Search NASA⌕ Search

SEARCH · Search NASA

Results for “Stem specific”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7

Sequence-defined structural transitions by calcium-responsive proteins

Biopolymer sequences dictate their functions, and protein-based polymers are a promising platform to establish sequence–function relationships for novel biopolymers. To efficiently explore vast sequence spaces of natural proteins, sequence repetition is a common strategy to tune and amplify specific functions. This strategy is applied to repeats-in-toxin (RTX) proteins with calcium-responsive folding behavior, which stems from tandem repeats of the nonapeptide GGXGXDXUX in which X can be any amino acid and U is a hydrophobic amino acid. To determine the functional range of this nonapeptide, we modified a naturally occurring RTX protein that forms β-roll structures in the presence of calcium. Sequence modifications focused on calcium-binding turns within the repetitive region, including either global substitution of nonconserved residues or complete replacement with tandem repeats of a consensus nonapeptide GGAGXDTLY. Some sequence modifications disrupted the typical transition from intrinsically disordered random coils to folded β rolls, despite conservation of the underlying nonapeptide sequence. Proteins enriched with smaller, hydrophobic amino acids adopted secondary structures in the absence of calcium and underwent structural rearrangements in calcium-rich environments. In contrast, proteins with bulkier, hydrophilic amino acids maintained intrinsic disorder in the absence of calcium. In conclusion, these results indicate a significant role of nonconserved amino acids in calcium-responsive folding, thereby revealing a strategy to leverage sequences in the design of tunable, calcium-responsive biopolymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transcriptomic and functional analyses uncover a conserved effector driving genotype-dependent virulence in the Sphaerulina musiva-Populus trichocarpa interaction

The introduction of invasive microbes compromises the structure, biodiversity, and function of naïve ecosystems. Sphaerulina musiva, a hemibiotrophic pathogen that causes leaf spot and stem cankers in Populus species, exemplifies an invasive fungal pathogen spread by human activities. However, the genetic mechanisms of pathogenicity and virulence are poorly understood, impeding mitigation strategies. We utilized RNA sequencing to identify fungal effectors linked to stem canker formation, informing the development of future strategies for effective disease management. Our analysis revealed 70 genes differentially expressed at 2 weeks and 110 genes at 3 weeks between inoculated trees and controls. Notably, the gene with the highest expression at 2 weeks and the second highest at 3 weeks was homologous to Extracellular protein 2 (Ecp2). Complementary genome-wide association studies linked sequence polymorphisms in this locus to phenotypic variation in disease severity. Infiltration of S. musiva Ecp2 into Populus trichocarpa leaves induced necrosis in susceptible genotypes. Gene disruption using a CRISPR-Cas9 RNP system resulted in a genotype-dependent reduction of stem canker and disease severity. Tracing the evolutionary history of this effector across the fungal kingdom, we uncovered clade-specific gene-family expansions and orthologs in new species. These findings raise questions about the function and adaptive significance of these gene families in fungal lifestyles. Our study provides the first tractable target for breeding resistant poplar genotypes, addressing the challenges of managing S. musiva and uncovering mechanisms that drive its virulence, and provides deeper insights into the evolutionary dynamics of a conserved small-secreted protein with a diversity of functions.

Sondreli, Kelsey L [Oregon State University]↗

Convergent Evolution in Breadth of Two V H 6-1-Encoded Influenza Antibody Clonotypes from a Single Donor

Understanding how broadly neutralizing antibodies (bnAbs) to influenza hemagglutinin (HA) naturally develop in humans is critical to the design of universal influenza vaccines. Several classes of bnAbs directed to the conserved HA stem were found in multiple individuals, including one encoded by heavy-chain variable domain V H 6-1. We describe two genetically similar V H 6-1 bnAb clonotypes from the same individual that exhibit different developmental paths toward broad neutralization activity. One clonotype evolved from a germline precursor recognizing influenza group 1 subtypes to gain breadth to group 2 subtypes. The other clonotype recognized group 2 subtypes and developed binding to group 1 subtypes through somatic hypermutation. Crystal structures reveal that the specificity differences are primarily mediated by complementarity-determining region H3 (CDR H3). Thus, while V H 6-1 provides a framework for development of HA stem-directed bnAbs, sequence differences in CDR H3 junctional regions during VDJ recombination can alter reactivity and evolutionary pathways toward increased breadth.

