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Results for “aromatization”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Outer membrane vesicles catabolize lignin-derived aromatic compounds in Pseudomonas putida KT2440

Lignin is an abundant and recalcitrant component of plant cell walls. While lignin degradation in nature is typically attributed to fungi, growing evidence suggests that bacteria also catabolize this complex biopolymer. However, the spatiotemporal mechanisms for lignin catabolism remain unclear. Improved understanding of this biological process would aid in our collective knowledge of both carbon cycling and microbial strategies to valorize lignin to value-added compounds. Here, we examine lignin modifications and the exoproteome of three aromatic–catabolic bacteria: Pseudomonas putida KT2440, Rhodoccocus jostii RHA1, and Amycolatopsis sp. ATCC 39116. P. putida cultivation in lignin-rich media is characterized by an abundant exoproteome that is dynamically and selectively packaged into outer membrane vesicles (OMVs). Interestingly, many enzymes known to exhibit activity toward lignin-derived aromatic compounds are enriched in OMVs from early to late stationary phase, corresponding to the shift from bioavailable carbon to oligomeric lignin as a carbon source. In vivo and in vitro experiments demonstrate that enzymes contained in the OMVs are active and catabolize aromatic compounds. Taken together, this work supports OMV-mediated catabolism of lignin-derived aromatic compounds as an extracellular strategy for nutrient acquisition by soil bacteria and suggests that OMVs could pote

biological funneling↗
DOE OSTI2022

Continuous hydrodeoxygenation of lignin to jet-range aromatic hydrocarbons

Sustainable aviation fuel (SAF) is essential to decrease the carbon footprint of the aviation industry. Although many strategies have been developed to provide the branched, aliphatic components of SAF, few viable strategies have been demonstrated to supply the aromatic and cycloalkane fraction of SAF at the necessary scale from bio-based feedstocks. Lignin is the largest natural source of renewable aromatic compounds, yet major challenges in deoxygenation have prevented its use as a feedstock for SAF. Here we report a continuous, two-stage catalytic process using molybdenum carbide to deoxygenate lignin from poplar into aromatic hydrocarbons with 87.5% selectivity towards aromatic hydrocarbons at 86% of the theoretical carbon recovery. This work demonstrates an effective approach to convert lignin into aromatic SAF blendstocks.

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

MassIVE MSV000085948 - Utilization of syringyl lignin-derived compounds and production of 2-pyrone-4,6-dicarboxylic acid by Pseudomonas putida KT2440: Lignin is an abundant aromatic polymer formed in plants by coupling reactions of p-coumaryl, coniferyl, and sinapyl alcohols. Pseudomonas putida KT2440 (P. putida KT2440), a robust soil bacterium, naturally catabolizes many aromatic compounds derived from lignin as carbon and energy sources and has been extensively engineered to valorize guaiacyl (G) and p-hydroxyphenyl (H) lignin-derived aromatic species to valuable chemicals. However, only a few studies report the capacity of Pseudomonads to grow on syringyl (S) lignin-derived compounds. In this work, we demonstrate that P. putida KT2440 catabolizes syringate in the presence of an auxiliary energy source. Overexpression of vanAB, encoding a native Rieske non-heme iron monooxygenase, enabled catabolism of syringate and syringaldehyde without an additional carbon and energy source. In vitro biochemical characterization of VanAB confirmed that this enzyme O-demethylates syringate to 3-O-methylgallate and, subsequently, 3-O-methylgallate to gallate, albeit 4- and 55-fold less efficiently than vanillate, respectively. Transcriptomics and proteomics experiments demonstrate that the galADBC transcripts and enzymes required for gallate catabolism are induced when vanAB is overexpressed during cultivation in syringate. Further, we show that that the endogenous protocatechuate-3,4-dioxygenase PcaHG ring-opens gallate to produce 2-pyrone-4,6-dicarboxylic acid (PDC), a promising bio-based chemical. Constitutive overexpression of vanAB and pcaHG along with galA deletion enabled PDC production from SA at a 70% (mol/mol) yield. Furthermore, leveraging the LigAB dioxygenase from Sphingobium sp. SYK-6 and VanAB O-demethylase from Pseudomonas sp. HR199 enabled simultaneous conversion of monomers with S-, G-, and H-type functionality to PDC at 82% (mol/mol) yield. Overall, this study elucidates a native pathway for catabolism of syringyl lignin-derived compounds in P. putida KT2440 and demonstrates the potential of this robust host for biological funneling of substrates derived from all three canonical monolignols.

