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Hyperspectral Fluorescence and Reflectance Imaging Instrument

The system is a single hyperspectral imaging instrument that has the unique capability to acquire both fluorescence and reflectance high-spatial-resolution data that is inherently spatially and spectrally registered. Potential uses of this instrument include plant stress monitoring, counterfeit document detection, biomedical imaging, forensic imaging, and general materials identification. Until now, reflectance and fluorescence spectral imaging have been performed by separate instruments. Neither a reflectance spectral image nor a fluorescence spectral image alone yields as much information about a target surface as does a combination of the two modalities. Before this system was developed, to benefit from this combination, analysts needed to perform time-consuming post-processing efforts to co-register the reflective and fluorescence information. With this instrument, the inherent spatial and spectral registration of the reflectance and fluorescence images minimizes the need for this post-processing step. The main challenge for this technology is to detect the fluorescence signal in the presence of a much stronger reflectance signal. To meet this challenge, the instrument modulates artificial light sources from ultraviolet through the visible to the near-infrared part of the spectrum; in this way, both the reflective and fluorescence signals can be measured through differencing processes to optimize fluorescence and reflectance spectra as needed. The main functional components of the instrument are a hyperspectral imager, an illumination system, and an image-plane scanner. The hyperspectral imager is a one-dimensional (line) imaging spectrometer that includes a spectrally dispersive element and a two-dimensional focal plane detector array. The spectral range of the current imaging spectrometer is between 400 to 1,000 nm, and the wavelength resolution is approximately 3 nm. The illumination system consists of narrowband blue, ultraviolet, and other discrete wavelength light-emitting-diode (LED) sources and white-light LED sources designed to produce consistently spatially stable light. White LEDs provide illumination for the measurement of reflectance spectra, while narrowband blue and UV LEDs are used to excite fluorescence. Each spectral type of LED can be turned on or off depending on the specific remote-sensing process being performed. Uniformity of illumination is achieved by using an array of LEDs and/or an integrating sphere or other diffusing surface. The image plane scanner uses a fore optic with a field of view large enough to provide an entire scan line on the image plane. It builds up a two-dimensional image in pushbroom fashion as the target is scanned across the image plane either by moving the object or moving the fore optic. For fluorescence detection, spectral filtering of a narrowband light illumination source is sometimes necessary to minimize the interference of the source spectrum wings with the fluorescence signal. Spectral filtering is achieved with optical interference filters and absorption glasses. This dual spectral imaging capability will enable the optimization of reflective, fluorescence, and fused datasets as well as a cost-effective design for multispectral imaging solutions. This system has been used in plant stress detection studies and in currency analysis.

Ryan, Robert E.↗

Investigation into the Origin of the RF Phase Noise for the LISA Laser Transmitter

The Laser Interferometer Space Antenna (LISA) mission is a collaborative consortium led by the European Space Agency (ESA)in cooperation with the National Aeronautics and Space Administration (NASA). LISA’s goal is to capture gravitational wave events, such as spacetime distortions caused by massive orbiting bodies. Multiple low noise, single frequency master oscillator power amplifier (MOPA) lasers with a polarization-maintaining Yb-fiber amplifier will serve as the light sources for the LISA observatory. The NASA Goddard Space Flight Center (GSFC)is currently developing the laser transmitters for this project. The LISA lasers will carry radio frequency (RF)sidebands for exchanging reference RF clock information between spacecrafts. Excess phase noise, especially carrier-sideband differential phase noise added to the modulation side band by the phase modulator and the fiber amplifier, becomes a concern. In the gravitational wave frequency ranges, leading sources of this RF “differential” phase noise can be both intrinsic and extrinsic. Examples of intrinsic sources include thermal load on the active fiber, thermo-mechanical induced birefringence, and nonlinearities in the various passive and active fibers. Extrinsic sources can include external temperature fluctuations and infrasonic mechanical strain or vibrations. These noise spectra usually include both white and pink (1/f) thermal noise contributions. This work investigates the physical origins and impact of these sources of RF phase noise, and their characteristic spectra and management will be discussed.

