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Results for “degradation pathway models”

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 55 records · Page 3

Modeling Time to Failure in Potential-Induced Degradation of Silicon Solar Modules based on Quantitative Sodium Kinetics

We present a physics-based simulation environment for the prediction of potential-induced-degradation (PID) failure time in silicon solar modules. Our model is based on experimental sodium migration kinetics obtained from our recently developed trap-corrected bias-stress-temperature method and from secondary ion mass spectrometry measurements. Furthermore, we model sodium migration to stacking faults and subsequent formation of conductive pathways through the p-n junction, which causes a decrease of the shunt resistance and loss of efficiency.

42 ENGINEERING↗

High reactivity of mesoporous CeO 2 to dissociate chemical warfare agent sarin

We perform spectroscopic surface characterization on mesoporous ceria (CeO 2 ) under exposure of sarin gas, also known as GB. We find mesoporous CeO 2 displays extraordinary reactivity towards GB dissociation under high vacuum. The spectroscopic results combined with density functional theory (DFT) calculations suggest that the cleavage of the P–F and P–OR bonds are both possible pathways for GB to dissociate on the CeO 2 surfaces. The modeling reveals differences in dissociation pathways of GB on the crystallographic (111)- and (110)-surfaces of ceria. Here we also report some dissociation of GB on mesoporous CeO 2 under ambient conditions. The finding that mesoporous CeO 2 can degrade GB under mild conditions is encouraging and implies the strong potential of ceria-based materials to be applied in combating chemical warfare agents related to the GB series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN)

This study investigated the reaction pathway of 2,4-dinitroanisole (DNAN) on the pyrogenic carbonaceous matter (PCM) to assess the scope and mechanism of PCM-facilitated surface hydrolysis. DNAN degradation was observed at pH 11.5 and 25 °C with a model PCM, graphite, whereas no significant decay occurred without graphite. Experiments were performed at pH 11.5 due to the lack of DNAN decay at pH below 11.0, which was consistent with previous studies. Graphite exhibited a 1.78-fold enhancement toward DNAN decay at 65 °C and pH 11.5 relative to homogeneous solution by lowering the activation energy for DNAN hydrolysis by 54.3 ± 3.9%. This is supported by our results from the computational modeling using Car–Parrinello simulations by ab initio molecular dynamics/molecular mechanics (AIMD/MM) and DFT free energy simulations, which suggest that PCM effectively lowered the reaction barriers by approximately 8 kcal mol –1 compared to a homogeneous solution. Quaternary ammonium (QA)-modified activated carbon performed the best among several PCMs by reducing DNAN half-life from 185 to 2.5 days at pH 11.5 and 25 °C while maintaining its reactivity over 10 consecutive additions of DNAN. We propose that PCM can affect the thermodynamics and kinetics of hydrolysis reactions by confining the reaction species near PCM surfaces, thus making them less accessible to solvent molecules and creating an environment with a weaker dielectric constant that favors nucleophilic substitution reactions. Nitrite formation during DNAN decay confirmed a denitration pathway, whereas demethylation, the preferred pathway in homogeneous solution, produces 2,4-dinitrophenol (DNP). Denitration catalyzed by PCM is advantageous to demethylation because nitrite is less toxic than DNAN and DNP. These findings provide critical insights for reactive adsorbent design that has broad implications for catalyst design and pollutant abatement.

