Results for “fluorescent composites” — Page 22

DOE OSTI2020

X-Ray Fluorescence Microscopy: A Method of Measuring Ion Concentrations in the Ear

This technical note describes synchrotron x-ray fluorescence microscopy (XFM) as a method for measuring the concentrations of various elements in cross-sections of the ear at extremely high resolution. This method could be of great importance for addressing many open questions in hearing research. XFM uses synchrotron radiation to evoke emissions from many biologically relevant elements in the tissue. The intensity and wavelength of the emitted radiation provide a fingerprint of the tissue composition that can be used to measure the concentration of the elements in the sampled location. Here, we focus on energies that target biologically-relevant elements of the periodic table between magnesium and zinc. Since a highly focused x-ray beam is used, the spot size is well below 1 mu m and the samples can be scanned at a nanometer lateral resolution. This study shows that measurement of the concentrations of different elements is possible in a mid-modiolar cross-section of a mouse cochlea. Images are presented that indicate potassium and chloride "hot spots" in the spiral ligament and the spiral limbus, providing experimental evidence for the potassium recycling pathway and showing the cochlear structures involved. Scans of a section obtained from the incus, one of the middle ear ossicles, in a developing mouse have shown that zinc is not uniformly distributed This supports the hypothesis that zinc plays a special role in the process of ossification. Although limited by sophisticated sample preparation and sectioning, the method provides ample exciting opportunities, to understand the role of genetics and epigenetics on hearing mechanisms in ontogeny and phylogeny.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Demonstrating Agreement between Radio and Fluorescence Measurements of the Depth of Maximum of Extensive Air Showers at the Pierre Auger Observatory

We show, for the first time, radio measurements of the depth of shower maximum ( X max ) of air showers induced by cosmic rays that are compared to measurements of the established fluorescence method at the same location. Using measurements at the Pierre Auger Observatory we show full compatibility between our radio and the previously published fluorescence dataset, and between a subset of air showers observed simultaneously with both radio and fluorescence techniques, a measurement setup unique to the Pierre Auger Observatory. Furthermore, we show radio X max resolution as a function of energy and demonstrate the ability to make competitive high-resolution X max measurements with even a sparse radio array. With this, we show that the radio technique is capable of cosmic-ray mass composition studies, both at Auger and at other experiments. Published by the American Physical Society 2024

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2024

Identifying Critical Mineral Binding Mechanisms and Distribution in Acid Mine Drainage Treatment Solids to Inform Targeted Recovery Methods

In this study, micro-X-ray Fluorescence and micro/bulk X-ray Adsorption Near Edge Spectroscopy were collected at Stanford Synchrotron Radiation Lightsource and the Advanced Photon Source to: (1) gain a detailed characterization of critical minerals in Fe/Mn (hydr)oxide host phases; and (2) investigate the Co/Ni coordination and redox speciation associated with Fe/Mn (hydr)oxides phases in AMD solids with diverse composition (e.g., Al-rich, Mn-rich, Al/Mn/Fe-rich). Preliminary results show co-location of Co/Ni within Mn-rich hotspots, while Fe-rich hotspots were associated with heavy REEs. In Al-rich solids, Mn speciation was mostly comprised of Mn+3/+4 oxides, while the Mn-rich solids contain predominately Mn+4. These results suggest the AMD matrix plays an important role in how Co/Ni are coordinated, which aids in evaluating the efficacy to utilize AMD solids as a resource, and informs other novel sorbent and recovery technologies.

