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Sample records for molecularly thin alkane

  1. Thermally driven smoothening of molecular thin films: Structural transitions in n-alkane layers studied in real-time

    SciTech Connect

    Pithan, Linus; Weber, Christopher; Zykov, Anton; Sauer, Katrein; Opitz, Andreas; Kowarik, Stefan; Meister, Eduard; Brütting, Wolfgang; Jin, Chenyu; Riegler, Hans

    2015-10-28

    We use thermal annealing to improve smoothness and to increase the lateral size of crystalline islands of n-tetratetracontane (TTC, C{sub 44}H{sub 90}) films. With in situ x-ray diffraction, we find an optimum temperature range leading to improved texture and crystallinity while avoiding an irreversible phase transition that reduces crystallinity again. We employ real-time optical phase contrast microscopy with sub-nm height resolution to track the diffusion of TTC across monomolecular step edges which causes the unusual smoothing of a molecular thin film during annealing. We show that the lateral island sizes increase by more than one order of magnitude from 0.5 μm to 10 μm. This desirable behavior of 2d-Ostwald ripening and smoothing is in contrast to many other organic molecular films where annealing leads to dewetting, roughening, and a pronounced 3d morphology. We rationalize the smoothing behavior with the highly anisotropic attachment energies and low surface energies for TTC. The results are technically relevant for the use of TTC as passivation layer and as gate dielectric in organic field effect transistors.

  2. Melting of thin films of alkanes on magnesium oxide

    NASA Astrophysics Data System (ADS)

    Arnold, T.; Barbour, A.; Chanaa, S.; Cook, R. E.; Fernandez-Canato, D.; Landry, P.; Seydel, T.; Yaron, P.; Larese, J. Z.

    2009-02-01

    Recent incoherent neutron scattering investigations of the dynamics of thin alkane films adsorbed on the Magnesium Oxide (100) surface are reported. There are marked differences in the behaviour of these films, as a function of temperature and coverage, compared to similar measurements on graphite. In particular, it has previously been shown that adsorbed multilayer films on graphite exhibit an interfacial solid monolayer that coexists with bulk-like liquid, well above the bulk melting point. In contrast, these studies show that the alkane films on MgO exhibit no such stabilization of the solid layer closest to the substrate as a function of the film thickness, even though the monolayer crystal structures are remarkably similar. These studies are supported by extensive thermodynamic data, a growing body of structural data from neutron diffraction and state of the art computer modelling

  3. n-alkane profiles of engine lubricating oil and particulate matter by molecular sieve extraction.

    PubMed

    Caravaggio, Gianni A; Charland, Jean-Pierre; Macdonald, Penny; Graham, Lisa

    2007-05-15

    As part of the Canadian Atmospheric Fine Particle Research Program to obtain reliable primary source emission profiles, a molecular sieve method was developed to reliably determine n-alkanes in lubricating oils, vehicle emissions, and mobile source dominated ambient particulate matter (PM). This work was also initiated to better calculate carbon preference index values (CPI: the ratio of the sums of odd over even n-alkanes), a parameter for estimating anthropogenic versus biogenic contributions in PM. n-Alkanes in lubricating oil and mobile source dominated PM are difficult to identify and quantify by gas chromatography due to the presence of similar components that cannot be fully resolved. This results in a hump, the unresolved complex mixture (UCM) that leads to incorrect n-alkane concentrations and CPI values. The sieve method yielded better chromatography, unambiguous identification of n-alkanes and allowed examination of differences between n-alkane profiles in light (LDV) and heavy duty vehicle (HDV) lubricating oils that would have been otherwise difficult. These profile differences made it possible to relate the LDV profile to that of the PM samples collected during a tunnel study in August 2001 near Vancouver (British Columbia, Canada). The n-alkane PM data revealed that longer sampling times result in a negative artifact, i.e., the desorption of the more volatile n-alkanes from the filters. Furthermore, the sieve procedure yielded n-alkane data that allowed calculation of accurate CPI values for lubricating oils and PM samples. Finally, this method may prove helpful in estimating the respective diesel and gasoline contributions to ambient PM.

  4. Liquid alkanes with targeted molecular weights from biomass-derived carbohydrates.

    PubMed

    West, Ryan M; Liu, Zhen Y; Peter, Maximilian; Dumesic, James A

    2008-01-01

    Liquid transportation fuels must burn cleanly and have high energy densities, criteria that are currently fulfilled by petroleum, a non-renewable resource, the combustion of which leads to increasing levels of atmospheric CO(2). An attractive approach for the production of transportation fuels from renewable biomass resources is to convert carbohydrates into alkanes with targeted molecular weights, such as C(8)-C(15) for jet-fuel applications. Targeted n-alkanes can be produced directly from fructose by an integrated process involving first the dehydration of this C(6) sugar to form 5-hydroxymethylfurfural, followed by controlled formation of C-C bonds with acetone to form C(9) and C(15) compounds, and completed by hydrogenation and hydrodeoxygenation reactions to form the corresponding n-alkanes. Analogous reactions are demonstrated starting with 5-methylfurfural or 2-furaldehyde, with the latter leading to C(8) and C(13) n-alkanes.

  5. Predicting hydrophobic solvation by molecular simulation: 1. Testing united-atom alkane models.

    PubMed

    Jorge, Miguel; Garrido, Nuno M; Simões, Carlos J V; Silva, Cândida G; Brito, Rui M M

    2017-03-05

    We present a systematic test of the performance of three popular united-atom force fields-OPLS-UA, GROMOS and TraPPE-at predicting hydrophobic solvation, more precisely at describing the solvation of alkanes in alkanes. Gibbs free energies of solvation were calculated for 52 solute/solvent pairs from Molecular Dynamics simulations and thermodynamic integration making use of the IBERCIVIS volunteer computing platform. Our results show that all force fields yield good predictions when both solute and solvent are small linear or branched alkanes (up to pentane). However, as the size of the alkanes increases, all models tend to increasingly deviate from experimental data in a systematic fashion. Furthermore, our results confirm that specific interaction parameters for cyclic alkanes in the united-atom representation are required to account for the additional excluded volume within the ring. Overall, the TraPPE model performs best for all alkanes, but systematically underpredicts the magnitude of solvation free energies by about 6% (RMSD of 1.2 kJ/mol). Conversely, both GROMOS and OPLS-UA systematically overpredict solvation free energies (by ∼13% and 15%, respectively). The systematic trends suggest that all models can be improved by a slight adjustment of their Lennard-Jones parameters. © 2016 Wiley Periodicals, Inc.

  6. Molecular mobility depending on chain length and thermally induced molecular motion of n-alkane/urea inclusion compounds

    NASA Astrophysics Data System (ADS)

    Nakaoki, Takahiko; Nagano, Hiromasa; Yanagida, Toshinori

    2004-08-01

    Solid-state high resolution 13C NMR was used to analyze the end group conformation and molecular mobility of n-alkanes in a urea host as a function of the carbon number of the n-alkane. It was shown that the chemical shift of the inner methylenes could be interpreted by the γ- gauche effect. Of further interest is our finding that the chemical shift of 3-methylene is independent of both chain length and temperature, a result indicating that the torsional rotation of the bond ω 3 between the 4-methylene and 5-methylene carbons is so inhibited that there is little gauche conformation. The chemical shift of the inner methylenes indicated a different tendency between the even- and the odd-numbered n-alkanes. The fact that the signals of the even-numbered n-alkanes were observed at a comparatively more upfield location than those of the odd-numbered ones indicated that the even-numbered n-alkane had a higher molecular mobility and tended to adopt a more gauche conformation. The decomposition temperature obtained by thermal analysis also suggested a difference between the even- and odd-numbered n-alkanes. The decomposition temperature of the even-numbered n-alkane/urea inclusion compounds was a little lower than that of the odd-numbered ones, a disparity corresponding to the higher molecular mobility of the n-alkane in the urea host. The spin-lattice relaxation time ( T1C) increased with increasing chain length for chains with less than the 14 carbon atoms but reached a constant value for all longer chains. This result is completely different from that for the n-alkane crystal, which gave a longer T1C depending on the chain length, and can be explained by a reduced intermolecular interaction between the n-alkane and the urea host. Clearly, T1C measurements can be applied to confirm the formation of inclusion compounds. However, the different T1C values between the methyl, 2-, 3-, and inner methylene carbons indicates that the n-alkane molecule does not rotate so fast

  7. Progressive compression of 1,ω-diammonium-alkanes inside a rigid crystalline molecular cage.

    PubMed

    Dumitrescu, Dan; Legrand, Yves-Marie; Petit, Eddy; van der Lee, Arie; Barboiu, Mihail

    2014-11-25

    We present herein the compression mechanisms of linear 1,ω-diammonium-alkanes, confined within a molecular cage self-assembled in water. The exact coiling behaviour is determined from atomic resolution X-ray diffraction and shows crenel-like conformations in the compressed states.

  8. Prediction of alkane enthalpies by means of correlation weighting of Morgan extended connectivity in molecular graphs

    NASA Astrophysics Data System (ADS)

    Toropov, A. A.; Toropova, A. P.; Nesterova, A. I.; Nabiev, O. M.

    2004-01-01

    Labeled hydrogen-filled graphs (LHFGs) together with graphs of atomic orbitals (GAOs) have been used to represent the molecular structure of alkanes. The GAO is an attempt at taking into account the structures of atoms (i.e., atomic orbitals such as, 1s 1, 2p 2, 3d 10) for QSPR/QSAR analyses. As a method of alkane enthalpies modeling, optimization of correlation weights of local invariants (OCWLI) of the LHFGs and the GAOs has been used. Statistical characteristics of such models based on the OCWLI of the GAO are better than those based on the OCWLI of the LHFGs.

  9. Molecular simulation of diffusion of hydrogen, carbon monoxide, and water in heavy n-alkanes.

    PubMed

    Makrodimitri, Zoi A; Unruh, Dominik J M; Economou, Ioannis G

    2011-02-17

    The self-diffusion and mutual diffusion coefficients of hydrogen (H(2)), carbon monoxide (CO), and water (H(2)O) in n-alkanes were studied by molecular dynamics simulation. n-Alkane molecules were modeled based on the TraPPE united atom force field. NPT molecular dynamics (MD) simulations were performed for n-C(12) to n-C(96) at different temperature and pressure values to validate the accuracy of the force field. In all cases, good agreement was obtained between literature experimental data and model predictions for the density and structure properties of the n-alkanes. Subsequently, the self-diffusion coefficient of the three light components in the various n-alkanes was calculated at different temperatures. Model predictions were in very good agreement with limited experimental data. Furthermore, the Maxwell-Stefan diffusion coefficients of H(2) and CO in two n-alkanes, namely n-C(12) and n-C(28), were calculated based on long MD NVT simulations for different solute concentrations in the n-alkanes. Finally, the Fick diffusion coefficient of the components was calculated as a product of the Maxwell-Stefan diffusion coefficient and a thermodynamic factor. The latter was estimated from the statistical associating fluid theory (SAFT). The Fick diffusion coefficient was found to be higher than the Maxwell-Stefan diffusion coefficient for H(2) and CO in n-C(28). The empirical Darken equation was used to estimate the Maxwell-Stefan diffusion coefficient, and calculations were found to be in good agreement with simulation results.

  10. Modeling the influence of alkane molecular structure on secondary organic aerosol formation.

    PubMed

    Aumont, Bernard; Camredon, Marie; Mouchel-Vallon, Camille; La, Stéphanie; Ouzebidour, Farida; Valorso, Richard; Lee-Taylor, Julia; Madronich, Sasha

    2013-01-01

    Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapor pressure. Intermediate Volatility Organic Compounds (IVOC) emitted to the atmosphere are expected to be a substantial source of SOA. These emitted IVOC constitute a complex mixture including linear, branched and cyclic alkanes. The explicit gas-phase oxidation mechanisms are here generated for various linear and branched C10-C22 alkanes using the GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) and SOA formation is investigated for various homologous series. Simulation results show that both the size and the branching of the carbon skeleton are dominant factors driving the SOA yield. However, branching appears to be of secondary importance for the particle oxidation state and composition. The effect of alkane molecular structure on SOA yields appears to be consistent with recent laboratory observations. The simulated SOA composition shows, however, an unexpected major contribution from multifunctional organic nitrates. Most SOA contributors simulated for the oxidation of the various homologous series are far too reduced to be categorized as highly oxygenated organic aerosols (OOA). On a carbon basis, the OOA yields never exceeded 10% regardless of carbon chain length, molecular structure or ageing time. This version of the model appears clearly unable to explain a large production of OOA from alkane precursors.

  11. Molecular conformation of linear alkane molecules: From gas phase to bulk water through the interface

    NASA Astrophysics Data System (ADS)

    Murina, Ezequiel L.; Fernández-Prini, Roberto; Pastorino, Claudio

    2017-08-01

    We studied the behavior of long chain alkanes (LCAs) as they were transferred from gas to bulk water, through the liquid-vapor interface. These systems were studied using umbrella sampling molecular dynamics simulation and we have calculated properties like free energy profiles, molecular orientation, and radius of gyration of the LCA molecules. The results show changes in conformation of the solutes along the path. LCAs adopt pronounced molecular orientations and the larger ones extend appreciably when partially immersed in the interface. In bulk water, their conformations up to dodecane are mainly extended. However, larger alkanes like eicosane present a more stable collapsed conformation as they approach bulk water. We have characterized the more probable configurations in all interface and bulk regions. The results obtained are of interest for the study of biomatter processes requiring the transfer of hydrophobic matter, especially chain-like molecules like LCAs, from gas to bulk aqueous systems through the interface.

  12. Molecular conformation of linear alkane molecules: From gas phase to bulk water through the interface.

    PubMed

    Murina, Ezequiel L; Fernández-Prini, Roberto; Pastorino, Claudio

    2017-08-14

    We studied the behavior of long chain alkanes (LCAs) as they were transferred from gas to bulk water, through the liquid-vapor interface. These systems were studied using umbrella sampling molecular dynamics simulation and we have calculated properties like free energy profiles, molecular orientation, and radius of gyration of the LCA molecules. The results show changes in conformation of the solutes along the path. LCAs adopt pronounced molecular orientations and the larger ones extend appreciably when partially immersed in the interface. In bulk water, their conformations up to dodecane are mainly extended. However, larger alkanes like eicosane present a more stable collapsed conformation as they approach bulk water. We have characterized the more probable configurations in all interface and bulk regions. The results obtained are of interest for the study of biomatter processes requiring the transfer of hydrophobic matter, especially chain-like molecules like LCAs, from gas to bulk aqueous systems through the interface.

  13. Molecular dynamics simulations of transport and separation of carbon dioxide-alkane mixtures in carbon nanopores.

    PubMed

    Firouzi, Mahnaz; Nezhad, Kh Molaai; Tsotsis, Theodore T; Sahimi, Muhammad

    2004-05-01

    The configurational-bias Monte Carlo method, which is used for efficient generation of molecular models of n-alkane chains, is combined for the first time with the dual control-volume grand-canonical molecular-dynamics simulation, which has been developed for studying transport of molecules in pores under an external potential gradient, to investigate transport and separation of binary mixtures of n-alkanes, as well as mixtures of CO2 and n-alkanes, in carbon nanopores. The effect of various factors, such as the temperature of the system, the composition of the mixture, and the pore size, on the separation of the mixtures is investigated. We also report the preliminary results of an experimental study of transport and separation of some of the same mixtures in a carbon molecular-sieve membrane with comparable pore sizes. The results indicate that, for the mixtures considered in this paper, even in very small carbon nanopores the energetic effects still play a dominant role in the transport and separation properties of the mixtures, whereas in a real membrane they are dominated by the membrane's morphological characteristics. As a result, for the mixtures considered, a single pore may be a grossly inadequate model of a real membrane, and hence one must resort to three-dimensional molecular pore network models of the membrane.

  14. Separation and molecular-level segregation of complex alkane mixtures in metal-organic frameworks.

    PubMed

    Dubbeldam, David; Galvin, Casey J; Walton, Krista S; Ellis, Donald E; Snurr, Randall Q

    2008-08-20

    In this computational work we explore metal-organic frameworks (MOFs) for separating alkanes according to the degree of branching. We show that the structure MOF-1 shows an adsorption hierarchy for a 13-component light naphtha mixture precisely as desired for increasing the research octane number of gasoline. In addition we report an unusual molecular-level segregation of molecules based on their degree of branching.

  15. Molecular simulation and macroscopic modeling of the diffusion of hydrogen, carbon monoxide and water in heavy n-alkane mixtures.

    PubMed

    Makrodimitri, Zoi A; Unruh, Dominik J M; Economou, Ioannis G

    2012-03-28

    The self-diffusion coefficient of hydrogen (H(2)), carbon monoxide (CO) and water (H(2)O) in n-alkanes was studied by molecular dynamics simulation. Diffusion in a few pure n-alkanes (namely n-C(8), n-C(20), n-C(64) and n-C(96)) was examined. In addition, binary n-C(12)-n-C(96) mixtures with various compositions as well as more realistic five- and six-n-alkane component mixtures were simulated. In all cases, the TraPPE united atom force field was used for the n-alkane molecules. The force field for the mixture of n-alkanes was initially validated against experimental density values and was shown to be accurate. Moreover, macroscopic correlations for predicting diffusion coefficient of H(2), CO and H(2)O in n-alkanes and mixtures of n-alkanes were developed. The functional form of the correlation was based on the rough hard sphere theory (RHS). The correlation was applied to simulation data and an absolute average deviation (AAD) of 5.8% for pure n-alkanes and 3.4% for n-alkane mixtures was obtained. Correlation parameters vary in a systematic way with carbon number and so they can be used to provide predictions in the absence of any experimental or molecular simulation data. Finally, in order to reduce the number of adjustable parameters, for the n-alkane mixtures the "pseudo-carbon number" approach was used. This approach resulted in relatively higher deviation from MD simulation data (AAD of 18.2%); however, it provides a convenient and fast method to predict diffusion coefficients. The correlations developed here are expected to be useful for engineering calculations related to the design of the Gas-to-Liquid process.

  16. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    SciTech Connect

    Rastogi, Monisha; Vaish, Rahul

    2015-05-15

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  17. Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

    NASA Astrophysics Data System (ADS)

    Rastogi, Monisha; Vaish, Rahul

    2015-05-01

    The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant- pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs.

  18. Thermodiffusion, molecular diffusion and Soret coefficients of aromatic+n-alkane binary mixtures

    NASA Astrophysics Data System (ADS)

    Larrañaga, Miren; Bou-Ali, M. Mounir; Lapeira, Estela; Lizarraga, Ion; Santamaría, Carlos

    2016-10-01

    In the present work, we have measured the thermodiffusion coefficient of 51 binary liquid mixtures at 25 oC. These mixtures correspond to the series of the aromatics toluene and 1-methylnaphthalene with n-alkanes nCi (i = 6, 8, 10, 12, and 14) at different mass fractions in the whole range. For that, we have used the thermogravitational technique. It is shown that the thermodiffusion coefficient is a linear function of the mass fraction in all the mixtures. Extrapolating the lines, we obtain the thermodiffusion coefficient in dilute solutions of n-alkanes for both toluene and 1-methylnaphthalene. These limiting values show a linear dependence with the inverse of the product of the molecular weights. In addition, we have measured the molecular diffusion coefficient of all the mixtures at 0.5 of mass fraction and at 25 oC, by the sliding symmetric tubes technique. It is observed that the product of this coefficient with the viscosity at the same concentrations takes a constant value for each of the series considered. Finally, we have also determined the Soret coefficient of the equimass mixtures by the combination of the measurements of thermodiffusion and molecular diffusion coefficients.

  19. Characteristic of quaternary sedimentation on a shelf of the Laptev Sea according to the molecular composition of n-alkanes

    NASA Astrophysics Data System (ADS)

    Ulyantsev, A. S.; Romankevich, E. A.; Bratskaya, S. Yu.; Prokuda, N. A.; Sukhoverkhov, S. V.; Semiletov, I. P.; Sergienko, V. I.

    2017-04-01

    The molecular composition and distribution of the concentration of n-alkanes are considered for sediments of boreholes drilled in the shallow part of the Laptev Sea, in the area of Buor Khaya Gulf. The diverse molecular composition of n-alkanes is dominated by long-chain odd homologs, which indicate terrigenous organic matter (OM). Heterogeneous distribution and burial of OM are shown under conditions of pulsating contribution of river and thermoabrasive material and multiple changes in them up to hiatuses in sedimentation.

  20. Controlling Morphology and Molecular Packing of Alkane Substituted Phthalocyanine Blend Bulk Heterojunction Solar Cells.

    PubMed

    Jurow, Matthew J; Hageman, Brian A; Dimasi, Elaine; Nam, Chang-Yong; Pabon, Cesar; Black, Charles T; Drain, Charles Michael

    2013-02-07

    Systematic changes in the exocyclic substiution of core phthalocyanine platform tune the absorption properties to yield commercially viable dyes that function as the primary light absorbers in organic bulk heterojunction solar cells. Blends of these complementary phthalocyanines absorb a broader portion of the solar spectrum compared to a single dye, thereby increasing solar cell performance. We correlate grazing incidence small angle x-ray scattering structural data with solar cell performance to elucidate the role of nanomorphology of active layers composed of blends of phthalocyanines and a fullerene derivative. A highly reproducible device architecture is used to assure accuracy and is relevant to films for solar windows in urban settings. We demonstrate that the number and structure of the exocyclic motifs dictate phase formation, hierarchical organization, and nanostructure, thus can be employed to tailor active layer morphology to enhance exciton dissociation and charge collection efficiencies in the photovoltaic devices. These studies reveal that disordered films make better solar cells, short alkanes increase the optical density of the active layer, and branched alkanes inhibit unproductive homogeneous molecular alignment.

  1. Semifluorinated Alkanes at the Air-Water Interface: Tailoring Structure and Rheology at the Molecular Scale.

    PubMed

    Theodoratou, Antigoni; Jonas, Ulrich; Loppinet, Benoit; Geue, Thomas; Stangenberg, Rene; Keller, Rabea; Li, Dan; Berger, Rüdiger; Vermant, Jan; Vlassopoulos, Dimitris

    2016-04-05

    Semifluorinated alkanes form monolayers with interesting properties at the air-water interface due to their pronounced amphi-solvophobic nature and the stiffness of the fluorocarbons. In the present work, using a combination of structural and dynamic probes, we investigated how small molecular changes can be used to control the properties of such an interface, in particular its organization, rheology, and reversibility during compression-expansion cycles. Starting from a reference system perfluor(dodecyl)dodecane, we first retained the linear structure but changed the linkage groups between the alkyl chains and the fluorocarbons, by introducing either a phenyl group or two oxygens. Next, the molecular structure was changed from linear to branched, with four side chains (two fluorocarbons and two hydrocarbons) connected to extended aromatic cores. Neutron reflectivity at the air-water interface and scanning force microscopy on deposited films show how the changes in the molecular structure affect molecular arrangement relative to the interface. Rheological and compression-expansion measurements demonstrate the significant consequences of these changes in molecular structure and interactions on the interfacial properties. Remarkably, even with these simple molecules, a wide range of surface rheological behaviors can be engineered, from viscous over viscoelastic to brittle solids, for very similar values of the surface pressure.

  2. Self-consistent molecular dynamics calculation of diffusion in higher n-alkanes

    NASA Astrophysics Data System (ADS)

    Kondratyuk, Nikolay D.; Norman, Genri E.; Stegailov, Vladimir V.

    2016-11-01

    Diffusion is one of the key subjects of molecular modeling and simulation studies. However, there is an unresolved lack of consistency between Einstein-Smoluchowski (E-S) and Green-Kubo (G-K) methods for diffusion coefficient calculations in systems of complex molecules. In this paper, we analyze this problem for the case of liquid n-triacontane. The non-conventional long-time tails of the velocity autocorrelation function (VACF) are found for this system. Temperature dependence of the VACF tail decay exponent is defined. The proper inclusion of the long-time tail contributions to the diffusion coefficient calculation results in the consistency between G-K and E-S methods. Having considered the major factors influencing the precision of the diffusion rate calculations in comparison with experimental data (system size effects and force field parameters), we point to hydrogen nuclear quantum effects as, presumably, the last obstacle to fully consistent n-alkane description.

  3. Molecular dynamics study of the molecular weight dependence of surface tensions of normal alkanes and methyl methacrylate oligomers.

    PubMed

    Li, Chunli; Choi, Phillip

    2006-04-06

    Surface tensions (gamma) of normal alkanes and methyl methacrylate (MMA) oligomers at various molecular weights in the low molecular weight range were computed using a newly proposed molecular dynamics (MD) simulation strategy which was developed based on the definition of gamma = ( partial differential U/ partial differential sigma)n,V,S. The MD simulations, even with the use of a generic force field, reproduced the experimentally observed molecular weight dependence of gamma (i.e., gamma proportional Mn(-2/3), where Mn is the number-average molecular weight) for both series of oligomers. Analysis of the data reveals that solvent accessible surface area, one of the key input variables used for the calculation of gamma, exhibits an Mn(2/3) (rather than Mn(1)) dependence. The reason for such dependence is that solvent accessible surface area formed by the chainlike small molecules depends, to a larger extent, on their orientations rather than their size. However, this is not the case for high molecular weight molecules as solvent accessible surface area of such surfaces are determined by the orientations of their segments which are determined by the conformations of the molecules. This may explain why surface tension of polymers experimentally exhibits an Mn(-1) dependence. It is inferred that the corresponding molecular weight dependence of the entropy changes associated with molecules in the low and high molecular weight ranges would be different.

  4. Molecular modelling and quantum biochemistry computations of a naturally occurring bioremediation enzyme: Alkane hydroxylase from Pseudomonas putida P1.

    PubMed

    de Sousa, B G; Oliveira, J I N; Albuquerque, E L; Fulco, U L; Amaro, V E; Blaha, C A G

    2017-09-01

    Many species of bacteria involved in degradation of n-alkanes have an important constitutional metabolic enzyme, the alkane hydroxylase called AlkB, specialized in the conversion of hydrocarbons molecules that can be used as carbon and/or energy source. This enzyme plays an important role in the microbial degradation of oil, chlorinated hydrocarbons, fuel additives, and many other compounds. A number of these enzymes has been biochemically characterized in detail because the potential of alkane hydroxylases to catalyse high added-value reactions is widely recognized. Nevertheless, the industrial and process bioremediation application of them is restricted, owing to their complex biochemistry, challenging process requirements, and the limited number of their three-dimensional structures. Furthermore, AlkB has great potential as biocatalysts for selective transformation of a wide range of chemically inert unreactive alkanes into reactive chemical precursors that can be used as tools for bioremediation and bioprocesses. Aiming to understand the possible ways the AlkB enzyme Pseudomonas putida P1 interacts with octane, octanol and 1-octyne, we consider its suitable biochemical structure taking into account a 3-D homology modelling. Besides, by using a quantum chemistry computational model based on the density functional theory (DFT), we determine possible protein-substrate interaction regions measured by means of its binding energy simulated throughout the Molecular Fractionation with Conjugated Caps (MFCC) approach. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Quantitative Vapor-phase IR Intensities and DFT Computations to Predict Absolute IR Spectra based on Molecular Structure: I. Alkanes

    SciTech Connect

    Williams, Stephen D.; Johnson, Timothy J.; Sharpe, Steven W.; Yavelak, Veronica; Oats, R. P.; Brauer, Carolyn S.

    2013-11-13

    Recently recorded quantitative IR spectra of a variety of gas-phase alkanes are shown to have integrated intensities in both the C-H stretching and C-H bending regions that depend linearly on the molecular size, i.e. the number of C-H bonds. This result is well predicted from CH4 to C15H32 by DFT computations of IR spectra at the B3LYP/6-31+G(d,p) level of DFT theory. A simple model predicting the absolute IR band intensities of alkanes based only on structural formula is proposed: For the C-H stretching band near 2930 cm-1 this is given by (in km/mol): CH¬_str = (34±3)*CH – (41±60) where CH is number of C-H bonds in the alkane. The linearity is explained in terms of coordinated motion of methylene groups rather than the summed intensities of autonomous -CH2- units. The effect of alkyl chain length on the intensity of a C-H bending mode is explored and interpreted in terms of conformer distribution. The relative intensity contribution of a methyl mode compared to the total C-H stretch intensity is shown to be linear in the number of terminal methyl groups in the alkane, and can be used to predict quantitative spectra a priori based on structure alone.

  6. Quantitative vapor-phase IR intensities and DFT computations to predict absolute IR spectra based on molecular structure: I. Alkanes

    NASA Astrophysics Data System (ADS)

    Williams, Stephen D.; Johnson, Timothy J.; Sharpe, Steven W.; Yavelak, Veronica; Oates, R. P.; Brauer, Carolyn S.

    2013-11-01

    Recently recorded quantitative IR spectra of a variety of gas-phase alkanes are shown to have integrated intensities in both the C3H stretching and C3H bending regions that depend linearly on the molecular size, i.e. the number of C3H bonds. This result is well predicted from CH4 to C15H32 by density functional theory (DFT) computations of IR spectra using Becke's three parameter functional (B3LYP/6-31+G(d,p)). Using the experimental data, a simple model predicting the absolute IR band intensities of alkanes based only on structural formula is proposed: For the C3H stretching band envelope centered near 2930 cm-1 this is given by (km/mol) CH_str=(34±1)×CH-(41±23) where CH is number of C3H bonds in the alkane. The linearity is explained in terms of coordinated motion of methylene groups rather than the summed intensities of autonomous -CH2-units. The effect of alkyl chain length on the intensity of a C3H bending mode is explored and interpreted in terms of conformer distribution. The relative intensity contribution of a methyl mode compared to the total C3H stretch intensity is shown to be linear in the number of methyl groups in the alkane, and can be used to predict quantitative spectra a priori based on structure alone.

  7. Origins of n-alkanes, carbonyl compounds and molecular biomarkers in atmospheric fine and coarse particles of Athens, Greece.

    PubMed

    Andreou, G; Rapsomanikis, S

    2009-10-15

    The abundance and origin of aliphatic hydrocarbons, carbonyl compounds and molecular biomarkers found in the aliphatic fraction of PM(10-2.5) and PM(2.5) in the centre of Athens Greece are discussed in an attempt to reveal seasonal air pollution characteristics of the conurbation. Each extract was fractionated into individual compound classes and was analyzed using gas chromatography coupled to mass spectrometry. Normal alkanes, ranging from C(14) to C(35), were abundant in PM(10-2.5) and PM(2.5) samples during both sampling campaigns. The daily concentration of total n-alkanes was up to 438 ng m(-3) for PM(10-2.5) and up to 511 ng m(-3) for PM(2.5). Additionally, gaseous concentrations of n-alkanes were calculated, revealing that the relative proportions between gaseous and particle phases of individual compounds may differ significantly between summer and late winter. Normal alkanals and alkan-2-ones were only detected in the fine fraction of particulate matter and their concentrations were much lower than the n-alkane concentrations. Several geochemical parameters were used to qualitatively reconcile the sources of organic aerosol. The carbon preference index (CPI) of the coarse particles in August had the highest value, while in March the leaf wax contribution decreased significantly and the CPI value was very close to unity for both sites. Maximum concentrations of carbonyl compounds were reported in the range of C(15)-C(20), demonstrating that they were formed from anthropogenic activity or from atmospheric oxidative processes. 6, 10, 14-trimethylpentadecan-2-one, a marker of biogenic input, was also detected in our samples. Molecular biomarker compounds confirmed that ca. 60% of the aliphatic fraction on the sampled atmospheric particles originated from petroleum and not from any contemporary biogenic sources. Pristane and phytane were detected in the fine fraction with their presence indicating sources of fossil fuel in the range of C(16)-C(20). At all

  8. Elucidating alkane adsorption in sodium-exchanged zeolites from molecular simulations to empirical equations

    NASA Astrophysics Data System (ADS)

    García-Pérez, E.; Torréns, I. M.; Lago, S.; Dubbeldam, D.; Vlugt, T. J. H.; Maesen, T. L. M.; Smit, B.; Krishna, R.; Calero, S.

    2005-10-01

    Configurational-bias Monte Carlo (CBMC) simulations provide adsorption isotherms, Henry coefficients and heats of adsorption of linear alkanes in sodium-exchanged MFI- and FAU-type zeolites. These simulations were carried out using our newly developed force field that reproduces experimental sodium positions in the dehydrated zeolites, and successfully predicts alkane adsorption properties over a wide range of sodium cation densities, temperatures, and pressures. We derived empirical expressions from the simulation data to describe the adsorption of linear alkanes in MFI- and FAU-type zeolites. These expressions afford a suitable substitute for complex CBMC simulations. In the low coverage regime we provide simple expressions that adequately describe the Henry coefficient and adsorption enthalpy of n-alkanes as a function of sodium density and temperature. The predicted Henry coefficients and heats of adsorption compare extremely well to available experimental data. In the high coverage regime we provide an expression for saturation capacities of linear alkanes in the zeolite. This expression, combined with the expression for the Henry coefficients, provides of the complete adsorption isotherms of pure adsorbents and mixtures, in good agreement with the adsorption isotherms obtained from CBMC.

  9. Phase equilibria of molecular fluids via hybrid Monte Carlo Wang-Landau simulations: applications to benzene and n-alkanes.

    PubMed

    Desgranges, Caroline; Delhommelle, Jerome

    2009-06-28

    In recent years, powerful and accurate methods, based on a Wang-Landau sampling, have been developed to determine phase equilibria. However, while these methods have been extensively applied to study the phase behavior of model fluids, they have yet to be applied to molecular systems. In this work, we show how, by combining hybrid Monte Carlo simulations in the isothermal-isobaric ensemble with the Wang-Landau sampling method, we determine the vapor-liquid equilibria of various molecular fluids. More specifically, we present results obtained on rigid molecules, such as benzene, as well as on flexible chains of n-alkanes. The reliability of the method introduced in this work is assessed by demonstrating that our results are in excellent agreement with the results obtained in previous work on simple fluids, using either transition matrix or conventional Monte Carlo simulations with a Wang-Landau sampling, and on molecular fluids, using histogram reweighting or Gibbs ensemble Monte Carlo simulations.

  10. Added Alkane Allows Thermal Thinning of Supramolecular Columns by Forming Superlattice-An X-ray and Neutron Study.

    PubMed

    Yen, Ming-Huei; Chaiprapa, Jitrin; Zeng, Xiangbing; Liu, Yongsong; Cseh, Liliana; Mehl, Georg H; Ungar, Goran

    2016-05-11

    We report a columnar superlattice formed by blends of dendron-like Li 3,4,5-tris(n-alkoxy)benzoates with n-alkanes. Without the alkane, the wedge-shaped molecules form liquid crystal columns with 3 dendrons in a supramolecular disk. The same structure exists in the blend, but on heating one dendron is expelled from the disks in every third column and is replaced by the alkane. This superlattice of unequal columns is confirmed by complementary X-ray and neutron diffraction studies. Lateral thermal expansion of dendrons normally leads to the expulsion of excess molecules from the column, reducing the column diameter. However, in the already narrow columns of pure Li salt, expulsion of one of only three dendrons in a disk is not viable. The added alkane facilitates the expulsion, as it replaces the missing dendron. Replacing the alkane with a functional compound can potentially lead to active nanoarrays with relatively large periodicity by using only small molecules.

  11. Adsorption and Diffusion of C1 to C4 Alkanes in Dual-Porosity Zeolites by Molecular Simulations.

    PubMed

    Rezlerová, Eliška; Zukal, Arnošt; Čejka, Jiří; Siperstein, Flor R; Brennan, John K; Lísal, Martin

    2017-07-20

    We employ grand canonical Monte Carlo and molecular dynamics simulations to systematically study the adsorption and diffusion of C1 to C4 alkanes in hierarchical ZSM-5 zeolite with micropores (∼1 nm) and mesopores (>2 nm). The zeolite is characterized by a large surface area of active sites on the microporous scale with high permeability and access to the active sites, which arises from the enhanced transport at the mesoporous scale. We model this zeolite as a microporous Na(+)-exchanged alumino-sillicate zeolite ZSM-5/35 (Si/Al = 35) in which cylindrical mesopores with a diameter of 4 nm have been built by deleting atoms accordingly. We use the TraPPE and Vujić-Lyubartsev force fields along with the Lorentz-Berthelot combining rules to describe adsorbate-adsorbate and adsorbate-adsorbent interactions. The performance of the force fields is assessed by comparing against experimental single-component adsorption isotherms of methane and ethane in microporous ZSM-5/35, which we measured as part of this work. We compare the adsorption isotherms and diffusivities of the adsorbed alkanes in the dual-porosity zeolite with those in microporous ZSM-5/35 and discern the specific behavior at each porosity scale on the overall adsorption, self-diffusion, and transport behavior in zeolites with dual micro/mesoporosities.

  12. Effect of the molecular structure on the hierarchical self-assembly of semifluorinated alkanes at the air/water interface.

    PubMed

    de Viguerie, Laurence; Keller, Rabea; Jonas, Ulrich; Berger, Rüdiger; Clark, Christopher G; Klein, Christopher O; Geue, Thomas; Müllen, Klaus; Butt, Hans-Jürgen; Vlassopoulos, Dimitris

    2011-07-19

    Semifluorinated alkanes (C(n)F(2n+1)C(m)H(2m+1)), short FnHm display local phase separation of mutually incompatible hydrocarbon and fluorocarbon chain moieties, which has been utilized as a structure-forming motif in supramolecular architectures. The packing of semifluorinated alkanes, nominally based on dodecyl subunits, such as perfluoro(dodecyl)dodecane (F12H12) and perfluoro(dodecyl)eicosane (F12H20), as well as a core extended analogue, 1,4-dibromo-2-((perfluoroundecyl)methoxy)-5-(dodecyloxy)benzene) (F11H1-core-H12), was studied at the air/water interface. Langmuir monolayers were investigated by means of neutron reflectivity directly at the air/water interface and scanning force microscopy after transfer to silicon wafers. Narrowly disperse surface micelles formed in all three cases; however, they were found to bear different morphologies with respect to molecular orientation and assembly dimensionality, which gives rise to different hierarchical aggregate topologies. For F12H12, micelles of ca. 30 nm in diameter, composed of several circular or "spherical cap" substructures, were observed and a monolayer model with the fluorocarbon block oriented toward air is proposed. F12H20 molecules formed larger (ca. 50 nm diameter) hexagonally shaped surface micelles that were hexagonally, densely packed, besides more elongated but tightly interlocked wormlike structures. Conversely, F11H1-core-H12 films organized into linear rows of elongated surface micelles with comparable width, but an average length of ca. 400 nm, apparently formed by antiparallel molecular packing.

  13. 1-Octanol/Water Partition Coefficients of n-Alkanes from Molecular Simulations of Absolute Solvation Free Energies.

    PubMed

    Garrido, Nuno M; Queimada, António J; Jorge, Miguel; Macedo, Eugénia A; Economou, Ioannis G

    2009-09-08

    The 1-octanol/water partition coefficient is an important thermodynamic variable usually employed to understand and quantify the partitioning of solutes between aqueous and organic phases. It finds widespread use in many empirical correlations to evaluate the environmental fate of pollutants as well as in the design of pharmaceuticals. The experimental evaluation of 1-octanol/water partition coefficients is an expensive and time-consuming procedure, and thus, theoretical estimation methods are needed, particularly when a physical sample of the solute may not yet be available, such as in pharmaceutical screening. 1-Octanol/water partition coefficients can be obtained from Gibbs free energies of solvation of the solute in both the aqueous and the octanol phases. The accurate evaluation of free energy differences remains today a challenging problem in computational chemistry. In order to study the absolute solvation Gibbs free energies in 1-octanol, a solvent that can mimic many properties of important biological systems, free energy calculations for n-alkanes in the range C1-C8 were performed using molecular simulation techniques, following the thermodynamic integration approach. In the first part of this paper, we test different force fields by evaluating their performance in reproducing pure 1-octanol properties. It is concluded that all-atom force fields can provide good accuracy but at the cost of a higher computational time compared to that of the united-atom force fields. Recent versions of united-atom force fields, such as Gromos and TraPPE, provide satisfactory results and are, thus, useful alternatives to the more expensive all-atom models. In the second part of the paper, the Gibbs free energy of solvation in 1-octanol is calculated for several n-alkanes using three force fields to describe the solutes, namely Gromos, TraPPE, and OPLS-AA. Generally, the results obtained are in excellent agreement with the available experimental data and are of similar

  14. Characterization of sorbent properties of soil organic matter and carbonaceous geosorbents using n-alkanes and cycloalkanes as molecular probes.

    PubMed

    Endo, Satoshi; Grathwohl, Peter; Haderlein, Stefan B; Schmidt, Torsten C

    2009-01-15

    Nonspecific interactions and modes (i.e., adsorption vs absorption) of sorption by noncondensed, amorphous organic phases (here termed organic matter; OM) in soils and by rigid, aromatic, and condensed phases (termed carbonaceous geosorbents; CGs) were investigated using n-alkanes and cycloalkanes as molecular probes. Sorption isotherms of n- and cyclooctane from water for seven CGs (charcoal, lignite coke, activated carbon, graphite, partially oxidized graphite, diesel soot, bituminous coal), four sorbents with a predominance of OM (lignite, peat, two sapric soils), and two soils containing OM and high amounts of CGs were measured in batch systems. The peat and the sapric soils showed extensively linear sorption, while the CGs exhibited highly nonlinear (Freundlich exponents 0.2-0.7) and strong (Koc values being up to 10(5) times those for the OM-rich materials at low concentrations) sorption for the alkanes studied, showing that enhanced sorption by CGs can occur to completely apolar sorbates that do not undergo any specific interaction. Sorption by CGs was generally stronger and more nonlinear for n-octane than for cyclooctane, which suggests a strong dependence of sorption on the 3-D structure of sorbate molecules. The n-octane-to-cyclooctane sorption coefficient ratios (Kn/Kc) for adsorption to CGs were > or = 1, being distinctly different from those for absorption to the OM-rich materials (Kn/Kc < 1). The measured sorption isotherms and the CG compositions in the soils determined by quantitative petrography analysis suggest, however, that CGs occurring in soils may be far less effective sorbents than the reference CGs used in the sorption experiments at least for nonspecifically interacting sorbates, probably because of competitive sorption and/or pore blocking by natural OM. The presented approaches and results offer a basis for interpreting sorption data for other organic compounds, as nonspecific interactions and sorption modes are relevant for any

  15. Characterization of sorbent properties of soil organic matter and carbonaceous geosorbents using n-alkanes and cycloalkanes as molecular probes

    SciTech Connect

    Satoshi Endo; Peter Grathwohl; Stefan B. Haderlein; Torsten C. Schmidt

    2009-01-15

    Nonspecific interactions and modes (i.e., adsorption vs absorption) of sorption by noncondensed, amorphous organic phases (here termed organic matter; OM) in soils and by rigid, aromatic, and condensed phases (termed carbonaceous geosorbents; CGs) were investigated using n-alkanes and cycloalkanes as molecular probes. Sorption isotherms of and cyclooctane from water for seven CGs (charcoal, lignite coke, activated carbon, graphite, partially oxidized graphite, diesel soot, bituminous coal), four sorbents with a predominance of OM (lignite, peat, two sapric soils), and two soils containing OM and high amounts of CGs were measured in batch systems. The peat and the sapric soils showed extensively linear sorption, while the CGs exhibited highly nonlinear and strong (K{sub oc} values being up to 105 times those for the OM-rich materials at low concentrations) sorption for the alkanes studied, showing that enhanced sorption by CGs can occur to completely apolar sorbates that do not undergo any specific interaction. The n-octane-to-cyclooctane sorption coefficient ratios for adsorption to CGs were {ge}1, being distinctly different from those for absorption to the OM-rich materials. The measured sorption isotherms and the CG compositions in the soils determined by quantitative petrography analysis suggest, however, that CGs occurring in soils may be far less effective sorbents than the reference CGs used in the sorption experiments at least for nonspecifically interacting sorbates, probably because of competitive sorption and/or pore blocking by natural OM. The presented approaches and results offer a basis for interpreting sorption data for other organic compounds, as nonspecific interactions and sorption modes are relevant for any compound. 47 refs., 4 figs., 2 tabs.

  16. A molecular dynamics study of the effect of thermal boundary conductance on thermal transport of ideal crystal of n-alkanes with different number of carbon atoms

    SciTech Connect

    Rastgarkafshgarkolaei, Rouzbeh; Zeng, Yi; Khodadadi, J. M.

    2016-05-28

    Phase change materials such as n-alkanes that exhibit desirable characteristics such as high latent heat, chemical stability, and negligible supercooling are widely used in thermal energy storage applications. However, n-alkanes have the drawback of low thermal conductivity values. The low thermal conductivity of n-alkanes is linked to formation of randomly oriented nano-domains of molecules in their solid structure that is responsible for excessive phonon scattering at the grain boundaries. Thus, understanding the thermal boundary conductance at the grain boundaries can be crucial for improving the effectiveness of thermal storage systems. The concept of the ideal crystal is proposed in this paper, which describes a simplified model such that all the nano-domains of long-chain n-alkanes are artificially aligned perfectly in one direction. In order to study thermal transport of the ideal crystal of long-chain n-alkanes, four (4) systems (C{sub 20}H{sub 42}, C{sub 24}H{sub 50}, C{sub 26}H{sub 54}, and C{sub 30}H{sub 62}) are investigated by the molecular dynamics simulations. Thermal boundary conductance between the layers of ideal crystals is determined using both non-equilibrium molecular dynamics (NEMD) and equilibrium molecular dynamics (EMD) simulations. Both NEMD and EMD simulations exhibit no significant change in thermal conductance with the molecular length. However, the values obtained from the EMD simulations are less than the values from NEMD simulations with the ratio being nearly three (3) in most cases. This difference is due to the nature of EMD simulations where all the phonons are assumed to be in equilibrium at the interface. Thermal conductivity of the n-alkanes in three structures including liquid, solid, and ideal crystal is investigated utilizing NEMD simulations. Our results exhibit a very slight rise in thermal conductivity values as the number of carbon atoms of the chain increases. The key understanding is that thermal transport can be

  17. A molecular dynamics study of the effect of thermal boundary conductance on thermal transport of ideal crystal of n-alkanes with different number of carbon atoms

    NASA Astrophysics Data System (ADS)

    Rastgarkafshgarkolaei, Rouzbeh; Zeng, Yi; Khodadadi, J. M.

    2016-05-01

    Phase change materials such as n-alkanes that exhibit desirable characteristics such as high latent heat, chemical stability, and negligible supercooling are widely used in thermal energy storage applications. However, n-alkanes have the drawback of low thermal conductivity values. The low thermal conductivity of n-alkanes is linked to formation of randomly oriented nano-domains of molecules in their solid structure that is responsible for excessive phonon scattering at the grain boundaries. Thus, understanding the thermal boundary conductance at the grain boundaries can be crucial for improving the effectiveness of thermal storage systems. The concept of the ideal crystal is proposed in this paper, which describes a simplified model such that all the nano-domains of long-chain n-alkanes are artificially aligned perfectly in one direction. In order to study thermal transport of the ideal crystal of long-chain n-alkanes, four (4) systems (C20H42, C24H50, C26H54, and C30H62) are investigated by the molecular dynamics simulations. Thermal boundary conductance between the layers of ideal crystals is determined using both non-equilibrium molecular dynamics (NEMD) and equilibrium molecular dynamics (EMD) simulations. Both NEMD and EMD simulations exhibit no significant change in thermal conductance with the molecular length. However, the values obtained from the EMD simulations are less than the values from NEMD simulations with the ratio being nearly three (3) in most cases. This difference is due to the nature of EMD simulations where all the phonons are assumed to be in equilibrium at the interface. Thermal conductivity of the n-alkanes in three structures including liquid, solid, and ideal crystal is investigated utilizing NEMD simulations. Our results exhibit a very slight rise in thermal conductivity values as the number of carbon atoms of the chain increases. The key understanding is that thermal transport can be significantly altered by how the molecules and the

  18. Molecular simulations of the n -alkane liquid-vapor interface: interfacial properties and their long range corrections.

    PubMed

    Ibergay, C; Ghoufi, A; Goujon, F; Ungerer, P; Boutin, A; Rousseau, B; Malfreyt, P

    2007-05-01

    Monte Carlo simulations have been performed to study the interfacial properties of the liquid-vapor interface of alkanes. We highlight the chemical equilibrium of the liquid-vapor interface by calculating a local chemical potential including the appropriate long-range corrections profiles. We extend the "test-area" (TA) technique developed by Gloor [J. Chem. Phys. 123, 134703 (2005)] on Lennard-Jones and square-well fluids to molecular systems. We establish both operational expressions of the TA approach for the calculation of the surface tension profile and the corresponding long-range corrections by underlining the approximations used. We compare the results between the different operational expressions of the surface tension and focus on the truncation procedures to explain the difference between the different techniques using either the potential or force equations. We make the results of surface tension identical between the different methods by using consistent potential and force equations. In the case of a relatively small cutoff, we propose to show that the Irving-Kirkwood definition and TA methods lead to the same value of the surface tension under condition that appropriate long-range corrections be included in the calculation. We end this paper by calculation of the entropy change profile and a comparison with experiments.

  19. Preface: Thin films of molecular organic materials

    NASA Astrophysics Data System (ADS)

    Fraxedas, J.

    2008-03-01

    This special issue is devoted to thin films of molecular organic materials and its aim is to assemble numerous different aspects of this topic in order to reach a wide scientific audience. Under the term 'thin films', structures with thicknesses spanning from one monolayer or less up to several micrometers are included. In order to narrow down this relaxed definition (how thin is thin?) I suggest joining the stream that makes a distinction according to the length scale involved, separating nanometer-thick films from micrometer-thick films. While the physical properties of micrometer-thick films tend to mimic those of bulk materials, in the low nanometer regime new structures (e.g., crystallographic and substrate-induced phases) and properties are found. However, one has to bear in mind that some properties of micrometer-thick films are really confined to the film/substrate interface (e.g. charge injection), and are thus of nanometer nature. Supported in this dimensionality framework, this issue covers the most ideal and model 0D case, a single molecule on a surface, through to the more application-oriented 3D case, placing special emphasis on the fascinating 2D domain that is monolayer assembly. Thus, many aspects will be reviewed, such as single molecules, self-organization, monolayer regime, chirality, growth, physical properties and applications. This issue has been intentionally restricted to small molecules, thus leaving out polymers and biomolecules, because for small molecules it is easier to establish structure--property relationships. Traditionally, the preparation of thin films of molecular organic materials has been considered as a secondary, lower-ranked part of the more general field of this class of materials. The coating of diverse surfaces such as silicon, inorganic and organic single crystals, chemically modified substrates, polymers, etc., with interesting molecules was driven by the potential applications of such molecular materials

  20. On the atomistic mechanisms of alkane (methane-pentane) separation by distillation: a molecular dynamics study.

    PubMed

    Zahn, Dirk

    2007-11-01

    Insights into the liquid-vapor transformation of methane-pentane mixtures were obtained from transition path sampling molecular dynamics simulations. This case study of the boiling of non-azeotropic mixtures demonstrates an unprejudiced identification of the atomistic mechanisms of phase separation in the course of vaporization which form the basis of distillation processes. From our simulations we observe spontaneous segregation events in the liquid mixture to trigger vapor nucleation. The formation of vapor domains stabilizes and further promotes the separation process by preferential evaporation of methane molecules. While this discrimination holds for all mixtures of different composition studied, a full account of the boiling process requires a more complex picture. At low methane concentration the nucleation of the vapor domains includes both methane and pentane molecules. The pentane molecules, however, tend to form small aggregates and undergo rapid re-condensation within picoseconds to nanoseconds scales. Accordingly, two aspects of selectivity accounting for methane-pentane separation in the course of liquid-vapor transformations were made accessible to molecular dynamics simulations: spontaneous segregation in the liquid phase leading to selective vapor nucleation and growth favoring methane vaporization and selective re-condensation of pentane molecules.

  1. Examination of surface nucleation during the growth of long alkane crystals by molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Bourque, Alexander; Rutledge, Gregory

    2015-03-01

    Crystal growth from the melt of n-pentacontane (C50) was studied by molecular dynamics simulation using a validated united atom model. By quenching below the melting temperature of C50 (370 K), propagation of the crystal growth front into the C50 melt from a crystalline polyethylene surface was observed. By tracking the location of the midpoint in the orientational order parameter profile between the crystal and melt, crystal growth rates between 0.015-0.040 m/s were observed, for quench depths of 10 to 70 K below the melting point. In this work, surface nucleation is identified with the formation of 2D clusters of crystalline sites within layers parallel to the propagating growth front, by analogy to the formation of 3D clusters in primary, homogeneous nucleation. These surface nucleation events were tracked over several layers and numerous simulations, and a mean first passage time analysis was employed to estimate critical nucleus sizes, induction times and rates for surface nucleation. Based on new insights provided by the detailed molecular trajectories obtained from simulation, the classical theory proposed by Lauritzen and Hoffman is re-examined.

  2. Optical Properties of Thin Film Molecular Mixtures

    NASA Technical Reports Server (NTRS)

    Jaworske, Donald A.; Shumway, Dean A.; Lyons, Valerie (Technical Monitor)

    2002-01-01

    Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, alpha, and low infrared emittance, epsilon. On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator. A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450C, a sharp transition at 1.8 micrometers is desired. The radiator completes the heat flow through the Carnot cycle. Additional work has been done supporting the use of molecular mixtures for terrestrial applications. Sputter deposition provides a means to apply coatings to the tubes that carry a working fluid at the focus of trough

  3. Porous Organic Cage Thin Films and Molecular-Sieving Membranes.

    PubMed

    Song, Qilei; Jiang, Shan; Hasell, Tom; Liu, Ming; Sun, Shijing; Cheetham, Anthony K; Sivaniah, Easan; Cooper, Andrew I

    2016-04-06

    Porous organic cage molecules are fabricated into thin films and molecular-sieving membranes. Cage molecules are solution cast on various substrates to form amorphous thin films, with the structures tuned by tailoring the cage chemistry and processing conditions. For the first time, uniform and pinhole-free microporous cage thin films are formed and demonstrated as molecular-sieving membranes for selective gas separation.

  4. Optical Properties of Thin Film Molecular Mixtures

    NASA Technical Reports Server (NTRS)

    Jaworske, Donald A.; Shumway, Dean A.

    2003-01-01

    Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling the degree of molecular mixing, the solar selective coatings can be tailored to have the combined properties of high solar absorptance, , and low infrared emittance, . On orbit, these combined properties would simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. Mini-satellites equipped with solar collectors coated with these cermet coatings may utilize the captured heat energy to power a heat engine to generate electricity, or to power a thermal bus that directs heat to remote regions of the spacecraft. Early work in this area identified the theoretical boundary conditions needed to operate a Carnot cycle in space, including the need for a solar concentrator, a solar selective coating at the heat inlet of the engine, and a radiator.1 A solar concentrator that can concentrate sunlight by a factor of 100 is ideal. At lower values, the temperature of the solar absorbing surface becomes too low for efficient heat engine operation, and at higher values, cavity type heat receivers become attractive. In designing the solar selective coating, the wavelength region yielding high solar absorptance must be separated from the wavelength region yielding low infrared emittance by establishing a sharp transition in optical properties. In particular, a sharp transition in reflectance is desired in the infrared to achieve the desired optical performance. For a heat engine operating at 450 C, a sharp transition at 1.8 micrometers is desired.2 The radiator completes the heat flow through the Carnot cycle.

  5. CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes.

    PubMed

    Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E; Yadav, Jagjit S

    2013-04-01

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills).

  6. CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes

    PubMed Central

    Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.

    2013-01-01

    Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

  7. Patterns and conformations in molecularly thin films

    NASA Astrophysics Data System (ADS)

    Basnet, Prem B.

    Molecularly thin films have been a subject of great interest for the last several years because of their large variety of industrial applications ranging from micro-electronics to bio-medicine. Additionally, molecularly thin films can be used as good models for biomembrane and other systems where surfaces are critical. Many different kinds of molecules can make stable films. My research has considered three such molecules: a polymerizable phospholipid, a bent-core molecules, and a polymer. One common theme of these three molecules is chirality. The phospolipid molecules studied here are strongly chiral, which can be due to intrinsically chiral centers on the molecules and also due to chiral conformations. We find that these molecules give rise to chiral patterns. Bent-core molecules are not intrinsically chiral, but individual molecules and groups of molecules can show chiral structures, which can be changed by surface interactions. One major, unconfirmed hypothesis for the polymer conformation at surface is that it forms helices, which would be chiral. Most experiments were carried out at the air/water interface, in what are called Langmuir films. Our major tools for studying these films are Brewster Angle Microscopy (BAM) coupled with the thermodynamic information that can be deduced from surface pressure isotherms. Phospholipids are one of the important constituents of liposomes -- a spherical vesicle com-posed of a bilayer membrane, typically composed of a phospholipid and cholesterol bilayer. The application of liposomes in drug delivery is well-known. Crumpling of vesicles of polymerizable phospholipids has been observed. With BAM, on Langmuir films of such phospholipids, we see novel spiral/target patterns during compression. We have found that both the patterns and the critical pressure at which they formed depend on temperature (below the transition to a i¬‘uid layer). Bent-core liquid crystals, sometimes knows as banana liquid crystals, have drawn

  8. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    PubMed

    Pierce, Flint; Tsige, Mesfin; Perahia, Dvora; Grest, Gary S

    2008-12-18

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  9. Liquid-liquid interfaces of semifluorinated alkane diblock copolymers with water, alkanes, and perfluorinated alkanes.

    SciTech Connect

    Perahia, Dvora, Dr.; Pierce, Flint; Tsige, Mesfin; Grest, Gary Stephen, Dr.

    2008-08-01

    The liquid-liquid interface between semifluorinated alkane diblock copolymers of the form F3C(CF2)n-1-(CH2)m-1CH3 and water, protonated alkanes, and perfluorinated alkanes are studied by fully atomistic molecular dynamics simulations. A modified version of the OPLS-AA (Optimized Parameter for Liquid Simulation All-Atom) force field of Jorgensen et al. has been used to study the interfacial behavior of semifluorinated diblocks. Aqueous interfaces are found to be sharp, with correspondingly large values of the interfacial tension. Due to the reduced hydrophobicity of the protonated block compared to the fluorinated block, hydrogen enhancement is observed at the interface. Water dipoles in the interfacial region are found to be oriented nearly parallel to the liquid-liquid interface. A number of protonated alkanes and perfluorinated alkanes are found to be mutually miscible with the semifluorinated diblocks. For these liquids, interdiffusion follows the expected Fickian behavior, and concentration-dependent diffusivities are determined.

  10. Molecular dynamics study of solubilization of immiscible solutes by a micelle: Free energy of transfer of alkanes from water to the micelle core by thermodynamic integration method

    NASA Astrophysics Data System (ADS)

    Fujimoto, K.; Yoshii, N.; Okazaki, S.

    2010-08-01

    Free energy of transfer, ΔGw→m, from water phase to a sodium dodecyl sulfate (SDS) micelle core has been calculated for a series of hydrophobic solutes originally immiscible with water by thermodynamic integration method combined with molecular dynamics calculations. The calculated free energy of transfer is in good correspondence to the experiment as well as the theoretical free energy of transfer. The calculated ΔGw→m's are all negative, implying that the alkane molecules are more stable in the micelle than in the water phase. It decreases almost linearly as a function of the number of carbon atoms of the alkanes longer than methane with a decrement of 3.3 kJ mol-1 per one methylene group. The calculated free energy of transfer indicates that, for example, at the micelle concentration of 50 CMC (critical micelle concentration), about only 1 of 6 micelles or 1 of 32 000 micelles does not contain a solute methane or n-octane molecule, respectively.

