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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 19 records

Pu-238 Production Progress at Idaho National Laboratory From December 2023 to November 2024

Idaho National Laboratory (INL) has continued in the effort to produce Pu-238 to support NASA deep space missions. In support of the production goal of contributing 700 g to the 1.5 kg per year constant rate production of Pu-238 heat source material in the United States by 2026. All available inner core positions of the Advanced Test Reactor (ATR) have been qualified for production for a 20% Np target, with efforts nearing completion for a 30% Np target further increasing production amounts. This includes the North East Flux Trap (NEFT), South Flux Trap (SFT), Inner A, H positions. With the completion of qualifying the inner core of ATR, work has started on the qualifying the outer core. The portion of the outer core that will produce Pu-238 includes the Large and Medium I positions. With the continued qualification work, INL is on track to contribute to the production goal by 2026.

07 - ISOTOPES AND RADIATION SOURCES↗

Refinery gas processing method

A process for hydrogen recovery from refinery gas system comprising supplying the refinery gas to an inlet manifold fluidly coupled to a conditioning stage, the conditioning stage comprising a reactor having a reforming catalyst deposited on an ultra-short-channel-length metal substrate; supplying oxidant to the conditioning stage via the inlet manifold; supplying steam from a steam generator to the conditioning stage via the inlet , manifold; reacting the refinery gas in the conditioning stage; and discharging a product through a discharge outlet fluidly coupled to the conditioning stage, the discharge outlet configured to flow the product for use by a downstream reformer. The process allows to either increase the H2 production rate or lower the firing rate while maintaining a constant H2 production rate for the downstream steam reformer, independent of the feed compositional variability of the refinery or still gas.

Vilekar, Saurabh↗

Mechanism and kinetics of the oxidation of 1,3-butadien-1-yl (n-C 4 H 5 ): a theoretical study

Here, ab initio CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the C 4 H 5 O 2 potential energy surface have been combined with Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations of temperature- and pressure-dependent rate constants and product branching ratios to unravel the mechanism and kinetics of the n-C 4 H 5 + O 2 reaction. The results indicate that the reaction is fast, with the total rate constant being in the range of 3.4–5.6 × 10 –11 cm 3 molecule –1 s –1 . The main products include 1-oxo-n-butadienyl + O and acrolein + HCO, with their cumulative yield exceeding 90% at temperatures above 1500 K. Two conformers of 1-oxo-n-butadienyl + O are formed via a simple mechanism of O 2 addition to the radical site of n-C 4 H 5 followed by the cleavage of the O–O bond proceeding via a van der Waals C 4 H 5 O∙∙∙O complex. Alternatively, the pathways leading to acrolein + HCO involve significant reorganization of the heavy-atom skeleton either via formal migration of one O atom to the opposite end of the molecule or its insertion into the C1–C2 bond. Not counting thermal stabilization of the initial peroxy adducts, which prevails at low temperatures and high pressures, all other products share a minor yield of under 5%. Rate constants for the significant reaction channels have been fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the oxidation of aromatic molecules and 1,3-butadiene. As a secondary reaction, n-C 4 H 5 + O 2 can be a source for the formation of acrolein observed experimentally in oxidation of the phenyl radical at low combustion temperatures, whereas another significant (secondary) product of the C 6 H 5 + O 2 reaction, furan, could be formed through unimolecular decomposition of 1-oxo-n-butadienyl. Both the n-C 4 H 5 + O 2 reaction and unimolecular decomposition of its 1-oxo-n-butadienyl primary product are shown not to be a substantial source of ketene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of Phenanthrene via Recombination of Indenyl and Cyclopentadienyl Radicals: A Theoretical Study

