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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Iodine-Catalyzed Isomerization of Dimethyl Muconate

cis,cis -Muconic acid is a platform biobased chemical that can be upgraded to drop-in commodity and novel monomers. Among the possible drop-in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels-Alder cycloaddition, and dehydrogenation. The isomerization of cis,cis -dimethyl muconate ( cc DMM) to the trans,trans -form ( tt DMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high-purity tt DMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine-catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations due to the large number of halogen-diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely due to solvent complexation with iodine. Under select conditions, tt DMM yields of 95% were achieved in <1 h with methanol, followed by high purity recovery (>98%) with crystallization. Lastly, post-reaction iodine can be recovered and recycled with minimal loss of activity. Altogether, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for biobased chemicals.

09 BIOMASS FUELS↗
DOE OSTI2016

Estimating uncertainty in ambient and saturation nutrient uptake metrics from nutrient pulse releases in stream ecosystems

Nutrient spiraling is an important ecosystem process characterizing nutrient transport and uptake in streams. Various nutrient addition methods are used to estimate uptake metrics; however, uncertainty in the metrics is not often evaluated. A method was developed to quantify uncertainty in ambient and saturation nutrient uptake metrics estimated from saturating pulse nutrient additions (Tracer Additions for Spiraling Curve Characterization; TASCC). Using a Monte Carlo (MC) approach, the 95% confidence interval (CI) was estimated for ambient uptake lengths (S w-amb ) and maximum areal uptake rates (U max ) based on 100,000 datasets generated from each of four nitrogen and five phosphorous TASCC experiments conducted seasonally in a forest stream in eastern Tennessee, U.S.A. Uncertainty estimates from the MC approach were compared to the CIs estimated from ordinary least squares (OLS) and non-linear least squares (NLS) models used to calculate S w-amb and U max , respectively, from the TASCC method. The CIs for Sw-amb and Umax were large, but were not consistently larger using the MC method. Despite the large CIs, significant differences (based on nonoverlapping CIs) in nutrient metrics among seasons were found with more significant differences using the OLS/NLS vs. the MC method. Lastly, we suggest that the MC approach is a robust way to estimate uncertainty, as the calculation of S w-amb and U max violates assumptions of OLS/NLS while the MC approach is free of these assumptions. The MC approach can be applied to other ecosystem metrics that are calculated from multiple parameters, providing a more robust estimate of these metrics and their associated uncertainties.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Crystallographic study of red fluorescent protein eqFP578 and its far-red variant Katushka reveals opposite pH-induced isomerization of chromophore

The wild type red fluorescent protein eqFP578 (from sea anemone Entacmaea quadricolor, {lambda}{sub ex} = 552 nm, {lambda}{sub em} = 578 nm) and its bright far-red fluorescent variant Katushka ({lambda}{sub ex} = 588 nm, {lambda}{sub em} = 635 nm) are characterized by the pronounced pH dependence of their fluorescence. The crystal structures of eqFP578f (eqFP578 with two point mutations improving the protein folding) and Katushka have been determined at the resolution ranging from 1.15 to 1.85 {angstrom} at two pH values, corresponding to low and high level of fluorescence. The observed extinguishing of fluorescence upon reducing pH in eqFP578f and Katushka has been shown to be accompanied by the opposite trans-cis and cis-trans chromophore isomerization, respectively. Asn143, Ser158, His197 and Ser143, Leu174, and Arg197 have been shown to stabilize the respective trans and cis fluorescent states of the chromophores in eqFP578f and Katushka at higher pH. The cis state has been suggested as being primarily responsible for the observed far-red shift of the emission maximum of Katushka relative to that of eqFP578f.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