  11. Structure and Phase Transitions of Monolayers of Intermediate-length n-alkanes on Graphite Studied by Neutron Diffraction and Molecular Dynamics Simulation

    SciTech Connect

    Taub, H.; Hansen, F.Y.; Diama, Amand; Matthies, Blake; Criswell, Leah; Mo, Haiding; Bai, M; Herwig, Kenneth W

    2009-01-01

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a 'smectic' phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  12. Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation.

    PubMed

    Diama, A; Matthies, B; Herwig, K W; Hansen, F Y; Criswell, L; Mo, H; Bai, M; Taub, H

    2009-08-28

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C(24)H(50) denoted as C24) and dotriacontane (n-C(32)H(66) denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26 A=sqrt[3a(g)], where a(g)=2.46 A is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by approximately 10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.

  13. Elastic Properties of Molecular Glass Thin Films

    NASA Astrophysics Data System (ADS)

    Torres, Jessica

    2011-12-01

    This dissertation provides a fundamental understanding of the impact of bulk polymer properties on the nanometer length scale modulus. The elastic modulus of amorphous organic thin films is examined using a surface wrinkling technique. Potential correlations between thin film behavior and intrinsic properties such as flexibility and chain length are explored. Thermal properties, glass transition temperature (Tg) and the coefficient of thermal expansion, are examined along with the moduli of these thin films. It is found that the nanometer length scale behavior of flexible polymers correlates to its bulk Tg and not the polymers intrinsic size. It is also found that decreases in the modulus of ultrathin flexible films is not correlated with the observed Tg decrease in films of the same thickness. Techniques to circumvent reductions from bulk modulus were also demonstrated. However, as chain flexibility is reduced the modulus becomes thickness independent down to 10 nm. Similarly for this series minor reductions in T g were obtained. To further understand the impact of the intrinsic size and processing conditions; this wrinkling instability was also utilized to determine the modulus of small organic electronic materials at various deposition conditions. Lastly, this wrinkling instability is exploited for development of poly furfuryl alcohol wrinkles. A two-step wrinkling process is developed via an acid catalyzed polymerization of a drop cast solution of furfuryl alcohol and photo acid generator. The ability to control the surface topology and tune the wrinkle wavelength with processing parameters such as substrate temperature and photo acid generator concentration is also demonstrated. Well-ordered linear, circular, and curvilinear patterns are also obtained by selective ultraviolet exposure and polymerization of the furfuryl alcohol film. As a carbon precursor a thorough understanding of this wrinkling instability can have applications in a wide variety of

  14. Structural insights into diversity and n-alkane biodegradation mechanisms of alkane hydroxylases

    PubMed Central

    Ji, Yurui; Mao, Guannan; Wang, Yingying; Bartlam, Mark

    2013-01-01

    Environmental microbes utilize four degradation pathways for the oxidation of n-alkanes. Although the enzymes degrading n-alkanes in different microbes may vary, enzymes functioning in the first step in the aerobic degradation of alkanes all belong to the alkane hydroxylases. Alkane hydroxylases are a class of enzymes that insert oxygen atoms derived from molecular oxygen into different sites of the alkane terminus (or termini) depending on the type of enzymes. In this review, we summarize the different types of alkane hydroxylases, their degrading steps, and compare typical enzymes from various classes with regard to their three-dimensional structures, in order to provide insights into how the enzymes mediate their different roles in the degradation of n-alkanes and what determines their different substrate ranges. Through the above analyzes, the degrading mechanisms of enzymes can be elucidated and molecular biological methods can be utilized to expand their catalytic roles in the petrochemical industry or in bioremediation of oil-contaminated environments. PMID:23519435

  15. Molecular tribology of fluid lubrication - Shear thinning

    SciTech Connect

    Carson, G.; Hu, Hsuan-Wei; Granick, S. )

    1992-07-01

    An investigation of the boundary layer viscosity of films of nonpolar liquid lubricants, hexadecane and a silicone oil, octamethyl-cyclotetrasiloxane, confined between parallel atomically smooth single crystals of muscovite mica, is reported. The effective viscosity (eta sub eff) showed a zone of linear response and a second zone of extreme shear thinning. In the zone of linear response, (eta sub eff) increased exponentially with increasing net normal pressure, increasing from 250 to 2200 poises as the pressure was raised from 0.03 to 0.15 MPa. However, very large shear thinning (decay by more than one order of magnitude) was observed as the effective shear rate was varied from 1/sec to 10,000/sec, and the transition to glassy solid response (critical shear stress behavior) was impeded by continuous shear. These experiments show that the rheology of a lubricant within a zone of contact can be strikingly different from that in the bulk. Possible engineering applications of these findings are discussed. 25 refs.

  16. Molecular tribology of fluid lubrication - Shear thinning

    NASA Astrophysics Data System (ADS)

    Carson, George; Hu, Hsuan-Wei; Granick, Steve

    1992-07-01

    An investigation of the boundary layer viscosity of films of nonpolar liquid lubricants, hexadecane and a silicone oil, octamethyl-cyclotetrasiloxane, confined between parallel atomically smooth single crystals of muscovite mica, is reported. The effective viscosity (eta sub eff) showed a zone of linear response and a second zone of extreme shear thinning. In the zone of linear response, (eta sub eff) increased exponentially with increasing net normal pressure, increasing from 250 to 2200 poises as the pressure was raised from 0.03 to 0.15 MPa. However, very large shear thinning (decay by more than one order of magnitude) was observed as the effective shear rate was varied from 1/sec to 10,000/sec, and the transition to glassy solid response (critical shear stress behavior) was impeded by continuous shear. These experiments show that the rheology of a lubricant within a zone of contact can be strikingly different from that in the bulk. Possible engineering applications of these findings are discussed.

  17. Predicting hydrophobic solvation by molecular simulation: 2. New united-atom model for alkanes, alkenes, and alkynes.

    PubMed

    Jorge, Miguel

    2017-03-05

    Existing united-atom models for non-polar hydrocarbons lead to systematic deviations in predicted solvation free energies in hydrophobic solvents. In this article, an improved set of parameters is proposed for alkane molecules that corrects this systematic deviation and accurately predicts solvation free energies in hydrophobic media, while simultaneously providing a very good description of pure liquid densities. The model is then extended to alkenes and alkynes, again yielding very accurate predictions of solvation free energies and densities for these classes of compounds. For alkynes in particular, this work represents the first attempt at a systematic parameterization using the united-atom approach. Averaging over all 95 solute/solvent pairs tested, the mean signed deviation from experimental data is very close to zero, indicating no systematic error in the predictions. The fact that predictions are robust even for relatively large molecules suggests that the new model may be applicable to solvation of non-polar macromolecules without accumulation of errors. The root mean squared deviation of the simulations is only 0.6 kJ/mol, which is lower than the estimated uncertainty in the experimental measurements. This excellent performance constitutes a solid basis on which a more general model can be parameterized to describe solvation in both polar and non-polar environments. © 2016 Wiley Periodicals, Inc.

  18. Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.

    ERIC Educational Resources Information Center

    Seymour, Raymond B.

    1989-01-01

    Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)

  19. Products of Chemistry: Alkanes: Abundant, Pervasive, Important, and Essential.

    ERIC Educational Resources Information Center

    Seymour, Raymond B.

    1989-01-01

    Discusses the history and commercialization of alkanes. Examines the nomenclature and uses of alkanes. Studies polymerization and several types of polyethylenes: low-density, high-density, low-molecular-weight, cross-linked, linear low-density, and ultrahigh-molecular-weight. Includes a glossary of hydrocarbon terms. (MVL)

  20. Depolarized light scattering in dilute solutions of alkanes: A comparison of the bond additive and interacting atom approximations to the molecular polarizability

    SciTech Connect

    Keyes, T.; Evans, G.T.; Ladanyi, B.M.

    1981-04-01

    The molecular polarizability of a few small alkane (4--10 bond) chains has been represented by (1) an interacting atom model (IAM), wherein the atoms are treated as isotropic point polarizabilities interacting by the dipole tensor; and (2) the bond additive approximation (BAA) in which each bond is assigned an axially symmetric polarizability tensor, and the total molecular polarizability is the sum of the individual bond values. For selected values of the gauche--trans energy difference (0.3 kcal/mole), the calculated mean anisotropy per backbone atom /N increases linearly with N for the IAM and is essentially independent of N in the BAA. Orientational correlation functions have been determined for several second rank tensors characterizing the flexible chains using a modified version of Fixman's Brownian dynamics programs. The orientational correlation functions displayed an effective nonanalytic decay for short times merging into an exponential for long times. Single particle correlation times for the IAM increased more rapidly with N than did those of the BAA. Relaxation of the end-to-end vector (actually its second rank analog) was found to be the slowest process, followed by the IAM and the BAA polarizabilities, and finally the fastest was a local rotational mode.

  1. Catalytic conversion of light alkanes

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  2. Microbial biosynthesis of alkanes.

    PubMed

    Schirmer, Andreas; Rude, Mathew A; Li, Xuezhi; Popova, Emanuela; del Cardayre, Stephen B

    2010-07-30

    Alkanes, the major constituents of gasoline, diesel, and jet fuel, are naturally produced by diverse species; however, the genetics and biochemistry behind this biology have remained elusive. Here we describe the discovery of an alkane biosynthesis pathway from cyanobacteria. The pathway consists of an acyl-acyl carrier protein reductase and an aldehyde decarbonylase, which together convert intermediates of fatty acid metabolism to alkanes and alkenes. The aldehyde decarbonylase is related to the broadly functional nonheme diiron enzymes. Heterologous expression of the alkane operon in Escherichia coli leads to the production and secretion of C13 to C17 mixtures of alkanes and alkenes. These genes and enzymes can now be leveraged for the simple and direct conversion of renewable raw materials to fungible hydrocarbon fuels.

  3. Fluidization and Active Thinning by Molecular Kinetics in Active Gels.

    PubMed

    Oriola, David; Alert, Ricard; Casademunt, Jaume

    2017-02-24

    We derive the constitutive equations of an active polar gel from a model for the dynamics of elastic molecules that link polar elements. Molecular binding kinetics induces the fluidization of the material, giving rise to Maxwell viscoelasticity and, provided that detailed balance is broken, to the generation of active stresses. We give explicit expressions for the transport coefficients of active gels in terms of molecular properties, including nonlinear contributions on the departure from equilibrium. In particular, when activity favors linker unbinding, we predict a decrease of viscosity with activity-active thinning-of kinetic origin, which could explain some experimental results on the cell cortex. By bridging the molecular and hydrodynamic scales, our results could help understand the interplay between molecular perturbations and the mechanics of cells and tissues.

  4. Bubble bursting as an aerosol generation mechanism during an oil spill in the deep-sea environment: molecular dynamics simulations of oil alkanes and dispersants in atmospheric air/salt water interfaces.

    PubMed

    Liyana-Arachchi, Thilanga P; Zhang, Zenghui; Ehrenhauser, Franz S; Avij, Paria; Valsaraj, Kalliat T; Hung, Francisco R

    2014-01-01

    Potential of mean force (PMF) calculations and molecular dynamics (MD) simulations were performed to investigate the properties of oil n-alkanes [i.e., n-pentadecane (C15), n-icosane (C20) and n-triacontane (C30)], as well as several surfactant species [i.e., the standard anionic surfactant sodium dodecyl sulfate (SDS), and three model dispersants similar to the Tween and Span species present in Corexit 9500A] at air/salt water interfaces. This study was motivated by the 2010 Deepwater Horizon (DWH) oil spill, and our simulation results show that, from the thermodynamic point of view, the n-alkanes and the model dispersants have a strong preference to remain at the air/salt water interface, as indicated by the presence of deep free energy minima at these interfaces. The free energy minimum of these n-alkanes becomes deeper as their chain length increases, and as the concentration of surfactant species at the interface increases. The n-alkanes tend to adopt a flat orientation and form aggregates at the bare air/salt water interface. When this interface is coated with surfactants, the n-alkanes tend to adopt more tilted orientations with respect to the vector normal to the interface. These simulation results are consistent with the experimental findings reported in the accompanying paper [Ehrenhauser et al., Environ. Sci.: Processes Impacts 2013, in press, (DOI: 10.1039/c3em00390f)]. The fact that these long-chain n-alkanes show a strong thermodynamic preference to remain at the air/salt water interfaces, especially if these interfaces are coated with surfactants, makes these species very likely to adsorb at the surface of bubbles or droplets and be ejected to the atmosphere by sea surface processes such as whitecaps (breaking waves) and bubble bursting. Finally, the experimental finding that more oil hydrocarbons are ejected when Corexit 9500A is present in the system is consistent with the deeper free energy minima observed for the n-alkanes at the air/salt water

  5. Molecular, 13C, and 14C evidence for the allochthonous and ancient origin of C 16C 18n-alkanes in modern soils

    NASA Astrophysics Data System (ADS)

    Lichtfouse, Éric; Bardoux, Gerard; Mariotti, Andre; Balesdent, Jerome; Ballentine, Donna C.; Macko, Stephen A.

    1997-05-01

    The heterogeneous isotopic composition of C 3 and C 4 plants can be used to to follow the fate of plant carbon into soil organic molecules. Thus, after 23 years of maize cropping (C 4) on a soil which was previously under C 3 vegetation, C 25C 33 soil n-alkanes are 13C-enriched up to 9ℵ. relatively to the initial C 3 soil, reflecting the input of 13C-enriched n-alkanes from maize waxes. In sharp contrast, C 16C 18 soil n-alkanes do not show any significant 13C/ 12C variation over the same time interval. This absence of isotopic variation, along with consideration of their relative concentration, absolute concentration, and biodegradability, demonstrate that these substances must represent a regular input from an external source. Evidence of a large contribution of an ancient source, amounting to more than 65% of the alkane fraction, is given by a 14C-age of 8510 yrs BP. Moreover, short-chain n-alkanes from soils, diesel fuel, diesel automobile exhaust, and petroleum products exhibit similar distributions and δ 13C values. These findings suggests that C 16C 18 soil n-alkanes represent a non-point source pollution of ancient hydrocarbons either carried by aerosols or entering the soil via continuous hydrocarbon seepage from the deep sedimentary rocks of the Paris basin.

  6. Shear-thinning of molecular fluids in Couette flow

    NASA Astrophysics Data System (ADS)

    Raghavan, Bharath V.; Ostoja-Starzewski, Martin

    2017-02-01

    We use non-equilibrium molecular dynamics simulations, the Boltzmann equation, and continuum thermomechanics to investigate and characterize the shear-thinning behavior of molecular fluids undergoing Couette flow, interacting via a Lennard-Jones (LJ) potential. In particular, we study the shear-stress under steady-state conditions and its dependency on fluid density and applied shear-strain rate. Motivated by kinetic theory, we propose a rheological equation of state that fits observed system responses exceptionally well and captures the extreme shear-thinning effect. We notice that beyond a particular strain-rate threshold, the fluid exhibits shear-thinning, the degree of which is dependent on the density and temperature of the system. In addition, we obtain a shear-rate dependent model for the viscosity which matches the well established Cross viscosity model. We demonstrate how this model arises naturally from the Boltzmann equation and possesses an inherent scaling parameter that unifies the rheological properties of the LJ fluid. We compare our model with those in the literature. Finally, we formulate a dissipation function modeling the LJ fluid as a quasilinear fluid.

  7. Molecular dynamics simulation of friction of hydrocarbon thin films

    SciTech Connect

    Tamura, Hiroyuki; Yoshida, Muneo; Kusakabe, Kenichi

    1999-10-26

    Molecular Dynamics (MD) simulations were performed to investigate the dynamic behavior of hydrocarbon molecules under shear conditions. Frictional properties of cyclohexane, n-hexane, and iso-hexane thin films confirmed between two solid surfaces were calculated. Because the affinity of the solid surfaces in these simulations is strong, slippages occurred at inner parts of the confined films, whereas no slippages were observed at the solid boundaries. The hexagonal closest packing structure was observed for the adsorbed cyclohexane molecular layers. The branched methyl groups in the iso-hexane molecules increase the shear stress between the molecular layers. For the n-hexane monolayer, molecules were observed to roll during the sliding simulations. Rolling of the n-hexane molecules decreased the shear stress.

  8. SAFT-γ force field for the simulation of molecular fluids: 2. Coarse-grained models of greenhouse gases, refrigerants, and long alkanes.

    PubMed

    Avendaño, Carlos; Lafitte, Thomas; Adjiman, Claire S; Galindo, Amparo; Müller, Erich A; Jackson, George

    2013-03-07

    In the first paper of this series [C. Avendaño, T. Lafitte, A. Galindo, C. S. Adjiman, G. Jackson, and E. A. Müller, J. Phys. Chem. B2011, 115, 11154] we introduced the SAFT-γ force field for molecular simulation of fluids. In our approach, a molecular-based equation of state (EoS) is used to obtain coarse-grained (CG) intermolecular potentials that can then be employed in molecular simulation over a wide range of thermodynamic conditions of the fluid. The macroscopic experimental data for the vapor-liquid equilibria (saturated liquid density and vapor pressure) of a given system are represented with the SAFT-VR Mie EoS and used to estimate effective intermolecular parameters that provide a good description of the thermodynamic properties by exploring a wide parameter space for models based on the Mie (generalized Lennard-Jones) potential. This methodology was first used to develop a simple single-segment CG Mie model of carbon dioxide (CO2) which allows for a reliable representation of the fluid-phase equilibria (for which the model was parametrized), as well as an accurate prediction of other properties such as the enthalpy of vaporization, interfacial tension, supercritical density, and second-derivative thermodynamic properties (thermal expansivity, isothermal compressibility, heat capacity, Joule-Thomson coefficient, and speed of sound). In our current paper, the methodology is further applied and extended to develop effective SAFT-γ CG Mie force fields for some important greenhouse gases including carbon tetrafluoride (CF4) and sulfur hexafluoride (SF6), modeled as simple spherical molecules, and for long linear alkanes including n-decane (n-C10H22) and n-eicosane (n-C20H42), modeled as homonuclear chains of spherical Mie segments. We also apply the SAFT-γ methodology to obtain a CG homonuclear two-segment Mie intermolecular potential for the more challenging polar and asymmetric compound 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), a novel replacement

  9. Molecular-dynamics simulation of thin-film growth

    NASA Astrophysics Data System (ADS)

    Schneider, M.; Schuller, I. K.; Rahman, A.

    1987-01-01

    The epitaxial growth of thin films has been studied by molecular-dynamics computer simulation. In these simulations atoms are projected towards a temperature-controlled substrate, and the equations of motion of all atoms are solved for a given interaction potential. The calculations give insight into the microscopic structure of thin films, the dynamics of the adsorption process, and they help answer the way in which substrate temperature, form of the substrate, flux of impinging atoms, and form of the interaction potential, affect epitaxial growth. Simulations were performed for monatomic and binary systems with spherically symmetric atomic interactions, and for systems in which the atoms are interacting via a three-body potential to simulate the epitaxial growth of silicon.

  10. Abundance and diversity of n-alkane-degrading bacteria in a forest soil co-contaminated with hydrocarbons and metals: a molecular study on alkB homologous genes.

    PubMed

    Pérez-de-Mora, Alfredo; Engel, Marion; Schloter, Michael

    2011-11-01

    Unraveling functional genes related to biodegradation of organic compounds has profoundly improved our understanding of biological remediation processes, yet the ecology of such genes is only poorly understood. We used a culture-independent approach to assess the abundance and diversity of bacteria catalyzing the degradation of n-alkanes with a chain length between C(5) and C(16) at a forest site co-contaminated with mineral oil hydrocarbons and metals for nearly 60 years. The alkB gene coding for a rubredoxin-dependent alkane monooxygenase enzyme involved in the initial activation step of aerobic aliphatic hydrocarbon metabolism was used as biomarker. Within the area of study, four different zones were evaluated: one highly contaminated, two intermediately contaminated, and a noncontaminated zone. Contaminant concentrations, hydrocarbon profiles, and soil microbial respiration and biomass were studied. Abundance of n-alkane-degrading bacteria was quantified via real-time PCR of alkB, whereas genetic diversity was examined using molecular fingerprints (T-RFLP) and clone libraries. Along the contamination plume, hydrocarbon profiles and increased respiration rates suggested on-going natural attenuation at the site. Gene copy numbers of alkB were similar in contaminated and control areas. However, T-RFLP-based fingerprints suggested lower diversity and evenness of the n-alkane-degrading bacterial community in the highly contaminated zone compared to the other areas; both diversity and evenness were negatively correlated with metal and hydrocarbon concentrations. Phylogenetic analysis of alkB denoted a shift of the hydrocarbon-degrading bacterial community from Gram-positive bacteria in the control zone (most similar to Mycobacterium and Nocardia types) to Gram-negative genotypes in the contaminated zones (Acinetobacter and alkB sequences with little similarity to those of known bacteria). Our results underscore a qualitative rather than a quantitative response of

  11. Molecular release from patterned nanoporous gold thin films

    NASA Astrophysics Data System (ADS)

    Kurtulus, Ozge; Daggumati, Pallavi; Seker, Erkin

    2014-05-01

    Nanostructured materials have shown significant potential for biomedical applications that require high loading capacity and controlled release of drugs. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising novel material that benefits from compatibility with microfabrication, tunable pore morphology, electrical conductivity, well-established gold-thiol conjugate chemistry, and biocompatibility. While np-Au's non-biological applications are abundant, its performance in the biomedical field is nascent. In this work, we employ a combination of techniques including nanoporous thin film synthesis, quantitative electron microscopy, fluorospectrometry, and electrochemical surface characterization to study loading capacity and molecular release kinetics as a function of film properties and discuss underlying mechanisms. The sub-micron-thick sputter-coated nanoporous gold films provide small-molecule loading capacities up to 1.12 μg cm-2 and molecular release half-lives between 3.6 hours to 12.8 hours. A systematic set of studies reveals that effective surface area of the np-Au thin films on glass substrates plays the largest role in determining loading capacity. The release kinetics on the other hand depends on a complex interplay of micro- and nano-scale morphological features.Nanostructured materials have shown significant potential for biomedical applications that require high loading capacity and controlled release of drugs. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising novel material that benefits from compatibility with microfabrication, tunable pore morphology, electrical conductivity, well-established gold-thiol conjugate chemistry, and biocompatibility. While np-Au's non-biological applications are abundant, its performance in the biomedical field is nascent. In this work, we employ a combination of techniques including nanoporous thin film synthesis, quantitative electron microscopy

  12. Molecular dynamics simulations of cholesterol-rich membranes using a coarse-grained force field for cyclic alkanes

    NASA Astrophysics Data System (ADS)

    MacDermaid, Christopher M.; Kashyap, Hemant K.; DeVane, Russell H.; Shinoda, Wataru; Klauda, Jeffery B.; Klein, Michael L.; Fiorin, Giacomo

    2015-12-01

    The architecture of a biological membrane hinges upon the fundamental fact that its properties are determined by more than the sum of its individual components. Studies on model membranes have shown the need to characterize in molecular detail how properties such as thickness, fluidity, and macroscopic bending rigidity are regulated by the interactions between individual molecules in a non-trivial fashion. Simulation-based approaches are invaluable to this purpose but are typically limited to short sampling times and model systems that are often smaller than the required properties. To alleviate both limitations, the use of coarse-grained (CG) models is nowadays an established computational strategy. We here present a new CG force field for cholesterol, which was developed by using measured properties of small molecules, and can be used in combination with our previously developed force field for phospholipids. The new model performs with precision comparable to atomistic force fields in predicting the properties of cholesterol-rich phospholipid bilayers, including area per lipid, bilayer thickness, tail order parameter, increase in bending rigidity, and propensity to form liquid-ordered domains in ternary mixtures. We suggest the use of this model to quantify the impact of cholesterol on macroscopic properties and on microscopic phenomena involving localization and trafficking of lipids and proteins on cellular membranes.

  13. Molecular dynamics simulations of cholesterol-rich membranes using a coarse-grained force field for cyclic alkanes

    SciTech Connect

    MacDermaid, Christopher M. Klein, Michael L.; Fiorin, Giacomo; Kashyap, Hemant K.; DeVane, Russell H.; Shinoda, Wataru; Klauda, Jeffery B.

    2015-12-28

    The architecture of a biological membrane hinges upon the fundamental fact that its properties are determined by more than the sum of its individual components. Studies on model membranes have shown the need to characterize in molecular detail how properties such as thickness, fluidity, and macroscopic bending rigidity are regulated by the interactions between individual molecules in a non-trivial fashion. Simulation-based approaches are invaluable to this purpose but are typically limited to short sampling times and model systems that are often smaller than the required properties. To alleviate both limitations, the use of coarse-grained (CG) models is nowadays an established computational strategy. We here present a new CG force field for cholesterol, which was developed by using measured properties of small molecules, and can be used in combination with our previously developed force field for phospholipids. The new model performs with precision comparable to atomistic force fields in predicting the properties of cholesterol-rich phospholipid bilayers, including area per lipid, bilayer thickness, tail order parameter, increase in bending rigidity, and propensity to form liquid-ordered domains in ternary mixtures. We suggest the use of this model to quantify the impact of cholesterol on macroscopic properties and on microscopic phenomena involving localization and trafficking of lipids and proteins on cellular membranes.

  14. Molecular tailoring of interfaces for thin film on substrate systems

    NASA Astrophysics Data System (ADS)

    Grady, Martha Elizabeth

    Thin film on substrate systems appear most prevalently within the microelectronics industry, which demands that devices operate in smaller and smaller packages with greater reliability. The reliability of these multilayer film systems is strongly influenced by the adhesion of each of the bimaterial interfaces. During use, microelectronic components undergo thermo-mechanical cycling, which induces interfacial delaminations leading to failure of the overall device. The ability to tailor interfacial properties at the molecular level provides a mechanism to improve thin film adhesion, reliability and performance. This dissertation presents the investigation of molecular level control of interface properties in three thin film-substrate systems: photodefinable polyimide films on passivated silicon substrates, self-assembled monolayers at the interface of Au films and dielectric substrates, and mechanochemically active materials on rigid substrates. For all three materials systems, the effect of interfacial modifications on adhesion is assessed using a laser-spallation technique. Laser-induced stress waves are chosen because they dynamically load the thin film interface in a precise, noncontacting manner at high strain rates and are suitable for both weak and strong interfaces. Photodefinable polyimide films are used as dielectrics in flip chip integrated circuit packages to reduce the stress between silicon passivation layers and mold compound. The influence of processing parameters on adhesion is examined for photodefinable polyimide films on silicon (Si) substrates with three different passivation layers: silicon nitride (SiNx), silicon oxynitride (SiOxNy), and the native silicon oxide (SiO2). Interfacial strength increases when films are processed with an exposure step as well as a longer cure cycle. Additionally, the interfacial fracture energy is assessed using a dynamic delamination protocol. The high toughness of this interface (ca. 100 J/m2) makes it difficult

  15. A martensitic-like transition in a normal alkane

    NASA Astrophysics Data System (ADS)

    Hutter, Jeffrey; Nene, Shailesh; Karhu, Eric; Flemming, Roberta

    2009-03-01

    The normal alkanes, CnH2n+2, with a structure consisting of a single chain, are the simplest hydrocarbons. These are an interesting class of material, both in terms of their intrinsic properties and the fact that many biological molecules contain hydrocarbon domains. Normal alkanes exhibit an unusual phase diagram with several solid phases, some of which---the ``rotator phases''---are characterized by positional order without long-range orientational order. We have found a striking pattern of twinned, striped domains that occurs in thin layers the monoclinic rotator RV phase of tricosane (C23H48). We have studied this structure, and its transitions to other phases, by X-ray diffraction, as well as by optical and atomic-force microscopy. Intriguingly, transitions between the RV phase and the RI orthorhombic phase lying at higher temperatures appear to be diffusionless, and preserve molecular-scale features even after multiple transitions between the phases. These properties are reminiscent of martensitic transformations, which are better-known in metal alloys, but occur here at convenient temperatures and with slow kinetics.

  16. Contact potential difference measurements of doped organic molecular thin films

    NASA Astrophysics Data System (ADS)

    Chan, Calvin; Gao, Weiying; Kahn, Antoine

    2004-07-01

    The possibility of nonequilibrium conditions in doped organic molecular thin films is investigated using a combination of ultraviolet photoemission spectroscopy (UPS) and contact potential difference measurements. Surface or interface photovoltage is of particular concern in materials with large band gap and appreciable band (or energy level) bending at interfaces. We investigate here zinc phthalocyanine (ZnPc) and N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'biphenyl-4,4'' diamine (α-NPD) p-doped with the acceptor molecule, tetrafluorotetracyanoquinodimethane (F4-TCNQ). In both cases, we observe an upward movement of the vacuum level away from the metal interface with respect to the Fermi level, consistent with the formation of a depletion region. We show that photovoltage is not a significant factor in these doped films, under ultraviolet illumination during UPS. We suggest that the carrier recombination rate in organic films is sufficiently fast to exclude any photovoltage effects at room temperature. .

  17. Preparation of Robust, Thin Zeolite Membrane Sheet for Molecular Separation

    SciTech Connect

    Liu, Wei; Zhang, Jian; Canfield, Nathan L.; Saraf, Laxmikant V.

    2011-10-19

    This paper reports a feasibility study on the preparation of zeolite membrane films on a thin, porous metal support sheet (50-{micro}m thick). Zeolite sodium A (NaA) and silicalite zeolite frameworks are chosen to represent synthesis of respective hydrophilic-type and hydrophobic-type zeolite membranes on this new support. It is found that a dense, continuous inter-grown zeolite crystal layer at a thickness less than 2 {micro}m can be directly deposited on such a support by using direct and secondary growth techniques. The resulting membrane shows excellent adhesion on the metal sheet. Molecular-sieving functions of the prepared membranes are characterized with ethanol/water separation, CO2 separation, and air dehumidification. The results show great potential to make flexible metal-foil-like zeolite membranes for a range of energy conversion and environmental applications.

  18. Untypical even-to-odd predominance in the low-molecular n-alkanes of water, suspended matter, and bottom sediments in some regions of the Arctic Basin

    NASA Astrophysics Data System (ADS)

    Drozdova, Anastasia; Belyaev, Nikolay; Ponyaev, Mikhail

    2014-05-01

    Over the years, several studies have shown an unusual predominance of even-carbon number n-alkanes in dissolved and particulate phase samples and sediment samples from various regions of the World Ocean [Nachman, 1985; Nishimura and Baker, 1985; Elias et al., 1997]. Different possible sources were proposed such as diagenesis (diagenetic origin from co-occurring fatty acids and alcohols), direct microbial input, microbial degradation of algal detritus, etc. Some researchers, however, are incredulous about this phenomenon and consider relatively high content of even-carbon number n-alkanes as contamination during the experiments. We report here the results of GC and GC-MS analysis of water, suspended particulate matter and sediment samples collected during 7 marine and coastal scientific expeditions to the White and Kara Seas, and to the central Arctic Basin (2004-2013). Many of the above samples (more than 30) present n-alkane distribution with a strong even-carbon number predominance of n-C14H30, and n-C16H34. Maximum enrichment was observed in some suspended matter samples with predominance of n-C16H34. The origin of even-carbon number n-alkanes in marine ecosystems is still not clear. In Antarctic region n-C16 and n-C18 and other even chain n-alkanes were reported to be dominant in the samples of the sea-ice algae, zooplankton and fish [Green et al. 1997] however in the Arctic region this phenomenon has not been demonstrated yet. Increasing of bacteria number and δ13C values observed in course of the accompanying studies [Lein et al., 2013] suggest existence of mechanism of phytoplankton bacterial destruction in the Arctic ecosystems, leading to formation of even-carbon number n-alkanes. R.J. Nachman - Lipids, Vol. 20, No 9, pp. 629-633 (1985). M. Nishimura, E.W. Baker - Geochim. et Cosmochim. Acta, Vol. 50, pp. 299-305 (1986). V.O. Elias, B.R.T. Simoneit, J.N. Cardoso - Naturwissenschaften, Vol. 84, pp. 415-420 (1997). G. Green et al. - Marine Pollution

  19. Reflectance spectroscopy of organic compounds: 1. Alkanes

    USGS Publications Warehouse

    Clark, R.N.; Curchin, J.M.; Hoefen, T.M.; Swayze, G.A.

    2009-01-01

    Reflectance spectra of the organic compounds comprising the alkane series are presented from the ultraviolet to midinfrared, 0.35 to 15.5 /??m. Alkanes are hydrocarbon molecules containing only single carbon-carbon bonds, and are found naturally on the Earth and in the atmospheres of the giant planets and Saturn's moon, Titan. This paper presents the spectral properties of the alkanes as the first in a series of papers to build a spectral database of organic compounds for use in remote sensing studies. Applications range from mapping the environment on the Earth, to the search for organic molecules and life in the solar system and throughout the. universe. We show that the spectral reflectance properties of organic compounds are rich, with major diagnostic spectral features throughout the spectral range studied. Little to no spectral change was observed as a function of temperature and only small shifts and changes in the width of absorption bands were observed between liquids and solids, making remote detection of spectral properties throughout the solar system simpler. Some high molecular weight organic compounds contain single-bonded carbon chains and have spectra similar to alkanes even ' when they fall into other families. Small spectral differences are often present allowing discrimination among some compounds, further illustrating the need to catalog spectral properties for accurate remote sensing identification with spectroscopy.

  20. Revised charge equilibration potential for liquid alkanes.

    PubMed

    Davis, Joseph E; Warren, G Lee; Patel, Sandeep

    2008-07-17

    We present a revised liquid alkane force field based on the charge equilibration formalism for incorporating electrostatic nonadditive effects arising from local polarization. The model is a revision of earlier work by Patel and Brooks, specifically addressing deficiencies in the dihedral potential, electrostatic, and Lennard-Jones (van der Waals) parameters of the force field. We discuss refinement of the alkane backbone torsion potential to match high-level ab initio relative conformational energetics for pentane, hexane, and heptane. We further discuss refinement of the electrostatic and Lennard-Jones (van der Waals) parameters to reproduce the experimental polarizability, liquid density, and vaporization enthalpy of hexane. Finally, we calculate bulk liquid properties including densities, vaporization enthalpies, self-diffusion constants, isothermal compressibilities, constant pressure heat capacities, and NMR T 1 relaxation times for a series of linear alkanes ranging from hexane to pentadecane based on the current revised model. We also compute free energies of hydration for pentane, hexane, and heptane. The revised force field offers a significantly improved overall description of these properties relative to the original parametrization. The current alkane force field represents a platform for ongoing development of a CHARMM (Chemistry at Harvard Molecular Mechanics) polarizable force field for lipids and integral membrane proteins.

  1. The vapor-particle partitioning of n-alkanes

    SciTech Connect

    Doskey, P.V.

    1994-04-01

    A mixed-phase partitioning model has been proposed to predict the distribution of n-alkanes between the vapor and particle phases in the atmosphere. n-Alkanes having terrestrial plant wax and petroleum origins are assumed to be associated with atmospheric particles as microcrystalline solids and subcooled liquids, respectively. The fraction of n-alkanes on atmospheric particles having plant wax and petroleum origins is estimated with carbon preference indices. Hypothetical terrestrial plant wax and petroleum mixtures are used to estimate the mole fractions of the n-alkanes in each phase and the molecular weights of the phases. Solid and subcooled liquid phase n-alkane vapor pressures are used in the model to predict the fraction of n-alkanes associated with particles in the atmosphere. Trends in the prediction of vapor-particle partitioning using these assumptions agree well with field observations. However, the fraction of particle phase n-alkanes predicted by the model was significantly different from the field observations.

  2. Molecularly Oriented Polymeric Thin Films for Space Applications

    NASA Technical Reports Server (NTRS)

    Fay, Catharine C.; Stoakley, Diane M.; St.Clair, Anne K.

    1997-01-01

    The increased commitment from NASA and private industry to the exploration of outer space and the use of orbital instrumentation to monitor the earth has focused attention on organic polymeric materials for a variety of applications in space. Some polymeric materials have exhibited short-term (3-5 yr) space environmental durability; however, future spacecraft are being designed with lifetimes projected to be 10-30 years. This gives rise to concern that material property change brought about during operation may result in unpredicted spacecraft performance. Because of their inherent toughness and flexibility, low density, thermal stability, radiation resistance and mechanical strength, aromatic polyimides have excellent potential use as advanced materials on large space structures. Also, there exists a need for high temperature (200-300 C) stable, flexible polymeric films that have high optical transparency in the 300-600nm range of the electromagnetic spectrum. Polymers suitable for these space applications were fabricated and characterized. Additionally, these polymers were molecularly oriented to further enhance their dimensional stability, stiffness, elongation and strength. Both unoriented and oriented polymeric thin films were also cryogenically treated to temperatures below -184 C to show their stability in cold environments and determine any changes in material properties.

  3. Supercritical fluid molecular spray thin films and fine powders

    DOEpatents

    Smith, Richard D.

    1988-01-01

    Solid films are deposited, or fine powders formed, by dissolving a solid material into a supercritical fluid solution at an elevated pressure and then rapidly expanding the solution through a short orifice into a region of relatively low pressure. This produces a molecular spray which is directed against a substrate to deposit a solid thin film thereon, or discharged into a collection chamber to collect a fine powder. The solvent is vaporized and pumped away. Solution pressure is varied to determine, together with flow rate, the rate of deposition and to control in part whether a film or powder is produced and the granularity of each. Solution temperature is varied in relation to formation of a two-phase system during expansion to control porosity of the film or powder. A wide variety of film textures and powder shapes are produced of both organic and inorganic compounds. Films are produced with regular textural feature dimensions of 1.0-2.0 .mu.m down to a range of 0.01 to 0.1 .mu.m. Powders are formed in very narrow size distributions, with average sizes in the range of 0.02 to 5 .mu.m.

  4. Molecular solution processing of metal chalcogenide thin film solar cells

    NASA Astrophysics Data System (ADS)

    Yang, Wenbing

    The barrier to utilize solar generated electricity mainly comes from their higher cost relative to fossil fuels. However, innovations with new materials and processing techniques can potentially make cost effective photovoltaics. One such strategy is to develop solution processed photovoltaics which avoid the expensive vacuum processing required by traditional solar cells. The dissertation is mainly focused on two absorber material system for thin film solar cells: chalcopyrite CuIn(S,Se)2 (CISS) and kesterite Cu2ZnSn(S,Se) 4 organized in chronological order. Chalcopyrite CISS is a very promising material. It has been demonstrated to achieve the highest efficiency among thin film solar cells. Scaled-up industry production at present has reached the giga-watt per year level. The process however mainly relies on vacuum systems which account for a significant percentage of the manufacturing cost. In the first section of this dissertation, hydrazine based solution processed CISS has been explored. The focus of the research involves the procedures to fabricate devices from solution. The topics covered in Chapter 2 include: precursor solution synthesis with a focus on understanding the solution chemistry, CISS absorber formation from precursor, properties modification toward favorable device performance, and device structure innovation toward tandem device. For photovoltaics to have a significant impact toward meeting energy demands, the annual production capability needs to be on TW-level. On such a level, raw materials supply of rare elements (indium for CIS or tellurium for CdTe) will be the bottleneck limiting the scalability. Replacing indium with zinc and tin, earth abundant kesterite CZTS exhibits great potential to reach the goal of TW-level with no limitations on raw material availability. Chapter 3 shows pioneering work towards solution processing of CZTS film at low temperature. The solution processed devices show performances which rival vacuum

  5. Effects of pure n-alkanes and crude oil on bacterial phospholipid classes and molecular species determined by electrospray ionization mass spectrometry.

    PubMed

    Mazzella, Nicolas; Molinet, Josiane; Syakti, Agung Dhamar; Barriol, Alexandre; Dodi, Alain; Bertrand, Jean-Claude; Doumenq, Pierre

    2005-08-05

    Phospholipids are major components of bacterial membrane. Furthermore, the growth in vitro on xenobiotics such as n-alkanes, aromatic compounds or alkanols bring about to a bacterial membrane adaptive response. Concerning this work, we studied the membrane lipid composition of a hydrocarbon-degrading gram-positive bacterium (Corynebacterium sp.) on a soluble substrate and we detected four different phospholipid classes: phosphatidylglycerol, phosphatidylinositol, cardiolipin and acyl phosphatidylglycerol. In addition, a study of the lipid composition was performed after an in vitro culture on either pure n-alkane or crude oil. The growths on such hydrophobic substrates showed major qualitative and quantitative modifications. In the case of a growth on either heneicosane or crude oil, an increase of odd-numbered fatty acids was observed. Furthermore, the phospholipid polar head group composition was highly influenced by the crude oil addition. These modifications were, respectively, interpreted as the consequence of hydrocarbon assimilation and membrane fluidity adaptation. Finally, Corynebacterium sp. was taken back on the initial ammonium acetate substrate in order to determine its restoration abilities after a petroleum contamination.

  6. Molecular Aspects of Transport in Thin Films of Controlled Architecture

    SciTech Connect

    Paul W. Bohn

    2009-04-16

    Our laboratory focuses on developing spatially localized chemistries which can produce structures of controlled architecture on the supermolecular length scale -- structures which allow us to control the motion of molecular species with high spatial resolution, ultimately on nanometer length scales. Specifically, nanocapillary array membranes (NCAMs) contain an array of nanometer diameter pores connecting vertically separated microfluidic channels. NCAMs can manipulate samples with sub-femtoliter characteristic volumes and attomole sample amounts and are opening the field of chemical analysis of mass-limited samples, because they are capable of digital control of fluid switching down to sub-attoliter volumes; extension of analytical “unit operations” down to sub-femtomole sample sizes; and exerting spatiotemporal control over fluid mixing to enable studies of reaction dynamics. Digital flow switching mediated by nanocapillary array membranes can be controlled by bias, ionic strength, or pore diameter and is being studied by observing the temporal characteristics of transport across a single nanopore in thin PMMA membranes. The control of flow via nanopore surface characteristics, charge density and functional group presentation, is being studied by coupled conductivity and laser-induced fluorescence (LIF) measurements. Reactive mixing experiments previously established low millisecond mixing times for NCAM-mediated fluid transfer, and this has been exploited to demonstrate capture of mass-limited target species by Au colloids. Voltage and thermally-activated polymer switches have been developed for active control of transport in NCAMs. Thermally-switchable and size-selective transport was achieved by grafting poly(N-isopropylacrylamide) brushes onto the exterior surface of a Au-coated polycarbonate track-etched membrane, while the voltage-gated properties of poly(hydroxyethylmethacrylate) were characterized dynamically. Electrophoretic separations have been

  7. Alkanes in Natural and Synthetic Petroleums: Comparison of Calculated and Actual Compositions.

    PubMed

    Friedel, R A; Sharkey, A G

    1963-03-22

    A similarity exists between the low molecular weight alkane isomers in crude oil and Fischer-Tropsch catalytic synthesis products. The composition of the C(4) through C(7) alkane isomers in a crude oil was calculated quantitatively with the equations previously used to calculate the alkane isomers in Fischer-Tropsch products. These results may have significance in ascertaining the origin of the volatile hydrocarbons in crude oils.

  8. A diffusionless transition in a normal alkane

    NASA Astrophysics Data System (ADS)

    Nene, Shailesh; Karhu, Eric; Flemming, Roberta L.; Hutter, Jeffrey L.

    2009-12-01

    The normal alkanes are an interesting class of material, both in terms of their intrinsic properties and because many biological materials contain hydrocarbon domains. The normal alkanes often exhibit complicated phase behavior, with phase diagrams containing multiple solid phases. We report here a study of a curious pattern of twinned domains seen in one phase of tricosane (C 23H 48), which we have studied by X-ray diffraction, as well as by optical and atomic force microscopy. This pattern is seen in the rotator R V phase, a monoclinic arrangement of tricosane molecules without orientational order. Transitions between this polymorph and the orthorhombic R I rotator phase lying at higher temperatures preserve features at the molecular level, and thus represent a diffusionless, martensitic-like transformation.

  9. Hydrogen-hydrogen bonds in highly branched alkanes and in alkane complexes: A DFT, ab initio, QTAIM, and ELF study.

    PubMed

    Monteiro, Norberto K V; Firme, Caio L

    2014-03-06

    The hydrogen-hydrogen (H-H) bond or hydrogen-hydrogen bonding is formed by the interaction between a pair of identical or similar hydrogen atoms that are close to electrical neutrality and it yields a stabilizing contribution to the overall molecular energy. This work provides new, important information regarding hydrogen-hydrogen bonds. We report that stability of alkane complexes and boiling point of alkanes are directly related to H-H bond, which means that intermolecular interactions between alkane chains are directional H-H bond, not nondirectional induced dipole-induced dipole. Moreover, we show the existence of intramolecular H-H bonds in highly branched alkanes playing a secondary role in their increased stabilities in comparison with linear or less branched isomers. These results were accomplished by different approaches: density functional theory (DFT), ab initio, quantum theory of atoms in molecules (QTAIM), and electron localization function (ELF).

  10. Molecular Beam Epitaxy Growth and Characterization of Thin Layers of Semiconductor Tin

    DTIC Science & Technology

    2016-09-01

    heating. The α-Sn layers were also characterized with high-resolution X-ray diffraction, Hall, and atomic force microscopy (AFM) measurements...ARL-TR-7838 ● SEP 2016 US Army Research Laboratory Molecular Beam Epitaxy Growth and Characterization of Thin Layers of...Laboratory Molecular Beam Epitaxy Growth and Characterization of Thin Layers of Semiconductor Tin by P Folkes, P Taylor, C Rong, B Nichols

  11. Self-diffusion in molecular liquids: Medium-chain n-alkanes and coenzyme Q10 studied by quasielastic neutron scattering

    NASA Astrophysics Data System (ADS)

    Smuda, Christoph; Busch, Sebastian; Gemmecker, Gerd; Unruh, Tobias

    2008-07-01

    A systematic time-of-flight quasielastic neutron scattering (TOF-QENS) study on diffusion of n-alkanes in a melt is presented for the first time. As another example of a medium-chain molecule, coenzyme Q10 is investigated in the same way. The data were evaluated both in the frequency and in the time domain. TOF-QENS data can be satisfactorily described by different models, and it turned out that the determined diffusion coefficients are largely independent of the applied model. The derived diffusion coefficients are compared with values measured by pulsed-field gradient nuclear magnetic resonance (PFG-NMR). With increasing chain length, an increasing difference between the TOF-QENS diffusion coefficient and the PFG-NMR diffusion coefficient is observed. This discrepancy in the diffusion coefficients is most likely due to a change of the diffusion mechanism on a nanometer length scale for molecules of medium-chain length.

  12. Ultrafast Polarization Switching in a Biaxial Molecular Ferroelectric Thin Film: [Hdabco]ClO4.

    PubMed

    Tang, Yuan-Yuan; Zhang, Wan-Ying; Li, Peng-Fei; Ye, Heng-Yun; You, Yu-Meng; Xiong, Ren-Gen

    2016-12-07

    Molecular ferroelectrics are attracting much attention as valuable complements to conventional ceramic ferroelectrics owing to their solution processability and nontoxicity. Encouragingly, the recent discovery of a multiaxial molecular ferroelectric, tetraethylammonium perchlorate, is expected to be able to solve the problem that in the technologically relevant thin-film form uniaxial molecular ferroelectrics have been found to perform considerably more poorly than in bulk. However, it can show good polarization-electric field (P-E) hysteresis loops only at very low frequency, severely hampering practical applications such as ferroelectric random access memory. Here, we present a biaxial molecular ferroelectric thin film of [Hdabco]ClO4 (dabco = 1,4-diazabicyclo[2.2.2]octane) (1), where a perfect ferroelectric hysteresis loop can be observed even at 10 kHz. It is the first example of a molecular ferroelectric thin film whose polarization can be switched at such a high frequency. Moreover, using piezoresponse force microscopy, we clearly observed the coexistence of 180° and non-180° ferroelectric domains and provided direct experimental proof that 180° ferroelectric switching and non-180° ferroelastic switching are both realized; that is, a flexible alteration of the polarization axis direction can occur in the thin film by applying an electric field. These results open a new avenue for applications of molecular ferroelectrics and will inspire further exploration of high-performance multiaxial molecular ferroelectric thin films.

  13. Lubricant shear thinning behavior correlated with variation of radius of gyration via molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Liu, Pinzhi; Lu, Jie; Yu, Hualong; Ren, Ning; Lockwood, Frances E.; Wang, Q. Jane

    2017-08-01

    The shear thinning of a lubricant significantly affects lubrication film generation at high shear rates. The critical shear rate, defined at the onset of shear thinning, marks the transition of lubricant behaviors. It is challenging to capture the entire shear-thinning curve by means of molecular dynamics (MD) simulations owing to the low signal-to-noise ratio or long calculation time at comparatively low shear rates (104-106 s-1), which is likely coincident with the shear rates of interest for lubrication applications. This paper proposes an approach that correlates the shear-thinning phenomenon with the change in the molecular conformation characterized by the radius of gyration of the molecule. Such a correlation should be feasible to capture the major mechanism of shear thinning for small- to moderate-sized non-spherical molecules, which is shear-induced molecular alignment. The idea is demonstrated by analyzing the critical shear rate for squalane (C30H62) and 1-decene trimer (C30H62); it is then implemented to study the behaviors of different molecular weight poly-α-olefin (PAO) structures. Time-temperature-pressure superpositioning (TTPS) is demonstrated and it helps further extend the ranges of the temperature and pressure for shear-thinning behavior analyses. The research leads to a relationship between molecular weight and critical shear rate for PAO structures, and the results are compared with those from the Einstein-Debye equation.

  14. Revised Charge Equilibration Parameters for More Accurate Hydration Free Energies of Alkanes.

    PubMed

    Davis, Joseph E; Patel, Sandeep

    2010-01-01

    We present a refined alkane charge equilibration (CHEQ) force field, improving our previously reported CHEQ alkane force field[1] to better reproduce experimental hydration free energies. Experimental hydration free energies of ethane, propane, butane, pentane, hexane, and heptane are reproduced to within 3.6% on average. We demonstrate that explicit polarization results in a shift in molecular dipole moment for water molecules associated with the alkane molecule. We also show that our new parameters do not have a significant effect on the alkane-water interactions as measured by the radial distribution function (RDF).

  15. Degradation of alkanes by bacteria.

    PubMed

    Rojo, Fernando

    2009-10-01

    Pollution of soil and water environments by crude oil has been, and is still today, an important problem. Crude oil is a complex mixture of thousands of compounds. Among them, alkanes constitute the major fraction. Alkanes are saturated hydrocarbons of different sizes and structures. Although they are chemically very inert, most of them can be efficiently degraded by several microorganisms. This review summarizes current knowledge on how microorganisms degrade alkanes, focusing on the biochemical pathways used and on how the expression of pathway genes is regulated and integrated within cell physiology.

  16. Enhanced Rates of Photoinduced Molecular Orientation in a Series of Molecular Glassy Thin Films.

    PubMed

    Snell, Kristen E; Hou, Renjie; Ishow, Eléna; Lagugné-Labarthet, François

    2015-07-07

    Photoinduced orientation in a series of molecular glasses made of small push-pull azo derivatives is dynamically investigated for the first time. Birefringence measurements at 632.8 nm are conducted with a temporal resolution of 100 ms to probe the fast rate of the azo orientation induced under polarized light and its temporal stability over several consecutive cycles. To better evaluate the influence of the azo chemical substituents and their electronic properties on the orientation of the whole molecule, a series of push-pull azo derivatives involving a triphenylaminoazo core substituted with distinct electron-withdrawing moieties is studied. All resulting thin films are probed using polarization modulation infrared spectroscopy that yields dynamical linear dichroism measurements during a cycle of orientation followed by relaxation. We show here in particular that the orientation rates of small molecule-based azo materials are systematically increased up to 7-fold compared to those of a reference polymer counterpart. For specific compounds, the percentage of remnant orientation is also higher, which makes these materials of great interest and promising alternatives to azobenzene-containing polymers for a variety of applications requiring a fast response and absolute control over the molecular weight.

  17. Interfacial properties of semifluorinated alkane diblock copolymers

    NASA Astrophysics Data System (ADS)

    Pierce, Flint; Tsige, Mesfin; Borodin, Oleg; Perahia, Dvora; Grest, Gary S.

    2008-06-01

    The liquid-vapor interfacial properties of semifluorinated linear alkane diblock copolymers of the form F3C(CF2)n-1(CH2)m-1CH3 are studied by fully atomistic molecular dynamics simulations. The chemical composition and the conformation of the molecules at the interface are identified and correlated with the interfacial energies. A modified form of the Optimized Parameter for Liquid Simulation All-Atom (OPLS-AA) force field of Jorgensen and co-workers [J. Am. Chem. Soc. 106, 6638 (1984); 118, 11225 (1996); J. Phys. Chem. A 105, 4118 (2001)], which includes specific dihedral terms for H-F blocks-and corrections to the H-F nonbonded interaction, is used together with a new version of the exp-6 force field developed in this work. Both force fields yield good agreement with the available experimental liquid density and surface tension data as well as each other over significant temperature ranges and for a variety of chain lengths and compositions. The interfacial regions of semifluorinated alkanes are found to be rich in fluorinated groups compared to hydrogenated groups, an effect that decreases with increasing temperature but is independent of the fractional length of the fluorinated segments. The proliferation of fluorine at the surface substantially lowers the surface tension of the diblock copolymers, yielding values near those of perfluorinated alkanes and distinct from those of protonated alkanes of the same chain length. With decreasing temperatures within the liquid state, chains are found to preferentially align perpendicular to the interface, as previously seen.

  18. Vibrational modes and changing molecular conformation of perfluororubrene in thin films and solution.

    PubMed

    Anger, F; Scholz, R; Gerlach, A; Schreiber, F

    2015-06-14

    We investigate the vibrational properties of perfluororubrene (PF-RUB) in thin films on silicon wafers with a native oxide layer as well as on silicon wafers covered with a self-assembled monolayer and in dichloromethane solution. In comparison with computed Raman and IR spectra, we can assign the molecular modes and identify two molecular conformations with twisted and planar tetracene backbones of the molecule. Moreover, we employ Raman imaging techniques to study the morphology and distribution of the molecular conformation in PF-RUB thin films.

  19. Direct Photoalignment and Optical Patterning of Molecular Thin Films.

    PubMed

    Pithan, Linus; Beyer, Paul; Bogula, Laura; Zykov, Anton; Schäfer, Peter; Rawle, Jonathan; Nicklin, Chris; Opitz, Andreas; Kowarik, Stefan

    2017-02-01

    A novel strategy for direct photoalignment of molecular materials using optothermal re-orientation is introduced. Photoalignment for molecular materials such as the organic semiconductor tetracene is shown, without relying on additional photoreactive dopants or alignment layers. Patterning and polarized light emission, e.g., for polarized organic light emitting diodes is demonstrated.

  20. Fluidization and Active Thinning by Molecular Kinetics in Active Gels

    NASA Astrophysics Data System (ADS)

    Oriola, David; Alert, Ricard; Casademunt, Jaume

    2017-02-01

    We derive the constitutive equations of an active polar gel from a model for the dynamics of elastic molecules that link polar elements. Molecular binding kinetics induces the fluidization of the material, giving rise to Maxwell viscoelasticity and, provided that detailed balance is broken, to the generation of active stresses. We give explicit expressions for the transport coefficients of active gels in terms of molecular properties, including nonlinear contributions on the departure from equilibrium. In particular, when activity favors linker unbinding, we predict a decrease of viscosity with activity—active thinning—of kinetic origin, which could explain some experimental results on the cell cortex. By bridging the molecular and hydrodynamic scales, our results could help understand the interplay between molecular perturbations and the mechanics of cells and tissues.

  1. Anomalous scaling behavior and surface roughening in molecular thin-film deposition

    SciTech Connect

    Yim, S.; Jones, T. S.

    2006-04-15

    The thin film growth dynamics of a molecular semiconductor, free-base phthalocyanine (H{sub 2}Pc), deposited by organic molecular beam deposition, has been studied by atomic force microscopy (AFM) and height difference correlation function (HDCF) analysis. The measured dynamic scaling components ({alpha}{sub loc}=0.61{+-}0.12, {beta}=1.02{+-}0.08, and 1/z=0.72{+-}0.13) are consistent with rapid surface roughening and anomalous scaling behavior. A detailed analysis of AFM images and simple growth models suggest that this behavior arises from the pronounced upward growth of crystalline H{sub 2}Pc mounds during the initial stages of thin film growth.

  2. Role of Molecular Conformations in Rubrene Thin Film Growth

    SciTech Connect

    Kaefer, D.; Ruppel, L.; Witte, G.; Woell, Ch.

    2005-10-14

    A systematic analysis of the growth of rubrene (C{sub 42}H{sub 28}), an organic molecule that currently attracts considerable attention with regard to its application in molecular electronics, is carried out by using x-ray absorption spectroscopy and thermal desorption spectroscopy. The results allow us to unravel a fundamental mechanism that effectively limits organic epitaxy for a large class of organic molecules. If the structure of the free molecule differs substantially from that of the corresponding molecular structure in the bulk, the crystallization is severely hampered.

  3. Defect-Controlled Preparation of UiO-66 Metal-Organic Framework Thin Films with Molecular Sieving Capability.

    PubMed

    Zhang, Caiqin; Zhao, Yajing; Li, Yali; Zhang, Xuetong; Chi, Lifeng; Lu, Guang

    2016-01-01

    Metal-organic framework (MOF) UiO-66 thin films are solvothermally grown on conducting substrates. The as-synthesized MOF thin films are subsequently dried by a supercritical process or treated with polydimethylsiloxane (PDMS). The obtained UiO-66 thin films show excellent molecular sieving capability as confirmed by the electrochemical studies for redox-active species with different sizes.

  4. Surface freezing in binary alkane-alcohol mixtures

    SciTech Connect

    Ofer, E.; Sloutskin, E.; Tamam, L.; Deutsch, M.; Ocko, B. M.

    2006-08-15

    Surface freezing was detected and studied in mixtures of alcohol and alkane molecules, using surface tensiometry and surface-specific x-ray scattering methods. Considering that surface freezing in pure alkanes forms an ordered monolayer and in alcohols it forms an ordered bilayer, the length mismatch repulsion was minimized by varying the carbon number of the alkane component around 2n, where n is the carbon number of the alcohol molecule. A solutionlike behavior was found for all mixtures, where the ideal liquid mixture phase-separates upon freezing both in the bulk and the surface. The solid exhibits a herringbone crystalline phase below an alkane mole fraction {phi}{sub t}{approx_equal}0.8 and a rotator phase above it. The surface frozen film below {phi}{sub t} is an alkane monolayer exhibiting a next-nearest neighbor molecular tilt of a composition-dependent magnitude. Above {phi}{sub t}, no diffraction peaks were observed. This could be explained by the intrinsically shorter-range order of the rotator phase and a possible proliferation of defects.

  5. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    SciTech Connect

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  6. Sigma-pi molecular dielectric multilayers for low-voltage organic thin-film transistors.

    PubMed

    Yoon, Myung-Han; Facchetti, Antonio; Marks, Tobin J

    2005-03-29

    Very thin (2.3-5.5 nm) self-assembled organic dielectric multilayers have been integrated into organic thin-film transistor structures to achieve sub-1-V operating characteristics. These new dielectrics are fabricated by means of layer-by-layer solution phase deposition of molecular silicon precursors, resulting in smooth, nanostructurally well defined, strongly adherent, thermally stable, virtually pinhole-free, organosiloxane thin films having exceptionally large electrical capacitances (up to approximately 2,500 nF.cm(-2)), excellent insulating properties (leakage current densities as low as 10(-9) A.cm(-2)), and single-layer dielectric constant (k)of approximately 16. These 3D self-assembled multilayers enable organic thin-film transistor function at very low source-drain, gate, and threshold voltages (<1 V) and are compatible with a broad variety of vapor- or solution-deposited p- and n-channel organic semiconductors.

