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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Effect of Al on the formation and structure of alkali-silica reaction products

The use of Al-rich supplementary cementitious materials can effectively reduce the expansion of concrete caused by alkali-silica reaction (ASR). However, the role of Al in mitigating the formation and structure of ASR products is only poorly understood, since direct investigation of the reaction in the micro-scale veins of aggregates is difficult. Recent successful synthesis of ASR products provides a unique opportunity to directly assess the role of Al in ASR. In this study, the effect of Al on the formation and structure of ASR products synthesized at 40 and 80 °C is investigated. It is found that the presence of Al in concentration lower than 0.1 mM neither prevents ASR nor alters the structure of the crystalline ASR products formed at 40 °C. However, formation of the crystalline ASR product at 80 °C is lowered at higher Al content due to the formation of a zeolitic precursor.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Formation, structure, and thermal stability evolution of ternesite based on a single-stage sintering process

Highlights: • The synthesis of high-purity ternesite based on a single-stage sintering process was firstly studied. • The formation mechanism and crystallization behaviour of ternesite during sintering were investigated. • The structure perfection and symmetry of ternesite crystals were increased with its growth. • The growth and structural development of ternesite crystals during sintering resulted in a higher thermal stability of itself. Ternesite was prepared via a single-stage solid-state reaction from stoichiometric quantities of the CaCO{sub 3}, SiO{sub 2} and CaSO{sub 4}·2H{sub 2}O precursors. In this paper, the formation, structure, and thermal stability evolution of ternesite during sintering were investigated ex situ after quenching. The optimal sintering temperature for the formation of high-purity ternesite was approximately 1200 °C for 12 h, of which the purity level can reach as high as 96.3%. The results from scanning electron microscopy analysis suggest that the formation of ternesite benefited from the preformation of the intermediate silicate phase. Increasing the sintering temperature from 1100 °C to approximately 1250 °C was favourable for the growth of ternesite crystals, and a prolonged duration can also promote this behaviour. The structural perfection and symmetry of ternesite crystals increased with its growth, which was demonstrated by a multimethod approach. By means of thermal analysis, the growth and structural development of ternesite crystals during sintering eventually resulted in a higher thermal stability.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Comparative geochemistry of flowback chemistry from the Utica/Point Pleasant and Marcellus formations

Flowback/Produced fluid samples were collected from several wells from two Utica/Point Pleasant (UPP) sites (UPPW and UPPS) in Ohio, and one Marcellus (Marcellus Shale Energy and Environment Laboratory (MSEEL)) site in West Virginia over a period of approximately two years. Although these formations have different ages, depositional environments, diagenetic histories, and geochemical and mineralogical compositions (i.e. the UPP is significantly more carbonate rich than the Marcellus which is more siliceous), analysis of trends in fluid species over time shows that, overall, the TDS and major solubilized elements (Na, Ca, Cl) in the UPP and Marcellus brines are remarkably similar. Total dissolved solutes (TDS) in these brines ranged from approximately 40 to 250 g/L salt, and in general, concentrations increased with time elapsed since natural gas well completion and stimulation. The behavior of Na, Br, and Cl suggests that the produced water signatures from these formations are largely derived from the native formational brines which display evidence of originating from evaporated seawater. There is a strong correlation between Cl and Br, indicating that both species behave conservatively, and the similarity among each of these brines suggests no appreciable contribution of salt from halite dissolution because Br is excluded from the halite structure. Cl/Br ratios in the brines range from ~80 to 120 (mg/L/mg/L). Other elements, such as K, which readily reacts between fluids and ion exchange sites on clays, generally exhibit conservative behavior for an individual site, but show significant variations among each of the different well pads. The concentrations of Sr and Ba vary dramatically among well sites, and increase with respect to Cl- over time, suggesting increasing solubilization, presumably from desorption from clay minerals or dissolution of carbonates or sulfates from the source formation(s). The UPPW well site has very low Ba due to high-sulfate input fluid, which resulted in precipitation of barite/celestite in the brines. In contrast the UPPS well site had elevated Sr (~ 3500 mg/L), presumably due to the use of Sr-rich recycled brine used in hydraulic fracturing. The Marcellus site had the highest Ba concentrations (up to 10 g/L) and highest Ba/Sr ratios in the fluids, due to the high concentration of barium in the Marcellus target (~ 1000 ppm, as compared to ~200 ppm in the UPP). These observations suggest that solutes in the FP fluids are derived from native brines, water-rock interactions that have occurred over geologic time scales, as well as some contribution from contemporaneous reactions in the subsurface. The results also show that the composition of the injected fluid can influence flowback fluid chemistry and possibly production efficiency.

