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At least 1,027 records · Page 57

Observing the three-dimensional dynamics of supported metal complexes

Dynamics are intricately linked with activity and selectivity when it comes to catalysis, as noted for instance in the enzymatic principles of induced fit and allostery, and yet the range of motions heterogeneous catalytic sites are able to undergo is poorly understood. Solid-state nuclear magnetic resonance (NMR) spectroscopy is perhaps the only tool capable of probing the rapid conformational dynamics found in heterogeneous catalysts but has historically been restricted by its low sensitivity, limiting the detail with which structures can be resolved. In this work, we apply solid-state NMR and dynamic nuclear polarization, in combination with density functional theory modeling, to reveal the high-resolution structure and motional freedom of a scandium supported complex in three dimensions. The results are contrasted with the study of the analogous homoleptic complex in the crystalline state, highlighting the impacts that surface structure may have on the dynamics of supported complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cyber Attack Sequences Generation for Electric Power Grid

Security assessment of cyber-physical energy systems (CPESs) such as the electric power grid is a critical operation to maintain availability, reliability, and quality of service in the presence of persistent threats from malicious cyber actors. Existing security assessment approaches such as penetration testing and red teaming rely on subject matter expert experience and forensic cyber analysis of historical events to perform realistic, threat-informed assessments of CPES defense. CPESs have a large attack surface because of the heterogeneity and complexity of underlying topology, devices, measurements, and vulnerabilities. The aforementioned approaches lead to partial coverage of the attack surface with a large set of unknown but possible exploits. There is a need to automate the CPES attack surface discovery and contextualize it for relevant, highly probable, real-world attack scenarios. We propose a methodology and framework to facilitate the discovery of the CPES attack surface. We present a multilayer attack graph with ranked attack sequences to describe CPES failure scenarios. We present a work-in-progress framework that lists key components to automate the attack modeling and sequence generation. We demonstrate the published National Electric Sector Cybersecurity Organization Resource CPES failure scenario to highlight the trustworthiness of generated attack sequences.

Dutta, Ashutosh↗

Polarization Properties of Rotation Powered Pulsars

Polarization measurements of rotation-powered pulsars and their nebulae have unique diagnostic potential. The polarization position angle of the pulsar wind nebula, as is know for the Crab pulsar, can tell us the orientation of the spin axis. Phase-resolved polarimetry of pulsars has had enormous diagnostic capability at radio and optical wavelengths and could also be a powerful diagnostic in the X-ray range. Measurement of the polarization properties as a function of pulse phase can therefore provide a multidimensional mapping of the pulsar emission. In the 'rotating vector' model, radiation originating near a magnetic pole is expected to show a characteristic S-shaped swing of the position angle vs. pulse phase. In this case it is possible to determine the magnetic inclination and viewing angles. Radiation originating further from the poles or further above the neutron star surface will have a more complex polarization signature, as a result of relativistic effects of aberration and time-of-flight delays and may also cause depolarization of the signal. I will discuss predicted polarization properties of pulsed emission in polar cap models, where radiation originates near the neutron star surface at the magnetic poles, and in slot gap and outer gap models, where radiation originates over a range of altitudes out to the speed-of-light cylinder.

Harding Alice K.↗

ADVANCES IN PLUME-SURFACE INTERACTION SIMULATION CAPABILITY UNDER LUNAR LANDING CONDITIONS

The Fluid Dynamics Branch at theNASA Marshall Space Flight Center has assembled a portfolio of simulation tools to predict Plume-SurfaceInteraction (PSI) environments during extra-terrestrial propulsive landings. Particular focus is on engineering support for lunar landers such as robotic CommercialLunar Payload Services (CLPS) and the HumanLander System (HLS). Extension of existing PSI simulation capabilities are required to accurately capture the complex plume flow conditions and surface soil particle composition effects that arise in the lunar environment. The required model development and implementation, and extensive verification and validation of the key simulation tools, Loci/Chem [1]and Loci/Boltzmann [2], and Loci/GGFS [3] are now performed under a NASA Space Technology MissionDirectorate (STMD) funded multi-year GameChanging Development (GCD) project. The project will implement and mature these new modeling features and verify and validate them for the Mars andMoon environments with the aid of existing and new experiments to be performed under this project

Plume Surface Interaction↗

Size matters: altering the metal-surface coordination in micropores via structural confinement effects