Hoffman, Colleen↗

NASA NTRSDate not supplied

ARCTRON: A Rapid Experimental Proving Ground for TPS Experiments and Arcjet Technology Development

Innovation in high-enthalpy facilities is fundamentally limited by the cost and risk of experimentation. New concepts for plasma control, diagnostics, facility components, and plasma-material interaction often require repeated iterations that are impractical to perform in production arcjets. As a result, promising ideas may remain unexplored or reach operational facilities only after significant development effort. ARCTRON is being developed as a rapid experimental proving ground where new ideas in plasma science, arcjet engineering, diagnostics, and material response can be conceived, tested, and quantitatively evaluated before transition to large-scale facilities. The platform combines radio-frequency (RF) and DC arc plasma generation, externally applied magnetic fields, configurable gas composition, reduced-pressure operation, laser heating, electrical biasing, and modular diagnostic access. These capabilities permit the plasma source, applied forcing, test article, and measurement configuration to be modified independently, allowing individual physical mechanisms to be isolated more readily than in a traditional test environment. One class of investigations addresses fundamental plasma-surface interaction physics. Conventional material tests often expose a specimen simultaneously to convective heating, reactive species, pressure, shear, radiation, and surface-current effects. The resulting material response may be measured accurately, while the contribution of each mechanism remains difficult to identify. ARCTRON is designed to vary these effects selectively. Plasma chemistry can be changed independently through configurable gas mixtures; magnetic fields and electrical biasing can modify charged-particle transport; laser heating can provide a non-plasma thermal input; and pressure, flow, and discharge mode can be varied over a broad operating space. This enables controlled tests of hypotheses involving surface catalycity, reactive-species transport, plasma-assisted oxidation, electromagnetic effects, shear, and the relative contributions of thermal and chemical loading. A second class of investigations enabled by this approach concerns the engineering of high-enthalpy facilities themselves. Arc-heated facilities are limited by electrode erosion, unstable arc attachment, localized heating, and damage to nozzles and other plasma-facing components. ARCTRON provides a lower-cost environment for testing concepts intended to mitigate these limitations. Candidate investigations include the use of applied magnetic fields to alter current paths and reduce plasma interaction with nozzle walls, ExB forcing to introduce controlled plasma rotation, magnetic or geometric approaches for distributing arc attachment, and alternative electrode or discharge configurations intended to reduce erosion and improve stability. Because the platform is reconfigurable, these concepts can be evaluated through repeated design--build--test cycles before they are considered for implementation in operational facilities. The platform also supports the development and validation of diagnostics that may be difficult to introduce initially into a large arcjet. Current and planned measurements include spatially resolved optical emission spectroscopy, electrostatic probes, fast imaging, pyrometry, calorimetry, laser-induced fluorescence, and absorption spectroscopy. These diagnostics are intended not merely to document a nominal operating condition, but to constrain the local plasma state and its relationship to component or material response. The modular facility geometry allows diagnostic concepts to be tested, calibrated, and compared under repeatable conditions before deployment in more demanding environments. ARCTRON is also supported by an integrated software suite. Automated control and data acquisition allow discharge parameters, gas composition, magnetic fields, diagnostic timing, and test configuration to be recorded as part of each experiment (STARDAC - Software for Testing, Analysis, Research Data, and Control). The Backend for Experiment Analysis, Storage, and Traceability (BEAST) is a database that provides the infrastructure needed to associate heterogeneous measurements with facility configuration, specimen identity, calibration state, geometry, and analysis provenance. This backend is particularly important for exploratory campaigns, in which many related configurations may be tested, and the value of an individual experiment depends on its connection to earlier and subsequent iterations. Complementary analysis capabilities, including computer-vision-based transient response measurements (arcjetCV), three-dimensional surface reconstruction (STARSCAN), and model-based Bayesian inference (SHIELD), and tomography data analysis (TOMATO, PuMA) can be incorporated when required by a specific hypothesis without becoming the focus of every campaign. The central objective of ARCTRON is therefore not to maximize heat flux or reproduce a complete flight environment. Its purpose is to reduce the cost and time required to ask consequential questions about plasma behavior, plasma-facing materials, diagnostics, and arcjet technology. By providing a controlled environment for rapid reconfiguration, mechanism isolation, quantitative measurement, and iterative engineering, ARCTRON can help mature concepts that would otherwise remain too speculative or too risky for evaluation in production facilities. The resulting knowledge can then guide the design of material models, focus test objectives in larger arcjets, reduce facility-development risk, and improve the physical basis of high-enthalpy ground testing. This work will present the ARCTRON architecture, operating modes, diagnostic suite, and digital experimental workflow. Initial experimental results from the first integrated operation of the facility will be presented, including flow characterization, power limitations, and deployment of the initial diagnostic suite. Ongoing development efforts aimed at catalycity characterization, magnetic plasma control, and advanced optical diagnostics will also be discussed, illustrating how the platform supports rapid iteration from concept to experiment.

