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At least 1,171 records · Page 65

Validation of the DESI 2024 Lyman alpha forest BAL masking strategy

Broad absorption line quasars (BALs) exhibit blueshifted absorption relative to a number of their prominent broad emission features. These absorption features can contribute to quasar redshift errors and add absorption to the Lyman-α (Lyα) forest that is unrelated to large-scale structure. We present a detailed analysis of the impact of BALs on the Baryon Acoustic Oscillation (BAO) results with the Lyα forest from the first year of data from the Dark Energy Spectroscopic Instrument (DESI). The baseline strategy for the first year analysis is to mask all pixels associated with all BAL absorption features that fall within the wavelength region used to measure the forest. We explore a range of alternate masking strategies and demonstrate that these changes have minimal impact on the BAO measurements with both DESI data and synthetic data. This includes when we mask the BAL features associated with emission lines outside of the forest region to minimize their contribution to redshift errors. We identify differences in the properties of BALs in the synthetic datasets relative to the observational data, as well as use the synthetic observations to characterize the completeness of the BAL identification algorithm, and demonstrate that incompleteness and differences in the BALs between real and synthetic data also do not impact the BAO results for the Lyα forest.

Lyman alpha forest↗

Asymmetric response of Amazon forest water and energy fluxes to wet and dry hydrological extremes reveals onset of a local drought-induced tipping point

Understanding the effects of intensification of Amazon basin hydrological cycling—manifest as increasingly frequent floods and droughts—on water and energy cycles of tropical forests is essential to meeting the challenge of predicting ecosystem responses to climate change, including forest “tipping points”. Here, we investigated the impacts of hydrological extremes on forest function using 12+ years of observations (between 2001–2020) of water and energy fluxes from eddy covariance, along with associated ecological dynamics from biometry, at the Tapajós National Forest. Measurements encompass the strong 2015–2016 El Niño drought and La Niña 2008–2009 wet events. We found that the forest responded strongly to El Niño-Southern Oscillation (ENSO): Drought reduced water availability for evapotranspiration ( ET ) leading to large increases in sensible heat fluxes ( H ). Partitioning ET by an approach that assumes transpiration ( T ) is proportional to photosynthesis, we found that water stress-induced reductions in canopy conductance ( G s ) drove T declines partly compensated by higher evaporation ( E ). By contrast, the abnormally wet La Niña period gave higher T and lower E , with little change in seasonal ET . Both El Niño-Southern Oscillation (ENSO) events resulted in changes in forest structure, manifested as lower wet-season leaf area index. However, only during El Niño 2015–2016, we observed a breakdown in the strong meteorological control of transpiration fluxes (via energy availability and atmospheric demand) because of slowing vegetation functions (via shutdown of G s and significant leaf shedding). Drought-reduced T and G s , higher H and E , amplified by feedbacks with higher temperatures and vapor pressure deficits, signaled that forest function had crossed a threshold, from which it recovered slowly, with delay, post-drought. In conclusion, identifying such tipping point onsets (beyond which future irreversible processes may occur) at local scale is crucial for predicting basin-scale threshold-crossing changes in forest energy and water cycling, leading to slow-down in forest function, potentially resulting in Amazon forests shifting into alternate degraded states.

54 ENVIRONMENTAL SCIENCES↗

Biopower: Impact of Biofuels Deployment to Replace Petroleum Liquids in Stationary Power Applications