This work presents quantum chemical G3(MP2,CC)//B2PLYPD3/6-311G(d,p) calculations of the potential energy surface for the indenyl (C 9 H 7 ) + cyclopentadienyl (C 5 H 5 ) reaction followed by unimolecular decomposition of the C 14 H 11 radicals formed as the primary products, as well as the Rice–Ramsperger–Kassel–Marcus master equation (RRKM-ME) calculations to predict temperature- and pressure-dependent reaction rate constants and product branching ratios. The reaction begins with the barrierless recombination of indenyl and cyclopentadienyl forming a C 14 H 12 molecule with a new C–C bond connecting two five-membered rings, which subsequently dissociates to C 14 H 11 radicals by H losses. The primary products of the C 9 H 7 + C 5 H 5 → C 14 H 11 + H reaction can directly decompose by another H loss to benzofulvalene, and this pathway is most favorable in terms of the entropy factor and hence is preferable at higher temperatures. Otherwise, the initial C 14 H 11 isomers can undergo significant structural rearrangements before eliminating an H atom and producing phenanthrene, anthracene, or benzoazulenes, among which the formation of phenanthrene via the “spiran” pathway is clearly preferred. The calculated barriers along the computed favorable dissociation pathways are relatively low, in the ~30–40 kcal/mol range, making the C 14 H 11 radicals unstable at temperatures above 1000–1250 K at 1 atm. The results of RRKM-ME calculations show that, under typical combustion conditions, the decomposition of the C 14 H 11 radicals predominantly leads to benzofulvalene. However, the latter can be rapidly converted to phenanthrene via H-assisted isomerization with the rate constant for the benzofulvalene + H → phenanthrene + H reaction being close to 10 –11 cm 3 molecule –1 s –1 at 1000–1500 K and 1 atm. Here, the results provide further support for the hypothesis that recombination of two π radicals containing five-membered rings can lead to a growth of PAH with the formation of two fused six-membered rings, but the reaction mechanism may not be direct and is likely to involve two consecutive H atom losses leading to a fulvalene-like product, with subsequent H-assisted isomerization of the latter to a benzenoid PAH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

History of Pu-238 Production Restart Efforts at Idaho National Laboratory and Oak Ridge National Laboratory

In the early 2010s, efforts to restart production in the U.S. of plutonium-238 heat source (HSPu) material for NASA deep space missions were initiated. Processes, procedures, hardware, and chemical separations were developed and implemented to enable the production of heat source material at Oak Ridge National Laboratory (ORNL) and Idaho National Laboratory (INL). Here, this review provides an overview of the timeline and efforts associated with the restart of production, as well as upcoming efforts to increase production.

07 ISOTOPE AND RADIATION SOURCES↗

Theoretical study of the reaction mechanism and kinetics of the phenyl + propargyl association

Potential energy surface for the phenyl + propargyl radical recombination reaction has been studied at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G** level of theory for the closed-shell singlet species and at the triplet–singlet gap CASPT2/cc-pVTZ-CCSD(T)-F12/cc-pVTZ-f12//CASSCF/cc-pVTZ level of theory for the diradical species. High-pressure limit rate constants for the barrierless channels were evaluated with variable reaction coordinate transition state theory (VRC-TST). Rice–Ramsperger–Kassel–Marcus Master Equation (RRKM-ME) calculations have been performed to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. Here, the entrance channels of the radical association reaction produce 3-phenyl-1-propyne and phenylallene which can further dissociate/isomerize into a variety of unimolecular and bimolecular products. Theoretical evidence is presented that, at combustion relevant conditions, the phenyl + propargyl recombination provides a feasible mechanism for the addition of a second five-member ring to the first six-member aromatic ring producing the prototype two-ring species indene and indenyl. Rate expressions for all important reaction channels in a broad range of temperatures and pressures have been generated for kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of phenanthrenyl radicals via the reaction of acenaphthyl with acetylene

Ab initio G3(MP2,CC)/B3LYP/6–31G** calculations of the potential energy surface for the reaction of 3-acenaphthyl radical with acetylene were combined with Rice-Ramsperger-Kassel-Marcus Master Equation calculations of the temperature- and pressure-dependent reaction rate constants and product branching ratios with the goal to examine the transformation of an edge five-membered ring into a six-membered one. The reaction mechanism has been shown to contain two stages: (1) the formation of 3-ethynylacenaphthylene + H in the 3-acenaphthyl + C 2 H 2 reaction via acetylene addition to the radical site and an H loss, (2) the formation of the 1-phenanthrenyl radical in the 3-ethynylacenaphthylene + H reaction via H addition to the five-membered ring followed by the ring flip. The results of kinetic modeling show this pathway being faster than the pathway proposed earlier featuring the CCH chemisorption on the six-membered ring without involvement of the five-membered ring. A kinetic test demonstrated the dominance of the former pathway for the formation of pyrene from naphthalene. Here, it is expected that the new mechanism plays a major role in the transformation of five-membered rings on edges of PAH structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical Study of the Phenoxy Radical Recombination with the O( 3 P) Atom, Phenyl plus Molecular Oxygen Revisited

