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At least 73 records · Page 4

Growth and Characterization of Epitaxial FeWO 4 Thin Films with Controlled Oxygen Stoichiometry

Here, we report the growth of single-phase epitaxial FeWO 4 thin films, using plasma-assisted molecular beam epitaxy, and investigate structural, optical, and electronic properties. The FeWO 4 films grow in (100) orientation on c-plane sapphire (0001) substrates and exhibit 3 rotational twin variants where FeWO 4 [001] is aligned to sapphire [100] equivalent in-plane directions. X-ray diffraction measurements indicate that the epitaxial FeWO 4 (100) structure is optimized when 80-100 W of rf power is applied to an atomic oxygen source during growth, yielding films with minimal strain and impurity phases or other orientations. In films grown with 120 W of rf power, FeWO 4 crystallites develop inhomogeneous and homogeneous strains and are potentially contaminated with Fe 3+ oxide phase impurities. In films grown with 60 W of rf power, FeWO 4 crystallites do not form fully epitaxial layers. X-ray photoelectron spectroscopy indicates that the structural changes are correlated with the Fe 3+ /Fe 2+ oxidation state ratio increasing from 0.6-1.4 with rf power from 60-120 W. X-ray fluorescence spectroscopy indicates that the Fe/W composition ratio is also increasing from 1.1-1.8 with rf power from 60-120 W. Ultraviolet and visible optical absorption spectra indicate a 1.8 ± 0.1 eV band gap with an additional interband absorption feature at 3.1 ± 0.1 eV in the 80-100 W films, with similar onsets observed in the 60 W films. In the 120 W films, the higher lying transition is shifted to 2.7 ± 0.1 eV due to the Fe 3+ enrichment. Electrical resistivity decreases over 2 orders of magnitude with oxidation from 10 4 -10 5 Ω cm in 60 W films to 120 ± 10 Ω cm in 120 W films. Thermopower measurements show p-type to n-type conductivity conversion when oxidation states shift from Fe 2+ majority in the 100 W films to Fe 3+ majority in the 120 W films. We conclude that electron polaron hopping driven by Fe 3+ is a dominant transport mechanism and a source of n-type conductivity in overoxidized FeWO 4 films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical and morphological changes of reusable surface insulation coatings as a function of convectively heated cyclic testing

The effects of convective heating upon reusable surface insulation coatings were studied utilizing scanning electron microscopy, X-ray fluorescence, and X-ray diffraction. Samples of coated silica, mullite, and ceramic mullite fiber were cycled in an arc plasma stream up to 15 times for 15 minutes per cycle at surface temperatures simulating those on the space shuttle vehicle. The surfaces of ceramic mullite fiber and mullite coatings were roughened substantially by the convectively heated environment while the silica was significantly smoothed after testing. Scanning electron microscopy also showed surface cracking of varying degrees in all of the coatings. The surface chemistry of the coatings as examined by X-ray fluorescence revealed that significant changes in composition were occurring during cycling, particularly within the mullite coating.

Leiser, D. B.↗

Experimental and Theoretical Analysis of Chemical Vapor Deposition with Prediction of Gravity Effects

A combined experimental and theoretical study to characterize the effects of gravitationally-induced transport on atmospheric pressure silicon epitaxy by SiH4 pyrolysis is planned. Experimentally, flow regimes in which free convective transport contributes to the Chemical Vapor Deposition (CVD) process will be identified, and, for these conditions, the flow and deposition process will be characterized. Specifically, this will include measurements of three dimensional temperature variations using in situ Rayleigh scattering, gas phase composition profiles using laser absorption and fluorescence techniques, and deposition rates and defect densities. Subsequently, the free convective transport contribution to the CVD process will be minimized and/or altered while leaving deposition chemistry unaltered, and the characterization will be repeated. Based on these analyses, the effects of gravitationally-induced transport on atmospheric pressure CVD will be assessed.

