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At least 19 records

Comparison of Chain Conformation of Poly(vinyl alcohol) in Solutions and Melts from Quantum Chemistry Based Molecular Dynamics Simulations

Confirmations of 2,4-dihydroxypentane (DHP), a model molecule for poly(vinyl alcohol), have been studied by quantum chemistry (QC) calculations and molecular dynamics (MD) simulations. QC calculations at the 6-311G MP2 level show the meso tt conformer to be lowest in energy followed by the racemic tg, due to intramolecular hydrogen bond between the hydroxy groups. The Dreiding force field has been modified to reproduce the QC conformer energies for DHP. MD simulations using this force field have been carried out for DHP molecules in the gas phase, melt, and CHCl3 and water solutions. Extensive intramolecular hydrogen bonding is observed for the gas phase and CHCl3 solution, but not for the melt or aqueous solution, Such a condensed phase effect due to intermolecular interactions results in a drastic change in chain conformations, in agreement with experiments.

Jaffe, Richard↗

Extended chain crystals of linear high polymers.

Studies of extended chain crystals carried out over the last 10 years have been reviewed. Crystallization in an extended chain conformation is possible either by chain folding followed by extension in the solid state, or by crystallization during polymerization. The equilibrium isometric crystal habit is only rarely exhibited. Crystals which derive from folded chain macroconformation by subsequent chain extension have lamellar habit, crystals which crystallize during polymerization often show fibrillar habit because of nucleation limitation. The morphology of extended chain crystals is analogous to folded chain crystals. Their properties have been shown to be close to the extrapolated equilibrium properties.

Wunderlich, B.↗

Equilibrium and Dynamics Properties of Poly(oxyethylene) Melts and Related Poly(alkylethers) from Simulations and Ab Initio Calculations

Molecular dynamics simulations of POE melts have been performed utilizing a potential force field parameterized to reproduce conformer energies and rotational energy barriers in dimethoxyethane as determined from ab initio electronic structure calculations. Chain conformations and dimensions of POE from the simulations were found to be in good agreement with predictions of a rotational isomeric state (RIS) model based upon the ab initio conformational. energies. The melt chains were found to be somewhat extended relative to chains at theta conditions. This effect will be discussed in light of neutron scattering experiments which indicate that POE chains are extended in the melt relative to theta solutions. The conformational characteristics of POE chains will also be compared with those of other poly (alkylethers), namely poly(oxymethylene), poly(oxytrimethylene) and poly(oxytetramethylene). Local conformational dynamics were found to be more rapid than in polymethylene. Calculated C-H vector correlation times were found to be in reasonable agreement with experimental values from C-13 NMR spin-lattice relaxation times. The influence of ionic salts on local conformations and dynamics will also be discussed.

Smith, Grant D.↗

Monte Carlo lattice models for adsorbed polymer conformation

The adhesion between a polymer film and a metal surface is of great technological interest. However, the prediction of adhesion and wear properties of polymer coated metals is quite difficult because a fundamental understanding of the polymer surface interaction does not yet exist. A computer model for the conformation of a polymer molecule adsorbed on a surface is discussed. The chain conformation is assumed to be described by a partially directed random walk on a three dimensional simple cubic lattice. An attractive surface potential is incorporated into the model through the use of a random walk step probability distribution that is anisotropic in the direction normal to the attractive surface. The effects of variations in potential characteristics are qualitatively included by varying both the degree of anisotropy of the step distribution and the range of the anisotropy. Polymer conformation is characterized by the average end to end distance, average radius of gyration, and average number of chain segments adsorbed on the surface.

Good, B. S.↗

Finding the global minimum: a fuzzy end elimination implementation

The 'fuzzy end elimination theorem' (FEE) is a mathematically proven theorem that identifies rotameric states in proteins which are incompatible with the global minimum energy conformation. While implementing the FEE we noticed two different aspects that directly affected the final results at convergence. First, the identification of a single dead-ending rotameric state can trigger a 'domino effect' that initiates the identification of additional rotameric states which become dead-ending. A recursive check for dead-ending rotameric states is therefore necessary every time a dead-ending rotameric state is identified. It is shown that, if the recursive check is omitted, it is possible to miss the identification of some dead-ending rotameric states causing a premature termination of the elimination process. Second, we examined the effects of removing dead-ending rotameric states from further considerations at different moments of time. Two different methods of rotameric state removal were examined for an order dependence. In one case, each rotamer found to be incompatible with the global minimum energy conformation was removed immediately following its identification. In the other, dead-ending rotamers were marked for deletion but retained during the search, so that they influenced the evaluation of other rotameric states. When the search was completed, all marked rotamers were removed simultaneously. In addition, to expand further the usefulness of the FEE, a novel method is presented that allows for further reduction in the remaining set of conformations at the FEE convergence. In this method, called a tree-based search, each dead-ending pair of rotamers which does not lead to the direct removal of either rotameric state is used to reduce significantly the number of remaining conformations. In the future this method can also be expanded to triplet and quadruplet sets of rotameric states. We tested our implementation of the FEE by exhaustively searching ten protein segments and found that the FEE identified the global minimum every time. For each segment, the global minimum was exhaustively searched in two different environments: (i) the segments were extracted from the protein and exhaustively searched in the absence of the surrounding residues; (ii) the segments were exhaustively searched in the presence of the remaining residues fixed at crystal structure conformations. We also evaluated the performance of the method for accurately predicting side chain conformations. We examined the influence of factors such as type and accuracy of backbone template used, and the restrictions imposed by the choice of potential function, parameterization and rotamer database. Conclusions are drawn on these results and future prospects are given.

