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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Sub-Nanometer Nanoclusters of Copper Atop Single-Atom Copper Moieties toward Electrochemical CO 2 Hydrogenation to Methane

The electrochemical CO 2 reduction (eCO 2 R) offers a compelling route for converting CO 2 into value-added fuels and chemicals. Among CO 2 -derived products, methane (CH 4 ) occupies a distinct position, serving both as a key intermediate for emerging cascade electro-oxidation to oxygenates and as a strategically important extraterrestrial fuel that can be generated in situ from off-planet CO 2 resources. Although Cu-based catalysts capable of selectively producing CH 4 have been reported, they seldom sustain high selectivity at practically relevant current densities. Here, we created a single-step co-pyrolysis strategy toward generating and anchoring Cu sub-nanometer clusters (Cu SNC ) atop Cu-N x single-atom (SA) motifs embedded within N-doped carbon (NC), with controllable nanostructures through tuning of the synthesis parameters. Complementary spectroscopic analyses and density functional theory (DFT) calculations help reveal a structure−activity correlation that could guide the catalyst design. The Cu SNC @NC sample synthesized at 550 °C pyrolysis temperature (best described and modeled as Cu 3 -CuN 4 domains) represents the most effective combination of cluster size, metal-nitrogen coordination, and adsorption energetics needed to selectively promote CH 4 generation versus other eCO 2 R products. Incorporating pulsed electrolysis and hydrophobicity-modulated transport tuning at the triple-phase boundary (TPB) further enhanced CH 4 production achieving a partial CH 4 current density of ∼321 mA cm −2 , 53% Faradaic efficiency (FECH 4 ), and less than 4% combined FE for other eCO 2 R products, simplifying downstream CH 4 purification or upgrading. This work establishes generalizable principles for controlling Cu cluster atomicity and metal−nitrogen coordination, both of which are recognized determinants of CH 4 -efficient eCO 2 R.

CH4 production↗
DOE OSTI2026

Bond Dissociation Energies of the Actinide Halides AnX, An = Ac–Lr and X = F–I, Utilizing Relativistic Composite Coupled Cluster Approaches

Bond dissociation energies (BDEs) have been calculated for the set of actinide halides AnX with An=Ac, Pa, and Np-Lr and X=F-I. Two composite thermochemistry methods based on the Feller-Peterson-Dixon (FPD) approach have been utilized, one involving spinor-based relativistic CCSD(T) calculations where spin-orbit (SO) was included at the orbital level and another using scalar relativistic CCSD(T) with a posteriori SO contributions based on 2-component multireference configuration interaction calculations. The method that was chosen for a given actinide halide was based on which representation yielded the best single determinant reference determinant for the coupled cluster calculation. The spinor-based method was chosen for all cases except for AmX, CmX, and BkX. Both composite approaches included contributions accounting for basis set truncation, outer-core correlation, the Gaunt interaction, and QED. The scalar FPD results, as well as the spinor-based calculations for AcF, also included higher order electron correlation up through CCSDT(Q). In addition to BDEs, CCSD(T) equilibrium bond lengths, harmonic frequencies, and vibrational anharmonicity constants are reported for all species. Last, the FPD BDEs for the fluorides were used to confirm the trend across the actinide series previously predicted by Gibson using bonding models based atomic promotion energies that provide a single 6d electron for bonding. In particular the local minimum in the BDEs at AmF is confirmed in the present calculations. Furthermore, the BDEs for LrX are predicted to be slightly larger than those of AcX, making them the largest in the actinide halide series.

Actinides↗
DOE OSTI2021

Is solid copper oxalate a spin chain or a mixture of entangled spin pairs?

Macroscopic assemblies of interacting spins give rise to a broad spectrum of behaviors determined by the spatial arrangement of the magnetic sites and the electronic interactions between them. Compounds of copper (II), in which each copper carries spin 1/2, exhibit a vast variety of physical properties. For antiferromagnetically coupled spin sites, there are two limiting scenarios: spin chains in which the spins can exhibit a long-range order or a mixture of dimers in which the spins within each pair are entangled but do not communicate with the spins from other dimers. In principle, the two types can be distinguished on the basis of experimental observations and modeling using empirically parameterized effective Hamiltonians, but in practice, ambiguity may persist for decades, as is the case for copper oxalate. Here we use high-level ab initio calculations to establish the validity of the nearest-site Heisenberg model and to predict the interaction strength between the magnetic sites. Finally, the computed magnetic susceptibility provides an unambiguous interpretation of magnetic experiments performed throughout half a century, clearly supporting the infinite spin-chain behavior of solid copper oxalate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Torsional Flexibility Tuning of Hexa-Carboxylate Ligands to Unlock Distinct Topological Access to Zirconium Metal–Organic Frameworks