Quantum chemical calculations of the C 6 H 5 O 2 potential energy surface (PES) were carried out to study the mechanism of the phenoxy + O( 3 P) and phenyl + O 2 reactions. CASPT2(15e,13o)/CBS//CASSCF(15e,13o)/DZP multi-reference calculations were utilized to map out the minimum energy path for the entrance channels of the phenoxy + O( 3 P) reaction. Stationary points on the C 6 H 5 O 2 PES were explored at the CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311++G** level for the species with a single-reference character of the wave function and at the CASPT2(15e,13o)/CBS//B3LYP/6-311++G** level of theory for the species with a multi-reference character of the wave function. Conventional, variational, and variable reaction coordinate transition state theories were employed in Rice-Ramsperger-Kassel-Marcus Master Equation calculations to assess temperature- and pressure-dependent phenomenological rate constants and product branching ratios. Here, the main bimolecular product channels of the phenoxy + O( 3 P) reaction are concluded to be para/ortho-benzoquinone + H, 2,4-cyclopentadienone + HCO, and, at high temperatures, also phenyl + O 2 . The main bimolecular product channels of the phenyl + O 2 reaction include 2,4-cyclopentadienone + HCO at lower temperatures, and phenoxy + O( 3 P) at higher temperatures. Both for the phenoxy + O( 3 P) and phenyl + O 2 reactions, the collisional stabilization of peroxybenzene at low temperatures and high pressures competes with the bimolecular product channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimization of Solid Oxide Electrolysis Cell Systems Accounting for Long-Term Performance and Health Degradation

This study focuses on optimizing solid oxide electrolysis cell (SOEC) systems for efficient and durable long-term hydrogen (H2) production. While the elevated operating temperatures of SOECs offer advantages in terms of efficiency, they also lead to chemical degradation, which shortens cell lifespan. To address this challenge, dynamic degradation models are coupled with a steady-state, two-dimensional, non-isothermal SOEC model and steady-state auxiliary balance of plant equipment models, within the IDAES modeling and optimization framework. A quasi-steady state approach is presented to reduce model size and computational complexity. Long-term dynamic simulations at constant H2 production rate illustrate the thermal effects of chemical degradation. Dynamic optimization is used to minimize the lifetime cost of H2 production, accounting for SOEC replacement, operating, and energy expenses. Several optimized operating profiles are compared by calculating the Levelized Cost of Hydrogen (LCOH).

Giridhar, Nishant↗

Optimization of Solid Oxide Electrolysis Cell Systems Accounting for Long-Term Performance and Health Degradation

This study focuses on optimizing solid oxide electrolysis cell (SOEC) systems for efficient and durable long-term hydrogen (H2) production. While the elevated operating temperatures of SOECs offer advantages in terms of efficiency, they also lead to chemical degradation, which shortens cell lifespan. To address this challenge, dynamic degradation models are coupled with a steady-state, two-dimensional, non-isothermal SOEC model and steady-state auxiliary balance of plant equipment models, within the IDAES modeling and optimization framework. A quasi-steady state approach is presented to reduce model size and computational complexity. Long-term dynamic simulations at constant H2 production rate illustrate the thermal effects of chemical degradation. Dynamic optimization is used to minimize the lifetime cost of H2 production, accounting for SOEC replacement, operating, and energy expenses. Several optimized operating profiles are compared by calculating the Levelized Cost of Hydrogen (LCOH).

