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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Enhancing T c in a composite superconductor/metal bilayer system: A dynamical cluster approximation study

It has been proposed that the superconducting transition temperature T c of an unconventional superconductor with a large pairing scale but strong phase fluctuations can be enhanced by coupling it to a metal. However, the general efficacy of this approach across different parameter regimes remains an open question. Using the dynamical cluster approximation, we study this question in a system composed of an attractive Hubbard layer in the intermediate coupling regime, where the magnitude of the attractive Coulomb interaction |U| is slightly larger than the bandwidth W, hybridized with a noninteracting metallic layer. We find that while the superconducting transition becomes more mean-field-like with increasing interlayer hopping, the superconducting transition temperature T c exhibits a nonmonotonic dependence on the strength of the hybridization t ⊥ . Furthermore, this behavior arises from a reduction of the effective pairing interaction in the correlated layer that outcompetes the growth in the intrinsic pair-field susceptibility induced by the coupling to the metallic layer. We find that the largest T c inferred here for the composite system is comparable to the maximum value currently estimated for the isolated negative-U Hubbard model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

ReNCAT: The Resilient Node Cluster Analysis Tool

ReNCAT is a software application that suggests microgrid portfolios that reduce the impact of large-scale disruptions to power, as measured by the Social Burden Metric. ReNCAT examines a power distribution network to identify regions that can be isolated into microgrids that enable critical services to be provided even if the remainder of the study area is left without power. ReNCAT operates on a simplified representation of the power grid, one that aggregates and approximates loads and conductors. Microgrids are formed within the power network by setting switch states to split or join portions of the grid. ReNCAT identifies candidate microgrid portfolios with varying tradeoffs between cost and service availability.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2022

Functional CeO x nanoglues for robust atomically dispersed catalysts

Single-atom catalysts make exceptionally efficient use of expensive noble metals and can bring out unique properties. However, applications are usually compromised by limited catalyst stability, which is due to sintering. Although sintering can be suppressed by anchoring the metal atoms to oxide supports, strong metal–oxygen interactions often leave too few metal sites available for reactant binding and catalysis, and when exposed to reducing conditions at sufficiently high temperatures, even oxide-anchored single-atom catalysts eventually sinter. Here we show that the beneficial effects of anchoring can be enhanced by confining the atomically dispersed metal atoms on oxide nanoclusters or ‘nanoglues’, which themselves are dispersed and immobilized on a robust, high-surface-area support. We demonstrate the strategy by grafting isolated and defective CeO x nanoglue islands onto high-surface-area SiO 2 ; the nanoglue islands then each host on average one Pt atom. Further, we find that the Pt atoms remain dispersed under both oxidizing and reducing environments at high temperatures, and that the activated catalyst exhibits markedly increased activity for CO oxidation. We attribute the improved stability under reducing conditions to the support structure and the much stronger affinity of Pt atoms for CeO x than for SiO 2 , which ensures the Pt atoms can move but remain confined to their respective nanoglue islands. The strategy of using functional nanoglues to confine atomically dispersed metals and simultaneously enhance their reactivity is general, and we anticipate that it will take single-atom catalysts a step closer to practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Is Jet Re-orientation the Elusive Trigger for Star Formation Suppression in Radio Galaxies?

Abstract Jet re-orientation associated with the time evolution of radio quasars explains the formation of X-shaped radio galaxies and their preference for isolated environments. But since X-shaped radio galaxies are generally not found in dense environments (e.g., groups/clusters), the jet re-orientation phenomenon for radio galaxies in groups and clusters has been ignored. We take a closer look at the re-orientation of FRI jets with respect to FRII jets, and find that it may constitute the as-yet unidentified trigger for star formation suppression in radio galaxies. We show how the recently explored radio “red geyser” galaxies can be interpreted in this context and ultimately reveal a deeper understanding of why FRII radio galaxies are on one side of the star formation enhancement/suppression divide compared to FRI radio galaxies.

