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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Identification of the acetaldehyde oxide Criegee intermediate reaction network in the ozone-assisted low-temperature oxidation of trans -2-butene

Uni- and bi-molecular reactions involving Criegee intermediates (CIs) have been the focus of many studies due to the role these molecules play in atmospheric chemistry. The reactivity of CIs is known to strongly depend on their structure. The reaction network of the second simplest CI, acetaldehyde oxide (CH 3 CHOO), is investigated in this work in an atmospheric pressure jet-stirred reactor (JSR) during the ozonolysis of trans-2-butene to explore the kinetic pathways relevant to atmospheric chemistry and low-temperature combustion. The mole fraction profiles of reactants, intermediates, and final products are determined by means of molecular-beam mass spectrometry in conjunction with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. A network of CI reactions is identified in the temperature region below 600 K, characterized by CI addition to trans-2-butene, water, formaldehyde, formic acid, and methanol. No sequential additions of the CH 3 CHOO CI are observed, in contrast with the reactivity of the simplest CI (H 2 COO) and the earlier observation of an extensive reaction network with up to four H 2 COO sequential additions (Phys. Chem. Chem. Phys., 2019, 21, 7341–7357). Experimental photoionization efficiency scans recorded at 300 K and 425 K and ab initio threshold energy calculations lead to the identification and quantification of previously elusive intermediates, such as ketohydroperoxide and hydroperoxide species. Specifically, the C 4 H 8 + O 3 adduct is identified as a ketohydroperoxide (KHP, 3-hydroperoxybutan-2-one, CH 3 C([double bond, length as m-dash]O)CH(CH 3 )OOH), while hydroxyacetaldehyde (glycolaldehyde, HCOCH 2 OH) formation is attributed to unimolecular isomerization of the CIs. Other hydroperoxide species such as methyl hydroperoxide (CH 3 OOH), ethyl hydroperoxide (C 2 H 5 OOH), butyl hydroperoxide (OOH), hydroperoxyl acetaldehyde (HOOCH 2 CHO), hydroxyethyl hydroperoxide (CH 3 CH(OH)OOH), but-1-enyl-3-hydroperoxide, and 4-hydroxy-3-methylpentan-2-one (HOCH(CH 3 )CH(CH 3 )C([double bond, length as m-dash]O)CH 3 ) are also identified. Detection of additional oxygenated species such as methanol, ethanol, ketene, and aldehydes suggests multiple active oxidation routes. Finally, these results provide additional evidence that CIs are key intermediates of the ozone-unsaturated hydrocarbon reactions providing critical inputs for improved kinetics models.

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

Bacterial genome editing by coupling Cre-lox and CRISPR-Cas9 systems

The past decade has been a golden age for microbiology, marked by the discovery of an unprecedented increase in the number of novel bacterial species. Yet gaining biological knowledge of those organisms has not kept pace with sequencing efforts. To unlock this genetic potential there is an urgent need for generic (i.e. non-species specific) genetic toolboxes. Recently, we developed a method, termed chassis-independent recombinase-assisted genome engineering (CRAGE), enabling the integration and expression of large complex gene clusters directly into the chromosomes of diverse bacteria. Here we expand upon this technology by incorporating CRISPR-Cas9 allowing precise genome editing across multiple bacterial species. To do that we have developed a landing pad that carries one wild-type and two mutant lox sites to allow integration of foreign DNA at two locations through Cre-lox recombinase-mediated cassette exchange (RMCE). The first RMCE event is to integrate the Cas9 and the DNA repair protein genes RecET, and the second RMCE event enables the integration of customized sgRNA and a repair template. Following this workflow, we achieved precise genome editing in four different gammaproteobacterial species. We also show that the inserted landing pad and the entire editing machinery can be removed scarlessly after editing. We report here the construction of a single landing pad transposon and demonstrate its functionality across multiple species. The modular design of the landing pad and accessory vectors allows design and assembly of genome editing platforms for other organisms in a similar way. We believe this approach will greatly expand the list of bacteria amenable to genetic manipulation and provides the means to advance our understanding of the microbial world.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1999

