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At least 433 records · Page 24

Formation of Ordered Arrays of Proteins on Surfaces

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. While the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models, with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation and crystal growth.

Lenhoff, A. M.↗

Van der Waals Interactions Involving Proteins

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models. with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth.

Roth, Charles M.↗

Theoretical Modeling of Interstellar Chemistry

The chemistry of complex interstellar organic molecules will be described. Gas phase processes that may build large carbon-chain species in cold molecular clouds will be summarized. Catalytic reactions on grain surfaces can lead to a large variety of organic species, and models of molecule formation by atom additions to multiply-bonded molecules will be presented. The subsequent desorption of these mixed molecular ices can initiate a distinctive organic chemistry in hot molecular cores. The general ion-molecule pathways leading to even larger organics will be outlined. The predictions of this theory will be compared with observations to show how possible organic formation pathways in the interstellar medium may be constrained. In particular, the success of the theory in explaining trends in the known interstellar organics, in predicting recently-detected interstellar molecules, and, just as importantly, non-detections, will be discussed.

Charnley, Steven↗

An Evaluation of Fractal Surface Measurement Methods for Characterizing Landscape Complexity from Remote-Sensing Imagery

The rapid increase in digital data volumes from new and existing sensors necessitates the need for efficient analytical tools for extracting information. We developed an integrated software package called ICAMS (Image Characterization and Modeling System) to provide specialized spatial analytical functions for interpreting remote sensing data. This paper evaluates the three fractal dimension measurement methods: isarithm, variogram, and triangular prism, along with the spatial autocorrelation measurement methods Moran's I and Geary's C, that have been implemented in ICAMS. A modified triangular prism method was proposed and implemented. Results from analyzing 25 simulated surfaces having known fractal dimensions show that both the isarithm and triangular prism methods can accurately measure a range of fractal surfaces. The triangular prism method is most accurate at estimating the fractal dimension of higher spatial complexity, but it is sensitive to contrast stretching. The variogram method is a comparatively poor estimator for all of the surfaces, particularly those with higher fractal dimensions. Similar to the fractal techniques, the spatial autocorrelation techniques are found to be useful to measure complex images but not images with low dimensionality. These fractal measurement methods can be applied directly to unclassified images and could serve as a tool for change detection and data mining.

Lam, Nina Siu-Ngan↗

A Model-based Approach to Developing the Concept of Operations for Potential Mars Sample Return

Mars Sample Return (MSR) is a proposed multi-agency effort that would return soil and rock samples from the surface of Mars to Earth. Both the complexity of the potential missions, as well as the involvement of multiple geographically distributed organizations, presents a challenge from an information management perspective. In this paper, a Model-based Systems Engineering (MBSE) approach to developing the Concept of Operations of a potential Mars Sample Return effort using the System Modeling Language(SysML) is presented.

Muirhead, Brian↗

Plant Phenology Evaluation of CRESCENDO Land Surface Models–Part 1: Start and End of the Growing Season

Plant phenology plays a fundamental role in land–atmosphere interactions, and its variability and variations are an indicator of climate and environmental changes. For this reason, current land surface models include phenology parameterizations and related biophysical and biogeochemical processes. In this work, the climatology of the beginning and end of the growing season, simulated by the land component of seven state-of-the-art European Earth system models participating in the CMIP6, is evaluated globally against satellite observations. The assessment is performed using the vegetation metric leaf area index and a recently developed approach, named four growing season types. On average, the land surface models show a 0.6-month delay in the growing season start, while they are about 0.5 months earlier in the growing season end. The difference with observation tends to be higher in the Southern Hemisphere compared to the Northern Hemisphere. High agreement between land surface models and observations is exhibited in areas dominated by broadleaf deciduous trees, while high variability is noted in regions dominated by broadleaf deciduous shrubs. Generally, the timing of the growing season end is accurately simulated in about 25 % of global land grid points versus 16 % in the timing of growing season start. The refinement of phenology parameterization can lead to better representation of vegetation-related energy, water, and carbon cycles in land surface models, but plant phenology is also affected by plant physiology and soil hydrology processes. Consequently, phenology representation and, in general, vegetation modelling is a complex task, which still needs further improvement, evaluation, and multi-model comparison.