Dis3- and exosome subunit-responsive 3 Prime mRNA instability elements

Highlights: Black-Right-Pointing-Pointer Successful use of a novel RNA-specific bioinformatic tool, RNA SCOPE. Black-Right-Pointing-Pointer Identified novel 3 Prime UTR cis-acting element that destabilizes a reporter mRNA. Black-Right-Pointing-Pointer Show exosome subunits are required for cis-acting element-mediated mRNA instability. Black-Right-Pointing-Pointer Define precise sequence requirements of novel cis-acting element. Black-Right-Pointing-Pointer Show that microarray-defined exosome subunit-regulated mRNAs have novel element. -- Abstract: Eukaryotic RNA turnover is regulated in part by the exosome, a nuclear and cytoplasmic complex of ribonucleases (RNases) and RNA-binding proteins. The major RNase of the complex is thought to be Dis3, a multi-functional 3 Prime -5 Prime exoribonuclease and endoribonuclease. Although it is known that Dis3 and core exosome subunits are recruited to transcriptionally active genes and to messenger RNA (mRNA) substrates, this recruitment is thought to occur indirectly. We sought to discover cis-acting elements that recruit Dis3 or other exosome subunits. Using a bioinformatic tool called RNA SCOPE to screen the 3 Prime untranslated regions of up-regulated transcripts from our published Dis3 depletion-derived transcriptomic data set, we identified several motifs as candidate instability elements. Secondary screening using a luciferase reporter system revealed that one cassette-harboring four elements-destabilized the reporter transcript. RNAi-based depletion of Dis3, Rrp6, Rrp4, Rrp40, or Rrp46 diminished the efficacy of cassette-mediated destabilization. Truncation analysis of the cassette showed that two exosome subunit-sensitive elements (ESSEs) destabilized the reporter. Point-directed mutagenesis of ESSE abrogated the destabilization effect. An examination of the transcriptomic data from exosome subunit depletion-based microarrays revealed that mRNAs with ESSEs are found in every up-regulated mRNA data set but are underrepresented or missing from the down-regulated data sets. Taken together, our findings imply a potentially novel mechanism of mRNA turnover that involves direct Dis3 and other exosome subunit recruitment to and/or regulation on mRNA substrates.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Cloning and expressing a highly functional and substrate specific farnesoic acid o-methyltransferase from the Asian citrus psyllid ( Diaphorina citri Kuwayama)

The Asian citrus psyllid, Diaphorina citri , transmits a phloem-limited bacterium, Candidatus ‘Liberibacter’ asiaticus that causes citrus greening disease. Because juvenile hormone (JH) plays an important role in adult and nymphal development, we studied the final steps in JH biosynthesis in D. citri . A putative JH acid methyltransferase ortholog gene ( jmt D) and its cognate cDNA were identified by searching D. citri genome database. Expression analysis shows expression in all life stages. In adults, it is expressed in the head-thorax, (containing the corpora allata), and the abdomen (containing ovaries and male accessory glands). A 3D protein model identified the catalytic groove with catalytically active amino acids and the S-adenosyl methionine (SAM)-binding loop. The cDNA was expressed in Escherichia coli cells and the purified enzyme showed high preference for farnesoic acid (FA) and homoFA ( k cat of 0.752 × 10 –3 and 0.217 × 10 –3 s –1 , respectively) as compared to JH acid I (JHA I) ( cis/trans/cis ; 2 Z , 6 E , 10 cis ), JHA III (2 E , 6 E , 10cis ), and JHA I ( trans / cis / cis ; 2 E , 2 Z , 10 cis ) ( k cat of 0.081 × 10 –3 , 0.013 × 10 –3 , and 0.003 × 10 –3 s –1 , respectively). This suggests that this ortholog is a Dc FA-o-methyl transferase gene ( fmt D), not a jmt D, and that JH biosynthesis in D. citri proceeds from FA to JH III through methyl farnesoate (MF). Dc FA-o-MT does not require Ca 2+ , Mg 2+ or Zn 2+ , however, Zn 2+ (1 mM) completely inhibits the enzyme probably by binding H115 at the active groove. This represents the first purified FA-o-MT from Hemiptera with preferred biological activity for FA and not JHA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

High-dose-rate Intracavitary Radiotherapy in the Management of Cervical Intraepithelial Neoplasia 3 and Carcinoma In Situ Presenting With Poor Histologic Factors After Undergoing Excisional Procedures