2,4-dinitroanisole (DNAN)↗

In-Situ TEM Molten Salt Corrosion

Molten salt reactors (MSRs) offer a compelling pathway for next-generation nuclear energy, with advantages in thermal efficiency, inherent safety, and flexible fuel management. Yet, halide-based molten salts introduce significant materials challenges, particularly alloy corrosion. Alloy performance in these environments ultimately depends on understanding how corrosion initiates and progresses at the nanoscale, however most existing models rely on post-exposure characterization, leaving degradation mechanisms largely inferred rather than directly observed. NiCr alloys have garnered interest in MSRs applications as the Ni-based matrix provides strength and creep resistance, while Cr content offers oxidation resistance in air. However, NiCr corrosion resistance in chloride salts has proven poor due to preferential chromium dissolution, the formation of Cr-depleted pathways, and grain-boundary attack. This work aims to directly visualize corrosion of Ni-20Cr exposed to LiCl-KCl using in-situ Transmission Electron Microscopy (TEM) to capture real-time microstructural evolution during corrosion. Experiments will be performed at ~800 °C under controlled pressure conditions while utilizing Energy-Dispersive X-ray Spectroscopy (EDS) to analyze elemental redistribution. Observation of chromium depletion fronts, associated surface restructuring, and localized chloride enrichment are expected. Ultimately, this study is expected to provide a link between microscale processes and the macroscopic degradation behaviors relevant to MSR operation in advanced reactor environments. Simultaneously, this approach enables future in-situ investigations regarding alloy composition, salt chemistry, and their influence on corrosion pathways and long-term stability.?

36 - MATERIALS SCIENCE↗

Solvent-mediated oxide hydrogenation in layered cathodes

Self-discharge and chemically induced mechanical effects degrade calendar and cycle life in intercalation-based electrochromic and electrochemical energy storage devices. In rechargeable lithium-ion batteries, self-discharge in cathodes causes voltage and capacity loss over time. The prevailing self-discharge model centers on the diffusion of lithium ions from the electrolyte into the cathode. Here, we demonstrate an alternative pathway, where hydrogenation of layered transition metal oxide cathodes induces self-discharge through hydrogen transfer from carbonate solvents to delithiated oxides. In self-discharged cathodes, we further observe opposing proton and lithium ion concentration gradients, which contribute to chemical and structural heterogeneities within delithiated cathodes, accelerating degradation. Hydrogenation occurring in delithiated cathodes may affect the chemo-mechanical coupling of layered cathodes as well as the calendar life of lithium-ion batteries.

25 ENERGY STORAGE↗

Endothelial surface translocation of mitochondrial PDCE2 involves the non-canonical secretory autophagy pathway: Putative molecular target for radiation-guided drug delivery

Highlights: • Radiation induces ectopic endothelial surface exposure of mitochondrial PDCE2. • PDCE2 translocation is associated with late-stage inhibition of autophagic flux. • Radiation damage overloads the degradative lysosomal pathway of autophagy. • PDCE2 trafficking occurs via autophagosomes and non-canonical secretory autophagy. • Surface PDCE2 provides a novel target for radiation-guided vascular drug delivery. Radiation has been proposed as a priming agent to induce discriminatory luminal biomarkers for vascular targeting and drug delivery in disorders such as brain arteriovenous malformations and cancers. We previously observed ectopic expression of intracellular proteins such as mitochondrial PDCE2 on irradiated endothelium in animal models. In this study we examined the mechanism of PDCE2 trafficking in human endothelial cells to better understand its suitability as a vascular target. Ionizing radiation induced PDCE2 surface localization in association with accumulation of autophagosome markers (L3CB and p62) indicative of late-stage inhibition of autophagic flux. This effect was abolished in the presence of Rapamycin, an autophagy-inducer, but replicated in the presence of Bafilomycin A, an autophagy blocker. PDCE2 co-localized with lysosomal markers of the canonical degradative autophagy pathway in response to radiation but also with recycling endosomes and SNARE proteins responsible for autophagosome-plasma membrane fusion. These findings demonstrate that radiation-induced blockade of autophagic flux stimulates redirection of intracellular molecules such as PDCE2 to the cell surface via a non-canonical secretory autophagy pathway. Intracellular membrane proteins trafficked in this way could provide a unique pool of radiation biomarkers for therapeutic drug delivery.

