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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Electrical Conductivities and Association Constants in Dilute Aqueous NdCl 3 Solutions from 298 to 523 K along an Isobar of 25 MPa

Here, electrical measurements were performed in dilute aqueous NdCl 3 solutions from 298 to 523 K along the 25 MPa isobar to obtain limiting conductivities and association constants. The specific conductivity data were estimated using a continuous flow cell and a Markov Chain Monte Carlo (MCMC) correction algorithm. The limiting conductivities for the salts in water were derived by regressing the mean spherical approximation model and speciation analyses based on the MCMC algorithm and the deep earth water model. The limiting conductivities derived from the experimental data were correlated using the Zimmerman-Arcis-Tremaine correlation and agreed well with a predictive correlation proposed by Smolyakov, Anderko, and Lencka. Only the first association constant between neodymium and chloride could be derived at low temperatures (<373 K) due to the apparent large statistical uncertainty of the second association constant. Above 373 K, both association constants could be derived and show a reasonable agreement with Migdisov and Williams-Jones and Gammons et al.

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

Effect of Pressure on Crystal Structure and Phonon Density of States of FeSi

The strongly correlated material FeSi displays several unusual thermal, magnetic, and structural properties under varying pressure-temperature (P-T) conditions. It is a potential thermoelectric alloy and a material with several geochemical implications as a possible constituent at the Earth's core-mantle boundary (CMB). Previous theoretical studies predicted a pressure-induced B20-B2 transition at ambient temperature below 40 GPa; however, experimentally, the structural transition is observed only at high P-T conditions. In this study, we have performed high-pressure powder X-ray diffraction (XRD) up to 90 GPa and Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements up to 120 GPa to understand the phase stability and lattice dynamics. Our study provides evidence for a non-hydrostatic stress-induced B20-B2 transition in FeSi at around 36 GPa. We deduced the Fe partial phonon density of states (PDOS) and thermal parameters from NRIXS measurements up to 120 GPa and compared them with density functional theory (DFT) calculations. Furthermore, the computations show pressure-induced metallization and the band gap closing around 12 GPa.

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

Resonant Tender X-ray Scattering for Disclosing the Backbone Conformation of Conjugated Polymers

The backbone conformation of conjugated polymers (CPs) is essential to their performance in electronic applications. Contrast-variation small-angle neutron scattering (CV-SANS) techniques were used to assess the CP’s backbone conformation, which relies on synthesis of deuterated polymers. Such a technique has been proven mature and effective. One drawback is that deuteration labeling might subtly alter polymer’s physical properties due to structural modifications. To address these challenges, we introduce a novel approach utilizing tender Xray scattering near the sulfur K-edge to distinctly evaluate the backbone versus whole chain conformation for a low-bandgap donor−acceptor CP, poly[(5,6-difluoro- 2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-dialkyl-2,2′;5′,2″;5″,2‴-quaterthiophen-5,5‴- diyl)] (PffBT4T). For PffBT4T dissolved in trimethylbenzene (TMB), the sulfur K-edge is identified at approximately 2477 eV using near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Tender X-ray scattering conducted at presulfur K-edge and on-sulfur K-edge at elevated temperatures facilitated the distinction between the backbone and whole chain conformations. The results demonstrate that for highly flexible polymer, the backbone’s persistence length could be lower than that of the whole chains, suggesting a more flexible backbone. This rapid, label-free method enhances our ability to characterize CP’s backbone conformation efficiently, offering significant implications for the design and optimization of CPs for advanced electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Machine Learning Framework for Characterizing Processing–Structure Relationship in Block Copolymer Thin Films