Zirconium-based metal–organic frameworks (Zr-MOFs) exhibit remarkable structural diversity and functionality. However, uncovering new topological types within this family remains a considerable challenge today. Herein, we report two new hexa-topic ligands designed through the introduction of torsional flexibility, which enable the construction of two Zr-MOFs featuring rare network topologies. The (4,4′,4″,4‴,4‴′,4‴′′-((2-carboxybenzene-1,3,5-triyl)tris(9H-carbazole-9,3,6-triyl))hexabenzoic acid ligand (BTCH)) was obtained by replacing the rigid triptycene core in the H6PET-1 ligand (4,4′,4″,4‴,4‴′,4‴′′-(9,10-dihydro-9,10-[1,2]benzenoanthracene-2,3,6,7,14,15-hexayl)hexabenzoic acid) with a benzene-tricarbazole unit. Owing to its torsionally flexible core that allows rotational freedom to the arms, this ligand directs the construction of NU-2620 (NU represents Northwestern University), a Zr-MOF with 8-connected Zr6 clusters and the rare nuh topology. Further flexibilization of the carbazole units to benzene rings yielded the even more torsionally flexible 5′,5‴-bis(4-carboxyphenyl)-5″-(4,4″-dicarboxy-[1,1′:3′,1″-terphenyl]-5′-yl)-[1,1′:3′,1″:3″,1‴:3‴,1‴′-quinquephenyl]-4,4‴′-dicarboxylic acid ligand (CCTT), which forms NU-2630 featuring 6-connected clusters and the pcu topology. Both frameworks exhibit good chemical stability, prompting evaluation of their performance in CO2 photoreduction catalysis. Under low-concentration CO2 conditions, NU-2620 displays markedly higher catalytic activity than its benzene-based analogue, NU-2630, thanks to the abundance of photoactive carbazole units within its structure. These results demonstrate that introducing torsional flexibility in high-connected linkers can unlock access to new topologies and accelerates the reticular expansion of Zr-MOFs.

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

Evaluating Energy Efficiency Opportunities from Connected and Automated Vehicle Deployments Coupled with Shared Mobility in California

Connected and Automated Vehicles (CAVs) can be considered to be a disruptive transportation technology, with the potential to significantly improve overall transportation system efficiency; however, CAVs may increase induce vehicle miles traveled (VMT) and bring on greater energy consumption. Further, shared mobility is another disruptive transportation event that is reshaping our travel patterns. The primary goal of this project was to extensively collect data from vehicles and associated infrastructure equipped with CAV technologies from both real-world experiments and simulation studies mainly deployed in California, and develop a comprehensive framework for evaluating energy efficiency opportunities from large-scale (e.g., statewide) introduction of CAVs and a wide deployment of shared mobility systems in a variety of scenarios. To quantify the combined impact of CAV and shared mobility on travel behavior, traffic performance, and energy efficiency, a unique mesoscopic simulation-based model was developed for mobility and energy efficiency evaluation considering these disruptive transportation technologies. As a complement to existing studies on nationwide evaluation of CAVs’ energy impacts, this project was focused on data collection efforts and CAV applications under congested traffic environments that are frequently experienced on a massive scale across the major metropolitan areas in California. Extensive real-world data collection supplemented with simulation studies were conducted to cover a variety of CAV and shared mobility scenarios, particularly on scenarios less-explored in the existing research. Another key component of this project was to consider the interaction between different CAV technologies and shared mobility models, and the compound effect on energy efficiency. A comprehensive modeling suite was developed to quantify the impact of new mobility technologies on travel behavior and traffic performance. The developed modeling framework includes an energy intensity module, mode choice module and activity generation module that are integrated into an agent-based BEAM simulation platform to perform impact analysis based on a variety of scenarios. In addition, the RouteE model has been upgraded to incorporate the impact of CAVs on traffic flow, VMT and energy intensity, using micro-simulation data collected from both freeways and urban arterials. A novel fundamental influencing factor (FIF) mode choice model was developed to link CAV and shared mobility components with travel behaviors, and adapted into the BEAM-centered model framework. A statewide energy inventory was constructed under various CAV technology deployment scenarios by incorporating datasets and models for predicting vehicle market share and vehicle usage, which are tightly associated with the penetration of shared mobility systems. Based applying this modeling suite to a calibrated network in Riverside California, it was found that cooperative automated driving in general will improve mobility, but automated vehicles, even when deployed in a shared autonomous fleet, will likely bring an increase of VMT (up to 36%) due to mode shifts and deadheading. Ride-hailing vehicles typically have better energy efficiency and a higher share of electric vehicles, which helps offset the negative impact from VMT increases when estimating the system-level energy consumption. In general, simulation results show a 6% increase in energy consumption for the scenarios with an increasing shift to ride-hailing modes. The statewide analysis based on the National Household Travel Survey (NHTS) sample data is consistent with the findings from the Riverside network and validate the developed clustering-prediction modeling methodology. The outcomes from this project will help close the knowledge gap on recognizing the potential performance and energy impacts of a broad deployment of CAV and shared mobility technologies across a wide range of roadway infrastructure with varying levels of congestion. Results from this project: 1) will support policymakers in steering CAV development and deployment towards an energy favorable direction; 2) reduce uncertainties in estimating energy saving opportunities from new mobility technologies and services; 3) increase the confidence of CAV technology investors both on the infrastructure side (i.e., transportation agencies) and on the vehicle side (i.e., OEMs); and 4) expedite the deployment of energy-efficient CAV and shared mobility applications.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Discovery of an ultraspecific triuret hydrolase (TrtA) establishes the triuret biodegradation pathway