Solid-state NMR experiments were used to investigate the dynamics of supported complexes grafted to a series of silica gel materials of varied pore sizes. Through dipolar recoupling measurements, we found that ligand dynamics were impeded in the more confined environments, as would be expected. A new form of motion involving the complex as a whole, however, appeared in the most restricted environment consisting of 22 Å diameter pores. These motions persisted down to –100 °C at which point the ligands were frozen on the NMR timescale. The newly observed dynamics could only result from the breaking of secondary dative metal–siloxane interactions that otherwise lock the complex in a preferred orientation on the surface. Crucially, these results show that confinement effects alone can be sufficient to reduce a grafted metal's effective coordination number in direct analogy to the synthesis of undercoordinated complexes using bulky ligands. Finally, this finding could have important implications in the synthesis of more active heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Experimental Method to Measure Gaseous Diffusivity in Tight and Partially Saturated Porous Media via Continuously Monitored Mass Spectrometry

Detection of radioxenon and radioargon produced by underground nuclear explosions is one of the primary methods by which the Comprehensive Nuclear-Test–Ban Treaty (CTBT) monitors for nuclear activities. However, transport of these noble gases to the surface via barometric pumping is a complex process relying on advective and diffusive processes in a fractured porous medium to bring detectable levels to the surface. To better understand this process, experimental measurements of noble gas and chemical surrogate diffusivity in relevant lithologies are necessary. However, measurement of noble gas diffusivity in tight or partially saturated porous media is challenging due to the transparent nature of noble gases, the lengthy diffusion times, and difficulty maintaining consistent water saturation. Here, the quasi-steady-state Ney–Armistead method is modified to accommodate continuous gas sampling via effusive flow to a mass spectrometer. An analytical solution accounting for the cumulative sampling losses and induced advective flow is then derived. Experimental results appear in good agreement with the proposed theory, suggesting the presence of retained groundwater reduces the effective diffusivity of the gas tracers by 10–1000 times. Finally, by using a mass spectrometer, the method described herein is applicable to a broad range of gas species and porous media.

47 OTHER INSTRUMENTATION↗

Active control of wake/blade-row interaction noise through the use of blade surface actuators

A combined analytical/computational approach for controlling of the noise generated by wake/blade-row interaction through the use of anti-sound actuators on the blade surfaces is described. A representative two-dimensional section of a fan stage, composed of an upstream fan rotor and a downstream fan exit guide vane (FEGV), is examined. An existing model for the wakes generated by the rotor is analyzed to provide realistic magnitudes for the vortical excitations imposed at the inlet to the FEGV. The acoustic response of the FEGV is determined at multiples of the blade passing frequency (BPF) by using the linearized unsteady flow analysis, LINFLO. Acoustic field contours are presented at each multiple of BPF illustrating the generated acoustic response disturbances. Anti-sound is then provided by placing oscillating control surfaces, whose lengths and locations are specified arbitrarily, on the blades. An analysis is then conducted to determine the complex amplitudes required for the control surface motions to best reduce the noise. It is demonstrated that if the number of acoustic response modes to be controlled is equal to the number of available independent control surfaces, complete noise cancellation can be achieved. A weighted least squares minimization procedure for the control equations is given for cases in which the number of acoustic modes exceeds the number of available control surfaces. The effectiveness of the control is measured by the magnitude of a propagating acoustic response vector, which is related to the circumferentially averaged sound pressure level (SPL), and is minimized by a standard least-squares minimization procedure.

Kousen, Kenneth A.↗

Space-Based Solar Power: An Enabler for Expanded Lunar Surface Exploration and Mobility Operations

The achievement of industrial and scientific goals set by the National Aeronautics and Space Administration (NASA) Artemis missions within the Moon to Mars (M2M) architecture greatly relies on the breadth and efficacy of lunar surface exploration. The lunar surface environment presents various challenges and complexities to sustainable mission operations and activities. Power generation and distribution capabilities are vital for exploration on the lunar surface, which can enable activities such as subsurface sample collection, permanently shadowed region (PSR) prospecting, and lunar terrain mapping. Innovative power technologies that demonstrate flexibility, reliability, and high capacity are desirable to achieve sustainable operations and infrastructure on the lunar surface. Studies have proposed solar-powered spacecraft in cislunar orbit capable of beaming power to lunar surface assets as a solution to this problem. This study analyzes the benefit that space-based solar power (SBSP) assets could deliver to the M2M architecture by measuring its potential to augment lunar surface exploration opportunity. Qualitative measures of SBSP’s potential impact will include, but not be limited to, power available across surface elements, surface mobility range, and delivered landed mass. These measures are assessed for a notional surface architecture measured against its baseline configuration (no external power augmentation). Additionally, this presentation will provide an overview of the SBSP system design configuration trade space, subsystem parameter trade space, and results from preliminary spacecraft concept of operations (ConOps) and sizing.

