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At least 433 records · Page 24

Stochastic Effects in Computational Biology of Space Radiation Cancer Risk

Estimating risk from space radiation poses important questions on the radiobiology of protons and heavy ions. We are considering systems biology models to study radiation induced repair foci (RIRF) at low doses, in which less than one-track on average transverses the cell, and the subsequent DNA damage processing and signal transduction events. Computational approaches for describing protein regulatory networks coupled to DNA and oxidative damage sites include systems of differential equations, stochastic equations, and Monte-Carlo simulations. We review recent developments in the mathematical description of protein regulatory networks and possible approaches to radiation effects simulation. These include robustness, which states that regulatory networks maintain their functions against external and internal perturbations due to compensating properties of redundancy and molecular feedback controls, and modularity, which leads to general theorems for considering molecules that interact through a regulatory mechanism without exchange of matter leading to a block diagonal reduction of the connecting pathways. Identifying rate-limiting steps, robustness, and modularity in pathways perturbed by radiation damage are shown to be valid techniques for reducing large molecular systems to realistic computer simulations. Other techniques studied are the use of steady-state analysis, and the introduction of composite molecules or rate-constants to represent small collections of reactants. Applications of these techniques to describe spatial and temporal distributions of RIRF and cell populations following low dose irradiation are described.

Cucinotta, Francis A.↗

4BMS-X Design and Test Activation

In support of the NASA goals to reduce power, volume and mass requirements on future CO2 (Carbon Dioxide) removal systems for exploration missions, a 4BMS (Four Bed Molecular Sieve) test bed was fabricated and activated at the NASA Marshall Space Flight Center. The 4BMS-X (Four Bed Molecular Sieve-Exploration) test bed used components similar in size, spacing, and function to those on the flight ISS flight CDRA system, but were assembled in an open framework. This open framework allows for quick integration of changes to components, beds and material systems. The test stand is highly instrumented to provide data necessary to anchor predictive modeling efforts occurring in parallel to testing. System architecture and test data collected on the initial configurations will be presented.

Peters, Warren T.↗

Fully-polarimetric millimeter-wave spectrometers for measurement of Earth's magnetic field

Earth’s ionosphere responds dynamically over a wide range of temporal and spatial scales to changes in the magnetosphere and solar wind from above, and to neutral atmospheric dynamics from below. Determining the dynamics and coupling of Earth's magnetosphere, ionosphere, and atmosphere by vector magnetic field measurements at all altitudes is essential, as the field plays a major role in controlling the distribution of ionospheric plasma. It is difficult to measure the magnetic B-field, either locally or globally, at the altitudes of the upper mesosphere and lower thermosphere (UMLT) where the transfer of energy and momentum between the plasma and neutral components of the system occur. The 118-GHz imaging magnetometer will measure all four Stokes parameters as a function of frequency about the Zeeman-split center of the 118-GHz molecular oxygen line. We are developing an array of fully-polarimetric millimeterwave radiometer/spectrometers operating near 118 GHz. These low cost, low power, low mass polarimetric 118 GHz millimeter-wave array receivers do not require cooling to meet the sensitivity requirements. With digital spectrometers we will be able to integrate the complete end-to-end system. This work will enable a second generation small satellite mission with an off-nadir viewing instrument comprised of 120 such receivers (arranged so that each spot on the Earth is observed simultaneously by four receivers each) that will globally map the magnetic field in the mesosphere at 42-76 km altitude at a horizontal resolution ~100 km with 1-sigma error of 40-120 nT, in typical mesospheric temperature conditions.

Mannucci, Anthony↗

Brown dwarfs and Jovian planets: A comparison

The recent detection of a subluminous companion to the M dwarf star VB8 has renewed interest in the characteristics of objects spanning the mass range from Jupiter to hydrogen burning stars. Atmospheric and interior models were constructed for objects in this mass regime, up to 30 Jupiter masses, with emphasis on understanding the relationship of brown dwarfs such as the VB8 companion to the better-studied Jovian planets. The atmospheric model solves the equation of radiative transfer assuming frequency dependent molecular opacity sources H2, He, H2O, CO, and CH4 which are important by virtue of the high cosmic abundance of their constituent atoms. Condensation of cosmochemically important materials, iron and silicates, in the atmosphere is possible, and the effect of such grains as opacity sources is assessed. The luminosity of the object is presumed due to degenerate cooling following a collapse phase and possibly deuterium burning and an interior model is constructed using as an outer boundary condition the temperature and pressure level at which the atmosphere becomes convective. The interior model is analogous to Jupiter, with a large liquid metallic-hydrogen core and a thinner molecular-hydrogen envelope. The oxidation state of carbon in the outer envelope of a brown dwarf of similar age to Jupiter is a function of the object's mass. This makes the wavelength dependence of the atmospheric opacity sensitive to the carbon to oxygen ratio, since the abundance of the primary source of molecular opacity, H2O, decreases as more oxygen is tied up as CO.