Giridhar, Nishant↗

Effect of Strength of Soluble and Solid Acid Catalysts on Selectivity in Aldol Reactions

Aldol reactions can follow the classical condensation path and produce an α,β-unsaturated carbonyl compound and water, however in some cases, aldol chemistry may be steered towards a fission that gives an olefin and a carboxylic acid. This investigation examines how the strength of Brønsted acid sites—both in homogeneous and heterogeneous catalysis—controls these two pathways and their kinetics. The cross-aldol reaction between benzaldehyde and 3-pentanone served as test case. Batch reactions, conducted in toluene as solvent at a temperature of 140 °C under autogenous pressure, were analyzed by GC and in situ ATR-FTIR spectroscopy to determine product distributions and rate constants for condensation and fission pathways. A series of soluble acids including a family of sulfonic acids mostly favored the condensation pathway, with formic acid as the weakest in the series by its pKa being inactive for aldol chemistry. Significant amounts of fission products were rare except for the known selectivity of phosphoric acid, and the circumstances were difficult to delineate. For the sulfonic acid family, the logarithm of the first-order condensation rate constants scaled only roughly with pKa (water) values, whereas a good correlation was obtained with calculated deprotonation Gibbs energies in toluene. A series of H-forms of isomorphously substituted beta zeolites, HESiBEA with E = Al, Ga, Fe, or B, favored the fission pathway. Site density and site strength were characterized by calorimetric measurements of the heats of adsorption of isopropylamine, which decreased in the order Al > Ga, Fe > B. The logarithm of the site-normalized first-order fission rate constants scaled roughly with the heats of adsorption and correlated excellently with reported deprotonation energies. In conclusion, acid strength mainly affects activity and can be seen as a pre-requisite for either aldol condensation or fission chemistry, whereas additional, yet to be full clarified catalyst properties and reaction conditions are required to steer aldol chemistry towards fission selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of acenaphthalene to phenalene via methylation: A theoretical study

Ab initio calculations of the C 13 H 10 and C 13 H 9 potential energy surfaces related to the reaction of 1-acenaphthyl and methyl radicals and secondary isomerization of C 13 H 9 primary radical products have been performed at the chemically accurate G3(MP2,CC)//B3LYP/6-311G** level of theory to unravel the mechanism of conversion of acenaphthalene to phenalene or phenalenyl radical + H. The computed energetics and molecular parameters were utilized in Rice-Ramsperger-Kassel-Marcus Master Equation (RRKM-ME) calculations of reaction rate constants and relative product yields. The 1-acenaphthyl + CH 3 reaction is predicted to proceed by a fast radical-radical recombination mechanism and to predominantly produce collisionally stabilized 1-methylacenaphthalene B1 or a C 13 H 9 benzylic radical A1 + H with exothermicities of 106.8 and 25.2 kcal/mol, respectively. The A1 + H channel is preferable at higher temperatures, whereas the stabilization of 1-methylacenaphthalene is favored at higher pressures. The radical A1 can nearly irreversibly interconvert to phenalenyl radical AP via a 22.7 kcal/mol exothermic isomerization process involving formal insertion of the CH 2 group into a C-C bond of the five-member ring leading to the expansion of this ring to a six-member ring. The rate constants for the H addition reaction to phenalenyl radical to form phenalene and the reverse H loss from phenalene were also computed and the strength of the weakest C-H bond in the CH 2 group of phenalene is evaluated as 62.2 kcal/mol. The analysis of the reaction kinetics allowed us to deduce a mechanism for the conversion of 1-acenaphthyl radical to phenalene or phenalenyl radical + H via methylation involving the formation of A1 via a well-skipping channel or stabilization and dissociation of (or H abstraction from) B1 followed by isomerization of A1 to phenalenyl AP, which can add an H atom producing phenalene. As a result, rate constants for the significant elementary reactions are fitted to modified Arrhenius expressions and are proposed for kinetic modeling of the expansion of a five-member ring on a zigzag edge of PAH to a six-member ring by methylation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Algal Biofoundries for the Production of Polyurethane Precursors

