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At least 1,297 records · Page 72

Structural Manipulation of a Zirconocene-Based Porous Coordination Cage Using External and Host–Guest Stimuli

Porous coordination cages (PCCs) constructed from a zirconocene-based cluster have drawn great attention for their high stability and structural tunability. These features have enabled these cages to be utilized for a wide array of applications. Here this work demonstrates the structural flexibility and stimulus-responsive features of two interconvertible zirconocene-based PCCs. The subjects, PCC-20c (capsular) and PCC-20t (tetrahedral), are constructed from the same cluster and ligand but exhibit different shapes and properties. In the synthetic study of the cages, it is found that higher temperatures of synthesis yield PCC-20c in several different crystalline phases while lower temperatures of synthesis yield pure phase PCC-20t. Thermodynamic studies on the interconversion of the two cages show that the conversion from PCC-20t into PCC-20c is an entropically driven process and can be largely affected by the solvent environment. Additionally, the process of PCC-20t/c conversion can be mediated by the counter anions and light irradiation as evidenced by the change in equilibrium constants under these influences. The current studies are conducted to decipher how the PCC-20t/c phase can be controllably synthesized, interconverted, and their properties can be modified under the use of external stimuli: heat, light, and guest molecules.

36 MATERIALS SCIENCE↗

Observation of a promethium complex in solution

Lanthanide rare-earth metals are ubiquitous in modern technologies, but we know little about chemistry of the 61st element, promethium (Pm), a lanthanide that is highly radioactive and inaccessible. Despite its importance, Pm has been conspicuously absent from the experimental studies of lanthanides, impeding our full comprehension of the so-called lanthanide contraction phenomenon: a fundamental aspect of the periodic table that is quoted in general chemistry textbooks. Here we demonstrate a stable chelation of the 147 Pm radionuclide (half-life of 2.62 years) in aqueous solution by the newly synthesized organic diglycolamide ligand. The resulting homoleptic Pm III complex is studied using synchrotron X-ray absorption spectroscopy and quantum chemical calculations to establish the coordination structure and a bond distance of promethium. These fundamental insights allow a complete structural investigation of a full set of isostructural lanthanide complexes, ultimately capturing the lanthanide contraction in solution solely on the basis of experimental observations. Our results show accelerated shortening of bonds at the beginning of the lanthanide series, which can be correlated to the separation trends shown by diglycolamides. The characterization of the radioactive Pm III complex in an aqueous environment deepens our understanding of intra-lanthanide behaviour and the chemistry and separation of the f-block elements.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Pilot land data system

During the fall of 1983, the Information Systems Office of NASA's Office of Space Science and Applications assembled a Working Group to develop initial plans for a Pilot Land Data System (PLDS). Workshops coordinated planning and concept development activities between land-related and computer science disciplines, and examined land research requirements, information science technology requirements, PLDS architecture, and methodologies for system evaluation. The PLDS will be a limited-scale distributed information system to explore scientific, technical and management approaches to satisfy land science research needs. PLDS will pave the way for a Land Data System to improve data access, processing, transfer and analysis, fostering an environment in which land science information synthesis can occur on a scale not previously possible owing to limits to data assembly and access and efficiency of processing.

Cressy, P. J.↗

Development of a residual acceleration data reduction and dissemination plan

A major obstacle in evaluating the residual acceleration environment in an orbiting space laboratory is the amount of data collected during a given mission: gigabytes of data will be available as SAMS units begin to fly regularly. Investigators taking advantage of the reduced gravity conditions of space should not be overwhelmed by the accelerometer data which describe these conditions. We are therefore developing a data reduction and analysis plan that will allow principal investigators of low-g experiments to create experiment-specific residual acceleration data bases for post-flight analysis. The basic aspects of the plan can also be used to characterize the acceleration environment of earth orbiting laboratories. Our development of the reduction plan is based on the following program of research: the identification of experiment sensitivities by order of magnitude estimates and numerical modelling; evaluation of various signal processing techniques appropriate for the reduction, supplementation, and dissemination of residual acceleration data; and testing and implementation of the plan on existing acceleration data bases. The orientation of the residual acceleration vector with respect to some set of coordinate axes is important for experiments with known directional sensitivity. Orientation information can be obtained from the evaluation of direction cosines. Fourier analysis is commonly used to transform time history data into the frequency domain. Common spectral representations are the amplitude spectrum which gives the average of the components of the time series at each frequency and the power spectral density which indicates the power or energy present in the series per unit frequency interval. The data reduction and analysis scheme developed involves a two tiered structure to: (1) identify experiment characteristics and mission events that can be used to limit the amount of accelerator data an investigator should be interested in; and (2) process the data in a way that will be meaningful to the experiment objectives. A general outline of the plan is given.