The morphology of block copolymers (BCPs) critically influences material properties and applications. This work introduces a machine learning (ML)-enabled, high-throughput framework for analyzing grazing incidence small-angle X-ray scattering (GISAXS) data and atomic force microscopy (AFM) images to characterize BCP thin film morphology. A convolutional neural network was trained to classify AFM images by surface features, achieving 97% testing accuracy. Classified images were then analyzed to extract 2D grain size measurements from the samples in a high-throughput manner. ML models were trained to predict domain orientation based on processing parameters such as solvent ratio, additive type, and additive ratio. GISAXS-based properties were predicted with strong performances (R 2 > 0.75), while AFM-based property predictions were less accurate (R 2 < 0.60), likely due to the localized nature of AFM measurements compared to the bulk information captured by GISAXS. Beyond model performance, interpretability was addressed using SHapley Additive exPlanations (SHAP). SHAP analysis revealed that the additive ratio had the largest impact on morphological predictions, where additive provides the BCP chains with increased volume to rearrange into thermodynamically favorable morphologies. This interpretability helps validate model predictions and offers insight into parameter importance. Altogether, the presented framework combining high-throughput characterization and interpretable ML offers an approach to exploring and optimizing BCP thin film morphology across a broad processing landscape.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Mechanisms of Metal Additive-Induced Ordering During SNIPS Membrane Formation

Isoporous membranes can be fabricated by combining self-assembly with nonsolvent induced phase separation (SNIPS) using an amphiphilic block copolymer like polystyrene-b-poly(4-vinylpyridine) (SV). Poly(4-vinylpyridine) (V) is known to complex with metal salts, which are hypothesized to stabilize solution ordering and preserve structure during casting. We explored how the molar ratio of metal additive to the poly(4-vinylpyridine) block affected the final membrane morphology via scanning electron microscopy (SEM). Dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and in situ grazing-incidence SAXS were used to track changes in solution ordering and chain conformation as a function of the molar ratio of the additive to the V block. Additives induced aggregation, promoted the formation of more compact conformations in solution, and facilitated micelle ordering onto lattices at optimal ratios. Furthermore, these experimental results were supported by random phase approximation calculations, which helped explain how the thermodynamic order–disorder transition shifts with additive binding strength. Stronger additive–polymer interactions reduced the block copolymer volume fraction required for ordering in solution, allowing ordered domains to form at lower polymer concentrations.

Additives↗
DOE OSTI2021

Signature of Many-Body Localization of Phonons in Strongly Disordered Superlattices

Many-body localization (MBL) has attracted significant research attention due to its immunity to thermalization, role in logarithmic entanglement entropy growth, and opportunities to reach exotic quantum orders. However, experimental realization of MBL in solid-state systems has remained challenging. Here we report evidence of a possible phonon MBL phase in disordered GaAs/AlAs superlattices. Through grazing-incidence inelastic X-ray scattering, we observe a strong deviation of the phonon population from equilibrium in disordered samples doped with ErAs nanodots at low temperature, signaling a departure from thermalization. This behavior occurs within finite phonon energy and wavevector windows, suggesting a localization-thermalization crossover. We support our observation by proposing a theoretical model for the effective phonon Hamiltonian in disordered superlattices, and showing that it can be mapped exactly to a disordered 1D Bose-Hubbard model with a known MBL phase. The large on-site repulsion qualitatively explains the experimental findings. Furthermore, our work provides mode-resolved experimental evidence of phonon localization, potentially extending the scope of MBL to disordered solid-state systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Surface Dynamics of Charge Transport in LaAlO 3 /SrTiO 3 with Time-Resolved Kelvin Probe Force Microscopy

Time-resolved Kelvin probe force microscopy (tr-KPFM) was used to map surface potential dynamics in LAO/STO under its critical thickness, where it acts as an insulator, as polarizing and depolarizing electric fields were applied to planar electrodes in ambient conditions. Two time constants, for polarization and relaxation (i.e., depolarization) each, were derived and were shown to be independent of the direction of electrical field, revealing the reproducibility and recovery of the surfaces. Ambient aging or recent electrical history did not change the surface kinetics as determined by tr-KPFM. During polarization, the faster time constant (~3–6 s) is likely associated with the transport of H+ ions through the full length of the channel. The slower time constant (~40–50 s), on the other hand, is observed across only half the channel width near the higher-potential–more positive–electrode, which is likely associated with an electrochemical reaction such as the dissociation of water. This slower time constant drops to ~10–20 s toward the middle of the channel which could represent the transport of OH– ions. Furthermore, during relaxation, the fast time constant is consistent with polarization and is correlated to the same mechanism while the slower time constant is higher than it was during polarization and may represent the reabsorption of moisture from the atmosphere.