  7. Modeling Ellipsometry Measurements of Molecular Thin-Film Contamination on Genesis Array Samples

    NASA Technical Reports Server (NTRS)

    Calaway, Michael J.; Stansbery, E. K.; McNamara, K. M.

    2006-01-01

    The discovery of a molecular thin-film contamination on Genesis flown array samples changed the course of preliminary assessment strategies. Analytical techniques developed to measure solar wind elemental abundances must now compensate for a thin-film contamination. Currently, this is done either by experimental cleaning before analyses or by depth-profiling techniques that bypass the surface contamination. Inside Johnson Space Center s Genesis dedicated ISO Class 4 (Class 10) cleanroom laboratory, the selection of collector array fragments allocated for solar wind analyses are based on the documentation of overall surface quality, visible surface particle contamination greater than 1 m, and the amount of thin film contamination measured by spectroscopic ellipsometry. Documenting the exact thickness, surface topography, and chemical composition of these contaminates is also critical for developing accurate cleaning methods. However, the first step in characterization of the molecular film is to develop accurate ellipsometry models that will determine an accurate thickness measurement of the contamination film.

  8. Rubredoxins Involved in Alkane Oxidation

    PubMed Central

    van Beilen, Jan B.; Neuenschwander, Martin; Smits, Theo H. M.; Roth, Christian; Balada, Stefanie B.; Witholt, Bernard

    2002-01-01

    Rubredoxins (Rds) are essential electron transfer components of bacterial membrane-bound alkane hydroxylase systems. Several Rd genes associated with alkane hydroxylase or Rd reductase genes were cloned from gram-positive and gram-negative organisms able to grow on n-alkanes (Alk-Rds). Complementation tests in an Escherichia coli recombinant containing all Pseudomonas putida GPo1 genes necessary for growth on alkanes except Rd 2 (AlkG) and sequence comparisons showed that the Alk-Rds can be divided in AlkG1- and AlkG2-type Rds. All alkane-degrading strains contain AlkG2-type Rds, which are able to replace the GPo1 Rd 2 in n-octane hydroxylation. Most strains also contain AlkG1-type Rds, which do not complement the deletion mutant but are highly conserved among gram-positive and gram-negative bacteria. Common to most Rds are the two iron-binding CXXCG motifs. All Alk-Rds possess four negatively charged residues that are not conserved in other Rds. The AlkG1-type Rds can be distinguished from the AlkG2-type Rds by the insertion of an arginine downstream of the second CXXCG motif. In addition, the glycines in the two CXXCG motifs are usually replaced by other amino acids. Mutagenesis of residues conserved in either the AlkG1- or the AlkG2-type Rds, but not between both types, shows that AlkG1 is unable to transfer electrons to the alkane hydroxylase mainly due to the insertion of the arginine, whereas the exchange of the glycines in the two CXXCG motifs only has a limited effect. PMID:11872724

  9. On droplet combustion of biodiesel fuel mixed with diesel/alkanes in microgravity condition

    SciTech Connect

    Pan, Kuo-Long; Li, Je-Wei; Chen, Chien-Pei; Wang, Ching-Hua

    2009-10-15

    The burning characteristics of a biodiesel droplet mixed with diesel or alkanes such as dodecane and hexadecane were experimentally studied in a reduced-gravity environment so as to create a spherically symmetrical flame without the influence of natural convection due to buoyancy. Small droplets on the order of 500 {mu}m in diameter were initially injected via a piezoelectric technique onto the cross point intersected by two thin carbon fibers; these were prepared inside a combustion chamber that was housed in a drag shield, which was freely dropped onto a foam cushion. It was found that, for single component droplets, the tendency to form a rigid soot shell was relatively small for biodiesel fuel as compared to that exhibited by the other tested fuels. The soot created drifted away readily, showing a puffing phenomenon; this could be related to the distinct molecular structure of biodiesel leading to unique soot layers that were more vulnerable to oxidative reactivity as compared to the soot generated by diesel or alkanes. The addition of biodiesel to these more traditional fuels also presented better performance with respect to annihilating the soot shell, particularly for diesel. The burning rate generally follows that of multi-component fuels, by some means in terms of a lever rule, whereas the mixture of biodiesel and dodecane exhibits a somewhat nonlinear relation with the added fraction of dodecane. This might be related to the formation of a soot shell. (author)

  10. A quantitative comparison between the flow factor approach model and the molecular dynamics simulation results for the flow of a confined molecularly thin fluid film

    NASA Astrophysics Data System (ADS)

    Zhang, Yongbin

    2015-06-01

    Quantitative comparisons were made between the flow factor approach model and the molecular dynamics simulation (MDS) results both of which describe the flow of a molecularly thin fluid film confined between two solid walls. Although these two approaches, respectively, calculate the flow of a confined molecularly thin fluid film by different ways, very good agreements were found between them when the Couette and Poiseuille flows, respectively, calculated from them were compared. It strongly indicates the validity of the flow factor approach model in modeling the flow of a confined molecularly thin fluid film.

  11. Shear Viscous Response of Molecularly Thin Liquid Films

    NASA Astrophysics Data System (ADS)

    Tschirhart, Charles; Troian, Sandra

    2014-11-01

    Fluids that exhibit Newtonian response at the macroscale can display interesting deviations at the nanoscale caused by internal fluid microstructure or conformational entropy reduction near an adjacent solid boundary. Such deviations signal the breakdown of the continuum and isotropic fluid approximations at molecular length scales. These effects are particularly pronounced near the interface separating a liquid film from a supporting solid substrate where molecular layering in the fluid can result in inhomogeneity in the shear viscosity. Here we describe ellipsometric measurements of the surface deformation of non-volatile liquid nanofilms subject to a constant interfacial shear stress. For simple Newtonian response, the slope of the deformation can be used to extract the value of the shear viscosity in ultrathin films, which in our experiments range from 2 - 200 nm in thickness. For complex films, we observe deviations from linear deformation which require augmentation of the analytic model normally used to describe the viscous response. These findings may be helpful for improved parametrization of the shear response of supported free surface films as well as course grained models for nanofluidic applications. Support from the Fred and Jean Felberg and Winifred and Robert Gardner Summer Undergraduate Research Fellowships is gratefully acknowledged.

  12. Simulation studies of the tribological behavior of molecularly thin films

    NASA Astrophysics Data System (ADS)

    He, Gang

    2002-09-01

    In this thesis I used molecular dynamics simulations to study two nanotribological problems. The first is the frictional behavior of adsorbed molecules. Macroscopic objects almost always exhibit a finite static friction and a kinetic friction that is slightly smaller at low velocities. However, molecular scale theories of friction between bare surfaces predict that the static friction almost always vanishes and is not closely related to the kinetic friction. Of course most real surfaces are not bare, but are coated with a layer of adsorbed molecules. Our simulation results show that these molecules naturally lead to a finite static friction that is consistent with macroscopic friction laws. We found that parameters that are not controlled in experiments, i.e., crystalline alignment, sliding direction, and the number of adsorbed molecules have little effect on the friction. Temperature, molecular geometry and interaction potentials can have larger effects on friction. The kinetic friction is found to rise logarithmically with velocity as in many experimental systems. Variations in static and kinetic friction are highly correlated. This correlation is understood through analogy with the Tomlinson model and the trends are explained with a hard-sphere picture. We also studied the microscopic flow boundary condition due to rough surfaces: Generally slip at the interface can be quantified by a slip length S that represents the additional width of fluid that would be needed to accommodate any velocity difference at the interface. Previous simulations with atomically flat surfaces show that S can be very large in certain limits. A dramatic divergence of S as shear rate increases has also been reported. We have extended these simulations to surfaces with random roughness, steps, and angled facets typical of twin boundaries. In all cases, S decreases rapidly as the roughness increases. When peak-to-peak roughness is only two atomic diameters, values of S have dropped from

  13. An investigation of clustering during the early stages of sculptured thin film growth via molecular dynamics

    NASA Astrophysics Data System (ADS)

    Yurick, Thomas J., Jr.

    2005-11-01

    As nano-technology continues to revolutionize our daily lives, nano-engineered materials take on a more prominent role. One example of a nano-engineered material is that of sculptured thin films. Sculptured thin films or STFs are a special class of thin films that have a characteristic shape imparted to them on the nano-scale, during the deposition process. This characteristic shape can be that of a zig-zag, chevron, or helices. Applications for these STFs vary from micro-electronics to medical applications, however, it is most likely that the best use of them is yet to be discovered. As with any engineering problem, simulation can play a key role in gaining understanding and insight. This is certainly true with the deposition of STFs as well. However, the simulation of an STF entails the capability of simulating each and every atom that makes up the STF. It is the manipulation of the impinging film atoms, during the deposition, that produce the characteristic shape. Luckily, today's fast computer processors coupled with an atomistic simulation method called Molecular Dynamics allows for such a simulation. This work focused on the use of a custom parallel Molecular Dynamics program for the simulation of cluster formation during very early stages of STF growth. Once the simulated thin film morphology was obtained, a qualitative analysis of the simulated thin film morphology was performed by visualizing the thin film surface. A qualitative analysis of the thin film morphology was also performed by estimating the fractal dimension of the simulated surface via the Slit-Island Method.

  14. Removal of alkanes from drinking water using membrane technologies

    SciTech Connect

    Fronk, C.A.

    1995-10-01

    Increasingly, the public is concerned about the quality of its drinking water. The chlorinated alkanes are saturated, aliphatic, synthetic organic compounds (SOC`s). When hydrocarbon feedstocks are chlorinated, a wide variety of chlorocarbons and chlorohydrocarbons are produced that are used as industrial solvents, degreasers and intermediaries. Because compounds such as Carbon Tetrachloride and 1,2-Dichloroethane are widely used, they often find their way into drinking water, particularly groundwaters. Surface waters are somewhat less affected bemuse of the high volatility of many chlorinated alkanes. The Drinking Water Research Division is responsible for evaluating various membrane technologies that may be feasible for meeting Maximum Contaminant Levels. Several membrane processes are under investigation to determine their effectiveness in removing SOC`s from drinking water. One study addressed the removal of a variety of alkanes from spiked groundwater by six reverse osmosis membranes: a cellulose acetate, a polyamide (hollow fiber), and four different types of thin-film composite membranes. Progressive chlorination of methanes, ethanes and propanes produces compounds that exhibit differing physicochemical properties. The differences in compound properties have an effect on the removal of these compounds by reverse osmosis membranes. For example only 25% of the methylene chloride (Dichloromethane) was removed by one thin-film composite versus 90% removal of the carbon tetrachloride. In addition, the various membranes are made of different polymeric materials and showed a wide range of removals. Generally, the thin-film composite membranes out performed the other membranes and the more highly chlorinated the compound the better the removal. Pervaporation is yet another membrane process that may prove effective in removal of alkanes and future studies will address its usefulness as a drinking water.

  15. Biochemistry of Short-Chain Alkanes (Tissue-Specific Biosynthesis of n-Heptane in Pinus jeffreyi).

    PubMed

    Savage, T. J.; Hamilton, B. S.; Croteau, R.

    1996-01-01

    Short-chain (C7-C11) alkanes accumulate as the volatile component of oleoresin (pitch) in several pine species native to western North America. To establish the tissue most amenable for use in detailed studies of short-chain alkane biosynthesis, we examined the tissue specificity of alkane accumulation and biosynthesis in Pinus jeffreyi Grev. & Balf. Short-chain alkane accumulation was highly tissue specific in both 2-year-old saplings and mature trees; heart-wood xylem accumulated alkanes up to 7.1 mg g-1 dry weight, whereas needles and other young green tissue contained oleoresin with monoterpenoid, rather than paraffinic, volatiles. These tissue-specific differences in oleoresin composition appear to be a result of tissue-specific rates of alkane and monoterpene biosynthesis; incubation of xylem tissue with [14C]sucrose resulted in accumulation of radiolabel in alkanes but not monoterpenes, whereas incubation of foliar tissue with 14CO2 resulted in the accumulation of radiolabel in monoterpenes but not alkanes. Furthermore, incubation of xylem sections with [14C]acetate resulted in incorporation of radiolabel into alkanes at rates up to 1.7 nmol h-1 g-1 fresh weight, a rate that exceeds most biosynthetic rates reported with other plant systems for the incorporation of this basic precursor into natural products. This suggests that P. jeffreyi may provide a suitable model for elucidating the enzymology and molecular biology of short-chain alkane biosynthesis.

  16. Biochemistry of Short-Chain Alkanes (Tissue-Specific Biosynthesis of n-Heptane in Pinus jeffreyi).

    PubMed Central

    Savage, T. J.; Hamilton, B. S.; Croteau, R.

    1996-01-01

    Short-chain (C7-C11) alkanes accumulate as the volatile component of oleoresin (pitch) in several pine species native to western North America. To establish the tissue most amenable for use in detailed studies of short-chain alkane biosynthesis, we examined the tissue specificity of alkane accumulation and biosynthesis in Pinus jeffreyi Grev. & Balf. Short-chain alkane accumulation was highly tissue specific in both 2-year-old saplings and mature trees; heart-wood xylem accumulated alkanes up to 7.1 mg g-1 dry weight, whereas needles and other young green tissue contained oleoresin with monoterpenoid, rather than paraffinic, volatiles. These tissue-specific differences in oleoresin composition appear to be a result of tissue-specific rates of alkane and monoterpene biosynthesis; incubation of xylem tissue with [14C]sucrose resulted in accumulation of radiolabel in alkanes but not monoterpenes, whereas incubation of foliar tissue with 14CO2 resulted in the accumulation of radiolabel in monoterpenes but not alkanes. Furthermore, incubation of xylem sections with [14C]acetate resulted in incorporation of radiolabel into alkanes at rates up to 1.7 nmol h-1 g-1 fresh weight, a rate that exceeds most biosynthetic rates reported with other plant systems for the incorporation of this basic precursor into natural products. This suggests that P. jeffreyi may provide a suitable model for elucidating the enzymology and molecular biology of short-chain alkane biosynthesis. PMID:12226177

  17. Rupture mechanism of liquid crystal thin films realized by large-scale molecular simulations

    NASA Astrophysics Data System (ADS)

    Nguyen, Trung Dac; Carrillo, Jan-Michael Y.; Matheson, Michael A.; Brown, W. Michael

    2014-02-01

    The ability of liquid crystal (LC) molecules to respond to changes in their environment makes them an interesting candidate for thin film applications, particularly in bio-sensing, bio-mimicking devices, and optics. Yet the understanding of the (in)stability of this family of thin films has been limited by the inherent challenges encountered by experiment and continuum models. Using unprecedented large-scale molecular dynamics (MD) simulations, we address the rupture origin of LC thin films wetting a solid substrate at length scales similar to those in experiment. Our simulations show the key signatures of spinodal instability in isotropic and nematic films on top of thermal nucleation, and importantly, for the first time, evidence of a common rupture mechanism independent of initial thickness and LC orientational ordering. We further demonstrate that the primary driving force for rupture is closely related to the tendency of the LC mesogens to recover their local environment in the bulk state. Our study not only provides new insights into the rupture mechanism of liquid crystal films, but also sets the stage for future investigations of thin film systems using peta-scale molecular dynamics simulations.The ability of liquid crystal (LC) molecules to respond to changes in their environment makes them an interesting candidate for thin film applications, particularly in bio-sensing, bio-mimicking devices, and optics. Yet the understanding of the (in)stability of this family of thin films has been limited by the inherent challenges encountered by experiment and continuum models. Using unprecedented large-scale molecular dynamics (MD) simulations, we address the rupture origin of LC thin films wetting a solid substrate at length scales similar to those in experiment. Our simulations show the key signatures of spinodal instability in isotropic and nematic films on top of thermal nucleation, and importantly, for the first time, evidence of a common rupture mechanism

  18. Molecular-orientation-induced rapid roughening and morphology transition in organic semiconductor thin-film growth.

    PubMed

    Yang, Junliang; Yim, Sanggyu; Jones, Tim S

    2015-03-24

    We study the roughening process and morphology transition of organic semiconductor thin film induced by molecular orientation in the model of molecular semiconductor copper hexadecafluorophthalocyanine (F16CuPc) using both experiment and simulation. The growth behaviour of F16CuPc thin film with the thickness, D, on SiO2 substrate takes on two processes divided by a critical thickness: (1) D ≤ 40 nm, F16CuPc thin films are composed of uniform caterpillar-like crystals. The kinetic roughening is confirmed during this growth, which is successfully analyzed by Kardar-Parisi-Zhang (KPZ) model with scaling exponents α = 0.71 ± 0.12, β = 0.36 ± 0.03, and 1/z = 0.39 ± 0.12; (2) D > 40 nm, nanobelt crystals are formed gradually on the caterpillar-like crystal surface and the film growth shows anomalous growth behaviour. These new growth behaviours with two processes result from the gradual change of molecular orientation and the formation of grain boundaries, which conversely induce new molecular orientation, rapid roughening process, and the formation of nanobelt crystals.

  19. Histological Stratification of Thick and Thin Plaque Psoriasis Explores Molecular Phenotypes with Clinical Implications

    PubMed Central

    Kim, Dong Joo; Brodmerkel, Carrie; Correa da Rosa, Joel; Krueger, James G.; Suárez-Fariñas, Mayte

    2015-01-01

    Psoriasis, which presents as red, scaly patches on the body, is a common, autoimmune skin disease that affects 2 to 3 percent of the world population. To leverage recent molecular findings into the personalized treatment of psoriasis, we need a strategy that integrates clinical stratification with molecular phenotyping. In this study, we sought to stratify psoriasis patients by histological measurements of epidermal thickness, and to compare their molecular characterizations by gene expression, serum cytokines, and response to biologics. We obtained histological measures of epidermal thickness in a cohort of 609 psoriasis patients, and identified a mixture of two subpopulations—thick and thin plaque psoriasis—from which they were derived. This stratification was verified in a subcohort of 65 patients from a previously published study with significant differences in inflammatory cell infiltrates in the psoriatic skin. Thick and thin plaque psoriasis shared 84.8% of the meta-analysis-derived psoriasis transcriptome, but a stronger dysregulation of the meta-analysis-derived psoriasis transcriptome was seen in thick plaque psoriasis on microarray. RT-PCR revealed that gene expression in thick and thin plaque psoriasis was different not only within psoriatic lesional skin but also in peripheral non-lesional skin. Additionally, differences in circulating cytokines and their changes in response to biologic treatments were found between the two subgroups. All together, we were able to integrate histological stratification with molecular phenotyping as a way of exploring clinical phenotypes with different expression levels of the psoriasis transcriptome and circulating cytokines. PMID:26176783

  20. Molecular-Orientation-Induced Rapid Roughening and Morphology Transition in Organic Semiconductor Thin-Film Growth

    PubMed Central

    Yang, Junliang; Yim, Sanggyu; Jones, Tim S.

    2015-01-01

    We study the roughening process and morphology transition of organic semiconductor thin film induced by molecular orientation in the model of molecular semiconductor copper hexadecafluorophthalocyanine (F16CuPc) using both experiment and simulation. The growth behaviour of F16CuPc thin film with the thickness, D, on SiO2 substrate takes on two processes divided by a critical thickness: (1) D ≤ 40 nm, F16CuPc thin films are composed of uniform caterpillar-like crystals. The kinetic roughening is confirmed during this growth, which is successfully analyzed by Kardar-Parisi-Zhang (KPZ) model with scaling exponents α = 0.71 ± 0.12, β = 0.36 ± 0.03, and 1/z = 0.39 ± 0.12; (2) D > 40 nm, nanobelt crystals are formed gradually on the caterpillar-like crystal surface and the film growth shows anomalous growth behaviour. These new growth behaviours with two processes result from the gradual change of molecular orientation and the formation of grain boundaries, which conversely induce new molecular orientation, rapid roughening process, and the formation of nanobelt crystals. PMID:25801646

  1. Theoretical study of the rhenium–alkane interaction in transition metal–alkane σ-complexes

    PubMed Central

    Cobar, Erika A.; Khaliullin, Rustam Z.; Bergman, Robert G.; Head-Gordon, Martin

    2007-01-01

    Metal–alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)CC(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal–alkane interaction sites. In all cases examined, the manganese–alkane binding energies were predicted to be significantly lower than those for the analogous rhenium–alkane complexes. The metal (Mn or Re)–alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70–80% of total charge transfer) and from the metal complex to the alkane (20–30% of the total charge transfer). PMID:17442751

  2. Theoretical study of the rhenium-alkane interaction in transition metal-alkane sigma-complexes.

    PubMed

    Cobar, Erika A; Khaliullin, Rustam Z; Bergman, Robert G; Head-Gordon, Martin

    2007-04-24

    Metal-alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)C[triple bond]C(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal-alkane interaction sites. In all cases examined, the manganese-alkane binding energies were predicted to be significantly lower than those for the analogous rhenium-alkane complexes. The metal (Mn or Re)-alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70-80% of total charge transfer) and from the metal complex to the alkane (20-30% of the total charge transfer).

  3. YCo5±x thin films with perpendicular anisotropy grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Sharma, S.; Hildebrandt, E.; Sharath, S. U.; Radulov, I.; Alff, L.

    2017-06-01

    The synthesis conditions of buffer-free (00l) oriented YCo5 and Y2Co17 thin films onto Al2O3 (0001) substrates have been explored by molecular beam epitaxy (MBE). The manipulation of the ratio of individual atomic beams of Yttrium, Y and Cobalt, Co, as well as growth rate variations allows establishing a thin film phase diagram. Highly textured YCo5±x thin films were stabilized with saturation magnetization of 517 emu/cm3 (0.517 MA/m), coercivity of 4 kOe (0.4 T), and anisotropy constant, K1, equal to 5.34 ×106 erg/cm3 (0.53 MJ/m3). These magnetic parameters and the perpendicular anisotropy obtained without additional underlayers make the material system interesting for application in magnetic recording devices.

  4. Thin film phase diagram of iron nitrides grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Gölden, D.; Hildebrandt, E.; Alff, L.

    2017-01-01

    A low-temperature thin film phase diagram of the iron nitride system is established for the case of thin films grown by molecular beam epitaxy and nitrided by a nitrogen radical source. A fine-tuning of the nitridation conditions allows for growth of α ‧ -Fe8Nx with increasing c / a -ratio and magnetic anisotropy with increasing x until almost phase pure α ‧ -Fe8N1 thin films are obtained. A further increase of nitrogen content below the phase decomposition temperature of α ‧ -Fe8N (180 °C) leads to a mixture of several phases that is also affected by the choice of substrate material and symmetry. At higher temperatures (350 °C), phase pure γ ‧ -Fe4N is the most stable phase.

  5. Facile nucleation of gold nanoparticles on graphene-based thin films from Au144 molecular precursors

    NASA Astrophysics Data System (ADS)

    Venter, Andrei; Hesari, Mahdi; Shafiq Ahmed, M.; Bauld, Reg; Workentin, Mark S.; Fanchini, Giovanni

    2014-04-01

    We demonstrate a facile and cost effective method to obtain gold nanoparticles on graphene by dispersing Au144 molecular nanoclusters by spin coating them in thin layers on graphene-based films and subsequent annealing in a controlled atmosphere. The graphene-based thin films used for these experiments are prepared by solvent-assisted exfoliation of graphite in water in the presence of ribonucleic acid as a surfactant and by subsequent vacuum filtration of the resulting graphene-containing suspensions. Not only is this method easily reproducible, but it leads to gold nanoparticles that are not dependent in size on the number of graphene layers beneath them. This is a distinct advantage over other methods. Plasmonic effects have been detected in our gold nanoparticle-decorated graphene layers, indicating that these thin films may be useful in applications such as plasmonic solar cells and optical memory devices.

  6. Excitation-dependent fluorescence from atomic/molecular layer deposited sodium-uracil thin films.

    PubMed

    Pale, Ville; Giedraityte, Zivile; Chen, Xi; Lopez-Acevedo, Olga; Tittonen, Ilkka; Karppinen, Maarit

    2017-08-01

    Atomic/molecular layer deposition (ALD/MLD) offers unique possibilities in the fabrication of inorganic-organic thin films with novel functionalities. Especially, incorporating nucleobases in the thin-film structures could open new avenues in the development of bio-electronic and photonic devices. Here we report an intense blue and widely excitation-dependent fluorescence in the visible region for ALD/MLD fabricated sodium-uracil thin films, where the crystalline network is formed from hydrogen-bonded uracil molecules linked via Na atoms. The excitation-dependent fluorescence is caused by the red-edge excitation shift (REES) effect taking place in the red-edge of the absorption spectrum, where the spectral relaxation occurs in continuous manner as demonstrated by the time-resolved measurements.

  7. Surface freezing and molecular miscibility of binary alkane-alkane and fluoroalkane-alkane liquid mixtures.

    PubMed

    Takiue, Takanori; Shimasaki, Mayuko; Tsuura, Miyako; Sakamoto, Hiroyasu; Matsubara, Hiroki; Aratono, Makoto

    2014-02-13

    The surface freezing (SF) of liquid n-heptadecane (C17)-n-octadecane (C18) and 1-perfluorooctyl decane (F8H10)-C18 mixtures were studied by surface tension and external reflection absorption FTIR (ERA-FTIR) measurements. The surface tension versus temperature curves of all pure liquids show a sharp break point at Ts corresponding to a surface liquid (SL)-SF transition. The entropy of surface formation is very negative, indicating a well-ordered structure of the SF layer. The ERA-FTIR spectra in the SF state suggested that the C18 molecules are densely packed in the solid state, while the packing of the hydrocarbon (HC) part of F8H10 is a little looser than the fluorocarbon (FC) part because of the difference in the cross-sectional area. In the C17-C18 mixture, the SL-SF transition was found at all bulk compositions. The estimation of the surface composition suggested that two components are miscible both in SL and SF states. The excess entropy of the surface is almost zero in both states, and thus, it was concluded that the two components are mixed almost ideally at the surface. In the case of the F8H10-C18 system, on the other hand, the SL layer is enriched in F8H10 with lower surface tension than C18 compared to bulk liquid. The surface composition in the SF state is almost zero or unity, indicating that F8H10 and C18 molecules are practically immiscible mainly due to the weak interaction between different components. Furthermore, the negative excess entropy in the SL layer suggests domain formation of F8H10 molecules at the surface.

  8. Rupture mechanism of liquid crystal thin films realized by large-scale molecular simulations

    SciTech Connect

    Nguyen, Trung D; Carrillo, Jan-Michael Y; Brown, W Michael; Matheson, Michael A

    2014-01-01

    The ability of liquid crystal (LC) molecules to respond to changes in their environment makes them an interesting candidate for thin film applications, particularly in bio-sensing, bio-mimicking devices, and optics. Yet the understanding of the (in)stability of this family of thin films has been limited by the inherent challenges encountered by experiment and continuum models. Using unprecedented largescale molecular dynamics (MD) simulations, we address the rupture origin of LC thin films wetting a solid substrate at length scales similar to those in experiment. Our simulations show the key signatures of spinodal instability in isotropic and nematic films on top of thermal nucleation, and importantly, for the first time, evidence of a common rupture mechanism independent of initial thickness and LC orientational ordering. We further demonstrate that the primary driving force for rupture is closely related to the tendency of the LC mesogens to recover their local environment in the bulk state. Our study not only provides new insights into the rupture mechanism of liquid crystal films, but also sets the stage for future investigations of thin film systems using peta-scale molecular dynamics simulations.

  9. Molecular and electronic structure of organic semiconductors on ultra-thin oxide films

    NASA Astrophysics Data System (ADS)

    Conrad, Brad; Cullen, William; Williams, Ellen

    2009-03-01

    We utilize scanning tunneling microscopy (STM) to molecularly image and probe the interactions of organic semiconductors. To mimic a device substrate and growth modes, ultra-thin oxide (UTO) films less than 1 nm thick are grown on Si(111) in ultrahigh vacuum at room temperature. These films are characterized by STM and display a long range RMS roughness of 0.109 nm versus a typical RMS roughness of 0.3 nm for thick SiO2. UTO films are then used as substrates for growth of pentacene, C60, and PCBM. Standing up pentacene is molecularly resolved and described by a thin-film phase unit cell with a=0.76nm and b=0.59nm in the ab-plane. The morphology and electronic structure of co-depositions of pentacene, C60, and PCBM are then deposited on UTO films and will be presented. http://arxiv.org/abs/0811.2515

  10. Molecular orientation in soft matter thin films studied by resonant soft X-ray reflectivity

    SciTech Connect

    Mezger, Markus; Jerome, Blandine; Kortright, Jeffrey B.; Valvidares, Manuel; Gullikson, Eric; Giglia, Angelo; Mahne, Nicola; Nannarone, Stefano

    2011-01-12

    We present a technique to study depth profiles of molecular orientation in soft matter thin films with nanometer resolution. The method is based on dichroism in resonant soft X-ray reflectivity using linear s- and p-polarization. It combines the chemical sensitivity of Near-Edge X-ray Absorption Fine Structure spectroscopy to specific molecular bonds and their orientation relative to the polarization of the incident beam with the precise depth profiling capability of X-ray reflectivity. We demonstrate these capabilities on side chain liquid crystalline polymer thin films with soft X-ray reflectivity data at the carbon K edge. Optical constants of the anisotropic refractive index ellipsoid were obtained from a quantitative analysis using the Berreman formalism. For films up to 50 nm thickness we find that the degree of orientation of the long axis exhibits no depth variation and isindependent of the film thickness.

  11. Interfacial alkane films

    NASA Astrophysics Data System (ADS)

    Xia, T. K.; Ouyang, Jian; Ribarsky, M. W.; Landman, Uzi

    1992-09-01

    Adsorbed n-hexadecane films of thickness ~10, 20, and 40 Å are studied at 350 K via molecular-dynamics simulations. In the thickest film periodic oscillations of the density extend ~18 Å from the solid-liquid interface, the roughness fluctuations at the liquid-vapor interface are Gaussian, and the density tail is fitted by an error function. Molecules in the first adsorbed layer lie preferentially parallel to the surface exhibiting domains of intermolecular orientational alignment. The diffusion is anisotropic with the component parallel to the surface greatly enhanced in the liquid-vapor region.

  12. Molecular layer-by-layer assembled thin-film composite membranes for water desalination.

    PubMed

    Gu, Joung-Eun; Lee, Seunghye; Stafford, Christopher M; Lee, Jong Suk; Choi, Wansuk; Kim, Bo-Young; Baek, Kyung-Youl; Chan, Edwin P; Chung, Jun Young; Bang, Joona; Lee, Jung-Hyun

    2013-09-14

    Molecular layer-by-layer (mLbL) assembled thin-film composite membranes fabricated by alternating deposition of reactive monomers on porous supports exhibit both improved salt rejection and enhanced water flux compared to traditional reverse osmosis membranes prepared by interfacial polymerization. Additionally, the well-controlled structures achieved by mLbL deposition further lead to improved antifouling performance. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Electrically controllable molecular spin crossover switching in Fe(phen)2 (NCS)2 thin film

    NASA Astrophysics Data System (ADS)

    Mondal, Chaitali; Mandal, Swapan K.

    2016-10-01

    Spin crossover molecular complex Fe(phen)2(NCS)2 in thin film form (20-300 nm) is obtained by simple dip-coating technique on glass substrates. The growth of the molecular films is confirmed by optical and X-ray diffraction data. The morphology of the samples shows distributed nanocrystals with an average size ca. 12 nm. We measure the current (I)-voltage (V) characteristics of a device with 300 nm film thickness and show that application of electric field can induce spin state switching. The electric field experienced by individual nanocrystals separated by nanometric gap is supposed to be quite high and is plausibly playing the crucial role in instigating switching in molecular nanocrystals. The result is quite significant towards developing room temperature molecular spin cross-over switching devices in the nanoscale limit.

  14. Analyses of n-alkanes degrading community dynamics of a high-temperature methanogenic consortium enriched from production water of a petroleum reservoir by a combination of molecular techniques.

    PubMed

    Zhou, Lei; Li, Kai-Ping; Mbadinga, Serge Maurice; Yang, Shi-Zhong; Gu, Ji-Dong; Mu, Bo-Zhong

    2012-08-01

    Despite the knowledge on anaerobic degradation of hydrocarbons and signature metabolites in the oil reservoirs, little is known about the functioning microbes and the related biochemical pathways involved, especially about the methanogenic communities. In the present study, a methanogenic consortium enriched from high-temperature oil reservoir production water and incubated at 55 °C with a mixture of long chain n-alkanes (C(15)-C(20)) as the sole carbon and energy sources was characterized. Biodegradation of n-alkanes was observed as methane production in the alkanes-amended methanogenic enrichment reached 141.47 μmol above the controls after 749 days of incubation, corresponding to 17 % of the theoretical total. GC-MS analysis confirmed the presence of putative downstream metabolites probably from the anaerobic biodegradation of n-alkanes and indicating an incomplete conversion of the n-alkanes to methane. Enrichment cultures taken at different incubation times were subjected to microbial community analysis. Both 16S rRNA gene clone libraries and DGGE profiles showed that alkanes-degrading community was dynamic during incubation. The dominant bacterial species in the enrichment cultures were affiliated with Firmicutes members clustering with thermophilic syntrophic bacteria of the genera Moorella sp. and Gelria sp. Other represented within the bacterial community were members of the Leptospiraceae, Thermodesulfobiaceae, Thermotogaceae, Chloroflexi, Bacteroidetes and Candidate Division OP1. The archaeal community was predominantly represented by members of the phyla Crenarchaeota and Euryarchaeota. Corresponding sequences within the Euryarchaeota were associated with methanogens clustering with orders Methanomicrobiales, Methanosarcinales and Methanobacteriales. On the other hand, PCR amplification for detection of functional genes encoding the alkylsuccinate synthase α-subunit (assA) was positive in the enrichment cultures. Moreover, the appearance of a new ass

  15. Highly-oriented molecular arrangements and enhanced magnetic interactions in thin films of CoTTDPz using PTCDA templates.

    PubMed

    Eguchi, Keitaro; Nanjo, Chihiro; Awaga, Kunio; Tseng, Hsiang-Han; Robaschik, Peter; Heutz, Sandrine

    2016-07-14

    In the present work, the templating effect of thin layers of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) on the growth of cobalt tetrakis(thiadiazole)porphyrazine (CoTTDPz) thin films was examined. X-ray diffraction and optical absorption spectra indicate that while CoTTDPz forms amorphous thin films on the bare substrates, it forms crystalline thin films on the PTCDA templates, in which the molecular planes of CoTTDPz are considered to be parallel to the substrates. Magnetic measurements reveal a significantly enhanced antiferromagnetic interaction of CoTTDPz in the templated thin films, with values reaching over 13 K. The ability to generate crystalline films and to control their orientation using molecular templates is an important strategy in the fields of organic electronics and spintronics in order to tailor the physical properties of organic thin films to suit their intended application.

  16. Crystallization features of normal alkanes in confined geometry.

    PubMed

    Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

    2014-01-21

    How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D

  17. Shape selective properties of the Al-fumarate metal-organic framework in the adsorption and separation of n-alkanes, iso-alkanes, cyclo-alkanes and aromatic hydrocarbons.

    PubMed

    Bozbiyik, Belgin; Lannoeye, Jeroen; De Vos, Dirk E; Baron, Gino V; Denayer, Joeri F M

    2016-01-28

    The primary goal of this work is to study the adsorption of a wide range of hydrocarbon adsorbates in the Al-fumarate metal-organic framework in order to identify and explore trends in adsorption behaviour that can be related to the sorbate's molecular properties and as well as the properties of this MOF. The pulse chromatographic technique was used to study the adsorption properties of C5-C8 linear, branched, cyclic and aromatic hydrocarbons in vapour phase at low coverage and at high temperatures (150-250 °C). Chromatograms of alkanes having the same number of carbon atoms (C5-C8) clearly show that the linear alkane is retained the longest over its branched and cyclic isomers. Moreover, xylene isomers are also clearly separated by Al-fumarate, with retention times increasing in the order: ortho-xylene < meta-xylene < para-xylene. Differences in adsorption enthalpy of more than 10 kJ mol(-1) between linear alkanes and their di/tri-branched or cyclo-alkane isomers were observed, clearly showing that steric effects imposed by the pore structure of the adsorbent cause the difference in adsorption between linear alkanes and their isomers. In conclusion, Al-fumarate behaves as a shape selective material with respect to structural isomers of linear alkanes, with properties resembling those of medium pore size zeolites.

  18. Metal-organic framework for the separation of alkane isomers

    DOEpatents

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  19. Chain length dependence of the thermodynamic properties of linear and cyclic alkanes and polymers.

    PubMed

    Huang, Dinghai; Simon, Sindee L; McKenna, Gregory B

    2005-02-22

    The specific heat capacity was measured with step-scan differential scanning calorimetry for linear alkanes from pentane (C(5)H(12)) to nonadecane (C(19)H(40)), for several cyclic alkanes, for linear and cyclic polyethylenes, and for a linear and a cyclic polystyrene. For the linear alkanes, the specific heat capacity in the equilibrium liquid state decreases as chain length increases; above a carbon number N of 10 (decane) the specific heat asymptotes to a constant value. For the cyclic alkanes, the heat capacity in the equilibrium liquid state is lower than that of the corresponding linear chains and increases with increasing chain length. At high enough molecular weights, the heat capacities of cyclic and linear molecules are expected to be equal, and this is found to be the case for the polyethylenes and polystyrenes studied. In addition, the thermal properties of the solid-liquid and the solid-solid transitions are examined for the linear and cyclic alkanes; solid-solid transitions are observed only in the odd-numbered alkanes. The thermal expansion coefficients and the specific volumes of the linear and cyclic alkanes are also calculated from literature data and compared with the trends in the specific heats.

  20. MIR and NIR group spectra of n-alkanes and 1-chloroalkanes

    NASA Astrophysics Data System (ADS)

    Kwaśniewicz, Michał; Czarnecki, Mirosław A.

    2015-05-01

    Numerous attempts were undertaken to resolve the absorption originating from different parts of alkanes. The separation of the contributions from the terminal and midchain methylene units was observed only in the spectra of solid alkanes at low temperatures. On the other hand, for liquid alkanes this effect was not reported as yet. In this study, ATR-IR, Raman and NIR spectra of eight n-alkanes and seven 1-chloroalkanes in the liquid phase were measured from 1000 to 12,000 cm-1. The spectra were analyzed by using two-dimensional (2D) correlation approach and chemometrics methods. It was shown that in 2D asynchronous contour plots, constructed from the spectra of n-alkanes and 1-chloroalkanes, the methylene band was resolved into two components. These two components were assigned to the terminal and midchain methylene groups. For the first time, the contributions from these two molecular fragments were resolved in the spectra of liquid n-alkanes and 1-chloroalkanes. MCR-ALS resolved these spectra into two components that were assigned to the ethyl and midchain methylene groups. These components represent the group spectra that can be used for assignment, spectral analysis and prediction of unknown spectra. The spectral prediction based on the group spectra provides very good results for n-alkanes, especially in the first and second overtone regions.

  1. Porphyrin Molecular Multilayer Thin-Films on Gold (111) Electrodes for Electro-optical Applications

    NASA Astrophysics Data System (ADS)

    Krawicz, Alexandra; Qian, Guoguang; Lewis, Kim; Dinolfo, Peter

    2012-02-01

    We have developed a Layer-by-Layer (LbL) method for the fabrication of thin-film molecular multilayers on gold (111) electrodes. Copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) coupling reactions were used for surface attachment and subsequent LbL deposition of porphyrin building blocks. The electrochemical and photophysical properties of the thin-films can be tuned through synthetic modification of the individual components, resulting in new porphyrin multilayers for applications in light harvesting and molecular electronics. Herein, we demonstrate the reproducible growth trends and optical properties of these films. Multilayer growth was followed by UV-Vis absorption and reflectance spectroscopy. Film thickness (FT) and optical constants were obtained from spectroscopic ellipsometry. Topology and surface roughness was examined by TM-AFM, while the copper content was quantified by XPS. The redox characteristics were studied by electrochemical methods, whereas the conductance of individual porphyrin constructs was examined by STM using the molecular break junction method. The multilayers show consistent linear growth in absorbance and FT over tens of layers and continuity in their molecular structure.

  2. Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films

    SciTech Connect

    Hsu, Chin-Hao; Dong, Xuehui; Lin, Zhiwei; Ni, Bo; Lu, Pengatao; Jiang, Zhang; Tian, Ding; Cheng, Stephen Z.D.

    2016-01-01

    The self-assembly behaviors of specifically designed giant surfactants are systematically studied in thin films using grazing incident X-ray and transmission electron microscopy (TEM), focusing on the effects of head surface functionalities and molecular architectures on nanostructure formation. Two molecular nanoparticles (MNPs) with different affinities, i.e., hydrophilic carboxylic acid functionalized [60]fullerene (AC60) and omniphobic fluorinated polyhedral oligomeric silsesquioxane (FPOSS), are utilized as heads of the giant surfactants. By covalently tethering these functional MNPs onto the chain end or the junction point of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, linear and star-like giant surfactants possess distinct molecular architectures are constructed. With fixed length of the PEO block, the molecular weight change of the PS block originates the phase formation and transition. Due to the distinct affinity, the AC60-based giant surfactants form two-component morphologies, while three-component morphologies are found in the FPOSS-based ones. A PS block stretching parameter is introduced to characterize the PS chain conformation in different morphologies. The highly diverse self-assembly behaviors and the tunable dimensions in thin films suggest the giant surfactants could be a promising and robust platform for nanolithography applications.

  3. Alkane biohydroxylation: Interests, constraints and future developments.

    PubMed

    Soussan, Laurence; Pen, Nakry; Belleville, Marie-Pierre; Marcano, José Sanchez; Paolucci-Jeanjean, Delphine

    2016-03-20

    Alkanes constitute one of the vastest reserves of raw materials for the production of fine chemicals. This paper focuses on recent advances in alkane biohydroxylation, i.e. the bioactivation of alkanes into their corresponding alcohols. Enzyme and whole-cell biocatalysts have been reviewed. Process considerations to implement such biocatalysts in bioreactors at large scale by coupling the bioconversion with cofactor regeneration and product removal are also discussed.

  4. Surface vibrational structure at alkane liquid/vapor interfaces.

    PubMed

    Esenturk, Okan; Walker, Robert A

    2006-11-07

    Broadband vibrational sum frequency spectroscopy (VSFS) has been used to examine the surface structure of alkane liquid/vapor interfaces. The alkanes range in length from n-nonane (C(9)H(20)) to n-heptadecane (C(17)H(36)), and all liquids except heptadecane are studied at temperatures well above their bulk (and surface) freezing temperatures. Intensities of vibrational bands in the CH stretching region acquired under different polarization conditions show systematic, chain length dependent changes. Data provide clear evidence of methyl group segregation at the liquid/vapor interface, but two different models of alkane chain structure can predict chain length dependent changes in band intensities. Each model leads to a different interpretation of the extent to which different chain segments contribute to the anisotropic interfacial region. One model postulates that changes in vibrational band intensities arise solely from a reduced surface coverage of methyl groups as alkane chain length increases. The additional methylene groups at the surface must be randomly distributed and make no net contribution to the observed VSF spectra. The second model considers a simple statistical distribution of methyl and methylene groups populating a three dimensional, interfacial lattice. This statistical picture implies that the VSF signal arises from a region extending several functional groups into the bulk liquid, and that the growing fraction of methylene groups in longer chain alkanes bears responsibility for the observed spectral changes. The data and resulting interpretations provide clear benchmarks for emerging theories of molecular structure and organization at liquid surfaces, especially for liquids lacking strong polar ordering.

  5. Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight

    DOE PAGES

    Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; ...

    2017-08-23

    Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene-r-propylene) blocks (B), and end-capped by a poly(t-butylstyrene) blockmore » (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.« less

  6. Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight.

    PubMed

    Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; Grest, Gary S

    2017-09-08

    Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene-r-propylene) blocks (B), and end-capped by a poly(t-butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. The water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.

  7. Molecular Dynamics of Polymers at Nanometric Length Scales: From Thin Layers to Isolated Coils

    NASA Astrophysics Data System (ADS)

    Kremer, F.; Mapesa, E. U.; Tress, M.; Reiche, M.

    The (dynamic) glass transition of polymers in nanometer thin layers is both a prevailing but as well a highly controversial topic. In the current review the literature for the most studied case of polystyrene (as freestanding films or as deposited and suspended layers) will be discussed. Based on this, the extraordinary impact of sample preparation is immediately evident and outlined in detail. Recent results are presented on nanometric thin (≥5 nm) layers of polystyrene (PS) having widely varying molecular weights and polymethylmethacrylate (PMMA) deposited on different substrates. For the dielectric measurements two sample geometries are employed: the conventional technique using evaporated electrodes and a recently developed approach taking advantage of silica nanostructures as spacers. All applied methods deliver the concurring result that deviations from glassy dynamics and from the glass transition of the bulk never exceed margins of ±3 K independent of the layer thickness, the molecular weight of the polymer under study and the underlying substrate. Novel experiments are described on thin layers of polyisoprene, a type A polymer, having relaxation processes on two different length scales, the segmental and the normal mode. A further exciting perspective is the measurement of the dynamics of isolated polymer coils, for which first results will be presented.

  8. Molecularly thin fluoro-polymeric nanolubricant films: tribology, rheology, morphology, and applications.

    PubMed

    Chung, Pil Seung; Jhon, Myung S; Choi, Hyoung Jin

    2016-03-21

    Molecularly thin perfluoropolyether (PFPE) has been used extensively as a high-performance lubricant in various applications and, more importantly, on carbon overcoats to enhance the reliability and lubrication of micro-/nanoelectro-mechanical systems, where the tribological performance caused by its molecular architecture is a critical issue, as are its physical properties and rheological characteristics. This Highlight addresses recent trends in the development of fluoro-polymeric lubricant films with regard to their tribology, rheology, and physio-chemical properties as they relate to heat-assisted magnetic recording. Nanorheology has been employed to examine the dynamic response of nonfunctional and functional PFPEs, while the viscoelastic properties of nanoscale PFPE films and the relaxation processes as a function of molecular structure and end-group functionality were analyzed experimentally; furthermore, the characteristics of binary blends were reported.

  9. Alkanes in flower surface waxes of Momordica cochinchinensis influence attraction to Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae).

    PubMed

    Mukherjee, A; Sarkar, N; Barik, A

    2013-08-01

    Extraction, thin-layer chromatography, and gas chromatography-mass spectrophotometry analyses revealed 15 alkanes representing 97.14% of the total alkanes in the surface waxes of Momordica cochinchinensis Spreng flowers. Nonacosane was the prevailing alkane followed by hexatriacontane, nonadecane, heptacosane, and hentriacontane, accounting for 39.08%, 24.24%, 13.52%, 6.32%, and 5.12%, respectively. The alkanes from flower surface waxes followed by a synthetic mixture of alkanes mimicking alkanes of flower surface waxes elicited attraction of the female insect, Aulacophora foveicollis Lucas (Coleoptera: Chrysomelidae) between 2 and 10-μg/mL concentrations in a Y-shaped glass tube olfactometer bioassay under laboratory conditions. Synthetic nonadecane from 178.28-891.37 ng, heptacosane from 118.14-590.72 ng, and nonacosane at 784.73 ng showed attraction of the insect. A synthetic mixture of 534.82 ng nonadecane, 354.43 ng heptacosane, and 2,354.18 ng nonacosane elicited highest attraction of A. foveicollis.

  10. HfSe2 thin films: 2D transition metal dichalcogenides grown by molecular beam epitaxy.

    PubMed

    Yue, Ruoyu; Barton, Adam T; Zhu, Hui; Azcatl, Angelica; Pena, Luis F; Wang, Jian; Peng, Xin; Lu, Ning; Cheng, Lanxia; Addou, Rafik; McDonnell, Stephen; Colombo, Luigi; Hsu, Julia W P; Kim, Jiyoung; Kim, Moon J; Wallace, Robert M; Hinkle, Christopher L

    2015-01-27

    In this work, we demonstrate the growth of HfSe2 thin films using molecular beam epitaxy. The relaxed growth criteria have allowed us to demonstrate layered, crystalline growth without misfit dislocations on other 2D substrates such as highly ordered pyrolytic graphite and MoS2. The HfSe2 thin films exhibit an atomically sharp interface with the substrates used, followed by flat, 2D layers with octahedral (1T) coordination. The resulting HfSe2 is slightly n-type with an indirect band gap of ∼ 1.1 eV and a measured energy band alignment significantly different from recent DFT calculations. These results demonstrate the feasibility and significant potential of fabricating 2D material based heterostructures with tunable band alignments for a variety of nanoelectronic and optoelectronic applications.

  11. Atomic dynamics in molecular dynamics simulations of glassy CuTi thin films

    NASA Astrophysics Data System (ADS)

    Vauth, Sebastian; Mayr, S. G.

    2005-02-01

    We present results on atomic dynamics in metallic glass thin films below the glass transition temperature using molecular dynamics simulations. Thin CuTi films of different compositions are prepared by quenching the liquid to an amorphous state. The atomic dynamics on the amorphous surface and inside the bulk of the samples are quantitatively compared by calculating diffusion constants and jump length distributions. Here, we focus on the collective or single particle character of the diffusion mechanism in dependence of the atom type. In addition, single atom exemplifications are analyzed for the different kinds of atomic dynamics. We find that Cu surface atoms diffuse with a single atom jump dynamics, whereas inside the bulk collective behavior dominates for both species.

  12. Dependence of equilibrium stacking fault width on thickness of Cu thin films: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Rohith, P.; Sainath, G.; Choudhary, B. K.

    2017-05-01

    In face centered cubic systems, due to decrease in energy all perfect dislocations dissociates into two Shockley partials separated by stacking fault width. The stacking fault width, which influences the deformation behavior depends on many factors such as composition, stacking fault energy, temperature, surface energy and applied stress. Additionally in thin films, thickness also influences the stacking fault width of dissociated dislocations. In this paper, we investigate the effect of thin film thickness on stacking fault width in Cu using molecular dynamics simulations. The results indicate that with increase in film thickness from 1.25 nm to 11 nm, the stacking fault width increases from 1.6 nm to 3.12 nm. A bi-linear behavior has been observed. Above 11 nm thickness, the width of stacking fault has attained a saturation at higher thickness. This thickness dependent dissociation has been explained using the concept of image dislocations and associated image forces.

  13. CYP153A6, a Soluble P450 Oxygenase Catalyzing Terminal-Alkane Hydroxylation

    PubMed Central

    Funhoff, Enrico G.; Bauer, Ulrich; García-Rubio, Inés; Witholt, Bernard; van Beilen, Jan B.

    2006-01-01

    The first and key step in alkane metabolism is the terminal hydroxylation of alkanes to 1-alkanols, a reaction catalyzed by a family of integral-membrane diiron enzymes related to Pseudomonas putida GPo1 AlkB, by a diverse group of methane, propane, and butane monooxygenases and by some membrane-bound cytochrome P450s. Recently, a family of cytoplasmic P450 enzymes was identified in prokaryotes that allow their host to grow on aliphatic alkanes. One member of this family, CYP153A6 from Mycobacterium sp. HXN-1500, hydroxylates medium-chain-length alkanes (C6 to C11) to 1-alkanols with a maximal turnover number of 70 min−1 and has a regiospecificity of ≥95% for the terminal carbon atom position. Spectroscopic binding studies showed that C6-to-C11 aliphatic alkanes bind in the active site with Kd values varying from ∼20 nM to 3.7 μM. Longer alkanes bind more strongly than shorter alkanes, while the introduction of sterically hindering groups reduces the affinity. This suggests that the substrate-binding pocket is shaped such that linear alkanes are preferred. Electron paramagnetic resonance spectroscopy in the presence of the substrate showed the formation of an enzyme-substrate complex, which confirmed the binding of substrates observed in optical titrations. To rationalize the experimental observations on a molecular scale, homology modeling of CYP153A6 and docking of substrates were used to provide the first insight into structural features required for terminal alkane hydroxylation. PMID:16816194

  14. CYP153A6, a soluble P450 oxygenase catalyzing terminal-alkane hydroxylation.

    PubMed

    Funhoff, Enrico G; Bauer, Ulrich; García-Rubio, Inés; Witholt, Bernard; van Beilen, Jan B

    2006-07-01

    The first and key step in alkane metabolism is the terminal hydroxylation of alkanes to 1-alkanols, a reaction catalyzed by a family of integral-membrane diiron enzymes related to Pseudomonas putida GPo1 AlkB, by a diverse group of methane, propane, and butane monooxygenases and by some membrane-bound cytochrome P450s. Recently, a family of cytoplasmic P450 enzymes was identified in prokaryotes that allow their host to grow on aliphatic alkanes. One member of this family, CYP153A6 from Mycobacterium sp. HXN-1500, hydroxylates medium-chain-length alkanes (C6 to C11) to 1-alkanols with a maximal turnover number of 70 min(-1) and has a regiospecificity of > or =95% for the terminal carbon atom position. Spectroscopic binding studies showed that C6-to-C11 aliphatic alkanes bind in the active site with Kd values varying from approximately 20 nM to 3.7 microM. Longer alkanes bind more strongly than shorter alkanes, while the introduction of sterically hindering groups reduces the affinity. This suggests that the substrate-binding pocket is shaped such that linear alkanes are preferred. Electron paramagnetic resonance spectroscopy in the presence of the substrate showed the formation of an enzyme-substrate complex, which confirmed the binding of substrates observed in optical titrations. To rationalize the experimental observations on a molecular scale, homology modeling of CYP153A6 and docking of substrates were used to provide the first insight into structural features required for terminal alkane hydroxylation.

  15. Reaction pathway for alkane dehydrocyclization

    SciTech Connect

    Shi, Buchang; Davis, B.H.

    1996-08-01

    Naphtha reforming to produce high octane gasoline is an important process. Many reaction mechanisms are involved in this process. For example, the study of the fundamentals of this process led to the concept of bi- or poly-functional catalysis. The results of this study provide additional mechanistic information about the dehydrocyclization of an n-alkane to produce aromatics. The reaction coordinate diagram advanced to account for the observation of irreversible adsorption should be modified to account for the present results. 32 refs., 1 fig.

  16. Development of Layered Multiscale Porous Thin Films by Tuning Deposition Time and Molecular Weight of Polyelectrolytes.

    PubMed

    Yu, Jing; Sanyal, Oishi; Izbicki, Andrew P; Lee, Ilsoon

    2015-09-01

    This work focuses on the design of porous polymeric films with nano- and micro-sized pores existing in distinct zones. The porous thin films are fabricated by the post-treatment of layer-by-layer assembled poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) multilayers. In order to improve the processing efficiency, the deposition time is shortened to ≈ 10 s. It is found that fine porous structures can be created even by significantly reducing the processing time. The effect of using polyelectrolytes with widely different molecular weights is also studied. The pore size is increased by using high molecular weight PAH, while high molecular weight PAA minimizes the pore size to nanometer scale. Having gained a precise control over the pore size, layered multiscale porous thin films are further built up with either a microsized porous zone on top of a nanosized porous zone or vice versa. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates

    NASA Astrophysics Data System (ADS)

    Huber, George W.; Chheda, Juben N.; Barrett, Christopher J.; Dumesic, James A.

    2005-06-01

    Liquid alkanes with the number of carbon atoms ranging from C7 to C15 were selectively produced from biomass-derived carbohydrates by acid-catalyzed dehydration, which was followed by aldol condensation over solid base catalysts to form large organic compounds. These molecules were then converted into alkanes by dehydration/hydrogenation over bifunctional catalysts that contained acid and metal sites in a four-phase reactor, in which the aqueous organic reactant becomes more hydrophobic and a hexadecane alkane stream removes hydrophobic species from the catalyst before they go on further to form coke. These liquid alkanes are of the appropriate molecular weight to be used as transportation fuel components, and they contain 90% of the energy of the carbohydrate and H2 feeds.

  18. Changes in iso- and n-alkane distribution during biodegradation of crude oil under nitrate and sulphate reducing conditions.

    PubMed

    Hasinger, Marion; Scherr, Kerstin E; Lundaa, Tserennyam; Bräuer, Leopold; Zach, Clemens; Loibner, Andreas Paul

    2012-02-20

    Crude oil consists of a large number of hydrocarbons with different susceptibility to microbial degradation. The influence of hydrocarbon structure and molecular weight on hydrocarbon biodegradation under anaerobic conditions is not fully explored. In this study oxygen, nitrate and sulphate served as terminal electron acceptors (TEAs) for the microbial degradation of a paraffin-rich crude oil in a freshly contaminated soil. During 185 days of incubation, alkanes from n-C11 to n-C39, three n- to iso-alkane ratios commonly used as weathering indicators and the unresolved complex mixture (UCM) were quantified and statistically analyzed. The use of different TEAs for hydrocarbon degradation resulted in dissimilar degradative patterns for n- and iso-alkanes. While n-alkane biodegradation followed well-established patterns under aerobic conditions, lower molecular weight alkanes were found to be more recalcitrant than mid- to high-molecular weight alkanes under nitrate-reducing conditions. Biodegradation with sulphate as the TEA was most pronounced for long-chain (n-C32 to n-C39) alkanes. The observation of increasing ratios of n-C17 to pristane and of n-C18 to phytane provides first evidence of the preferential degradation of branched over normal alkanes under sulphate reducing conditions. The formation of distinctly different n- and iso-alkane biodegradation fingerprints under different electron accepting conditions may be used to assess the occurrence of specific degradation processes at a contaminated site. The use of n- to iso-alkane ratios for this purpose may require adjustment if applied for anaerobic sites. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Morphological Behavior of Thin Polyhedral Oligomeric Silsesquioxane Films at the Molecular Scale

    SciTech Connect

    G Evmenenko; B Stripe; P Dutta

    2011-12-31

    Synchrotron X-ray reflectivity (XRR) was used to study the structure of thin films of polyhedral oligomeric silsesquioxanes (POSS) with side organic chains of different flexibility and containing terminal epoxy groups. POSS films were deposited from volatile solvents on hydroxylated and hydrogen-passivated silicon surfaces. The XRR data show a variety of structural morphologies, including autophobic molecular monolayers and bilayers as well as uniform films. The role of conformational and energetic factors governing the development of different morphologies in a restricted geometry is discussed.

  20. Crystallographic dependence of photocatalytic activity of WO3 thin films prepared by molecular beam epitaxy.

    PubMed

    Li, Guoqiang; Varga, Tamas; Yan, Pengfei; Wang, Zhiguo; Wang, Chongmin; Chambers, Scott A; Du, Yingge

    2015-06-21

    We investigated the impact of crystallographic orientation on the photocatalytic activity of single crystalline WO3 thin films prepared by molecular beam epitaxy on the photodegradation of rhodamine B (RhB). A clear effect is observed, with (111) being the most reactive surface, followed by (110) and (001). Photoreactivity is directly correlated with the surface free energy determined by density functional theory calculations. The RhB photodegradation mechanism is found to involve hydroxyl radicals in solution formed from photo-generated holes and differs from previous studies performed on nanoparticles and composites.

  1. Imaging the condensation and evaporation of molecularly thin ethanol films with surface forces apparatus

    SciTech Connect

    Zhao, Gutian; Tan, Qiyan; Xiang, Li; Zhang, Di; Ni, Zhonghua E-mail: yunfeichen@seu.edu.cn; Yi, Hong; Chen, Yunfei E-mail: yunfeichen@seu.edu.cn

    2014-01-15

    A new method for imaging condensation and evaporation of molecularly thin ethanol films is reported. It is found that the first adsorbed layer of ethanol film on mica surface behaves as solid like structure that cannot flow freely. With the increase of exposure time, more ethanol molecules condense over the mica surface in the saturated ethanol vapor condition. The first layer of adsorbed ethanol film is about 3.8 Å thick measured from the surface forces apparatus, which is believed to be the average diameter of ethanol molecules while they are confined in between two atomically smooth mica surfaces.