Petroleum-based liquids are used in a portion of power generation applications in the United States, predominantly in the New England, Middle Atlantic, South Atlantic, and Pacific-Noncontiguous regions. Power plants that burn petroleum liquids, such as distillate or residual fuel oils, are generally used for short periods to accommodate peak electricity demands. The Energy Information Administration (EIA) estimated the U.S. consumption of petroleum liquids for electricity generation at 27 million barrels in 2018, representing a cost of $2.4 billion annually. This study assesses the potential to displace all or part of the petroleum liquids in U.S. power generation with biofuels. The biofuels for this application are assumed to be derived from terrestrial feedstocks, with conversion routes of both fast pyrolysis (bio-oil) and hydrothermal liquefaction (bio-crude). Regional models were used to assess the availability and cost of three different base materials: clean wood, forest residues, and corn stover; each was evaluated in the laboratory at small or experimental scales for conversion to bio-oil or bio-crude. The estimated biofuel production quantities depend on equivalent heating versus the current heavy fuel. In this report, the availability of each type of biomass for each section of the U.S. Census division is estimated using a conservative broker price (in each case) of $ 80 per dry tonne. The results show that the petroleum-liquid power generation in each of the Census Divisions could be supplied by one or more of the feedstocks evaluated. For all regions, clean wood supplies (only) could provide ample supply. For all but two regions (Middle Atlantic and New England), forest residues alone are sufficient. Finally, for all regions but three (Middle Atlantic, New England, and South Atlantic), corn stover alone is adequate. The Minimum Fuel Selling Price (MFSP) of bio-oil and bio-crude were also estimated for each feedstock type and Census Division. This analysis showed that fast pyrolysis bio-oil projections to be lower (14% on average) than current wholesale petroleum-based heating oil prices in each of the regions, assuming 100 dry tonnes/day processing capacity. However, bio-crude predictions were significantly higher (2X) in all cases. The effect of biorefinery size was also quantified. Based on the preliminary results in this study, it is apparent the biofuels could be an economical alternative for current petroleum liquids in U.S. power generation. However, additional research is needed to determine the necessary biofuel characteristics to support existing generation equipment. It is recommended that both power generation and biofuel production stakeholders to be engaged to outline the research and testing needed to identify the technical hurdles to enable the opportunity.

02 PETROLEUM↗

Multi-scale Simulation, Calibration, and Optimization of Calcium Carbonate Precipitation in Microbial Communities

Ensuring the efficient engineering of microbially induced calcium carbonate precipitation (MICP) is crucial for a variety of environmental and civil engineering applications, such as soil stabilization and carbon sequestration. Addressing this need, we present a comprehensive multi-scale workflow that begins with the isolation of calcium carbonate-producing microbes from soil samples, followed by metagenomic sequencing and metabolic reconstruction. We then characterize microbial growth phenotypes under diverse nutrient conditions, compare observed growth with metabolic model predictions, and apply the Consistent Reproduction of Phenotype (CROP) algorithm to refine these models. Furthermore, we analyze metabolite consumption and production, and develop a consumer-resource model that is calibrated using time-series measurements of growth rates, pH levels, and calcium carbonate precipitation. The primary benefit of our approach lies in its ability to predict and control MICP outcomes, facilitated by a Bayesian methodology that incorporates priors on initial conditions and parameters. This allows us to compute posteriors by integrating experimental data, and to solve a risk optimization problem under uncertainty to identify nutrient conditions that maximize calcium carbonate production. In contrast to non-Bayesian methods, which fail to quantify uncertainty accurately, our approach provides a more reliable pathway to optimizing nutrient conditions, enhancing the likelihood of achieving desired MICP outcomes. This positions our method as a superior alternative in the quest to improve MICP through engineered microbial consortia.

54 ENVIRONMENTAL SCIENCES↗

AES and LEED study of the zinc blende SiC(100) surface

Auger and LEED measurements have been carried out on the (100) surface of zinc blende SiC. Two different phases of the clean surface, in addition to two kinds of oxygen-covered surfaces, have been obtained, identified, and discussed. In the oxygen-covered surface, the oxygen is bonded to the Si. The carbon-rich phase is reconstructed (2 x 1), similar to the (100) clean surfaces of Si, Ge, and diamond. The Si-topped surface is reconstructed. A model of alternating Si dimers is suggested for this surface.

Dayan, M.↗

SAMSS: An in-progress review of the Spacecraft Assembly, Maintenance, and Servicing Study

The Spacecraft Assembly, Maintenance, and Servicing Study (SAMSS) is an effort to define and verify the most cost effective approach to spacecraft servicing, as a alternative to replacement, in the 1990's and beyond. The intent of the study is to assess the servicing of satellites in all orbit regimes. Elements of a space servicing infrastructure are developed and cost estimates are generated. Readiness is assessed and proof of concept demonstrations are identified. Cryogenic fuel resupply is discussed.

Burt, William W.↗

An advanced concentrator for solar dynamic power systems in space

Solar concentrators based on rigidized stretched-membrane technology, which have been shown to be a possible alternative to rigid segmented concentrators for solar dynamic power applications in space, are discussed. Membrane concentrators offer an advantage in weight, efficiency of structure use, deployability, and cost. Predeployment packaging and subsequent deployment of a prototype membrane concentrator has been demonstrated. Attractive membrane fabrication techniques have been identified and demonstrated. The concept is described, and materials selection and membrane fabrication are examined.

