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DOE OSTI2021

Propagation of Cryogenic Thermal Fractures from Unconfined PMMA Boreholes

In cryogenic fracturing, a rock surface exposed to cryogenic fluids undergoes a large thermal gradient, and the resultant local tensile stress overcomes rock strength and initiates fractures. This study investigates the development of cracks generated from the cryogenic treatment of a borehole under no external confining stress on specimens. The experiments were performed on transparent PMMA specimens to observe fracture proliferation around boreholes. Liquid nitrogen was flowed through the boreholes to cool the borehole surface. The results show that initial fracture growth is characterized by abrupt starts and stops, and as the fracture propagates outward, the growth appears more continuous. In an early stage, horizontal/radial fractures and vertical fractures are the defining patterns. Horizontal fractures tend to be separated by a specific exclusion distance (i.e., spacing between cracks). While distinct horizontal/vertical fractures and exclusion distance manifest themselves at an early stage, fractures resulting from fracture interactions and curvatures can develop into complex shapes at later stages. Cryogenic thermal loading induces distinctively curved fractures. The tendency of curvature may prevent greater penetration. An increase in the borehole pressure during liquid nitrogen flow, however, can lessen fracture tortuosity and facilitate radial propagation. A high flow pressure and rate are also advantageous in that they accelerate cooling and fracture propagation.

42 ENGINEERING↗

DOE OSTI2026

Coupled machine learning–ecosystem ensemble models substantially improve predictions of nitrous oxide (N 2 O) fluxes from US croplands

Nitrous oxide (N 2 O) is a potent and persistent greenhouse gas, with rising atmospheric concentrations driven in part by inefficient use of synthetic nitrogen (N) fertilizers in agriculture. Predicting soil N 2 O emissions is challenging due to high spatial and temporal variability arising from complex soil biogeochemical processes. Process-based ecosystem models and standalone machine learning (ML) approaches without extensive site-specific calibration often miss high-emission episodes. Here, we show how an Ensemble Modeling System (EMS) based on outputs from an ensemble of ecosystem models coupled to an ensemble of ML models can improve predictions and understanding of N 2 O fluxes from US cropland. Trained and validated on ~12,000 N 2 O chamber measurements at 17 US Midwest sites (six crops, 35 management practices), the EMS accurately predicted daily fluxes of N 2 O at both training (R 2 = 0.84, RMSE = 16.4 g N ha −1 d −1 ) and held-out testing sites (R 2 = 0.84, RMSE = 6.2 g N ha −1 d −1 ). Analyses identified six dominant N 2 O drivers: soil organic carbon (SOC), NH 4 + , NO 3 - , water-filled pore space, temperature, and aboveground biomass production. Wet, warm soils produced large N 2 O peaks only with sufficient SOC and mineral N; in low-SOC soils, fluxes remained low. Incorporating these drivers into process-based models might significantly improve their predictive capacity. The EMS demonstrates a strong potential to predict N 2 O fluxes at unseen sites, enabling more reliable regional inventories, improved gap-filling where measurements are sparse, and enhanced understanding of mechanisms to advance targeted mitigation strategies in food, feed, and bioenergy crops.

AI↗

DOE OSTI2020

Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine

A series of three new actinide tetrahalide coordination compounds containing 2,2'-bipyridinium (H 2 bpy) have been synthesized by room temperature evaporation and characterized via single crystal X-ray diffraction, Raman spectroscopy, and infrared spectroscopy. The solid-state compounds (Np1, U1, and U2) contain the AnO 2 2+ cation coordinated to four halide (chloride or bromide) atoms to form the anionic tetrahalide molecular unit [AnO 2 X 4 ] 2– (X = Cl, Br) and are charge balanced by the 2,2'-bipyridinium cations that engage in electrostatic interactions with the actinyl complex. Np1 (N 2 C 10 H 10 )[NpO 2 Cl 4 ] contains 2,2'-bipyridine in the cis conformation where both the nitrogen atoms are directed towards the [NpO 2 Cl 4 ] 2– monomer. Within U1 (N 2 C 10 H 9 )[UO 2 Cl 4 ], the 2,2'-bipyridine is in a trans conformation, and found in the same orientation in the isomorphous structure U2 (N 2 C 10 H 9 )[UO 2 Br 4 ]. The compounds were further characterized by vibrational spectroscopy with specific interest in the actinyl cation. Raman spectroscopy provided information on the actinyl symmetric stretch (ν 1 ) whereas IR spectroscopy is used to determine the location of the asymmetric stretch (ν 3 ). Here, spectral similarities are observed between the two isomorphous structures, but slight variations across the series of structures are found to be associated with bipyridine bands in the various conformations. Additional analysis of these vibrational features in U1 and U2 provided information on the actinyl force constants, allowing insight into the relative uranyl bond strength that was compared to similar tetrahalide compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Characterizing Complex Gas–Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe–N–C Catalysts

Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe–N–C) are receiving significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe–N–C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O 2 and a set of five structurally different Fe–N–C materials. Detailed characterization of the Fe speciation was performed with 57 Fe Mössbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L 3,2 -edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O 2 at 80 °C (O 2 -rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O 2 -rich. Correlation with Mössbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O 2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O 2 -rich. This implies that these sites have a weaker interaction with O 2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O 2 -rich environment. The nature of these weakly and strongly O 2 -adsorbing FeN x C y sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe–N–C materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Low-temperature formation of pyridine and (iso)quinoline via neutral–neutral reactions

Aromatic molecules represent fundamental building blocks in prebiotic chemistry and are contemplated as vital precursors to DNA and RNA nitrogen bases. However, despite the identification of some 300 molecules in extraterrestrial environments, the pathways to pyridine (C 5 H 5 N), pyridinyl (C 5 H 4 N•), and (iso)quinoline (C 9 H 7 N) – the simplest represen-tative of mono and bicyclic aromatic molecule carrying nitrogen – are elusive. Here, we afford compelling evidence on the gas-phase formation of methylene amidogen (H 2 CN•) and cyanomethyl (H 2 CCN•) radicals via molecular beam studies and electronic structure calcula-tions. The modeling of the chemistries of Taurus Molecular Cloud (TMC-1) and Titan’s atmosphere contemplates a complex chain of reactions synthesizing pyridine, pyridinyl, and (iso)quinoline from H 2 CN• and H 2 CCN• at levels of up to 75%. Furthermore, this study affords unique entry points to precursors of DNA and RNA nitrogen bases in hydrocarbon-rich extraterrestrial environments thus changing the way we think about the origin of prebiotic molecules in our Galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2025

In Situ Neutron Reflectometry Reveals the Interfacial Microenvironment Driving Electrochemical Ammonia Synthesis

Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li–N 2 R) is key for realizing efficient ammonia (NH 3 ) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li–N 2 R conditions. We found that the LiBF 4 -based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO 4 , highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF 4 -derived SEI under Li–N 2 R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm 2 ), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. Here, we used isotope contrast methods with d 6 -EtOH and d 8 -THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Microbial contribution to post-fire tundra ecosystem recovery over the 21st century

Abstract Tundra ecosystems have experienced an increased frequency of fire, and this trend is predicted to continue throughout the 21 st Century. Post-fire recovery is underpinned by complex interactions between microbial functional groups that drive nutrient cycling. Here we use a mechanistic model to demonstrate an acceleration of the nitrogen cycle post-fire driven by changes in niche space and microbial competitive dynamics. We show that over the first 5-years post-fire, fast-growing bacterial heterotrophs colonize regions of the soil previously occupied by slower-growing saprotrophic fungi. The bacterial heterotrophs mineralize organic matter, releasing nutrients into the soil. This pathway outweighs new sources of nitrogen and facilitates the recovery of plant productivity. We broadly show here that while consideration of distinct microbial metabolisms related to carbon and nutrient cycling remains rare in terrestrial ecosystem models, they are important when considering the rate of ecosystem recovery post-disturbance and the feedback to soil nutrient cycles on centennial timescales.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Site-specific generation of excited state wavepackets with high-intensity attosecond x rays

