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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 37 records · Page 2

Light-triggered electrochemical biosensor using singlet oxygen for self-powered operation and glucose detection

This study introduces a light-activated sensing strategy that integrates photosensitization with electrochemical detection. The sensor employs Eosin Y, a photosensitizer that generates singlet oxygen ( 1 O 2 ) via type II photosensitization. Immobilized within a thin polymer matrix on a carbon working electrode, Eosin Y produces 1 O 2 , under green light (520 nm) illumination, initiating a redox process that yields a measurable current. To incorporate biosensing capabilities and enable self-powered operation, this 1 O 2 – mediated process was coupled with glucose oxidase (GOx) to construct a fully operational glucose biosensor. The addition of glucose reverses the current flow by causing GOx to compete for electrons, with the resulting current magnitude correlating with glucose concentration providing a sensitive measure of glucose. The biosensor, as proof-of-principle, demonstrated excellent performance over a range of glucose concentrations (0–73 mM), achieving a detection limit (LOD) of 2.8 mM for steady state photocurrent under oxygen-saturated conditions. This platform leverages light and 1 O 2 as stimuli for tunable, on-demand signal control, offering a novel approach for adaptive, real-time biosensing technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon‐negative hydrogen from ethanol via catalytic oxidative reforming

Abstract This study evaluated a commercial technology for producing low‐ or negative‐carbon hydrogen through ethanol catalytic oxidative reforming, focusing on the life cycle greenhouse gas emissions, or carbon intensity (CI). Various scenarios were analyzed: (a) comparing corn ethanol (first‐generation or Gen1 ethanol) and cellulosic ethanol (second‐generation or Gen2 ethanol) as feedstocks; (b) assessing carbon capture and sequestration (CCS) for CO 2 from upstream fermentation; and (c) evaluating oxygen sourcing via air separation units vs. on‐site or off‐site water electrolysis using a proton exchange membrane. Findings indicate that the CI for hydrogen production using Gen2 ethanol from corn stover is lower than that of Gen1 corn ethanol. Additionally, using proton exchange membrane‐generated oxygen results in a lower CI than air separation unit‐generated oxygen, regardless of the sourcing method. Implementing CCS for the hydrogen production plant's evolved CO 2 is essential for achieving a net‐negative CI for hydrogen from Gen1 ethanol. All examined scenarios, including both ethanol generations, oxygen sources, and CCS applications, demonstrated a net‐negative carbon intensity, surpassing the life cycle greenhouse gas emissions threshold of 0.45 kg CO 2 e/kg to enable policy credits as outlined in the Inflation Reduction Act §45V. In comparison, the CI for hydrogen from steam methane reforming stands at 3.4 kg CO 2 e/kg with CCS and 9.4 kg CO 2 e/kg without CCS.

08 HYDROGEN↗

From photosynthetic electron flow to gene regulation: redox signal transduction in cyanobacteria

In cyanobacteria, the free-living ancestors of chloroplasts, photosynthesis simultaneously sustains growth and generates reactive oxygen species (ROS) that damage proteins, lipids, and DNA when light capture outpaces carbon fixation. Maintaining redox balance, therefore, requires cells to read photosynthetic electron flow as a signal that continuously tunes gene expression and protein activity. This review traces how these redox signals are transduced to transcription machinery through three routes: membrane-localized sensors, cytoplasmic redox sensors downstream of photosystem I, and ROS generated when electron sinks are saturated. Membrane-bound histidine kinases (two-component systems) relay the redox state of the plastoquinone pool to control photosystem remodeling, pigment biosynthesis, and circadian timing. Cytoplasmic one-component regulators, by contrast, sense redox directly through thiol-disulfide switches, glutathionylation, iron-sulfur clusters, and metal-catalyzed oxidation to control photosystem-cofactor, electron-carrier, and transition-metal homeostasis. Because many of these regulators persist in algal and plant chloroplasts, cyanobacteria illuminate principles of redox control across photosynthetic eukaryotes. Post-transcriptional and translational control further shapes redox-dependent gene expression programs through transcript stability, ribosome assembly, and translation initiation, extending redox regulation beyond transcription to every step of protein synthesis and even activity modulation. Finally, we connect redox regulation to photosynthetic physiology, stress resilience, and the rational engineering of cyanobacteria for sustainable bioproduction.

