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At least 433 records · Page 24

Genomics and physiology of Catenibacillus, human gut bacteria capable of polyphenol C-deglycosylation and flavonoid degradation

The genusCatenibacillus(familyLachnospiraceae, phylumBacillota) includes only one cultivated species so far,Catenibacillus scindens,isolated from human faeces and capable of deglycosylating dietary polyphenols and degrading flavonoid aglycones. Another human intestinalCatenibacillusstrain not taxonomically resolved at that time was recently genome-sequenced. We analysed the genome of this novel isolate, designatedCatenibacillus decagia, and showed its ability to deglycosylateC-coupled flavone and xanthone glucosides andO-coupled flavonoid glycosides. Most of the resulting aglycones were further degraded to the corresponding phenolic acids. Including the recently sequenced genome ofC. scindensand ten faecal metagenome-assembled genomes assigned to the genusCatenibacillus, we performed a comparative genome analysis and searched for genes encoding potentialC-glycosidases and other polyphenol-converting enzymes. According to genome data and physiological characterization, the core metabolism ofCatenibacillusstrains is based on a fermentative lifestyle with butyrate production and hydrogen evolution. BothC. scindensandC. decagiaencode a flavonoidO-glycosidase, a flavone reductase, a flavanone/flavanonol-cleaving reductase and a phloretin hydrolase. Several gene clusters encode enzymes similar to those of the flavonoidC-deglycosylation system ofDoreastrain PUE (DgpBC), while separately located genes encode putative polyphenol-glucoside oxidases (DgpA) required forC-deglycosylation. The diversity ofdgpAanddgpBCgene clusters might explain the broadC-glycoside substrate spectrum ofC. scindensandC. decagia. The otherCatenibacillusgenomes encode only a few potential flavonoid-converting enzymes. Our results indicate that severalCatenibacillusspecies are well-equipped to deglycosylate and degrade dietary plant polyphenols and might inhabit a corresponding, specific niche in the gut.

Genetics & Heredity↗

Development of dispensing hardware for safe fueling of heavy duty vehicles

The development of safe dispensing equipment for the fueling of heavy duty (HD) vehicles is critical to the expansion of this newly and quickly expanding market. This paper discusses the development of a HD dispenser and nozzles assembly (nozzle, hose, breakaway) for these new, larger vehicles where flow rates are more than double compared to light duty (LD) vehicles. This equipment must operate at nominal pressures of 700 bar, -40o C gas temperature, and average flow rate of 5-10 kg/min at a high throughput commercial hydrogen fueling station without leaking hydrogen. The project surveyed HD vehicle manufacturers, station developers, and component suppliers to determine the basic specifications of the dispensing equipment and nozzle assembly. The team also examined existing codes and standards to determine necessary changes to accommodate HD components. From this information, the team developed a set of specifications which will be used to design the dispensing equipment. In order to meet these goals, the team performed computational fluid dynamic, pressure modelling, and temperature analysis in order to determine the necessary parameters to meet existing safety standards modified for HD fueling. The team also considered user, operational, and maintenance requirements, such as freeze lock which has been an issue which prevents the removal of the nozzle from LD vehicles. The team also performed a failure mode and effects analysis (FMEA) to identify the possible failures in the design. The dispenser and nozzle assembly will be tested separately, and then installed on an innovative, HD fueling station which will use a HD vehicle simulator to test the entire system.

08 HYDROGEN↗

Tailoring the Coordination Micro‐Environment in Nanotraps for Efficient Platinum/Palladium Separation

Abstract Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high‐tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties. Herein, a breakthrough approach is presented by sophisticatedly tailoring the coordination micro‐environment in a series of aminopyridine‐based porous organic polymers, which enables the creation of platinum‐specific nanotraps for efficient separation of binary PGMs (platinum/palladium). The newly synthesized POP‐o2NH 2 ‐Py demonstrates record uptakes and selectivity toward platinum over palladium, with the amino groups adjacent to the pyridine moieties being vital in improving platinum binding performance. Further breakthrough experiments underline its remarkable ability to separate platinum and palladium. Spectroscopic analysis reveals that POP‐o2NH 2 ‐Py offers a more favorable coordination fashion to platinum ions compared to palladium ions owing to the greater interaction between N and Pt 4+ and stronger intramolecular hydrogen bonding between the amino groups and four coordinating chlorines at platinum. These findings underscore the importance of fine‐tuning the coordination micro‐environment of nanotraps through subtle modifications that can greatly enhance the selectivity toward the desired metal ions.