Space-based solar power↗

Large seasonal variations in Triton's atmosphere

Consideration is given to the consequences of Triton's surface covering of volatile substances in view of the circularity of Neptune's orbit, which implies that Triton would have virtually no seasonal variations in either surface temperature or atmospheric bulk despite the complex precessional effects of its orbit. It is hypothesized that Triton's most volatile surface substances are probably relegated to latitudes higher than 35 deg, probably forming polar caps whose temperatures would be nearly equal even during the midwinter/midsummer peak insolation of the summer pole. If the summer pole completely sublimates during one of the 'major' summers, Triton's atmosphere may begin to freeze out over the winter caps and yield large and complex seasonal variations.

Trafton, L.↗

Characteristics of Hydrogen Sensors Based on Thin Tin Dioxide Films Modified with Platinum, Palladium, Silver, and Yttrium

The dependence of the characteristics of hydrogen sensors based on thin Pt/Pd/SnO{sub 2}:Sb, Ag, Y and Ag/SnO{sub 2}:Sb, Ag, Y films obtained by the method of magnetron sputtering at a direct current on the humidity level of the gas mixture during operation in thermal cyclic mode is investigated. The analysis of the experimental data was carried out using the expressions obtained on the basis of the dissociative adsorption model of hydrogen and water molecules on the SnO{sub 2} surface, taking into account the presence of three types of adsorbed particles: O{sup –}, OH, OН{sup –}. The use of complex modifiers Pt/Pd, Ag on the surface and Ag + Y in the bulk of tin dioxide films allows to reduce the influence of humidity on the characteristics of sensors. The role of these modifying additives in the process of dissociative adsorption of hydrogen molecules on the surface of SnO{sub 2} films in humid environment is established.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modification of the SiO{sub 2}/Si interface by pulsed fibre laser radiation{sup *}

We report a detailed study of structural modification of the silicon–silica interface under the effect of laser pulses at a wavelength of 1.07 μm. A thermal oxide layer on the silicon surface has been shown to have a significant effect on the defect formation process and surface microstructuring because of the complex stress state of such a structure. (paper)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Toward Fast and Reliable Potential Energy Surfaces for Metallic Pt Clusters by Hierarchical Delta Neural Networks

Data-driven machine learning force fields (MLF) are more and more popular in atomistic simulations, and exploit machine learning methods to predict energies and forces for unknown structures based on the knowledge learned from an existing reference database. The latter usually comes from density functional theory calculations. One main drawback of MLFs is that physical laws are not incorporated in the machine learning models and instead, MLFs are designed to be very flexible to simulate complex quantum chemistry potential energy surface (PES). In general, MLFs have poor transferability, and hence a very large trainset is required to span all the target feature space to get a reliable MLF. This procedure becomes more troublesome when the PES is complicated, with a large number of degrees of freedom, in which building a large database is inevitable and very expensive, especially when accurate but costly exchange-correlation functionals have to be used. In this manuscript, we exploit a high dimensional neural network potential (HDNNP) on Pt clusters of size 6 to 20 as one example. Furthermore, our standard level of energy calculation is DFT GGA (PBE) using a plane wave basis set. We introduce an approximate but fast level with the PBE functional and a minimal atomic orbital basis set, then a more accurate but expensive level, using a hybrid functional or non-local vdw functional and a plane wave basis set, is reliably predicted by learning the difference with HDNNP. Findings show that such a differential approach (named ΔHDNNP) can deliver very accurate predictions (error < 10 meV/atom) in reference to converged basis set energies as well as more accurate but expensive xc functional. The overall speedup can be as large as 900 for 20 atom Pt cluster. More importantly, ΔHDNNP shows much better transferability due to the intrinsic smoothness of delta potential energy surface, and accordingly one can use much smaller trainset data to obtain better accuracy than the conventional HDNNP. A multi-layer ΔHDNNP is thus proposed to obtain very accurate predictions versus expensive non-local vdW functional calculations in which the required trainset is further reduced. The approach can be easily generalized to any other machine learning methods and opens a path to study the structure and dynamics of Pt clusters and nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling of three-dimensional surfaces using high-level canonical piecewise-linear functions in cylindrical coordinates

In this paper, the potential application of the high-level canonical piecewise-linear model in the field of three-dimensional visualization is proposed. This idea emerges from the premise that a three-dimensional surface can be modeled by a continuous two-dimensional function. In this regard, the main contribution consists in providing a methodology for the construction of such function. For this purpose, the well-known algorithm used in the high-level canonical piecewise-linear model has been modified to achieve functions with greater graphing capability. One of the most notorious changes made with respect to the traditional methodology is the use of a new scheme of function domain partition. Contrary to the simplicial partitioning, in our proposal, an equally distributed angular partitioning is considered. With this, the resulting approximate function is expressed in cylindrical coordinates which overcome the typical limitation of graphs in Cartesian coordinates of only representing single-valued surfaces. Another remarkable change can be found in the range of evaluation of the function. Instead of using an open interval, in our approach, a closed interval from 0 to 2π is adopted. To support this proposal, illustrative case studies are reported. Numerical simulations demonstrate the effectiveness of this type of representation model not only in visual perception of three-dimensional surfaces, but also in more complex tasks like volume estimation.

