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Data-guided Multi-Map variables for ensemble refinement of molecular movies

Driving molecular dynamics simulations with data-guided collective variables offer a promising strategy to recover thermodynamic information from structure-centric experiments. In this study, the three-dimensional electron density of a protein, as it would be determined by cryo-EM or x-ray crystallography, is used to achieve simultaneously free-energy costs of conformational transitions and refined atomic structures. Unlike previous density-driven molecular dynamics methodologies that determine only the best map-model fits, our work employs the recently developed Multi-Map methodology to monitor concerted movements within equilibrium, non-equilibrium, and enhanced sampling simulations. Construction of all-atom ensembles along the chosen values of the Multi-Map variable enables simultaneous estimation of average properties, as well as real-space refinement of the structures contributing to such averages. Using three proteins of increasing size, we demonstrate that biased simulation along the reaction coordinates derived from electron densities can capture conformational transitions between known intermediates. The simulated pathways appear reversible with minimal hysteresis and require only low-resolution density information to guide the transition. The induced transitions also produce estimates for free energy differences that can be directly compared to experimental observables and population distributions. The refined model quality is superior compared to those found in the Protein Data Bank. We find that the best quantitative agreement with experimental free-energy differences is obtained using medium resolution density information coupled to comparatively large structural transitions. Practical considerations for probing the transitions between multiple intermediate density states are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mass Spectrometry Imaging of Biological Tissue: An Approach for Multicenter Studies

Mass spectrometry imaging has become a popular tool for probing the chemical complexity of biological surfaces. This led to the development of a wide range of instrumentation and preparation protocols. It is thus desirable to evaluate and compare the data output from different methodologies and mass spectrometers. Here, we present an approach for the comparison of mass spectrometry imaging data from different laboratories (often referred to as multicenter studies). This is exemplified by the analysis of mouse brain sections in five laboratories in Europe and the USA. The instrumentation includes matrix-assisted laser desorption/ionization (MALDI)-time-of-flight (TOF), MALDI-QTOF, MALDIFourier transform ion cyclotron resonance (FTICR), atmospheric-pressure (AP)-MALDI-Orbitrap, and cluster TOF-secondary ion mass spectrometry (SIMS). Experimental parameters such as measurement speed, imaging bin width, and mass spectrometric parameters are discussed. All datasets were converted to the standard data format imzML and displayed in a common open-source software with identical parameters for visualization, which facilitates direct comparison of MS images. The imzML conversion also allowed exchange of fully functional MS imaging datasets between the different laboratories. The experiments ranged from overview measurements of the full mouse brain to detailed analysis of smaller features (depending on spatial resolution settings), but common histological features such as the corpus callosum were visible in all measurements. High spatial resolution measurements of AP-MALDI-Orbitrap and TOF-SIMS showed comparable structures in the low-micrometer range. We discuss general considerations for planning and performing multicenter studies in mass spectrometry imaging. This includes details on the selection, distribution, and preparation of tissue samples as well as on data handling. Such multicenter studies in combination with ongoing activities for reporting guidelines, a common data format (imzML) and a public data repository can contribute to more reliability and transparency of MS imaging studies.

Environmental Molecular Sciences Laboratory↗

Stress relaxation in quasi-two-dimensional self-assembled nanoparticle monolayers

Here, we experimentally probed the stress relaxation of a monolayer of iron oxide nanoparticles at the water-air interface. Upon drop-casting onto a water surface, the nanoparticles self-assembled into islands of two-dimensional hexagonally close packed crystalline domains surrounded by large voids. When compressed laterally, the voids gradually disappeared as the surface pressure increased. After the compression was stopped, the surface pressure (as measured by a Wilhelmy plate) evolved as a function of the film aging time with three distinct timescales. These aging dynamics were intrinsic to the stressed state built up during the non-equilibrium compression of the film. Utilizing x-ray photon correlation spectroscopy, we measured the characteristic relaxation time (tau) of in-plane nanoparticle motion as a function of the aging time through both second-order and two-time autocorrelation analysis. Compressed and stretched exponential fitting of the intermediate scattering function yielded exponents (beta) indicating different relaxation mechanisms of the films under different compression stresses. For a monolayer compressed to a lower surface pressure (between 20 mN/m and 30 mN/m), the relaxation time (tau) decreased continuously as a function of the aging time, as did the fitted exponent, which transitioned from being compressed (>1) to stretched (<1), indicating that the monolayer underwent a stress release through crystalline domain reorganization. However, for a monolayer compressed to a higher surface pressure (around 40 mN/m), the relaxation time increased continuously and the compressed exponent varied very little from a value of 1.6, suggesting that the system may have been highly stressed and jammed Despite the interesting stress relaxation signatures seen in these samples, the structural ordering of the monolayer remained the same over the sample lifetime, as revealed by grazing incidence x-ray diffraction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Impedance-Based Detection of NO 2 Using Ni-MOF-74: Influence of Competitive Gas Adsorption