Laser Interferometer Space Antenna↗

A study of the flaring and quiescent X-ray and UV emission from II Pegasi

An investigation has been conducted of the rotational modulation of the transition-region UV and coronal X-ray emission for the RS CVn system II Pegasi. The X-ray light curve is dominated by a strong flare detected at orbital phase, where the minimum of the photometric wave occurred. The flare parameters derived show that the flare originates with a height greater than half the stellar radius. The characteristics of the flare are similar to those of a solar two-ribbon flare; a comparison of the midtransition region density with that in the coronal region shows a very steep pressure gradient.

Tagliaferri, G.↗

SS Cygni as a hard X-ray source identified with the scanning modulation collimator on HEAO 1

Hard X-ray emission from a 15 min by 1.5 deg area containing SS Cygni had previously been reported and identified with SS Cygni. This paper reports a 0.4 sq arc min measurement of the position of the X-ray source with the HEAO 1 modulation collimator experiment which leads to an unequivocal identification of SS Cygni as an X-ray emitter in the 2-10 keV energy range. The historical light curve in hard X-rays was also investigated by analyzing relevant Uhuru data, and two instances of possible source detection in the 2-6 keV band were noted. From Ariel 5 observations it is calculated that the X-ray luminosity of SS Cygni in the 2-10 keV energy range is of the order of 10 to the 33rd erg/sec in the optical low state and probably at least an order of magnitude less in the high state. By contrast, the soft X-ray luminosity increases by an order of magnitude between the optical low and high states. A coronal model or accretion onto the white dwarf can account for the inverse correlation of the soft and hard X-rays.

Fabbiano, G.↗

Charge coupled device integration-time coding for detection of images moving with unknown velocities

Existing techniques for the detection of a moving low light level image by a CCD array have required velocity synchronism between the image and the photogenerated charges. This was necessary to prevent blurring during the long duration of charge integration. A new detection scheme is described which causes the image to be convolved with a clock modulation signal as the photocharges are collected. The charge accumulating from each image point will now be spread over many photoelements due to the absence of velocity synchronism, but the output is not blurred in the usual sense. Instead the charge is distributed through the array in a controlled way so that the image can be reconstructed.

White, J. M.↗

ASCA Observation of MS 1603.6+2600 (=UW Coronae Borealis): A Dipping Low-Mass X-ray Binary in the Outer Halo?

MS 1603.6+2600 is a high-latitude X-ray binary with a 111 min orbital period, thought to be either an unusual cataclysmic variable or an unusual low-mass X-ray binary. In an ASCA observation in 1997 August, we find a burst whose light curve suggests a Type 1 (thermonuclear flash) origin. We also find an orbital X-ray modulation in MS 1603.6+2600, which is likely to be periodic dips, presumably due to azimuthal structure in the accretion disk. Both are consistent with this system being a normal low-mass X-ray binary harboring a neutron star, but at a great distance. We tentatively suggest that MS 1603.6+2600 is located in the outer halo of the Milky Way, perhaps associated with the globular cluster Palomar 14, 11 deg away from MS 1603.6+2600 on the sky at an estimated distance of 73.8 kpc.

Mukai, Koji↗

NASA Tech Briefs, January 2010

Topics covered include: Cryogenic Flow Sensor; Multi-Sensor Mud Detection; Gas Flow Detection System; Mapping Capacitive Coupling Among Pixels in a Sensor Array; Fiber-Based Laser Transmitter for Oxygen A-Band Spectroscopy and Remote Sensing; Low-Profile, Dual-Wavelength, Dual-Polarized Antenna; Time-Separating Heating and Sensor Functions of Thermistors in Precision Thermal Control Applications; Cellular Reflectarray Antenna; A One-Dimensional Synthetic-Aperture Microwave Radiometer; Electrical Switching of Perovskite Thin-Film Resistors; Two-Dimensional Synthetic-Aperture Radiometer; Ethernet-Enabled Power and Communication Module for Embedded Processors; Electrically Variable Resistive Memory Devices; Improved Attachment in a Hybrid Inflatable Pressure Vessel; Electrostatic Separator for Beneficiation of Lunar Soil; Amorphous Rover; Space-Frame Antenna; Gear-Driven Turnbuckle Actuator; In-Situ Focusing Inside a Thermal Vacuum Chamber; Space-Frame Lunar Lander; Wider-Opening Dewar Flasks for Cryogenic Storage; Silicon Oxycarbide Aerogels for High-Temperature Thermal Insulation; Supercapacitor Electrolyte Solvents with Liquid Range Below -80 C; Designs and Materials for Better Coronagraph Occulting Masks; Fuel-Cell-Powered Vehicle with Hybrid Power Management; Fine-Water-Mist Multiple-Orientation-Discharge Fire Extinguisher; Fuel-Cell Water Separator; Turbulence and the Stabilization Principle; Improved Cloud Condensation Nucleus Spectrometer; Better Modeling of Electrostatic Discharge in an Insulator; Sub-Aperture Interferometers; Terahertz Mapping of Microstructure and Thickness Variations; Multiparallel Three-Dimensional Optical Microscopy; Stabilization of Phase of a Sinusoidal Signal Transmitted Over Optical Fiber; Vacuum-Compatible Wideband White Light and Laser Combiner Source System; Optical Tapers as White-Light WGM Resonators; EPR Imaging at a Few Megahertz Using SQUID Detectors; Reducing Field Distortion in Magnetic Resonance Imaging; Fluorogenic Cell-Based Biosensors for Monitoring Microbes; A Constant-Force Resistive Exercise Unit; GUI to Facilitate Research on Biological Damage from Radiation; On-Demand Urine Analyzer; More-Realistic Digital Modeling of a Human Body; and Advanced Liquid-Cooling Garment Using Highly Thermally Conductive Sheets.

