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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Three-dimensional cross-field flows at the plasma-material interface in an oblique magnetic field

This article describes experimental evidence that the magnetic presheath is a fully three-dimensional structure modified by ion–neutral collisions. Velocity distributions of both ions and neutrals, obtained via laser-induced fluorescence, show that cross field ion drifts do not result from entrainment of ions in a flowing neutral background. Ion flows parallel to E x B arise and accelerate to as much as 0.2c s within several ion gyroradii of the boundary surface, where c s is the sound speed. Within measurement resolution, the onset of the E x B aligned flow occurs at the same distance to the surface that ions begin to deflect from travel along magnetic field lines. Collisional fluid and particle-in-cell simulations of the boundary region are compared to the experimental measurements. We find that, in contrast to the classical collisionless Chodura model, collisional effects between the ions and the non-flowing neutral population are essential to quantitatively predict the observed ion drift velocities. No momentum coupling between ions and neutrals, separable from noise and other effects, is observed in either signal. Here, we discuss several explanations and implications of this observation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Demonstration of Selective Single-Barium Ion Detection with Dry Diazacrown Ether Naphthalimide Turn-on Chemosensors

Single-molecule fluorescence imaging (SMFI) of gas-phase ions has been proposed for “barium tagging,” a burgeoning area of research in particle physics to detect individual barium daughter ions. This has potential to significantly enhance the sensitivity of searches for neutrinoless double-beta decay (0νββ) that is obscured by background radiation events. The chemistry required to make such sensitive detection of Ba 2+ by SMFI in dry Xe gas at solid interfaces has implications for solid-phase detection methods but has not been demonstrated. Here, we synthesized simple, robust, and effective Ba 2+ -selective chemosensors capable of function within ultrapure high-pressure 136 Xe gas. Turn-on fluorescent naphthalimide-(di)azacrown ether chemosensors were Ba 2+ -selective and achieved SMFI in a polyacrylamide matrix. Here, fluorescence and NMR experiments supported a photoinduced electron transfer mechanism for turn-on sensing. Ba 2+ selectivity was achieved with computational calculations correctly predicting the fluorescence responses of sensors to barium, mercury, and potassium ions. With these molecules, dry-phase single-Ba 2+ ion imaging with turn-on fluorescence was realized using an oil-free microscopy technique for the first time—a significant advance toward single-Ba 2+ ion detection within large volumes of 136 Xe, plausibly enabling a background-independent technique to search for the hypothetical process of 0νββ.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS2019

Achieving Improved Reliability with Failure Analysis

Reliability is the ability of a product to properly function, within specified performance limits, for a specified period of time, under the life cycle application conditions. Failure analysis is a vital tool in the effort to ensure reliability of electronic products and systems throughout their product lifecycle. Today, organizations involved in activities within the electronics supply chain are facing new challenges, not just from complex assembly styles, harsher lifecycle environments, and sophisticated supply chains, but also from customers who are demanding a quicker turn-around. Unfortunately, root cause failure analysis is often performed incompletely, leading to a poor understanding of failure mechanisms and causes and, customer dissatisfaction due to recurring failures. The PDC (Professional Development Course) starts with an introduction to reliability concepts, physics of failure and an overview of failure mechanisms that affect PCBs (Printed Circuit Boards), PCBAs (Printed Circuit Board Assembly) and components. The PDC then dives into root cause hypothesizing techniques (Pareto, FMEA (Failure Modes and Effects Analysis), fishbone (Cause-And-Effect Diagram), FTA (Fault Tree Analysis)), non-destructive and destructive analysis and, materials characterization will be discussed. Numerous failure analysis case studies will be used to illustrate the techniques and analysis principles to arrive at the root cause(s) of field failures on printed circuit boards, active components, and assemblies. What Attendees will Learn: Topics include: Overview of Reliability Concepts Failure mechanisms of electronic products Root cause analysis Failure analysis techniques -Non-destructive techniques (optical, CSAM (Confocal Scanning Electron Microscopy) etc.) -Destructive analysis (DPA (Destructive Physical Analysis), Decap (Decapsulation), FIB (Focused Ion Beam) etc.) -Materials characterization (XRF (X-Ray Fluorescence) , EDS (Error Detection Sequential), TMA/DSC (Thermal Mechanical Analysis/Differential Scanning Calorimetry) etc.)