Chemically robust, low-power sensors are needed for the direct electrical detection of toxic gases. Metal–organic frameworks (MOFs) offer exceptional chemical and structural tunability to meet this challenge, though further understanding is needed regarding how coadsorbed gases influence or interfere with the electrical response. To probe the influence of competitive gases on trace NO 2 detection in a simulated flue gas stream, a combined structure–property study integrating synchrotron powder diffraction and pair distribution function analyses was undertaken, to elucidate how structural changes associated with gas binding inside Ni-MOF-74 pores correlate with the electrical response from Ni-MOF-74-based sensors. Data were evaluated for 16 gas combinations of N 2 , NO 2 , SO 2 , CO 2 , and H 2 O at 50 °C. Fourier difference maps from a rigid-body Rietveld analysis showed that additional electron density localized around the Ni-MOF-74 lattice correlated with large decreases in Ni-MOF-74 film resistance of up to a factor of 6 × 10 3 , observed only when NO 2 was present. These changes in resistance were significantly amplified by the presence of competing gases, except for CO 2 . Without NO 2 , H 2 O rapidly (<120 s) produced small (1–3×) decreases in resistance, though this effect could be differentiated from the slower adsorption of NO 2 by the evaluation of the MOF’s capacitance. Furthermore, samples exposed to H 2 O displayed a significant shift in lattice parameters toward a larger lattice and more diffuse charge density in the MOF pore. Evaluating the Ni-MOF-74 impedance in real time, NO 2 adsorption was associated with two electrically distinct processes, the faster of which was inhibited by competitive adsorption of CO 2 . Together, this work points to the unique interaction of NO 2 and other specific gases (e.g., H 2 O, SO 2 ) with the MOF’s surface, leading to orders of magnitude decrease in MOF resistance and enhanced NO2 detection. Finally, understanding and leveraging these coadsorbed gases will further improve the gas detection properties of MOF materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neutron Compton Scattering as a Probe of Hydrogen Bonded (and other) Systems

One of the two major themes of the proposal was to study quantum coherence in stressed hydrogen bond networks. Our experiments on double wall carbon nanotubes and two versions of Nafion, together with earlier work on water confined in xerogel and in single wall carbon nanotubes demonstrate that water confined in dimensions on the order of 20 Angstroms is in a qualitatively different quantum ground state than bulk water. It cannot be described as a collection of molecules interacting only electrostatically. This has major implications for biology, where most of the water in the cell is confined to distances on that order, and for fuel cell development using Nafion like materials, where the conduction mechanism is expected to be strongly affected by the quantum state of the water. We have demonstrated its importance in the binding of water molecules to DNA. Protein folding experiments at several concentrations have been carried out and are presently being analyzed. Initial analysis shows strong temperature dependent effects on the proton momentum distribution. The theoretical work proposed has been completed, and complements the experiments by demonstrating that even in room temperature bulk water, the electron density overlap between donor and acceptor molecules in the hydrogen bond has a significant measurable effect on the momentum distribution of the protons. The electrons are distributed throughout the hydrogen bond network, not simply in localized molecules. We had proposed to look at low coverage experiments on MCM-41, and have done so, revealing the details of the interaction of water molecules with silanol groups. Related experiments, not proposed, on water layers on SnO2 and TiO2 powders have confirmed the strong deviations of the proton momentum distribution for water molecules adsorbed on these surfaces. These results are not yet published. Another major theme was to measure Born-Oppenheimer potentials in M3H(XO4)2 systems. We have done this for Rb3(SO4)2, observing a strongly temperature dependent potential, despite the absence of a phase transition, and have data not yet analyzed for Rb3(SeO4)2. The remaining samples proposed have not been done yet. Our priorities were to explore the quantum coherence in confined water and water on surfaces, and, due to the limitations of time on VESUVIO, the experiments on Nafion and the surface experiments displaced these. We hope to carry them out under the renewal proposal. A third theme was to confront the theory of the intensity deficit developed by the PI and P. Platzman with experiments on H2. This has been done, and, although the analysis is preliminary, and not yet published, it appears that the predictions of this theory are not born out, and that the intensity deficit is due to other sources. Finally, experiments on the simple tunneling system MnH0.07 have been carried out with larger samples. The results refute the earlier measurements, and defy theoretical expectations as to the temperature dependence and shape of the momentum distribution. This remains a puzzle.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The development of optical microscopy techniques for the advancement of single-particle studies

