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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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

High-temperature phonon-mediated superconductivity in monolayer Mg 2 B 4 C 2

A two-dimensional material – Mg 2 B 4 C 2 , belonging to the family of the conventional superconductor MgB 2 , is theoretically predicted to exhibit superconductivity with critical temperature T c estimated in the 47–48 K range (predicted using the McMillian-Allen-Dynes formula) without any tuning of external parameters such as doping, strain, or substrate-induced effects. The origin of such a high intrinsic T c is ascribed to the presence of strong electron-phonon coupling and large density of states at the Fermi level. This system is obtained after replacing the chemically active boron-boron surface layers in a MgB 2 slab by chemically inactive boron-carbon layers. Hence, the surfaces of this material are inert. Our calculations confirm the stability of 2D Mg 2 B 4 C 2 . We also find that the key features of this material remain essentially unchanged when its thickness is increased by modestly increasing the number of inner MgB 2 layers.

36 MATERIALS SCIENCE↗
DOE OSTI2023

High temperature and high beam current compatible targets and methods thereof for generating noble gas/radiohalogen generators for medical isotopes

A method of providing alpha particle emitters and materials suitable for use in generating the alpha particles for medical treatment is disclosed. Metal oxide targets, preferentially Bi 2 O 3 pellets and Bi 2 O 3 coatings on metallic or metal oxide substrates are formed. The targets placed in a heated vacuum chamber subjecting to irradiation using a 6 Li beam at an elevated temperature below the melting point of the target generate a radioactive gas, such as 211 Rn, the radioactive gas is carried by an inert gas which is delivered a carrier for, such as a carbon column or oil for delivery to a treatment facility. The radioactive gas such as 211 Rn generates 211 At, which has a useable half-life of at least about 14 hours, in turn releases alpha particles which are effective for use in medical procedures.

Sampathkumaran, Uma↗
DOE OSTI2020

Atomically dispersed palladium catalyses Suzuki–Miyaura reactions under phosphine-free conditions

Single-atom catalysts have emerged as a new frontier in catalysis science. However, their applications are still limited to small molecule activations in the gas phase, the classic organic transformations catalyzed by single-atom catalysts are still rare. Here, we report the use of a single-atom Pd catalyst for the classic Suzuki–Miyaura carbon–carbon coupling reaction under phosphine-free and open-air conditions at room temperature. The single-atom Pd catalyst is prepared through anchoring Pd on bimetal oxides (Pd-ZnO-ZrO 2 ). The significant synergetic effect of ZnO and ZrO 2 is observed. The catalyst exhibits high activity and tolerance of a wide scope of substrates. Characterization demonstrates that Pd single atoms are coordinated with two oxygen atoms in Pd-ZnO-ZrO 2 catalyst. The catalyst can be fabricated on a multi-gram scale using a simple in situ co-precipitation method, which endows this catalytic system with great potential in practical applications.

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

Impact of moisture on microbial decomposition phenotypes and enzyme dynamics

Soil organic matter decomposition is a complex process reflecting microbial composition and environmental conditions. Moisture can modulate the connectivity and interactions of microbes. Due to heterogeneity, a deeper understanding of the influence of soil moisture on the dynamics of organic matter decomposition and resultant phenotypes remains a challenge. Soils from a long-term field experiment exposed to high and low moisture treatments were incubated in the laboratory to investigate organic matter decomposition using chitin as a model substrate. By combining enzymatic assays, biomass measurements, and microbial enrichment via activity-based probes, we determined the microbial functional response to chitin amendments and field moisture treatments at both the community and cell scales. Chitinolytic activities showed significant responses to the amendment of chitin, independent of differences in field moisture treatments. However, for other measurements of carbon metabolism and cellular functions, soils from high moisture field treatments had greater potential enzyme activity than soils from low moisture field treatments. A cell tagging approach was used to enrich and quantify bacterial taxa that are actively producing chitin-degrading enzymes. By integrating organism, community, and soil core measurements we show that (i) a small subset of taxa compose the majority (>50%) of chitinase production despite broad functional redundancy, (ii) the identity of key chitin degraders varies with moisture level, and (iii) extracellular enzymes that are not cell-associated account for most potential chitinase activity measured in field soil.