Charter D. Stinespring↗

Highly oriented Tl2Ba2Ca2Cu3O10 thin films by pulsed laser evaporation

Superconducting thin films on MgO (100) substrates with nearly pure Tl2Ba2Ca2Cu3O10 (2:2:2:3) phase using pulsed laser evaporation and postannealing have been fabricated. The films had c axes perpendicular to the substrates. Superconducting films with onset temperatures of 125 K and zero resistance at 110 K were obtained. X-ray microprobe fluorescence measurements indicate that a typical composition of films is Tl(0.66)Ba(1.77)Ca(1.46)Cu3O(x) which is low in Tl compared to that expected for the 2:2:2:3 phase. A typical grain size is greater than 10 microns revealed by scanning electron microscopy.

Liou, S. H.↗

The mini-CIDEX GC/IMS: Analysis of cometary ice and dust

Comets are recognized as among the most scientifically important objects in the solar system. They are presumed relics of the early primitive material in the solar nebula and are believed to have provided a general enrichment of volatiles to the inner solar system. The Cometary Coma Chemical Composition (C4) Mission, a proposed Discovery-Class Mission, will analyze materials released into the coma, providing information leading to the understanding of the chemical composition and make-up of the cometary nucleus. As one of two scientific instruments in the C4 spacecraft, an advanced and streamlined version of the Cometary Ice and Dust Experiment (CIDEX), a mini-CIDEX, will employ an X-Ray Fluorescence (XRF) spectrometer to determine bulk elemental composition of cometary dust grains and a Gas Chromatograph/Ion Mobility Spectrometer (GC/IMS) for determination of the molecular composition of dust and ices following stepwise pyrolysis and combustion. A description of the mini-CIDEX IMS will be provided as well as data from analyses conducted using the mini-CIDEX breadboard instrument.

Kojiro, Daniel R.↗

In Situ Resource Utilization (ISRU) on the Moon: Moessbauer Spectroscopy as a Process Monitor for Oxygen Production

Essential consumables like oxygen must to be produced from materials on the lunar surface to enable a sustained, long-term presence of humans on the Moon. The Outpost Precursor for ISRU and Modular Architecture (OPTIMA) field test on Mauna Kea, Hawaii, facilitated by the Pacific International Space Center for Exploration Systems (PISCES) of the University of Hawaii at Hilo, was designed to test the implementation of three hardware concepts to extract oxygen from the lunar regolith: Precursor ISRU Lunar Oxygen Testbed (PILOT) developed by Lockheed Martin in Littleton, CO; Regolith & Environmental Science and Oxygen & Lunar Volatiles Extraction (RESOLVE) developed at the NASA Kennedy Space Center in Cape Canaveral, FL; and ROxygen developed at the NASA Johnson Space Center in Houston, TX. The three concepts differ in design, but all rely on the same general principle: hydrogen reduction of metal cations (primarily Fe2+) bonded to oxygen to metal (e.g., Fe0) with the production of water. The hydrogen source is residual hydrogen in the fuel tanks of lunar landers. Electrolysis of the water produces oxygen and hydrogen (which is recycled). We used the miniaturized M ssbauer spectrometer MIMOS II to quantify the yield of this process on the basis of the quantity of Fe0 produced. Iron M ssbauer spectroscopy identifies iron-bearing phases, determines iron oxidation states, and quantifies the distribution of iron between mineral phases and oxidation states. The oxygen yield can be calculated by quantitative measurements of the distribution of Fe among oxidation states in the regolith before and after hydrogen reduction. A M ssbauer spectrometer can also be used as a prospecting tool to select the optimum feedstock for the oxygen production plants (e.g., high total Fe content and easily reduced phases). As a demonstration, a MIMOS II backscatter spectrometer (SPESI, Germany) was mounted on the Cratos rover (NASA Glenn Research Center in Cleveland, OH), which is one of several rover concepts designed to excavate and transfer regolith to the stationary hydrogen reduction plants. Spaceflight versions of the MIMOS II are part of the instrument payloads of NASA s Mars Exploration Rovers and still operating five years after landing on the surface of the planet. MIMOS II was also selected for Phobos-Grunt, a Russian sample return mission to the martian moon Phobos scheduled to launch in 2009, and ESA s ExoMars rover, an exobiology mission scheduled to launch in 2013. An advanced version of the instrument is currently under development. A new detector system with a higher energy resolution will not only reduce the necessary measurement time considerably, but also allow the simultaneous acquisition of an X-ray fluorescence spectrum to determine the elemental composition of samples.

