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At least 109 records · Page 6

Molecular Simulations in Astrobiology

One of the main goals of astrobiology is to understand the origin of cellular life. In the absence of any record of the earliest ancestors of contemporary cells, protocells, the most direct way to test our understanding of their characteristics is to construct laboratory models of protocells. Such efforts, currently underway in the NASA Astrobiology Program, are accompanied by computational studies aimed at explaining self-organization of simple molecules into ordered structures and developing designs of molecules that are capable of performing protocellular functions. Many of these functions, such as importing nutrients, capturing and storing energy, and responding to changes in the environment, are carried out by proteins bound to membranes. We use computer simulations to address the following, questions about these proteins: (1) How do small proteins (peptides) organize themselves into ordered structures at water-membrane interfaces and insert into membranes? (2) How do peptides aggregate to form membrane-spannin(y structures (e.g., channels)? (3) By what mechanisms do such aggregates perform their functions? The simulations are performed using the molecular dynamics (MD) method. In this method, Newton's equations of motion for each atom in the system are solved iteratively. At each time step, the forces exerted on each atom by the remaining atoms are evaluated by dividing them into two parts. Short-range forces are calculated directly in real space while long-range forces are evaluated in reciprocal space, usually using a particle-mesh algorithm which is of order O(NlnN). Currently, a time step of 2 femtoseconds is typically used, thereby making studies of problems occurring on multi-nanosecond time scales (10(exp 6) - 10(exp 8) time steps) accessible. To address a broader range of problems, simulations need to be extended by three orders of magnitude. Such an extension requires both algorithmic improvements and codes scalable to a large number of parallel processors. Work in this direction is in progress. Two specific series of simulations that demonstrate how peptides self-organize and function in membranes are discussed. In one series of simulations, it was shown that nonpolar peptides, disordered in water, translocate to the nonpolar interior of the membrane and, simultaneously, fold into two different helical structures, which remain in equilibrium. Once in the membrane, the peptides can readily change their orientation, especially in response to local electric fields. This structural and orientational flexibility of peptides with changing conditions may have provided a mechanism of transmitting signals between the environment and the interior of the protocell. In another series of simulations, the mechanism by which a simple protein channel efficiently mediates proton transport across membranes was investigated. This process is a key step in cellular bioenergetics. In the channel under study, proton transport is gated by four histidines that occlude the channel pore. The simulations demonstrate that protons move through the gate by a "shuttle" mechanism, wherein one histidine is protonated on the extracellular side and, subsequently, the proton bound on the opposite side is released.

Pohorille, Andrew↗

Simulation of Peptides at Aqueous Interfaces

Behavior of peptides at water-membrane interfaces is of great interest in studies on cellular transport and signaling, membrane fusion, and the action of toxins and antibiotics. Many peptides, which exist in water only as random coils, can form sequence-dependent, ordered structures at aqueous interfaces, incorporate into membranes and self-assembly into functional units, such as simple ion channels. Multi -nanosecond molecular dynamics simulations have been carried out to study the mechanism and energetics of interfacial folding of both non-polar and amphiphilic peptides, their insertion into membranes and association into higher-order structures. The simulations indicate that peptides fold non-sequentially, often through a series of amphiphilic intermediates. They further incorporate into the membrane in a preferred direction as folded monomers, and only then aggregate into dimers and, possibly, further into "dimers of dimers".

Pohorille, Andrew↗

Inter and Intra Molecular Phase Separation Environment Effects on PI-PEO Block Copolymers for Batteries and Fuel Cells

Rod-coil molecules have been introduced as a novel type of block copolymers with unique microstructure due to their ability to self-assemble to various ordered morphologies on a nanometer length scale. These molecules, comprised two homo polymers joined together at one end, microphase separate into ordered, periodic arrays of spheres, cylinders in the bulk state and or solution. To get ordered structure in a reasonable scale, additional force field are applied, such as mechanical shearing, electric field and magnetic field. Recently, progress has made it a possible to develop a new class of polyimides (PI)-Polyethylene oxide (PEO) that are soluble in polar organic solvents. The solvent-soluble PI-PEO has a wide variety of applications in microelectronics, since these PI-PEO films exhibit a high degree of thermal and chemical stability. In this paper, we report the self-assembled ordered structure of PI-PEO molecules formed from concentrate solution.