activity-based probes↗
DOE OSTI2024

Lambda-PFLOTRAN 1.0: a workflow for incorporating organic matter chemistry informed by ultra high resolution mass spectrometry into biogeochemical modeling

Abstract. Organic matter (OM) composition plays a central role in microbial respiration of dissolved organic matter and subsequent biogeochemical reactions. Here, a direct connection of organic matter chemistry and thermodynamics to reactive transport simulators has been achieved through the newly developed Lambda-PFLOTRAN workflow tool that succinctly incorporates carbon chemistry data generated from Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) into reaction networks to simulate organic matter degradation and the resulting biogeochemistry. Lambda-PFLOTRAN is a Python-based workflow, executed through a Jupyter notebook interface, that digests raw FTICR-MS data, develops a representative reaction network based on substrate-explicit thermodynamic modeling (also termed lambda modeling due to its key thermodynamic parameter λ used therein), and completes a biogeochemical simulation with the open source, reactive flow and transport code PFLOTRAN. The workflow consists of the following five steps: configuration, thermodynamic (lambda) analysis, sensitivity analysis, parameter estimation, and simulation output and visualization. Two test cases are provided to demonstrate the functionality of the Lambda-PFLOTRAN workflow. The first test case uses laboratory incubation data of temporal oxygen depletion to fit lambda parameters (i.e., maximum utilization rate and microbial carrying capacity). A slightly more complex second test case fits multiple lambda formulation and soil organic matter release parameters to temporal greenhouse gas generation measured during a soil incubation. Overall, the Lambda-PFLOTRAN workflow facilitates upscaling by using molecular-scale characterization to inform biogeochemical processes occurring at larger scales.

58 GEOSCIENCES↗
DOE OSTI2020

Superhydrophobic coating and process of making same

An improved superhydrophobic coating and a process of making it is provided herein. More particularly, a robust superhydrophobic coating is produced by using carbon dioxide to enhance the integration of a binder material into the superhydrophobic coating. The carbon dioxide may be used to infiltrate and fill the interstitial voids of a superhydrophobic material, such as diatomaceous earth. Consequently, occupying these voids in the superhydrophobic material effectively blocks other components (e.g., binders) from entering the voids. As a result, the coating formulations of the present invention are more robust and may strongly adhere to the substrates to which they are applied.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Engineering Escherichia coli to produce medium chain oleochemicals from C 2 substrates

Many strategies to create a circular bioeconomy have been proposed. To be successful, CO 2 must be reduced with renewable energy into chemical building blocks, from which the chemical industry can be supported. Circular strategies include leveraging photosynthesis to produce sugar and lipid intermediates or renewable electricity to produce hydrogen or other electron carriers to support CO 2 reduction. Acetogens can anaerobically reduce CO 2 with H 2 to produce mixtures of small organic molecules in gas fermentations. We previously demonstrated that acetate, a common product of gas fermentation, can be converted to the model oleochemical dodecanol in engineered Escherichia coli. Here, we explored the conversion of ethanol and mixtures of ethanol and acetate to the same model oleochemicals. Co-feeding ethanol can supply both carbon and additional reducing power relative to acetate alone. In this work, we engineered E. coli to catabolize ethanol and expressed two distinct ethanol metabolism pathways in different operons and combined them with improved engineered acetate activation. We evaluated the performance of these operons in dodecanol-producing strains when fed ethanol or acetate and found ethanol to be a better carbon source when judged by product titers. The engineered strains fed ethanol produced about two-fold more dodecanol than the strains fed acetate. This increase was in part, due to change in product distribution. Cells fed ethanol produced predominantly dodecanol, whereas cells fed acetate generated a mixture of dodecanol and dodecanoic acid. Dodecanol titers were further improved by employing feeding strategies in controlled bioreactors.