Single particle orientation and rotational tracking (SPORT) has recently become a powerful optical microscopy tool that can expose many molecular motions. Unfortunately, there is not yet a single microscopy technique that can decipher all particle motions in all environmental conditions, thus there are limitations to current technologies. Within, the two powerful microscopy tools of total internal reflection and interferometry are advanced to determine the position, orientation, and optical properties of metallic nanoparticles in a variety of environments. Total internal reflection is an optical phenomenon that has been applied to microscopy to produce either fluorescent or scattered light. The non-invasive far-field imaging technique is coupled with a near-field illumination scheme that allows for better axial resolution than confocal microscopy and epi-fluorescence microscopy. By controlling the incident illumination angle using total internal reflection fluorescence (TIRF) microscopy, a new type of imaging probe called “non-blinking” quantum dots (NBQDs) were super-localized in the axial direction to sub-10-nm precision. These particles were also used to study the rotational motion of microtubules being propelled by the motor protein kinesin across the substrate surface. The same instrument was modified to function under total internal reflection scattering (TIRS) microscopy to study metallic anisotropic nanoparticles and their dynamic interactions with synthetic lipid bilayers. Utilizing two illumination lasers with opposite polarization directions at wavelengths corresponding to the short and long axis surface plasmon resonance (SPR) of the nanoparticles, both the in-plane and out-of-plane movements of many particles could be tracked simultaneously. When combined with Gaussian point spread function (PSF) fitting for particle super-localization, the binding status and rotational movement could be resolved without degeneracy. TIRS microscopy was also used to find the 3D orientation of stationary metallic anisotropic nanoparticles utilizing only long-axis SPR enhancement. The polarization direction of the illuminating light was rotated causing the relative intensity of p-polarized and s-polarized light within the evanescent field to change. The interaction of the evanescent field with the particles is dependent on the orientation of the particle producing an intensity curve. This curve and the in-plane angle can be compared with simulations to accurately determine the 3D orientation. Differential interference contrast (DIC) microscopy is another non-invasive far-field technique based upon interferometry that does not rely on staining or other contrast enhancing techniques. In addition, high numerical aperture condensers and objectives can be used to give a very narrow depth of field allowing for the optical tomography of samples, which makes it an ideal candidate to study biological systems. DIC microscopy has also proven itself in determining the orientation of gold nanorods in both engineered environments and within cells. Many types of nanoparticles and nanostructures have been synthesized using lithographic techniques on silicon wafer substrates. Traditionally, reflective mode DIC microscopes have been developed and applied to the topographical study of reflective substrates and the imaging of chips on silicon wafers. Herein, a laser-illuminated reflected-mode DIC was developed for studying nanoparticles on reflective surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy setup for pulsed and constant wave X-ray light sources

An apparatus for sub-nanosecond time-resolved ambient-pressure X-ray photoelectron spectroscopy studies with pulsed and constant wave X-ray light sources is presented. A differentially pumped hemispherical electron analyzer is equipped with a delay-line detector that simultaneously records the position and arrival time of every single electron at the exit aperture of the hemisphere with ∼0.1 mm spatial resolution and ∼150 ps temporal accuracy. The kinetic energies of the photoelectrons are encoded in the hit positions along the dispersive axis of the two-dimensional detector. Pump-probe time-delays are provided by the electron arrival times relative to the pump pulse timing. An average time-resolution of (780 ± 20) ps (FWHM) is demonstrated for a hemisphere pass energy E{sub p} = 150 eV and an electron kinetic energy range KE = 503–508 eV. The time-resolution of the setup is limited by the electron time-of-flight (TOF) spread related to the electron trajectory distribution within the analyzer hemisphere and within the electrostatic lens system that images the interaction volume onto the hemisphere entrance slit. The TOF spread for electrons with KE = 430 eV varies between ∼9 ns at a pass energy of 50 eV and ∼1 ns at pass energies between 200 eV and 400 eV. The correlation between the retarding ratio and the TOF spread is evaluated by means of both analytical descriptions of the electron trajectories within the analyzer hemisphere and computer simulations of the entire trajectories including the electrostatic lens system. In agreement with previous studies, we find that the by far dominant contribution to the TOF spread is acquired within the hemisphere. However, both experiment and computer simulations show that the lens system indirectly affects the time resolution of the setup to a significant extent by inducing a strong dependence of the angular spread of electron trajectories entering the hemisphere on the retarding ratio. The scaling of the angular spread with the retarding ratio can be well approximated by applying Liouville's theorem of constant emittance to the electron trajectories inside the lens system. The performance of the setup is demonstrated by characterizing the laser fluence-dependent transient surface photovoltage response of a laser-excited Si(100) sample.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