Xue, Chen-Chen↗

Self-healing macromolecular crystal materials

Hybrid materials are disclosed including molecular/protein crystals integrated with synthetic polymers. The disclosed materials combine the structural order and periodicity of crystals, the adaptiveness and tunable mechanical properties of polymeric networks, and the chemical versatility of protein building blocks. Some of the properties of the disclosed materials include the following: 1) allows crystals—which are typically rigid and brittle—to expand and contract reversibly; 2) incorporates polymers to increase the mechanical toughness of the crystals and allow self-healing; 3) reversibly expand/contract crystal lattices and mobilize the protein components therein may provide a new means to improve X-ray diffraction quality and explore otherwise inaccessible protein structural states using 3D protein crystallography; 4) creation of chemically and mechanically differentiated domains within single crystals. Some example embodiments combine the properties of hydrogels (flexibility, adaptability, elasticity, self-healing), crystals (structural order) and proteins (chemical and genetic tailorability).

Tezcan, Faik↗

Diffraction-quality, ultraflexible protein single crystals engineered with DNA

DNA-functionalized colloidal nanoparticles assemble through flexible, nanoscale DNA hybridization interactions that limit atomic-level structural order. Here, we report a valence-centric strategy that enables DNA-bonded, protein single crystals with unconventional mechanical properties. An octameric enzyme, glutarate L-2-hydroxylase, was site- and number-selectively conjugated with eight self-complementary single-stranded DNA, yielding octavalent molecular bonds. The resulting conjugate assembled into the designed body-centered tetragonal crystals that diffracted to 1.42- to 2.61-angstrom resolution, with contacts mediated by B-form DNA helices spanning 17 to 25 angstroms. Increasing oligonucleotide length induces anisotropic lattice expansion while preserving atomic periodicity, even with partial DNA occupancy. Mechanistic studies suggest that the dynamic motion of unhybridized DNA facilitates crystallization, analogous to fluctuating electron clouds in atomic bonding. Compared with native protein crystals, DNA-hybridized crystals are 23-fold softer. These results challenge the assumption that flexibility is incompatible with structural order and establish a programmable framework for biomolecular crystallization and nanomaterials engineering with atomic precision.

Han, Zhenyu [Department of Chemistry, Northwestern↗

The N–terminal zinc finger of CELLULOSE SYNTHASE6 is critical in defining its functional properties by determining the level of homodimerization in Arabidopsis

Primary cell wall cellulose is synthesized by the cellulose synthase complex (CSC) containing CELLULOSE SYNTHASE1 (CESA1), CESA3 and one of four CESA6–like proteins in Arabidopsis. It has been proposed that the CESA6–like proteins occupy the same position in the CSC, but their underlying selection mechanism remains unclear. We produced a chimeric CESA5 by replacing its N–terminal zinc finger with its CESA6 counterpart to investigate the consequences for its homodimerization, a crucial step in forming higher–order structures during assembly of the CSC. We found that the mutant phenotypes of prc1–1, a cesa6 null mutant, were rescued by the chimeric CESA5, and became comparable to the wild type (WT) and prc1–1 complemented by WT CESA6 in regard to plant growth, cellulose content, cellulose microfibril organization, CSC dynamics and subcellular localization. Bimolecular fluorescence complementation assays were employed to evaluate pairwise interactions between the N–terminal regions of CESA1, CESA3, CESA5, CESA6 and the chimeric CESA5. We verified that the chimeric CESA5 explicitly interacted with all the other CESA partners, comparable to CESA6, whereas interaction between CESA5 with itself was significantly weaker than that of all other CESA pairs. Furthermore, our findings suggest that the homodimerization of CESA6 through its N–terminal zinc finger is critical in defining its functional properties, and possibly determines its intrinsic roles in facilitating higher–order structures in CSCs.

