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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Orientational Dependence of Cofacial Porphyrin–Quinone Electronic Interactions within the Strong Coupling Regime

We examine the relative magnitudes of electronic coupling HDA in two face-to-face rigid and diastereomeric (porphinato)zinc(II)–quinone (PZn–Q) as-semblies, 1β-ZnA and 1β-ZnB, in which the six quinonyl carbon atoms lie in virtually identical arrangements relative to the PZn plane at sub-van der Waals donor–acceptor (D–A) interplanar separations. Steady-state and time-resolved transient optical data and computational studies show that minor differences in relative D–A cofacial orientation give rise to disparate H DA magnitudes for both photoinduced charge separation (CS) and thermal charge recombination (CR). Here, time-dependent density functional theory (TDDFT) computations illuminate the nature of direct charge transfer states and the electronic structural factors that give rise to these differential H DA s. These data show more extensive mixing of locally excited (LE) and CS states in 1β-ZnA relative to 1β-ZnB and that these H DA differences track the magnitudes of electronic coupling matrix elements determined from steady-state electronic spectral data and thermal CR rate constants measured via pump–probe spectroscopy. Collectively, this work shows that electron transfer dynamics may be manipulated in cofacial D–A systems, even at sub-van der Waals contact, provided that conformational rigidity precludes structural fluctuations that modulate D–A interactions on the charge transfer time scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Protein Conformational Populations and Functionally Relevant Sub-states

Functioning proteins do not remain fixed in a unique structure, but instead they sample a range of conformations facilitated by motions within the protein. Even in the native state, a protein exists as a collection of interconverting conformations driven by thermodynamic fluctuations. Motions on the fast time scale allow a protein to sample conformations in the nearby area of its conformational landscape, while motions on slower time scales give it access to conformations in distal areas of the landscape. Emerging evidence indicates that protein landscapes contain conformational substates with dynamic and structural features that support the designated function of the protein. Nuclear magnetic resonance (NMR) experiments provide information about conformational ensembles of proteins. X-ray crystallography allows researchers to identify the most populated states along the landscape, and computational simulations give atom-level information about the conformational substates of different proteins. This ability to characterize and obtain quantitative information about the conformational substates and the populations of proteins within them is allowing researchers to better understand the relationship between protein structure and dynamics and the mechanisms of protein function. In this Account, we discuss recent developments and challenges in the characterization of functionally relevant conformational populations and substates of proteins. In some enzymes, the sampling of functionally relevant conformational substates is connected to promoting the overall mechanism of catalysis. For example, the conformational landscape of the enzyme dihydrofolate reductase has multiple substates, which facilitate the binding and the release of the cofactor and substrate and catalyze the hydride transfer. For the enzyme cyclophilin A, computational simulations reveal that the long time scale conformational fluctuations enable the enzyme to access conformational substates that allow it to attain the transition state, therefore promoting the reaction mechanism. In the long term, this emerging view of proteins with conformational substates has broad implications for improving our understanding of enzymes, enzyme engineering, and better drug design. Researchers have already used photoactivation to modulate protein conformations as a strategy to develop a hypercatalytic enzyme. In addition, the alteration of the conformational substates through binding of ligands at locations other than the active site provides the basis for the design of new medicines through allosteric modulation.

Agarwal, Pratul K↗
DOE OSTI2019

Investigation of Corrosion of 304 Stainless, Inconel 625, and Haynes 230 in a Chloride-Salt-Based Thermal Storage Medium

One of the critical challenges for latent heat thermal energy storage systems in concentrating solar power applications is corrosion of metallic alloys as containment and heat transfer fluid tube materials in corrosive salts at high temperatures. In this study, the effects of MgCl 2 on the corrosion of stainless steel 304, Inconel 625, and Haynes 230 alloys were investigated through embedded metal samples in the graphite foam/MgCl 2 storage medium. Four experimental testing modules were fabricated, and experimental tests were conducted under controlled environment by heating the testing modules to and keeping them at 750 °C for 100, 200, 500, and 1000 h. The estimated corrosion rates based on the weight losses for stainless steel 304, Inconel 625, and Haynes 230 were 94, 9, and 8 μm/year, respectively. The fitted equations for the loss of the thickness as functions of the exposure time show that the corrosion rates decrease with the exposure time. Additionally, the results on the corrosion zones or depths and chromium segregation ranges of the experimental samples are also presented.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molecular Picture of the Transient Nature of Lipid Rafts