  2. Towards active microfluidics: Interface turbulence in thin liquid films with floating molecular machines

    NASA Astrophysics Data System (ADS)

    Alonso, Sergio; Mikhailov, Alexander S.

    2009-06-01

    Thin liquid films with floating active protein machines are considered. Cyclic mechanical motions within the machines, representing microscopic swimmers, lead to molecular propulsion forces applied to the air-liquid interface. We show that when the rate of energy supply to the machines exceeds a threshold, the flat interface becomes linearly unstable. As a result of this instability, the regime of interface turbulence, characterized by irregular traveling waves and propagating machine clusters, is established. Numerical investigations of this nonlinear regime are performed. Conditions for the experimental observation of the instability are discussed.

  3. Molecular dynamics simulations of grain boundaries in thin nanocrystalline silicon films

    SciTech Connect

    Berman, G.P.; Doolen, G.D.; Mainieri, R.; Campbell, D.K.; Luchnikov, V.A. |

    1997-10-01

    Using molecular dynamics simulations, the grain boundaries in thin polycrystalline silicon films (considered as promising material for future nanoelectronic devices) are investigated. It is shown that in polysilicon film with randomly oriented grains the majority of grain boundaries are disordered. However, some grains with small mutual orientation differences can form extended crystalline patterns. The structure of the grain boundaries satisfies the thermodynamical criterion. The majority of atoms in the grain boundaries are tetrahedrally coordinated with the nearest neighbors, even though the grain boundaries are disordered. The grain boundary matter is characterized as an amorphous phase with a characteristic tetragonality value.

  4. Magnetically engineered smart thin films: toward lab-on-chip ultra-sensitive molecular imaging.

    PubMed

    Hassan, Muhammad A; Saqib, Mudassara; Shaikh, Haseeb; Ahmad, Nasir M; Elaissari, Abdelhamid

    2013-03-01

    Magnetically responsive engineered smart thin films of nanoferrites as contrast agent are employed to develop surface based magnetic resonance imaging to acquire simple yet fast molecular imaging. The work presented here can be of significant potential for future lab-on-chip point-of-care diagnostics from the whole blood pool on almost any substrates to reduce or even prevent clinical studies involve a living organism to enhance the non-invasive imaging to advance the '3Rs' of work in animals-replacement, refinement and reduction.

  5. Alkane-Based Urethane Potting Compounds

    NASA Technical Reports Server (NTRS)

    Morris, D. E.

    1986-01-01

    New low viscosity urethanes easily mixed, molded, and outgassed. Alkane-based urethanes resist hydrolysis and oxidation and have excellent dielectric properties. Low-viscosity alkane-based urethane prepolymer prepared by one-step reaction of either isophorone diisocyanate or methyl-bis (4-cyclohexyl isocyanate) with hydrogenated, hydroxy-terminated polybutadiene (HTPBD).

  6. Alkane Coiling in Perfluoroalkane Solutions: A New Primitive Solvophobic Effect.

    PubMed

    Morgado, Pedro; Garcia, Ana Rosa; Martins, Luís F G; Ilharco, Laura M; Filipe, Eduardo J M

    2017-10-02

    In this work, we demonstrate that n-alkanes coil when mixed with perfluoroalkanes, changing their conformational equilibria to more globular states, with a higher number of gauche conformations. The new coiling effect is here observed in fluids governed exclusively by dispersion interactions, contrary to other examples in which hydrogen bonding and polarity play important roles. FTIR spectra of liquid mixtures of n-hexane and perfluorohexane unambiguously reveal that the population of n-hexane molecules in all-trans conformation reduces from 32% in the pure n-alkane to practically zero. The spectra of perfluorohexane remain unchanged, suggesting nanosegregation of the hydrogenated and fluorinated chains. Molecular dynamics simulations support this analysis. The new solvophobic effect is prone to have a major impact on the structure, organization, and therefore thermodynamic properties and phase equilibria of fluids involving mixed hydrogenated and fluorinated chains.

  7. Structure and dynamics of fluorinated alkanes on silicon dioxide surfaces

    NASA Astrophysics Data System (ADS)

    Tsige, Mesfin

    2007-03-01

    Despite their great promise in various applications, the structure and dynamics of fluorinated alkanes at interfaces is still an open question. In particular, the knowledge from both theoretical and experimental perspectives is very limited when it comes to understanding the interface between these systems and a solid substrate. Molecular dynamics simulations based on the All Atom OPLS model are used to predict the equilibrium structure and dynamics of short fluorinated alkanes on both amorphous and crystalline silicon dioxide surfaces. In order to understand the effect of layer-layer interaction on the ordering of chains in a given layer, the thickness of the liquid film is increased layer-by-layer from monolayer to multilayers. Results for structural and dynamics of the liquid films near the silicon dioxide surfaces will be presented.

  8. Increase of translatable mRNA for major microsomal proteins in n-alkane-grown Candida maltosa

    SciTech Connect

    Sunairi, M.; Watabe, K.; Takagi, M.; Yano, K.

    1984-12-01

    In an n-alkane-assimilating Candida sp., transfer from glucose- to n-alkane-containing medium induced changes in the microsomal proteins, and several distinctive polypeptides were demonstrated in the solubilized microsomal fraction derived from n-alkane-grown cells. Long-term-labeling and pulse-labeling experiments in vivo demonstrated the synthesis of the specific microsomal polypeptides. The polypeptides were synthesized as in vitro translation products directed by polyadenylated RNA extracted from n-alkane-grown cells. Two major polypeptides were partially purified from the microsomal fraction from n-alkane-grown cells, and antiserum was prepared in a rabbit. Immunoprecipitation of these two polypeptides was accompanied by an increase in the amount of translatable mRNA. The molecular weights of the polypeptides derived from long-term-labeling, pulse-labeling and in vitro translation experiments appeared to be identical.

  9. Mesoporous thin films of ``molecular squares'' as sensors for volatile organic compounds

    SciTech Connect

    Keefe, M.H.; Slone, R.V.; Hupp, J.T.; Czaplewski, K.F.; Snurr, R.Q.; Stern, C.L.

    2000-04-18

    Mesoporous thin films of rhenium-based molecular squares, [Re(CO){sub 3}Cl(L)]{sub 4} (L = pyrazine, 4,4{prime}-bipyridine), have been utilized as sensors for volatile organic compounds (VOCs). The sensing was conducted using a quartz crystal microbalance with the target compounds present in the gas phase at concentrations ranging from 0.05 to 1 mM. Quartz crystal microbalance studies with these materials allowed for distinction between the following VOCs: (1) small aromatic versus aliphatic molecules of almost identical size and volatility and (2) an array of benzene molecules derivatized with electron donating/withdrawing substituents. The experiments suggest that the mesoporous host materials interact with VOC guest molecules through both van der Waals and weak charge-transfer interactions. In addition, size selectivity is shown by exposure of the molecular squares to cyclic ethers of differing size.

  10. Molecular doping for control of gate bias stress in organic thin film transistors

    NASA Astrophysics Data System (ADS)

    Hein, Moritz P.; Zakhidov, Alexander A.; Lüssem, Björn; Jankowski, Jens; Tietze, Max L.; Riede, Moritz K.; Leo, Karl

    2014-01-01

    The key active devices of future organic electronic circuits are organic thin film transistors (OTFTs). Reliability of OTFTs remains one of the most challenging obstacles to be overcome for broad commercial applications. In particular, bias stress was identified as the key instability under operation for numerous OTFT devices and interfaces. Despite a multitude of experimental observations, a comprehensive mechanism describing this behavior is still missing. Furthermore, controlled methods to overcome these instabilities are so far lacking. Here, we present the approach to control and significantly alleviate the bias stress effect by using molecular doping at low concentrations. For pentacene and silicon oxide as gate oxide, we are able to reduce the time constant of degradation by three orders of magnitude. The effect of molecular doping on the bias stress behavior is explained in terms of the shift of Fermi Level and, thus, exponentially reduced proton generation at the pentacene/oxide interface.

  11. Molecular Weight Effects on the Glass Transition and Confinement Behavior of Polymer Thin Films.

    PubMed

    Xia, Wenjie; Hsu, David D; Keten, Sinan

    2015-08-01

    Nanoscale polymer thin films exhibit strong confinement effects on Tg arising from free surfaces. However, the coupled influence of molecular weight (MW) and surface effects on Tg is not well understood for low MW film systems below the entanglement length. Utilizing atomistically informed coarse-grained molecular dynamics simulations for poly(methyl methacrylate) (PMMA), it is demonstrated that the decrease in free-standing film Tg with respect to bulk is more significant for low MW compared to high MW systems. Investigation of the local interfacial properties reveals that the increase in the local free volume near the free surface is greater for low MW, explaining the MW dependence of Tg -confinement behaviors. These findings corroborate recent experiments on low MW films, and highlight the relationship between nanoconfinement phenomena and local free volume effects arising from free surfaces. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Molecularly imprinted protein recognition thin films constructed by controlled/living radical polymerization.

    PubMed

    Sasaki, Shogo; Ooya, Tooru; Kitayama, Yukiya; Takeuchi, Toshifumi

    2015-02-01

    We demonstrated the synthesis of molecularly imprinted polymers (MIPs) with binding affinity toward a target protein, ribonuclease A (RNase) by atom transfer radical polymerization (ATRP) of acrylic acid, acrylamide, and N,N'-methylenebisacrylamide in the presence of RNase. The binding activity of the MIPs was evaluated by surface plasmon resonance (SPR) of the MIP thin layers prepared on the gold-coated sensor chips. The MIPs prepared by ATRP (MIP-ATRP) had a binding affinity toward RNase with larger binding amount compared to MIPs prepared by conventional free radical polymerization methods (MIP-RP). Moreover, protein selectivity was evaluated using reference proteins (cytochrome c, myoglobin, and α-lactalbumin) and was confirmed in MIP-ATRP of optimum film thickness determined experimentally to be 15-30 nm; however, protein selectivity was not achieved in all MIP-RP. We have shown that ATRP is powerful technique for preparing protein recognition materials by molecular imprinting.

  13. Photoluminescence of localized excitons in ZnCdO thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Wu, T. Y.; Huang, Y. S.; Hu, S. Y.; Lee, Y. C.; Tiong, K. K.; Chang, C. C.; Shen, J. L.; Chou, W. C.

    2016-07-01

    We have investigated the luminescence characteristics of Zn1-xCdxO thin films with different Cd contents grown by molecular beam epitaxy system. The temperature-dependent photoluminescence (PL) and excitation power-dependent PL spectra were measured to clarify the luminescence mechanisms of the Zn1-xCdxO thin films. The peak energy of the Zn1-xCdxO thin films with increasing the Cd concentration is observed as redshift and can be fitted by the quadratic function of alloy content. The broadened full-width at half-maximum (FWHM) estimated from the 15 K PL spectra as a function of Cd content shows a larger deviation between the experimental values and theoretical curve, which indicates that experimental FWHM values are affected not only by alloy compositional disorder but also by localized excitons occupying states in the tail of the density of states. The Urbach energy determined from an analysis of the lineshape of the low-energy side of the PL spectrum and the degree of localization effect estimated from the temperature-induced S-shaped PL peak position described an increasing mean exciton-localization effects in ZnCdO films with increasing the Cd content. In addition, the PL intensity and peak position as a function of excitation power are carried out to clarify the types of radiative recombination and the effects of localized exciton in the ZnCdO films with different Cd contents.

  14. Probing the structure of liquids with 129Xe NMR spectroscopy: n-alkanes, cycloalkanes, and branched alkanes.

    PubMed

    Morgado, Pedro; Bonifácio, Rui; Martins, Luís F G; Filipe, Eduardo J M

    2013-08-01

    The liquid organization of linear, branched, and cyclic alkanes was studied using atomic (129)Xe as a NMR probe. (129)Xe chemical shifts have been experimentally determined for xenon dissolved in a total of 21 alkanes. In order to allow the comparison of the different solvents at similar thermodynamic conditions, the measurements were performed over a wide range of temperatures, from the melting point of the solvent up to 350 K. The results were rationalized in terms of the density, nature, and organization of the chemical groups within xenon's coordination sphere. Additionally, molecular dynamics simulations were performed using established atomistic force fields to interpret and clarify the conclusions suggested by the experimental results. The analysis is able to interpret previous results in the literature for ethane and propane at very different experimental conditions.

  15. Organic and inorganic–organic thin film structures by molecular layer deposition: A review

    PubMed Central

    Sundberg, Pia

    2014-01-01

    Summary The possibility to deposit purely organic and hybrid inorganic–organic materials in a way parallel to the state-of-the-art gas-phase deposition method of inorganic thin films, i.e., atomic layer deposition (ALD), is currently experiencing a strongly growing interest. Like ALD in case of the inorganics, the emerging molecular layer deposition (MLD) technique for organic constituents can be employed to fabricate high-quality thin films and coatings with thickness and composition control on the molecular scale, even on complex three-dimensional structures. Moreover, by combining the two techniques, ALD and MLD, fundamentally new types of inorganic–organic hybrid materials can be produced. In this review article, we first describe the basic concepts regarding the MLD and ALD/MLD processes, followed by a comprehensive review of the various precursors and precursor pairs so far employed in these processes. Finally, we discuss the first proof-of-concept experiments in which the newly developed MLD and ALD/MLD processes are exploited to fabricate novel multilayer and nanostructure architectures by combining different inorganic, organic and hybrid material layers into on-demand designed mixtures, superlattices and nanolaminates, and employing new innovative nanotemplates or post-deposition treatments to, e.g., selectively decompose parts of the structure. Such layer-engineered and/or nanostructured hybrid materials with exciting combinations of functional properties hold great promise for high-end technological applications. PMID:25161845

  16. A molecular scale perspective: Monte Carlo simulation for rupturing of ultra thin polymer film melts

    NASA Astrophysics Data System (ADS)

    Singh, Satya Pal

    2017-04-01

    Monte Carlo simulation has been performed to study the rupturing process of thin polymer film under strong confinement. The change in mean square displacement; pair correlation function; density distribution; average bond length and microscopic viscosity are sampled by varying the molecular interaction parameters such as the strength and the equilibrium positions of the bonding, non-bonding potentials and the sizes of the beads. The variation in mean square angular displacement χθ = [ < Δθ2 > - < Δθ>2 ] fits very well to a function of type y (t) = A + B *e-t/τ. This may help to study the viscous properties of the films and its dependence on different parameters. The ultra thin film annealed at high temperature gets ruptured and holes are created in the film mimicking spinodal dewetting. The pair correlation function and density profile reveal rich information about the equilibrium structure of the film. The strength and equilibrium bond length of finite extensible non-linear elastic potential (FENE) and non-bonding Morse potential have clear impact on microscopic rupturing of the film. The beads show Rouse or repetition motion forming rim like structures near the holes created inside the film. The higher order interaction as dipole-quadrupole may get prominence under strong confinement. The enhanced excluded volume interaction under strong confinement may overlap with the molecular dispersion forces. It can work to reorganize the molecules at the bottom of the scale and can imprint its signature in complex patterns evolved.

  17. Growth of SrVO{sub 3} thin films by hybrid molecular beam epitaxy

    SciTech Connect

    Eaton, Craig; Brahlek, Matthew; Engel-Herbert, Roman; Moyer, Jarrett A.; Alipour, Hamideh M.; Grimley, Everett D.; LeBeau, James M.

    2015-11-15

    The authors report the growth of stoichiometric SrVO{sub 3} thin films on (LaAlO{sub 3}){sub 0.3}(Sr{sub 2}AlTaO{sub 6}){sub 0.7} (001) substrates using hybrid molecular beam epitaxy. This growth approach employs a conventional effusion cell to supply elemental A-site Sr and the metalorganic precursor vanadium oxytriisopropoxide (VTIP) to supply vanadium. Oxygen is supplied in its molecular form through a gas inlet. An optimal VTIP:Sr flux ratio has been identified using reflection high-energy electron-diffraction, x-ray diffraction, atomic force microscopy, and scanning transmission electron microscopy, demonstrating stoichiometric SrVO{sub 3} films with atomically flat surface morphology. Away from the optimal VTIP:Sr flux, characteristic changes in the crystalline structure and surface morphology of the films were found, enabling identification of the type of nonstoichiometry. For optimal VTIP:Sr flux ratios, high quality SrVO{sub 3} thin films were obtained with smallest deviation of the lattice parameter from the ideal value and with atomically smooth surfaces, indicative of the good cation stoichiometry achieved by this growth technique.

  18. Molecular orientation dependence of hole-injection barrier in pentacene thin film on the Au surface in organic thin film transistor

    NASA Astrophysics Data System (ADS)

    Ihm, Kyuwook; Kim, Bongsoo; Kang, Tai-Hee; Kim, Ki-Jeong; Joo, Min Ho; Kim, Tae Hyeong; Yoon, Sang Soo; Chung, Sukmin

    2006-07-01

    We have investigated the effects of a buffer layer insertion on the performance of the pentacene based thin film transistor with a bottom contact structure. When the pentacene molecules have a standing up coordination on the Au surface that is modified by the benzenethiol or methanethiol, the transition region in the pentacene thin film is removed along the boundary between the Au and silicon oxide region, and the hole-injection barrier decreases by 0.4eV. Pentacene on various surfaces showed that the highly occupied molecular level is 0.2-0.4eV lower in the standing up coordination than in the lying down coordination.

  19. Oxidation Products of Semi-volatile Alkanes by Hydroxyl Radicals

    NASA Astrophysics Data System (ADS)

    Zhang, H.; Worton, D. R.; Nah, T.; Goldstein, A. H.; Wilson, K. R.

    2013-12-01

    Alkanes are ubiquitous in the atmosphere and are important components that influence atmospheric chemistry. Semi-volatile alkanes are partitioned between the gas- and the particle-phases and can be readily oxidized in both phases. Previous studies have demonstrated that reaction rates and the products of OH oxidation are very different for organic compounds in the gas- and particle phases. In the present study, n-octadecane (C18H38), n-eicosane (C20H42), n-docosane (C22H46), n-tricosane (C24H50), and n-pentadecylcyclohexane (C21H42) were chosen as model compounds for semi-volatile alkanes to examine their OH-initiated oxidation reactions in a flow tube reactor. OH exposure was varied in the experiments, equivalent to oxidation of up to one week in the atmosphere. Oxidation products were collected on filters and analyzed using two-dimensional gas chromatography coupled to a high-resolution time-of-flight electron impact ionization and vacuum ultraviolet photoionization mass spectrometer. Most of the oxygenated higher molecular weight isomers were separated and quantified. Our results suggest that aerosol samples formed in the n-octadecane experiment were more oxidized than the other model compounds (i.e., functionalization products with three oxygen atoms per molecule compared to two oxygen atoms per molecule) at similar OH exposures and aerosol mass loadings. This is likely due to the concentration of n-octadecane in the gas phase where oxidation is more rapid. We find that the first-generation gas-phase oxidation products quickly partition to the particle phase after which higher-generation oxidation likely occurs in the particle phase. Interestingly, functionalized carbonyl isomers for the normal alkanes were only observed on the 4 carbon positions closest to the molecule end in all cases, which is in contrast to structure-reactivity relationship (SRR) predictions for gas-phase reactions. For n-octadecane, the concentrations of first-generation functionalization

  20. Solar Selective Coatings Prepared From Thin-Film Molecular Mixtures and Evaluated

    NASA Technical Reports Server (NTRS)

    Jaworske, Don A.

    2003-01-01

    Thin films composed of molecular mixtures of metal and dielectric are being considered for use as solar selective coatings for a variety of space power applications. By controlling molecular mixing during ion-beam sputter deposition, researchers can tailor the solar selective coatings to have the combined properties of high solar absorptance and low infrared emittance. On orbit, these combined properties simultaneously maximize the amount of solar energy captured by the coating and minimize the amount of thermal energy radiated. The solar selective coatings are envisioned for use on minisatellites, for applications where solar energy is used to power heat engines or to heat remote regions in the interior of the spacecraft. Such systems may be useful for various missions, particularly those to middle Earth orbit. Sunlight must be concentrated by a factor of 100 or more to achieve the desired heat inlet operating temperature. At lower concentration factors, the temperature of the heat inlet surface of the heat engine is too low for efficient operation, and at high concentration factors, cavity type heat receivers become attractive. The an artist's concept of a heat engine, with the annular heat absorbing surface near the focus of the concentrator coated with a solar selective coating is shown. In this artist's concept, the heat absorbing surface powers a small Stirling convertor. The astronaut's gloved hand is provided for scale. Several thin-film molecular mixtures have been prepared and evaluated to date, including mixtures of aluminum and aluminum oxide, nickel and aluminum oxide, titanium and aluminum oxide, and platinum and aluminum oxide. For example, a 2400- Angstrom thick mixture of titanium and aluminum oxide was found to have a solar absorptance of 0.93 and an infrared emittance of 0.06. On the basis of tests performed under flowing nitrogen at temperatures as high as 680 C, the coating appeared to be durable at elevated temperatures. Additional durability

  1. Re-orientation transition in molecular thin films: Potts model with dipolar interaction.

    PubMed

    Hoang, Danh-Tai; Kasperski, Maciej; Puszkarski, Henryk; Diep, H T

    2013-02-06

    We study the low-temperature behavior and the phase transition of a thin film by Monte Carlo simulation. The thin film has a simple cubic lattice structure where each site is occupied by a Potts parameter which indicates the molecular orientation of the site. We take only three molecular orientations in this paper, which correspond to the three-state Potts model. The Hamiltonian of the system includes (i) the exchange interaction J(ij) between nearest-neighbor sites i and j, (ii) the long-range dipolar interaction of amplitude D truncated at a cutoff distance r(c), and (iii) a single-ion perpendicular anisotropy of amplitude A. We allow J(ij) = J(s) between surface spins, and J(ij) = J otherwise. We show that the ground state depends on the ratio D/A and r(c). For a single layer, for a given A, there is a critical value D(c) below (above) which the ground-state (GS) configuration of molecular axes is perpendicular (parallel) to the film surface. When the temperature T is increased, a re-orientation transition occurs near D(c): the low-T in-plane ordering undergoes a transition to the perpendicular ordering at a finite T, below the transition to the paramagnetic phase. The same phenomenon is observed in the case of a film with a thickness. Comparison with the Fe/Gd experiment is given. We show that the surface phase transition can occur below or above the bulk transition depending on the ratio J(s)/J. Surface and bulk order parameters as well as other physical quantities are shown and discussed.

  2. Molecular dynamics simulations of disjoining pressure effect in ultra-thin water film on a metal surface

    NASA Astrophysics Data System (ADS)

    Hu, H.; Sun, Y.

    2013-12-01

    Molecular dynamics (MD) simulations are used to examine the disjoining pressure effect of a water thin film adsorbed on a metal surface. The model was validated against experiments and verified against previous MD simulations. The variation of vapor pressure with film thickness was examined for a water thin film adsorbed on a gold surface. The results agree well with the classic disjoining pressure theory without surface charges and show that liquid layering does not affect disjoining pressure. However, surface charges of the gold substrate enhance the disjoining pressure of the water thin film, consistent with experimental evidences for polar liquids.

  3. ClogP(alk): a method for predicting alkane/water partition coefficient.

    PubMed

    Kenny, Peter W; Montanari, Carlos A; Prokopczyk, Igor M

    2013-05-01

    Alkane/water partition coefficients (P(alk)) are less familiar to the molecular design community than their 1-octanol/water equivalents and access to both data and prediction tools is much more limited. A method for predicting alkane/water partition coefficient from molecular structure is introduced. The basis for the ClogP(alk) model is the strong (R² = 0.987) relationship between alkane/water partition coefficient and molecular surface area (MSA) that was observed for saturated hydrocarbons. The model treats a molecule as a perturbation of a saturated hydrocarbon molecule with the same MSA and uses increments defined for functional groups to quantify the extent to which logP(alk) is perturbed by the introduction each functional group. Interactions between functional groups, such as intramolecular hydrogen bonds are also parameterized within a perturbation framework. The functional groups and interactions between them are specified substructurally in a transparent and reproducible manner using SMARTS notation. The ClogP(alk) model was parameterized using data measured for structurally prototypical compounds that dominate the literature on alkane/water partition coefficients and then validated using an external test set of 100 alkane/water logP measurements, the majority of which were for drugs.

  4. ClogPalk: a method for predicting alkane/water partition coefficient

    NASA Astrophysics Data System (ADS)

    Kenny, Peter W.; Montanari, Carlos A.; Prokopczyk, Igor M.

    2013-05-01

    Alkane/water partition coefficients (Palk) are less familiar to the molecular design community than their 1-octanol/water equivalents and access to both data and prediction tools is much more limited. A method for predicting alkane/water partition coefficient from molecular structure is introduced. The basis for the ClogPalk model is the strong (R2 = 0.987) relationship between alkane/water partition coefficient and molecular surface area (MSA) that was observed for saturated hydrocarbons. The model treats a molecule as a perturbation of a saturated hydrocarbon molecule with the same MSA and uses increments defined for functional groups to quantify the extent to which logPalk is perturbed by the introduction each functional group. Interactions between functional groups, such as intramolecular hydrogen bonds are also parameterized within a perturbation framework. The functional groups and interactions between them are specified substructurally in a transparent and reproducible manner using SMARTS notation. The ClogPalk model was parameterized using data measured for structurally prototypical compounds that dominate the literature on alkane/water partition coefficients and then validated using an external test set of 100 alkane/water logP measurements, the majority of which were for drugs.

  5. Efficient bulk heterojunction photovoltaic cells using small-molecular-weight organic thin films.

    PubMed

    Peumans, Peter; Uchida, Soichi; Forrest, Stephen R

    2003-09-11

    The power conversion efficiency of small-molecular-weight and polymer organic photovoltaic cells has increased steadily over the past decade. This progress is chiefly attributable to the introduction of the donor-acceptor heterojunction that functions as a dissociation site for the strongly bound photogenerated excitons. Further progress was realized in polymer devices through use of blends of the donor and acceptor materials: phase separation during spin-coating leads to a bulk heterojunction that removes the exciton diffusion bottleneck by creating an interpenetrating network of the donor and acceptor materials. The realization of bulk heterojunctions using mixtures of vacuum-deposited small-molecular-weight materials has, on the other hand, posed elusive: phase separation induced by elevating the substrate temperature inevitably leads to a significant roughening of the film surface and to short-circuited devices. Here, we demonstrate that the use of a metal cap to confine the organic materials during annealing prevents the formation of a rough surface morphology while allowing for the formation of an interpenetrating donor-acceptor network. This method results in a power conversion efficiency 50 per cent higher than the best values reported for comparable bilayer devices, suggesting that this strained annealing process could allow for the formation of low-cost and high-efficiency thin film organic solar cells based on vacuum-deposited small-molecular-weight organic materials.

  6. Lipoate-based imprinted self-assembled molecular thin films for biosensor applications.

    PubMed

    Tappura, Kirsi; Vikholm-Lundin, Inger; Albers, Willem M

    2007-01-15

    Lipoate derivatives were used for the formation of imprinted self-assembled molecular thin films for the recognition of morphine. A large collection of lipoate derivatives was screened by molecular dynamics simulations in various solvents. A set of ligands showing favourable interactions with morphine in aqueous environment was selected for synthesis. Morphine-imprinted layers were then produced on gold substrates in mixed monolayers with morphine added as the template. The binding of ligands and morphine to gold, as well as the association/dissociation of morphine to the formed layers were studied with Surface Plasmon Resonance. Imprinted factors were highly variable and were dependent on ligand/morphine mixing ratio, lipoate derivative and monolayer preparation method. The imprinted factors were as high as 100 and 600 for one of the ligands. The results show that the simulations are able to provide correct information of the relative strengths of the molecular interactions between the ligand and morphine molecules in different solutions. The liquid phase simulations are, however, not able to predict the imprinted factors (i.e. distinguish between specific and non-specific binding), because the specificity is not formed before self-assembly on the surface.

  7. Evaporation characteristics of thin film liquid argon in nano-scale confinement: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Hasan, Mohammad Nasim; Shavik, Sheikh Mohammad; Rabbi, Kazi Fazle; Haque, Mominul

    2016-07-01

    Molecular dynamics simulation has been carried out to explore the evaporation characteristics of thin liquid argon film in nano-scale confinement. The present study has been conducted to realize the nano-scale physics of simultaneous evaporation and condensation inside a confined space for a three phase system with particular emphasis on the effect of surface wetting conditions. The simulation domain consisted of two parallel platinum plates; one at the top and another at the bottom. The fluid comprised of liquid argon film at the bottom plate and vapor argon in between liquid argon and upper plate of the domain. Considering hydrophilic and hydrophobic nature of top and bottom surfaces, two different cases have been investigated: (i) Case A: Both top and bottom surfaces are hydrophilic, (ii) Case B: both top and bottom surfaces are hydrophobic. For all cases, equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. Then the lower wall was set to four different temperatures such as 110 K, 120 K, 130 K and 140 K to perform non-equilibrium molecular dynamics (NEMD). The variation of temperature and density as well as the variation of system pressure with respect to time were closely monitored for each case. The heat fluxes normal to top and bottom walls were estimated and discussed to illuminate the effectiveness of heat transfer in both hydrophilic and hydrophobic confinement at various boundary temperatures of the bottom plate.

  8. Thermodiffusion in multicomponent n-alkane mixtures.

    PubMed

    Galliero, Guillaume; Bataller, Henri; Bazile, Jean-Patrick; Diaz, Joseph; Croccolo, Fabrizio; Hoang, Hai; Vermorel, Romain; Artola, Pierre-Arnaud; Rousseau, Bernard; Vesovic, Velisa; Bou-Ali, M Mounir; Ortiz de Zárate, José M; Xu, Shenghua; Zhang, Ke; Montel, François; Verga, Antonio; Minster, Olivier

    2017-01-01

    Compositional grading within a mixture has a strong impact on the evaluation of the pre-exploitation distribution of hydrocarbons in underground layers and sediments. Thermodiffusion, which leads to a partial diffusive separation of species in a mixture due to the geothermal gradient, is thought to play an important role in determining the distribution of species in a reservoir. However, despite recent progress, thermodiffusion is still difficult to measure and model in multicomponent mixtures. In this work, we report on experimental investigations of the thermodiffusion of multicomponent n-alkane mixtures at pressure above 30 MPa. The experiments have been conducted in space onboard the Shi Jian 10 spacecraft so as to isolate the studied phenomena from convection. For the two exploitable cells, containing a ternary liquid mixture and a condensate gas, measurements have shown that the lightest and heaviest species had a tendency to migrate, relatively to the rest of the species, to the hot and cold region, respectively. These trends have been confirmed by molecular dynamics simulations. The measured condensate gas data have been used to quantify the influence of thermodiffusion on the initial fluid distribution of an idealised one dimension reservoir. The results obtained indicate that thermodiffusion tends to noticeably counteract the influence of gravitational segregation on the vertical distribution of species, which could result in an unstable fluid column. This confirms that, in oil and gas reservoirs, the availability of thermodiffusion data for multicomponent mixtures is crucial for a correct evaluation of the initial state fluid distribution.

  9. Determination of the n-alkane profile of epicuticular wax extracted from mature leaves of Cestrum nocturnum (Solanaceae: Solanales).

    PubMed

    Chowdhury, Nandita; Ghosh, Anupam; Bhattacharjee, Indranil; Laskar, Subrata; Chandra, Goutam

    2010-09-01

    An n-hexane extract of fresh, mature leaves of Cestrum nocturnum (Solanales: Solanaceae) containing thin layer epicuticular waxes was analysed by thin-layer chromatography, infrared and gas liquid chromatography using standard hydrocarbons. Seventeen long chain alkanes (n-C(18) to n-C(34)) were identified and quantified. Hentriacontane (n-C(31)) was established as the major n-alkane, while nonadecane (n-C(19)) was the least abundant component of the extracted wax fraction. The carbon preference index calculated for the sample was 1.30, showing an odd to even carbon number predominance.

  10. Hydrogen isotope alteration of normal alkanes during artificial maturation experiments

    NASA Astrophysics Data System (ADS)

    Wang, C.; Eley, Y.; Oakes, A.; Hren, M. T.

    2016-12-01

    Hydrogen isotopes of normal alkanes provide a record of past climate, hydrocarbon source and migration, and thermal history. Numerous authors have investigated the preservation potential of organic compounds during burial diagenesis and developed a range of molecular indicators of thermal maturity. A key uncertainty in application of organic biomarkers for paleoenvironmental work is how the δD values of individual molecular compounds changes during burial heating and thermal cracking. Studies suggest that n-alkanes are unlikely to exchange hydrogen at modest temperatures (below 150°C) over geologic time, however there is still debate over the potential for alteration of primary isotopic signatures due to the combined effect of exchange and cracking of more complex molecules. We conducted a suite of heating experiments in ambient air and oxygen-free systems using pure alkane mixtures and natural soil extracts to evaluate the preservation potential of the hydrogen isotopic composition of both short (nC20) carbon chain n-alkanes. Our data show that for pure mixtures, there is a positive shift in the δD of long carbon chains during heating of up to 12‰ and a negative shift in short chains of up to 28‰. Experiments with natural sediment extracts show 2H enrichment of long carbon chains during heating in both ambient air and oxygen free systems, and at temperatures below 150°C. These changes are accompanied by shifts in the carbon preference and average chain length. Experimental data show that there is potential for 2H/1H alteration of long-carbon chain normal alkanes during shallow burial, however these changes rarely exceed 10-15‰ before compounds are degraded to quantities below useful abundances for isotope measurements. A potentially significant result is that low temperature alteration of organics within sediments can shift the average chain length, particularly in the presence of oxygen. Thus, lithology and gas permeability may play an important role in

  11. Multiple alkane hydroxylase systems in a marine alkane degrader, Alcanivorax dieselolei B-5.

    PubMed

    Liu, Chenli; Wang, Wanpeng; Wu, Yehui; Zhou, Zhongwen; Lai, Qiliang; Shao, Zongze

    2011-05-01

    Alcanivorax dieselolei strain B-5 is a marine bacterium that can utilize a broad range of n-alkanes (C(5) -C(36) ) as sole carbon source. However, the mechanisms responsible for this trait remain to be established. Here we report on the characterization of four alkane hydroxylases from A. dieselolei, including two homologues of AlkB (AlkB1 and AlkB2), a CYP153 homologue (P450), as well as an AlmA-like (AlmA) alkane hydroxylase. Heterologous expression of alkB1, alkB2, p450 and almA in Pseudomonas putida GPo12 (pGEc47ΔB) or P. fluorescens KOB2Δ1 verified their functions in alkane oxidation. Quantitative real-time RT-PCR analysis showed that these genes could be induced by alkanes ranging from C(8) to C(36) . Notably, the expression of the p450 and almA genes was only upregulated in the presence of medium-chain (C(8) -C(16) ) or long-chain (C(22) -C(36) ) n-alkanes, respectively; while alkB1 and alkB2 responded to both medium- and long-chain n-alkanes (C(12) -C(26) ). Moreover, branched alkanes (pristane and phytane) significantly elevated alkB1 and almA expression levels. Our findings demonstrate that the multiple alkane hydroxylase systems ensure the utilization of substrates of a broad chain length range.

  12. Supported organoiridium catalysts for alkane dehydrogenation

    SciTech Connect

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  13. Growth Parameters for Thin Film InBi Grown by Molecular Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Keen, B.; Makin, R.; Stampe, P. A.; Kennedy, R. J.; Sallis, S.; Piper, L. J.; McCombe, B.; Durbin, S. M.

    2014-04-01

    The alloying of bismuth with III-V semiconductors, in particular GaAs and InAs thin films grown by molecular beam epitaxy (MBE), has attracted considerable interest due to the accompanying changes in band structure and lattice constant. Specifically, bismuth incorporation in these compounds results in both a reduction in band gap (through shifting of the valence band) and an increase in the lattice constant of the alloy. To fully understand the composition of these alloys, a better understanding of the binary endpoints is needed. At present, a limited amount of literature exists on the III-Bi family of materials, most of which is theoretical work based on density functional theory calculations. The only III-Bi material known to exist (in bulk crystal form) is InBi, but its electrical properties have not been sufficiently studied and, to date, the material has not been fabricated as a thin film. We have successfully deposited crystalline InBi on (100) GaAs substrates using MBE. Wetting of the substrate is poor, and regions of varying composition exist across the substrate. To obtain InBi, the growth temperature had to be below 100 °C. It was found that film crystallinity improved with reduced Bi flux, into an In-rich regime. Additionally, attempts were made to grow AlBi and GaBi.

  14. Multiferroic fluoride BaCoF4 Thin Films Grown Via Molecular Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Borisov, Pavel; Johnson, Trent; García-Castro, Camilo; Kc, Amit; Schrecongost, Dustin; Cen, Cheng; Romero, Aldo; Lederman, David

    Multiferroic materials exhibit exciting physics related to the simultaneous presence of multiple long-range orders, in many cases consisting of antiferromagnetic (AF) and ferroelectric (FE) orderings. In order to provide a new, promising route for fluoride-based multiferroic material engineering, we grew multiferroic fluoride BaCoF4 in thin film form on Al2O3 (0001) substrates by molecular beam epitaxy. The films grow with the orthorhombic b-axis out-of-plane and with three in-plane structural twin domains along the polar c-axis directions. The FE ordering in thin films was verified by FE remanent hysteresis loops measurements at T = 14 K and by room temperature piezoresponse force microscopy (PFM). An AF behavior was found below Neel temperature TN ~ 80 K, which is in agreement with the bulk properties. At lower temperatures two additional magnetic phase transitions at 19 K and 41 K were found. First-principles calculations demonstrated that the growth strain applied to the bulk BaCoF4 indeed favors two canted spin orders, along the b- and a-axes, respectively, in addition to the main AF spin order along the c-axis. Supported by FAME (Contract 2013-MA-2382), WV Research Challenge Grant (HEPC.dsr.12.29), and DMREF-NSF 1434897.

  15. Thin film growth of CaFe2As2 by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Hatano, T.; Kawaguchi, T.; Fujimoto, R.; Nakamura, I.; Mori, Y.; Harada, S.; Ujihara, T.; Ikuta, H.

    2016-01-01

    Film growth of CaFe2As2 was realized by molecular beam epitaxy on six different substrates that have a wide variation in the lattice mismatch to the target compound. By carefully adjusting the Ca-to-Fe flux ratio, we obtained single-phase thin films for most of the substrates. Interestingly, an expansion of the CaFe2As2 lattice to the out-of-plane direction was observed for all films, even when an opposite strain was expected. A detailed microstructure observation of the thin film grown on MgO by transmission electron microscope revealed that it consists of cube-on-cube and 45°-rotated domains. The latter domains were compressively strained in plane, which caused a stretching along the c-axis direction. Because the domains were well connected across the boundary with no appreciable discontinuity, we think that the out-of-plane expansion in the 45°-rotated domains exerted a tensile stress on the other domains, resulting in the unexpectedly large c-axis lattice parameter, despite the apparently opposite lattice mismatch.

  16. Surface molecular aggregation structure and surface physicochemical properties of poly(fluoroalkyl acrylate) thin films

    NASA Astrophysics Data System (ADS)

    Honda, K.; Yamaguchi, H.; Kobayashi, M.; Morita, M.; Takahara, A.

    2008-03-01

    Effect of side chain length on the molecular aggregation states and surface properties of poly(fluoroalkyl acrylate)s [PFA-Cy, where y is fluoromethylene number in Rf group] thin films were systematically investigated. Spin-coated PFA-Cy thin films were characterized by static and dynamic contact angle measurements, X-ray photoelectron spectroscopy (XPS), and grazing- incidence X-ray diffraction (GIXD). The receding contact angles showed small values for PFA-Cy with short side chain (y<=6) and increased above y>=8. GIXD revealed that fluoroalkyl side chain of PFA-Cy with y>=8 was crystallized and formed ordered structures at the surface region as well as bulk one. These results suggest that water repellent mechanism of PFA-Cy can be attributed to the presence of highly ordered fluoroalkyl side chains at the outermost surfaces. The results of XPS in the dry and hydrated states and contact angle measurement in water support the mechanism of lowering contact angle for water by exposure of carbonyl group to the water interface through reorientation of short fluoroalkyl chains. The surface nanotextured PFA-C8 through imprinting of anodic aluminum oxide mold showed extremely high hydrophobicity as well as high oleophobicity.

  17. Neat monolayer tiling of molecularly thin two-dimensional materials in 1 min

    PubMed Central

    Matsuba, Kazuaki; Wang, Chengxiang; Saruwatari, Kazuko; Uesusuki, Yusuke; Akatsuka, Kosho; Osada, Minoru; Ebina, Yasuo; Ma, Renzhi; Sasaki, Takayoshi

    2017-01-01

    Controlled arrangement of molecularly thin two-dimensional (2D) materials on a substrate, particularly into precisely organized mono- and multilayer structures, is a key to design a nanodevice using their unique and enhanced physical properties. Several techniques such as mechanical transfer process and Langmuir-Blodgett deposition have been applied for this purpose, but they have severe restrictions for large-scale practical applications, for example, limited processable area and long fabrication time, requiring skilled multistep operations. We report a facile one-pot spin-coating method to realize dense monolayer tiling of various 2D materials, such as graphene and metal oxide nanosheets, within 1 min over a wide area (for example, a 30-mmφ substrate). Centrifugal force drives the nanosheets in a thin fluid layer to the substrate edge where they are packed edge to edge all the way to the central region, without forming overlaps. We investigated the relationship between precursor concentration, rotation speed, and ultraviolet-visible absorbance and developed an effective method to optimize the parameters for neat monolayer films. The multilayer buildup is feasible by repeating the spin-coating process combined with a heat treatment at moderate temperature. This versatile solution-based technique will provide both fundamental and practical advancements in the rapid large-scale production of artificial lattice-like films and nanodevices based on 2D materials. PMID:28695198

  18. Temperature stabilized effusion cell evaporation source for thin film deposition and molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Tiedje, H. F.; Brodie, D. E.

    2000-05-01

    A simple effusion cell evaporation source for thin film deposition and molecular-beam epitaxy is described. The source consists of a crucible with a thermocouple temperature sensor heated by a resistive crucible heater. Radiation heat transfer from the crucible to the thermocouple produces a consistent and reproducible thermocouple temperature for a given crucible temperature, without direct contact between the thermocouple and the crucible. The thermocouple temperature is somewhat less than the actual crucible temperature because of heat flow from the thermocouple junction along the thermocouple lead wires. In a typical case, the thermocouple temperature is 1007 °C while the crucible is at 1083 °C. The crucible temperature stability is estimated from the measured sensitivity of the evaporation rate of indium to temperature, and the observed variations in the evaporation rate for a fixed thermocouple temperature. The crucible temperature peak-to-peak variation over a one hour period is 1.2 °C. Machined molybdenum crucibles were used in the indium and copper sources for depositing CuInSe2 thin films for solar cells.

  19. Thermal stabilization of thin gold nanowires by surfactant-coating: a molecular dynamics study.

    PubMed

    Huber, Stefan E; Warakulwit, Chompunuch; Limtrakul, Jumras; Tsukuda, Tatsuya; Probst, Michael

    2012-01-21

    The thermal stabilization of thin gold nanowires with a diameter of about 2 nm by surfactants is investigated by means of classical molecular dynamics simulations. While the well-known melting point depression leads to a much lower melting of gold nanowires compared to bulk gold, coating the nanowires with surfactants can reverse this, given that the attractive interaction between surfactant molecules and gold atoms lies beyond a certain threshold. It is found that the melting process of coated nanowires is dominated by surface instability patterns, whereas the melting behaviour of gold nanowires in a vacuum is dominated by the greater mobility of atoms with lower coordination numbers that are located at edges and corners. The suppression of the melting by surfactants is explained by the isotropic pressure acting on the gold surface (due to the attractive interaction) which successfully suppresses large-amplitude thermal motions of the gold atoms.

  20. Structural and optical characterizations of InPBi thin films grown by molecular beam epitaxy.

    PubMed

    Gu, Yi; Wang, Kai; Zhou, Haifei; Li, Yaoyao; Cao, Chunfang; Zhang, Liyao; Zhang, Yonggang; Gong, Qian; Wang, Shumin

    2014-01-13

    InPBi thin films have been grown on InP by gas source molecular beam epitaxy. A maximum Bi composition of 2.4% is determined by Rutherford backscattering spectrometry. X-ray diffraction measurements show good structural quality for Bi composition up to 1.4% and a partially relaxed structure for higher Bi contents. The bandgap was measured by optical absorption, and the bandgap reduction caused by the Bi incorporation was estimated to be about 56 meV/Bi%. Strong and broad photoluminescence signals were observed at room temperature for samples with xBi < 2.4%. The PL peak position varies from 1.4 to 1.9 μm, far below the measured InPBi bandgap.

  1. Improved Stability Of Amorphous Zinc Tin Oxide Thin Film Transistors Using Molecular Passivation

    SciTech Connect

    Rajachidambaram, Meena Suhanya; Pandey, Archana; Vilayur Ganapathy, Subramanian; Nachimuthu, Ponnusamy; Thevuthasan, Suntharampillai; Herman, Gregory S.

    2013-10-21

    The role of back channel surface chemistry on amorphous zinc tin oxide (ZTO) bottom gate thin film transistors (TFT) have been characterized by positive bias-stress measurements and x-ray photoelectron spectroscopy. Positive bias-stress turn-on voltage shifts for ZTO-TFTs were significantly reduced by passivation of back channel surfaces with self-assembled monolayers of n-hexylphosphonic acid (n-HPA) when compared to ZTO-TFTs with no passivation. These results indicate that adsorption of molecular species on exposed back channel of ZTO-TFTs strongly influence observed turn-on voltage shifts, as opposed to charge injection into the dielectric or trapping due to oxygen vacancies.

  2. Molecular orientation and anisotropic carrier mobility in poorly soluble polythiophene thin films

    NASA Astrophysics Data System (ADS)

    Hosokawa, Yuki; Misaki, Masahiro; Yamamoto, Satoshi; Torii, Masafumi; Ishida, Kenji; Ueda, Yasukiyo

    2012-05-01

    Oriented thin films of a poorly soluble polythiophene, poly[benzo[1,2-d:4,5-d']bisthiazole-2,6-diyl(3',4,4″,4″'-tetradodecyl[2,2':5',2″:5″,2″'-quaterthiophene]-5,5″'-diyl)], were fabricated using the friction-transfer technique. The detail of the film structure was investigated using polarized UV-vis spectroscopy, transmission electron microscopy, and grazing-incidence x-ray diffraction observations. The friction-transfer technique enables control of the anisotropic carrier transport according to the face-on and/or edge-on molecular orientations in films with one-directionally aligned polymer backbones.

  3. Preparation and rapid thermal annealing of AlN thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Liu, B.; Gao, J.; Wu, K. M.; Liu, C.

    2009-05-01

    AlN films were grown at 785 ∘C on (0001) sapphire substrates by radio-frequency assisted molecular beam epitaxy. Post-growth rapid thermal annealing (RTA) was carried out from 900 to 1200 ∘C for 10 s in flowing N 2. The morphological and structural properties of the AlN epilayers before and after the RTA were studied by atomic force microscopy, x-ray diffraction and transmission electron microscopy. It is found that the threading dislocations can be decreased to an order of magnitude by using an interlayer growth method. The surface roughness (RMS) of the AlN thin films becomes larger with the increase of annealing temperature. The full width at half maximum of AlN (0002) rocking curve reaches its minimum after the RTA at 1000 ∘C.

  4. Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode.

    PubMed

    Kim, Jeong Soo; Kim, Byung-Man; Kim, Un-Young; Shin, HyeonOh; Nam, Jung Seung; Roh, Deok-Ho; Park, Jun-Hyeok; Kwon, Tae-Hyuk

    2017-10-11

    We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 μm transparent and 2.5-μm TiO2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; VOC = 0.73 V, JSC = 15.4 mA·cm(-2), and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m(-2)), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only JSC through improved ICT but also VOC through the evenly distributed sensitizer surface coverage.

  5. Defect-free thin InAs nanowires grown using molecular beam epitaxy.

    PubMed

    Zhang, Zhi; Chen, Ping-Ping; Lu, Wei; Zou, Jin

    2016-01-21

    In this study, we designed a simple method to achieve the growth of defect-free thin InAs nanowires with a lateral dimension well below their Bohr radius on different substrate orientations. By depositing and annealing a thin layer of Au thin film on a (100) substrate surface, we have achieved the growth of defect-free uniform-sized thin InAs nanowires. This study provides a strategy to achieve the growth of pure defect-free thin nanowires.

  6. Molecular beam epitaxy deposition of Gd2O3 thin films on SrTiO3 (100) substrate

    NASA Astrophysics Data System (ADS)

    Wang, Jinxing; Hao, Jinghua; Zhang, Yangyang; Wei, Hongmei; Mu, Juyi

    2016-06-01

    Gd2O3 thin films are grown on the SrTiO3 (100) substrate by molecular beam epitaxy (MBE) deposition. X-ray diffraction (XRD) analysis, conventional transmission electron microscopy (TEM) and aberration-corrected scanning transmission electron microscopy (STEM) are performed to investigate the microstructure of deposited thin films. It is found that the as-deposited thin film possesses a very uniform thickness of ∼40 nm and is composed of single cubic phase Gd2O3 grains. STEM and TEM observations reveal that Gd2O3 thin film grows epitaxially on the SrTiO3 (100) substrate with (001)Gd2O3//(100)STO and [110]Gd2O3//[001]STO orientations. Furthermore, the Gd atoms are found to diffuse into the SrTiO3 substrate for a depth of one unit cell and substitute for the Sr atoms near the interface.

  7. Solar photothermochemical alkane reverse combustion.

    PubMed

    Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H; MacDonnell, Frederick M

    2016-03-08

    A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180-200 °C) and pressures (1-6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical-thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions.

  8. Solar photothermochemical alkane reverse combustion

    PubMed Central

    Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H.; MacDonnell, Frederick M.

    2016-01-01

    A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180–200 °C) and pressures (1–6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical–thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions. PMID:26903631

  9. Invertebrate muscles: thin and thick filament structure; molecular basis of contraction and its regulation, catch and asynchronous muscle

    PubMed Central

    Hooper, Scott L.; Hobbs, Kevin H.; Thuma, Jeffrey B.

    2008-01-01

    This is the second in a series of canonical reviews on invertebrate muscle. We cover here thin and thick filament structure, the molecular basis of force generation and its regulation, and two special properties of some invertebrate muscle, catch and asynchronous muscle. Invertebrate thin filaments resemble vertebrate thin filaments, although helix structure and tropomyosin arrangement show small differences. Invertebrate thick filaments, alternatively, are very different from vertebrate striated thick filaments and show great variation within invertebrates. Part of this diversity stems from variation in paramyosin content, which is greatly increased in very large diameter invertebrate thick filaments. Other of it arises from relatively small changes in filament backbone structure, which results in filaments with grossly similar myosin head placements (rotating crowns of heads every 14.5 nm) but large changes in detail (distances between heads in azimuthal registration varying from three to thousands of crowns). The lever arm basis of force generation is common to both vetebrates and invertebrates, and in some invertebrates this process is understood on the near atomic level. Invertebrate actomyosin is both thin (tropomyosin:troponin) and thick (primarily via direct Ca++ binding to myosin) filament regulated, and most invertebrate muscles are dually regulated. These mechanisms are well understood on the molecular level, but the behavioral utility of dual regulation is less so. The phosphorylation state of the thick filament associated giant protein, twitchin, has been recently shown to be the molecular basis of catch. The molecular basis of the stretch activation underlying asynchronous muscle activity, however, remains unresolved. PMID:18616971

  10. Invertebrate muscles: thin and thick filament structure; molecular basis of contraction and its regulation, catch and asynchronous muscle.

    PubMed

    Hooper, Scott L; Hobbs, Kevin H; Thuma, Jeffrey B

    2008-10-01

    This is the second in a series of canonical reviews on invertebrate muscle. We cover here thin and thick filament structure, the molecular basis of force generation and its regulation, and two special properties of some invertebrate muscle, catch and asynchronous muscle. Invertebrate thin filaments resemble vertebrate thin filaments, although helix structure and tropomyosin arrangement show small differences. Invertebrate thick filaments, alternatively, are very different from vertebrate striated thick filaments and show great variation within invertebrates. Part of this diversity stems from variation in paramyosin content, which is greatly increased in very large diameter invertebrate thick filaments. Other of it arises from relatively small changes in filament backbone structure, which results in filaments with grossly similar myosin head placements (rotating crowns of heads every 14.5 nm) but large changes in detail (distances between heads in azimuthal registration varying from three to thousands of crowns). The lever arm basis of force generation is common to both vertebrates and invertebrates, and in some invertebrates this process is understood on the near atomic level. Invertebrate actomyosin is both thin (tropomyosin:troponin) and thick (primarily via direct Ca(++) binding to myosin) filament regulated, and most invertebrate muscles are dually regulated. These mechanisms are well understood on the molecular level, but the behavioral utility of dual regulation is less so. The phosphorylation state of the thick filament associated giant protein, twitchin, has been recently shown to be the molecular basis of catch. The molecular basis of the stretch activation underlying asynchronous muscle activity, however, remains unresolved.

  11. Effect of nanostructures on evaporation and explosive boiling of thin liquid films: a molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Morshed, A. K. M. M.; Paul, Taitan C.; Khan, Jamil A.

    2011-11-01

    Molecular dynamics simulations have been employed to investigate the boiling phenomena of thin liquid films adsorbed on a nanostructured solid surface. The molecular system was comprised of the following: solid platinum wall, liquid argon, and argon vapor. A few layers of the liquid argon were placed on the nanoposts decorated solid surface. The nanoposts height was varied keeping the liquid film thickness constant to capture three scenarios: (i) liquid-film thickness is higher than the height of the nanoposts, (ii) liquid-film and nanoposts are of same height, and (iii) liquid-film thickness is less than the height of the nanoposts. The rest of the simulation box was filled with argon vapor. The simulation was started from its initial configuration, and once the equilibrium of the three phase system was established, the wall was suddenly heated to a higher temperature which resembles an ultrafast laser heating. Two different jump temperatures were selected: a few degrees above the boiling point to initiate normal evaporation and far above the critical point to initiate explosive boiling. Simulation results indicate nanostructures play a significant role in both cases: Argon responds very quickly for the nanostructured surface, the transition from liquid to vapor becomes more gradual, and the evaporation rate increases with the nanoposts height.

  12. Photochemical functionalization of gallium nitride thin films with molecular and biomolecular layers.

    PubMed

    Kim, Heesuk; Colavita, Paula E; Metz, Kevin M; Nichols, Beth M; Sun, Bin; Uhlrich, John; Wang, Xiaoyu; Kuech, Thomas F; Hamers, Robert J

    2006-09-12

    We demonstrate that photochemical functionalization can be used to functionalize and photopattern the surface of gallium nitride crystalline thin films with well-defined molecular and biomolecular layers. GaN(0001) surfaces exposed to a hydrogen plasma will react with organic molecules bearing an alkene (C=C) group when illuminated with 254 nm light. Using a bifunctional molecule with an alkene group at one end and a protected amine group at the other, this process can be used to link the alkene group to the surface, leaving the protected amine exposed. Using a simple contact mask, we demonstrate the ability to directly pattern the spatial distribution of these protected amine groups on the surface with a lateral resolution of <12 mum. After deprotection of the amines, single-stranded DNA oligonucleotides were linked to the surface using a bifunctional cross-linker. Measurements using fluorescently labeled complementary and noncomplementary sequences show that the DNA-modified GaN surfaces exhibit excellent selectivity, while repeated cycles of hybridization and denaturation in urea show good stability. These results demonstrate that photochemical functionalization can be used as an attractive starting point for interfacing molecular and biomolecular systems with GaN and other compound semiconductors.

  13. Long-range correlated dynamics in ultra-thin molecular glass films

    NASA Astrophysics Data System (ADS)

    Zhang, Yue; Glor, Ethan C.; Li, Mu; Liu, Tianyi; Wahid, Kareem; Zhang, William; Riggleman, Robert A.; Fakhraai, Zahra

    2016-09-01

    It has been previously shown that the free surface of molecular glasses has enhanced surface diffusion compared to the bulk. However, the degree by which the glass dynamics are affected by the free surface remains unexplored. Here, we measure enhanced dynamics in ultra-thin molecular glass films as a function of film thickness. We demonstrate that these films exhibit a sharp transition from glassy solid to liquid-like behavior when the thickness is reduced below 30 nm. This liquid-like behavior persists even at temperatures well below the glass transition temperature, Tg. The enhanced dynamics in these films can produce large scale morphological features during physical vapor deposition and lead to a dewetting instability in films held at temperatures as low as Tg - 35 K. The effective viscosity of these films are measured by monitoring the dewetting kinetics. These measurements combined with cooling-rate dependent Tg measurements show that the apparent activation barrier for rearrangement decreases sharply in films thinner than 30 nm. This sharp transition in the dynamics suggests that long-range correlated dynamics exists in these films such that the enhancement induced by the free surface can strongly affect the dynamics of the film over a length scale that is ten times larger than the size of the molecules.

  14. Metathesis of alkanes and related reactions.

    PubMed

    Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

    2010-02-16

    The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

  15. Phases, line tension and pattern formation in molecularly thin films at the air-water interface

    NASA Astrophysics Data System (ADS)

    Mandal, Pritam

    A Langmuir film, which is a molecularly thin insoluble film on a liquid substrate, is one practical realization of a quasi-two dimensional matter. The major advantages of this system for the study of phase separation and phase co-existence are (a) it allows accurate control of the components and molecular area of the film and (b) it can be studied by various methods that require very flat films. Phase separation in molecularly thin films plays an important role in a range of systems from biomembranes to biosensors. For example, phase-separated lipid nano-domains in biomembranes are thought to play crucial roles in membrane function. I use Brewster Angel Microscopy (BAM) coupled with Fluorescence Microscopy (FM) and static Light Scattering Microscopy (LSM) to image phases and patterns within Langmuir films. The three microscopic techniques --- BAM, FM and LSM --- are complimentary to each other, providing distinct sets of information. They allow direct comparison with literature results in lipid systems. I have quantitatively validated the use of detailed hydrodynamic simulations to determine line tension in monolayers. Line tension decreases as temperature rises. This decrease gives us information on the entropy associated with the line, and thus about line structure. I carefully consider the thermodynamics of line energy and entropy to make this connection. In the longer run, LSM will be exploited to give us further information about line structure. I have also extended the technique by testing it on domains within the curved surface of a bilayer vesicle. I also note that in the same way that the presence of surface-active agents, known as surfactants, affects surface energy, the addiction of line active agents alters the inter-phase line energy. Thus my results set to stage to systematically study the influence of line active agents ---'linactants' --- on the inter-phase line energy. Hierarchal self-assembled chiral patterns were observed as a function of

  16. Evolution of an alkane-inducible biosensor for increased responsiveness to short-chain alkanes.

    PubMed

    Reed, Ben; Blazeck, John; Alper, Hal

    2012-04-15

    Synthetic alkane-inducible biosensors have applications as detectors for environmental hydrocarbon contamination and as novel inducible expression systems with low-cost inducers. Here, we have assembled and evolved an alkane-responsive biosensor with a fluorescence output signal in Escherichia coli by utilizing regulatory machinery from Pseudomonas putida's alkane metabolism. Within our system, the transcriptional regulator, AlkSp, is activated by the presence of alkanes and binds to the P(alkB) promoter, stimulating transcription of a Green Fluorescent Protein reporter. Through two successive rounds of directed evolution via error prone PCR and fluorescence activated cell sorting, we isolated alkS mutants enabling up to a 5 fold increase in fluorescence output signal in response to short-chain alkanes such as hexane and pentane. Further characterization of selected mutants demonstrated altered responsiveness to a wide range of linear alkanes (pentane to dodecane). Sequence analysis highlighted the S470T mutation as a likely candidate responsible for increased effectiveness of the AlkS protein for short-chain alkanes. This work represents the first evolution of a synthetic biosensor system for alkanes.