58 GEOSCIENCES↗
DOE OSTI2022

Formation of PAHs, phenol, benzofuran, and dibenzofuran in a flow reactor from the oxidation of ethylene, toluene, and n-decane

The necessity to reveal the formation mechanism of not only polycyclic aromatic hydrocarbons (PAHs) but also oxygenated PAHs (OPAHs) during combustion is increasing. Although many studies on PAHs have been conducted, fundamental studies investigating OPAH formation are still limited. Phenol, benzofuran, and dibenzofuran were selected as OPAHs in this study. We experimentally investigated fuel-rich oxidation in a flow reactor at atmospheric pressure, mean gas temperatures from 1050 to 1350 K, residence times from 0.2 to 1.5 s, and equivalence ratios from 3.0 to 12.0. Ethylene, toluene, and n-decane were used as fuels. Three kinds of OPAHs as well as 23 kinds of PAHs including monocyclic structures were quantitatively measured through a direct sampling using gas chromatography mass spectrometry. The results showed that concentrations of PAHs and OPAHs were strongly affected by the fuel type, with increasing concentrations in the following order: ethylene < n-decane < toluene. A chemical kinetic model for OPAH formation was developed based on a recent PAH growth model. The model showed that the predicted concentrations of OPAHs and PAHs were in reasonable agreement with the measured data in this study. Some modifications were made to the previous model based on recent literature studies and on the comparison of the simulated and measured results. The effect of the fuel type on the formation of PAHs and OPAHs was investigated through kinetic analysis using the model to discuss their reaction pathways.

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

Density functional study of atomic arrangements in CrMnFeCoNi high-entropy alloy and their impact on vacancy formation energy and segregation

Here, using the density functional theory-coupled Monte Carlo approach, we explored the chemical short-range order (SRO) and element segregation in equimolar CrMnFeCoNi alloy. We found that state-of-the-art approximation of random element distribution is only applicable at > 1100 K close to the melting temperature, while the Cr-Cr repulsion driving the system stabilization and accompanying the formation of cubic Cr sublattice, and mild Ni-Ni attraction are the most prominent pair interactions at lower temperatures. Chemical potential and vacancy formation energy calculations indicate that Cr is most sensitive to the local chemical environment, making Cr atoms most stabilized when the preferred SRO is introduced. While the vacancy formation is predicted equally probable among five constituting elements in the random solid solution, Cr and Ni atoms show the lowest vacancy formation energies in the structure with SRO. Furthermore, distinct element segregation was predicted in the vicinity of planar defects, including symmetric tilt grain boundary and stacking fault, which we correlated to the site- and chemistry-dependent atomic volume and bond lengths. It suggests that the local mechanical strain and bond energy induce the SRO development and element segregation: Namely, the system takes advantage of segregation of Ni atoms having large atomic volume or Cr-Cr pairs having elongated bond lengths to fill in the excess volume at defects that relaxes the mechanical strain field and optimizes bond energy distribution. The correlation between the SRO and properties of CrMnFeCoNi alloy needs further investigations, which is expected to greatly help understand and control the properties of high-entropy alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Interfacial Void Formation and Self-Healing in Oxide Scales on Al-containing High-Entropy Alloy