Rogers, Melissa J. B.↗

Sloshing dynamics modulated angular momentum fluctuations actuated by gravity gradient acceleration associated with spacecraft slew motion

The mathematical formulation of orbital spacecraft sloshing dynamics for a partially filled cryogenic superfluid liquid helium II in a dewar container actuated by the gravity gradient acceleration associated with slew motion is studied. The Advanced X-Ray Astrophysics Facility-Spectroscopy (AXAF-S) spacecraft is chosen as a practical example in this study. Explicit mathematical expressions which manage orbital galaxy gradient acceleration with slew motion which is acting on the spacecraft fluid systems are derived. The numerical computation of sloshing dynamics is based on the non-inertia frame spacecraft bound coordinates and the solution of time-dependent, three-dimensional formulations of partial differential equations subject to initial and boundary conditions. This study discloses the capillary effect of sloshing dynamics governed liquid-vapor interface fluctuations, angular momentum and moment fluctuations of fluid system, and also buble mass center fluctuations driven by the gravity gradient acceleration associated with slew motion which affects the stability of the orbital spacecraft fluid system in a microgravity environment.

Hung, R. J.↗

NASA/Mir Phase 1: A Lesson Learned in Long Duration Mission Planning and Operations

The NASA/Mir Phase I Program is a precursor to the assembly and operations of the International Space Station (ISS). The Phase I Program covers a four-year period and encompasses over ten shuttle flights to the Mir, culminating with the flight of STS-91 in June 1998. The Mir-Orbiting Station (Mir-OS) provides an excellent environment, both onboard and on the ground, for learning and studying the characteristics associated with crew-tended operations on long duration missions. By the end of the Phase I program, NASA astronauts will have accumulated over two years of continuous operations experience working and living onboard the Mir-OS. Ground controllers, working in Russia and at remote sites in the United States, will have gained valuable experience in the generation, maintenance, and coordination of the information and products required to support the long duration crew members onboard the Mir-OS. The experience gained by the crew and ground support personnel in the area of long duration mission operations has resulted in a number of factors that need to be considered in the definition and implementation of the processes and products for the ISS. While there are many areas in which experience has been gained, this paper focuses on the lessons learned regarding the level of detail and flexibility of crew timelines. Provided in this paper is an overview of the characteristics associated with long duration mission timeline development and execution, a summary of applicable lessons learned identified and documented through participation in the NASA/Mir Phase I Program, a detailed discussion of "Gross Timelines" as implementation which addresses the lessons learned. Also discussed are the challenges that must be overcome in getting the ISS program to recognize, evaluate, and learn from the crew and ground controller experience gained through participation in the NASA/Mir Phase I Program.