High-intensity attosecond x rays can produce coherent superpositions of valence-excited states through two-photon Raman transitions. The broad-bandwidth, high-field nature of the pulses results in a multitude of accessible excited states. Multiconfigurational quantum chemistry with the time-dependent Schrödinger equation is used to examine population transfer dynamics in stimulated x-ray Raman scattering of the nitric oxide oxygen and nitrogen K-edges. Two pulse schemes initiate wavepackets of different characters and demonstrate how chemical differences between core-excitation pathways affect the dynamics. The population transfer to valence-excited states is found to be sensitive to the electronic structure and pulse conditions, highlighting complexities attributed to the Rabi frequency. The orthogonally polarized two- color-pulse setup has increased selectivity while facilitating longer, less intense pulses than the one-pulse setup. Population transfer in the 1s → Rydberg region is more effective but less selective at the nitrogen K-edge; the selectivity is reduced by double core-excited states. Result interpretation is aided by resonant inelastic x-ray scattering maps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

The Story of 5d Metallocorroles: From Metal–Ligand Misfits to New Building Blocks for Cancer Phototherapeutics

Porphyrin chemistry is Shakespearean: over a century of study has not withered the field’s apparently infinite variety. Heme proteins continually astonish us with novel molecular mechanisms, while new porphyrin analogues bowl us over with unprecedented optical, electronic, and metal-binding properties. Within the latter domain, corroles occupy a special place, exhibiting a unique and rich coordination chemistry. The 5d metallocorroles are arguably the icing on that cake. New Zealand chemist Penny Brothers has used the word “misfit” to describe the interactions of boron, a small atom with a predilection for tetrahedral coordination, and porphyrins, classic square-planar ligands. Steve Jobs lionized misfits as those who see things differently and push humanity forward. Both perspectives have inspired us. The 5d metallocorroles are misfits in that they encapsulate a large 5d transition metal ion within the tight cavity of a contracted porphyrin ligand. Given the steric mismatch inherent in their structures, the syntheses of some 5d metallocorroles are understandably capricious, proceeding under highly specific conditions and affording poor yields. Three broad approaches may be distinguished. (a) In the metal–alkyl approach, a free-base corrole is exposed to an alkyllithium and the resulting lithio-corrole is treated with an early transition metal chloride; a variant of the method eschews alkyllithium and deploys a transition metal–alkyl instead, resulting in elimination of the alkyl group as an alkane and insertion of the metal into the corrole. This approach is useful for inserting transition metals from groups 4, 5, and, to some extent, 6, as well as lanthanides and actinides. (b) In our laboratory, we have often deployed a low-valent organometallic approach for the middle transition elements (groups 6, 7, 8, and 9). The reagents are low-valent metal–carbonyl or −olefin complexes, which lose one or more carbon ligands at high temperature, affording coordinatively unsaturated, sticky metal fragments that are trapped by the corrole nitrogens. (c) Finally, a metal acetate approach provides the method of choice for gold and platinum insertion (groups 10 and 11). This Account provides a first-hand perspective of the three approaches, focusing on the last two, which were largely developed in our laboratory. In general, the products were characterized with X-ray crystallography, electrochemistry, and a variety of spectroscopic methods. The physicochemical data, supplemented by relativistic DFT calculations, have provided fascinating insights into periodic trends and relativistic effects. An unexpected feature of many 5d metallocorroles, given their misfit character, is their remarkable stability under thermal, chemical, and photochemical stimulation. Many of them also exhibit long triplet lifetimes on the order of 100 μs and effectively sensitize singlet oxygen formation. Many exhibit phosphorescence in the near-infrared under ambient conditions. Furthermore, water-soluble ReO and Au corroles exhibit impressive photocytotoxicity against multiple cancer cell lines, promising potential applications as cancer phototherapeutics. We thus envision a bright future for the compounds as rugged building blocks for new generations of therapeutic and diagnostic (theranostic) agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

The Low-Lying Electronic States of NO 2 : Potential Energy and Dipole Surfaces, Bound States, and Electronic Absorption Spectrum