59 BASIC BIOLOGICAL SCIENCES↗

Atomic‐Scale Mechanisms of Nucleation and Stabilization in CuCrO 2 and CuFeO 2 Delafossite Thin Films on Al 2 O 3

Abstract Delafossite thin films exhibit a range of intriguing physical properties derived from their layered structure, which consists of alternating noble metal ( A + ) and ( B O 2 − ) sublayers in an AB O 2 stoichiometry. The integration of these properties into functional devices requires the successful epitaxial growth of delafossites as thin films on appropriate substrates. Unfortunately, their unique lattice geometry complicates growth, as different delafossites display variable behavior on the same substrate, often unrelated to lattice mismatch. This suggests the presence of yet unidentified stabilization mechanisms that enable the selective growth of certain delafossites, allowing them to be grown either as films themselves or to be used as buffer layers for subsequent deposition. In this study, advanced scanning transmission electron microscopy (STEM) is employed to investigate the nucleation mechanisms governing the stable growth of Cu‐based delafossites on Al 2 O 3 , specifically CuCrO 2 and CuFeO 2 thin films synthesized via molecular‐beam epitaxy. These findings reveal that a combination of a misfit dislocation network at the interface and monolayer‐deep chemical intermixing effectively relieves lattice mismatch strain. This mechanism, which differs fundamentally from that observed in Pd‐based delafossites, provides key insights into the controlled epitaxy of delafossite materials.

Scheid, Anna [Max Planck Institute for Solid State↗

Magnetic structure, excitations and short-range order in honeycomb Na 2 Ni 2 TeO 6

Na 2 Ni 2 TeO 6 has a layered hexagonal structure with a honeycomb lattice constituted by Ni 2+ and a chiral charge distribution of Na + that resides between the Ni layers. In the present work, the antiferromagnetic transition temperature of Na 2 Ni 2 TeO 6 is confirmed at TN˜ 27 K, and further, it is found to be robust up to 8 T magnetic field and 1.2 GPa external pressure; and, without any frequency-dependence. Slight deviations from nominal Na-content (up to 5%) does not seem to influence the magnetic transition temperature, TN. Isothermal magnetization curves remain almost linear up to 13 T. Our analysis of neutron diffraction data shows that the magnetic structure of Na 2 Ni 2 TeO 6 is faithfully described by a model consisting of two phases described by the commensurate wave vectors vec kc, (0.5 0 0) and (0.5 0 0.5), with an additional short-range order component incorporated in to the latter phase. Consequently, a zig-zag long-range ordered magnetic phase of Ni 2+ results in the compound, mixed with a short-range ordered phase, which is supported by our specific heat data. Theoretical computations based on density functional theory (DFT) predict predominantly in-plane magnetic exchange interactions that conform to a J1-J2-J3 model with a strong J3 term. The computationally predicted parameters lead to a reliable estimate for TN and the experimentally observed zig-zag magnetic structure. A spin wave excitation in Na 2 Ni 2 TeO 6 at E ˜ 5 meV at T = 5 K is mapped out through inelastic neutron scattering experiments, which is reproduced by linear spin wave theory calculations using the J values from our computations. Our specific heat data and inelastic neutron scattering data strongly indicate the presence of short-range spin correlations, at T > TN, stemming from incipient antiferromagnetic clusters.

36 MATERIALS SCIENCE↗

Heinz-resistant tomato cultivars exhibit a lignin-based resistance to field dodder ( Cuscuta campestris ) parasitism

Cuscuta species (dodders) are agriculturally destructive, parasitic angiosperms. These parasitic plants use haustoria as physiological bridges to extract nutrients and water from hosts. Cuscuta campestris has a broad host range and wide geographical distribution. While some wild tomato relatives are resistant, cultivated tomatoes are generally susceptible to C. campestris infestations. However, some specific Heinz tomato (Solanum lycopersicum) hybrid cultivars exhibit resistance to dodders in the field, but their defense mechanism was previously unknown. Here, we discovered that the stem cortex in these resistant lines responds with local lignification upon C. campestris attachment, preventing parasite entry into the host. Lignin Induction Factor 1 (LIF1, an AP2-like transcription factor), SlMYB55, and Cuscuta R-gene for Lignin-based Resistance 1, a CC-NBS-LRR (CuRLR1) are identified as factors that confer host resistance by regulating lignification. SlWRKY16 is upregulated upon C. campestris infestation and potentially negatively regulates LIF1 function. Intriguingly, CuRLR1 may play a role in signaling or function as an intracellular receptor for receiving Cuscuta signals or effectors, thereby regulating lignification-based resistance. In summary, these four regulators control the lignin-based resistance response in specific Heinz tomato cultivars, preventing C. campestris from parasitizing resistant tomatoes. This discovery provides a foundation for investigating multilayer resistance against Cuscuta species and has potential for application in other essential crops attacked by parasitic plants.