Quantitative Interpretation of Optical Emission Sensors for Microgravity Experiments

Microgravity flight experiments uniquely test our knowledge and understanding of the coupling between chemistry and fluid mechanics. However, compared to ground based laboratory experiments the number of useful diagnostic tools suitable for microgravity environments is severely limited by the space, weight, power consumption, and operator complexity requirements. One of the available tools is the observation of optical emission, and total emission has already proven useful for observations of stable "flame balls" on the space shuttle. Wavelength resolved tomographic measurements of flame emission offer the promise of diagnostics to test our understanding of flame chemistry and structure. Individual emissions from electronically excited radicals, e.g., CH*, OH*, and C2*, can be identified in a methane/air flame. Spatially resolved measurements of the intensity of this resolved optical emission from a specific excited molecule enable chemically resolved flame structure studies. Wavelength resolved emission measurements to determine such structure in diffusion flames are being readied for flight experiments by a group at Yale headed by Profs. Smooke and Long. A quantitative relationship between emission intensity and flame properties, as expressed by a flame model, is needed for species specific optical emission measurements to fulfill its promise. The Yale group compared models and measurements of optical emission in laboratory tests at 1-g. Unfortunately, these experiments show disagreement between measurement and state-of-the-art flame models by over a factor of 50. Therefore, an improved chemical mechanism for optical emission from flames is needed to enable quantitative tests of microgravity flame models. The connection between excited state emission and flame chemistry is not yet adequate.

Jeffries, Jay B.↗
DOE OSTI2021

A comprehensive modeling method for proton exchange membrane electrolyzer development

Hydrogen attracts significant interests as an effective energy carrier that can be derived from renewable sources. Hydrogen production using a proton-exchange membrane (PEM) electrolyzer can efficiently convert renewable power via water splitting in wide scales—from large, centralized generation to on-site production. Mathematical models with multiple scales and fidelities facilitate the continuing improvements of PEM electrolyzer development to improve performance, cost, and reliability. The model scopes and methods are presented in this paper, which also introduces a comprehensive PEM electrolysis modeling tool based on computational fluid dynamics (CFD) software, ANSYS/Fluent. The modeling tool incorporates electrochemical model of a PEM electrolysis cell to simulate the performance of coupled thermal-fluid, species transport, and electrochemical processes in a product-scale cell or stack by leveraging the powerful meshing generation and CFD solver of ANSYS/Fluent. The thermal-fluid modeling includes liquid water/gas two-phase flow and simulates a PEM electrolysis cell by using Fluent user-defined functions as add-on modules accounting for PEM-specific species transport and electrochemical processes. The modeling outcomes expediate PEM electrolyzer scaling up from basic material development and laboratory testing.

08 HYDROGEN↗
DOE OSTI2024

Updates to the Alliance of Genome Resources central infrastructure

The Alliance of Genome Resources (Alliance) is an extensible coalition of knowledgebases focused on the genetics and genomics of intensively studied model organisms. The Alliance is organized as individual knowledge centers with strong connections to their research communities and a centralized software infrastructure, discussed here. Model organisms currently represented in the Alliance are budding yeast, Caenorhabditis elegans, Drosophila, zebrafish, frog, laboratory mouse, laboratory rat, and the Gene Ontology Consortium. The project is in a rapid development phase to harmonize knowledge, store it, analyze it, and present it to the community through a web portal, direct downloads, and application programming interfaces (APIs). Here, we focus on developments over the last 2 years. Specifically, we added and enhanced tools for browsing the genome (JBrowse), downloading sequences, mining complex data (AllianceMine), visualizing pathways, full-text searching of the literature (Textpresso), and sequence similarity searching (SequenceServer). We enhanced existing interactive data tables and added an interactive table of paralogs to complement our representation of orthology. To support individual model organism communities, we implemented species-specific “landing pages” and will add disease-specific portals soon; in addition, we support a common community forum implemented in Discourse software. We describe our progress toward a central persistent database to support curation, the data modeling that underpins harmonization, and progress toward a state-of-the-art literature curation system with integrated artificial intelligence and machine learning (AI/ML).

