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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

A New Nitrogen-Rich Energetic Material with So Many Tautomers

A new nitrogen-rich triazolo-triazole compound, (3-(6-methyl-1H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-3-yl)-1H-1,2,4-triazol-5-amine), TTT1, has been prepared, and its acid–base and tautomeric behavior has been investigated. In the pH range of 0.3–12, TTT1 can accept up to two protons, forming a monocation and a dication, and can deliver one proton, forming a monoanion. The tautomeric behavior is particularly rich for the monocation, for which computational analysis predicts four different tautomers in a narrow energy range of 2 kcal/mol. Two of these tautomers (2H-7H-8H and 3H-7H-8H) have been isolated in salts of the monocation with suitable counterions (chloride, bromide, perchlorate). Surprisingly, the most stable predicted tautomer, 1H-3H-7H, has not been found in the four crystallized salts of the monocation. The energetic perchlorate salt of the monocation (3H-7H-8H tautomer) shows good thermal stability and good stability to impact, friction, and electric discharge. The packing of this compound shows the formation of H-bonded dimers with interactions between N8–H···N1. The crystal structure of this energetic salt was studied experimentally up to 2.8 GPa; no phase change or decomposition was observed.

Chemical structure↗
DOE OSTI2022

Comparative metabolomic analysis reveals shared and unique chemical interactions in sponge holobionts

Sponges are ancient sessile metazoans, which form with their associated microbial symbionts a complex functional unit called a holobiont. Sponges are a rich source of chemical diversity; however, there is limited knowledge of which holobiont members produce certain metabolites and how they may contribute to chemical interactions. To address this issue, we applied non-targeted liquid chromatography tandem mass spectrometry (LC-MS/MS) and gas chromatography mass spectrometry (GC-MS) to either whole sponge tissue or fractionated microbial cells from six different, co-occurring sponge species. Several metabolites were commonly found or enriched in whole sponge tissue, supporting the notion that sponge cells produce them. These include 2-methylbutyryl-carnitine, hexanoyl-carnitine and various carbohydrates, which may be potential food sources for microorganisms, as well as the antagonistic compounds hymenialdisine and eicosatrienoic acid methyl ester. Metabolites that were mostly observed or enriched in microbial cells include the antioxidant didodecyl 3,3'-thiodipropionate, the antagonistic compounds docosatetraenoic acid, and immune-suppressor phenylethylamide. This suggests that these compounds are mainly produced by the microbial members in the sponge holobiont, and are potentially either involved in inter-microbial competitions or in defenses against intruding organisms. This study shows how different chemical functionality is compartmentalized between sponge hosts and their microbial symbionts and provides new insights into how chemical interactions underpin the function of sponge holobionts.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Deuteron off-resonance rotating frame relaxation for the characterization of slow motions in rotating and static solid-state proteins

Here, we demonstrate the feasibility of deuterium solid-state NMR off-resonance rotating frame relaxation measurements for studies of slow motions in biomolecular solids. The pulse sequence, which includes adiabatic pulses for magnetization alignment, is illustrated for static and magic-angle spinning conditions away from rotary resonances. We apply the measurements for three systems with selective deuterium labels at methyl groups: a) a model compound, Fluorenylmethyloxycarbonyl methionine-D 3 amino acid, for which the principles of the measurements and corresponding motional modeling based on rotameric interconversions are demonstrated; b) amyloid-β 1-40 fibrils labeled at a single alanine methyl group located in the disordered N-terminal domain. This system has been extensively studied in prior work and here serves as a test of the method for complex biological systems. The essential features of the dynamics consist of large-scale rearrangements of the disordered N-terminal domain and the conformational exchange between the free and bound forms of the domain, the latter one due to transient interactions with the structured core of the fibrils. and c) a 15-residue helical peptide which belongs to the predicted α-helical domain near the N-terminus of apolipoprotein B. The peptide is solvated with triolein and incorporates a selectively labeled leucine methyl groups. The method permits model refinement, indicating rotameric interconversions with a distribution of rate constants.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Ignition Delay Measurements of Four Component Model Gasolines Exploring the Impacts of Biofuels and Aromatics