Beninga, Kelly↗

Findings of the Joint Workshop on Evaluation of Impacts of Space Station Freedom Ground Configurations

At the workshop, experts from the plasma interactions community evaluated the impacts of environmental interactions on the Space Station Freedom (SSF) under each of the proposed grounding schemes. The grounding scheme chosen for the SSF power system was found to have serious implications for SSF design. Interactions of the SSF power system and structure with the low Earth orbit (LEO) plasma differ significantly between different proposed grounding schemes. Environmental constraints will require modification of current SSF designs under any grounding scheme. Maintaining the present negative-grounding scheme compromises SSF safety, structural integrity, and electromagnetic compatibility. It also will increase contamination rates over alternative grounding schemes. One alternative, positive grounding of the array, requires redesign of the primary power system in work package four. Floating the array reduces the number of circuit changes to work package four but adds new hardware. Maintaining the current design will affect all work packages; however, no impacts were identified on work packages one, two, or three by positively grounding or floating the array, with the possible exception of extra corona protection in multi-wire connectors.

Ferguson, Dale C.↗

Archiving of Wideband Plasma Wave Data

Beginning with the third year of funding, we began a more ambitious archiving production effort, minimizing work on new software and concentrating on building representative archives of the missions mentioned above, recognizing that only a small percentage of the data from any one mission can be archived with reasonable effort. We concentrated on data from Dynamics Explorer and ISEE 1, archiving orbits or significant fractions of orbits which attempt to capture the essence of the mission and provide data which will hopefully be sufficient for ongoing and new research as well as to provide a reference to upcoming and current ISTP missions which will not fly in the same regions of space as the older missions and which will not have continuous wideband data. We archived approximately 181 Gigabytes of data, accounting for some 1582 hours of data. Included in these data are all of the AMPTE chemical releases, all of the Spacelab 2/PDP data obtained during the free-flight portion of its mission, as well as significant portions of the S3, DE-1, Imp-6, Hawkeye, Injun 5, and ISEE 1 and 2 data sets. Table 1 summarizes these data. All of the data archived are summarized in gif-formatted images of frequency-time spectrograms which are directly accessible via the internet. Each of the gif files are identified by year, day, and time as described in the Web page. This provides a user with a specific date/time in mind a way of determining very quickly if there is data for the interval in question and, by clicking on the file name, browsing the data. Alternately, a user can browse the data for interesting features and events simply by viewing each of the gif files. When a user finds data of interest, he/she can notify us by email of the time period involved. Based on the user's needs, we can provide data on a convenient medium or by ftp, or we can mount the appropriate data and provide access to our analysis tools via the network. We can even produce products such as plots or spectrograms in hardcopy form based on the specific request of the user.

Kurth, William S.↗

Duplex Direct Data Distribution System

The NASA Glenn Research Center (GRC) is developing and demonstrating communications and network technologies that are helping to enable the near-Earth space Internet. GRC envisions several service categories. The first of these categories is direct data distribution or D3 (pronounced "D-cubed"). Commercially provided D3 will make it possible to download a data set from a spacecraft, like the International Space Station. as easily as one can extract a file from a remote server today, using a file transfer protocol. In a second category, NASA spacecraft will make use of commercial satellite communication (SATCOM) systems. Some of those services will come from purchasing time on unused transponders that cover landmasses. While it is likely there will be gaps in service coverage, Internet services should be available using these systems. This report addresses alternative methods of implementing a full duplex enhancement of the GRC developed experimental Ka-Band Direct Data Distribution (D3) space-to-ground communication link. The resulting duplex version is called the Duplex Direct Data Distribution (D4) system. The D4 system is intended to provide high-data-rate commercial direct or internet-based communications service between the NASA spacecraft in low earth orbit (LEO) and the respective principal investigators associated with these spacecraft. Candidate commercial services were assessed regarding their near-term potential to meet NASA requirements. Candidates included Ka-band and V-band geostationary orbit and non-geostationary orbit satellite relay services and direct downlink ("LEO teleport") services. End-to-end systems concepts were examined and characterized in terms of alternative link layer architectures. Alternatives included a Direct Link, a Relay Link, a Hybrid Link, and a Dual Mode Link. The direct link assessment examined sample ground terminal placements and antenna angle issues. The SATCOM-based alternatives examined existing or proposed commercial SATCOM services that could be available in the 2005 time frame. The alternatives were evaluated and compared in terms of average daily system throughput and cost per bit. Throughput was estimated based on hypothetical scenarios supporting the International Space Station and polar orbiting missions. The feasibility of using standard TCP and a modified TCP was evaluated and risks were identified. An estimate of the TCP acknowledgment data rate required to support a return channel rate of 622 Mbps was developed using OPNET.

