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At least 433 records · Page 24

Star & Planet Formation Studies and Opportunities with SOFIA

Star formation, the most fundamental process in the universe, is linked to planet formation and thus to the origin and evolution of life. We have a general outline of how planets and stars form, yet unraveling the details of the physics and chemistry continues to challenge us. The infrared and submillimeter part of the spectrum hold the most promise for studying the beginnings of star formation. The observational landscape recently shaped by Spitzer, Herschel and ALMA, continues to challenge our current theories. SOFIA, the Stratospheric Observatory for Infrared Astronomy, equipped with state-of-the-art infrared instrumentation to a vantage point at 45,000 feet (13.7 kilometers) flight altitude that is above 99.9 percent of the Earth's water vapor, enables observations in the infrared through terahertz frequencies not possible from the ground. SOFIA is a community observatory, about to start its sixth annual observing cycle. My talk will focus on recent results in advancing star and planet formation processes using SOFIAʼs imaging and polarimetric capabilities, and the upcoming science enabled by the 3rd generation instrument High-Resolution Mid-Infrared Spectrometer (HIRMES) to be commissioned in 2019. I will show how mid-infrared imaging is used to test massive star formation theories, how far-infrared polarimetry on sub-parsec scales is directly testing the role of magnetic fields in molecular clouds, and how velocity-resolved high-resolution spectroscopy will push forward our understanding of proto-planetary disk science. I will also summarize upcoming opportunities with the SOFIA observatory. For the latest news about your flying observatory, see https://sofia.usra.edu/.

Star formation↗

High Resolution UV Spectroscopy of H2 and N2 Applied to Observations of the Planets by Spacecraft

The next generation of high resolution UV imaging Spacecraft are being prepared for studying the airglow and aurora of the Earth, the other terrestrial planets and the Jovian planets. To keep pace with these technological improvements we have developed a laboratory program to provide electron impact collision cross sections of the major molecular planetary gases. This program is described in detail.

Spectroscopy↗

High-voltage picosecond photoconductor switch based on low-temperature-grown GaAs

A GaAs material grown by molecular beam epitaxy at a low substrate temperature was used to fabricate a photoconductor switch that produces 6-V picosecond electrical pulses. The pulses were produced on a microwave coplanar-strip transmission line lithographically patterned on the low-temperature (LT) GaAs. A 150-fs laser pulse was used to generate carriers in the LT GaAs gap between the metal strips, partially shorting a high DC voltage placed across the lines. The 6-V magnitude of the electrical pulses obtained is believed to be limited by the laser pulse power and not by the properties of the LT GaAs. Experiments were also performed on a picosecond photoconductor switch fabricated on a conventional ion-damaged silicon-on-sapphire substrate. Although comparable pulse durations were obtained, the highest pulse voltage achieved with the latter device was 0.6 V.

Frankel, Michael Y.↗

A Remarkable Auroral Event on Jupiter Observed in the Ultraviolet with the Hubble Space Telescope

Two sets of ultraviolet images of the Jovian north aurora were obtained with the Faint Object Camera on board the Hubble Space Telescope. The first series shows an intense discrete arc in near corotation with the planet. The maximum apparent molecular hydrogen emission rate corresponds to an electron precipitation of approximately 1 watt per square meter, which is about 30,000 times larger than the solar heating by extreme ultraviolet radiation. Such a particle heating rate of the auroral upper atmosphere of Jupiter should cause a large transient temperature increase and generate strong thermospheric winds. Twenty hours after initial observations, the discrete arc had decreased in brightness by more than one order of magnitude. The time scale and magnitude of the change in the ultraviolet aurora leads us to suggest that the discrete Jovian auroral precipitation is related to large-scale variations in the current system as is the case of for Earth's discrete aurorae.

Gerard, J. C.↗

Concentration Effects and Ion Properties Controlling the Fractionation of Halides during Aerosol Formation

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air−water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO2, NaNO3, NaClO4, and NaIO4. The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of anions (f (Isub x-)) and their correlation with ion properties. Although no correlation exists between f (sub x-) and the limiting equivalent ionic conductivity, the correlation coefficient of the linear fit with the size of the anions R(sub x-), dehydration free-energy ΔGdehyd, and polarizability alpha, follows the order: (R(sub x-)(exp −2)) > (R(sub x-)(exp −1)) >(R(sub x-) > delta G(sub dehyd) > alpha. The same pure physical process is observed in H2O and D2O. The factor f (sub x-) does not change with pH (6.8−8.6), counterion (Li+, Na+, K+, and Cs+) substitution effects, or solvent polarity changes in methanol − and ethanol−water mixtures (0 <= xH2O <= 1). Sodium polysorbate 20 surfactant is used to modify the structure of the interface. Despite the observed enrichment of I− on the air−water interface of equimolar solutions, our results of seawater mimic samples agree with a model in which the interfacial composition is increasingly enriched in I− < Br− < Cl− over the oceanic boundary layer due to concentration effects in sea spray aerosol formation.