59 BASIC BIOLOGICAL SCIENCES↗

Detection of atomic oxygen and its electronic coherence decays using time-resolved ultrafast coherent Raman scattering

We report the detection of atomic oxygen and quantitative measurements of its electronic Raman coherence decays in flames and low-temperature plasmas using time-resolved hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (CARS). Atomic oxygen was detected using the Raman transitions between the spin–orbit coupled triplet ground states. Atomic oxygen was generated in an H 2 /O 2 /Ar diffusion flame and an O 2 /Ar pulsed plasma discharge. Single exponential decays were observed for the O( 3 P 2 )–O( 3 P 1 ) Raman transition at 158.3 cm −1 and the O( 3 P 2 )–O( 3 P 0 ) Raman transition at 227 cm −1 . From the decay measurements, the atomic O Raman linewidths were obtained from 25 to 150 Torr in non-equilibrium plasma and at 760 Torr in a flame. Enhanced signal-to-noise ratios (SNRs) of atomic oxygen and atomic to molecular oxygen signal contrasts were obtained by taking advantage of electronic triplet coherence beating. Enhancement of up to seven times in the atomic O SNR was observed. Furthermore, we also found that the dephasing rates of O 2 (v = 0–3, N = 37) were similar, which provides evidence for the assumption that vibrational excitation does not influence the dephasing of diatomic molecular rotational CARS transitions.

Atomic and molecular spectroscopy↗

Temporal multi-omic analysis uncovers sex-biased molecular programs underlying skeletal muscle adaptation to endurance training

Background. Exercise training is known to benefit health and reduce disease risk. While adaptations in skeletal muscles are fundamental to many of the health benefits of exercise training, the common and sex-specific molecular regulators that mediate these adaptations remain to be fully elucidated. Methods. To this end, we leveraged skeletal muscle multi-omics data generated by the Molecular Transducers of Physical Activity Consortium (MoTrPAC), where 6 month-old male and female rats endurance trained for 1, 2, 4, or 8 weeks. Our objective was to identify shared and sex-specific multi-omic molecular responses to endurance training in skeletal muscle, and relate them to phenotypic adaptations. Results. We identified largely sexually-conserved transcriptomic and proteomic enrichments in the gastrocnemius, which correlated with skeletal muscle responses from a published exercise study in humans. We uncovered sex-consistent post-translational modifications, including decreased oxidation of MYH2 and deacetylation of the ß-oxidation enzyme HADHA. Pathway enrichment analyses revealed sex-specific remodeling across the acetylome, redox proteome, and phosphoproteome; females decreased mitochondrial protein oxidation and increased mitochondrial cristae proteins, indicative of enhanced redox buffering and mitochondrial efficiency. Despite observed decreases in the oxidation of key mitochondrial proteins, females displayed increases in the oxidation of proteins involved in glucose catabolism relative to males after 8 weeks of training, suggestive of sex-biased subcellular reactive oxygen species generation. Conclusions. This work shows a large portion of the adaptive response to endurance training in skeletal muscle is shared between females and males, while there are distinct and nuanced sex-specific adaptations that are evident, particularly at the level of post-translational regulation.

Many, Gina M.↗

An Active Oxygen Electrode for Proton-Conducting Solid Oxide Electrolysis Cells with High Faradaic Efficiency

Addressing the challenges posed by inferior electrochemical performance at low temperatures and the uncertain Faradaic efficiency (FE) represents a pivotal undertaking in the development of high performance and efficient proton-conducting solid oxide electrolysis cells (P-SOECs). In this work, a novel oxygen electrode material BaCo0.8Zr0.1Zn0.1O3-d (BCZZ) is first designed and synthesized. At 600 °C, P-SOECs with BCZZ oxygen electrode achieve an electrolysis current density of 1.98 A cm-2 with an ˜90% FE at 1.3 V. Utilizing 1-inch P-SOECs as a reliable platform, the effect of extrinsic operating conditions (i.e., steam concentration, voltage, current density, and temperature) and intrinsic properties of P-SOECs (i.e., electrolyte material and electrolyte thickness) on FE are further systemically investigated, both experimentally and theoretically.

08 - HYDROGEN↗

Regulating the Third Metal to Design and Engineer Multilayered NiFeM (M: Co, Mn, and Cu) Nanofoam Anode Catalysts for Anion-Exchange Membrane Water Electrolyzers

