH{double_bond}CHCH{sub 3} are also observed. A rate-limiting intramolecular isomerization (2,1-hydrogen shift) in the surface ethylidene species produces gas phase CH{sub 2}{double_bond}CH{sub 2}. The chlorine freed from the dissociation of CH{sub 3}CHCl{sub 2} binds at the five-coordinate surface Cr{sup 3+} sites on the stoichiometric surface, completing the octahedral coordination sphere, and inhibits the surface chemistry by simple site blocking. No surface carbon deposition is observed from the thermal reaction of 1,1-dichloroethane under the conditions of this study, demonstrating that the ethylidene intermediate is not a primary coke forming intermediate over (10{sub {bar 1}} > 2) facets of {alpha}-Cr{sub 2}O{sub 3} under the conditions of this study.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2011

Synthesis of silica supported AuCu nanoparticle catalysts and the effects of pretreatment conditions for the CO oxidation reaction

The reaction of CH{sub 3}CHCl{sub 2} over the nearly-stoichiometric {alpha}-Cr{sub 2}O{sub 3} (10{bar 1} > 2) surface produces an ethylidene intermediate that yields primarily gas phase CH{sub 2} {double_bond} CH{sub 2} and surface chlorine adatoms; however, trace amounts of HC {triple_bond} CH, CH{sub 3}CH{sub 3}, H{sub 2} and CH{sub 3}CH {double_bond} CHCH{sub 3} are also observed. A rate-limiting intramolecular isomerization (2,1-hydrogen shift) in the surface ethylidene species produces gas phase CH{sub 2} {double_bond} CH{sub 2}. The chlorine freed from the dissociation of CH{sub 3}CHCl{sub 2} binds at the five-coordinate surface Cr{sup 3+} sites on the stoichiometric surface, completing the octahedral coordination sphere, and inhibits the surface chemistry by simple site blocking. No surface carbon deposition is observed from the thermal reaction of 1,1-dichloroethane under the conditions of this study, demonstrating that the ethylidene intermediate is not a primary coke forming intermediate over (10{bar 1} > 2) facets of {alpha}-Cr{sub 2}O{sub 3} under the conditions of this study.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2011

Stearoyl-acyl carrier protein desaturases are associated with floral isolation in sexually deceptive orchids

The orchids Ophrys sphegodes and O. exaltata are reproductively isolated from each other by the attraction of two different, highly specific pollinator species. For pollinator attraction, flowers chemically mimic the pollinators sex pheromones, the key components of which are alkenes with different double-bond positions. This study identifies genes likely involved in alkene biosynthesis, encoding stearoyl-acyl carrier protein (ACP) desaturase (SAD) homologs. The expression of two isoforms, SAD1 and SAD2, is flower-specific and broadly parallels alkene production during flower development. SAD2 shows a significant association with alkene production, and in vitro assays show that O. sphegodes SAD2 has activity both as an 18:0-ACP {Delta}{sup 9} and a 16:0-ACP {Delta}{sup 4} desaturase. Downstream metabolism of the SAD2 reaction products would give rise to alkenes with double-bonds at position 9 or position 12, matching double-bond positions observed in alkenes in the odor bouquet of O. sphegodes. SAD1 and SAD2 show evidence of purifying selection before, and positive or relaxed purifying selection after gene duplication. By contributing to the production of species-specific alkene bouquets, SAD2 is suggested to contribute to differential pollinator attraction and reproductive isolation among these species. Taken together, these data are consistent with the hypothesis that SAD2 is a florally expressed barrier gene of large phenotypic effect and, possibly, a genic target of pollinator-mediated selection.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1982

High-temperature resins

The basic chemistry, cure processes, properties, and applications of high temperature resins known as polyimides are surveyed. Condensation aromatic polymides are prepared by reacting aromatic diamines with aromatic dianhydrides, aromatic tetracarboxylic acids, or with dialkyl esters of aromatic tetracarboxylic acids, depending on the intended end use. The first is for coatings or films while the latter two are more suitable for polyimide matrix resins. Prepreg solutions are made by dissolving reactants in an aprotic solvent, and advances in the addition of a diamine on the double bond and radical polymerization of the double bond are noted to have yielded a final cure product with void-free characteristics. Attention is given to properties of the Skybond, Pyralin, and NR-150B polyimide prepreg materials and characteristics of aging in the NP-150 polyimides. Finally, features of the NASA-developed PMR polyimides are reviewed.