Phenology↗

Towards LES Models of Jets and Plumes

As pointed out by Rodi standard integral solutions for jets and plumes developed for discharge into infinite, quiescent ambient are difficult to extend to complex situations, particularly in the presence of boundaries such as the sea floor or ocean surface. In such cases the assumption of similarity breaks down and it is impossible to find a suitable entrainment coefficient. The models are also incapable of describing any but the most slowly varying unsteady motions. There is therefore a need for full time-dependent modeling of the flow field for which there are three main approaches: (1) Reynolds averaged numerical simulation (RANS), (2) large eddy simulation (LES), and (3) direct numerical simulation (DNS). Rodi applied RANS modeling to both jets and plumes with considerable success, the test being a match with experimental data for time-averaged velocity and temperature profiles as well as turbulent kinetic energy and rms axial turbulent velocity fluctuations. This model still relies on empirical constants, some eleven in the case of the buoyant jet, and so would not be applicable to a partly laminar plume, may have limited use in the presence of boundaries, and would also be unsuitable if one is after details of the unsteady component of the flow (the turbulent eddies). At the other end of the scale DNS modeling includes all motions down to the viscous scales. Boersma et al. have built such a model for the non-buoyant case which also compares well with measured data for mean and turbulent velocity components. The model demonstrates its versatility by application to a laminar flow case. As its name implies, DNS directly models the Navier-Stokes equations without recourse to subgrid modeling so for flows with a broad spectrum of motions (high Re) the cost can be prohibitive - the number of required grid points scaling with Re(exp 9/4) and the number of time steps with Re(exp 3/4). The middle road is provided by LES whereby the Navier-Stokes equations are formally filtered with the filter chosen to only exclude the smallest turbulent motions. If successful, LES should provide much of the detail available to DNS but at more bearable cost. Fatica et al. in comparing LES with DNS for a low Reynolds number jet showed that the LES could simulate the temporally evolving behavior including growth of the jet thickness. It is the intention of this report to explore the application of an LES model to jets and plumes. As always, before tackling complex situations, the model must be tested for the simplest of cases and so we address only two, a non-buoyant axisymmetric jet issuing steadily from an orifice into a semi-infinite stationary environment and a buoyant jet in the same environment. The work is a continuation of Basu and Mansour.

Webb, A. T.↗

Complex Dependence of Calcite Crack Kinetics on Salinity: The Role of DLVO and Hydration Forces