Hagopian, Jeff↗

Hand-Eye Calibration of Robonaut

NASA's Human Space Flight program depends heavily on Extra-Vehicular Activities (EVA's) performed by human astronauts. EVA is a high risk environment that requires extensive training and ground support. In collaboration with the Defense Advanced Research Projects Agency (DARPA), NASA is conducting a ground development project to produce a robotic astronaut's assistant, called Robonaut, that could help reduce human EVA time and workload. The project described in this paper designed and implemented a hand-eye calibration scheme for Robonaut, Unit A. The intent of this calibration scheme is to improve hand-eye coordination of the robot. The basic approach is to use kinematic and stereo vision measurements, namely the joint angles self-reported by the right arm and 3-D positions of a calibration fixture as measured by vision, to estimate the transformation from Robonaut's base coordinate system to its hand coordinate system and to its vision coordinate system. Two methods of gathering data sets have been developed, along with software to support each. In the first, the system observes the robotic arm and neck angles as the robot is operated under external control, and measures the 3-D position of a calibration fixture using Robonaut's stereo cameras, and logs these data. In the second, the system drives the arm and neck through a set of pre-recorded configurations, and data are again logged. Two variants of the calibration scheme have been developed. The full calibration scheme is a batch procedure that estimates all relevant kinematic parameters of the arm and neck of the robot The daily calibration scheme estimates only joint offsets for each rotational joint on the arm and neck, which are assumed to change from day to day. The schemes have been designed to be automatic and easy to use so that the robot can be fully recalibrated when needed such as after repair, upgrade, etc, and can be partially recalibrated after each power cycle. The scheme has been implemented on Robonaut Unit A and has been shown to reduce mismatch between kinematically derived positions and visually derived positions from a mean of 13.75cm using the previous calibration to means of 1.85cm using a full calibration and 2.02cm using a suboptimal but faster daily calibration. This improved calibration has already enabled the robot to more accurately reach for and grasp objects that it sees within its workspace. The system has been used to support an autonomous wrench-grasping experiment and significantly improved the workspace positioning of the hand based on visually derived wrench position. estimates.

Nickels, Kevin↗

The terrestrial gravitational wave environment from known sources

The objective of this project was to produce a gravitational wave spectral line list of all known binary stars producing expected strain amplitudes at Earth in excess of h = 10 (exp -21), or gravitational wave fluxes in excess of F = 10 (exp -12) erg cm(exp -2) s(exp -1). These strain and flux limits lie above the anticipated detection thresholds for space-borne laser interferometers capable of detecting gravitational radiation in the 10 micron Hz to 1 Hz frequency range. The source list was intended to provide frequency (including each harmonic), amplitude and phase (for each polarization and harmonic), and celestial coordinates for each system, lacking only the orientation of the principal polarization axis with respect to the pole of the coordinate system, and the sign of the source phase and frequency (or, equivalently, of the sense of rotation of the strain tensor with time) from providing a complete source description. Such a spectral line list would lay essential groundwork for high-sensitivity, low-frequency searches for gravitational radiation.

Webbink, Ronald F.↗

Vibrational signature of hydrated protons confined in MXene interlayers

Here, the hydration structure of protons has been studied for decades in bulk water and protonated clusters due to its importance but has remained elusive in planar confined environments. Two-dimensional (2D) transition metal carbides known as MXenes show extreme capacitance in protic electrolytes, which has attracted attention in the energy storage field. We report here that discrete vibrational modes related to protons intercalated in the 2D slits between Ti 3 C 2 T x MXene layers can be detected using operando infrared spectroscopy. The origin of these modes, not observed for protons in bulk water, is attributed to protons with reduced coordination number in confinement based on Density Functional Theory calculations. This study therefore demonstrates a useful tool for the characterization of chemical species under 2D confinement.

36 MATERIALS SCIENCE↗

Online Optimization for Networked Distributed Energy Resources With Time-Coupling Constraints

This paper proposes a Lyapunov optimization-based online distributed (LOOD) algorithmic framework for active distribution networks (ADNs) with numerous photovoltaic inverters and inverter air conditionings (IACs). In the proposed scheme, ADNs can track an active power setpoint reference at the substation in response to transmission-level requests while concurrently minimizing the social utility loss and ensuring the security of voltages. Conventional distributed optimization methods are rarely feasible to track the optimal solutions in fast variable environments using a fine-grained sampling interval where the underlying optimization problem evolves with the iterations of the algorithms. In contrast, based on the framework of online convex optimization (OCO), the developed approach uses a distributed algebraic update to compute the next round decisions relying on the current feedback of measurements. Notably, the time-coupling constraints of IACs are decoupled for online implementation with Lyapunov optimization technique. An incentive scheme is tailored to coordinate the customer-owned assets in lieu of the direct control from network operators. Optimality and convergency are characterized analytically. Finally, we corroborate the proposed method on a modified version of 33-node test feeder. Benchmark tests show that the proposed method is computationally and economically efficient, and outperforming existing algorithms.