Nitrogen dioxide, NO 2 , is a free radical composed of the two most abundant elements in Earth’s atmosphere, nitrogen and oxygen, and is relevant to atmospheric and combustion chemistry. The electronic structure of even its lowest-lying states is remarkably complex, with various conical intersections and Renner–Teller pairings, giving rise to complex and perturbed vibronic states. Here we report some analysis of the 18 molecular states of doublet spin-multiplicity formed by combining ground-state N( 4 S u ) and O( 3 P g ) atoms. In this work, three-dimensional potential energy surfaces were fit at the MRCI(Q)-F12/VTZ-F12 level, describing the lowest four ($\tilde X$, $\tilde A$, $\tilde B$, and $\tilde C$) electronic states. A properties-based diabatization procedure was applied to accommodate the intersections, producing energies in a quasidiabatic representation and yielding couplings that were also fit into surfaces. The low-lying vibrational levels on the ground $\tilde X$ state were computed and compared with experimental measurements. Compared to experiment, the lowest 125 calculated vibrational levels (up to 8500 cm –1 above the zero-point energy) have a root-mean-squared error of 16.5 cm –1 . In addition, dipole moments for each of the lowest four electronic states—and the transition dipoles between them—were also computed and fit. With the coupled energy and dipole surfaces, the electronic spectrum was calculated in absolute intensity and compared with experimental measurements. Detailed structure in the experimental spectrum was successfully reproduced, and the total integrated intensity matches experiment to an accuracy of ~1.5% with no empirical adjustments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Present and Future Changes in Land‐Atmosphere Coupling of Water and Energy Over Extratropical Forest Regions

Abstract Couplings between land and the near surface atmosphere are modulated by interactions between soil conditions, vegetation dynamics, turbulent fluxes, and atmospheric properties. How the land‐atmosphere coupling responds to warming and elevated CO 2 are important for understanding the land surface carbon, energy, and water cycles. In this work, we documented this coupled land‐atmosphere network based on observations and the Energy Exascale Earth System Model (E3SM) simulations over extratropical forest ecosystems. We employed a transfer entropy approach and novel network metrics to reveal patterns and strength of the land‐atmosphere coupling under historical conditions and a future high emission scenario (SSP585). We found that, in observations, the present‐day extratropical forest coupling network has high network connectivity (72%–88% of the targeted processes are coupled). E3SM reasonably captured the extratropical forest coupling network (modeled network connectivity was 81%–96%) and predicted that the coupling strength would significantly increase by 28% (±3%) under warming and elevated CO 2 conditions. Furthermore, E3SM factorial coupled experiments suggested that warming enhanced soil nitrogen mineralization favoring plant nitrogen uptake and vegetation growth were responsible for the strengthening future land‐atmosphere coupling. This work provides new metrics to analyze and document complex couplings for coupled earth system processes and highlights the important roles soil nutrient availability and biogeochemistry have on land‐atmosphere coupling.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Subsurface Redox Interactions Regulate Ebullitive Methane Flux in Heterogeneous Mississippi River Deltaic Wetland

Abstract As interfaces connecting terrestrial and ocean ecosystems, coastal wetlands develop temporally and spatially complex redox conditions, which drive uncertainties in greenhouse gas emission as well as the total carbon budget of the coastal ecosystem. To evaluate the role of complex redox reactions in methane emission from coastal wetlands, a coupled reactive‐transport model was configured to represent subsurface biogeochemical cycles of carbon, nitrogen, and sulfur, along with production and transport of multiple gas species through diffusion and ebullition. This model study was conducted at multiple sites along a salinity gradient in the Barataria Basin at the Mississippi River Deltaic Plain. Over a freshwater to saline gradient, simulated total flux of methane was primarily controlled by its subsurface production and consumption, which were determined by redox reactions directly (e.g., methanogenesis, methanotrophy) and indirectly (e.g., competition with sulfate reduction) under aerobic and/or anaerobic conditions. At fine spatiotemporal scales, surface methane fluxes were also strongly dependent on transport processes, with episodic ebullitive fluxes leading to higher spatial and temporal variability compared to the gradient‐driven diffusion flux. Ebullitive methane fluxes were determined by methane fraction in total ebullitive gas and the frequency of ebullitive events, both of which varied with subsurface methane concentrations and other gas species. Although ebullition thresholds are constrained by local physical factors, this study indicates that redox interactions not only determine gas composition in ebullitive fluxes but can also regulate ebullition frequency through gas production.