experimental diagnostics↗

NASA NTRSDate not supplied

ARCTRON: A Rapid Experimental Proving Ground for TPS Experiments and Arcjet Technology Development

Innovation in high-enthalpy facilities is fundamentally limited by the cost and risk of experimentation. New concepts for plasma control, diagnostics, facility components, and plasma-material interaction often require repeated iterations that are impractical to perform in production arcjets. As a result, promising ideas may remain unexplored or reach operational facilities only after significant development effort. ARCTRON is being developed as a rapid experimental proving ground where new ideas in plasma science, arcjet engineering, diagnostics, and material response can be conceived, tested, and quantitatively evaluated before transition to large-scale facilities. The platform combines radio-frequency (RF) and DC arc plasma generation, externally applied magnetic fields, configurable gas composition, reduced-pressure operation, laser heating, electrical biasing, and modular diagnostic access. These capabilities permit the plasma source, applied forcing, test article, and measurement configuration to be modified independently, allowing individual physical mechanisms to be isolated more readily than in a traditional test environment. One class of investigations addresses fundamental plasma-surface interaction physics. Conventional material tests often expose a specimen simultaneously to convective heating, reactive species, pressure, shear, radiation, and surface-current effects. The resulting material response may be measured accurately, while the contribution of each mechanism remains difficult to identify. ARCTRON is designed to vary these effects selectively. Plasma chemistry can be changed independently through configurable gas mixtures; magnetic fields and electrical biasing can modify charged-particle transport; laser heating can provide a non-plasma thermal input; and pressure, flow, and discharge mode can be varied over a broad operating space. This enables controlled tests of hypotheses involving surface catalycity, reactive-species transport, plasma-assisted oxidation, electromagnetic effects, shear, and the relative contributions of thermal and chemical loading. A second class of investigations enabled by this approach concerns the engineering of high-enthalpy facilities themselves. Arc-heated facilities are limited by electrode erosion, unstable arc attachment, localized heating, and damage to nozzles and other plasma-facing components. ARCTRON provides a lower-cost environment for testing concepts intended to mitigate these limitations. Candidate investigations include the use of applied magnetic fields to alter current paths and reduce plasma interaction with nozzle walls, ExB forcing to introduce controlled plasma rotation, magnetic or geometric approaches for distributing arc attachment, and alternative electrode or discharge configurations intended to reduce erosion and improve stability. Because the platform is reconfigurable, these concepts can be evaluated through repeated design--build--test cycles before they are considered for implementation in operational facilities. The platform also supports the development and validation of diagnostics that may be difficult to introduce initially into a large arcjet. Current and planned measurements include spatially resolved optical emission spectroscopy, electrostatic probes, fast imaging, pyrometry, calorimetry, laser-induced fluorescence, and absorption spectroscopy. These diagnostics are intended not merely to document a nominal operating condition, but to constrain the local plasma state and its relationship to component or material response. The modular facility geometry allows diagnostic concepts to be tested, calibrated, and compared under repeatable conditions before deployment in more demanding environments. ARCTRON is also supported by an integrated software suite. Automated control and data acquisition allow discharge parameters, gas composition, magnetic fields, diagnostic timing, and test configuration to be recorded as part of each experiment (STARDAC - Software for Testing, Analysis, Research Data, and Control). The Backend for Experiment Analysis, Storage, and Traceability (BEAST) is a database that provides the infrastructure needed to associate heterogeneous measurements with facility configuration, specimen identity, calibration state, geometry, and analysis provenance. This backend is particularly important for exploratory campaigns, in which many related configurations may be tested, and the value of an individual experiment depends on its connection to earlier and subsequent iterations. Complementary analysis capabilities, including computer-vision-based transient response measurements (arcjetCV), three-dimensional surface reconstruction (STARSCAN), and model-based Bayesian inference (SHIELD), and tomography data analysis (TOMATO, PuMA) can be incorporated when required by a specific hypothesis without becoming the focus of every campaign. The central objective of ARCTRON is therefore not to maximize heat flux or reproduce a complete flight environment. Its purpose is to reduce the cost and time required to ask consequential questions about plasma behavior, plasma-facing materials, diagnostics, and arcjet technology. By providing a controlled environment for rapid reconfiguration, mechanism isolation, quantitative measurement, and iterative engineering, ARCTRON can help mature concepts that would otherwise remain too speculative or too risky for evaluation in production facilities. The resulting knowledge can then guide the design of material models, focus test objectives in larger arcjets, reduce facility-development risk, and improve the physical basis of high-enthalpy ground testing. This work will present the ARCTRON architecture, operating modes, diagnostic suite, and digital experimental workflow. Initial experimental results from the first integrated operation of the facility will be presented, including flow characterization, power limitations, and deployment of the initial diagnostic suite. Ongoing development efforts aimed at catalycity characterization, magnetic plasma control, and advanced optical diagnostics will also be discussed, illustrating how the platform supports rapid iteration from concept to experiment.