The exceptional high-temperature oxidation resistance of Al-containing high-entropy alloys (HEAs) is often attributed to the formation of a protective α-Al 2 O 3 scale. However, the dynamic, atomic-scale mechanisms governing the stability of this scale—including interfacial void formation and the often-postulated but rarely visualized “self-healing” capacity—remain poorly understood. Herein, we reveal the complex evolution of the triple-layer oxide scale on an Al 10 CoCrFeNi HEA through combined electron microscopy and diffraction study. We show that interfacial voids are an inherent consequence of the scaling process, originating from two distinct mechanisms: the Kirkendall effect at the interface between the γ-Al 2 O 3 /α-Al 2 O 3 and alloy driven by cationic diffusion imbalance and volumetric contraction due to phase transformations at the spinel/Cr 2 O 3 interface. Crucially, we provide microstructural evidence consistent with an intrinsic self-healing response. This process is driven by coupled inward diffusion of oxygen and outward diffusion of metal cations, leading to the in-situ formation of transient θ-Al 2 O 3 and spinel phases that partially fill and seal the voids. Here, these results provide atomic-scale insights into the phase evolution, defect formation, and self-repair of oxide scales in HEAs—highlighting pathways to enhance their oxidation resistance in extreme environments.

High-entropy alloy↗
DOE OSTI2021

Assessment of sulfur trioxide formation due to enhanced interaction of nitrogen oxides and sulfur oxides in pressurized oxy-combustion

Pressurized oxy-combustion is emerging to be one of the best technologies for significantly decreasing the energy penalty for CO 2 capture in coal-fired power plants. However, the higher pressure boosts the formation of acid gases, including SO 3 and NO 2 , which could increase the risk of corrosion. The synergistic promotion of SO 3 and NO 2 formation in pressurized oxy-combustion is kinetically evaluated under representative conditions (1 ~ 30 atm, 600 ~ 1200 °C, NO/SO 2 = 0.1 ~ 5). We begin with a comprehensive mechanism (72 species and 428 reactions), covering nitrogen and sulfur chemistry, relying on GRI-Mech 3.0. This analysis shows that the interaction of SO X and NO X enhances the conversion rates of SO 2 → SO 3 , and this effect is more apparent at elevated pressures and lower temperatures. Mechanism analyses indicate that at elevated pressures, the formation pathways of SO 3 through HOSO 2 + O 2 = SO 3 + HO 2 , and NO 2 through HO 2 + NO = NO 2 + OH, are promoted due to the strong interaction between SO X and NO X . The intermediate between these two reactions is SO 2 + OH + M = HOSO 2 + M, resulting in a strong cycle, that can be expressed by the global reaction NO + SO 2 + O 2 = NO 2 + SO 3 . Finally, a nine-step reduced chemistry is developed and validated to accurately predict the formation of SO 3 in the post-flame region at elevated pressures.

42 ENGINEERING↗
DOE OSTI2021

Gas hydrate deposit formation in transient flowloop tests and mitigation with a surface treatment

Thermodynamic and thermal mitigation strategies are traditionally utilized to prevent gas hydrate formation but may be rendered ineffective for certain unplanned, extended shut-in scenarios. Unfortunately, the current knowledge regarding transient gas hydrate formation has been extremely limited to only a few studies and unable to address this complex issue adequately. This work, conducted in a lab-scale flowloop, aims to add to the understanding of this area by delving into the implications of transient conditions on gas hydrate formation mechanisms, while also exploring a possible mitigation strategy of a surface treatment. Specifically, the effects of phase separation on gas hydrate formation locations, transportability, and plugging are presented for an oil-dominated system. An omniphobic surface treatment is shown to affect initial gas hydrate deposition and its wall adherence strength, as well as the overall plugging outcome. Overall, this work combines observational information with process data measurements to provide a better understanding of phase separated gas hydrate systems and passive deposition mitigation strategies. This can further aid advanced gas hydrate modeling efforts, which currently do not adequately address transient flow effects on phase separation/dispersion. Here, it offers representative gas hydrate testing for coatings, which have exclusively been limited to non-flowing and/or bench-scale analysis, to give confidence in their potential application as advanced deposition prevention tools.

