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At least 91 records · Page 5

Properties of powder-impregnated graphite/PEKK

Poly Ether Ketone Ketone (PEKK) powders were prepregged on AS4 (12K), IM7 (12K), and G30-500 (12K) carbon fibers and consolidated into unidirectional laminates. The preferred formulation of PEKK for the dry powder process was identified. Mechanical test data on panels prepared via the powder process agreed well with flex, short beam shear, and double cantilever beam values obtained previously on melt-impregnated material. IM7/PEKK composites showed superior mechanical properties to AS4/PEKK and G30-500/PEKK composites. Transverse flexural strength and fiber/resin contact angle correlated well as measures of the fiber/matrix interfacial strength.

Bucher, R. A.↗

Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures are given for tetraalkyl, tetraacid and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethane; (2) 1,1-bis (dicarboxyaryl) 1-aryl-2,2,2 trifluoroethane; or (3) cyclic dianhydride or diamine of 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Substituted 1,1,1-Triaryl-2,2,2-Trifluoroethanes and Processes for their Synthesis

Synthetic procedures to tetraalkyls. tetraacids and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1.1-bis(dialkylaryl)-1-aryl-2,2,2 -trifluoroethane, (2) 1,1-bis(dicarboxyaryl)-1-aryl-2.2,2- trifluoroethane or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl)-1-aryl-2,2,2- trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anihnes. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

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.↗

Measurements of Oxygenated Organic Chemicals In the Pacific Troposphere During TRACE-P: Higher Aldehydes (less than C(sub 1)), Their Sources, and Potential Role In Atmospheric Oxidation

Airborne measurements of a large number of oxygenated organics were carried out in the Pacific troposphere (to 12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measurements included acetaldehyde, propanaldehyde, acetone, methylethyl ketone, methanol, ethanol, PAM and organic nitrates. Independent measurements of formaldehyde, peroxides, and tracers were also available. Highly polluted as well as pristine air masses were sampled. Oxygenated organics were abundant in the clean In troposphere and were greatly enhanced in the outflow regions from Asia. Extremely high concentrations of aldehydes could be measured in the troposphere. It is not possible to explain the large abundances of aldehydes in the background troposphere without invoking significant oceanic sources. A strong correlation between the observed mixing ratios of formaldehyde and acetaldehyde is present. We infer that higher aldehydes (such as acetaldehyde and propanaldehyde) may provide a large source of formaldehyde and sequester Cox throughout the troposphere. The atmospheric behavior of acetone, methylethyl ketone, and methanol is generally indicative of their common terrestrial sources with a Image contribution from biomass/biofuel burning. A vast body of data has been collected and it is being analyzed both statistically and with the help of models to better understand the role that oxygenated organics play in the atmosphere and to unravel their sources and sinks. These results will be presented.

Singh, Hanwant B.↗

Micro-machined planar field asymmetric ion mobility spectrometer as a gas chromatographic detector

A planar high field asymmetric waveform ion mobility spectrometer (PFAIMS) with a micro-machined drift tube was characterized as a detector for capillary gas chromatography. The performance of the PFAIMS was compared directly to that of a flame ionization detector (FID) for the separation of a ketone mixture from butanone to decanone. Effluent from the column was continuously sampled by the detector and mobility scans could be obtained throughout the chromatographic analysis providing chemical inforrmation in mobility scans orthogonal to retention time. Limits of detection were approximately I ng for measurement of positive ions and were comparable or slightly better than those for the FID. Direct comparison of calibration curves for the FAIMS and the FID was possible over four orders of magnitude with a semi-log plot. The concentration dependence of the PFAIMS mobility scans showed the dependence between ion intensity and ion clustering, evident in other mobility spectrometers and atmospheric pressure ionization technologies. Ions were identified using mass spectrometry as the protonated monomer and the proton bound dimer of the ketones. Residence time for column effluent in the PFAIMS was calculated as approximately 1 ms and a 36% increase in extra-column broadening versus the FID occurred with the PFAIMS.

NASA Discipline Life Sciences Technologies↗

Diels-Alder Trapping of Photochemically Generated Dienes with Acrylic Esters: A Novel Approach to Photocured Polymer Film Development

Diels-Alder cycloadditions have often been utilized in polymer synthesis as an alternative to condensation reactions. In our earlier efforts, we developed a new method for the preparation of linear aromatic polyimides, which employs o-quionodimethanes (o-QDMs), generated by a well-known photochemical reaction: the photoenolization of o-methylphenyl ketones. Photolysis of o-methylbenzophenone 1 produces hydroxy-o-quino- diemthane 2, which can be trapped with dienophiles, such as dimethyl acetylenedicarboxylate, to efficiently yield the corresponding cycloadduct (Scheme 1). Here we extend this approach to a novel photocuring process for development of polymer films. We synthesized a series of molecules with multi o-mehtylphenyl ketone functionalities. We further investigated these molecules as photoreactive monomers to obtain polyester films through Diels-Alder cycloadditions.