NASA Tech Briefs, April 2013

Topics covered include: Fully Integrated, Miniature, High-Frequency Flow Probe Utilizing MEMS Leadless SOI Technology; Nanoscale Surface Plasmonics Sensor With Nanofluidic Control; Advanced Dispersed Fringe Sensing Algorithm for Coarse Phasing Segmented Mirror Telescopes; Neural Network Back-Propagation Algorithm for Sensing Hypergols; Bulk Moisture and Salinity Sensor; Change-Based Satellite Monitoring Using Broad Coverage and Targetable Sensing; Circularly Polarized Microwave Antenna Element with Very Low Off-Axis Cross-Polarization; Ultra-Low Heat-Leak, High-Temperature Superconducting Current Leads for Space Applications; Flash Cracking Reactor for Waste Plastic Processing; An Automated Safe-to-Mate (ASTM) Tester; Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch; Compute Element and Interface Box for the Hazard Detection System; DOT Transmit Module; Composite Aerogel Multifoil Protective Shielding; Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems; Polymer-Reinforced, Non-Brittle, Lightweight Cryogenic Insulation; Controlled, Site-Specific Functionalization of Carbon Nanotubes with Diazonium Salts; Regenerable Sorbent for CO2 Removal; Sprayable Aerogel Bead Compositions With High Shear Flow Resistance and High Thermal Insulation Value; Lexan Linear Shaped Charge Holder with Magnets and Backing Plate; Robotic Ankle for Omnidirectional Rock Anchors; Wind, Wave, and Tidal Energy Without Power Conditioning; An Active Heater Control Concept to Meet IXO Type Mirror Module Thermal-Structural Distortion Requirement; Waterless Clothes-Cleaning Machine; Integrated Electrical Wire Insulation Repair System; LVGEMS Time-of-Flight Mass Spectrometry on Satellites; Surface Inspection Tool for Optical Detection of Surface Defects; Per-Pixel, Dual-Counter Scheme for Optical Communications; Certification-Based Process Analysis; Surface Navigation Using Optimized Waypoints and Particle Swarm Optimization; Smart-Divert Powered Descent Guidance to Avoid the Backshell Landing Dispersion Ellipse; Estimating Foreign-Object-Debris Density from Photogrammetry Data; Adaptive Sampling of Spatiotemporal Phenomena with Optimization Criteria; Building a 2.5D Digital Elevation Model From 2D Imagery; Eyes on the Earth 3D; Target Trailing With Safe Navigation for Maritime Autonomous Surface Vehicles; Adams-Based Rover Terramechanics and Mobility Simulator - ARTEMIS; ISTP CDF Skeleton Editor; Uplink Summary Generator (ULSGEN) Version 1.0; Robotics On-Board Trainer (ROBoT); Software Engineering Tools for Scientific Models; Automatic Data Filter Customization Using a Genetic Algorithm; Tracker Toolkit; Towards Efficient Scientific Data Management Using Cloud Storage; On a Formal Tool for Reasoning About Flight Software Cost Analysis; A Nanostructured Composites Thermal Switch Controls Internal and External Short Circuit in Lithium Ion Batteries; Spacecraft Crew Cabin Condensation Control; and Functional Near-Infrared Spectroscopy Signals Measure Neuronal Activity in the Cortex.

Source record↗

Assessing the Effects of Various Surface Textures and Features on Turbulent Heat Transfer in Hypersonic Flight

Experiments were conducted in the NASA Ames Hypervelocity Free Flight Aerodynamic Facility (ballistic range) to quantify the effects on turbulent convective heat transfer of distributed surface roughness, and of isolated features, representative of thermal protection systems on atmospheric entry vehicles. The surface textures and features were applied on the conic frusta of 45o sphere-cone models having a nose-to-base radius ratio of 0.5, similar to the forebody geometry of the Galileo and Pioneer-Venus entry probes. Test conditions were selected to provide turbulent roughness Reynolds numbers, k+, in the ranges expected for outer planet entry missions. Turbulent flow on the conic frustum was achieved by tripping the flow on the sphere-segment nose cap with distributed surface roughness, created by sand-blasting the nose cap. Surface textures included distributed, acreage, roughness, as well as cavity and groove discrete features. The majority of the data to be presented are results for distributed roughness, which includes both random, sand-grain-like roughness, and regular pattern roughness. The pattern roughness was designed to represent the roughness on woven thermal protection system materials, such as NASA’s 3-D Medium Density Carbon Phenolic (3MDCP), also known as HEEET, developed by the Heatshield for Extreme Entry Environments Technology project. The pattern roughness tested is a 3-D wavy surface, and includes three different roughness element height-to-spacing ratios representative of two configurations of 3MDCP, and spanning ratios measured both before, and after, ablation in an arc jet test facility. The patterns tested in the ballistic range were laser-etched on metal models, and represented an idealized version of the real-world materials in which each roughness element was nearly identical. Additional tests were performed wherein the laser-etched patterns were degraded by sand-blasting with various sized grit media, to produce regular patterns with superimposed irregular roughness, more representative of flight materials. Results of each will be compared. The discrete features tested included cylindrical cavities and rectangular grooves of various width-to-depth ratios. Cavities represent either heatshield damage, such as from micro-meteoroid and orbital debris (MMOD) damage, or from designed penetrations, such as on the Genesis sample return capsule. The grooves were scaled representations of seams between segments of HEEET material in a notional tiled thermal protection system. The tests examined the effects on turbulent heating downstream of the isolated features. The tests were conducted at speeds between 3 km/s and 4 km/s in air between 0.15 atm and 0.25 atm (Mach numbers between 9 and 12). Roughness Reynolds numbers, k+, ranged from 12 to 70 for the sand roughness, and as high as 200 for the pattern roughness. Boundary-layer parameters required for calculating k+ were evaluated using computational fluid dynamics simulations using the DPLR (Data Parallel Line Relaxation) code. Each model included both rough- and smooth-wall segments, and heat transfer augmentation factors were determined as the ratio of the rough-wall to smooth-wall heat flux measured on each test.

hypersonic↗

Final scientific report for DOE award title: Improving the Representation of Ice Sedimentation Rates in Global Climate Models