NASA Program Exobiology↗

TPSAS-NF1676L-34417-DND

A boron nitride nanotube (BNNT), an electrically-insulating counterpart of a carbon nanotube (CNT), is a great nanofiller candidate for ferroelectric polymeric nanocomposites due to BNNT?s exceptional properties in piezoelectricity, thermal stability, mechanical strength, and radiation shielding capability. Fast and high-yield polar crystallization of polyvinylidene fluoride (PVDF) was accomplished by incorporating BNNTs as a nucleating agent. As-fabricated BNNT-PVDF nanocomposites were characterized by Fourier-transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (XRD), and differential scanning calorimetry (DSC) to identify and quantify chain conformations. Besides, piezoelectric constants, d33 of BNNT-PVDF nanocomposites were measured and compared with that of a mechanically drawn beta phase polar PVDF. The polar transformation due to BNNT incorporation has a great advantage over conventional beta or gamma transformation methods that require (1) mechanical drawing often resulting in defects or (2) high-temperature annealing for an extended time. In addition to the fast polar crystallization, BNNTs had a role of reinforcement of the polymer matrix. The improved Young?s modulus and electromechanical coupling coefficient of BNNT-PVDF nanocomposites indicated potential applications in energy harvesting under harsh environments such as large deformation, wide temperature cycles, and high radiation.

Dongwon Lee↗

Conformational Characteristics of Poly(tetrafluoroethylene) (PTFE) Based Upon Ab Initio Electronic Structure Calculations on Model Molecules

Conformational energy contours of perfluoroalkanes, determined from ab initio calculations, confirm the well-known spitting of trans states into two minima at plus or minus 17 degrees but also show that the gauche states split as well, with minima at plus or minus 124 degrees and plus or minus 84 in order to relieve steric crowding. The directions of such split distortions from the perfectly staggered states are strongly coupled for adjacent pairs of bonds in a manner identical to the intradyad pair for poly (isobutylene) chains. These conformational characteristics are fully represented by a six-state rotational isomeric state (RIS) model for PTFE comprised of t(+), t(-), g(sup +)+, g(sup +)-, g(sup -) + and g(sup -)-states, located at the split energy minima. The resultant 6 x 6 statistical weight matrix is described by first-order interaction parameters for the g+(+) (ca. 0.6 kcal/mol) and g+- (ca. 2.0 kcal/mol) states, and second order parameters for the g(sup +)+g(sup +)+ (ca 0.6 kcal/mol) and g(sup +)+g(sup -)+ (ca. 1.0 kcal/mol) states. This six-state RIS model, without adjustment of the geometric or energy parameters as determined from the ab initio calculations, predicts the unperturbed chain dimensions and the fraction of gauche bonds as a function of temperature for PTFE in good agreement with available experimental values.

Smith, Grant D.↗

Molecular arrangements and conformations of liquid n-tridecane chains confined between two hard walls

Monte Carlo simulations based on united CH2 atoms linked with fixed bond lengths and angles, and continuously varying torsional angles subject to appropriate interaction energies, were used to study liquid n-tridecane chains confined between two parallel hard walls with 5 mm separation. The molecules located in the central region are noted to be in very close agreement with ideal unperturbed chains. Nearly all the chain units in the first segmental layer adjacent to the walls belong to two-dimensional chains, and exhibit considerable orientational correlations between neighboring segments of different chains.

