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DOE OSTI2024

Bifunctional Metal‐Organic Nanoballs Featuring Lewis Acidic and Basic Sites as a New Platform for One‐Pot Tandem Catalysis

Abstract The design and synthesis of polyhedra using coordination‐driven self‐assembly has been an intriguing research area for synthetic chemists. Metal‐organic polyhedra are a class of intricate molecular architectures that have garnered significant attention in the literature due to their diverse structures and potential applications. Hereby, we reportCu‐MOP, a bifunctional metal‐organic cuboctahedra built using 2,6‐dimethylpyridine‐3,5‐dicarboxylic acid and copper acetate at room temperature. The presence of both Lewis basic pyridine groups and Lewis acidic copper sites imparts catalytic activity to Cu‐MOP for the tandem one‐pot deacetalization‐Knoevenagel/Henry reactions. The effect of solvent system and time duration on the yields of the reactions was studied, and the results illustrate the promising potential of these metal‐organic cuboctahedra, also known as nanoballs for applications in catalysis.

Chemistry↗

DOE OSTI2021

Toward the Minimal Floating Operation Count Cholesky Decomposition of Electron Repulsion Integrals

As quantum chemistry calculations deal with molecular systems of increasing size, the memory requirement to store electron-repulsion integrals (ERIs) greatly outpaces the physical memory available in computing hardware. Here, the Cholesky decomposition of ERIs provides a convenient yet accurate technique to reduce the storage requirement of integrals. Recent developments of a two-step algorithm have drastically reduced the memory operation (MOP) count, leaving the floating operation (FLOP) count as the last frontier of cost reduction in the Cholesky ERI algorithm. In this report, we introduce a dynamic integral tracking, reusing, and compression/elimination protocol embedded in the two-step Cholesky ERI method. Benchmark studies suggest that this technique becomes particularly advantageous when the basis set consists of many computationally expensive high-angular-momentum basis functions. With this dynamic ERI improvement, the Cholesky ERI approach proves to be a highly efficient algorithm with minimal FLOP and MOP count.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Imaging and speciation of intracellular metallic implant debris using synchrotron-based X-ray fluorescence micro-spectroscopy: a study of two cases

Debris generated from total hip arthroplasty (THA) components made from metal alloys can cause, in some cases, inflammatory cell (e.g., macrophages) responses that lead to adverse local tissue reactions (ALTR) and implant failure. The lack of information on intracellular chemical alterations of metal debris has hindered the understanding of the pathogenesis of ALTR. The goal of this study was to characterize intracellular debris within macrophages using Synchrotron imaging and spectroscopy. We studied periprosthetic tissues of two retrieved THAs with (1) a metal-on-metal (MoM) articulation and (2) a metal-on-polyethylene (MoP) articulation exhibiting corrosion of the metal femoral head. The MoM-THA exhibited different valence states of chromium- and cobalt-containing debris, suggesting three different moieties: Cr 2 O 3 , CrPO 4 , and an alloy-oxide mixture. The findings further suggest that Cr 2 O 3 formed in the tribological interfaces of the implant, while CrPO 4 is a by-product of the phagocytosis process of cobalt alloy-containing debris. Titanium debris appeared to occur in a mixed crystalline/amorphous oxide state. It remains unclear if this chemical state results from the tribochemical processes at the implant surface or intracellular alterations. The MoP-THA specimen exhibited no intracellular particulate debris associated with macrohpages, indicating that the ALTR may be entirely triggered by metal ionic species in this case. A better understanding of in vivo chemical alteration of implant debris will aid in assessing the risk for ALTR during implant design and material choice. However, various techniques are needed to accurately determine the interaction between metal particles and the inta- and extra-cellular environment.

