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At least 37 records · Page 2

A plano–convex thick-lens velocity map imaging apparatus for direct, high resolution 3D momentum measurements of photoelectrons with ion time-of-flight coincidence

Since their inception, velocity map imaging (VMI) techniques have received continued interest in their expansion from 2D to 3D momentum measurements through either reconstructive or direct methods. Recently, much work has been devoted to the latter of these by relating electron time-of-flight (TOF) to the third momentum component. The challenge is having a timing resolution sufficient to resolve the structure in the narrow (<10 ns) electron TOF spread. Here, we build upon the work in VMI lens design and 3D VMI measurement by using a plano–convex thick-lens (PCTL) VMI in conjunction with an event-driven camera (TPX3CAM) providing TOF information for high resolution 3D electron momentum measurements. We perform simulations to show that, with the addition of a mesh electrode to the thick-lens geometry, the resulting plano–convex electrostatic field extends the detectable electron cutoff energy range while retaining the high resolution. This design also extends the electron TOF range, allowing for a better momentum resolution along this axis. We experimentally demonstrate these capabilities by examining above-threshold ionization in xenon, where the apparatus is shown to collect electrons of energy up to ∼7 eV with a TOF spread of ∼30 ns, both of which are improved compared to a previous work by factors of ∼1.4 and ∼3.75, respectively. Finally, the PCTL-VMI is equipped with a coincident ion TOF spectrometer, which is shown to effectively extract unique 3D momentum distributions for different ionic species in a gas mixture. These techniques have the potential to lend themselves to more advanced measurements involving systems where the electron momentum distributions possess non-trivial symmetries.

Instruments & Instrumentation↗

Miniature Focusing Time-of-Flight Mass Spectrometer

An improved miniature time-of-flight mass spectrometer has been developed in a continuing effort to minimize the sizes, weights, power demands, and costs of mass spectrometers for such diverse applications as measurement of concentrations of pollutants in the atmosphere, detecting poisonous gases in mines, and analyzing exhaust gases of automobiles. Advantageous characteristics of this mass spectrometer include the following: It is simple and rugged. Relative to prior mass spectrometers, it is inexpensive to build. There is no need for precise alignment of its components. Its mass range is practically unlimited Relative to prior mass spectrometers, it offers high sensitivity (ability to measure relative concentrations as small as parts per billion). Its resolution is one dalton (one atomic mass unit). An entire mass spectrum is recorded in a single pulse. (In a conventional mass spectrometer, a spectrum is recorded mass by mass.) The data-acquisition process takes only seconds. It is a lightweight, low-power, portable instrument. Although time-of-flight mass spectrometers (TOF-MSs) have been miniaturized previously, their performances have not been completely satisfactory. An inherent adverse effect of miniaturization of a TOF-MS is a loss of resolution caused by reduction of the length of its flight tube. In the present improved TOF-MS, the adverse effect of shortening the flight tube is counteracted by (1) using charged-particle optics to constrain ion trajectories to the flight-tube axis while (2) reducing ion velocities to increase ion flight times. In the present improved TOF-MS, a stream of gas is generated by use of a hypodermic needle. The stream of gas is crossed by an energy-selected, pulsed beam of electrons (see Figure 1). The ions generated by impingement of the electrons on the gas atoms are then focused by three cylindrical electrostatic lenses, which constitute a segmented flight tube. After traveling along the flight tube, the ions enter a charged-particle detector. The output of the detector is fed to a counting circuit to obtain data on the counting rate as a function of time. Inasmuch as time of flight is directly proportional to the ion mass, a plot of the counting rate versus time of flight is equivalent to a mass spectrum (see Figure 2).