  17. Fatty aldehyde dehydrogenase multigene family involved in the assimilation of n-alkanes in Yarrowia lipolytica.

    PubMed

    Iwama, Ryo; Kobayashi, Satoshi; Ohta, Akinori; Horiuchi, Hiroyuki; Fukuda, Ryouichi

    2014-11-28

    In the n-alkane assimilating yeast Yarrowia lipolytica, n-alkanes are oxidized to fatty acids via fatty alcohols and fatty aldehydes, after which they are utilized as carbon sources. Here, we show that four genes (HFD1-HFD4) encoding fatty aldehyde dehydrogenases (FALDHs) are involved in the metabolism of n-alkanes in Y. lipolytica. A mutant, in which all of four HFD genes are deleted (Δhfd1-4 strain), could not grow on n-alkanes of 12-18 carbons; however, the expression of one of those HFD genes restored its growth on n-alkanes. Production of Hfd2Ap or Hfd2Bp, translation products of transcript variants generated from HFD2 by the absence or presence of splicing, also supported the growth of the Δhfd1-4 strain on n-alkanes. The FALDH activity in the extract of the wild-type strain was increased when cells were incubated in the presence of n-decane, whereas this elevation in FALDH activity by n-decane was not observed in Δhfd1-4 strain extract. Substantial FALDH activities were detected in the extracts of Escherichia coli cells expressing the HFD genes. Fluorescent microscopic observation suggests that Hfd3p and Hfd2Bp are localized predominantly in the peroxisome, whereas Hfd1p and Hfd2Ap are localized in both the endoplasmic reticulum and the peroxisome. These results suggest that the HFD multigene family is responsible for the oxidation of fatty aldehydes to fatty acids in the metabolism of n-alkanes, and raise the possibility that Hfd proteins have diversified by gene multiplication and RNA splicing to efficiently assimilate or detoxify fatty aldehydes in Y. lipolytica. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Supramolecular Scaffold for Tailoring the Two-Dimensional Assembly of Functional Molecular Units into Organic Thin Films.

    PubMed

    Leung, Franco King-Chi; Ishiwari, Fumitaka; Kajitani, Takashi; Shoji, Yoshiaki; Hikima, Takaaki; Takata, Masaki; Saeki, Akinori; Seki, Shu; Yamada, Yoichi M A; Fukushima, Takanori

    2016-09-14

    Tailoring structurally anisotropic molecular assemblies while controlling their orientation on solid substrates is an important subject for advanced technologies that use organic thin films. Here we report a supramolecular scaffold based on tripodal triptycene assemblies, which enables functional molecular units to assemble into a highly oriented, multilayered two-dimensional (2D) structure on solid substrates. The triptycene building block carries an ethynyl group and three flexible side chains at the 10- and 1,8,13-positions, respectively. These bridgehead-substituted tripodal triptycenes self-assembled on solid substrates to form a well-defined "2D hexagonal + 1D lamellar" structure, which developed parallel to the surface of the substrates. Remarkably, the assembling properties of the triptycene building blocks, particularly for a derivative with tri(oxyethylene)-containing side chains, were not impaired when the alkyne terminal was functionalized with a large molecular unit such as C60, which is comparable in diameter to the triptycene framework. Consequently, thin films with a multilayered 2D assembly of the C60 unit were obtained. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements revealed that the C60 film exhibits highly anisotropic charge-transport properties. Bridgehead-substituted tripodal triptycenes may provide a versatile supramolecular scaffold for tailoring the 2D assembly of molecular units into a highly oriented thin film, and in turn for exploiting the full potential of anisotropic molecular functions.

  19. Femtosecond Dynamics Of Fluoro-Aluminum Phthalocyanine And Linear Alkane Molecules

    NASA Astrophysics Data System (ADS)

    Ho, Z. Z.; Williams, V.; Peyghambarian, N.; Hetherington, W. M.

    1988-12-01

    The dynamics of fluoro-aluminum phthalocyanine polycrystalline thin films is studied using differential transmission spectroscopy with femtosecond laser pulses. Following excitation by 620 nm pulses into the first electronic transition a very rapid energy redistribution of the excitons is directly observed within the 55 fs duration of the pump pulse. Following this process two extremely fast decay routes lead to the recovery of the ground state : exciton-exciton annihilation with an intensity dependent decay of 550 fs at power density of 1.2 GW/cm2 and exciton-phonon coupling with a 4 ps decay time. A complete interpretation of the decay mechanisms based on the Frenkel exciton terminology successfully accounts for the observed results. We have analyzed the nonlinear dynamics of a series of linear alkane molecules in pure liquid state using the time-resolved optical Kerr effect. The results show that the Kerr nonlinearity increases linearly with the number of atoms. However, for those molecules with more than eight carbons, a surprisingly large deviation from the bond additivity approximation was observed. The molecular orientational contribution to the nonlinear response is negligible for these types of molecules. A small component, with less than 8% of the total nonlinear Kerr response, is attributed to translational anisotropy and has a 450 fs lifetime. The nonlinear dynamics and the length dependence of optical Kerr nonlinearities will be discussed.

  20. Mass effect on the Soret coefficient in n-alkane mixtures

    SciTech Connect

    Alonso de Mezquia, David; Mounir Bou-Ali, M.; Madariaga, J. Antonio; Santamaría, Carlos

    2014-02-28

    We have determined the Soret coefficient of different equimolar and non equimolar n-alkane mixtures from measurements of the molecular diffusion and thermal diffusion coefficients. It is shown that equimolar mixtures behave as isotopic-like mixtures in which only the mass effect contributes to the Soret effect. In non equimolar mixtures, a small linear dependence with the molar fraction is observed. Finally, we have obtained a new correlation, which allows the determination of the Soret coefficient of n-alkane mixtures using the data of viscosity, the thermal expansion coefficient of the pure components, and the density of the equimolar mixture.

  1. Length-dependent nucleation mechanisms rule the vaporization of n-alkanes

    NASA Astrophysics Data System (ADS)

    Zahn, Dirk

    2008-12-01

    The liquid → vapor transition of a series of n-alkanes is explored by means of molecular dynamics simulations. From the comparison of the vaporization of methane, pentane and decane we elaborate the dependence of the nucleation mechanisms on the chain length. While the boiling of methane may be characterized as 'ideal' vapor bubble nucleation and growth, our studies related to pentane and decane reveal an increasing importance of liquid droplets acting as intermediates of the vaporization process. With increasing chain length the investigated n-alkanes were found to avoid the formation of large liquid-vapor interfaces by following a different nucleation mechanism.

  2. Molecular dynamics simulations of disjoining pressure effects in ultra-thin water films on a metal surface

    NASA Astrophysics Data System (ADS)

    Hu, Han; Sun, Ying

    2013-11-01

    Disjoining pressure, the excess pressure in an ultra-thin liquid film as a result of van der Waals interactions, is important in lubrication, wetting, flow boiling, and thin film evaporation. The classic theory of disjoining pressure is developed for simple monoatomic liquids. However, real world applications often utilize water, a polar liquid, for which fundamental understanding of disjoining pressure is lacking. In the present study, molecular dynamics (MD) simulations are used to gain insights into the effect of disjoining pressure in a water thin film. Our MD models were firstly validated against Derjaguin's experiments on gold-gold interactions across a water film and then verified against disjoining pressure in an argon thin film using the Lennard-Jones potential. Next, a water thin film adsorbed on a gold surface was simulated to examine the change of vapor pressure with film thickness. The results agree well with the classic theory of disjoining pressure, which implies that the polar nature of water molecules does not play an important role. Finally, the effects of disjoining pressure on thin film evaporation in nanoporous membrane and on bubble nucleation are discussed.

  3. Effects of sapphire annealing on the structural properties of AIN thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Liu, Yun; Zhang, Jia

    2010-03-01

    The effects of sapphire annealing on high-quality AlN growth by molecular beam epitaxy have been studied. AlN thin films grown on annealed sapphire (1200 °C, 12 h) were hole-free. The full width at half maximum of the (0 0 0 2) and (1 0 1bar 5)ω-rocking curves for 260 nm-thick AlN thin films grown on annealed sapphires were 200 and 900 arcsec, respectively. The substantial improvement of AlN quality is ascribed to reduction of dislocation density by sapphire annealing.

  4. Growth of Pseudomonas chloritidismutans AW-1(T) on n-alkanes with chlorate as electron acceptor.

    PubMed

    Mehboob, Farrakh; Junca, Howard; Schraa, Gosse; Stams, Alfons J M

    2009-06-01

    Microbial (per)chlorate reduction is a unique process in which molecular oxygen is formed during the dismutation of chlorite. The oxygen thus formed may be used to degrade hydrocarbons by means of oxygenases under seemingly anoxic conditions. Up to now, no bacterium has been described that grows on aliphatic hydrocarbons with chlorate. Here, we report that Pseudomonas chloritidismutans AW-1(T) grows on n-alkanes (ranging from C7 until C12) with chlorate as electron acceptor. Strain AW-1(T) also grows on the intermediates of the presumed n-alkane degradation pathway. The specific growth rates on n-decane and chlorate and n-decane and oxygen were 0.5 +/- 0.1 and 0.4 +/- 0.02 day(-1), respectively. The key enzymes chlorate reductase and chlorite dismutase were assayed and found to be present. The oxygen-dependent alkane oxidation was demonstrated in whole-cell suspensions. The strain degrades n-alkanes with oxygen and chlorate but not with nitrate, thus suggesting that the strain employs oxygenase-dependent pathways for the breakdown of n-alkanes.

  5. Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes

    NASA Astrophysics Data System (ADS)

    Ahuja, Ritu; Punji, Benudhar; Findlater, Michael; Supplee, Carolyn; Schinski, William; Brookhart, Maurice; Goldman, Alan S.

    2011-02-01

    Aromatic hydrocarbons are among the most important building blocks in the chemical industry. Benzene, toluene and xylenes are obtained from the high temperature thermolysis of alkanes. Higher alkylaromatics are generally derived from arene-olefin coupling, which gives branched products—that is, secondary alkyl arenes—with olefins higher than ethylene. The dehydrogenation of acyclic alkanes to give alkylaromatics can be achieved using heterogeneous catalysts at high temperatures, but with low yields and low selectivity. We present here the first catalytic conversion of n-alkanes to alkylaromatics using homogeneous or molecular catalysts—specifically ‘pincer’-ligated iridium complexes—and olefinic hydrogen acceptors. For example, the reaction of n-octane affords up to 86% yield of aromatic product, primarily o-xylene and secondarily ethylbenzene. In the case of n-decane and n-dodecane, the resulting alkylarenes are exclusively unbranched (that is, n-alkyl-substituted), with selectivity for the corresponding o-(n-alkyl)toluene.

  6. Organic Molecular Thin Films: Growth, Structure, and Manipulation Studied by Scanning Tunneling Microscopy

    NASA Astrophysics Data System (ADS)

    Stock, Taylor J. Z.

    Room temperature scanning tunneling microscopy (RT-STM) has been used to observe the growth modes, morphologies and crystal structures of sub-monolayer (ML) to multilayer thin films of phthalocyanines (H2Pc and CuPc), C60 fullerenes, and CuPc:C60 composites, grown on the Cu(111) surface. In addition to imaging these films, STM has been used to manipulate the various molecules via hot tunneling electron injection. At sub-ML coverage the phthalocyanines are mobile on the Cu(111) and form a diffuse 2D gas. Molecules in this mobile phase can be immobilized on the substrate through exposure to tunneling electrons at a bias voltage exceeding a threshold value. The bias threshold value and strength of the induced molecular immobilization is dependent on the particular phthalocyanine molecule/substrate combination. At approximately one ML coverage the phthalocyanine molecules become sterically confined and lie flat on the Cu(111), forming an ordered 2D lattice. As coverage is increased beyond 1ML in the Cu(111)-CuPc system, the molecule-substrate interaction diminishes in strength and the intermolecular interaction becomes dominant, causing the molecular crystal lattice parameters to evolve towards the bulk α-phase. This trend continues for the layer-by-layer growth of three complete ML, and then gives way to 3D island growth at a coverage of 4 ML. The 3D island growth mode of the pure CuPc films is dramatically suppressed by the inclusion of C60 during deposition. X-ray diffraction (XRD) and STM studies reveal that the CuPc molecular packing is altered upon C 60 inclusion, producing disordered CuPc-C60 interfaces. The ordered molecular stacking of CuPc is found to be disrupted completely when C60 concentration reaches 30 wt.%. This disorder in the CuPc:C 60 composites is explained in terms of the relative strengths of the intermolecular interactions. Furthermore, an understanding of these relative interaction strengths is exploited to grow ordered composite films

  7. Novel photoresist thin films with in-situ photoacid generator by molecular layer deposition

    NASA Astrophysics Data System (ADS)

    Zhou, Han; Bent, Stacey F.

    2013-03-01

    Current photoresist materials are facing many challenges introduced by advanced lithographies, particularly the need for excellent compositional homogeneity and ultrathin film thickness. Traditional spin-on polymeric resists have inherent limitations in achieving a high level of control over the chemical composition, leading to interest in development of alternative methods for making photoresists. In this work, we demonstrate that molecular layer deposition (MLD) is a potential method for synthesizing photoresists because it allows for precise control over organic film thickness and composition. MLD utilizes sequential, self-limiting reactions of organic precursors to build a thin film directly on a substrate surface and grows organic films by depositing only one molecular layer at each precursor dose, which in turn allows for fine-tuning of the position and concentration of various functionalities in the deposited film. In this study, we use bifunctional precursors, diamine and diisocyanate, to build polyurea resist films via urea coupling reaction between the amine and isocyanate groups. Acid-labile groups and photoacid generators (PAGs) are embedded in the backbone of the resist films with a highly uniform distribution. The resist films were successfully deposited and characterized for both materials properties and resist response. E-beam patterning was achieved with the resist films. Cross-linking behavior of the resist films was observed, likely due to the aromatic rings in the films, which is undesirable for application as a positive-tone photoresist. Moreover, the in-situ polymer-bound PAGs had low sensitivity. It is suggested that this effect may arise because the PAG is cation-bound, leading to lower efficiency of sulfur-carbon bond cleavage in the sulfonium cation, which is needed to produce the photoacid, and consequently a lower photoacid yield. Further work is needed to improve the performance of the MLD resist films.

  8. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography

    NASA Astrophysics Data System (ADS)

    Winter, Gregory T.; Wilhide, Joshua A.; LaCourse, William R.

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

  9. Molecular Hydrogen Bubbles Formation on Thin Vacuum Deposited Aluminum Layers After Proton Irradiation

    NASA Astrophysics Data System (ADS)

    Sznajder, Maciej; Geppert, Ulrich

    2014-06-01

    Metals are the most common materials used in space technology. Metal structures, while used in space, are subjected to the full spectrum of the electromagnetic radiation together with particle irradiation. Hence, they undergo degradation. Future space missions are planned to proceed in the interplanetary space, where the protons of the solar wind play a very destructive role on metallic surfaces. Unfortunately, their real degradation behavior is to a great extent unknown.Our aim is to predict materials' behavior in such a destructive environment. Therefore both, theoretical and experimental studies are performed at the German Aerospace Center (DLR) in Bremen, Germany.Here, we report the theoretical results of those studies. We examine the process of H2-bubble formation on metallic surfaces. H2-bubbles are metal caps filled with Hydrogen molecular gas resulting from recombination processes of the metal free electrons and the solar protons. A thermodynamic model of the bubble growth is presented. Our model predicts e.g. the velocity of that growth and the reflectivity of foils populated by bubbles.Formation of bubbles irreversibly changes the surface quality of irradiated metals. Thin metallic films are especially sensitive for such degradation processes. They are used e.g. in the solar sail propulsion technology. The efficiency of that technology depends on the thermoptical properties of the sail materials. Therefore, bubble formation processes have to be taken into account for the planning of long-term solar sail missions.

  10. Growth and characterization of polymer thin films grown using molecular layer deposition with heterobifunctional precursors

    NASA Astrophysics Data System (ADS)

    Gibbs, Zachary Michael Conway

    In this work, growth of thin polymer films using molecular layer deposition with heterobifunctional precursors is investigated. Several growth phenomena are observed including: loss or gain of reactive sites as a result of precursor reactivity or vapor pressure; precursor diffusion and reaction within the porous polymer film; and crosslinking. Reactions were investigated using quartz crystal microbalance, Fourier transform infrared spectroscopy, and various ex situ techniques. Reactions involving 4-azidophenylisothiocyanate and 4-aminobenzonitrile were shown to stop growth after only a few cycles which is attributed to a loss in reactive sites which was modeled by an exponentially decaying growth rate. Growth of 4-carboxyphenylisothiocyanate with TMA and water was investigated as well. Active site multiplication as a result of the trifunctionality of the TMA molecule was proposed to explain the significantly higher growth rate for TMA/CI films. TMA/H2O/CI films showed the ability to crosslink through aluminum hydroxyl condensation reactions. Upon increasing the reaction temperature, reactant diffusion was observed in the form of mass removal upon TMA exposure. This same phenomena is thought to be occurring in films grown using Diels-Alder reactions in the third section of this thesis. These films showed a strong growth rate dependence upon reactant purge time and growth temperature. FTIR seems to weakly support Diels-Alder reaction, but it appears that the primary film growth mechanism is through CVD-like diffusion and condensation reactions.

  11. Producing and imaging a thin line of He*₂ molecular tracers in helium-4.

    PubMed

    Gao, J; Marakov, A; Guo, W; Pawlowski, B T; Van Sciver, S W; Ihas, G G; McKinsey, D N; Vinen, W F

    2015-09-01

    Cryogenic helium-4 has long been recognized as a useful material in fluids research. The unique properties of helium-4 in the gaseous phase and the normal liquid phase allow for the generation of turbulent flows with exceptionally high Reynolds and Rayleigh numbers. In the superfluid phase, helium-4 exhibits two-fluid hydrodynamics and possesses fascinating properties due to its quantum nature. However, studying the flows in helium-4 has been very challenging largely due to the lack of effective visualization and velocimetry techniques. In this article, we discuss the development of novel instrumentation for flow-visualization in helium based on the generation and imaging of thin lines of metastable He*₂ tracer molecules. These molecular tracers are created via femtosecond-laser field-ionization of helium atoms and can be imaged using a laser-induced fluorescence technique. By observing the displacement and distortion of the tracer lines in helium, quantitative information about the flow field can be extracted. We present experimental results in the study of thermal counterflow in superfluid helium that validate the concept of this technique. We also discuss anticipated future developments of this powerful visualization technique.

  12. Molecular Ionization-Desorption Analysis Source (MIDAS) for Mass Spectrometry: Thin-Layer Chromatography.

    PubMed

    Winter, Gregory T; Wilhide, Joshua A; LaCourse, William R

    2016-02-01

    Molecular ionization-desorption analysis source (MIDAS), which is a desorption atmospheric pressure chemical ionization (DAPCI) type source, for mass spectrometry has been developed as a multi-functional platform for the direct sampling of surfaces. In this article, its utility for the analysis of thin-layer chromatography (TLC) plates is highlighted. Amino acids, which are difficult to visualize without staining reagents or charring, were detected and identified directly from a TLC plate. To demonstrate the full potential of MIDAS, all active ingredients from an analgesic tablet, separated on a TLC plate, were successfully detected using both positive and negative ion modes. The identity of each of the compounds was confirmed from their mass spectra and compared against standards. Post separation, the chemical signal (blue permanent marker) as reference marks placed at the origin and solvent front were used to calculate retention factor (Rf) values from the resulting ion chromatogram. The quantitative capabilities of the device were exhibited by scanning caffeine spots on a TLC plate of increasing sample amount. A linear curve based on peak are, R2 = 0.994, was generated for seven spots ranging from 50 to 1000 ng of caffeine per spot.

  13. Single orientation graphene synthesized on iridium thin films grown by molecular beam epitaxy

    SciTech Connect

    Dangwal Pandey, A. Grånäs, E.; Shayduk, R.; Noei, H.; Vonk, V.; Krausert, K.; Franz, D.; Müller, P.; Keller, T. F.; Stierle, A.

    2016-08-21

    Heteroepitaxial iridium thin films were deposited on (0001) sapphire substrates by means of molecular beam epitaxy, and subsequently, one monolayer of graphene was synthesized by chemical vapor deposition. The influence of the growth parameters on the quality of the Ir films, as well as of graphene, was investigated systematically by means of low energy electron diffraction, x-ray reflectivity, x-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Our study reveals (111) oriented iridium films with high crystalline quality and extremely low surface roughness, on which the formation of large-area epitaxial graphene is achieved. The presence of defects, like dislocations, twins, and 30° rotated domains in the iridium films is also discussed. The coverage of graphene was found to be influenced by the presence of 30° rotated domains in the Ir films. Low iridium deposition rates suppress these rotated domains and an almost complete coverage of graphene was obtained. This synthesis route yields inexpensive, air-stable, and large-area graphene with a well-defined orientation, making it accessible to a wider community of researchers for numerous experiments or applications, including those which use destructive analysis techniques or irreversible processes. Moreover, this approach can be used to tune the structural quality of graphene, allowing a systematic study of the influence of defects in various processes like intercalation below graphene.

  14. Single orientation graphene synthesized on iridium thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Dangwal Pandey, A.; Krausert, K.; Franz, D.; Grânäs, E.; Shayduk, R.; Müller, P.; Keller, T. F.; Noei, H.; Vonk, V.; Stierle, A.

    2016-08-01

    Heteroepitaxial iridium thin films were deposited on (0001) sapphire substrates by means of molecular beam epitaxy, and subsequently, one monolayer of graphene was synthesized by chemical vapor deposition. The influence of the growth parameters on the quality of the Ir films, as well as of graphene, was investigated systematically by means of low energy electron diffraction, x-ray reflectivity, x-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Our study reveals (111) oriented iridium films with high crystalline quality and extremely low surface roughness, on which the formation of large-area epitaxial graphene is achieved. The presence of defects, like dislocations, twins, and 30° rotated domains in the iridium films is also discussed. The coverage of graphene was found to be influenced by the presence of 30° rotated domains in the Ir films. Low iridium deposition rates suppress these rotated domains and an almost complete coverage of graphene was obtained. This synthesis route yields inexpensive, air-stable, and large-area graphene with a well-defined orientation, making it accessible to a wider community of researchers for numerous experiments or applications, including those which use destructive analysis techniques or irreversible processes. Moreover, this approach can be used to tune the structural quality of graphene, allowing a systematic study of the influence of defects in various processes like intercalation below graphene.

  15. Molecular dynamics study of deformation and fracture in a tantalum nano-crystalline thin film

    NASA Astrophysics Data System (ADS)

    Smith, Laura; Zimmerman, Jonathan A.; Hale, Lucas M.; Farkas, Diana

    2014-06-01

    We present results from molecular dynamics simulations of two nano-crystalline tantalum thin films that illuminate the variety of atomic-scale mechanisms of incipient plasticity. Sample 1 contains approximately 500 K atoms and 3 grains, chosen to facilitate study at 105 s-1 strain rate; sample 2 has 4.6 M atoms and 30 grains. The samples are loaded in uniaxial tension at deformation rates of 105-109 s-1, and display phenomena including emission of perfect 1/2<1 1 1>-type dislocations and the formation and migration of twin boundaries. It was found that screw dislocation emission is the first deformation mechanism activated at strain rates below 108 s-1. Deformation twins emerge as a deformation mechanism at higher strains, with twins observed to cross grain boundaries as larger strains are reached. At high strain rates atoms are displaced with the characteristic twin vector at a ratio of 3 : 1 (108 s-1) or 4 : 1 (109 s-1) to characteristic dislocation vectors. Fracture is nucleated through a nano-void growth process. Grain boundary sliding does not scale with increasing strain rate. Detailed analysis of nano-scale deformation using these tools enhances our understanding of deformation mechanisms in tantalum.

  16. Reduced graphene oxide/molecular imprinted polymer-organic thin film transistor for amino acid detection

    NASA Astrophysics Data System (ADS)

    Halim, Nurul Farhanah AB.; Musa, Nur Hazwani; Zakaria, Zulkhairi; Von Schleusingen, Mubaraq; Ahmad, Mohd Noor; Derman, Nazree; Shakaff, Ali Yeon Md.

    2017-03-01

    This works reports the electrical performance of reduced graphene oxide (RGO)/Molecular imprinted polymer (MIP)- organic thin film transistor (OTFT) for amino-acid detection, serine. These biomimetic sensors consider MIP as man-tailored biomimetic recognition sites that play an important role in signal transduction. MIP provides recognition sites compatible with serine molecules was developed by dispersing serine with methylacrylate acid (MAA) as functional monomer and Ethylene glycol dimethylacrylate (EGDMA) as cross-linker. The imprinted polymeric were mixed with reduced graphene oxide to produced sensing layer for the sensor. RGO-MIP layer was introduced between source and drain of OTFT via spin coating as a detecting layer for serine molecules. RGO was introduced into MIP, to allow a highly conductive sensing material thus enhanced selectivity and sensitivity of the sensor. By analyzing the electrical performance of the sensors, the performances of OTFT sensor enhanced with RGO/MIP interlayer and OTFT sensor with MIP interlayer when exposed to serine analyte were obtained. The results showed that there were remarkable shifts of drain current (ID) obtained from OTFT sensor with RGO/MIP interlayer after exposed to serine analyte. Moreover, the sensitivity of OTFT sensor with RGO/MIP interlayer was nearly higher than the OTFT sensor with MIP interlayer. Hence, it proved that RGO successfully enhanced the sensing performance of OTFT sensor.

  17. Conversion of alkanes to organoseleniums and organotelluriums

    DOEpatents

    Periana, Roy A.; Konnick, Michael M.; Hashiguchi, Brian G.

    2016-11-29

    The invention provides processes and materials for the efficient and costeffective functionalization of alkanes and heteroalkanes, comprising contacting the alkane or heteroalkane and a soft oxidizing electrophile comprising Se(VI) or Te(VI), in an acidic medium, optionally further comprising an aprotic medium, which can be carried out at a temperature of less than 300 C. Isolation of the alkylselenium or alkyltellurium intermediate allows the subsequent conversion to products not necessarily compatible with the initial reaction conditions, such as amines, stannanes, organosulfur compounds, acyls, halocarbons, and olefins.

  18. Improved Alkane Production in Nitrogen-Fixing and Halotolerant Cyanobacteria via Abiotic Stresses and Genetic Manipulation of Alkane Synthetic Genes.

    PubMed

    Kageyama, Hakuto; Waditee-Sirisattha, Rungaroon; Sirisattha, Sophon; Tanaka, Yoshito; Mahakhant, Aparat; Takabe, Teruhiro

    2015-07-01

    Cyanobacteria possess the unique capacity to produce alkane. In this study, effects of nitrogen deficiency and salt stress on biosynthesis of alkanes were investigated in three kinds of cyanobacteria. Intracellular alkane accumulation was increased in nitrogen-fixing cyanobacterium Anabaena sp. PCC7120, but decreased in non-diazotrophic cyanobacterium Synechococcus elongatus PCC7942 and constant in a halotolerant cyanobacterium Aphanothece halophytica under nitrogen-deficient condition. We also found that salt stress increased alkane accumulation in Anabaena sp. PCC7120 and A. halophytica. The expression levels of two alkane synthetic genes were not upregulated significantly under nitrogen deficiency or salt stress in Anabaena sp. PCC7120. The transformant Anabaena sp. PCC7120 cells with additional alkane synthetic gene set from A. halophytica increased intracellular alkane accumulation level compared to control cells. These results provide a prospect to improve bioproduction of alkanes in nitrogen-fixing halotolerant cyanobacteria via abiotic stresses and genetic engineering.

  19. In situ detection of anaerobic alkane metabolites in subsurface environments

    PubMed Central

    Agrawal, Akhil; Gieg, Lisa M.

    2013-01-01

    Alkanes comprise a substantial fraction of crude oil and refined fuels. As such, they are prevalent within deep subsurface fossil fuel deposits and in shallow subsurface environments such as aquifers that are contaminated with hydrocarbons. These environments are typically anaerobic, and host diverse microbial communities that can potentially use alkanes as substrates. Anaerobic alkane biodegradation has been reported to occur under nitrate-reducing, sulfate-reducing, and methanogenic conditions. Elucidating the pathways of anaerobic alkane metabolism has been of interest in order to understand how microbes can be used to remediate contaminated sites. Alkane activation primarily occurs by addition to fumarate, yielding alkylsuccinates, unique anaerobic metabolites that can be used to indicate in situ anaerobic alkane metabolism. These metabolites have been detected in hydrocarbon-contaminated shallow aquifers, offering strong evidence for intrinsic anaerobic bioremediation. Recently, studies have also revealed that alkylsuccinates are present in oil and coal seam production waters, indicating that anaerobic microbial communities can utilize alkanes in these deeper subsurface environments. In many crude oil reservoirs, the in situ anaerobic metabolism of hydrocarbons such as alkanes may be contributing to modern-day detrimental effects such as oilfield souring, or may lead to more beneficial technologies such as enhanced energy recovery from mature oilfields. In this review, we briefly describe the key metabolic pathways for anaerobic alkane (including n-alkanes, isoalkanes, and cyclic alkanes) metabolism and highlight several field reports wherein alkylsuccinates have provided evidence for anaerobic in situ alkane metabolism in shallow and deep subsurface environments. PMID:23761789

  20. 40 CFR 721.536 - Halogenated phenyl alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated phenyl alkane. 721.536... Substances § 721.536 Halogenated phenyl alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated phenyl alkane (PMN P-89-867)...

  1. 40 CFR 721.10163 - Chloro fluoro alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chloro fluoro alkane (generic). 721... Substances § 721.10163 Chloro fluoro alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as chloro fluoro alkane (PMN...

  2. 40 CFR 721.535 - Halogenated alkane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane (generic). 721.535... Substances § 721.535 Halogenated alkane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halogenated alkane (PMN P-01-433) is...

  3. In situ detection of anaerobic alkane metabolites in subsurface environments.

    PubMed

    Agrawal, Akhil; Gieg, Lisa M

    2013-01-01

    Alkanes comprise a substantial fraction of crude oil and refined fuels. As such, they are prevalent within deep subsurface fossil fuel deposits and in shallow subsurface environments such as aquifers that are contaminated with hydrocarbons. These environments are typically anaerobic, and host diverse microbial communities that can potentially use alkanes as substrates. Anaerobic alkane biodegradation has been reported to occur under nitrate-reducing, sulfate-reducing, and methanogenic conditions. Elucidating the pathways of anaerobic alkane metabolism has been of interest in order to understand how microbes can be used to remediate contaminated sites. Alkane activation primarily occurs by addition to fumarate, yielding alkylsuccinates, unique anaerobic metabolites that can be used to indicate in situ anaerobic alkane metabolism. These metabolites have been detected in hydrocarbon-contaminated shallow aquifers, offering strong evidence for intrinsic anaerobic bioremediation. Recently, studies have also revealed that alkylsuccinates are present in oil and coal seam production waters, indicating that anaerobic microbial communities can utilize alkanes in these deeper subsurface environments. In many crude oil reservoirs, the in situ anaerobic metabolism of hydrocarbons such as alkanes may be contributing to modern-day detrimental effects such as oilfield souring, or may lead to more beneficial technologies such as enhanced energy recovery from mature oilfields. In this review, we briefly describe the key metabolic pathways for anaerobic alkane (including n-alkanes, isoalkanes, and cyclic alkanes) metabolism and highlight several field reports wherein alkylsuccinates have provided evidence for anaerobic in situ alkane metabolism in shallow and deep subsurface environments.

  4. Molecular Packing Structure of Mesogenic Octa-Hexyl Substituted Phthalocyanine Thin Film by X-ray Diffraction Analysis.

    PubMed

    Ohmori, Masashi; Higashi, Takuya; Fujii, Akihiko; Ozaki, Masanori

    2016-04-01

    The molecular packing structure in a thin film of the liquid crystalline phthalocyanine, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2), which is a promising small-molecular material for solution-processable organic thin-film solar cells, has been investigated by X-ray diffraction (XRD) measurement. The crystal structure of C6PcH2 in the spin-coated film was determined to be a centered rectangular structure (a = 36.4 Å, b = 20.3 Å). The tilt angle of the phthalocyanine core normal vector was 34-39° from the column axis, and the shortest intermolecular distance was 3.9-4.0 A. The crystal structure determined by XRD analysis was ascertained to be consistent with that calculated by Fourier analvsis.

  5. RESEARCH ON THE ELECTRONIC AND OPTICAL PROPERTIES OF POLYMER AND OTHER ORGANIC MOLECULAR THIN FILMS

    SciTech Connect

    ALEXEI G. VITUKHNOVSKY; IGOR I. SOBELMAN - RUSSIAN ACADEMY OF SCIENCES

    1995-09-06

    Optical properties of highly ordered films of poly(p-phenylene) (PPP) on different substrates, thin films of mixtures of conjugated polymers, of fullerene and its composition with polymers, molecular J-aggregates of cyanine dyes in frozen matrices have been studied within the framework of the Agreement. Procedures of preparation of high-quality vacuum deposited PPP films on different substrates (ITO, Si, GaAs and etc.) were developed. Using time-correlated single photon counting technique and fluorescence spectroscopy the high quality of PPP films has been confirmed. Dependence of structure and optical properties on the conditions of preparation were investigated. The fluorescence lifetime and spectra of highly oriented vacuum deposited PPP films were studied as a function of the degree of polymerization. It was shown for the first time that the maximum fluorescence quantum yield is achieved for the chain length approximately equal to 35 monomer units. The selective excitation of luminescence of thin films of PPP was performed in the temperature range from 5 to 300 K. The total intensity of luminescence monotonically decreases with decreasing temperature. Conditions of preparation of highly cristallyne fullerene C{sub 60} films by the method of vacuum deposition were found. Composites of C{sub 60} with conjugated polymers PPV and polyacetylene (PA) were prepared. The results on fluorescence quenching, IR and resonant Raman spectroscopy are consistent with earlier reported ultrafast photoinduced electron transfer from PPV to C{sub 60} and show that the electron transfer is absent in the case of the PA-C{sub 60} composition. Strong quenching of PPV fluorescence was observed in the PPV-PA blends. The electron transfer from PPV to PA can be considered as one of the possible mechanisms of this quenching. The dynamics of photoexcitations in different types of J-aggregates of the carbocyanine dye was studied at different temperatures in frozen matrices. The optical

  6. Low molecular weight protein enrichment on mesoporous silica thin films for biomarker discovery.

    PubMed

    Fan, Jia; Gallagher, James W; Wu, Hung-Jen; Landry, Matthew G; Sakamoto, Jason; Ferrari, Mauro; Hu, Ye

    2012-04-17

    The identification of circulating biomarkers holds great potential for non invasive approaches in early diagnosis and prognosis, as well as for the monitoring of therapeutic efficiency.(1-3) The circulating low molecular weight proteome (LMWP) composed of small proteins shed from tissues and cells or peptide fragments derived from the proteolytic degradation of larger proteins, has been associated with the pathological condition in patients and likely reflects the state of disease.(4,5) Despite these potential clinical applications, the use of Mass Spectrometry (MS) to profile the LMWP from biological fluids has proven to be very challenging due to the large dynamic range of protein and peptide concentrations in serum.(6) Without sample pre-treatment, some of the more highly abundant proteins obscure the detection of low-abundance species in serum/plasma. Current proteomic-based approaches, such as two-dimensional polyacrylamide gel-electrophoresis (2D-PAGE) and shotgun proteomics methods are labor-intensive, low throughput and offer limited suitability for clinical applications.(7-9) Therefore, a more effective strategy is needed to isolate LMWP from blood and allow the high throughput screening of clinical samples. Here, we present a fast, efficient and reliable multi-fractionation system based on mesoporous silica chips to specifically target and enrich LMWP.(10,11) Mesoporous silica (MPS) thin films with tunable features at the nanoscale were fabricated using the triblock copolymer template pathway. Using different polymer templates and polymer concentrations in the precursor solution, various pore size distributions, pore structures, connectivity and surface properties were determined and applied for selective recovery of low mass proteins. The selective parsing of the enriched peptides into different subclasses according to their physicochemical properties will enhance the efficiency of recovery and detection of low abundance species. In combination with mass

  7. Low Molecular Weight Protein Enrichment on Mesoporous Silica Thin Films for Biomarker Discovery

    PubMed Central

    Fan, Jia; Gallagher, James W.; Wu, Hung-Jen; Landry, Matthew G.; Sakamoto, Jason; Ferrari, Mauro; Hu, Ye

    2012-01-01

    The identification of circulating biomarkers holds great potential for non invasive approaches in early diagnosis and prognosis, as well as for the monitoring of therapeutic efficiency.1-3 The circulating low molecular weight proteome (LMWP) composed of small proteins shed from tissues and cells or peptide fragments derived from the proteolytic degradation of larger proteins, has been associated with the pathological condition in patients and likely reflects the state of disease.4,5 Despite these potential clinical applications, the use of Mass Spectrometry (MS) to profile the LMWP from biological fluids has proven to be very challenging due to the large dynamic range of protein and peptide concentrations in serum.6 Without sample pre-treatment, some of the more highly abundant proteins obscure the detection of low-abundance species in serum/plasma. Current proteomic-based approaches, such as two-dimensional polyacrylamide gel-electrophoresis (2D-PAGE) and shotgun proteomics methods are labor-intensive, low throughput and offer limited suitability for clinical applications.7-9 Therefore, a more effective strategy is needed to isolate LMWP from blood and allow the high throughput screening of clinical samples. Here, we present a fast, efficient and reliable multi-fractionation system based on mesoporous silica chips to specifically target and enrich LMWP.10,11 Mesoporous silica (MPS) thin films with tunable features at the nanoscale were fabricated using the triblock copolymer template pathway. Using different polymer templates and polymer concentrations in the precursor solution, various pore size distributions, pore structures, connectivity and surface properties were determined and applied for selective recovery of low mass proteins. The selective parsing of the enriched peptides into different subclasses according to their physicochemical properties will enhance the efficiency of recovery and detection of low abundance species. In combination with mass

  8. Reprint of "Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects"

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2013-06-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  9. Stable hydrogen and carbon isotopic compositions of long-chain (C21-C33) n-alkanes and n-alkenes in insects

    NASA Astrophysics Data System (ADS)

    Chikaraishi, Yoshito; Kaneko, Masanori; Ohkouchi, Naohiko

    2012-10-01

    We report the molecular and stable isotopic (δD and δ13C) compositions of long-chain n-alkanes in common insects including the cabbage butterfly, swallowtail, wasp, hornet, grasshopper, and ladybug. Insect n-alkanes are potential candidates of the contamination of soil and sedimentary n-alkanes that are believed to be derived from vascular plant waxes. Long-chain n-alkanes (range C21-33; maximum C23-C29) are found to be abundant in the insects (31-781 μg/dry g), with a carbon preference index (CPI) of 5.1-31.5 and an average chain length (ACL) of 24.9-29.3. The isotopic compositions (mean ± 1σ, n = 33) of the n-alkanes are -195 ± 16‰ for hydrogen and -30.6 ± 2.4‰ for carbon. The insect n-alkanes are depleted in D by approximately 30-40‰ compared with wax n-alkanes from C3 (-155 ± 25‰) and C4 vascular plants (-167 ± 13‰), whereas their δ13C values fall between those of C3 (-36.2 ± 2.4‰) and C4 plants (-20.3 ± 2.4‰). Thus, the contribution of insect-derived n-alkanes to soil and sediment could potentially shift δD records of n-alkanes toward more negative values and potentially muddle the assumed original C3/C4 balance in the δ13C records of the soil and sedimentary n-alkanes. n-Alkenes are also found in three insects (swallowtail, wasp and hornet). They are more depleted in D relative to the same carbon numbered n-alkanes (δDn-alkene - δDn-alkane = -17 ± 16‰), but the δ13C values are almost identical to those of the n-alkanes (δ13Cn-alkene - δ13Cn-alkane = 0.1 ± 0.2‰). These results suggest that these n-alkenes are desaturated products of the same carbon numbered n-alkanes.

  10. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1994-01-18

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.

  11. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1994-01-01

    Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.

  12. Nitrated metalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been replaced with one or more nitro groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  13. Regulation of alkane oxidation in Pseudomonas putida.

    PubMed Central

    Grund, A; Shapiro, J; Fennewald, M; Bacha, P; Leahy, J; Markbreiter, K; Nieder, M; Toepfer, M

    1975-01-01

    We have studied the appearance of whole-cell oxidizing activity for n-alkanes and their oxidation products in strains of Pseudomonas putida carrying the OCT plasmid. Our results indicate that the OCT plasmid codes for inducible alkane-hydroxylating and primary alcohol-dehydrogenating activities and that the chromosome codes for constitutive oxidizing activities for primary alcohols, aliphatic aldehydes, and fatty acids. Mutant isolation confirms the presence of an alcohol dehydrogenase locus on the OCT plasmid and indicated the presence of multiple alcohol and aldehyde dehydrogenase loci on the P. putida chromosome. Induction tests with various compounds indicate that inducer recognition has specificity for chain length and can be affected by the degree of oxidation of the carbon chain. Some inducers are neither growth nor respiration substrates. Growth tests with and without a gratuitous inducer indicate that undecane is not a growth substrate because it does not induce alkane hydroxylase activity. Using a growth test for determining induction of the plasmid alcohol dehydrogenase it is possible to show that heptane induces this activity in hydroxylase-negative mutants. This suggests that unoxidized alkane molecules are the physiological inducers of both plasmid activities. PMID:1150626

  14. Phase sensitive molecular dynamics of self-assembly glycolipid thin films: A dielectric spectroscopy investigation

    NASA Astrophysics Data System (ADS)

    Velayutham, T. S.; Ng, B. K.; Gan, W. C.; Majid, W. H. Abd.; Hashim, R.; Zahid, N. I.; Chaiprapa, Jitrin

    2014-08-01

    Glycolipid, found commonly in membranes, is also a liquid crystal material which can self-assemble without the presence of a solvent. Here, the dielectric and conductivity properties of three synthetic glycolipid thin films in different thermotropic liquid crystal phases were investigated over a frequency and temperature range of (10-2-106 Hz) and (303-463 K), respectively. The observed relaxation processes distinguish between the different phases (smectic A, columnar/hexagonal, and bicontinuous cubic Q) and the glycolipid molecular structures. Large dielectric responses were observed in the columnar and bicontinuous cubic phases of the longer branched alkyl chain glycolipids. Glycolipids with the shortest branched alkyl chain experience the most restricted self-assembly dynamic process over the broad temperature range studied compared to the longer ones. A high frequency dielectric absorption (Process I) was observed in all samples. This is related to the dynamics of the hydrogen bond network from the sugar group. An additional low-frequency mechanism (Process II) with a large dielectric strength was observed due to the internal dynamics of the self-assembly organization. Phase sensitive domain heterogeneity in the bicontinuous cubic phase was related to the diffusion of charge carriers. The microscopic features of charge hopping were modelled using the random walk scheme, and two charge carrier hopping lengths were estimated for two glycolipid systems. For Process I, the hopping length is comparable to the hydrogen bond and is related to the dynamics of the hydrogen bond network. Additionally, that for Process II is comparable to the bilayer spacing, hence confirming that this low-frequency mechanism is associated with the internal dynamics within the phase.

  15. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes.

    PubMed

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-03-30

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes.

  16. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes

    PubMed Central

    Xia, Qineng; Chen, Zongjia; Shao, Yi; Gong, Xueqing; Wang, Haifeng; Liu, Xiaohui; Parker, Stewart F.; Han, Xue; Yang, Sihai; Wang, Yanqin

    2016-01-01

    Being the only sustainable source of organic carbon, biomass is playing an ever-increasingly important role in our energy landscape. The conversion of renewable lignocellulosic biomass into liquid fuels is particularly attractive but extremely challenging due to the inertness and complexity of lignocellulose. Here we describe the direct hydrodeoxygenation of raw woods into liquid alkanes with mass yields up to 28.1 wt% over a multifunctional Pt/NbOPO4 catalyst in cyclohexane. The superior performance of this catalyst allows simultaneous conversion of cellulose, hemicellulose and, more significantly, lignin fractions in the wood sawdust into hexane, pentane and alkylcyclohexanes, respectively. Investigation on the molecular mechanism reveals that a synergistic effect between Pt, NbOx species and acidic sites promotes this highly efficient hydrodeoxygenation of bulk lignocellulose. No chemical pretreatment of the raw woody biomass or separation is required for this one-pot process, which opens a general and energy-efficient route for converting raw lignocellulose into valuable alkanes. PMID:27025898

  17. Adsorption of alkyltrimethylammonium bromides at water/alkane interfaces: competitive adsorption of alkanes and surfactants.

    PubMed

    Fainerman, V B; Mucic, N; Pradines, V; Aksenenko, E V; Miller, R

    2013-11-12

    The adsorption of members of the homologous series of alkyl trimethylammonium bromides (C(n)TAB) is studied at water/alkane interfaces by drop profile analysis tensiometry. The results are discussed in terms of a competitive adsorption process of alkane and surfactant molecules. A thermodynamic model, derived originally for the adsorption of surfactant mixtures, is adapted such that it describes a competitive adsorption of the surfactant molecules from the aqueous phase and alkane molecules from the oil phase. This new model involves the interspecies attraction coefficient, which mutually increases the adsorption activities of the alkane and C(n)TAB. The effects of the alkyl chain length n of C(n)TABs and the influence of the number of C atoms in the alkane chain are discussed, and the physical quantities are compared to those determined at the aqueous solution/air interface. The new theoretical model for aqueous solution/oil interfaces is also compared to a theory that does not consider the adsorption of alkane. The proposed new model demonstrates good agreement with the experimental data.

  18. Homology modeling and protein engineering of alkane monooxygenase in Burkholderia thailandensis MSMB121: in silico insights.

    PubMed

    Jain, Chakresh Kumar; Gupta, Money; Prasad, Yamuna; Wadhwa, Gulshan; Sharma, Sanjeev Kumar

    2014-07-01

    The degradation of hydrocarbons plays an important role in the eco-balancing of petroleum products, pesticides and other toxic products in the environment. The degradation of hydrocarbons by microbes such as Geobacillus thermodenitrificans, Burkhulderia, Gordonia sp. and Acinetobacter sp. has been studied intensively in the literature. The present study focused on the in silico protein engineering of alkane monooxygenase (ladA)-a protein involved in the alkane degradation pathway. We demonstrated the improvement in substrate binding energy with engineered ladA in Burkholderia thailandensis MSMB121. We identified an ortholog of ladA monooxygenase found in B. thailandensis MSMB121, and showed it to be an enzyme involved in an alkane degradation pathway studied extensively in Geobacillus thermodenitrificans. Homology modeling of the three-dimensional structure of ladA was performed with a crystal structure (protein databank ID: 3B9N) as a template in MODELLER 9v11, and further validated using PROCHECK, VERIFY-3D and WHATIF tools. Specific amino acids were substituted in the region corresponding to amino acids 305-370 of ladA protein, resulting in an enhancement of binding energy in different alkane chain molecules as compared to wild protein structures in the docking experiments. The substrate binding energy with the protein was calculated using Vina (Implemented in VEGAZZ). Molecular dynamics simulations were performed to study the dynamics of different alkane chain molecules inside the binding pockets of wild and mutated ladA. Here, we hypothesize an improvement in binding energies and accessibility of substrates towards engineered ladA enzyme, which could be further facilitated for wet laboratory-based experiments for validation of the alkane degradation pathway in this organism.

  19. Surface-plasmon cross coupling in molecular fluorescence near a corrugated thin metal film

    NASA Technical Reports Server (NTRS)

    Gruhlke, R. W.; Holland, W. R.; Hall, D. G.

    1968-01-01

    Surface plasmons on opposite sides of a thin metal film can cross couple in the presence of a surface corrugation, or grating. The observation of this cross-coupling phenomenon as a radiative-decay mechanism for molecules near a corrugated thin metal film is reported.

  20. Anaerobic biodegradation of longer-chain n-alkanes coupled to methane production in oil sands tailings.

    PubMed

    Siddique, Tariq; Penner, Tara; Semple, Kathleen; Foght, Julia M

    2011-07-01

    Extraction of bitumen from mined oil sands ores produces enormous volumes of tailings that are stored in settling basins (current inventory ≥ 840 million m(3)). Our previous studies revealed that certain hydrocarbons (short-chain n-alkanes [C(6)-C(10)] and monoaromatics [toluene, o-xylene, m-xylene]) in residual naphtha entrained in the tailings are biodegraded to CH(4) by a consortium of microorganisms. Here we show that higher molecular weight n-alkanes (C(14), C(16), and C(18)) are also degraded under methanogenic conditions in oil sands tailings, albeit after a lengthy lag (~180 d) before the onset of methanogenesis. Gas chromatographic analyses showed that the longer-chain n-alkanes each added at ~400 mg L(-1) were completely degraded by the resident microorganisms within ~440 d at ~20 °C. 16S rRNA gene sequence analysis of clone libraries implied that the predominant pathway of longer-chain n-alkane metabolism in tailings is through syntrophic oxidation of n-alkanes coupled with CO(2) reduction to CH(4). These studies demonstrating methanogenic biodegradation of longer-chain n-alkanes by microbes native to oil sands tailings may be important for effective management of tailings and greenhouse gas emissions from tailings ponds.

  1. Water solubility of selected C9-C18 alkanes using a slow-stir technique: Comparison to structure - property models.

    PubMed

    Letinski, Daniel J; Parkerton, Thomas F; Redman, Aaron D; Connelly, Martin J; Peterson, Brian

    2016-05-01

    Aqueous solubility is a fundamental physical-chemical substance property that strongly influences the distribution, fate and effects of chemicals upon release into the environment. Experimental water solubility was determined for 18 selected C9-C18 normal, branched and cyclic alkanes. A slow-stir technique was applied to obviate emulsion formation, which historically has resulted in significant overestimation of the aqueous solubility of such hydrophobic liquid compounds. Sensitive GC-MS based methods coupled with contemporary sample extraction techniques were employed to enable reproducible analysis of low parts-per billion aqueous concentrations. Water solubility measurements for most of the compounds investigated, are reported for the first time expanding available data for branched and cyclic alkanes. Measured water solubilities spanned four orders of magnitude ranging from 0.3 μg/L to 250 μg/L. Good agreement was observed for selected alkanes tested in this work and reported in earlier literature demonstrating the robustness of the slow-stir water solubility technique. Comparisons of measured alkane water solubilities were also made with those predicted by commonly used quantitative structure-property relationship models (e.g. SPARC, EPIWIN, ACD/Labs). Correlations are also presented between alkane measured water solubilities and molecular size parameters (e.g. molar volume, solvent accessible molar volume) affirming a mechanistic description of empirical aqueous solubility results and prediction previously reported for a more limited set of alkanes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Molecular dynamics simulation of Cu/Au thin films under temperature gradient

    NASA Astrophysics Data System (ADS)

    Li, Qibin; Peng, Xianghe; Peng, Tiefeng; Tang, Qizhong; Zhang, Xiaomin; Huang, Cheng

    2015-12-01

    Three modulation period thin films, 1.8 nm Cu/3.6 nm Au, 2.7 nm Cu/2.7 nm Au and 3.6 nm Cu/1.8 nm Au, are obtained from deposition method and ideal modeling based on lattice constant, to examine their structures and thermophysical characteristics under temperature gradient. The coherent lattice interface is found both at deposit and ideal thin films after annealing. Also, the vacancies are observed clearly in the deposit thin films. The defect and component of thin films will influence the energy transportation in the coatings. The vacancies and lattice mismatch can enlarge the mobility of atoms and result in the failure of coating under the thermal stress. The power spectrum of atoms' movement has no apparent rule for phonon transportation in thin films. The results are helpful to reveal the micro-mechanism and provide reasonable basis for the failure of metallic coatings.

  3. Molecular organization and mixing in thin solid films of novel perylene tetracarboxylic dianhydride derivatives: Infrared and surface enhanced Raman studies

    NASA Astrophysics Data System (ADS)

    Kam, Alicia Patricia

    The present work focuses on the fabrication and spectroscopic characterization of submicron thin solid films of novel organic dyes. The synthesis, thin film fabrication, electronic and vibrational spectra of neat materials are described. The main group of organic dyes studied here are novel perylene tetracarboxylic derivatives. The fabrication of thin solid films on a variety of substrates is demonstrated and the long-range molecular organization in the films, extracted using mainly infrared techniques, is illustrated. The starting point in using vibrations as structural probes, is the vibrational assignments of the characteristic perylene tetracarboxylic fundamentals for each dye under study. The assigned vibrational spectra are employed as references to extract the molecular organization in the vacuum evaporated films using data from the complementary techniques: transmission infrared and reflection-absorption infrared spectroscopy. The understanding of the molecular organization opens the door to changing and controlling the molecular film structure with thermal annealing, and these studies are illustrated for bis(n-propylimido) perylene films. It is shown that reorientation can be induced in thin films of bisPTCD dye. The factors that may determine reorientation on thermal annealing are investigated. Surface-enhanced spectroscopic studies of metal island films coated with the dyes were carried out. The surface-enbanced vibrational spectroscopy (SEVS) used encompasses spectral data obtained from surface-enhanced Raman scattering (SERS), surface-enhanced-resonance Raman scattering- (SERRS) and surface-enhanced infrared (SEIR). The first systematic study of mixed thin solid films of PTDC materials and phthalocyanines, using vacuum co-evaporation, is presented. Mixed films of Perylene and phthalocyanine derivatives were fabricated and investigated using SERS, SERRS and SERRS imaging. It is demonstrated that SERRS global imaging is a powerful analytical tool that

  4. The long-chain alkane metabolism network of Alcanivorax dieselolei.

    PubMed

    Wang, Wanpeng; Shao, Zongze

    2014-12-12

    Alkane-degrading bacteria are ubiquitous in marine environments, but little is known about how alkane degradation is regulated. Here we investigate alkane sensing, chemotaxis, signal transduction, uptake and pathway regulation in Alcanivorax dieselolei. The outer membrane protein OmpS detects the presence of alkanes and triggers the expression of an alkane chemotaxis complex. The coupling protein CheW2 of the chemotaxis complex, which is induced only by long-chain (LC) alkanes, sends signals to trigger the expression of Cyo, which participates in modulating the expression of the negative regulator protein AlmR. This change in turn leads to the expression of ompT1 and almA, which drive the selective uptake and hydroxylation of LC alkanes, respectively. AlmA is confirmed as a hydroxylase of LC alkanes. Additional factors responsible for the metabolism of medium-chain-length alkanes are also identified, including CheW1, OmpT1 and OmpT2. These results provide new insights into alkane metabolism pathways from alkane sensing to degradation.

  5. Determination of molecular anisotropy in thin films of discotic assemblies using attenuated total reflectance UV-visible spectroscopy.

    PubMed

    Flora, Ware H; Mendes, Sergio B; Doherty, Walter J; Saavedra, S Scott; Armstrong, Neal R

    2005-01-04

    We report here an investigation of absorbance anisotropy in highly ordered, single bilayer (ca. 5.6 nm) Langmuir-Blodgett (LB) thin films of discotic liquid-crystalline phthalocyanines, using a recently introduced broad-band attenuated total reflectance (ATR) spectroscopic technique, capable of measuring dichroism in such films in the UV--visible optical region down to absorbances of ca. 0.003 absorbance units. On the basis of the ATR measurements of LB-deposited films, a thorough treatment was established to determine the ensemble average of the Cartesian components and the associated optical anisotropy of transition dipoles in the molecular film. In an effort to recover order parameters of molecular orientation, those results were interpreted with a circular dipole model, which is the expected model for the isolated molecule based on symmetry properties. We measured a strong dipole component normal to the film plane that cannot be explained in terms of a truly circular model, indicating that the molecular transition dipoles were perturbed upon aggregation. The utility of the experimental approach was further demonstrated by (a) investigating the effect of substrate modifiers (methyl- and phenyl-terminated silanes) on the ordering within the phthalocyanine film and (b) the effect of water immersion and re-annealing of the thin film on molecular ordering and optical anisotropy.

  6. The integration of plant-derived n-alkanes into sedimentary archives across the Swiss Alps; implications for paleoclimate studies.

    NASA Astrophysics Data System (ADS)

    Newberry, S. L.; Kahmen, A.

    2016-12-01

    The compound-specific δ2H values of terrestrial plant leaf wax n-alkanes are a potentially powerful paleoclimate proxy. Important biotic and abiotic processes that drive n-alkane δ2H values at the individual leaf scale have already been described. One critical aspect that requires elucidation is how processes operating at the individual leaf level become integrated at the landscape level producing the sedimentary n-alkane δ2H value chronologies we make paleoclimate reconstructions from. Our goal was to assess how the n-alkanes present in extent vegetation relate to those preserved in surface soils and lacustrine surface sediments, specifically investigating what signals are recorded and where. For this, we selected 6 self-contained alpine lake catchments in the Swiss Alps on the basis of variable altitude, vegetation coverage, species composition, size, and topography. We mapped the 5 dominant plant species and their % coverage, and sampled for leaf water δ2H, xylem water δ2H, n-alkane δ2H and n-alkane concentration. With this information we build n-alkane concentration- plant species biomass weighted- integrated spatial analyses of n-alkane δ2H values from the existing vegetation and compared these to the n-alkane δ2H values recovered from soils throughout the catchment and lake sediment. Results suggest the δ2H values of extent vegetation are highly variable with 120 ‰ δ2H variability observed for nC29 from a single site, collected at the same time. Much of this variability can be explained by broad plant functional groups, with grass species averaging -220 ‰ δ2H for nC29; while woody plant species average -150 ‰ δ2H. Significant differences in surface sedimentary n-alkane δ2H values, molecular distributions, and concentrations between the different lake catchments suggest some catchments, and some specific n-alkane chains, are more appropriate for paleoreconstructions over others. These findings have significant implications for paleoclimate

  7. Oxidation of Light Alkanes Using Photocatalytic Thin Films

    DTIC Science & Technology

    2006-01-01

    Methods 4.2.1 Catalyst Preparation and Characterization All catalysts were prepared using sol - gel methods [26]. Binary oxides were mixed...chemical vapor deposition, sputtering, sol - gel , etc.). The versatility of TiO2 has led to numerous applications discussed in thousands of literature...Catalyst Preparation The mixed-oxide catalyst material used in this study was prepared using a sol - gel method [11] in which titania and zirconia sols

  8. Distribution, activity and function of short-chain alkane degrading phylotypes in hydrothermal vent sediments

    NASA Astrophysics Data System (ADS)

    Adams, M. M.; Joye, S. B.; Hoarfrost, A.; Girguis, P. R.

    2012-12-01

    hydrocarbon species characteristic of these metalliferous sediments. These systems are also characterized by sharp physicochemical gradients that have been shown to have a pronounced effect on microbial ecology and activity. Sediments were collected from a Middle Valley field with relatively high concentrations of short-chain alkanes and incubated in anaerobic batch reactors with each individual alkane (C1, C2, C3 and C4, respectively) at a range of temperatures (25, 55 and 75 °C) to mimic environmental physico-chemical conditions in a closed system. Stable carbon isotope ratios and radiotracer incubations provide clear evidence for C2-C4 alkane oxidation in the sediments over time. Upon identifying sediments with anaerobic alkane oxidation activity, microbial communities were screened via 16S rRNA pyrosequencing, and key phylotypes were then quantified using both molecular and microscopic methods. There were shifts in overall community composition and putative alkane-oxidizing phylotypes after the incubation period with the alkane substrates. These are the first evidence to date indicating that anaerobic C2-C4 alkane oxidation occurs across a broad range of temperatures in metalliferous sediments.