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

Visualizing Charge Transport and Nanoscale Electrochemistry by Hyperspectral Kelvin Probe Force Microscopy

Charge-transport and electrochemical processes are heavily influenced by the local microstructure. Kelvin probe force microscopy (KPFM) is a widely used technique to map electrochemical potentials at the nanometer scale; however, it offers little information on local charge dynamics. In this study, we implement a hyperspectral KPFM approach for spatially mapping bias-dependent charge dynamics in timescales ranging from the sub-millisecond to the second regime. As a proof of principle, we investigate the role mobile surface charges play in a three-unit-cell LaAlO 3 /SrTiO 3 oxide heterostructure. We explore machine learning approaches to assist with visualization, pattern recognition, and interpretation of the information-rich data sets. Linear unmixing methods reveal hidden bias-dependent interfacial processes, most likely water splitting, which are essentially unnoticed by functional fitting of the dynamic response alone. Hyperspectral KPFM will be beneficial for investigating nanoscale charge transport and local reactivity in systems involving a possible combination of electronic, ionic, and electrochemical phenomena.

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

Multicaloric Cryocooling Using Heavy Rare-Earth Free La(Fe,Si) 13 -Based Compounds

The transition toward a carbon-neutral society based on renewable energies goes hand in hand with the availability of energy-efficient technologies. Here, magnetocaloric cooling is a very promising refrigeration technology to fulfill this role regarding cryogenic gas liquefaction. However, the current reliance on highly resource critical, heavy rare-earth-based compounds as magnetocaloric material makes global usage unsustainable. Here, we aim to mitigate this limitation through the utilization of a multicaloric cooling concept, which uses the external stimuli of isotropic pressure and magnetic field to tailor and induce magnetostructural phase transitions associated with large caloric effects. In this study, La 0.7 Ce 0.3 Fe 11.6 Si 1.4 is used as a nontoxic, low-cost, low-criticality multiferroic material to explore the potential, challenges, and peculiarities of multicaloric cryocooling, achieving maximum isothermal entropy changes up to −28 J (kg K) −1 in the temperature range from 190 K down to 30 K. Thus, the multicaloric cooling approach offers an additional degree of freedom to tailor the phase transition properties and may lead to energy-efficient and environmentally friendly gas liquefaction based on designed-for-purpose, noncritical multiferroic materials.

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

First-Principles Assessment of ZnTe and CdSe as Prospective Tunnel Barriers at the InAs/Al Interface

Majorana zero modes are predicted to emerge in semiconductor/ superconductor interfaces, such as InAs/Al. Majorana modes could be utilized for fault tolerant topological qubits. However, their realization is hindered by materials challenges. The coupling between the superconductor and the semiconductor may be too strong for Majorana modes to emerge, due to effective doping of the semiconductor by the metallic contact. This could be mediated by adding a tunnel barrier of controlled thickness. We use density functional theory (DFT) with Hubbard U corrections, whose values are machine-learned via Bayesian optimization (BO), to assess ZnTe and CdSe as prospective tunnel barriers for the InAs/Al interface. The results of DFT +U(BO) for ZnTe are validated by comparison to angle resolved photoemission spectroscopy (ARPES). We then study bilayer interfaces of the three semiconductors with each other and with Al, as well as trilayer interfaces with a varying number of ZnTe or CdSe layers inserted between InAs and Al. We find that 16 atomic layers of either material completely insulate the InAs from metal induced gap states (MIGS). However, ZnTe and CdSe differ significantly in their band alignment, such that ZnTe forms an effective barrier for electrons, whereas CdSe forms a barrier for holes. Because of Fermi level pinning in the conduction band at the interface, only electron transport is relevant for InAs-based Majorana devices. Therefore, ZnTe is the better choice. Based on the results of our simulations, we suggest conducting experiments with ZnTe barriers in the thickness range of 6–18 atomic layers.