Serafini, T. T.↗
NASA NTRS1977

Carotenoid diagenesis in a marine sediment

The major carotenoids at three levels (3, 40, and 175 m below the sediment-water interface) in a core from a marine sediment (Cariaco Trench, off Venezuela) have been examined. Mass and electronic spectral data have provided evidence for the onset of a progressive reduction of carotenoids in the geological column. The time scale of the process appears to depend on the particular carotenoid. Reduction of up to two double bonds is observed for the diol, zeaxanthin, in the oldest sediment (about 340,000 years old) but no reduction is observed in the younger samples (about 5000 and 56,000 years old). The diketone, canthaxanthin, shows evidence of reduction of up to two double bonds in the 56,000-yr sample and up to five double bonds in the oldest sample. No reduction of beta-carotene was observed in any of the samples.

Watts, C. D.↗
DOE OSTI2020

Effects of stereoisomeric structure and bond location on the ignition and reaction pathways of hexenes

The current work presents new experimental autoignition and speciation data on the two cis-hexene isomers: cis-2-hexene and cis-3-hexene. The new data provide insights on the effects of carbon-carbon double bond location and stereoisomeric structures on ignition delay times and reaction pathways for linear hexene isomers. Experiments were performed using the University of Michigan rapid compression facility to determine ignition delay times from pressure-time histories. Stoichiometric (Φ = 1.0) mixtures at dilution levels of inert gas to O 2 = 7.5:1 (mole basis) were investigated at an average pressure of 11 atm and temperatures from 809 to 1052 K. Speciation experiments were conducted at T = 900 K for the two cis-hexene isomers, where fast-gas sampling and gas chromatography were used to identify and quantify the two cis-hexene isomers and stable intermediate species. The ignition delay time data showed negligible sensitivity to the location of the carbon-carbon double bond and the stereoisomeric structure (cis-trans), and the species data showed no correlation with the stereoisomeric structure, but there was a strong correlation of some of the measured species with the location of the double bond in the hexene isomer. In particular, 2-hexene showed strong selectivity to propene, acetaldehyde, and 1,3-butadiene, and 3-hexene showed selectivity to propanal. Model predictions of ignition delay times were in excellent agreement with the experimental data. Furthermore, there was generally good agreement for the model predictions of the species data for 2-hexene; however, the mechanism overpredicted some of the small aldehyde (C 2 -C 4 ) species for 3-hexene. Reaction pathway analysis indicates the hexenes are almost exclusively consumed by H-atom abstraction reactions at the conditions studied (P = 11 atm, T > 900 K), and not by C 3 -C 4 scission as observed in high-temperature (>1300 K) hexene ignition studies. Improved estimates for 3-hexene + OH reactions may improve model predictions for the species measured in this work.

42 ENGINEERING↗
DOE OSTI2018

A diuranium carbide cluster stabilized inside a C 80 fullerene cage

Unsupported non-bridged uranium–carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing I h (7)-C 80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I h (7)-C 80 . This endohedral fullerene was prepared utilizing the Krätschmer–Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (Ni II -OEP) to produce UCU@I h (7)-C 80 ·[Ni II -OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium–carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@I h (7)-C 80 and the covalent nature of the U(f 1 )=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Rhodoxanthin synthase from honeysuckle; a membrane diiron enzyme catalyzes the multistep conversation of β-carotene to rhodoxanthin