Greenfield, Israel↗

Characteristic archaebacterial 16S rRNA oligonucleotides

A method of analyzing 16S rRNA catalog data has been developed in which groupings at various taxonomic levels can be characterized in terms of specific "signature" oligonucleotides. This approach provides an alternative means for evaluating higher order branching possibilities and can be used to assess the phylogenetic position of isolates that are poorly placed by the usual clustering procedures. This signature approach has been applied to forty archaebacterial catalogs and every oligonucleotide with significant signature value has been identified. Sets of specific oligonucleotides were identified for every major group on a dendrogram produced by cluster analysis procedures. Signatures that would establish between group relationships were also sought and found. In the case of the Methanobacteriaceae the clustering methods suggest a specific relationship to the Methanococcaceae. This inclusion is in fact supported by six strong signature oligonucleotides. However there are also significant numbers of signature oligonucleotides supporting a specific relationship of the Methanobacteriaceae to either the Halobacteriaceae or the Methanomicrobiaceae. Thus the placement of the Methanobacteriaceae is less certain than the usual dendrograms imply. The signature approach also was used to assess the phylogenetic position of Thermoplasma acidophilum which is found to be more closely related to the methanogen/halophile Division than to the sulfur dependent Division of the archaebacteria. This does not imply however that Thermoplasma acidophilum is properly regarded as being in the methanogen/halophile Division.

NASA Discipline Exobiology↗

Systems Analysis Developed for All-Electric Aircraft Propulsion

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane (PEM) and solid oxide fuel cells (SOFCs), alternative fuels and fuel processing, and fuel storage. A multidisciplinary effort is underway at the NASA Glenn Research Center to develop and evaluate concepts for revolutionary, nontraditional fuel cell power and propulsion systems for aircraft applications. As part of this effort, system studies are being conducted to identify concepts with high payoff potential and associated technology areas for further development. To support this effort, a suite of component models was developed to estimate the mass, volume, and performance for a given system architecture. These models include a hydrogen-air PEM fuel cell; an SOFC; balance-of-plant components (compressor, humidifier, separator, and heat exchangers); compressed gas, cryogenic, and liquid fuel storage tanks; and gas turbine/generator models for hybrid system applications. First-order feasibility studies were completed for an all-electric personal air vehicle utilizing a fuel-cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including a PEM fuel cell with liquid hydrogen storage, a direct methanol PEM fuel cell, and a direct internal reforming SOFC/turbine hybrid system using liquid methane fuel. Each configuration was compared with the baseline case on a mass and range basis.

Kohout, Lisa L.↗

Simulation Framework to Estimate the Performance of CO2 and O2 Sensing from Space and Airborne Platforms for the ASCENDS Mission Requirements Analysis

The Active Sensing of CO2 Emissions over Nights Days and Seasons (ASCENDS) mission recommended by the NRC Decadal Survey has a desired accuracy of 0.3% in carbon dioxide mixing ratio (XCO2) retrievals requiring careful selection and optimization of the instrument parameters. NASA Langley Research Center (LaRC) is investigating 1.57 micron carbon dioxide as well as the 1.26-1.27 micron oxygen bands for our proposed ASCENDS mission requirements investigation. Simulation studies are underway for these bands to select optimum instrument parameters. The simulations are based on a multi-wavelength lidar modeling framework being developed at NASA LaRC to predict the performance of CO2 and O2 sensing from space and airborne platforms. The modeling framework consists of a lidar simulation module and a line-by-line calculation component with interchangeable lineshape routines to test the performance of alternative lineshape models in the simulations. As an option the line-by-line radiative transfer model (LBLRTM) program may also be used for line-by-line calculations. The modeling framework is being used to perform error analysis, establish optimum measurement wavelengths as well as to identify the best lineshape models to be used in CO2 and O2 retrievals. Several additional programs for HITRAN database management and related simulations are planned to be included in the framework. The description of the modeling framework with selected results of the simulation studies for CO2 and O2 sensing is presented in this paper.