In biological membranes, lipid rafts are now thought to be transient and nanoscopic. However, the mechanism responsible for these nanoscopic assemblies remains poorly understood, even in the case of model membranes. Therefore, it has proven extremely challenging to probe the physicochemical properties of lipid rafts at the molecular level. Here, we use all-atom molecular dynamics (MD) simulations and inelastic X-ray scattering (IXS), an intrinsically nanoscale technique, to directly probe the energy transfer and collective short-wavelength dynamics (phonons) of biologically relevant model membranes. We show that the nanoscale propagation of stress in lipid rafts takes place in the form of collective motions made up of longitudinal (compression waves) and transverse (shear waves) molecular vibrations. Importantly, we provide a molecular picture for the so-called van der Waals mediated "force from lipid" [Anishkin, A. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 7898], a key parameter for the ionic channel mechano-transduction and the mechanism for the lipid transfer of molecular level stress [Aponte-Santamaría, C. et al. J. Am. Chem. Soc. 2017, 139, 13588]. Specifically, we describe how lipid rafts are formed and maintained through the propagation of molecular stress, lipid raft rattling dynamics, and a relaxation process. Eventually, the rafts dissipate through the self-diffusion of lipids making up the rafts. We also show that the molecular stress and viscoelastic properties of transient lipid rafts can be modulated through the use of hydrophobic biomolecules such as melatonin and tryptophan. Overall, the herein proposed mechanism describing the molecular interactions for the formation and dissolution of lipid rafts may offer insights as to how lipid rafts enable biological function.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A Theory of Ultrafast Charge Transfer Relaxation with Non-Innocent Solvent Molecules

In this work we revisit the photodynamics of tetracyanoethylene-hexamethylbenzene (TCNE- HMB), the molecular complex studied by Hochstrasser et al. [J. Chem. Phys. 100, 4797–4810, 1994] that has long challenged the applicability of Marcus’s theory of elec- tron transfer for predicting photochemical reactions. Using a novel black-box electronic structure algorithm (time-dependent density functional theory with one double, TD- DFT-1D) to efficiently run molecular dynamics that can treat charge recombination, we run ab initio surface hopping molecular dynamics and confirm that, for a polar solvent, charge recombination rates can be incredibly fast (indeed faster than the sol- vent relaxation time); for non-polar solvents, the rate is much slower. We demonstrate that, although Marcus theory cannot be directly applied, these nonequilibrium (and sometimes incredibly fast) photoexcited dynamics can be effectively explained within a two-state model without any evidence of a transition through a conical intersection. Most importantly, for this paradigmatic model system, we are able to identify two nuclear coordinates of interest (rather than the single coordinate predicted by Marcus or a full set of internal quantum modes studied by Bixon and Jortner): the solvent relaxation in the first shell (that strongly modulates the energies of the charge trans- fer state and differentiates time scales for relaxation) and a nuclear displacement in the TCNE-HMB complex arising from a handful of vibrations that induces non-Born Oppenheimer motion and eventually facilitates an abrupt electronic transition to the ground state. Altogether, these findings suggest a tractable generalization of Marcus theory for future simulations of photochemistry with non-innocent solvent environ- ments in the spirit of a Hamiltonian suggested by Stuchebrukhov (J. Chem. Phys. 107, 3821, 1997).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Modulation of Carrier Type in Nanocrystal-in-Matrix Composites by Interfacial Doping