Abstract Subcritical crack growth (SCG) plays an important role in many geological processes such as delayed earth rupture and rock weathering. The complex dependency of SCG on the in‐crack fluid chemistry, however, is still poorly understood. In this study, we utilize the newly developed surface force‐based fracture theory (SFFT) to elucidate the relative contributions of surface forces and solute transport to the crack growth kinetics of calcite in NaCl solutions. Expanding on Barenblatt's cohesive crack model, SFFT introduces an effective stress intensity at the crack tip that encompasses all the relevant intermolecular forces across the crack in addition to the external far‐field stresses. The nonlinear system of equations portraying the crack opening profile, the solute distribution in a propagating crack, and the crack growth velocity are numerically solved via an implicit scheme. After carefully calibrating the model for calcite‐water systems, the SFFT is used to predict the SCG response of calcite at different NaCl concentrations, based on various hypotheses. These predictions are then compared to existing SCG data from the literature. We demonstrate that the experimentally observed variation of SCG rate with NaCl concentration cannot be explained solely by DLVO forces (electrostatic and Van der Waals interactions). This can be remediated by introducing an exponentially decaying hydration force with a nonlinear, nonmonotonic dependence on NaCl concentration. Furthermore, we demonstrate that accounting for both diffusive and advective transport of ions is important in explaining the absence of a stage‐II SCG response for calcite in electrolyte solutions. Plain Language Summary Subcritical crack growth (SCG) refers to the slow propagation of cracks in materials under a stress below the threshold for catastrophic failure. SCG is a key process in many geological events, for example, delayed earth ruptures and rock weathering. New initiatives such as underground CO 2 and H 2 storage in carbonate reservoirs further call for better understanding of SCG in carbonate minerals subjected to varying fluid chemistry. This study examines the SCG of calcite, a key mineral found in carbonate rocks, intergranular cement in sandstones, and filling material in mineral veins and faults, determining their deformation and strength. A mathematical model is developed to describe how the crack opens and propagates, how solutes (like salts) distribute within the crack, and how the crack surfaces interact with each other. We used the model to predict calcite SCG in water at different salt concentrations and compared it with experimental data. Our results revealed that the hydration force is the dominating factor in determining the complex, non‐linear dependency of SCG on salinity. We also found that both the movement of ions by diffusion and by bulk water flow are crucial for explaining the SCG rates, especially when the cracks grow quickly. Key Points Surface Force‐Based Fracture Theory predicts the complex subcritical crack growth patterns of calcite crystals immersed in NaCl solutions Results highlight the dominant role of hydration forces in altering the fracture behavior of calcite compared to VdW and electric double‐layer forces Advective solute transport explains the absence of stages‐II and ‐III subcritical crack growth responses in solid‐liquid systems

DLVO↗

Dissociative electron attachment to 5-bromo-uracil: non-adiabatic dynamics on complex-valued potential energy surfaces

Electron induced dissociation reactions are relevant to many fields, ranging from prebiotic chemistry to cancer treatments. However, the simulation of dissociation electron attachment (DEA) dynamics is very challenging because the auto-ionization widths of the transient negative ions must be accounted for. We propose an adaptation of the ab initio multiple spawning (AIMS) method for complex-valued potential energy surfaces, along the lines of recent developments based on surface hopping dynamics. Our approach combines models for the energy dependence of the auto-ionization widths, obtained from scattering calculations, with survival probabilities computed for the trajectory basis functions employed in the AIMS dynamics. The method is applied to simulate the DEA dynamics of 5-bromouracil in full dimensionality, i.e., taking all the vibrational modes into consideration. The propagation starts on the $π_{2}^{*}$ resonance state and describes the formation of Br - anions mediated by non-adiabatic couplings. The potential energies, gradients and non-adiabatic couplings were computed with the fractional-occupancy molecular orbital complete-active-space configuration-interaction method, and the calculated DEA cross section are consistent with the observed DEA intensities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contamination sensitivity of typical mirror coatings - A parametric study

Contamination budgeting for space optical systems basically starts at understanding the sensitivity of component performance, e.g. mirror reflectance, window transmittance, etc., to surface deposits. To evaluate contamination sensitivity for mirror coatings, eight types representative of those used in the vacuum ultraviolet, visible, and infrared were modeled assuming that the contaminant is uniformly deposited on the mirror surface. Parametric studies over a range of complex refractive indices combined with an examination of optical data available for several organic materials suggested division of the contaminant layer index into three categories, N = 1.5 + 0.1i, N = 1.5 + 0.5i, and N = 1.5 + 2.0i. Contaminant thickness sensitivity curves were then calculated for each of the selected mirror coatings. For comparative purposes, critical thicknesses for each type were extracted, assuming a reflectance loss of 10 percent was allowable. Critical thicknesses ranged from about 10 A to 1000 A depending on the specifics of coating design and spectral region.

Osantowski, J. F.↗

Navier Stokes solution of the flowfield over ice accretion shapes

The numerical simulation of flow about ice accretion shapes has been accomplished by solving the Navier-Stokes equations using MacCormack's explicit finite difference scheme. The computations were performed on a CRAY-XMP computer. The influence of turbulence is taken into account by means of an algebraic eddy-viscosity model. In order to optimize the grid spacing and to achieve near orthogonality at the surface of the complex ice shapes, a hyperbolic grid generation scheme is utilized. Particular attention is given to the heat transfer process for which good agreement between the numerical and experimental results is achieved. In addition, liquid water droplet trajectories are coupled within the flowfield along with the resulting collection efficiencies using a parabolized Navier-Stokes formulation.

