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At least 811 records · Page 45

Structure-based design of prefusion-stabilized human metapneumovirus fusion proteins

The human metapneumovirus (hMPV) fusion (F) protein is essential for viral entry and is a key target of neutralizing antibodies and vaccine development. The prefusion conformation is thought to be the optimal vaccine antigen, but previously described prefusion F proteins expressed poorly and were not well stabilized. Here, we use structures of hMPV F to guide the design of 42 variants containing stabilizing substitutions. Through combinatorial addition of disulfide bonds, cavity-filling substitutions, and improved electrostatic interactions, we describe a prefusion-stabilized F protein (DS-CavEs2) that expresses at 15mg/L and has a melting temperature of 71.9°C. Crystal structures of two prefusion-stabilized hMPV F variants reveal that antigenic surfaces are largely unperturbed. Importantly, immunization of mice with DS-CavEs2 elicits significantly higher neutralizing antibody titers against hMPV A1 and B1 viruses than postfusion F. The improved properties of DS-CavEs2 will advance the development of hMPV vaccines and the isolation of therapeutic antibodies.

59 BASIC BIOLOGICAL SCIENCES↗

Robust Stabilizing Compensators for Flexible Structures with Collocated Controls

For flexible structures with collocated rate and attitude sensors/actuators, we characterize compensator transfer functions which guarantee modal stability even when stiffness/inertia parameters are uncertain. While the compensators are finite-dimensional, the structure models are allowed to be infinite-dimensional (continuum models), with attendant complexity of the notion of stability; thus exponential stability is not possible and the best we can obtain is strong stability. Robustness is interpreted essentially as maintaining stability in the worst case. The conditions require that the compensator transfer functions be positive real and use is made of the Kalman-Yakubovic lemma to characterize them further. The concept of positive realness is shown to be equivalent to dissipativity in infinite dimensions. In particular we show that for a subclass of compensators it is possible to make the system strongly stable as well as dissipative in an appropriate energy norm.

Balakrishman, A. V.↗

A Reliable Earth Return System for Safe Recovery of Mars Samples

The objective of a Mars sample return mission is to bring selected Mars surface materials to Earth. Numerous approaches for the Earth-return segment have been analyzed including propulsive or aerocapture return to low-Earth orbit followed by Space Shuttle rendezvous and direct entry. Of these approaches, ballistic entry of a small capsule terminating in a ground landing has been shown to be the lowest risk strategy. Over the past two years, significant work has been performed towards development of a robust direct entry vehicle for Mars sample return. In June 1999, the NASA Planetary Protection Officer provided initial guidance to the former Mars Sample Return Project. The sample return phase of the mission was assigned a restricted Earth return planetary protection classification. The draft mission requirement states that the total mean probability of release of unsterilized Mars material into the Earth;s biosphere must be less than 1.0E-06 (1 in a million). This strict requirement drives the approach and design of the Earth return system. To meet this requirement, selection of the Earth return strategy and development of the Earth return system must be guided by risk, not performance, based decisions. An initial Probabilistic Risk Assessment (PRA) was performed to address the direct entry Earth return system containment assurance reliability and to identify high-risk elements of this system. The results of this PRA identified risk elements that include thermal protection system performance during entry, spin-eject orientation and aerodynamic stability during entry, structural integrity under atmospheric deceleration and impact loads, and tracking/recovery of this system. This initial probabilistic risk quantification demonstrates that, with the proper development program, a prototypical direct entry design can satisfy the containment assurance reliability requirement. Through the current Mars Sample Return Advanced Technology Development effort, an extensive design, analysis, and test program is presently proceeding with the aim of reducing the containment assurance risk of this system. This technology development effort, guided by a continuing PRA, focuses on key risk areas of a direct entry Earth return system including: the thermal protection system, impact dynamics, structural performance, aerodynamic stability, and ground recovery. This development program will culminate in a system validation flight test, 1-2 years prior to launch of the flight system. This flight test would include the launch, entry, and recovery of a full-scale Earth return system, as a scientific validation of the key risk elements to verify nominal design performance. The results of the initial PRA suggested several dominant failure sequences that can be validated in a flight test. These include: demonstrating the thermal protection system reliability and performance during entry, demonstrating the spin-eject orientation and aero-dynamic stability during entry, demonstrating the structural integrity under atmospheric deceleration and impact loads, and demonstrating tracking and recovery of the Earth return system. This single test will directly address over 50% of the total containment assurance risk elements. This presentation will begin by presenting the relative risk of various Earth return strategies. The results of the initial probabilistic risk assessment will be presented followed by a discussion of the development accomplishments and plans for demonstration of a highly reliable direct entry Earth return system.