experimental diagnostics↗

DOE OSTI2022

Major to trace element imaging and analysis of iron age glasses using stage scanning in the analytical dual beam microscope (tandem)

Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO 2 ) along with trace apatite (Ca 5 (PO 4 ) 3 [Cl,OH]) and zircon (ZrSiO 4 ). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis.

36 MATERIALS SCIENCE↗

NASA NTRS1978

Evidence for a high-magnesium subsurface basalt in Mare Crisium from orbital X-ray fluorescence data

Orbital X-ray fluorescence data taken by the Apollo 15 mission over Mare Crisium are analyzed in order to detect surface occurrences of the magnesium-rich materials found in the Luna 24 core sample. Apollo 15 data of the surface soils of the Luna 24 landing site, expressed as Al/Si and Mg/Si ratios, are found to be well correlated with the composition of the less than 74 micron fraction of the core sample. Orbital data indicate that most surface areas of the southern part of Mare Crisium have magnesium contents lower than or equal to that of the landing site, with the exception of areas in the vicinities of the post-mare craters Picard and Pierce and an area northeast of the Luna 24 site. The crater material is interpreted to be a magnesium-rich subsurface basalt excavated by crater formation, which may represent the material from which magnesium-rich Luna 24 samples, including olivine gabbro and olivine vitrophyre, were derived.

Andre, C. G.↗

NASA NTRS2004

X-ray Probes of Magnetospheric Interactions with Jupiter's Auroral zones, the Galilean Satellites, and the Io Plasma Torus

Remote observations with the Chandra X-ray Observatory and the XMM-Newton Observatory have shown that the Jovian system is a source of x-rays with a rich and complicated structure. The planet's polar auroral zones and its disk are powerful sources of x-ray emission. Chandra observations revealed x-ray emission from the Io Plasma Torus and from the Galilean moons Io, Europa, and possibly Ganymede. The emission from these moons is certainly due to bombardment of their surfaces of highly energetic protons, oxygen and sulfur ions from the region near the Torus exciting atoms in their surfaces and leading to fluorescent x-ray emission lines. Although the x-ray emission from the Galilean moons is faint when observed fiom Earth orbit, an imaging x-ray spectrometer in orbit around these moons, operating at 200 eV and above with 150 eV energy resolution, would provide a detailed mapping (down to 40 m spatial resolution) of the elemental composition in their surfaces. Here we describe the physical processes leading to x-ray emission fiom the surfaces of Jupiter's moons and the instrumental properties, as well as energetic ion flux models or measurements, required to map the elemental composition of their surfaces. We discuss the proposed scenarios leading to possible surface compositions. For Europa, the two most extreme are (1) a patina produced by exogenic processes such as meteoroid bombardment and ion implantation, and (2) upwelling of material fiom the subsurface ocean. We also describe the characteristics of X - m , an imaging x-ray spectrometer under going a feasibility study for the JIM0 mission, with the ultimate goal of providing unprecedented x-ray studies of the elemental composition of the surfaces of Jupiter's icy moons and Io, as well as of Jupiter's auroral x-ray emission.