In this study, alkaline anion-exchange membrane water electrolyzers (AEMWEs) for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant platinum group metal (PGM)-free catalysts. Herein, the third metal is incorporated into NiFe-based catalysts to regulate their electronic structures and morphologies, aiming to achieve sufficient oxygen evolution reaction (OER) activity and performance in AEMWEs. The ternary NiFeM (M: Cu, Co, or Mn) catalysts are featured with multiple layered structures and nanofoam network morphologies, consisting of highly OER-active amorphous Ni-rich oxide shells and electrically conductive metallic alloy cores. The physical and electronic perturbations to the NiFe induced by a third element lead to a fine-tuning of the redox ability of the metal sites at the reaction centers, which breaks the scaling relationship between OH* and O* intermediates at the reaction centers. Thus, the unique structural configuration and electronic regulation simultaneously benefit catalytic activity and performance improvements. These NiFeM nanofoam catalysts demonstrated promising anode performance in actual AEMWEs, comparable to the IrO 2 reference, especially at high current densities. Notably, using various electrolytes (e.g., KOH solution or pure water) for AEMWEs exhibited a different performance trend among studied NiFeM catalysts, likely due to dynamic changes of catalysts under various OER environments.

25 ENERGY STORAGE↗

Ozonolysis of selenium: an alternative oxidation method for radiochemical separations of arsenic and selenium

Many arsenic and selenium radiochemical separation methods use hydrogen peroxide (H 2 O 2 ) to oxidize selenite (Se(IV)) to selenate (Se(VI)), but this reaction is challenging to control and replicate. Here, this study introduces a simple ozonolysis apparatus with an in-line oxygen-ozone generator and impinger system for rapid selenium oxidation in aqueous samples as an alternative to H 2 O 2 . The system quickly converts Se(IV) to Se(VI), enabling successful separations of arsenic-73 and selenium-75 with high recoveries using ion-exchange chromatography (1-X8). Compared to traditional H 2 O2 treatment, ozone oxidation is a faster and more easily controlled method for selenium redox chemistry.

and nuclear chemistry↗

Development of Half-Sandwich Ru, Os, Rh, and Ir Complexes Bearing the Pyridine-2-ylmethanimine Bidentate Ligand Derived from 7-Chloroquinazolin-4(3H)-one with Enhanced Antiproliferative Activity

Kinesin spindle protein (KSP) inhibitors are one of the most promising anticancer agents developed in recent years. Herein, we report the synthesis of ispinesib-core pyridine derivative conjugates, which are potent KSP inhibitors, with half-sandwich complexes of ruthenium, osmium, rhodium, and iridium. Conjugation of 7-chloroquinazolin-4(3H)-one with the pyridine-2-ylmethylimine group and the organometallic moiety resulted in up to a 36-fold increased cytotoxicity with IC 50 values in the micromolar and nanomolar range also toward drug-resistant cells. All studied conjugates increased the percentage of cells in the G 2 /M phase, simultaneously decreasing the number of cells in the G 1 /G 0 phase, suggesting mitotic arrest. Additionally, ruthenium derivatives were able to generate reactive oxygen species (ROS); however, no significant influence of the organometallic moiety on KSP inhibition was observed, which suggests that conjugation of a KSP inhibitor with the organometallic moiety modulates its mechanism of action.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating physicochemical interfaces enables li-rich oxides based ceramic solid-state li batteries under ambient conditions

Li-rich layered oxides exhibit promising potential applications in high-energy-density solid-state lithium metal batteries. Nevertheless, the strong oxidative oxygen species generate at high voltage, which poses great challenges to positive electrode-side interface stability. Herein, a robust in-situ polymerization gel polymer electrolyte with bifunctional additives is designed for interface modification. These additives, include lithium difluoro(oxalate) borate and LiPO 2 F 2 , regulate the Li + chemical environment in gel polymer electrolyte to enhance crosslink density without residual oligomer, which reduce gas generation and suppress contact loss, thus avoiding interfacial impedance divergence. Concurrently, the designed gel polymer electrolyte enables a wide electrochemical stability window (up to 4.7 V) and a high Li + transference number (0.82). Additionally, the additives induced F- and B-rich inorganic cathode-electrolyte interphase inhibits side reactions and oxygen/transition metal loss effectively, stabilizing the chemical interface. The as-constructed Li-rich layered oxides-based ceramic solid-state lithium metal batteries with gel polymer electrolyte interface modification exert a high discharge capacity of 276.5 mAh g -1 at 30 °C without external pressure, delivering a retention of 81.7% after 100 cycles at 25 mA g -1 during 2.0-4.7 V. This work provides a guideline for developing high-voltage solid-state lithium metal batteries via interfacial design.