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Beckham, Gregg↗
DOE OSTI2024

The anti-aromatic dianion and aromatic tetraanion of [18]annulene

π-Conjugated macrocycles behave differently from analogous linear chains because their electronic wavefunctions resemble a quantum particle on a ring, leading to aromaticity or anti-aromaticity. [18]Annulene, (CH) 18 , is the archetypal non-benzenoid aromatic hydrocarbon. Molecules with circuits of 4 n +2 π electrons, such as [18]annulene ( n =4), are aromatic, with enhanced stability and diatropic ring currents (magnetic shielding inside the ring), whereas those with 4 n π electrons, such as the dianion of [18]annulene, are expected to be anti-aromatic and exhibit the opposite behaviour. Here we use 1 H NMR spectroscopy to re-evaluate the structure of the [18]annulene dianion. We also show that it can be reduced further to an aromatic tetraanion, which has the same shape as the dianion. The crystal structure of the tetraanion lithium salt confirms its geometry and reveals a metallocene-like sandwich, with five Li + cations intercalated between two [18]annulene tetraanions. We also report a heteroleptic sandwich, with [18]annulene and corannulene tetraanion decks.

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

Improving Cooperative Interactions Between Halogenated Aromatic Additives and Aromatic Side Chain Acceptors for Realizing 19.22% Efficiency Polymer Solar Cells

Processing additive plays an important role in the standard operation procedures for fabricating top performing polymer solar cells (PSCs) through efficient interactions with key photovoltaic materials. However, improving interaction study of acceptor materials to high performance halogenated aromatic additives such as diiodobenzene (DIB) is a widely neglected route for molecular engineering toward more efficient device performances. Here, in this work, two novel Y-type acceptor molecules of BTP-TT and BTP-TTS with different aromatic side chains on the outer positions are designed and synthesized. The resulting aromatic side chains significantly enhanced the interactions between the acceptor molecules and DIB through an arene/halogenated arene interaction, which improved the crystallinity of the acceptor molecules and induced a polymorph with better photovoltaic performances. Thus, high power conversion efficiencies (PCEs) of 18.04% and 19.22% are achieved in binary and ternary blend devices using BTP-TTS as acceptor and DIB as additive. Aromatic side chain engineering for improving additive interactions is proved to be an effective strategy for achieving much higher performance photovoltaic materials and devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Atomic Layer Deposition with TiO2 for Enhanced Reactivity and Stability of Aromatic Hydrogenation Catalysts

Hydrogenation of aromatic molecules in fossil- and bio-derived fuels is essential for decreasing emissions of harmful combustion products and addressing growing concerns around urban air pollution. In this work, we used atomic layer deposition to significantly enhance the hydrogenation performance of a conventional supported Pd catalyst by applying an ultrathin coating of TiO2 in a scalable powder coating process. The TiO2-coated catalyst showed substantial gains in the conversion of multiple aromatic molecules, including a 5-fold improvement in turnover frequency versus the uncoated catalyst in the hydrogenation of naphthalene. This activity enhancement was maintained upon scaling the coating synthesis process from 3 to 100 g. Based on the results from Xray photoelectron spectroscopy, X-ray absorption spectroscopy, and computational modeling, the activity enhancement was attributed to ensemble effects resulting from partial TiO2 coverage of the Pd surface rather than fundamental changes to the Pd electronic structure. Additional durability testing confirmed that the TiO2 coating improved the thermal and hydrothermal stability of the catalyst as well as tolerance toward sulfur impurities in the reactant stream. Using an economic model of an industrial deep hydrogenation process, we found that an increase in catalyst activity or lifetime of 2× would justify even a relatively high estimate for the cost of TiO2 atomic layer deposition coatings at scale

atomic layer↗
DOE OSTI2023

Rapid Biocatalytic Synthesis of Aromatic Acid CoA Thioesters by Using Microbial Aromatic Acid CoA Ligases

Abstract Chemically labile ester linkages can be introduced into lignin by incorporation of monolignol conjugates, which are synthesized in planta by acyltransferases that use a coenzyme A (CoA) thioester donor and a nucleophilic monolignol alcohol acceptor. The presence of these esters facilitates processing and aids in the valorization of renewable biomass feedstocks. However, the effectiveness of this strategy is potentially limited by the low steady‐state levels of aromatic acid thioester donors in plants. As part of an effort to overcome this, aromatic acid CoA ligases involved in microbial aromatic degradation were identified and screened against a broad panel of substituted cinnamic and benzoic acids involved in plant lignification. Functional fingerprinting of this ligase library identified four robust, highly active enzymes capable of facile, rapid, and high‐yield synthesis of aromatic acid CoA thioesters under mild aqueous reaction conditions mimicking in planta activity.