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Changes in above- versus belowground biomass distribution in permafrost regions in response to climate warming

Permafrost regions contain approximately half of the carbon stored in land ecosystems and have warmed at least twice as much as any other biome. This warming has influenced vegetation activity, leading to changes in plant composition, physiology, and biomass storage in aboveground and belowground components, ultimately impacting ecosystem carbon balance. Yet, little is known about the causes and magnitude of long-term changes in the above- to belowground biomass ratio of plants (η). Here, in this study, we analyzed η values using 3,013 plots and 26,337 species-specific measurements across eight sites on the Tibetan Plateau from 1995 to 2021. Our analysis revealed distinct temporal trends in η for three vegetation types: a 17% increase in alpine wetlands, and a decrease of 26% and 48% in alpine meadows and alpine steppes, respectively. These trends were primarily driven by temperature-induced growth preferences rather than shifts in plant species composition. Our findings indicate that in wetter ecosystems, climate warming promotes aboveground plant growth, while in drier ecosystems, such as alpine meadows and alpine steppes, plants allocate more biomass belowground. Furthermore, we observed a threefold strengthening of the warming effect on η over the past 27 y. Soil moisture was found to modulate the sensitivity of η to soil temperature in alpine meadows and alpine steppes, but not in alpine wetlands. Our results contribute to a better understanding of the processes driving the response of biomass distribution to climate warming, which is crucial for predicting the future carbon trajectory of permafrost ecosystems and climate feedback.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Direct Measurement of Crossover and Interfacial Resistance of Ion-Exchange Membranes in All-Vanadium Redox Flow Batteries

Among various components commonly used in redox flow batteries (RFBs), the separator plays a significant role, influencing resistance to current as well as capacity decay via unintended crossover. It is well-established that the ohmic overpotential is dominated by the membrane and interfacial resistance in most aqueous RFBs. The ultimate goal of engineering membranes is to improve the ionic conductivity while keeping crossover at a minimum. One of the major issues yet to be addressed is the contribution of interfacial phenomena in the influence of ionic and water transport through the membrane. In this work, we have utilized a novel experimental system capable of measuring the ionic crossover in real-time to quantify the permeability of ionic species. Specifically, we have focused on quantifying the contributions from the interfacial resistance to ionic crossover. The trade-off between the mass and ionic transport impedance caused by the interface of the membranes has been addressed. The MacMullin number has been quantified for a series of electrolyte configurations and a correlation between the ionic conductivity of the contacting electrolyte and the Nafion® membrane has been established. The performance of individual ion-exchange membranes along with a stack of various separators have been explored. We have found that utilizing a stack of membranes is significantly beneficial in reducing the electroactive species crossover in redox flow batteries compared to a single membrane of the same fold thickness. For example, we have demonstrated that the utilization of five layers of Nafion ® 211 membrane reduces the crossover by 37% while only increasing the area-specific resistance (ASR) by 15% compared to a single layer Nafion ® 115 membrane. Therefore, the influence of interfacial impedance in reducing the vanadium ion crossover is substantially higher compared to a corresponding increase in ASR, indicating that mass and ohmic interfacial resistances are dissimilar. We have expanded our analysis to a combination of commercially available ion-exchange membranes and provided a design chart for membrane selection based on the application of interest (short duration/high-performance vs. long-term durability). The results of this study provide a deeper insight into the optimization of all-vanadium redox flow batteries (VRFBs).

UV/Vis spectroscopy↗
NASA NTRS2019

Improved assessment of mangrove forests in Sundarbans East Wildlife Sanctuary using WorldView 2 and TanDEM-X high resolution imagery