60 APPLIED LIFE SCIENCES↗

NASA NTRS1976

Imaging air pollutants in the near ultraviolet

This paper discusses a program for remote sensing of air pollutants called Multispectral Observation of Pollutants System (MOPS). The broad objective of the program is to photograph 'invisible' gaseous pollutants by combining ultraviolet imaging in several spectral bands with portable data processing equipment. Electronic cameras using solid state imaging arrays of large dynamic range will permit very low contrast images to be electronically ratioed and contrast enhanced, thus bringing out pollutant images which are below the contrast threshold of film. Such photographs will allow synoptic coverage of geographic areas providing source, sink, and flow data on pollutants, and will provide reconnaissance and pointing information for other remote sensors. The principle gases to be mapped by MOPS will be ozone, sulfur dioxide, and nitrogen dioxide.

Norris, D.↗

NASA NTRS1989

Detection of the earth with the SETI microwave observing system assumed to be operating out in the Galaxy

The maximum range is calculated at which radar signals from the earth could be detected by a search system similar to the NASA SETI Microwave Observing Project (SETI MOP) assumed to be operating out in the Galaxy. Figures are calculated for the Targeted Search and for the Sky Survey parts of the MOP, both planned to be operating in the 1990s. The probability of detection is calculated for the two most powerful transmitters, the planetary radar at Arecibo (Puerto Rico) and the ballistic missile early warning systems (BMEWSs), assuming that the terrestrial radars are only in the eavesdropping mode. It was found that, for the case of a single transmitter within the maximum range, the highest probability is for the sky survey detecting BMEWSs; this is directly proportional to BMEWS sky coverage and is therefore 0.25.

Billingham, John↗

NASA NTRS1991

NASA-SETI microwave observing project: Targeted Search Element (TSE)

The Targeted Search Element (TSE) performs one of two complimentary search strategies of the NASA-SETI Microwave Observing Project (MOP): the targeted search. The principle objective of the targeted search strategy is to scan the microwave window between the frequencies of one and three gigahertz for narrowband microwave emissions eminating from the direction of 773 specifically targeted stars. The scanning process is accomplished at a minimum resolution of one or two Hertz at very high sensitivity. Detectable signals will be of a continuous wave or pulsed form and may also drift in frequency. The TSE will possess extensive radio frequency interference (RFI) mitigation and verification capability as the majority of signals detected by the TSE will be of local origin. Any signal passing through RFI classification and classifiable as an extraterrestrial intelligence (ETI) candidate will be further validated at non-MOP observatories using established protocol. The targeted search will be conducted using the capability provided by the TSE. The TSE provides six Targeted Search Systems (TSS) which independently or cooperatively perform automated collection, analysis, storage, and archive of signal data. Data is collected in 10 megahertz chunks and signal processing is performed at a rate of 160 megabits per second. Signal data is obtained utilizing the largest radio telescopes available for the Targeted Search such as those at Arecibo and Nancay or at the dedicated NASA-SETI facility. This latter facility will allow continuous collection of data. The TSE also provides for TSS utilization planning, logistics, remote operation, and for off-line data analysis and permanent archive of both the Targeted Search and Sky Survey data.

Webster, L. D.↗

NASA NTRS1994

A high-precision radial-velocity survey for other planetary systems

The precise measurement of variations in stellar radial velocities provides one of several promising methods of surveying a large sample of nearby solar type stars to detect planetary systems in orbit around them. The McDonald Observatory Planetary Search (MOPS) was started in 1987 September with the goal of detecting other nearby planetary systems. A stabilized I2 gas absorption cell placed in front of the entrance slit to the McDonald Observatory 2.7 m telescope coude spectrograph serves as the velocity metric. With this I2 cell we can achieve radial velocity measurement precision better than 10 m/s in an individual measurement. At this level we can detect a Jupiter-like planet around a solar-type star, and have some hope of detecting Saturn-like planets in a long-term survey. The detectability of planets is ultimately limited by stellar pulsation modes and photospheric motions. Monthly MOPS observing runs allow us to obtain at least 5 independent observations per year of the 33 solar-type (F5-K7) stars on our observing list. We present representative results from the first five years of the survey.