03 NATURAL GAS↗
DOE OSTI2021

Influence of trace level As or Ni on pyrite formation kinetics at low temperature

Pyrite formation at low temperature during early diagenesis in (sub-)surface sediments is an essential step of Fe and S biogeochemical cycles and the presence of this ubiquitous mineral of surface environments is often used as an indicator of paleo-redox conditions. Pathways of pyrite formation are usually discussed in environmental settings by involving a variety of nanosized Fe-S mineralogical precursors as a function of the local geochemical conditions. However, the influence of trace element impurities such as Ni and As in the solution at the time of pyrite formation has been poorly studied, whereas specific chemical signatures of trace elements are commonly observed in sedimentary pyrites. Here, a better understanding of the impact of Ni and As incorporation at trace levels on pyrite formation is essential to help refining the use of these elements as paleo-redox indicators and to evaluate the role of pyrite as a sink regulating the biogeochemical cycle of potentially toxic trace elements.

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

Nickel-rich, volatile depleted iron meteorites: Relationships and formation processes

Ungrouped iron meteorites Tishomingo, Willow Grove, and Chinga, and group IVB iron meteorites, are Ni-rich. Similarities include enrichments of 10–100 × CI for some refractory siderophile elements, and equivalent depletions in more volatile siderophile elements. Superimposed on the overall enrichment/depletion trend, certain siderophile elements (P, W, Fe, Mo) are depleted relative to elements of similar volatility. All three ungrouped irons derive from parent bodies formed in the early Solar System. Willow Grove and Chinga are characterized by cosmic ray exposure corrected 182 W/ 184 W consistent with metal-silicate segregation on their parent bodies within 1–3 Myr of Solar System formation, within the age range determined for segregation of magmatic iron meteorite parent bodies, including group IVB irons. Tishomingo is characterized by a younger model age 4–5 Myr subsequent to Solar System formation, reflecting either late stage melting resulting from 26 Al decay, or an impact resetting. The discovery of stishovite in Tishomingo, indicating exposure to a minimum shock pressure of 8–9 GPa, is consistent with the latter. Stishovite in Tishomingo and chromite included in troilite-daubréelite in IVB irons allows oxygen isotopic composition comparison between these meteorites. Different mass independent oxygen isotopic compositions of IVB irons and Tishomingo indicate genetically distinct parent bodies. By contrast, mass independent Mo isotopic compositions overlap within analytical uncertainties, indicating a similar, carbonaceous chondrite (CC) type genetic heritage. Molybdenum and 183 W isotopic data for Chinga and Willow Grove indicate derivation from CC type parent bodies. Willow Grove shares Mo and 183 W isotopic compositions with the Ni-rich South Byron Trio (SBT) grouplet and the Milton pallasite. These Ni-rich meteorites likely formed in the same general nebular environment as other CC planetesimals, likely the outer Solar System. Highly siderophile element (HSE) abundances of Willow Grove and Tishomingo are similar to some IVB meteorites, consistent with formation by moderate degrees of fractional crystallization from initial metallic melts with low S and P, and modestly fractionated HSE. The comparable HSE abundances of Tishomingo and Willow Grove to some IVB irons, yet substantially higher Ni concentrations, indicate formation on parent bodies with lower bulk HSE abundances or HSE concentration in proportionally smaller volumes of metal. HSE abundances in Chinga are considerably lower than in IVB irons, highly fractionated, and processes responsible for these remain elusive. For IVB irons and these ungrouped irons, high temperature condensation likely dominated the enrichment and depletion of the refractory and volatile siderophile elements, respectively. Parent body degassing may have also played a role. Relative depletion of volatile siderophile elements is not, however, a universal feature of high-Ni meteorites. The SBT and Milton pallasite are Ni-rich, but less depleted in the more volatile siderophile elements. Nickel enrichment was likely driven by oxidation of Fe metal during parent body accretion or core segregation. Oxidation of the Tishomingo and Willow Grove parent bodies may have occurred at ~ IW + 1, indicated by relative Mo and W depletions due to metal/water reaction during differentiation. Late-stage reduction, indicated by the presence of Cr-bearing sulfides in Tishomingo and IVB irons, may have resulted from exhaustion of the oxidant.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Reaction path model of the formation of abiotic immiscible hydrocarbon fluids in subducted carbonated serpentinites, Lanzo Massif (Western Italian Alps)

Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH 4 -H 2 -rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH 4,f , C 2 H 6,f , C 3 H 8,f , isoC 4 H 10,f , CO 2,f , H 2,f ). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals. We developed a predictive reaction path model of invasive H 2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO 2 , and aqueous species. CH 4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H 2 O formed due to oxidation of H 2 . More hydrocarbons and H 2 O formed in models with lower fluid/rock mass ratios or with more reactant H 2 . Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final log fO 2 and pH. As a result, our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H 2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.