Purpose: To assess the effectiveness of high-dose-rate intracavitary radiotherapy (HDR-ICR) in patients with cervical intraepithelial neoplasia 3 (CIN 3) and carcinoma in situ (CIS) presenting with poor histologic factors for predicting residual disease after undergoing diagnostic excisional procedures. Methods and Materials: This study was a retrospective analysis of 166 patients with CIN 3 (n=15) and CIS (n=151) between October 1986 and December 2005. They were diagnosed by conization (n=158) and punch biopsy (n=8). Pathologic analysis showed 135 cases of endocervical gland involvement (81.4%), 74 cases of positive resection margins (44.5%), and 52 cases of malignant cells on endocervical curettage (31.3%). All patients were treated with HDR-ICR using Co{sup 60} or Ir{sup 192} at a cancer center. The dose was prescribed at point A located 2 cm superior to the external os and 2 cm lateral to the axis of the tandem for intact uterus. Results: Median age was 61 years (range, 29-77). The median total dose of HDR-ICR was 30 Gy/6 fractions (range, 30-52). At follow-up (median, 152 months), 2 patients developed recurrent diseases: 1 CIN 2 and 1 invasive carcinoma. One hundred and forty patients survived and 26 patients died, owing to nonmalignant intercurrent disease. Rectal bleeding occurred in one patient; however, this symptom subsided with conservative management. Conclusions: Our data showed HDR-ICR is an effective modality for CIN 3 and CIS patients presenting with poor histologic factors after excisional procedures. HDR-ICR should be considered as a definitive treatment in CIN 3 and CIS patients with possible residual disease after undergoing excisional procedures.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2021

Life Cycle Analysis of Renewable Natural Gas and Lactic Acid Production from Waste Feedstocks

Producing fuels and chemicals from waste is considered economically favorable, due to low feedstock cost, and environmentally favorable, due to avoided emissions from conventional waste management practices. In this study, we evaluate the life cycle greenhouse gas (GHG) emission reduction benefits of renewable natural gas (RNG) and lactic acid (LA) production from four types of wet waste feedstocks (wastewater sludge, food waste, swine manure, and fats, oil, and grease [FOG]) via anaerobic digestion (AD) and LA fermentation, respectively. RNG can be used as an alternative to fossil natural gas, while LA from waste feedstocks can displace conventional LA production pathways (mainly from corn via fermentation). Providing comprehensive life cycle GHG emissions of the combinations of waste feedstocks and products through different routes helps identify the GHG hotspots and show where emissions savings come from. The results show that the carbon intensities (CIs) of waste-derived RNG and LA are much lower than those of their counterparts. We estimated the life cycle GHG emissions for RNG to be between -146 and 27 g carbon dioxide equivalent (CO2e)/MJ, much lower than the CI of fossil fuels. Waste-derived LA pathways also show substantially lower CIs, ranging from -4.2 to -1.4 kgCO2e/kg LA, compared to the CIs of LA from corn and corn stover (1.2 and 0.3 kgCO2e/kg LA, respectively). We will also discuss that the low CIs of waste-derived products can come from low yields leading to high emission credits. Thus, life cycle analysis results presented per weight of treated waste can be used to support decisions about which waste feedstocks and products are to be used for sustainable waste valorization. In addition, we found that monetary emission reduction credits can play an important role in driving waste valorization.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

Life cycle analysis of gasification and Fischer-Tropsch conversion of municipal solid waste for transportation fuel production

Non-recyclable municipal solid waste (MSW) can be used as feedstock for liquid fuel production via gasification followed by Fischer-Tropsch (FT) processes. Given the heterogeneity of MSW material composition and variation in material properties, its convertibility to liquid hydrocarbon fuels could vary widely, affecting the sustainability of utilizing non-recyclable MSW for fuel production. This study evaluates the life cycle greenhouse gas (GHG) emissions (carbon intensities [CIs]) of FT fuels from non-recyclable MSW. Key issues that could greatly affect the CIs were examined, including fossil carbon content of the MSW, emission implications of diverting non-recyclable MSW from landfills to fuel production, and conversion efficiency. Results show that the CIs of fuels produced from various waste streams range 80–105 gCO2e/MJ, which may exceed the CI of petroleum fuels. Higher fossil carbon content in the MSW feedstock tends to incur higher GHG emissions as biogenic carbon emissions are considered carbon neutral. Meanwhile, diverting different fractions of non-recyclable MSW, such as food waste and low-quality paper, from landfills may result in GHG emissions that may include the potential avoidance of methane emissions and potential sequestration of biogenic carbon that is foregone. To reduce GHG emissions, a carbon capture and sequestration option in the fuel production stage is considered, which could reduce the CI by 53–64 gCO2e/MJ. Carbon fates of different non-recyclable MSW in landfills are further evaluated to determine how they vary and impact the CIs of MSW-derived fuels.