Braun, R.↗

Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization

Lithium (Li) pulverization and associated large volume expansion during cycling is one of the most critical barriers for the safe operation of Li-metal batteries. Here, we report an approach to minimize the Li pulverization using an electrolyte based on a fluorinated orthoformate solvent. The solid–electrolyte interphase (SEI) formed in this electrolyte clearly exhibits a monolithic feature, which is in sharp contrast with the widely reported mosaic- or multilayer-type SEIs that are not homogeneous and could lead to uneven Li stripping/plating and fast Li and electrolyte depletion over cycling. The highly homogeneous and amorphous SEI not only prevents dendritic Li formation, but also minimizes Li loss and volumetric expansion. Furthermore, this new electrolyte strongly suppresses the phase transformation of the LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode (from layered structure to rock salt) and stabilizes its structure. In conclusion, tests of high-voltage Li||NMC811 cells show long-term cycling stability and high rate capability, as well as reduced safety concerns.

25 ENERGY STORAGE↗

A SURVEY OF RESEARCH ON THE STABILITY OF HYDROSTATICALLYLOADED SHELL STRUCTURES CONDUCTED AT THE DAVID TAYLOR MODEL BASIN

Experimental and theoretical studies have been carried out to investigate the stability of ring-stiffened cylinders and hemispherical shells under hydrostatic pressure. The use of accurately machined models has been found extremely valuable in improving the quality of experimental data, thereby permitting a more careful examination of theory. As a result, the effects of boundary conditions and other factors usually masked by the influence of structural imperfections have been clarified. So far these studies have caused the investigators to regard classical small-deflection theory with increasing confidence.

ROCKET NOZZLE↗

Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution

Two thorium(IV) compounds, [Th(H 2 O) 4 Cl 4 ]·2 (HPy·Cl) ( 1 ) and (HPy) 3 [Th 3 (H 2 O) 2 Cl 10 (OH) 5 ]·4(HPy·Cl) ( 2 ) (HPy = pyridinium), were isolated from acidic aqueous solution. The compounds were synthesized at room temperature and subsequently characterized using single crystal X-ray diffraction along with Raman and IR spectroscopies. Whereas compound 1 is built from discrete mononuclear Th(H 2 O) 4 Cl 4 units, compound 2 consists of a novel hydroxo-bridged trimeric [Th 3 (OH) 5 ] 7+ core. Such species are largely absent from discussions of Th solution and solid-state chemistry and their isolation may be attributed to outer coordination sphere interactions that help stabilize the structural units; extensive hydrogen bonding and $π–π$ stacking interactions are present in 1 and 2 . Density functional theory calculations were performed to predict the respective vibrational frequencies of the structural units, and their relative stability was predicted at the correlated molecular theory level. Small-angle X-ray scattering analysis of [Th 3 (OH) 5 ] 7+ in water indicates that the trimeric structural unit remains intact and that it is indeed an important species that necessitates consideration in geochemical models and for design of Th materials from water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li 7‐3 x Ga x La 3 Zr 2 O 12 Garnet‐Type Electrolytes