Lunine, J. I.↗

Molecular tori in Seyfert galaxies - Feeding the monster and hiding it

The principal properties of the tori of gas which surround Seyfert nuclei are discussed. The internal state of the clouds and their size distribution function are examined, and it is shown that the Jeans mass scale results in clouds which are individually sufficiently opaque to block out the nucleus, and that the balance of processes which controls their size distribution function also forces the covering factor to be of the order of or greater than unity. Where the gravitational potential is dominated by stars, cloud-cloud collisions keep the molecular clouds close to the equatorial plane. Stirring by stellar processes is never strong enough to compete with collisional losses. The position of the inner edge of the torus is determined by a balance between the inward flow of clouds and the rate at which the nuclear continuum can evaporate them.

Krolik, Julian H.↗

Formation of Carbon Nanotube Based Gears: Quantum Chemistry and Molecular Mechanics Study of the Electrophilic Addition of o-Benzyne to Fullerenes, Graphene, and Nanotubes

Considerable progress has been made in recent years in chemical functionalization of fullerene molecules. In some cases, the predominant reaction products are different from those obtained (using the same reactants) from polycyclic aromatic hydrocarbons (PAHs). One such example is the cycloaddition of o-benzyne to C60. It is well established that benzyne adds across one of the rings in naphthalene, anthracene and other PAHs forming the [2+4] cycloaddition product (benzobicyclo[2.2.2.]-octatriene with naphthalene and triptycene with anthracene). However, Hoke et al demonstrated that the only reaction path for o-benzyne with C60 leads to the [2+2] cycloaddition product in which benzyne adds across one of the interpentagonal bonds (forming a cyclobutene ring in the process). Either reaction product results in a loss of aromaticity and distortion of the PAH or fullerene substrate, and in a loss of strain in the benzyne. It is not clear, however, why different products are preferred in these cases. In the current paper, we consider the stability of benzyne-nanotube adducts and the ability of Brenner's potential energy model to describe the structure and stability of these adducts. The Brenner potential has been widely used for describing diamondoid and graphitic carbon. Recently it has also been used for molecular mechanics and molecular dynamics simulations of fullerenes and nanotubes. However, it has not been tested for the case of functionalized fullerenes (especially with highly strained geometries). We use the Brenner potential for our companion nanogear simulations and believe that it should be calibrated to insure that those simulations are physically reasonable. In the present work, Density Functional theory (DFT) calculations are used to determine the preferred geometric structures and energetics for this calibration. The DFT method is a kind of ab initio quantum chemistry method for determining the electronic structure of molecules. For a given basis set expansion, it is comparable in accuracy to the MP2 method (better than Hartree Fock, but less accurate than more extensive electron correlation methods such as MP4 or CCSD). However, for systems with large numbers of basis functions it more efficient than any other methods that include electron correlation effects. In this presentation we show the results of DFT calculations for the reaction of benzyne with naphthalene, C60, and nanotube models. We compare energies for [2+2] and [2+4] cycloaddition products. The preferred products for the naphthalene and C60 reactions have been determined by experiment and, thus, these cases serve as a validation of our quantum chemical approach. We also compare the DFT and Brenner potential results. Finally we can predict the likelihood of reaction between benzyne and nanotubes.

Jaffe, Richard↗

Protein Solvation in Membranes and at Water-Membrane Interfaces

Different salvation properties of water and membranes mediate a host of biologically important processes, such as folding, insertion into a lipid bilayer, associations and functions of membrane proteins. These processes will be discussed in several examples involving synthetic and natural peptides. In particular, a mechanism by which a helical peptide becomes inserted into a model membrane will be described. Further, the molecular mechanism of recognition and association of protein helical segments in membranes will be discussed. These processes are crucial for proper functioning of a cell. A membrane-spanning domain of glycophorin A, which exists as a helical dimer, serves as the model system. For this system, the free energy of dissociation of the helices is being determined for both the wild type and a mutant, in which dimerization is disrupted.

