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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 55 records · Page 3

Quantitative temporally and spatially resolved X-ray fluorescence microprobe characterization of the manganese dissolution-deposition mechanism in aqueous Zn/α-MnO 2 batteries

Rechargeable aqueous Zn/α-MnO 2 batteries are a possible alternative to lithium ion batteries for scalable stationary energy storage applications due to their low cost, safety and environmentally benign components. A critical need for advancement of this battery system is a full understanding of the electrochemical reaction mechanisms, which remain unclear. In this report, operando , spatiotemporal resolved synchrotron X-ray fluorescence mapping measurements on a custom aqueous Zn/α-MnO 2 cell provided direct evidence of a Mn dissolution-deposition faradaic mechanism that governs the electrochemistry. Simultaneous visualization and quantification of the Mn distribution in the electrolyte revealed the formation of aqueous Mn species during discharge and depletion on charge. The findings are supported by ex situ transmission electron microscopy (TEM), X-ray diffraction, Mn K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. The elucidated mechanism is fundamentally different from the previously proposed Zn 2+ insertion or conversion reactions. These findings provide a foundation for developing dissolution- deposition chemistries suitable for scalable stationary energy storage with aqueous electrolyte.

25 ENERGY STORAGE↗

Cyanine-Incorporated Amorphous Polymeric Carbon Dots for Optical Reactive Oxygen Species Sensing

Reactive oxygen species (ROS) are common cellular oxidants that when overproduced by cellular stressors cause harm to cells. Detection of ROS is of utmost importance to understanding a wide variety of cellular function and toxicity mechanisms. Conventional ROS fluorescence assays involve using a single dye to visualize the ROS quantity. Herein, we describe ROS-sensitive, fluorescent-dye-incorporated carbon dots with dual fluorescence capabilities and good biocompatibility. Carbon dots (CDs) made of citric acid and urea were synthesized with incorporated cyanine-3-amine (Cy3), a bright red fluorescent dye, to create Cy3-CDs. Additionally, to get Cy3 into the ROS-sensitive form, this work demonstrated that Cy3 alone and Cy3 within carbon dots can be electrochemically reduced to their colorless ROS-sensitive form. Cy3, CDs, and Cy3-CDs are all responsive to additions of superoxide, leading to an increase in the fluorescence. Overall, this work examines how O 2 •– and additional oxidizers interact with CDs, Cy3, and Cy3-CDs, and molecular-level hypotheses are explored that will inform the design of future carbon dot-based ROS sensors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast X-Ray Probes of Elementary Molecular Events

Elementary events that determine photochemical outcomes and molecular functionalities happen on the femtosecond and subfemtosecond timescales. Among the most ubiquitous events are the nonadiabatic dynamics taking place at conical intersections. These facilitate ultrafast, nonradiative transitions between electronic states in molecules that can outcompete slower relaxation mechanisms such as fluorescence. The rise of ultrafast X-ray sources, which provide intense light pulses with ever-shorter durations and larger observation bandwidths, has fundamentally revolutionized our spectroscopic capabilities to detect conical intersections. Recent theoretical studies have demonstrated an entirely new signature emerging once a molecule traverses a conical intersection, giving detailed insights into the coupled nuclear and electronic motions that underlie, facilitate, and ultimately determine the ultrafast molecular dynamics. Following a summary of current sources and experiments, we survey these techniques and provide a unified overview of their capabilities. We discuss their potential to dramatically increase our understanding of ultrafast photochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metabolic multireactor: Practical considerations for using simple oxygen sensing optodes for high-throughput batch reactor metabolism experiments

We present a system for carrying out small batch reactor oxygen consumption experiments on water and sediment samples for environmental questions. In general, it provides several advantages that can help researchers achieve impactful experiments at relatively low costs and high data quality. In particular, it allows for multiple reactors to be operated and their oxygen concentrations to be measured simultaneously, providing high throughput and high time-resolution data, which can be advantageous. Most existing literature on similar small batch-reactor metabolic studies is limited to either only a few samples, or only a few time points per sample, which can restrict the ability for researchers to learn from their experiments. The oxygen sensing system is based very directly on the work of Larsen, et al. [2011], and similar oxygen sensing technology is widely used in the literature. As such we do not delve deeply into the specifics of the fluorescent dye sensing mechanism. Instead, we focus on practical considerations. We describe the construction and operation of the calibration and experimental systems, and answer many of the questions likely to come up when other researchers choose to build and operate a similar system themselves (questions we ourselves had when we first built the system). In this way, we hope to provide an approachable and easy to use research article that can help other researchers construct and operate a similar system that can be tailored to ask their own research questions, with a minimum of confusion and missteps along the way.

