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NASA NTRS2000

TAK1 is activated in the myocardium after pressure overload and is sufficient to provoke heart failure in transgenic mice

The transforming-growth-factor-beta-activated kinase TAK1 is a member of the mitogen-activated protein kinase kinase kinase family, which couples extracellular stimuli to gene transcription. The in vivo function of TAK1 is not understood. Here, we investigated the potential involvement of TAK1 in cardiac hypertrophy. In adult mouse myocardium, TAK1 kinase activity was upregulated 7 days after aortic banding, a mechanical load that induces hypertrophy and expression of transforming growth factor beta. An activating mutation of TAK1 expressed in myocardium of transgenic mice was sufficient to produce p38 mitogen-activated protein kinase phosphorylation in vivo, cardiac hypertrophy, interstitial fibrosis, severe myocardial dysfunction, 'fetal' gene induction, apoptosis and early lethality. Thus, TAK1 activity is induced as a delayed response to mechanical stress, and can suffice to elicit myocardial hypertrophy and fulminant heart failure.

NASA Discipline Cardiopulmonary↗

NASA NTRS2000

Caveolin-1 regulates shear stress-dependent activation of extracellular signal-regulated kinase

Fluid shear stress activates a member of the mitogen-activated protein (MAP) kinase family, extracellular signal-regulated kinase (ERK), by mechanisms dependent on cholesterol in the plasma membrane in bovine aortic endothelial cells (BAEC). Caveolae are microdomains of the plasma membrane that are enriched with cholesterol, caveolin, and signaling molecules. We hypothesized that caveolin-1 regulates shear activation of ERK. Because caveolin-1 is not exposed to the outside, cells were minimally permeabilized by Triton X-100 (0.01%) to deliver a neutralizing, polyclonal caveolin-1 antibody (pCav-1) inside the cells. pCav-1 then bound to caveolin-1 and inhibited shear activation of ERK but not c-Jun NH(2)-terminal kinase. Epitope mapping studies showed that pCav-1 binds to caveolin-1 at two regions (residues 1-21 and 61-101). When the recombinant proteins containing the epitopes fused to glutathione-S-transferase (GST-Cav(1-21) or GST-Cav(61-101)) were preincubated with pCav-1, only GST-Cav(61-101) reversed the inhibitory effect of the antibody on shear activation of ERK. Other antibodies, including m2234, which binds to caveolin-1 residues 1-21, had no effect on shear activation of ERK. Caveolin-1 residues 61-101 contain the scaffolding and oligomerization domains, suggesting that binding of pCav-1 to these regions likely disrupts the clustering of caveolin-1 or its interaction with signaling molecules involved in the shear-sensitive ERK pathway. We suggest that caveolae-like domains play a critical role in the mechanosensing and/or mechanosignal transduction of the ERK pathway.

Non-NASA Center↗

NASA NTRS1999

T cell activation responses are differentially regulated during clinorotation and in spaceflight

Studies of T lymphocyte activation with mitogenic lectins during spaceflight have shown a dramatic inhibition of activation as measured by DNA synthesis at 72 h, but the mechanism of this inhibition is unknown. We have investigated the progression of cellular events during the first 24 h of activation using both spaceflight microgravity culture and a ground-based model system that relies on the low shear culture environment of a rotating clinostat (clinorotation). Stimulation of human peripheral blood mononuclear cells (PBMCs) with soluble anti-CD3 (Leu4) in clinorotation and in microgravity culture shows a dramatic reduction in surface expression of the receptor for IL-2 (CD25) and CD69. An absence of bulk RNA synthesis in clinorotation indicates that stimulation with soluble Leu4 does not induce transition of T cells from G0 to the G1 stage of the cell cycle. However, internalization of the TCR by T cells and normal levels of IL-1 synthesis by monocytes indicate that intercellular interactions that are required for activation occur during clinorotation. Complementation of TCR-mediated signaling by phorbol ester restores the ability of PBMCs to express CD25 in clinorotation, indicating that a PKC-associated pathway may be compromised under these conditions. Bypassing the TCR by direct activation of intracellular pathways with a combination of phorbol ester and calcium ionophore in clinorotation resulted in full expression of CD25; however, only partial expression of CD25 occurred in microgravity culture. Though stimulation of purified T cells with Bead-Leu4 in microgravity culture resulted in the engagement and internalization of the TCR, the cells still failed to express CD25. When T cells were stimulated with Bead-Leu4 in microgravity culture, they were able to partially express CD69, a receptor that is constitutively stored in intracellular pools and can be expressed in the absence of new gene expression. Our results suggest that the inhibition of T cell proliferative response in microgravity culture is a result of alterations in signaling events within the first few hours of activation, which are required for the expression of important regulatory molecules.