Hu, Xinchao [Xiamen University (China)]↗

Production of the light-activated elsinochrome phytotoxin in the soybean pathogen Coniothyrium glycines hints at virulence factor

The Dothideomycete pathogenConiothyrium glycinescauses red leaf blotch of soybean, a major disease in Africa. It is one of two fungal plant pathogens on the USDA PPQ Select Agents and Toxins list of pathogens important to the biosecurity of the United States, reflective of its potential to be highly destructive if introduced. Despite its importance, there are no published reports regarding the molecular basis of host infection. Examination of theC. glycinesgenome revealed a secondary metabolite gene cluster that is similar in gene content and organization to clusters that synthesize light-activated perylenequinone toxins, such as cercosporin. Perylenequinones are non-host specific toxins that, upon exposure to light, generate reactive oxygen species, which have near-universal toxicity to plant hosts.Coniothyrium glycinesisolates from eastern and southern Africa were cultured axenically under light and dark conditions. Light-grown cultures produced red-pink pigmentation typical of perylenequinones. Differential gene expression analysis showed that six of the eight genes in the biosynthetic gene cluster, including the polyketide synthase gene, were significantly upregulated in light. Liquid chromatography-mass spectrometry confirmed production of the perylenequinone elsinochrome A, a known virulence factor in other fungal pathogens. On leaves incubated in the dark, significantly fewer lesions formed and symptoms were delayed, compared to leaves incubated in the light. In addition, we identified orthologous gene clusters in more distantly related Dothideomycete plant pathogens where their presence was previously unknown, indicating a broader importance of these toxins to agriculture and fungal ecology. This work provides the first evidence that elsinochrome A may contribute to the virulence ofC. glycines.

Science & Technology - Other Topics↗

Exploring pH Dynamics in Amino Acid Solutions Under Low-Temperature Plasma Exposure

Low-temperature plasma (LTP) offers a promising alternative for cancer therapy, as it targets malignant cells selectively while minimizing damage to healthy tissues. Upon interaction with an aqueous solution, LTP generates reactive oxygen and nitrogen species and thereby influences the solution’s pH, which is a crucial factor in cancer proliferation and response to treatment. This study investigated the effects of LTP on the pH of aqueous solutions, with a focus on the effect of LTP parameters such as voltage, frequency, and irradiation time. In addition, it explored the influence of solution composition, specifically the presence of the amino acids, glycine and serine, on pH changes; these amino acids are known to play significant roles in cancer proliferation. Our results indicated that LTP induces acidification in deionized water, in which the extent of acidification increased proportionally with plasma parameters. In glycine-containing solutions, pH changes were concentration-dependent, whereas serine-containing solutions maintained a constant pH across all tested concentrations. To investigate potential changes to the structural properties of glycine and serine exposed to LTP that could be responsible for different pH responses, we analyzed the samples using FTIR spectroscopy. A significant decrease in absorbance was observed for solutions with low concentrations of amino acids, suggesting their degradation.

Biochemistry & Molecular Biology↗

Investigating the mechanism of chloroplast singlet oxygen signaling in the Arabidopsis thaliana accelerated cell death 2 mutant

As sessile organisms, plants have evolved complex signaling mechanisms to sense stress and acclimate. This includes the use of reactive oxygen species (ROS) generated during dysfunctional photosynthesis to initiate signaling. One such ROS, singlet oxygen ( 1 O 2 ), can trigger retrograde signaling, chloroplast degradation, and programmed cell death. However, the signaling mechanisms are largely unknown. Several proteins (e.g. PUB4, OXI1, EX1) are proposed to play signaling roles across three Arabidopsis thaliana mutants that conditionally accumulate chloroplast 1 O 2 (fluorescent in blue light (flu), chlorina 1 (ch1), and plastid ferrochelatase 2 (fc2)). We previously demonstrated that these mutants reveal at least two chloroplast 1 O 2 signaling pathways (represented by flu and fc2/ch1). Here, we test if the 1 O 2 -accumulating lesion mimic mutant, accelerated cell death 2 (acd2), also utilizes these pathways. The pub4–6 allele delayed lesion formation in acd2 and restored photosynthetic efficiency and biomass. Conversely, an oxi1 mutation had no measurable effect on these phenotypes. acd2 mutants were not sensitive to excess light (EL) stress, yet pub4–6 and oxi1 both conferred EL tolerance within the acd2 background, suggesting that EL-induced 1 O 2 signaling pathways are independent from spontaneous lesion formation. Thus, 1 O 2 signaling in acd2 may represent a third (partially overlapping) pathway to control cellular degradation.