  9. Design, synthesis, and characterization of ultra-thin robust films with molecular control

    NASA Astrophysics Data System (ADS)

    Kohli, Punit

    The work reported in this dissertation has demonstrated new ways to design, synthesize and characterize robust thin films with controlled molecular dimensions. The central point of this work is to provide the fundamental knowledge and understanding of layered-material assemblies to advance the field. We are especially interested in controlled layer-by-layer multilayer assemblies in which the properties of these films such as film thickness, linear and non-linear optical response, electrical and electronic behavior, and porosity can be controlled. Ultimately, these ultra-thin films may find applications in the areas of controlled released delivery systems, nonlinear optical devices, chemical interfaces and interfacial sciences, separation science, nanoelectronics, biocatalysis, and biotechnology. There are some requirements for successful films and coatings. For example, the films must be stable in their surrounding environment in which are used. Furthermore, the control of the properties of the films is also an important issue. Keeping these requirements in mind, we used maleimide-vinyl ether (MVE) copolymers to deposit coatings where we have ability to change the pendant groups on the maleimide monomers. We used MVE polymers because they form strictly alternating polymers and their structure and properties are well studied by others. They also possess excellent thermal and chemical resistant. Since changing the pendant groups on the succinimide groups gives us a great ability to control various properties makes MVE copolymers ideal candidates. We have used zirconium phosphonate (ZP) interlayer linking chemistry which is robust and allows for exquisite control over layered material assembly. Thus the use of polymer chains and ZP complexation led to quasi-2-dimensional films where we can control the properties of each layer of the films. These films are found to be robust to both chemical and thermal treatments. Although these coatings may find uses in various

  10. Thin-film growth and patterning techniques for small molecular organic compounds used in optoelectronic device applications.

    PubMed

    Biswas, Shaurjo; Shalev, Olga; Shtein, Max

    2013-01-01

    Rapid advances in research and development in organic electronics have resulted in many exciting discoveries and applications, including organic light-emitting devices for information display and illumination, solar cells, photodetectors, chemosensors, and logic. Organic optoelectronic materials are broadly classified as polymeric or small molecular. For the latter category, solvent-free deposition techniques are generally preferred to form well-defined interfaces and improve device performance. This article reviews several deposition and patterning methods for small molecular thin films and devices, including organic molecular beam deposition, vacuum thermal evaporation, organic vapor phase deposition, and organic vapor jet printing, and compares them to several other methods that have been proposed recently. We hope this review provides a compact but informative summary of the state of the art in organic device processing and addresses the various techniques' governing physical principles.

  11. Theory of phase equilibria for model mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants

    NASA Astrophysics Data System (ADS)

    Dos Ramos, María Carolina; Blas, Felipe J.

    2007-05-01

    An extension of the SAFT-VR equation of state, the so-called hetero-SAFT approach [Y. Peng, H. Zhao, and C. McCabe, Molec. Phys. 104, 571 (2006)], is used to examine the phase equilibria exhibited by a number of model binary mixtures of n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock surfactants. Despite the increasing recent interest in semifluorinated alkanes (or perfluoroalkylalkane diblock molecules), the phase behaviour of mixtures involving these molecules with n-alkanes or perfluoroalkanes is practically unknown from the experimental point of view. In this work, we use simple molecular models for n-alkanes, perfluoroalkanes and perfluoroalkylalkane diblock molecules to predict, from a molecular perspective, the phase behaviour of selected model mixtures of perfluoroalkylalkanes with n-alkanes and perfluoroalkanes. In particular, we focus our interest on the understanding of the microscopic conditions that control the liquid-liquid separation and the stabilization of these mixtures. n-Alkanes and perfluoroalkanes are modelled as tangentially bonded monomer segments with molecular parameters taken from the literature. The perfluoroalkylalkane diblock molecules are modelled as heterosegmented diblock chains, with parameters for the alkyl and perfluoroalkyl segments developed in earlier work. This simple approach, which was proposed in previous work [P. Morgado, H. Zhao, F. J. Blas, C. McCabe, L. P. N. Rebelo, and E. J. M. Filipe, J. Phys. Chem. B, 111, 2856], is now extended to describe model n-alkane (or perfluoroalkane) + perfluroalkylalkane binary mixtures. We have obtained the phase behaviour of different mixtures and studied the effect of the molecular weight of n-alkanes and perfluoroalkanes on the type of phase behaviour observed in these mixtures. We have also analysed the effect of the number of alkyl and perfluoroalkyl chemical groups in the surfactant molecule on the phase behaviour. In addition to the usual vapour-liquid phase

  12. Fidelity of fossil n-alkanes from leaf to paleosol and applications to the Paleocene-Eocene Thermal Maximum

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.; Baczynski, A. A.; Wing, S. L.

    2011-12-01

    modern plant data. These results suggest that n-alkanes extracted directly from a fossil leaf provide a true signature of an individual leaf fossil rather than a mixture from the entire plant community. Therefore, comparisons between fossil morphotypes and between fossil and related modern taxa should be robust. Furthermore, by placing fossil leaf data within the context of the chemostratigraphy of Bighorn Basin sediments across the P-E boundary, fossil leaf n-alkanes can be used to bridge the gap between our understanding of modern plant lipids and bulk lipid data from sediments across the PETM. It has been hypothesized that changes in the both the molecular distribution and carbon isotope composition of n-alkanes across the PETM were due to changes in the local plant community, which included a large proportion of deciduous gymnosperms before and after-but not during-the PETM. Analysis of fossils such as Ginkgo and angiosperms provides the opportunity to compare and distinguish the molecular and isotopic signatures of gymnosperms and angiosperms. These comparisons shed light on the dynamics of climate and ecosystem changes as they are recorded in the signatures of lipid biomarkers.

  13. Magnetic properties of low-moment ferrimagnetic Heusler Cr 2 CoGa thin films grown by molecular beam epitaxy

    DOE PAGES

    Jamer, Michelle E.; Sterbinsky, George E.; Stephen, Gregory M.; ...

    2016-10-31

    Recently, theorists have predicted many materials with a low magnetic moment and large spin-polarization for spintronic applications. These compounds are predicted to form in the inverse Heusler structure; however, many of these compounds have been found to phase segregate. In this study, ordered Cr2CoGa thin films were synthesized without phase segregation using molecular beam epitaxy. The present as-grown films exhibit a low magnetic moment from antiferromagnetically coupled Cr and Co atoms as measured with superconducting quantum interface device magnetometry and soft X-ray magnetic circular dichroism. Electrical measurements demonstrated a thermally-activated semiconductor-like resistivity component with an activation energy of 87 meV.more » These results confirm spin gapless semiconducting behavior, which makes these thin films well positioned for future devices.« less

  14. The Structure of Ice Nanoclusters and Thin-films of Water Ice: Implications for Icy Grains in Cold Molecular Clouds

    NASA Technical Reports Server (NTRS)

    Delzeit, Lance; Blake, David; Uffindell, Christine; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    The cubic to hexagonal phase transformation in water ice (I(sub c) yields I(sub h)) is used to measure the extent to which surface structure and impurities control bulk properties. In pure crystalline (I(sub c)) water ice nanoclusters and in thin-films of impure water ice, I(sub c) yields I(sub h) occurs at lower temperatures than in thin-films of pure water ice. The disordered surface of the 20 nm diameter nanoclusters promotes transformations or reactions which would otherwise be kinetically hindered. Likewise, impurities such as methanol introduce defects into the ice network, thereby allowing sluggish structural transitions to proceed. Such surface-related phenomena play an important role in promoting chemical reactions on interstellar ice grains within cold molecular clouds, where the first organic compounds are formed.

  15. Communication: Stiffening of dilute alcohol and alkane mixtures with water

    NASA Astrophysics Data System (ADS)

    Ashbaugh, Henry S.; Wesley Barnett, J.; Saltzman, Alexander; Langrehr, Mae E.; Houser, Hayden

    2016-11-01

    We probe the anomalous compressibilities of dilute mixtures of alcohols and alkane gases in water using molecular simulations. The response to increasing solute concentration depends sensitively on temperature, with the compressibility decreasing upon solute addition at low temperatures and increasing at elevated temperatures. The thermodynamic origin of stiffening is directly tied to the solute's partial compressibility, which is negative at low temperatures and rises above water's compressibility with increasing temperature. Hydration shell waters concurrently tilt towards clathrate-like structures at low temperatures that fade with heating. Kirkwood-Buff theory traces the solute's partial compressibility to changes in the solute-water association volume upon heating and incongruous packing of waters at the boundary between the more structured hydration shell and bulk water.

  16. Density functional steric analysis of linear and branched alkanes.

    PubMed

    Ess, Daniel H; Liu, Shubin; De Proft, Frank

    2010-12-16

    Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (E(s)[ρ]), an electrostatic energy term (E(e)[ρ]), and a fermionic quantum energy term (E(q)[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes.

  17. Density Functional Steric Analysis of Linear and Branched Alkanes

    SciTech Connect

    Ess, Daniel H.; Liu, Shubin; De Proft, Frank

    2010-11-18

    Branched alkane hydrocarbons are thermodynamically more stable than straight-chain linear alkanes. This thermodynamic stability is also manifest in alkane bond separation energies. To understand the physical differences between branched and linear alkanes, we have utilized a novel density functional theory (DFT) definition of steric energy based on the Weizäcker kinetic energy. Using the M06-2X functional, the total DFT energy was partitioned into a steric energy term (Ee[[ρ]), an electrostatic energy term (Ee[ρ]), and a fermionic quantum energy term (Eq[[ρ]). This analysis revealed that branched alkanes have less (destabilizing) DFT steric energy than linear alkanes. The lower steric energy of branched alkanes is mitigated by an equal and opposite quantum energy term that contains the Pauli component of the kinetic energy and exchange-correlation energy. Because the steric and quantum energy terms cancel, this leaves the electrostatic energy term that favors alkane branching. Electrostatic effects, combined with correlation energy, explains why branched alkanes are more stable than linear alkanes.

  18. The effects of external stimuli on molecular organization in organic thin films by infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Hietpas, Geoffrey David

    The study of organic thin films has been an active field of research for nearly 100 years. Two general types of organic thin film systems have received considerable attention. The first of these is the field of self-assembled monolayers (SAM's), where a reactive adsorbate is spontaneously organized at a substrate through ionic or covalent bonding. The second area is comprised of thin films of polymeric materials which may also be ordered and chemically attached like SAM's, but also includes disordered systems pinned by random attachment, and purely physisorbed films held by Van der Waals forces. The incentive for research on these systems has focused on potential improvements in applications such as biocompatable implants, lithographic masks or resists, chromatographic coatings, biosensors, and providing corrosion protection for the underlying substrate. For virtually any application, an organic thin film must remain stable such that its structure is either unaltered or reversibly changed in a manner that does not affect performance. In this thesis, the technique of infrared spectroscopy is applied to the study of thin film stability in response to external stimuli. Both polymer thin films (thickness < 0.5 mum) and SAM systems are studied, and chemical as well as mechanical methods of structural perturbation are explored. Taken together, the studies in this thesis demonstrate that organic thin films are fragile systems, often more susceptible to external perturbation than the bulk material. For any thin film system the substrate/film and film/air interfaces as well as the extremely small quantities of film material, all affect the adsorbate material in a manner not present to a significant extent in the bulk state. All of these variables are also potential sources of failure in the film. Therefore, any organic thin film system is sensitive to its immediate surroundings, and an externally applied chemical and mechanical stimuli may 'attack' this structure on several

  19. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, Harold H.; Chaar, Mohamed A.

    1988-01-01

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  20. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, H.H.; Chaar, M.A.

    1988-10-11

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  1. Self-regulated growth of LaVO{sub 3} thin films by hybrid molecular beam epitaxy

    SciTech Connect

    Zhang, Hai-Tian; Engel-Herbert, Roman; Dedon, Liv R.; Martin, Lane W.

    2015-06-08

    LaVO{sub 3} thin films were grown on SrTiO{sub 3} (001) by hybrid molecular beam epitaxy. A volatile metalorganic precursor, vanadium oxytriisopropoxide (VTIP), and elemental La were co-supplied in the presence of a molecular oxygen flux. By keeping the La flux fixed and varying the VTIP flux, stoichiometric LaVO{sub 3} films were obtained for a range of cation flux ratios, indicating the presence of a self-regulated growth window. Films grown under stoichiometric conditions were found to have the largest lattice parameter, which decreased monotonically with increasing amounts of excess La or V. Energy dispersive X-ray spectroscopy and Rutherford backscattering measurements were carried out to confirm film compositions. Stoichiometric growth of complex vanadate thin films independent of cation flux ratios expands upon the previously reported self-regulated growth of perovskite titanates using hybrid molecular beam epitaxy, thus demonstrating the general applicability of this growth approach to other complex oxide materials, where a precise control over film stoichiometry is demanded by the application.

  2. Multilayer Growth of Porphyrin-Based Polyurea Thin Film Using Solution-Based Molecular Layer Deposition Technique.

    PubMed

    Uddin, S M Nizam; Nagao, Yuki

    2017-10-12

    Controllable synthesis of organic thin film materials on solid surfaces is a challenging issue in the research field of surface science as it is affected by several physical parameters. In this work, we demonstrated a solution-based molecular layer deposition (MLD) approach to prepare porphyrin-based covalent organic molecular networks on a 3-aminopropyl trimethoxysilane (APTMS) modified substrate surface using the urea coupling reaction between 1,4-phenylene diisocyanate (1,4-PDI) and 5,10,15,20-tetrakis-(4-aminophenyl) porphyrin (H2TAPP) at room temperature (22 ± 2 ºC). Multilayer growth was investigated under different relative humidity (RH) conditions of the reaction chamber. Sequential molecular growth at low relative humidity (≤10% RH) was observed using UV-vis absorption spectroscopy and atomic force microscopy (AFM). The high-RH condition shows limited film growth. Infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) revealed the polyurea bond formation in sequential multilayer thin films, demonstrating that stepwise multilayer film growth was achieved using the urea coupling reaction.

  3. Molecular dynamics simulation of polymerlike thin films irradiated by fast ions: A comparison between FENE and Lennard-Jones potentials

    NASA Astrophysics Data System (ADS)

    Lima, N. W.; Gutierres, L. I.; Gonzalez, R. I.; Müller, S.; Thomaz, R. S.; Bringa, E. M.; Papaléo, R. M.

    2016-11-01

    In this paper, the surface effects of individual heavy ions impacting thin polymerlike films were investigated, using molecular dynamics simulations with the finite extensible nonlinear elastic (FENE) potential to describe the molecular chains. The perturbation introduced by the ions in the lattice was modeled assuming that the initial excitation energy in the ion track is converted into an effective temperature, as in a thermal spike. The track was heated only within the film thickness h , leaving a nonexcited substrate below. The effect of decreasing thickness on cratering and sputtering was evaluated. The results were compared to experimental data of thin polymer films bombarded by MeV-GeV ions and to simulations performed with the Lennard-Jones potential. While several qualitative results observed in the experiments were also seen in the simulations, irrespective of the potential used, there are important differences observed on FENE films. Crater dimensions, rim volume, and sputtering yields are substantially reduced, and a threshold thickness for molecular ejection appears in FENE simulations. This is attributed to the additional restrictions on mass transport out of the excited track region imposed by interchain interactions (entanglements) and by the low mobility of the molten phase induced by the spike.

  4. Effect of native oxide layers on copper thin-film tensile properties: A reactive molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Skarlinski, Michael D.; Quesnel, David J.

    2015-12-01

    Metal-oxide layers are likely to be present on metallic nano-structures due to either environmental exposure during use, or high temperature processing techniques such as annealing. It is well known that nano-structured metals have vastly different mechanical properties from bulk metals; however, difficulties in modeling the transition between metallic and ionic bonding have prevented the computational investigation of the effects of oxide surface layers. Newly developed charge-optimized many body [Liang et al., Mater. Sci. Eng., R 74, 255 (2013)] potentials are used to perform fully reactive molecular dynamics simulations which elucidate the effects that metal-oxide layers have on the mechanical properties of a copper thin-film. Simulated tensile tests are performed on thin-films while using different strain-rates, temperatures, and oxide thicknesses to evaluate changes in yield stress, modulus, and failure mechanisms. Findings indicate that copper-thin film mechanical properties are strongly affected by native oxide layers. The formed oxide layers have an amorphous structure with lower Cu-O bond-densities than bulk CuO, and a mixture of Cu2O and CuO charge character. It is found that oxidation will cause modifications to the strain response of the elastic modulii, producing a stiffened modulii at low temperatures (<75 K) and low strain values (<5%), and a softened modulii at higher temperatures. While under strain, structural reorganization within the oxide layers facilitates brittle yielding through nucleation of defects across the oxide/metal interface. The oxide-free copper thin-film yielding mechanism is found to be a tensile-axis reorientation and grain creation. The oxide layers change the observed yielding mechanism, allowing for the inner copper thin-film to sustain an FCC-to-BCC transition during yielding. The mechanical properties are fit to a thermodynamic model based on classical nucleation theory. The fit implies that the oxidation of the films

  5. [Composition of n-alkanes in soils of the Yellow River Estuary Wetlands and their potential as organic matter source indicators].

    PubMed

    Yao, Peng; Yin, Hong-Zhen; Yao, Qing-Zhen; Chen, Hong-Tao; Liu, Yue-Liang

    2012-10-01

    Abstract: Surface soil samples from the Yellow River Estuary Wetlands were analyzed for total organic carbon (TOC) and n-alkanes. Molecular indicators of n-alkanes were calculated and their potential as organic matter source indicators was discussed and compared among different sampling areas and times. C25-C33 n-alkanes with odd-to-even predominance were observed in most surface soils of the wetlands, suggesting the dominant contribution of terrestrial higher plants for the soil organic matter (SOM), and the ubiquitous presence of unresolved complex mixture indicated the presence of petroleum contamination. Total n-alkane concentrations in soils varied from 0.57 microg x g(-1) to 3.90 microg x g(-1), and distinct spatial and temporal differences were observed. In April 2009 (dry season), total n-alkane concentration was higher than that in June 2009 (during water-sediment regulation) with the maximum concentration observed at the core area of the wetlands, followed by the north side of the Yellow River after the last pontoon bridge, and the abandoned channel area of the Yellow River. The opposite trend of total n-alkane concentration was observed in June. The variation of total n-alkane concentration at two sampling time points were positively correlated with TOC and negatively correlated with sediment grain size, suggesting the influence of hydro-environment on the accumulation of soil organic matter. Molecular indicators of n-alkanes, such as average chain length (ACL), odd-even predominance (OEP), alkane index (AI), carbon preference index (CPI) and Terrigenous/ Aquatic Ratio (TAR) indicated that the maturity of organic matter in soils of the wetlands was low, and the dominant source of the SOM was terrestrial higher plants and mainly herbaceous plants. Compared with other indicators, TAR is better in reflecting the variation of hydro-environment.

  6. Molecular architecture of thin films fabricated via physical vapor deposition and containing a poly(azo)urethane.

    PubMed

    Aléssio, Priscila; Constantino, Carlos José Leopoldo; Job, Aldo Eloizo; Aroca, Ricardo; González, Eduardo René Pérez

    2010-05-01

    Organic thin films are widely applied as transducers in devices whose performance is determined by the optical and electrical properties of the films. In this context, the molecular architecture of the thin films plays an important role. In this work we report the fabrication and characterization of a poly(azo)urethane synthesized fixing CO2 in bis-epoxide followed by a copolymerization reaction with an azodiamine without using isocyanate. The poly(azo)urethane thin films were fabricated by physical vapor deposition (PVD) technique using vacuum thermal evaporation. The molecular architecture of the PVD films was investigated under control growth at nanometer level of thickness, as well as the surface morphology at micro and nanometer scales and the molecular organization. The thermal stability of the poly(azo)urethane molecules, which is a challenge in itself considering the thermal evaporation process, was followed by thermogravimetric analysis (TG) and also by both Fourier transform infrared absorption (FTIR) and ultraviolet-visible (UV-vis) absorption spectroscopies. The UV-vis absorption spectra showed a linear growth of the absorbance of the PVD films with the mass thickness measured by a quartz crystal balance. A random distribution of the poly(azo)urethane molecules in the PVD films was revealed by FTIR spectra. The film morphology was investigated at microscopic level combining chemical and topographical information through micro-Raman technique. At nanoscopic scale, the morphology was investigated by atomic force microscopy (AFM) for films fabricated using distinct evaporation rates. As a proof of principle (for potential applications), the film luminescence was measured over a wide range of temperature. Interestingly, an unusual increase of fluorescence intensity was observed at +150 degrees C after a monotonic decrease from -150 degrees C.

  7. Nanoporous poly(3-hexylthiophene) thin film structures from self-organization of a tunable molecular bottlebrush scaffold

    DOE PAGES

    Ahn, Suk-kyun; Carrillo, Jan-Michael Y.; Keum, Jong K.; ...

    2017-04-07

    The ability to widely tune the design of macromolecular bottlebrushes provides access to self-assembled nanostructures formed by microphase segregation in melt, thin film and solution that depart from structures adopted by simple linear copolymers. A series of random bottlebrush copolymers containing poly(3-hexylthiophene) (P3HT) and poly(D,L-lactide) (PLA) side chains grafted on a poly(norbornene) backbone were synthesized via ring-opening metathesis polymerization (ROMP) using the grafting through approach. P3HT side chains induce a physical aggregation of the bottlebrush copolymers upon solvent removal by vacuum drying, primarily driven by attractive π–π interactions; however, the amount of aggregation can be controlled by adjusting side chainmore » composition or by adding linear P3HT chains to the bottlebrush copolymers. Coarse-grained molecular dynamics simulations reveal that linear P3HT chains preferentially associate with P3HT side chains of bottlebrush copolymers, which tends to reduce the aggregation. The nanoscale morphology of microphase segregated thin films created by casting P3HT–PLA random bottlebrush copolymers is highly dependent on the composition of P3HT and PLA side chains, while domain spacing of nanostructures is mainly determined by the length of the side chains. The selective removal of PLA side chains under alkaline conditions generates nanoporous P3HT structures that can be tuned by manipulating molecular design of the bottlebrush scaffold, which is affected by molecular weight and grafting density of the side chains, and their sequence. Furthermore, the ability to exploit the unusual architecture of bottlebrushes to fabricate tunable nanoporous P3HT thin film structures may be a useful way to design templates for optoelectronic applications or membranes for separations.« less

  8. Correlation of high-pressure diffusion and viscosity coefficients for n-alkanes

    SciTech Connect

    Dymond, J.H.; Awan, M.A. )

    1989-09-01

    Self-diffusion coefficient and viscosity coefficient data for liquid n-alkanes over the whole pressure range at different temperatures are satisfactorily correlated simultaneously by a method which is just an extension of that previously used to apply the smooth hard-sphere theory of transport properties to individual transport coefficients. Universal curves are developed for reduced quantities D* and {eta}* as a function of reduced volume. A consistent set of values is derived for the characteristic volume V{sub 0} and for parameters R{sub D} and R{sub {eta}}, introduced to account for effects of nonspherical molecular shape and molecular roughness. On this basis, accurate calculation can be made of self-diffusion and viscosity coefficients for other members of the n-alkane series, for which data are at present limited.

  9. Improving stability of photoluminescence of ZnSe thin films grown by molecular beam epitaxy by incorporating Cl dopant

    SciTech Connect

    Wang, J. S.; Shen, J. L.; Chen, W. J.; Tsai, Y. H.; Wang, H. H.; Yang, C. S.; Chen, R. H.; Tsai, C. D.

    2011-01-10

    This investigation studies the effect of chlorine (Cl) dopant in ZnSe thin films that were grown by molecular beam epitaxy on their photoluminescence (PL) and the stability thereof. Free excitonic emission was observed at room-temperature in the Cl-doped sample. Photon irradiation with a wavelength of 404 nm and a power density of 9.1 W/cm{sup 2} has a much stronger effect on PL degradation than does thermal heating to a temperature of 150 deg. C. Additionally, this study shows that the generation of nonradiative centers by both photon irradiation and thermal heating can be greatly inhibited by incorporating Cl dopant.

  10. Effect of molecular coverage on the electric conductance of a multi-walled carbon nanotube thin film

    NASA Astrophysics Data System (ADS)

    Kokabu, Takuya; Inoue, Shuhei; Matsumura, Yukihiko

    2016-06-01

    We investigated the influence of water adsorption on a CNT thin film. When we assumed that the magnitude of the change in electrical resistance was correlated with the surface coverage of the adsorbed molecules, this phenomenon could be explained by two-layer adsorption. The first layer was expressed by Langmuir adsorption and that on the second layer was expressed by Fowler-Guggenheim adsorption, which was derived by Bragg-Williams approximation and involved a lateral molecular interaction. The adsorption energy estimated by this assumption was on the same order as derived by DFT calculation.

  11. Molecular fouling resistance of zwitterionic and amphiphilic initiated chemically vapor-deposited (iCVD) thin films

    SciTech Connect

    Yang, R; Goktekin, E; Wang, MH; Gleason, KK

    2014-08-08

    Biofouling is a universal problem in various applications ranging from water purification to implantable biomedical devices. Recent advances in surface modification have created a rich library of antifouling surface chemistries, many of which can be categorized into one of the two groups: hydrophilic surfaces or amphiphilic surfaces. We report the straightforward preparation of antifouling thin film coatings in both categories via initiated chemical vapor deposition. A molecular force spectroscopy-based method is demonstrated as a rapid and quantitative assessment tool for comparing the differences in antifouling characteristics. The fouling propensity of single molecules, as opposed to bulk protein solution or bacterial culture, is assessed. This method allows for the interrogation of molecular interaction without the complication resulted from protein conformational change or micro-organism group interactions. The molecular interaction follows the same trend as bacterial adhesion results obtained previously, demonstrating that molecular force probe is a valid method for the quantification and mechanistic examination of fouling. In addition, the molecular force spectroscopy-based method is able to distinguish differences in antifouling capability that is not resolvable by traditional static protein adsorption tests. To lend further insight into the intrinsic fouling resistance of zwitterionic and amphiphilic surface chemistries, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, advancing and receding water contact angles, and atomic force microscopy are used to elucidate the film properties that are relevant to their antifouling capabilities.

  12. Analysis of Molecular Orientation in Organic Semiconducting Thin Films Using Static Dynamic Nuclear Polarization Enhanced Solid-State NMR.

    PubMed

    Suzuki, Katsuaki; Kubo, Shosei; Aussenac, Fabien; Engelke, Frank; Fukushima, Tatsuya; Kaji, Hironori

    2017-10-09

    Molecular orientation in amorphous organic semiconducting thin film devices is an important issue affecting device performances. However, to date it has not been possible to analyze the "distribution" of the orientations. Although solid-state NMR (ssNMR) can provide information on the distribution of molecular orientations, the technique is limited because of the small amounts of sample in the devices and the low sensitivity of ssNMR. Here, we report the first application of dynamic nuclear polarization enhanced ssNMR (DNP-ssNMR) to orientational analysis of amorphous phenyldi(pyren-1-yl)phosphine oxide (POPy2). The 31P DNP-ssNMR spectra exhibited a sufficient signal-to-noise ratio to quantify the distribution of molecular orientations in amorphous films: the P=O axis of the vacuum-deposited and drop-cast POPy2 shows anisotropic and isotropic distribution, respectively. The different molecular orientations reflect the molecular origin of the different charge transport behaviors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. N-Alkane oxidation enzymes of a pseudomonad.

    PubMed Central

    Parekh, V R; Traxler, R W; Sobek, J M

    1977-01-01

    A nicotinamide adenine dinucleotide (NAD)-dependent n-alkane dehydrogenase and an NAD phosphate (reduced form)-dependent alkane hydroxylase have been purified from cell-free extracts of Pseudomonas sp. strain 196Aa grown anaerobically on n-alkane. The n-alkane dehydrogenase (fraction R-3), obtained as a single peak from Bio-Gel P-60, showed an overall 135-fold purification and was demonstrated by infrared spectroscopy and gas chromatography to convert n-decane to 1-decene. The alkene hydroxylase activity in the S-3 fraction, purified 167 times from diethylaminoethyl-cellulose, was shown by the same methodology to convert decene to decanol. Commercial ferredoxin has been shown to increase the alkane dehydrogenase activity. An NAD-, flavine adenine dinucleotide-, and iron-dependent alcohol dehydrogenase was demonstrated in the R-3 fraction. A mechanism for the anaerobic conversion of n-alkane to fatty acid has been proposed. PMID:869535

  14. Structure, Wettability, and Thermal Stability of Organic Thin-Films on Gold Generated from the Molecular Self-Assembly of Unsymmetrical Oligo(ethylene glycol) Spiroalkanedithiols.

    PubMed

    Chinwangso, Pawilai; Lee, Han Ju; Jamison, Andrew C; Marquez, Maria D; Park, Chul Soon; Lee, T Randall

    2017-02-28

    Organic thin-films on gold were prepared from a set of new, custom-designed bidentate alkanethiols possessing a mixture of normal alkane and methoxy-terminated tri(ethylene glycol) chains. The new unsymmetrical spiroalkanedithiol adsorbates were of the form [CH3O(CH2CH2O)3(CH2)5]-[CH3(CH2)n+1]C[CH2SH]2 where n = 3 and 14; designated EG3C7-C7 and EG3C7-C18, respectively. Their corresponding self-assembled monolayers (SAMs) on gold were characterized and compared with monothiol SAMs derived from an analogous normal alkanethiol (C18SH) and an alkanethiol terminated with an oligo(ethylene glycol) (OEG) moiety (i.e., EG3C7SH). Ellipsometric data revealed reduced film thicknesses for the double-chained dithiolate SAMs, which perhaps arose from the phase-incompatible merger of a hydrocarbon chain with an OEG moiety, contributing to disorder in the films and/or an increase in chain tilt. The comparable wettabilities of the SAMs derived from EG3C7SH and EG3C7-C7, using water as the contacting liquid, are consistent with exposure of the OEG moieties at both interfaces, whereas the lower wettability of the SAM derived from EG3C7-C18 is consistent with exposure of hydrocarbon chains at the interface. The data collected by X-ray photoelectron spectroscopy confirmed the formation of the new OEG-terminated dithiolate SAMs, and also revealed them as less densely packed monolayers due in part to the large molecular cross section of the OEG moieties and to their double-chained structure with dual surface bonds. Mixed SAMs formed from pairs of monothiols having chain compositions analogous to those of the chains of the new dithiols showed that an EG3C7SH/heptanethiol-mixed SAM and the EG3C7-C7 SAM produced almost identical characterization data, revealing the favorable film formation dynamics for adsorbate structures where the alkyl chains can assemble beneath the phase-incompatible OEG termini. For the mixed SAM formed from EG3C7SH/C18SH, the data indicate that the EG3C7SH component

  15. Characterization of the Non-uniform Reaction in Chemically Amplified Calix[4]resorcinarene Molecular Resist Thin Films

    SciTech Connect

    V Prabhu; S Kang; R Kline; D DeLongchamp; D Fischer; W Wu; S Satija; P Bonnesen; J Sha; C Ober

    2011-12-31

    The ccc stereoisomer-purified tert-butoxycarbonyloxy-protected calix[4]resorcinarene molecular resists blended with photoacid generator exhibit a non-uniform photoacid-catalyzed reaction in thin films. The surface displays a reduced reaction extent, compared with the bulk, with average surface-layer thickness 7.0 {+-} 1.8 nm determined by neutron reflectivity with deuterium-labelled tert-butoxycarbonyloxy groups. Ambient impurities (amines and organic bases) are known to quench surface reactions and contribute, but grazing-incidence X-ray diffraction shows an additional effect that the protected molecular resists are preferentially oriented at the surface, whereas the bulk of the film displays diffuse scattering representative of amorphous packing. The surface deprotection reaction and presence of photoacid were quantified by near-edge X-ray absorption fine-structure measurements.

  16. Sequence control of phase separation and dewetting in PS/PVME blend thin films by changing molecular weight of PS

    NASA Astrophysics Data System (ADS)

    Xia, Tian; Qin, Yaping; Huang, Yajiang; Huang, Ting; Xu, Jianhui; Li, Youbing

    2016-11-01

    The morphology evolution mechanism of polystyrene (PS)/poly (vinyl methyl ether) (PVME) blend thin films with different PS molecular weights (Mw) was studied. It was found that the morphology evolution was closely related to the molecular weight asymmetry between PS and PVME. In the film where Mw(PS) ≈ Mw(PVME), dewetting happened at the interface between the bottom layer and substrate after SD phase separation. While in the film where Mw(PS) >> Mw(PVME), dewetting happened at the interface between the middle PS/PVME blend layer and bottom PVME layer near the substrate prior to phase separation. The different sequences of phase separation and dewetting and different interface for dewetting occurrence were studied by regarding the competitive effects of viscoelasticity contrast between polymer components and preferential wetting between PVME and the substrate. The viscoelastic nature of the PS component played a crucial role in the sequence of phase separation and dewetting.

  17. High mobility n-type organic thin-film transistors deposited at room temperature by supersonic molecular beam deposition

    SciTech Connect

    Chiarella, F. Barra, M.; Ciccullo, F.; Cassinese, A.; Toccoli, T.; Aversa, L.; Tatti, R.; Verucchi, R.

    2014-04-07

    In this paper, we report on the fabrication of N,N′-1H,1H-perfluorobutil dicyanoperylenediimide (PDIF-CN{sub 2}) organic thin-film transistors by Supersonic Molecular Beam Deposition. The devices exhibit mobility up to 0.2 cm{sup 2}/V s even if the substrate is kept at room temperature during the organic film growth, exceeding by three orders of magnitude the electrical performance of those grown at the same temperature by conventional Organic Molecular Beam Deposition. The possibility to get high-mobility n-type transistors avoiding thermal treatments during or after the deposition could significantly extend the number of substrates suitable to the fabrication of flexible high-performance complementary circuits by using this compound.

  18. Water at a hydrophilic solid surface probed by ab-initio molecular dynamics: inhomogeneous thin layers of dense fluid

    SciTech Connect

    Cicero, G; Grossman, J; Galli, G; Catellani, A

    2005-01-28

    We present a microscopic model of the interface between liquid water and a hydrophilic, solid surface, as obtained from ab-initio molecular dynamics simulations. In particular, we focused on the (100)surface of cubic SiC, a leading candidate semiconductor for bio-compatible devices. Our results show that, in the liquid in contact with the clean substrate, molecular dissociation occurs in a manner unexpectedly similar to that observed in the gas phase. After full hydroxylation takes place, the formation of a thin ({approx}3 {angstrom})interfacial layer is observed, which has higher density than bulk water and forms stable hydrogen bonds with the substrate. The liquid does not uniformly wet the surface, rather molecules preferably bind along directions parallel to the Si dimer rows. Our calculations also predict that one dimensional confinement between two hydrophilic surfaces at about 1.3 nm distance does not affect the structural and electronic properties of the whole water sample.

  19. Characterization of the non-uniform reaction in chemically-amplified calix[4]resorcinarene molecular resist thin films

    SciTech Connect

    Prabhu, Vivek M.; Kang, Shuhui; Kline, R. Joseph; DeLongchamp, Dean M.; Fischer, Daniel A.; Wu, Wen-li; Satija, Sushil K.; Bonnesen, Peter V; Sha, Jing; Ober, Christoper K.

    2011-01-01

    The ccc stereoisomer-purified tert-butoxycarbonyloxy (t-Boc) protected calix[4]resorcinarene molecular resists blended with photoacid generator exhibit a non-uniform photoacid catalyzed reaction in thin films. The surface displays a reduced reaction extent, compared to the bulk, with average surface-layer thickness (7.0 1.8) nm determined by neutron reflectivity with deuterium-labeled t-Boc groups. Ambient impurities (amines and organic bases) are known to quench surface reactions and contribute, but grazing incidence X-ray diffraction shows an additional effect that the protected molecular resist are preferentially oriented at the surface, while the bulk of the film displayed diffuse scattering representative of amorphous packing. The surface deprotection reaction and presence of photoacid was quantified by near-edge X-ray absorption fine structure measurements.

  20. Atomic/Molecular Layer Deposition of Lithium Terephthalate Thin Films as High Rate Capability Li-Ion Battery Anodes.

    PubMed

    Nisula, Mikko; Karppinen, Maarit

    2016-02-10

    We demonstrate the fabrication of high-quality electrochemically active organic lithium electrode thin films by the currently strongly emerging combined atomic/molecular layer deposition (ALD/MLD) technique using lithium terephthalate, a recently found anode material for lithium-ion battery (LIB), as a proof-of-the-concept material. Our deposition process for Li-terephthalate is shown to well comply with the basic principles of ALD-type growth including the sequential self-saturated surface reactions, a necessity when aiming at micro-LIB devices with three-dimensional architectures. The as-deposited films are found crystalline across the deposition temperature range of 200-280 °C, which is a trait highly desired for an electrode material but rather unusual for hybrid inorganic-organic thin films. Excellent rate capability is ascertained for the Li-terephthalate films with no conductive additives required. The electrode performance can be further enhanced by depositing a thin protective LiPON solid-state electrolyte layer on top of Li-terephthalate; this yields highly stable structures with capacity retention of over 97% after 200 charge/discharge cycles at 3.2 C.

  1. Assessment of Gaussian-3 and Density Functional Theories for Enthalpies of Formation of C1-C16 Alkanes

    SciTech Connect

    Redfern, Paul C.; Zapol, Peter; Curtiss, Larry A.

    2000-06-22

    We have examined the performance of Gaussian-3 (G3) theory and six related methods for the calculation of enthalpies of formation of n-alkanes of up to 16 carbons and isoalkanes of up to 10 carbons. We have also examined the accuracy of the B3LYP density functional theory for the n-alkanes. The G3 enthalpies of formation of the n-alkanes have errors of less than 2 kcal/mol compared to experiment. There is a small accumulation of error (0.04 kcal/mol per bond) that increases the deviation with chain length. The effects of conformational averaging on the G3 enthalpies of the n-alkanes are estimated to be small, but are in the direction to reduce the error. The branched alkanes have errors of less than 1 kcal/mol. Four of the variations of G3 theory [G3(MP3), G3(MP2), G3(MP2)//B3LYP, and G3(MP2,CCSD)//B3LYP] also have errors similar to or smaller than G3 theory while two of the variations [G3(CCSD) and G3(MP2,CCSD)] have maximum errors for the n-alkanes of about 2.5 kcal/mol. The B3LYP method does very poorly for the calculation of enthalpies of formation of the larger n-alkanes with an error of over 30 kcal/mol for hexadecane. This suggests that B3LYP has a significant problem with accumulation of errors as the molecular size increases. Several schemes for correcting systematic errors in B3LYP calculations for large molecules are also explored.

  2. A Coarse-Grained Model Based on Morse Potential for Water and n-Alkanes.

    PubMed

    Chiu, See-Wing; Scott, H Larry; Jakobsson, Eric

    2010-03-09

    In order to extend the time and distance scales of molecular dynamics simulations, it is essential to create accurate coarse-grained force fields, in which each particle contains several atoms. Coarse-grained force fields that utilize the Lennard-Jones potential form for pairwise nonbonded interactions have been shown to suffer from serious inaccuracy, notably with respect to describing the behavior of water. In this paper, we describe a coarse-grained force field for water, in which each particle contains four water molecules, based on the Morse potential form. By molecular dynamics simulations, we show that our force field closely replicates important water properties. We also describe a Morse potential force field for alkanes and a simulation method for alkanes in which individual particles may have variable size, providing flexibility in constructing complex molecules comprised partly or solely of alkane groups. We find that, in addition to being more accurate, the Morse potential also provides the ability to take larger time steps than the Lennard-Jones, because the short distance repulsion potential profile is less steep. We suggest that the Morse potential form should be considered as an alternative for the Lennard-Jones form for coarse-grained molecular dynamics simulations.

  3. Regioselective functionalization of alkanes by sequential dehydrogenation-hydrozirconation.

    PubMed

    Kuninobu, Yoichiro; Ureshino, Tomonari; Yamamoto, Shun-ichi; Takai, Kazuhiko

    2010-08-07

    We have succeeded in formal regioselective functionalization of alkanes by iridium-catalyzed dehydrogenation, hydrozirconation of the resulting alkenes, and electrophilic reaction of the generated alkylzirconium intermediate.

  4. Expanding the alkane oxygenase toolbox: new enzymes and applications.

    PubMed

    van Beilen, Jan B; Funhoff, Enrico G

    2005-06-01

    As highly reduced hydrocarbons are abundant in the environment, enzymes that catalyze the terminal or subterminal oxygenation of alkanes are relatively easy to find. A number of these enzymes have been biochemically characterized in detail, because the potential of alkane hydroxylases to catalyze high added-value reactions is widely recognized. Nevertheless, the industrial application of these enzymes is restricted owing to the complex biochemistry, challenging process requirements, and the limited number of cloned and expressed enzymes. Rational and evolutionary engineering approaches have started to yield more robust and versatile enzyme systems, broadening the alkane oxygenase portfolio. In addition, metagenomic approaches provide access to many novel alkane oxygenase sequences.

  5. Diverse Bacterial Groups Contribute to the Alkane Degradation Potential of Chronically Polluted Subantarctic Coastal Sediments

    SciTech Connect

    Guibert, Lilian M.; Loviso, Claudia L.; Borglin, Sharon; Jansson, Janet K.; Dionisi, Hebe M.; Lozada, Mariana

    2015-11-07

    We aimed to gain insight into the alkane degradation potential of microbial communities from chronically polluted sediments of a subantarctic coastal environment using a combination of metagenomic approaches. A total of 6178 sequences annotated as alkane-1-monooxygenases (EC 1.14.15.3) were retrieved from a shotgun metagenomic dataset that included two sites analyzed in triplicate. The majority of the sequences binned with AlkB described in Bacteroidetes (32 ± 13 %) or Proteobacteria (29 ± 7 %), although a large proportion remained unclassified at the phylum level. Operational taxonomic unit (OTU)-based analyses showed small differences in AlkB distribution among samples that could be correlated with alkane concentrations, as well as with site-specific variations in pH and salinity. A number of low-abundance OTUs, mostly affiliated with Actinobacterial sequences, were found to be only present in the most contaminated samples. On the other hand, the molecular screening of a large-insert metagenomic library of intertidal sediments from one of the sampling sites identified two genomic fragments containing novel alkB gene sequences, as well as various contiguous genes related to lipid metabolism. Both genomic fragments were affiliated with the phylum Planctomycetes, and one could be further assigned to the genus Rhodopirellula due to the presence of a partial sequence of the 23S ribosomal RNA (rRNA) gene. This work highlights the diversity of bacterial groups contributing to the alkane degradation potential and reveals patterns of functional diversity in relation with environmental stressors in a chronically polluted, high-latitude coastal environment. In addition, alkane biodegradation genes are described for the first time in members of Planctomycetes.

  6. Diverse Bacterial Groups Contribute to the Alkane Degradation Potential of Chronically Polluted Subantarctic Coastal Sediments.

    PubMed

    Guibert, Lilian M; Loviso, Claudia L; Borglin, Sharon; Jansson, Janet K; Dionisi, Hebe M; Lozada, Mariana

    2016-01-01

    We aimed to gain insight into the alkane degradation potential of microbial communities from chronically polluted sediments of a subantarctic coastal environment using a combination of metagenomic approaches. A total of 6178 sequences annotated as alkane-1-monooxygenases (EC 1.14.15.3) were retrieved from a shotgun metagenomic dataset that included two sites analyzed in triplicate. The majority of the sequences binned with AlkB described in Bacteroidetes (32 ± 13 %) or Proteobacteria (29 ± 7 %), although a large proportion remained unclassified at the phylum level. Operational taxonomic unit (OTU)-based analyses showed small differences in AlkB distribution among samples that could be correlated with alkane concentrations, as well as with site-specific variations in pH and salinity. A number of low-abundance OTUs, mostly affiliated with Actinobacterial sequences, were found to be only present in the most contaminated samples. On the other hand, the molecular screening of a large-insert metagenomic library of intertidal sediments from one of the sampling sites identified two genomic fragments containing novel alkB gene sequences, as well as various contiguous genes related to lipid metabolism. Both genomic fragments were affiliated with the phylum Planctomycetes, and one could be further assigned to the genus Rhodopirellula due to the presence of a partial sequence of the 23S ribosomal RNA (rRNA) gene. This work highlights the diversity of bacterial groups contributing to the alkane degradation potential and reveals patterns of functional diversity in relation with environmental stressors in a chronically polluted, high-latitude coastal environment. In addition, alkane biodegradation genes are described for the first time in members of Planctomycetes.

  7. Electric Field Tuning Molecular Packing and Electrical Properties of Solution-Shearing Coated Organic Semiconducting Thin Films

    DOE PAGES

    Molina-Lopez, Francisco; Yan, Hongping; Gu, Xiaodan; ...

    2017-01-17

    Recent improvements in solution-coated organic semiconductors (OSCs) evidence their high potential for cost-efficient organic electronics and sensors. Molecular packing structure determines the charge transport property of molecular solids. However, it remains challenging to control the molecular packing structure for a given OSC. Here, the application of alternating electric fields is reported to fine-tune the crystal packing of OSC solution-shearing coated at ambient conditions. First, a theoretical model based on dielectrophoresis is developed to guide the selection of the optimal conditions (frequency and amplitude) of the electric field applied through the solution-shearing blade during coating of OSC thin films. Next, electricmore » field-induced polymorphism is demonstrated for OSCs with both herringbone and 2D brick-wall packing motifs in 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene and 6,13-bis(triisopropylsilylethynyl) pentacene, respectively. Favorable molecular packing can be accessible in some cases, resulting in higher charge carrier mobilities. In conclusion, this work provides a new approach to tune the properties of solution-coated OSCs in functional devices for high-performance printed electronics.« less

  8. Maximizing the dielectric response of molecular thin films via quantum chemical design.

    PubMed

    Heitzer, Henry M; Marks, Tobin J; Ratner, Mark A

    2014-12-23

    Developing high-capacitance organic gate dielectrics is critical for advances in electronic circuitry based on unconventional semiconductors. While high-dielectric constant molecular substances are known, the mechanism of dielectric response and the fundamental chemical design principles are not well understood. Using a plane-wave density functional theory formalism, we show that it is possible to map the atomic-scale dielectric profiles of molecule-based materials while capturing important bulk characteristics. For molecular films, this approach reveals how basic materials properties such as surface coverage density, molecular tilt angle, and π-system planarity can dramatically influence dielectric response. Additionally, relatively modest molecular backbone and substituent variations can be employed to substantially enhance film dielectric response. For dense surface coverages and proper molecular alignment, conjugated hydrocarbon chains can achieve dielectric constants of >8.0, more than 3 times that of analogous saturated chains, ∼2.5. However, this conjugation-related dielectric enhancement depends on proper molecular orientation and planarization, with enhancements up to 60% for proper molecular alignment with the applied field and an additional 30% for conformations such as coplanarity in extended π-systems. Conjugation length is not the only determinant of dielectric response, and appended polarizable high-Z substituents can increase molecular film response more than 2-fold, affording estimated capacitances of >9.0 μF/cm2. However, in large π-systems, polar substituent effects are substantially attenuated.

  9. Comprehensive chemical kinetic modeling of the oxidation of C8 and larger n-alkanes and 2-methylalkanes

    SciTech Connect

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M; Togbe, C; Dagaut, P; Wang, H; Oehlschlaeger, M; NIemann, U; Seshadri, K; Veloo, P S; Ji, C; Egolfopoulos, F; Lu, T

    2011-03-16

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed and reduced chemical kinetic mechanism for singly methylated iso-alkanes (i.e., 2-methylalkanes) ranging from C{sub 8} to C{sub 20}. The mechanism also includes an updated version of our previously published C{sub 8} to C{sub 16} n-alkanes model. The complete detailed mechanism contains approximately 7,200 species 31,400 reactions. The proposed model is validated against new experimental data from a variety of fundamental combustion devices including premixed and nonpremixed flames, perfectly stirred reactors and shock tubes. This new model is used to show how the presence of a methyl branch affects important combustion properties such as laminar flame propagation, ignition, and species formation.

  10. Anaerobic oxidation of long-chain n-alkanes by the hyperthermophilic sulfate-reducing archaeon, Archaeoglobus fulgidus.

    PubMed

    Khelifi, Nadia; Amin Ali, Oulfat; Roche, Philippe; Grossi, Vincent; Brochier-Armanet, Céline; Valette, Odile; Ollivier, Bernard; Dolla, Alain; Hirschler-Réa, Agnès

    2014-11-01

    The thermophilic sulfate-reducing archaeon Archaeoglobus fulgidus strain VC-16 (DSM 4304), which is known to oxidize fatty acids and n-alkenes, was shown to oxidize saturated hydrocarbons (n-alkanes in the range C10-C21) with thiosulfate or sulfate as a terminal electron acceptor. The amount of n-hexadecane degradation observed was in stoichiometric agreement with the theoretically expected amount of thiosulfate reduction. One of the pathways used by anaerobic microorganisms to activate alkanes is addition to fumarate that involves alkylsuccinate synthase as a key enzyme. A search for genes encoding homologous enzymes in A. fulgidus identified the pflD gene (locus-tag AF1449) that was previously annotated as a pyruvate formate lyase. A phylogenetic analysis revealed that this gene is of bacterial origin and was likely acquired by A. fulgidus from a bacterial donor through a horizontal gene transfer. Based on three-dimensional modeling of the corresponding protein and molecular dynamic simulations, we hypothesize an alkylsuccinate synthase activity for this gene product. The pflD gene expression was upregulated during the growth of A. fulgidus on an n-alkane (C16) compared with growth on a fatty acid. Our results suggest that anaerobic alkane degradation in A. fulgidus may involve the gene pflD in alkane activation through addition to fumarate. These findings highlight the possible importance of hydrocarbon oxidation at high temperatures by A. fulgidus in hydrothermal vents and the deep biosphere.

  11. Anaerobic oxidation of long-chain n-alkanes by the hyperthermophilic sulfate-reducing archaeon, Archaeoglobus fulgidus

    PubMed Central

    Khelifi, Nadia; Amin Ali, Oulfat; Roche, Philippe; Grossi, Vincent; Brochier-Armanet, Céline; Valette, Odile; Ollivier, Bernard; Dolla, Alain; Hirschler-Réa, Agnès

    2014-01-01

    The thermophilic sulfate-reducing archaeon Archaeoglobus fulgidus strain VC-16 (DSM 4304), which is known to oxidize fatty acids and n-alkenes, was shown to oxidize saturated hydrocarbons (n-alkanes in the range C10–C21) with thiosulfate or sulfate as a terminal electron acceptor. The amount of n-hexadecane degradation observed was in stoichiometric agreement with the theoretically expected amount of thiosulfate reduction. One of the pathways used by anaerobic microorganisms to activate alkanes is addition to fumarate that involves alkylsuccinate synthase as a key enzyme. A search for genes encoding homologous enzymes in A. fulgidus identified the pflD gene (locus-tag AF1449) that was previously annotated as a pyruvate formate lyase. A phylogenetic analysis revealed that this gene is of bacterial origin and was likely acquired by A. fulgidus from a bacterial donor through a horizontal gene transfer. Based on three-dimensional modeling of the corresponding protein and molecular dynamic simulations, we hypothesize an alkylsuccinate synthase activity for this gene product. The pflD gene expression was upregulated during the growth of A. fulgidus on an n-alkane (C16) compared with growth on a fatty acid. Our results suggest that anaerobic alkane degradation in A. fulgidus may involve the gene pflD in alkane activation through addition to fumarate. These findings highlight the possible importance of hydrocarbon oxidation at high temperatures by A. fulgidus in hydrothermal vents and the deep biosphere. PMID:24763368

  12. Synthesis of Hexagonal FeMnP Thin Films from a Single-Source Molecular Precursor.

    PubMed

    Leitner, Andrew P; Schipper, Desmond E; Chen, Jing-Han; Colson, Adam C; Rusakova, Irene; Kumar Rai, Binod; Morosan, Emilia; Whitmire, Kenton Herbert

    2017-03-08

    The first heterobimetallic phosphide thin film containing iron, manganese, and phosphorus derived from the single-source precursor FeMn(CO)8(μ-PH2) has been prepared using a home-built metal-organic chemical vapor deposition apparatus. The thin film contains the same ratio of iron, manganese, and phosphorus as the initial precursor. The film becomes oxidized when deposited on a quartz substrate whereas the film deposited on an alumina substrate provides a more homogeneous product. Powder X-ray diffraction confirms the formation of metastable, hexagonal FeMnP phase that was previously only observed at temperatures above 1200 ºC. Selected area electron diffraction on single crystals isolated from the films were indexed to the hexagonal phase. The effective moment of the films (µeff = 3.68µB) matches the previously reported theoretical value for the metastable hexagonal phase whereas the more stable orthorhombic phase is known to be antiferromagnetic. These results not only demonstrate the successful synthesis of a bimetallic, ternary thin film from a single-source precursor, but also the first low temperature approach to the hexagonal phase of FeMnP.

  13. Comment on “Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions” [J. Chem. Phys. 141, 064905 (2014)

    SciTech Connect

    McDaniel, Jesse G.; Yethiraj, Arun

    2016-04-06

    The manuscript by Ballal et al.(Ref 1) presents an interesting study demonstrating the inability of popular force fields with standard combination rules to accurately describe water/alkane interactions. The authors find that the Lorentz-Berthelot combination rules on the SPC/E water and TraPPE alkane potentials give a cross interaction that fails to predict the (low-water content) water solubility in various alkanes. Realizing that both explicit polarization as well as the static octupole moment of methane are missing in these potentials, the authors examine the effect of these terms, but are still unable to resolve the discrepancy. They conclude with the statement that “the research community lacks a complete picture of water-alkane interactions at the molecular level.

  14. Comment on “Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions” [J. Chem. Phys. 141, 064905 (2014)

    SciTech Connect

    McDaniel, Jesse G.; Yethiraj, Arun

    2016-04-06

    The manuscript by Ballal et al.(Ref 1) presents an interesting study demonstrating the inability of popular force fields with standard combination rules to accurately describe water/alkane interactions. The authors find that the Lorentz-Berthelot combination rules on the SPC/E water and TraPPE alkane potentials give a cross interaction that fails to predict the (low-water content) water solubility in various alkanes. Realizing that both explicit polarization as well as the static octupole moment of methane are missing in these potentials, the authors examine the effect of these terms, but are still unable to resolve the discrepancy. They conclude with the statement that “the research community lacks a complete picture of water-alkane interactions at the molecular level.

  15. Comment on “Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions” [J. Chem. Phys. 141, 064905 (2014)

    DOE PAGES

    McDaniel, Jesse G.; Yethiraj, Arun

    2016-04-06

    The manuscript by Ballal et al.(Ref 1) presents an interesting study demonstrating the inability of popular force fields with standard combination rules to accurately describe water/alkane interactions. The authors find that the Lorentz-Berthelot combination rules on the SPC/E water and TraPPE alkane potentials give a cross interaction that fails to predict the (low-water content) water solubility in various alkanes. Realizing that both explicit polarization as well as the static octupole moment of methane are missing in these potentials, the authors examine the effect of these terms, but are still unable to resolve the discrepancy. They conclude with the statement thatmore » “the research community lacks a complete picture of water-alkane interactions at the molecular level.« less

  16. Source apportionment of polycyclic aromatic hydrocarbons and n-alkanes in the soil-sediment profile of Jianghan Oil Field, China.

    PubMed

    Ma, Jie; Liu, Hui; Tong, Lei; Wang, Yan; Liu, Shan; Zhao, Lei; Hou, Liangjun

    2017-05-01

    Surface soil in oil exploration area always contains high contents of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. To investigate the migration possibility of PAHs and n-alkanes from surface through aquitard and aquiclude to aquifer, the distribution, together with the source apportionment using several indicators, such as composition pattern, fluoranthene/(fluoranthene+pyrene) (Flt/(Flt+Pyr)), anthracene/(anthracene+phenanthrene) (Ant/(Ant+PA)), and the carbon preference index (CPI) of n-alkanes, in a 30-m-deep soil-sediment profile were studied. Results showed that there were considerable PAHs and n-alkanes not only in surface soil but also in aquitard, aquiclude, and aquifer sediments. The PAHs and n-alkanes in surface soil strongly suggested petroleum pollution. The high molecular weight PAHs and the n-alkanes with both long and short chains could not migrate into deep sediments as their sources in surface soil and deep sediment were different. Whereas the aquitard and aquiclude had significant input of low molecular weight PAHs (LMWPAHs) from petroleum sources, the LMWPAHs in confined aquifer suggested pyrogenic sources. Therefore, LMWPAHs migrated from surface to aquitard and aquiclude, but did not cause aquifer pollution in Jianghan Oil Field. However, the high mobility of LMWPAHs from surface to aquitard and aquiclude suggested that the long-term risk of groundwater pollution from oil exploration should be concerned.

  17. Prediction of static contact angles on the basis of molecular forces and adsorption data

    NASA Astrophysics Data System (ADS)

    Diaz, M. Elena; Savage, Michael D.; Cerro, Ramon L.

    2016-08-01

    At a three-phase contact line, a liquid bulk phase is in contact with and coexists with a very thin layer of adsorbed molecules. This adsorbed film in the immediate vicinity of a liquid wedge modifies the balance of forces between the liquid and solid phases such that, when included in the balance of forces, a quantitative relationship emerges between the adsorbed film thickness and the static contact angle. This relationship permits the prediction of static contact angles from molecular forces and equilibrium adsorption data by means of quantities that are physically meaningful and measurable. For n-alkanes on polytetrafluoroethylene, for which there are experimental data available on adsorption and contact angles, our computations show remarkable agreement with the data. The results obtained are an improvement on previously published calculations—particularly for alkanes with a low number of carbon atoms, for which adsorption is significant.

  18. Prediction of static contact angles on the basis of molecular forces and adsorption data.

    PubMed

    Diaz, M Elena; Savage, Michael D; Cerro, Ramon L

    2016-08-01

    At a three-phase contact line, a liquid bulk phase is in contact with and coexists with a very thin layer of adsorbed molecules. This adsorbed film in the immediate vicinity of a liquid wedge modifies the balance of forces between the liquid and solid phases such that, when included in the balance of forces, a quantitative relationship emerges between the adsorbed film thickness and the static contact angle. This relationship permits the prediction of static contact angles from molecular forces and equilibrium adsorption data by means of quantities that are physically meaningful and measurable. For n-alkanes on polytetrafluoroethylene, for which there are experimental data available on adsorption and contact angles, our computations show remarkable agreement with the data. The results obtained are an improvement on previously published calculations-particularly for alkanes with a low number of carbon atoms, for which adsorption is significant.

  19. Effect of native oxide layers on copper thin-film tensile properties: A reactive molecular dynamics study

    SciTech Connect

    Skarlinski, Michael D.; Quesnel, David J.