NASA Experiment Number 9403079 1/2↗

NASA NTRS1997

CCAAT/enhancer-binding protein delta activates insulin-like growth factor-I gene transcription in osteoblasts. Identification of a novel cyclic AMP signaling pathway in bone

Insulin-like growth factor-I (IGF-I) plays a key role in skeletal growth by stimulating bone cell replication and differentiation. We previously showed that prostaglandin E2 (PGE2) and other cAMP-activating agents enhanced IGF-I gene transcription in cultured primary rat osteoblasts through promoter 1, the major IGF-I promoter, and identified a short segment of the promoter, termed HS3D, that was essential for hormonal regulation of IGF-I gene expression. We now demonstrate that CCAAT/enhancer-binding protein (C/EBP) delta is a major component of a PGE2-stimulated DNA-protein complex involving HS3D and find that C/EBPdelta transactivates IGF-I promoter 1 through this site. Competition gel shift studies first indicated that a core C/EBP half-site (GCAAT) was required for binding of a labeled HS3D oligomer to osteoblast nuclear proteins. Southwestern blotting and UV-cross-linking studies showed that the HS3D probe recognized a approximately 35-kDa nuclear protein, and antibody supershift assays indicated that C/EBPdelta comprised most of the PGE2-activated gel-shifted complex. C/EBPdelta was detected by Western immunoblotting in osteoblast nuclear extracts after treatment of cells with PGE2. An HS3D oligonucleotide competed effectively with a high affinity C/EBP site from the rat albumin gene for binding to osteoblast nuclear proteins. Co-transfection of osteoblast cell cultures with a C/EBPdelta expression plasmid enhanced basal and PGE2-activated IGF-I promoter 1-luciferase activity but did not stimulate a reporter gene lacking an HS3D site. By contrast, an expression plasmid for the related protein, C/EBPbeta, did not alter basal IGF-I gene activity but did increase the response to PGE2. In osteoblasts and in COS-7 cells, C/EBPdelta, but not C/EBPbeta, transactivated a reporter gene containing four tandem copies of HS3D fused to a minimal promoter; neither transcription factor stimulated a gene with four copies of an HS3D mutant that was unable to bind osteoblast nuclear proteins. These results identify C/EBPdelta as a hormonally activated inducer of IGF-I gene transcription in osteoblasts and show that the HS3D element within IGF-I promoter 1 is a high affinity binding site for this protein.