Chemistry↗

Geochemical and Microbial Dynamics of Hydrogen in a Methane Storage Reservoir

Hydrogen has been identified as a flexible energy carrier with zero or negative emission across multiple energy systems, and existing natural gas infrastructure could be leveraged if hydrogen gas (H2) was blended with methane (CH4). For example, subsurface methane storage reservoirs could be slightly modified to also store hydrogen if a methane/hydrogen blend were injected. However, the compatibility of methane storage reservoirs to include H2 injection has not been fully demonstrated, and this could lead to geochemical and microbiological reactions that alter the reservoir and stored gas content. It is essential that we understand the impact of H2 gas on the biogeochemistry of subsurface storage reservoirs before deploying large-scale H2-CH4 storage, We collected produced fluid from two separate methane storage reservoirs in the Southwestern US. First, we completed a baseline analysis of the biogeochemistry through qPCR, 16S rRNA sequencing, metagenomic sequencing, and geochemical analysis. Each reservoir was found to have unique geochemical conditions and a unique microbial community structure, with Site 1 having a higher TDS and an abundance of Shewanella and Site 2 having a lower TDS and high abundance of Eubacterium and Acetobacterium. Next, we ran a series of high pressure, high temperature reactors under hydrogen storage conditions with the biological sample from one of the storage reservoirs and a 20% H2-80% CH4 gas blend for up to 7 days. Our results show a decrease of hydrogen by 5% in reactors as early as 1-3 days. Previous hydrogen storage work has linked subsurface microorganisms with methanogenesis hydrogen sulfide production, acid production, and microbial corrosion. Our results show minimal change in the fluid chemistry, with the exception of a decrease in dissolved sulfate concentrations. Taxonomic sequencing demonstrated the presence of microorganisms capable of iron redox, acid generation, and hydrogen sulfide production throughout the reactors, suggesting microbial hydrogen consumption may occur through various metabolic pathways. This work demonstrates that site-specific geochemistry and microbiology may impact the efficiency of hydrogen storage in methane storage reservoirs.

environmental microbiology↗

Direct synthesis of branched hydrocarbons from CO 2 over composite catalysts in a single reactor

The thermocatalytic hydrogenation of CO 2 to hydrocarbons using a composite catalyst system in a single reactor under mild reaction conditions was investigated, by combining methanol synthesis, methanol dehydration and dimethyl ether homologation catalysts. High selectivity to isoparaffins, which are versatile precursors to sustainable aviation fuels, was achieved. The use of Cu/BEA significantly improved both the conversion of oxygenates and the hydrocarbon yield compared to HBEA by facilitating H-incorporation in the C-chain growth during the homologation reaction. A study of catalyst composition and reaction conditions revealed that nearly complete conversion of oxygenates was achieved using a stacked-bed configuration, providing high C-selectivity to C 4+ hydrocarbons (34.1% among all products and 95.5% in products excluding CO). The ability to completely convert oxygenates to hydrocarbons and achieve high CO-free selectivity to desired hydrocarbon products is unprecedented in CO 2 -to-hydrocarbon reports, and advantageous for downstream separation, as CO can be easily separated and recycled to improve overall hydrocarbon production in an integrated process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Conversion of Ethane to Oxygenates, Ethylene, and Hydrogen in a Noncatalytic Biphasic Plasma Microreactor