Escherichia coli↗
DOE OSTI2024

Genomic insights into redox-driven microbial processes for carbon decomposition in thawing Arctic soils and permafrost

Climate change is rapidly transforming Arctic landscapes where increasing soil temperatures speed up permafrost thaw. This exposes large carbon stocks to microbial decomposition, possibly worsening climate change by releasing more greenhouse gases. Understanding how microbes break down soil carbon, especially under the anaerobic conditions of thawing permafrost, is important to determine future changes. Here, we studied the microbial community dynamics and soil carbon decomposition potential in permafrost and active layer soils under anaerobic laboratory conditions that simulated an Arctic summer thaw. The microbial and viral compositions in the samples were analyzed based on metagenomes, metagenome-assembled genomes, and metagenomic viral contigs (mVCs). Following the thawing of permafrost, there was a notable shift in microbial community structure, with fermentative Firmicutes and Bacteroidota taking over from Actinobacteria and Proteobacteria over the 60-day incubation period. The increase in iron and sulfate-reducing microbes had a significant role in limiting methane production from thawed permafrost, underscoring the competition within microbial communities. We explored the growth strategies of microbial communities and found that slow growth was the major strategy in both the active layer and permafrost. Our findings challenge the assumption that fast-growing microbes mainly respond to environmental changes like permafrost thaw. Instead, they indicate a common strategy of slow growth among microbial communities, likely due to the thermodynamic constraints of soil substrates and electron acceptors, and the need for microbes to adjust to post-thaw conditions. The mVCs harbored a wide range of auxiliary metabolic genes that may support cell protection from ice formation in virus-infected cells.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Upcycling plastic waste into polyhydroxyalkanoates with high carbon conversion via CO 2 plasma-enabled deconstruction

Plastic deconstruction into fermentable intermediates is a key step for microbial bio-upcycling into value-added products. In this study, CO 2 plasma deconstruction was used as an electrified route to convert polyethylene into oxygenated intermediates and liquid (OIL). The resulting OIL was rich in fatty acids, fatty alcohols, and hydrocarbons, making it a suitable feedstock for medium-chain-length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida NRRL B-14688 and Pseudomonas resinovorans NRRL B-2649. Compared with batch fermentation and monocultures, fed-batch co-cultivation markedly improved biomass formation and PHA accumulation, likely due to complementary substrate utilization, particularly hydrocarbon conversion by P. resinovorans. Using virgin polyethylene-derived OIL (Vir-OIL), the co-culture achieved 40.11% mcl-PHA content and about 18% PHA yield based on total OIL fed. More importantly, OIL produced from post-consumer single-use plastic films (PCR-OIL) was directly fermented and well supported the cell growth and PHA accumulation, achieving 38.11% PHA content and about 14.7% PHA yield. Based on emulsified OIL fractions, PHA yields for Vir-OIL and PCR-OIL were comparable (∼28%). PHA granules were extracted from PCR-OIL-grown cells with high recovery (88.25%) and purity (94.8%). Five monomers were identified in the polymer, including 3-hydroxyhexanoate (3HHx), 3-hydroxyoctanoate (3HO), 3-hydroxydecanoate (3HD), 3-hydroxydodecanoate (3HDD), and 3-hydroxytetradecanoate (3HTD), with 3HO (44.28%) and 3HD (40.60%) as the dominant units. The polymer exhibited moderate molecular weight and narrow dispersity (M n = 65.4 kDa, M w = 92.1 kDa, Đ = 1.40) and low crystallinity (T m ≈ 76.6 °C, X c ≈ 15.5%). These characteristics indicate elastomer-like behavior, making the material suitable for flexible applications such as films, coatings, adhesives, and blend modifiers. Overall, this study establishes a CO 2 plasma-assisted route for generating fermentable polyethylene-derived intermediates and demonstrates that fed-batch co-culture fermentation can effectively funnel plastic-derived carbon into mcl-PHA.