Kanik, Isik↗

Using Macro- and Microscale Preservation in Vertebrate Fossils as Predictors for Molecular Preservation in Fluvial Environments

Exceptionally preserved fossils retain soft tissues and often the biomolecules that were present in an animal during its life. The majority of terrestrial vertebrate fossils are not traditionally considered exceptionally preserved, with fossils falling on a spectrum ranging from very well-preserved to poorly preserved when considering completeness, morphology and the presence of microstructures. Within this variability of anatomical preservation, high-quality macro-scale preservation (e.g., articulated skeletons) may not be reflected in molecular-scale preservation (i.e., biomolecules). Excavation of the Hayden Quarry (HQ; Chinle Formation, Ghost Ranch, NM, USA) has resulted in the recovery of thousands of fossilized vertebrate specimens. This has contributed greatly to our knowledge of early dinosaur evolution and paleoenvironmental conditions during the Late Triassic Period (~212 Ma). The number of specimens, completeness of skeletons and fidelity of osteohistological microstructures preserved in the bone all demonstrate the remarkable quality of the fossils preserved at this locality. Because the Hayden Quarry is an excellent example of good preservation in a fluvial environment, we have tested different fossil types (i.e., bone, tooth, coprolite) to examine the molecular preservation and overall taphonomy of the HQ to determine how different scales of preservation vary within a single locality. We used multiple high-resolution mass spectrometry techniques (TOF-SIMS, GC-MS, FT-ICR MS) to compare the fossils to unaltered bone from extant vertebrates, experimentally matured bone, and younger dinosaurian skeletal material from other fluvial environments. FT-ICR MS provides detailed molecular information about complex mixtures, and TOF-SIMS has high elemental spatial sensitivity. Using these techniques, we did not find convincing evidence of a molecular signal that can be confidently interpreted as endogenous, indicating that very good macro- and microscale preservation are not necessarily good predictors of molecular preservation.

59 BASIC BIOLOGICAL SCIENCES↗

Enhancing the Cherenkov over scintillation ratio using dichroic filters in BGO and TlCl for TOF-PET

Abstract The Cherenkov emission in inorganic crystal scintillators has been shown to dramatically improve time resolution for time-of-flight positron emission tomography (TOF-PET) for in slow scintillators with a high refractive index such as bismuth germanium oxide (BGO). This is due to the faster nature of the Cherenkov emission (tens of picoseconds) with respect to scintillation (nanosecond). However, the presence of slower scintillation light and the inability of existing detectors to distinguish between Cherenkov and scintillation make it difficult for BGO to achieve a good CTR for all the detected coincidence events. In this paper, we exploit the difference between the Cherenkov and scintillation emission spectra and use dichroic filters to enhance the Cherenkov over scintillation ratio. Dichroic filters transmit or reflect photons based on their wavelength, with a photon attenuation lower than 10%. We investigate several shortpass and longpass dichroic filters in a single-photon configuration with BGO and find the optimal filter that maximizes the Cherenkov over scintillation ratio. We demonstrate that we can enhance the ratio of Cherenkov to scintillation photons by a factor of 2.17 ± 0.38 by employing a shortpass dichroic filter with a cut-off wavelength of 450 nm for BGO, and by a factor of 2.87 ± 0.40 using a longpass dichroic filter with a cut-on wavelength of 550 nm for iodine/beryllium-doped thallium chloride.

Science & Technology - Other Topics↗

Simulation of a Miniature, Low-Power Time-of-Flight Mass Spectrometer for In Situ Analysis of Planetary Atmospheres

We are implementing nano- and micro-technologies to develop a miniaturized electron impact ionization mass spectrometer for planetary science. Microfabrication technology is used to fabricate the ion and electron optics, and a carbon nanotube (CNT) cathode is used to generate the ionizing electron beam. Future NASA planetary science missions demand miniaturized, low power mass spectrometers that exhibit high resolution and sensitivity to search for evidence of past and present habitability on the surface and in the atmosphere of priority targets such as Mars, Titan, Enceladus, Venus, Europa, and short-period comets. Toward this objective, we are developing a miniature, high resolution reflectron time-of-flight mass spectrometer (Mini TOF-MS) that features a low-power CNT field emission electron impact ionization source and microfabricated ion optics and reflectron mass analyzer in a parallel-plate geometry that is scalable. Charged particle electrodynamic modeling (SIMION 8.0.4) is employed to guide the iterative design of electron and ion optic components and to characterize the overall performance of the Mini TOF-MS device via simulation. Miniature (less than 1000 cubic centimeters) TOF-MS designs (ion source, mass analyzer, detector only) demonstrate simulated mass resolutions greater than 600 at sensitivity levels on the order of 10(exp -3) cps/molecule N2/cc while consuming 1.3 W of power and are comparable to current spaceflight mass spectrometers. Higher performance designs have also been simulated and indicate mass resolutions approximately 1000, though at the expense of sensitivity and instrument volume.