58 GEOSCIENCES↗
DOE OSTI2024

Formation of five-membered ring structures via reactions of o -benzyne

The formation of five-membered ring structures is important for the generation of curved and bowl-shaped polycyclic aromatic hydrocarbons (PAHs) under combustion conditions. Here, we report the identification of the indenyl (C 9 H 7 ) radical – the simplest aromatic hydrocarbon radical carrying an adjacent five- and six-membered ring, as the major product of the o-benzyne (o-C 6 H 4 ) reaction with propargyl (C 3 H 3 ). Because real flames exhibit a complex chemistry, elucidation of a specific reaction is very challenging. Instead, we studied the o-C 6 H 4 + C 3 H 3 reaction in a resistively heated microtubular SiC reactor at controlled conditions of 1150 K and a pressure near 10–20 Torr. To this end, the reactants o-benzyne and propargyl were pyrolytically generated from benzoyl chloride and propargyl bromide. We identified the reactants and the indenyl radical isomer-selectively utilizing photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). In conclusion, the experimentally observed predominant formation of indenyl radicals finally confirms the theoretical predictions of Matsugi and Miyoshi [Phys. Chem. Chem. Phys. 14 (2012), 9722–9728] and highlights a versatile route for the formation of five-membered rings and curved PAHs via reactions of o-benzyne that favor the formation of multiring species over aliphatically substituted aromatic species.

Molecular-weight growth↗
DOE OSTI2023

Environmental impact of solution pH on the formation and migration of iron colloids in deep subsurface energy systems

Deep subsurface stimulation processes often promote fluid-rock interactions that can lead to the formation of small colloidal particles that are suspected to migrate through the rock matrix, partially or fully clog pores and microfractures, and promote the mobilization of contaminants. Thus, the goal of this work is to understand the geochemical changes of the host rock in response to reservoir stimulation that promote the formation and migration of colloids. Two different carbonate-rich shales were exposed to different solution pHs (pH = 2 and 7). In this study, iron and other mineral transformations at the shale-fluid interface were first characterized by synchrotron-based XRF mapping. Then, colloids that were able to migrate from the shale into the bulk fluid were characterized by synchrotron-based extended X-ray absorption structure (EXAFS), scanning electron microscopy (SEM), and single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS). When exposed to the pH = 2 solution, extensive mineral dissolution and secondary precipitation was observed; iron-(oxyhydr)oxide colloids colocated with silicates were observed by SEM at the fluid-shale interfaces, and the mobilization of chromium and nickel with these iron colloids into the bulk fluid was detected by sp-icpTOF-MS. Iron EXAFS spectra of the solution at the shale-fluid interface suggests the rapid (within minutes) formation of ferrihydrite-like nanoparticles. Thus, we demonstrate that the pH neutralization promotes the mobilization of existing silicate minerals and the rapid formation of new iron colloids. These Fe colloids have the potential to migrate through the shale matrix and mobilize other heavy metals (such as Cr and Ni, in this study) and impacting groundwater quality, as well produced waters from these hydraulic fracturing operations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Differential localization patterns of pyruvate kinase isoforms in murine naïve, formative, and primed pluripotent states

