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At least 1,333 records · Page 74
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

Bioenergetics and mitochondrial transmembrane potential during differentiation of cultured osteoblasts

To evaluate the relationship between osteoblast differentiation and bioenergetics, cultured primary osteoblasts from fetal rat calvaria were grown in medium supplemented with ascorbate to induce differentiation. Before ascorbate treatment, the rate of glucose consumption was 320 nmol. h(-1). 10(6) cells(-1), respiration was 40 nmol. h(-1). 10(6) cells(-1), and the ratio of lactate production to glucose consumption was approximately 2, indicating that glycolysis was the main energy source for immature osteoblasts. Ascorbate treatment for 14 days led to a fourfold increase in respiration, a threefold increase in ATP production, and a fivefold increase in ATP content compared with that shown in immature cells. Confocal imaging of mitochondria stained with a transmembrane potential-sensitive vital dye showed that mature cells possessed abundant amounts of high-transmembrane-potential mitochondria, which were concentrated near the culture medium-facing surface. Acute treatment of mature osteoblasts with metabolic inhibitors showed that the rate of glycolysis rose to maintain the cellular energy supply constant. Thus progressive differentiation coincided with changes in cellular metabolism and mitochondrial activity, which are likely to play key roles in osteoblast function.

NASA Center ARC↗
DOE OSTI2025

Photosynthetic Biohybrid System for Enhanced Abiotic N 2 -to-NH 3 Conversion under Ambient Conditions

Photosynthetic biohybrid systems (PBSs) offer an eco-friendly approach to transforming solar energy into value-added products by integrating biological entities with inorganic semiconductors. However, the chemical conversion capacity of most PBSs has inherent limitations, as whole-cell bacteria and isolated enzymes require fine-tuning of environmental conditions. Here, in this study, we report a new PBS developed by introducing free-standing ceria nanoparticles into the purple membrane (PM) of Halobacterium salinarum archaea, which can unidirectionally transfer charge carriers in response to incident photons, even after separation from living archaea at various conditions. Our microscopy, spectroscopy, and synchrotron X-ray scattering analyses confirm that the electrostatic assembly between ceria and PM creates seamless interfacial contact, thereby enhancing the photocatalytic capacity of ceria. Although the conversion of dinitrogen (N 2 ) to ammonia (NH 3 ) is thermodynamically challenging due to the triple bond in N 2 and a series of charge-transfer reactions, our PM–ceria (PMC) hybrid nanoparticle efficiently produces NH 3 by reducing N 2 using solar energy even under atmospheric pressure and room temperature while simultaneously converting glycerol into value-added derivatives. Additionally, our PMC nanoparticle involves neither toxic/precious metals nor bioengineering processes to achieve enhanced photocatalytic N 2 -to-NH 3 conversion. This study sheds light on the new aspect of PBSs by employing PM to potentially resolve the global energy and environmental challenges posed by the conventional Haber–Bosch process.

Jang, Jinhyeong [Argonne National Laboratory (ANL)↗
DOE OSTI2021

Development of High Capacity Energy Storage Materials

Hydrogen fuel cells have the potential to offer energy and power density advantages over lithium ion batteries in automotive and portable power applications when paired with an appropriate hydrogen storage system. Development of the ideal hydrogen storage material has been immensely sought after but plagued by limitations present in each type of material. These limitations typically include nonidealistic operational temperatures, low capacities, excessive costs, lack of reversibility, or evolution of impurities which irreversibly damage fuel cell performance. Many complex metal hydrides possess suitable hydrogen capacities but unfortunately suffer from impurity release. In order to address this problem, our team has explored in-situ catalyst doping of alkali metal amides to demonstrate methodologies to reduce ammonia release. The incorporation of iridium metal in lithium amide significantly reduces the ammonia release and decomposes the ammonia to provide additional hydrogen. Furthermore, we demonstrate, for the first time, high resistance of low temperature fuel cells to ammonia in comparison with typical proton exchange membrane fuel cells. The utilization of these two approaches in tandem provides a novel pathway for the development and implementation of high capacity energy storage materials for fuel cell applications.