59 BASIC BIOLOGICAL SCIENCES↗

Multi-angle Precession Electron Diffraction (MAPED): A Versatile Approach to 4D-STEM Precession

Precession of a converged beam during acquisition of a 4D-STEM dataset improves strain, orientation, and phase mapping accuracy by averaging over continuous angles of illumination. Precession experiments usually rely on integrated systems, where automatic alignments lead to fast, high-quality results. The dependence of these experiments on specific hardware and software is evident even when switching to nonintegrated detectors on a precession tool, as experimental set-up becomes challenging and time-consuming. Here, we introduce multi-angle precession electron diffraction (MAPED): a method to perform electron diffraction by collecting sequential 4D-STEM scans at different incident beam tilts. The multiple diffraction datasets are averaged together postacquisition, resulting in a single dataset that minimizes the impact of the curvature and orientation of the Ewald sphere relative to the crystal under study. Our results demonstrate that even four additional tilts improved measurement of material properties, namely strain and orientation, as compared to single-tilt 4D-STEM experiments. We show the versatility and flexibility of our MAPED approach with data collected on a number of microscopes with different hardware configurations and a variety of detectors.

4D-STEM↗

Near-term transition and longer-term physical climate risks of greenhouse gas emissions pathways

Policy, business, finance and civil society stakeholders are increasingly looking to compare future emissions pathways across both their associated physical climate risks stemming from increasing temperatures and their transition climate risks stemming from the shift to a low-carbon economy. Herein, we present an integrated framework to explore near-term (to 2030) transition risks and longer-term (to 2050) physical risks, globally and in specific regions, for a range of plausible greenhouse gas emissions and associated temperature pathways, spanning 1.5–4 °C levels of long-term warming. By 2050, physical risks deriving from major heatwaves, agricultural drought, heat stress and crop duration reductions depend greatly on the temperature pathway. By 2030, transition risks most sensitive to temperature pathways stem from economy-wide mitigation costs, carbon price increases, fossil fuel demand reductions and coal plant capacity reductions. Considering several pathways with a 2 °C target demonstrates that transition risks also depend on technological, policy and socio-economic factors.

54 ENVIRONMENTAL SCIENCES↗

Human perception of ionizing radiation

Here, in this work, we address the question of whether humans can perceive ionizing radiation. We conducted a thorough review of the clinical and experimental literature related to ionizing radiation, with a focus on its acute effects. Specifically, we examined the three domains of X-ray perception found in animals (abdominal, olfactory, and retinal), which led us to instances of ionizing radiation-induced hearing and taste sensory phenomena in humans thus suggesting that humans can perceive X-rays across various sensory modalities via multiple mechanisms. We also analyzed literature to understand the mechanisms associated with reported symptoms, this led us to the concept of radiomodulation, an understudied modulatory effect of sub-ablative ionizing radiation doses on neurons. Based on this review of the literature we propose the hypothesis that a significant radiomodulation mechanism is the formation of reactive oxygen species from radiolysis which activates immune and sensory signal transduction mechanisms specifically related to the redox activity in TRP and K+ channels. Additionally, we find evidence to support the previous claims of perception stemming from Cherenkov radiation and ozone production which are perceived using canonical sensory modalities. Finally, for we provide a concise summary of the applications of ionizing radiation in clinical imaging and therapy, as well as prospects for future developments of radiation technologies for biomedical and fundamental research.

Ionizing radiation↗

A New Type of Hybrid Copper Iodide as Nontoxic and Ultrastable LED Emissive Layer Material

Perovskite-based light-emitting diodes (PeLEDs) are promising candidates for next-generation solid-state lighting and display technologies. However, all current high-performance PeLEDs contain a toxic element (lead) and suffer from relatively low stability. Herein, we report a new type of lead-free LED using low-cost, eco-friendly, and robust copper(I) iodide hybrid material as the emissive layer (EML). Specifically, they are composed of copper iodide chains and organic ligands through ionic and coordinate bonds. Their remarkable stability and solution processability stem from this unique multifold bonding feature. High-quality thin films of 1D-Cu 4 I 6 (bttmp) 2 were fabricated by a simple, one-step spin-coating process. They exhibit high photoluminescence quantum yield (91%) and long-term air stability (>2000 h). An EQE of 5.02% was achieved for a prototype yellow LED using 1D-Cu 4 I 6 (bttmp) 2 EML. Its half-lifetime of 35.5 h obtained in open air outperforms that of most PeLEDs reported to date. Finally, this work opens a new direction for making LEDs based on ecofriendly and robust hybrid materials.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Regulation of sarcomere formation and function in the healthy heart requires a titin intronic enhancer