We selectively upgrade ethane (C 2 H 6 ) to ethanol (C 2 H 5 OH), methanol (CH 3 OH), and acetic acid (CH 3 COOH) in a catalyst-free, continuous, argon/water biphasic plasma microreactor. The water (H 2 O) evaporates and electron- dissociates into OH· radicals. OH· recombines with alkyl radicals, produced via electron dissociation of ethane, to generate the oxygenates that absorb into H 2 O. A plasma-assisted path, reminiscent of the low-temperature thermocatalytic ethane steam reforming, leads to significant H 2 coproduction. The gaseous stream also comprises CO 2 and C 2 H 4 . Up to 1.3 and 1 μmol min –1 of liquid C 2 H 5 OH and CH 3 OH are attained, respectively. Compared to CO 2 -assisted ethane plasma conversion, which produces many oxygenates with low selectivity, the carbon selectivity can range from >70% C 2 H 5 OH, CH 3 OH, and CH 3 COOH to 60% C 2 H 4 . Furthermore, the low carbon footprint, electrified, modular, intensified process using a reactive evaporation and separation plasma could pave the way for the valorization of underutilized shale gas resources in remote areas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental Setup to Investigate Hydrogen Isotope Retention on Powder Samples as Slag/Dust Proxies for Advanced Fusion Reactors

Slag/dust formation is one of the critical issues regarding tritium retention in advanced fusion reactors. We upgraded an ultrahigh vacuum device, the sample exposure station (SES), to perform temperature-programmed desorption (TPD), also known as thermal desorption spectroscopy, to investigate deuterium (D) retention in powder samples that are utilized as proxies for slag/dust particles formed in fusion reactors. TPD analysis, calibrated for the desorption rate, was successfully performed on commercially available crystalline/amorphous boron (B) powder after D 2 neutral gas or D + ion exposure. We calibrated the B powder temperature measurement for TPD analysis utilizing a D 2 desorption peak from B-D bonding known for its desorption temperature ~700 K. We introduce a separation procedure of observed D TPD signals, convoluted for corresponding D retention pathways, that was necessary for TPD analysis. This is the first report on the retention of D 2 neutral gas to B, and this observation was enabled by utilizing the B powder sample, which has a larger surface area than films commonly used in laboratory experiments. In conclusion, the upgraded SES system will enable us to investigate hydrogen isotope behaviors for powder/dust samples of various elemental compositions, including metals.

Plasma-facing component debris↗

Hydrogen and deuterium tunneling in niobium

We use density functional methods to identify the atomic configurations of H and D atoms trapped by O impurities embedded in bulk Nb. The O atoms are located at the octahedral position in the Nb body-centered cubic (BCC) lattice, and H (D) atoms tunnel between two degenerate tetrahedral sites separated by a mirror plane. Using nudged elastic band (NEB) methods, we calculate the double-well potential for O-H and O-D impurities and the wave functions and tunnel splittings for H and D atoms. Our results agree with those obtained from analysis of heat capacity and neutron scattering measurements on Nb with low concentrations of O-H and O-D.

density functional theory↗

Enhancing organic matter removal, product recovery, and hydrogen generation from fermentation wastewater

Existing ethanol biorefineries produce billions of gallons of wastewater (stillage) that must be treated extensively prior to discharge or concentrated in an energy intense evaporation step to produce animal feed as a value-added bioproduct. Yeasts and filamentous fungi were screened for growth and reduction of soluble organic compounds, carbohydrates, and protein from stillage to identify species capable of rapidly concentrating organic compounds into readily separable biomass in an attempt to concentrate the product using a much more efficient centrifugation step. Yeasts amenable to production of biomass derived products including bio-oils (Yarrowia lipolytica and Rhodotorula pallida), chitosan (Aspergillus niger) and animal feed (Cyberlindnera jadinii) were identified as well as microbes capable of efficient production of small organic acids with applications as bioderived polymers including 3-hydroxypropionic acid (engineered A. niger) and lactic acid using a co-culture of Debaryomyces udenii and Lactobacillus pentosus. The filamentous fungus A. niger eliminated all specifically measured soluble organics (glycerol, acetate, lactate, ethanol, and citrate) in under 48 hours and reduced total soluble protein content by 46% and total carbohydrate content by 83% within 96 hours, the greatest reduction in organic content observed. During this process an A. niger strain engineered to produce 3-hydroxypropionic acid achieved a yield of 0.35 C-mol 3HP / C-mol non-protein organics consumed at an overall rate of 0.09 g/Lh in unmodified stillage without pH control. Stillage treated by the fodder yeast C. jadinii as well as stillage containing acetic or lactic acid was found to be most suitable for growth by electrogenic bacteria with applications in production of electricity or hydrogen from wastewater. This work establishes fungal and bacterial strains appropriate for biological treatment of stillage to produce biomass derived products, soluble commodity chemicals, energy, and treated water to reduce the energy intensity and improve the economics of ethanol biorefineries.