PCB quality↗
DOE OSTI2021

Exploring chemistry with single-molecule and -particle fluorescence microscopy

The evolution of single-molecule and -particle fluorescence microscopy imaging techniques for the investigation of chemical reactions yielded achievements at all fronts, from synthetic organic chemistry to materials science. The removal of ensemble averaging effects uncovers unique, otherwise hidden reaction intermediates, reactivity, and kinetics. Thus, new insights can be obtained even for well-explored chemical reactions and processes. The aim of this article is to serve as a guide and a source of inspiration for scientists who wish to develop single-molecule and -particle fluorescence microscopy to answer questions in chemistry. Here, we describe the current status of technical accomplishments in the field and point out technical and conceptual obstacles for overcoming in the near future, with focus on improvement of bench-scale synthetic reactions.

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

Proton Transfer Dynamics in the Aprotic Proton Accepting Solvent 1-Methylimidazole

The dynamics of proton transfer to the aprotic solvent 1-methylimidazole (MeIm, proton acceptor) from the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) were investigated using fast fluorescence measurements. The closely related molecule, 8- methoxypyrene-1,3,6-trisulfonic acid trisodium salt (MPTS), which is not a photoacid, was also studied for comparison. Following optical excitation, the wavelength-dependent population dynamics of HPTS in MeIm resulting from the deprotonation process were collected over the entire fluorescence emission window. Analysis of the time-dependent fluorescence spectra revealed four distinct fluorescence bands that appear and decay on different time scales. We label these four states as: protonated (P), associated I (A I ), associated II (A II ), and deprotonated (D). We find that the simple kinetic scheme of P → A I → A II → D is not consistent with the data. Instead, the kinetic scheme that describes the data has P decaying into A I , which mainly goes on to deprotonation (D), but AI can also feed into A II . A II can return to A I or decay to the ground state, but does not deprotonate within experimental error. Finally, quantum chemistry and excitedstate QM/MM Born-Oppenheimer molecular dynamics simulations indicate that A I and A II are two H-bonding conformations of MeIm to the HPTS hydroxyl, axial and equatorial, respectively.

14 SOLAR ENERGY↗
DOE OSTI2025

The Impact of Carotenoid Energy Levels on the Exciton Dynamics and Singlet–Triplet Annihilation in Isolated Bacterial Light-Harvesting 2 Complexes

The light-harvesting 2 (LH2) complex of purple phototrophic bacteria plays a critical role in absorbing solar energy and distributing the excitation energy. Exciton dynamics within LH2 complexes are controlled by the structural arrangement and energy levels of the bacteriochlorophyll (BChl) and carotenoid (Car) pigments. However, there is still debate over the competing light-harvesting versus energy-dissipation pathways. In this work, we compared five variants of the LH2 complex from genetically modified strains of Rhodobacter sphaeroides, all containing the same BChls but different Cars with increasing conjugation: zeta-carotene (N = 7; LH2 Zeta ), neurosporene (N = 9; LH2 Neu ), spheroidene (N = 10; LH2 Spher ), lycopene (N = 11; LH2 Lyco ), and spirilloxanthin (N = 13; LH2 Spir ). Absorption measurements confirmed that the Car excited-state energy decreased with increasing conjugation. Similarly, fluorescence spectra showed that the B850 BChl emission peak had an increasing red shift from LH2 Zeta →(LH2 Neu /LH2 Spher )→LH2 Lyco →LH2 Spir . In contrast, time-resolved fluorescence and ultrafast transient absorption (fs-TA) revealed similar excited-state lifetimes (∼1 ns) for all complexes except LH2 Spir (∼0.7 ns). From fs-TA analysis, an additional ∼7 ps nonradiative dissipation step from B850 BChl was observed for LH2 Zeta . Further, singlet− singlet and singlet−triplet annihilation studies showed a ∼50% average fluorescence lifetime reduction in LH2Zeta at high laser power and high repetition rate, compared to ∼10−15% reductions in LH2 Neu /LH2 Spher /LH2 Lyco and minimal lifetime change in LH2 Spir . In LH2 Zeta , the fastest decay component (<50 ps) became prominent at high repetition rates, consistent with strong singlet−triplet annihilation. Nanosecond TA measurements revealed long-lived (>40 μs) BChl triplet states in LH2 Zeta and signs of damage caused by singlet oxygen, whereas other LH2s showed faster triplet quenching (∼18 ns) by Cars. These findings highlight a key design principle of LH2 complexes: the Car triplet energy must be significantly lower than the BChl triplet energy to efficiently quench BChl triplets that otherwise act as potent “trap states,” causing exciton annihilation in laser-based experiments or photodamage in native membranes.