Recent developments of remote sensing techniques which can capture both the structure and function of the ecosystem provide a more representative view of the landscape. These unique Earth observations were used to help improve traditional forestry surveys by providing species-specific land cover classes for mangrove forests in the Sundarbans East Wildlife Sanctuary. By combining optical data from WorldView2 (WV2; 2 m pixel) and a canopy height model derived using radar data from TanDEM-X (TDX; 12 m pixel), we identified nine mangrove and five non-mangrove classes by following an Iterative Self-Organizing Data Analysis Algorithm. Three dominant mangrove species accounted for nearly 50% of the sanctuary. Heritieria fomes disproportionately covered the largest area at 43%, overturning previous field-based estimates of Excoecaria agallocha dominance. E. agallocha and Sonneratia apetala, covered 3% and 1.47% of the sanctuary, respectively. Four mixed species classes were also identified with clear vegetation zonation patterns that trended toward species homogeneity with increasing distance from shore. The overall land cover accuracy (WV2: 89.33%; WV2-TDX: 89.89%), the Kappa Coefficient (WV2:0.88; WV2-TDX: 0.89) and change statistics between WV2 and WV2-TDX landcover classifications indicate that the WV2 imagery can separate mangrove community types without structural data. The combination of the land cover classifications and the canopy height model indicated that H. fomes were not only the most dominant forest but also, on average, the tallest (12.3 m) among the other eight mangrove types. Our large-scale mapping with high resolution optical and radar platforms can capture subtle changes in mangrove vegetation and canopy structural gradients more accurately and be used to monitor biodiversity changes and Aichi Biodiversity Targets and Indicators, which would contribute to biodiversity policy updating.

Md Mizanur Rahman↗
DOE OSTI2022

Plasma production and composition from hypervelocity impacts on solar cell cover glass

Satellites are subjected to detrimental effects from the space environment, including impacts by orbital debris and meteoroids that can cause mechanical or electrical damage. While mechanical damage is well studied, electrical effects resulting from hypervelocity impact (HVI) remain poorly understood. In HVIs, where the projectile speed exceeds the speed of sound in the target material, the impact energy ionizes the material near the surface, creating a plasma that can cause radio frequency emission. This emission is the main source of electrical anomalies in satellites, but the mechanism behind its creation is still unknown. Ground-based experiments have been used to characterize HVI plasma, including the empirical power law relations that describe the impact charge produced as a function of impactor mass and speed. Quantifying these power law relations gives us a better understanding of the species formed in the impact which can eventually lead to plasma evolution models and help us first, understand the mechanism behind radio frequency emission and second, ways to prevent its damage to the satellites. In this paper, we interpret the results of the HVI experiments on solar cell coverglass targets and identify the potential chemical or molecular reactions that form the impact ion species. This is done by looking simultaneously at multiple data sets for different species within the same impact configuration, and using a new technique for quantifying the power law relations for each emitted species. We use time of flight analysis (TOF) to detect the charged particle compositions and determine their initial speeds. The results suggest that the charge production power law is species specific, with different formation mechanisms involved in a single HVI event, some of which are associated with dissociation and some with ionization of a molecule. Furthermore, our results also show that electrons have different power laws that depend on the spacecraft surface charge. TOF measurements of ions from impact events on solar cell cover glass shows the presence of SiO + and SiO – 2 as the dominant species present in plasmas on positively and negatively charged targets, respectively, as well as the formation of FeO + .

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Using butterfly survey data to model habitat associations in urban developments

Abstract One approach for measuring the potential biodiversity in new urban construction projects is through ecological models that predict how wildlife will respond. For the United Kingdom, such models have only been developed for birds, but to maximise the extent to which models represent overall biodiversity, species from different indicator groups must be considered. Here, we assess this possibility for butterflies by combining citizen science survey data with high‐resolution digital maps. We derive detailed characteristics of urban landscapes around survey sites using previously established methods and quantify their relationship to counts of adults of 18 butterfly species in urban and peri‐urban settings. Higher butterfly counts were found when traversing urban sites with larger areas of semi‐natural grassland, other managed greenspaces and adjacent arable land. Most of the butterfly community were found to have negative relationships with highly built‐up or fragmented landscapes. We found high species‐specificity for different details of urban form, particularly in habitat elements such as gardens, vegetation around railways and grass verges. Policy implications . Improving biodiversity is now part of legislation governing new construction projects from England and Wales. However, predicting quantitative changes from hypothetical land‐use modifications remains challenging. Our models provide the foundation through which butterfly abundance could be integrated into an urban biodiversity assessment tool, providing species‐ and community‐level statistics to non‐specialists from the urban planning and design sector. This would allow them to hone configurations for built surfaces, private gardens, greenspaces and wildlife areas and assess their capacity to provide residents with the intended access to nature.