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

Identification of In Situ Generated High-Spin Fe(II)-N 4 Active Sites for Acidic Oxygen Reduction Reaction via Operando 57 Fe Mössbauer Spectroscopy

Iron-nitrogen-carbon (FeNC) catalysts are considered among the most promising alternative to Pt catalysts in acidic oxygen reduction reaction (ORR), yet the geometric and electronic structures of the true active site under reaction conditions have not been clearly elucidated. Herein, we synthesized a representative FeNC catalyst by pyrolyzing Fe 3+ absorbed on ZIF-8-derived N-doped carbon at a mild temperature under the H 2 /Ar atmosphere, where a formation mechanism of FeN 4 sites through a Zn-mediated Fe nanoparticle atomization process was proposed. The resulting FeNC-750 catalyst shows high acidic ORR activity with a half-wave potential of 0.838 V and a peak power density of 1 W cm -2 in proton-exchange membrane fuel cell (PEMFC). By using operando 57 Fe Mössbauer spectroscopy on FeNC-750, it was revealed that the pyrrolic N-coordinated high-spin Fe 2+ N 4 sites, which are in situ generated from high-spin Fe 3+ N 4 during ORR, are identified as catalytic active states. Density functional theory calculations further verified that, compared to the pyridinic N-coordinated low-spin Fe 2+ N 4 , the pyrrolic N-coordinated high-spin Fe 2+ exhibits optimized adsorption energy for reaction intermediates, thereby lowering the energy barrier of the rate-determining step (RDS) and facilitating OH* desorption. In conclusion, this work provides both experimental and theoretical evidence of the true active site in the FeNC during acidic ORR, offering significant insights for the rational design of high-performance materials for acidic fuel cells.

FeNC catalyst↗
DOE OSTI2021

Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ 41 K and δ 87 Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.

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

Hg Accumulation by Single-Cell Sulfate-Reducing Bacteria Methylating Mercury

Methylmercury (MeHg) is a potent neurotoxin that poses risks to ecosystems and human health. MeHg is produced by microbes following saturating-like kinetics. We hypothesize that this saturation reflects a limited intracellular mercury (Hg) accumulation. Here, in this study, we investigated Hg accumulation in Pseudodesulfovibrio hydrargyri BerOc1, a sulfate-reducing model strain able to methylate Hg. Cells were incubated with 0.5 and 2 μM of mercury (HgCl 2 ), and mercury localization was studied using synchrotron-based nano-X-ray fluorescence and high-resolution analytical electron microscopy. For both concentrations, Hg was detected in the bacterial cytosol, in addition to extracellular (Hg, S)-containing nanoparticles. Intracellular Hg levels were slightly higher at 2 μM than at 0.5 μM (1.61 vs 1.40 pg.mm –2 ), suggesting a regulated accumulation. However, the population exhibited heterogeneity in Hg accumulation, particularly at the highest Hg exposure, with some cells being Hg hyperaccumulators. Correlative imaging between Hg localization and cell viability revealed that these hyperaccumulating cells were non-active. Our results suggest that active cells regulate Hg accumulation. From an analytical perspective, a minor subpopulation of hyperaccumulating cells can bias bulk measurements and should be considered in interpreting Hg accumulation in microorganisms. Environmentally, these cells can impact Hg cycling by acting as a metal sink.

Intracellular accumulation↗
DOE OSTI2026

Oligoether-Functionalized PEDOT: Combining an EDOT Backbone with Polar Side Chains for Solution Processability and High Electrical Conductivity

Conjugated polymers functionalized with oligoether (OE)-based side chains are a key class of materials for various organic electronic applications, including transparent electrodes, thermoelectrics, electrochromic displays, and electrochemical transistors. Herein, we report a highly soluble OE-functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) homopolymer, prepared by direct (hetero)arylation polymerization, which allows solution processing to yield films with comparable redox properties to oxidatively polymerized PEDOT. This polymer, PEDOT(OE3), when optimally oxidatively doped, reaches among the highest electrical conductivities of any OE-functionalized polymer and is comparable to more synthetically complex OE-functionalized polymers. X-ray scattering and spectroscopy were utilized to rationalize the transport properties resulting from varying the doping level. Comparison of PEDOT(OE3) to a series of OE-functionalized dioxythiophenes with varying amounts of 3,4-ethylenedioxythiophene units allows for a deeper understanding of structure–property relationships through charge-transport models. Ultimately, PEDOT(OE3) is shown to be a material with exceptional charge-transport properties and is promising for various applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