Scott, J. N.↗

Beaming of Uranian kilometric radiation and implications for the planetary magnetic field

Radio waves from Uranus at 481.2 kHz detected by Voyager 2 show a strong beaming effect. When the data are analyzed according to the magnetic latitude of the observer in an offset tilted dipole field model, a sharply defined emission beam extending from 25 to 55 deg latitude is evident consistent with a source over the south magnetic pole. The lack of prominent emission from the north magnetic pole can be attributed to the large spatial offset of the magnetic dipole resulting in much lower source frequencies. For proper alignment of the beam, an advance of the dipole axis longitude by 23 deg from the standard model is required. This phase shift is interpreted as the result of higher order magnetic moments producing a skew of the field lines at low altitudes in the polar source region. This conclusion further substantiates models of the interior of Uranus which predict a complex intrinsic field with significant nondipolar contributions to the surface magnetic field.

Barbosa, D. D.↗

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↗

Prairie State Generating Company Static and Dynamic Modeling

A reservoir modeling study was conducted to assess the feasibility of storing 162.5 million tonnes (8.125 million tonnes annually) of industrially sourced carbon dioxide (CO 2 ) in the St. Peter – Everton and Knox storage complexes at the Prairie State Generating Company’s (PSGC) site near Marissa, Washington County, Illinois (PSGC site). Two separate models were constructed for the St. Peter – Everton and the Knox storage complexes. The St. Peter and Everton sandstones are the target storage units for the St. Peter – Everton storage complex. The Knox Group formations are the target storage units for the Knox storage complex. The Maquoketa Shale is the primary confining unit for both storage complexes. The static reservoir models used as input to the dynamic reservoir models of the storage complexes were developed from interpretations of logs (e.g., gamma ray, resistivity, porosity, photoelectric, and sonic), structure surfaces using data from 36 wells, thickness maps, well test data, seismic data, and permeability data in PetrelTM.

01 COAL, LIGNITE, AND PEAT↗

Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fed production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.

Johnson, M. S.↗

Substitution Models of Protein Evolution with Selection on Enzymatic Activity

Abstract Substitution models of evolution are necessary for diverse evolutionary analyses including phylogenetic tree and ancestral sequence reconstructions. At the protein level, empirical substitution models are traditionally used due to their simplicity, but they ignore the variability of substitution patterns among protein sites. Next, in order to improve the realism of the modeling of protein evolution, a series of structurally constrained substitution models were presented, but still they usually ignore constraints on the protein activity. Here, we present a substitution model of protein evolution with selection on both protein structure and enzymatic activity, and that can be applied to phylogenetics. In particular, the model considers the binding affinity of the enzyme–substrate complex as well as structural constraints that include the flexibility of structural flaps, hydrogen bonds, amino acids backbone radius of gyration, and solvent-accessible surface area that are quantified through molecular dynamics simulations. We applied the model to the HIV-1 protease and evaluated it by phylogenetic likelihood in comparison with the best-fitting empirical substitution model and a structurally constrained substitution model that ignores the enzymatic activity. We found that accounting for selection on the protein activity improves the fitting of the modeled functional regions with the real observations, especially in data with high molecular identity, which recommends considering constraints on the protein activity in the development of substitution models of evolution.