60 APPLIED LIFE SCIENCES↗

Modeling the impact of high thermal conductivity paper on the performance and life of power transformers

Degradation of insulation paper is a key contributor to the failure of power transformers. Insulation degradation accelerates at elevated temperatures, which highlights the potential for better thermal management to prolong life. While several studies have analyzed the benefits of high thermal conductivity oil for reducing temperatures inside a transformer, this study is an initial assessment of the benefits of high thermal conductivity paper on transformer life. Blending particulates with cellulosic fibers offers a pathway for high thermal conductivity paper (with good dielectric properties), which can reduce internal temperatures. Presently, life extensions that can be achieved by the use of such thermally conducting papers were estimated, with the thermal conductivity of the paper being the key parameter under study. The analytical-numerical thermal model used in this study was validated against experimental measurements in a distribution transformer, adding confidence to the utility of the model. This model was then used to provide estimates of hot-spot temperature reduction resulting from the use of papers with higher thermal conductivity than baseline. Transformer life was predicted conventionally by tracking the degree of polymerization of paper over time, based on an Arrhenius model. Results indicate that increasing the thermal conductivity of paper from 0.2 W/mK (baseline) to 1W/mK reduces the hot spot temperature by 10°C. While degradation significantly depends on the moisture and oxygen content, the model shows that such a temperature reduction can increase life for all conditions, by as much as a factor of three.

42 ENGINEERING↗

The N-end rule pathway catalyzes a major fraction of the protein degradation in skeletal muscle

In skeletal muscle, overall protein degradation involves the ubiquitin-proteasome system. One property of a protein that leads to rapid ubiquitin-dependent degradation is the presence of a basic, acidic, or bulky hydrophobic residue at its N terminus. However, in normal cells, substrates for this N-end rule pathway, which involves ubiquitin carrier protein (E2) E214k and ubiquitin-protein ligase (E3) E3alpha, have remained unclear. Surprisingly, in soluble extracts of rabbit muscle, we found that competitive inhibitors of E3alpha markedly inhibited the 125I-ubiquitin conjugation and ATP-dependent degradation of endogenous proteins. These inhibitors appear to selectively inhibit E3alpha, since they blocked degradation of 125I-lysozyme, a model N-end rule substrate, but did not affect the degradation of proteins whose ubiquitination involved other E3s. The addition of several E2s or E3alpha to the muscle extracts stimulated overall proteolysis and ubiquitination, but only the stimulation by E3alpha or E214k was sensitive to these inhibitors. A similar general inhibition of ubiquitin conjugation to endogenous proteins was observed with a dominant negative inhibitor of E214k. Certain substrates of the N-end rule pathway are degraded after their tRNA-dependent arginylation. We found that adding RNase A to muscle extracts reduced the ATP-dependent proteolysis of endogenous proteins, and supplying tRNA partially restored this process. Finally, although in muscle extracts the N-end rule pathway catalyzes most ubiquitin conjugation, it makes only a minor contribution to overall protein ubiquitination in HeLa cell extracts.

Non-NASA Center↗

Mechanism for Utilization of the Populus-Derived Metabolite Salicin by a Pseudomonas—Rahnella Co-Culture

Pseudomonas fluorescens GM16 associates with Populus, a model plant in biofuel production. Populus releases abundant phenolic glycosides such as salicin, but P. fluorescens GM16 cannot utilize salicin, whereas Pseudomonas strains are known to utilize compounds similar to the aglycone moiety of salicin–salicyl alcohol. We propose that the association of Pseudomonas to Populus is mediated by another organism (such as Rahnella aquatilis OV744) that degrades the glucosyl group of salicin. In this study, we demonstrate that in the Rahnella–Pseudomonas salicin co-culture model, Rahnella grows by degrading salicin to glucose 6-phosphate and salicyl alcohol which is secreted out and is subsequently utilized by P. fluorescens GM16 for its growth. Using various quantitative approaches, we elucidate the individual pathways for salicin and salicyl alcohol metabolism present in Rahnella and Pseudomonas, respectively. Furthermore, we were able to establish that the salicyl alcohol cross-feeding interaction between the two strains on salicin medium is carried out through the combination of their respective individual pathways. The research presents one of the potential advantages of salicyl alcohol release by strains such as Rahnella, and how phenolic glycosides could be involved in attracting multiple types of bacteria into the Populus microbiome.

