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At least 127 records · Page 7

Lower-curing-temperature PMR polyimides

Studies were performed to achieve a lower-curing-temperature PMR polyimide. The use of m-aminostyrene as the end-cap instead of the monoalkyl ester of 5-normbornene-2,3 dicarboxylic acid was investigated in typical PMR formulations. Model compound studies were also performed. Differential scanning calorimetry studies were performed on model compounds and neat resins to establish their melting and curing characteristics. The elevated temperature weight loss characteristics of neat resins and graphite fiber composites were determined. The room temperature and short-time 260 C (500 F) mechanical properties of the composites were also determined. The use of m-aminostyrene end-caps reduced the final cure temperature of PMR resins by about 55 C (100 F), but the composites prepared with these resins are limited to use temperatures of about 260 C (500 F).

Serafini, T. T.↗

Novel improved PMR polyimides

A series of N-phenylnadimide (PN) modified PMR polyimide composites reinforced with graphite fibers was investigated. The improved flow matrix resins consist of N-phenylnadimide (PN), monomenthyl ester of 5-norbornene-2, 3-dicarboxylic acid (NE), dimethyl ester of 3,3, 4,4-benzophenonetetracarboxylic acide (BTDE), and 4,4 methylenedianiline (MDA). Five modified PMR resin systems were formulated by the addition of 4 to 20 mole percent N-phenylnadimide to the standard PMR-15 composition. These formulations and the control PMR resin were evaluated for rheological characteristics. The initial thermal and mechanical properties of the PN modified PMR and the control PMR/Celion 6000 composites were determined. The results show that the addition of N-phenylnadimide to PMR-15 significantly improved the resin flow characteristics without sacrificing the composites properties. Concentrations of 4 and 9 mole percent PN appear to improve the thermoxidative stability of PMR composites.

Pater, R. H.↗

Lower-curing-temperature PMR polyimides

Partial substitution of a p-aminostyrene end-cap for the monomethyl ester of 5-norbornene-2, 3-dicarboxylic acid lowered the final cure temperature of typical PMR resins from 600 F to 500 F. The weight loss characteristics of neat resins and graphite fiber composites prepared by using the mixed end-cap approach were determined at 600 F. The room temperature and short-time elevated temperature mechanical properties of the composites at 550 F and 600 F were determined. The mechanical property retention characteristics of the composites at 550 F and 600 F are discussed.

Delvigs, P.↗

Lower-curing-temperature PMR polyimides

Partial substitution of a p-aminostyrene end-cap for the monomethyl ester of 5-norbornene-2, 3-dicarboxylic acid lowered the final cure temperature of typical PMR resins from 600 F to 500 F. The weight loss characteristics of neat resins and graphite fiber composites prepared by using the mixed end-cap approach were determined at 600 F. The room temperature and short-time elevated temperature mechanical properties of the composites at 550 F and 600 F were determined. The mechanical property retention characteristics of the composites at 550 F and 600 F are discussed. Previously announced in STAR as N83-10118

Delvigs, P.↗

PMR polyimides from solutions containing mixed endcaps

Previous studies have shown that partial substitution of p-aminostyrene (PAS) for the monomethylester of endo-5-norbornene-2, 3-dicarboxylic acid (NE) lowered the cure temperature of PMR polyimides from 316 to 260 C, but the modified PMR polyimides required higher compression-molding pressures than state-of-the-art PMR-15. In this study PMR polyimides are prepared employing three encaps: NE, PAS, and endo-N-phenyl-5-norbornene-2,3-dicarboximide (PN). The effect of PN addition on the processing characteristics and glass transition temperatures of graphite fiber-reinforced PMR composites is studied. The room temperature and short-time 316 C mechanical properties of the composites are determined. The weight loss and mechanical property retention characteristics of the composites after exposure in air at 316 C are also determined.

Delvigs, P.↗

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↗

Extraterrestrial Organic Compounds and Cyanide in the CM2 Carbonaceous Chondrites Aguas Zarcas and Murchison

Evaluating the water-soluble organic composition of carbonaceous chondrites is key to understanding the inventory of organic matter present at the origins of the solar system and the subsequent processes that took place inside asteroid parent bodies. Here, we present a side-by-side analysis and comparison of the abundance and molecular distribution of aliphatic amines, aldehydes, ketones, mono- and dicarboxylic acids, and free and acid-releasable cyanide species in the CM2 chondrites Aguas Zarcas and Murchison. The Aguas Zarcas meteorite is a recent fall that occurred in central Costa Rica and constitutes the largest recovered mass of a CM-type meteorite after Murchison. The overall content of organic species we investigated was systematically higher in Murchison than in Aguas Zarcas. Similar to previous meteoritic organic studies, carboxylic acids were one to two orders of magnitude more abundant than other soluble organic compound classes investigated in both meteorite samples. We did not identify free cyanide in Aguas Zarcas and Murchison; however, cyanide species analyzed after acid-digestion of the water-extracted meteorite mineral matrix were detected and were quantified at slightly higher abundances in Aguas Zarcas compared to Murchison. Although there were differences in the total abundances of specific compound classes, these two carbonaceous chondrites showed similar isomeric distributions of aliphatic amines and carboxylic acids, with common traits such as a complete suite of structural isomers that decreases in concentration with increasing molecular weight. These observations agree with their petrologic CM type-2 classification, suggesting that these meteorites experienced similar organic formation processes and/or conditions during parent body aqueous alteration.