02 PETROLEUM↗
DOE OSTI2023

Prevalence of Listeria monocytogenes , Salmonella spp., Shiga toxin-producing Escherichia coli , and Campylobacter spp. in raw milk in the United States between 2000 and 2019: A systematic review and meta-analysis

Raw (unpasteurized) milk is available for sale and direct human consumption within some states in the United States (US); it cannot be sold or distributed in interstate commerce. Raw milk may contain pathogenic microorganisms that, when consumed, may cause illness and sometimes may result in death. No comprehensive review for prevalence and levels of the major bacterial pathogens in raw milk in the US exists. The objective of the present research was to systematically review the scientific literature published from 2000 to 2019 to estimate the prevalence and levels of Listeria monocytogenes, Salmonella spp., Shiga toxin-producing Escherichia coli (STEC), and Campylobacter spp. in raw milk in the US. Peer-reviewed studies were retrieved systematically from PubMed®, Embase®, and Web of ScienceTM. The unique complete nonduplicate references were uploaded into the Health Assessment Work Collaborative (HAWC). Based on the selection criteria, twenty studies were included in the systematic review and meta-analysis. Comprehensive Meta-Analysis (CMA) was used for statistical analyses, specifically, random effects meta-analyses were used to synthesize raw bulk tank milk (BTM) and milk filters (MF) data. Data from studies using culture and non–culture-based detection methods were included. Forest plots generated in CMA (Biostat, Englewood, NJ) were used to visualize the results. The average prevalence (event rate) of L. monocytogenes, Salmonella spp., STEC, and Campylobacter spp. in raw BTM in the US was estimated at 4.3% (95% confidence intervals [CIs], 2.8–6.5%), 3.6% (95% CIs, 2.0–6.2%), 4.3% (95% CIs, 2.4–7.4%), and 6.0% (95% CIs, 3.2–10.9%), respectively. Estimated prevalence was generally larger in MF than in BTM. There was not enough data to perform a meta-analysis for the prevalence or levels of pathogens in raw milk from retail establishments or other milk categories.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Fabrication of high quality copper indium disulphide absorbers by bell-like wave modulated electrodeposition

Highlights: • Cu/In bilayer was fabricated by BMSMW deposition technique. • High quality CIS film was successfully fabricated. • A preferable ratio of Cu:In:S close to 1:1:2 was approached. • The SPV response as high as 6 mV was achieved. - Abstract: High-quality CuInS{sub 2} (CIS) thin films have been fabricated by sulfurization of electrodeposited copper–indium bilayer. A novel bell-like wave modulated square wave (BWMSW) electrodeposition technique is employed for the deposition of copper thin film. Three independent parameters (current or potential, frequency, duty cycle) are available for the BWMSW electrodeposition, which is different from the traditional electrodeposition technique with only one adjustable parameter (current or potential). The influences of deposition parameters such as frequency, duty cycle and the concentration of complexing agent are investigated. Benefited from the high quality copper film obtained by the BWMSW technique, the indium film is electrodeposited successfully on the copper layer to form a compact copper–indium alloy bilayer. After sulfurized at 600 °C for 60 min, the phase pure CIS film is obtained with better crystallinity. The structures, morphologies and optoelectronic properties of the CIS film are also characterized.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electronic influences of bridging and chelating diimine ligand coordination in formamidinate-bridged Rh 2 (II,II) dimers