Cooper, Joseph E. J.↗
DOE OSTI2021

Trade-Offs in Phosphorus Acquisition Strategies of Five Common Tree Species in a Tropical Forest of Puerto Rico

Tree species that are successful in tropical lowlands have different acquisition strategies to overcome soil phosphorus (P) limitations. Some of these strategies belowground include adjustments in fine-root traits, such as morphology, architecture, association with arbuscular mycorrhizal fungi, and phosphatase activity. Trade-offs among P-acquisition strategies are expected because of their respective carbon cost. However, empirical evidence remains scarce which hinders our understanding of soil P-acquisition processes in tropical forests. Here, we measured seven fine-root functional traits related to P acquisition of five common tree species in three sites of the Luquillo Experimental Forest in Puerto Rico. We then described species-specific P-acquisition strategies and explored the changes in fine-root trait expression from 6 months before to 6 months after two consecutive hurricanes, Irma and María, passed over the island. We found that variations in root trait expression were driven mainly by the large interspecific differences across the three selected sites. In addition, we revealed a trade-off between highly colonized fine roots with high phosphatase activity and fine roots that have a high degree of branching. Furthermore, the former strategy was adopted by pioneer species ( Spathodea campanulata and Cecropia schreberiana ), whereas the latter was adopted by non-pioneer species (mostly Dacryodes excelsa and Prestoea montana ). Additionally, we found that root trait expression did not change comparing 6 months before and after the hurricanes, with the exception of root phosphatase activity. Altogether, our results suggest a combination of structural and physiological root traits for soil P acquisition in P-poor tropical soils by common tropical tree species, and show stability on most of the root trait expression after hurricane disturbances.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Avirulent Isolates of Penicillium chrysogenum to Control the Blue Mold of Apple Caused by P. expansum

Blue mold is an economically significant postharvest disease of pome fruit that is primarily caused by Penicillium expansum. To manage this disease and sustain product quality, novel decay intervention strategies are needed that also maintain long-term efficacy. Biocontrol organisms and natural products are promising tools for managing postharvest diseases. Here, two Penicillium chrysogenum isolates, 404 and 413, were investigated as potential biocontrol agents against P. expansum in apple. Notably, 404 and 413 were non-pathogenic in apple, yet they grew vigorously in vitro when compared to the highly aggressive P. expansum R19 and Pe21 isolates. Whole-genome sequencing and species-specific barcoding identified both strains as P. chrysogenum. Each P. chrysogenum strain was inoculated in apple with the subsequent co-inoculation of R19 or Pe21 simultaneously, 3, or 7 days after prior inoculation with 404 or 413. The co-inoculation of these isolates showed reduced decay incidence and severity, with the most significant reduction from the longer establishment of P. chrysogenum. In vitro growth showed no antagonism between species, further suggesting competitive niche colonization as the mode of action for decay reduction. Both P. chrysogenum isolates had incomplete patulin gene clusters but tolerated patulin treatment. Finally, hygromycin resistance was observed for both P. chrysogenum isolates, yet they are not multiresistant to apple postharvest fungicides. Overall, we demonstrate the translative potential of P. chrysogenum to serve as an effective biocontrol agent against blue mold decay in apples, pending practical optimization and formulation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Indexing habitat opportunity for juvenile anadromous fishes in tidal-fluvial wetland systems

In intertidal wetlands, annual habitat use by migrating juvenile salmon is limited by both physical and biological constraints. Physical limits are set by inundation patterns and water quality parameters, while biological bounds are determined by species specific migration timing and seasonal residency behaviors. We developed a new metric called the fish habitat opportunity index (FHOI) to quantify the total time per calendar year that salmon could access intertidal sites, based on periods of inundation and juvenile salmon seasonal migration. The index was applied using data collected at a recently reconnected tidal freshwater wetland area during 2006-2009. We found the wetland to be accessible to different salmon species for different lengths of time and periods of the year. On average, chum salmon (Oncorhynchus keta) had remarkably consistent opportunities to use marsh habitat over the 4 years sampled, while opportunities were more variable for Chinook (O. tshawytscha), and coho salmon (O. kisutch). Inundation varied nonlinearly with tidal height, and fish had access to the productive marsh edge for approximately 40-50% of the time during periods of access. The FHOI is widely applicable to wetland systems throughout the tidal fluvial continuum, and provides a metric for assessing fish habitat opportunity that is more realistic than simple wetted area calculations. Finally, the FHOI affords a method of a priori comparison among potential restoration sites to help resource managers predict the likely relative benefit to juvenile salmon.