25 ENERGY STORAGE↗
DOE OSTI2021

High-Resolution Scanning Coded-Mask-Based X-ray Multi-Contrast Imaging and Tomography

Near-field X-ray speckle tracking has been used in phase-contrast imaging and tomography as an emerging technique, providing higher contrast images than traditional absorption radiography. Most reported methods use sandpaper or membrane filters as speckle generators and digital image cross-correlation for phase reconstruction, which has either limited resolution or requires a large number of position scanning steps. Recently, we have proposed a novel coded-mask-based multi-contrast imaging (CMMI) technique for single-shot measurement with superior performance in efficiency and resolution compared with other single-shot methods. We present here a scanning CMMI method for the ultimate imaging resolution and phase sensitivity by using a coded mask as a high-contrast speckle generator, the flexible scanning mode, the adaption of advanced maximum-likelihood optimization to scanning data, and the multi-resolution analysis. Scanning CMMI can outperform other speckle-based imaging methods, such as X-ray speckle vector tracking, providing higher quality absorption, phase, and dark-field images with fewer scanning steps. Scanning CMMI is also successfully demonstrated in multi-contrast tomography, showing great potentials in high-resolution full-field imaging applications, such as in vivo biomedical imaging.

Qiao, Zhi (ORCID:0000000233928732)↗
DOE OSTI2023

Evolutionary diversity of proton and water channels on the oxidizing side of photosystem II and their relevance to function

One of the reasons for the high efficiency and selectivity of biological catalysts arise from their ability to control the pathways of substrates and products using protein channels, and by modulating the transport in the channels using the interaction with the protein residues and the water/hydrogen-bonding network. Here, this process is clearly demonstrated in Photosystem II (PS II), where its light-driven water oxidation reaction catalyzed by the Mn 4 CaO 5 cluster occurs deep inside the protein complex and thus requires the transport of two water molecules to and four protons from the metal center to the bulk water. Based on the recent advances in structural studies of PS II from X-ray crystallography and cryo-electron microscopy, in this review we compare the channels that have been proposed to facilitate this mass transport in cyanobacteria, red and green algae, diatoms, and higher plants. The three major channels (O1, O4, and Cl1 channels) are present in all species investigated; however, some differences exist in the reported structures that arise from the different composition and arrangement of membrane extrinsic subunits between the species. Among the three channels, the Cl1 channel, including the proton gate, is the most conserved among all photosynthetic species. We also found at least one branch for the O1 channel in all organisms, extending all the way from Ca/O1 via the ‘water wheel’ to the lumen. However, the extending path after the water wheel varies between most species. The O4 channel is, like the Cl1 channel, highly conserved among all species while having different orientations at the end of the path near the bulk. The comparison suggests that the previously proposed functionality of the channels in T. vestitus (Ibrahim et al., Proc Natl Acad Sci USA 117:12624–12635, 2020; Hussein et al., Nat Commun 12:6531, 2021) is conserved through the species, i.e. the O1-like channel is used for substrate water intake, and the tighter Cl1 and O4 channels for proton release. The comparison does not eliminate the potential role of O4 channel as a water intake channel. However, the highly ordered hydrogen-bonded water wire connected to the Mn 4 CaO 5 cluster via the O4 may strongly suggest that it functions in proton release, especially during the S 0 → S 1 transition (Saito et al., Nat Commun 6:8488, 2015; Kern et al., Nature 563:421–425, 2018; Ibrahim et al., Proc Natl Acad Sci USA 117:12624–12635, 2020; Sakashita et al., Phys Chem Chem Phys 22:15831–15841, 2020; Hussein et al., Nat Commun 12:6531, 2021).