Triuret (carbonyldiurea) is an impurity found in industrial urea fertilizer (<0.1% w/w) that is applied, worldwide, around 300 million pounds each year on agricultural lands. In addition to anthropogenic sources, endogenous triuret has been identified in amoeba and human urine, the latter being diagnostic for hypokalemia. The present study is the first to describe the metabolic breakdown of triuret, which funnels into biuret metabolism. We identified the gene responsible for triuret decomposition ( trtA ) in bacterial genomes, clustered with biuH , which encodes biuret hydrolase and has close protein sequence homology. TrtA is a member of the isochorismatase-like hydrolase (IHL) protein family, similarly to BiuH, and has a catalytic efficiency (k cat/ K M ) of 6 x 10 5 M –1 s –1 , a K M for triuret of 20 μM, and exquisite substrate specificity. Indeed, TrtA has four orders of magnitude less activity with biuret. Crystal structures of TrtA in apo and holo form were solved and compared with the BiuH structure. The high substrate selectivity was found to be conveyed by second shell residues around each active site. Mutagenesis of residues conserved in TrtA to the alternate consensus found in BiuHs revealed residues critical to triuret hydrolase activity but no single mutant evolved more biuret activity, and likely a combination of mutations is required to interconvert between TrtA, BiuH functions. TrtA-mediated triuret metabolism is relatively rare in recorded genomes (1–2%), but is largely found in plant-associated, nodulating, and endophytic bacteria. This study suggests functions for triuret hydrolase in certain eukaryotic intermediary processes and prokaryotic intermediary or biodegradative metabolism.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Pd(II) and Rh(I) Catalytic Precursors for Arene Alkenylation: Comparative Evaluation of Reactivity and Mechanism Based on Experimental and Computational Studies

We combine experimental and computational investigations to compare and understand catalytic arene alkenylation using the Pd(II) and Rh(I) precursors Pd(OAc) 2 and [(η 2 -C 2 H 4 ) 2 Rh(µ-OAc)] 2 with arene, olefin and Cu(II) carboxylate at elevated temperature (> 120 °C). Under specific conditions, previous computational and experimental efforts have identified heterotrimetallic cyclic PdCu 2 (η 2 -C 2 H 4 ) 3 (μ-OPiv) 6 and [(η 2 -C 2 H 4 ) 2 Rh(µ-OPiv) 2 ] 2 (µ-Cu) (OPiv = pivalate) species as likely active catalysts for these processes. Further studies of catalyst speciation suggest a complicated equilibrium between Cu(II)-containing complexes containing one Rh or Pd atom with complexes containing two Rh or Pd atoms. At 120 °C, Rh catalysis produces styrene > 20-fold more rapidly than Pd. Also, at 120 °C, Rh is ~98% selective for styrene formation while Pd is ~82% selective. Furthermore, our studies indicate that Pd catalysis has a higher predilection toward olefin functionalization to form undesired vinyl ester, while Rh catalysis is more selective for arene/olefin coupling. However, at elevated temperatures, Pd converts vinyl ester and arene to vinyl arene, which is proposed to occur through low valent Pd(0) clusters that are formed in situ. Regardless of arene functionality, the regioselectivity for alkenylation of mono-substituted arenes with the Rh catalyst gives an approximate 2:1 meta:para ratio with minimal ortho C–H activation. In contrast, Pd selectivity is significantly influenced by arene electronics with electron-rich arenes giving an approximate 1:2:2 ortho:meta:para ratio while the electron deficient (α,α,α)-trifluorotoluene gives a 3:1 meta:para ratio with minimal ortho functionalization. Kinetic intermolecular arene ethenylation competition experiments find that Rh reacts most rapidly with benzene, and the rate of mono-substituted arene alkenylation does not correlate with arene electronics. In contrast, with Pd catalysis, electron-rich arenes react more rapidly than benzene while electron-deficient arenes react less rapidly than benzene. These experimental findings, in combination with computational results, are consistent with the arene C–H activation step for Pd catalysis involving significant η 1 -arenium character due to Pd-mediated electrophilic aromatic substitution character. In contrast, the mechanism for Rh catalysis is not sensitive to arene substituent electronics, which we propose indicates less electrophilic aromatic substitution character for the Rh-mediated arene C–H activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2020