Astronomy & Astrophysics↗
DOE OSTI2023

Electrocatalytic Hydrogen Evolution at Full Atomic Utilization over ITO-Supported Sub-nano-Pt n Clusters: High, Size-Dependent Activity Controlled by Fluxional Pt Hydride Species

A combination of density functional theory (DFT) and experiments with atomically size-selected Pt n clusters deposited on indium-tin oxide (ITO) electrodes was used to examine the effects of applied potential and Pt n size on the electrocatalytic activity of Pt n (n = 1, 4, 7, 8) for the hydrogen evolution reaction (HER). Activity is found to be negligible for isolated Pt atoms on ITO, increasing rapidly with Pt n size, such that Pt 7 /ITO and Pt 8 /ITO have roughly double the activity per Pt atom compared to atoms in the surface layer of polycrystalline Pt. Both DFT and experiment find that hydrogen under-potential deposition (H upd ) results in Pt n /ITO (n = 4, 7, 8) adsorbing ~2 H atoms/Pt atom at the HER threshold potential, equal to ca. double the Hupd observed for Pt bulk or nanoparticles. Here, the cluster catalysts under electrocatalytic conditions are hence best described as a Pt hydride compound, significantly departing from a metallic Pt cluster. The exception is Pt 1 /ITO, where H adsorption at the HER threshold potential is energetically unfavorable. Theory combines global optimization with grand canonical approaches for the influence of potential, uncovering that several metastable structures contribute to HER, changing with the applied potential. It is hence critical to include reactions of the ensemble of energetically accessible Pt n H x /ITO structures to correctly predict the activity vs. Pt n size and applied potential. For the small clusters, spillover of H ads from the clusters to the ITO support is significant, resulting in a competing channel for loss of H ads , particularly at slow potential scan rates.

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

Joint galaxy–galaxy lensing and clustering constraints on galaxy formation

ABSTRACT We compare predictions for galaxy–galaxy lensing profiles and clustering from the Henriques et al. public version of the Munich semi-analytical model (SAM) of galaxy formation and the IllustrisTNG suite, primarily TNG300, with observations from KiDS + GAMA and SDSS-DR7 using four different selection functions for the lenses (stellar mass, stellar mass and group membership, stellar mass and isolation criteria, and stellar mass and colour). We find that this version of the SAM does not agree well with the current data for stellar mass-only lenses with $M_\ast \gt 10^{11}\, \mathrm{ M}_\odot$. By decreasing the merger time for satellite galaxies as well as reducing the radio-mode active galactic nucleus accretion efficiency in the SAM, we obtain better agreement, both for the lensing and the clustering, at the high-mass end. We show that the new model is consistent with the signals for central galaxies presented in Velliscig et al. Turning to the hydrodynamical simulation, TNG300 produces good lensing predictions, both for stellar mass-only (χ2 = 1.81 compared to χ2 = 7.79 for the SAM) and locally brightest galaxy samples (χ2 = 3.80 compared to χ2 = 5.01). With added dust corrections to the colours it matches the SDSS clustering signal well for red low-mass galaxies. We find that both the SAMs and TNG300 predict $\sim 50\, {{\ \rm per\ cent}}$ excessive lensing signals for intermediate-mass red galaxies with 10.2 < log10M*[M⊙] < 11.2 at $r \approx 0.6\, h^{-1}\, \text{Mpc}$, which require further theoretical development.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Crystalline phase transitions and water-soluble complexes of copper(Ⅰ) 2-hydroxyethanethiolate

We report the coordination polymer copper(I) 2-hydroxyethanethiolate, (CuSCH 2 CH 2 OH) n , though insoluble in all common solvents, dissolved readily in basic aqueous solutions of the thiolate anion (HOCH 2 CH 2 S – ) of 2-mercaptoethanol to form a single species: the tetranuclear cluster [Cu 4 (μ-SCH 2 CH 2 OH) 6 ] 2– . From this solution were grown X-ray quality single crystals of copper(I) 2-hydroxyethanethiolate. This compound underwent a hitherto unknown crystal phase transition at ca. 6 °C, from point group P2 1 2 1 2 1 to Pna2 1 , with noticeable changes in the geometry of the Cu-S layer and in the orientation of the alkylthiolate side chains. When the bulky base tetrabutylammonium hydroxide was employed in the aqueous thiolate solution used to dissolve (CuSCH 2 CH 2 OH) n , the water-soluble polynuclear copper(I) complex bis(tetrabutylammonium) hexakis(μ-2-hydroxyethanethiolato) tetracuprate(I), [(C 4 H 9 ) 4 N] 2 [Cu 4 (μ-SCH 2 CH 2 OH) 6 ], could be isolated as X-ray quality crystals. Structural characterization of this complex revealed a tetrahedral arrangement of copper(I) centers with thiolates bridging the edges of the tetrahedra. On standing, this complex degraded to a larger polynuclear Cu(I) sulfide cluster.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