iodine↗

A Dominant Arabidopsis Thaliana ACTIN7 Mutant for Studies of Cytoskeletal-Mediated Root Gravity and Spaceflight Stress Responses

A forward genetic screen for Arabidopsis thaliana mutants that exhibited differential sensitivity to the actin-disrupting compound, latrunculin B (LatB), was conducted to uncover new players involved in actin-mediated root gravity responses. This to the isolation of a mutant that exhibited robust primary root growth at 100 nM LatB, which is a concentration that severely inhibits wild-type root elongation. Phenotypic analysis revealed that hypocotyl elongation in the dark and root hair tip growth in the mutant could tolerate LatB concentrations that impaired these processes in wild type. A cross between the mutant and wild type resulted in progeny resistance to LatB, which indicated that the mutant is dominant (hereafter referred to as LBR1 for LatB Resistant1). Filamentous-actin (F-actin) organization in LBR1 primary roots remained intact at 100 nM LatB, while that of wild type exhibited fragmented F-actin. Next generation sequencing revealed that LBR1 had a single nucleotide polymorphism (SNP) in the AT5G09810 gene that changed cytosine to a thiamine at the first exon. AT5G09810 encodes ACTIN7 (ACT7), which is one of three vegetative actin isoforms in A. thaliana. The SNP in the ACT7 gene led to a change in a single amino acid from proline at position 32 to a serine. Transgenic complementation of LBR1 plants with wild-type ACT7 under the control of the ACT7 promoter (pACT7:ACT7) and wild-type plants with LBR1, which contained the proline to serine mutation, also under the ACT7 promoter (pACT7:LBR1) confirmed that LBR1 is ACT7. The pACT7:LBR1 construct was also able to confer LatB resistance to the act7-5 and act2-3 vegetative ACT mutants. Moreover, LBR1 exhibited partial tolerance to salt and low phosphate, and enhanced root skewing on a clinostat, suggesting that site-directed engineering of vegetative ACT presents a strategy for generating stress-tolerant plants for spaceflight applications and studies of actin-mediated gravity responses.

Plant Space Biology↗

A Dominant Arabidopsis Thaliana ACTIN7 Mutant for Studies of Cytoskeletal-Mediated Root Gravity and Spaceflight Stress Responses

A forward genetic screen for Arabidopsis thaliana mutants that exhibited differential sensitivity to the actin-disrupting compound, latrunculin B (LatB), was conducted to uncover new players involved in actin-mediated root gravity responses. This led to the isolation of a mutant that exhibited robust primary root growth at 100 nM LatB, which is a concentration that severely inhibits wild-type root elongation. Phenotypic analysis revealed that hypocotyl elongation in the dark and root hair tip growth in the mutant could tolerate LatB concentrations that impaired these processes in wild type. A cross between the mutant and wild type resulted in progeny resistance to LatB, which indicated that the mutant is dominant (hereafter referred to as LBR1 for LatB Resistant1). Filamentous-actin (F-actin) organization in LBR1 primary roots remained intact at 100 nM LatB, while that of wild type exhibited fragmented F-actin. Next generation sequencing revealed that LBR1 had a single nucleotide polymorphism (SNP) in the AT5G09810 gene that changed cytosine to a thiamine at the first exon. AT5G09810 encodes ACTIN7 (ACT7), which is one of three vegetative actin isoforms in A. thaliana. The SNP in the ACT7 gene led to a change in a single amino acid from proline at position 32 to a serine. Transgenic complementation of LBR1 plants with wild-type ACT7 under the control of the ACT7 promoter (pACT7:ACT7) and wild-type plants with LBR1, which contained the proline to serine mutation, also under the ACT7 promoter (pACT7:LBR1) confirmed that LBR1 is ACT7. The pACT7:LBR1 construct was also able to confer LatB resistance to the act7-5 and act2-3 vegetative ACT mutants. Moreover, LBR1 exhibited partial tolerance to salt and low phosphate, and enhanced root skewing on a clinostat, suggesting that site-directed engineering of vegetative ACT presents a strategy for generating stress-tolerant plants for spaceflight applications and studies of actin-mediated gravity responses.