Cochran, William D.↗

NASA NTRS2002

Lidar Measurements of Wind, Moisture, and Boundary Layer Evolution in a Dry Line during 1HOP 2002

Variability in the convective boundary layer moisture, wind and temperature fields and their importance in the forecasting and understanding of storms have been discussed in the literature. These . variations have been reported in relation to frontal zones, stationary boundaries and during horizontal convective rolls. While all three vary substantially in the convective boundary layer, moisture poses a particular challenge. Moisture or water vapor concentration (expressed as a mass mixing ratio, g/kg), is conserved in all meteorological processes except condensation and evaporation. The water vapor mixing ratio often remains distinct across an air-mass boundary even when the temperature difference is indistinct. These properties make it an ideal choice in visualizing and understanding many of the atmosphere's dynamic features. However, it also presents a unique measurement challenge because water vapor content can vary by more than three orders of magnitude in the troposphere. Characterization of the 3D-distribution of water vapor is also difficult as water vapor observations can suffer from large sampling errors and substantial variability both in the vertical and horizontal. This study presents ground-based measurements of wind, boundary layer structure and water vapor mixing ratio measurements observed by three co-located lidars. This presentation will focus on the evolution and variability of moisture and wind in the boundary layer during a dry line event that occurred on 22 May 2002. These data sets and analyses are unique in that they combine simultaneous measurements of wind, moisture and CBL structure to study the detailed thermal variability in and around clear air updrafts during a dryline event. It will quantify the variation caused by, in and around buoyant plumes and across a dryline. The data presented here were collected in the panhandle of Oklahoma as part of the International H2O Project (MOP-2002), a field experiment that took place over the Southern Great Plains (SGP) of the United States from 13 May to 30 June 2002. The chief goal of MOP-2002 is to improve characterization of the four-dimensional (4-D) distribution of water vapor and its application to improving the understanding and prediction of convection

Demoz, Belay↗

NASA NTRS2003

Moisture, Wind, and Boundary Layer Evolution During a Dryline in IHOP-2002: May 22, 2002

As part of the International H2O Project (MOP-2002), three NASNGSFC lidars acquired high-resolution clear air data of wind, CBL evolution, and water vapor mixing ratio profiles during a dryline event that occurred on 22 May 2002. Together with the anciliary suite of instruments deployed in MOP-2002, these lidar data sets offer a unique look into the mesoscale evolution and convective scale dynamics in and around a dryline.

Demoz, B.↗

NASA NTRS2003

Tropospheric Wind Profiles Obtained with the GLOW Molecular Doppler Lidar during the 2002 International H2O Project

The Goddard Lidar Observatory for Winds (GLOW) is a mobile direct detection Doppler lidar system hich uses the double edge technique to measure the Doppler shift of the molecular backscattered laser signal at a wavelength of 355 nm. In the spring of 2002 GLOW was deployed to the western Oklahoma profiling site (36 deg 33.500 min N, 100 deg 36.371 min W) to participate in the International H2O Project (MOP). During the MOP campaign over 240 hours of wind profiles were obtained with the GLOW lidar in support of a variety of scientific investigations.

Gentry, Bruce M.↗

NASA NTRS2005

Lidar Applications in Atmospheric Dynamics: Measurements of Wind, Moisture and Boundary Layer Evolution

A large array of state-of-the-art ground-based and airborne remote and in-situ sensors were deployed during the International H2O Project (THOP), a field experiment that took place over the Southern Great Plains (SGP) of the United States from 13 May to 30 June 2002. These instruments provided extensive measurements of water vapor mixing ratio in order to better understand the influence of its variability on convection and on the skill of quantitative precipitation prediction (Weckwerth et all, 2004). Among the instrument deployed were ground based lidars from NASA/GSFC that included the Scanning Raman Lidar (SRL), the Goddard Laboratory for Observing Winds (GLOW), and the Holographic Airborne Rotating Lidar Instrument Experiment (HARLIE). A brief description of the three lidars is given below. This study presents ground-based measurements of wind, boundary layer structure and water vapor mixing ratio measurements observed by three co-located lidars during MOP at the MOP ground profiling site in the Oklahoma Panhandle (hereafter referred as Homestead). This presentation will focus on the evolution and variability of moisture and wind in the boundary layer when frontal and/or convergence boundaries (e.g. bores, dry lines, thunderstorm outflows etc) were observed.