Abstract One of the most promising electrolytes for all‐solid‐state lithium batteries is Li 7 La 3 Zr 2 O 12 . Previously, their thermodynamic stability, Li‐ion conductivity, and structural features induced by Ga‐doping have not been empirically determined or correlated. Here, their interplay was examined for Li 7−3 x Ga x La 3 Zr 2 O 12 with target x Ga=0, 0.25, 0.50, 0.75, and 1.00 atoms per formula unit (apfu). Formation enthalpies, obtained with calorimetry and found to be exothermic at all compositions, linearly decreased in stability with increased x Ga. At dilute x Ga substitution, the formation enthalpy curve shifted stepwise endothermically, and the conductivity increased to a maximum, coinciding with 0.529 Ga apfu. This correlated with percolation threshold analysis (0.558 Ga apfu). Further substitution (0.787 Ga apfu) produced a large decrease in the stability and conductivity due to a large increase in point defects and blocked Li‐migration pathways. At x Ga=1.140 apfu, a small exothermic shift was related to defect cluster organization extending the Li hopping distance and decreased Li‐ion conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of preheat on the structure of a swirl stabilized flame

The effect of preheat on the temperature and species distributions in propane flames stabilized on a NASA contraswirl can has been examined. Flames with compact stable structure, inner-swirler airflow of 0.0091 kg/s, outer-swirler-plus-bypass airflow of 0.0203 kg/s, and propane injected 1 mm upstream of the inner swirler hub have been selected for detailed study. Over the inlet-air-temperature range from 300 to 673 K the maximum temperature in the flame increased by 40 to 60 K per 100-K increase in inlet air temperature. The point of maximum temperature on the center line approached the exit plane as inlet air temperature was increased. Oxygen, CO, H2, and methane were found together in gas samples taken from the flame, including the regions of maximum flame temperature.

Thompson, D.↗

Vanadyl Phosphates A x VOPO 4 (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries

Vanadyl phosphates comprise a class of multielectron cathode materials capable of cycling two Li + , about 1.66 Na + , and some K + ions per redox center. In this review, structures, thermodynamic stabilities, and ion diffusion kinetics of various A x VOPO 4 (A = Li, Na, K, NH 4 ) polymorphs are discussed. Both the experimental data and first-principle calculations indicate kinetic limitations for alkali metal ions cycling, especially between for 0 ≤ x ≤ 1, and metastability of phases with x > 1. This creates challenges for multiple-ion cycling, as the slow kinetics call for nanosized particles, which being metastable and reactive with organic electrolytes are prone to side reactions. Thus, various synthesis approaches, surface coating, and transition metal ion substitution strategies are discussed here as possible ways to stabilize A x VOPO 4 structures and improve alkali metal ion diffusion. Finally, the role of advanced characterization techniques, such as X-ray absorption spectroscopy, diffraction, pair distribution function analysis and 7 Li and 31 P NMR, in understanding the reaction mechanism from both structural and electronic points of view is emphasized.

25 ENERGY STORAGE↗

The Effect of Irradiation with Si{sup +} Ions on Resistive Switching in Memristive Structures Based on Yttria-Stabilized Zirconia

We have studied the resistive switching in memristive structures based on 40-nm-thick yttria-stabilized zirconia (YSZ) films exposed to 6-keV Si{sup +} ion irradiation to a total dose of 5.4 × 10{sup 15} cm{sup –2}. It is established that the ion irradiation leads to increased stability of the parameters of resistive switching in YSZ based memristive structures. This effect is related to the fact that the diameter of conducting filaments in irradiated structures is limited by lateral dimensions of the region of atomic displacement cascades (i.e., the region occupied by point defects produced by bombarding ions). The oxidation of ion-modified filaments during resistive switching proceeds more effectively and leads to increasing resistance in the high-resistance state of memristive structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Spillover stabilization of large space structures

Active control of large flexible space structures is typically implemented to control only a few known elastic modes. This paper considers the stabilization of the neglected dynamics of the higher modes of vibration. An attempt is made to design modal controllers with improved spillover stability properties. Two formulations for designing the observer to improve spillover stability with minimum performance loss are proposed. One optimizes the noise statistics used in the design of the Kalman-Bucy Filter (KBF), while the other directly optimizes the the gain matrix of the KBF.