Jose Carlos Aponte Silva↗

Conversion of biomass to useful intermediates

An aspect of the present disclosure is a microbial cell that includes a genetic modification resulting in the expression of a deficient form of an endogenous dioxygenase, and a gene encoding an exogenous dioxygenase and a promoter sequence, where the endogenous dioxygenase includes PcaH and PcaG, the exogenous dioxygenase includes LigA and LigB, the microbial cell is capable of growth utilizing at least one of a cellulose decomposition molecule or a lignin decomposition molecule, and the microbial cell is capable of producing 2-hydroxy-2H-pyran-4,6-dicarboxylic acid.

Beckham, Gregg Tyler↗

Synthesis of functional polyurethanes and polyesters from biomass-derived monomers

A method of making polyesters and polyurethanes from biomass-derived polyols. The polyol is biomass-derived and has the structure: wherein dashed bonds are single or double bonds and R is selected from the group consisting of —OH and ═O. Polyurethanes are made by reacting the polyol with a diisocyanate. Polyesters are made by reacting the polyol with a dicarboxylic acid.

Chang, Hochan↗

Exploring the influence of transition metals on f-element bonding

The United States aims to triple its nuclear energy production by 2050, which will result in increased uranium usage and spent nuclear fuel generation. This highlights the need for a comprehensive understanding of actinide coordination chemistry, which is crucial for the extraction, processing, purification, and fabrication of uranium-based fuels. Moreover, it is vital for the reprocessing or safe disposal of nuclear waste and effective remediation efforts. Achieving this successfully requires an in-depth understanding of f-electron behavior, as “the role of 5f electrons in bond formation remains a fundamental topic in actinide chemistry”. Introducing a second metal into the system can increase structural dimensionality and diversify structural architecture. Heterometallic systems can also alter material properties, such as magnetic and spectroscopic characteristics, luminescence, and actinide mobility. Additionally, secondary transition metals, even when present only in the second coordination sphere and not directly coordinated, can influence the electron density at the actinyl metal center. In this study, uranium heterometallic single crystals were synthesized by incorporating transition metals such as iron(III), iron(II), nickel(II), manganese(II), copper(I), and cobalt(II). The crystals were formed using 2,6-pyridine dicarboxylic acid and other structurally similar ligands with varying functional groups. The synthesized crystals were analyzed using an extensive array of analytical and computational characterization techniques, including single crystal X-ray diffraction, Raman and infrared spectroscopy, and density functional theory calculations.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗

Transcriptomic data sets for Novosphingobium aromaticivorans grown with the β-5-linked aromatic dimer dehydrodiconiferyl alcohol and the related G-aromatic monomers vanillin and ferulic acid

ABSTRACT The transcriptomes of a 2-pyrone-4,6-dicarboxylic acid-producing strain of Novosphingobium aromaticivorans DSM12444 were determined when grown in minimal medium containing glucose alone or glucose plus vanillin, ferulic acid, or the β-5-linked aromatic dimer dehydrodiconiferyl alcohol as carbon sources. Here, we present the RNA-sequencing data we obtained.

Metz, Fletcher↗

Amino and fatty acids in carbonaceous meteorites

Analyses of two carbonaceous meteorites have provided much of the latest evidence which seems to support Oparin's theory on the origin of life. The meteorites involved are the Murray meteorite, which fell in 1950, and the Murchison meteorite, which fell in 1969. The amino acids in the two meteorites are similar in composition. Eight of the twenty amino acids found belong to amino acids present in proteins. A number of monocarboxylic and dicarboxylic fatty acids were also found in the meteorites.

Kvenvolden, K. A.↗

Polyethylene Upcycling to Diacids Using Acid-Only Activation

There is a pressing need to develop plastic recycling technologies. Chemical upcycling converts low-value waste plastics into higher-value products. Here, polyethylene (PE) upcycling is accomplished by using acid-only activation of PE (PEAA), thus eliminating costly and toxic organic solvents. Acid mixtures of chlorosulfuric acid (CSA) and sulfuric acid (SA) were used to effectively sulfonate PE, allowing for subsequent facile depolymerization. Molecular deconstruction of sulfonated PE using H 2 O 2 in the presence of an Fe(III) catalyst achieved molar yields of C 2 –C 4 diacids exceeding 40% (based on estimates of acids generated from sulfonates). The sulfonation step using PEAA is hypothesized to follow a shrinking core mechanism (SCM), in which PE particles quickly reach a saturated state in the outer sulfonated layer as CSA diffuses radially inward. This proposed mechanism is supported by the fact that, regardless of the extent of sulfonation, similar molar yields of products and ratios of liberated carbon to sulfur are observed. Modeling and experimentation show that deviations from the SCM occur by lowering the Damköhler number (Da) or increasing CSA solubility in PE. In both cases, CSA diffusion is enhanced, which favors kinetically limited sulfonation.