The Old, Unique C1 Chondrite Flensburg – Insight Into the First Processes of Aqueous Alteration, Brecciation, and the Diversity of Water-Bearing Parent Bodies and Lithologies

On September 12, 2019 at 12:49:48 (UT) a bolide was observed by hundreds of eye-witnesses from the Netherlands, Germany, Belgium, Denmark and the UK. One day later a small meteorite stone was found by accident in Flensburg. The presence of short-lived cosmogenic radionuclides with half-lives as short as 16 days proves the recent exposure of the found object to cosmic rays in space linking it clearly to the bolide event. An exceptionally short exposure time of ∼5000 years was determined. The 24.5 g stone has a fresh black fusion crust, a low density of <2 g/cm(exp 3), and a magnetic susceptibility of logχ = 4.35 (χ in 10−9 m(exp 3)/kg). The rock consists of relict chondrules and clusters of sulfide and magnetite grains set in a fine-grained matrix. The most abundant phases are phyllosilicates. Carbonates (∼3.9 vol.%) occur as calcites, dolomites, and a Na-rich phase. The relict chondrules (often surrounded by sulfide laths) are free of anhydrous silicates and contain abundant serpentine. Lithic clasts are also surrounded by similar sulfide laths partly intergrown with carbonates. Mn-53-Cr-53 ages of carbonates in Flensburg indicate that brecciation and contemporaneous formation of the pyrrhotite-carbonate intergrowths by hydrothermal activities occurred no later than 4564.6 ± 1.0 Ma (using the angrite D'Orbigny as the Mn-Cr age anchor). This corresponds to 2.6 ± 1.0 or 3.4 ± 1.0 Ma after formation of CAIs, depending on the exact absolute age of CAIs. This is the oldest dated evidence for brecciation and carbonate formation, which likely occurred during parent body growth and incipient heating due to decay of Al-26. In the three oxygen isotope diagram, Flensburg plots at the 16O-rich end of the CM chondrite field and in the transition field to CV-CK-CR chondrites. The mass-dependent Te isotopic composition of Flensburg is slightly different from mean CM chondrites and is most similar to those of the ungrouped C2 chondrite Tagish Lake. On the other hand, Ti-50 and Cr-54 isotope anomalies indicate that Flensburg is similar to CM chondrites, as do the ∼10 wt.% H2O of the bulk material. Yet, the bulk Zn, Cu, and Pb concentrations are about 30% lower than those of mean CM chondrites. The He, Ne, and Ar isotopes of Flensburg show no solar wind contribution; its trapped noble gas signature is similar to that of CMs with a slightly lower concentration of Ne(sub tr)-20. Based on the bulk H, C, and N elemental abundances and isotopic compositions, Flensburg is unique among chondrites, because it has the lightest bulk H and N isotopic compositions of any type 1 or 2 chondrite investigated so far. Moreover, the number of soluble organic compounds in Flensburg is even lower than that of the brecciated CI chondrite Orgueil. The extraordinary significance of Flensburg is evident from the observation that it represents the oldest chondrite sample in which the contemporaneous episodes of aqueous alteration and brecciation have been preserved. The characterization of a large variety of carbonaceous chondrites with different alteration histories is important for interpreting returned samples from the OSIRIS-REx and Hayabusa 2 missions.

C1 chondrite↗
DOE OSTI2025

NiAl–MoO 2 S 2 Nanoparticles: Structural Evolution and Mechanistic Insights into High-Performance Selenium Oxyanion Removal across Diverse pH Conditions

Advancing sorbent materials for the selective removal of toxic oxyanions from water requires synthetic control, tunable chemistry, and an atomic-level understanding of structure–function relationships. Here, we report the synthesis and detailed characterization of NiAl–MoO 2 S 2 , a novel layered double hydroxide (LDH) nanomaterial designed for the efficient sequestration of selenium oxoanions (SeO 3 2– and SeO 4 2– ) from complex aqueous environments. The material is synthesized through a room-temperature ion-exchange process, wherein interlayer NO 3 – anions in NiAl–LDH are replaced with MoO 2 S 2 2– clusters, forming high-surface-area, flower-like nanoparticles. Comprehensive structural analysis using the synchrotron X-ray pair distribution function, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy reveals a distinct chemical transformation of intercalated [MoO 2 S 2 ] 2– into [Mo 2 O 2 S 6 ] 2– -like clusters, generating redox-active interlayers that drive selenium capture. This tailored interfacial chemistry underpins the material’s exceptional sorption performance, achieving distribution coefficients (K d ) ≥ 10 6 mL/g and maximum capacities of 343 mg/g for SeO 4 2– and 514 mg/g for SeO 3 2– , outperforming state-of-the-art inorganic sorbents. Importantly, NiAl–MoO 2 S 2 maintains high selectivity and capacity across acidic, neutral, and alkaline pH, efficiently removing selenium from ppm to sub-10 ppb trace levels, even in the presence of competing ions typical of natural and industrial waters. The selenium uptake proceeds via reductive precipitation coupled with the oxidation of molybdenum and sulfide within the LDH framework. This study highlights the power of strategic synthetic modification and interlayer functionalization in LDHs to unlock new structural motifs and redox chemistries, offering a scalable route to advanced materials for environmental remediation.