The primary goal of the BEEPs project was to develop a process that could accelerate the development of algae as bioproduction platforms, from initial chemical product concept to an economically viable market supply. Under this program we elected to develop strains of algae that could generate polyurethane precursors, while simultaneously developing basic genetic tools to enable improved algal production systems. This program was specifically designed to incorporate National Laboratories as a means to utilize the expertise and facilities for new bio-production platforms. To that end, we designed a program to collaborate with the Agile BioFoundry at Lawrence Berkeley National Laboratory (LBNL) and computational platforms at Pacific Northwest National Laboratory (PNNL). In addition to these National Laboratory partners, we also had academic partners from UC Davis and Georgia Tech, as well as commercial partners Algenesis Materials and BASF. To achieve these goals, we initially focused on developing the genetic tools and high throughput screening technologies necessary to generate and assess production of polymer precursors (succinic acid) in algae and cyanobacteria, including advanced promoters and biosensors. In parallel, we computationally identified potential production bottlenecks and then used the developed genetic tools to increase production rates and yields. Constant feedback of data was used in conjunction with machine learning, high-throughput cell sorting, and synthetic biology, for additional targeted metabolic engineering. Multiple rounds of tool design, building, testing, and learning were supplied to partners at PNNL and LBNL to develop new models and tools that could expedite bioproduction platform development and increase yield performance. We targeted, and achieved, the FOA requirement yield metric of 20 g/L, as a milestone and deliverable from at least one of our engineered strains for the production of succinic acid.

09 BIOMASS FUELS↗

Solar Ammonia Production via Novel Two-step Thermochemical Looping of a Co 3 Mo 3 N/Co 6 Mo 6 N pair [Slides]

Ternary nitrides in the family A 3 B x N (A=Co, Ni, Fe; B=Mo; x=2,3) identified and synthesized. Experiments with Co 3 Mo 3 N in Ammonia Synthesis Reactor demonstrate cyclable NH3 production from bulk nitride under pure H 2 . Production rates were approx. constant in all the reduction steps with no evident dependence on the consumed solid-state nitrogen up to formation of 661. Material can be re-nitridized under pure N 2 (or 10% H 2 /N 2 ). Bulk N utilization per reduction step averaged between 25 – 40% of the total (2-3 hours). Rate equations and parameters extracted from data. NH 3 selectivity exceeds gas phase equilibrium at higher temperatures (in a large excess of H 2 ). Selectivity begins to decrease significantly above 650 C, N 2 production rapidly increases above 650 C seemingly due to reaction that is zero order in H 2 (thermal reduction of the nitride?). Poised to begin the systematics studies of relationships between materials and reactions.

14 SOLAR ENERGY↗

Mechanistic investigation of the aerobic oxidation of 2-pyridylacetate coordinated to a Ru(ii) polypyridyl complex

A new ruthenium polypyridyl complex, [Ru(bpy) 2 (acpy)] + (acpy = 2-pyridylacetate, bpy = 2,2'-bipyridine), was synthesized and fully characterized. Distinct from the previously reported analog, [Ru(bpy) 2 (pic)] + (pic = 2-pyridylcarboxylate), the new complex is unstable under aerobic conditions and undergoes oxidation to yield the corresponding α-keto-2-pyridyl-acetate (acpyoxi) coordinated to the Ru II center. The reaction is one of the few examples of C–H activation at mild conditions using O 2 as the primary oxidant and can provide mechanistic insights with important implications for catalysis. Theoretical and experimental investigations of this aerobic oxidative transformation indicate that it takes place in two steps, first producing the α-hydroxo-2-pyridyl-acetate analog and then the final product. The observed rate constant for the first oxidation was in the order of 10 -2 h -1 . The reaction is hindered in the presence of coordinating solvents indicating the role of the metal center in the process. Theoretical calculations at the M06-L level of theory were performed for multiple reaction pathways in order to gain insights into the most probable mechanism. Our results= indicate that O 2 binding to [Ru(bpy) 2 (acpy)] + is favored by the relative instability of the six-ring chelate formed by the acpy ligand and the resulting Ru III -OO˙- superoxo is stabilized by the carboxylate group in the coordination sphere. C–H activation by this species involves high activation free energies (ΔG ‡ = 41.1 kcal mol -1 ), thus the formation of a diruthenium μ-peroxo intermediate, [(Ru III (bpy) 2 (O-acpy)) 2 O 2 ] 2+ via interaction of a second [Ru(bpy) 2 (acpy)] + was examined as an alternative pathway. The dimer yields two Ru IV =O centers with a low ΔG ‡ of 2.3 kcal mol -1 . The resulting Ru IV =O species can activate C–H bonds in acpy (ΔG ‡ = 23.1 kcal mol -1 ) to produce the coordinated α-hydroxo-2-pyridylacetate. Further oxidation of this intermediate leads to the α-keto-2-pyridyl-acetate product. The findings provide new insights into the mechanism of C–H activation catalyzed by transition-metal complexes using O 2 as the sole oxygen source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic studies of excited singlet oxygen atom O( 1 D) reactions with ethanol