    2015-12-21

    Metal-oxide layers are likely to be present on metallic nano-structures due to either environmental exposure during use, or high temperature processing techniques such as annealing. It is well known that nano-structured metals have vastly different mechanical properties from bulk metals; however, difficulties in modeling the transition between metallic and ionic bonding have prevented the computational investigation of the effects of oxide surface layers. Newly developed charge-optimized many body [Liang et al., Mater. Sci. Eng., R 74, 255 (2013)] potentials are used to perform fully reactive molecular dynamics simulations which elucidate the effects that metal-oxide layers have on the mechanical properties of a copper thin-film. Simulated tensile tests are performed on thin-films while using different strain-rates, temperatures, and oxide thicknesses to evaluate changes in yield stress, modulus, and failure mechanisms. Findings indicate that copper-thin film mechanical properties are strongly affected by native oxide layers. The formed oxide layers have an amorphous structure with lower Cu-O bond-densities than bulk CuO, and a mixture of Cu{sub 2}O and CuO charge character. It is found that oxidation will cause modifications to the strain response of the elastic modulii, producing a stiffened modulii at low temperatures (<75 K) and low strain values (<5%), and a softened modulii at higher temperatures. While under strain, structural reorganization within the oxide layers facilitates brittle yielding through nucleation of defects across the oxide/metal interface. The oxide-free copper thin-film yielding mechanism is found to be a tensile-axis reorientation and grain creation. The oxide layers change the observed yielding mechanism, allowing for the inner copper thin-film to sustain an FCC-to-BCC transition during yielding. The mechanical properties are fit to a thermodynamic model based on classical nucleation theory. The fit implies that the oxidation of the

  20. Catalytic conversion of light alkanes. Quarterly progress report, April 1--June 30, 1992

    SciTech Connect

    Lyons, J.E.

    1992-06-30

    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  1. Catalytic conversion of light alkanes: Quarterly report, January 1-March 31, 1992

    SciTech Connect

    Biscardi, J.; Bowden, P.T.; Durante, V.A.; Ellis, P.E. Jr.; Gray, H.B.; Gorbey, R.G.; Hayes, R.C.; Hodge, J.; Hughes, M.; Langdale, W.A.; Lyons, J.E.; Marcus, B.; Messick, D.; Merrill, R.A.; Moore, F.A.; Myers, H.K. Jr.; Seitzer, W.H.; Shaikh, S.N.; Tsao, W.H.; Wagner, R.W.; Warren, R.W.; Wijesekera, T.P.

    1997-05-01

    The first Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between January 1. 1992 and March 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient porphryinic macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE III).

  2. Molecular solution approach to synthesize electronic quality Cu2ZnSnS4 thin films.

    PubMed

    Yang, Wenbing; Duan, Hsin-Sheng; Cha, Kitty C; Hsu, Chia-Jung; Hsu, Wan-Ching; Zhou, Huanping; Bob, Brion; Yang, Yang

    2013-05-08

    Successful implementation of molecular solution processing from a homogeneous and stable precursor would provide an alternative, robust approach to process multinary compounds compared with physical vapor deposition. Targeting deposition of chemically clear, high quality crystalline films requires specific molecular structure design and solvent selection. Hydrazine (N2H4) serves as a unique and powerful medium, particularly to incorporate selected metallic elements and chalcogens into a stable solution as metal chalcogenide complexes (MCC). However, not all the elements and compounds can be easily dissolved. In this manuscript, we demonstrate a paradigm to incorporate previously insoluble transitional-metal elements into molecular solution as metal-atom hydrazine/hydrazine derivative complexes (MHHD), as exemplified by dissolving of the zinc constituent as Zn(NH2NHCOO)2(N2H4)2. Investigation into the evolution of molecular structure reveals the hidden roadmap to significantly enrich the variety of building blocks for soluble molecule design. The new category of molecular structures not only set up a prototype to incorporate other elements of interest but also points the direction for other compatible solvent selection. As demonstrated from the molecular precursor combining Sn-/Cu-MCC and Zn-MHHD, an ultrathin film of copper zinc tin sulfide (CZTS) was deposited. Characterization of a transistor based on the CZTS channel layer shows electronic properties comparable to CuInSe2, confirming the robustness of this molecular solution processing and the prospect of earth abundant CZTS for next generation photovoltaic materials. This paradigm potentially outlines a universal pathway, from individual molecular design using selected chelated ligands and combination of building blocks in a simple and stable solution to fundamentally change the way multinary compounds are processed.

  3. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butoxy-substituted ether alkane. 721... Substances § 721.3435 Butoxy-substituted ether alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as butoxy-substituted ether...

  4. Melting of linear alkanes between swollen elastomers and solid substrates.

    PubMed

    Nanjundiah, Kumar; Dhinojwala, Ali

    2013-10-01

    We have measured the melting and freezing behavior of linear alkanes confined between cross-linked poly(dimethylsiloxane) (PDMS) elastomers and solid sapphire substrates. Small molecules are often used as lubricants to reduce friction or as plasticizers, but very little is directly known about the migration or changes in physical properties of these small molecules at interfaces, particularly the changes in transition temperatures upon confinement. Our previous studies highlighted striking differences between the crystal structure of confined and unconfined pentadecane crystals in contact with sapphire substrates. Here, we have used surface-sensitive infrared-visible sum-frequency-generation spectroscopy (SFG) to study the melting temperatures (Tm) of alkanes in nanometer thick interfacial regions between swollen PDMS elastomers in contact with sapphire substrate. We find that confined alkanes show depression in Tm compared to the melting temperature of unconfined bulk alkanes. The depression in Tm is a function of chain length, and these differences were smallest for shorter alkanes and largest for 19 unit long alkanes. In comparison, the DSC results for swollen PDMS elastomer show a broad distribution of melting points corresponding to different sizes of crystals formed within the network. The Tm for confined alkanes has been modeled using the combination of Flory-Rehner and Gibbs-Thomson models, and the depression in Tm is related to the thickness of the confined alkanes. These findings have important implications in understanding friction and adhesion of soft elastomeric materials and also the effects of confinement between two solid materials.

  5. Viscoelastic relaxations of high alcohols and alkanes: Effects of heterogeneous structure and translation-orientation coupling

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Tsuyoshi

    2017-03-01

    The frequency-dependent shear viscosity of high alcohols and linear alkanes, including 1-butanol, 1-octanol, 1-dodecanol, n-hexane, n-decane, and n-tetradecane, was calculated using molecular dynamics simulation. The relaxation of all the liquids was bimodal. The correlation functions of the collective orientation were also evaluated. The analysis of these functions showed that the slower relaxation mode of alkanes is assigned to the translation-orientation coupling, while that of high alcohols is not. The X-ray structure factors of all the alcohols showed prepeaks, as have been reported in the literature, and the intermediate scattering functions were calculated at the prepeak. Comparing the intermediate scattering function with the frequency-dependent shear viscosity based on the mode-coupling theory, it was demonstrated that the slower viscoelastic relaxation of the alcohols is assigned to the relaxation of the heterogeneous structure described by the prepeak.

  6. Visualization of molecular packing and tilting domains and interface effects in tetracene thin films on H/Si(001)

    DOE PAGES

    Tersigni, Andrew; Sadowski, Jerzy T.; Qin, Xiao-Rong

    2017-03-27

    Visualizing molecular crystalline domains and influence of substrate defects are important in understanding the charge transport in organic thin film devices. Vacuum evaporated tetracene films of four monolayers on hydrogen-terminated Si(001)-2x1 substrate, as a prototypical system, have been studied with ex situ atomic force microscopy (AFM), transverse shear microscopy (TSM), friction force microscopy (FFM), and low-energy electron microscopy (LEEM). Two differently oriented in-plane lattice domains are found due to the symmetry of the substrate lattice, with no visible azimuthal twist between adjacent molecular layers in surface islands, indicating significant bulk-like crystallization in the film. Meanwhile, two types of subdomains aremore » observed inside of each in-plane lattice domain. The subdomains are anisotropic in shape, and their sizes and distribution are highly influenced by the substrate atomic steps. TSM and FFM measurements indicate that these subdomains result from molecule-tilt orderings within the bulk-like lattice domains. Lastly, TSM evidently shows a sensitivity to probe vertical molecule-tilt anisotropy for the molecular crystals, in addition to its known ability to map the lateral lattice orientations.« less

  7. Hydrocarbon Metabolism by Brevibacterium erythrogenes: Normal and Branched Alkanes1

    PubMed Central

    Pirnik, M. P.; Atlas, R. M.; Bartha, R.

    1974-01-01

    Branched- and straight-chain alkanes are metabolized by Brevibacterium erythrogenes by means of two distinct pathways. Normal alkanes (e.g., n-pentadecane) are degraded, after terminal oxidation, by the beta-oxidation system operational in fatty acid catabolism. Branched alkanes like pristane (2,6,10,14-tetramethylpentadecane) and 2-methylundecane are degraded as dicarboxylic acids, which also undergo beta-oxidation. Pristane-derived intermediates are observed to accumulate, with time, as a series of dicarboxylic acids. This dicarboxylic acid pathway is not observed in the presence of normal alkanes. Release of 14CO2 from [1-14C]pristane is delayed, or entirely inhibited, in the presence of n-hexadecane, whereas CO2 release from n-hexadecane remains unaffected. These results suggest an inducible dicarboxylic acid pathway for degradation of branched-chain alkanes. PMID:4852318

  8. n-Alkane adsorption to polar silica surfaces.

    PubMed

    Brindza, Michael R; Ding, Feng; Fourkas, John T; Walker, Robert A

    2010-03-21

    The structures of medium-length n-alkane species (C(8)-C(11)) adsorbed to a hydrophilic silica/vapor interface were examined using vibrational sum frequency spectroscopy. Experiments sampling out-of-plane orientation show a clear pattern in vibrational band intensities that implies chains having primarily all-trans conformations lying flat along the interface. Further analysis shows that the methylene groups of the alkane chains have their local symmetry axes directed into and away from the surface. Spectra acquired under different polarization conditions interlock to reinforce this picture of interfacial structure and organization. Variation in signal intensities with chain length suggests that correlation between adsorbed monomers weakens with increasing chain length. This result stands in contrast with alkane behavior at neat liquid/vapor interfaces where longer length alkanes show considerably more surface induced ordering than short chain alkanes.

  9. Sophorolipids from Torulopsis bombicola: possible relation to alkane uptake.

    PubMed Central

    Ito, S; Inoue, S

    1982-01-01

    Torulopsis bombicola produces extracellular sophorolipids when it is grown on water-insoluble alkanes. Sophorolipids and related model compounds, which were not themselves used for growth, were found to stimulate markedly the growth of T. bombicola on alkanes. This stimulatory effect was restricted to growth on C10 to C20 alkanes, whereas no significantly influence was observed for growth on fatty alcohols, fatty acids, glucose, or glycerol. The nonionic methyl ester of the glycolipid supported the greatest cell yield. However, a number of synthetic nonionic surfactants were unable to replace the glycolipid. When organisms were grown on hexadecane, stimulation of growth by sophorolipids was observed almost exclusively with strains of Torulopsis yeasts. In contrast, the growth of other typical alkane-utilizing yeasts, such as candida and Pichia strains, was inhibited or not affected. It appears that sophorolipids are involved in alkane dissimilation by T. bombicola through an undetermined mechanism. PMID:7201782

  10. Alkanes in benthic organisms from the Buccaneer oil field

    SciTech Connect

    Middleditch, B.S.; Basile, B.

    1980-06-01

    About 200 g per day of alkanes are present in brine discharged from each of two production platforms in the Buccaneer oil field in the NW Gulf of Mexico. These alkanes disperse rapidly in the water column, so that seawater concentrations of petroleum alkanes in this region are generally very low. They can be taken up to some extent by plankton, fish, and barnacles, but the petroleum alkane concentrations in these organisms are also relatively low. The largest pool of petroleum alkanes is in the surficial sediments, where concentrations of up to 25 ppM are observed, with concentration gradients extending more than 20 m from the production platforms. Organisms are examined which are exposed to these sediments and, for comparison, other specimens from control sites around structures from which there are no discharges.

  11. Utilization of n-Alkanes by Cladosporium resinae

    PubMed Central

    Teh, J. S.; Lee, K. H.

    1973-01-01

    Four different isolates of Cladosporium resinae from Australian soils were tested for their ability to utilize liquid n-alkanes ranging from n-hexane to n-octadecane under standard conditions. The isolates were unable to make use of n-hexane, n-heptane, and n-octane for growth. In fact, these hydrocarbons, particularly n-hexane, exerted an inhibitory effect on spore germination and mycelial growth. All higher n-alkanes from n-nonane to n-octadecane were assimilated by the fungus, although only limited growth occurred on n-nonane and n-decane. The long chain n-alkanes (C14 to C18) supported good growth of all isolates, but there was no obvious correlation between cell yields and chain lengths of these n-alkanes. Variation in growth responses to individual n-alkane among the different isolates was also observed. The cause of this variation is unknown. PMID:4735447

  12. Role of molecular architecture on the vitrification of polymer thin films.

    PubMed

    Glynos, Emmanouil; Frieberg, Bradley; Oh, Hyunjoon; Liu, Ming; Gidley, David W; Green, Peter F

    2011-03-25

    We show that thin film star-shaped macromolecules exhibit significant differences in their average vitrification behavior, in both magnitude and thickness dependence, from their linear analogs. This behavior is dictated by a combination of their functionality and arm length. Additionally, the glass transition temperature at the free surface of a star-shaped molecule film may be higher than that of the interior, in contrast to their linear analogs where the opposite is true. These findings have implications for other properties, due largely to the origins, entropic, of this behavior.

  13. Molecular beam epitaxy of thin HfTe2 semimetal films

    NASA Astrophysics Data System (ADS)

    Aminalragia-Giamini, S.; Marquez-Velasco, J.; Tsipas, P.; Tsoutsou, D.; Renaud, G.; Dimoulas, A.

    2017-03-01

    Epitaxial thin films of 1T-HfTe2 semimetal are grown by MBE on AlN(0001) substrates. The measured in-plane lattice parameter indicates an unstrained film which is also azimuthally aligned with the AlN substrate, albeit with an in-plane mosaic spread, as it would be expected for van der Waals epitaxy. Angle resolved photoemission spectroscopy combined with first principles electronic band structure calculations show steep linearly dispersing conduction and valence bands which cross near the Brillouin zone center, providing evidence that HfTe2/AlN is an epitaxial topological Dirac semimetal.

  14. Potential for spin-based information processing in a thin-film molecular semiconductor

    NASA Astrophysics Data System (ADS)

    Warner, Marc; Din, Salahud; Tupitsyn, Igor; Morley, Gavin; Stoneham, Marshall; Gardener, Jules; Wu, Zhenlin; Fisher, Andrew; Heutz, Sandrine; Kay, Christopher; Aeppli, Gabriel

    2014-03-01

    Organic semiconductors are studied intensively for applications in electronics and optics, and even spin-based information technology, or spintronics. Fundamental quantities in spintronics are the population relaxation time (T1) and the phase memory time (T2) : T1 measures the lifetime of a classical bit, in this case embodied by a spin oriented either parallel or antiparallel to an external magnetic field, and T2 measures the corresponding lifetime of a quantum bit, encoded in the phase of the quantum state. Here we establish that these times are surprisingly long for a common, low-cost and chemically modifiable organic semiconductor, the blue pigment copper phthalocyanine, in easily processed thin-film form of the type used for device fabrication. At 5 K, a temperature reachable using inexpensive closed-cycle refrigerators, T1 and T2 are respectively 59 ms and 2.6 ms, and at 80 K, which is just above the boiling point of liquid nitrogen, they are respectively 10 ms and 1 ms, demonstrating that the performance of thin-film copper phthalocyanine is superior to that of single-molecule magnets over the same temperature range.

  15. Research on the electronic and optical properties of polymer and other organic molecular thin films

    SciTech Connect

    1997-02-01

    The main goal of the work is to find materials and methods of optimization of organic layered electroluminescent cells and to study such properties of polymers and other organic materials that can be used in various opto-electronic devices. The summary of results obtained during the first year of work is presented. They are: (1) the possibility to produce electroluminescent cells using a vacuum deposition photoresist technology for commercial photoresists has been demonstrated; (2) the idea to replace the polyaryl polymers by other polymers with weaker hole conductivity for optimization of electroluminescent cells with ITO-Al electrodes has been suggested. The goal is to obtain amorphous processable thin films of radiative recombination layers in electroluminescent devices; (3) procedures of preparation of high-quality vacuum-deposited poly (p-phenylene) (PPP) films on various substrates have been developed; (4) it was found for the first time that the fluorescence intensity of PPP films depends on the degree of polymerization; (5) the role of interfaces between organic compounds, on one side, and metals or semiconductors, on the other side, has been studied and quenching of the fluorescence caused by semiconductor layer in thin sandwiches has been observed; (6) studies of the dynamics of photoexcitations revealed the exciton self-trapping in quasi-one-dimensional aggregates; and (7) conditions for preparation of highly crystalline fullerene C{sub 60} films by vacuum deposition have been found. Composites of C{sub 60} with conjugated polymers have been prepared.

  16. Potential for spin-based information processing in a thin-film molecular semiconductor

    NASA Astrophysics Data System (ADS)

    Warner, Marc; Din, Salahud; Tupitsyn, Igor S.; Morley, Gavin W.; Stoneham, A. Marshall; Gardener, Jules A.; Wu, Zhenlin; Fisher, Andrew J.; Heutz, Sandrine; Kay, Christopher W. M.; Aeppli, Gabriel

    2013-11-01

    Organic semiconductors are studied intensively for applications in electronics and optics, and even spin-based information technology, or spintronics. Fundamental quantities in spintronics are the population relaxation time (T1) and the phase memory time (T2): T1 measures the lifetime of a classical bit, in this case embodied by a spin oriented either parallel or antiparallel to an external magnetic field, and T2 measures the corresponding lifetime of a quantum bit, encoded in the phase of the quantum state. Here we establish that these times are surprisingly long for a common, low-cost and chemically modifiable organic semiconductor, the blue pigment copper phthalocyanine, in easily processed thin-film form of the type used for device fabrication. At 5K, a temperature reachable using inexpensive closed-cycle refrigerators, T1 and T2 are respectively 59ms and 2.6μs, and at 80K, which is just above the boiling point of liquid nitrogen, they are respectively 10μs and 1μs, demonstrating that the performance of thin-film copper phthalocyanine is superior to that of single-molecule magnets over the same temperature range. T2 is more than two orders of magnitude greater than the duration of the spin manipulation pulses, which suggests that copper phthalocyanine holds promise for quantum information processing, and the long T1 indicates possibilities for medium-term storage of classical bits in all-organic devices on plastic substrates.

  17. Demonstration of 40 MHz thin-film electro-optic modulator using an organic molecular salt

    NASA Astrophysics Data System (ADS)

    Bhowmik, Achintya; Ahyi, Ayayi; Tan, Shida; Mishra, Alpana; Thakur, Mrinal

    2000-03-01

    Recently we reported the first demonstration of a single-pass thin-film electro-optic modulator based on a DAST single-crystal film.(M. Thakur, J. Xu, A. Bhowmik, and L. Zhou, Appl. Phys. Lett. 74, 635-637 (1999).) In this work, we report a larger modulation depth ( ~80%) and higher speed of operation. Excellent optical quality single-crystal films were prepared by a modified shear method.(M. Thakur and S. Meyler, Macromolecules 18, 2341 (1985); M. Thakur, Y. Shani, G. C. Chi, and K. O'Brien, Synth. Met. 28, D595 (1989).) Thin-film modulator was constructed by depositing electrodes across the polar axis. The beam from a Ti-Sapphire laser, tunable over 720-850 nm, was propagated perpendicular to the film surface. The modulated signal was detected using a fast photodetector, and displayed on a high bandwidth oscilloscope and a spectrum analyzer. The response was independent of the frequency of applied field over the measurement range (2 kHz - 40 MHz). A much higher speed (>100 GHz) of operation should be possible using these films. These modulators involve negligible losses compared to the waveguide structures, and have significant potential for a broad range of applications in high speed optical signal processing.

  18. A molecular dynamics study on thin film liquid boiling characteristics under rapid linear boundary heating: Effect of liquid film thickness

    NASA Astrophysics Data System (ADS)

    Rabbi, Kazi Fazle; Tamim, Saiful Islam; Faisal, A. H. M.; Mukut, K. M.; Hasan, Mohammad Nasim

    2017-06-01

    This study is a molecular dynamics investigation of phase change phenomena i.e. boiling of thin liquid films subjected to rapid linear heating at the boundary. The purpose of this study is to understand the phase change heat transfer phenomena at nano scale level. In the simulation, a thin film of liquid argon over a platinum surface has been considered. The simulation domain herein is a three-phase system consisting of liquid and vapor argon atoms placed over a platinum wall. Initially the whole system is brought to an equilibrium state at 90 K and then the temperature of the bottom wall is increased to a higher temperature (250K) within a finite time interval. Four different liquid argon film thicknesses have been considered (3 nm, 4 nm, 5 nm and 6 nm) in this study. The boundary heating rate (40×109 K/s) is kept constant in all these cases. Variation in system temperature, pressure, net evaporation number, spatial number density of the argon region with time for different film thickness have been demonstrated and analyzed. The present study indicates that the pattern of phase transition may be significantly different (i.e. evaporation or explosive boiling) depending on the liquid film thickness. Among the four cases considered in the present study, explosive boiling has been observed only for the liquid films of 5nm and 6nm thickness, while for the other cases, evaporation take place.

  19. Ultrafast carrier dynamics and the role of grain boundaries in polycrystalline silicon thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Titova, Lyubov V.; Cocker, Tyler L.; Xu, Sijia; Baribeau, Jean-Marc; Wu, Xiaohua; Lockwood, David J.; Hegmann, Frank A.

    2016-10-01

    We have used time-resolved terahertz spectroscopy to study microscopic photoconductivity and ultrafast photoexcited carrier dynamics in thin, pure, non-hydrogenated silicon films grown by molecular beam epitaxy on quartz substrates at temperatures ranging from 335 °C to 572 °C. By controlling the growth temperature, thin silicon films ranging from completely amorphous to polycrystalline with minimal amorphous phase can be achieved. Film morphology, in turn, determines its photoconductive properties: in the amorphous phase, carriers are trapped in bandtail states on sub-picosecond time scales, while the carriers excited in crystalline grains remain free for tens of picoseconds. We also find that in polycrystalline silicon the photoexcited carrier mobility is carrier-density-dependent, with higher carrier densities mitigating the effects of grain boundaries on inter-grain transport. In a film grown at the highest temperature of 572 °C, the morphology changes along the growth direction from polycrystalline with needles of single crystals in the bulk of the film to small crystallites interspersed with amorphous silicon at the top of the film. Depth profiling using different excitation wavelengths shows corresponding differences in the photoconductivity: the photoexcited carrier lifetime and mobility are higher in the first 100-150 nm from the substrate, suggesting that thinner, low-temperature grown polycrystalline silicon films are preferable for photovoltaic applications.

  20. 7-Octenyltrichrolosilane/trimethyaluminum hybrid dielectrics fabricated by molecular-atomic layer deposition on ZnO thin film transistors

    NASA Astrophysics Data System (ADS)

    Huang, Jie; Lee, Mingun; Lucero, Antonio T.; Cheng, Lanxia; Ha, Min-Woo; Kim, Jiyoung

    2016-06-01

    We demonstrate the fabrication of 7-octenytrichlorosilane (7-OTS)/trimethylaluminum (TMA) organic-inorganic hybrid films using molecular-atomic layer deposition (MALD). The properties of 7-OTS/TMA hybrid films are extensively investigated using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and electrical measurements. Our results suggest that uniform and smooth amorphous hybrid thin films with excellent insulating properties are obtained using the MALD process. Films have a relatively high dielectric constant of approximately 5.0 and low leakage current density. We fabricate zinc oxide (ZnO) based thin film transistors (TFTs) using 7-OTS/TMA hybrid material as a back gate dielectric with the top ZnO channel layer deposited in-situ via MALD. The ZnO TFTs exhibit a field effect mobility of approximately 0.43 cm2 V-1 s-1, a threshold voltage of approximately 1 V, and an on/off ratio of approximately 103 under low voltage operation (from -3 to 9 V). This work demonstrates an organic-inorganic hybrid gate dielectric material potentially useful in flexible electronics application.

  1. Synthesis, conformational and theoretical studies of 1,n-di(2-formyl-4-phenylazophenoxy)alkanes

    NASA Astrophysics Data System (ADS)

    Balachander, R.; Manimekalai, A.

    2016-01-01

    1,n-di(2-Formyl-4-phenylazophenoxy)alkanes 1 and 2 and 1,3-di(2-formyl-4-phenylazophenoxymethyl)benzene 3 were synthesis and characterized by FT-IR, UV-Vis, 1H, 13C NMR and mass spectral studies. The stable conformations of 1-3 were predicted theoretically and selected geometrical parameters were derived from optimized structures. The molecular parameters of HOMO-LUMO energies, polarizability, hyperpolarizability, natural bond orbital (NBO), atom in molecule (AIM) analysis and molecular electrostatic potential (MEP) surfaces were determined by the density functional theory (DFT) method and analysed.

  2. Polarization dependence of Raman scattering from a thin film involving optical anisotropy theorized for molecular orientation analysis.

    PubMed

    Itoh, Yuki; Hasegawa, Takeshi

    2012-06-14

    Polarized Raman scattering from a thin film involving uniaxial optical anisotropy deposited on a dielectric substrate has analytically been theorized. The analyte film is modeled as a three-phase system (air/film/substrate) to calculate the electromagnetic fields of the incident and scattered light propagating across the system with an aid of the transfer matrix method to exactly take the optical anisotropy of the film into account. On the new theory, a methodology for molecular orientation analysis of an extended polymethylene chain in the film is proposed, which is employed for determination of the tilt angles of the chains in single- and five-monolayer Langmuir-Blodgett (LB) films of cadmium stearate deposited on a glass plate. The results agree well with those obtained by infrared spectroscopy, which confirms reliability of the present method.

  3. Perpendicular Magnetic Anisotropy and Spin Glass-like Behavior in Molecular Beam Epitaxy Grown Chromium Telluride Thin Films.

    PubMed

    Roy, Anupam; Guchhait, Samaresh; Dey, Rik; Pramanik, Tanmoy; Hsieh, Cheng-Chih; Rai, Amritesh; Banerjee, Sanjay K

    2015-04-28

    Reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), vibrating sample magnetometry, and other physical property measurements are used to investigate the structure, morphology, magnetic, and magnetotransport properties of (001)-oriented Cr2Te3 thin films grown on Al2O3(0001) and Si(111)-(7×7) surfaces by molecular beam epitaxy. Streaky RHEED patterns indicate flat smooth film growth on both substrates. STM studies show the hexagonal arrangements of surface atoms. Determination of the lattice parameter from the atomically resolved STM image is consistent with the bulk crystal structures. Magnetic measurements show the film is ferromagnetic, having a Curie temperature of about 180 K, and a spin glass-like behavior was observed below 35 K. Magnetotransport measurements show the metallic nature of the film with a perpendicular magnetic anisotropy along the c-axis.

  4. Structural Evolution of Low-Molecular-Weight Poly(ethylene oxide)-block-polystyrene Diblock Copolymer Thin Film

    PubMed Central

    Huang, Xiaohua

    2013-01-01

    The structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm), the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite. PMID:24302862

  5. Structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene diblock copolymer thin film.

    PubMed

    Wu, Hui; Huang, Xiaohua

    2013-01-01

    The structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm), the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite.

  6. Single-crystal cubic boron nitride thin films grown by ion-beam-assisted molecular beam epitaxy

    SciTech Connect

    Hirama, Kazuyuki Taniyasu, Yoshitaka; Karimoto, Shin-ichi; Krockenberger, Yoshiharu; Yamamoto, Hideki

    2014-03-03

    We investigated the formation of cubic boron nitride (c-BN) thin films on diamond (001) and (111) substrates by ion-beam-assisted molecular beam epitaxy (MBE). The metastable c-BN (sp{sup 3}-bonded BN) phase can be epitaxially grown as a result of the interplay between competitive phase formation and selective etching. We show that a proper adjustment of acceleration voltage for N{sub 2}{sup +} and Ar{sup +} ions is a key to selectively discriminate non-sp{sup 3} BN phases. At low acceleration voltage values, the sp{sup 2}-bonded BN is dominantly formed, while at high acceleration voltages, etching dominates irrespective of the bonding characteristics of BN.

  7. Oxygen vacancy induced photoluminescence and ferromagnetism in SrTiO3 thin films by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Xu, Wenfei; Yang, Jing; Bai, Wei; Tang, Kai; Zhang, Yuanyuan; Tang, Xiaodong

    2013-10-01

    SrTiO3 thin films were epitaxially grown on (100) SrTiO3 substrates using molecular beam epitaxy. The temperature for growth of the films was optimized, which was indicated by x-ray diffraction and further confirmed by microstructural characterization. Photoluminescence spectra show that oxygen-vacancy contributes to red and blue luminescence of oxygen-deficient post-annealed films, and a red shift was observed in blue region. On the other hand, ferromagnetism in film form SrTiO3 was observed from 5 K to 400 K and could be further enhanced with decreasing oxygen plasma partial pressure in annealing processes, which might be explained by the theory involving d0 magnetism related to oxygen-vacancy. From the cooperative investigations of optical and magnetic properties, we conclude that intrinsic defects, especially oxygen-vacancy, can induce and enhance luminescence and magnetism in SrTiO3 films.

  8. Low-damping sub-10-nm thin films of lutetium iron garnet grown by molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Jermain, C. L.; Paik, H.; Aradhya, S. V.; Buhrman, R. A.; Schlom, D. G.; Ralph, D. C.

    2016-11-01

    We analyze the structural and magnetic characteristics of (111)-oriented lutetium iron garnet (Lu3Fe5O12) films grown by molecular-beam epitaxy, for films as thin as 2.8 nm. Thickness-dependent measurements of the in- and out-of-plane ferromagnetic resonance allow us to quantify the effects of two-magnon scattering, along with the surface anisotropy and the saturation magnetization. We achieve effective damping coefficients of 11.1 (9 )×10-4 for 5.3 nm films and 32 (3 )×10-4 for 2.8 nm films, among the lowest values reported to date for any insulating ferrimagnetic sample of comparable thickness.

  9. In vitro studies of PEG thin films with different molecular weights deposited by MAPLE

    NASA Astrophysics Data System (ADS)

    Paun, Irina Alexandra; Ion, Valentin; Luculescu, Catalin-Romeo; Dinescu, Maria; Canulescu, Stela; Schou, Jørgen

    2012-10-01

    In this work, polyethylene glycol (PEG) films were produced by Matrix Assisted Pulsed Laser Evaporation (MAPLE). The possibility to tailor the properties of the films by means of polymer molecular weight was explored. The films of PEG of average molecular weights 400 Da, 1450 Da, and 10000 Da (PEG400, PEG1450, and PEG10000) were investigated in vitro, in media similar with those inside the body (phosphate buffer saline PBS with pH 7.4 and blood). The mass of the polymer did not change during this treatment, but the polymer molecular weight was found to strongly influence the films properties and their behavior in vitro. Thus, immersion in PBS induced swelling of the PEG films, which was more pronounced for PEG polymers of higher molecular weight. Prior to immersion in PBS, the PEG films of higher molecular weight were more hydrophilic, the water contact angles decreasing from ˜66 grd for PEG400 to ˜41 grd for PEG1450 and to ˜15 grd for PEG10000. The same trend was observed during immersion of the PEG films in PBS. Before immersion in PBS, the refractive index of the films increased from ˜1.43 for PEG400 to ˜1.48 for PEG1450 and to ˜1.68 for PEG10000. During immersion in PBS the refractive index decreased gradually, but remained higher for the PEG molecules of higher mass. Finally, blood compatibility tests showed that the PEG films of higher molecular weight were most compatible with blood.

  10. Deviations from stoichiometry and molecularity in non-stoichiometric Ag-In-Se thin films: Effects on the optical and the electrical properties

    NASA Astrophysics Data System (ADS)

    Kim, Nam-Hoon; Yoo, Myoung Han; Ko, Pil Ju; Lee, Woo-Sun

    2016-12-01

    Non-stoichiometric Ag-In-Se (AIS) thin films were prepared using co-sputtering with InSe2 and Ag targets followed by rapid thermal annealing. The internal stress of the non-stoichiometric AIS thin films was strongly affected by the deviation from molecularity, Δ m. When Δ m was far from stoichiometry, the non-stoichiometric AIS thin films showed better crystallinity. The improvement in the crystallinity and the release of internal stress led to a reduction in the optical band gap from 1.63 to 1.19 eV and in the resistivity from 6.45 × 10-2 to 3.21 × 10-3 Ω·cm for the non-stoichiometric AIS thin films, with a similar tendency for the deviation from molecularity, Δ m. The non-stoichiometric AIS thin films, with Δ m < 0 and Δ s < 0, exhibited n-type conductivity with carrier concentrations on the order of magnitude of 1018 cm-3. The mean absorbance of the 200-nm-thick non-stoichiometric AIS thin films was 1.50, corresponding to an absorption of approximately 96.84 % of the incident light in the visible region.

  11. Engineering of an ultra-thin molecular superconductor by charge transfer

    DOEpatents

    Hla, Saw Wai; Hassanien, Abdelrahim; Kendal, Clark

    2016-06-07

    A method of forming a superconductive device of a single layer of (BETS).sub.2GaCl.sub.4 molecules on a substrate surface which displays a superconducting gap that increases exponentially with the length of the molecular chain is provided.

  12. System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers.

    PubMed

    Moultos, Othonas A; Zhang, Yong; Tsimpanogiannis, Ioannis N; Economou, Ioannis G; Maginn, Edward J

    2016-08-21

    Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

  13. System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers

    NASA Astrophysics Data System (ADS)

    Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N.; Economou, Ioannis G.; Maginn, Edward J.

    2016-08-01

    Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

  14. The taxonomic status of the endangered thin-spined porcupine, Chaetomys subspinosus (Olfers, 1818), based on molecular and karyologic data

    PubMed Central

    Vilela, Roberto V; Machado, Taís; Ventura, Karen; Fagundes, Valéria; de J Silva, Maria José; Yonenaga-Yassuda, Yatiyo

    2009-01-01

    Background The thin-spined porcupine, also known as the bristle-spined rat, Chaetomys subspinosus (Olfers, 1818), the only member of its genus, figures among Brazilian endangered species. In addition to being threatened, it is poorly known, and even its taxonomic status at the family level has long been controversial. The genus Chaetomys was originally regarded as a porcupine in the family Erethizontidae, but some authors classified it as a spiny-rat in the family Echimyidae. Although the dispute seems to be settled in favor of the erethizontid advocates, further discussion of its affinities should be based on a phylogenetic framework. In the present study, we used nucleotide-sequence data from the complete mitochondrial cytochrome b gene and karyotypic information to address this issue. Our molecular analyses included one individual of Chaetomys subspinosus from the state of Bahia in northeastern Brazil, and other hystricognaths. Results All topologies recovered in our molecular phylogenetic analyses strongly supported Chaetomys subspinosus as a sister clade of the erethizontids. Cytogenetically, Chaetomys subspinosus showed 2n = 52 and FN = 76. Although the sexual pair could not be identified, we assumed that the X chromosome is biarmed. The karyotype included 13 large to medium metacentric and submetacentric chromosome pairs, one small subtelocentric pair, and 12 small acrocentric pairs. The subtelocentric pair 14 had a terminal secondary constriction in the short arm, corresponding to the nucleolar organizer region (Ag-NOR), similar to the erethizontid Sphiggurus villosus, 2n = 42 and FN = 76, and different from the echimyids, in which the secondary constriction is interstitial. Conclusion Both molecular phylogenies and karyotypical evidence indicated that Chaetomys is closely related to the Erethizontidae rather than to the Echimyidae, although in a basal position relative to the rest of the Erethizontidae. The high levels of molecular and morphological

  15. The effect of surfaces on molecular ordering in thin liquid-crystal systems

    NASA Astrophysics Data System (ADS)

    Śliwa, I.; JeŻewski, W.; Zakharov, A. V.

    2016-08-01

    A theoretical method for analyzing the interplay between pair long-range intermolecular forces and nonlocal, relatively short-range, surface interactions in liquid crystals, confined between plates of thin planar cells, is developed. It is shown that this method, as involving the concept of local orientational and translational order parameters, enables detailed investigations of the emergence of smectic A, nematic, and isotopic phases, as well as yields an insight into phase transitions between them, in cases of systems strongly affected by surfaces. The evidence of various surface effects, including the coexistence of different phases and the inward propagation of surface melting under the increase of temperature, is also given. The underlying numerical procedure, based on the algorithm of self-consistent calculations of local order parameters, is found to be very effective, allowing one to consider model systems of rather large thicknesses, corresponding to thicknesses of real sample cells.

  16. Growth of Cr2CoGa and inverse Heusler thin films using Molecular Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Jamer, Michelle; Decapua, Matthew; Player, Gabriel; Heiman, Don

    Theoretical calculations have predicted the existence of inverse Heusler compounds that exhibit zero-moment magnetization while retaining their half-metallicity. These unique compounds have been labeled spin gapless semiconductors (SGS), where the density of states (DOS) can behave as a half-metal or gapless semiconductor. There is a special interest for zero-moment SGS compounds since traditional antiferromagnets cannot be spin-polarized. Such compounds are experimentally attractive for future spintronic devices due to their large magnetic transition temperature (400-800 K). This work focuses on zero-moment inverse Heusler compounds including Cr2CoGa and Mn3Al. Thin films have been grown using MBE and their magnetic, structural, and electrical properties of these compounds have been characterized by various techniques, including XMCD and magnetometry. The atomic moments are found to be large, but significant cancellations lead to small average moments. Supported by NSF Grant ECCS-1402738.

  17. Nanostructured organic and inorganic thin films with novel molecular recognition properties

    NASA Astrophysics Data System (ADS)

    Twardowski, Mariusz Z.

    An important theme in surface/interface science is the development of molecular level understandings of interactions at solid-liquid interfaces. The study of molecular recognition at such interfaces is well suited for modeling with self-assembled monolayers of alkanethiols (SAMs). For optimal studies, the SAM must be defect-free. Towards this end, a chemical treatment of the gold substrate was developed, consisting of a sequential treatment in "piranha" followed by dilute aqua regia. We found that the SAMs assembled on these treated substrates had exceptional barrier properties as measured by cyclic voltammetry(CV). X-ray diffraction(XRD) indicated that oxidative treatment induces significant bulk recrystallization of the metal. The dynamics suggest that recrystallization results from preferential dissolution of Au and/or impurities present at grain boundaries, leading to unpinning and merger into larger grains. Supported lipid layers were formed via fusion of unilamellar vesicles of 1,2-dimyristoyl-sn-glycero-3-phosphocholine(DMPC) to mixed SAMs containing ferrocene-functionalized hexadecanethiol chains(FcCO 2C16SH). The structures were characterized by several methods, including CV, ellipsometry and surface plasmon resonance(SPR). Studies revealed that the adsorbed DMPC strongly influences the interactions of the tethered ferrocene groups with secondary aqueous molecular redox probes. Permselective properties are seen. We believe that molecular scale defect structures in the adsorbed DMPC layer confer these molecular discrimination properties. Unilamellar vesicles of DMPC and varying quantities of 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)(sodium salt)(DMPG) were used to deposit lipid bilayer assemblies on SAMs. The coverages of the layers were measured with SPR and decreased with increasing DMPG. The assembly is reversible and the lipid adlayer removable with ethanol. Effects of the adsorbed lipid layer on the electrochemical interactions of the

  18. Stable hydrogen isotopic composition of n-alkanes in atmospheric aerosols as a tracer for the source region of terrestrial plant waxes

    NASA Astrophysics Data System (ADS)

    Yamamoto, S.; Kawamura, K.

    2009-12-01

    Studies on molecular composition and compound-specific carbon isotopic ratio (δ13C) of leaf wax n-alkanes in atmospheric aerosols have revealed a long-range atmospheric transport of terrestrial higher plant materials over the south Atlantic and western Pacific oceans. However, molecular and δ13C compositions of terrestrial plant waxes in the eastern part of the Asian continent are relatively constant reflecting C3-dominated vegetation, which makes it difficult to specify the source regions of plant materials in the atmospheric aerosols over the East Asia and northwest Pacific regions. Recent observation displays a large (>100‰) spatial variation in hydrogen isotopic composition (δD) of rainwater in East Asia. Because δD values of terrestrial higher plants sensitively reflect those of precipitation waters, δD of leaf waxes are expected to provide information on their source region. In this study, we measured the δD of n-alkanes in atmospheric aerosols from Tokyo to better understand the origin of leaf wax n-alkanes in atmospheric aerosols. The δD values of fossil fuel n-alkanes (C21 to C24) in Tokyo aerosols range from -65 to -94‰, which are in a range of those reported in marine crude oils. In contrast, the δD of higher molecular weight (C29 and C31) n-alkanes (δDHMW) show much larger values by ~70‰ than those of fossil fuel n-alkanes. Their values were found to exhibit concomitant variations with carbon preference index (CPI), suggesting that the δDHMW reflect the δD of leaf wax n-alkanes with a variable contribution from fossil fuel n-alkanes. Nevertheless, good positive correlation (r = 0.89, p < 0.01) between the δDHMW and CPI values enable us to remove the contribution of fossil fuels using a mass balance approach by assuming that CPI of fossil fuel is 1 and CPI of plant waxes is 5-15. Calculated n-alkane δD values averaged from -170 to -185‰ for C29 and from -155 to -168‰ for C31. These values are consistent with those reported from

  19. High-order harmonic generation in alkanes

    SciTech Connect

    Altucci, C.; Velotta, R.; Heesel, E.; Springate, E.; Marangos, J. P.; Vozzi, C.; Benedetti, E.; Calegari, F.; Sansone, G.; Stagira, S.; Nisoli, M.; Tosa, V.

    2006-04-15

    We have investigated the process of high-order harmonic generation in light alkanes by using femtosecond laser pulses. We show the experimental results cannot be matched by a model that assumes a single active electron only in a hydrogenic s orbital. Clear evidences are shown of the important role played by the p-like character originating from the covalent C-H bond. By constructing a suitable mixture of s-type and p-type atomic wave functions, an excellent agreement between measurements in methane and simulations is found, thus confirming the validity of the developed method as a general tool for the analysis of high-order harmonic generation in complex molecules.

  20. Kinetic study of asphaltene dissolution in amphiphile/alkane solutions

    SciTech Connect

    Permsukarome, P.; Chang, C.; Fogler, H.S.

    1997-09-01

    The kinetics of dissolution of pentane-insoluble solid asphaltene precipitates by amphiphile/alkane solutions were investigated using a differential reactor flow system. Two amphiphiles, dodecylbenzenesulfonic acid and nonylphenol, and five alkane solvents, ranging from hexane to hexadecane, were used. Results showed that the rate of asphaltene dissolution in amphiphile/alkane fluids could be approximated with a first-order kinetics with respect to the undissolved asphaltene mass in solution. The specific dissolution rate constant, k, varied with the concentration of amphiphiles, the type of alkane solvents, the temperature, and the fluid flow rate. The rate of asphaltene dissolution displayed a Langmuir-Hinshelwood kinetics with respect to the concentration of amphiphiles. Increasing the temperature of amphiphile/alkane fluids also enhanced the rate of asphaltene dissolution. The apparent activation energy for asphaltene dissolution was approximated to be 4--7 kcal/mol. The rate of asphaltene dissolution was also greater in amphiphile solutions containing lighter alkanes, such as hexane, with lower viscosities. These trends suggest that both surface reaction and mass transfer processes are important to the rate of asphaltene dissolution in amphiphile/alkane fluids.

  1. Expanding the product profile of a microbial alkane biosynthetic pathway.

    PubMed

    Harger, Matthew; Zheng, Lei; Moon, Austin; Ager, Casey; An, Ju Hye; Choe, Chris; Lai, Yi-Ling; Mo, Benjamin; Zong, David; Smith, Matthew D; Egbert, Robert G; Mills, Jeremy H; Baker, David; Pultz, Ingrid Swanson; Siegel, Justin B

    2013-01-18

    Microbially produced alkanes are a new class of biofuels that closely match the chemical composition of petroleum-based fuels. Alkanes can be generated from the fatty acid biosynthetic pathway by the reduction of acyl-ACPs followed by decarbonylation of the resulting aldehydes. A current limitation of this pathway is the restricted product profile, which consists of n-alkanes of 13, 15, and 17 carbons in length. To expand the product profile, we incorporated a new part, FabH2 from Bacillus subtilis , an enzyme known to have a broader specificity profile for fatty acid initiation than the native FabH of Escherichia coli . When provided with the appropriate substrate, the addition of FabH2 resulted in an altered alkane product profile in which significant levels of n-alkanes of 14 and 16 carbons in length are produced. The production of even chain length alkanes represents initial steps toward the expansion of this recently discovered microbial alkane production pathway to synthesize complex fuels. This work was conceived and performed as part of the 2011 University of Washington international Genetically Engineered Machines (iGEM) project.

  2. Heterologous biosynthesis and manipulation of alkanes in Escherichia coli.

    PubMed

    Cao, Ying-Xiu; Xiao, Wen-Hai; Zhang, Jin-Lai; Xie, Ze-Xiong; Ding, Ming-Zhu; Yuan, Ying-Jin

    2016-11-01

    Biosynthesis of alkanes in microbial foundries offers a sustainable and green supplement to traditional fossil fuels. The dynamic equilibrium of fatty aldehydes, key intermediates, played a critical role in microbial alkanes production, due to the poor catalytic capability of aldehyde deformylating oxygenase (ADO). In our study, exploration of competitive pathway together with multi-modular optimization was utilized to improve fatty aldehydes balance and consequently enhance alkanes formation in Escherichia coli. Endogenous fatty alcohol formation was supposed to be competitive with alkane production, since both of the two routes consumed the same intermediate-fatty aldehyde. Nevertheless, in our case, alkanes production in E. coli was enhanced from trace amount to 58.8mg/L by the facilitation of moderate fatty alcohol biosynthesis, which was validated by deletion of endogenous aldehyde reductase (AHR), overexpression of fatty alcohol oxidase (FAO) and consequent transcriptional assay of aar, ado and adhP genes. Moreover, alkanes production was further improved to 81.8mg/L, 86.6mg/L or 101.7mg/L by manipulation of fatty acid biosynthesis, lipids degradation or electron transfer system modules, which directly referenced to fatty aldehydes dynamic pools. A titer of 1.31g/L alkanes was achieved in 2.5L fed-batch fermentation, which was the highest reported titer in E. coli. Our research has offered a reference for chemical overproduction in microbial cell factories facilitated by exploring competitive pathway.

  3. Long-chain alkane production by the yeast Saccharomyces cerevisiae.

    PubMed

    Buijs, Nicolaas A; Zhou, Yongjin J; Siewers, Verena; Nielsen, Jens

    2015-06-01

    In the past decade industrial-scale production of renewable transportation biofuels has been developed as an alternative to fossil fuels, with ethanol as the most prominent biofuel and yeast as the production organism of choice. However, ethanol is a less efficient substitute fuel for heavy-duty and maritime transportation as well as aviation due to its low energy density. Therefore, new types of biofuels, such as alkanes, are being developed that can be used as drop-in fuels and can substitute gasoline, diesel, and kerosene. Here, we describe for the first time the heterologous biosynthesis of long-chain alkanes by the yeast Saccharomyces cerevisiae. We show that elimination of the hexadecenal dehydrogenase Hfd1 and expression of a redox system are essential for alkane biosynthesis in yeast. Deletion of HFD1 together with expression of an alkane biosynthesis pathway resulted in the production of the alkanes tridecane, pentadecane, and heptadecane. Our study provides a proof of principle for producing long-chain alkanes in the industrial workhorse S. cerevisiae, which was so far limited to bacteria. We anticipate that these findings will be a key factor for further yeast engineering to enable industrial production of alkane based drop-in biofuels, which can allow the biofuel industry to diversify beyond bioethanol.

  4. Molecular Dynamics Studies of Interfacial Properties of Complex Liquid Systems

    NASA Astrophysics Data System (ADS)

    Ouyang, Jian

    1995-01-01

    Molecular dynamics simulations have been used to investigate the interfacial properties of linear and branched chain alkane molecule condensed systems. The only notable effect of branching in our studies is the reduction of system ordering and layering since the degree of branching in the systems is very small. It is found that thin alkane films, adsorbed on a solid substrate at a temperature well above its bulk melting temperature, have about up to four well defined layers near the substrate. Within these layers, molecules are parallel to the substrate and exhibit domains of short range ordering. At the liquid-vapor interface, the molecular segment density tail is well fit by an error function indicating that the molecular height distribution obeys the Gaussian law predicted from the capillary wave model. At a temperature around the liquid bulk solidification temperature, a first order phase transition occurs at the liquid-vapor interfacial region of the alkane thin films. Molecules in this region pack hexagonally and align themselves parallel to the interface normal with a small cant angle. Below this crystalline monolayer, there are four sharp layers where molecules lie parallel to the substrate surface with enhanced domains of transverse ordering. It is observed that the contact angle of an alkane nanodroplet on top of a solid surface increases when the solid-liquid interaction strength decreases, or the molecule length increases. Due to the fact that almost all the molecules are in the liquid-vapor interfacial region, a nanodroplet with molecules of a length comparable to the droplet dimension has clear layers from the solid-liquid interface to the top of the droplet. This layering reduces when the size of the droplet increases or the molecule length decreases. Substrates do not create, but enhance the layering. It is also noticed that in the confined thin fluid films, liquid molecules exhibit partially solid-like characteristics behavior with the ability to

  5. A novel approach in controlling the conductivity of thin films using molecular layer deposition

    NASA Astrophysics Data System (ADS)

    Lushington, Andrew; Liu, Jian; Bannis, Mohammad N.; Xiao, Biwei; Lawes, Stephen; Li, Ruying; Sun, Xueliang

    2015-12-01

    Here we present a novel way to grow aluminum alkoxide films with tunable conductivity with molecular level accuracy with the use of molecular layer deposition (MLD). Alternating exposures of trimethylaluminum (TMA), ethylene glycol (EG), and terephthaloyl chloride (TC) are used to grow the aluminium alkoxide films. Control over film composition was accomplished by alternating cycles of EG and TC between cycles of TMA and EG. In this fashion the aluminum to carbon ratio can be accurately controlled. These films were then pyrolyzed under a reducing atmosphere to yield a conductive Al2O3/carbon composite. Raman spectroscopy determined that nanocrystalline sp2-graphitic carbon was formed following pyrolysis while sheet resistance measurements determined that conductivity of the film is directly related to aluminium-carbon ratio. To further elucidate the origin of conductivity within the film, synchrotron based XPS was performed.

  6. Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water.

    PubMed

    Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M; Gnecco, Enrico

    2014-07-21

    The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

  7. Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

    NASA Astrophysics Data System (ADS)

    McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

    2004-10-01

    Long-chain, odd-carbon-numbered C25 to C35n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N-28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.

  8. Rapid analysis of 13C in plant-wax n-alkanes for reconstruction of terrestrial vegetation signals from aquatic sediments

    NASA Astrophysics Data System (ADS)

    McDuffee, Kelsey E.; Eglinton, Timothy I.; Sessions, Alex L.; Sylva, Sean; Wagner, Thomas; Hayes, John M.

    2004-10-01

    Long-chain, odd-carbon-numbered C25 to C35 n-alkanes are characteristic components of epicuticular waxes produced by terrestrial higher plants. They are delivered to aquatic systems via eolian and fluvial transport and are preserved in underlying sediments. The isotopic compositions of these products can serve as records of past vegetation. We have developed a rapid method for stable carbon isotopic analyses of total plant-wax n-alkanes using a novel, moving-wire system coupled to an isotope-ratio mass spectrometer (MW-irMS). The n-alkane fractions are prepared from sediment samples by (1) saponification and extraction with organic solvents, (2) chromatographic separation using silica gel, (3) isolation of straight-chain carbon skeletons using a zeolite molecular sieve, and (4) oxidation and removal of unsaturated hydrocarbons with RuO4. Short-chain n-alkanes of nonvascular plant origin (alkane fractions essentially free of interfering components. The δ13C values obtained by MW-irMS did not differ significantly from weighted averages of individual n-alkane δ13C values obtained by irmGC-MS. Isotopic variations in compound-class n-alkane fractions from a latitudinal transect of core-top sediments from the Southwest African margin (3°N-28°S) were congruent with those measured by compound-specific isotopic analyses of plant-wax n-alkanes. The amplitude of the variations was smaller, indicating contributions from non-plant-wax hydrocarbons, but the measurements revealed variations in carbon isotopic composition that are consistent with vegetation zones on the adjacent continent.

  9. Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

    SciTech Connect

    Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; Stein, Gila E.; Green, Peter F.

    2016-09-18

    The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.

  10. Molecular dynamics study on the effect of boundary heating rate on the phase change characteristics of thin film liquid

    SciTech Connect

    Hasan, Mohammad Nasim Morshed, A. K. M. Monjur Rabbi, Kazi Fazle Haque, Mominul

    2016-07-12

    In this study, theoretical investigation of thin film liquid phase change phenomena under different boundary heating rates has been conducted with the help of molecular dynamics simulation. To do this, the case of argon boiling over a platinum surface has been considered. The study has been conducted to get a better understanding of the nano-scale physics of evaporation/boiling for a three phase system with particular emphasis on the effect of boundary heating rate. The simulation domain consisted of liquid and vapor argon atoms placed over a platinum wall. Initially the whole system was brought to an equilibrium state at 90 K with the help of equilibrium molecular dynamics and then the temperature of the bottom wall was increased to a higher temperature (250 K/130 K) over a finite heating period. Depending on the heating period, the boundary heating rate has been varied in the range of 1600×10{sup 9} K/s to 8×10{sup 9} K/s. The variations of argon region temperature, pressure, net evaporation number with respect to time under different boundary heating rates have been determined and discussed. The heat fluxes normal to platinum wall for different cases were also calculated and compared with theoretical upper limit of maximum possible heat transfer to elucidate the effect of boundary heating rate.

  11. Structural and magnetic phase transitions in chromium nitride thin films grown by rf nitrogen plasma molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Alam, Khan; Disseler, Steven M.; Ratcliff, William D.; Borchers, Julie A.; Ponce-Pérez, Rodrigo; Cocoletzi, Gregorio H.; Takeuchi, Noboru; Foley, Andrew; Richard, Andrea; Ingram, David C.; Smith, Arthur R.

    2017-09-01

    A magnetostructural phase transition is investigated in single-crystal chromium nitride (CrN) thin films grown by rf plasma molecular beam epitaxy on MgO(001) substrates. While still within the vacuum environment following molecular beam epitaxy growth, in situ low-temperature scanning tunneling microscopy, and in situ variable low-temperature reflection high-energy electron diffraction are applied, revealing an atomically smooth and metallic CrN(001) surface, and an in-plane structural transition from 1 ×1 (primitive CrN unit cell) to √{2 }×√{2 }-R 45∘ with a transition temperature of (278 ±3 ) K, respectively. Ex situ temperature-dependent measurements using neutron diffraction are also performed, looking at the structural peaks and likewise revealing a first-order structural transition along the [111] out-of-plane direction, with transition temperatures of (268 ± 3) K. Turning to the magnetic peaks, neutron diffraction confirms a clear magnetic transition from paramagnetic at room temperature to antiferromagnetic at low temperatures with a sharp, first-order phase transition and a Néel temperature of (270 ±2 ) K or (280 ±2 ) K for two different films. In addition to the experimental measurements of structural and magnetic ordering, we also discuss results from first-principles theoretical calculations which explore various possible magnetostructural models.

  12. Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

    SciTech Connect

    Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; Stein, Gila E.; Green, Peter F.

    2016-09-18

    The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.

  13. Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

    DOE PAGES

    Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; ...

    2016-09-18

    The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations andmore » the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.« less

  14. Molecular dynamics study on the effect of boundary heating rate on the phase change characteristics of thin film liquid

    NASA Astrophysics Data System (ADS)

    Hasan, Mohammad Nasim; Morshed, A. K. M. Monjur; Rabbi, Kazi Fazle; Haque, Mominul

    2016-07-01

    In this study, theoretical investigation of thin film liquid phase change phenomena under different boundary heating rates has been conducted with the help of molecular dynamics simulation. To do this, the case of argon boiling over a platinum surface has been considered. The study has been conducted to get a better understanding of the nano-scale physics of evaporation/boiling for a three phase system with particular emphasis on the effect of boundary heating rate. The simulation domain consisted of liquid and vapor argon atoms placed over a platinum wall. Initially the whole system was brought to an equilibrium state at 90K with the help of equilibrium molecular dynamics and then the temperature of the bottom wall was increased to a higher temperature (250K/130K) over a finite heating period. Depending on the heating period, the boundary heating rate has been varied in the range of 1600×109 K/s to 8×109 K/s. The variations of argon region temperature, pressure, net evaporation number with respect to time under different boundary heating rates have been determined and discussed. The heat fluxes normal to platinum wall for different cases were also calculated and compared with theoretical upper limit of maximum possible heat transfer to elucidate the effect of boundary heating rate.

  15. Heterogeneity of Alkane Chain Length in Freshwater and Marine Cyanobacteria

    PubMed Central

    Shakeel, Tabinda; Fatma, Zia; Fatma, Tasneem; Yazdani, Syed Shams

    2015-01-01

    The potential utilization of cyanobacteria for the biological production of alkanes represents an exceptional system for the next generation of biofuels. Here, we analyzed a diverse group of freshwater and marine cyanobacterial isolates from Indian culture collections for their ability to produce both alkanes and alkenes. Among the 50 cyanobacterial isolates screened, 32 isolates; 14 freshwater and 18 marine isolates; produced predominantly alkanes. The GC-MS/MS profiles revealed a higher percentage of pentadecane and heptadecane production for marine and freshwater strains, respectively. Oscillatoria species were found to be the highest producers of alkanes. Among the freshwater isolates, Oscillatoria CCC305 produced the maximum alkane level with 0.43 μg/mg dry cell weight, while Oscillatoria formosa BDU30603 was the highest producer among the marine isolates with 0.13 μg/mg dry cell weight. Culturing these strains under different media compositions showed that the alkane chain length was not influenced by the growth medium but was rather an inherent property of the strains. Analysis of the cellular fatty acid content indicated the presence of predominantly C16 chain length fatty acids in marine strains, while the proportion of C18 chain length fatty acids increased in the majority of freshwater strains. These results correlated with alkane chain length specificity of marine and freshwater isolates indicating that alkane chain lengths may be primarily determined by the fatty acid synthesis pathway. Moreover, the phylogenetic analysis showed clustering of pentadecane-producing marine strains that was distinct from heptadecane-producing freshwater strains strongly suggesting a close association between alkane chain length and the cyanobacteria habitat. PMID:25853127

  16. Combinatorial screening of halide perovskite thin films and solar cells by mask-defined IR laser molecular beam epitaxy.

    PubMed

    Kawashima, Kazuhiro; Okamoto, Yuji; Annayev, Orazmuhammet; Toyokura, Nobuo; Takahashi, Ryota; Lippmaa, Mikk; Itaka, Kenji; Suzuki, Yoshikazu; Matsuki, Nobuyuki; Koinuma, Hideomi

    2017-01-01

    As an extension of combinatorial molecular layer epitaxy via ablation of perovskite oxides by a pulsed excimer laser, we have developed a laser molecular beam epitaxy (MBE) system for parallel integration of nano-scaled thin films of organic-inorganic hybrid materials. A pulsed infrared (IR) semiconductor laser was adopted for thermal evaporation of organic halide (A-site: CH3NH3I) and inorganic halide (B-site: PbI2) powder targets to deposit repeated A/B bilayer films where the thickness of each layer was controlled on molecular layer scale by programming the evaporation IR laser pulse number, length, or power. The layer thickness was monitored with an in situ quartz crystal microbalance and calibrated against ex situ stylus profilometer measurements. A computer-controlled movable mask system enabled the deposition of combinatorial thin film libraries, where each library contains a vertically homogeneous film with spatially programmable A- and B-layer thicknesses. On the composition gradient film, a hole transport Spiro-OMeTAD layer was spin-coated and dried followed by the vacuum evaporation of Ag electrodes to form the solar cell. The preliminary cell performance was evaluated by measuring I-V characteristics at seven different positions on the 12.5 mm × 12.5 mm combinatorial library sample with seven 2 mm × 4 mm slits under a solar simulator irradiation. The combinatorial solar cell library clearly demonstrated that the energy conversion efficiency sharply changes from nearly zero to 10.2% as a function of the illumination area in the library. The exploration of deposition parameters for obtaining optimum performance could thus be greatly accelerated. Since the thickness ratio of PbI2 and CH3NH3I can be freely chosen along the shadow mask movement, these experiments show the potential of this system for high-throughput screening of optimum chemical composition in the binary film library and application to halide perovskite solar cell.