3D printing↗

High-resolution observation of the Venus dayglow spectrum 1250-1430 angstroms

The spectrum of the dayglow of Venus between 1250 and 1430 A was measured in high resolution with the International Ultraviolet Explorer. Seven exposures which were made with the short wavelength camera in the high dispersion mode using the large aperture were combined to give a total exposure time of 309 min. The atomic oxygen lines at 1302.2, 1304.9, 1306.0, and 1355.6 A are present. In addition, the (14,3) and (14,4) bands of the carbon monoxide fourth positive system at 1317 and 1354 A respectively are identified. These bands are compared with synthetic spectra, showing the excitation mechanism to be fluorescent scattering of solar Lyman alpha radiation.

Lane, A. L.↗

The dependence of electroglow on the solar flux

Data from Voyager 2 UV spectrometer observations of electroglow at wavelengths below 110 nm in the atmospheres of Saturn, Jupiter, and Uranus are presented in extensive tables and graphs, analyzed statistically, and compared with the predictions of theoretical models. Findings reported include (1) a dependence (to within 10 percent) of electroglow intensity on the inverse square of heliocentric distance, (2) Uranian electroglow spectra consistent with Rayleigh-Raman scattering of sunlight, and (3) local-time electroglow variations suggesting a solar-flux-dependent excitation mechanism. Mechanisms involving the fluorescence of solar UV radiation in the H2 Lyman and Werner bands or H(-) photolysis are discussed.

Yelle, Roger V.↗

On the carbon abundance in Comet Halley derived from the 3 micron feature: Comparison with interstellar dust

In spite of some similarities with the infrared features observed in the interstellar medium, the 3 micron signature observed in comet Halley's spectrum shows two distinct differences: (1) the 3.28 micron and 3.37 micron cometary features are both in emission, while the 3.37 micron interstellar feature is most often observed in absorption; and (2) there is no associated emission feature beyond 6 micron in the cometary spectrum. These two facts can be simply explained if it is assumed that the excitation mechanism is resonance fluorescence by the solar IR radiation field. With this assumption, it is found that hydrocarbons are present in roughly equal quantities in both the saturated forms, with a total carbon abundance of about 30 percent of H2O. This carbon abundance can be compared with the abundances derived for the interstellar dust when all condensed (or condensable) components are considered.

Encrenaz, Therese↗

Outer layers of a carbon star: The view from the Hubble Space Telescope

To advance our understanding of the relationship between stellar chromospheres and mass loss, which is a common property of carbon stars and other asymptotic giant branch stars, we have obtained ultraviolet spectra of the nearby N-type carbon star UU Aur using the Hubble Space Telescope (HST). In this paper we describe the HST observations, identify spectral features in both absorption and emission, and attempt to infer the velocity field in the chromosphere, upper troposphere, and circumstellar envelope from spectral line shifts. A mechanism for producing fluoresced emission to explain a previously unobserved emission line is proposed. Some related ground-based observations are also described.

Johnson, H. R.↗

Radiation-induced chromosome aberrations in ataxia telangiectasia cells: high frequency of deletions and misrejoining detected by fluorescence in situ hybridization

The mechanisms underlying the hyper-radiosensitivity of AT cells were investigated by analyzing chromosome aberrations in the G(2) and M phases of the cell cycle using a combination of chemically induced premature chromosome condensation (PCC) and fluorescence in situ hybridization (FISH) with chromosome painting probes. Confluent cultures of normal fibroblast cells (AG1522) and fibroblast cells derived from an individual with AT (GM02052) were exposed to gamma rays and allowed to repair at 37 degrees C for 24 h. At doses that resulted in 10% survival, GM02052 cells were approximately five times more sensitive to gamma rays than AG1522 cells. For a given dose, GM02052 cells contained a much higher frequency of deletions and misrejoining than AG1522 cells. For both cell types, a good correlation was found between the percentage of aberrant cells and cell survival. The average number of color junctions, which represent the frequency of chromosome misrejoining, was also found to correlate well with survival. However, in a similar surviving population of GM02052 and AG1522 cells, induced by 1 Gy and 6 Gy, respectively, AG1522 cells contained four times more color junctions and half as many deletions as GM02052 cells. These results indicate that both repair deficiency and misrepair may be involved in the hyper-radiosensitivity of AT cells.