This study explores the impacts of combinations of biofuel (ethanol, isobutanol and 2-methyl furan) and aromatic (toluene) compounds in a four component fuel blend, at fixed research octane number (RON) on ignition delay measured in an advanced fuel ignition delay analyzer (AFIDA 2805). Ignition delay measurements were performed over a range of temperatures from 400 to 725 °C (673 to 998 K) and two chamber pressures of 10 and 20 bar. The four component mixtures are compared to primary reference fuels at RON values of 90 and 100. The ignition delay measurements show that as the aromatic and biofuel concentrations increased, two stage ignition behavior was suppressed, at both initial chamber pressures. But both RON 100 (isooctane) and RON 90 reference fuels showed two stage ignition behavior, as did fuel mixtures with low biofuel and aromatic content. RON 90 fuels showed stronger two stage ignition behavior than RON 100 fuels, as expected. Depending on the type of biofuel in the mixture, the ignition delay at low chamber temperatures could be far greater than for the reference fuels. In particular, for the RON 100 mixtures at either 10 or 20 bar initial chamber pressure, the ignition delay at 400 °C (673 K) for the high level blend of 2-methyl furan and toluene (30 vol% of each) exhibited an ignition delay that was 10 times longer than for neat isooctane. The results show the strong non-linear octane blending response of these three biofuel compounds, especially in concert with the kinetic antagonism that toluene is known to display in mixtures with isooctane. These results have implications for the formulation of biofuel mixtures for spark ignition and advanced compression ignition engines, where this non-linear octane blending response could be exploited to improve knock resistance, or modulate the autoignition process.

2-methyl furan↗
DOE OSTI2023

Structure and Magnetic Properties of Homoleptic Trivalent Tris(alkyl)lanthanides

Six new solvent-free, homoleptic paramagnetic tris(alkyl)lanthanides Ln{C(SiHMe 2 ) 3 } 3 (1Ln) and Ln{C(SiHMe 2 ) 2 Ph} 3 (2Ln) (Ln = Gd, Dy, and Er) were synthesized to investigate the magnetic properties of 4f organometallic compounds stabilized by secondary Ln←H–Si and benzylic interactions. The unit cell of 1Gd contains one independent molecule (Z = 2), while 1Dy and 1Er crystallize with four independent isostructural molecules per unit cell (Z = 16). In all molecules, as in other 1Ln compounds, the three tris(dimethylsilyl)methyl ligands form a trigonal planar LnC 3 core, and six secondary interactions involving Ln←H–Si bonding in Ln{C(SiHMe 2 ) 3 } 3 form above and below the equatorial plane. Two and five crystallographically independent molecules of each 2Ln (2Gd, Z = 8; 2Dy, Z = 20) form with three π-coordinated phenyl groups in addition to either one or two secondary Ln←H–Si interactions per molecule. The packing of these midseries organolanthanide compounds contrasts the single crystallographically unique molecules in previously reported La{C(SiHMe 2 ) 3 } 3 (1La, Z = 2, Z' = 1) and La{C(SiHMe 2 ) 2 Ph} 3 (2La, Z = 2, Z' = 1/3). 2La doped with 2Dy can adopt the crystallographic structure of 2La, which promotes magnetic properties, namely a higher χ m T value at low temperatures as well as stronger magnetic anisotropy. The ac susceptibility data for 10% 2Dy doped into 2La suggests slow relaxation at low temperatures with a relaxation barrier of ~45 K. The computed saturated magnetization of 1Er (M ≈ 4.5 μ B ) and 1Dy (M ≈ 6 μ B ) matches the experimental values, while the computed value for 2Dy better matches the value measured for 2Dy diluted in 2La (M ≈ 5 μ B ). Gas-phase calculations predict that the ground-state and first excited-state multiplet separations are larger for 1Er than 2Er, while the ordering for dysprosium is 1Dy > 2Dy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Generating Novel Aroma Phenotypes Using Commercial Wine Samples to Characterize an F1 Population

Due to their disease tolerance and cold hardy nature, interspecific hybrid grapes are widely grown in the Midwestern and Northeastern United States, with additional interest worldwide in the face of increased abiotic and biotic stresses from climate change. However, the aroma profile of these hybrids is unique and generally less popular in comparison with Vitis vinifera grapes. One of the challenges in any phenotyping project is first defining the traits of interest. As wine quality was our ultimate metric of interest, the aroma profile of commercial wines produced from the parents of a breeding population ( Vitis aestivalis derived ‘Norton’ x V. vinifera . ‘Cabernet Sauvignon’) was first assessed for traits of interest. We investigated 11 commercial wines each of Norton, a popular hybrid in Missouri and Cabernet Sauvignon (Cab) for their volatile profiles using the more inclusive metabolomics-based workflow. We then analyzed 21 Norton and 21 Cab grapes from different sites and vintages for the free and bound volatile compounds using HS-SPME-GCMS to validate the differences in wine. The GCMS data was processed using XCMS software to find features that were different between the two cultivars. The two cultivars were found to have differences in their volatile profiles, with 304 features different for wine volatiles, 418 features different for free volatiles, and 302 features different for bound volatiles at 0.05 significance level and with at least a 1.5-fold change between the two cultivars. Those features were used to identify several odor-active compounds in both grapes and wines, including β-damascenone, β-ionone, eugenol, 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN), and methyl salicylate. Some of the identified compounds were higher in Norton than Cab; however, several features were higher in Cab. Using the identified aroma compounds as markers, we phenotyped an F1 population of Norton and Cab. The F1 population was found to be segregating for many aroma compounds with some genotypes demonstrating an even higher concentration of aroma volatiles than either of the parents. Ultimately, using commercially available samples paired with untargeted analysis proved to be an efficient way to determine phenotypes of interest for further analysis and may offer an easy way to choose potential parents with desired traits for breeding.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Predicting the Cetane Number, Sooting Tendency, and Energy Density of Terpene Fuel Additives