Vacatello, Michele↗

13C and 1H NMR (Nuclear Magnetic Resonance) studies of solid polyolefines

The basis of H-1 and C-13 high-resolution NMR investigations of solid polymers is outlined. The C-13 NMR spectra of solid syndiotactic and isotactic polypropene are discussed and their interpretation in terms of conformation and chain-packing effects are reviewed. The effects of decreasing temperature on the C-13 high-resolution spectrum of an annealed sample of isotactic polypropene is described and interpreted in terms of the crystal structure. The question of the proportion of the sample giving rise to C-13 signals is addressed and some results reported. The main cause for observing only part of the total sample is shown to be the H-1 rotating frame spin-lattice relaxation behavior. The H-1 spin-lattice relaxation and spectral characteristics of a number of polyolefin samples are summarized and the role of spin-diffusion discussed.

Cudby, M. E. A.↗

Dielectric Properties of Poly(ethylene oxide) from Molecular Dynamics Simulations

The order, conformations and dynamics of poly(oxyethylene) (POE) melts have been investigated through molecular dynamics simulations. The potential energy functions were determined from detailed ab initio electronic structure calculations of the conformational energies of the model molecules 1,2-dimethoxyethane (DME) and diethylether. The x-ray structure factor for POE from simulation will be compared to experiment. In terms of conformation, simulations reveal that chains are extended in the melt relative to isolated chains due to the presence of strong intermolecular O...H interactions, which occur at the expense of intramolecular O...H interactions. Conformational dynamics about the C-C bond were found to be significantly faster than in polymethylene, while conformational dynamics about the C-O bond even faster than the C-C dynamics. The faster local dynamics in POE relative to polymethylene is consistent with C-13 NMR spin-lattice relaxation experiments. Conformational transitions showed significant second-neighbor correlation, as was found for polymethylene. This correlation of transitions with C-C neighbors was found to be reduced relative to C-O neighbors. Dielectric relaxation from simulation will also be compared with experiment.

Smith, Grant D.↗

Molecular modeling of calmodulin: a comparison with crystallographic data

Two methods of side-chain placement on a modeled protein have been examined. Two molecular models of calmodulin were constructed that differ in the treatment of side chains prior to optimization of the molecule. A virtual bond analysis program developed by Purisima and Scheraga was used to determine the backbone conformation based on 2.2 angstroms resolution C alpha coordinates for the molecules. In the first model, side chains were initially constructed in an extended conformation. In the second model, a conformational grid search technique was employed. Calcium ions were treated explicitly during energy optimization using CHARMM. The models are compared to a recently published refined crystal structure of calmodulin. The results indicate that the initial choices for side-chains, but also significant effects on the main-chain conformation and supersecondary structure. The conformational differences are discussed. Analysis of these and other methods makes possible the formulation of a methodology for more appropriate side-chain placement in modeled proteins.

NASA Discipline Exobiology↗

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Nanofibers

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decision-making ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline (PANi) is an intriguing material because its electrical conductivity can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain, and when combined with polyethylene oxide (PEO), can be formed into nanofibers with diameters ranging from approximately 50 to 500 nm (depending on the deposition conditions). The initial goal of this work was to demonstrate transistor behavior in these nanofibers, thus creating a foundation for future logic devices.

Miranda, Felix A.↗

Field Effect Transistor Behavior in Electrospun Polyaniline/Polyethylene Oxide Demonstrated

Novel transistors and logic devices based on nanotechnology concepts are under intense development. The potential for ultra-low-power circuitry makes nanotechnology attractive for applications such as digital electronics and sensors. For NASA applications, nanotechnology offers tremendous opportunities for increased onboard data processing, and thus autonomous decisionmaking ability, and novel sensors that detect and respond to environmental stimuli with little oversight requirements. Polyaniline/polyethylene oxide (PANi/PEO) nanofibers are of interest because they have electrical conductivities that can be changed from insulating to metallic by varying the doping levels and conformations of the polymer chain. At the NASA Glenn Research Center, we have observed field effect transistor (FET) behavior in electrospun PANi/PEO nanofibers doped with camphorsulfonic acid. The nanofibers were deposited onto Au electrodes, which had been prepatterned onto oxidized silicon substrates. The preceding scanning electron image shows the device used in the transistor measurements. Saturation channel currents are observed at surprisingly low source/drain voltages (see the following graph). The hole mobility in the depletion regime is 1.4x10(exp -4)sq cm/V sec, whereas the one-dimensional charge density (at zero gate bias) is calculated to be approximately 1 hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx.10(exp -3) S/cm). Reducing or eliminating the PEO content in the fiber is expected to enhance device parameters. Electrospinning is thus proposed as a simple method of fabricating one-dimensional polymer FET's.