In situ Gas Cell TEM Investigation of Nanoporous and Zeolite-based Nanocatalysts

A crucial application of in situ transmission electron microscopy is the understanding of nanocatalysts and the effect of the environment on their structure. Pre-treatments, such as calcination or annealing, can dramatically impact the catalytic properties by modifying the morphology and composition of nanostructures. Zeolites and nanoporous structures are particularly sensitive to reactive environments as the porosity or the chemical state can substantially change during the interaction with gases at elevated temperatures.[1] For instance, it has been shown that heating in air causes redispersion of sintered Cu clusters on zeolite, improving the catalytic properties.[2] These observations are possible though innovative in situ TEM gas holders, where the samples are enclosed into a small cell with SiNx windows, isolating the reactive environment from the rest of the column. [3] Here, we present in situ gas cell experiments of sensitive nanoporous structure and zeolite-based nanocatalysts. Scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy were used to understand migration of Al during calcination. In situ diagnostics also help distinguish Al as Bronsted sites, extra-framework Lewis sites, or bulk alumina. More broadly, in situ gas-heating TEM experiments are useful to determine chemical changes and modification of morphology of sensitive nanocatalysts upon pre-treatment (Figure 1).[4] Detailed in situ STEM and energy-dispersive X-ray spectroscopy (EDS) demonstrated compositional changes in nanoporous CuAlTi structures for hydrogen-deuterium exchange (H2-D2) reaction. Coarsening due to annealing at high temperature, a necessary steps for the preparation of catalysts, can be reversed by applying a redox cycle. Using the wide range of gases and temperature, the diagnostics are helpful to derive fundamental understanding of these catalysts at the atomic scale and also provide general guidelines to improve their design.

Foucher, Alexandre [ORNL] (ORCID:0000000150424002)↗
DOE OSTI2024

CGOLS V: Disk-wide Stellar Feedback and Observational Implications of the Cholla Galactic Wind Model

Abstract We present the fifth simulation in the Cholla Galactic OutfLow Simulation (CGOLS) project—a set of isolated starburst galaxy simulations modeled over large scales (10 kpc) at uniformly high resolution (Δx≈ 5 pc). Supernova feedback in this simulation is implemented as a disk-wide distribution of clusters, and we assess the impact of this geometry on several features of the resulting outflow, including the radial profiles of various phases; mass, momentum, and energy outflow rates; covering fraction of cool gas; mock absorption-line spectra; and X-ray surface brightness. In general, we find that the outflow generated by this model is cooler, slower, and contains more mass in the cool phase than a more centrally concentrated outflow driven by a similar number of supernovae. In addition, the energy loading factors in the hot phase are an order of magnitude lower, indicating much larger losses due to radiative cooling in the outflow. However, coupling between the hot and cool phases is more efficient than in the nuclear burst case, with almost 50% of the total outflowing energy flux carried by the cool phase at a radial distance of 5 kpc. These physical differences have corresponding signatures in observable quantities: the covering fraction of cool gas is much larger, and there is greater evidence of absorption in low and intermediate ionization energy lines. Taken together, our simulations indicate that centrally concentrated starbursts are more effective at driving hot, low-density outflows that will expand far into the halo, while galaxy-wide bursts may be more effective at removing cool gas from the disk.

Astronomy & Astrophysics↗
DOE OSTI2021

Attention Network Forecasts Time-to-Failure in Laboratory Shear Experiments

Rocks under stress deform by creep mechanisms that include formation and slip on small-scale internal cracks. Intragranular cracks and slip along grain contacts release energy as elastic waves termed acoustic emissions (AE). AEs are thought to contain predictive information that can be used for fault failure forecasting. Here, we present a method using unsupervised classification and an attention network to forecast labquakes using AE waveform features. Our data were generated in a laboratory setting using a biaxial shearing device with granular fault gouge intended to mimic the conditions of tectonic faults. Here, we analyzed the temporal evolution of AEs generated throughout several hundred laboratory earthquake cycles. We used a Conscience Self-Organizing Map (CSOM) to perform topologically ordered vector quantization based on waveform properties. The resulting map was used to interactively cluster AEs. We examined the clusters over time to identify those with predictive ability. Finally, we used a variety of LSTM and attention-based networks to test the predictive power of the AE clusters. By tracking cumulative waveform features over the seismic cycle, the network is able to forecast the time-to-failure (TTF) of lab earthquakes. Our results show that analyzing the data to isolate predictive signals and using a more sophisticated network architecture are key to robustly forecasting labquakes. In the future, this method could be applied on tectonic faults to monitor earthquakes and augment early warning systems.