NASA Discipline Musculoskeletal↗

NASA NTRS2018

Discovery of Activities via Statistical Clustering of Fixation Patterns

Human behavior often consists of a series of distinct activities, each characterized by a unique pattern of interaction with the visual environment. This is true even in a restricted domain, such as a piloting an aircraft, where activities with distinct visual signatures might be things like communicating, navigating, and monitoring. We propose a novel analysis method for gaze-tracking data, to perform blind discovery of these hypothetical activities. The method is in some respects similar to recurrence analysis, but here we compare not individual fixations, but groups of fixations aggregated over a fixed time interval. The duration of this interval is a parameter that we will refer to as delta. We assume that the environment has been divided into a set of N different areas-of-interest (AOIs). For a given interval of time of duration delta, we compute the proportion of time spent fixating each AOI, resulting in an N-dimensional vector. These proportions can be converted to integer counts by multiplying by delta divided by the average fixation duration (another parameter that we fix at 280 milliseconds). We compare different intervals by computing the chi-square statistic. The p-value associated with the statistic is the likelihood of observing the data under the hypothesis that the data in the two intervals were generated by a single process with a single set of probabilities governing the fixation of each AOI. The method has been applied to approximately 100 hours of eye movement data collected from pilots in a high-fidelity B747 flight simulator, and the results have been compared to synthetic data in which the each activity is represented as first-order Markov process with random probabilities assigned to the AOIs. Randomly-generated synthetic activities can require thousands of fixations to be discriminated with statistical significance, while the human data can be clustered using averaging windows of some 10's of seconds, suggesting that the actual activities are much more narrowly focused than random Markov models.

activity analysis↗

NASA NTRS2021

A Comparison of the CIR- and CME-Induced Geomagnetic Activity Effects on Mesosphere and Lower Thermospheric Temperature

Neutral temperature responses in the mesosphere and lower thermosphere (MLT) to severe geomagnetic storms induced by coronal mass ejections (CMEs) are of growing interest to the space science research community. Recently, it was found that geomagnetic activities produced by the corotating interaction regions (CIRs) caused comparable effects on the Earth's upper atmosphere. In this work, we carried out a comparative study of the temperature responses in the MLT region to these two types of geomagnetic activities, using the temperature measured by the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instruments onboard the Thermosphere, Ionosphere, Mesosphere Energetics and Dynamics (TIMED) satellite. Our results demonstrate that CIR-induced geomagnetic activity produced temperature variations in the MLT region and that this effect can penetrate downward to ∼100 km at high latitudes in both hemispheres. Temperature enhancements penetrated deeper during CME-induced geomagnetic activities, but the heating effects lasted longer during CIR-induced geomagnetic activities. There is a hemispherical asymmetry in the geomagnetical activity induced temperature changes in the MLT region. The temperature enhancements are stronger in the southern hemisphere than in the northern hemisphere during CME events.

geomagnetic activity↗

DOE OSTI2025

Crystal structures of Salmonella enterica FraB deglycase reveal a conformational heterodimer with remarkable structural plasticity at the active site

Abstract Thefralocus ofSalmonella entericaencodes five genes for metabolism of fructose‐asparagine, an Amadori product formed by condensation of asparagine with glucose. In the last step of this pathway, the FraB deglycase cleaves 6‐phospho‐fructose‐aspartate into glucose‐6‐phosphate and aspartate. In homology models, FraB forms a homodimer with two equivalent active sites located at the dimer interface. E214 and H230, two invariant residues essential for catalysis, project into each active site cleft from opposing subunits of the dimer. Here, we have determined six crystal structures of FraB, three of a variant containing an N‐terminal His 6 tag and two mutations needed for crystallization (hereafter referred to as WT′), two with additional mutations to active site residues (E214A and P232A), and one of a variant with C‐terminal residues 313–325 deleted. Surprisingly, in the WT′ FraB structure, the two catalytic residues, E214 (general base) and H230 (general acid), are positioned ~22 Å apart. In the E214A and C‐terminus‐truncated FraB variants, however, a conformational change in the E214‐residing helix brings E214 and H230* to ~7 Å (* indicates residue from the second protomer that creates the inter‐subunit catalytic center). The loop bearing H230 also exhibits significant variation, ranging from being completely disordered to adopting open or closed states, with the nearby P232* residue being eithercisortrans. The C‐terminal residues 313–325 form a flexible “C‐tail” that can be fully disordered, bind in the active site to block access of substrate, or angle across the active site to wrap across the other subunit of the dimer and potentially close over substrate. Collectively, these structures reveal that FraB is a conformational heterodimer with two chemically identical subunits that are constrained to adopt different structures as they come together for catalysis. This plasticity likely involves correlated opening and closure of the two active sites for their respective binding and release of substrates and ligands.