Heterozygous truncating variants in the sarcomere protein titin (TTN) are the most common genetic cause of heart failure. To understand mechanisms that regulate abundant cardiomyocyte (CM) TTN expression, we characterized highly conserved intron 1 sequences that exhibited dynamic changes in chromatin accessibility during differentiation of human CMs from induced pluripotent stem cells (hiPSC-CMs). Homozygous deletion of these sequences in mice caused embryonic lethality, whereas heterozygous mice showed an allele-specific reduction in Ttn expression. A 296 bp fragment of this element, denoted E1, was sufficient to drive expression of a reporter gene in hiPSC-CMs. Deletion of E1 downregulated TTN expression, impaired sarcomerogenesis, and decreased contractility in hiPSC-CMs. Site-directed mutagenesis of predicted binding sites of NK2 homeobox 5 (NKX2-5) and myocyte enhancer factor 2 (MEF2) within E1 abolished its transcriptional activity. In embryonic mice expressing E1 reporter gene constructs, we validated in vivo cardiac-specific activity of E1 and the requirement for NKX2-5- and MEF2-binding sequences. Moreover, isogenic hiPSC-CMs containing a rare E1 variant in the predicted MEF2-binding motif that was identified in a patient with unexplained dilated cardiomyopathy (DCM) showed reduced TTN expression. Together, these discoveries define an essential, functional enhancer that regulates TTN expression. Manipulation of this element may advance therapeutic strategies to treat DCM caused by TTN haploinsufficiency.

Kim, Yuri↗

Polytypism in semi-disordered lizardite and amesite by low-dose HAADF-STEM

Serpentine minerals exert important controls on the physical properties of ultramafic rocks and have the potential to influence deformation phenomena in fault zones and to control the release of water in subducted slabs. Sheet serpentine generally, and lizardite and amesite specifically, can adopt alternative crystallographic stacking arrangements called polytypes. Polytypism has been extensively studied in fully ordered crystals, but it remains largely enigmatic in the more common semi-disordered crystals that in long-range analyses such as X-ray diffraction only exhibit random combinations of 0b and ±1/3b interlayer shifts. To date, atomic-resolution imaging to identify locally ordered polytypes has been precluded by the beam-sensitive nature of this hydrous magnesium silicate mineral. Here, in this study, we employed low-dose high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to study the polytypic structure of semi-disordered lizardite and amesite. Because the electron dose was as low as ~6000 e–/Å 2 , it was possible to directly resolve oxygen atomic columns and all the cations with a resolution of ~1 Å and reveal the short-range order. For lizardite, we identified long-period non-standard polytypes, including examples with 3, 4, 8, and 9 layers stemming from the ordering of the octahedral tilt along the a-axis. For amesite, we found short-range ordered polytypes with periodicities of up to 42 Å stemming from the ordering of interlayer shifts along the b-axis. The resolution was sufficient to determine the relative abundance of 6R 2 , 6R 1 , 2H 1 , and 2H 2 polytypes in amesite to be 46.1, 29.6, 7.7, and 1.9%, respectively. This is contrary to the expectation that the most common form of amesite is the 2H 2 polytype, which may be more likely to form macroscopic crystals suitable for conventional X-ray diffraction-based studies. We conclude that HAADF-STEM methods open the way for the characterization of beam-sensitive minerals and to resolve the structural details of less well-ordered (but possibly more abundant) minerals at a unit-cell scale.