Pohorille, Andrew↗

Cross-linking and the molecular packing of corneal collagen

We have quantitatively characterized, for the first time, the cross-linking in bovine cornea collagen as a function of age. The major iminium reducible cross-links were dehydro-hydroxylysinonorleucine (deH-HLNL) and dehydro-histidinohydroxymerodesmosine (deH-HHMD). The former rapidly diminished after birth; however, the latter persisted in mature animals at a level of 0.3 - 0.4 moles/mole of collagen. A nonreducible cross-link, histidinohydroxylysinonorleucine (HHL), previously found only in skin, was also found to be a major mature cross-link in cornea. The presence of HHL indicates that cornea fibrils have a molecular packing similar to skin collagen. However, like deH-HHMD, the HHL content in corneal fibrils only reaches a maximum value with time about half that of skin. These data suggest that the corneal fibrils are comprised of discrete filaments that are internally stabilized by HHL and deH-HHMD cross-links. This pattern of intermolecular cross-linking would facilitate the special collagen swelling property required for corneal transparency.

NASA Discipline Musculoskeletal↗

Local Elastic Constants for Epoxy-Nanotube Composites from Molecular Dynamics Simulation

A method from molecular dynamics simulation is developed for determining local elastic constants of an epoxy/nanotube composite. The local values of C11, C33, K12, and K13 elastic constants are calculated for an epoxy/nanotube composite as a function of radial distance from the nanotube. While the results possess a significant amount of statistical uncertainty resulting from both the numerical analysis and the molecular fluctuations during the simulation, the following observations can be made. If the size of the region around the nanotube is increased from shells of 1 to 6 in thickness, then the scatter in the data reduces enough to observe trends. All the elastic constants determined are at a minimum 20 from the center of the nanotube. The C11, C33, and K12 follow similar trends as a function of radial distance from the nanotube. The K13 decreases greater distances from the nanotube and becomes negative which may be a symptom of the statistical averaging.

Frankland, S. J. V.↗

A description of the mechanical behavior of composite solid propellants based on molecular theory

Both the investigation and the representation of the stress-strain response (including rupture) of gum and filled elastomers can be based on a simple functional statement. Internally consistent experiments are used to sort out the effects of time, temperature, strain and crosslink density on gum rubbers. All effects are readily correlated and shown to be essentially independent of the elastomer when considered in terms of non-dimensionalized stress, strain and time. A semiquantitative molecular theory is developed to explain this result. The introduction of fillers modifies the response, but, guided by the framework thus provided, their effects can be readily accounted for.

Landel, R. F.↗

Applying Contamination Modelling to Spacecraft Propulsion Systems Designs and Operations

Molecular and particulate contaminants generated from the operations of a propulsion system may impinge on spacecraft critical surfaces. Plume depositions or clouds may hinder the spacecraft and instruments from performing normal operations. Firing thrusters will generate both molecular and particulate contaminants. How to minimize the contamination impact from the plume becomes very critical for a successful mission. The resulting effect from either molecular or particulate contamination of the thruster firing is very distinct. This paper will discuss the interconnection between the functions of spacecraft contamination modeling and propulsion system implementation. The paper will address an innovative contamination engineering approach implemented from the spacecraft concept design, manufacturing, integration and test (I&T), launch, to on- orbit operations. This paper will also summarize the implementation on several successful missions. Despite other contamination sources, only molecular contamination will be considered here.

Chen, Philip T.↗

Electronic Transport through Self Assembled Thiol Molecules: Effect of Monolayer Order, Dynamics and Temperature