It is well known that cirrus clouds play a major role in regulating the earth’s climate, but the details of how this works are just beginning to be understood. This project targeted the main property of cirrus clouds that influence climate processes; the ice fall speed. That is, this project improves the representation of the mass-weighted ice particle fall velocity, V m , in climate models, used to predict future climate on global and regional scales. Prior to 2007, the dominant sizes of ice particles in cirrus clouds were poorly understood, making it virtually impossible to predict how cirrus clouds interact with sunlight and thermal radiation. Due to several studies investigating the performance of optical probes used to measure the ice particle size distribution (PSD), as well as the remote sensing results from our last ARM project, it is now well established that the anomalously high concentrations of small ice crystals often reported prior to 2007 were measurement artifacts. Advances in the design and data processing of optical probes have greatly reduced these ice artifacts that resulted from the shattering of ice particles on the probe tips and/or inlet tube, and PSD measurements from one of these improved probes (the 2-dimensional Stereo or 2D-S probe) are utilized in this project to parameterize V m for climate models. Our original plan in the proposal was to parameterize the ice PSD (in terms of temperature and ice water content) and ice particle mass and projected area (in terms of mass- and area-dimensional power laws or m-D/A-D expressions) since these are the microphysical properties that determine V m , and then proceed to calculate V m from these parameterized properties. But the 2D-S probe directly measures ice particle projected area and indirectly estimates ice particle mass for each size bin. It soon became apparent that the original plan would introduce more uncertainty in the V m calculations than simply using the 2D-S measurements to directly calculate V m . By calculating V m directly from the measured PSD, ice particle projected area and estimated mass, more accurate estimates of V m are obtained. These V m values were then parameterized for climate models by relating them to (1) sampling temperature and ice water content (IWC) and (2) the effective diameter (D e ) of the ice PSD. Parameterization (1) is appropriate for climate models having single-moment microphysical schemes whereas (2) is appropriate for double-moment microphysical schemes and yields more accurate V m estimates. These parameterizations were developed for tropical cirrus clouds, Arctic cirrus, mid-latitude synoptic cirrus and mid-latitude anvil cirrus clouds based on field campaigns in these regions. An important but unexpected result of this research was the discovery of microphysical evidence indicating the mechanisms by which ice crystals are produced in cirrus clouds. This evidence, derived from PSD measurements, indicates that homogeneous freezing ice nucleation dominates in mid-latitude synoptic cirrus clouds, whereas heterogeneous ice nucleation processes dominate in mid-latitude anvil cirrus. Based on these findings, D e was parameterized in terms of temperature (T) for conditions dominated by (1) homo- and (2) heterogeneous ice nucleation. From this, an experiment was designed for global climate models (GCMs). The net radiative forcing from cirrus clouds may be affected by the means ice is produced (homo- or heterogeneously), and this net forcing contributes to climate sensitivity (i.e. the change in mean global surface temperature resulting from a doubling of CO 2 ). The objective of this GCM experiment was to determine how a change in ice nucleation mode affects the predicted global radiation balance. In the first simulation (Run 1), the D e -T relationship for homogeneous nucleation is used at all latitudes, while in the second simulation (Run 2), the D e -T relationship for heterogeneous nucleation is used at all latitudes. For both runs, V m is calculated from D e . Two GCMs were used; the Community Atmosphere Model version 5 (CAM5) and a European GCM known as ECHAM5 (thanks to our European colleagues who collaborated with us). Similar results were obtained from both GCMs in the Northern Hemisphere mid-latitudes, with a net cooling of ~ 1.0 W m -2 due to heterogeneous nucleation, relative to Run 1. The mean global net cooling was 2.4 W m -2 for the ECHAM5 GCM while CAM5 produced a mean global net cooling of about 0.8 W m -2 . This dependence of the radiation balance on nucleation mode is substantial when one considers the direct radiative forcing from a CO 2 doubling is 4 W m -2 . The differences between GCMs in mean global net cooling estimates may demonstrate a need for improving the representation of cirrus clouds in GCMs, including the coupling between microphysical and radiative properties. Unfortunately, after completing this GCM experiment, we learned from the company that provided the 2D-S microphysical data that the data was corrupted due to a computer program coding problem. Therefore the microphysical data had to be reprocessed and reanalyzed, and the GCM experiments were redone under our current ASR project but using an improved experimental design.

54 ENVIRONMENTAL SCIENCES↗

Hayabusa2#’s Exploration to Asteroids 2001 CC21 and 1998 KY26 Provides Key Insights Into Planetary Defense

The Hayabusa2 extended mission, nicknamed Hayabusa2# (SHARP: Small Hazardous Asteroid Reconnaissance Probe), started its mission after the Hayabusa2 spacecraft successfully returned in December 2020 to the Earth with Ryugu's samples and released the Sample Return Capsule containing it. Hayabusa2#’s key operations include flying by Near Earth Asteroid (98943) 2001 CC21 and rendezvousing with Near-Earth Asteroid 1998 KY26. The flyby is planned to be in 2026, and the rendezvous will be in 2031. Detailed investigations of these targets enable maturing key knowledge and technologies necessary for planetary defense. This paper reviews the characteristics of these targets and strategies to maximize outcomes from the mission. The spacecraft will fly by 2001 CC21 at a speed of ~5 km/s in 2026. Given constraints on the spacecraft condition, not designed to perform a flyby operation, operational plans require careful assessments to maximize the proximity observations of this asteroid. The ~700 m diameter asteroid's shape is currently unknown, though lightcurve observations suggest the asteroid is elongated. While the spin pole is not constrained well, the spin period is about 5.02 h with uncertainties of 0.01 h [1]. The taxonomic class may be L-type, which implies the presence of Calcium-aluminum-rich inclusions (CAI), one of the primitive materials in the solar system [2], although there are studies suggesting an S-type. Therefore, this must be carefully examined. Photometric and spectroscopic observations will strongly constrain this asteroid’s properties. Our rendezvous target, 1998 KY26, is a ~30 m diameter roundish object spinning at a spin period of 10.7 min, which may represent one of the common groups of Near Earth Asteroids in size and composition that give a higher likelihood of threatening the Earth. Radar and optical observations reconstructed this asteroid's shape with high uncertainties and inferred that its surface composition might be similar to that of carbonaceous asteroids [3]. No spacecraft has ever visited such small bodies. Hayabusa2# visiting 1998 KY26 will be the first mission to document its geophysical properties, offering strong insights into what most frequent invaders look like [4].

