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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 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Antioxidant-induced transformations of a metal-acid hydrocracking catalyst in the deconstruction of polyethylene waste

Plastics are ideal for numerous applications, as driven by the development of complex formulations containing various additives to improve performance and processability. Unfortunately, chemical valorization strategies (e.g., catalytic deconstruction) often can be challenged by the presence of small-molecule additives, and quantification of the impact of these molecular constituents on upcycling processes remains elusive. Here, this dearth of information restricts catalyst design efforts to combine the robustness and performance necessary to improve plastics circularity. In this communication, we describe a systematic study of common plastics additives—phenolic antioxidants, and we quantify the relationship between additive content and deconstruction yields of high-density polyethylene (HDPE) over a platinum on tungstated zirconium (Pt/WO 3 /ZrO 2 ) hydrocracking catalyst. In the simplest case of a base (antioxidant- and slip agent-containing) HDPE resin versus a pure (additive-stripped) HDPE polymer, a two-fold decrease in the yield of gas and liquid products is noted for base HDPE resin. Furthermore, both antioxidant chemistry and concentration strongly impact conversion and individual product selectivities. Using infrared spectroscopy, we determine that antioxidants change the effective ratio of metal to acid sites (i.e., metal-acid balance) through reactions of phenols and/or other functional groups (e.g., acids, esters) with catalyst active sites. Overall, this work demonstrates the impact of one common set of additives on plastics deconstruction, and the analysis herein provides a blueprint for quantitatively assessing the effects of additives on plastics deconstruction processes and for evaluating the development of more robust catalytic strategies or more tolerable additive formulations.

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

High-Pressure Melting Experiments of Fe 3 C and a Thermodynamic Model of Fe-C Liquids for the Earth's Core

Melting experiments of Fe 3 C were conducted to 85 GPa in laser-heated diamond anvil cells with in situ X-ray diffraction and post-experiment textural observation. From the determined pressure-temperature conditions of the melting curve for Fe 3 C, together with literature data on the melting point of diamond and eutectic point of the system Fe-Fe 3 C/Fe 7 C 3 under high pressures, we established a self-consistent thermodynamic model for high-pressure melting of the system Fe-C including the mixing parameters for liquids. The results show that mixing of Fe and C liquids is negatively nonideal from 1 bar to the pressure at the center of the Earth. The departure from ideal mixing becomes progressively larger with increasing pressure, which leads to greatly stabilized liquids under core pressures. The modeled carbon content in eutectic melts under core pressures is 3.3–4.4 wt%. From the Gibbs free energy, we derived an internally consistent parameters for Fe-C outer cores which included the crystallizing points at their bottoms, isentropic thermal profiles, and densities and longitudinal seismic wave speeds (Vp). While the addition of carbon in excess of the eutectic melt composition effectively reduces the density of iron liquid, the Vp of iron liquid is not greatly changed. Therefore, the low density and high Vp of PREM relative to pure iron cannot be reconciled by an Fe-C liquid. Therefore, the Earth's core cannot be approximated by the system Fe-C and should include another light element.

58 GEOSCIENCES↗
DOE OSTI2021

Diffusion coefficient and nucleation density studies on electrochemical deposition of aluminum from chloroaluminate ionic liquid electrolytes