We present the charge transport and tunneling conductance of self assembled organic thiol molecules and discuss the influence of order and dynamics in the monolayer on the transport behavior and the effect of temperature. Conjugated thiol molecular wires and organometals such as terpyridine metal complexes provide a new platform for molecular electronic devices and we study their self assembly on Au(111) substrates by the scanning tunneling microscope. Determining the organization of the molecule and the ability to control the nature of its interface with the substrate is important for reliable performance of the molecular electronic devices. By concurrent scanning tunneling microscopy and spectroscopy studies on SAMs formed from oligo (phenelyne ethynelyne) monolayers with and without molecular order, we show that packing and order determine the response of a self assembled monolayer (SAM) to competing interactions. Molecular resolution STM imaging in vacuum shows that the OPES adopt an imcommensurate SAM structure on Au(111) with a rectangular unit cell. Tunneling spectroscopic measurements were performed on the SAM as a function of junction resistance. STS results show that the I-Vs are non linear and asymmetric due to the inherent asymmetry in the molecular structure, with larger currents at negative sample biases. The asymmetry increases with increasing junction resistance due to the asymmetry in the coupling to the leads. This is brought out clearly in the differential conductance, which also shows a gap at the Fermi level. We also studied the effect of order and dynamics in the monolayer on the charge transport and found that competing forces between the electric field, intermolecular interactions, tip-molecule physisorption and substrate-molecule chemisorption impact the transport measurements and its reliability and that the presence of molecular order is very important for reproducible transport measurements. Thus while developing new electronic platforms based on molecules, it is important to have a good control of the molecule-substrate interface, for the devices to perform reliably. While such a control would minimize fluctuations and dynamics in the ensemble, the real challenge is to develop device architectures that are tolerant to fluctuations, since they cannot be totally eliminated in these low dimensional soft systems. Results of temperature dependent STS measurements will also be discussed.

Dholakia, Geetha↗

New force theorem.

New force theorem for determining molecular energy derivatives with respect to internuclear distance derived from Hellmann-Feynman expression

MOLECULAR ENERGY↗

Solid-liquid phase transition in argon

Starting from the Lennard-Jones interatomic potential, a modified cell theory has been used to describe the solid-liquid phase transition in argon. The cell-size variations may be evaluated by a self-consistent condition. With the inclusion of cell-size variations, the transition temperature, the solid and liquid densities, and the liquid-phase radial-distribution functions have been calculated. These ab initio results are in satisfactory agreement with molecular-dynamics calculations as well as experimental data on argon.

Tsang, T.↗

Arsenic-induced intensity oscillations in reflection high-energy electron diffraction measurements

A technique of arsenic-induced RHEED intensity oscillations has been used to accurately measure arsenic incorporation rates as a function of substrate temperature during the homoepitaxial growths of both GaAs and InAs by molecular beam epitaxy (MBE). Measurements were made at growth temperatures from 350 to 650 C and at arsenic fluxes of 0.1 to 10.0 monolayer/s. The method measures only the arsenic actually incorporated into the growing film and does not include the arsenic lost in splitting the arsenic tetramers or lost by evaporation from the sample.

Lewis, B. F.↗

A rapid and accurate method for calculation of stratospheric photolysis rates with molecular scattering

A method for calculating the photodissociation rates needed for photochemical modeling of the stratosphere, which includes the effects of molecular scattering, is described. The procedure is based on Sokolov's method of averaging functional correction. The radiation model and approximations used to calculate the radiation field are examined. The approximated diffuse fields and photolysis rates are compared with exact data. It is observed that the approximate solutions differ from the exact result by 10 percent or less at altitudes above 15 km; the photolysis rates differ from the exact rates by less than 5 percent for altitudes above 10 km and all zenith angles, and by less than 1 percent for altitudes above 15 km.

Boughner, Robert E.↗

Windows in direct dissociative recombination cross sections

Model potential curves are used to show that large windows are present in direct dissociative-recombination cross sections from excited molecular-ion vibrational levels. The windows are due to the overlap of vibrational wave functions of the repulsive neutral states with the nodes of the ion vibrational wave function.

Guberman, Steven L.↗

Energetics of molecular-beam epitaxy models

The removal energies of constituent atoms from various unreconstructed semiconductor surfaces are calculated using a Green function method. An efficient difference-equation approach within the second-neighbor tight-binding model is employed. For a compound AB, binding energies for the A and B atoms on the (111), (-1 -1 -1), (100), and (110) surfaces are calculated. Analyses are made of the energy to remove an atom from the nearly full surface and from the nearly empty surface. Results are presented for Si, GaAs, CdTe, and HgTe; and the surface sublimation energies are found to depend on surface coverage and do not display a simple linear relationship to the number of bonds broken, as is often assumed in modeling growth by MBE.

Krishnamurthy, Srinivasan↗