King, Todd T.↗

Gallium oxide semiconductor-based large volume ultrafast radiation hard spectroscopic scintillators

We report on the development of the first-ever inorganic radiation-hard moisture-insensitive large volume spectroscopic semiconductor-based scintillator with less than 2 ns decay time and light yields as high as 8000 ph/MeV. Despite extensive research into scintillator materials, the quest for an ideal scintillator combining ultrafast decay times (akin to BaF 2 and Yb-doped scintillators such as Lu 2 O 3 :Yb), high light yields (exceeding 2000 photons per MeV), spectroscopic capabilities, and exceptional radiation hardness remain unfulfilled. In this study, we demonstrate and report for the first time the viability of large-volume (up to 20 mm thickness) gallium oxide (β-Ga 2 O 3 ) semiconductor-based scintillators for applications requiring these properties. These β-Ga 2 O 3 scintillators were grown using the fast turnaround (~2 days) crucible-free optical float zone (FZ) technique. The high light yield and ultrafast decay time of these high-purity n-type semiconductors with free carrier concentration of 6 × 10 17 cm –3 are attributed to native defects, specifically oxygen vacancies (V O ) and gallium–oxygen vacancy pairs (V Ga –V O ), generated during optimized FZ growth. The ultrafast decay, along with high light yield, enables excellent timing resolution and high count rate detection for applications like time-of-flight positron emission tomography, physics experiments, and nuclear safety. The radiation hardness of these devices has been documented in a separate publication.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Impacts of Dissolved Ni 2+ on the Solid Electrolyte Interphase on a Graphite Anode

Transition metal (e.g. Ni) ions dissolved from layered-structured Ni-rich cathodes can migrate to the anode side and accelerate the failure of lithium-ion batteries. The investigations of the impact and distribution of Ni species on the solid electrolyte interphase (SEI) on the anode are crucial to understand the failure mechanism. Herein, we used time-of-flight secondary ion mass spectroscopy (TOF-SIMS) coupled with multivariate curve resolution (MCR) analysis to intuitively characterize the distribution of Ni species in the SEI. We find that the SEI on the graphite electrode using an EC-based electrolyte exhibits a multi-stratum structure. During accelerated aging of the LiNi 0.88 Co 0.08 Mn 0.04 O 2 /graphite full cell, the dissolution of Ni aggravates significantly upon cycling. A strong correlation between the dissolved-Ni and organic species in the SEI on graphite is illustrated. Here, the ion-exchange reaction between Ni 2+ and Li + ions in the SEI is demonstrated to be the main reason for the increase of SEI resistivity.

25 ENERGY STORAGE↗

Agilent CRADA (Abstract)