Biochemistry & Molecular Biology↗

DOE OSTI2025

In-situ monitoring of atomically dispersed Pt sites supported on OMS-2 during CO 2 activation

Atomically dispersed catalysts have drawn great interest lately, as they showcase a high density of active sites, selectivity, and high turnover frequencies in oxidation chemistry due to labile oxygen activation. In contrast, the applications of these catalysts have lagged in reduction reactions due to the ambiguity caused by the sintering and restructuring of active sites. To bridge this gap, the evolution of Pt 4+ isomorphically substituted into an octahedral molecular sieve structure (OMS-2) under reductive conditions was correlatively characterized using multiple in-situ analytical techniques such as ambient pressure X-ray photoelectron spectroscopy, environmental transmission electron microscopy, and solid-state nuclear magnetic resonance. The surface dynamics of the Pt single atoms were revealed during the Reverse Water Gas Shift (RWGS) reaction, where the active sites were identified as two-coordinated platinum single atoms. Under reaction, we show nonbinding atoms adjacent to the single atoms restructured the motif of the single atoms to Pt 2+ via ion mobility of potassium, increasing the activation energy by 25.6 kJ/mol. Here, this work also highlights the potential for increased stability of the single atom sites via isomorphic substitution of the metal oxide support, since the Pt-OMS-2 catalyst retained activity for about 33 h before deactivation, after which nanoparticles were observed in TEM images. This work offers a new perspective in single atom synthesis using the metal oxide as the host for the single atom site, instead of adatoms on the surface

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Mixed lipid bilayers enable enhanced stability and activity retention of Lipase A in low-pH environments

Lipase A (LipA) from Bacillus subtilis is a versatile and industrially relevant enzyme, but its activity is compromised under acidic conditions due to aggregation and deactivation. In this study, we investigated the use of mixed lipid bilayers to stabilize and improve activity retention of LipA at low pH. Attachment to lipid bilayers, particularly those containing cationic lipids, greatly enhanced the long-term stability of LipA in acidic conditions while also leading to improvements in activity. Tethering to cationic bilayers not only shifted the apparent pH activity profile toward more acidic conditions, but also significantly enhanced activity retention upon incubation at pH 6. Notably, this protective effect persisted even without direct tethering, indicating that reversible, non-covalent interactions with the bilayer surface are sufficient for long-term stability. Circular dichroism further revealed that the secondary structure of LipA was retained, while dynamic light scattering suggested that activity loss in solution was primarily due to aggregation of the native state. Together, these findings support a model in which lipid bilayers mitigate aggregation and stabilize LipA through transient interactions and electrostatic modulation of the local surface environment. Furthermore, this approach exemplifies a simple, tether-free strategy for enhancing enzyme performance in acidic or destabilizing conditions, with implications for biocatalysis, biosensing, and therapeutic delivery.

Biocatalysis↗

DOE OSTI2025

Bat activity at ecovoltaic solar energy developments in the Midwestern United States

As global photovoltaic (PV) solar electricity generation continues to increase, some PV sites are co-prioritizing electricity generation and ecosystem function (“ecovoltaics”) to align renewable energy development with biodiversity conservation. Thus far, positive responses of plant and insect communities to native habitats at ecovoltaic sites have been observed, but there has been little research on bat responses to ecovoltaic designs in the U.S. We conducted passive ultrasonic monitoring in 2023 and 2024 at 12 solar sites and paired reference sites (agricultural fields) to investigate bat activity responses to ecovoltaic facilities in the Midwestern U.S. We found that average weekly overall bat activity was approximately 50?% higher within ecovoltaic sites than reference sites in the first half of the monitoring season. We also found species-specific differences in bat responses to ecovoltaic sites, with Hoary Bats showing higher activity on ecovoltaic sites throughout most of the monitoring season, Big Brown Bats showing higher activity on ecovoltaic sites during the first one-third of the monitoring season, and Silver-haired Bats showing no difference in activity between ecovoltaic sites and reference sites. There were no weeks in which bat activity was statistically greater on reference sites, suggesting that bats in the Midwestern U.S. do not avoid ecovoltaic solar sites. Rather, our results suggest that ecovoltaic sites in this region may provide early season (May-June) habitat at a time of year when resources may be limited in the surrounding landscape. These findings support a growing body of evidence on the positive ecological outcomes of ecovoltaic designs. Further investigations of the types of bat calls being recorded at PV sites and relationships with insect prey abundance are needed to understand the underlying drivers of species-specific responses to PV developments.