NASA Center JSC↗

Flame Flashback Investigations in Hydrogen-Enriched Low Swirl Flames using High-Speed Hydroxyl (OH) Planar Laser-Induced Fluorescence

This study reports flashback mechanism observed in hydrogen-enriched flames stabilized in a low swirl burner (LSB) at atmospheric pressure and temperature conditions. The fundamentals of hydrogen-rich stable flames and spatiotemporal investigation of flashback phenomena were observed experimentally using a high-repetition-rate nanosecond (ns)-duration hydroxyl radical planar laser-induced fluorescence (OH-PLIF) diagnostic. Testing was conducted in an optically accessible pre-mixing section of LSB with inlet pre-mixing velocities from 5 to 10 m/s for methane and hydrogen (50 – 90% by mole) blends. Swirlers with two different turning angles, 26 and 33 degrees and three different perforated plate hole diameters, 1.08, 1.12 and 1.16 mm with measured swirl numbers varying from 0.43 to 0.49 were used. The flashback propensity showed dependence on the proximity of the lifted flame to the burner exit which was dependent on pre-mixer velocity, hydrogen content and equivalence ratio (ER). High-speed OH-PLIF images revealed lifted flames were first observed at low ER condition which is changed to M-shaped flame attached to burner rim with the increase in ER. Then, further increase in ER triggers flame flashback into the nozzle. Flashback occurred when burning occurs in the outer shear layer and the leading flame brush ingresses into the nozzle.

Parajuli, Pradeep↗

Nanomechanical and Fluorescence Characterizations of Weathered PV Module Encapsulation

Nanoindentation and fluorescence spectroscopy provide spatially resolved mechanical and chemical characterization for degradation of poly (ethylene-co-vinyl acetate) (EVA) encapsulants aged under accelerated weathering and in field deployed photovoltaic (PV) modules. For the accelerated weathering tests, two different EVA formulations in the glass/EVA/glass-laminated coupons were exposed to ultraviolet (UV) light for 180 days at three different temperatures (40, 60, and 80 °C) and UV intensities (0.4, 2.2, and 2.9 W/m2/nm at 340 nm). The fluorescence spectra and moduli were uniform through the cross section of both EVA formulations at the lowest temperature and UV intensity; however, under the highest temperature and UV intensity, the UV irradiated sides showed lower moduli and higher fluorescence compared to the opposite sides. For EVA obtained from PV modules deployed 27 years in Sacramento, CA, USA, changes in fluorescence intensity across the thickness were relatively greater than changes in modulus. On the other hand, for EVA obtained from the same type of module stored in the shed for 27 years, no fluorescence was observed, and a uniform modulus was seen through the EVA layer, but with substantially higher values than those obtained from the field-deployed modules. The different extent of changes between laboratory and field exposures suggests the importance of considering effects of temperature and UV intensity for designing a reliable accelerated testing. This study uniquely demonstrates the capability of microscale characterization using nanoindentation and fluorescence microscopy to monitor mechanical and chemical degradation of EVA encapsulants in PV modules.

14 SOLAR ENERGY↗

Barium ion sensing with IPG K + molecular probes

Fluorophores covalently bound to azacrown ether ionophores can be assembled into sensitive turn-on chemosensors. The size specificity and electron-rich nature of the ionophore's binding domain contribute to both selectivity and strong turn-on fluorescence sensing by various mechanisms when properly constructed. Aza-18-crown-6 ethers are quite selective for binding to K + and Ba 2+ , yet the more electron-withdrawing dicationic nature of barium imposes a larger electronic effect on turn-on fluorescent sensors. Barium chemosensors can be important for measuring soluble Ba 2+ in drinking water and have gained recent attention for their potential to enhance the detection of rare events in xenon decay. Here we quantify the capability of three chemosensors, marketed for biologically useful K + sensing, as effective probes for Ba 2+ ions. Here, we present measurements from bulk spectrofluorometry to characterize the system in aqueous solutions and demonstrate the usefulness of these species for low-background single-ion fluorescence microscopy, revealing new candidates for Ba 2+ sensing.

Miller, R. L. [Department of Chemistry and Biochem↗

Recent observations of the OI 8446 A emission over Millstone Hill

Evening twilight spectra of the OI 8446 A emission were obtained during May and June of 1993 using a single-etalon, pressure scanning, Fabry-Perot interferometer located in the Millstone Hill Optical Facility. The goals of this work are to positively identify the 8446 A emission in the twilight airglow and to determine the intensity decay as a function of solar depression angle. Also, a study of the relative triplet line strengths is performed in hopes of establishing the importance of the primary excitation mechanisms (photoelectron impact or Bowen fluorescence) during the twilight period. Although absent in most of the data, a distinct auroral influence is also found to contribute considerably, on occasion, to the emission over Millstone Hill. The ratio of the combined 8446.26 A and 8446.38 A intensities to the 8446.76 A intensity varies as 0.13 +/- 0.03 per degree of solar depression angle, indicating that secondary excitation mechanisms are becoming increasingly important as evening twilight progresses. Bowen fluorescence is not found to be the primary excitation mechanism at any time during twilight, contributing just a few Rayleighs at most. These observations are an important first step toward a better characterization of highly variable thermospheric oxygen concentrations through ground-based measurements of the OI 8446 A emission.