42 ENGINEERING↗
DOE OSTI2022

Substantial carbon loss respired from a corn–soybean agroecosystem highlights the importance of careful management as we adapt to changing climate

Understanding agroecosystem carbon (C) cycle response to climate change and management is vital for maintaining their long-term C storage. We demonstrate this importance through an in-depth examination of a ten-year eddy covariance dataset from a corn–corn–soybean crop rotation grown in the Midwest United States. Ten-year average annual net ecosystem exchange (NEE) showed a net C sink of –0.39 Mg C ha –1 yr –1 . However, NEE in 2014 and 2015 from the corn ecosystem was 3.58 and 2.56 Mg C ha –1 yr –1 , respectively. Most C loss occurred during the growing season, when photosynthesis should dominate and C fluxes should reflect a net ecosystem gain. Partitioning NEE into gross primary productivity (GPP) and ecosystem respiration (ER) showed this C 'burp' was driven by higher ER, with a 51% (2014) and 57% (2015) increase from the ten-year average (15.84 Mg C ha –1 yr –1 ). GPP was also higher than average (16.24 Mg C ha –1 yr –1 ) by 25% (2014) and 37% (2015), but this was not enough to offset the C emitted from ER. This increased ER was likely driven by enhanced soil microbial respiration associated with ideal growing season climate, substrate availability, nutrient additions, and a potential legacy effect from drought.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

A Generic Sacrificial Layer for Wide-Range Freestanding Oxides with Modulated Magnetic Anisotropy

Freestanding oxide nanomembranes have promising applications because of their novel electronic states and flexible crystalline structures. Several materials have been developed as sacrificial layers to exfoliate thin films from substrates via wet-etching. However, these materials face great challenges in terms of either complicated crystalline structures or corrosive solutions. Herein, a new sacrificial material, SrCoO 2.5 , is presented, which can be coherently grown with wide-range strains and crystalline orientations and is also soluble in eco-friendly solutions such as acetic acid, vinegar, and even carbonated drinks. With SrCoO 2.5 as the sacrificial layer, high-quality freestanding ferromagnetic SrRuO 3 membranes are achieved from wide-range epitaxial strains and different crystalline orientations. By investigating the evolution of the magnetic properties of these samples, it is discovered that epitaxial strain causes a distinct modification of the magnetic anisotropy of (001) pc -oriented SrRuO 3 samples, while its influence on the (110) pc and (111) pc samples is insignificant. This study not only demonstrates the freestanding SrRuO 3 as a promising material for flexible spintronic devices, but also offers a great opportunity to engineer a wide range of strained and oriented complex oxides for novel freestanding electronics using this newly developed sacrificial material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Aligned 2D carbon nanotube liquid crystals for wafer-scale electronics

Semiconducting carbon nanotubes promise faster performance and lower power consumption than Si in field-effect transistors (FETs) if they can be aligned in dense arrays. Here, we demonstrate that nanotubes collected at a liquid/liquid interface self-organize to form two-dimensional (2D) nematic liquid crystals that globally align with flow. The 2D liquid crystals are transferred onto substrates in a continuous process generating dense arrays of nanotubes aligned within ±6°, ideal for electronics. Nanotube ordering improves with increasing concentration and decreasing temperature due to the underlying liquid crystal phenomena. The excellent alignment and uniformity of the transferred assemblies enable FETs with exceptional on-state current density averaging 520 μA μm -1 at only -0.6 V, and variation of only 19%. FETs with ion gel top gates demonstrate subthreshold swing as low as 60 mV decade -1 . Deposition across a 10-cm substrate is achieved, evidencing the promise of 2D nanotube liquid crystals for commercial semiconductor electronics.