36 MATERIALS SCIENCE↗

Engineering an Extremely Hybrid PKS for Adipic Acid Production

Polyketide synthases (PKSs) are modular enzymes with exceptional potential as biocatalysts for producing non-native compounds. Here, we report the first PKS-based pathway for adipic acid (AA), an industrial monomer for nylon production, by engineering one of the most extensively hybridized PKS systems to date. Using a retrobiosynthetic approach, we identified EtnB, a succinyl-CoA-loading module that uniquely retains the terminal carboxyl group, enabling access to dicarboxylic polyketide products, rarely produced by canonical PKSs. EtnB was coupled to a fully reducing extension module through an engineered communication linker, which improved ACP–KS interactions, enhanced titers, and demonstrated selective succinyl-CoA loading in vivo . This construct integrates genes from five organisms─with domains from seven PKS modules joined across six non-natural junctions─and functions in both Escherichia coli and Pseudomonas putida . Additional engineering that included AT domain exchanges, optimization of extender unit supply, and host strain metabolic rewiring further increased AA production. Together, this work demonstrates that highly chimeric PKSs can be rendered functional through rational design, expands the PKS toolkit with a carboxyl-retaining loading module, and establishes a versatile platform for engineering diacids and other noncanonical products through PKS pathways.

biomanufacturing↗

L–malic acid production from xylose by engineered Saccharomyces cerevisiae

L-malic acid is widely used in the food, chemical, and pharmaceutical industries. Here, we report on production of malic acid from xylose, the second most abundant sugar in lignocellulosic hydrolysates, by engineered Saccharomyces cerevisiae. To enable malic acid production in a xylose-assimilating S. cerevisiae, we overexpressed PYC1 and PYC2, coding for pyruvate carboxylases, a truncated MDH3 coding for malate dehydrogenase, and SpMAE1, coding for a Schizosaccharomyces pombe malate transporter. Additionally, both the ethanol and glycerol-producing pathways were blocked to enhance malic acid production. The resulting strain produced malic acid from both glucose and xylose, but it produced much higher titers of malic acid from xylose than glucose. Interestingly, the engineered strain had higher malic acid yield from lower concentrations (10 g L –1 ) of xylose, with no ethanol production, than from higher xylose concentrations (20 and 40 g L –1 ). As such, a fed-batch culture maintaining xylose concentrations at low levels was conducted and 61.2 g L –1 of malic acid was produced, with a productivity of 0.32 g L –1 h. Furthermore, these results represent successful engineering of S. cerevisiae for the production of malic acid from xylose, confirming that that xylose offers the efficient production of various biofuels and chemicals by engineered S. cerevisiae.

59 BASIC BIOLOGICAL SCIENCES↗

Ni Mediated Carboxylation and Oxidation of PE to C12/C14 Fatty Acids: Cooperative Research and Development Final Report, CRADA Number CRD-22-22451

Given its chemical structure, polyethylene (PE) waste may be a viable feedstock for the production of linear fatty alcohols (FALCs), a major surfactant produced either from palm kernel oil, vegetable oils, or via synthetic pathways that are associated with high carbon footprint. The BOTTLE Consortium will collaborate with Procter & Gamble (P&G) to develop FALCs from waste PE feedstocks.

09 BIOMASS FUELS↗

Phosphonate-based iron complex for a cost-effective and long cycling aqueous iron redox flow battery

Abstract A promising metal-organic complex, iron (Fe)-NTMPA 2 , consisting of Fe(III) chloride and nitrilotri-(methylphosphonic acid) (NTMPA), is designed for use in aqueous iron redox flow batteries. A full-cell testing, where a concentrated Fe-NTMPA 2 anolyte (0.67 M) is paired with a Fe-CN catholyte, demonstrates exceptional cycling stability over 1000 charge/discharge cycles, and noteworthy performances, including 96% capacity utilization, a minimal capacity fade rate of 0.0013% per cycle (1.3% over 1,000 cycles), high Coulombic efficiency and energy efficiency near 100% and 87%, respectively, all achieved under a current density of 20 mA·cm - ². Furthermore, density functional theory unveils two potential coordination structures for Fe-NTMPA 2 complexes, improving the understanding between the ligand coordination environment and electron transfer kinetics. When paired with a high redox potential Fe-Dcbpy/CN catholyte, 2,2′-bipyridine-4,4′-dicarboxylic (Dcbpy) acid and cyanide (CN) ligands, Fe-NTMPA 2 demonstrates a notably elevated cell voltage of 1 V, enabling a practical energy density of up to 9 Wh/L.

25 ENERGY STORAGE↗