Abstract Discovering renewable fuels and fuel additives is paramount in reducing carbon emissions from internal combustion engines. Terpenes, a group of compounds that can be synthesized from plant matter and microorganisms, have gained significant interest in recent years as promising candidates for fuels/additives. Terpenes are a diverse class of compounds that contain rings and methyl branches, resulting in high energy densities and optimal cold weather behavior. Their variation in bond order, carbon chains, and functional groups lead to varying degrees of soot formation and performance in existing engines. The present work leverages predictive models, namely artificial neural networks, to predict the cetane number (CN), sooting tendency (quantified with yield sooting index, YSI), and energy density (quantified with lower heating value, LHV) of terpenes and hydrogenated terpenes whose sooting propensities were previously determined through experimental means. Predicted sooting propensities of these terpenes are compared with experimental values, and predicted cetane numbers and energy densities are used to comment on the compounds’ ability to act as fuels/additives. Expected prediction errors for CN, YSI, and LHV, defined by blind test set median absolute error, are within 5.56 cetane units, 3.63 yield sooting index units, and 0.77 MJ/kg respectively. Additionally, the present work investigates a variety of correlation/dependence metrics for property-property relationships, furthering our understanding of how combustion-relevant properties are related.

09 BIOMASS FUELS↗
DOE OSTI2022

High-throughput platform for yeast morphological profiling predicts the targets of bioactive compounds

Abstract Morphological profiling is an omics-based approach for predicting intracellular targets of chemical compounds in which the dose-dependent morphological changes induced by the compound are systematically compared to the morphological changes in gene-deleted cells. In this study, we developed a reliable high-throughput (HT) platform for yeast morphological profiling using drug-hypersensitive strains to minimize compound use, HT microscopy to speed up data generation and analysis, and a generalized linear model to predict targets with high reliability. We first conducted a proof-of-concept study using six compounds with known targets: bortezomib, hydroxyurea, methyl methanesulfonate, benomyl, tunicamycin, and echinocandin B. Then we applied our platform to predict the mechanism of action of a novel diferulate-derived compound, poacidiene. Morphological profiling of poacidiene implied that it affects the DNA damage response, which genetic analysis confirmed. Furthermore, we found that poacidiene inhibits the growth of phytopathogenic fungi, implying applications as an effective antifungal agent. Thus, our platform is a new whole-cell target prediction tool for drug discovery.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Identification of Effector Metabolites Using Exometabolite Profiling of Diverse Microalgae

Dissolved exometabolites mediate algal interactions in aquatic ecosystems, but microalgal exometabolomes remain understudied. We conducted an untargeted metabolomic analysis of nonpolar exometabolites exuded from four phylogenetically and ecologically diverse eukaryotic microalgal strains grown in the laboratory, freshwater Chlamydomonas reinhardtii, brackish Desmodesmus sp., marine Phaeodactylum tricornutum, and marine Microchloropsis salina, to identify released metabolites based on relative enrichment in the exometabolomes compared to cell pellet metabolomes. Exudates from the different taxa were distinct, but we did not observe clear phylogenetic patterns. We used feature-based molecular networking to explore the identities of these metabolites, revealing several distinct di- and tripeptides secreted by each of the algae, lumichrome, a compound that is known to be involved in plant growth and bacterial quorum sensing, and novel prostaglandin-like compounds. We further investigated the impacts of exogenous additions of eight compounds selected based on exometabolome enrichment on algal growth. Of these compounds, five (lumichrome, 5'-S-methyl-5'-thioadenosine, 17-phenyl trinor prostaglandin A2, dodecanedioic acid, and aleuritic acid) impacted growth in at least one of the algal cultures. Two of these compounds (dodecanedioic acid and aleuritic acid) produced contrasting results, increasing growth in some algae and decreasing growth in others. Together, our results reveal new groups of microalgal exometabolites, some of which could alter algal growth when provided exogenously, suggesting potential roles in allelopathy and algal interactions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Formation of uranium oxy-carbide and uranium carbide via conversion of polymer covered uranium dioxide by laser-based thermal processing