Ilhan, Faysal↗

Novel Ultraviolet-Light-Curable Polyimides

Polyimides have found broad application in fiber-reinforced composites for aerospace components and as thin films for electronics packaging. Typical routes to processing these materials require temperatures above 200 C. As a result, tooling costs for fabricating components from these composites can be quite high. Recent efforts within the Polymers Branch at the NASA Lewis Research Center have been aimed at developing radiationcurable (with light or electron beams) polyimides. Such materials may enable the processing of polymers and composites at or near room temperature, leading to reduced tooling requirements and costs. A new Diels-Alder route to polyimides has been developed that employs ultraviolet light (UV), rather than heat, to effect polymerization. This approach, which can be carried out at room temperature, is based on a well-known photochemical reaction--the photoenolization of o-methylphenyl ketones. Irradiation of o-methylphenyl ketones, such as 1 in the preceding figure, with UV wavelengths above 300 nm produces a photoenol, 2. This photoenol is unstable, but it persists long enough to undergo Diels-Alder reactions with good dienophiles, such as maleimide, 3. By utilizing a diketone, such as 2,5-dibenzoylp-xylene, 5, and a bismalemide, 6, this chemistry has been used to make a number of polyimides, 7.

Meador, Michael A.↗

Analysis of Volatile Organic Compounds in the Apollo Next Generation Sample Analysis (ANGSA) 73002 Core Sample

Understanding the organic content of lunar regolith was an early priority upon the return of Apollo samples, with amino acids being of special interest because of their importance to life on Earth and their astrobiological relevance. Many initial studies focused on the detection of amino acids in these samples and attempts to determine the origin of those compounds. Although no consensus on the origin of the amino acids was reached in those early studies, more recent work determined that the detected amino acids originated from both terrestrial contamination and meteoritic or cometary in fall to the lunar surface. A majority of the amino acids in the Apollo samples studied originated from precursor molecules, either indigenous to the lunar samples or contaminants, that reacted during the water extraction and acid hydrolysis process for analysis in the laboratory, but the identities of the amino acid precursors still remain poorly understood. Such precursors could include hydrogen cyanide (HCN) and other volatile organic compounds such as amines, carboxylic acids, or aldehydes and ketones. The identities of these compounds, as well as the effects of years of curation on their abundances in lunar regolith samples stored at ambient temperature under nitrogen gas purge, are not clear. The specially curated samples available through the Apollo Next Generation Sample Analysis (ANGSA) program provide a unique opportunity to use state-of- the-art analytical techniques to examine previously unstudied lunar materials. The ANGSA samples include three types of samples: 1) samples stored frozen since <1 month after Earth arrival; 2) samples stored under helium; and 3) a double drive tube collected by Apollo 17 astronauts, with the bottom portion of the drive tube sealed under vacuum on the Moon and never opened. In contrast to the typically curated Apollo samples that have been kept for decades at room temperature under flowing nitrogen purge that may have significantly reduced the abundance of volatiles, the vacuum-sealed and frozen samples may have enhanced preservation of these volatiles. Our initial investigation examines amino acids and their potential volatile precursors, including hydrogen cyanide (HCN), aldehydes, ketones, amines, and mono-carboxylic acids, in a sample from the top portion of the Apollo 17 double drive tube. These results will aid in understanding the lunar abundances of these molecules and will also be compared to future analyses of other drive tube and frozen ANGSA samples.

Elsila, J. E.↗

Joining, Disassembly, and Reconfiguration of Thermoplastic Composites for Space Applications

Thermoplastic composites are increasingly being investigated for aerospace applications because of their relatively short processing time, good chemical and radiation resistance, and potential for reforming and reuse via melting. The manufacturing, reforming, and reuse of thermoplastic composites can be leveraged to advance joining, disassembly, and reassembly of structures for space exploration activities. Potential applications include, but are not limited to, habitats and on-orbit assembly and reassembly of large-scale truss structures. This work focuses on demonstrating the feasibility of joining, disassembly, and reassembly of a thermoplastic bond using heat and pressure. Polyether ether ketone (PEEK) composite adherends were joined using low-melt polyaryl ether ketone (LM-PAEK) thermoplastic films at the bonding interface. The single lap shear specimens with LM-PAEK film were tested and had a maximum shear strength between 5 and 8 MPa and consistently failed adhesively at the bondline. Reassembly of disassembled specimens was successfully demonstrated using additional thermoplastic interlayers. Thus, the reassembly of thermoplastic composite joints was found to be feasible. However, additional work is required to reduce film flowout and optimize consolidation parameters for an in space environment.