Inorganic nanocomposites synthesized by combination of colloidal nanocrystals (NCs) and inorganic clusters have recently emerged as new materials with novel and unique functionalities. Much of the demonstrated promise of nanocomposites derives from the unique interactions between NC and matrix components—this generates new material properties, which direct unique transport behavior in the overall solid or nanocomposite—be it mass, charge, or heat. While measured empirically, it has remained largely impossible to take an a priori look at material properties and use those as a guideline to design desired transport behavior. Fundamentally, this is because the structural and electronic changes manifest at those interfaces have remained hidden from examination. We provide experimental evidence that transport behavior in nanocrystal-in-matrix (NIM) composites is dictated primarily by interfacial charge transfer associated with electronic and structural reconstructions as the composite forms. Our approach building continuous composite superlattices serves as a starting point for systematic probing of the nanointerface of NIM composites via ultrathin films. A combination of field effect transistor device characterization and photoemission spectroscopy reveals the systematic dependence of the polarity of charge transfer on the selection of matrix materials in NIM composites. We use this insight to combine, by design, different components to tune the carrier type in NIM composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2010

Modal expansion approach to optical-frequency-comb generation with monolithic whispering-gallery-mode resonators

We describe a general framework based on modal expansion for the study of optical-frequency combs generated with monolithic whispering-gallery-mode resonators. We obtain a set of time-domain rate equations describing the dynamics of each mode as a function of the main characteristics of the cavity, namely, Kerr nonlinearity, absorption, coupling losses, and cavity dispersion (geometrical and material). A stability analysis of the various side modes is performed, which finds analytically the threshold power needed for comb generation. We show that the various whispering gallery modes are excited in a nontrivial way, strongly dependent on the value of the overall cavity dispersion. We demonstrate that the combs are not simply generated through a direct transfer of energy from the pumped mode to all their neighbors but rather through complex intermediate interactions. Anomalous cavity dispersion is also demonstrated to be critical for these cascading processes, and comb generation is thereby unambiguously linked to modulational instability. This theory accurately describes the emergence of spectral modulation and free spectral-range tunability in the comb. It also enables a clear understanding of the various phenomena responsible for the spectral span limitation. Our theoretical predictions are in excellent agreement with the numerical simulations, and they successfully explain the internal mechanisms responsible for the generation of hundreds of Kerr modes in monolithic whispering-gallery-mode resonators.

43 PARTICLE ACCELERATORS↗
DOE OSTI2025

LDRD conclusion poster - Synthesizing Heterometallic Uranium Single Crystals to Understand the Influence of the Secondary Metals on Uranyl Axial Bond Strength

Understanding how transition metals influenced the chemistry of lanthanide and actinide (f-element) materials is critical for advancing separation technologies, materials design, and coordination chemistry. This project examined how incorporating first-row transition metals affected the structural and spectroscopic properties of f-element coordination polymers. In uranium(VI)-based systems synthesized with 2,6-pyridinedicarboxylic acid (PDC) ligands, single-crystal X-ray diffraction and Raman spectroscopy revealed that the presence of transition metals shortened the uranyl axial bond and induced a blue shift in its symmetric stretching vibration—evidence of increased bond strength. Electronic structure analysis, including Density of States (DOS) calculations using density functional theory (DFT), revealed altered orbital overlaps and highlighted the role of transition metal d-orbitals in modulating bonding. Raman modes were modeled using truncated structural fragments in collaboration with the University of Notre Dame, and although the predicted frequencies were lower than experimental values, they remained within expected ranges. In parallel, similar experiments with cerium (Ce) in the presence of cobalt (Co) and PDC demonstrated multi-step single-crystal-to-single-crystal transformations—behavior not observed in the uranium systems. Initial products included light yellow, orange, and polycrystalline materials. Single-crystal X-ray diffraction studies, conducted in collaboration with the Colorado School of Mines, identified the yellow phase as monometallic Ce(PDC)2(H2O)2·4H2O and the orange phase as heterometallic Ce2Co(PDC)4(H2O)6. After standing in solution for one week, both phases fully transformed into a dark yellow crystalline phase, [Ce3(PDC)5(H2O)8].6(H2O). Remarkably, this transformation was reversible—disturbing the equilibrium by removing some crystals caused reversion to the initial Ce(PDC)2(H2O)2·4H2O phase, highlighting dynamic behavior. All three structures were previously unreported. Solid-state UV-visible and Raman spectroscopy further distinguished these phases, revealing ligand-to-metal charge transfer involving Ce and characteristic d–d transitions from Co(II). The precise mechanism driving these transformations remained unclear; however, pH-dependent experiments confirmed that the transformation did not occur when the pH decreased. Overall, the project demonstrated that transition metals could be employed to tune bonding interactions, structural dimensionality, and optical properties in f-element materials, establishing new pathways for designing functional heterometallic systems. The work resulted in several novel structural discoveries and fostered productive collaborations with the University of Notre Dame and the Colorado School of Mines.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2020