Rhodoxanthin is a vibrant red carotenoid found across the plant kingdom and in certain birds and fish. It is a member of the atypical retro class of carotenoids, which contain an additional double bond and a concerted shift of the conjugated double bonds relative to the more widely occurring carotenoid pigments, and whose biosynthetic origins have long remained elusive. In this work, we identify LHRS ( Lonicera hydroxylase rhodoxanthin synthase), a variant β-carotene hydroxylase (BCH)–type integral membrane diiron enzyme that mediates the conversion of β-carotene into rhodoxanthin. We identify residues that are critical to rhodoxanthin formation by LHRS. Substitution of only three residues converts a typical BCH into a multifunctional enzyme that mediates a multistep pathway from β-carotene to rhodoxanthin via a series of distinct oxidation steps in which the product of each step becomes the substrate for the next catalytic cycle. We introduce a biosynthetic pathway from β-carotene to rhodoxanthin.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.

Environmental Molecular Sciences Laboratory↗
NASA NTRS1992

Tough, high performance, addition-type thermoplastic polymers

A tough, high performance polyimide is provided by reacting a triple bond conjugated with an aromatic ring in a bisethynyl compound with the active double bond in a compound containing a double bond activated toward the formation of a Diels-Adler type adduct, especially a bismaleimide, a biscitraconimide, or a benzoquinone, or mixtures thereof. Addition curing of this product produces a high linear polymeric structure and heat treating the highly linear polymeric structure produces a thermally stable aromatic addition-type thermoplastic polyimide, which finds utility in the preparation of molding compounds, adhesive compositions, and polymer matrix composites.

Pater, Ruth H.↗
NASA NTRS1979

Singlet oxygenation of 1,2-poly/1,4-hexadiene/s

The microstructural changes that occur in cis and trans forms of 1,2-poly(1,4-hexadiene) during methylene blue-photosensitized oxidation were examined by infrared and (C-13)-NMR spectroscopy. The singlet oxygenation of these polymers yielded the expected allylic hydroperoxides accompanied by double bond shifts to new vinyl and trans-vinylene double bonds. The photosensitized oxidation exhibited zero-order kinetics; the relative rates for the cis- and trans-1,2-poly(1,4-hexadiene)s were approximately 3.8:1.0.

Golub, M. A.↗
NASA NTRS1988

Decrease in the etch rate of polymers in the oxygen afterglow with increasing gas flow rate

This paper reports the variation of the etch rate of polymers in the afterglow of a radio frequency discharge in oxygen as a function of total flow rate in the range 2-10 cu cm (STP)/min. The measurements were made at ambient temperature with the O(P-3) concentration held essentially constant. Results are reported on three polymers: cis-polybutadiene, a polybutadiene with 33 percent 1,2 double bonds, and a polybutadiene with 40 percent 1,2 double bonds. It has been observed that the etch rate of these polymers decreases significantly with increasing flow rate, strongly suggesting that the vapor-phase products of polymer degradation contribute to the degradation process.