In this study, aluminum was electrodeposited from ionic liquids comprising a melt of alkyl imidazolium chlorides and aluminum chloride (AlCl 3 ). The ionic liquids utilized in this study were 1-ethyl-3-methyl-imidazolium chloride (EMIC)-AlCl 3 , 1-butyl-3-methylimidazolium chloride (BMIC)-AlCl 3 , and 1-hexyl-3-methyl-imidazolium chloride (HMIC)-AlCl 3 at the AlCl 3 mole fraction of 0.667 (molar ratio of 1:2). The electrochemical behavior of chloroaluminate species in the three ionic liquids was investigated by cyclic voltammetry (CV) and chronoamperometry (CA) techniques at different temperatures. The cyclic voltammograms indicated that the reduction of Al 2 Cl 7 – species to metallic aluminum followed a diffusion-controlled phenomenon. Moreover, even at a less negative applied potential, the higher current density was obtained for EMIC-AlCl 3 ionic liquid. That indicates that EMIC-AlCl 3 favors less energy consumption during the electrodeposition. The chronoamperometric analysis revealed that the onset of aluminum deposition from such ionic liquids proceeds via a three-dimensional instantaneous nucleation process. The concentrations of Al 2 Cl 7 – ions in the ionic liquids were calculated based on the thermodynamic data, which were 2520, 2271, and 2035 mol m –3 for EMIC-AlCl 3 , BMIC-AlCl 3 , and HMIC-AlCl 3 , respectively. The diffusion coefficient (D) values of Al 2 Cl 7 – species in such ionic liquids were also calculated at various temperatures. The D values determined from the CA technique at 363 K are 2.16 × 10 –11 , 1.03 × 10 –11 , and 0.87 × 10 –11 m 2 s –1 for EMIC-AlCl 3 , BMICAlCl 3 , and HMIC-AlCl 3 , respectively. In addition, the D value increased as temperature increased and decreased as the hydrocarbon group in the ionic liquid increased. As a result, the calculated grain sizes of nucleation range from 2 to 4 μm for these ionic liquids and are in good agreement with experimental data obtained from SEM micrographs.

42 ENGINEERING↗
DOE OSTI2023

Flow rate optimization for a small liquid argon system at Fermilab.

This analysis highlights the dominant role of pressure loss in filter disks, emphasizing its crucial consideration during the design phase to ensure optimal fluid flow. Additionally, the significance of vapor quality at the transfer line inlet is identified as a key factor impacting the fill rate. Reducing inlet vapor quality and exploring the use of subcooled liquid are recommended approaches to enhance system performance.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Versatile Liquid Crystal Elastomer Formulations Using Amine-Acrylate Chemistry and Processing for Advanced Manufacturing

This study aims to tune rheological properties of liquid crystal elastomers (LCEs) through a strategic approach, leveraging the differing reaction rates of thiols and primary and secondary amines with acrylate monomers or the inclusion of processing additives to enable amenability to advanced manufacturing. We found that varying the time of oligomerization at elevated temperatures of amine-functional monomers with acrylate-functional monomers enabled simple control of rheological properties. Additionally, we could also control rheological properties by introducing reinforcing fillers or organic solvents. By varying the oligomerization conditions, we achieved a broad range of viscosities, from 1.1 Pa s to 560 Pa s as measured at 60 °C. When the rheological properties were varied through the incorporation of various solid and liquid inclusions, viscosities could range from less than 1 Pa s to nearly 1000 Pa s when measured at 60 °C. The shape morphing capabilities that are intrinsic to LCEs and the mechanical properties were also characterized. Here, we find that the oligomerization conditions and the addition of fillers influence shape morphing and energy absorption, as characterized by the stress–strain characteristics, further suggesting their potential to be used in energy dissipation applications where performance can be turned. Last, we demonstrate how the range of accessible rheological properties grants formulations amenable to various advanced manufacturing techniques.

Liquid chromatography↗
DOE OSTI2022

Spin-orbital liquids and insulator-metal transitions on the pyrochlore lattice

The two orbital Hubbard model, with the electrons additionally coupled to a complex magnetic background, arises in the pyrochlore molybdates. The background involves local moments Hund's coupled to the electrons, driving double exchange ferromagnetism, and antiferromagnetic (AF) tendency arising from competing superexchange. The key scales include the Hubbard repulsion and the superexchange, both of which can be tuned in these materials. They control the phase transition from a ferromagnetic metal to a spin glass metal and then to a spin glass (Mott) insulator. We provide a comprehensive description of the ground state of this model using an unrestricted Hartree-Fock scheme implemented via a simulated annealing procedure and establish the metal-insulator transition line for varying Hubbard interaction and superexchange. The electrons see an effective disorder, due to orbital frustration, already in the ferromagnetic phase. The disorder is further enhanced by antiferromagnetic coupling and the resulting magnetic disorder. As a result, increasing AF coupling shifts the metal-insulator transition to lower Hubbard interaction and gives it an additional "Anderson" character. In conclusion, we provide detailed results on the magnetic and orbital correlations, the density of states, and the optical conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