We report two new formamidinate-bridged Rh 2 II,II complexes, cis-[Rh 2 II,II (μ-DTolF) 2 (μ-np) 2 ] 2+ (3; DTolF = N,N'-di-p-tolylformamidinate; np = 1,8-naphthyridine) and cis-[Rh 2 II,II (μ-DTolF) 2 (κ 2 -dap) 2 ] 2+ (4; dap = 1,12-diazaperylene), were synthesized from cis-[Rh 2 II,II (μ-DTolF) 2 (CH 3 CN) 6 ](BF 4 ) 2 (1), and their properties were compared to those of cis-[Rh 2 II,II (μ-DTolF) 2 (phen) 2 ](BF 4 ) 2 (2). Density functional theory (DFT) and electrochemical analyses support the description of the highest occupied molecular orbitals (HOMOs) of 3 and 4 as possessing contributions from the metals and formamidinate bridging ligands, with Rh 2 /form character, and lowest unoccupied molecular orbitals (LUMOs) localized on the respective diimine ligand np and dap π* orbitals. Both 3 and 4 display strong, low energy Rh 2 /form → diimine(π*) metal/ligand-to-ligand charger transfer ( 1 ML–LCT) transitions with maxima at 566 nm (ε = 3600 M -1 cm -1 ) for 3 and at 630 nm (ε = 2900 M -1 cm -1 ) for 4 in CH 3 CN. Time dependent-DFT (TD-DFT) calculations support these assignments. Finally, the ability of both the bridging np and chelating dap diimine ligands to produce strong absorption of these Rh 2 II,II complexes throughout the visible region is potentially useful for the development of new photocatalysts for H 2 production and photochemotherapeutics.

14 SOLAR ENERGY↗
DOE OSTI2025

Isomerization kinetics of azobenzene crosslinked to a liquid crystal polymer network

Azobenzene is an important chromophore having numerous applications that are a direct implication of its ability to change shape upon irradiation with a suitable wavelength. Here, in this study, photoisomerization kinetics of a diacrylate azobenzene molecule (A3MA) cross-linked to a liquid crystal polymer network (LCN) is investigated. Isomerization experiments were conducted on planar LCN thin films with varying cross-linking densities for a fixed azobenzene concentration. The experiments were conducted at approximately 26 °C, which is significantly below each film’s glass transition temperature. The forward trans-cis and reverse cis-trans isomerization slows down in crosslinked azobenzene liquid crystal polymer networks (ALCNs) as compared to a solution and an uncrosslinked polymer mixture. The observed slowdown is due to the reduction in the free volume and increased steric hindrances with an increase in crosslinking. A single-term first-order kinetics rate equation is known to describe the isomerization kinetics in solutions or uncrosslinked mixtures while the same form fails to represent the reaction kinetics in moderate to highly cross-linked ALCNs. Our results for the first time indicate that a two-term first-order reaction rate is an accurate way to describe the forward trans-cis and reverse thermal cis-trans isomerization in crosslinked azobenzene liquid crystal polymer networks. In addition, the effect of film thickness and incident intensities on the reaction kinetics is investigated. Finally, the two-term isomerization kinetics is incorporated into a finite element photo-chemo-mechanical model to reveal the consequent slowdown in the actuation response of ALCN films. The current findings will be of particular interest to theoreticians and experimentalists alike, for it will help predict and understand accurately the responses of azobenzene-based coatings, and actuators and may have potential applications in underwater soft robotics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Dramatic Slowdown of Bimolecular Reactions of Criegee Intermediates in Organic Aerosols

Although Criegee intermediates (CIs) play a central role in driving the transformation of organic molecules, their condensed-phase reaction kinetics remains poorly understood. While CIs undergo unimolecular decomposition to produce OH radicals, stabilized CIs participate in a host of other bimolecular reactions forming larger molecular weight products, including secondary ozonides (kSOZ), alkoxyalkyl hydroperoxides (kAlAHP), and acyloxyalkyl hydroperoxides (kAcAHP). Here, we demonstrate, using prior literature and new measurements of heterogeneous organic aerosol reactions using O3 or OH radicals, that these condensed-phase bimolecular reaction rate coefficients kSOZ (10-20 cm3·molecule-1·s-1), kAlAHP, and kAcAHP (10-19 cm3·molecule-1·s-1) are 7-10 orders of magnitude slower than analogous gas-phase reactions (∼ 10-10-10-13 cm3·molecule-1·s-1). This contrasts with current evidence that the rate coefficients for unimolecular steps in the condensed phase are similar in magnitude to those in the gas phase. Kinetic models using gas-phase-like bimolecular coefficients consistently overestimate the importance of bimolecular relative to unimolecular pathways while underpredicting the aerosol reactivity by up to 30-fold. The slowing of bimolecular reactivity in aerosols is likely due to solvation effects and the increased steric hindrance of larger molecular weight CIs and their scavengers in the condensed phase. These results challenge the conventional view that the high reactant density of an organic aerosol should favor bimolecular over unimolecular reactions, underscoring the need for more accurate CI condensed-phase rate constants for reliable modeling of oxidative processes across a diverse set of atmospheric and environmental systems.