58 GEOSCIENCES↗
DOE OSTI2020

Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Isolating isomorphic compounds of tetravalent actinides (i.e., Th IV , U IV , Np IV , and Pu IV ) improve our understanding of the bonding behavior across the series, in addition to their relationship with tetravalent transition metals (Zr and Hf) and lanthanides (Ce). Similarities between these tetravalent metals are particularly illuminated in their hydrolysis and condensation behavior in aqueous systems, leading to polynuclear clusters typified by the hexamer [M IV 6 O 4 (OH) 4 ] 12+ building block. Prior studies have shown the predominance and coexistence of smaller species for Th IV (monomers, dimers, and hexamers) and larger species for U IV , Np IV , and Pu IV (including 38-mers and 70-mers). We show here that aqueous uranium(IV) sulfate also displays behavior similar to that of Th IV (and Zr IV ) in its isolated solidphase and solution speciation. Two single-crystal X-ray structures are described: a dihydroxide-bridged dimer (U 2 ) formulated as U 2 (OH) 2 (SO 4 ) 3 (H 2 O) 4 and a monomer-linked hexamer framework (U-U 6 ) as (U(H 2 O) 3.5 ) 2 U 6 O 4 (OH) 4 (SO 4 ) 10 (H 2 O) 9 . These structures are similar to those previously described for ThIV. Moreover, cocrystallization of monomer and dimer and of dimer and monomer–hexamer phases for both Th IV (prior) and U IV (current) indicates the coexistence of these species in solution. Because it was not possible to effectively study the sulfate-rich solutions via X-ray scattering from which U 2 and U-U 6 crystallized, we provide a parallel solution speciation study in low sulfate conditions, as a function of the pH. Raman spectroscopy, UV–vis spectroscopy, and small-angle X-ray scattering of these show decreasing sulfate binding, increased hydrolysis, increased species size, and increased complexity, with increasing pH. Furthermore, this study describes a bridge across the first half the actinide series, highlighting U IV similarities to Th IV , in addition to the previously known similarities to the transuranic elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ce IV 70 Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Abstract M IV molecular oxo‐clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms‐up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Here we introduce Ce 70 , a wheel‐shaped oxo‐cluster, [Ce IV 70 (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4− . Ce 70 crystallizes into intricate high pore volume frameworks with divalent transition metals and Ce‐monomer linkers. Eight crystal‐structures feature four framework types in which the Ce 70 ‐rings are linked as propellers, in offset‐stacks, in a tartan pattern, and as isolated rings. Small‐angle X‐ray scattering of Ce 70 dissolved in butylamine, with and without added cations (Ce IV , alkaline earths, Mn II ), shows the metals‘ differentiating roles in ring linking, leading to supramolecular assemblies. The large acidic pores and abundant terminal sulfates provide ion‐exchange behavior, demonstrated with U IV and Nd III . Frameworks featuring Ce III/IV ‐monomer linkers demonstrate both oxidation and reduction. This study opens the door to mixed‐metal, highly porous framework catalysts, and new clusters for metal‐organic framework design

Colliard, Ian↗
DOE OSTI2020

Characterization of Surface Heterogeneity-Induced Convection Using Cluster Analysis

Land-atmosphere interactions and boundary layer processes often control the formation of shallow clouds and subsequently deep convective precipitation over the Southern Great Plains. In this study, we examine the impacts of large-scale advection on the cloud populations and land-atmospheric coupling observed during the Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecosystems (HI-SCALE) field campaign in 2016. In this work, we performed two Large Eddy Simulations (LES) using the Weather Research and Forecasting Model for a day in which the transition from clear-sky to shallow precipitating clouds and isolated deep convection was observed. The control simulation reproduced the overall distribution of cloud populations by using realistic soil conditions with an interactive land model. In the sensitivity simulation where large-scale advection is removed, a strong relationship between the land and boundary layer is found. To study the timing, location, and intensity of convective initiation and the relationship of clouds with land surface properties, a cluster analysis of equivalent potential temperature is performed for the simulation without large-scale advection. That analysis shows that convective clouds first form over regions with higher surface sensible heat flux. Precipitation from those convective clouds likely triggers new updrafts nearby about two hours later through the lifting associated with cold pools. Furthermore, the cluster analysis also shows that in addition to the spatial pattern of soil moisture, land use and soil texture in western Oklahoma also influence the location of convective initiation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Diagnostic diagrams for ram pressure stripped candidates