MoS 2 Catalysts Selectively Achieve High Yield of Liquid Oxygenate from Direct Conversion of Methane via Hydroxyl Radicals

Directly converting methane (CH 4 ) into liquid oxygenates (e.g., methanol) can circumvent the cost and engineering limits of natural gas transportation and storage. However, oxygenate yields from CH 4 remain low, and sulfur present in natural gas hinders activity in most catalysts. Here, to overcome these barriers, we employ bulk molybdenum disulfide (MoS 2 ), a low-cost, robust catalyst which selectively produces large quantities of liquid oxygenates (>900 µmol/g cat ∙hr) from methane in the presence of hydroxyl (OH • ) radicals produced from dilute hydrogen peroxide (H 2 O 2 ) at 75°C. Under realistic reaction conditions, MoS 2 partially and reversibly adopts a metastable, more electrically conductive phase (1T’) that can only be observed through in situ structural probes. Herein, we elucidate that redox synergy between H 2 O 2 and MoS 2 produces active OH • radical species that selectively transform CH 4 to surface methoxy species at the gas-solid liquid interface, leading to the unitary production of liquid oxygenate at a rate competitive with more costly precious metal catalysts, without additional catalyst preparation steps.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Enhanced methanol production from photothermal CO 2 reduction via multilevel interface design

Photothermal CO 2 hydrogenation is a promising route to produce methanol as a sustainable liquid solar fuel. However, most existing catalysts require a combination of solar irradiation and additional heat input to achieve a satisfactory reaction rate. For the few that can be driven solely by light, their reaction rates are one order of magnitude lower. We develop a photothermal catalyst with multilevel interfaces that achieves improved methanol production from photothermal CO 2 hydrogenation without external heat. The catalyst features a layered structure comprising Cu/ZnO/Al 2 O 3 (CZA) covered by oxidized carbon black (oCB), where the oCB/CZA interface promotes efficient heat generation and transfer, and the Cu/oxide interface contributes to high catalytic activity. Under a mild pressure of 8 bar, our oCB/CZA catalyst shows a methanol selectivity of 64.7% with a superior production rate of 4.91 mmol·g cza −1 ·h −1 , at least one order of magnitude higher than other photothermal catalysts solely driven by light. This work demonstrates a photothermal catalyst design strategy for liquid solar fuel production.

CO2 hydrogenation↗
DOE OSTI2021

Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li 6–x PS 5–x ClBr x : An Unusual Compositional Space

Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. In this article, we report a new compositional space of argyrodite superionic conductors, Li 6– x PS 5– x ClBr x [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li 5.3 PS 4.3 ClBr 0.7 . In addition, the extremely low lithium migration barrier of 0.155 eV makes Li 5.3 PS 4.3 ClBr 0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination ( x > 0) leads to (i) retention of the parent Li 6 PS 5 Cl structure for a wide range of x in Li 6– x PS 5– x ClBr x (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl – , Br – , and S 2– at 4a/4d sites, and (iii) gradually increased Li + -ion dynamics, eventually yielding a “liquid-like” Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li 6– x PS 5– x ClBr x induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li + -ion transport in Li 6– x PS 5– x ClBr x . This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.

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

Track Matching in the DUNE Near Detectors

The Deep Underground Neutrino Experiment (DUNE) is an international particle physics experiment looking answer some of the largest unanswered questions in neutrino physics. DUNE uses a high power neutrino beam produced at Fermi National Accelerator Laboratory (Fermilab), and consists of a near detector (ND) also located at Fermilab and a far detector (FD) 1300 km away at the Sanford Underground Research Facility (SURF) in South Dakota. In the first phase of the experiment, the ND complex will contain a modular liquid argon TPC (ND-LAr) and a solid scintillator-based muon spectrometer (TMS), in addition to a beam monitoring detector (SAND) and systems for moving ND-LAr and TMS away from the neutrino beam axis (PRISM). A prototype of ND-LAr, the 2x2 demonstrator, alongside a solid scintillator muon tagger provided by repurposed MINERvA planes, has been built and taken data at Fermilab. For analyses with the ND, connecting particle tracks (such as muons) that exit the liquid argon active volume into the solid scintillator muon detector can improve particle identification and energy reconstruction, and alleviate pileup due to the intense beam. To match tracks between detectors during reconstruction, we have explored using Graph Neural Networks (GNNs) to connect tracks segments between the liquid argon detector region and the solid scintillator detector planes. We have trained a GNN on reconstructed simulated data from the 2×2 demonstrator and repurposed MINERvA planes. We will evaluate its performance and then train a similar network on reconstructed ND-LAr and TMS simulations.