active distribution networks↗

Effects of prolonged exposure to pure oxygen on human performance

In view of the pure oxygen atmosphere selected for Project Mercury, and in anticipation of subsequent manned space missions of increasing duration, it was apparent that there was a need to obtain more extensive physiological data on the prolonged effects of pure oxygen environments on the crews. This study, conducted by Republic Aviation Corporation under Contract NASR-92, was initiated in collaboration with General Charles Roadman, USAF (MC), Director of Aerospace Medicine (formerly the Office of Life Sciences, NASA Headquarters), and his staff in an effort to provide a greater breadth of scientific data on the prolonged effects of such an environment on human performance. Although the 5 psi environment of Project Mercury was the focal point of the study, a broader appraisal of the effects of pure oxygen in the absence of nitrogen was attempted by including studies at 7.4 psi and 3.8 psi in addition to a control group at sea level atmospheric conditions. After award of the contract, the technical monitoring of the study was provided by the Manned Spacecraft Center, Houston, Texas, where Mr. Edward Michel served as monitor and coordinator for these and related studies subsequently established in laboratories of the U.S. Navy and U. S. Air Force.

PSYCHOLOGICAL EFFECT↗

A Flight-Calibrated Methodology for Determination of Cassini Thruster On-Times for Reaction Wheel Biases

This paper describes a methodology for accurate and flight-calibrated determination of the on-times of the Cassini spacecraft Reaction Control System (RCS) thrusters, without any form of dynamic simulation, for the reaction wheel biases. The hydrazine usage and the delta V vector in body frame are also computed from the respective thruster on-times. The Cassini spacecraft, the largest and most complex interplanetary spacecraft ever built, continues to undertake ambitious and unique scientific observations of planet Saturn, Titan, Enceladus, and other moons of Saturn. In order to maintain a stable attitude during the course of its mission, this three-axis stabilized spacecraft uses two different control systems: the RCS and the reaction wheel assembly control system. The RCS is used to execute a commanded spacecraft slew, to maintain three-axis attitude control, control spacecraft's attitude while performing science observations with coarse pointing requirements, e.g. during targeted low-altitude Titan and Enceladus flybys, bias the momentum of reaction wheels, and to perform RCS-based orbit trim maneuvers. The use of RCS often imparts undesired delta V on the spacecraft. The Cassini navigation team requires accurate predictions of the delta V in spacecraft coordinates and inertial frame resulting from slews using RCS thrusters and more importantly from reaction wheel bias events. It is crucial for the Cassini spacecraft attitude control and navigation teams to be able to, quickly but accurately, predict the hydrazine usage and delta V for various reaction wheel bias events without actually having to spend time and resources simulating the event in flight software-based dynamic simulation or hardware-in-the-loop simulation environments. The methodology described in this paper, and the ground software developed thereof, are designed to provide just that. This methodology assumes a priori knowledge of thrust magnitudes and thruster pulse rise and tail-off time constants for eight individual attitude control thrusters, the spacecraft's wet mass and its center of mass location, and a few other key parameters.

Earth Mean Equatorial↗

Impact of Different Trajectory Option Set Participation Levels within an Air Traffic Management Collaborative Trajectory Option Program