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1992

Evolution of a phase separated gravity independent bioreactor

The evolution of a phase-separated gravity-independent bioreactor is described. The initial prototype, a zero head-space manifold silicone membrane based reactor, maintained large diffusional resistances. Obtaining oxygen transfer rates needed to support carbon-recycling aerobic microbes is impossible if large resistances are maintained. Next generation designs (Mark I and II) mimic heat exchanger design to promote turbulence at the tubing-liquid interface, thereby reducing liquid and gas side diffusional resistances. While oxygen transfer rates increased by a factor of ten, liquid channeling prevented further increases. To overcome these problems, a Mark III reactor was developed which maintains inverted phases, i.e., media flows inside the silicone tubing, oxygen gas is applied external to the tubing. This enhances design through changes in gas side driving force concentration and liquid side turbulence levels. Combining an applied external pressure of 4 atm with increased Reynolds numbers resulted in oxygen transfer intensities of 232 mmol O2/l per hr (1000 times greater than the first prototype and comparable to a conventional fermenter). A 1.0 liter Mark III reactor can potentially deliver oxygen supplies necessary to support cell cultures needed to recycle a 10-astronaut carbon load continuously.

Villeneuve, Peter E.↗
DOE OSTI2020

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

Deployment of proton-exchange membrane fuel cells is limited by the durability of Pt-nanoscale catalysts during cathodic oxygen reduction reactions. Dissolution processes on single crystalline and thin film surfaces are now correlated leading to the design of PtAu catalysts with suppressed dissolution. A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. Finally, this mitigation strategy was applied towards 3 nm Pt 3 Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Role of phosphate source in improving the proton conductivity of tin pyrophosphate and its composite electrolytes

Metal pyrophosphates (MPPs) in general, and tin pyrophosphate (TPP) in particular, have received significant interest in the last decade due to their potential as proton conductors for electrolyte application in intermediate temperature (IT)-fuel cells. However, for MPP based electrolytes, despite high reported proton conductivities, achieving good fuel cell performance and high open circuit voltage (OCV) remains a challenge with synthesis methods playing a crucial role in determining the final proton conductivity. Here we report the role of phosphate precursor in determining the TPP proton conductivity by examining five different precursors: (1) phosphoric acid (TPP-PA), (2) ammonium hydroxide + phosphoric acid (TPP-NH 4 OH), (3) diammonium phosphate (TPP-DAP), (4) tetramethylammonium sulphate + phosphoric acid (TPP-TMAP), and (5) tetrabutylammonium phosphate (TPP-TBAP), where a maximum conductivity of 88 mS cm -1 at 200 °C was obtained for TPP prepared from the TBAP precursor. TPP prepared from all of the different precursors formed the crystalline cubic Pa-3 with combining macron] phase after sintering at 650 °C for 2.5 hours. Furthermore, TPP-TBAP/Nafion® composite membranes prepared with a 90 : 10 ratio exhibited an OCV of 0.98 V and produced a maximum peak power density (PPD) of 630 mW cm -2 at an operating temperature of 220 °C. Our results demonstrate the significant impact of the TPP precursor on proton conductivity and fuel cell performance.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Unraveling the ecological success of Iodidimonas in a bioreactor treating oil and gas produced water

Iodidimonas sp., a bacterium found in bioreactors treating oil and gas produced water as well as iodide-rich brines, has garnered attention for its unique ability to oxidize iodine. However, little is known about the metabolic capabilities that enable Iodidimonas sp. to thrive in certain unique ecological niches. In this study, we isolated, characterized, and sequenced three strains belonging to the Iodidimonas genus from the sludge of a membrane bioreactor used for produced water treatment. We investigated the genomic features of these isolates and compared them with the four publicly available isolate genomes from this genus, as well as a metagenome-assembled genome from the source bioreactor. Our Iodidimonas isolates had several genes associated with mitigating salinity, heavy metal, and organic compound stress, which likely help these bacteria to survive in produced water. Phenotyping tests revealed that while the isolates could utilize a wide variety of simple carbon substrates, they failed to degrade aliphatic or aromatic hydrocarbons, consistent with the lack of genes associated with common hydrocarbon degradation pathways in their genomes. We hypothesize that these microbes may lead a scavenging lifestyle in the bioreactor and similar iodide-rich brines. IMPORTANCE: Occupying a niche habitat and having few representative isolates, the genus Iodidimonas is a relatively understudied alphaproteobacterial group. Its ability to corrode pipes in iodine production facilities has economic implications, and its ability to generate potentially carcinogenic iodinated organic compounds during treatment of oil and gas produced water may cause environmental and health concerns with the recycling of treated water. Therefore, detailed characterization of the metabolic potential of the Iodidimonas isolates in this study both sheds light on their adaptation to the environmental conditions they inhabit and has environmental and economic significance.