59 BASIC BIOLOGICAL SCIENCES↗

Closing the Gap Between Modeling and Experiments in the Self-assembly of Biomolecules at Interfaces and in Solution

Molecular self-assembly is a powerful tool in materials design, wherein non-covalent interactions like electrostatic, hydrophobic, hydrogen bonding, and van der Waals can be exploited to produce supramolecular nanostructures that are functional and highly tunable. Biomolecules are attractive building blocks, as they are biocompatible, biodegradable and adopt a wide array of higher order structures. Moreover, naturally occurring protein systems display a manifold of structures and interactions that can be replicated in synthetic biomolecules. In this perspective, we highlight advances in multiscale simulation techniques across broad spatiotemporal scales that can aid in characterizing self-assembly of hybrid and hierarchical bionanomaterial systems, with an emphasis on physics-based simulation approaches currently employed to study biomolecules at mineral interfaces. The power of these approaches is highlighted across a few recent areas where molecular simulations have advanced our understanding of self-assembly spanning peptides to protein self-assembly. Looking forward, we discuss how in the near future emerging methods in statistical and machine learning will advance this research field in all areas from expanding the capabilities of physics-based simulation methods to enabling new analyses of high throughput experiments. These advances will pave the way for understanding the molecular recognition patterns in systems that are dictated by self-assembly - biomineralizing peptides, hierarchical peptoids, and large protein assemblies, and will aid in the development of a new synthesis science for achieving precise molecular control in materials design

Sampath, Janani↗

A Nonstationary and Non-Gaussian Moving Average Model for Solar Irradiance

Historically, power has flowed from large power plants to customers. Increasing penetration of distributed energy resources such as solar power from rooftop photovoltaic has made the distribution network a two-way-street with power being generated at the customer level. The incorporation of renewables introduces additional uncertainty and variability into the power grid. Distribution network operation studies are being adapted to include renewables; however, such studies require high quality solar irradiance data that adequately reflect realistic meteorological variability. Data from satellite-based products are spatially complete, but temporally coarse, whereas solar irradiances exhibit high frequency variation at very fine timescales. We propose a new stochastic method for temporally downscaling global horizontal irradiance (GHI) to 1 min resolution, but we do not consider the spatial aspect due to limited availability of the in situ irradiance measurements. Solar irradiance's first and second-order structures vary diurnally and seasonally, and our model adapts to such nonstationarity. Empirical irradiance data exhibits highly non-Gaussian behavior; we develop a nonstationary and non-Gaussian moving average model that is shown to capture realistic solar variability at multiple timescales. We also propose a new estimation scheme based on Cholesky factors of empirical autocovariance matrices, bypassing difficult and inaccessible likelihood-based approaches. The model is demonstrated for a case study of three locations that are located in diverse climates through the United States. The model is compared against competitors from the literature and is shown to provide better uncertainty and variability quantification on testing data.

Cholesky factor↗

Pressure-induced changes in structure, magnetic order and superconductivity in the ferromagnetic topological insulator MnBi 8 Te 13

Introducing superconductivity (SC) in an intrinsic magnetic topological system remains a significant challenge in modern condensed matter physics. Here, we show that SC can be induced by applying high pressure to a promising ambient-pressure magnetic topological insulator candidate, MnBi 8 Te 13 . Using electrical transport, magnetic susceptibility, and synchrotron x-ray diffraction, we construct a detailed temperature - pressure phase diagram. The ambient-pressure ferromagnetic order is progressively suppressed and replaced by an antiferromagnetic state. Above 16.6 GPa, bulk SC emerges with a critical temperature up to 6.8 K. This pressure-induced SC may co-exist with another AFM dome. In contrast, the related compounds with higher magnetic ion (Mn) concentration show no SC, highlighting the crucial role of Mn concentration in stabilizing SC. The observation of pressure-induced FM-AFM-SC transitions in MnBi 8 Te 13 not only establishes it as a rare Mn-based SC but also provides a platform to study the interplay between magnetism, SC, and potentially nontrivial band topology in correlated magnetic materials.

Huyan, S. [Ames Laboratory, and Iowa State Univ., ↗

Itinerant ferromagnetism and intrinsic anomalous Hall effect in amorphous iron-germanium

The amorphous iron-germanium system ( a - Fe x Ge 1 - x ) lacks long-range structural order and hence lacks a significant Brillouin zone. The magnetization of a - Fe x Ge 1 - x is well explained by the Stoner model for Fe concentrations x above the onset of magnetic order around x = 0.4 , indicating that the local order of the amorphous structure preserves the spin-split density of states of the Fe- 3 d states sufficiently to polarize the electronic structure despite k being a bad quantum number. Measurements reveal an enhanced anomalous Hall resistivity ρ x y AH relative to crystalline FeGe; this ρ x y AH is compared to density-functional theory calculations of the anomalous Hall conductivity to resolve its underlying mechanisms. The intrinsic mechanism, typically understood as the Berry curvature integrated over occupied k states but shown here to be equivalent to the density of curvature integrated over occupied energies in aperiodic materials, dominates the anomalous Hall conductivity of a - Fe x Ge 1 - x ( 0.38 ≤ x ≤ 0.61 ). The density of curvature is the sum of spin-orbit correlations of local orbital states and can hence be calculated with no reference to k space. This effect and the accompanying Stoner-like model for the intrinsic anomalous Hall conductivity establish a unified understanding of the underlying physics of the anomalous Hall effect in both crystalline and disordered systems.