58 GEOSCIENCES↗

Tallo: A global tree allometry and crown architecture database

Abstract Data capturing multiple axes of tree size and shape, such as a tree's stem diameter, height and crown size, underpin a wide range of ecological research—from developing and testing theory on forest structure and dynamics, to estimating forest carbon stocks and their uncertainties, and integrating remote sensing imagery into forest monitoring programmes. However, these data can be surprisingly hard to come by, particularly for certain regions of the world and for specific taxonomic groups, posing a real barrier to progress in these fields. To overcome this challenge, we developed the Tallo database, a collection of 498,838 georeferenced and taxonomically standardized records of individual trees for which stem diameter, height and/or crown radius have been measured. These data were collected at 61,856 globally distributed sites, spanning all major forested and non‐forested biomes. The majority of trees in the database are identified to species (88%), and collectively Tallo includes data for 5163 species distributed across 1453 genera and 187 plant families. The database is publicly archived under a CC‐BY 4.0 licence and can be access from: https://doi.org/10.5281/zenodo.6637599 . To demonstrate its value, here we present three case studies that highlight how the Tallo database can be used to address a range of theoretical and applied questions in ecology—from testing the predictions of metabolic scaling theory, to exploring the limits of tree allometric plasticity along environmental gradients and modelling global variation in maximum attainable tree height. In doing so, we provide a key resource for field ecologists, remote sensing researchers and the modelling community working together to better understand the role that trees play in regulating the terrestrial carbon cycle.

Jucker, Tommaso↗

Ethanol Electrooxidation at 1–2 nm AuPd Nanoparticles

We report a systematic study of the electrocatalytic properties and stability of a series of 1–2 nm Au, Pd, and AuPd alloy nanoparticles (NPs) for the ethanol oxidation reaction (EOR). Following EOR electrocatalysis, NP sizes and compositions were characterized using aberration-corrected scanning transmission electron microscopy (ac-STEM) and energy dispersive spectroscopy (EDS). Two main findings emerge from this study. First, alloyed AuPd NPs exhibit enhanced electrocatalytic EOR activity compared to either monometallic Au or Pd NPs. Specifically, NPs having a 3:1 ratio of Au:Pd exhibit an ~8-fold increase in peak current density compared to Pd NPs, with an onset potential shifted ~200 mV more to the negative compared to Au NPs. Second, the size and composition of AuPd alloy NPs do not (within experimental error) change following 1.0 or 2.0 h chronoamperometry experiments, while monometallic Au NPs increase in size from 2 to 5 nm under the same conditions. Notably, this report demonstrates the importance of post-catalytic ac-STEM/EDS characterization for fully evaluating NP activity and stability, especially for 1–2 nm NPs that may change in size or structure during electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Species-Specific Duplication Event Associated with Elevated Levels of Nonstructural Carbohydrates in Sorghum bicolor

Simple sugars are the essential foundation to plant life, and thus, their production, utilization, and storage are highly regulated processes with many complex genetic controls. Despite their importance, many of the genetic and biochemical mechanisms remain unknown or uncharacterized. Sorghum, a highly productive, diverse C4 grass important for both industrial and subsistence agricultural systems, has considerable phenotypic diversity in the accumulation of nonstructural sugars in the stem. We use this crop species to examine the genetic controls of high levels of sugar accumulation, identify genetic mechanisms for the accumulation of nonstructural sugars, and link carbon allocation with iron transport. We identify a species-specific tandem duplication event controlling sugar accumulation using genome-wide association analysis, characterize multiple allelic variants causing increased sugar content, and provide further evidence of a putative neofunctionalization event conferring adaptability in Sorghum bicolor. Comparative genomics indicate that this event is unique to sorghum which may further elucidate evolutionary mechanisms for adaptation and divergence within the Poaceae. Furthermore, the identification and characterization of this event was only possible with the continued advancement and improvement of the reference genome. The characterization of this region and the process in which it was discovered serve as a reminder that any reference genome is imperfect and is in need of continual improvement.

59 BASIC BIOLOGICAL SCIENCES↗

Deconvoluting Structures of Component Plant Biopolymers Using Deuterium Labeled Brassica oleracea Stems