09 BIOMASS FUELS↗

Gas–Phase Synthesis of 3–Vinylcyclopropene via the Crossed Beam Reaction of the Methylidyne Radical (CH; X 2 Π) with 1,3–Butadiene (CH 2 CHCHCH 2 ; X 1 Ag)

The crossed molecular beam reactions of the methylidyne radical (CH; X 2 Π) with 1,3-butadiene (CH 2 CHCHCH 2 ; X 1 Ag) along with their (partially) deuterated counterparts were performed at collision energies of 20.8 kJ mol -1 under single collision conditions. Combining our laboratory data with ab initio calculations, we reveal that the methylidyne radical may add barrierlessly to the terminal carbon atom and/or carbon-carbon double bond of 1,3-butadiene, leading to doublet C 5 H 7 intermediates with life times longer than the rotation periods. Furthermore, these collision complexes undergo non-statistical unimolecular decomposition through hydrogen atom emission yielding the cyclic cis- and trans-3-vinyl-cyclopropene products with reaction exoergicities of 119±42 kJ mol -1 . Since this reaction is barrierless, exoergic, and all transition states are located below the energy of the separated reactants, these cyclic C 5 H 6 products are predicted to be accessed even in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and cold molecular clouds such as TMC-1.

3-vinylcyclopropene↗

Modeling Liquid Water by Climbing up Jacob’s Ladder in Density Functional Theory Facilitated by Using Deep Neural Network Potentials

Within the framework of Kohn–Sham density functional theory (DFT), the ability to provide good predictions of water properties by employing a strongly constrained and appropriately normed (SCAN) functional has been extensively demonstrated in recent years. Here, we further advance the modeling of water by building a more accurate model on the fourth rung of Jacob’s ladder with the hybrid functional, SCAN0. In particular, we carry out both classical and Feynman path-integral molecular dynamics calculations of water with the SCAN0 functional and the isobaric–isothermal ensemble. To generate the equilibrated structure of water, a deep neural network potential is trained from the atomic potential energy surface based on ab initio data obtained from SCAN0 DFT calculations. For the electronic properties of water, a separate deep neural network potential is trained by using the Deep Wannier method based on the maximally localized Wannier functions of the equilibrated trajectory at the SCAN0 level. The structural, dynamic, and electric properties of water were analyzed. The hydrogen-bond structures, density, infrared spectra, diffusion coefficients, and dielectric constants of water, in the electronic ground state, are computed by using a large simulation box and long simulation time. For the properties involving electronic excitations, we apply the GW approximation within many-body perturbation theory to calculate the quasiparticle density of states and bandgap of water. Compared to the SCAN functional, mixing exact exchange mitigates the self-interaction error in the meta-generalized-gradient approximation and further softens liquid water toward the experimental direction. For most of the water properties, the SCAN0 functional shows a systematic improvement over the SCAN functional. However, some important discrepancies remain. The H-bond network predicted by the SCAN0 functional is still slightly overstructured compared to the experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Butene-Rich Alkene Formation from 2,3-Butanediol through Dioxolane Intermediates