Elsner, R. F.↗

NASA NTRS2004

X-MIME: An Imaging X-ray Spectrometer for Detailed Study of Jupiter's Icy Moons and the Planet's X-ray Aurora

Remote observations with the Chandra X-ray Observatory and the XMM-Newton Observatory have shown that the Jovian system is a source of x-rays with a rich and complicated structure. The planet's polar auroral zones and its disk are powerful sources of x-ray emission. Chandra observations revealed x-ray emission from the Io Plasma Torus and from the Galilean moons Io, Europa, and possibly Ganymede. The emission from these moons is certainly due to bombardment of their surfaces of highly energetic protons, oxygen and sulfur ions from the region near the Torus exciting atoms in their surfaces and leading to fluorescent x-ray emission lines. Although the x-ray emission from the Galilean moons is faint when observed from Earth orbit, an imaging x-ray spectrometer in orbit around these moons, operating at 200 eV and above with 150 eV energy resolution, would provide a detailed mapping (down to 40 m spatial resolution) of the elemental composition in their surfaces. Such maps would provide important constraints on formation and evolution scenarios for the surfaces of these moons. Here we describe the characteristics of X-MIME, an imaging x-ray spectrometer under going a feasibility study for the JIMO mission, with the ultimate goal of providing unprecedented x-ray studies of the elemental composition of the surfaces of Jupiter's icy moons and Io, as well as of Jupiter's auroral x-ray emission.

Elsner, R. F.↗

NASA NTRS2004

Nanotube Activities at NASA-Johnson Space Center

Nanotube activities at NASA-Johnson Space Center include production, purification, characterization as well as applications of single wall carbon nanotubes (SWCNTs). A parametric study of the pulsed laser ablation process is recently completed to monitor the effect of production parameters including temperature, buffer gas, flow rate, pressure, and laser fluence. Enhancement of production is achieved by rastering the graphite target and by increasing the target surface temperature with a cw laser. In-situ diagnostics during production included time resolved passive emission and laser induced fluorescence from the plume. The improvement of the purity by a variety of steps in the purification process is monitored by characterization techniques including SEM, TEM, Raman, UV-VIS-NIR and TGA. A recently established NASA-JSC protocol for SWCNT characterization is undergoing revision with feedback from nanotube community. Efforts at JSC over the past five years in composites have centered on structural polymer/nanotube systems. Recent activities broadened this focus to multifunctional materials, supercapacitors, fuel cells, regenerable CO2 absorbers, electromagnetic shielding, radiation dosimetry and thermal management systems of interest for human space flight. Preliminary tests indicate improvement of performance in most of these applications because of the large Surface area as well as high electrical and thermal conductivity exhibited by SWCNTs. Comparison with existing technologies and possible future improvements in the SWCNT materials sill be presented.

Arepalli, Sivaram↗

NASA NTRS2011

Silica-Titania Composite (STC)'s Performance in the Photocatalytic Oxidation of Polar VOCs