Xing, Daniel [U. Colorado, Boulder]↗
DOE OSTI2024

Spray process of multi-component gasoline surrogate fuel under ECN Spray G conditions

As modern gasoline direct injection (GDI) engines utilize sophisticated injection strategies, a detailed understanding of the air-fuel mixing process is crucial to further improvements in engine emission and fuel economy. In this study, a comprehensive evaluation of the spray process of single-component iso-octane (IC8) and multi-component gasoline surrogate E00 (36 % n-pentane, 46 % iso-octane, and 18 % n-undecane, by volume) fuels was conducted using an Engine Combustion Network (ECN) Spray G injector. High-speed extinction, schlieren, and microscopy imaging campaigns were carried out under engine-like ambient conditions in a spray vessel. Experimental results including liquid/vapor penetration, local liquid volume fraction, droplet size, and projected liquid film on the nozzle tip were compared under ECN G1 (573 K, 3.5 kg/m 3 ), G2 (333 K, 0.5 kg/m 3 ), and G3 (333 K, 1.01 kg/m 3 ) conditions. In addition to the experiments, preferential evaporation process of the E00 fuel was elucidated by Large–Eddy Simulations (LES). The three-dimensional liquid volume fraction measurement enabled by the computed tomographic reconstruction showed substantial plume collapse for E00 under the G2 and G3 conditions having wider plume growth and plume-to-plume interaction due to the fuel high vapor pressure. Here, the CFD simulation of E00 showed an inhomogeneity in the way fuel components vaporized, with more volatile components carried downstream in the spray after the end of injection. The high vapor pressure of E00 also results in ~4 μm smaller average droplet diameter than IC8, reflecting a higher rate of initial vaporization even though the final boiling point temperature is higher. Consistent with high vapor pressure, E00 had a wider plume cone angle and enhanced interaction with the wall to cover the entire surface of the nozzle tip in a film. However, the liquid fuel underwent faster evaporation, so the final projected tip wetting area was smaller than the IC8 under the flash-boiling condition.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

Glaciation of mixed-phase clouds: insights from bulk model and bin-microphysics large-eddy simulation informed by laboratory experiment

Abstract. Mixed-phase clouds affect precipitation and radiation differently from liquid and ice clouds, posing greater challenges to their representation in numerical simulations. Recent laboratory experiments using the Pi Cloud Chamber explored cloud glaciation conditions based on increased injection of ice-nucleating particles. In this study, we use two approaches to reproduce the results of the laboratory experiments: a bulk scalar mixing model and large-eddy simulation (LES) with bin microphysics. The first approach assumes a well-mixed domain to provide an efficient assessment of the mean cloud properties for a wide range of conditions. The second approach resolves the energy-carrying turbulence, the particle size distribution, and their spatial distribution to provide more details. These modeling approaches enable a separate and detailed examination of liquid and ice properties, which is challenging in the laboratory. Both approaches demonstrate that, with an increased ice number concentration, the flow and microphysical properties exhibit the same changes in trends. Additionally, both approaches show that the ice integral radius reaches the theoretical glaciation threshold when the cloud is subsaturated with respect to liquid water. The main difference between the results of the two approaches is that the bulk model allows for the complete glaciation of the cloud. However, LES reveals that, in a dynamic system, the cloud is not completely glaciated as liquid water droplets are continuously produced near the warm lower boundary and subsequently mixed into the chamber interior. These results highlight the importance of the ice mass fraction in distinguishing the mixed-phase clouds and ice clouds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

3D Printing of Liquid Crystal Elastomer Foams for Enhanced Energy Dissipation Under Mechanical Insult