Absorption↗
DOE OSTI2021

Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity

Single molecule spectroscopy studies of local acidity along bifunctional acid-base gradients are reported. Gradients are prepared by directional vapor phase diffusion and subsequent reaction of 3-aminopropyl-trimethoxysilane with a uniform silica film. Gradient formation is confirmed by spectroscopic ellipsometry and by static water contact angle measurements. X-ray photoelectron spectroscopy is used to characterize the nitrogen content and degree of nitrogen protonation along the gradient. Nile Red is employed as the probe dye in single molecule spectroscopy studies of these gradients. While Nile Red is well-known for its solvent sensitivity, it is used here, for the first time, to sense the acid/base properties of the film in two-color wide-field fluorescence imaging experiments. The data reveal broad bimodal distributions of Nile Red emission spectra that vary along the gradient direction. The single-molecule results are consistent with solution-phase ensemble acid/base studies of the dye. The former reveal a gradual transition from a surface dominated by basic aminosilane sites at the high-amine end of the gradient to one dominated by acidic silanol sites at the low-amine end. The sub-diffraction-limited spatial resolution afforded by superlocalization of the single molecules reveals spatial correlations in the acid/base properties of the gradient over ~ 200 nm distances. Furthermore, these studies provide data relevant to the use of aminosilane-modified silica in bifunctional, cooperative chemical catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Photon-Sparse, Poisson Light-Sheet Microscopy

Light-sheet microscopy has revolutionized bioimaging by enabling approximately an order of magnitude reduction in specimen irradiance compared to confocal imaging. Here, we introduce a light-sheet imaging system that enables an additional order of magnitude reduction in specimen irradiance by operating at the Poisson limit. To operate at this limit, we integrated classical illumination with single-photon detection and wavelet-based image reconstruction. This integration enabled brightness quantification and object recognition from fewer than one detected photon per image pixel, corresponding to more than 10-fold lower irradiance levels than modern systems. We demonstrate how such photon-sparse imaging can eradicate photobleaching and enable both dim and bright object imaging, thus, further enhancing the related gains of light-sheet microscopy.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Phonon-exciton Interactions in WSe 2 under a quantizing magnetic field

Strong many-body interaction in two-dimensional transitional metal dichalcogenides provides a unique platform to study the interplay between different quasiparticles, such as prominent phonon replica emission and modified valley-selection rules. A large out-of-plane magnetic field is expected to modify the exciton-phonon interactions by quantizing excitons into discrete Landau levels, which is largely unexplored. Here, we observe the Landau levels originating from phonon-exciton complexes and directly probe exciton-phonon interaction under a quantizing magnetic field. Phonon-exciton interaction lifts the inter-Landau-level transition selection rules for dark trions, manifested by a distinctively different Landau fan pattern compared to bright trions. This allows us to experimentally extract the effective mass of both holes and electrons. The onset of Landau quantization coincides with a significant increase of the valley-Zeeman shift, suggesting strong many-body effects on the phonon-exciton interaction. Our work demonstrates monolayer WSe 2 as an intriguing playground to study phonon-exciton interactions and their interplay with charge, spin, and valley.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

De novo design of modular protein hydrogels with programmable intra- and extracellular viscoelasticity

Relating the macroscopic properties of protein-based materials to their underlying component microstructure is an outstanding challenge. Here, we exploit computational design to specify the size, flexibility, and valency of de novo protein building blocks, as well as the interaction dynamics between them, to investigate how molecular parameters govern the macroscopic viscoelasticity of the resultant protein hydrogels. We construct gel systems from pairs of symmetric protein homo-oligomers, each comprising 2, 5, 24, or 120 individual protein components, that are crosslinked either physically or covalently into idealized step-growth biopolymer networks. Through rheological assessment, we find that the covalent linkage of multifunctional precursors yields hydrogels whose viscoelasticity depends on the crosslink length between the constituent building blocks. In contrast, reversibly crosslinking the homo-oligomeric components with a computationally designed heterodimer results in viscoelastic biomaterials exhibiting fluid-like properties under rest and low shear, but solid-like behavior at higher frequencies. Exploiting the unique genetic encodability of these materials, we demonstrate the assembly of protein networks within living mammalian cells and show via fluorescence recovery after photobleaching (FRAP) that mechanical properties can be tuned intracellularly in a manner similar to formulations formed extracellularly. We anticipate that the ability to modularly construct and systematically program the viscoelastic properties of designer protein-based materials could have broad utility in biomedicine, with applications in tissue engineering, therapeutic delivery, and synthetic biology.