Hayabusa2#↗

Analyzers Measure Greenhouse Gases, Airborne Pollutants

In complete darkness, a NASA observatory waits. When an eruption of boiling water billows from a nearby crack in the ground, the observatory s sensors seek particles in the fluid, measure shifts in carbon isotopes, and analyze samples for biological signatures. NASA has landed the observatory in this remote location, far removed from air and sunlight, to find life unlike any that scientists have ever seen. It might sound like a scene from a distant planet, but this NASA mission is actually exploring an ocean floor right here on Earth. NASA established a formal exobiology program in 1960, which expanded into the present-day Astrobiology Program. The program, which celebrated its 50th anniversary in 2010, not only explores the possibility of life elsewhere in the universe, but also examines how life begins and evolves, and what the future may hold for life on Earth and other planets. Answers to these questions may be found not only by launching rockets skyward, but by sending probes in the opposite direction. Research here on Earth can revise prevailing concepts of life and biochemistry and point to the possibilities for life on other planets, as was demonstrated in December 2010, when NASA researchers discovered microbes in Mono Lake in California that subsist and reproduce using arsenic, a toxic chemical. The Mono Lake discovery may be the first of many that could reveal possible models for extraterrestrial life. One primary area of interest for NASA astrobiologists lies with the hydrothermal vents on the ocean floor. These vents expel jets of water heated and enriched with chemicals from off-gassing magma below the Earth s crust. Also potentially within the vents: microbes that, like the Mono Lake microorganisms, defy the common characteristics of life on Earth. Basically all organisms on our planet generate energy through the Krebs Cycle, explains Mike Flynn, research scientist at NASA s Ames Research Center. This metabolic process breaks down sugars for energy to fuel cellular functions. "We think this chemical process did not exist when life first formed on Earth," he says, "because it is based on oxygen being available, and there was little oxygen available on the early Earth." It is possible that there are anaerobic regions beneath the sea floor in which life forms like those early non-Krebs Cycle microbes may yet exist. To detect and potentially collect samples of life emerging from hydrothermal vents, Flynn and his colleagues created Medusa, a multi-sensor instrument designed for long-term observation of diked vents on the ocean floor. When the vents erupt, Medusa assesses indicators of life within the expelled water. If the results are positive, the observatory collects samples and detaches from the ocean floor, making the long journey to the surface for retrieval by scientists. One of the indicators Medusa measures is the ratio of carbon isotopes in the water, namely carbon-12 and carbon-13. Living organisms preferentially take up carbon-12, Flynn says, so examining the ratio of these isotopes can help to determine the source of carbon in an environment as either biological or non-biological. "On Mars, there is evidence of localized methane in the atmosphere, and that methane could come from biological sources or from geochemical ones," Flynn says. "Determining the background planetary carbon isotope ratios and then evaluating the specific carbon ratios in this methane would help to determine how it was formed." A long-duration observatory similar to Medusa could one day provide essential evidence for or against the presence of life on the Red Planet or beneath the ice-crusted oceans of Europa.

Source record↗

Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: Probing chemical composition of D{sub 2}O ice beneath a H{sub 2}O ice layer

In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D{sub 2}O ices by novel infrared (IR) laser ablation of a layered non-absorbing D{sub 2}O ice (spectator) containing the analytes and an ablation-active IR-absorbing H{sub 2}O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry, previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H{sub 2}O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D{sub 2}O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D{sub 2}O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was negligible. We also did not see any evidence for thermal or collisional chemistry of PAH molecules with H{sub 2}O molecules in the shockwave. We call this “shockwave mediated surface resonance enhanced subsurface ablation” technique as “two-step laser ablation and ionization mass spectrometry of actor-spectator ice layers.” This method has its roots in the well-established MALDI (matrix assisted laser desorption and ionization) method. Our method offers more flexibility to optimize both the processes—ablation and ionization. This new technique can thus be potentially employed to undertake in situ analysis of materials imbedded in diverse media, such as cryogenic ices, biological samples, tissues, minerals, etc., by covered with an IR-absorbing laser ablation medium and study the chemical composition and reaction pathways of the analyte in its natural surroundings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatio-Kinetic Electronic Heterogeneity in MoS 2 Revealed by Ultrafast Electron Microscopy: Implications for Optoelectronics

There is broad interest in layered, two-dimensional (2D) semiconductors owing to their high optical absorption and ability to heterogeneously integrate with various substrates. In such layered semiconductors, mesoscopic imperfections, such as surface step edges, may affect charge carrier kinetics and device performance, but studying their effects on carrier transport with sufficient spatial and temporal resolution is a challenge. Using scanning ultrafast electron microscopy, we image the near-surface charge carrier kinetics with μm/ps spatiotemporal resolution in single-crystal MoS 2 samples with surface steps tens of nanometers in height. We find an approximately 3-fold increase in surface trap density near such surface steps compared to the uniform, flat surface regions. Despite the difference in trap state density, filling of the traps occurs over the same time scale (∼100 ps), but carrier recovery is much slower near the step compared to the uniform regions of the material. Furthermore, these results provide an approach to measure ultrafast dynamics and determine the required uniformity of layered materials depending on the speed limit constraints for specific applications.