In-Sodium Testing of a Prototype Thermoacoustic Power Sensor for Sodium-Cooled Fast Reactors

The ultimate goal of this project is to develop and demonstrate a thermoacoustic power sensor (TAPS) for Sodium-Cooled Fast Reactors (SFRs), with potential application also envisioned to other nuclear technologies such as Lead-Cooled Fast Reactors (LFRs), Molten Salt Reactors (MSRs), in addition to Light Water Reactors (LWRs). The project was led by Westinghouse Electric Company, LLC (Westinghouse) and carried out in collaboration with Argonne National Laboratory (ANL) and the University of Pittsburgh. A TAPS is a passive (self-powered), non-invasive (wireless) sensor envisioned for measuring key parameters, such as local temperature and neutron flux, in a nuclear reactor core. The sensor generates pressure waves (i.e., sound waves) with a frequency and amplitude dependent upon nuclear operating conditions (coolant temperature or power changes). The acoustic waves are able to travel through the core and associated structures, and reach to the sensor network placed outside and/or inside of the reactor vessel. These sensors require a very small amount of power which, during loss of power events, can be provided, for example, by harvesting gamma radiation energy, thus resulting in a monitoring system that can function both during normal operation and during loss of power events. Westinghouse and the University of Pittsburgh designed and fabricated TAPS prototypes for Argonne National Laboratory (ANL) to carry out in-sodium testing to evaluate the effects of sodium on the TAPS and the performance of the TAPS technique in sodium. Argonne received a TAPS prototype from Westinghouse, and the prototype was modified such that it can be installed into a test vessel and function in sodium at elevated temperature without potentially leaking. A water mockup test apparatus was constructed to validate proper working of the prototype. An instrumentation and control (I&C) system, running on the National Instruments (NI) LabView platform, was developed to: 1) operate both the water mockup test and the in-sodium test facility; and 2) process and analyze the received acoustic signals from an array of accelerometers and the Argonne sodium-submersible high-temperature acoustic sensor. The prototype was successfully tested in a water bath at different temperatures. Water mockup tests demonstrated that the TAPS prototype is working properly and its resonance frequency changes linearly with the coolant (water) temperature. A TAPS test apparatus was constructed and integrated with the upgraded Under-Sodium Viewing (USV) sodium test facility. The integrated USV-TAPS sodium test facility has been operational. The TAPS prototype and a high-temperature sodium-submersible acoustic sensor (SSAS) developed by Argonne were both installed inside the TAPS test vessel. Being operated within argon cover gas under ambient conditions, the TAPS prototype demonstrated that it was functioning properly with a resonance frequency at 1407.2 Hz, which was successfully detected by the accelerometers mounted on the external wall of the vessel and the high-temperature SSAS installed inside the vessel. After successfully transferring sodium into the vessel, in-sodium tests of the prototype were conducted. Tests of the TAPS prototype demonstrated that the resonance frequency of the TAPS changes linearly with respect to the temperature difference between the interior of the TAPS and bulk sodium. The early tests showed that the TAPS prototype could not establish a continuous and consistent resonance in sodium. The resonance diminished before the prototype reached its operating temperature. A signal postprocessor was added to the DAQ module latterly to isolate interferences, enhance signal conditioning, improve peak detection, and generate resonance frequency versus temperature plots. After testing in molten sodium and immersion at higher temperature for several weeks, the TAPS prototype was able to establish a continuous resonance. Performance evaluation of the TAPS prototype was then conducted in sodium. The tests included the investigation of 1) the effects of the temperature difference between the TAPS and bulk sodium, 2) the effects of sodium flowrate; and 3) the performance of the different sensor-receiver systems positioned inside or outside the vessel. Results of a test demonstrated that, with limited sodium circulation, a continuous and consistent resonance of the TAPS prototype was established occasionally. The tests also demonstrated that, because of the nature of detection principles and mounting methods, the high temperature SSAS is more affected by acoustic noise, while accelerometers are more affected by vibrations, in the test environment. It is unknown why the TAPS prototype only occasionally established a continuous and consistent resonance when the TAPS temperature reached its operating temperature in molten sodium, and why it ultimately failed to resonate at all. A failure modes assessment was conducted and a few potential causes of failure were identified. Different post in-sodium tests were conducted to obtain additional information potentially relevant to the cause of the failure. Nondestructive evaluation techniques are suggested to examine the internal integrity as well as the gas mixture of the prototype. If they prove inconclusive, the prototype should be cut open to conduct a thorough inspection of its internal integrity and determine the state of the gas mixture.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Effect of a redox-mediating ligand shell on photocatalysis by CdS quantum dots