Morris, R.V.↗

A Large Drift Detector Array Lunar Orbiter Spectrometer

Measurement of-rays from the surface of objects can tell us about the chemical composition. Absorption of radiation causes characteristic fluorescence from material being irradiated. By measuring the spectrum ofthe radiation and identifying lines in the spectrum, the emitting element (s) can be identified.

Gaskin, Jessica A.↗

A Radiation-Hard Silicon Drift Detector Array for Extraterrestrial Element Mapping

Measurement of x-rays from the surface of objects can tell us about the chemical composition Absorption of radiation causes characteristic fluorescence from material being irradiated. By measuring the spectrum of the radiation and identifying lines in the spectrum, the emitting element (s) can be identified. This technique works for any object that has no absorbing atmosphere and significant surface irradiation : Our Moon, the icy moons of Jupiter, the moons of Mars, the planet Mercury, Asteroids and Comets

Gaskin, Jessica↗

Standards for Analysis of Ce, La, Pb, Rb, Se, Sr, Y, AND Zr in Rock Samples Using Laser-induced Breakdown Spectroscopy and X-ray Fluorescence

Analytical geochemistry has long depended on the availability of robust suites of rock standards with well-characterized compositions. Standard rock powders for wet chemistry and x-ray fluorescence were initially characterized and supplied to the community by the U.S. Geological Survey, which continues to distribute a few dozen standards. Many other rock standards have subsequently been developed by organizations such as the Centre de Recherches Pétrographiques et Géochimiques (CRPG) and Brammer Standard Company, Inc.

LIBS↗

X-ray fluorescence experiment

The preliminary results from the Sco X-1 and Cyg X-1 obtained from the Apollo 15 X-ray detector data are presented along with preliminary results of the X-ray fluorescence spectrometric data of the lunar surface composition. The production of the characteristic X-rays following the interaction of solar X-rays with the lunar surface is described along with the X-ray spectrometer. Preliminary analyses of the astronomical X-ray observation and the X-ray fluorescence data are presented.

Adler, I.↗

Impact of PrsA on membrane lipid composition during daptomycin-resistance-mediated β-lactam sensitization in clinical MRSA strains

Abstract Background The cyclic anionic lipopeptide daptomycin is used in the treatment of severe infections caused by Gram-positive pathogens, including MRSA. Daptomycin resistance, although rare, often results in treatment failure. Paradoxically, in MRSA, daptomycin resistance is usually accompanied by a concomitant decrease in β-lactam resistance in what is known as the ‘see-saw effect’. This resensitization is extensively used for the treatment of MRSA infections, by combining daptomycin and a β-lactam antibiotic, such as oxacillin. Objectives We aimed: (i) to investigate the combined effects of daptomycin and oxacillin on the lipid composition of the cellular membrane of both daptomycin-resistant and -susceptible MRSA strains; and (ii) to assess the involvement of the post-translocational protein PrsA, which plays an important role in oxacillin resistance in MRSA, in membrane lipid composition and remodelling during daptomycin resistance/β-lactam sensitization. Results The combination of microbiological and biochemical studies, with fluorescence microscopy using lipid probes, showed that the lipid composition and surface charge of the daptomycin-resistant cells exposed to daptomycin/oxacillin were dependent on antibiotic concentration and directly associated with PrsA, which influenced cardiolipin remodelling/relocation. Conclusions Our findings show that PrsA, in addition to its post-transcriptional role in the maturation of PBP 2a, is a key mediator of cell membrane remodelling connected to the see-saw effect and may have a key role in the resensitization of daptomycin-resistant strains to β-lactams, such as oxacillin.

de Carvalho, Carla C. C. R.↗

Adsorption and Solvation Modulate Rhodamine B Diffusion in Ethanol/Water-Filled Anodic Alumina Nanopores