Acharya, Shwetha M↗
NASA NTRS2010

Colorimetric Solid Phase Extraction (CSPE): Using Color to Monitor Spacecraft Water Quality

In August 2009, an experimental water quality monitoring kit based on Colorimetric Solid Phase Extraction (CSPE) technology was delivered to the International Space Station (ISS). The kit, called the Colorimetric Water Quality Monitoring Kit (CWQMK), was launched as a Station Development Test Objective (SDTO) experiment to evaluate the suitability of CSPE technology for routine use monitoring water quality on the ISS. CSPE is a sorption-spectrophotometric technique that combines colorimetric reagents, solid-phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water samples. In CSPE, a known volume of sample is metered through a membrane disk that has been impregnated with an analyte-specific colorimetric reagent and any additives required to optimize the formation of the analyte-reagent complex. As the sample flows through the membrane disk, the target analyte is selectively extracted, concentrated, and complexed. Formation of the analyte-reagent complex causes a detectable change in the color of the membrane disk that is proportional to the amount of analyte present in the sample. The analyte is then quantified by measuring the color of the membrane disk surface using a hand-held diffuse reflectance spectrophotometer (DRS). The CWQMK provides the capability to measure the ionic silver (Ag +) and molecular iodine (I2) in water samples on-orbit. These analytes were selected for the evaluation of CSPE technology because they are the biocides used in the potable water storage and distribution systems on the ISS. Biocides are added to the potable water systems on spacecraft to inhibit microbial growth. On the United States (US) segment of the ISS molecular iodine serves as the biocide, while the Russian space agency utilizes silver as a biocide in their systems. In both cases, the biocides must be maintained at a level sufficient to control bacterial growth, but low enough to avoid any negative effects on crew health. For example, the presence of high levels of iodine in water can cause taste and odor issues that result in decreased water consumption by the crew. There are also concerns about potential impacts on thyroid function following exposure to high levels of iodine. With silver, there is a risk of developing argyria, an irreversible blue-gray discoloration of the skin, associated with long term consumption of water containing high concentrations of silver. The need to ensure that safe, effective levels of biocide are maintained in the potable water systems on the ISS provides a perfect platform for evaluating the suitability of CSPE technology for in-flight water quality monitoring. This paper provides an overview of CSPE technology and details on the silver and iodine methods used in the CWQMK. It also reports results obtained during in-flight analyses performed with the CWQMK and briefly discusses other potential applications for CSPE technology in both the spacecraft and terrestrial environments.

Gazda, Daniel B.↗
DOE OSTI2023

Engineering endosomolytic nanocarriers of diverse morphologies using confined impingement jet mixing

The clinical translation of many biomolecular therapeutics has been hindered by undesirable pharmacokinetic (PK) properties, inadequate membrane permeability, poor endosomal escape and cytosolic delivery, and/or susceptibility to degradation. Overcoming these challenges merits the development of nanoscale drug carriers (nanocarriers) to improve the delivery of therapeutic cargo. Herein, we implement a flash nanoprecipitation (FNP) approach to produce nanocarriers of diverse vesicular morphologies by using various molecular weight PEG-bl-DEAEMA-co-BMA (PEG-DB) polymers. We demonstrated that FNP can produce uniform (PDI < 0.1) particles after 5 impingements, and that by varying the copolymer hydrophilic mass fraction, FNP enables access to a diverse variety of nanoarchitectures including micelles, unilamellar vesicles (polymersomes), and multi-compartment vesicles (MCVs). We synthesized a library of 2 kDa PEG block copolymers, with DEAEMA-co-BMA second block molecular weights of 3, 6, 12, 15, 20, and 30 kDa. All formulations were both pH responsive, endosomolytic, and capable of loading and cytosolically delivering small negatively charged molecules – albeit to different degrees. Using a B16.F10 melanoma model, we showcased the therapeutic potential of a lead FNP formulated PEG-DB nanocarrier, encapsulating the cyclic dinucleotide (CDN) cGAMP to activate the stimulator of interferon genes (STING) pathway in a therapeutically relevant context. Collectively, these data demonstrate that an FNP process can be used to formulate pH-responsive nanocarriers of diverse morphologies using a PEG-DB polymer system. As FNP is an industrially scalable process, these data address the critical translational challenge of producing PEG-DB nanoparticles at scale. Furthermore, the diverse morphologies produced may specialize in the delivery of distinct biomolecular cargos for other therapeutic applications, implicating the therapeutic potential of this platform in an array of disease applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhanced Anhydrous Proton Conductivity in Azole Phosphonic Acid Mixtures