The cost-effective production of sustainable aviation fuels (SAF) remains a major challenge within the energy sector. One approach to address this is the fermentation of biomass feedstocks into oxygenates followed by catalytic conversion to alkenes or other oligomerization precursors. 2,3-Butanediol (BDO) is a promising fermentation product due to its four-carbon nature, its decreased microorganism toxicity and associated higher maximum fermentation titers relative to other alcohols and oxygenates, and its capacity to be readily converted into butene isomers and longer chain alkenes. BDO conversion is currently constrained by separation challenges for BDO isolation due to its high boiling point and hydrophilicity. Here, this work expands upon previous BDO reactive separation via dioxolane formation over a solid acid catalyst by investigating the conversion of dioxolanes into alkene mixtures. Dioxolanes were formed from a range of aldehydes and subsequently converted over a Cu/ZSM-5 catalyst (448–523 K) via an ether cleavage, hydrogenation, and dehydration reaction network to form alkene-rich product mixtures (96% C 3+ alkene yield, 523 K). This selectivity is greater than that of direct BDO conversion to alkenes over an identical catalyst (89%, 523 K). C 3+ alkene selectivity is maximized between 498 and 523 K at complete dioxolane conversion without significant alkene hydrogenation to alkanes. The alkene product distributions can be tailored via both aldehyde selection during dioxolane formation and the dioxolane conversion reaction temperature. Alkene mixtures from dioxolane conversion predominantly reflect the carbon chain length and stereochemistry of BDO and the initial aldehyde at or below 498 K, yet higher reaction temperatures yield alkene mixtures of similar carbon chain distributions, regardless of initial aldehyde selection. Deactivation of the Cu/ZSM-5 catalyst is observed for multiple steps of the overall reaction network but can be minimized by facilitating the complete dioxolane-to-alkene reaction network at temperatures of at least 498 K.

2,3-butanediol↗

Asteroseismological analysis of the polluted ZZ Ceti star G 29 – 38 with TESS

G29 – 38 (TIC 422526868) is one of the brightest (V = 13.1) and closest (d = 17.51 pc) pulsating white dwarfs with a hydrogen-rich atmosphere (DAV/ZZ Ceti class). It was observed by the TESS spacecraft in sectors 42 and 56. The atmosphere of G 29 – 38 is polluted by heavy elements that are expected to sink out of visible layers on short time-scales. Here, the photometric TESS data set spans ~51 d in total, and from this, we identified 56 significant pulsation frequencies, that include rotational frequency multiplets. In addition, we identified 30 combination frequencies in each sector. The oscillation frequencies that we found are associated with g-mode pulsations, with periods spanning from ~ 260 to ~ 1400 s. We identified rotational frequency triplets with a mean separation δν ℓ = 1 of 4.67 μHz and a quintuplet with a mean separation δν ℓ = 2 of 6.67 μHz, from which we estimated a rotation period of about 1.35 ± 0.1 d. We determined a constant period spacing of 41.20 s for ℓ = 1 modes and 22.58 s for ℓ = 2 modes. We performed period-to-period fit analyses and found an asteroseismological model with M * /M ⊙ = 0.632 ± 0.03, K, and log g = 8.048 ± 0.005 (with a hydrogen envelope mass of M H ~ 5.6 × 10 –5 M * ), in good agreement with the values derived from spectroscopy. We obtained an asteroseismic distance of 17.54 pc, which is in excellent agreement with that provided by Gaia (17.51 pc).

79 ASTRONOMY AND ASTROPHYSICS↗

Scaling-up up-flow microbial electrolysis cells with a compact electrode configuration for continuous hydrogen production

Maintaining high current densities is a key challenge in scaling-up microbial electrolysis cell (MEC) reactors. In this study, a novel 10 L MEC reactor with a total electrode surface area > 1 m 2 was designed and evaluated to maximize the current density and H 2 recovery. Performances of the reactor suggest that the longitudinal structure with parallel vertical orientation of the electrodes encouraged high fluid mixing and the sheet metal electrode frames provided distributed electrical connection. Results also demonstrated that the electrode pairs located next to reactor walls decreased current density, as did separating the electrodes with separators. High volumetric H 2 production rate of 5.9 L/L/d was achieved at a volumetric current density of 970 A/m 3 (34 A/m 2 ). Furthermore, the observed current densities of the large reactor were accurately predicted based on the internal resistance analysis of small scale MECs (0.15 L), demonstrating the scalability of the single chamber MEC design.

