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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Rapid and Simultaneous Characterization of Drug Conjugation in Heavy and Light Chains of a Monoclonal Antibody Revealed by High-Resolution Ion Mobility Separations in SLIM

Antibody-drug conjugates (ADCs) have recently gained traction in the biomedical community due to their promise for human therapeutics and an alternative to chemotherapy for cancer. Crucial metrics for ADC efficacy, safety, and selectivity are their drug-antibody ratios (DARs). However, DAR characterization (i.e., determining the average number of conjugated drugs on the antibody) through analytical methods remains challenging due to the heterogeneity of drug conjugation as well as the numerous post-translational modifications possible in the monoclonal antibody. In this work, we report on the use of high-resolution ion mobility spectrometry separations in our structures for lossless ion manipulations coupled to mass spectrometry (SLIM IMS-MS) platform for the rapid and simultaneous characterization of the drug load profile (i.e., stoichiometric distribution of the number of conjugated drugs present on the mAb), determination of the weighted average DAR in both the heavy and light chains of a model antibody-drug conjugate, and calculation of the overall DAR of the ADC. After chemical reduction of the ADC and a subsequent 31.5 meter SLIM IMS separation the various drug bound antibody species could be well resolved for both chains. Furthermore, we also show that higher resolution separations were possible with SLIM IMS as compared to ones performed on a commercially available (~1 meter) drift tube IMS-MS platform. Interestingly, additional gas-phase substructures become evident with longer path length SLIM IMS, potentially providing insight related to how drug conjugation may alter the structural properties of a monoclonal antibody and thus affect its overall potency and/or selectivity for a given antigen. We expect high-resolution SLIM IMS separations will augment the existing toolbox for ADC characterization, particularly for structural confirmation to enable the rapid optimization of DAR for a given ADC and thus better understand its potential toxicity and potency.

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

Diversifying hierarchical ionic assembly by docking cations to anions as salt bridges

Here, we expand the diversity of building blocks available for ionic assembly by introducing tertiary (3°) ammonium cations into anion complexes. We use proton transfer between 3° amines and organo-phosphoric acids to generate H-bonding cations (R 3 NH + ) and anions (RHPO 4 – ) that co-assemble with cyanostar macrocycles into assemblies with 2:2:2 stoichiometry. At the heart is a supramolecular dimer where phosphate anions form salt bridges by H-bonding with cations. Unlike conventional 4° ammonium cations, 3,000 commercial amines provide diversity for high-throughput screening of 72 combinations (9 nitrogen bases and 8 acids), producing 13 privileged partners for quantitative assembly. Yields depend on the solvent and sterics of salt bridge formation. Ten more nitrogen bases connect to fluorophores (pyrene), photocatalysts (quinoline), drugs (Cipralex, Zytiga), and ionic liquids (imidazole). The synthesis and examination of 82 new salts exemplify how acid-base chemistry can open a pipeline to a diversity of building blocks for exploring hierarchical ionic assembly.

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

Anion modification for stable solid electrolyte interphase in anode-free lithium metal batteries

The durability of anode-free Li metal batteries is largely limited by the undesired Li plating/stripping irreversibility on the current collector due to the infinite volume change, uncontrollable Li dendrite growth, and continuous parasitic reactions between Li metal and the electrolyte. To address these challenges, the formation of a stable and robust solid electrolyte interphase (SEI) with high ionic conductivity and strong mechanical strength is critical. Here, we developed an advanced electrolyte by introducing LiNO 3 into the localized high concentration electrolyte (LHCE) with lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2-dimethoxyethane (DME) solvent, and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TFTE) diluent to in situ construct a LiF and Li x N y O z co-enriched passivation layer on the Cu current collector. The synergetic effect of high mechanical strength of LiF and high ionic conductivity of Li x N y O z endows the Li metal anode with a high Coulombic efficiency (CE) of 99.35%. In conclusion, in anode-free Li metal pouch cell using LiFePO 4 (LFP) as a cathode holds an exceptionally improved capacity retention under the charging/discharging rate of 1/3 C, demonstrating great promise for developing dendrite-free and safe Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Sequence-Controlled Secondary Structures and Stimuli Responsiveness of Bioinspired Polyampholytes

In this work, a comprehensive study focusing on the influence of the sequence charge pattern on the secondary structure preferences of annealed polyampholytes and their responsiveness to external stimuli is presented. Two sequences are designed composed entirely of ionizable amino acids (charge fraction f=1), and an equal number of positive and negative charges (f + =f - =0.5) with distinct charge-patterns consisting of lysine and glutamic acid monomers. The study reveals that the sequence charge pattern has a significant influence on the secondary structure preferences of polyampholytes at physiological pH. Furthermore, it shows that external stimuli such as pH, ionic strength and solvent dielectric constant can be used to modulate the secondary structure of the two designed sequences. The observed secondary structure transformations for the two sequences are also substantially different from those determined for uniformly charged polypeptides-homo-polypeptides under matching conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Direct Evidence of Charge Transfer upon Anion Intercalation in Graphite Cathodes through New Electronic States: An Experimental and Theoretical Study of Hexafluorophosphate