Highlights: • PKM1/2 protein abundance is greater in formative mEpiLCs compared to naïve mESCs or primed mEpiSCs. The ratio of PKM1/2 is maintained. • PKM1/2 are localized in both nuclear and cytoplasmic regions relative to GAPDH and OCT4 across the pluripotent continuum. • PKM1 localization is strongly correlated to OCT4 localization, and moderately to GAPDH in formative mEpiLCs. • PKM1/2 localization is moderately correlated to OCT4 and GAPDH localization in naïve mESCs. • PKM1/2 localization are moderately correlated to GAPDH localization in primed mEpiSCs. Mouse embryonic stem cells (mESCs) and mouse epiblast stem cells (mEpiSCs) represent opposite ends of the pluripotency continuum, referred to as naïve and primed pluripotent states, respectively. These divergent pluripotent states differ in several ways, including growth factor requirements, transcription factor expression, DNA methylation patterns, and metabolic profiles. Naïve cells employ both glycolysis and oxidative phosphorylation (OXPHOS), whereas primed cells preferentially utilize aerobic glycolysis, a trait shared with cancer cells referred to as the Warburg Effect. Until recently, metabolism has been regarded as a by-product of cell fate, however, evidence now supports metabolism as being a driver of stem cell state and fate decisions. Pyruvate kinase muscle isoforms (PKM1 and PKM2) are important for generating and maintaining pluripotent stem cells (PSCs) and mediating the Warburg Effect. Both isoforms catalyze the final, rate limiting step of glycolysis, generating adenosine triphosphate and pyruvate, however, the precise role(s) of PKM1/2 in naïve and primed pluripotency is not well understood. The primary objective of this study was to characterize the cellular expression and localization patterns of PKM1 and PKM2 in mESCs, chemically transitioned epiblast-like cells (mEpiLCs) representing formative pluripotency, and mEpiSCs using immunoblotting and confocal microscopy. The results indicate that PKM1 and PKM2 are not only localized to the cytoplasm, but also accumulate in differential subnuclear regions of mESC, mEpiLCs, and mEpiSCs as determined by a quantitative confocal microscopy employing orthogonal projections and airyscan processing. Importantly, we discovered that the subnuclear localization of PKM1/2 changes during the transition from mESCs, mEpiLCs, and mEpiSCs. Finally, we have comprehensively validated the appropriateness and power of the Pearson's correlation coefficient and Manders's overlap coefficient for assessing nuclear and cytoplasmic protein colocalization in PSCs by immunofluorescence confocal microscopy. We propose that nuclear PKM1/2 may assist with distinct pluripotency state maintenance and lineage priming by non-canonical mechanisms. These results advance our understanding of the overall mechanisms controlling naïve, formative, and primed pluripotency.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Tetramethylpyrazine inhibits neutrophil extracellular traps formation and alleviates hepatic ischemia/reperfusion injury in rat liver transplantation

Hepatic ischemia/reperfusion injury (IRI) is an adverse effect for liver transplantation which is characterized by immune response mediated inflammation. Recent studies report that neutrophil extracellular traps (NETs) are implicated in hepatic IRI. The aim of this study was to explore the mechanism of action of tetramethylpyrazine (TMP), the main chemical composition of Ligusticum chuanxiong in treatment of ischemic related diseases. Data showed that hepatic IRI increases the leak of alanine aminotransferase (ALT) and aspartate transaminase (AST), and stimulates formation of NETs. Extracellular DNA/NETs assay, hematoxylin-eosin (HE) staining, immunofluorescence assay, terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL) and Western blot assay, showed that TMP significantly reduces formation of NETs and alleviates hepatic IRI. Moreover, TMP and Diphenyleneiodonium (DPI) suppressed ROS production in neutrophils. In addition, analysis showed that activation of NADPH oxidase plays a role in formation of NETs triggered by hepatic IRI. Notably, TMP inhibited formation of NETs though inhibition of NADPH oxidase. Additionally, Combination treatment using TMP and DPI was more effective compared with monotherapy of either of the two drugs. These findings show that combination therapy using TMP and DPI is a promising method for treatment hepatic IRI.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2026

Formation of 1 H -Phenalene (C 13 H 10 ) in the Taurus Molecular Cloud via Methylidyne Addition-Cyclization-Aromatization (MACA)