Azole molecules are investigated as potential candidates for proton conductors under anhydrous conditions. Since 1,2,3-triazole has the lowest melting point (T m = 17 °C), it was blended with three phosphonic acid-containing molecules (small molecules with one and two phosphonic acids per molecule and a phosphonic acid polymer) to provide a source of excess protons to enhance the proton conductivity of the blends. Here we study a wide range of compositions in each system to find that these three mixtures show a maximum proton conductivity at moderate doping compositions, approximately 5–10 azole molecules per phosphonic acid group. Using NMR diffusometry, we show that the protons bonded to nitrogen move faster than the protons bonded to carbons of 1,2,3-triazole, suggesting proton hopping between azole proton carriers. Given the high proton conductivity at 90 °C of the best mixtures, in the range of 20–60 mS/cm, this work provides a path forward for future work in anhydrous proton-conducting polymer membranes. Additionally, Raman spectroscopy was used to accurately determine the molar percentage of protonated 1,2,3-triazole. Combining that with the proton diffusion results, we find that the phosphonic acid polymer shows the most proton hopping at low acid content.

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

Influence of the Dielectric Constant on the Ionic Current Rectification of Bipolar Nanopores

In this paper, we investigate how the dielectric constant, ϵ, of an electrolyte solvent influences the current rectification characteristics of bipolar nanopores. It is well recognized that bipolar nanopores with two oppositely charged regions rectify current when exposed to an alternating electric potential difference. Here, we consider dilute electrolytes with NaCl only and with a mixture of NaCl and charged nanoparticles. These systems are studied using two levels of description, all-atom explicit water molecular dynamics (MD) simulations and coarse-grained implicit solvent MD simulations. The charge density and electric potential profiles and current-voltage relationship predicted by the implicit solvent simulations with ϵ = 11.3 show good agreement with the predictions from the explicit water simulations. Under nonequilibrium conditions, the predictions of the implicit solvent simulations with a dielectric constant closer to the one of bulk water are significantly different from the predictions obtained with the explicit water model. Further, these findings are closely aligned with experimental data on the dielectric constant of water when confined to nanometric spaces, which suggests that ϵ decreases significantly compared to its value in the bulk. Moreover, the largest electric current rectification is observed in systems containing nanoparticles when ϵ = 78.8. Using enhanced sampling, we have shown that this larger rectification arises from the presence of a significantly deeper minimum in the free energy of the system with a larger ϵ, and when a negative voltage bias is applied. Since implicit solvent models and mean-field continuum theories are often used to design Janus membranes based on bipolar nanopores, this work highlights the importance of properly accounting for the effects of confinement on the dielectric constant of the electrolyte solvent. The results presented here indicate that the dielectric constant in implicit solvent simulations may be used as an adjustable parameter to approximately account for the effects of nanometric confinement on aqueous electrolyte solvents.