Semiconductor quantum dots (QDs) are efficient organic photoredox catalysts due to their high extinction coefficients and easily tunable band edge potentials. Despite the majority of the surface being covered by ligands, our understanding of the effect of the ligand shell on organic photocatalysis is limited to steric effects. We hypothesize that we can increase the activity of QD photocatalysts by designing a ligand shell with targeted electronic properties, namely, redox-mediating ligands. Herein, we functionalize our QDs with hole-mediating ferrocene (Fc) derivative ligands and perform a reaction where the slow step is hole transfer from QD to substrate. Surprisingly, we find that a hole-shuttling Fc inhibits catalysis, but confers much greater stability to the catalyst by preventing a build-up of destructive holes. We also find that dynamically bound Fc ligands can promote catalysis by surface exchange and creation of a more permeable ligand shell. Finally, we find that trapping the electron on a ligand dramatically increases the rate of reaction. Furthermore, these results have major implications for understanding the rate-limiting processes for charge transfer from QDs and the role of the ligand shell in modulating it.

Chemistry↗
DOE OSTI2017

Finding a partner in the ocean: molecular and evolutionary bases of the response to sexual cues in a planktonic diatom

Microalgae play a major role as primary producers in aquatic ecosystems. Cell signalling regulates their interactions with the environment and other organisms, yet this process in phytoplankton is poorly defined. Using the marine planktonic diatom Pseudo-nitzschia multistriata, we investigated the cell response to cues released during sexual reproduction, an event that demands strong regulatory mechanisms and impacts on population dynamics. We sequenced the genome of P. multistriata and performed phylogenomic and transcriptomic analyses, which allowed the definition of gene gains and losses, horizontal gene transfers, conservation and evolutionary rate of sex-related genes. We also identified a small number of conserved noncoding elements. Sexual reproduction impacted on cell cycle progression and induced an asymmetric response of the opposite mating types. G protein-coupled receptors and cyclic guanosine monophosphate (cGMP) are implicated in the response to sexual cues, which overall entails a modulation of cell cycle, meiosis-related and nutrient transporter genes, suggesting a fine control of nutrient uptake even under nutrient-replete conditions. The controllable life cycle and the genome sequence of P. multistriata allow the reconstruction of changes occurring in diatoms in a key phase of their life cycle, providing hints on the evolution and putative function of their genes and empowering studies on sexual reproduction

Plant Sciences↗
DOE OSTI2018

Photosystem II Water Oxidation: Mechanism, Efficiency and Flux in Diverse Oxygenic Phototrophs

In one year, we pursued four aims: 1) extend the VZAD model to allow analysis of PSII chlorophyll fluorescence emission as modulated by interaction with the WOC (partial success); 2) compare the solar energy conversion efficiencies of PSII-WOCs from intact cells, isolated thylakoid membranes and PSII core complexes and crystals from cyanobacterium Thermosynechococcus elongatus (collaboration with Lawrence Berkeley National Laboratory; some success after changing collaborator); 3) determine whether PSIIs can store light energy by pumping protons across the thylakoid membrane (PSII-cyclic electron flow) and how it is regulated within the green alga Chlorella ohadii (collaboration with the Hebrew University of Jerusalem; some success); and 4) genetically replace the native PSII-D1 protein subunit from a higher plant with two cyanobacterial D1 isoforms to test whether their functional advantages in growth and photoprotection can be transferred (collaboration with Rutgers University; success).