Confinement of solvents and solutes within nanoporous materials frequently leads to the emergence of unique mass transport behaviors that, once fully understood, may lead to improved chemical separations. Here, the diffusion of Rhodamine B (RhB) dye within 10 and 20 nm diameter anodic aluminum oxide (AAO) nanopores filled with binary ethanol/water mixtures is investigated. Mixture compositions spanning from pure ethanol to pure water are employed. The results of confocal fluorescence correlation spectroscopy studies reveal that RhB diffusion occurs by a two-component mechanism comprising composition-dependent fast and slow motions, characterized by diffusion coefficients D f and D s . The results are consistent with those of previous studies performed under more limited conditions [J. Phys. Chem. C, 2023, 127, 411-420]. The fast component scales with mixture viscosity and is assigned to hindered bulk-like diffusion in central pore regions. Slow diffusion likely involves adsorption of RhB to the pore surface and may be described by a desorption mediated mechanism. The occurrence of RhB adsorption to the AAO surface is verified at the single-molecule level by wide-field fluorescence imaging of membrane cross-sectional surfaces. Unique composition dependent trends in the autocorrelation amplitude and in D s that mimic bulk RhB solubility are revealed. D s is found to be smallest in pure ethanol and pure water and largest in intermediate mixtures. These results suggest that RhB surface adsorption is strongest in the pure liquids and weakest in mixtures of intermediate composition, where the dye is least soluble, and most soluble, respectively. As a result, molecular dynamics simulations reveal that a water layer appears on the pore surface under most conditions, while RhB is solvated primarily by ethanol. The composition dependence of RhB diffusion is concluded to reflect its solvation dependent interactions with the pore walls.

36 MATERIALS SCIENCE↗

Sulphate resistance of low‐clinker engineered cementitious composites examined by MicroXRF imaging

Abstract Engineered cementitious composites (ECC) are a class of high‐performing fibre‐reinforced cementitious materials recognised for their increased ductility and durability compared to conventional cement‐based materials, owing to their autogenously controlled tight crack widths, even when subjected to high strains. To reduce ECC's environmental impact, this research examines the use of a low‐clinker binder − limestone‐calcined clay cement (LC3) − as an alternative to portland cement (PC), along with fly ash to further reduce the clinker proportion and the embodied CO 2 of the formulations. In conventional concrete, LC3 hydrates to a denser microstructure resulting from the synergistic reaction between limestone and calcined clay. At the lower water contents typical of ECC and with the presence of fly ash, the influence of the binder composition on the microstructure is difficult to anticipate. To examine the influence of these compositional variables on microstructure, permeability and durability, the sulphate resistance of LC3‐based ECC is explored. Specifically, the ECC‐LC3 blends are designed with high clinker replacement rate of 75% by mass of binder and contain either conventional fly ash or reclaimed fly ash at 50% by mass of binder. Expansion of ECC‐LC3 samples subjected to standard sodium sulphate test conditions was measured up to 12 months and the depth of penetration of sulphates into the ECC‐LC3 of varying compositions was quantified using micro‐X‐Ray Fluorescence (microXRF) imaging and modelling. The expansion results show that the ECC‐LC3 formulations performed better than the PC samples and can provide adequate resistance to external sulphate attack, even when reclaimed fly ashes are used in place of the conventional ash. In addition, the shallow penetration of sulphate into these cementitious composites demonstrates the low diffusion coefficients values that were determined using the quantitative data from MicroXRF imaging.

Microscopy↗

Apollo 15 and 16 results of the integrated geochemical experiment.

A number of experiments carried in orbit on the Apollo 15 and 16 spacecraft were used in the compositional mapping of the lunar surface. The observations involved measurements of secondary (fluorescent) X-rays, gamma rays and alpha particle emissions. A large scale compositional map of over 20% of the lunar surface was obtained for the first time. It was possible to demonstrate significant chemical differences between the mare and the highlands, to find specific areas of high radioactivity and to learn something about the composition of the moon's hidden side.