Zeng, Meirong↗
DOE OSTI2015

Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)H with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(?3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the ?3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ?H‡ = 22.1 kcal/mol, ?S‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(?2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(?3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(?3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. We thank Monte Helm, Elliott Hulley and Deanna Miller for help on the crystallography, and Ming Fang for assistance on the electrochemical experiments.

Zhang, Shaoguang↗
DOE OSTI2015

Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor

Here, the thermal decomposition of cyclohexanone (C 6 H 10 =O) has been studied in a set of flash-pyrolysis microreactors. Decomposition of the ketone was observed when dilute samples of C 6 H 10 =O were heated to 1200 K in a continuous flow microreactor. Pyrolysis products were detected and identified by tunable VUV photoionization mass spectroscopy and by photoionization appearance thresholds. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures were roughly 100 Torr, and contact times with the microreactors were roughly 100 μs. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways, all of which open roughly simultaneously. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C 6 H 9 OH), is followed by retro-Diels–Alder cleavage to CH 2 =CH 2 and CH 2 =C(OH)–CH=CH 2 . Further isomerization of CH 2 =C(OH)–CH=CH 2 to methyl vinyl ketone (CH 3 CO–CH=CH 2 , MVK) was also observed. Photoionization spectra identified both enols, C 6 H 9 OH and CH 2 =C(OH)–CH=CH 2 , and the ionization threshold of C 6 H 9 OH was measured to be 8.2 ± 0.1 eV. Coupled cluster electronic structure calculations were used to establish the energetics of MVK. The heats of formation of MVK and its enol were calculated to be Δ f H 298 (cis-CH 3 CO–CH=CH 2 ) = -26.1 ± 0.5 kcal mol –1 and Δ f H 298 (s-cis-1-CH 2 =C(OH)–CH=CH 2 ) = -13.7 ± 0.5 kcal mol –1 . The reaction enthalpy Δ rxn H 298 (C 6 H 10 =O → CH 2 =CH 2 + s-cis-1-CH 2 =C(OH)–CH=CH 2 ) is 53 ± 1 kcal mol –1 and Δ rxn H 298 (C 6 H 10 =O → CH 2 =CH 2 + cis-CH 3 CO–CH=CH 2 ) is 41 ± 1 kcal mol –1 . At 1200 K, the products of cyclohexanone pyrolysis were found to be C 6 H 9 OH, CH 2 =C(OH)–CH=CH 2 , MVK, CH 2 CHCH 2 , CO, CH 2 =C=O, CH 3 , CH 2 =C=CH 2 , CH 2 =CH–CH=CH 2 , CH 2 =CHCH 2 CH 3 , CH 2 =CH 2 , and HC≡CH.

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

Molecular Dynamics and Free Energy Calculations of Dicyclohexano-18-crown-6 Diastereoisomers with Sm 2+ , Eu 2+ , Dy 2+ , Yb 2+ , Cf 2+ , and Three Halide Salts in Tetrahydrofuran and Acetonitrile Using the AMOEBA Force Field

With the continual development of lanthanides (Ln) in current technological devices, an efficient separation process is needed that can recover greater amounts of these rare elements. Dicyclohexano-18-crown-6(DCH18C6) is a crown ether that may be a promising candidate for Ln separation, but additional research is required. As such, molecular dynamics(MD) simulations have been performed on four divalent lanthanide halide salts(Sm 2+ , Eu 2+ , Dy 2+ , and Yb 2+ ) and one divalent actinide halide salt (Cf 2+ ) bound to three diastereoisomers of DCH18C6. Dy 2+ , Yb 2+ , Cf 2+ , DCH18C6, and tetrahydrofuran (THF) solvent were parameterized for the AMOEBA polarizable force field for the first time, whereas existing parameters for Sm 2+ and Eu 2+ were utilized from our previous efforts. A coordination number (CN) of six for Ln 2+ /An 2+ –O solvated in THF indicated that the cations interacted almost entirely with the oxygens of the polyether ring. A CN of one for Ln 2+ /An 2+ -N solvated in acetonitrile for systems containing iodide suggested that theN atom of acetonitrile was competitive with I – for cation interactions. Fluctuation between five and six CNs for Dy 2+ and Yb 2+ suggested that although the cations remained in the polyether ring, the size of the ring may not be an ideal fit as these cations possess comparatively smaller ionic radii. Gibbs binding free energies of Sm 2+ in all DCH18C6 diastereoisomers solvated in THF were calculated. The binding free energy of the cis-syn-cis diastereoisomer was the most favorable, followed by cis-anti-cis, and then trans-anti-trans. Lastly, two major types of conformation were observed for each diastereoisomer that were related to the electrostatic interactions and charge density of the cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Renewable unsaturated polyesters from muconic acid