thermoplastic composites↗

Solvent Reorganization and Surface–Species Interactions Control Transfer Hydrogenation Rates in Sn-Beta Zeolites

Reorganization of confined alcohol networks reshapes adsorption and activation thermodynamics in Lewis acid zeolites, yet the roles of adsorbate sterics and non-H-bonding cosolvents remain unclear. Here, we investigate transfer hydrogenation of methyl- (mCH) and tert-butylcyclohexanone (tbCH) with 2-butanol over hydrophobic Sn-Beta. First-order rates per defect-open Sn site are 2–5× higher for mCH than tbCH, but converge in the zero-order regime (333–393 K), indicating that solvent reorganization entropically drives adsorption, while bond activation is insensitive to ketone structure. Reactions in toluene or acetonitrile (with 1 M 2-butanol) show that intraporous solvent organization governs transition-state stabilization: on hydrophobic Sn-Beta, apparent enthalpies and entropies rise with decreasing solvent polarity, whereas hydrophilic zeolites display nearly constant barriers across solvents. Liquid-phase IR spectroscopy corroborates these trends, showing that hydrophilic pores enforce 2-butanol-like solvation environments even in toluene. Together, these results reveal how zeolite pores regulate the intraporous solvent structure, whose reorganization upon adsorption reshapes the thermodynamic landscape of Lewis acid catalysis

Adsorption↗

Revealing reaction intermediates in one-carbon elongation by thiamine diphosphate/CoA-dependent enzyme family

2-Hydroxyacyl-CoA lyase/synthase (HACL/S) is a thiamine diphosphate (ThDP)-dependent versatile enzyme originally discovered in the mammalian α-oxidation pathway. HACL/S natively cleaves 2-hydroxyacyl-CoAs and, in its reverse direction, condenses formyl-CoA with aldehydes or ketones. The one-carbon elongation biochemistry based on HACL/S has enabled the use of molecules derived from greenhouse gases as biomanufacturing feedstocks. We investigated several HACL/S family members with high activity in the condensation of formyl-CoA and aldehydes, and distinct chain-length specificities and kinetic parameters. Our analysis revealed the structures of enzymes in complex with acyl-CoA substrates and products, several covalent intermediates, bound ThDP and ADP, as well as the C-terminal active site region. One of these observed states corresponds to the intermediary α–carbanion with hydroxymethyl-CoA covalently attached to ThDP. This research distinguishes HACL/S from related sub-families and identifies key residues involved in substrate binding and catalysis. These findings expand our knowledge of acyloin-condensation biochemistry and offer attractive prospects for biocatalysis using carbon elongation.

2-hydroxyacyl-CoA lyase↗

Crossing the Oxo‐Peroxo Wall for Selective Electrochemical Epoxidation

Electrochemical oxidation in water requires the formation of reactive oxygen species to be able to oxidize unsaturated hydrocarbons to epoxides, aldehydes, and ketones. These reactions, broadly classified as alternative oxidation reactions (AOR), directly compete with the prevalent oxygen evolution reaction (OER). In molecular catalysis, the Oxo-Wall dictates a transition from a stable oxo intermediate (OER active) to a meta-stable metal-oxo (OER inactive) generally occurs. In this work on heterogeneous catalysis, the same Oxo-Wall applies, however, a meta-stable oxo preferentially coordinates with lattice oxygen to form a more stable surface peroxo intermediate. A universal free energy onset of this process is identified at 3.39 eV under electrochemical activation in water and show that it is completely decoupled from the OER oxo species. Such decoupling gives rise to a new region of oxygen reactivity relevant for AOR where a selective oxidation of the unsaturated C-C bonds is predicted to occur instead of OER. A distinct AOR overpotential volcano is constructed and identify recently reported electrocatalysts, including palladium-platinum for propylene epoxidation and silver-nickel for ethylene epoxidation, along with others such as TiO 2 and CuO. Broader implications and limitations of electrochemical AOR are discussed, highlighting their potential to enable electrochemically enhanced thermal catalysis.