Plant Space Biology↗

A preliminary spectroscopic assessment of the Spacelab 1/Shuttle optical environment

Attention is given to the Space Lab/Space Shuttle-borne Imaging Spectrometric Observatory's 1150-8000 A spectral data, which was gathered while this instrument package was looking tangentially away from the earth and into the velocity vector. The spectrum is noted to contain the expected atmospheric features, together with bright molecular bands between 6400 and 8000 A. These bands appear to be part of the N2 First Positive system. If most of the emission is due to this system, two excitation mechanisms are implied: direct collisional excitation of the local Shuttle atmosphere by the terrestrial atmosphere, or alternatively a surface interaction which generates metastable N2(A); this subsequently radiates via inverse first positive N2 transitions, followed by first positive transitions.

Torr, M. R.↗

Evidence of pathogenic microbes in the International Space Station drinking water: reason for concern?

Molecular analyses were carried out on four preflight and six postflight International Space Station (ISS)-associated potable water samples at various stages of purification, storage, and transport, to ascertain their associated microbial diversities and overall microbial burdens. Following DNA extraction, PCR amplification, and molecular cloning procedures, rDNA sequences closely related to pathogenic species of Acidovorax, Afipia, Brevundimonas, Propionibacterium, Serratia, and others were recovered in varying abundance. Retrieval of sequences arising from the iodine (biocide)-reducing Delftia acidovorans in postflight waters is also of concern. Total microbial burdens of ISS potable waters were derived from data generated by an ATP-based enumeration procedure, with results ranging from 0 to 4.9 x 10(4) cells/ml. Regardless of innate biases in sample collection and analysis, such circumstantial evidence for the presence of viable, intact pathogenic cells should not be taken lightly. Implementation of new cultivation approaches and/or viability-based assays are requisite to confirm such an occurrence.

STS-113 Shuttle Project↗

Mapping of Spacecraft Atmosphere Monitor Signal to Major Constituent Abundances

The Spacecraft Atmosphere Monitor (S.A.M.) follows the JPL’s commitment to introduce and develop next-generation instrumentation concepts for sensing the air quality on manned space flights via continuous sampling, measuring, and reporting in 2s intervals on all gaseous pollutants. The S.A.M. will have two modes of operation: the Major Constituent Analysis (MCA) mode and the Trace Gas Analysis (TGA) mode. The MCA mode will report on molecular analytes such as CH4, H2O, N2, O2, Ar, and CO2 while the TGA mode will acquire minute amounts of volatile organic compounds. Both modes assess the composition of the ambient air with twenty full mass spectra per second giving rise to a substantial amount of data to be processed by a set of small footprint software stacks hosted by an on-board computer. Mass spectra will be accumulated as the number of counts recorded in a given mass-to-charge channel and converted into the absolute abundances of detected species using an efficient algorithm. The decomposition algorithm contains four units: peak identification, mass calibration, background and dead time correction, and an abundance analysis unit. The abundance analysis module identifies target species through their characteristic fragmentation patterns in the presence of molecular isobars, such as CO and N2. For example, in order to identify N2 analyte, the code will simultaneously monitor abundance ratios of the 14, 28 and 29 Th signals and will adapt to any instability caused by a decrease in ambient pressure or changes in humidity. This requirement becomes critical for instruments designed to monitor the near real-time quality of cabin air and promptly provide accurate feedbacks.