42 ENGINEERING↗
DOE OSTI2021

Chemical-damage MINE: A database of curated and predicted spontaneous metabolic reactions

Spontaneous reactions between metabolites are often neglected in favor of emphasizing enzyme-catalyzed chemistry because spontaneous reaction rates are assumed to be insignificant under physiological conditions. However, synthetic biology and engineering efforts can raise natural metabolites' levels or introduce unnatural ones, so that previously innocuous or nonexistent spontaneous reactions become an issue. Problems arise when spontaneous reaction rates exceed the capacity of a platform organism to dispose of toxic or chemically active reaction products. While various reliable sources list competing or toxic enzymatic pathways' side-reactions, no corresponding compilation of spontaneous side-reactions exists, nor is it possible to predict their occurrence. We addressed this deficiency by creating the Chemical Damage (CD)-MINE resource. First, we used literature data to construct a comprehensive database of metabolite reactions that occur spontaneously in physiological conditions. We then leveraged this data to construct 148 reaction rules describing the known spontaneous chemistry in a substrate-generic way. We applied these rules to all compounds in the ModelSEED database, predicting 180,891 spontaneous reactions. The resulting (CD)-MINE is available at https://minedatabase.mcs.anl. gov/cdmine/#/home and through developer tools. We also demonstrate how damage-prone intermediates and end products are widely distributed among metabolic pathways, and how predicting spontaneous chemical damage helps rationalize toxicity and carbon loss using examples from published pathways to commercial products. We explain how analyzing damage-prone areas in metabolism helps design effective engineering strategies. Finally, we use the CD-MINE toolset to predict the formation of the novel damage product N-carbamoyl proline, and present mass spectrometric evidence for its presence in Escherichia coli.

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

A High-Quality Genome-Scale Model for Rhodococcus opacus Metabolism

Rhodococcus opacus is a bacterium that has a high tolerance to aromatic compounds and can produce significant amounts of triacylglycerol (TAG). Here, we present iGR1773, the first genome-scale model (GSM) of R. opacus PD630 metabolism based on its genomic sequence and associated data. The model includes 1773 genes, 3025 reactions, and 1956 metabolites, was developed in a reproducible manner using CarveMe, and was evaluated through Metabolic Model tests (MEMOTE). We combine the model with two Constraint-Based Reconstruction and Analysis (COBRA) methods that use transcriptomics data to predict growth rates and fluxes: E-Flux2 and SPOT (Simplified Pearson Correlation with Transcriptomic data). Growth rates are best predicted by E-Flux2. Flux profiles are more accurately predicted by E-Flux2 than flux balance analysis (FBA) and parsimonious FBA (pFBA), when compared to 44 central carbon fluxes measured by 13C-Metabolic Flux Analysis (13C-MFA). Under glucose-fed conditions, E-Flux2 presents an R2 value of 0.54, while predictions based on pFBA had an inferior R2 of 0.28. We attribute this improved performance to the extra activity information provided by the transcriptomics data. For phenol-fed metabolism, in which the substrate first enters the TCA cycle, E-Flux2’s flux predictions display a high R2 of 0.96 while pFBA showed an R2 of 0.93. We also show that glucose metabolism and phenol metabolism function with similar relative ATP maintenance costs. These findings demonstrate that iGR1773 can help the metabolic engineering community predict aromatic substrate utilization patterns and perform computational strain design.