Adsorption↗
NASA NTRS2016

Wilson Corners SWMU 001 2015 Annual Long Term Monitoring Report Kennedy Space Center, Florida

This document presents the findings of the 2015 Long Term Monitoring (LTM) that was completed at the Wilson Corners site, located at the National Aeronautics and Space Administration John F. Kennedy Space Center, Florida. The objectives of the 2015 LTM event were to evaluate the groundwater flow direction and gradient, to monitor the vertical and horizontal extent of the volatile organic compounds (VOCs; including the upgradient and sidegradient extents, which are monitored every five years), and to monitor select locations internal to the dissolved groundwater plume. The 2015 LTM event included several upgradient and sidegradient monitoring wells that are not sampled annually to verify the extent of VOCs in this portion of the site. The December 2015 LTM groundwater sampling event included, depth to groundwater measurements, 40 VOC samples collected using passive diffusion bags, and one VOC sample collected using low-flow techniques. Additionally, monitoring well MW0052DD was overdrilled and abandoned using rotasonic drilling techniques. The following conclusions can be made based on the 2015 LTM results: groundwater flow is generally to the west with northwest and southwest flow components from the water table to approximately 55 feet below land surface (ft BLS); peripheral monitoring wells generally delineate VOCs to groundwater cleanup target levels (GCTLs) except for monitoring wells MW0088, MW0090, MW0095, and NPSHMW0039, which had vinyl chloride (VC) concentrations near the GCTL and MW0062, which had trichloroethene (TCE), cis-1,2-dichloroethenen (cDCE), and VC concentrations above natural attenuation default concentrations (NADCs); VOCs in interior downgradient wells generally fluctuate within historic ranges except for monitoring wells in the north-northwest portion of the site, which have increasing VC concentrations indicating potential plume migration and expansion; Historically, the vertical extents of the VOCs were delineated by monitoring wells screened greater than 60 ft BLS (MW0083 through MW0086, and MW0078). The 2015 LTM results indicate that concentrations of daughter product cDCE is greater than the NADC in MW0078 and that cDCE and VC are greater than NADCs in MW0130. TCE was greater than the GCTL in monitoring well MW130 and not detected above method detection limits (9 micrograms per Liter) in monitoring well MW0078. No GCTL exceedances were identified in monitoring wells MW0083 or MW0086; the dissolved plume footprint appears generally stable, though not fully delineated by monitoring well data in the northeast portion of the site; and 2015 LTM results generally support the existing Conceptual Site Model. Geosyntec recommends modifying the LTM program, collecting a verification sample from monitoring well MW0062, and performing a direct push technology instigation in the northnortheastern portion of the site. A cluster of monitoring wells (MW0132 [2 to 12 ft BLS], MW0133 [15 to 25 ft BLS], and MW0134 [29 to 34 ft BLS]) is proposed to delineate impacts in the northnortheast portion of the site. Geosyntec recommends installation of a vertical extent well in the center of the site (Hot Spot 2 area) post-remediation implementation.

groundwater↗
DOE OSTI2025

Net Present Value Optimization of a Natural Gas Combined Cycle Plant with CO 2 Capture using a Water-Lean Solvent Considering Transient Electricity Price for Multiple Regions

Global CO 2 emissions are increasing at about a 1.5% rate per year. Fossil fuel-based plants are one of the main contributors to this rise. In the power generation industry, fossil fuel plants are dominant, and many plants are under development. In this study, a natural gas combined cycle (NGCC) power plant with postcombustion capture using a leading water-lean solvent is considered. For optimal design and operating schedule, large-scale dynamic optimization is undertaken for net present value (NPV) optimization. The first principle dynamic model of NGCC is developed, including a model of the highly efficient H-class gas turbines. For computational tractability of the dynamic optimization problem, a reduced-order model is developed by using the Hankel singular value decomposition. A waterlean solvent, N-(2-ethoxyethyl)-3-morpholinopropan-1-amine, is used for carbon capture. A model of the capture system is developed in Aspen Plus, which is used to develop a reduced-order model by using ALAMO, a machine learning software. In addition, a reduced model of the CO 2 compression system with a dehydration unit is also considered. The integrated system is used for NPV optimization by using the Python-based PYOMO platform. The PCC process is analyzed for three configurations-conventional packed bed, rotating packed bed (RPB), and a combination of RPB and direct contact cooler. The NPV optimization is performed for 14 regional markets by considering year-long clustered and continuous locational marginal price data with a 1 h interval. Optimization results show that the PCC can achieve 90% CO 2 capture with a positive NPV for six regions. Sensitivity studies conducted by using the PCC configurations indicate that the process is economically feasible for 9 regions out of 14 regional electricity markets with NPV values in the range of 33−540 $MM.