Ferreiro, David↗

On the Rapid Calculation of Binding Affinities for Antigen and Antibody Design and Affinity Maturation Simulations

The accurate and efficient calculation of protein-protein binding affinities is an essential component in antibody and antigen design and optimization, and in computer modeling of antibody affinity maturation. Such calculations remain challenging despite advances in computer hardware and algorithms, primarily because proteins are flexible molecules, and thus, require explicit or implicit incorporation of multiple conformational states into the computational procedure. The astronomical size of the amino acid sequence space further compounds the challenge by requiring predictions to be computed within a short time so that many sequence variants can be tested. In this study, we compare three classes of methods for antibody/antigen (Ab/Ag) binding affinity calculations: (i) a method that relies on the physical separation of the Ab/Ag complex in equilibrium molecular dynamics (MD) simulations, (ii) a collection of 18 scoring functions that act on an ensemble of structures created using homology modeling software, and (iii) methods based on the molecular mechanics-generalized Born surface area (MM-GBSA) energy decomposition, in which the individual contributions of the energy terms are scaled to optimize agreement with the experiment. When applied to a set of 49 antibody mutations in two Ab/HIV gp120 complexes, all of the methods are found to have modest accuracy, with the highest Pearson correlations reaching about 0.6. In particular, the most computationally intensive method, i.e., MD simulation, did not outperform several scoring functions. The optimized energy decomposition methods provided marginally higher accuracy, but at the expense of requiring experimental data for parametrization. Within each method class, we examined the effect of the number of independent computational replicates, i.e., modeled structures or reinitialized MD simulations, on the prediction accuracy. We suggest using about ten modeled structures for scoring methods, and about five simulation replicates for MD simulations as a rule of thumb for obtaining reasonable convergence. We anticipate that our study will be a useful resource for practitioners working to incorporate binding affinity calculations within their protein design and optimization process.

59 BASIC BIOLOGICAL SCIENCES↗

The Aguas Zarcas Breccia - Similarities to Surface Features of C-Complex Asteroids Ryugu and Bennu

Knowledge of the materials originally present in the proto-solar nebula is one of the most significant constraints for models concerning the formation of our solar system. The physicochemical properties of these original materials can be determined through two distinct and complementary approaches: astronomical observations of nascent stellar systems and the dense clouds from which they originated; and laboratory studies of available astromaterials such as meteorites, interplanetary dust particles, comets, as well as returned mission samples (e.g., from Hayabusa -1 -2;OSIRIS -Rex). Laboratory study of these extraterrestrial materials provides valuable information about the first solids portion of the early solar system and their evolution. Here, we present petrographic and mineralogical characteristics of the polymic beccias Aguas Zarcas based on the research results of [1].On April 23, 2019, at 21:07 local time, a meteorite fall occurred in Aguas Zarcas, San Carlos County, Alajuela province, Costa Rica. The rapid recovery of this brecciated carbonaceous chondrite after its fall provides an opportunity to study a freshly fallen, relatively uncontaminated, and highly brecciated meteorite to compare with samples returned by theHayabusa2 and OSIRIS-REx spacecraft from C-group asteroids. The study includes several pre-rain fragments [1].The X-ray Computed Tomography (XCT) results show many different lithologies. We describe the petrography and mineralogy of five different lithologies of the Aguas Zarcas meteorite. We also present data on bulk oxygen isotopes. We describe all fragments in detail and attempt to classify each lithology in order to understand the origin and formation history of the Aguas Zarcas parent body. Our results show that some lithologies of Aguas Zarcas are similar to those in CM chondrites, but others are unique. The different lithologies [1] also represent different degrees of hydration and heating, which are good analogues for the types of materials returned by the Bennu and Ryugu asteroids. Spectroscopic observations of the Ryugu and Bennu asteroids compared to laboratory measurements of meteorites suggest that the asteroids have some similarities to heated CM, heated CI, or CI chondrites[2-5]. Both asteroids are thought to be composed of materials altered by aqueous alteration (e.g., [5]) and formed by reaccretion after destruction by impacts and brecciation (e.g., [6-7]). Considering the different lithologies in Aguas Zarcas [2] and other CM chondrites [8-9], these types of carbonaceous chondrites can be considered good analogues for samples from the Ryugu and Bennu asteroids. The presence of unique and rare lithologies in the Aguas Zarcas, different from the typical CM chondrite lithologies, suggests complex mixing of different materials in a highly dynamic environment.

Imene Kerraouch↗