14 SOLAR ENERGY↗
DOE OSTI2021

Integrated Heat Exchanger-Phase Change Material Thermal Energy Storage System

The purpose of this study is to experimentally investigate the thermal performance of an innovative thermal energy storage (TES) system that combines the advantages of the phase-change material (PCM)/graphite foam latent heat TES medium developed at Argonne National Laboratory (Argonne) and the internally supported plate-fin (ISPE) cell architecture heat transfer fluid (HTF) flow channels developed at Brayton Energy (Brayton). Several essential tasks were accomplished: (1) Thermal property characterization. Thermal properties of the graphite foam were characterized, providing necessary data for experimental result analysis and numerical simulation. (2) Design and optimization of lab-scale test module. Based on Brayton’s full-scale heat exchanger (HX)-TES system, the experimental test module was designed, optimized, and fabricated. (3) Thermal performance testing and data analysis. Five cycle tests were successfully conducted—including one with approximately 3.5 psig of pressure applied to the diaphragms—to investigate the thermal performance of the experimental test module for charging and discharging. Temperature profiles were generated for each charging test and discharging test as a function of time. The temperature profiles clearly show three TES stages: sensible heat (temperature increase), latent heat (melting), and sensible heat (temperature increase) for the charging process. Similarly, the temperature profiles clearly show three thermal energy release stages: sensible heat (temperature decrease), latent heat (solidification), and sensible heat (temperature decrease). Melting and solidification of the PCM generally occurred in relatively narrow temperature ranges, indicated by the flattened temperature regions in the temperature profiles. These phase changes ranged approximately 3°C for melting and 3.5°C for solidification. The charging and discharging temperature profiles were similar for similar experimental parameter tests whether or not pressure was applied to the diaphragm to eliminate the gap between the HX surface and the TES subsystem. This indicates that the effect of a small gap between the HX surface and the TES subsystem is insignificant for charging and discharging. (4) Comparison of experimental data and simulation results. We compared the experimental data to the numerical simulation results. Numerical simulations were conducted by using the ANSYS FLUENT 2019 R3 commercial computational fluid dynamics software. The predicted phase-change times agreed reasonably well with those from the experimental data. In most cases, the estimated time differences between the relative phase changes were within 16%. The predicted start and end times for the charging process agreed well with those from the experimental data. However, the simulation results showed earlier start and end times than the experimental data for the discharging process. Overall, the experimental data and its comparison with the simulation predictions verified the technical viability of the integrated ISPF HX-PCM/graphite foam latent-heat TES system.

25 ENERGY STORAGE↗
DOE OSTI2018

Codon usage revisited: Lack of correlation between codon usage and the number of tRNA genes in enterobacteria

Highlights: • Average number of tRNA genes correlate with codon usage in highly expressed genes. • Changes in the number of tRNA genes do not correlate to codon usage. • Altered tRNA gene copy numbers do not correlate to changes of codon translation. • Our data indicates that tRNA gene copies adapt to codon usage, but not the contrary. It is widely believed that if a high number of genes are found for any tRNA in a rapidly replicating bacteria, then the cytoplasmic levels of that tRNA will be high and an open reading frame containing a higher frequency of the complementary codon will be translated faster. This idea is based on correlations between the number of tRNA genes, tRNA concentration and the frequency of codon usage observed in a limited number of strains as well as from the fact that artificially changing the number of tRNA genes alters translation efficiency and consequently the amount of properly folded protein synthesized. tRNA gene number may greatly vary in a genome due to duplications, deletions and lateral transfer which in turn would alter the levels and functionality of many proteins. Such changes are potentially deleterious for fitness and as a result it is expected that changes in tRNA gene numbers should be accompanied by a modification of the frequency of codon usage. In contrast to this model, when comparing the number of tRNA genes and the frequency of codon usage of several Salmonella enterica and Escherichia coli strains we found that changes in the number of tRNA genes are not correlated to changes in codon usage. Furthermore, these changes are not correlated with a change in the efficiency of codon translation. These results suggest that once a genome gains or loses tRNA genes, it responds by modulating the concentrations of tRNAs rather than modifying its frequency of codon usage.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Microscopic Origin of Twist-Dependent Electron Transfer Rate in Bilayer Graphene