03 NATURAL GAS↗

DOE OSTI2020

Tuned and screened range-separated hybrid density functional theory for describing electronic and optical properties of defective gallium nitride

We apply a hybrid density functional theory approach, based on a tuned and screened range-separated hybrid (SRSH) exchange-correlation functional, to describe the optoelectronic properties of defective gallium nitride (GaN). SRSH and time-dependent SRSH (TDSRSH) are tuned to produce accurate energetics for the pristine material and applied to the study of a series of point defects in bulk GaN, a blue light-emitting material that degrades in the presence of defects. We first establish the accuracy of the method by comparing the predicted quasiparticle gap and low-energy excitation spectra of (TD)SRSH and many-body perturbation theory for both pristine GaN and GaN containing a single nitrogen vacancy. Aided by the reduced computational cost of (TD)SRSH, we then report on three additional technologically relevant point defects and defect complexes in GaN: the gallium vacancy, the carbon interstitial, and the carbon-silicon complex. We compute the low-energy optical absorption spectra for these defects and show the presence of defect-centered transitions. Furthermore, by estimating the Stokes shift, we predict, in agreement with previous studies, that the carbon substitutional defect is a candidate for the detrimental yellow luminescence in GaN. Furthermore, this study indicates that TDSRSH is a promising and computationally feasible approach for quantitatively accurate, first-principles modeling of defective semiconductors.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Structural mechanism of Escherichia coli cyanase

Cyanase plays a vital role in the detoxification of cyanate and supplies a continuous nitrogen source for soil microbes by converting cyanate to ammonia and carbon dioxide in a bicarbonate-dependent reaction. The structures of cyanase complexed with dianion inhibitors, in conjunction with biochemical studies, suggest putative binding sites for substrates. However, the substrate-recognition and reaction mechanisms of cyanase remain unclear. Here, crystal structures of cyanase from Escherichia coli were determined in the native form and in complexes with cyanate, bicarbonate and intermediates at 1.5–1.9 Å resolution using synchrotron X-rays and an X-ray free-electron laser. Cyanate and bicarbonate interact with the highly conserved Arg96, Ser122 and Ala123 in the active site. Further, in the presence of a mixture of cyanate and bicarbonate, three different electron densities for intermediates were observed in the cyanase structures. Moreover, the observed electron density could explain the dynamics of the substrate or product. In addition to conformational changes in the substrate-binding pocket, dynamic movement of Leu151 was observed, which functions as a gate for the passage of substrates or products. These findings provide a structural mechanism for the substrate-binding and reaction process of cyanase.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Mechanistic Studies of a Primitive Homolog of Nitrogenase Involved in Coenzyme F430 Biosynthesis (Final Report)

03 NATURAL GAS↗

DOE OSTI2024

Mechanistic Studies of a Primitive Homolog of Nitrogenase Involved in Coenzyme F430 Biosynthesis