Pseudomonas↗

COST1 regulates autophagy to control plant drought tolerance

Plants balance their competing requirements for growth and stress tolerance via a sophisticated regulatory circuitry that controls responses to the external environments. We have identified a plant-specific gene, COST1 (constitutively stressed 1), that is required for normal plant growth but negatively regulates drought resistance by influencing the autophagy pathway. An Arabidopsis thaliana cost1 mutant has decreased growth and increased drought tolerance, together with constitutive autophagy and increased expression of drought-response genes, while overexpression of COST1 confers drought hypersensitivity and reduced autophagy. The COST1 protein is degraded upon plant dehydration, and this degradation is reduced upon treatment with inhibitors of the 26S proteasome or autophagy pathways. The drought resistance of a cost1 mutant is dependent on an active autophagy pathway, but independent of other known drought signaling pathways, indicating that COST1 acts through regulation of autophagy. In addition, COST1 colocalizes to autophagosomes with the autophagosome marker ATG8e and the autophagy adaptor NBR1, and affects the level of ATG8e protein through physical interaction with ATG8e, indicating a pivotal role in direct regulation of autophagy. We propose a model in which COST1 represses autophagy under optimal conditions, thus allowing plant growth. Under drought, COST1 is degraded, enabling activation of autophagy and suppression of growth to enhance drought tolerance. Our research places COST1 as an important regulator controlling the balance between growth and stress responses via the direct regulation of autophagy.

59 BASIC BIOLOGICAL SCIENCES↗

Revisiting Theoretical Tools and Approaches for the Valorization of Recalcitrant Lignocellulosic Biomass to Value-Added Chemicals

Biorefinery processes for converting lignocellulosic biomass to fuels and chemicals proceed via an integrated series of steps. Biomass is first pretreated and deconstructed using chemical catalysts and/or enzymes to liberate sugar monomers and lignin fragments. Deconstruction is followed by a conversion step in which engineered host organisms assimilate the released sugar monomers and lignin fragments, and produce value-added fuels and chemicals. Over the past couple of decades, a significant amount of work has been done to develop innovative biomass deconstruction and conversion processes that efficiently solubilize biomass, separate lignin from the biomass, maximize yields of bioavailable sugars and lignin fragments and convert the majority of these carbon sources into fuels, commodity chemicals, and materials. Herein, we advocate that advanced in silico approaches provide a theoretical framework for developing efficient processes for lignocellulosic biomass valorization and maximizing yields of sugars and lignin fragments during deconstruction and fuel and chemical titers during conversion. This manuscript surveys the latest developments in lignocellulosic biomass valorization with special attention given to highlighting computational approaches used in process optimization for lignocellulose pretreatment; enzyme engineering for enhanced saccharification and delignification; and prediction of the genome modification necessary for desired pathway fine-tuning to upgrade products from biomass deconstruction into value-added products. Physics-based modeling approaches such as density functional theory calculations and molecular dynamics simulations have been most impactful in studies aimed at exploring the molecular level details of solvent-biomass interactions, reaction mechanisms occurring in biomass-solvent systems, and the catalytic mechanisms and engineering of enzymes involved in biomass degradation. More recently, with ever increasing amounts of data from, for example, advanced mutli-omics experiments, machine learning approaches have begun to make important contributions in synthetic biology and optimization of metabolic pathways for production of biofuels and chemicals.

09 BIOMASS FUELS↗

GalR, GalX and AraR co-regulate $\tiny {D}$-galactose and $\tiny{L}$-arabinose utilization in Aspergillus nidulans

Filamentous fungi produce a wide variety of enzymes in order to efficiently degrade plant cell wall polysaccharides. The production of these enzymes is controlled by transcriptional regulators, which also control the catabolic pathways that convert the released monosaccharides. Two transcriptional regulators, GalX and GalR, control d-galactose utilization in the model filamentous fungus Aspergillus nidulans, while the arabinanolytic regulator AraR regulates l-arabinose catabolism. d-Galactose and l-arabinose are commonly found together in polysaccharides, such as arabinogalactan, xylan and rhamnogalacturonan I. Therefore, the catabolic pathways that convert d-galactose and l-arabinose are often also likely to be active simultaneously. In this study, we investigated the interaction between GalX, GalR and AraR in d-galactose and l-arabinose catabolism. For this, we generated single, double and triple mutants of the three regulators, and analysed their growth and enzyme and gene expression profiles. Our results clearly demonstrated that GalX, GalR and AraR co-regulate d-galactose catabolism in A. nidulans. GalX has a prominent role on the regulation of genes of d-galactose oxido-reductive pathway, while AraR can compensate for the absence of GalR and/or GalX.