ABSTRACT This paper presents a method for finding ram pressure stripped (RPS) galaxy candidates by performing a morphological analysis of galaxy images obtained from the Legacy survey. We consider a sample of about 600 galaxies located in different environments such as groups and clusters, tidally interacting pairs and the field. The sample includes 160 RPS previously classified in the literature into classes from J1 to J5, based on the increasing level of disturbances. Our morphological analysis was done using the astromorphlib software followed by the inspection of diagnostic diagrams involving combinations of different parameters like the asymmetry (A), concentration (C), Sérsic index (n), and bulge strength parameters $F(G,\, M_{20})$. We found that some of those diagrams display a distinct region in which galaxies classified as J3, J4, and J5 decouples from isolated galaxies. We call this region as the morphological transition zone and we also found that tidally interacting galaxies in pairs are predominant within this zone. Nevertheless, after visually inspecting the objects in the morphological transition zone to discard obvious contaminants, we ended up with 33 bona fide new RPS candidates in the studied nearby groups and clusters (Hydra, Fornax, and CLoGS sample), of which one-third show clear evidence of unwinding arms. Future works may potentially further increase significantly the samples of known RPS using such method.

Astronomy & Astrophysics↗
DOE OSTI2023

Lewis Acid Supported Nickel Nitrenoids

Abstract Metalation of the polynucleating ligand F,tbs LH 6 (1,3,5‐C 6 H 9 (NC 6 H 3 −4‐F−2‐NSiMe 2 t Bu) 3 ) with two equivalents of Zn(N(SiMe 3 ) 2 ) 2 affords the dinuclear product ( F,tbs LH 2 )Zn 2 ( 1 ), which can be further deprotonated to yield ( F,tbs L)Zn 2 Li 2 (OEt 2 ) 4 ( 2 ). Transmetalation of 2 with NiCl 2 (py) 2 yields the heterometallic, trinuclear cluster ( F,tbs L)Zn 2 Ni(py) ( 3 ). Reduction of 3 with KC 8 affords [KC 222 ][( F,tbs L)Zn 2 Ni] ( 4 ) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to 4 generates the bridging μ 3 ‐nitrenoid adduct [K(THF) 3 ][( F,tbs L)Zn 2 Ni(μ 3 ‐NAd)] ( 5 ). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state ( S = ). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K 2 (THF) 9 ][( F,tbs L)Zn 2 Ni(μ 3 ‐NAd)] ( 6 ) was isolated and characterized while the neutral redox isomer was observed to undergo both intra‐ and intermolecular H‐atom abstraction processes. Ni K‐edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn 2 Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for 5 .

Juda, Cristin E.↗
DOE OSTI2026

Combining ToF‐SIMS and Multivariate Analysis to Resolve Active Sites on Ni‐Based HER Catalysts

Unambiguous identification of active sites in heterogeneous catalysis remains a major challenge, particularly for materials with ultrathin, chemically mixed surface layers. Here, we demonstrate a generalizable approach that combines time-of-flight secondary ion mass spectrometry (ToF-SIMS) with multivariate statistical analysis (principal component analysis [PCA] and multivariate curve resolution [MCR]) to resolve catalytically relevant motifs at the nanoscale. Using Ni electrodes as a model system, PCA distinguished hydroxide-enriched domains from oxide- and metal-rich regions, while MCR decomposed depth profiles and 3D images into hydroxide, oxide, and metallic layers with nanometer resolution. A unique secondary-ion fragment, NiO 3 H 3 − (m/z 108.94), emerged as a marker of hydroxide-rich environments and correlated with hydrogen evolution reaction (HER) activity across a series of Ni electrodes. Complementary density functional theory (DFT) calculations revealed that Ni(OH) 2 clusters adjacent to metallic Ni offer the most favorable water dissociation energetics, establishing the structural origin of the marker. While illustrated here for Ni-based HER, this workflow provides a broadly applicable framework to isolate and rank near-surface patterns that govern catalytic activity, thereby extending ToF-SIMS from a qualitative probe to a predictive tool for active site identification.