Adler, I.↗

Evolution of glass structure during femtosecond laser assisted crystallization of LaBGeO 5 in glass

Single crystal LaBGeO 5 architecture formed in La 2 O 3 -B 2 O 3 -2GeO 2 glass serves as a model system for understanding of the transformation from glass to single crystal under fs laser irradiation. This transformation is highly sensitive to glass composition, raising the need to understand how the glass structure and composition evolve during crystallization. In this work, micro X-ray absorption spectroscopy and X-ray fluorescence mapping were used to study the glass structure and composition preceding LaBGeO5 crystallization in the region surrounding the single crystal growth front. The results show precipitation of germanium nanoparticles, as well as anisotropic segregation of Ge and La prior to LaBGeO5 crystallization, which are explained assuming electromigration in high fields within the plasma formed by the fs laser irradiation. However, these nanoparticles do not serve as sites for heterogeneous nucleation. Furthermore, the similarity of local structure around Ge in the starting glass and the ultimate crystal appears to enhance the crystallization process.

36 MATERIALS SCIENCE↗

Biophysical Characterization of Membrane Proteins Embedded in Nanodiscs Using Fluorescence Correlation Spectroscopy

Proteins embedded in biological membranes perform essential functions in all organisms, serving as receptors, transporters, channels, cell adhesion molecules, and other supporting cellular roles. These membrane proteins comprise ~30% of all human proteins and are the targets of ~60% of FDA-approved drugs, yet their extensive characterization using established biochemical and biophysical methods has continued to be elusive due to challenges associated with the purification of these insoluble proteins. In response, the development of nanodisc techniques, such as nanolipoprotein particles (NLPs) and styrene maleic acid polymers (SMALPs), allowed membrane proteins to be expressed and isolated in solution as part of lipid bilayer rafts with defined, consistent nanometer sizes and compositions, thus enabling solution-based measurements. Fluorescence correlation spectroscopy (FCS) is a relatively simple yet powerful optical microscopy-based technique that yields quantitative biophysical information, such as diffusion kinetics and concentrations, about individual or interacting species in solution. Here, we first summarize current nanodisc techniques and FCS fundamentals. We then provide a focused review of studies that employed FCS in combination with nanodisc technology to investigate a handful of membrane proteins, including bacteriorhodopsin, bacterial division protein ZipA, bacterial membrane insertases SecYEG and YidC, Yersinia pestis type III secretion protein YopB, yeast cell wall stress sensor Wsc1, epidermal growth factor receptor (EGFR), ABC transporters, and several G protein-coupled receptors (GPCRs).

59 BASIC BIOLOGICAL SCIENCES↗

Laboratory tank studies of a single species of phytoplankton using a remote sensing fluorosensor

Phytoplankton were grown in the laboratory for the purpose of testing a remote fluorosensor. The fluorosensor uses a unique four-wavelength dye laser system to excite phytoplankton bearing chlorophyll and to measure the chlorophyll fluorescence generated by this excitation. Six different species were tested, one at a time, and each was grown two to four times. Fluorescence measured by the fluorosensor provides good quantitative measurement of chlorophyll concentrations for all species tested while the cultures were in log phase growth. Fluorescene cross section ratios obtained in the single species tank tests support the hypothesis that the shape of the fluorescence cross section curve remains constant with the species (differences in fluorescence cross section ratios are a basis for determining composition of phytoplankton according to color group when a multiwavelength source of excitation is used. Linear relationships exist between extracted chlorophyll concentration and fluorescence measured by the remote fluorosensor during the log phase growth of phytoplankton cultures tested.

Brown, C. A., Jr.↗

Lunar composition from Apollo orbital measurements

Several spectrometers carried in the Service Module of the Apollo 15 and Apollo 16 spacecraft were employed for the compositional mapping of the lunar surface. The observations involved the measurements of secondary (fluorescent) X-rays, gamma rays and alpha particle emissions. A large scale compositional map of over 20 percent of the lunar surface was obtained for the first time. It was possible to demonstrate interesting chemical differences between the mare and the highlands, to find specific areas of high radioactivity and to learn something about the composition of the moon's hidden side. Further the same devices were used to obtain useful astronomical data during the return to earth.

Adler, I.↗