59 BASIC BIOLOGICAL SCIENCES↗

Review—“Knees” in Lithium-Ion Battery Aging Trajectories

Lithium-ion batteries can last many years but sometimes exhibit rapid, nonlinear degradation that severely limits battery lifetime. In this work, we review prior work on “knees” in lithium-ion battery aging trajectories. We first review definitions for knees and three classes of “internal state trajectories” (termed snowball, hidden, and threshold trajectories) that can cause a knee. We then discuss six knee “pathways”, including lithium plating, electrode saturation, resistance growth, electrolyte and additive depletion, percolation-limited connectivity, and mechanical deformation—some of which have internal state trajectories with signals that are electrochemically undetectable. Additionally, we also identify key design and usage sensitivities for knees. Finally, we discuss challenges and opportunities for knee modeling and prediction. Our findings illustrate the complexity and subtlety of lithium-ion battery degradation and can aid both academic and industrial efforts to improve battery lifetime.

25 ENERGY STORAGE↗

Colocalized Raman spectroscopy – scanning electrochemical microscopy investigation of redox flow battery dialkoxybenzene redoxmer degradation pathways

Non-aqueous redox flow batteries offer high voltages for grid-level energy storage technologies. However, decomposition of the redoxmers - redox-active molecules that make up the anolyte and catholyte in the negative and positive cell compartments - is an important challenge to overcome for long-term storage. Here, we present a spectroelectrochemical study of the catholyte candidate 2,3-dimethyl-1,4-dialkoxybenzene (C7) and its decomposition mechanisms in the presence of a model nucleophilic base, pyridine. We utilize colocalized Raman microscopy and scanning electrochemical microscopy (Raman-SECM) to quantify the chemical rates of decom-position and qualitatively identify the reaction intermediates and products. A detailed study on how the Raman-SECM parameters (electrode distance, substrate electrode, and laser focal height) influence the Raman signal of the charged catholyte C7 ∙+ is presented. Using optimized conditions, we monitored the deprotonation of C7 ∙+ via Raman spectroscopy and the subsequent hydrogen abstraction from solvent molecules to regenerate C7 via electrochemistry. Finite element modeling was used to fit electrochemical and spectroscopic data, quantifying the deprotonation rates as k dep = 2000 and 700 L mol -1 s -1 and abstraction rates as k abs = 0.5 and 0.2 s - 1 in propylene carbonate and acetonitrile solvents, respectively. Our results show the value of spatiotemporal reso-lution in evaluating the chemical and electrochemical behavior of materials for redox flow batteries.

25 ENERGY STORAGE↗

A systems engineering framework for the optimization of food supply chains under circular economy considerations

The current linear “take-make-waste-extractive” model leads to the depletion of natural resources and environmental degradation. Circular Economy (CE) aims to address these impacts by building supply chains that are restorative, regenerative, and environmentally benign. This can be achieved through the re-utilization of products and materials, the extensive usage of renewable energy sources, and ultimately by closing any open material loops. Such a transition towards environmental, economic and social advancements requires analytical tools for quantitative evaluation of the alternative pathways. Here, in this work, we present a novel CE system engineering framework and decision-making tool for the modeling and optimization of food supply chains. First, the alternative pathways for the production of the desired product and the valorization of wastes and by-products are identified. Then, a Resource-Task-Network representation that captures all these pathways is utilized, based on which a mixed-integer linear programming model is developed. This approach allows the holistic modeling and optimization of the entire food supply chain, taking into account any of its special characteristics, potential constraints as well as different objectives. Considering that typically CE introduces multiple, often conflicting objectives, we deploy here a multi-objective optimization strategy for trade-off analysis. A representative case study for the supply chain of coffee is discussed, illustrating the steps and the applicability of the framework. Single and multi-objective optimization formulations under five different coffee-product demand scenarios are presented. The production of instant coffee as the only final product is shown to be the least energy and environmental efficient scenario. On the contrary, the production solely of whole beans sets a hypothetical upper bound on the optimal energy and environmental utilization. In both problems presented, the amount of energy generated is significant due to the utilization of waste generated for the production of excess energy.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Electric-vehicle battery second-life and recycling pathways: How economics depend on chemistry, processing, and application