59 BASIC BIOLOGICAL SCIENCES↗

Microstructure-based modeling of inner oxygen pressure in solid oxide electrolysis cells: Analysis of electrode delamination and mitigation

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here a microstructure-based electrochemical model, which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

25 ENERGY STORAGE↗

Microstructure-Based Modeling of Inner Oxygen Pressure in Solid Oxide Electrolysis Cells

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here, a microstructure-based electrochemical model which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

Xue, Fei↗

Generation of a fluorescent short-lifetime oxygen nanosensor by coupling of an exciplex forming dye pair

Typical oxygen-sensitive dyes have lifetimes in the μs-ms regime for sensitive oxygen detection based on molecular quenching. Due to the long triplet-state lifetimes and poor quenching efficiency of these probes, it has been difficult to develop short lifetime probes. We have developed oxygen sensors using a short-lifetime dye (∼30–60 ns) that forms an anthracene-aniline exciplex, which is quenched by molecular oxygen through an excited-state charge transfer mechanism. To achieve measurements in aqueous systems, we have tethered the dyes together via a C3 alkyl linker to facilitate greater exciplex formation at low dye concentration (20 μg mL −1 ) and encapsulated the resulting compound into polymeric nanoparticles to form an aqueous-dispersible short-lifetime oxygen nanosensor. The sensors emit at 420 nm (unfolded dye) and 500 nm (exciplex), and the ratiometric Stern-Volmer Constant is 1.52 ± 0.02 L mol −1 , showing good sensitivity from 0 % to 40 % dissolved oxygen without the tradeoff of a long lifetime needed for direct molecular quenching. In this paper, we characterize this sensor for both lifetime-based measurements using time-correlated single-photon counting and ratiometric intensity-based measurements using the unfolded dye emission as an internal reference peak.

Biological and medical sciences↗

Fundamental Insights into Cathode Stability: Linking Compositional Tuning and Local Coordination in Complex Metal Oxides under Aqueous Transformations

Compositional tuning of complex metal oxides in Li-ion battery materials influences their performance as well as their end-of-life behavior, in particular, the tendency to release toxic metal cations in aqueous solution. We modeled ternary variants of a parent LiCoO 2 delafossite structure by varying the metal identity and relative amounts. This yielded ten model formulations of Li(A 4/6 B 1/6 C 1/6 )O 2 , where the material is enriched with the A metal and doped with B and C, with Ni, Mn, Co, Fe, Al, V, and Ti as constituent metals. To assess their stability in aqueous conditions, metal release energetics were calculated using a combination of Density Functional Theory calculations and thermodynamics. Metal release in ternary oxides is dictated by subtle variations in the coordination environment of the leaving group. To identify governing chemical features across diverse compositions with varying local coordination environments, we leverage random forest regression and descriptor importance analysis. A key result is that metal–oxygen orbital hybridization, quantified using a projected density-of-states-derived descriptor, H d/p , provides a physically grounded measure of interaction strength that governs metal release energetics. This refined perspective goes beyond conventional oxidation state considerations and offers more robust insights for materials science. Finally, we model defect surface-bound O 2 dimer formation as a proxy for reactive oxygen species (ROS) generation. The results show that Ni-rich compositions more readily stabilize spin-polarized O 2 dimers, corroborating experimental reports of an increased ROS-driven biological response. In conclusion, our results establish a compositional and electronic basis for metal release and surface oxygen reactivity that form a rationale for complex metal oxide design principles.

36 MATERIALS SCIENCE↗

Plastoquinone redox status influences carboxysome integrity via a RpaA ‐ and reactive oxygen species‐dependent regulatory network

SUMMARY Carboxysomes are bacterial microcompartments that encapsulate Rubisco and are a core component of the cyanobacterial carbon concentration mechanism (CCM). While carboxysome number, size, and spatial organization vary in different environmental conditions (CO 2 , light availability, redox state, temperature, and light quality), the molecular mechanisms underlying this potentially adaptive process remain elusive. Herein, we observe that mutants of the circadian rhythm/metabolism factor, Regulator of Phycobilisome Association A (RpaA), exhibit a striking breakdown of carboxysomes under certain environmental conditions. We find that conditions leading to overreduction of the plastoquinone (PQ) pool (mixotrophic growth, high irradiance, or chemical inhibition of electron transfer from PQ to the cytochromeb 6 fcomplex) are accompanied by an elevated generation of reactive oxygen species (ROS) and correlate with the loss of carboxysome integrity. Carboxysome breakdown is reversed by environmental conditions or chemical inhibitors that prevent PQ overreduction and accompanying ROS generation. Taken together, our data support a novel link between the redox status of the PQ pool and carboxysome integrity. Our results have implications for the fundamental understanding of cyanobacterial energy‐balancing pathways and may indicate new research directions for understanding how the carboxysome is remodeled in response to changing environments.

Plant Sciences↗