Mueller, Carl H.↗

R6 Hexameric Insulin Complexed with m-Cresol or Rescorcinol

The structures of three R6 human insulin hexamers have been determined. Crystals of monoclinic m-cresol/insulin, monoclinic resorcinol/insulin, and rhombohedral m-cresol/insulin crystals diffracted to 1.9, 1.9 and 1,78 Angstroms, respectively, and have been refined to residuals of 0.195, 0.179, and 0.200, respectively. In all three structures, a phenolic derivative is found to occupy the phenolic binding site where it forms hydrogen bonds to the carbonyl oxygen of A6 Cys and the nitrogen of A11 Cys. Two additional phenolic derivative binding sites were identified within or between hexamers. The structures of all three hexamers are nearly identical although a large displacement of the N-terminus of one B-chain in both monoclinic structures results from coordination to a sodium ion which is located between symmetry related hexamers. Other minor differences in structure are a consequence of differences in packing in the monoclinic cell as compared to the rhombohedral cell. Based upon the differences in conformation of the B13 Glu side chains in T6, T3R3, and R6 hexamers, the deprotonation of these side chains appears to be associated with the T (right arrow) R conformational transition.

Smith, G. David↗

Simulation studies for surfaces and materials strength

Computer simulation studies were conducted to investigate materials properties. All the calculations were carried out using atomic level simulation techniques which are based on semiempirical or model functions. During this project, functions with varying degrees of complexity were derived and employed in simulations. Investigations include covalently bonded materials as well as systems involving metal atoms. For small clusters calculated results provided information on various energy- and structure-related properties along with vibrational characteristics. Also, energy barriers for configurational transitions were calculated for selected cases. Simulation calculations for surfaces produced new results in areas related to surface energies, reconstructions and relaxations, surface defects, surface stresses as well as adsorption and nucleation processes. Simulations were also performed on bulk materials. Calculated results provided an atomic level understanding on energetics and structures of point defects, crystal stability, elastic properties, and materials strength for various systems. Calculations involving polymeric materials include studies of polar polymer melts and polymer/solid interfaces. Simulations employing specially developed codes provided significant information about energetics and conformational characteristics of different polymeric chains.

Halicioglu, Timur↗

An improved approach to the analysis of drug-protein binding by distance geometry

The calculation of side chain centers of coordinates and the subsequent generation of side chain-side chain and side chain-backbone distance matrices is suggested as an improved method for viewing interactions inside proteins and for the comparison of protein structures. The use of side chain distance matrices is demonstrated with free PTI, and the use of difference distance matrices for side chains is shown for free and trypsin-bound PTI as well as for the X-ray structures of trypsin complexes with PTI and with benzamidine. It is found that conformational variations are reflected in the side chain distance matrices much more than in the standard C-C distance representations.

NASA Discipline Exobiology↗

Determination of physical and chemical states of lubricants in concentrated contacts, part 1

A Fourier emission infrared microspectrometer, set up on a vibration-proof optical table and interfaced to a dedicated minicomputer, was used to record infrared emission spectra from elastohydrodynamic bearing contacts. Its range was extended to cover the entire mid-infrared from 2 to 15 micron. A series of experiments with 5P4E polyphenyl ether showed the existence of a temperature gradient through the lubricant in an ehd contact, which is perpendicular to the flow direction. The experiments also show marked polarization of some of the spectral bands, indicating a molecular alignment. Alignment is less evident at high pressure than at low pressure. To account for this behavior, a model is suggested along the lines developed for the conformational changes observed in long-chain polymers when subjected to increased pressure--to accommodate closer packing, molecules become kinked and curl up. Experiments with a traction fluid showed periodic changes of flow pattern associated with certain spectral changes. These observations will be studied further. A study by infrared attenuated total reflection spectrophotometry was undertaken to determine whether gamma irradiation would change polyethylene wear specimens. The results were negative.

Lauer, J. L.↗

Emergence of a replicating species from an in vitro RNA evolution reaction

The technique of self-sustained sequence replication allows isothermal amplification of DNA and RNA molecules in vitro. This method relies on the activities of a reverse transcriptase and a DNA-dependent RNA polymerase to amplify specific nucleic acid sequences. We have modified this protocol to allow selective amplification of RNAs that catalyze a particular chemical reaction. During an in vitro RNA evolution experiment employing this modified system, a unique class of "selfish" RNAs emerged and replicated to the exclusion of the intended RNAs. Members of this class of selfish molecules, termed RNA Z, amplify efficiently despite their inability to catalyze the target chemical reaction. Their amplification requires the action of both reverse transcriptase and RNA polymerase and involves the synthesis of both DNA and RNA replication intermediates. The proposed amplification mechanism for RNA Z involves the formation of a DNA hairpin that functions as a template for transcription by RNA polymerase. This arrangement links the two strands of the DNA, resulting in the production of RNA transcripts that contain an embedded RNA polymerase promoter sequence.

Non-NASA Center↗