The CRADA between Agilent Technologies Inc. and Battelle will focus on five software components as listed below: Prototype 4D Feature Finding functionality with a particular focus on recovering low level features and extending the bottom end dynamic range of IM-MS technology. Compare and contrast developments to current 4D Feature Finding capabilities. Highlight important algorithmic aspects employed. Implement the PNNL saturation correction algorithm. Agilent will give PNNL the needed data file access API and assistance in understanding it implementation and any needed instrumental aspects. Supported high resolution products to include Agilent’s TOF, QTOF and IM-QTOF mass spectrometers. PNNL will then work with Agilent to benchmark performance. Implementation of the PNNL Hadamard de-multiplexing algorithm. Agilent will give provide PNNL the needed date file access API access and as needed assistance in understanding the current Agilent multiplexed IM offering. PNNL will then work with Agilent on benchmark performance. Add ion mobility collision cross sections to existing and new metabolomic libraries for data analysis with Agilent’s informatics program MPP/ID Browser. PNNL will work with Agilent to create a software pipeline that takes data from chemical and metabolic standards and properly formats it for inclusion in MPP accessible libraries, using the collision cross section as a new separation dimension. Improvements of MPP multidimensional matching to identify metabolomic features using multiple characteristics beyond retention time and accurate mass. Most significantly matching will include analyte collision cross section with proposed support for sample fraction or RapidFire cartridge and fragmentation spectra. PNNL will work with Agilent to modify and improve the current MPP analysis pipeline to allow for creating, aligning, and identifying MS features defined by accurate mass, collision cross section and chromatographic retention time. As additional criteria such as fraction or RapidFire cartridge type are supported in the identification process, then they also will become part of the automation workflow. This includes the automation of said system to work with command line program (i.e. not a GUI) sufficient for programmatic execution in a pipeline.

97 MATHEMATICS AND COMPUTING↗

Ruggedizing a Commercial Depth Camera for Novel Lunar Exploration.

The novel contribution of this instrument is to take the first depth images on the moon. A commercial Kinect camera from Microsoft has been ruggedized for a CLPS mission to the Lunar South Pole. The 12-megapixel color camera is combined with a 1-megapixel color time-of-flight (ToF) depth sensor. The solid-state depth sensor/LIDAR provides greater resolution, a wider field of view, pixel binning, and reduced power consumption. The high-resolution data collected from the mission can be used to construct a near-field virtual environment of the lunar surface for scientific applications. The depth camera can provide a 360-degree view of the target area by combining ToF data with RGB imagery and rover turning. The unit was evaluated for space flight compliant materials and parts at NASA Ames. The microphone array, RF shield, front face, and outer body parts were removed to reduce mass. Plastic parts were replaced with vacuum-compatible materials; manufactured cables were added to properly interface with the host rover, built by Lunar Outpost. The environmental testing was performed on the Kinect with Random Vibration/Sine Testing (Fig 1a), per GEVS (NASA’s General Environmental Verification Standard for spaceflight launch survival). Thermal Vacuum testing cycled the instrument between expected hot (+ 85 C) and cold survival temperatures, as well as +50 C and -25 C operational temps (Fig 1b). The instrument functioned nominally at the conclusion of vibration and thermal cycling tests. The Azure Kinect is manifested on the Nova-C lander which flies on the Intuitive Machines mission IM-2, landing at the lunar south pole for a mission duration of 14 days (one lunar daylight cycle). The unit will be integrated to the MAPP (Mobile Autonomous Prospecting Platform) rover at Lunar Outpost. The Azure Kinect with ToF feature will improve the resolution of lunar geology data near the south pole and enable ground-based VR experience of details of the lunar surface (Fig 1c).

V. Jha↗

Direct Measurement of the Composition of Aqueous Fluids from the Parent Body of Asteroid 162173 Ryugu

Imaging using X-ray absorption contrast by synchrotron nano-computed tomography (47.4 nm/voxel, 7keV) of a Ryugu pyrrhotite crystal (C0002-FC012-from the second touch-down site) revealed probable fluid inclusions (Fig. 1A,B) [1]. The inclusions were completely encapsuled in pyrrhotite, suggesting the fluids were trapped in the early stages of crystal growth, and filled with low-Z material. We performed Time-of Flight-Secondary Ion Mass Spectrometry (TOF-SIMS) depth profiling and high-resolution map-ping at -120°C to exposure and measure the composition of the trapped fluids in a frozen state.