Source record↗

Variation in Coronal Activity from Solar Cycle 24 Minimum to Maximum Using Three-Dimensional Reconstructions of the Coronal Electron Density from STEREO/COR1

Three-dimensional electron density distributions in the solar corona are reconstructed for 100 Carrington rotations (CR 2054 - 2153) during 2007/03 - 2014/08 using the spherically symmetric method from polarized white-light observations with the inner coronagraph (COR1) onboard the twin Solar Terrestrial Relations Observatory (STEREO). These three-dimensional electron density distributions are validated by comparison with similar density models derived using other methods such as tomography and a magnetohydrodynamics (MHD) model as well as using data from the Solar and Heliospheric Observatory (SOHO)/Large Angle and Spectrometric Coronagraph (LASCO)-C2. Uncertainties in the estimated total mass of the global corona are analyzed based on differences between the density distributions for COR1-A and -B. Long-term variations of coronal activity in terms of the global and hemispheric average electron densities (equivalent to the total coronal mass) reveal a hemispheric asymmetry during the rising phase of Solar Cycle 24, with the northern hemisphere leading the southern hemisphere by a phase shift of 7 - 9 months. Using 14 CR (approx. equal to 13-month) running averages, the amplitudes of the variation in average electron density between Cycle 24 maximum and Cycle 23/24 minimum (called the modulation factors) are found to be in the range of 1.6 - 4.3. These modulation factors are latitudinally dependent, being largest in polar regions and smallest in the equatorial region. These modulation factors also show a hemispheric asymmetry: they are somewhat larger in the southern hemisphere. The wavelet analysis shows that the short-term quasi-periodic oscillations during the rising and maximum phases of Cycle 24 have a dominant period of 7 - 8 months. In addition, it is found that the radial distribution of the mean electron density for streamers at Cycle 24 maximum is only slightly larger (by approx. equal to 30%) than at cycle minimum.

Wang, Tongjiang↗

A 5.57 hr modulation in the optical counterpart of 2S 1822-371

A periodic 5.57 hr modulation has been observed in the optical counterpart of the X-ray source 2S 1822-371. Two alternative periods are consistent with the data: P = 0.232114d and P = 0.232191d, with statistical uncertainties of 0.000015d in each case. Minimum light occurred at JD 2,444,105.668 + or - 0.005. The amplitude of the modulation is about 1 mag, independent of UBV color, and no variability exceeding the 2% level other than the 5.57 hr effect is found on time scales down to a few seconds. The light curve of the star can be understood in terms of a highly inclined close binary system which contains a relatively large, luminous accretion disk that is periodically occulted by a companion star and an associated gas stream. On the assumption that the companion is a main-sequence star, the distance of the system is found to be more than 600 pc, based on the absence of color variations commensurate with the 5.57 hr intensity cycle.