14 SOLAR ENERGY↗

DOE OSTI2024

Multiple-charging effects on the CCN activity and hygroscopicity of surrogate black carbon particles

Accurate measurements of cloud condensation nuclei (CCN) activity and hygroscopicity of black carbon (BC)-containing particles are particularly important because of the positive climate forcing from these particles. Such measurements are typically conducted on particles selected by a Differential Mobility Analyzer (DMA), which in addition to singly charged particles transmits multiply charged larger particles that have the same electrical mobility. These larger particles activate at lower supersaturations than the singly charged particles, biasing measurements and resulting in overestimation of CCN activity and hygroscopicity parameter (κ). Here, we measure the CCN activity and determine κ for different BC surrogates with electrical mobility diameters from 100 to 200 nm selected 1) only by electrical mobility with a DMA, and 2) by both electrical mobility and mass using a DMA and a Centrifugal Particle Mass Analyzer (CPMA), thus allowing selection of only singly charged particles. We demonstrate the use of the DMA-CPMA system in resolving biases caused by multiply charged particles, and we show that the effect of multiple charging on the CCN activity of the BC particles is strongly influenced by morphology dispersion, i.e., the variability due to the range of morphologies of particles that have the same electrical mobility and mass. Finally, our findings show that electrical mobility-based methods alone are unlikely to lead to accurate results in measurements of CCN activation and hygroscopicity of BC particles, even for those with a more compact morphology.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Activity-Based Protein Profiling to Probe Relationships between Cytochrome P450 Enzymes and Early-Age Metabolism of Two Polycyclic Aromatic Hydrocarbons (PAHs): Phenanthrene and Retene

A growing body of literature has linked early life exposures to polycyclic aromatic hydrocarbons (PAH) with adverse neurodevelopmental effects. Once in the body, metabolism serves as a powerful mediator of PAH toxicity by bioactivating and detoxifying PAH metabolites. Since enzyme expression and activity varies considerably throughout human development, we evaluated infant metabolism of PAHs as a potential contributing factor to PAH susceptibility. Here, we measured and compared rates of phenanthrene and retene (two primary PAH constituents of woodsmoke) metabolism in human hepatic microsomes from individuals ≤21 months of age to a pooled sample (n = 200) consisting primarily of adults. We used activity-based protein profiling (ABPP) to characterize cytochrome P450 enzymes (CYPs) in the same hepatic microsome samples. Once incubated in microsomes, phenanthrene demonstrated rapid depletion. Best fit models for phenanthrene metabolism demonstrated either 1 or 2 phases, depending on the sample, indicating that multiple enzymes could metabolize phenanthrene. We observed no statistically significant differences in phenanthrene metabolism as a function of age, although samples from the youngest individuals had the slowest phenanthrene metabolism rates. We observed slower rates of retene metabolism compared to phenanthrene also in multiple phases. Rates of retene metabolism increased in an age-dependent manner until adult (pooled) levels were achieved at ~12 mo. ABPP identified 28 unique CYPs among all samples, and we observed lower amounts of active CYPs in individuals ≤21 months of age compared to the pooled sample. Phenanthrene metabolism correlated to CYPs 1A1, 1A2, 2C8, 4A22, 3A4, and 3A43 and activities and retene metabolism correlated to CYPs 1A1, 1A2, and 2C8 activities measured by ABPP and vendor-supplied substrate marker activities. These results will aid efforts to determine human health risk and susceptibility to PAHs exposures during early life.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2026