Lerner, N. R.↗
DOE OSTI2011

Sulfur Versus Iron Oxidation in an Iron-Thiolate Model Complex

In the absence of base, the reaction of [Fe{sup II}(TMCS)]PF{sub 6} (1, TMCS = 1-(2-mercaptoethyl)-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane) with peracid in methanol at -20 C did not yield the oxoiron(IV) complex (2, [Fe{sup IV}(O)(TMCS)]PF{sub 6}), as previously observed in the presence of strong base (KO{sup t}Bu). Instead, the addition of 1 equiv of peracid resulted in 50% consumption of 1. The addition of a second equivalent of peracid resulted in the complete consumption of 1 and the formation of a new species 3, as monitored by UV-vis, ESI-MS, and Moessbauer spectroscopies. ESI-MS showed 3 to be formulated as [Fe{sup II}(TMCS) + 2O]{sup +}, while EXAFS analysis suggested that 3 was an O-bound iron(II)-sulfinate complex (Fe-O = 1.95 {angstrom}, Fe-S = 3.26 {angstrom}). The addition of a third equivalent of peracid resulted in the formation of yet another compound, 4, which showed electronic absorption properties typical of an oxoiron(IV) species. Moessbauer spectroscopy confirmed 4 to be a novel iron(IV) compound, different from 2, and EXAFS (Fe{double_bond}O = 1.64 {angstrom}) and resonance Raman ({nu}{sub Fe{double_bond}O} = 831 cm{sup -1}) showed that indeed an oxoiron(IV) unit had been generated in 4. Furthermore, both infrared and Raman spectroscopy gave indications that 4 contains a metal-bound sulfinate moiety ({nu}{sub s}(SO{sub 2}) {approx} 1000 cm{sup -1}, {nu}{sub as}(SO{sub 2}) {approx} 1150 cm{sup -1}). Investigations into the reactivity of 1 and 2 toward H{sup +} and oxygen atom transfer reagents have led to a mechanism for sulfur oxidation in which 2 could form even in the absence of base but is rapidly protonated to yield an oxoiron(IV) species with an uncoordinated thiol moiety that acts as both oxidant and substrate in the conversion of 2 to 3.

10 SYNTHETIC FUELS↗
DOE OSTI2015

An europium( iii ) diglycolamide complex: insights into the coordination chemistry of lanthanides in solvent extraction

The synthesis, stoichiometry, and structural characterization of a homoleptic, cationic europium(III) complex with three neutral tetraalkyldiglycolamide ligands are reported. The tri(bismuth tetrachloride)tris(N,N,N',N'-tetra-n-octyldiglycolamide)Eu salt, [Eu(TODGA)3][(BiCl4)3] obtained from methanol was examined by Eu L3-edge X-ray absorption spectroscopy (XAS) to reveal an inner-sphere coordination of Eu3+ that arises from 9 O atoms and two next-nearest coordination spheres that arise from 6 carbon atoms each. A structural model is proposed in which each TODGA ligand with its O[double bond, length as m-dash]Ca–Cb–O–Cb–Ca[double bond, length as m-dash]O backbone acts as a tridentate O donor, where the two carbonyl O atoms and the one ether O atom bond to Eu3+. Given the structural rigidity of the tridentate coordination motif in [Eu(TODGA)3]3+ with six 5-membered chelate rings, the six Eu–Ca and six Eu–Cb interactions are readily resolved in the EXAFS (extended X-ray absorption fine structure) spectrum. The three charge balancing [BiCl4]- anions are beyond the cationic [Eu(TODGA)3]3+ cluster in an outer sphere environment that is too distant to be detected by XAS. Despite their sizeable length and propensity for entanglement, the four n-octyl groups of each TODGA (for a total of twelve) do not perturb the Eu3+ coordination environment over that seen from previously reported single-crystal structures of tripositive lanthanide (Ln3+) complexes with tetraalkyldiglycolamide ligands (of the same 1 : 3 metal-to-ligand ratio stoichiometry) but having shorter i-propyl and i-butyl groups. The present results set the foundation for understanding advanced solvent extraction processes for the separation of the minor, tripositive actinides (Am, Cm) from the Ln3+ ions in terms of the local structure of Eu3+ in a solid state coordination complex with TODGA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Inverse patchy colloids with two and three patches. Analytical and numerical study

We propose an analytical solution of the multi-density Ornstein-Zernike equation supplemented by the associative Percus-Yevick closure relations specifically designed to describe the equilibrium properties of the novel class of patchy colloidal particles represented by the inverse patchy colloids with arbitrary number of patches. Using Baxter’s factorization method, we reduce solution of the problem to the solution of one nonlinear algebraic equation for the fraction of the particles with one non-bonded patch. We present closed-form expressions for the structure (structure factor) and thermodynamic (internal energy) properties of the system in terms of this fraction (and parameters of the model). We perform computer simulation studies and compare theoretical and computer simulation predictions for the pair distribution function, internal energy, and number of single and double bonds formed in the system, for two versions of the model, each with two and three patches. We consider the models with formation of the double bonds blocked by the patch-patch repulsion and the models without patch-patch repulsion. In general very good agreement between theoretical and computer simulation results is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Challenging World of Simple Inorganic Rings: Revisiting Roesky's Ketone and Roesky's Sulfoxide