The objective of this paper is to determine the performance of a Silica-Titania Composite (STC) in the photocatalytic oxidation (PCO) of polar VOCs for potential applications in trace contaminant control within space habitats such as the ISS and CEV Orion. Tests were carried out in a bench scale STC-packed annular reactor under continuous illumination by either a UV-C germicidal lamp(lambda (sub max) = 254 nm) or UV-A fluorescent BLB (lambda(sub max) = 365 nm) for the removal of ethanol (a predominant polar VOC in the ISS cabin). The STC's performance was evaluated in terms of the ethanol mineralization rate, mineralization efficiency, and the extent of its oxidation intermediate (acetaldehyde) formation in response to the type of light source (photon energy and photon flux) and relative humidity (RH) implemented. Results demonstrated that acetaldehyde was the only quantifiable intermediate in the effluent under UV illumination, but was not found in the dark adsorption experiments. The mineralization rate increased with an increase in photon energy (UV-C greater than UV-A), even though both lamps were adjusted to emit the same incident photon flux, and also increased with increasing photon flux. However, photonic efficiency decreased as the photon flux increased. More importantly, a higher photon flux gave rise to a lower effluent acetaldehyde concentration. The effect of RH on PCO was complex and intriguing because it affected both physical adsorption and photocatalytic oxidation. In general, increasing RH caused a decrease in adsorption capacity for ethanol and reduced the mineralization efficiency with a concomitant higher acetaldehyde evolution rate. The effect of RH was less profound than that of photon flux.

Levine, Lanfang H.↗

NASA NTRS2020

New Insights into the Chemical Composition of Five Oort Cloud Comets After Re-analysis of their Infrared Spectra

We present revised results for the main molecular species in five Oort Cloud (OC) comets observed with NIRSPEC at the Keck Observatory between 1999 and 2012 (C/1999 S4 (LINEAR), C/2001 A2 (LINEAR), C/2007 W1 (Boattini), C/2012 F6 (Lemmon), and C/2012 S1 (ISON)). The re-evaluation of these data shows the improvement of results in some of the datasets, in particular for comets observed and analyzed before the advent of new and revised fluorescence models and terrestrial retrieval methods introduced since 2011. We observe significant improvements in the resulting rotational temperatures and production rates for all species, and in mixing ratios of minor species (relative to water). The re-analysis also allowed us to quantify species not analyzed previously, mostly due to the lack of molecular models (e.g., ammonia and formaldehyde). We note, however, that the improvement of these revised values is less substantial for comets observed (and/or analyzed) since 2010.

Manuela Lippi↗

DOE OSTI2024

Wildfire‐induced increases in photosynthesis in boreal forest ecosystems of North America

Abstract Observations of the annual cycle of atmospheric CO 2 in high northern latitudes provide evidence for an increase in terrestrial metabolism in Arctic tundra and boreal forest ecosystems. However, the mechanisms driving these changes are not yet fully understood. One proposed hypothesis is that ecological change from disturbance, such as wildfire, could increase the magnitude and change the phase of net ecosystem exchange through shifts in plant community composition. Yet, little quantitative work has evaluated this potential mechanism at a regional scale. Here we investigate how fire disturbance influences landscape‐level patterns of photosynthesis across western boreal North America. We use Alaska and Canadian large fire databases to identify the perimeters of wildfires, a Landsat‐derived land cover time series to characterize plant functional types (PFTs), and solar‐induced fluorescence (SIF) from the Orbiting Carbon Observatory‐2 (OCO‐2) as a proxy for photosynthesis. We analyze these datasets to characterize post‐fire changes in plant succession and photosynthetic activity using a space‐for‐time approach. We find that increases in herbaceous and sparse vegetation, shrub, and deciduous broadleaf forest PFTs during mid‐succession yield enhancements in SIF by 8–40% during June and July for 2‐ to 59‐year stands relative to pre‐fire controls. From the analysis of post‐fire land cover changes within individual ecoregions and modeling, we identify two mechanisms by which fires contribute to long‐term trends in SIF. First, increases in annual burning are shifting the stand age distribution, leading to increases in the abundance of shrubs and deciduous broadleaf forests that have considerably higher SIF during early‐ and mid‐summer. Second, fire appears to facilitate a long‐term shift from evergreen conifer to broadleaf deciduous forest in the Boreal Plain ecoregion. These findings suggest that increasing fire can contribute substantially to positive trends in seasonal CO 2 exchange without a close coupling to long‐term increases in carbon storage.