Unraveling Fundamental Activity–Stability Relationships in Rutile Oxides

The oxygen evolution reaction (OER) is a key anodic half-cell reaction that accompanies several critical electrochemical reduction reactions of interest to a variety of applications. Despite steady advances in understanding and qualitatively predicting OER activity and selectivity trends, a comprehensive description or prediction of material aqueous (in)stability and degradation mechanisms remains elusive, even though these processes critically influence device lifetime and economic feasibility. In this work, we investigate the interplay, or lack thereof, between OER activity and material aqueous stability across rutile oxides, with a particular focus on iridium oxide (IrO 2 ). By applying a Born–Haber cycle, we calculate the thermodynamic driving force for metal dissolution as a function of the applied bias and electrolyte conditions. We apply interpretable machine learning techniques, including principal component analysis and symbolic regression, to analyze trends across rutile oxides and find that key thermodynamic descriptors for OER activity and surface stability are only very weakly correlated. Instead, the local atomic environment─especially electronic structure signatures for interactions between the active site and its neighbors─plays a more important role in predicting material stability. Leveraging these insights, we investigate the impact of doping IrO 2 with a range of transition metals and show that the stability of Ir active sites can be tuned largely independently of its predicted OER activity. These insights lay the foundation for material design to improve stability with respect to corrosion, with the ultimate aim to enhance long-term stability without sacrificing catalytic performance in the OER.

evolution reactions↗

DOE OSTI2025

Temperature Evolution of the Activation Barriers Leads to Meyer−Neldel Rules for Structural Relaxation and Transport in Polymers

Understanding activation barriers controlling structural relaxation in glass-forming liquids, molecular transport, and ionic conductivity in amorphous polymers is a grand challenge of fundamental scientific and materials engineering interest across disciplines. Over decades, intriguing but puzzling empirical correlations between the elementary time scale of activated barrier crossing and the apparent Arrhenius activation energy, the so-called Meyer−Neldel (MN) rules, have been discovered in diverse liquids and glasses. Here, in this study, we formulate and successfully apply a new experimental analysis and an explicitly dynamical theoretical framework which provides an understanding of the origin, validity, and failure of such correlations, that bridge and unify the three fields of structural relaxation, molecular transport, and ionic conductivity in liquids and quenched glasses. Distinct quasi-universal laws are predicted in equilibrated liquids and nonequilibrium glasses, consistent with experiments. Our analysis reveals that even if the relaxation appears Arrhenius over a limited temperature range, the physical activation barrier is generally temperature-dependent in polymeric systems even below glass transition temperature. In addition, we show that the approximate validity of classical MN rules hinges on a linear temperature dependence of this barrier and the temperature range probed in experiments. Our findings are relevant for controlling the activation barrier in functional soft polymeric materials relevant to molecular separations, barrier coatings, and charge transport, and also provide new constraints on the theoretical understanding of the mechanism underlying slow activated dynamics in glass-forming condensed matter.

Meyer-Neldel rules↗

DOE OSTI2024

Dislocation-Activated Low Platinum-Loaded PtCu Nanoparticles Welded onto the Substrate for Practical Acidic Hydrogen Generation

Although transition metal (M) alloying with platinum (Pt) is a promising approach to reduce the Pt dosage required in the hydrogen evolution reaction (HER), the catalytic activity and durability of PtM alloy are often unsatisfactory for acidic HER, especially at high currents, due to a reduced number of highly active sites (Pt) at the atomic level and challenges in stabilizing them to prevent detachment and aggregation. Herein, we report a robust functional structure integrated electrode (D-PtCu/CF) with abundant edge dislocations and very low platinum content (0.1 mg cm -2 ) to achieve high activity and stability in acidic HER within a proton exchange membrane water electrolysis cell (PEMWE). D-PtCu/CF exhibits high Pt mass activity (10.28 A mg Pt -1 ) and excellent operational stability (negligible decay after 200 h). X-ray absorption spectroscopy and in situ electrochemical experiments reveal that the lattice distortion caused by edge dislocations in PtCu mainly affects Pt atoms by compressing strain, reducing their ability to adsorb H. At the same time, Cu atoms are subjected to tensile strain, enhancing the bonding between Cu and H. Therefore, edge dislocations not only improve the intrinsic catalytic activity of Pt atoms but also increase the number of active sites (Cu) available for hydrogen adsorption, which synergistically accelerates the kinetics of the HER reaction. Finally, the PEMWE employing the D-PtCu/CF catalytic electrode can operate stably for 100 h at an industrial-level current density of 500 mA cm -2 with 1.63 V.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2026