Abstract The surprising differences between the experimental solid‐state and calculated gas‐phase structures of 5‐oxo‐1,3,2,4‐dithiadiazole (Roesky's ketone,1) and 1‐oxo‐1,2,4,3,5‐trithiadiazole (Roesky's sulfoxide,2), identified and studied in a series of papers published between 2004 and 2010 but then never satisfactorily explained, have been revisited, making use of the more advanced computational possibilities currently available. The previous calculations’ considerable overestimations of the C−S and S−S bond lengths in1and2, respectively, have been partly explained based on the results of periodic calculations and the application of Valence Bond (VB) Theory. In the case of1, the crystal environment appears to stabilize a structure with a highly polarized C=O bond, which features a C−S bond with considerable double‐bond character – an effect which does not exist for the isolated molecule – explaining the much shorter bond in the solid state. For2, a similar conclusion can be drawn for the S−S distance. For both compounds, though, packing effects are not the sole source of the differences: the inability of Density Functional Theory (DFT) to properly deal with the electronic structures of these apparently simple main‐group systems remains a contributing factor.

Chemistry↗
DOE OSTI2015

Hydrothermal synthesis and solid-state structures of polynuclear technetium iodide compounds

Two new technetium iodide compounds, Tc-2(O2CCH3)(4)I and K[Tc-8(mu-I)(8)I-4] I, were synthesized in an autoclave from the reaction of KTcO4 in glacial acetic acid with hydroiodic acid and/or alkali metal iodide salts at 210 degrees C under 60-70 atm hydrogen pressure. The structures of Tc-2(O2CCH3)(4)I and K[Tc-8(mu-I)(8)I-4] I were solved by single-crystal X-ray diffraction. The compound Tc-2(O2CCH3)(4)I crystallizes in the monoclinic space group C2/m with a = 7.1194(6) angstrom, b = 14.5851(13) angstrom, c = 7.1586(6) angstrom, and beta = 110.9540(10)degrees. The structure of Tc-2(O2CCH3)(4)I consists of infinite chains of Tc-2(O2CCH3)(4)(+) units linked by bridging iodides, an arrangement similar to the one found in Tc-2(O2CCH3)(4)X (X = Cl, Br). The TcATc separation in Tc-2 (O2CCH3)(4)I (i.e., 2.1146(4) angstrom) is consistent with the presence of a TcATc bond of order 3.5. Magnetic susceptibility measurements reveal Tc-2(O2CCH3)(4)I to be paramagnetic (mu(eff) = 1.84 B.M.) and support the electronic configuration sigma(2)pi(2)delta(2)delta*(1) for the Tc-2(5+) unit in the compound. The compound K[Tc-8(mu-I)(8)I-4]I crystallizes in the monoclinic space group P2(1)/n with a = 8.0018(5) angstrom, b = 14.5125(10) angstrom, c = 13.1948(9) angstrom, and beta = 102.3090(10) degrees, and is the first octanuclear technetium iodide cluster to be reported. The Tc-Tc separations in the [Tc-8(mu-I)(8)I-4] cluster (i.e., 2.164(3) angstrom, 2.5308(8) angstrom and 2.72(3) angstrom suggest the presence of Tc equivalent to Tc triple bonds, Tc=Tc double bonds and Tc-Tc single bonds.

Kerlin, William M.↗
DOE OSTI2017

Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States

To describe static correlation, we create a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We demonstrate that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn–Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle–particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical findings show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