Biodiversity & Conservation↗

DOE OSTI2023

Visible to NIR‐II Photoluminescence of Atomically Precise Gold Nanoclusters

Abstract Atomically precise gold nanoclusters (NCs) have emerged as a new class of precision materials and attracted wide interest in recent years. One of the unique properties of such nanoclusters pertains to their photoluminescence (PL), for it can widely span visible to near‐infrared–I and –II wavelengths (NIR‐I/II), and even beyond 1700 nm by manipulating the size, structure, and composition. The current research efforts focus on the structure–PL correlation and the development of strategies for raising the PL quantum yields, which is nontrivial when moving from the visible to the near‐infrared wavelengths, especially in the NIR–II regions. This review summarizes the recent progress in the field, including i) the types of PL observed in gold NCs such as fluorescence, phosphorescence, and thermally activated delayed fluorescence, as well as dual emission; ii) some effective strategies that are devised to improve the PL quantum yield (QY) of gold NCs, such as heterometal doping, surface rigidification, and core phonon engineering, with double‐digit QYs for the NIR PL on the horizons; and iii) the applications of luminescent gold NCs in bioimaging, photosensitization, and optoelectronics. Finally, the remaining challenges and opportunities for future research are highlighted.

Liu, Zhongyu↗

DOE OSTI2021

Ca2+ Effects on Fe(II) Interactions with Mn-Binding Sites in Mn-Depleted Oxygen-Evolving Complexes of Photosystem II and on Fe Replacement of Mn in Mn-Containing, Ca-Depleted Complexes

Fe(II) cations bind with high efficiency and specificity at the high-affinity (HA), Mn-binding site (termed the “blocking effect” since Fe blocks further electron donation to the site) of the oxygen-evolving complex (OEC) in Mn-depleted, photosystem II (PSII) membrane fragments (Semin et al. in Biochemistry 41:5854, 2002). Furthermore, Fe(II) cations can substitute for 1 or 2Mn cations (pH dependent) in Ca-depleted PSII membranes (Semin et al. in Journal of Bioenergetics and Biomembranes 48:227, 2016; Semin et al. in Journal of Photochemistry and Photobiology B 178:192, 2018). In the current study, we examined the effect of Ca2+ cations on the interaction of Fe(II) ions with Mn-depleted [PSII(-Mn)] and Ca-depleted [PSII(-Ca)] photosystem II membranes. We found that Ca2+ cations (about 50 mM) inhibit the light-dependent oxidation of Fe(II) (5 µM) by about 25% in PSII(-Mn) membranes, whereas inhibition of the blocking process is greater at about 40%. Blocking of the HA site by Fe cations also decreases the rate of charge recombination between QA- and YZ•+ from t1/2?=?30 ms to 46 ms. However, Ca2+ does not affect the rate during the blocking process. An Fe(II) cation (20 µM) replaces 1Mn cation in the Mn4CaO5 catalytic cluster of PSII(-Ca) membranes at pH 5.7 but 2 Mn cations at pH 6.5. In the presence of Ca2+ (10 mM) during the substitution process, Fe(II) is not able to extract Mn at pH 5.7 and extracts only 1Mn at pH 6.5 (instead of two without Ca2+). Measurements of fluorescence induction kinetics support these observations. Inhibition of Mn substitution with Fe(II) cations in the OEC only occurs with Ca2+ and Sr2+ cations, which are also able to restore oxygen evolution in PSII(-Ca) samples. Nonactive cations like La3+, Ni2+, Cd2+, and Mg2+ have no influence on the replacement of Mn with Fe. These results show that the location and/or ligand composition of one Mn cation in the Mn4CaO5 cluster is strongly affected by calcium depletion or rebinding and that bound calcium affects the redox potential of the extractable Mn4 cation in the OEC, making it resistant to reduction.

calcium↗

DOE OSTI2025

Silver diamine fluoride differentially affects dentin and hypomineralized enamel permeabilities