Graphite intercalation compounds continue to be central to technologies for electrochemical energy storage from anodes in established Li-ion batteries to cathodes in beyond Li-ion concepts paired with multivalent anodes. When used as a cathode, graphite intercalates a variety of anions with PF 6 - being among the most common. Paired with Li intercalation at the anode, the corresponding dual carbon battery yields high energy and power densities. Given the available choice of anions as intercalants, it is important to elucidate how the graphite structure accommodates them in order to tailor the molecular species to maximize charge and reversibility. However, the changes in electronic structure of the host graphite lattice upon anion intercalation are poorly understood compared to cations, which represent a fundamentally different reaction. Herein, PF 6 -intercalated graphite has been studied using techniques sensitive to electronic structure, namely, X-ray Raman spectroscopy (XRS), X-ray absorption near-edge spectroscopy (XANES), and X-ray emission spectroscopy (XES). Complementary full-potential, all-electron density functional theory calculations yielded excellent agreement with the spectra, thus providing insight into charge compensation in the graphite lattice. In particular, a pre-$π^*$ feature emerged in XRS/XANES, which is direct evidence of the removal of charge from the host lattice to compensate the intercalated anions, leading to an overall lowering of the Fermi energy level. This is expected to be characteristic of many intercalants in anion-intercalated graphite. The unambiguous identification of the origin of the pre-$π^*$ spectral feature, which is frequently seen in graphitic systems, is of broad interest to the spectroscopy of graphitic systems beyond the practical implications of anion-induced changes in the electronic properties for real devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electronic reconstruction at the polar (111)-oriented oxide interface

Atomically flat (111) interfaces between insulating perovskite oxides provide a landscape for new electronic phenomena. For example, the graphene-like coordination between interfacial metallic ion layer pairs can lead to topologically protected states [Xiao et al., Nat. Commun. 2, 596 (2011) and A. Rüegg and G. A. Fiete, Phys. Rev. B 84, 201103 (2011)]. The metallic ion/metal oxide bilayers that comprise the unit cell of the perovskite (111) heterostructures require the interface to be polar, generating an intrinsic polar discontinuity [Chakhalian et al., Nat. Mater. 11, 92 (2012)]. Here, we investigate epitaxial heterostructures of (111)-oriented LaAlO 3 /SrTiO 3 (LAO/STO). We find that during heterostructure growth, the LAO overlayer eliminates the structural reconstruction of the STO (111) surface with an electronic reconstruction, which determines the properties of the resulting two-dimensional conducting gas. This is confirmed by transport measurements, direct determination of the structure and atomic charge from coherent Bragg rod analysis, and theoretical calculations of electronic and structural characteristics. Interfacial behaviors of the kind discussed here may lead to new growth control parameters useful for electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Lithium-Ion Batteries with Lithium Manganese Iron Phosphate Cathodes and Lithium Titanate Anodes: Linking Electrode Dynamics to Cell Performance

This study examines the electrochemical performance, impedance behavior, and aging mechanisms of lithium-ion cells pairing lithium manganese iron phosphate (LiMn 0.6 Fe 0.4 PO 4 , LMFP64) cathodes with lithium titanate (Li 4 Ti 5 O 12 , LTO) anodes. LMFP64 half-cells display distinct Fe and Mn redox plateaus at ∼3.5 and ∼4.1 V, respectively, and deliver excellent rate capability. Three-electrode measurements show that LMFP64 dominates cell impedance, which changes sharply across the Fe–Mn redox transition and decreases with increasing temperature (30 °C–50 °C). Voltage hysteresis arises mainly from the cathode, with higher C-rates shortening redox plateaus and broadening the transition region. Elevated temperature lowers impedance, especially near the Mn-redox and transition regions, but accelerates capacity fade. Post-cycling analyses of electrodes confirm structural stability of LMFP64 and indicate loss of lithium inventory (LLI) as the source of capacity fade. This LLI causes potential slippage between the LMFP64 and LTO electrodes, which decreases the Fe-redox plateau width. Long-term cycling highlights the critical role of electrode overhang: cathode overhang mitigates capacity fade by buffering lithium loss, whereas anode overhang cells experience faster capacity decline due to uncompensated lithium depletion. These results clarify LMFP64/LTO battery impedance evolution, thermal effects, and degradation pathways and provide insights for their applications in electric vehicles.