36 MATERIALS SCIENCE↗
NASA NTRS1984

Results from the X-ray polychromator on SMM

Observations of the soft X-ray emitting plasma by means of the X-Ray Polychromator (XRP) on the Solar Maximum Mission satellite are described. The scientific advances achieved by use of the XRP are in the areas of: (1) flare morphology, (2) spectroscopy and plasma diagnostics, (3) chromospheric evaporation and the physics of flare loops, (4) studies of the microwave emission mechanisms of active regions, (5) the fluorescent excitation of Fe II K-alpha radiation, (6) measurement of variations of calcium abundance for X-ray plasmas, and (7) soft X-ray observations of spray transients. The findings in each of these areas are discussed.

Culhane, J. L.↗
NASA NTRS1999

Novel optical methodologies in studying mechanical signal transduction in mammalian cells

For the last 3 decades evidence has been accumulating that some types of mammalian cells respond to their mechanically active environment by altering their morphology, growth rate, and metabolism. The study of such responses is very important in understanding, physiological and pathological conditions ranging from bone formation to atherosclerosis. Obtaining this knowledge has been the goal for an active research area in bioengineering termed cell mechanotransduction. The advancement of optical methodologies used in cell biology research has given the tools to elucidate cellular mechanisms that would otherwise be impossible to visualize. Combined with molecular biology techniques, they give engineers invaluable tools in understanding the chemical pathways involved in mechanotransduction. Herein we briefly review the current knowledge on mechanical signal transduction in mammalian cells, focusing on the application of novel optical techniques in the ongoing research.

NASA Discipline Cell Biology↗
DOE OSTI2020

Electrochemical Switching of a Fluorescent Molecular Rotor Embedded within a Bistable Rotaxane

We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely, an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state coconformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF2+ dication, the CBPQT4+ ring is forced toward the molecular rotor, leading to an increased energy barrier for the excited state to rotate the rotor into the state with a high nonradiative rate constant, resulting in an overall 3.4-fold fluorescence enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge-transfer state between the BODIPY rotor and the CBPQT4+ ring, movement of the ring toward the BODIPY rotor produces an unexpectedly strong fluorescence signal decrease as the result of photoinduced electron transfer from the BODIPY rotor to the CBPQT4+ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories, and molecular logic gates.

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

Resolution-enhanced X-ray fluorescence microscopy via deep residual networks

Abstract Multimodal hard X-ray scanning probe microscopy has been extensively used to study functional materials providing multiple contrast mechanisms. For instance, combining ptychography with X-ray fluorescence (XRF) microscopy reveals structural and chemical properties simultaneously. While ptychography can achieve diffraction-limited spatial resolution, the resolution of XRF is limited by the X-ray probe size. Here, we develop a machine learning (ML) model to overcome this problem by decoupling the impact of the X-ray probe from the XRF signal. The enhanced spatial resolution was observed for both simulated and experimental XRF data, showing superior performance over the state-of-the-art scanning XRF method with different nano-sized X-ray probes. Enhanced spatial resolutions were also observed for the accompanying XRF tomography reconstructions. Using this probe profile deconvolution with the proposed ML solution to enhance the spatial resolution of XRF microscopy will be broadly applicable across both functional materials and biological imaging with XRF and other related application areas.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Spectroscopic and computational investigations of organometallic complexation of group 12 transition metals by methanobactins from Methylocystis sp. SB2