wetland restoration, estuary, habitat opportunity,↗
DOE OSTI2023

Role of Intradomain Heterogeneity on Ion and Polymer Dynamics in Block Polymer Electrolytes: Investigating Interfacial Mobility and Ion-Specific Dynamics and Transport

Block polymers show promise as solid-state battery electrolytes due to the optimization of conductive and mechanical properties enabled via tuning of block chemistry and length. We investigate a polystyrene-block-poly(oligo-oxyethylene methacrylate) (PS-b-POEM) electrolyte doped with various lithium salts to investigate the role of molecular structure on ion transport properties and on local ion dynamics and associations. Anion charge becomes more delocalized with increasing size, reducing the coupling between salt ions while increasing coupling between ion and polymer chain motions and creating a more mobile overall environment. We observe support for this ion-polymer coupling via 1 H, 7 Li and 19 F NMR spectroscopy, from which we obtain ion-specific mobility transition temperatures that differ from the polymer glass transition temperature. We also note faster transport and weaker local energetic interactions with anion size using temperature-dependent NMR diffusometry. 1 H NMR spectroscopy further elucidates polymer chain dynamics and enables quantification of the temperature-dependent fraction of the conducting block that is immobile near the PS-POEM domain interface. As a result, NMR thus represents a species-specific and timescale-specific platform to quantify phase and interface behavior, and to correlate ion-specific transport with polymer chain dynamics.

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

Host phylogeny matters: Examining sources of variation in infection risk by blood parasites across a tropical montane bird community in India

Abstract Background Identifying patterns and drivers of infection risk among host communities is crucial to elucidate disease dynamics and predict infectious disease risk in wildlife populations. Blood parasites of the genera Plasmodium and Haemoproteus are a diverse group of vector-borne protozoan parasites that affect bird populations globally. Despite their widespread distribution and exceptional diversity, factors underlying haemosporidian infection risk in wild bird communities remain poorly understood. While some studies have examined variation in avian haemosporidian risk, researchers have primarily focused on host ecological traits without considering host phylogenetic relationships. In this study, we employ a phylogenetically informed approach to examine the association between host ecological traits and haemosporidian infection risk in endemic bird communities in the Western Ghats Sky Islands. Methods We used parasite sequence data based on partial mitochondrial cytochrome b gene, that was amplified from genomic DNA extracted from 1177 birds (28 species) across the Western Ghats to assess infection of birds with haemosporidian parasites. We employed a Bayesian phylogenetic mixed effect modelling approach to test whether haemosporidian infection risk was affected by seven species-specific and four individual-level ecological predictors. We also examined the effect of host phylogenetic relationships on the observed patterns of variation in haemosporidian infection risk by estimating phylogenetic signal. Results Our study shows that host ecological traits and host phylogeny differentially influence infection risk by Plasmodium (generalist parasite) and Haemoproteus (specialist parasite). For Plasmodium , we found that sociality, sexual dimorphism and foraging strata were important ecological predictors. For Haemoproteus , patterns of infection risk among host species were associated with sociality, species elevation and individual body condition. Interestingly, variance in infection risk explained by host phylogeny was higher for Haemoproteus parasites compared to Plasmodium . Conclusions Our study highlights that while host ecological traits promoting parasite exposure and host susceptibility are important determinants of infection risk, host phylogeny also contributes substantially to predicting patterns of haemosporidian infection risk in multi-host communities. Importantly, infection risk is driven by joint contributions of host ecology and host phylogeny and studying these effects together could increase our ability to better understand the drivers of infection risk and predict future disease threats. Graphical abstract