Area Specific Impedance↗
DOE OSTI2023

Verification Testing of OLI Systems Mixed Solvent Electrolyte Model for the Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 ) System to High Ionic Strength at 25°C

This technical report summarizes model verification results and summary statistics for 41 evaporite mineral solubility cases evaluated by Savannah River National Laboratory using OLI Systems’ aqueous electrolyte thermodynamic modeling software. The 41 verification cases containing a total of 60 solubility curves comprise mineral solubility data from low to high ionic strength at 25°C for the eight-component system Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 O as reported by Harvie et al. (1984). Thermodynamic calculations were executed using OLI Systems’ Stream Analyzer computation module within the OLI Studio software platform (Ver. 11.0, Rev. 11.0.1.9). The Mixed Solvent Electrolyte (MSE) thermodynamic framework was chosen for this investigation because of its superiority in modeling high ionic-strength inorganic salt solutions and actinide redox chemistry and solubility, both of which are relevant to the geological repository conditions at the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Mineral solubility data in various inorganic salt solutions were digitized and extracted from figures generated by Harvie et al. (1984). For each of the 60 solubility curves, a case-specific chemistry model and input file were generated in OLI Studio using OLI Stream Analyzer and the MSE (H 3 O + ion) public databank provided by OLI Systems. Model simulation results were exported to Microsoft Excel to calculate summary statistics and to generate graphs comparing the OLI model predictions to the solubility data. Summary statistics include residuals (model – data) and concordance (accuracy × precision, where precision is indicated by the Pearson correlation coefficient and accuracy accounts for bias and scale differential). Private databanks were not developed, and activity coefficient model regressions were not performed to improve OLI model fits to the data. Of the 41 model verification plots, 83% have a mean of the percent residuals less than or equal to 25%. Similarly, 75% display a concordance greater than or equal to 0.75. Only seven of the 41 verification plots fail to show good agreement between the model and data. Of these seven, three are relevant to the WIPP repository because they involve the Mg-OH-Cl-SO 4 -CO 3 aqueous system. The remaining four address salt solubilities at the pH extremes (strong acid and strong base). It should be noted that in two of the three Mg-OH-Cl-SO 4 -CO 3 system cases, the regressed Harvie et al. (1984) solubility curve also deviated from the data. Lack of agreement between the OLI model-predicted solubility curves and the data is attributable to one or more of the following: specific solid species are not included in the OLI MSE databank; there is significant variation among the different solubility datasets chosen by Harvie et al. (1984); the OLI MSE model’s thermodynamic parameters were determined using different solubility datasets; and the activity coefficient parameters for certain relevant ion-ion and ion-molecule pairs have not been optimized via data regression. Two recommendations for future work are to (1) evaluate solubility data for the Mg-OH-Cl-SO 4 -CO 3 system at high ionic strength and, if necessary, develop a private OLI MSE database that includes missing species and, where necessary, regressed standard state properties and interaction parameters; (2) perform similar verification testing of the OLI model for actinide solubility data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Lepton pair production through two photon process in heavy ion collisions

This paper investigates the electromagnetic production of lepton pairs with low total transverse momentum in relativistic heavy-ion collisions. First, we estimate the initial photons' transverse momentum contributions by employing models where the average transverse momentum squared of the incoming photon can be calculated in the equivalent photon approximation. We further derive an all order QED resummation for the soft photon radiation, which gives an excellent description of the ATLAS data in ultraperipheral collisions at the LHC. For peripheral and central collisions, additional pT-broadening effects from multiple interactions with the medium and the magnetic field contributions from the quark-gluon plasma are also discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

The role of plasma instabilities in relativistic radiation-mediated shocks: stability analysis and particle-in-cell simulations

ABSTRACT Relativistic radiation-mediated shocks are likely formed in prodigious cosmic explosions. The structure and emission of such shocks are regulated by copious production of electron–positron pairs inside the shock-transition layer. It has been pointed out recently that substantial abundance of positrons inside the shock leads to a velocity separation of the different plasma constituents, which is expected to induce a rapid growth of plasma instabilities. In this paper, we study the hierarchy of plasma microinstabilities growing in an electron-ion plasma loaded with pairs and subject to a radiation force. Linear stability analysis indicates that such a system is unstable to the growth of various plasma modes which ultimately become dominated by a current filamentation instability driven by the relative drift between the ions and the pairs. These results are validated by particle-in-cell simulations that further probe the non-linear regime of the instabilities, and the pair-ion coupling in the microturbulent electromagnetic field. Based on this analysis, we derive a reduced-transport equation for the particles via pitch-angle scattering in the microturbulence and demonstrate that it can couple the different species and lead to non-adiabatic compression via a Joule-like heating. The heating of the pairs and, conceivably, the formation of non-thermal distributions, arising from the microturbulence, can affect the observed shock-breakout signal in ways unaccounted for by current single-fluid models.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