36 MATERIALS SCIENCE↗

A subgrid-scale model based on the second-order velocity structure function

A series of tests were performed to help extend the use of a subgrid-scale model to compressible and wall-bounded flows. A priori tests were done in the case of the incompressible turbulent channel flow. They showed that a 1-D formulation of the structure-function model is more appropriate, leading to a satisfactory behavior of the model at the walls without requiring any damping function. This model is consistent with the original formulation of Metais & Lesieur (1990). In large-eddy simulations of compressible isotropic turbulence, both models performed well up to an initial rms Mach number of 0.6.

Comte, P.↗

The Fe2(+)-Mg interdiffusion in orthopyroxene: Constraints from cation ordering and structural data and implications for cooling rates of meteorites

Orthopyroxene crystals in a number of meteorites exhibit compositional zoning of Fe and Mg, which provide important constraint on their cooling rates. However, attempts to model cooling rate of these crystals from Fe-Mg zoning profiles suffer from the lack of any measured or theoretically well constrained Fe-Mg interdiffusion data in OP(x) It has been assumed that Fe-Mg interdiffusion in OP(x) only slightly slower than that in olivine. The purpose of this paper is to (1) calculate the Fe-Mg fractionation, and (2) provide analytical formulation relating cooling rate to the length of the diffusion zone across the interface of the overgrowth of a mineral on itself with application to Mg diffusion profile across OP(x) growth on OP(x) in certain mesosiderites.

Ganguly, J.↗

Metal foils with ordered crystal structure and method for producing metal foils

A method for producing a metal foil comprising depositing metal onto an oxidizable substrate to form a metal film on the substrate; oxidizing the substrate at an interface between the metal film and the substrate; and removing the metal film from the substrate to yield a metal foil. A method for forming a thin metal film comprising pre-polarizing a single-crystal Si substrate by application of a potential which is negative of a potential at which Si oxidizes, which pre-polarization occurs in the presence of metal ions to form metal growth nucleation sites on the substrate, followed by application of a potential at which both oxidation of Si and electrodeposition of the metal occur to grow the metal film and oxidize the Si to SiOx, which potential is more positive than the potential applied in the pre-polarization step.

Switzer, Jay A.↗

Range and strength of mechanical interactions of force dipoles in elastic fiber networks

Mechanical forces generated by myosin II molecular motors drive diverse cellular processes, most notably shape change, division and locomotion. These forces may be transmitted over long range through the cytoskeletal medium – a disordered, viscoelastic network of biopolymers. The resulting cell size scale force chains can in principle mediate mechanical interactions between distant actomyosin units, leading to self-organized structural order in the cell cytoskeleton. Inspired by such force transmission through elastic structures in the cytoskeleton, we consider a percolated fiber lattice network, where fibers are represented as linear elastic elements that can both bend and stretch, and the contractile activity of myosin motors is represented by force dipoles. Then, by using a variety of metrics, we show how two such contractile force dipoles interact with each other through their mutual mechanical deformations of the elastic fiber network. As a prelude to two-dipole interactions, we quantify how forces propagate through the network from a single anisotropic force dipole by analyzing clusters of nodes connected by highly strained bonds, as well as through the decay rate of strain energy with distance from a force dipole. We show that predominant fiber bending screens out force propagation, resulting in reduced and strongly network configuration-dependent dipole interactions. On the other hand, stretching-dominated networks support longer-ranged inter-dipole interactions that recapitulate the predictions of linear elasticity theory. By characterizing the differences between tensile and compressive force propagation in the fiber network, we show how inter-dipole interaction depends on the dipoles’ mutual separation and orientation. The resulting elastic interaction energy may mediate a force between multiple distant dipoles, leading to their self-organization into ordered configurations. In conclusion, this provides a potential pathway for active mechanical force-driven structural order in elastic biopolymer networks.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