Using Domain Insertion to Create Sulfite Reductases That Present Chemical-Dependent Activities

Domain insertion can be used to create oxidoreductases whose activities are dependent upon analyte binding. To date, most domain insertion studies have targeted relatively small oxidoreductases of known structure, so it remains unclear how to apply this protein engineering approach to large hetero-oligomeric proteins that require dynamic conformational changes for catalysis. To address this question, we studied the effects of peptide and domain insertions on the activity of NADPH-dependent sulfite reductase (SiR) from Escherichia coli, a dodecameric oxidoreductase containing four hemoprotein and eight flavoprotein subunits. SiR mutational tolerance was first evaluated using systematic octapeptide insertion and a cellular selection, which identified regions across the hemoprotein structure that retain parent-like activity following insertion. When a ligand-binding domain was inserted at backbone locations tolerant to peptide insertion, including sites proximal and distal from the intersubunit interfaces, ∼90% retained catalytic activity, and >50% presented activity that is regulated by an endocrine disruptor. With one domain insertion variant, the conditional production of sulfide could be monitored electrochemically from cells using a bioelectrochemical reactor. These results show how systematic peptide insertion can be used to inform domain insertion in a large heterooligomeric protein complex, and they illustrate how SiR can be engineered to convert chemical information in the environment into a redox-active metabolite that diffuses across the cell membrane.

bacteria↗

DOE OSTI2024

Dynamic Behavior of Pt Multimetallic Alloys for Active and Stable Propane Dehydrogenation Catalysts

Improving the use of platinum in propane dehydrogenation catalysts is a crucial aspect to increasing the efficiency and sustainability of propylene production. A known and practiced strategy involves incorporating more abundant metals in supported platinum catalysts, increasing its activity and stability while decreasing the overall loading. Here, using colloidal techniques to control the size and composition of the active phase, we show that Pt/Cu alloy nanoparticles supported on alumina (Pt/Cu/Al 2 O 3 ) displayed elevated rates for propane dehydrogenation at low temperature compared to a monometallic Pt/Al 2 O 3 catalyst. We demonstrate that the enhanced catalytic activity is correlated with a higher surface Cu content and formation of a Pt-rich core and Cu-rich shell that isolates Pt sites and increases their intrinsic activity. However, rates declined on stream because of dynamic metal diffusion processes that led to a more uniform alloy structure. This transformation was only partially inhibited by adding excess hydrogen to the feed stream. Instead, cobalt was introduced to provide trimetallic Pt/Cu/Co catalysts with stabilized surface structure and stable activity and higher rates than the original Pt/Cu system. In conclusion, the structure–activity relationship insights in this work offer improved knowledge of propane dehydrogenation catalyst development featuring reduced Pt loadings and notable thermal stability for propylene production.

Alloys↗

DOE OSTI2025

Optimizing CO 2 -Loaded Aqueous Amine Solutions for Higher Electrocatalytic CO 2 Reduction Activity

The activity of aqueous-based carbon dioxide reduction (CO 2 R) reactions is often limited by the solubility of CO 2 . The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO 2 from dilute streams. Here, in this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO 2 R to CO activity of a molecular Ni(cyclam)Cl 2 catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor–liquid equilibrium modeling (VLE), 13 C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO 2 R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO 2 R activity and selectivity and describe amine properties that lead to these higher performance metrics.

Amines↗