Nikolic, D.↗

Genesis Solar Wind Sample Curation Documentation

Introduction: A scientist with experience as a sample science analyst, provider of flight hardware for multiple missions, and senior engineer in an ISO 2000-rated manufacturing plant has described the timeline of key participants in any PI-led sample return mission, the breadth of the organizations involved [1,2], and, of interest to this meeting, choosing the types of data to preserve and issues of future data accessibility. This work broadens that perspective by giving similar lessons from Genesis sample curation point-of-view. Curation participation regarding data gathering was part of the mission review process from the beginning. Genesis’ story illustrates outcome of several choices about types of data to record and preserve. Precision analysis of solar wind atoms captured in pure, ultraclean substrates is the driving science goal; therefore, detailed documentation was captured from all mission and curation phases and from investigator laboratories because these processes affect the final analytical results [3]. Pre-flight: Design and fabrication of the spacecraft. Like many modern small sample return missions, Genesis was a tightly managed team integrated across science, engineering and curation. Communication across the team was excellent, and, for the most part, the hands-on engineering technicians understood the impacts of “small choices” they routinely make, and the eyes-on oversight of manufacturing processes by scientists was mindful of details. The payload was designed by the Jet Propulsion Laboratory and the spacecraft by Lockheed Martin. Solar wind collectors and instruments were fabricated by multiple vendors and laboratories. The main portion of the payload was assembled at JSC. Fabrication procedures and contamination-control data (with witness coupons) were stored primarily at JSC. The original composition, dimensions and configuration of components, results of thermal testing, etc. are still needed for interpretation of analytical data. At times, these must be estimated from secondary information acquired pre-flight. Moreover, some files (e.g., original 3-D models and early Powerpoint) cannot be opened using software. Archived curation data includes 2-D drawings, material usage lists, QA documentation and analyses of consumables used during fabrication. Important chemical information still resides in archived hardware, paints and lubricants, material coupons, cleaning coupons, environmental witness plates and reference materials from manufacturing facilities. Purity and cleanliness of collector substrates. Semi-conductor vendors provided surface cleanliness data and some purity data. Purity for specific elements of interest was verified by science team members in their laboratories [4]. Curation archived procurement and shipping records, analysis reports, and non-proprietary fabrication data. A physical archive of flight collector reference materials is maintained for future use so additional data can be collected as analytical techniques improve. These are of increased value due to the hard landing upon re-entry. Cleaning and cleanliness assessments of flight hardware. Cleaning of the science canister payload was performed at JSC in a dedicated ISO 4 cleanroom using ultrapure water (UPW). The cleanliness of this UPW was monitored throughout processing. The archive for the clean lab also includes airborne particle counts, airborne molecular and inorganic contamination measurements as well as cleanroom construction material coupons and witness coupons. Hardware cleanliness was assessed by particle counts in rinse water batches. This information is recorded in batch cleaning forms and logbooks, and are, perhaps, of decreased value due to the hard landing. Post-flight: Curation-generated data. The curation handling history of each Genesis sample is documented in a typical astromaterials sample database which captures sample location, physical description and characterization data. Samples have a “shelf life”. Crucial to the preservation of samples is ongoing documentation of the sample environment, initially under curatorial control but is now a separate facility function with requires coordination. PI-generated data. Data on sample characterization and cleaning techniques continues to be generated by sample users [5]. These are often captured in LPSC abstracts, but these “engineering” results often are not publishable as stand-alone papers. We are actively looking for ways to make this information more accessible to users. Ion implants into samples have aided science return and can be shared among investigators. These (and similar) materials should be added to the curatorial collection with appropriate process and characterization data generated externally. Summary: Complete data archives for returned astromaterial samples must be broad in types and formats, and inclusive of environmental monitoring.

Genesis↗

GJ 229B: Solving the Puzzle of the First Known T Dwarf with the APOLLO Retrieval Code

GJ 229B was the first T dwarf to be discovered in 1995, and its spectrum has been more thoroughly observed than that of most other brown dwarfs. Yet a full spectroscopic analysis of its atmosphere has not been done with modern techniques. This spectrum has several peculiar features, and recent dynamical estimates of GJ 229B’s mass and orbit have disagreed widely, both of which warrant closer investigation. With a separation of tens of astronomical units from its host star, GJ 229B falls near the border of the planet and stellar population formation regimes, so its atmosphere could provide clues to formation processes for intermediate objects of this type. In an effort to resolve these questions, we performed retrievals on published spectra of GJ 229B over a wide range of wavelengths (0.5–5.1 μm) using the open-source APOLLO code. Based on these retrievals, we present a more precise mass estimate of 41.6 ± 3.3MJ and an effective temperature estimate of 869 +5 −7 K, which are more consistent with evolutionary models for brown dwarfs and suggest an older age for the system of >1.0 Gyr. We also present retrieved molecular abundances for the atmosphere, including replicating the previously observed high CO abundance, and discuss their implications for the formation and evolution of this object. This retrieval effort will give us insight into how to study other brown dwarfs and directly imaged planets, including those observed with JWST and other next-generation telescopes.