cabon capture↗
DOE OSTI2026

Microscopic Dynamics Controls Coupling and Cluster Formation in Brush Particle Solids

Thermodynamics-based models predict the structure of polymer-grafted nanoparticles (PGNs) as well as their assembly behavior based on geometric parameters such as particle size, degree of polymerization, and density of grafted chains. The role of microscopic polymer dynamics, such as the mobility of repeat units in the melt state, in the evolution of the structure and properties remains unknown. Brillouin light spectroscopy (BLS), due to its capability to concurrently discern the local and global elastic properties of PGN assemblies, enables the probing of microscopic processes, such as brush interdigitation, sensitive to the annealing of the assembly. For poly(methyl methacrylate) (PMMA)-grafted silica (SiO 2 ) PGNs in the dry powder state and annealed above the glass transition temperature, BLS revealed fully reversible local elasticity, indicative of limited interdigitation between adjacent PGNs. This contrasts with polystyrene (PS)−SiO 2 analogs that displayed ready (and irreversible) fusion of brush layers during annealing. The retardation of brush interdigitation in PMMA-grafted systems is surprising, given the similar thermomechanical properties of both polymers, and is rationalized as the consequence of higher friction between PMMA repeats compared to PS. Microscopic dynamics thus has a profound impact on the kinetic path of structure (and property) evolution and thus should be considered during the processing of PGNs into functional hybrid materials.

chemical structure↗
DOE OSTI2023

Identification of 2-Hydroxyacyl-CoA Synthases with High Acyloin Condensation Activity for Orthogonal One-Carbon Bioconversion

One-carbon (C1) compounds are emerging as cost-effective and potentially carbon-negative feedstocks for biomanufacturing, which require efficient, versatile metabolic platforms for the synthesis of value-added products. Synthetic formyl-CoA elongation (FORCE) pathways allow diverse product synthesis from C1 compounds via iterative C1 elongation, operating independently from the host metabolism with reduced engineering complexity and improved theoretical yields. However, a major bottleneck was identified as the suboptimal kinetics of the core C1–C1 condensation enzyme, 2-hydroxyacyl-CoA synthase (HACS), catalyzing the acyloin condensation reaction between formaldehyde and formyl-CoA. Furthermore, we used a combinatorial approach of bioprospecting and rational protein engineering to identify multiple HACS variants with significantly improved activities toward C1 substrates. Sequence and structure alignment of the active variants elucidated the key regions for the catalytic function, which were targeted for mutagenesis, leading to improved catalytic efficiency. In parallel, a consecutive round of bioprospecting for homologs with high similarity with active variants revealed a highly active HACS variant exhibiting up to 7-fold improvement in catalytic efficiency (k cat /K M ) and 14-fold improvement in the FORCE pathway flux in vivo compared to the previous reports. Upon further optimization of the downstream pathway, the orthogonal C1-to-product bioconversion system showed a metabolic flux of up to 700 μM glycolate OD –1 h –1 (2.1 mmol gDCW –1 h –1 ) and an industrially relevant glycolate titer, rate, and yield of 5.2 g L –1 (67.8 mM), 0.22 g L –1 h –1 , and 94% carbon yield, respectively.

2-hydroxyacyl-CoA synthase↗
DOE OSTI2025

The Power of Many: An Ensemble Approach to Spectral Similarity

Quantifying the similarity between two mass spectra─a known reference mass spectrum and an unidentified sample mass spectrum─is at the heart of compound identification workflows in gas chromatography–mass spectrometry (GC-MS). The reference spectrum most like the sample is assigned as its identification (provided some quantitative similarity threshold is met, e.g., 80%) and thus accurately measuring similarity is essential. Significant research has gone toward developing metrics for this purpose, each of which has attempted to improve upon existing methods by incorporating GC-MS-specific information (e.g., peak ratios or retention times) or adopting various statistical and algorithmic frameworks. While this active development has led to a plethora of similarity metrics with demonstrated value across different contexts, the unfortunate consequence has been confusion surrounding which metric should be used as a global standard. No such metric is currently accepted as the standard method because different metrics have demonstrated optimal performance in different contexts. In this work, we propose an ensemble approach to spectral similarity scoring that combines the collective information from across existing similarity metrics to form an improved, globally representative similarity metric as a step toward establishing a global standard method. In conclusion, the resulting ensemble metrics are evaluated on over 88,000 spectra of varying complexity and demonstrate improved abilities to accurately rank the correct reference spectrum as the top-matching candidate for a sample relative to the rankings generated by individual similarity scores.