On-Chip Tuning of Superconductivity in Fullerides via Current-Driven Rb + Intercalation

An in-operando electro-intercalation method for the on-chip synthesis of alkali-metal-intercalated materials and their Raman spectroscopic and transport characterization in ultrahigh vacuum (UHV) is developed. We apply this method to synthesize fulleride superconductors via Rb + intercalation into a C 60 film. During the intercalation, we monitor the stoichiometry via UHV-Raman spectroscopy and probe superconductivity via transport measurements. An increase of the superconducting transition temperature from 7.0 K to 14.5 K is observed when the stoichiometry is tuned from Rb 2.7 C 60 to Rb 3 C 60 . In our experiment, an ionic Rb+ flux into the host material is induced by an applied electronic current via a Butler–Volmer-type mechanism. Electro-intercalation captivates through improved stoichiometric precision, the ability to smoothly vary stoichiometry via duration of current application, and the absence of a lower limit of the volume of the host material. It represents a powerful concept for the on-chip synthesis of intercalated materials, battery research, and beyond.

Raman↗
DOE OSTI2020

Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes

High-valent nonheme Fe IV –oxido species are key intermediates in biological oxidation, and their properties are proposed to be influenced by the unique microenvironments present in protein active sites. Microenvironments are regulated by noncovalent interactions, such as hydrogen bonds (H-bonds) and electrostatic interactions; however, there is little quantitative information about how these interactions affect crucial properties of high valent metal–oxido complexes. To address this knowledge gap, we introduced a series of Fe IV –oxido complexes that have the same S = 2 spin ground state as those found in nature and then systematically probed the effects of noncovalent interactions on their electronic, structural, and vibrational properties. The key design feature that provides access to these complexes is the new tripodal ligand [poat] 3– , which contains phosphinic amido groups. An important structural aspect of [Fe IV poat(O)] - is the inclusion of an auxiliary site capable of binding a Lewis acid (LA II ); we used this unique feature to further modulate the electrostatic environment around the Fe–oxido unit. Experimentally, studies confirmed that H-bonds and LA II s can interact directly with the oxido ligand in Fe IV –oxido complexes, which weakens the Fe=O bond and has an impact on the electronic structure. Additionally, we found that relatively large vibrational changes in the Fe–oxido unit correlate with small structural changes that could be difficult to measure, especially within a protein active site. Our work demonstrates the important role of noncovalent interactions on the properties of metal complexes, and that these interactions need to be considered when developing effective oxidants.

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

What Is the Right Level of Activation of a High-Spin {FeNO} 7 Complex to Enable Direct N–N Coupling? Mechanistic Insight into Flavodiiron NO Reductases

Flavodiiron nitric oxide reductases (FNORs), found in pathogenic bacteria, are capable of reducing nitric oxide (NO) to nitrous oxide (N 2 O) to detoxify NO released by the human immune system. Previously, we reported the first FNOR model system that mediates direct NO reduction (Dong, H. T.; et al. J. Am. Chem. Soc. 2018, 140, 13429-13440), but no intermediate of the reaction could be characterized. Here, we present a new set of model complexes that, depending on the ligand substitution, can either mediate direct NO reduction or stabilize a highly activated high-spin (hs) {FeNO} 7 complex, the first intermediate of the reaction. The precursors, [{Fe II (MPA-(RPhO) 2 )} 2 ] (1, R = H and 2, R = t Bu, Me), were prepared first and fully characterized. Complex 1 (without steric protection) directly reduces NO to N 2 O almost quantitatively, which constitutes only the second example of this reaction in model systems. Contrarily, the reaction of sterically protected 2 with NO forms the stable mononitrosyl complex 3, which shows one of the lowest N-O stretching frequencies (1689 cm -1 ) observed so far for a mononuclear hs-{FeNO} 7 complex. Here this study confirms that an N-O stretch & LE;1700 cm -1 represents the appropriate level of activation of the FeNO unit to enable direct NO reduction. The higher activation level of these hs-{FeNO} 7 complexes required for NO reduction compared to those formed in FNORs emphasizes the importance of hydrogen bonding residues in the active sites of FNORs to activate the bound NO ligands for direct N-N coupling and N2O formation. The implications of these results for FNORs are further discussed.

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