Mason, K. O.↗

Impact of Halogen Groups on the Properties of PEA–Based 2D Pb–Sn Halide Perovskites

Tuning broad emission in 2D Pb–Sn halide perovskites (HPs) is essential for advancing optoelectronic applications, particularly for color-tunable and white-light-emitting devices. This broad emission is linked to structural factors, such as defects and phase segregation of the Pb component within the Pb–Sn system, which are strongly influenced by the molecular structure and chemical properties of spacer cations. Atomic tuning of the spacers via halogenation opens up a new way to fine-tune the molecular properties, enabling further augmentations of HP functionalities. Nevertheless, the distinct broad emission's sensitivity to spacer chemistry remains underexplored. Here, halogenation's influence is systematically investigated on 2D HP emission characteristics using a high-throughput workflow. These findings reveal that the F-containing phenethylammonium (4F-PEA) spacer narrows the broadband PL, whereas Cl broadens it. Through a correlative study, it is found that 4F-PEA reduces not only the local phase segregation but also the defect levels and microstrains in 2D HPs. This is likely attributed to the manifestation of less lattice distortion via stronger surface coordination of the dipole-augmented 4F-PEA. Furthermore, these results highlight halogenation as a key factor in modulating phase segregation and defect density in 2D Pb–Sn HPs, offering a promising pathway to tune the emission for enhanced optoelectronic performance.

2D Pb-Sn halide perovskites↗

Safe, High Power/Voltage Battery Module Design Challenges

NASA seeks to demonstrate a path for achieving safe, high power, and high performing Li-ion battery designs for the purpose of establishing design guidelines for our aeronautic and spacecraft applications. Safe means passively resistant to thermal runaway propagation of any single cell catastrophic thermal runaway. High power means capable of 3C continuous discharge without overheating. High performing means achieving > 160 Wh/kg, 200 Wh/L. The biggest challenge has been balancing a high flux light weight path for cell heat dissipation during the high rate discharge that minimizes thermal gradients between cells and also protects adjacent cells from the heat load of thermal runaway cell. Our solution includes an oscillating heat pipe spine that contacts every 18650 cell in the pack and careful cell design selection to maximize the range of initial temperatures conditions where the battery can safely complete the 3C discharge.

Thermal runaway↗

A 5.57 hour modulation of the X-ray flux from 4U 1822-37

The X-ray flux of 4U 1822-37 is shown to be modulated with the 5.57 hr period of its optical counterpart. The X-ray light curve is two component, with a smooth sinusoidal-like 25% semiamplitude modulation and a 30 minute dip of approximately 0.2 in phase following the other minimum; the dip center occurs 0.04 in phase after the optical minimum. The X-ray spectrum is a relatively flat power law up to 17 keV, above which it steepens; iron emission is detected at 6.7 keV with a 4 keV FWHM and an equivalent width of 1100 eV. An excess below 2 keV is consistent with either a 0.25 keV thermal component of 350 eV equivalent width iron L emission. Modeling the eclipse for a 0.5-0.7 solar radius companion gives a system inclination of 70-79 deg and a spherical cloud radius of 0.2-0.3 solar radius. Models for the long-term modulation are considered, and a comparison of the properties of 4U 1822-37 with those of Cyg X-3 shows that they are similar systems.

White, N. E.↗

The X-ray orbital lightcurve of TY Pyx - A 3.2-day eclipsing RS CVn system

An Exosat observation of one orbital cycle of the eclipsing 3.2-d RS CVn system TY Pyx is reported. This system contains two almost identical GV stars, which is unusual because most RS CVns contain F or G main-sequence star and a K subgiant. The X-ray light curves of the primary and secondary eclipses are different above and below 1 keV. At lower energies a sharp eclipse is seen, but at higher energies it is absent. This confirms earlier observations that the 1.5-4.0 x 10 to the 7th K emission from the RS CVn systems is not eclipsed and comes from an extended region, whereas the 7 x 10 to the 6th K emission comes from more compact solarlike active regions. Modeling the X-ray eclipse detected at low energies requires two emission regions, one on each star, covering less than 20 percent of the stellar surface. To avoid a strong orbital modulation caused by both regions being either simultaneously visible, or not visible, they must be located 180 deg apart in longitude. The derived longitudes are 0 and 180 deg; i.e., they point at each other on the inward faces of the two stars.