Conventional formation of carbonaceous uranium compounds requires bulk processing using furnace-based approaches. Here, a methodology employing polymer covered uranium dioxide and laser-based heating is explored to enable rapid, localized formation of carbonaceous uranium compounds. Specifically, heating of poly(methyl methacrylate) covered uranium dioxide powder to high temperatures using laser irradiation in argon and methane gaseous environments was investigated. Decomposition of material and reactions induced by laser irradiation were probed in situ by residual gas analysis using a benchtop mass spectrometer. In this study, to determine the effect on the resultant material phase, three different process parameters were varied: gaseous atmosphere, laser power, and laser irradiation time. Material processed under varying conditions was analyzed using powder X-ray diffraction and scanning electron microscopy. This work realized the conversion of uranium dioxide into uranium oxy-carbide(s) and uranium carbide(s) phases, at over 60 wt.%, via the polymer surface application and laser-based thermal decomposition methodology.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Neutron Diffraction Study of Significant sp 3 and sp 2 C–H Bond Shortening in a Fluorinated Pyridinium Saccharinate

Here we have experimentally shown by neutron diffraction significant shortening of both $sp^3$- and $sp^2$-hybridized C–H bonds to 1.092(2) and 1.081(1) Å in a hydrogen-bonded crystal of a difluorinated compound, 4-((2,2-difluoroethoxy)methyl)pyridinium saccharinate. Both MP2 and DFT calculations affirmed the C–H bond shrinkages. Sanderson’s electronegativity equalization principle provides insight into the shortening of the C–H covalent bond lengths for both $sp^3$- and $sp^2$-hybridized carbon atoms. To the best of our knowledge, this neutron diffraction study has revealed the largest extents of $sp^3$ and $sp^2$ C–H bond shrinkages with a 3-sigma rule being satisfied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 ga l-1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . ∙ For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. ∙ Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 gal -1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Development, Application, and Mechanistic Interrogation of a Dual Ni Catalysis Approach to Photoredox-Based C(sp 3 )–C(sp 3 ) Cross-Coupling

The installation of alkyl substituents such as methyl groups is a crucial tactic for the synthesis and diversification of medicinal compounds with improved pharmacological profiles. However, strategies that leverage methyl radical for C(sp 3 ) methylation remain underdeveloped due to the challenge of obtaining cross-selectivity between fleeting aliphatic radicals and alkyl electrophiles. Here, we report the development, application, and interrogation of a conceptually novel mechanistic framework for C(sp 3 )–Me bond formation using two distinct Ni catalysts capable of cross-coupling sterically and electronically diverse alkyl halides (chlorides and bromides) with methyl radical generated photocatalytically from benzaldehyde dimethyl acetal. Furthermore, by modifying the alkyl substituents on the acetal coupling partner, we demonstrate cross-couplings beyond methylation to access an array of 1°–1° and 1°–2° alkyl–alkyl bonds. Experimental and computational mechanistic studies provide support for cooperativity between an in situ-generated (bpy)Ni I (X) catalyst that facilitates XAT and inner-sphere C–C bond formation and a (Tp*)Ni II (acac) cocatalyst that captures methyl radical and engages in concurrent outer-sphere S H 2 coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Arsenolipids in Cultured Picocystis Strain ML and Their Occurrence in Biota and Sediment from Mono Lake, California