Plitau, Denis↗

Mars Sample Return Using Commercial Capabilities: Mission Architecture Overview

Mars Sample Return (MSR) is the highest priority science mission for the next decade as recommended by the recent Decadal Survey of Planetary Science. This paper presents an overview of a feasibility study for a MSR mission. The objective of the study was to determine whether emerging commercial capabilities can be used to reduce the number of mission systems and launches required to return the samples, with the goal of reducing mission cost. The major element required for the MSR mission are described and include an integration of the emerging commercial capabilities with small spacecraft design techniques; new utilizations of traditional aerospace technologies; and recent technological developments. We report the feasibility of a complete and closed MSR mission design using the following scenario that covers three synodic launch opportunities, beginning with the 2022 opportunity: A Falcon Heavy injects a SpaceX Red Dragon capsule and trunk onto a Trans Mars Injection (TMI) trajectory. The capsule is modified to carry all the hardware needed to return samples collected on Mars including a Mars Ascent Vehicle (MAV); an Earth Return Vehicle (ERV); and hardware to transfer a sample collected in a previously landed rover mission to the ERV. The Red Dragon descends to land on the surface of Mars using Supersonic Retro Propulsion (SRP). After previously collected samples are transferred to the ERV, the single-stage MAV launches the ERV from the surface of Mars to a Mars phasing orbit. The MAV uses a storable liquid, pump fed bi-propellant propulsion system. After a brief phasing period, the ERV, which also uses a storable bi-propellant system, performs a Trans Earth Injection (TEI) burn. Once near Earth the ERV performs Earth and lunar swing-bys and is placed into a Lunar Trailing Orbit (LTO0 - an Earth orbit, at lunar distance. A later mission, using a Dragon and launched by a Falcon Heavy, performs a rendezvous with the ERV in the lunar trailing orbit, retrieves the sample container and breaks the chain of contact with Mars by transferring the sample into a sterile and secure container. With the sample contained, the retrieving spacecraft, makes a controlled Earth re-entry preventing any unintended release of pristine Martian materials into the Earth's biosphere. Other capsule type vehicles and associated launchers may be applicable. The analysis methods employed standard and specialized aerospace engineering tools. Mission system elements were analyzed with either direct techniques or by using parametric mass estimating relationships (MERs). The architecture was iterated until overall mission convergence was achieved on at least one path. Subsystems analyzed in this study include support structures, power system, nose fairing, thermal insulation, actuation devices, MAV exhaust venting, and GN&C. Best practice application of loads, mass growth contingencies, and resource margins were used. For Falcon Heavy capabilities and Dragon subsystems we utilized publically available data from SpaceX; published analyses from other sources; as well as our own engineering and aerodynamic estimates. Earth Launch mass is under 11 mt, which is within the estimated capability of a Falcon Heavy, with margin. Total entry masses between 7 and 10 mt were considered with closure occurring between 9 and 10 mt. Propellant mass fractions for each major phase of the EDL - Entry, Terminal Descent, and Hazard Avoidance - have been derived. An assessment of the entry conditions on the thermal protection system (TPS), currently in use for Dragon missions, has been made. And shows no significant stressors. A useful mass of 2.0 mt is provided and includes mass growth allowances for the MAV, the ERV, and mission unique equipment. We also report on alternate propellant options for the MAV and options for the ERV, including propulsion systems; crewed versus robotic retrieval mission; as well as direct Earth entry. International Planetary Protection Policies as well as verifiable means of compliance will have a large impact on any MSR mission design. We identify areas within our architecture where such impacts occur. This work shows that emerging commercial capabilities can be used to effectively integrated into a mission to achieve an important planetary science objective.