Culhane, J. L.↗

Phytochrome-Dependent Regulation of ZFP6 and ZFPH Impacts Photomorphogenesis in Arabidopsis thaliana

Phytochromes (phy) are key regulators of photomorphogenesis in plants. Among the different phys characterized in higher plants (i.e., phyA to phyE), phyA and phyB primarily regulate phenotypic responses in plants under far-red (FR) and red (R) conditions, respectively. Recent findings suggest that some zinc finger proteins (ZFPs) are involved in plant light-modulated morphogenesis. However, the interaction(s) between phyA, phyB and ZFP homologs potentially involved in photomorphogenesis, as well as their phenotypic and molecular effects in Arabidopsis seedlings exposed to R and FR light remain to be elucidated fully. Prior analyses with phytochrome chromophore deficient lines indicated that ZFP6 expression is misregulated compared to levels in Col-0 wild type (WT). Here, we used plants with phytochrome chromophore or apoprotein (specifically phyA and phyB) deficiencies, lines with mutations in ZFP6 and ZFP6 HOMOLOG ( ZFPH ) genes, and plants overexpressing ZFP6 to examine regulatory interactions between phytochromes, ZFP6, and ZFPH. Our results indicate that phytochromes are required for downregulation of ZFP6 and ZFPH and suggest a role for light-regulated control of ZFP levels in phytochrome-dependent photomorphogenesis. Conversely, PHYB is downregulated in zfp6 mutants under R light. Analyses of a zfp6zfph double mutant confirmed disruption in photomorphogenic phenotypes, including the regulation of hypocotyl elongation in seedlings grown under FR light. In addition, PIF3 and PIF4 levels are transcriptionally regulated by ZFP6 and ZFPH in a gibberellic acid-dependent manner. ZFP6 overexpression resulted in opposite phenotypic responses to those observed in the zfp6 and zfph mutants grown in FR and R light, as well as a reduction in the rosette size of mature ZFP6 OX plants relative to WT under white light. Based on these observations, we provide insight into how phy and ZFPs interact to regulate specific aspects of light-dependent processes in Arabidopsis.

59 BASIC BIOLOGICAL SCIENCES↗

Search for Pulsations from a Nearby Millisecond Pulsar and Wasilewski 49: Mirror for a Hidden Seyfert 1 Nucleus