OBJECTIVES: To investigate the physicochemical effect of silver diamine fluoride (SDF) by correlating permeability with mineral density and elemental composition of hypomineralized enamel and carious dentin. METHODS: Enamel and dentin from human carious primary teeth with and without SDF treatment in-vivo, and hypomineralized enamel from permanent molars with and without SDF treatment in-vitro were scanned using micro X-ray computed tomography. Spatial maps of biometals (calcium, zinc), phosphorus, and silver were generated using X-ray fluorescence microprobe. Permeabilities were computed using Porous Microstructure Analysis software. RESULTS: The intrinsic permeability of SDF-treated carious dentin was 14.3 % lower than untreated sound dentin (6.39e-15 ± 3.01e-15 m² vs 7.46e-15 ± 1.82e-15 m²; P < 0.0001), while untreated carious dentin was 98.4 % higher (1.48e-14 ± 7.11e-15 m²; P < 0.0001). SDF-treated and untreated transparent dentin showed similar reduced permeabilities (75.6 % and 78.4 % lower than untreated sound dentin, respectively; P = 0.93). Severely hypomineralized enamel showed permeability reaching 108.1 % of adjacent sound dentin (5.71e-15 ± 2.04e-15 m² vs 5.28e-15 ± 1.30e-15 m²; P = 0.1409) and was significantly higher than mildly hypomineralized enamel (1.39e-15 ± 1.04e-15 m²; P < 0.0001). SDF treatment did not significantly impact the permeability of severely hypomineralized enamel (12.4 % reduction; P = 0.07). Principal component regression identified Zn level as a significant effector of tissue permeabilities in carious primary teeth (P < 0.0001). SIGNIFICANCE: This study introduces a computational method to measure dental tissue permeability, and demonstrates that SDF significantly reduces permeability in carious dentin but not intact hypomineralized enamel. The study reveals biometal Zn localization can alter dentin and enamel permeabilities, providing new insights into pathobiological mechanisms underlying caries and hypomineralization.

Chou, Conrad↗

DOE OSTI2022

Habitat‐adapted microbial communities mediate Sphagnum peatmoss resilience to warming

Summary Sphagnum peatmosses are fundamental members of peatland ecosystems, where they contribute to the uptake and long‐term storage of atmospheric carbon. Warming threatens Sphagnum mosses and is known to alter the composition of their associated microbiome. Here, we use a microbiome transfer approach to test if microbiome thermal origin influences host plant thermotolerance. We leveraged an experimental whole‐ecosystem warming study to collect field‐grown Sphagnum , mechanically separate the associated microbiome and then transfer onto germ‐free laboratory Sphagnum for temperature experiments. Host and microbiome dynamics were assessed with growth analysis, Chl a fluorescence imaging, metagenomics, metatranscriptomics and 16S rDNA profiling. Microbiomes originating from warming field conditions imparted enhanced thermotolerance and growth recovery at elevated temperatures. Metagenome and metatranscriptome analyses revealed that warming altered microbial community structure in a manner that induced the plant heat shock response, especially the HSP70 family and jasmonic acid production. The heat shock response was induced even without warming treatment in the laboratory, suggesting that the warm‐microbiome isolated from the field provided the host plant with thermal preconditioning. Our results demonstrate that microbes, which respond rapidly to temperature alterations, can play key roles in host plant growth response to rapidly changing environments.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1990

The 3.3 micron feature, H2, and ionized gas in the Orion bar

The results of spectroscopy of the 3.3 micron feature, H2 emission, P-alpha, and Br-alpha, obtained along a line perpendicular to the Orion ionization front, are presented. The intensity of the 3.3 micron feature reaches a maximum between the ionization front and the H2 peak. The 3.33 micron spatial distribution appears to be due to destruction of the emitting material within the H II region and extinction of the exciting radiation between the edge of the H II region and the H2 peak, resulting in a maximum between the ionization front and the H2 peak. The H2 peak is consistent with either being due to a shock front or being due to UV-pumped fluorescence from dense clumps of H2. The width of the 3.3 micron feature observed at high spectral resolution is constant in regions of varying UV flux. It is suggested that the strength of the UV field is not the cause of the variations in the 3.3 micron feature width observed in other sources, but rather that these variations are caused by a compositional change related to the age of the emitting material.

Sellgren, K.↗