Demoz, Belay↗

NASA NTRS2016

Flight Test Overview for UAS Integration in the NAS Project

The National Aeronautics and Space Administration is conducting a series of flight tests intended to support the reduction of barriers that prevent unmanned aircraft from flying without the required waivers from the Federal Aviation Administration. The most recent testing supported two separate test configurations. The first investigated the timing of Detect and Avoid (DAA) alerting thresholds using a radar-equipped unmanned vehicle and multiple live intruders flown at varying encounter geometries. The second configuration included a surrogate unmanned vehicle (flown from a ground control station, with a safety pilot on board) flying a mission in a virtual air traffic control airspace sector using research pilot displays and DAA advisories to maintain separation from live and virtual aircraft. The test was conducted over a seven-week span in the summer of 2015. The data from over 100 encounter sorties will be used to inform the RTCA Phase 1 Detect and Avoid and Command and Control Minimum Operating Performance Standards (MOPS) intended to be completed by the summer of 2016. Follow-on flight-testing is planned for the spring of 2016 to capture remaining encounters and support validation of the MOPS.

UAS↗

NASA NTRS2015

Analysis of UAS DAA Alerting in Fast-Time Simulations without DAA Mitigation

Realization of the expected proliferation of Unmanned Aircraft System (UAS) operations in the National Airspace System (NAS) depends on the development and validation of performance standards for UAS Detect and Avoid (DAA) Systems. The RTCA Special Committee 228 is charged with leading the development of draft Minimum Operational Performance Standards (MOPS) for UAS DAA Systems. NASA, as a participating member of RTCA SC-228 is committed to supporting the development and validation of draft requirements for DAA alerting system performance. A recent study conducted using NASA's ACES (Airspace Concept Evaluation System) simulation capability begins to address questions surrounding the development of draft MOPS for DAA alerting systems. ACES simulations were conducted to study the performance of alerting systems proposed by the SC-228 DAA Alerting sub-group. Analysis included but was not limited to: 1) correct alert (and timeliness), 2) false alert (and severity and duration), 3) missed alert, and 4) probability of an alert type at the time of loss of well clear. The performance of DAA alerting systems when using intent vs. dead-reckoning for UAS ownship trajectories was also compared. The results will be used by SC-228 to inform decisions about the surveillance standards of UAS DAA systems and future requirements development and validation efforts.

alerting↗

NASA NTRS2015

Analysis of UAS DAA Surveillance in Fast-Time Simulations without DAA Mitigation

Realization of the expected proliferation of Unmanned Aircraft System (UAS) operations in the National Airspace System (NAS) depends on the development and validation of performance standards for UAS Detect and Avoid (DAA) Systems. The RTCA Special Committee 228 is charged with leading the development of draft Minimum Operational Performance Standards (MOPS) for UAS DAA Systems. NASA, as a participating member of RTCA SC-228 is committed to supporting the development and validation of draft requirements for DAA surveillance system performance. A recent study conducted using NASA's ACES (Airspace Concept Evaluation System) simulation capability begins to address questions surrounding the development of draft MOPS for DAA surveillance systems. ACES simulations were conducted to study the performance of sensor systems proposed by the SC-228 DAA Surveillance sub-group. Analysis included but was not limited to: 1) number of intruders (both IFR and VFR) detected by all sensors as a function of UAS flight time, 2) number of intruders (both IFR and VFR) detected by radar alone as a function of UAS flight time, and 3) number of VFR intruders detected by all sensors as a function of UAS flight time. The results will be used by SC-228 to inform decisions about the surveillance standards of UAS DAA systems and future requirements development and validation efforts.