Carbohydrates↗
DOE OSTI2026

Concordant Mode Approach (CMA): Vibrational Analysis of New and Upgraded Intermolecular Benchmarks for Noncovalent Bonding

The Concordant Mode Approach (CMA) is a novel method that offers tremendous potential for increasing the system size and the level of theory attainable in quantum chemical computations of molecular vibrational frequencies. To investigate the extension of CMA to intermolecular vibrations, computations with coupled cluster singles and doubles with perturbative triples theory [CCSD(T)] using two augmented correlation-consistent polarized-valence triple-ζ basis sets (aug-cc-pVTZ or h-aug-ccpVTZ) were performed on 17 prototypical loosely bound complexes of hydrogen-bonded, dispersion, and mixed character. These Level A results provide new and upgraded benchmarks for noncovalent bonding and a severe test for CMA vibrational analyses. The Level A target frequencies were recovered remarkably well using second-order Møller−Plesset perturbation theory (MP2) with h-aug-cc-pVTZ for generating the underlying (Level B) normal modes of the CMA scheme. Employing this Level B within the lowest-rung CMA-0A method reproduces the 435 benchmark frequencies with a mean absolute error (MAE) of 0.23 cm −1 and a corresponding standard deviation (σ) of 0.84 cm −1 ; strikingly, the corresponding subset of 106 interfragment frequencies exhibits MAE = 0.34 cm −1 and σ = 0.90 cm −1 . Subsequent application of the higher-rung CMA-2A scheme eliminates all outliers and reduces the overall MAE to a minuscule 0.08 cm −1 with the inclusion of only 3.0% of the off-diagonal couplings not accounted for by CMA-0A. Accordingly, the highly efficient CMA methodology proves to be robust even for vibrations on flat potential energy surfaces.

Aromatic compounds↗
DOE OSTI2021

Mechanistic Similarities and Differences for Hydrogenation of Aromatic Heterocycles and Aliphatic Carbonyls on Sulfided Ru Nanoparticles

This study establishes the contrasting reactivity trends for the hydrogenation of aromatic hydrocarbons (AHCs = C n H m X, X = N, S, O, and C) and aliphatic carbonyls [R a C(O)R b ; R a = alkyl group, R b = CH 3 or H] on sulfided Ru clusters arising from the difference in the elementary proton and hydride attack catalytic sequence. Both reactions require sequential additions of a proton from either Ru n+ –(SH 2 ) or S 2 –(H δ+ ) species and a hydride from Ru n+ –(H δ– ) species to the unsaturated C=X bonds. For the five-membered-ring aromatic heterocycles (AHCs = pyrrole, thiophene, and furan), an initial proton addition limits the catalytic turnovers; thus, their hydrogenation reactivity increases with increasing gas-phase proton affinities of the AHCs. Pyridine as the more basic six-membered N-AHC is more susceptible to protonation; therefore, it is more reactive, and its initial proton addition is quasi-equilibrated, followed by the kinetically relevant hydride addition. Conversely, aliphatic carbonyls prefer to undergo hydrogen additions in a reverse sequence, where a Ru n+ –(H δ– ) hydride initially attacks the electron-deficient carbonyl C atom as the kinetically relevant step before a subsequent rapid S 2 –(H δ+ ) proton addition on the electron-rich O atom, as confirmed by isotopic exchange studies with butanal-D 2 and 1-butanol-D 2 mixtures and density functional theory calculations on S-deficient RuS 2 (100) surfaces. For these reasons, their hydrogenation reactivity increases with increasing gas-phase hydride affinities of the carbonyls. On metallic Ru surfaces without sulfur, hydrogen adatoms (H*) are the only reactive hydrogen species; the reactivity of their attack on aromatic heterocycles increases with increasing reactant proton affinities much more sensitively than that on sulfided Ru surfaces. This work illustrates the distinct catalytic roles of the diverse hydrogen species in hydrogenation—the interplay between proton and hydride additions has marked catalytic consequences in shaping the free energy landscape of the reactions, which in turn leads to the observed kinetic dependences, kinetic parameters, reactivity trends, and scaling relations between the measured barriers and the appropriate kinetic descriptors, that is, proton affinity of AHCs and hydride affinity of carbonyls in hydrogenation catalysis. Here, these mechanistic similarities and differences provide explanations of the observed reactivity trends and thus have profound implications for industrial hydrogenation and hydrotreating catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Bismuth-Polyoxocation Coordination Networks: Controlling Nuclearity and Dimension-Dependent Photocatalysis