Alex R Howe↗

Optical Properties of Thin Film Molecular Mixtures

Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, alpha, and low infrared emittance, epsilon. On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator. A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450C, a sharp transition at 1.8 micrometers is desired. The radiator completes the heat flow through the Carnot cycle. Additional work has been done supporting the use of molecular mixtures for terrestrial applications. Sputter deposition provides a means to apply coatings to the tubes that carry a working fluid at the focus of trough-style collectors. Sputtering offers considerable flexibility in coating conditions, including a wide variety of metal and dielectric targets. Coating designs range from simple two or three layer coatings to complex coatings that are purposely graded to be metal-rich at their base and oxide-rich at their surface in order to yield the desired solar selective properties. In these cermet coatings, molecular islands of metal are thought to be embedded in a three dimensional matrix of dielectric. Recent work has identified the use of custom made ion beam sputter deposition targets to produce coatings containing molecular mixtures of metal and dielectric. The targets are cylindrical and the surface consists of a gradually changing composition of metal and dielectric. Rotating the cylinder under the beam during ion beam sputter deposition yields a coating that is a molecular mixture of metal and dielectric, with the composition changing through the thickness of the coating. The optical properties of these coatings are not only dependent on their thickness and chemical composition, but are also dependent on the extent of the through thickness gradient established during deposition. This paper presents a summary of the optical properties of several thin film molecular mixtures designed as solar selective coatings. Optical performance is first identified as a function of wavelength, from the ultraviolet to the visible and infrared. Coating composition, thickness, and gradient from metal to dielectric also play an important role. Additional work for future activities is also identified.

Jaworske, Donald A.↗

Mariner 9 ultraviolet spectrometer experiment - Mars airglow spectroscopy and variations in Lyman alpha.

Mariner 9 ultraviolet spectrometer observations show the Mars airglow consists principally of emissions that arise from the interaction of solar ultraviolet radiation with carbon dioxide, the principal constituent of the Mars atmosphere. Two minor constituents, atomic hydrogen and atomic oxygen, also produce airglow emissions. The airglow measurements show that ionized carbon dioxide is only a minor constituent of the ionosphere. Using the airglow measurements of atomic oxygen, it is possible to infer that the major ion is ionized molecular oxygen. The escape rate of atomic hydrogen measured by Mariner 9 is approximately the same as that measured two years earlier by Mariner 6 and 7. If the current escape rate has been operating for 4.5 billion years and if water vapor is the ultimate source, an amount of oxygen has been generated that is far in excess of that observed at present. Mariner 9 observations of Mars Lyman alpha emission over a period of 120 days show variations of 20%.

Barth, C. A.↗

International Space Station Program Phase 3 Integrated Atmosphere Revitalization Subsystem Test

Testing of the International Space Station (ISS) U.S. Segment baseline configuration of the Atmosphere Revitalization Subsystem (ARS) by NASA's Marshall Space Flight Center (MSFC) was conducted as part of the Environmental Control and Life Support System (ECLSS) design and development program. This testing was designed to answer specific questions regarding the control and performance of the baseline ARS subassemblies in the ISS U.S. Segment configuration. These questions resulted from the continued maturation of the ISS ECLSS configuration and design requirement changes since 1992. The test used pressurized oxygen injection, a mass spectrometric major constituent analyzer, a Four-Bed Molecular Sieve Carbon Dioxide Removal Assembly, and a Trace Contaminant Control Subassembly to maintain the atmospheric composition in a sealed chamber at ISS specifications for 30 days. Human metabolic processes for a crew of four were simulated according to projected ISS mission time lines. The performance of a static feed water electrolysis Oxygen Generator Assembly was investigated during the test preparation phases; however, technical difficulties prevented its use during the integrated test. The Integrated ARS Test (IART) program built upon previous closed-door and open-door integrated testing conducted at MSFC between 1987 and 1992. It is the most advanced test of an integrated ARS conducted by NASA to demonstrate its end-to-end control and overall performance. IART test objectives, facility design, pretest analyses, test and control requirements, and test results are presented.

Perry, J. L.↗

Testbed Results for Scalar and Vector Radiative Transfer Computations of Light in Atmosphere-Ocean Systems