Primary production in Mono Lake, a hypersaline soda lake rich in dissolved inorganic arsenic, is dominated by Picocystis strain ML. We set out to determine if this photoautotrophic picoplankter could metabolize inorganic arsenic and in doing so form unusual arsenolipids (e.g., arsenic bound to 2-O-methyl ribosides) as reported in other saline ecosystems and by halophilic algae. We cultivated Picocystis strain ML on a seawater-based medium with either low (37 µM) or high (1000 µM) phosphate in the presence of arsenite (400 µM), arsenate (800 µM), or without arsenic additions (ca 0.025 µM). Cultivars formed a variety of organoarsenic compounds, including a phytyl 2-O-methyl arsenosugar, depending upon the cultivation conditions and arsenic exposure. When the cells were grown at low P, the organoarsenicals they produced when exposed to both arsenite and arsenate were primarily arsenolipids (~88%) with only a modest content of water-soluble organoarsenic compounds (e.g., arsenosugars). When grown at high P, sequestration shifted to primarily water-soluble, simple methylated arsenicals such as dimethylarsinate; arsenolipids still constituted ~32% of organoarsenic incorporated into cells exposed to arsenate but < 1% when exposed to arsenite. Curiously, Picocystis strain ML grown at low P and exposed to arsenate sequestered huge amounts of arsenic into the cells accounting for 13.3% of the dry biomass; cells grown at low P and arsenite exposure sequestered much lower amounts, equivalent to 0.35% of dry biomass. Extraction of a resistant phase with trifluoroacetate recovered most of the sequestered arsenic in the form of arsenate. Uptake of arsenate into low P-cultivated cells was confirmed by X-ray fluorescence, while XANES/EXAFS spectra indicated the sequestered arsenic was retained as an inorganic iron precipitate, similar to scorodite, rather than as an As-containing macromolecule. Samples from Mono Lake demonstrated the presence of a wide variety of organoarsenic compounds, including arsenosugar phospholipids, most prevalent in zooplankton (Artemia) and phytoplankton samples, with much lower amounts detected in the bottom sediments. These observations suggest a trophic transfer of organoarsenicals from the phytoplankton (Picocystis) to the zooplankton (Artemia) community, with efficient bacterial mineralization of any lysis-released organoarsenicals back to inorganic oxyanions before they sink to the sediments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Ethanol to Para-xylene via Methyl Benzaldehyde

Para-xylene is an intermediate compound to several valuable commodity chemicals including polyethylene terephthalate (PET) and currently produced from fossil feedstock through a complex sequence of steps utilizing energy intensive process. Recent work from PNNL has demonstrated the conversion of ethanol produced from waste feedstocks such as municipal solid waste to para-xylene via simple three step process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exploiting the Liquid Phase to Enhance the Cross-Coupling of Alcohols over Nanoporous Gold Catalysts

Controlling selectivity in the cross-coupling of two similar compounds is a classic challenge in heterogeneous catalysis. Here it is shown that the phase in which the catalysis is performed has a dramatic impact on the selectivity of the oxidative coupling of alcohols to esters over unsupported nanoporous gold catalysts, affording nearly optimal cross-coupling to a single ester at equimolar concentrations in the liquid. Operation in the liquid vs the gas phase affects 1) the relative C-H activation rates of methoxy and 1-propoxy, 2) the fraction of C-H activation which leads to esters vs aldehydes, and 3) the fraction of esters which result from cross-coupling vs self-coupling. While activation of the critical adsorbed reactive alkoxy intermediate is faster for 1-propoxy than methoxy in both phases, the liquid phase is more effective in coupling the resulting aldehyde with adsorbed methoxy or 1-propoxy to yield an ester. Additionally, operation in the liquid phase promotes cross-coupling to methyl propionate, whereas in the gas-phase self-coupling of 1-propanol to propyl propionate is favored. The promotion of self-coupling in the gas phase results from the stabilization of larger alkoxides on the surface by Au-alkyl van der Waals forces. However, such forces do not appear dominant in the liquid phase, as evidenced by similar cross-coupling selectivities of methanol with ethanol, 1-propanol, and 1-butanol. Introducing steric hindrance into the higher alcohol (i.e., 2-methyl-1-propanol) further promotes cross-coupling. Here, this promotion is attributed to a kinetic preference for an aldehyde to couple with less-hindered alkoxides. Altogether, these findings demonstrate that alcohol cross-coupling selectivities are strongly impacted by the phase in which the catalysis is conducted, thus altering the phase provides opportunities for selective and efficient chemical syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Metal Phosphide Nanoparticles Generated via a Molecular Precursor Route for Hydrotreatment of Methyl Laurate

Transition metal phosphide nanoparticles supported on silica were used as catalysts to investigate the hydrodeoxygenation of methyl laurate (used as a model compound for vegetable oils). Ni 2 P, Ni 1 Mo 1 P, and Ni 1.6 Mo 0.4 P were synthesized using a molecular precursor route. The nanoparticles were added to the silica support without any changes in their structure or particle size. As a reference and for comparison, MoP/SiO 2 was also prepared by the phosphite method. The prepared catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and chemical analysis. A higher conversion is reached with the MoP/SiO 2 monometallic catalyst, close to that with Ni 1 Mo 1 P/SiO 2 . However, this observation is misleading because the differences in dispersion obscure the result that the intrinsic activity (turnover frequency) of the bimetallic catalyst, prepared by a molecular precursor route, is significantly higher than that of the monometallic catalyst, prepared by the phosphite route, revealing a synergistic effect on the catalytic activity due to the formation of the bimetallic phosphide.

09 BIOMASS FUELS↗