unmanned aircraft systems↗

NASA NTRS2016

ACES M and S: Unmitigated Factorial Encounter Study on DAA/TCAS Interoperability

Realization of the expected proliferation of Unmanned Aircraft System (UAS) operations in the National Airspace System (NAS) depends on the development and validation of standards for UAS Detect and Avoid (DAA) Systems. The RTCA Special Committee 228 is charged with leading the development of draft Minimum Operational Performance Standards (MOPS) for UAS DAA Systems. NASA, as a participating member of RTCA SC-228 is committed to supporting the development and validation of draft requirements for DAA alerting and guidance systems. This presentation contains the results of two combinatorial encounter analysis studies using NASA's SAA Control fast-time simulation capability for this purpose. In these studies, encounters between two aircraft were simulated one at a time for the full factorial combination of encounter geometries (e.g., encounter angle, CPA offset) and aircraft performance (e.g., ownership and intruder ground speeds and vertical rates). The first study analyzes the relationships (e.g., timeline) between the different alerting-safety regions in the SC-228 MOPS (in order of increasing severity): 1) DAA warning alert, 2) well clear recovery (WCR) guidance, 3) DAA-Collision Avoidance (CA), and 4) TCAS RA. This study will focus primarily on encounter situations in which TCAS RA occurs prior to any of the other alerting-safety boundaries. In particular, this study will investigate whether using vertical distance or vertical distance at closest point of approach (i.e., vertical miss distance or VMD) is more appropriate for the definition of the DAA-CA region. In addition, cases where transitions between different regions skip an intermediate region will be analyzed. The second study in this presentation explores a proposal to use an altitude rate error threshold to determine if vertical maneuvers are acceptable for DAA WCR guidance against non-cooperative intruders. This study incorporates the radar from the Honeywell sensor model and examines a series of pairwise encounters between a non-cooperative intruder and a UAS ownship, with different combinations of intruder states and ownship performance levels. The study uses SAA Control as a simulation platform and pilot model, and Omnibands to provide DWC recovery guidance. Two simulation sets, one that allows vertical DWC recovery guidance and one that does not, are compared to determine if encounters with altitude rate errors above 250 feet-per-minute are more likely to have more severe losses of well clear, as determined by the Loss of Well-Clear Severity metric.

SaaControl↗

NASA NTRS2016

UAS Integration in the NAS Project: Flight Test 3 Data Analysis of JADEM-Autoresolver Detect and Avoid System

The Unmanned Aircraft Systems Integration in the National Airspace System project, or UAS Integration in the NAS, aims to reduce technical barriers related to safety and operational challenges associated with enabling routine UAS access to the NAS. The UAS Integration in the NAS Project conducted a flight test activity, referred to as Flight Test 3 (FT3), involving several Detect-and-Avoid (DAA) research prototype systems between June 15, 2015 and August 12, 2015 at the Armstrong Flight Research Center (AFRC). This report documents the flight testing and analysis results for the NASA Ames-developed JADEM-Autoresolver DAA system, referred to as 'Autoresolver' herein. Four flight test days (June 17, 18, 22, and July 22) were dedicated to Autoresolver testing. The objectives of this test were as follows: 1. Validate CPA prediction accuracy and detect-and-avoid (DAA, formerly known as self-separation) alerting logic in realistic flight conditions. 2. Validate DAA trajectory model including maneuvers. 3. Evaluate TCAS/DAA interoperability. 4. Inform final Minimum Operating Performance Standards (MOPS). Flight test scenarios were designed to collect data to directly address the objectives 1-3. Objective 4, inform final MOPS, was a general objective applicable to the UAS in the NAS project as a whole, of which flight test is a subset. This report presents analysis results completed in support of the UAS in the NAS project FT3 data review conducted on October 20, 2015. Due to time constraints and, to a lesser extent, TCAS data collection issues, objective 3 was not evaluated in this analysis.