We assess the economics of repurposing and recycling electric vehicle (EV) batteries by estimating the maximum acquisition price repurposers and recyclers could pay for used EV packs across cathode chemistries, first-life conditions, second-life applications, and recycling processes. We develop a novel open-source process-based cost model of a UL-1974-certified repurposing facility and leverage battery degradation models to estimate the maximum acquisition price repurposers could pay for used EV batteries while producing second-life battery energy storage systems with life-adjusted costs equivalent to new systems. We compare these maximum price estimates to maximum prices for recyclers based on cost and revenue estimates from the EverBatt model. We find that repurposing is more economical than recycling for lithium iron phosphate (LFP) batteries, due to their relatively long life and low value materials; recycling is generally more economical than repurposing for lithium nickel cobalt aluminum oxide (NCA) batteries, due to their shorter life and higher value materials; and the economics for lithium nickel manganese cobalt oxide (NMC) batteries depend more heavily on first life retirement conditions and second life application intensity. These results suggest an overall strategy: reuse LFP, recycle NCA, and sort NMC into recycling or repurposing pathways based on state of health and second-life application.

25 ENERGY STORAGE↗

Electrochemo-mechanics unlocks hidden dynamics of lithium plating under stacking pressure

Understanding and mitigating lithium plating remains one of the most pressing challenges in advancing the safety and longevity of lithium-ion batteries (LIBs). Here, we present a novel integrative framework that combines in-operando swelling force measurements with a physics-based electro-chemo-mechanical model to uncover previously inaccessible insights into lithium plating dynamics under mechanical constraints. Unlike existing approaches that focus primarily on electrochemical signatures, our approach captures the coupled mechanical responses of commercial pouch cells during cycling, revealing how mechanical constraints fundamentally alter degradation pathways. We demonstrate that the use of a moderate stacking pressure suppresses lithium plating and enhances lithium stripping. This mechanically driven structural effect, coupled with the electrochemical process, significantly extends the linear aging regime in LIBs. Intriguingly, intermittent capacity recovery events that were observed during the battery cycling suggest dynamic lithium reactivation, a phenomenon rarely captured in real-time. This study pioneers a stress-aware methodology for diagnosing and managing lithium plating, establishing a new paradigm for real-time battery health monitoring. The findings offer transformative implications for the design of durable, high-performance LIB systems, opening new avenues for intelligent control strategies in battery management systems.

Bhowmick, Amit↗

Kinetic modeling of anaerobic degradation of plant-derived aromatic mixtures by Rhodopseudomonas palustris

Abstract Rhodopseudomonas palustris is a model microorganism for studying the anaerobic metabolism of aromatic compounds. While it is well documented which aromatics can serve as sole organic carbon sources, co-metabolism of other aromatics is poorly understood. This study used kinetic modeling to analyze the simultaneous degradation of aromatic compounds present in corn stover hydrolysates and model the co-metabolism of aromatics not known to support growth of R. palustris as sole organic substrates. The simulation predicted that p -coumaroyl amide and feruloyl amide were hydrolyzed to p -coumaric acid and ferulic acid, respectively, and further transformed via p -coumaroyl-CoA and feruloyl-CoA. The modeling also suggested that metabolism of p -hydroxyphenyl aromatics was slowed by substrate inhibition, whereas the transformation of guaiacyl aromatics was inhibited by their p -hydroxyphenyl counterparts. It also predicted that substrate channeling may occur during degradation of p -coumaroyl-CoA and feruloyl-CoA, resulting in no detectable accumulation of p -hydroxybenzaldehyde and vanillin, during the transformation of these CoA ligated compounds to p- hydroxybenzoic acid and vanillic acid, respectively. While the simulation correctly represented the known transformation of p -hydroxybenzoic acid via the benzoyl-CoA pathway, it also suggested co-metabolism of vanillic acid and syringic acid, which are known not to serve as photoheterotrophic growth substrate for R. palustris .

59 BASIC BIOLOGICAL SCIENCES↗