08 HYDROGEN↗

High‐Concentration Alcohol Generation in Bipolar Membrane CO Electrolyzer

Electrochemical reduction of carbon dioxide and carbon monoxide offers an electricity‐powered route to make multicarbon liquid products. However, in conventional systems employing anion exchange membranes (AEMs), significant liquid product crossover leads to dilute product streams, increasing separation costs; and also produces unwanted anodic oxidation, further decreasing overall efficiency. Here, we report a forward‐biased bipolar membrane (FB‐BPM) system that achieves <10% liquid product crossover while sustaining a highly alkaline environment near the cathode, suppressing ethylene and hydrogen and favoring liquid products. By tuning catalyst composition to modulate the adsorption of *H and *OH, we steer selectivity toward acetate and alcohols. Using the FB‐BPM system, we achieve >25 wt% acetate on CuZn and >15 wt% alcohols on CuSn directly from the cathode outlet stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mapping in situ the assembly and dynamics in aqueous supramolecular polymers

Supramolecular polymers, bonded through directional non-covalent interactions, closely mimic dynamic behaviors of biological nanofibers. However, the complexity of assembly pathways makes it highly challenging to unravel the nature of supramolecular dynamics in aqueous environments. Here we introduce a precise combinatorial titration methodology to probe in situ the assembly of peptide amphiphiles (PAs). This approach reveals a binary assembly mechanism governed by equilibrium between spheroidal micelles and β-sheet polymers. Weakening hydrogen bonding shifts the equilibrium towards micelles and decreases the internal structural order of filamentous polymers, promoting supramolecular dynamics. Extending this methodology to two-component copolymerization systems, we find a surprising tendency to form blocky nanostructures with reduced internal phase separation as the mismatch in peptide sequence decreases. Interestingly, while well-mixed copolymers acquire different dynamics, mismatched ones retain the characteristic supramolecular motion of their homopolymer counterparts. These critical insights into supramolecular dynamics offer strategies to tailor the dynamic functions of supramolecular nanomaterials.

Molecular self-assembly↗

Reweighting configurations generated by transferable, machine learned models for protein sidechain backmapping

Multiscale modeling requires the linking of models at different levels of detail, with the goal of gaining accelerations from lower fidelity models while recovering fine details from higher resolution models. Communication across resolutions is particularly important in modeling soft matter, where tight couplings exist between molecular-level details and mesoscale structures. While multiscale modeling of biomolecules has become a critical component in exploring their structure and self-assembly, backmapping from coarse-grained to fine-grained, or atomistic, representations presents a challenge, despite recent advances through machine learning. A major hurdle, especially for strategies utilizing machine learning, is that backmappings can only approximately recover the atomistic ensemble of interest. We demonstrate conditions for which backmapped configurations may be reweighted to exactly recover the desired atomistic ensemble. By training separate decoding models for each sidechain type, we develop an algorithm based on normalizing flows and geometric algebra attention to autoregressively propose backmapped configurations for any protein sequence. Critical for reweighting with modern protein force fields, our trained models include all hydrogen atoms in the backmapping and make probabilities associated with atomistic configurations directly accessible. We also demonstrate, however, that reweighting is extremely challenging despite state-of-the-art performance on recently developed metrics and generation of configurations with low energies in atomistic protein force fields. Through detailed analysis of configurational weights, we show that machine-learned backmappings must not only generate configurations with reasonable energies, but also correctly assign relative probabilities under the generative model. These are broadly important considerations in generative modeling of atomistic molecular configurations.

Monroe, Jacob I. [Univ. of Arkansas, Fayetteville,↗

Lignin to liquid fuels and polyols using biomass-derived solvents

A process of producing a distillate fuel from lignin includes: preparing a biomass-derived lignin solvent; dissolving the lignin in the biomass-derived solvent; and separating undissolved lignin and mineral matter to produce a syncrude. In certain embodiments, the process further includes subjecting the syncrude to a hydrotreatment/hydrogenation process to produce a distillate fuel. A process to improve direct lignin liquefaction includes: using a non-hydrogenated lipid in a direct lignin liquefaction process to facilitate lignin depolymerization. A process for using a biomass-derived feedstock as a hydrogen donor includes: providing a biomass-derived feedstock; modifying the feedstock to improve its usefulness as a hydrogen donor; and conducting a transfer hydrogenation process using the modified feedstock as a hydrogen donor.

Chauhan, Satya P.↗