cis,cis -Muconic acid is an unsaturated dicarboxylic acid that can be produced in high yields via biological conversion of sugars and lignin-derived aromatic compounds. Muconic acid is often targeted as an intermediate to direct replacement monomers such as adipic or terephthalic acid. However, the alkene groups in muconic acid provide incentive for its direct use in polymers, for example, in the synthesis of unsaturated polyester resins. Here, biologically derived muconic acid is incorporated into polyesters via condensation polymerization using the homologous series of poly(ethylene succinate), poly(propylene succinate), poly(butylene succinate), and poly(hexylene succinate). Additionally, dimethyl cis,cis -muconate is synthesized and subsequently incorporated into poly(butylene succinate). NMR measurements demonstrate that alkene bonds are present in the polymer backbones. In all cases, the glass transition temperatures are increased whereas the melting and degradation temperatures are decreased. In the case of poly(butylene succinate), utilization of neat muconic acid yields substoichiometric incorporation consistent with a tapered copolymer structure, whereas the muconate diester exhibits stoichiometric incorporation and a random copolymer structure based on thermal and mechanical properties. Prototypical fiberglass panels were produced by infusing a mixture of low molecular weight poly(butylene succinate-co-muconate) and styrene into a woven glass mat and thermally initiating polymerization resulting in thermoset composites with shear moduli in excess of 30 GPa, a value typical of commercial composites. The increased glass transition temperatures with increasing mucconic incorporation leads to improved composites properties. We find that the molecular tunability of poly(butylene succinate-co-muconate) as a tapered or random copolymer enables the tunability of composite properties. Altogether, this study demonstrates the utility of muconic acid as a monomer suitable for direct use in commercial composites.

09 BIOMASS FUELS↗
DOE OSTI2014

Optimizing the Electronic Properties of Photoactive Anticancer Oxypyridine-Bridged Dirhodium(II,II) Complexes

A series of partial paddlewheel dirhodium compounds of general formula cis-[Rh 2 (xhp) 2 (CH 3 CN) n ][BF 4 ] 2 (n = 5 or 6) were synthesized {xhp = 6-R-2-oxypyridine ligands, R = -CH 3 (mhp), -F (fhp), -Cl (chp)}. X-ray crystallographic studies indicate the aforementioned compounds contain two cis-oriented bridging xhp ligands, with the remaining sites being coordinated by CH 3 CN ligands. The lability of the equatorial (eq) CH 3 CN groups in these complexes in solution is in the order -CH 3 > -Cl > -F, in accord with the more electron rich bridging ligands exerting a stronger trans effect. In the case of cis-[Rh 2 (chp) 2 (CH 3 CN) 6 ][BF 4 ] 2 (5), light irradiation enhances the production of the aqua adducts in which eq CH 3 CN is replaced by H 2 O molecules, whereas the formation of the aqua species for cis-[Rh 2 (fhp) 2 (CH 3 CN) 6 ][BF 4 ] 2 (7) is only slightly increased by irradiation. The potential of both compounds to act as photochemotherapy agents was evaluated. A 16.4-fold increase in cytotoxicity against the HeLa cell line was observed for 5 upon 30 min irradiation (λ > 400 nm), in contrast to the nontoxic compound 7, which is in accord with the results from the photochemistry. Furthermore, the cell death mechanism induced by 5 was determined to be apoptosis. In conclusion, these results clearly demonstrate the importance of tuning the ligand field around the dimetal center to maximize the photoreactivity and achieve the best photodynamic action.

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