M Zolensky↗

Update on Measurement of the Composition of Ryugu Fluid Inclusions

Imaging using X-ray absorption contrast by synchrotron nano-computed tomography of a Ryugu pyrrhotite crystal (C0002-FC012 - from the second Hayabusa2 spacecraft touch-down site) revealed probable fluid inclusions in the center of a crystal of pyrrhotite, suggesting the parent fluids were trapped in the early stages of crystal growth on Ryugu’s parent asteroid. We previously described the performance of Time-of Flight-Secondary Ion Mass Spectrometry (TOF-SIMS) depth profiling and high-resolution mapping at -120°C to expose and measure the composition of the trapped fluids in a frozen state in two Ryugu inclusions [1,2]. Here we report results from follow-on measurements of additional inclusions in the same pyrrhotite crystal, and the initial results of measurement of standards. The ultimate goal is to reveal the quantitative composition of the fluids that caused aqueous alteration, in particular the H2O:CO2 ratio, which will also facilitate cosmochemical modeling of the alteration process.

M Zolensky↗

Direct Analyses of Aqueous Fluids from C-Class Asteroid 162173 Ryugu

Imaging using X-ray absorption contrast by synchrotron nano-computed tomography (47.4 nm/voxel, 7keV) of a Ryugu pyrrhotite crystal revealed probable fluid inclusions. The inclusions were completely encapsuled in pyrrhotite, suggesting the fluids were trapped in the early stages of crystal growth, and filled with low-Z material. We performed Time-of Flight-Secondary Ion Mass Spectrometry (TOF-SIMS) depth profiling and high-resolution mapping at -120°C to exposure and measure the composition of the trapped fluids in a frozen state. These measurements revealed that the ancient, trapped fluids on Ryugu’s parent asteroid were saline aqueous solutions containing H2O, CO2, sulfur species, and nitrogen- and chlorine-bearing organic compounds identified by representative secondary ion species including O(-), OH(-), CO(-), S(-), Cl(-), C2(-), C2H(-), and CN(-). The inferred presence of CO2 indicates formation of the sulfides, and by implication the Ryugu parent body, beyond the H2O and CO2 snow lines of the early solar system, i.e. > 3-4 au from the Sun.

M Zolensky↗

SUDA: A SUrface Dust Analyser for Compositional Mapping of the Galilean Moon Europa

Abstract The Surface Dust Analyser (SUDA) is a mass spectrometer onboard the Europa Clipper mission for investigating the surface composition of the Galilean moon Europa. Atmosphereless planetary moons such as the Galilean satellites are wrapped into a ballistic dust exosphere populated by tiny samples from the moon’s surface produced by impacts of fast micrometeoroids. SUDA will measure the composition of such surface ejecta during close flybys of Europa to obtain key chemical signatures for revealing the satellite’s composition such as organic molecules and salts, history, and geological evolution. Because of their ballistic orbits, detected ejecta can be traced back to the surface with a spatial resolution roughly equal to the instantaneous altitude of the spacecraft. SUDA is a Time-Of-Flight (TOF), reflectron-type impact mass spectrometer, optimized for a high mass resolution which only weakly depends on the impact location. The instrument will measure the mass, speed, charge, elemental, molecular, and isotopic composition of impacting grains. The instrument’s small size of$268 ~\mathrm {mm} \times 250 ~\mathrm {mm} \times 171$ 268 mm × 250 mm × 171 $~\mathrm {mm}$ mm , radiation-hard design, and rather large sensitive area of 220 cm 2 matches well the challenging demands of the Clipper mission.