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Strategies for the Photoreduction of Tc-99 Pertechnetate to Low-Valent Tc by Keggin Polyoxometalates

Technetium-99 (half-life of 2.1 × 10 5 yrs, β max = 0.29 MeV) is a hazardous radiological contaminant, which, in its predominant form of pertechnetate (TcO 4 – ), is highly mobile in the environment. Most strategies for the removal of pertechnetate from the environment involve uptake and/or absorption of pertechnetate using resins, clays, cationic metal-organic frameworks and even thorium borate ceramic like materials. Alternative approaches have involved the reduction and subsequent sequestration of lower valent technetium species using iron, sulfides, or iron sulfides. Here, our lab has explored this strategy using the lacunary alpha-2 Wells–Dawson polyoxometalate (α 2 -[P 2 W 17 O 61 ] 10– ) to both reduce and sequester lower valent technetium, and we have reported on the ligand features that stabilize the reduced species. In this work we investigate the potential of “plenary” Keggin POMs (XW 12 O 40 n – ) (X = P, Si, Al, n = 3, 4, 5, respectively) to both reduce TcO 4 – and stabilize the reduced Tc species. Specifically, we report on the mechanism by which the reduction of technetium occurs and find that PW 12 , SiW 12 , and AlW 12 promote the reduction of TcO 4 – to lower valent states. X-ray absorption spectroscopy was used to confirm a combination of Tc IV {in the form of TcO 2 · 2H 2 O and Tc 2 (µ-O) 2 4+ } and Tc V , which is subsequently complexed into a POM defect as a Tc V =O species.

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

An essential and highly selective protein import pathway encoded by nucleus-forming phage

Targeting proteins to specific subcellular destinations is essential in prokaryotes, eukaryotes, and the viruses that infect them. Chimalliviridae phages encapsulate their genomes in a nucleus-like replication compartment composed of the protein chimallin (ChmA) that excludes ribosomes and decouples transcription from translation. These phages selectively partition proteins between the phage nucleus and the bacterial cytoplasm. Currently, the genes and signals that govern selective protein import into the phage nucleus are unknown. Here, we identify two components of this protein import pathway: a species-specific surface-exposed region of a phage intranuclear protein required for nuclear entry and a conserved protein, PicA (Protein importer of chimalliviruses A), that facilitates cargo protein trafficking across the phage nuclear shell. We also identify a defective cargo protein that is targeted to PicA on the nuclear periphery but fails to enter the nucleus, providing insight into the mechanism of nuclear protein trafficking. Using CRISPRi-ART protein expression knockdown of PicA, we show that PicA is essential early in the chimallivirus replication cycle. Together, our results allow us to propose a multistep model for the Protein Import Chimallivirus pathway, where proteins are targeted to PicA by amino acids on their surface and then licensed by PicA for nuclear entry. The divergence in the selectivity of this pathway between closely related chimalliviruses implicates its role as a key player in the evolutionary arms race between competing phages and their hosts.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Single-nuclei transcriptome analysis of the shoot apex vascular system differentiation in Populus

ABSTRACT Differentiation of stem cells in the plant apex gives rise to aerial tissues and organs. Presently, we lack a lineage map of the shoot apex cells in woody perennials – a crucial gap considering their role in determining primary and secondary growth. Here, we used single-nuclei RNA-sequencing to determine cell type-specific transcriptomes of the Populus vegetative shoot apex. We identified highly heterogeneous cell populations clustered into seven broad groups represented by 18 transcriptionally distinct cell clusters. Next, we established the developmental trajectories of the epidermis, leaf mesophyll and vascular tissue. Motivated by the high similarities between Populus and Arabidopsis cell population in the vegetative apex, we applied a pipeline for interspecific single-cell gene expression data integration. We contrasted the developmental trajectories of primary phloem and xylem formation in both species, establishing the first comparison of vascular development between a model annual herbaceous and a woody perennial plant species. Our results offer a valuable resource for investigating the principles underlying cell division and differentiation conserved between herbaceous and perennial species while also allowing us to examine species-specific differences at single-cell resolution.

59 BASIC BIOLOGICAL SCIENCES↗