Five studies are reported in this final report. The recently discovered 5.3 ms pulsar J1012+5307 at a distance of 520 pc is in an area of the sky which is particularly deficient in absorbing gas. The column density along the line of sight is less than 7.5 x 10(exp 19) CM(exp -2) which facilitates soft X-ray observations. Halpern reported a possible ROSAT Position Sensitive Proportional Counter (PSPC) detection of the pulsar in a serendipitous, off-axis observation. We have now confirmed the X-ray emission of PSR J1012+,5307 in a 23 ksec observation with the ROSAT High Resolution Imager (HRI). A point source is detected within 3" of the radio position. Its count rate of 1.6 +/- 0.3 x 10(exp -3) s(exp -1) corresponds to an unabsorbed 0. 1-2.4 keV flux of 6.4 x 10(exp -14) ergs cm(exp -2) s(exp -1), similar to that reported previously. This counts-to-flux conversion is valid for N(sub H) = 5 x 10(exp 19) cm(exp -2), and either a power-law spectrum of photon index 2.5 or a blackbody of kT = 0.1 keV. The implied X-ray luminosity of 2.0 x 10(exp 30) ergs s(exp -1) is 5 X 10(exp -4) of the pulsar's spin-down power dot-E, and similar to that of the nearest millisecond pulsar J0437-4715, which is nearly a twin of J1012+5307 in P dot-E. We subjected the 37 photons (and 13 background counts) within the source region to a pulsar search, but no evidence for pulsation was found. The pulsar apparently emits over a large fraction of its rotation cycle, and the absence of sharp modulation can be taken as evidence for surface thermal emission, as is favored for PSR J0437-4715, rather than magnetospheric X-ray emission which is apparent in the sharp pulses of the much more energetic millisecond pulsar B1821-24. A further test of this interpretation will be made with a longer ROSAT observation, which will increase the number of photons collected by a factor of 5, and permit a more sensitive examination of the light curve for modulation due to emission from heated polar caps. If found, such modulation will be further evidence that surface reheating by the impact of particles accelerated along open fiel;d lines operates in these approximately 10(exp -9) year old pulsars. In a second study, a new AM Her star serendipitously in a 25 day observation was detected with the EUVE satellite. A coherent period of 85.82 min is present in the EUVE Deep Survey imager light curve of this source. A spectroscopic optical identification is made with a 19th magnitude blue star that has H and He emission lines, and broad cyclotron humps typical of a magnetic cataclysmic variable. A lower limit to the polar magnetic field of 50 MG is estimated from the spacing of the cyclotron harmonics. EUVE J0425.6-5714 is also detected in archival ROSAT HRI observations spanning two months, and its stable and highly structured light curve permits us to fit a coherent ephemeris linking the ROSAT and EUVE data over a 1.3 yr gap. The derived period is 85.82107 +/- 0.00020 min, and the ephemeris should be accurate to 0.1 cycles until the year 2005. A narrow but partial X-ray eclipse suggests that this object belongs to the group of AM Her stars whose viewing geometry is such that the accretion stream periodically occults the soft X-ray emitting accretion spot on the surface of the white dwarf. A non-detection of hard X-rays from ASCA observations that are contemporaneous with the ROSAT HRI shows that the soft X-rays must dominate by at least an order of magnitude, which is consistent with a known trend among AM Her stars with large magnetic field. This object should not be confused with the Seyfert galaxy IH 0419-577 (= LB 1727), another X-ray/EUV source which lies only 3'95 away, and was the principal target of these monitoring observations. In a third report; the identity of the persistent high-energy (> 100 MeV) gamma-ray sources in the Galaxy, still largely a mystery is investigated. The second installment of the EGRET (2EG) lists a total of 128 sources, of which 51 are likely or possibly identified with AGNs, five with rotation-powered pulsars, and one is the LMC. There are 71 unidentified sources, of which 33, or almost half, lie in the narrow band of absolute value of b < 10 degrees along the Galactic plane. This excess of low-latitude sources must, therefore, constitute a Galactic population that is either similar to the already identified gamma-ray pulsars, or an entirely new class of gamma-ray emitters associated with the disk population. We are continuing our program, begun in A06, that is aimed at intermediate-latitude sources, arguing that X-ray detection of them is the most plausible method of identifying the Galactic population. The sources at high latitude must statistically be mostly AGNS, and are more straightforwardly identified through radio and optical means. For the fourth report, identification of the EGRET Source the identity of the persistent, high-energy gamma-ray sources in the Galactic plane is a mystery. The most likely scenario is a population of middle-aged pulsars, many of which could be radio quiet like Geminga. We have an ongoing program of ROSAT, VLA, and optical observations of selected EGRET error circles at intermediate Galactic latitude. For one of these fields, at (l, b) = (106 degrees, +3), our complete census of X-ray and radio sources, reveals a remarkable association between a radio shell with unique properties, and a complete census of X-ray and radio sources reveals a remarkable association between a radio shell with unique properties, and a compact X-ray source. Further observations are needed to determine whether or not this source has a hard X-ray spectrum like that of other gamma ray pulsars and, ideally, to find its pulsations. A fifth report reviews, Wasilewski 49, an interacting pair of Seyfert galaxies at z = 0.063, one of which contains a hidden Seyfert I nucleus as evidenced by broad wings on its Balmer lines.

Halpern, Jules P.↗

A 5.57 hour modulation of the X-ray flux of 4U1822-37: A new model for CYG X-3

The X-ray flux of 4U1822-37 is shown to be modulated with the 5.57 hour period of its optical counterpart. The X-ray light curve is two component with a smooth sinusoidal like 25 percent semiamplitude modulation and a 30 minute dip approximately 0.2 in phase following the other minimum. The X-ray spectrum is a relatively flat power law up to 17 keV, above which its steepens. Iron emission is detected at 6.7 keV with a 4 keV FWHM and an equivalent width of 1100 eV. There is an excee below 2 keV that is consistent with either a 0.25 keV thermal component or 350 eV equivalent width iron L emission. A slight softening of the spectrum is seen during both X-ray minima. The dip is interpreted as the partial occultation of an extended cloud of optically thick highly ionized material surrounding the central X-ray source. Modeling the eclipse gives a system inclination of 70-79 deg and a spherical cloud radius of 0.2-0.3 solar radius. Models for the long term modulation are considered. The properties of this source are compared to those of Cyg X-3. It is concluded that they are similar systems.