Polymer foams are an essential class of lightweight materials used to protect assets against mechanical insults, such as shock and vibration. Two features are important to enhance their energy absorption characteristics: the foam structure and the matrix phase mechanical behavior. This study investigates novel approaches to control both of these features to enhance the energy absorption capability of flexible lattice foams. First, we consider 3D printing via digital light processing (DLP) as a method to control the foam mesostructure across a suite of periodic unit cells. Second, we introduce an additional energy dissipation mechanism in the solid matrix phase material by 3D printing the lattice foams with polydomain liquid crystal elastomer (LCE), which undergo a mechanically induced phase transition under large strains. This phase transition is associated with LC mesogen rotation and alignment and provides a second mechanism for mechanical energy dissipation in addition to the viscoelastic relaxation of the polymer network. Here, we contrast the 3D printed LCE lattices with conventional, thermomechanically near-equivalent elastomer lattice foams to quantify the energy-absorbing enhancement the LCE matrix phase provides. Under cyclic quasi-static uniaxial compression conditions, the LCE lattices show dramatically enhanced energy dissipation in uniaxial compression compared to the non-LCE equivalent foams printed with a commercially available photocurable elastomer resin. The lattice geometry also plays a prominent role in determining the energy dissipation ratio between the LCE and non-LCE foams. We show that when increasing the lattice connectivity, the foam deformation transitions from bending-dominated to stretching-dominated deformations, which generates higher axial strains in the struts and higher energy dissipation in the lattice foam, as stretching allows greater mesogen rotation than bending. The LCE foams demonstrate superior energy absorption during the repeated dynamic loading during drop testing compared with the non-LCE equivalent foams, demonstrating the potential of LCEs to enhance physical protection systems against mechanical impact.

3D printing↗
DOE OSTI2022

Deep eutectic solvent-based polymer electrolyte for solid-state lithium metal batteries

Poly(ethylene) oxide (PEO)-based electrolytes have been widely studied for solid-state lithium batteries while their ionic conductivity and lithium-ion transference number still need to be further improved. Herein, using the combined experimental and theoretical approach, we demonstrate a novel, solid-state PEO-deep eutectic solvent (DES) electrolyte for the first time. We found that the in situ formation of DES can reduce the crystallinity of PEO matrix and more Li + ions can move freely owing to the weakened coordination between ether oxygens and Li-ions. Besides, we show that more Li + ions can be dissociated from Li salts in PEO-DES electrolyte using the molecular dynamics simulations. Such liquid-free PEO-DES electrolytes showed good ionic conductivity (2.1 × 10 −4 S cm −1 ) which is 160% higher than that of conventional PEO-LiTFSI (8.1 × 10 −5 S cm −1 ) electrolyte at 60 °C. Additionally, the PEO-DES electrolyte showed 136% increase of Li-ion transference number (0.33) compared with ionic liquid-doped PEO-LiTFSI (0.14) at 60 °C. Moreover, the PEO-DES exhibited good compatibility with Li metal and stable Li plating/stripping behavior with little morphology change of Li metal. In conclusion, this research also provides new insights into the enhancement mechanisms of novel polymer electrolytes, improving our fundamental understanding of critical challenges that have impeded the adoption of solid-state lithium metal batteries.

Deep eutectic solvent↗
DOE OSTI2021

Production of Gaseous Olefins from Syngas over a Cobalt-HZSM-5 Catalyst

Light olefins (C2–C5) are high-value platform chemicals used to produce plastics, lubricants, coating material, and surfactants, and can be intermediates to produce transportation fuels. In this study we report on the development of a Co-based catalyst for direct conversion of fossil as well as biomass derived syngas into light olefins that enables high conversion and olefin/paraffin (O/P) product ratio, minimal selectivity to CO2 (<?1%) and wax formation (C14+ selectivity?<?1%). Over a Co/HZSM-5 bi-functional catalyst 38% CO conversion with C2–C5 olefin selectivity of 48%, and O/P ratio of 4.0 was achieved at 240 °C, 17 bar, and 1.5 L/(g–h). In addition to a gaseous olefin-rich stream a C6–C13 mixed olefin/paraffin liquid byproduct was also produced with 25% selectivity. Both Co loading and the HZSM-5 acidity levels were optimized to maintain the balance between the hydrogenation and the cracking activity to generate high levels of C2–C4 olefins. A suite of catalyst characterization tools were used to correlate the physical and chemical property of the catalyst to the performance of the catalyst towards syngas conversion and C2–C4 olefin selectivity.