HER active sites↗
DOE OSTI2020

Fluorescence Enhancement in the Solid State by Isolating Perylene Fluorophores in Metal–Organic Frameworks

Polycyclic aromatic hydrocarbons such as perylene, pyrene, and their derivatives are highly emissive fluorophores in solution. Furthermore, the practical applications of these materials in the field of molecular electronic and light emitting devices are often hindered by self-quenching effects due to the formation of non-fluorescent aggregates in concentrated solutions or in the solid state. Herein, we demonstrate that aggregation caused quenching of perylenes can be minimalized by molecular incorporation into metalorganic frameworks (MOFs). This study utilized a stable Zr 6 cluster-based MOF, UiO-67, as a matrix. Linear linkers containing the photo-responsive moieties were designed and incorporated into the parent UiO-67 scaffold through the partially replacement of the non-fluorescent linkers of a similar length, forming mixed-linker MOFs. Here, the average distance between perylene moieties was tuned by changing the linker ratios, thus controlling the fluorescence intensity, emission wavelength, and quantum yield. Molecular modeling was further adopted to correlate the number of isolated perylene linkers within the framework to the ratio between the two linkers, therefore rationalizing the change in the observed fluorescent properties. Taking advantage of the tunable fluorescence, inherent porosity, and high chemical stability of this MOF platform, it was applied as a fluorescent sensor for oxygen detection in the gas phase, a model reaction, showing fast response and good recyclability.

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

EPR studies of ferredoxin in spinach and cyanobacterial thylakoids related to photosystem I-driven NADP + reduction

Photosynthetic light-dependent reactions occur in thylakoid membranes where embedded proteins capture light energy and convert it to chemical energy in the form of ATP and NADPH for use in carbon fixation. One of these integral membrane proteins is Photosystem I (PSI). PSI catalyzes light-driven transmembrane electron transfer from plastocyanin (Pc) to oxidized ferredoxin (Fd). Electrons from reduced Fd are used by the enzyme ferredoxin-NADP + reductase (FNR) for the reduction of NADP + to NADPH. Fd and Pc are both small soluble proteins whereas the larger FNR enzyme is associated with the membrane. To investigate electron shuttling between these diffusible and embedded proteins, thylakoid photoreduction of NADP + was studied. As isolated, both spinach and cyanobacterial thylakoids generate NADPH upon illumination without extraneous addition of Fd. These findings indicate that isolated thylakoids either (i) retain a “pool” of Fd which diffuses between PSI and membrane bound FNR or (ii) that a fraction of PSI is associated with Fd, with the membrane environment facilitating PSI-Fd-FNR interactions which enable multiple turnovers of the complex with a single Fd. To explore the functional association of Fd with PSI in thylakoids, electron paramagnetic resonance (EPR) spectroscopic methodologies were developed to distinguish the signals for the reduced Fe-S clusters of PSI and Fd. Temperature-dependent EPR studies show that the EPR signals of the terminal [4Fe-4S] cluster of PSI can be distinguished from the [2Fe-2S] cluster of Fd at > 30 K. At 50 K, the cw X-band EPR spectra of cyanobacterial and spinach thylakoids reduced with dithionite exhibit EPR signals of a [2Fe-2S] cluster with g-values g x = 2.05, g y = 1.96, and g z = 1.89, confirming that Fd is present in thylakoid preparations capable of NADP + photoreduction. Quantitation of the EPR signals of P 700 + and dithionite reduced Fd reveal that Fd is present at a ratio of ~ 1 Fd per PSI monomer in both spinach and cyanobacterial thylakoids. Light-driven electron transfer from PSI to Fd in thylakoids confirms Fd is functionally associated (< 0.4 Fd/PSI) with the acceptor end of PSI in isolated cyanobacterial thylakoids. Furthermore, these EPR experiments provide a benchmark for future spectroscopic characterization of Fd interactions involved in multistep relay of electrons following PSI charge separation in the context of photosynthetic thylakoid microenvironments.

Electron paramagnetic resonance↗