Several Brassica species are cultivated globally for the production of seed oils as food, lubricants, and increasingly biofuels. The stem and leaf residues of these herbaceous dicotyledonous crops constitute another feedstock for biofuels and other products. Plant cell walls are complex, multipolymeric structures that consist primarily of polysaccharides and lignin. Cellulose chains coalesce to form crystalline microfibrils while the amorphous biopolymers, hemicellulose, and lignin form a network structure and fill the interstitial space. Neutron scattering has been used for the structural study of the assembly and deconstruction of the plant cell walls. However, similar neutron sensitivity of the different amorphous biopolymers has made structural association to individual component biopolymers nontrivial and ambiguous. To improve the association of structural features to specific biopolymer components, partial deuteration of the plant cell wall can be employed to increase the difference in the neutron scattering length density between amorphous carbohydrate and lignin plant polymers. Vegetative stems from partially deuterated Brassica oleracea acephala (kale) plants were obtained commercially, and the plant cell wall structures were studied by contrast-variation small-angle neutron scattering (CV-SANS) and Fourier-transform infrared spectroscopy (FTIR). FTIR results indicated that deuterium substitution for hydrogen in the carbohydrates was higher than that in lignin. By combining CV-SANS and FTIR results, the neutron scattering length density (nSLD) of the polysaccharides and lignin was determined to match nSLD of 65%:35% and 48%:52% D 2 O/H 2 O solvent mixtures, respectively. These nSLD values were higher than the nSLD values of polysaccharides and lignin for H 2 O grown biopolymers. The nSLD increase correlates to replacing about 42.5% of hydrogens present as both C–H and O–H groups in cellulose with deuterium atoms, while only 21% for lignin. In conclusion, this study lays the foundation to use partially deuterated plants to deconvolute structural features of the different component biopolymers, especially cellulose, hemicellulose, and lignin, of the plant cell wall without introducing unintended structural modifications due to the pretreatment extraction processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biomass formation and sugar release efficiency of Populus modified by altered expression of a NAC transcription factor

Woody biomass is an important feedstock for biofuel production. Manipulation of wood properties that enable efficient conversion of biomass to biofuel reduces cost of biofuel production. Wood cell wall composition is regulated at several levels that involve expression of transcription factors such as wood-/secondary cell wall-associated NAC domains (WND or SND). In Arabidopsis thaliana, SND1 regulates cell wall composition through activation of its down-stream targets such as MYBs. The functional aspects of SND1 homologs in the woody Populus have been studied through transgenic manipulation. In this study, we investigated the role of PdWND1B, Populus SND1 sequence ortholog, in wood formation using transgenic manipulation through over-expression or silencing under the control of a vascular-specific 4-coumarate-CoA ligase (4CL) promoter. As compared with control plants, PdWND1B-RNAi plants were shorter in height, with significantly reduced stem diameter and dry biomass, whereas there were no significant differences in growth and productivity of PdWND1B over-expression plants. Conversely, PdWND1B over-expression lines showed a significant reduction in cellulose and increase in lignin content, whereas there was no significant impact on lignin content of downregulated lines. Stem carbohydrate composition analysis revealed a decrease in glucose, mannose, arabinose, and galactose, but an increase in xylose in the over-expression lines. Transcriptome analysis revealed upregulation of several downstream transcription factors and secondary cell wall related structural genes in the PdWND1B over-expression lines, partly explaining the observed phenotypic changes in cell wall chemistry. Relative to the control, glucose release efficiency and ethanol production from stem biomass was significantly reduced in over-expression lines. Our results show that PdWND1B is an important factor determining biomass productivity, cell wall chemistry and its conversion to biofuels in Populus.

09 BIOMASS FUELS↗

Selective oxidation and nickel enrichment hinders the repassivation kinetics of multi-principal element alloy surfaces

Robust and sustained corrosion resistance in multi-principal element alloys (MPEA) requires rapid repassivation, i.e. regrowth of the passive layer once it is damaged or destroyed at the surface. In this study, we show that the repassivation of Al 0.1 CrCoFeNi MPEA in 0.6 M NaCl solution is hindered at pH of ~ 2.4 - 6.8 due to the formation of a Ni-enriched subsurface layer as a result of selective oxidation and dissolution of several principal elements, which can be fully restored at pH of ~ 14 from the oxidation of all principal elements. Specifically, surface characterization via X-ray photoelectron spectroscopy (XPS), high-angle annular dark-field (HAADF) imaging in scanning transmission electron microscopy (STEM), and atom probe tomography (APT), are coupled with density functional theory (DFT) calculations to determine surface composition, oxidation state, and electron work function to uncover the structural origin of the pH-dependent repassivation mechanisms. It was found that selective oxidation of Cr, Co, and Fe in the acidic to neutral solutions altered the surface composition to be significantly enriched in Ni as compared to the bulk. Once the original passive film is destroyed locally by either pitting or tribocorrosion, this altered surface composition exhibited a much poorer repassivation capability due to the increased electron work function and reduced surface reactivity at higher Ni concentration. Finally, these understandings could shed light on the future compositional design of non-equiatomic MPEAs towards sustained repassivation and corrosion resistance over a wide pH range.

36 MATERIALS SCIENCE↗