White, N. E.↗

Modulating Mid-Gap Electronic States Through Site-Selective Modification in B-Pbx/B'-CuyV2O5/CdS Heterostructures for Photocatalytic Hydrogen Evolution

We interfaced ..beta..-Pbx/..beta..'-CuyV2O5 compounds, with varying stoichiometries of precisely positioned Pb-ions (x) and Cu-ions (y) in interstitial sites along a tunnel-structured ?-V2O5 framework, with cysteine-capped CdS (cysCdS) quantum dots (QDs) to yield heterostructured photocatalysts. ..beta..-Pbx/..beta..'-CuyV2O5 compounds exhibit midgap electronic states with orbital contributions from both Cu 3d and stereochemically active Pb 6s states that show distinctive light-initiated reactivity with photoexcited QDs. ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures were prepared by linker-assisted assembly (LAA). Scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy revealed that cysCdS QDs were deposited onto surfaces of ..beta..-Pbx/..beta..'-CuyV2O5 via LAA. HAXPES revealed that the site-selective positioning of Pb-ions and Cu-ions promoted close energetic alignment of the midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds with the valence-band maximum of cysCdS QDs. Transient absorption spectroscopy revealed that photogenerated holes were transferred from CdS QDs to midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds on time scales <50 ps. Finally, photoelectrochemical and photochemical experiments revealed that ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the photocatalytic reduction of H+ to H2. In photoelectrochemical experiments, under oxidative conditions, for all ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at a Pt counter electrode while a sacrificial donor was oxidized at the heterostructure-functionalized working electrode. In contrast, under reductive conditions, for ..beta..-Pb0.152V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, H2 was evolved at the working electrode. In photochemical experiments, dispersed ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures promoted the reduction of H+ to H2 under white-light illumination; ..beta..'-Cu0.55V2O5/CdS and ..beta..-Pbx/..beta..'-CuyV2O5/CdS heterostructures, for which midgap states have Cu 3d orbital character, generated 2-fold more H2 than ..beta..-Pb0.152V2O5/CdS heterostructures. Cu-ion insertion thus appends additional acceptor surface states that improve ligand-mediated hole transfer from photoexcited QDs, but such states are intrinsically limited in mediating hole transport to the substrate as a result of the low mobility of holes in narrow Cu 3d-states. Our results reveal that the density and orbital character of midgap states of ..beta..-Pbx/..beta..'-CuyV2O5 compounds, tunable through recently developed site-selective ion insertion strategies, determine efficiencies of charge-transfer and charge-transport mechanisms that underpin photocatalysis.

36 MATERIALS SCIENCE↗

General Approach to Solving Spin Moiré Superstructures

Recently, a host of exciting magnetic textures such as topologically protected skyrmion lattices has been discovered in several bulk metallic lanthanide compounds. In addition to hosting skyrmion phases, a hallmark of this class of materials is the appearance of numerous spin textures characterized by superposition of multiple magnetic modulations: spin moiré superlattices. In order to understand the multitude of complex phases often present in these materials, we require a general-purpose experimental and theoretical framework. Here, we demonstrate such an approach in EuAg4⁢Sb2 by comprehensively characterizing and modeling its three complex zero-field magnetic textures. Systematic symmetry-breaking experiments using uniaxial strain determine that the ground-state incommensurate magnetic phase (ICM1) is single 𝑞, meaning the magnetic moments modulate along one magnetic propagation vector. In contrast, ICM2 and ICM3 are both double 𝑞, meaning they are formed from the superposition of two sinusoidal spin modulations, i.e., spin moiré superlattices. Further, through application of polarized small-angle neutron scattering and spherical neutron polarimetry, we demonstrate that ICM1 is a single-𝑞 cycloid and ICM2 and ICM3 are double-𝑞 vortex lattices. Despite the quasi-two-dimensional nature of EuAg4⁢Sb2, the modulations propagate out of the ab plane, leading to a shift of the spin texture between triangular lattice planes. Further, the ICM3 to ICM2 transition includes an unusual 45° rotation of the magnetic vortex lattice. Motivated by the coexistence of such drastically different phases in this compound, we conclude by developing a phenomenological model that sheds light on the energetic origins of these varied phases. Our experimental probes and theoretical modeling definitively characterize three different and tunable phases in one material and provide insight for the design of topological spin-texture materials.

Neves, Paul [Massachusetts Institute of Technology↗