Astronomy & Astrophysics↗

Mass spectral imaging showing the plant growth-promoting rhizobacteria's effect on the Brachypodium awn

The plant growth-promoting rhizobacteria (PGPR) on the host plant surface play a key role in biological control and pathogenic response in plant functions and growth. However, it is difficult to elucidate the PGPR effect on plants. Such information is important in biomass production and conversion. Brachypodium distachyon (Brachypodium), a genomics model for bioenergy and native grasses, was selected as a C3 plant model; and the Gram-negative Pseudomonas fluorescens SBW25 ( P.) and Gram-positive Arthrobacter chlorophenolicus A6 ( A.) were chosen as representative PGPR strains. The PGPRs were introduced to the Brachypodium seed's awn prior to germination, and their possible effects on the seeding and growth were studied using different modes of time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements, including a high mass-resolution spectral collection and delayed image extraction. We observed key plant metabolic products and biomarkers, such as flavonoids, phenolic compounds, fatty acids, and auxin indole-3-acetic acid in the Brachypodium awns. Furthermore, principal component analysis and two-dimensional imaging analysis reveal that the Brachypodium awns are sensitive to the PGPR, leading to chemical composition and morphology changes on the awn surface. Our results show that ToF-SIMS can be an effective tool to probe cell-to-cell interactions at the biointerface. This work provides a new approach to studying the PGPR effects on awn and shows its potential for the research of plant growth in the future.

metabolite↗

Probing drift velocity dispersion in MAPbI 3 photovoltaic cells with nonlinear photocurrent spectroscopy

Conventional time-of-flight (TOF) measurements yield charge carrier mobilities in photovoltaic cells with time resolution limited by the RC time constant of the device, which is on the order of 0.1–1 µs for the systems targeted in the present work. We have recently developed an alternate TOF method, termed nonlinear photocurrent spectroscopy (NLPC), in which carrier drift velocities are determined with picosecond time resolution by applying a pair of laser pulses to a device with an experimentally controlled delay time. In this technique, carriers photoexcited by the first laser pulse are “probed” by way of recombination processes involving carriers associated with the second laser pulse. Here, we report NLPC measurements conducted with a simplified experimental apparatus in which synchronized 40 ps diode lasers enable delay times up to 100 µs at 5 kHz repetition rates. Carrier mobilities of ∼0.025 cm 2 /V/s are determined for MAPbI 3 photovoltaic cells with active layer thicknesses of 240 and 460 nm using this instrument. Here, our experiments and model calculations suggest that the nonlinear response of the photocurrent weakens as the carrier densities photoexcited by the first laser pulse trap and broaden while traversing the active layer of a device. Based on this aspect of the signal generation mechanism, experiments conducted with co-propagating and counter-propagating laser beam geometries are leveraged to determine a 60 nm length scale of drift velocity dispersion in MAPbI 3 films. Contributions from localized states induced by thermal fluctuations are consistent with drift velocity dispersion on this length scale.

14 SOLAR ENERGY↗

Molecular imaging of plant-microbe interactions on the Brachypodium seed surface

Plant growth-promoting rhizobacteria (PGPR) play a crucial role in biological control and pathogenic defense on and with-in plant tissues, however the mechanism(s) by which plants associate with PGPR to elicit such beneficial effects needs further study. Here, we present high mass resolution time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging of Brachypodium distachyon (Brachypodium) seeds with and without exposure to two model PGPR, i.e., Gram-negative Pseudomonas fluorescens SBW25::GFP (P.) and Gram-positive Arthrobacter chlorophenolicus A6::GFP (A.). Delayed image extraction was used to image PGPB-treated seed sections to reveal morphological changes. ToF-SIMS spectral compari-son, principal component analysis (PCA), and two-dimensional (2D) imaging show that the selected PGPR have different effects on the host seed surface, resulting in changes in chemical composition and morphology. Metabolite prod-ucts and biomarkers, such as flavonoids, phenolic com-pounds, fatty acids, and indole-3-acetic acid (IAA), were ob-served on the PGPR-treated seed surfaces. These compounds had different distributions on the Brachypodium seed surface for the two PGPR, indicating that the different bacteria elicited distinct responses from the host. Our results illustrate that ToF-SIMS is an effective tool to study plant-microbe interac-tions and to provide insightful information with submicrome-ter lateral resolution of the chemical distributions associated with morphological features, potentially offering a new way to study the mechanisms underlying beneficial roles of PGPR.

PGPR, Brachypodium distachyon, ToF-SIMS, metabolit↗