97 MATHEMATICS AND COMPUTING↗

Developing an Empirical Model for Jet-Surface Interaction Noise

The process of developing an empirical model for jet-surface interaction noise is described and the resulting model evaluated. Jet-surface interaction noise is generated when the high-speed engine exhaust from modern tightly integrated or conventional high-bypass ratio engine aircraft strikes or flows over the airframe surfaces. An empirical model based on an existing experimental database is developed for use in preliminary design system level studies where computation speed and range of configurations is valued over absolute accuracy to select the most promising (or eliminate the worst) possible designs. The model developed assumes that the jet-surface interaction noise spectra can be separated from the jet mixing noise and described as a parabolic function with three coefficients: peak amplitude, spectral width, and peak frequency. These coefficients are fit to functions of surface length and distance from the jet lipline to form a characteristic spectra which is then adjusted for changes in jet velocity and/or observer angle using scaling laws from published theoretical and experimental work. The resulting model is then evaluated for its ability to reproduce the characteristic spectra and then for reproducing spectra measured at other jet velocities and observer angles; successes and limitations are discussed considering the complexity of the jet-surface interaction noise versus the desire for a model that is simple to implement and quick to execute.

Brown, Clifford A.↗

Developing an Empirical Model for Jet-Surface Interaction Noise

The process of developing an empirical model for jet-surface interaction noise is described and the resulting model evaluated. Jet-surface interaction noise is generated when the high-speed engine exhaust from modern tightly integrated or conventional high-bypass ratio engine aircraft strikes or flows over the airframe surfaces. An empirical model based on an existing experimental database is developed for use in preliminary design system level studies where computation speed and range of configurations is valued over absolute accuracy to select the most promising (or eliminate the worst) possible designs. The model developed assumes that the jet-surface interaction noise spectra can be separated from the jet mixing noise and described as a parabolic function with three coefficients: peak amplitude, spectral width, and peak frequency. These coefficients are t to functions of surface length and distance from the jet lipline to form a characteristic spectra which is then adjusted for changes in jet velocity and/or observer angle using scaling laws from published theoretical and experimental work. The resulting model is then evaluated for its ability to reproduce the characteristic spectra and then for reproducing spectra measured at other jet velocities and observer angles; successes and limitations are discussed considering the complexity of the jet-surface interaction noise versus the desire for a model that is simple to implement and quick to execute.

Brown, Clif↗

Strategy for Nonenzymatic Harvesting of Cells via Decoupling of Adhesive and Disjoining Domains of Nanostructured Stimulus-Responsive Polymer Films

The nanostructured polymer film introduces a novel mechanism of nonenzymatic cell harvesting by decoupling solid cell-adhesive and soft stimulus-responsive cell-disjoining areas on the surface. The key characteristics of this architecture are the decoupling of adhesion from detachment and the impermeability to the integrin protein complex of the adhesive domains. This surface design eliminates inherent limitations of thermoresponsive coatings, namely, the necessity for the precise thickness of the coating, grafting or cross-linking density, and material of the basal substrate. The concept is demonstrated with nanostructured thermoresponsive films made of cell-adhesive epoxy photoresist domains and cell-disjoining poly(N-isopropylacrylamide) brush domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and use of domain-specific antibodies in a characterization of the large subunits of soybean photosystem 1

The molecular architecture of the soybean photosystem 1 reaction center complex was examined using a combination of surface labeling and immunological methodology on isolated thylakoid membranes. Synthetic peptides (12 to 14 amino acids in length) were prepared which correspond to the N-terminal regions of the 83 and 82.4 kDa subunits of photosystem 1 (the PsaA and PsaB proteins, respectively). Similarly, a synthetic peptide was prepared corresponding to the C-terminal region of the PsaB subunit. These peptides were conjugated to a carrier protein, and were used for the production of polyclonal antibodies in rabbits. The resulting sera could distinguish between the PsaA and PsaB photosystem 1 subunits by Western blot analysis, and could identify appropriate size classes of cyanogen bromide cleavage fragments as predicted from the primary sequences of these two subunits. When soybean thylakoid membranes were surface-labeled with N-hydroxysuccinimidobiotin, several subunits of the complete photosystem 1 lipid/protein complex incorporated label. These included the light harvesting chlorophyll proteins of photosystem 1, and peptides thought to aid in the docking of ferredoxin to the complex during photosynthetic electron transport. However, the PsaA and PsaB subunits showed very little biotinylation. When these subunits were examined for the domains to which biotin did attach, most of the observed label was associated with the N-terminal domain of the PsaA subunit, as identified using a domain-specific polyclonal antisera.

NASA Program NSCORT↗