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

Negative linear compressibility in Se at ultra-high pressure above 120 GPa

A series of in situ synchrotron X-ray diffraction (XRD) measurements were carried out, combined with first-principles calculations, to study structural phase transitions of selenium at high pressures and room temperature. Several phase transitions were observed, among which an isostructural phase transition was found at around 120 GPa for the first time. Evolved from the rhombohedral (space group R$\bar{3}$m) structure (Se-V), the new phase (Se-V') exhibited an interesting increase of lattice parameter a at pressures from 120 to 148 GPa, known as negative linear compressibility (NLC). The discovery of NLC behavior observed in this work is mainly attributed to the accuracy and fine steps controlled by the membrane system for in situ XRD data collected with an exposure time of 0.5 s. After 140 GPa, a body-centered cubic (b.c.c.) structure Se-VI (space group Im$\bar{3}$m) was formed, which remains stable up to 210 GPa, the highest pressure achieved in this study. The bulk moduli of phases Se-V, Se-V' and Se-VI were estimated to be 83 ± 2, 321 ± 2 and 266 ± 7 GPa, respectively, according to the P–V curve fit by the third-order Birch–Murnaghan equation of state. The Se-V' phase shows a bulk modulus almost 4 times larger than that of the Se-V phase, which is mainly due to the effect of its NLC. NLC in a higher pressure range is always more significant in terms of fundamental mechanism and new materials discovery, yet it has barely been reported at pressures above 100 GPa. This will hopefully inspire future studies on potential NLC behaviors in other materials at ultra-high pressure.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Decarbonizing Hydrogen Production: Assessing A Net-Negative Pathway

Hydrogen is gaining prominence as a key factor in the world's transition to a cleaner energy future. The International Energy Agency (IEA)'s Global Hydrogen Review 2023 reports that the number of low-emission hydrogen production projects is increasing rapidly. The potential for growth in new applications such as heavy industry, transportation, and power generation is significant. The IEA urges more decisive action to spur demand for low-emission hydrogen to achieve climate goals. While hydrogen is produced through various industrial methods, each with its own advantages and disadvantages, low-carbon hydrogen is critical for mitigating climate change and is incentivized by the Clean Hydrogen Production Tax Credit (45V). To this end, we have evaluated a commercial technology that can produce low- or negative-carbon hydrogen via ethanol catalytic oxidative reforming. This study assessed life cycle greenhouse gas emissions (carbon intensity or CI) associated with the hydrogen production technology. A total of 24 scenarios were evaluated, encompassing (a) Gen1 versus Gen2 ethanol inputs, (b) carbon capture and sequestration (CCS) of upstream fermentation CO2, and (c) oxygen sourcing via air separation unit (ASU) versus purchased or on-site production of oxygen as a byproduct of hydrogen electrolysis with a proton exchange membrane (PEM). Key findings include that the base case CI for hydrogen production using Gen2 ethanol from corn stover is lower than Gen1 dry mill corn ethanol. The study also points out that the CI for hydrogen production using PEM-O2 is lower than that using ASU-O2, whether the PEM-O2 is produced on-site or off-site (importing). When sourcing oxygen from on-site PEM-O2, the Gen1 and Gen2 ethanol-derived hydrogen exhibit favorable net-negative CI values for all evaluated scenarios, especially if the upstream ethanol CCS is included. As a reference, the 45V regulatory threshold for generating clean hydrogen tax credits is a CI below 0.45 kg CO2e/kg hydrogen.

BIOMASS FUELS,HYDROGEN↗
DOE OSTI2021

Neuroprotectin D1 Attenuates Blast Overpressure Induced Reactive Microglial Cells in the Cochlea