We generate and tabulate reflectance values of the Stokes parameters I, Q, and U of upwelling radiance just above a rough ocean surface and at the top of the atmosphere (TOA) for 100 scattering geometries, four atmosphere-ocean systems, and four wavelengths. The atmosphere-ocean systems increase in complexity from (a) a molecular atmosphere above a rough ocean surface (AOS-I model); to (b) a pure water body below a rough ocean surface (AOS-II model); to (c) a fully-coupled simple atmosphere-ocean system (AOS-III model) containing a molecular atmosphere, rough ocean surface, and pure water; to (d) a fully-coupled complex atmosphere-ocean system (AOS-IV model) that includes scattering by molecules, rough ocean surface, pure water, and hydrosols. Our wavelengths (350, 450, 550, and 650 nm) capture the ultraviolet-visible range. Our tables provide radiative transfer (RT) testbed results for atmosphere-ocean systems with an accuracy that surpasses the measurement accuracy of state-of-the-art polarimeters. To validate the accuracy of these tables we performed computations using three independent RT codes that provide deterministic numerical solutions for the RT equation. The agreement is 10(exp –5) for AOS-IV model, and 10(exp –6) for the other models. The degree of linear polarization computed by these RT codes differs by ≤0.2% for 15 isolated cases of tabulated reflectance values, and by ≤0.1% for all remaining cases. We also provide comparisons with results obtained by a stochastic RT code for AOS-I model. The agreement between the deterministic and stochastic results for this model is 10(exp –5) at TOA, and 10(exp –6) above the ocean surface.

Polarimeters↗

Evolution in vitro of an RNA enzyme with altered metal dependence

The Tetrahymena group I ribozyme catalyses a sequence-specific phosphodiester cleavage reaction on an external RNA oligonucleotide substrate in the presence of a divalent metal cation cofactor. This reaction proceeds readily with either Mg2+ or Mn2+, but no detectable reaction has been reported when other divalent cations are used as the sole cofactor. Cations such as Ca2+, Sr2+ and Ba2+ can stabilize the correct folded conformation of the ribozyme, thereby partially alleviating the Mg2+ or Mn2+ requirement. But catalysis by the ribozyme involves coordination of either Mg2+ or Mn2+ at the active site, resulting in an overall requirement for one of these two cations. Here we use an in vitro evolution process to obtain variants of the Tetrahymena ribozyme that are capable of cleaving an RNA substrate in reaction mixtures containing Ca2+ as the divalent cation. These findings extend the range of different chemical environments available to RNA enzymes and illustrate the power of in vitro evolution in generating macromolecular catalysts with desired properties.

NASA Discipline Exobiology↗

Mixed-Domain Charge Transport in S-Se Alloys as a Li-S Battery Cathode Material

Lithium-sulfur batteries are emerging candidate systems for the next-generation long-range electric aircraft application owing to their potential to deliver high energy density per weight. Their cathodes are to be made primarily with sulfur, but sulfur by itself has much too low electron conductivity to serve as a useful cathode. An idea that has been suggested to overcome this bottleneck is to alloy sulfur with selenium in the hope that electron mobility, which is thought to improve charge transport at some expense of increased weight and reduced energy density. However, understanding of these alloy structures and their transport mechanism is insufficient, and electron mobility at varying degrees of selenium content is not well charted, which are critical for determining the optimum selenium content and testing whether this strategy is generally feasible. The difficulty of computationally characterizing these alloy systems is rooted in the structure. The structures of both sulfur and selenium exhibit eight-atom rings that pack together in various orientations to form their respective crystals. For one, because these crystals (and presumably their alloys as well) feature multiple polymorphs such that their structural coherence is rather unclear. Secondly, these are also relatively large systems (32 atoms per cell) with low-symmetry, which complicate computation both in terms of accuracy and efficiency. Thirdly, such semi-molecular, semi-crystalline structures lead to a combination of band-transport characteristics and hopping-transport characteristics, each of which is a domain with its own physics and set of computational, theoretical challenges. In addition, there is a general dearth of experimental transport data for sulfur-selenium alloys. In this study, we make a comprehensive attempt to tackle this problem using a wide array of first-principles methods. We generate special quasirandom structures to simulate alloy structures, and compute their first-principles Raman spectra for comparison with experimental data to ensure their structural soundness. We then proceed to use recently developed, state-of-the-art tool (AMSET) in order to efficiently compute electronic mobilities under band transport of pure sulfur, pure selenium, as well as their alloys of various compositions at a reasonable accuracy. We then sample numerous dimer configurations of nearest-neighbor eight-atom-ring-pairs and compute electronic hopping rates between them, which yields hopping mobility. A combination of these efforts lead to a general mapping of electron transport behaviors throughout the alloy range. Preliminary results show that introduction of selenium into sulfur initially damages electron mobility due to disorder but eventually improves it beyond that of pure sulfur with additional selenium content, ultimately peaking at the pure-selenium limit. Band transport dominates for holes in sulfur and electrons in selenium, but in all other cases, hopping transport is dominant. Ongoing efforts include determination of charge concentration and conductivity, as well as performing multiphysics modeling to determine the optimum selenium content for best tradeoff between conductivity and energy density for aircraft range.

Junsoo Park↗