Bismuth-oxocluster nodes for metal–organic frameworks (MOFs) and coordination networks/polymers are less prolific than other families featuring zinc, zirconium, titanium, lanthanides, etc. However, Bi 3+ is non-toxic, it readily forms polyoxocations, and its oxides are exploited in photocatalysis. This family of compounds provides opportunity in medicinal and energy applications. Here, we show that Bi node nuclearity depends on solvent polarity, leading to a family of Bi x -sulfonate/carboxylate coordination networks with x = 1–38. Larger nuclearity-node networks were obtained from polar and strongly coordinating solvents, and we attribute the solvent’s ability to stabilize larger species in solution. Here, the strong role of the solvent and the lesser role of the linker in defining node topologies differ from other MOF syntheses, and this is due to the Bi 3+ intrinsic lone pair that leads to weak node–linker interactions. We describe this family by single-crystal X-ray diffraction (eleven structures), obtained in pure forms and high yields. Ditopic linkers include NDS (1,5-naphthalenedisulfonate), DDBS (2,2'-[biphenyl-4,4'-diylchethane-2,1-diyl] dibenzenesulphonate), and NH 2 -benzendicarboxylate (BDC). While the BDC and NDS linkers yield more open-framework topologies that resemble those obtained by carboxylate linkers, topologies with DDBS linkers appear to be in part driven by association between DDBS molecules. An in situ small-angle X-ray scattering study of Bi 38 -DDBS reveals stepwise formation, including Bi 38 -assembly, pre-organization in solution, followed by crystallization, confirming the less important role of the linker. We demonstrate photocatalytic hydrogen (H 2 ) generation with select members of the synthesized materials without the benefit of a co-catalyst. Band gap determination from X-ray photoelectron spectroscopy (XPS) and UV–vis data suggest the DDBS linker effectively absorbs in the visible range with ligand-to-Bi-node charge transfer. In addition, materials containing more Bi (larger Bi 38 -nodes or Bi 6 inorganic chains) exhibit strong UV absorption, also contributing to effective photocatalysis by a different mechanism. All tested materials became black with extensive UV–vis exposure, and XPS, transmission electron microscopy, and X-ray scattering of the black Bi 38 -framework suggest that Bi o is formed in situ, without phase segregation. This evolution leads to enhanced photocatalytic performance, perhaps due to increased light absorption.

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

Evidence for autotrophic growth of purple sulfur bacteria using pyrite as electron and sulfur source

ABSTRACT Purple sulfur bacteria (PSB) are capable of anoxygenic photosynthesis via oxidizing reduced sulfur compounds and are considered key drivers of the sulfur cycle in a range of anoxic environments. In this study, we show that Allochromatium vinosum (a PSB species) is capable of autotrophic growth using pyrite as the electron and sulfur source. Comparative growth profile, substrate characterization, and transcriptomic sequencing data provided valuable insight into the molecular mechanisms underlying the bacterial utilization of pyrite and autotrophic growth. Specifically, the pyrite-supported cell cultures (“py”’) demonstrated robust but much slower growth rates and distinct patterns from their sodium sulfide-amended positive controls. Up to ~200-fold upregulation of genes encoding various c - and b -type cytochromes was observed in “py,” pointing to the high relevance of these molecules in scavenging and relaying electrons from pyrite to cytoplasmic metabolisms. Conversely, extensive downregulation of genes related to LH and RC complex components indicates that the electron source may have direct control over the bacterial cells’ photosynthetic activity. In terms of sulfur metabolism, genes encoding periplasmic or membrane-bound proteins (e.g., FccAB and SoxYZ) were largely upregulated, whereas those encoding cytoplasmic proteins (e.g., Dsr and Apr groups) are extensively suppressed. Other notable differentially expressed genes are related to flagella/fimbriae/pilin(+), metal efflux(+), ferrienterochelin(−), and [NiFe] hydrogenases(+). Characterization of the biologically reacted pyrite indicates the presence of polymeric sulfur. These results have, for the first time, put the interplay of PSB and transition metal sulfide chemistry under the spotlight, with the potential to advance multiple fields, including metal and sulfur biogeochemistry, bacterial extracellular electron transfer, and artificial photosynthesis. IMPORTANCE Microbial utilization of solid-phase substrates constitutes a critical area of focus in environmental microbiology, offering valuable insights into microbial metabolic processes and adaptability. Recent advancements in this field have profoundly deepened our knowledge of microbial physiology pertinent to these scenarios and spurred innovations in biosynthesis and energy production. Furthermore, research into interactions between microbes and solid-phase substrates has directly linked microbial activities to the surrounding mineralogical environments, thereby enhancing our understanding of the relevant biogeochemical cycles. Our study represents a significant step forward in this field by demonstrating, for the first time, the autotrophic growth of purple sulfur bacteria using insoluble pyrite (FeS2) as both the electron and sulfur source. The presented comparative growth profiles, substrate characterizations, and transcriptomic sequencing data shed light on the relationships between electron donor types, photosynthetic reaction center activities, and potential extracellular electron transfer in these organisms capable of anoxygenic photosynthesis. Furthermore, the findings of our study may provide new insights into early-Earth biogeochemical evolutions, offering valuable constraints for understanding the environmental conditions and microbial processes that shaped our planet’s history.

59 BASIC BIOLOGICAL SCIENCES↗