This paper presents the methodology and results of a Human-In-The-Loop (HITL) simulation study conducted in the Airspace Operations Laboratory at NASA Ames Research Center. This study is a part of NASA's ongoing research into developing an Integrated Demand Management (IDM) concept, whose aim is to improve traffic flow management (TFM) by coordinating the FAA's strategic Traffic Flow Management System (TFMS) with its more tactical Time-Based Flow Management (TBFM) system. The purpose of TFM is to regulate air traffic demand so that it is delivered efficiently through constrained airspace resources without exceeding their capacity limits. The IDM concept leverages a new TFMS capability called the Collaborative Trajectory Options Program (CTOP) to strategically pre-condition traffic demand flowing into a TBFM-managed arrival environment, where TBFM is responsible for managing traffic tactically by generating precise arrival schedules. Unlike other TFM tools, CTOP gives flight operators the option of submitting a set of user-preferred alternative trajectories for each flight. CTOP can then use these trajectory option sets (or TOSs) to find user-preferred alternative routes to reduce demand on an overloaded resource. CTOP's effectiveness in redistributing demand is limited, however, by the availability of flights with alternative routes. The research presented in this paper focuses on evaluating the impact on TFM operations by varying the percentage of flights that submit a multiple-option TOS ('TOS participation levels'). Results show the impact on overall system performance and on the rerouted flights themselves. The simulation used a Newark (EWR) airport arrival scenario, with en route weather affecting traffic inbound from the west. Participants were asked to control each of the three arrival flows (north, west, and south) to meet their individual capacity constraints while simultaneously ensuring efficient utilization of the capacity at the destination airport. A large, permeable convective weather cell located southeast of Chicago severely reduced the capacity of the west flow. The study evaluated the impact of five different TOS participation levels on CTOP's ability to re-allocate traffic from the west and improve TFM performance in terms of delay assignment and traffic delivery rate to the airport. Overall, the results showed that increasing TOS submissions allowed the overall system delays to be reduced and fairly distributed among the three arrival flows, at the same time achieving the airport throughput rate. Moreover, it was found that aircraft who submitted a TOS saw a greater reduction in delay, even when they were assigned longer routes. This was particularly true when fewer aircraft submitted a TOS. The results confirm that the CTOP operations with higher TOS participation levels helped utilize the overall National Airspace System (NAS) resources as well as benefited the users who participated.

Yoo, Hyo-Sang↗

Flash Communication: Flexibility of a Biologically Inspired Ligand Framework for Intramolecular C–H Activation

High-valent iron complexes play a crucial role in the oxidation of organic substrates, especially in C–H bond functionalization reactions in biology. This paper investigates the reactivity of nonporphyrin tripodal ligands featuring a secondary coordination sphere, focusing on their prospective ability to stabilize high-valent iron-oxo species. Using NMR spectroscopy and X-ray crystallography, we detail the formation of an Fe(III)-alkoxide complex through intramolecular C–H bond activation, providing insight into the potential transient formation of a high-valent iron-oxo intermediate. While attempts to observe an Fe(IV)-oxo complex were unsuccessful, our findings underscore the significance of the ligand electronic environment in stabilizing reactive iron species for C–H bond activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bonding and reactivity of isostructural uranyl and neptunyl peroxide phases

Understanding the reactivity of actinide peroxides is critical for predicting the behavior of spent nuclear fuel in radiolytic environments. Herein, we report the synthesis and characterization of a lithium neptunyl(VI) hydroxo peroxo compound (LiNp), which is isostructural to the uranyl analogue (LiU). Single-crystal X-ray diffraction reveals that LiNp contains both [NpO 2 (O 2 ) 3 ] 4- and [NpO 2 (OH) 4 ] 2- units stabilized by Li + and hydrogen bonding and Raman spectroscopy shows systematic redshifts in neptunyl vibrational modes relative to uranyl. DFT calculations highlight the importance of secondary coordination in reproducing vibrational and structural features, but challenges remain with correctly modeling strong sigma donors. Solid-state EPR spectroscopy and DFT confirm superoxide stabilization within LiU and calculations suggest favorability of the analogous radical species in LiNp. Solution state EPR spectroscopy with the radical spin trap 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide (BMPO) reveal evidence of superoxide in the LiU and LiNp phases and suggests stabilization of superoxide within actinyl triperoxide complexes, forming [AnO 2 (O 2 ) 2 (O) 2 • ] 3- .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Synthesis, structure, and electrochemical properties of [LNi(R f )(C 4 F 8 )] - and [LNi(R f ) 3 ] - complexes