Methanotrophic bacteria catalyze the aerobic oxidation of methane to methanol using Cu-containing enzymes, thereby exerting a modulating influence on the global methane cycle. To facilitate the acquisition of Cu ions, some methanotrophic bacteria secrete small modified peptides known as “methanobactins,” which strongly bind Cu and function as an extracellular Cu recruitment relay, analogous to siderophores and Fe. In addition to Cu, methanobactins form complexes with other late transition metals, including the Group 12 transition metals Zn, Cd, and Hg, although the interplay among solution-phase configurations, metal interactions, and the spectroscopic signatures of methanobactin-metal complexes remains ambiguous. In this study, the complexation of Zn, Cd, and Hg by methanobactin from Methylocystis sp. strain SB2 was studied using a combination of absorbance, fluorescence, extended x-ray absorption fine structure (EXAFS) spectroscopy, and time-dependent density functional theory (TD-DFT) calculations. We report changes in sample absorbance and fluorescence spectral dynamics, which occur on a wide range of experimental timescales and characterize a clear stoichiometric complexation dependence. Mercury L3-edge EXAFS and TD-DFT calculations suggest a linear model for Hg--S coordination, and TD-DFT suggests a tetrahedral model for Zn 2+ and Cd 2+ . We observed an enhancement in the fluorescence of methanobactin upon interaction with transition metals and propose a mechanism of complexation-hindered isomerization drawing inspiration from the wild-type Green Fluorescent Protein active site. Collectively, our results represent the first combined computational and experimental spectroscopy study of methanobactins and shed new light on molecular interactions and dynamics that characterize complexes of methanobactins with Group 12 transition metals.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1980

Excitation mechanisms for the unidentified infrared emission features

Infrared and radio observations of various objects are analyzed to put observational constraints on the mechanism which gives rise to the unidentified emission features at 3.3, 3.4, 6.2, 7.7, 8.6, and 11.3 microns. The results show that gas-grain collisions or fluorescence is not likely to be the excitation mechanism responsible for the observed features. Thermal emission by dust is reanalyzed and it is concluded that this mechanism can explain the emission features. A simple model in which the emission features arise in a population of small, hot, interstellar grains is constructed. These grains are very efficient radiators, and the emitting materials only need be a minor grain constituent to provide the power that is emitted in the features. The model offers, therefore, a simple explanation for the absence of these features in absorption.

Dwek, E.↗
DOE OSTI2025

The Reaction Rates of Amidogen and Ammonia with Nitrous Oxide: Implications for Combustion Mechanisms

Pulsed laser photolysis experiments with laser-induced fluorescence detection of NH 2 set an upper limit to the rate constant for reaction with N 2 O of k < 1 × 10 −15 cm 3 molecule −1 s −1 at 513 K. Computations were based on geometries and anharmonic frequency analysis (B2PLYP-D3/cc-pVTZ) followed by coupled cluster calculations extrapolated to the infinite basis set limit, with corrections for core−valence electron correlation, scalar relativistic effects, and correlation up to CCSDT(Q). Species that showed multireference character were quantified with MRCI(7,7)+Q/cc-pVTZ theory. Rate constants were obtained for the dominant product channel H 2 NN + NO, along with HN 3 + OH, H 2 NO + N 2 , NNH + HNO, ON(NH) 2 and HNNH + NO. The last channel is slow even at 2500 K, contrary to an early empirical estimate and confirming recent suggestions. Modeling of literature experiments on oxidation of NH 3 by N 2 O shows that all channels are too slow to make a significant impact on the loss of N 2 O in ammonia flames. Similarly, the direct NH 3 + N 2 O reaction is found to be negligibly slow.

Ammonia↗
DOE OSTI2020

Nonlinear fluorescence spectroscopy of layered perovskite quantum wells

Interest in layered organohalide perovskites is motivated by their potential for use in optoelectronic devices. In these systems, the smallest and largest quantum wells are primarily concentrated near the glass and air interfaces of a film, thereby establishing a gradient in the average values of the bandgaps. It has been suggested that this layered architecture promotes the funneling of electronic excitations through space in a manner similar to light-harvesting processes in photosynthetic antennae. Whereas energy and charge transfer are difficult to distinguish by conventional transient absorption techniques, it has recently been shown that these competing relaxation mechanisms may be separately targeted with nonlinear fluorescence (NLFL) and photocurrent “action spectroscopies.” Here, we present perturbative rate functions to describe NLFL experiments conducted on layered perovskite systems. The formulas reproduce the patterns of resonances observed in experimental measurements and show how signatures of energy transfer manifest in two-dimensional spectra. Overall, this work suggests that NLFL spectroscopy may be used to fully reveal the trajectories of electronic excitations by correlating ultrafast energy transfer pathways to fluorescence emission from the thickest quantum wells.

Ouyang, Zhenyu↗