Czajkowski, Eva A.↗

Magnetic phase diagram of A 2 [FeCl 5 (H 2 O)] ( A = K, Rb, NH 4 )

Here, erythrosiderites with the formula A 2 FeX 5 ∙H 2 O, where A = Rb, K, and (NH 4 ) and X = Cl and Br are intriguing systems that possess various magnetic and electric phases, as well as multiferroic phases in which magnetism and ferroelectricity are coupled. In this report, we study the magnetic phase diagram of erythrosiderites as a function of superexchange interactions and magnetic anisotropies. To this end, we perform classical Monte Carlo simulations on magnetic Hamiltonians that contain five different superexchange interactions with single-ion anisotropies. Our phase diagram contains all magnetic ground states that have been experimentally observed in these materials. We argue that the ground states can be explained by varying the ratio of $\frac{J_4}{J_2}$. For $\frac{J_4}{J_2}$ > 0.95 a cycloidal spins structure is stabilized as observed in (NH 4 ) 2 FeCl 5 ∙H 2 O and otherwise a collinear spin structure is stabilized as observed in (K,Rb) 2 FeCl 5 ∙H 2 O. We also show that the difference in the single-ion anisotropy along a- and c- axes is essential to stabilize the intermediate state observed in (NH) 2 FeCl 5 ∙H 2 O.

36 MATERIALS SCIENCE↗

Impact of Structural Defects and Hydronium Ion Concentration on the Stability of Zeolite BEA in Aqueous Phase

The presence of fluoride anions in the synthesis gel leads to zeolite BEA with high hydrothermal stability. This longer lifetime is caused by a lower concentration of internal silanol defects that are sites of the initial framework hydrolysis eventually destroying the lattice structure. The lifetime of these zeolites was the higher the lower the concentration of framework bridging hydroxyl groups that form hydronium ions was. While lattice hydrolysis was initiated at defect sites in all cases, the role of defects became less important as the concentration of hydronium ions increased. At higher concentration of hydrated hydronium ions, the presence of water associated with the hydrated hydronium ions limits the useful lifetime of zeolite catalysts in water. For such materials, the selective hydrophobization of the external surface extends the lifetime. Acknowledgments: S.P. and M.A.D. acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. H.S. and H.W. were supported by the Chemical Transformation Initiative (CTI) conducted under Laboratory Directed Research & Development Program at PNNL. J.A.L. was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

Prodinger, Sebastian↗

Stability and Interaction of Coherent Structure in Supersonic Reactive Wakes

A theoretical formulation and analysis is presented for a study of the stability and interaction of coherent structure in reacting free shear layers. The physical problem under investigation is a premixed hydrogen-oxygen reacting shear layer in the wake of a thin flat plate. The coherent structure is modeled as a periodic disturbance and its stability is determined by the application of linearized hydrodynamic stability theory which results in a generalized eigenvalue problem for reactive flows. Detailed stability analysis of the reactive wake for neutral, symmetrical and antisymmetrical disturbance is presented. Reactive stability criteria is shown to be quite different from classical non-reactive stability. The interaction between the mean flow, coherent structure and fine-scale turbulence is theoretically formulated using the von-Kaman integral technique. Both time-averaging and conditional phase averaging are necessary to separate the three types of motion. The resulting integro-differential equations can then be solved subject to initial conditions with appropriate shape functions. In the laminar flow transition region of interest, the spatial interaction between the mean motion and coherent structure is calculated for both non-reactive and reactive conditions and compared with experimental data wherever available. The fine-scale turbulent motion determined by the application of integral analysis to the fluctuation equations. Since at present this turbulence model is still untested, turbulence is modeled in the interaction problem by a simple algebraic eddy viscosity model. The applicability of the integral turbulence model formulated here is studied parametrically by integrating these equations for the simple case of self-similar mean motion with assumed shape functions. The effect of the motion of the coherent structure is studied and very good agreement is obtained with previous experimental and theoretical works for non-reactive flow. For the reactive case, lack of experimental data made direct comparison difficult. It was determined that the growth rate of the disturbance amplitude is lower for reactive case. The results indicate that the reactive flow stability is in qualitative agreement with experimental observation.