Methyl-coenzyme M reductase (MCR) is the key enzyme in the biological formation and anaerobic oxidation of methane (AOM). Methane is a potent greenhouse gas and the major component of natural gas. Given the abundance of natural gas reserves in remote areas, there is great current interest in a scalable bio-based process for the conversion of methane to liquid fuel or other high-value commodity chemicals. MCR holds much promise for use in such a methane bioconversion strategy. However, MCR cannot currently be produced in an active form in a heterologous host, due in large part to the lack of genetic and biochemical information about the production of holo MCR. In an effort to overcome this deficiency, our laboratory elucidated the biosynthetic pathway of the unique nickel-containing coenzyme of MCR, F430. The key step in coenzyme F430 biosynthesis (Cfb) was found to involve an unprecedented reductive cyclization reaction that converts Ni-sirohydrochlorin a , c -diamide to 15,17 3 -seco-F430-17 3 -acid. This remarkable transformation, which involves a 6-electron reduction of the isobacteriochlorin ring system, cyclization of the c -acetamide side chain to form a γ-lactam ring, and the formation of 7 stereocenters, is catalyzed by a primitive homolog of nitrogenase (CfbCD). Nitrogenase is a two-component metalloenzyme that catalyzes the ATP-dependent reduction of dinitrogen to ammonia (nitrogen fixation). Homologs of nitrogenase are also involved in the biosynthesis of the photosynthetic pigments chlorophyll and bacteriochlorophyll. Phylogenetic analysis of the CfbCD complex suggests that it is representative of a more ancient lineage of the nitrogenase superfamily, and a thorough investigation of its structure and function is likely to shed light on the mechanisms and evolution of these important metalloenzymes that catalyze multi-electron redox reactions. Moreover, a detailed understanding of the mechanism of the CfbCD complex may aid in the development of specific inhibitors to help reduce natural greenhouse gas emissions and can be exploited for the heterologous production of MCR for methane bioconversion. Towards these goals, the following Specific Aims will be pursued to determine the: 1) Identity of the CfbCD reaction product. The exact reaction catalyzed by CfbCD, including the number of electrons transferred and whether it involves enzymatic cyclization, is unclear. Several approaches, including reaction stoichiometry measurements, spectroelectrochemistry, and magnetic resonance spectroscopy will be applied to elucidate the structure of the reaction product and establish whether CfbCD is a reductase or reductive cyclase. 2) Structure, conformational dynamics, and oligomerization state changes of CfbCD. Significant insight into the mechanism and allosteric regulation of CfbCD can be obtained by assessing changes in the structure and dynamics of the complex during the catalytic cycle. To accomplish this, a combination of size-exclusion chromatography, hydrogen-deuterium exchange mass spectrometry, molecular dynamics simulations, and high-resolution structural methods will be employed. 3) Source, order, and stereochemistry of proton additions during CfbCD catalysis. Details regarding the order and stereochemistry of proton additions during the CfbCD reaction will be uncovered using a combined spectroscopic and computational approach. Complementary mechanistic studies employing site-directed mutagenesis and substrate analogs will establish the identity of active site acid residues and the possible involvement of substrate-assisted catalysis during the CfbCD reaction.

09 BIOMASS FUELS↗

DOE OSTI2023

Editorial for Special Issue “Advances in Soil Microbiome”

The soil microbiome (the community of all soil microorganisms and their surrounding environment) is a critical part of our ecological network. These microbial communities carry out several important functions, including the promotion of plant growth and the cycling of carbon and nitrogen sources. Despite the importance of this community, and the recent advances in multi-omic analysis and other methods designed to query complex systems, there is a still a large knowledge gap regarding the soil microbiome, its response to changing climates and moisture levels, the specific molecular mechanisms that drive its role in the environment, and how these questions can be answered through the use of model systems. Here, we present eleven new papers that seek to answer these questions and expand our knowledge of the soil microbiome.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Stabilization of a Heme-HNO Model Complex Using a Bulky Bis-Picket Fence Porphyrin and Reactivity Studies with NO

Nitroxyl, HNO/NO – , the one-electron reduced form of NO, is suggested to take part in distinct signaling pathways in mammals and is also a key intermediate in various heme-catalyzed NO x interconversions in the nitrogen cycle. Cytochrome P450nor (Cyt P450nor) is a heme-containing enzyme that performs NO reduction to N 2 O in fungal denitrification. The reactive intermediate in this enzyme, termed “Intermediate I”, is proposed to be an Fe-NHO/Fe-NHOH type species, but it is difficult to study its electronic structure and exact protonation state due to its instability. Here, we utilize a bulky bis-picket fence porphyrin to obtain the first stable heme-HNO model complex, [Fe(3,5-Me-BAFP)(MI)(NHO)], as a model for Intermediate I, and more generally HNO adducts of heme proteins. Due to the steric hindrance of the bis-picket fence porphyrin, [Fe(3,5-Me-BAFP)(MI)(NHO)] is stable (τ 1/2 = 56 min at -30 °C), can be isolated as a solid, and is available for thorough spectroscopic characterization. In particular, we were able to solve a conundrum in the literature and provide the first full vibrational characterization of a heme-HNO complex using IR and nuclear resonance vibrational spectroscopy (NRVS). Reactivity studies of [Fe(3,5-Me-BAFP)(MI)(NHO)] with NO gas show a 91 ± 10% yield for N 2 O formation, demonstrating that heme-HNO complexes are catalytically competent intermediates for NO reduction to N 2 O in Cyt P450nor. In conclusion, the implications of these results for the mechanism of Cyt P450nor are further discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