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

Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn 2 Sb 5 ] 3-

Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. Here we report the synthesis, experimental, and theoretical characterizations of four ternary clusters ([M 2 (CO) 6 Sn 2 Sb 5 ] 3- (M = Cr, Mo), and [(MSn 2 Sb 5 ) 2 ] 4- , (M = Cu, Ag)) in the process of capturing the hypho - [Sn 2 Sb 5 ] 3- in ethylenediamine (en) solution. We show that the coordination of the binary anion to transition-metal ions or fragments provides additional stabilization due to the formation of locally σ-aromatic units, producing a spherical aromatic shielding region in the cages. While in the case of [Mo 2 (CO) 6 Sn 2 Sb 5 ] 3- stabilization arises from locally σ-aromatic three-centre and five-centre two-electron bonds, aromatic islands in [(AgSn 2 Sb 5 ) 2 ] 4- and [(CuSn 2 Sb 5 ) 2 ] 4- render them globally antiaromatic. This work describes the coordination chemistry of the versatile building block [Sn 2 Sb 5 ] 3- , thus providing conceptual advances in the field of metal-metal bonding in clusters.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Bridging the Void: Halogen Bonding and Aromatic Interactions to Program Luminescence and Electronic Properties of π -Conjugated Materials in the Solid State

π-Conjugated materials are promising candidates for emerging organic optoelectronic devices empowered by molecular design. The unsolved challenges of predicting and controlling their packing as solids, central to their properties and performance, currently limits their practical application. As noncovalent interactions drive packing, control over such interactions are critical to bridging from chemical structure to functional properties. In molecular crystals, halogen bonding and interactions of aromatic rings have emerged as versatile tools for noncovalent control with tailored luminescence and electronic properties. Here, we describe how the interplay of these directional and tunable interactions can engineer properties, including stimuli-responsive behavior. Specifically, halogen bonding can provide robust designs for directing 2D molecular assembly, whereas the intentional interactions of aromatic rings can yield metastable, switchable packing modes, as well as programmed stacking between layers of chromophores. Examples, herein, demonstrate clear relationships between assembly by design and resulting solid-state properties, and strategies presented offer guidance for future designs of π-conjugated molecular materials using specific aromatic interactions and halogen bonding.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Characterization of aromatic acid/proton symporters in Pseudomonas putida KT2440 toward efficient microbial conversion of lignin-related aromatics

Pseudomonas putida KT2440 (hereafter KT2440) is a well-studied platform bacterium for the production of industrially valuable chemicals from heterogeneous mixtures of aromatic compounds obtained from lignin depolymerization. KT2440 can grow on lignin-related monomers, such as ferulate (FA), 4-coumarate (4CA), vanillate (VA), 4-hydroxybenzoate (4HBA), and protocatechuate (PCA). Genes associated with their catabolism are known, but knowledge about the uptake systems remains limited. In this work, we studied the KT2440 transporters of lignin-related monomers and their substrate selectivity. Based on the inhibition by protonophores, we focused on five genes encoding aromatic acid/H+ symporter family transporters categorized into major facilitator superfamily that uses the proton motive force. Furthermore, the mutants of PP_1376 (pcaK) and PP_3349 (hcnK) exhibited significantly reduced growth on PCA/4HBA and FA/4CA, respectively, while no change was observed on VA for any of the five gene mutants. At pH 9.0, the conversion of these compounds by hcnK mutant (FA/4CA) and vanK mutant (VA) was dramatically reduced, revealing that these transporters are crucial for the uptake of the anionic substrates at high pH. Uptake assays using 14 C-labeled substrates in Escherichia coli and biosensor-based assays confirmed that PcaK, HcnK, and VanK have ability to take up PCA, FA/4CA, and VA/PCA, respectively. Additionally, analyses of the predicted protein structures suggest that the size and hydropathic properties of the substrate-binding sites of these transporters determine their substrate preferences. Overall, this study reveals that at physiological pH, PcaK and HcnK have a major role in the uptake of PCA/4HBA and FA/4CA, respectively, and VanK is a VA/PCA transporter. This information can contribute to the engineering of strains for the efficient conversion of lignin-related monomers to value-added chemicals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Hybrid-Lipid Bilayers Induce n -Alkyl-Chain Order in Reversed-Phase Chromatographic Surfaces, Impacting their Shape Selectivity for Aromatic Hydrocarbon Partitioning