Menon, Suresh↗

PySIDT: Subgraph Isomorphic Decision Trees for Molecular Property Prediction

Accurate molecular property prediction is important across all fields of chemistry. Deep neural networks (DNNs) have become increasingly popular due to their ability to train automatically, avoiding the incredibly tedious process of constructing and extending traditional property estimation schemes. However, DNNs require large amounts of training data, are challenging to interpret, require large amounts of memory to load even during inference, and have severe difficulties incorporating qualitative chemical knowledge, which are often desired for molecular property prediction tasks. Here, in this study, we present PySIDT (https://github.com/zadorlab/PySIDT), a software for training and running inference on Subgraph Isomorphic Decision Trees (SIDTs). SIDTs are graph-based decision trees made of nodes associated with molecular substructures. Inference is done by descending target molecular structures down the decision tree to nodes with matching subgraph isomorphic substructures and making predictions based on the final (most specific) nodes matched. SIDTs scale down well to dataset sizes much smaller than is feasible for DNNs. As trees of molecular substructures, SIDTs are inherently readable and easy to visualize, making them easy to analyze. They are also straightforward to extend and retrain, facilitate uncertainty estimation, and enable easy integration of expert knowledge. We demonstrate the SIDT approach discussing its application to a diverse range of molecular prediction tasks: rate coefficient estimation, diffusion coefficient estimation, thermochemistry estimation, transition state bond stretch prediction, p K a prediction, stability of molecular structures, stability of surface structures, and prediction of surface lateral interaction energetics. Additionally, we demonstrate the power of the SIDT algorithms in two direct learning curve vanilla comparisons with the popular DNN-based software Chemprop and the popular gradient boosted trees-based software XGBoost on enthalpy of formation and rate coefficient prediction tasks. In particular, in the enthalpy of formation case, vanilla PySIDT is able to outperform vanilla Chemprop and XGBoost across the full range of training/validation set sizes out to 11,560 data points.

Johnson, Matthew Sean [Sandia National Laboratorie↗

STABILITY PROBLEMS IN MISSILE STRUCTURES

A number of specific buckling problems relating to missile propellant tanks and transition sections are enumerated. In some cases approximate techniques used by missile designers to determine stability are mentioned. The inadequacies of these approximate methods and the unavailability of appropriate usable information is stressed. Furthermore, the mathematical complexities of nonlinear buckling problems are considered. Some possibly fruitful areas of mathematics to simplify these complexities are discussed with the hope that research in these areas will provide a batter means through which the analyst may supply the designer with more realistic and accurate theoretical data.

MISSILE↗

Robust control of systems with real parameter uncertainty and unmodelled dynamics

During this research period we have made significant progress in the four proposed areas: (1) design of robust controllers via H infinity optimization; (2) design of robust controllers via mixed H2/H infinity optimization; (3) M-delta structure and robust stability analysis for structured uncertainties; and (4) a study on controllability and observability of perturbed plant. It is well known now that the two-Riccati-equation solution to the H infinity control problem can be used to characterize all possible stabilizing optimal or suboptimal H infinity controllers if the optimal H infinity norm or gamma, an upper bound of a suboptimal H infinity norm, is given. In this research, we discovered some useful properties of these H infinity Riccati solutions. Among them, the most prominent one is that the spectral radius of the product of these two Riccati solutions is a continuous, nonincreasing, convex function of gamma in the domain of interest. Based on these properties, quadratically convergent algorithms are developed to compute the optimal H infinity norm. We also set up a detailed procedure for applying the H infinity theory to robust control systems design. The desire to design controllers with H infinity robustness but H(exp 2) performance has recently resulted in mixed H(exp 2) and H infinity control problem formulation. The mixed H(exp 2)/H infinity problem have drawn the attention of many investigators. However, solution is only available for special cases of this problem. We formulated a relatively realistic control problem with H(exp 2) performance index and H infinity robustness constraint into a more general mixed H(exp 2)/H infinity problem. No optimal solution yet is available for this more general mixed H(exp 2)/H infinity problem. Although the optimal solution for this mixed H(exp 2)/H infinity control has not yet been found, we proposed a design approach which can be used through proper choice of the available design parameters to influence both robustness and performance. For a large class of linear time-invariant systems with real parametric perturbations, the coefficient vector of the characteristic polynomial is a multilinear function of the real parameter vector. Based on this multilinear mapping relationship together with the recent developments for polytopic polynomials and parameter domain partition technique, we proposed an iterative algorithm for coupling the real structured singular value.

Chang, Bor-Chin↗