Using molecular simulation and continuum dielectric theory, we consider how electrochemical kinetics are modulated by the twist angle in bilayer graphene electrodes. By establishing a connection between the twist angle and the screening length of charge carriers within the electrode, we investigate how tunable metallicity modifies the statistics of the electron transfer energy gap. Constant potential molecular simulations show that the activation free energy for electron transfer increases with screening length, leading to a non-monotonic dependence on the twist angle. Here, the twist angle alters the density of states, tuning the number of thermally accessible channels for electron transfer and the reorganization energy by affecting the stability of the vertically excited state through attenuated image charge interactions. Understanding these effects allows us to express the Marcus rate of interfacial electron transfer as a function of the twist angle in a manner consistent with experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Pam2 lipopeptides systemically increase myeloid-derived suppressor cells through TLR2 signaling

Myeloid-derived suppressor cells (MDSCs) are immature myeloid cells that exhibit potent immunosuppressive activity. They are increased in tumor-bearing hosts and contribute to tumor development. Toll-like receptors (TLRs) on MDSCs may modulate the tumor-supporting properties of MDSCs through pattern-recognition. Pam2 lipopeptides represented by Pam2CSK4 serve as a TLR2 agonist to exert anti-tumor function by dendritic cell (DC)-priming that leads to NK cell activation and cytotoxic T cell proliferation. On the other hand, TLR2 enhances tumor cell progression/invasion by activating tumor-infiltrating macrophages. How MDSCs respond to TLR2 agonists has not yet been determined. In this study, we found intravenous administration of Pam2CSK4 systemically up-regulated the frequency of MDSCs in EG7 tumor-bearing mice. The frequency of tumor-infiltrating MDSCs was accordingly increased in response to Pam2CSK4. MDSCs were not increased by Pam2CSK4 stimuli in TLR2 knockout (KO) mice. Adoptive transfer experiments using CFSE-labeled MDSCs revealed that the TLR2-positive MDSCs survived long in tumor-bearing mice in response to Pam2CSK4 treatment. Since the increased MDSC population sustained immune-suppressive properties, our study suggests that Pam2CSK4-triggered TLR2 activation enhances the MDSC potential and suppress antitumor immune response in tumor microenvironment. - Highlights: • Pam2CSK4 administration induces systemic accumulation of CD11b{sup +}Gr1{sup +} MDSCs. • TLR2 is essential for Pam2CSK4-induced accumulation of CD11b{sup +}Gr1{sup +} MDSCs. • Pam2CSK4 supports survival of CD11b{sup +}Gr1{sup +} MDSCs in vivo.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Achieving Multimodal and Multicolor Luminescence in LaAlO 3 :Pr 3+ , Gd 3+ via Trap Engineering and Energy Transfer

Achieving multimodal luminescence within a single phosphor is vital for multifunctional applications but remains challenging due to complex color tuning and trap engineering. In this study, we report Pr 3+ and Gd 3+ co‐doped LaAlO 3 (LAO:PG) phosphors, designed through careful modulation of multilevel traps and Pr 3+ → Gd 3+ energy transfer dynamics. These materials exhibit diverse luminescence modes, including down‐conversion luminescence (DCL), up‐conversion luminescence (UCL), persistent luminescence (PersL), optically stimulated luminescence (OSL), and thermally stimulated luminescence (TSL) across a wide spectral range. Unlike previously studied Pr 3+ ‐doped LAO, the co‐doped LAO:PG shows DCL in both UV‐visible and NIR regions and displays ultraviolet‐C UCL under visible excitation. Notably, we observe, for the first time, PersL lasting several minutes in these phosphors—an improvement over the non‐PersL behavior of Pr 3+ ‐only doped LAO. Additionally, the LAO:PG phosphors exhibit strong OSL response. TSL analysis reveals five distinct trap levels linked to these properties. Density functional theory calculations further correlate intrinsic defects to these traps, supporting a proposed mechanism for the observed multimodal luminescence. These findings highlight LAO:PG as a promising platform for developing advanced phosphors with integrated luminescence modes, paving the way for future applications in data storage, phototherapy, and anti‐counterfeiting technologies.