The formation of 1H-phenalene (C 13 H 10 ) in cold molecular clouds, such as the Taurus Molecular Cloud-1 (TMC-1), presents a significant challenge to traditional astrochemical models, which predominantly suggest high-temperature pathways for polycyclic aromatic hydrocarbon (PAH) formation. In this study, we explore computationally the Methylidyne Addition-Cyclization-Aromatization (MACA) mechanism as a viable, barrierless pathway for phenalene synthesis under low-temperature conditions. Through electronic structure calculations and Rice–Ramsperger–Kassel–Marcus (RRKM) statistical methods, we demonstrate that the reaction of 1-vinylnaphthalene (C 10 H 7 C 2 H 3 ) with the methylidyne radical (CH) leads to the formation of 1H-phenalene via a bimolecular reaction, a process that is exoergic and without entrance barrier. The MACA mechanism facilitates the growth of the aromatic carbon backbone via a [5 + 1] ring annulation, providing a new insight into PAH formation in cold molecular clouds. Notably, the MACA mechanism has previously been shown to form indene (C9H8), which was detected in TMC-1 as well, via a [4 + 1] annulation, demonstrating its potential to produce a variety of complex PAHs by addition of a five- and six-membered ring to a benzene moiety via [4 + 1] and [5 + 1] annulation, respectively. As a result, this work highlights the importance of barrierless, exoergic reactions involving MACA in the synthesis of complex aromatic molecules in space, expanding our physicochemical understanding of carbon-rich chemistry in cold molecular clouds.

Aromatic compounds↗
DOE OSTI2021

Formation of Gas-Phase Allyl Radicals from Glycerol on Rutile TiO2(110)

The reaction pathways of glycerol on partially reduced TiO2(110) have been studied by a combination of molecular beam dosing and temperature-programmed desorption (TPD). Glycerol is found to bind more strongly to TiO2(110) than glycols due to an additional hydroxyl group in the molecule. When the Ti surface sites are saturated by glycerol, the majority of glycerol molecules (~ 95%) undergo further reactions to yield carbon-free (water and hydrogen) and carbon-containing products that are desorbed during the TPD ramp. In contrast to glycols for which both water and hydrogen arise exclusively from the cleavage of glycol O-H bonds, we identify two distinct reaction channels resulting from the cleavage of O-H and C-H bonds, respectively, for both water and hydrogen evolution from glycerol on TiO2(110). Quantitative determination of the desorption yields of water and hydrogen reveals that the C-H bond scission channel which occurs at higher temperature than the O-H bond scission channel, is a minor reaction channel for water formation, while it is a major reaction channel responsible for hydrogen evolution. For the carbon-containing products, we exclude both carbon deposition and carbon oxides (CO and CO2) formation, and identify the allyl radical as the major carbon-containing product. The formation of the allyl radical is accompanied by the formation of various minor carbon-containing products including propylene, acrolein, allyl alcohol, acetone, formaldehyde and ethylene. The different surface chemistries observed between glycerol and simpler alcohols and glycols on TiO2(110), suggest that smaller oxygenates cannot serve as models for larger oxygenates in probing their reaction pathways on oxide surfaces. The new reaction channels observed for glycerol on TiO2(110) may open up a new way to convert bio-renewable glycerol directly to pure hydrogen and hydrocarbons on TiO2. This work was supported by the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, and performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.

Chen, Long↗
DOE OSTI2023

Effects of Sodium and Magnesium Ions on the Photochemically Induced Heterogeneous Formation of Manganese Oxides and Their Structural Evolution

Manganese (Mn) oxides are abundant in aquatic and terrestrial environments, where they play significant roles in redox cycling and biological metabolisms. We recently observed that Mn oxides were homogeneously formed during the abiotic oxidation of Mn 2+ (aq) to Mn(IV) by O 2 •– via nitrate photolysis, at a rate comparable to that of biotic Mn oxide formation. On the other hand, for the heterogeneous formation of Mn oxides, the presence of a substrate can alter the required thermodynamic driving force, which may affect their crystalline phases and further influence the oxidative capability of redox cycling in environmental systems. However, little is known about the photochemically induced heterogeneous formation of Mn oxides on substrates. In this study, we investigated the heterogeneous formation of Mn oxides on a quartz substrate in the presence of two environmentally abundant cations, Na + and Mg 2+ . In contrast to homogeneously generated Mn oxides, the heterogeneously formed Mn oxides displayed faster crystalline phase evolutions and morphological changes over time. Additionally, the coexistence of Na + and Mg 2+ ions greatly affected the initial crystalline phases and the phase evolution, as well as the surface morphologies of the Mn oxides. Finally, these discoveries contribute to our understanding of how various Mn oxides form in nature and provide insights into the processes involved in manufacturing specific Mn oxide crystalline structures for engineering applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