Maddi, Balakrishna↗
DOE OSTI2025

The total neutron cross section of liquid and solid ammonia

Ammonia is a material of interest for future neutron moderators at high-power sources due to its high hydrogen density, low melting point, and resistance to polymerization in an intense radiation field. Its performance in such applications cannot currently be calculated due to the absence of suitable computer models for the interaction of neutrons with ammonia under relevant conditions. In an effort to develop suitable scattering kernels for computer simulations of moderator performance, we have conducted a series of Density Functional Theory and Molecular Dynamics calculations of the molecular-level thermal properties of ammonia at various temperatures within both the solid and liquid phases. In this paper, we compare computer calculations for the energy-dependent total neutron cross section of ammonia, based on these models, to experimental measurements of those cross sections at temperatures of 221 K, 180 K, and 35 K. The experimental data were collected over an energy range from 0.1 meV to 10 eV using time-of-flight techniques at the Low Energy Neutron Source (LENS) facility at Indiana University. This comparison provides a first validation in the development of thermal scattering libraries for Monte Carlo source design simulations based on liquid and solid ammonia. In conclusion, we also provide some insights into where additional development of tools for creating such models may be needed.

Ammonia↗
DOE OSTI2025

Process Feasibility Analysis of Waste Biomass Valorization to Biochar and Bio-Oil via Slow and Fast Pyrolysis

The United States has abundant biomass and waste feedstock to support the nation's energy addition and affordability targets. Pyrolysis, a thermochemical conversion process, decomposes lignocellulosic feedstocks into liquid, solid, and gaseous fuels that can contribute to the domestic production of biofuels, biopower, and bioproducts. Growing private sector interest in this technology is a key motivation for this comprehensive techno-economic process modeling analysis of a respective biorefinery that includes feedstock preprocessing, slow and fast pyrolysis, and product separation to bio-oil, biochar, and syngas hydrocarbons. Results show that biochar from slow pyrolysis could achieve minimum selling prices (MSPs) of $\$$188-$\$$260/t, competitive with reported market values, while bio-oil from fast pyrolysis is estimated to yield MSPs of $\$$6.49-$\$$9.68/GGE, approximately twice conventional fuel benchmarks. Sensitivity analysis identifies feedstock cost, product yield, and scale as primary cost drivers, while scenarios involving biochar carbon credits and high value applications may substantially improve economics. Overall, these results suggest that continued innovation in feedstock logistics, process integration, and market development will be critical to achieving economically viable and scalable bioproducts.

09 BIOMASS FUELS↗
DOE OSTI2026

Revealing Hidden Quinones Through Diagnostic MS² Fragmentation of Peptide–Quinone Adducts

Quinones are redox-active components of natural organic matter that mediate electron transfer and influence biogeochemical processes, but many quinones in pyrogenic organic matter (PyOM) remain unresolved because they ionize poorly by mass spectrometry. Here, we present a peptide-tagging approach to improve detection of cysteine-reactive electrophiles in PyOM, with quinones expected to be a dominant subset based on reaction chemistry and selectivity experiments. A cysteine-containing peptide was used to form Michael-addition adducts, enhancing electrospray ionization and enabling untargeted screening by high-performance liquid chromatography-high-resolution tandem mass spectrometry. The method was benchmarked with five quinone standards and applied to extracts from charred plant material as a discovery-level screen for cysteine-reactive targets. We identified 98 quinone-candidate adducts (mean neutral mass ~603 Da), of which more than 70% were not detectable in native MS1 data. Among formula-assigned features, hidden quinone candidates had median (O+N)/C of 0.391 and normalized oxidation state of carbon of -0.281, consistent with relatively low polarity and low oxidation state. These results reveal a previously inaccessible pool of hidden redox-active compounds in PyOM and provide a framework for prioritizing quinone-like electrophiles for confirmation and incorporation into models of fire-driven biogeochemical cycling.

LC-MS/MS↗