Objective/Hypothesis We examined a neuroinflammatory response associated with glial activation in the cochlea exposed to blast overpressure and evaluated the potential therapeutic efficacy of specialized pro‐resolving mediators such as neuroprotectin D1, NPD1; (10R, 17S‐dihydroxy‐4Z, 7Z, 11E, 13E, 15Z, 19Z‐docosahexaenoic acid) in a rodent blast‐induced auditory injury model. Study Design Animal Research. Methods A compressed‐air driven shock tube was used to expose anesthetized adult male Long‐Evan rats to shock waves simulating an open‐field blast exposure. Approximately 30 minutes after blast exposure, rats were treated with NPD1 (100 ng/kg body wt.) or vehicle delivered intravenously via tail vein injection. Rats were then euthanized 48 hours after blast exposure. Unexposed rats were included as controls. Tissue sections containing both middle and inner ear were prepared with hematoxylin–eosin staining to elucidate histopathological changes associated with blast exposure. Cochlear tissues were evaluated for relative expression of ionized calcium‐binding adaptor 1 (Iba1), as an indicator of microglial activation by immunohistochemistry and western blot analyses. Results Our animal model resulted in an acute injury mechanism manifested by damage to the tympanic membrane, hemorrhage, infiltration of inflammatory cells, and increased expression of Iba1 protein. Moreover, therapeutic intervention with NPD1 significantly reduced Iba1 expression in the cochlea, suggesting a reduction of a neuroinflammatory response caused by blast overpressure. Conclusions Blast overpressure resulted in an increased expression of proteins involved in gliosis within the auditory system, which were reduced by NPD1. Treatment of NPD1 suggests an effective strategy to reduce or halt auditory microglial cell activation due to primary blast exposure. Level of Evidence NA Laryngoscope , 131:E2018–E2025, 2021

Ríos, José David↗
DOE OSTI2023

Quaternary Ammonium-Functionalized Poly(Arylene Ether Sulfone) Random Copolymers for Direct Air Capture

Direct air capture (DAC) is a promising tool for reducing CO 2 concentrations in the atmosphere and fighting climate change. We synthesized a series of quaternary ammonium (QA) functionalized poly(arylene ether sulfone) copolymers with varying mole fractions of charge content and demonstrated their potential as sorbents for DAC. Molecular weight analysis determined high monomer conversion was achieved in <6 h and relatively high molecular weights for all copolymer compositions. Thermal analysis revealed all polymers had degradation temperatures >240 °C and a single glass transition temperature (T g ); the T g decreased with an increase in ion exchange capacity (IEC). Fractional free volume and water uptake percentage increased and water contact angle decreased with the number of QA sites when compared to a neutral, commercially available polysulfone (Udel® P-1700 PSU). Next, the novel series of ammonium-functionalized copolymers exhibited a moisture-mediated capture and release of atmospheric CO 2 . When exposed to air containing 30% relative humidity the polymers captured CO 2 and the capacity increased with the IEC. When the relative humidity was increased to 95% the samples released the CO 2 . This study demonstrates a promising CO 2 DAC sorbent and highlights the possibility for continuous DAC with purpose-built free-standing membranes.

42 ENGINEERING↗
DOE OSTI2023

Mass spectrometry imaging of natural carbonyl products directly from agar-based microbial interactions using 4-APEBA derivatization

Aliphatic carboxylic acids, aldehydes, and ketones play diverse roles in microbial adaptation to their microenvironment, from excretion as toxins to adaptive metabolites for membrane fluidity. However, the spatial distribution of these molecules throughout biofilms and how microbes in these environments exchange these molecules remain elusive for many of these bioactive species due to inefficient molecular imaging strategies. Herein, we apply on-tissue chemical derivatization (OTCD) using 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide (4-APEBA) on a co-culture of a soil bacterium (Bacillus subtilis NCIB 3610) and fungus (Fusarium sp. DS 682) grown on agar as our model system. Using matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI), we spatially resolved more than 300 different metabolites containing carbonyl groups within this model system. Various spatial patterns are observable in these species, which indicate possible extracellular or intercellular processes of the metabolites and their up- or downregulation during microbial interaction. The unique chemistry of our approach allowed us to bring additional confidence in accurate carbonyl identification, especially when multiple isomeric candidates were possible, and this provided the ability to generate hypotheses about the potential role of some aliphatic carbonyls in this B. subtilis/Fusarium sp. interaction. The results shown here demonstrate the utility of 4-ABEBA-based OTCD MALDI-MSI in probing interkingdom interactions directly from microbial co-cultures, and these methods will enable future microbial interaction studies with expanded metabolic coverage.

4-APEBA↗