In this work, themultichannel reaction of excited singlet oxygen atom with ethanol, O( 1 D) + C 2 H 5 OH (1), was studied in a photolysis flow reactor coupled with mid-infrared Faraday rotation spectroscopy (FRS) and UV-IR direct absorption spectroscopy (DAS) at 297 K with reactor pressures of 60, 120, and 150 Torr (bath He). The excited singlet oxygen atom was generated through the photolysis of O 3 at 266 nm. The photon flux and O( 1 D) concentrations were determined by in situ actinometry based on O 3 depletion. Temporal profiles of OH and H 2 O were monitored via DAS signals at ca. 3568.62 and 3568.29 cm –1 , while temporal profiles of HO 2 were measured via FRS signals at ca. 1396.90 cm –1 . The branching ratios of the target reaction (1) were determined by fitting temporal profiles to simulations from an in-house reaction mechanism. Two major reaction channels were identified as CH 3 CHOH + OH and CH 3 O + CH 2 OH, and their branching ratios were determined as 0.46 ± 0.12 and 0.42 ± 0.11, respectively. A specific HO 2 + RO 2 reaction between HO 2 and O 2 CH 2 CH 2 OH (β-RO 2 ) at the low-temperature range is estimated in this work as HO 2 + O 2 CH 2 CH 2 OH → products with a rate constant of 7 × 10 –12 cm 3 molecule –1 s –1 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactivity of the Hydrated Electron

Hydrated electrons are created in virtually every radiation environment and in many photochemical or electrochemical environments where liquid water is present, so their reaction products and reaction rate constants are naturally important in applications. Thanks to the strong optical absorbance of (e - ) aq , these rate constants are easy to measure, and a large database has been accumulated. It is not generally appreciated that no working theory of hydrated electron reaction rates presently exists. We discuss key experimental observations of hydrated electron reactions in the context of recent progress in theoretical and simulation developments toward understanding them, made possible by ever increasing computational power.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NfoR: Chromate Reductase or Flavin Mononucleotide Reductase?

Soil bacteria can detoxify Cr(VI) ions by reduction. Within the last 2 decades, numerous reports of chromate reductase enzymes have been published. These reports describe catalytic reduction of chromate ions by specific enzymes. These enzymes each have sequence similarity to known redox-active flavoproteins. We investigated the enzyme NfoR from Staphylococcus aureus, which was reported to be upregulated in chromate-rich soils and to have chromate reductase activity (H. Han, Z. Ling, T. Zhou, R. Xu, et al., Sci Rep 7:15481, 2017, https://doi.org/10.1038/s41598-017-15588-y). We show that NfoR has structural similarity to known flavin mononucleotide (FMN) reductases and reduces FMN as a substrate. NfoR binds FMN with a dissociation constant of 0.4 μM. The enzyme then binds NADPH with a dissociation constant of 140 μM and reduces the flavin at a rate of 1,350 s -1 . Turnover of the enzyme is apparently limited by the rate of product release that occurs, with a net rate constant of 0.45 s -1 . The rate of product release limits the rate of observed chromate reduction, so the net rate of chromate reduction by NfoR is orders of magnitude lower than when this process occurs in solution. We propose that NfoR is an FMN reductase and that the criterion required to define chromate reduction as enzymatic has not been met. That NfoR expression is increased in the presence of chromate suggests that the survival adaption was to increase the net rate of chromate reduction by facile, adventitious redox processes.

59 BASIC BIOLOGICAL SCIENCES↗