Roell, Garrett W.↗
DOE OSTI2025

Chelator-mediated Fenton post-treatment enhances methane yield from lignocellulosic residues via microbial community modulation

Advancing biomethane production from anaerobic digestion (AD) is essential for building a more reliable and resilient bioenergy system. However, incomplete conversion of lignocellulose-rich agricultural waste remains a key limitation, often leaving energy-dense residues in the digestate by-product. In this study, we introduce a novel application of chelator-mediated Fenton (CMF) post-treatment to recover untapped biomethane potential from these recalcitrant residues, representing a significant departure from conventional pre-treatment strategies. By systematically varying pH, iron-chelator concentration, and hydrogen peroxide dosage, we identified reaction conditions (pH 6–8, 5 mM Fe 2+ -dihydroxybenzene, 3–4 wt.% H 2 O 2 ) that enhanced lignocellulose deconstruction and increased dissolved organic carbon (DOC) availability for methanogenesis. CMF post-treatment led to up to a tenfold increase in biomethane potential compared to untreated controls. Microbial community analysis revealed enrichment of cellulolytic species, suggesting enhanced hydrolytic activity as a driver of improved conversion. Application of the CMF post-treatment method to isolated poplar lignin further demonstrated its versatility for diverse lignocellulosic substrates. These findings position CMF post-treatment as a promising strategy to enhance AD efficiency and valorize digestate.

Martinez, Daniella Victoria [Sandia National Labor↗
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 OSTI2023

Comparison of wild-type KT2440 and genome-reduced EM42 Pseudomonas putida strains for muconate production from aromatic compounds and glucose

Pseudomonas putida KT2440 is a robust, aromatic catabolic bacterium that has been widely engineered to convert bio-based and waste-based feedstocks to target products. Towards industrial domestication of P. putida KT2440, rational genome reduction has been previously conducted, resulting in P. putida strain EM42, which exhibited characteristics that could be advantageous for production strains. Here, we compared P. putida KT2440-and EM42-derived strains for cis,cis-muconic acid production from an aromatic compound, p-coumarate, and in separate strains, from glucose. To our surprise, the EM42-derived strains did not outperform the KT2440-derived strains in muconate production from either substrate. In bioreactor cultivations, KT2440-and EM42-derived strains produced muconate from p-coumarate at titers of 45 g/L and 37 g/L, respectively, and from glucose at 20 g/L and 13 g/L, respectively. To provide additional insights about the differences in the parent strains, we analyzed growth profiles of KT2440 and EM42 on aromatic compounds as the sole carbon and energy sources. In general, the EM42 strain exhibited reduced growth rates but shorter growth lags than KT2440. We also observed that EM42-derived strains resulted in higher growth rates on glucose compared to KT2440-derived strains, but only at the lowest glucose concentrations tested. Transcriptomics revealed that genome reduction in EM42 had global effects on transcript levels and showed that the EM42-derived strains that produce muconate from glucose exhibit reduced modulation of gene expression in response to changes in glucose concentrations. Overall, our results highlight that additional studies are warranted to understand the effects of genome reduction on microbial metabolism and physiology, especially when intended for use in production strains.

09 BIOMASS FUELS↗
DOE OSTI2020

Characterization of a Mo-Nitrogenase Variant Containing a Citrate-Substituted Cofactor

Nitrogenase converts N 2 to NH 3 , and CO to hydrocarbons, at its cofactor site. In this work, we report a biochemical and spectroscopic characterization of a Mo-nitrogenase variant expressed in an Azotobacter vinelandii strain containing a deletion of nifV, the gene encoding the homocitrate synthase. Designated NifDK Cit , the catalytic component of this Mo-nitrogenase variant contains a citrate-substituted cofactor analogue. Activity analysis of NifDK Cit reveals a shift of CO reduction from H 2 evolution toward hydrocarbon formation and an opposite shift of N 2 reduction from NH 3 formation toward H 2 evolution. Consistent with a shift in the Mo K-edge energy of NifDK Cit relative to that of its wild-type counterpart, EPR analysis demonstrates a broadening of the line-shape and a decrease in the intensity of the cofactor-originated S=3/2 signal, suggesting a change in the spin properties of the cofactor upon citrate substitution. These observations point to a crucial role of homocitrate in substrate reduction by nitrogenase and the possibility to tune product profiles of nitrogenase reactions via organic ligand substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