flight test↗

NASA NTRS2017

Unmanned Aircraft Systems Minimum Operations Performance Standards End-to-End Verification and Validation (E2-V2) Simulation

As Unmanned Aircraft Systems (UAS) make their way to mainstream aviation operations within the National Airspace System (NAS), research efforts are underway to develop a safe and effective environment for their integration into the NAS. Detect and Avoid (DAA) systems are required to account for the lack of "eyes in the sky" due to having no human on-board the aircraft. The current NAS relies on pilot's vigilance and judgement to remain Well Clear (CFR 14 91.113) of other aircraft. RTCA SC-228 has defined DAA Well Clear (DAAWC) to provide a quantified Well Clear volume to allow systems to be designed and measured against. Extended research efforts have been conducted to understand and quantify system requirements needed to support a UAS pilot's ability to remain well clear of other aircraft. The efforts have included developing and testing sensor, algorithm, alerting, and display requirements. More recently, sensor uncertainty and uncertainty mitigation strategies have been evaluated. This paper discusses results and lessons learned from an End-to-End Verification and Validation (E2-V2) simulation study of a DAA system representative of RTCA SC-228's proposed Phase I DAA Minimum Operational Performance Standards (MOPS). NASA Langley Research Center (LaRC) was called upon to develop a system that evaluates a specific set of encounters, in a variety of geometries, with end-to-end DAA functionality including the use of sensor and tracker models, a sensor uncertainty mitigation model, DAA algorithmic guidance in both vertical and horizontal maneuvering, and a pilot model which maneuvers the ownship aircraft to remain well clear from intruder aircraft, having received collective input from the previous modules of the system. LaRC developed a functioning batch simulation and added a sensor/tracker model from the Federal Aviation Administration (FAA) William J. Hughes Technical Center, an in-house developed sensor uncertainty mitigation strategy, and implemented a pilot model similar to one from the Massachusetts Institute of Technology's Lincoln Laboratory (MIT/LL). The resulting simulation provides the following key parameters, among others, to evaluate the effectiveness of the MOPS DAA system: severity of loss of well clear (SLoWC), alert scoring, and number of increasing alerts (alert jitter). The technique, results, and lessons learned from a detailed examination of DAA system performance over specific test vectors and encounter cases during the simulation experiment will be presented in this paper.

Ghatas, Rania W.↗

NASA NTRS2017

DANTi: Detect and Avoid iN The Cockpit

Mid-air collision risk continues to be a concern for manned aircraft operations, especially near busy non-towered airports. The use of Detect and Avoid (DAA) technologies and draft standards developed for unmanned aircraft systems (UAS), either alone or in combination with other collision avoidance technologies, may be useful in mitigating this collision risk for manned aircraft. This paper describes a NASA research effort known as DANTi (DAA iN The Cockpit), including the initial development of the concept of use, a software prototype, and results from initial flight tests conducted with this prototype. The prototype used a single Automatic Dependent Surveillance - Broadcast (ADS-B) traffic sensor and the own aircraft's position, track, heading and air data information, along with NASA-developed DAA software to display traffic alerts and maneuver guidance to manned aircraft pilots on a portable tablet device. Initial flight tests with the prototype showed a successful DANTi proof-of-concept, but also demonstrated that the traffic separation parameter set specified in the RTCA SC-228 Phase I DAA MOPS may generate excessive false alerts during traffic pattern operations. Several parameter sets with smaller separation values were also tested in flight, one of which yielded more timely alerts for the maneuvers tested. Results from this study may further inform future DANTi efforts as well as Phase II DAA MOPS development.

Chamberlain, James↗