The new anionic nickelate complexes [(MeCN)Ni(C 4 F 8 )(CF 3 )] -, [(MeCN)Ni(C 4 F 8 )(C 2 F 5 )] - , [(IMes)Ni(C 4 F 8 )(CF 3 )] - , [(IMes)Ni(CF 3 ) 3 ] - (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), and [(F-NHC)Ni(Rf) 3 ] - (F-NHC = 1,3-bis(2,4-F2Ph), 2,4,6-F 3 Ph- or 3,4,5-F 3 Ph)imidazol-2-ylidene; (R f = CF 3 or C 2 F 5 ) were synthesized and structurally characterized. The electrochemical properties of all new compounds were revealed by cyclic voltammetry studies and compared to the known CF 3 analogue [(MeCN)Ni(CF 3 ) 3 ] -. The IMes-coordinated complexes exhibited initial oxidation events that were well-separated from a second oxidation process in the cyclic voltammograms. The complexes containing F-substituted NHC ligands [(F-NHC)Ni(CF 3 ) 3 ] - are structurally quite similar to the IMes derivative and reveal also two separated oxidation waves in their cyclic voltammograms. The absolute potentials as well as the separation between the two waves vary with the substitution pattern, suggesting that the NHC ligand environment (NHC = N-heterocyclic carbene) is an interesting platform for the development of new redox-triggered reactions that release trifluoromethyl and perfluoroalkyl radicals upon oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accurate prediction of global-density-dependent range-separation parameters based on machine learning

In this work, we develop an accurate and efficient XGBoost machine learning model for predicting the global-density-dependent range-separation parameter, ωGDD, for long-range corrected functional (LRC)-ωPBE. This ωGDDML model has been built using a wide range of systems (11 466 complexes, ten different elements, and up to 139 heavy atoms) with fingerprints for the local atomic environment and histograms of distances for the long-range atomic correlation for mapping the quantum mechanical range-separation values. The promising performance on the testing set with 7046 complexes shows a mean absolute error of 0.001 117 a0−1 and only five systems (0.07%) with an absolute error larger than 0.01 a0−1, which indicates the good transferability of our ωGDDML model. In addition, the only required input to obtain ωGDDML is the Cartesian coordinates without electronic structure calculations, thereby enabling rapid predictions. LRC-ωPBE(ωGDDML) is used to predict polarizabilities for a series of oligomers, where polarizabilities are sensitive to the asymptotic density decay and are crucial in a variety of applications, including the calculations of dispersion corrections and refractive index, and surpasses the performance of all other popular density functionals except for the non-tuned LRC-ωPBE. Finally, LRC-ωPBE (ωGDDML) combined with (extended) symmetry-adapted perturbation theory is used in calculating noncovalent interactions to further show that the traditional ab initio system-specific tuning procedure can be bypassed. The present study not only provides an accurate and efficient way to determine the range-separation parameter for LRC-ωPBE but also shows the synergistic benefits of fusing the power of physically inspired density functional LRC-ωPBE and the data-driven ωGDDML model.

Chemistry↗

Direct Demonstration of Unified Brønsted-Evans-Polanyi Relationships for Proton-Coupled Electron Transfer Reactions on Transition Metal Surfaces

Brønsted-Evans-Polanyi (BEP) relationships, which relate elementary reaction barriers to reaction thermodynamics, have long been discussed in electrochemical science, but demonstration of their existence in heterogeneous electrocatalysis, across many different catalyst surfaces and voltages, is lacking. In this contribution, the BEP model is demonstrated to describe both multiple catalyst surfaces and variable voltages in electrochemical environments. For proton-coupled electron transfer (PCET) to surface nitrogen (N*) and nitric oxide (NO*), reaction energies and activation barriers are calculated using Density Functional Theory (DFT) on a parallel plate capacitor model at three different potentials and for nine different transition metal surfaces. Linear BEP relations that describe all potentials and catalyst surfaces are obtained for these elementary reactions, and the slopes of the correlations are shown to be directly related to the fractional coordinate of the transition states (FCTS) of the reactions. The results, which are explained in terms of Marcus Theory, prove a direct equivalence between unified BEP coefficients, describing both variable catalyst surfaces and voltages, and electrochemical symmetry factors and provide a straightforward means of estimating this quantify for PCET reactions on transition metal surfaces. The resulting relationships, in turn, could lead to predictions of electrocatalytic reactivity trends of enhanced accuracy and efficiency.

Electrochemistry↗