Electrocatalysis↗

Is a Malleable Active Site Loop the Key to High Substrate Promiscuity? Hybrid, Biocatalytic Route to Structurally Diverse Taxoid Side Chains with Remarkable Dual Stereocontrol

Abstract These studies reveal the first structure ofClostridium acetobutylicumalcohol dehydrogenase (CaADH), a protein exhibiting remarkable substrate promiscuity and stereochemical fidelity. The CaADH enzyme is utilized here for synthesizing 20 potential aryl isoserine side chains for the Taxotere family of tubulin‐binding chemotherapeutics. The approach involves dynamic reductive kinetic resolution (DYRKR) upon the corresponding α‐chloro‐β‐keto esters, showing high D‐synstereoselectivity, including those leading to the clinically relevant milataxel (Ar = 2‐furyl) and simotaxel (Ar = 2‐thienyl) side chains. Furthermore, various cross‐coupling chemistries performed on thep‐bromophenyl isoserine side chain significantly enhance the structural diversity of the taxoid side chain library obtained (16 additional taxoid side chains). The CaADH structure is notable: (i) the nicotinamide cofactor is bound in ananti‐conformation, with the amide carbonyl occupying the ketone binding pocket, and (ii) a flexible loop near the active site likely contributes to the remarkable substrate promiscuity observed in CaADH. We present our perspective on the dynamic nature of the CaADH active site through molecular dynamics simulation, proposing a halogen bonding model as a potential mechanism for the remarkable selectivity for an (S)‐configured C─Cl bond, in addition to the D‐facial selectivity, demonstrated across 20 diverse substrates by this remarkable short‐chain dehydrogenase enzyme.

Chemistry↗

A Multicopper Oxidase from Paenibacillus Polyethylenelyticus JNU01 Oxidizes Polyethylene

Polyethylene (PE) is a widely used plastic that persists in the environment and resists breakdown via microbial degradation. In this work, we discovered a new bacterium, Paenibacillus polyethylenelyticus JNU01, that grows on a PE-like wax (PELW, 4 kDa) as its sole carbon source, causing chemical modifications to the substrate and releasing small-molecule products. Genomic and transcriptomic analyses identified a multicopper oxidase (PpMmcO) as a key enzyme candidate for this observed activity. PpMmcO promoted surface oxidation, increased hydrophilicity, and the release of small-molecule products such as ketones, alkanes, and alkenoic acids. Scanning electron microscopy confirmed surface damage on both PELW and post-use greenhouse PE films. Weight loss analysis showed mass losses of 5.2% for the PELW powder and 1.6% for the greenhouse PE film after treatment with wild-type PpMmcO. We propose a radical-mediated pathway catalyzed by PpMmcO. These findings identify a new bacterium and enzyme capable of promoting partial PE oxidation and provide insight into biological processes that may act on polyethylene.

36 MATERIALS SCIENCE↗

Microextraction-Single Particle-Inductively Coupled Plasma-Mass Spectrometry for the Direct Analysis of Nanoparticles on Surfaces

A novel employment of single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) was developed, where a microextraction (ME) probe is used to sample nanoparticles from a surface and analyze them in a single analytical step. The effects of several parameters on the performance of ME-SP-ICP-MS were investigated, including the flow rate, choice of carrier solution, particle size, and the design of the microextraction probe head itself. The optimized ME-SP-ICP-MS technique was used to compare the extraction efficiency (EE, defined as the ratio of particles measured to particles deposited on the surface) of the commercial probe head to a newly designed SP polyether ether ketone (PEEK) probe head. The SP PEEK probe head was found to have increased EE compared to the commercial probe head (8.5 ± 3% vs 3.9 ± 3%, respectively). Increasing the carrier solution flow rate was found to decrease the total analysis time at the cost of decreasing EE. Extraction efficiencies for ME-SP-ICP-MS were typically 4–10%, which is similar to transport efficiencies (1–10%) for conventional SP-ICP-MS. Lastly, ME-SP-ICP-MS was employed for the analysis of nano- and microparticles. The sizes of gold nanoparticles, 30 ± 3 and 51 ± 1.9 nm (certified sizes), and iron-based microparticles, 1000 ± 50 nm (certified size), were accurately determined to be 32.2 ± 2.5, 50.8 ± 3.4, and 1030 ± 57 nm, respectively, by ME-SP-ICP-MS. Further, this work demonstrates the potential of ME-SP-ICP-MS for the direct analysis of particles on common collection surfaces (GSR tabs, carbon planchettes, etc.) while retaining spatial information on particle distribution across the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