Mars Sample Return↗

Implementing Mixed Reality Tools to Support Mission Delivery at Hanford - 20520

Mission Support Alliance's (MSA) Public Works and Information Systems organizations have been working with Microsoft Corporation to develop and implement mixed reality operational solutions using their HoloLens technology. This collaborative effort is intended to drive innovative solutions and significantly improve MSA's efficiency in performing work at the Hanford Site. HoloLens, a mixed reality tool, is a commercial off-the-shelf technology that combines a head-mounted viewing screen with applications to help people and organizations learn, communicate, and collaborate more effectively through the use of mixed reality. https://microsoft.com/en-us/hololens MSA's initial pilot successfully demonstrated its ability to use mixed reality utilizing HoloLens' advanced features in a variety of ways, illustrating the potential efficiency gains previously stated as goals of this pilot. These achievements include the development of proprietary technology that allows synchronization between a HoloLens device and a mobile device or alternate global positioning system (GPS) device. This synchronization enables the HoloLens device to access real time GPS location data anywhere on the Hanford Site. This real time location data, combined with MSA's improved Hanford Geographical Information System (GIS) data, enables the mixed reality pilot application to identify underground utility systems as well as related utility attributes. This ability will aid utility workers in several areas, including excavation activities, the placement of large cranes, identifying interactions and conflicts with future underground utility placements and, eventually, recognizing and de-conflicting tank waste transfer system valve alignments. The HoloLens mixed reality application is also able to provide full or small scale holographic images of a facility's digital twin. This feature will allow MSA's Water and Sewer Utilities team to train and validate procedures associated with the new water treatment facility virtually, before it is constructed. This reduces the amount of time it takes to complete the training and procedure validation, and accelerates the overall construction schedule. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

I-80 Mid-America Clean Fuels Corridor: Deployment Plan Report

The I-80 Mid-America Clean Fuels Corridor, which spans I-80 from Fort Lee, New Jersey, to Council Bluffs, Iowa, was designated an Alternative Fuels Corridor (AFC) in Round 1 of the Alternative Fuels Corridor program administered by the U.S. Department of Transportation’s (DOT’s) Federal Highway Administration (FHWA). Originally called the “I-80 Mid-America Alternative Fuels Corridor,” it is now named the “I-80 Mid-America Clean Fuels Corridor.” As of Round 6 AFC designation, parts of the corridor have sufficient direct current fast charging (DCFC) stations to be designated Electric Vehicle (EV)-Ready and sufficient compressed natural gas (CNG) fueling stations to be designated CNG-Ready. However, much of the corridor’s approximately 1,240 miles (mi) are not yet EV- or CNG-Ready. This includes about 1,130 mi that are designated EV-Pending and 700 mi that are designated CNG-Pending. This report presents a plan to develop EV charging and CNG fueling infrastructure sufficient to convert the entire length of the corridor to EV-Ready and CNG-Ready. Specific sites are not identified for future infrastructure. Rather, priority exits are identified, and information, analysis, and additional steps are recommended to support further refinement of these locations, as well as additional outreach and deployment efforts.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Mobile radio alternative systems study satellite/terrestrial (hybrid) systems concepts

The use of satellites for mobile radio service in non-urban areas of the United States in the years from 1985 to 2000 was investigated. Several satellite concepts are considered: a system with single-beam coverage of the fifty United States and Puerto Rico, and multi-beam satellites with greater capacity. All of the needed functions and services identified in the market study are provided by the satellite systems, including nationwide radio access to vehicles without knowledge of vehicle location wideband data transmission from remote sites, two way exchange of short data and control messages between vehicles and dispatch or control centers, and automatic vehicle location (surveillance). The costs of providing the services are within acceptable limits, and the desired returns to the system investors are attractive. The criteria by which the Federal Communication judges the competing demands for public radio spectrum are reviewed with comments on how the criteria might apply to the consideration of land mobile satellites. Institutional arrangements for operating a mobile satellite system are based on the present institutional arrangements in which the services are offered to the end users through wireline and radio common carriers, with direct access by large private and government users.

Kiesling, J. D.↗

Modulating Electrostatic Interactions in Ion Pair Intermediates To Alter Site Selectivity in the C−O Deoxygenation of Sugars

Abstract Controlling which products one can access from the predefined biomass‐derived sugars is challenging. Changing from CH 2 Cl 2 to the greener alternative toluene alters which C−O bonds in a sugar are cleaved by the tris(pentafluorophenyl)borane/HSiR 3 catalyst system. This increases the diversity of high‐value products that can be obtained through one‐step, high‐yielding, catalytic transformations of the mono‐, di‐, and oligosaccharides. Computational methods helped identify this non‐intuitive outcome in low dielectric solvents to non‐isotropic electrostatic enhancements in the key ion pair intermediates, which influence the reaction coordinate in the reactivity‐/selectivity‐determining step. Molecular‐level models for these effects have far‐reaching consequences in stereoselective ion pair catalysis.

Lowe, Jared M.↗