SEM↗

Effect of Anoxic Iron Corrosion on WIPP Brine Geochemistry FY23 Final Report (U)

A 280-day study was completed to evaluate the effect of zero-valent iron (Fe 0 ) on the Waste Isolation Pilot Plant (WIPP) brine geochemistry under anticipated reducing conditions. Hydrogen (H 2 ) gas is expected to be present in the repository after closure due to the anoxic corrosion of a vast quantity of iron contained in the waste forms disposed at WIPP; therefore, a background argon atmosphere containing H 2 was chosen for this study. WIPP groundwater brine pH and E h will impact the mobility and fate of plutonium within the repository. Modeling and laboratory results for Castile WIPP brine indicate that equilibrium fa values relative to the standard hydrogen electrode (SHE) are 40 mV more reducing (i.e., more negative) than those for Salado WIPP brine (-480 mV vs. -440 mV, respectively) because of the higher pH of the Castile brine (pH 9 .3 for Castile vs. pH 8.8 for Salado). The E h and pH data were corrected for the effects of high ionic strength. The experimental results for both brines are consistent with thermodynamic predictions using OLI Systems' Mixed Solvent Electrolyte chemical equilibrium model. The measured and corrected pH and E h data from this study are provided in Table ES-I and Table ES-2, respectively. The experimental study, with four test conditions in triplicate, was performed in a dual glovebox with a nominally 3 vol.% H 2 in argon atmosphere (target H 2 range: 3 ± I vol.%). Simulants containing MgO only ( experimental control) and MgO+Fe 0 (WIPP base case) were prepared for both the Salado and Castile brines. MgO was included in all simulants to account for the use of bulk magnesium oxide in the WIPP repository. Fe 0 was included in some simulants to incorporate the effects of the anoxic corrosion of iron and in-situ hydrogen generation in the study. The brine compositions were developed by Sandia National Laboratory (SNL; Xiong, 2008) and have been used in previous WIPP evaluations. The test method (agitation, etc.) is partially based on ASTM D3987-12. Twelve rounds of periodic measurements of pH and E h were performed over the course of the study. Chemical analysis results for liquids and solids (ICP-MS, ICP-ES, IC Anion, TIC, SEM-EDX) are consistent with the pH, E h , and thermodynamic modeling results. This study included the following conditions that deviate from anticipated post-closure conditions following brine intrusion, but were selected to facilitate bench-scale testing to validate modeling of pH and E h for the post-closure WIP P repository: an anoxic glove box atmosphere containing ≤ 4 vol. % H 2 vs. substantially higher H 2 gas concentrations assumed in the WIPP Performance Assessment (PA); a significantly higher liquid-to-solid test ratio compared to the much lower phase ratio anticipated in the WIP P repository; agitation of the simulant bottles to maximize mass transfer; and finally the use of Fe 0 reagents having a much greater surface area than expected in the WIP P repository. Non-representative conditions were chosen for various reasons such as: to provide bounding conservative results, to provide a margin of safety for testing, or to facilitate simulant sub-sampling and analysis. In a parallel effort, aqueous electrolyte thermodynamic models were developed for the synthetic Salado and Castile brines to inform the experimental design, facilitate laboratory data interpretation, and allow extension of evaluations beyond the parameters tested. Thermodynamic modeling simulations including the MgO and Fe 0 additives that are directly relevant to the experimental measurements (e.g., pH calibration curve, ORP corrections) are included in this report. The measured fa of the simulants was close to the OLI model predictions for both brines and was largely controlled by the background H 2 partial pressure in the vapor phase as well as H 2 generated in situ in the aqueous phase by the Fe 0 corrosion. The H 2 gas-phase concentration tested and thermodynamically evaluated was much lower than is assumed in the WIPP PA; however, H 2 (g) concentrations significantly below this level are still predicted to result in very reducing conditions. In conclusion: • The experimental results are consistent with thermodynamic model predictions for fa, pH, and the effects of high ionic strength. • Evidence to date suggests that the H2 concentration in the glovebox atmosphere ultimately determined the final E h values of the simulants and resulted in highly reducing conditions. As a result, little difference was observed between the control simulants containing only MgO and the WIPP base-case simulants that contained MgO and Fe 0 . • This test methodology is recommended for future studies evaluating WIPP repository conditions. The methodology includes: (1) background H 2 in argon with agitation ( or could alternatively include in-situ-generated H 2 in sealed bottles); (2) carefully measured and corrected ORP data ( with much effort focused on allowing the probes to fully stabilize); and (3) ionic-strength-corrected pH data. Other best practices, such as simulant sparging/handling, ORP probe replacement, etc., should also be considered. • The coupling of experimental studies and thermodynamic modeling is also highly recommended because these methods inform and direct one another leading to greater confidence in and understanding of the results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rhizosphere Soil Biogeochemical Data and Photosynthetic Data of Vicia Faba in a Rhizobox