Chemistry↗
DOE OSTI2019

First Annual Report on Pulsed Thermal Tomography Nondestructive Evaluation of Additively Manufactured Reactor Materials and Components: Pulsed Thermal Tomography Nondestructive Examination of Additively Manufactured Reactor Materials and Components

Additive manufacturing (AM, or 3D printing) for commercial nuclear energy applications is an emerging method for cost-efficient manufacturing aimed at replacing aging nuclear reactor parts and reducing costs for new construction. Because of the geometry of metallic structures of interest for nuclear applications, which consist of planar primitives with no symmetry of revolution, limited options are available for nondestructive evaluation (NDE), either during or post manufacturing. Known material flaws in AM include low-density regions consisting of non-sintered powder, which have to be detected to ensure the safety of long-term performance nuclear reactor components. As a solution to NDE of AM, we are developing pulsed thermal tomography (PTT) models and depth inversion algorithms for 3D imaging. PTT has many advantages because the method is non-contact and allows for in-service, NDE of AM nuclear reactor parts. By analyzing transients of surface temperature response due to internal thermal resistances, one can obtain 3D reconstructions of material effusivity using a unique inversion algorithm developed at Argonne. This report provides results of preliminary performance evaluation of PTT capability in detection of flaws in metallic structures, as well imaging complex geometry AM structures. Performance of PTT was investigated through modeling and experiments, Computer models of PTT were developed using COMSOL Heat Transfer module. Defects were modeled as cylindrical flat bottom holes (FBH), which is a common model of calibrated material flaws in thermal tomography experiments. Materials considered in this study include stainless steel 316 (SS316), stainless steel 304 (SS304), and Inconel 718. Theoretical analyses were conducted to validate inversion of simulated PTT data with COMSOL for a plate. Subsequently, 3D reconstructions were performed on COMSOL simulations for FBH, revealing a decrease in spatial resolution over depth due to thermal diffusion. The results of this study show that the performance of the inversion algorithm for detecting smaller defects depends strongly on the depth of the defect as well as the incident heat flux. The size of detectable defect was estimated by fitting a Gaussian function to surface temperature profile. The criteria for detectability was taken as 20mK noise equivalent temperature difference (NETD), which is currently the sensitivity limit of high-performance infrared cameras. It was determined through computer simulations that the smallest detectable FBH in SS316 has a 50µm diameter and is located 0.5mm below the plate surface. Preliminary experimental studies were performed to evaluate PTT performance in detecting calibrated flaws using metallic specimens with AM defects simulated as drilled-in FBH’s. High strength Stainless Steel 316 and Inconel 718 alloys were considered, as well as lower grade Stainless Steel 304, Nickel 200, and Hastelloy C276. Specimens investigated in this report consisted of approximately 1/4in-thick plates made out of these alloys using conventional manufacturing methods. The diameters of FBH’s varied from 1mm to 8mm, and their depths below the plate flat surface varied between 1mm and 6mm. The size of the smallest FBH was limited to 1mm because conventional mechanical drills were used for creating the holes. PTT imaging results have shown that 1mm-diameter FBH located 1mm and 2mm below the surface were detectable. Larger size FBH were detectable at greater depth. For example, 6mm-diameter FBH could be detected at 8mm depth. Image contrast varied slightly between the specimens, with the best reconstructions obtained in SS316 and C276 plates. Finally, PTT capability in imaging several AM structures fabricated from Inconel 718 (IN718) powder feedstock was investigated. The AM structures have complex geometry, but do not have calibrated internal defects. The objective is to determine PTT settings, such as the total integration time, for imaging of representative AM structures. A new FLIR X8500sc IR camera with higher spatial resolution (1280x1024 at 181Hz frame rate) was integrated into the PTT laboratory setup. Software tools were developed to ensure compatibility of new camera files with legacy effusivity reconstruction codes. The new camera was used to obtain 3-D reconstructions of AM IN718 nozzle plate and a particle filter plate. It was shown that PTT can scan through 2/3in-thick Inconel 718 plates in approximately 15s. Several modes of 3-D data visualization were explored, including using ImageJ and MATLAB software packages. The results demonstrate the capability of PTT in 3-D imaging of complex geometry AM structures. Intermediate results demonstrated in this report will be developed further to investigate detection of flaws in AM specimens.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