Lancaster, R. S.↗

Spectrum synthesis of CN in comets

The CN B-X (0-0) R branch fluorescence spectra for three comets (Austin, Bennett, Halley) were calculated and compared to the observed spectra. The synthesized spectrum in each case was shifted to allow for the comparison of the individual line intensities. The Swings effect (excitation of CN band in comet spectra by solar fluorescence) is clearly visible. In addition to the R(0-0) band in the CN spectrum, the P(1-1) band also contributes lines in the spectral region of observation. This branch was calculated and compared to P/Halley. The overall agreement between observations and the CN spectral model is quite good. An exception to this statement would be the high J rotation lines intensities within the R(0-0) branch of P/Halley. Additional analysis is necessary to determine if this difference is due to mechanisms in addition to fluorescence (e.g., collisions).

Kleine, Marvin↗

PBT2 acts through a different mechanism of action than other 8-hydroxyquinolines: an X-ray fluorescence imaging study

8-Hydroxyquinolines (8HQs) comprise a family of metal-binding compounds that have been used or tested for use in numerous medicinal applications, including as treatments for bacterial infection, Alzheimer's disease, and cancer. Two key 8HQs, CQ (5-chloro-7-iodo-8-hydroxyquinoline) and PBT2 (2-(dimethylamino)methyl-5,7-dichloro-8-hydroxyquinoline), have drawn considerable interest and have been the focus of many studies investigating their in vivo properties. These drugs have been described as copper and zinc ionophores because they do not cause metal depletion, as would be expected for a chelation mechanism, but rather cellular accumulation of these ions. In studies of their anti-cancer properties, CQ has been proposed to elicit toxic intracellular copper accumulation and to trigger apoptotic cancer cell death through several possible pathways. In this study we used synchrotron X-ray fluorescence imaging, in combination with biochemical assays and light microscopy, to investigate 8HQ-induced alterations to metal ion homeostasis, as well as cytotoxicity and cell death. We used the bromine fluorescence from a bromine labelled CQ congener (5,7-dibromo-8-hydroxyquinoline; B2Q) to trace the intracellular localization of B2Q following treatment and found that B2Q crosses the cell membrane. We also found that 8HQ co-treatment with Cu(ii) results in significantly increased intracellular copper and significant cytotoxicity compared with 8HQ treatments alone. PBT2 was found to be more cytotoxic, but a weaker Cu(ii) ionophore than other 8HQs. Moreover, treatment of cells with copper in the presence of CQ or B2Q resulted in copper accumulation in the nuclei, while PBT2-guided copper was distributed near to the cell membrane. Furthermore, these results suggest that PBT2 may be acting through a different mechanism than that of other 8HQs to cause the observed cytotoxicity.

60 APPLIED LIFE SCIENCES↗

Dramatic changes in mitochondrial subcellular location and morphology accompany activation of the CO 2 concentrating mechanism

Dynamic changes in intracellular ultrastructure can be critical for the ability of organisms to acclimate to environmental conditions. Microalgae, which are responsible for ~50% of global photosynthesis, compartmentalize their Ribulose 1,5 Bisphosphate Carboxylase/Oxygenase (Rubisco) into a specialized structure known as the pyrenoid when the cells experience limiting CO 2 conditions; this compartmentalization is a component of the CO 2 Concentrating Mechanism (CCM), which facilitates photosynthetic CO 2 fixation as environmental levels of inorganic carbon (Ci) decline. Changes in the spatial distribution of mitochondria in green algae have also been observed under CO 2 limitation, although a role for this reorganization in CCM function remains unclear. We used the green microalga Chlamydomonas reinhardtii to monitor changes in mitochondrial position and ultrastructure as cells transition between high CO 2 and Low/Very Low CO 2 (LC/VLC). Upon transferring cells to VLC, the mitochondria move from a central to a peripheral cell location and orient in parallel tubular arrays that extend along the cell’s apico-basal axis. We show that these ultrastructural changes correlate with CCM induction and are regulated by the CCM master regulator CIA5. The apico-basal orientation of the mitochondrial membranes, but not the movement of the mitochondrion to the cell periphery, is dependent on microtubules and the MIRO1 protein, with the latter involved in membrane–microtubule interactions. Furthermore, blocking mitochondrial respiration in VLC-acclimated cells reduces the affinity of the cells for Ci. Overall, our results suggest that mitochondrial repositioning functions in integrating cellular architecture and energetics with CCM activities and invite further exploration of how intracellular architecture can impact fitness under dynamic environmental conditions.

CO2 concentrating mechanism↗