The effects of dose, dose rate, and irradiation type and their equivalence on radiation-induced segregation in binary alloy systems via phase-field simulations

Radiation-induced segregation is a phenomenon commonly observed in many alloys which consists of the redistribution of elements (solute or interstitial impurities) under irradiation. The onset and development of radiation-induced segregation can only occur when a sufficient flux of defects is sustained and defect sinks are present. Irradiation dose, dose rate, and particle types all affect defect flux. In this work, we employ a phase-field model to examine the effects of dose, dose rate, and type of incident particles on radiation-induced segregation behavior in a model binary alloy. The phase-field model takes into account the formation and evolution of point defects as well as defect clusters, the diffusion and clustering of alloy species, the presence of additional extrinsic defect sinks in the form of dislocations, and two different methods of radiation-damage insertion, which are intended to simulate either light-ion/electron irradiation via Frenkel pairs or heavy-ion irradiation in the form of cascades. Our results show a dose-rate and particle-type dependence on the amount of solute segregation. We show that the material systems exposed to higher dose rates are less subjected to solute segregation at equivalent doses. We also show that such dose-rate-dependence behavior is due to a delay of the incubation dose at which radiation-induced segregation effectively starts. Particle type and the presence of dislocations can accentuate this behavior. Our model predictions correlate with many experimental observations made over the years on radiation-induced segregation providing credence to the simulation results. The methodology presented in this study allows for a first-order prediction of the dose rate at which proxy irradiation experiments could be performed to approximate radiation-induced segregation behaviors seen in targeted irradiation conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Revealing the Correlation between the Solvation Structures and the Transport Properties of Water-in-Salt Electrolytes

Water-in-salt (WIS) electrolytes containing 21 m lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) have been considered as a safe and environment-friendly alternative to common organic electrolytes used in lithium-ion batteries. However, the relation between the solvation structures and transport properties of these materials remains elusive. Here, for this paper, we performed small-angle X-ray scattering (SAXS), small-angle neutron scattering (SANS), and X-ray pair distribution function (PDF) measurements of LiTFSI aqueous solutions at a wide range of concentrations. Combined with molecular dynamics simulations, the detailed solvation structures from long to short length scale were resolved. We found that the TFSI– solvation structures consist of TFSI– solvated structures and TFSI– networks; the former corresponds to solvent separated ion pairs, while the latter corresponds to contact ion pairs and cation–anion aggregates. In addition, we found that the relaxation time in the q range associated with the anion network structure exhibits the same concentration dependence as the viscosity. By combining the results from the experiments and simulations, this study revealed a correlation between the solvation structures of LiTFSI and the transport properties of the solutions, which is critical to understand the relation between the transport properties and the dynamics of the ions for imide-based lithium-ion salt aqueous electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Device to manipulate ions of same or different polarities

An apparatus includes a first pair of opposing electrode arrangements that confine ions between them in a portion of a confinement volume inwardly laterally in a first confinement direction with respect to a longitudinal ion propagation direction, each opposing electrode arrangement including an arrangement of RF electrodes situated to receive an unbiased RF voltage having an alternate phase between adjacent RF electrodes of the arrangement of RF electrodes so as to provide the confining of ions between the first pair of opposing electrode arrangements, and a second pair of opposing electrode arrangements that confine the ions between the second pair in the confinement volume inwardly laterally in a second confinement direction that complements the first confinement direction, each opposing electrode arrangement of the second pair including an arrangement of RF electrodes that receive an unbiased RF voltage having an alternate phase between adjacent RF electrodes.

42 ENGINEERING↗
DOE OSTI2023

Metal-Mediated DNA Nanotechnology in 3D: Structural Library by Templated Diffraction

DNA double helices containing metal-mediated DNA (mmDNA) base pairs are constructed from Ag + and Hg 2+ ions between pyrimidine:pyrimidine pairs with the promise of nanoelectronics. Rational design of mmDNA nanomaterials is impractical without a complete lexical and structural description. Here, in this study, the programmability of structural DNA nanotechnology toward its founding mission of self-assembling a diffraction platform for biomolecular structure determination is explored. The tensegrity triangle is employed to build a comprehensive structural library of mmDNA pairs via X-ray diffraction and generalized design rules for mmDNA construction are elucidated. Two binding modes are uncovered: N3-dominant, centrosymmetric pairs and major groove binders driven by 5-position ring modifications. Energy gap calculations show additional levels in the lowest unoccupied molecular orbitals (LUMO) of mmDNA structures, rendering them attractive molecular electronic candidates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