Here we share the data in column format via csv files for pH, redox, and dissolved oxygen collected at hourly resolution from microelectrodes. Dissolved organic carbon concentrations collected from TOC are also provided in a similar format but are composited samples from hourly microdialysis collection. This provided resolution of diel rhizosphere dynamics belowground. Plant physiological data was also collected at every 5 min for 24 hr cycles in order to capture diel dynamics aboveground. This data was used to parameterize the reaction transport model eSTOMP-ROOTS, which examines the rhizosphere biogeochemistry of a growing Vicia faba plant. The aim was to investigate plant activity and belowground biogeochemical processes, particularly their impact on mineral-organic associations in the rhizosphere. We combined in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the behavior of dissolved organic carbon (DOC) in the rhizosphere. Over several days, microdialysis probes placed at the root-soil interface in live soil showed distinct daily patterns of DOC concentration in the pore water. Spikes in DOC concentrations during the day aligned with peaks in leaf-level photosynthesis, accompanied by decreasing redox potential and dissolved oxygen levels, and increasing pH in the rhizosphere. This new mechanistic modeling framework, which integrates aboveground plant physiological data with non-destructive, high-resolution monitoring of rhizosphere processes, offers significant potential for studying the factors that control carbon storage in soils.

54 ENVIRONMENTAL SCIENCES↗

Propane Dehydrogenation Catalyzed by Supported Group IV (Ti, Zr, Hf) Organometallics on Silicon Nitride

Mesoporous silicon nitride (Si 3 N 4 ) enables access to chemisorbed group IV organometallics catalysts active for propane dehydrogenation (PDH) compared to the organometallic analogues on mesoporous silica under the same reaction conditions. The series of Si 3 N 4 -supported materials are active catalysts, (Zr > Hf > Ti k f = 290, 232, and 162 mol mol Metal -1 h -1 at 450 °C with 2% C 3 H 8 in Ar, respectively) with selectivity above 95%, demonstrating additional examples of Ti and Hf systems for PDH. However, the underlying mechanism of the improved performance relative to oxide supported homologues is not well-understood. Characterization of thermally treated samples (DRIFTS, XAS and SSNMR) and computational modeling of this catalyst series was utilized to differentiate between potential amido - (C-H activation along the M-N bond) and imido - (C-H activation along the M=N bond) mechanisms. Due to remaining mechanistic ambiguity, a Ga analogue was synthesized and evaluated for PDH activity as an indirect probe to experimentally differentiate pathways. An inversion of the oxide/nitride performance trend is observed for the Ga congener which does not form a Ga=N bond, most consistent with different mechanisms dictating the performance of the group IV/Si 3 N 4 catalysts vs Ga/Si 3 N 4 .

heterolytic cleavage↗

The Probing In-Situ With Neutron and Gamma Rays (PING) Instrument for Planetary Composition Measurements

The Probing In situ with Neutrons and Gamma rays (PING) instrument (formerly named PNG-GRAND) [I] experiment is an innovative application of the active neutron-gamma ray technology successfully used in oil field well logging and mineral exploration on Earth over many decades. The objective of our active neutron-gamma ray technology program at NASA Goddard Space Flight Center (NASA/GSFC) is to bring PING to the point where it can be flown on a variety of surface lander or rover missions to the Moon, Mars, Venus, asteroids, comets and the satellites of the outer planets and measure their bulk surface and subsurface elemental composition without the need to drill into the surface. Gamma-Ray Spectrometers (GRS) have been incorporated into numerous orbital planetary science missions. While orbital measurements can map a planet, they have low spatial and elemental sensitivity due to the low surface gamma ray emission rates reSUlting from using cosmic rays as an excitation source, PING overcomes this limitation in situ by incorporating a powerful neutron excitation source that permits significantly higher elemental sensitivity elemental composition measurements. PING combines a 14 MeV deuterium-tritium Pulsed Neutron Generator (PNG) with a gamma ray spectrometer and two neutron detectors to produce a landed instrument that can determine the elemental composition of a planet down to 30 - 50 cm below the planet's surface, The penetrating nature of .5 - 10 MeV gamma rays and 14 MeV neutrons allows such sub-surface composition measurements to be made without the need to drill into or otherwise disturb the planetary surface, thus greatly simplifying the lander design, We are cun'ently testing a PING prototype at a unique outdoor neutron instrumentation test facility at NASA/GSFC that provides two large (1.8 m x 1.8 m x ,9 m) granite and basalt test formations placed outdoors in an empty field, Since an independent trace elemental analysis has been performed on both these Columbia River basalt and Concord Gray granite materials, these large samples present two known standards with which to compare PING's experimentally measured elemental composition results, We will present both gamma ray and neutron experimental results from PING measurements of the granite and basalt test formations in various layering configurations and compare the results to the known composition.

Parsons, A.↗