Shape selectivity is important in reversed-phase liquid chromatographic separations, where stationary phases are capable of separating geometric isomers, thereby resolving solutes based on their three-dimensional structure or shape rather than other chemical differences. Numerous chromatographic studies have been carried out using n-alkyl-chain-modified columns to understand how molecular shape affects retention. For polycyclic aromatic hydrocarbons (PAHs), it was found that planar compounds were selectively retained over non-planar structures of comparable molecular weight on surfaces with longer n-alkyl chains, higher chain-density, or at lower temperatures, where selectivity likely arises with greater ordering of the n-alkyl chains. A limitation of these studies, however, is the small range of chain ordering that can be achieved and lack of a direct measure of the n-alkyl-chain order of the stationary phases. In this work, we employ a C 18 stationary phase modified with a monolayer of phospholipid as a means of significantly varying the n-alkyl chain order. These hybrid-supported lipid bilayers, which have previously been employed as membrane-like stationary phases for measuring lipophilicity, provide a unique approach to control n-alkyl chain ordering by varying the acyl chain length and degree of unsaturation of the phospholipid modifier. The degree of alkyl-chain order of the resulting modified surfaces is determined from the ratio of trans- versus gauche-conformers, measured in situ within individual porous particles by confocal Raman microscopy. This methodology was also used to assess the affinity of these surfaces for planar versus non-planar PAH molecules. The retention selectivity for the planar versus non-planar compounds, thus determined, was found to vary significantly and systematically with the degree of order of the acyl/alkyl chains in the hybrid-supported lipid bilayers. Furthermore, the investigation also demonstrates the utility of confocal Raman microscopy for interrogating the impact of solute partitioning on stationary-phase structure within porous chromatographic particles.

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

Aromatic heterobicycle-fused porphyrins: impact on aromaticity and excited state electron transfer leading to long-lived charge separation

A new synthetic method to fuse benzo[4,5]imidazo[2,1-a]isoindole to the porphyrin periphery at the β,β-positions has been developed, and its impact on the aromaticity and electronic structures is investigated. Reactivity investigation of the fused benzoimidazo-isoindole component reveals fluorescence quenching of a zinc porphyrin (AMIm-2) upon treatment with a Brønsted acid. The reaction of the zinc porphyrin (AMIm-2) with methyl iodide initiated a new organic transformation, resulting in the ring-opening of isoindole with the formation of an aldehyde and dimethylation of the benzoimidazo component. The fused benzoimidazo-isoindole component acted as a good ligand to bind platinum(II), forming novel homobimetallic and heterobimetallic porphyrin complexes. The fusion of benzoimidazo-isoindole on the porphyrin ring resulted in bathochromically shifted absorptions and emissions, reflecting the extended conjugation of the porphyrin π-system. Time-resolved emission and transient absorption spectroscopy revealed stable excited state species of the benzoimidazo-isoindole fused porphyrins. Zinc porphyrin AMIm-2 promoted excited state electron transfer upon coordinating with an electron acceptor, C60, generating a long-lived charge-separated state, in the order of 37.4 μs. The formation of the exceptionally long-lived charge-separated state is attributed to the involvement of both singlet and triplet excited states of AMIm-2, which is rarely reported in porphyrins.

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

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↗
DOE OSTI2024

Harnessing Metal-Carbon Interactions to Obtain Enhanced Yield in Aromatics and Improved Coking Resistance in Methane Aromatization

Direct CH 4 conversion to value-added products in one step will transform the carbon-based world of fuel and energy, while valorizing an underutilized resource and reducing flared carbon into the atmosphere. Catalytic methane dehydroaromatization (MDA) directly converts CH 4 to value-added aromatic products such as benzene, light hydrocarbons and a significant amount of hydrogen, all of which are chemical commodities [6 CH 4 (g) → C 6 H 6 (g) + 9 H 2 (g)]. The remarkable feature of this reaction is that the formation of the first C-C bonds from CH 4 and oligomerization of the C 2 species occur in one direct step, thus lowering process costs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