  17. Development of molecular precursors for deposition of indium sulphide thin film electrodes for photoelectrochemical applications.

    PubMed

    Ehsan, Muhammad Ali; Peiris, T A Nirmal; Wijayantha, K G Upul; Olmstead, Marilyn M; Arifin, Zainudin; Mazhar, Muhammad; Lo, K M; McKee, Vickie

    2013-08-14

    Symmetrical and unsymmetrical dithiocarbamato pyridine solvated and non-solvated complexes of indium(III) with the general formula [In(S2CNRR')3]·n(py) [where py = pyridine; R,R' = Cy, n = 2 (1); R,R' = (i)Pr, n = 1.5 (2); NRR' = Pip, n = 0.5 (3) and R = Bz, R' = Me, n = 0 (4)] have been synthesized. The compositions, structures and properties of these complexes have been studied by means of microanalysis, IR and (1)H-NMR spectroscopy, X-ray single crystal and thermogravimetric (TG/DTG) analyses. The applicability of these complexes as single source precursors (SSPs) for the deposition of β-In2S3 thin films on fluorine-doped SnO2 (FTO) coated conducting glass substrates by aerosol-assisted chemical vapour deposition (AACVD) at temperatures of 300, 350 and 400 °C is studied. All films have been characterized by powder X-ray diffraction (PXRD) and energy dispersive X-ray analysis (EDX) for the detection of phase and stoichiometry of the deposit. Scanning electron microscopy (SEM) studies reveal that precursors (1)-(4), irrespective of different metal ligand design, generate comparable morphologies of β-In2S3 thin films at different temperatures. Direct band gap energies of 2.2 eV have been estimated from the UV-vis spectroscopy for the β-In2S3 films fabricated from precursors (1) and (4). The photoelectrochemical (PEC) properties of β-In2S3 were confirmed by recording the current-voltage plots under light and dark conditions. The plots showed anodic photocurrent densities of 1.25 and 0.65 mA cm(-2) at 0.23 V vs. Ag/AgCl for the β-In2S3 films made at 400 and 350 °C from the precursors (1) and (4), respectively. The photoelectrochemical performance indicates that the newly synthesised precursors are highly useful in fabricating β-In2S3 electrodes for solar energy harvesting and optoelectronic application.

  18. Catalytic conversion of light alkanes phase II. Topical report, January 1990--January 1993

    SciTech Connect

    1998-12-31

    The Topical Report on Phase II of the project entitled, Catalytic Conversion of Light Alkanes reviews work done between January 1, 1990 and September 30, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products which can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon transportation fuel. This Topical Report documents our efforts to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. Research on the Cooperative Agreement is divided into three Phases relating to three molecular environments for the active catalytic species that we are trying to generate. In this report we present our work on catalysts which have oxidation-active metals in polyoxoanions (PHASE II).

  19. Diffusion of methane and other alkanes in metal-organic frameworks for natural gas storage

    SciTech Connect

    Borah, B; Zhang, HD; Snurr, RQ

    2015-03-03

    Diffusion of methane, ethane, propane and n-butane was studied within the micropores of several metal organic frameworks (MOFs) of varying topologies, including the MOFs PCN-14, NU-125, NU-1100 and DUT-49. Diffusion coefficients of the pure components, as well as methane/ethane, methane/ propane and methane/butane binary mixtures, were calculated using molecular dynamics simulations to understand the effect of the longer alkanes on uptake of natural gas in MOB. The calculated self diffusion coefficients of all four components are on the order of 10(-8) m(2)/s. The diffusion coefficients of the pure components decrease as a function of chain length in all of the MOFs studied and show different behaviour as a function of loading in different MOB. The self-diffusivities follow the trend DPCN-14 < DNU-125 approximate to DNU-1100 < DDUT-49, which is exactly the reverse order of the densities of the MOFs: PCN-14 > NU-125 approximate to NU-1100 > DUT-49. By comparing the diffusion of pure methane and methane mixtures vvith the higher alkancs, it is observed that the diffusivity of methane is unaffected by the presence of the higher alkanes in the MOFs considered, indicating that the diffusion path of methane is not blocked by the higher alkanes present in natural gas. (C) 2014 Elsevier Ltd. All rights reserved.

  20. Succession of Alkane Conformational Motifs Bound within Hydrophobic Supramolecular Capsular Assemblies.

    PubMed

    Barnett, J Wesley; Gibb, Bruce C; Ashbaugh, Henry S

    2016-10-06

    n-Alkane encapsulation experiments within dimeric octa-acid cavitand capsules in water reveal a succession of packing motifs from extended, to helical, to hairpin, to spinning top structures with increasing chain length. Here, we report a molecular simulation study of alkane conformational preferences within these host-guest assemblies to uncover the factors stabilizing distinct conformers. The simulated alkane conformers follow the trends inferred from (1)H NMR experiments, while guest proton chemical shifts evaluated from Gauge Invariant Atomic Orbital calculations provide further evidence our simulations capture guest packing within these assemblies. Analysis of chain length and dihedral distributions indicates that packing under confinement to minimize nonpolar guest and host interior contact with water largely drives the transitions. Mean intramolecular distance maps and transfer free energy differences suggest the extended and helical motifs are members of a larger family of linear guest structures, for which the guest gauche population increases with increasing chain length to accommodate the chains within the complex. Breaks observed between the helical/hairpin and hairpin/spinning top motifs, on the other hand, indicate the hairpin and spinning top conformations are distinct from the linear family. Our results represent the first bridging of empirical and simulation data for flexible guests encapsulated within confined nanospaces, and constitute an effective strategy by which guest packing motifs within artificial or natural compartments can be rationalized and/or predicted a priori.

  1. Gene Structures and Regulation of the Alkane Hydroxylase Complex in Acinetobacter sp. Strain M-1

    PubMed Central

    Tani, Akio; Ishige, Takeru; Sakai, Yasuyoshi; Kato, Nobuo

    2001-01-01

    In the long-chain n-alkane degrader Acinetobacter sp. strain M-1, two alkane hydroxylase complexes are switched by controlling the expression of two n-alkane hydroxylase-encoding genes in response to the chain length of n-alkanes, while rubredoxin and rubredoxin ruductase are encoded by a single gene and expressed constitutively. PMID:11160120

  2. Molecular and thin film properties of cobalt half-sandwich compounds for optoelectronic application.

    PubMed

    Reinhardt, Maxwell; Dalgleish, Simon; Shuku, Yoshiaki; Reissig, Louisa; Matsushita, Michio M; Crain, Jason; Awaga, Kunio; Robertson, Neil

    2017-03-01

    The structure and electronic properties of a novel cobalt half sandwich complex of cyclopentadiene (Cp) and diaminonaphthalene (DAnap) [CpCo(DAnap)] are described and compared to the previously reported diaminobenzene derivative [CpCo(DAbnz)] in view of their potential for (opto)electronic device application. Both complexes show stable redox processes, tunable through the diaminoacene ligand, and show strong absorption in the visible region, with additional transitions stretching into the near infrared (NIR). CpCo(DAnap) crystallises with a particularly large unit cell (9301 Å(3)), comprising 32 molecules, with a gradual rotation over 8 molecules along the long c-axis. In the solid state the balance of the optical transitions in both complexes is reversed, with a suppression of the visible band and an enhancement of the NIR band, attributed to extensive intermolecular electronic interaction. In the case of CpCo(DAnap), highly crystalline thin films could be formed under physical vapor deposition, which show a photocurrent response stretching into the NIR, and p-type semiconductor behavior in field effect transistors with mobility values of the order 1 × 10(-4) cm(2) V(-1) s(-1). The device performance is understood through investigation of the morphology of the grown films.

  3. Fundamental performance limits of carbon nanotube thin-film transistors achieved using hybrid molecular dielectrics.

    PubMed

    Sangwan, Vinod K; Ortiz, Rocio Ponce; Alaboson, Justice M P; Emery, Jonathan D; Bedzyk, Michael J; Lauhon, Lincoln J; Marks, Tobin J; Hersam, Mark C

    2012-08-28

    In the past decade, semiconducting carbon nanotube thin films have been recognized as contending materials for wide-ranging applications in electronics, energy, and sensing. In particular, improvements in large-area flexible electronics have been achieved through independent advances in postgrowth processing to resolve metallic versus semiconducting carbon nanotube heterogeneity, in improved gate dielectrics, and in self-assembly processes. Moreover, controlled tuning of specific device components has afforded fundamental probes of the trade-offs between materials properties and device performance metrics. Nevertheless, carbon nanotube transistor performance suitable for real-world applications awaits understanding-based progress in the integration of independently pioneered device components. We achieve this here by integrating high-purity semiconducting carbon nanotube films with a custom-designed hybrid inorganic-organic gate dielectric. This synergistic combination of materials circumvents conventional design trade-offs, resulting in concurrent advances in several transistor performance metrics such as transconductance (6.5 μS/μm), intrinsic field-effect mobility (147 cm(2)/(V s)), subthreshold swing (150 mV/decade), and on/off ratio (5 × 10(5)), while also achieving hysteresis-free operation in ambient conditions.

  4. Ferredoxin molecular thin film with intrinsic switching mechanism for biomemory application.

    PubMed

    Yagati, Ajay Kumar; Kim, Sang-Uk; Min, Junhong; Choi, Jeong-Woo

    2010-05-01

    A biomemory device consisting of cysteine modified ferredoxin molecules which possess a memory effect via a charge transfer mechanism was developed. For achieving an efficient bioelectronic device, cysteine modified ferredoxin was developed by embodying cysteine residues in ferredoxin by site--directed mutagenesis method to directly coordinate with the gold (Au) surface without use of any additional linkers. The thin film formation of ferredoxin molecules on Au electrode is confirmed by surface plasmon resonance (SPR) spectroscopy and scanning tunneling microscope (STM). Cyclic voltammetry (CV) and open circuit potential amperometry (OCPA) methods were used to verify the memory switching characteristics of the fabricated device. The charge transfer between ferredoxin protein molecules and Au electrode enables a bi-stable electrical conductivity allowing the system to be used as a digital memory device. Data storage is achieved by applying redox voltages which are within the range of -500 mV. These results suggest that the proposed device has a function of memory and can be used for the construction of a nano-scale bioelectronic device.

  5. Involvement of an alkane hydroxylase system of Gordonia sp. strain SoCg in degradation of solid n-alkanes.

    PubMed

    Lo Piccolo, Luca; De Pasquale, Claudio; Fodale, Roberta; Puglia, Anna Maria; Quatrini, Paola

    2011-02-01

    Enzymes involved in oxidation of long-chain n-alkanes are still not well known, especially those in gram-positive bacteria. This work describes the alkane degradation system of the n-alkane degrader actinobacterium Gordonia sp. strain SoCg, which is able to grow on n-alkanes from dodecane (C(12)) to hexatriacontane (C(36)) as the sole C source. SoCg harbors in its chromosome a single alk locus carrying six open reading frames (ORFs), which shows 78 to 79% identity with the alkane hydroxylase (AH)-encoding systems of other alkane-degrading actinobacteria. Quantitative reverse transcription-PCR showed that the genes encoding AlkB (alkane 1-monooxygenase), RubA3 (rubredoxin), RubA4 (rubredoxin), and RubB (rubredoxin reductase) were induced by both n-hexadecane and n-triacontane, which were chosen as representative long-chain liquid and solid n-alkane molecules, respectively. Biotransformation of n-hexadecane into the corresponding 1-hexadecanol was detected by solid-phase microextraction coupled with gas chromatography-mass spectrometry (SPME/GC-MS) analysis. The Gordonia SoCg alkB was heterologously expressed in Escherichia coli BL21 and in Streptomyces coelicolor M145, and both hosts acquired the ability to transform n-hexadecane into 1-hexadecanol, but the corresponding long-chain alcohol was never detected on n-triacontane. However, the recombinant S. coelicolor M145-AH, expressing the Gordonia alkB gene, was able to grow on n-triacontane as the sole C source. A SoCg alkB disruption mutant that is completely unable to grow on n-triacontane was obtained, demonstrating the role of an AlkB-type AH system in degradation of solid n-alkanes.

  6. Molecular layer deposition of functional thin films for advanced lithographic patterning.

    PubMed

    Zhou, Han; Bent, Stacey F

    2011-02-01

    Photoresist materials comprise one of the main challenges faced by lithography to meet the requirements of electronic device size scaling. Here we report for the first time the use of molecular layer deposition (MLD) to produce photoresist materials with controllable placement of functional moieties. Polyurea resists films are deposited by MLD using urea coupling reactions between 1,4-phenylene diisocyanate (PDIC) and ethylenediamine (ED) or 2,2'-(propane-2,2-diylbis(oxy))diethanamine (PDDE) monomers in a layer-by-layer fashion with a linear growth rate, allowing acid-labile groups to be incorporated into the film at well-controlled positions. The films are deposited with stoichiometric compositions and have highly uniform surface morphology as investigated using atomic force microscopy. We show that acid treatment can cleave the backbone of the polyurea film at positions where the acid-labile groups are embedded. We further show that after soaking the polyurea film with photoacid generator (PAG), it acts as a photoresist material and we present several UV patterning demonstrations. This approach presents a new way to make molecularly designed resist films for lithography.

  7. The performance of thin layers produced by molecular plating as α-particle sources

    NASA Astrophysics Data System (ADS)

    Vascon, A.; Wiehl, N.; Reich, T.; Drebert, J.; Eberhardt, K.; Düllmann, Ch. E.

    2013-09-01

    Sources for α-spectroscopy studies were prepared. Constant current density molecular plating was used to produce layers containing the α-particle emitter 147Sm. Different parameters of the molecular plating process were varied, namely the plating solvent (an isopropanol/isobutanol mixture, pyridine, and N,N-dimethylformamide), the applied deposition time (90, 180, and 360 min), and the surface roughness of the deposition substrate (ca. 10, 20, and 300 nm). Using different analytical techniques, Sm deposition yields, chemical composition of the produced surfaces, surface homogeneity, roughness and morphology were investigated. Alpha spectra were recorded with a Si solid-state detector for samples belonging to the different types of characterized sources, and big differences in the peak shape and position of the peak maximum were observed, as well as significant differences in the fraction of α particles reaching the detector positioned above the samples. An explanation for the observed features is presented. The results of these studies led to the identification of the key plating parameters, namely the plating solvent and the roughness of the deposition substrate, which most affect the quality of the α spectra.

  8. Realization of Cu-Doped p-Type ZnO Thin Films by Molecular Beam Epitaxy.

    PubMed

    Suja, Mohammad; Bashar, Sunayna B; Morshed, Muhammad M; Liu, Jianlin

    2015-04-29

    Cu-doped p-type ZnO films are grown on c-sapphire substrates by plasma-assisted molecular beam epitaxy. Photoluminescence (PL) experiments reveal a shallow acceptor state at 0.15 eV above the valence band edge. Hall effect results indicate that a growth condition window is found for the formation of p-type ZnO thin films, and the best conductivity is achieved with a high hole concentration of 1.54 × 10(18) cm(-3), a low resistivity of 0.6 Ω cm, and a moderate mobility of 6.65 cm(2) V(-1) s(-1) at room temperature. Metal oxide semiconductor capacitor devices have been fabricated on the Cu-doped ZnO films, and the characteristics of capacitance-voltage measurements demonstrate that the Cu-doped ZnO thin films under proper growth conditions are p-type. Seebeck measurements on these Cu-doped ZnO samples lead to positive Seebeck coefficients and further confirm the p-type conductivity. Other measurements such as X-ray diffraction, X-ray photoelectron, Raman, and absorption spectroscopies are also performed to elucidate the structural and optical characteristics of the Cu-doped p-type ZnO films. The p-type conductivity is explained to originate from Cu substitution of Zn with a valency of +1 state. However, all p-type samples are converted to n-type over time, which is mostly due to the carrier compensation from extrinsic defects of ZnO.

  9. Molecular aspects of polyene- and sterol-dependent pore formation in thin lipid membranes.

    PubMed

    Dennis, V W; Stead, N W; Andreoli, T E

    1970-03-01

    Amphotericin B modifies the permeability properties of thin lipid membranes formed from solutions containing sheep red cell phospholipids and cholesterol. At 10(-6)M amphotericin B, the DC membrane resistance fell from approximately 10(8) to approximately 10(2) ohm-cm(2), and the membranes became Cl(-)-, rather than Na(+)-selective; the permeability coefficients for hydrophilic nonelectrolytes increased in inverse relationship to solute size, and the rate of water flow during osmosis increased 30-fold. These changes may be rationalized by assuming that the interaction of amphotericin B with membrane-bound sterol resulted in the formation of aqueous pores. N-acetylamphotericin B and the methyl ester of N-acetylamphotericin B, but not the smaller ring compounds, filipin, rimocidin, and PA-166, produced comparable permeability changes in identical membranes, and amphotericin B and its derivatives produced similar changes in the properties of membranes formed from phospholipid-free sterol solutions. However, amphotericin B did not affect ionic selectivity or water and nonelectrolyte permeability in membranes formed from solutions containing phospholipids and no added cholesterol, or when cholesterol was replaced by either cholesterol palmitate, dihydrotachysterol, epicholesterol, or Delta5-cholesten-3-one. Phospholipid-free sterol membranes exposed to amphotericin B or its derivatives were anion-selective, but the degree of Cl(-) selectivity varied among the compounds, and with the aqueous pH. The data are discussed with regard to, first, the nature of the polyene-sterol interactions which result in pore formation, and second, the functional groups on amphotericin B responsible for membrane anion selectivity.

  10. Molecular Aspects of Polyene- and Sterol-Dependent Pore Formation in Thin Lipid Membranes

    PubMed Central

    Dennis, Vincent W.; Stead, Nancy W.; Andreoli, Thomas E.

    1970-01-01

    Amphotericin B modifies the permeability properties of thin lipid membranes formed from solutions containing sheep red cell phospholipids and cholesterol. At 10-6 M amphotericin B, the DC membrane resistance fell from ≈108 to ≈102 ohm-cm2, and the membranes became Cl--, rather than Na+-selective; the permeability coefficients for hydrophilic nonelectrolytes increased in inverse relationship to solute size, and the rate of water flow during osmosis increased 30-fold. These changes may be rationalized by assuming that the interaction of amphotericin B with membrane-bound sterol resulted in the formation of aqueous pores. N-acetylamphotericin B and the methyl ester of N-acetylamphotericin B, but not the smaller ring compounds, filipin, rimocidin, and PA-166, produced comparable permeability changes in identical membranes, and amphotericin B and its derivatives produced similar changes in the properties of membranes formed from phospholipid-free sterol solutions. However, amphotericin B did not affect ionic selectivity or water and nonelectrolyte permeability in membranes formed from solutions containing phospholipids and no added cholesterol, or when cholesterol was replaced by either cholesterol palmitate, dihydrotachysterol, epicholesterol, or Δ5-cholesten-3-one. Phospholipid-free sterol membranes exposed to amphotericin B or its derivatives were anion-selective, but the degree of Cl- selectivity varied among the compounds, and with the aqueous pH. The data are discussed with regard to, first, the nature of the polyene-sterol interactions which result in pore formation, and second, the functional groups on amphotericin B responsible for membrane anion selectivity. PMID:4938534

  11. On the dynamic and static manifestation of molecular absorption in thin films probed by a microcantilever

    SciTech Connect

    Finot, Eric; Fabre, Arnaud; Passian, Ali; Thundat, Thomas

    2014-03-01

    Mechanical resonators shaped like microcantilevers have been demonstrated as a platform for very sensitive detection of chemical and biological analytes. However, its use as an analytical tool will require fundamental understanding of the molecular absorption-induced effects in the static and dynamic sensor response. The effect of absorption-induced surface stress on the microcantilever response is here investigated using palladium hydride formation. It is shown that the resonance and deformation states of the cantilever monitored simultaneously exhibit excellent correlation with the phase of the hydride formation. However, the associated frequency shifts and quasistatic bending are observed to be independent during solid solution phase. Importantly, absorption-induced changes in the elastic parameters of the palladium film are found to play a dominant role in the static and dynamic response. The presented results help in discerning the parameters that control the cantilever response as well as the relationships between these parameters.

  12. Synthesis of atomically thin hexagonal boron nitride films on nickel foils by molecular beam epitaxy

    SciTech Connect

    Nakhaie, S.; Wofford, J. M.; Schumann, T.; Jahn, U.; Ramsteiner, M.; Hanke, M.; Lopes, J. M. J. Riechert, H.

    2015-05-25

    Hexagonal boron nitride (h-BN) is a layered two-dimensional material with properties that make it promising as a dielectric in various applications. We report the growth of h-BN films on Ni foils from elemental B and N using molecular beam epitaxy. The presence of crystalline h-BN over the entire substrate is confirmed by Raman spectroscopy. Atomic force microscopy is used to examine the morphology and continuity of the synthesized films. A scanning electron microscopy study of films obtained using shorter depositions offers insight into the nucleation and growth behavior of h-BN on the Ni substrate. The morphology of h-BN was found to evolve from dendritic, star-shaped islands to larger, smooth triangular ones with increasing growth temperature.

  13. Mechanism of Charge Transport in Cobalt and Iron Phthalocyanine Thin Films Grown by Molecular Beam Epitaxy

    SciTech Connect

    Kumar, Arvind; Samanta, Soumen; Singh, Ajay; Debnath, A. K.; Aswal, D. K.; Gupta, S. K.

    2011-12-12

    Cobalt phthalocyanine (CoPc), iron phthalocyanine (FePc) and their composite (CoPc-FePc) films have been grown by molecular beam epitaxy (MBE). Grazing incidence X-ray diffraction (GIXRD) and scanning electron microscope (SEM) studies showed that composite films has better structural ordering compared to individual CoPc and FePc films. The temperature dependence of resistivity (in the temperature range 25 K- 100 K) showed that composite films are metallic, while individual CoPc and FePc films are in the critical regime of metal-to-insulator (M-I) transition The composite films show very high mobility of 110 cm{sup 2} V{sup -1} s{sup -1} at room temperature i.e. nearly two order of magnitude higher compared to pure CoPc and FePc films.

  14. Process for converting light alkanes to higher hydrocarbons

    DOEpatents

    Noceti, Richard P.; Taylor, Charles E.

    1988-01-01

    A process is disclosed for the production of aromatic-rich, gasoline boiling range hydrocarbons from the lower alkanes, particularly from methane. The process is carried out in two stages. In the first, alkane is reacted with oxygen and hydrogen chloride over an oxyhydrochlorination catalyst such as copper chloride with minor proportions of potassium chloride and rare earth chloride. This produces an intermediate gaseous mixture containing water and chlorinated alkanes. The chlorinated alkanes are contacted with a crystalline aluminosilicate catalyst in the hydrogen or metal promoted form to produce gasoline range hydrocarbons with a high proportion of aromatics and a small percentage of light hydrocarbons (C.sub.2 -C.sub.4). The light hydrocarbons can be recycled for further processing over the oxyhydrochlorination catalyst.

  15. DITERMINAL OXIDATION OF LONG-CHAIN ALKANES BY BACTERIA1

    PubMed Central

    Kester, A. S.; Foster, J. W.

    1963-01-01

    Kester, A. S. (The University of Texas, Austin) and J. W. Foster. Diterminal oxidation of long-chain alkanes by bacteria. J. Bacteriol. 85:859–869. 1963.—A corynebacterial organism capable of growing in mineral salts with individual pure alkanes as carbon sources produces a series of acids from the C10-C14 alkanes. They have been isolated in pure form and identified as monoic, ω-hydroxy monoic, and dioic acids containing the same number of carbon atoms as the substrate alkane. Oxidation took place at both terminal methyl groups—“diterminal oxidation.” Appropriate labeling experiments indicate that omega oxidation of fatty acids occurs in this organism and that an oxygenation with O2 occurs. Images PMID:14044955

  16. Specifics of freezing of Lennard-Jones fluid confined to molecularly thin layers

    NASA Astrophysics Data System (ADS)

    Vishnyakov, Aleksey; Neimark, Alexander V.

    2003-04-01

    Freezing of a Lennard-Jones fluid between solid surfaces was studied using grand canonical Monte Carlo and molecular dynamics simulations. We explored the formation of frozen phases of hexagonal and orthorhombic symmetry in mono-, bi-, and tri-layer structures. The freezing transition, the type of lattice, and translational and orientational ordering were identified on the basis of orientational order parameters, in-plane two-body and three-body translational correlation functions, orientational correlation functions, and analysis of molecular mobilities. We have found that the freezing temperature is a nonmonotonous function of the pore width: orthorhombic bi-layer freezes at lower temperatures than hexagonal monolayer and hexagonal bi-layer. As the pore width increases, the transition from a hexagonal monolayer to an orthorhombic bi-layer occurred via disordered liquidlike and quasi-long-range four-fold ordered bi-layers. The latter, "quadratic" structure is characterized by an algebraically decaying four-fold orientational correlation function. The transition from crystalline hexagonal bi-layer to orthorhombic tri-layer occurs through a bi-layer structure with two uncoupled hexagonal monolayers. The quadratic phase was observed also as an intermediate structure during freezing of a liquidlike bi-layer into an orthorhombic quasi-crystal. The formation of the quadratic phase was associated with step-wise densification of fluid, a sharp increase of the local orientational order parameter, and a significant reduction of fluid mobility. In the process of solidification, the system passed through a sequence of high-density jammed structures, in which the four-fold symmetry developed progressively, as the temperature decreased.

  17. Site-selective Alkane Dehydrogenation of Fatty Acids

    DTIC Science & Technology

    2011-12-14

    dehydrogenation of fatty acids Contract/Grant#: FA9550-10-1-0532 Final Reporting Period: 15 September 2011 to 14 September 2011...directly incorporate fatty acids into the ligand. The preparation of the acyl phosphines (1-5) was easily accomplished starting from the corresponding...AFOSR Final Report Final Report 
 The proposed research examines the site-selective dehydrogenation of alkanes. The alkanes employed were fatty

  18. Electrical and mechanical properties of molecularly functionalized mesoporous silica thin films

    NASA Astrophysics Data System (ADS)

    Singh, Amit Pratap

    Mesoporous silica (MPS) thin films are attractive for achieving low relative dielectric permittivity (low-kappa) interlayer isolation in integrated circuit wiring, but are susceptible to instabilities in electrical behavior due to water uptake and copper diffusion. This work investigates the electrical, chemical, and thermal instabilities, Cu diffusion, and adhesion of these materials for evaluating and enabling their use for applications as interlayer insulators in nanodevice wiring. Upon annealing Al/MPS/Si(001)/Al capacitors between 80 to 200°C, the flat-band voltage first increases, reaches a maximum, and then decreases. Concurrently, the initially observed deep depletion behavior is replaced by strong inversion. Subsequent air-exposure restores the preanneal C-V characteristics. Kinetics analyses reveal two thermally activated processes: proton generation through fissure of silanol bonds (activation energy Ea1 = 0.42 +/- 0.04 eV) and proton-induced depassivation of dangling bond traps (Ea2 = 0.54 +/- 0.05 eV) at the MPS/Si interface. We present an empirical model correlating these processes with the C-V characteristics. Further, we show that capping MPS films with a trimethyl-terminated organosilane irreversibly suppresses moisture-induced capacitance instabilities, and decreases the relative dielectric permittivity and Cu-induced leakage currents. Analysis of capacitance-voltage and current-voltage characteristics along with infrared spectroscopy shows that the trimethyl organosilanes inhibit hydrogen bonding of water molecules by rendering the dielectric surfaces hydrophobic. Fracture behavior and mechanical properties of pristine (i.e., un-functionalized MPS) and silylated mesoporous silica (SMPS) films were studied by four-point bend tests and nanoindentation measurements. Four-point bend measurements on Si/epoxy/Ti/Cu/MPS/Si stacks show that structures with un-silylated MPS films fracture at ˜3 J/m2, while those with SMPS films show a ˜50% lower

  19. Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle

    PubMed Central

    Lea-Smith, David J.; Biller, Steven J.; Davey, Matthew P.; Cotton, Charles A. R.; Perez Sepulveda, Blanca M.; Turchyn, Alexandra V.; Scanlan, David J.; Smith, Alison G.; Chisholm, Sallie W.; Howe, Christopher J.

    2015-01-01

    Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2–540 pg alkanes per mL per day, which translates into a global ocean yield of ∼308–771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities. PMID:26438854

  20. Product Repression of Alkane Monooxygenase Expression in Pseudomonas butanovora

    PubMed Central

    Doughty, D. M.; Sayavedra-Soto, L. A.; Arp, D. J.; Bottomley, P. J.

    2006-01-01

    Physiological and regulatory mechanisms that allow the alkane-oxidizing bacterium Pseudomonas butanovora to consume C2 to C8 alkane substrates via butane monooxygenase (BMO) were examined. Striking differences were observed in response to even- versus odd-chain-length alkanes. Propionate, the downstream product of propane oxidation and of the oxidation of other odd-chain-length alkanes following β-oxidation, was a potent repressor of BMO expression. The transcriptional activity of the BMO promoter was reduced with as little as 10 μM propionate, even in the presence of appropriate inducers. Propionate accumulated stoichiometrically when 1-propanol and propionaldehyde were added to butane- and ethane-grown cells, indicating that propionate catabolism was inactive during growth on even-chain-length alkanes. In contrast, propionate consumption was induced (about 80 nmol propionate consumed · min−1 · mg protein−1) following growth on the odd-chain-length alkanes, propane and pentane. The induction of propionate consumption could be brought on by the addition of propionate or pentanoate to the growth medium. In a reporter strain of P. butanovora in which the BMO promoter controls β-galactosidase expression, only even-chain-length alcohols (C2 to C8) induced β-galactosidase following growth on acetate or butyrate. In contrast, both even- and odd-chain-length alcohols (C3 to C7) were able to induce β-galactosidase following the induction of propionate consumption by propionate or pentanoate. PMID:16547046

  1. Contribution of cyanobacterial alkane production to the ocean hydrocarbon cycle.

    PubMed

    Lea-Smith, David J; Biller, Steven J; Davey, Matthew P; Cotton, Charles A R; Perez Sepulveda, Blanca M; Turchyn, Alexandra V; Scanlan, David J; Smith, Alison G; Chisholm, Sallie W; Howe, Christopher J

    2015-11-03

    Hydrocarbons are ubiquitous in the ocean, where alkanes such as pentadecane and heptadecane can be found even in waters minimally polluted with crude oil. Populations of hydrocarbon-degrading bacteria, which are responsible for the turnover of these compounds, are also found throughout marine systems, including in unpolluted waters. These observations suggest the existence of an unknown and widespread source of hydrocarbons in the oceans. Here, we report that strains of the two most abundant marine cyanobacteria, Prochlorococcus and Synechococcus, produce and accumulate hydrocarbons, predominantly C15 and C17 alkanes, between 0.022 and 0.368% of dry cell weight. Based on global population sizes and turnover rates, we estimate that these species have the capacity to produce 2-540 pg alkanes per mL per day, which translates into a global ocean yield of ∼ 308-771 million tons of hydrocarbons annually. We also demonstrate that both obligate and facultative marine hydrocarbon-degrading bacteria can consume cyanobacterial alkanes, which likely prevents these hydrocarbons from accumulating in the environment. Our findings implicate cyanobacteria and hydrocarbon degraders as key players in a notable internal hydrocarbon cycle within the upper ocean, where alkanes are continually produced and subsequently consumed within days. Furthermore we show that cyanobacterial alkane production is likely sufficient to sustain populations of hydrocarbon-degrading bacteria, whose abundances can rapidly expand upon localized release of crude oil from natural seepage and human activities.

  2. Hydrogen isotopic composition of individual n-alkanes as an intrinsic tracer for bioremediation and source identification of petroleum contamination.

    PubMed

    Pond, Kristy L; Huang, Yongsong; Wang, Yi; Kulpa, Charles F

    2002-02-15

    The isotopic signatures of crude oil hydrocarbons are potentially powerful intrinsic tracers to their origins and the processes by which the oils are modified in the environment. Stable carbon isotopic data are of limited use for studying petroleum contaminants because of the relatively small amount of isotopic fractionation that occurs during natural processes. Hydrogen isotopes, in contrast, are commonly fractionated to a much greater extent and as a result display larger variations in delta values. We studied the effect of in vitro aerobic biodegradation on the hydrogen isotopic composition of individual n-alkanes from crude oil. The isotopic analysis was conducted using gas chromatography-thermal conversion-isotope ratio mass spectrometry. In general, biodegradation rates decreased with increasing hydrocarbon chain length, consistent with previous studies. More importantly the n-alkanes that were degraded at the fastest rates (n-C15 to n-C18) also showed the largest overall isotopic fractionation (approximately 12-25 per thousand deuterium enrichment), suggesting that the lower molecular weight n-alkanes can be used to monitor in-situ bioremediation of crude oil contamination. The hydrogen isotopic compositions of the longer chain alkanes (n-C19 to n-C27) were relatively stable during biodegradation (<5%o overall deuterium enrichment), indicating that these compounds are effective tracers for oil-source identification studies.

  3. Enthalpy difference between conformations of normal alkanes: effects of basis set and chain length on intramolecular basis set superposition error

    NASA Astrophysics Data System (ADS)

    Balabin, Roman M.

    2011-03-01

    The quantum chemistry of conformation equilibrium is a field where great accuracy (better than 100 cal mol-1) is needed because the energy difference between molecular conformers rarely exceeds 1000-3000 cal mol-1. The conformation equilibrium of straight-chain (normal) alkanes is of particular interest and importance for modern chemistry. In this paper, an extra error source for high-quality ab initio (first principles) and DFT calculations of the conformation equilibrium of normal alkanes, namely the intramolecular basis set superposition error (BSSE), is discussed. In contrast to out-of-plane vibrations in benzene molecules, diffuse functions on carbon and hydrogen atoms were found to greatly reduce the relative BSSE of n-alkanes. The corrections due to the intramolecular BSSE were found to be almost identical for the MP2, MP4, and CCSD(T) levels of theory. Their cancelation is expected when CCSD(T)/CBS (CBS, complete basis set) energies are evaluated by addition schemes. For larger normal alkanes (N > 12), the magnitude of the BSSE correction was found to be up to three times larger than the relative stability of the conformer; in this case, the basis set superposition error led to a two orders of magnitude difference in conformer abundance. No error cancelation due to the basis set superposition was found. A comparison with amino acid, peptide, and protein data was provided.

  4. Absolute photoluminescence quantum yield of molecular organic thin films: effects of doping with strongly fluorescent rubrene

    NASA Astrophysics Data System (ADS)

    Mattoussi, Hedi M.; Murata, Hideyuki; Merritt, Charles D.; Kafafi, Zakya H.

    1998-12-01

    We present data on the absolute photoluminescence quantum yield (phi) PL, for a set of pure and molecularly doped organic solid films. The procedure uses an integrating sphere to provide accurate measure of the photoluminescence efficiency for solid, sub-micron thickness, films. Host materials include a common hole transport compounds, N,N- dipheny-N,N-bis(3-methylphenyl)-1,1-biphenyl-4,4-diamine, TPD, and two metal chelates used as electron transport and/or light emitting materials, tris (8- hydroxyquinolinolato) aluminum (III), Alq3, and one of its methyl derivatives, tris (8- trimethylhydroxyquinolinolator) aluminum (III), Almq3, Tetraphenylnapthacene, or rubrene, is used as the dopant. A substantial increase in (phi) PL is measured with respect to the pure host. For example, the measured (phi) PL increases from 0.25 and 0.40 for pure Alq3 and Almq3, respectively, to near unity upon doping with rubrene at approximately 1 mol percent. The data are discussed within the framework of Foerster energy transfer.

  5. Molecular dynamics simulation of nano-indentation on Ti-V multilayered thin films

    NASA Astrophysics Data System (ADS)

    Feng, Chao; Peng, Xianghe; Fu, Tao; Zhao, Yinbo; Huang, Cheng; Wang, Zhongchang

    2017-03-01

    We developed a second nearest-neighbor modified embedded-atom method potential for binary Ti-V system. The potential parameters were identified by fitting the lattice parameter, cohesive energy and elastic constants of CsCl-type TiV, and further validated by reproducing the fundamental physical and mechanical properties of Ti-V systems with other crystal structures. In addition, we also performed molecular dynamics simulations of nano-indentation processes of pure Ti film, pure V film, and two kinds of four-layer Ti-V films, V-Ti-V-Ti and Ti-V-Ti-V. We found that the indentation force-depth curve for the pure V film turns flat at an indentation depth of 2.8 nm, where a prismatic loop was observed. Such prismatic loop is not found in the V/Ti/V/Ti multilayer because the thickness of each layer is insufficient for the formation of such prismatic loops, which accounts for the increase of stress in the multilayer.

  6. International Symposium on Molecular Beams (14th) Held in Pacific Grove, California on June 7 -12, 1992.

    DTIC Science & Technology

    1993-08-09

    simulations: a) Hg(H 2 0) 8 b) HgAr 8 330 Molecular Beam Studies of Alkane Adsorption Dynamics on Clean and Adsorbate-Modified Pt(111) Mark C. McMaster...The first step in furthering this understanding is investigating the adsorption dynamics of alkanes on a platinum surface. By use of molecular beam...techniques, this area has been examined in our laboratory: 1) Dissociative adsorption dynamics of alkanes of varying molecular weight on a clean Pt( 111

  7. Hydrogen bond fluctuations and dispersive interactions of alcohol/alkane mixtures. An ultrasonic relaxation study

    NASA Astrophysics Data System (ADS)

    Kaatze, Udo; Behrends, Ralph

    2011-06-01

    The relaxation behaviour of 1-hexanol/n-heptane and 1-dodecanol/n-tetradecane mixtures has been studied at some compositions using ultrasonic attenuation spectrometry in the frequency range 0.4-3000 MHz. All mixtures reveal a relaxation term due to hydrogen network fluctuations. It is discussed in conjunction with the principle dielectric relaxation of alcohol/alkane mixtures, indicating a dynamically micro-heterogeneous liquid structure. The spectra of the long-chain alcohol system display an additional relaxation due to the structural isomerisation of the hydrocarbon chains. In terms of a torsional oscillator model this relaxation reveals the effect of molecular ordering on the enthalpy of activation.

  8. Photoconductivity of ultra-thin Ge(GeSn) layers grown in Si by low-temperature molecular beam epitaxy

    SciTech Connect

    Talochkin, A. B.; Chistokhin, I. B.; Mashanov, V. I.

    2016-04-07

    Photoconductivity (PC) spectra of Si/Ge(GeSn)/Si structures with the ultra-thin (1.0–2.3 nm) Ge and GeSn alloy layers grown by the low-temperature (T = 100 °C) molecular beam epitaxy are studied. Photoresponse in the range of 1.2–0.4 eV related to light absorption in the buried Ge(GeSn) layer is observed. It is shown that in case of lateral PC, a simple diffusion model can be used to determine the absorption coefficient of this layer α ∼ 10{sup 5 }cm{sup −1}. This value is 100 times larger than that of a single Ge quantum dot layer and is reached significantly above the band gap of most bulk semiconductors. The observed absorption is caused by optical transitions between electron and hole states localized at the interfaces. The anomalous high value of α can be explained by the unusual state of Ge(GeSn) layer with high concentration of dangling bonds, the optical properties of which have been predicted theoretically by Knief and von Niessen (Phys. Rev. B 59, 12940 (1999)).

  9. Avoiding polar catastrophe in the growth of polarly orientated nickel perovskite thin films by reactive oxide molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Yang, H. F.; Liu, Z. T.; Fan, C. C.; Yao, Q.; Xiang, P.; Zhang, K. L.; Li, M. Y.; Liu, J. S.; Shen, D. W.

    2016-08-01

    By means of the state-of-the-art reactive oxide molecular beam epitaxy, we synthesized (001)- and (111)-orientated polar LaNiO3 thin films. In order to avoid the interfacial reconstructions induced by polar catastrophe, screening metallic Nb-doped SrTiO3 and iso-polarity LaAlO3 substrates were chosen to achieve high-quality (001)-orientated films in a layer-by-layer growth mode. For largely polar (111)-orientated films, we showed that iso-polarity LaAlO3 (111) substrate was more suitable than Nb-doped SrTiO3. In situ reflection high-energy electron diffraction, ex situ high-resolution X-ray diffraction, and atomic force microscopy were used to characterize these films. Our results show that special attentions need to be paid to grow high-quality oxide films with polar orientations, which can prompt the explorations of all-oxide electronics and artificial interfacial engineering to pursue intriguing emergent physics like proposed interfacial superconductivity and topological phases in LaNiO3 based superlattices.

  10. Spectral analysis of nonequilibrium molecular dynamics: Spectral phonon temperature and local nonequilibrium in thin films and across interfaces

    NASA Astrophysics Data System (ADS)

    Feng, Tianli; Yao, Wenjun; Wang, Zuyuan; Shi, Jingjing; Li, Chuang; Cao, Bingyang; Ruan, Xiulin

    2017-05-01

    Although extensive experimental and theoretical works have been conducted to understand the ballistic and diffusive phonon transport in nanomaterials recently, direct observation of temperature and thermal nonequilibrium of different phonon modes has not been realized. Herein, we have developed a method within the framework of molecular dynamics to calculate the temperatures of phonons in both real and phase spaces. Taking silicon thin film and graphene as examples, we directly obtained the spectral phonon temperature (SPT) and observed the local thermal nonequilibrium between the ballistic and diffusive phonons. Such nonequilibrium also generally exists across interfaces and is surprisingly large, and it provides a significant additional thermal interfacial resistance mechanism besides phonon reflection. Our SPT results directly show that the vertical thermal transport across the dimensionally mismatched graphene-substrate interface is through the coupling between flexural acoustic phonons of graphene and the longitudinal phonons in the substrate with mode conversion. In the dimensionally matched interfaces, e.g., graphene-graphene junction and graphene-boron nitride planar interfaces, strong coupling occurs between the acoustic phonon modes on both sides, and the coupling decreases with interfacial mixing. The SPT method together with the spectral heat flux can eliminate the size effect of the thermal conductivity prediction induced from ballistic transport.

  11. Epitaxial CuInSe2 thin films grown by molecular beam epitaxy and migration enhanced epitaxy

    NASA Astrophysics Data System (ADS)

    Abderrafi, K.; Ribeiro-Andrade, R.; Nicoara, N.; Cerqueira, M. F.; Gonzalez Debs, M.; Limborço, H.; Salomé, P. M. P.; Gonzalez, J. C.; Briones, F.; Garcia, J. M.; Sadewasser, S.

    2017-10-01

    While CuInSe2 chalcopyrite materials are mainly used in their polycrystalline form to prepare thin film solar cells, epitaxial layers have been used for the characterization of defects. Typically, epitaxial layers are grown by metal-organic vapor phase epitaxy or molecular beam epitaxy (MBE). Here we present epitaxial layers grown by migration enhanced epitaxy (MEE) and compare the materials quality to MBE grown layers. CuInSe2 layers were grown on GaAs (0 0 1) substrates by co-evaporation of Cu, In, and Se using substrate temperatures of 450 °C, 530 °C, and 620 °C. The layers were characterized by high resolution X-ray diffraction (HR-XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and atomic force microscopy (AFM). HR-XRD and HR-TEM show a better crystalline quality of the MEE grown layers, and Raman scattering measurements confirm single phase CuInSe2. AFM shows the previously observed faceting of the (0 0 1) surface into {1 1 2} facets with trenches formed along the [1 1 0] direction. The surface of MEE-grown samples appears smoother compared to MBE-grown samples, a similar trend is observed with increasing growth temperature.

  12. Avoiding polar catastrophe in the growth of polarly orientated nickel perovskite thin films by reactive oxide molecular beam epitaxy

    SciTech Connect

    Yang, H. F.; Liu, Z. T.; Fan, C. C.; Xiang, P.; Zhang, K. L.; Li, M. Y.; Liu, J. S.; Yao, Q.; Shen, D. W.

    2016-08-15

    By means of the state-of-the-art reactive oxide molecular beam epitaxy, we synthesized (001)- and (111)-orientated polar LaNiO{sub 3} thin films. In order to avoid the interfacial reconstructions induced by polar catastrophe, screening metallic Nb-doped SrTiO{sub 3} and iso-polarity LaAlO{sub 3} substrates were chosen to achieve high-quality (001)-orientated films in a layer-by-layer growth mode. For largely polar (111)-orientated films, we showed that iso-polarity LaAlO{sub 3} (111) substrate was more suitable than Nb-doped SrTiO{sub 3}. In situ reflection high-energy electron diffraction, ex situ high-resolution X-ray diffraction, and atomic force microscopy were used to characterize these films. Our results show that special attentions need to be paid to grow high-quality oxide films with polar orientations, which can prompt the explorations of all-oxide electronics and artificial interfacial engineering to pursue intriguing emergent physics like proposed interfacial superconductivity and topological phases in LaNiO{sub 3} based superlattices.

  13. Spinodal decomposition in thin films: Molecular-dynamics simulations of a binary Lennard-Jones fluid mixture

    NASA Astrophysics Data System (ADS)

    Das, Subir K.; Puri, Sanjay; Horbach, Jürgen; Binder, Kurt

    2006-03-01

    We use molecular dynamics (MD) to simulate an unstable homogeneous mixture of binary fluids (AB), confined in a slit pore of width D . The pore walls are assumed to be flat and structureless and attract one component of the mixture (A) with the same strength. The pairwise interactions between the particles are modeled by the Lennard-Jones potential, with symmetric parameters that lead to a miscibility gap in the bulk. In the thin-film geometry, an interesting interplay occurs between surface enrichment and phase separation. We study the evolution of a mixture with equal amounts of A and B, which is rendered unstable by a temperature quench. We find that A-rich surface enrichment layers form quickly during the early stages of the evolution, causing a depletion of A in the inner regions of the film. These surface-directed concentration profiles propagate from the walls towards the center of the film, resulting in a transient layered structure. This layered state breaks up into a columnar state, which is characterized by the lateral coarsening of cylindrical domains. The qualitative features of this process resemble results from previous studies of diffusive Ginzburg-Landau-type models [S. K. Das, S. Puri, J. Horbach, and K. Binder, Phys. Rev. E 72, 061603 (2005)], but quantitative aspects differ markedly. The relation to spinodal decomposition in a strictly two-dimensional geometry is also discussed.

  14. Mechanical response of nanocrystalline platinum via molecular dynamics: size effects in bulk versus thin-film samples

    NASA Astrophysics Data System (ADS)

    Kim, Hojin; Strachan, Alejandro

    2015-09-01

    We use large-scale molecular dynamics simulations to characterize the mechanical responses of nanocrystalline bulk and thin-film samples with average grain size ranging from 5 to 40 nm and at two strain rates. Our simulations show Hall-Petch maxima for both yield and flow stresses and for both sets of specimens. We find that the presence of free surface decreases both the yield and flow stresses and, interestingly, the Hall-Petch maximum for slabs occur at a larger grain size than for the bulk samples. A quantitative analysis of plastic slip on grain interiors and boundaries reveals that the shift in the maximum results from a combination of higher intergranular slip and weaker size dependence of dislocation activity in the slabs as compared with the bulk. Finally, increasing strain rate increases both yield and flow stresses and this rate effect is dominated by the plasticity involving full dislocations; plastic slip by partial dislocations and grain boundary processes exhibit weaker size effects.

  15. Molecular-dynamics simulations of thin polyisoprene films confined between amorphous silica substrates

    SciTech Connect

    Guseva, D. V.; Komarov, P. V.; Lyulin, Alexey V.

    2014-03-21

    Constant temperature–constant pressure (NpT) molecular-dynamics computer simulations have been carried out for the united-atom model of a non-crosslinked (1,4) cis-polyisoprene (PI) melt confined between two amorphous, fully coordinated silica surfaces. The Lennard-Jones 12-6 potential was implemented to describe the polymer–silica interactions. The thickness H of the produced PI–silica film has been varied in a wide range, 1 < H/R{sub g} < 8, where R{sub g} is the individual PI chain radius of gyration measured under the imposed confinement. After a thorough equilibration, the PI film stratified structure and polymer segmental dynamics have been studied. The chain structure in the middle of the films resembles that in a corresponding bulk, but the polymer-density profile shows a pronounced ordering of the polymer segments in the vicinity of silica surfaces; this ordering disappears toward the film middles. Tremendous slowing down of the polymer segmental dynamics has been observed in the film surface layers, with the segmental relaxation more than 150 times slower as compared to that in a PI bulk. This effect increases with decreasing the polymer-film thickness. The segmental relaxation in the PI film middles shows additional relaxation process which is absent in a PI bulk. Even though there are fast relaxation processes in the film middle, its overall relaxation is slower as compared to that in a bulk sample. The interpretation of the results in terms of polymer glassy bridges has been discussed.

  16. (19)F Oximetry with semifluorinated alkanes.

    PubMed

    Kegel, Stefan; Chacon-Caldera, Jorge; Tsagogiorgas, Charalambos; Theisinger, Bastian; Glatting, Gerhard; Schad, Lothar R

    2016-12-01

    This work examines the variation of longitudinal relaxation rate R1(= 1/T1) of the (19)F-CF3-resonance of semifluorinated alkanes (SFAs) with oxygen tension (pO2), temperature (T) and pH in vitro. Contrary to their related perfluorocarbons (PFCs), SFA are amphiphilic and facilitate stable emulsions, a prerequisite for clinical use. A linear relationship between R1 and pO2 was confirmed for the observed SFAs at different temperatures. Using a standard saturation recovery sequence, T1 has been successfully measured using fluorine (19)F-MRI with a self-constructed birdcage resonator at 9.4 T. A calibration curve to calculate pO2 depending on T and R1 was found for each SFA used. In contrast to the commonly used PFC, SFAs are less sensitive to changes in pO2, but more sensitive to changes in temperature. The influence of pH to R1 was found to be negligible.

  17. Properties of Langmuir monolayers from semifluorinated alkanes

    NASA Astrophysics Data System (ADS)

    Broniatowski, M.; Macho, I. Sandez; Miñones, J.; Dynarowicz-Łątka, P.

    2005-06-01

    The aim of this study was to characterize several semifluorinated alkanes (SFA), of the general formula F(CF 2) m(CH 2) nH (in short F mH n), containing 25 carbon atoms in total (pentacosanes) differing in the m/ n ratio, as Langmuir monolayers at the free water surface. The following compounds have been studied: F6H19, F8H17, F10H15 and F12H13. Surface pressure ( π) and electric surface potential (Δ V) isotherms were recorded in addition to quantitative Brewster angle microscopy results. The negative sign of Δ V evidenced for the orientation of all the investigated semifluorinated pentacosanes, regardless the length of the hydrogenated segment, with their perfluorinated parts directed towards the air. As inferred from apparent dipole moment values and relative reflectivity results, the fluorinated pentacosanes with shorter perfluorinated fragment (F6H19 and F8H17) were found to be vertically oriented at the air/water interface, while those with longer perfluorinated moiety (F10H15 and F12H13) remain titled even in the vicinity of the film collapse.

  18. Molecular Processes Underlying the Structure and Assembly of Thin Films and Nanoparticles at Complex interfaces

    SciTech Connect

    Richmond, Geraldine

    2016-06-03

    Since 1995 we have pursued a number of different studies that are quite diverse in nature but with the common theme of using novel laser based methods to study important processes at buried interfaces. Studies of Corrosion, Passivation on n-GaAs(100)Methanol Photoelectrochemical Cell In these studies we have used picosecond photoluminescence and electrochemical studies to understand the GaAs/methanol interface. In our most extensive set of studies we conducted photo-illumination and XPS experiments to understand the chemistry occurring in the GaAs/methanol photoelectrochemical during photoexcitation. An important distinction between photocorrosion and photoetching of GaAs is elucidated by these studies. The dependence of GaAs photocorrosion on light intensity has been explored to better understand intrinsic differences between the lamplight studies and the picosecond photoluminescence studies. The effect of coating the GaAs with a sulfide layer prior to immersion in the cell has also been explored. This last result has led us to examine n-GaAs as a function of crystallographic orientation after exposure to aqueous Na2S containing solutions has been studied as a function of crystallographic orientation of the GaAs surface. The (100) and (110) surfaces are relatively similar, with significant amounts of As-S species present at the interface. The (111)B surface lacks this constituent, but shows significant amounts of metallic As. The XPS results have been correlated with the results of previous photocorrosion and passivation studies conducted in a photoelectrochemical cell. The studies indicate that the metallic As present at (111)B surface contributes strongly to the large surface recombination velocity found there, and to the inability of Na2S to passivate the (111)B surface. SAMS Under Water: Water Molecular Structure and Bonding at Hydrophobic Surfaces In these DOE sponsored studies we have been interested in learning the similarities and

  19. Length dependence of the thermal conductance of alkane-based single-molecule junctions: An ab initio study

    NASA Astrophysics Data System (ADS)

    Klöckner, J. C.; Bürkle, M.; Cuevas, J. C.; Pauly, F.

    2016-11-01

    Motivated by recent experiments, we present here a systematic ab initio study of the length dependence of the thermal conductance of single-molecule junctions. We make use of a combination of density functional theory with nonequilibrium Green's function techniques to investigate the length dependence of the phonon transport in single-alkane chains, contacted with gold electrodes via both thiol and amine anchoring groups. Additionally, we study the effect of the substitution of the hydrogen atoms in the alkane chains by heavier fluorine atoms to form polytetrafluoroethylenes. Our results demonstrate that (i) the room-temperature thermal conductance is fairly length independent for chains with more than 5 methylene units and (ii) the efficiency of the thermal transport is strongly influenced by the strength of the phononic metal-molecule coupling. Our study sheds light on the phonon transport in molecular junctions, and it provides clear guidelines for the design of molecular junctions for thermal management.

  20. Distinct kinetics of molecular gelation in a confined space and its relation to the structure and property of thin gel films.

    PubMed

    Liu, Yu; Zhao, Wen-Jing; Li, Jing-Liang; Wang, Rong-Yao

    2015-03-28

    Thin films of molecular gels formed in a confined space have potential applications in transdermal delivery, artificial skin, molecular electronics, etc. The microstructures and properties of thin gel films can be significantly different from those of their bulk counterparts. However, so far a comprehensive understanding of the effects of spatial confinement on the molecular gelation kinetics, fiber network structure and related mechanical properties is still lacking. In this work, using rheological techniques, we investigated the effect of one-dimensional confinement on the formation kinetics of fiber networks in the molecular gelation process. Fractal analyses of the kinetic information in terms of an extended Dickinson model enabled us to describe quantitatively the distinct kinetic signature of molecular gelation. The structural features derived from gelation kinetics support well the fractal patterns of the fiber networks acquired by optical and electron microscopy. With the kinetics-structure correlation, we can gain an in-depth understanding of the confinement-induced differences in the structure and consequently the mechanical properties of a model molecular gelling system. Particularly, the confinement induced structural transition, from a three-dimensional, dense and compact spherulitic network composed of highly branched fibers to a quasi-two-dimensional sparse spherulitic network composed of less branched fibers and entangled fibrils at the boundary areas, renders a gel film to become less stiff but more ductile. Our study suggests here a new strategy of engineering the fiber network microstructure to achieve functional gel films with unusual but useful properties.

  1. Sensitive detection of n-alkanes using a mixed ionization mode proton-transfer-reaction mass spectrometer

    NASA Astrophysics Data System (ADS)

    Amador-Muñoz, Omar; Misztal, Pawel K.; Weber, Robin; Worton, David R.; Zhang, Haofei; Drozd, Greg; Goldstein, Allen H.

    2016-11-01

    to compare sensitivities for n-alkane detection between experiments. Double hydride abstraction was observed from the reaction with O2+. Sensitivity to CT increased with carbon chain length from n-pentane to n-dodecane, sensitivity to HA increased from n-heptane to n-dodecane and sensitivity to PT increased from n-decane to n-tridecane. Sensitivity to CT exponentially decreased with molecular ionization energy, which is inversely related to the carbon chain length. We introduce a calibrated fragmentation algorithm as a method to determine the concentrations of n-alkanes and demonstrate its effectiveness using a custom n-alkane mixture and a much more complex oil example representing perhaps the most difficult mixture available for application of the method. We define optimum conditions for using the mixed ionization mode to measure n-alkanes in conventional PTR-MS instruments regardless of whether they are equipped with switchable reagent ion (SRI) capabilities.

  2. Molecular orientation in thin films of bis(1,2,5-thiadiazolo)-p-quinobis(1,3-dithiole) on graphite studied by angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Hasegawa, Shinji; Tanaka, Shoji; Yamashita, Yoshiro; Inokuchi, Hiroo; Fujimoto, Hitoshi; Kamiya, Koji; Seki, Kazuhiko; Ueno, Nobuo

    1993-07-01

    Angle-resolved ultraviolet photoelectron spectra using synchrotron radiation were measured for oriented thin films of bis(1,2,5-thiadiazolo)-p-quinobis(1,3-dithiole) on a cleaved highly oriented pyrolytic graphite (HOPG) surface. The observed takeoff angle dependence of the photoelectron intensity was analyzed by using the independent-atomic-center approximation and modified neglect of diatomic overlap molecular-orbital calculations. The calculated results agree well with the experimental ones. From the comparison between these results, the molecules in the thin film are estimated to lie flat with the inclination angle β<=10° to the HOPG surface. This analysis method is useful as a first step to a quantitative analysis for angular distribution of photoelectrons from thin films of large and complex organic molecules.

  3. The growth of strontium titanate and lutetium ferrite thin films by molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Brooks, Charles M.

    Included in this work is a range of studies on films of homoeptaxial and heteroepitaxial films of SrTiO3 and the first reported phase-pure films of LuFe2O4. We report the structural properties of homoepitaxial (100) SrTiO3 films grown by reactive molecular-beam epitaxy (MBE). The lattice spacing and x-ray diffraction (XRD) rocking curves of stoichiometric MBEgrown SrTiO3 films are indistinguishable from the underlying SrTiO3 substrates. The effect of off-stoichiometry for both strontium-rich and strontium-poor compositions results in lattice expansion with significant changes to the shuttered reflection high-energy electron diffraction oscillations, XRD, film microstructure, and thermal conductivity. Up to an 80% reduction in Sr(1+x)TiO3 film thermal conductivity is measured for x = -0.1 to 0.5. Significant reduction, from 11.5 to ˜2 W˙m-1K-1, occurs through the formation of Ruddlesden-Popper planar faults. The ability to deposit films with a reduction in thermal conductivity is applicable to thermal barrier coatings and thermoelectrics. Scanning transmission electron microscopy is used to examine the formation of Ruddlesden-Popper planar faults in films with strontium excess. We also show that the band gap of SrTiO3 can be altered by >10% (0.3 eV) by using experimentally realizable biaxial strains providing a new means to accomplish band gap engineering of SrTiO3 and related perovskites. Such band gap manipulation is relevant to applications in solar cells water splitting, transparent conducting oxides, superconductivity, two-dimensional electron liquids, and other emerging oxide electronics. This work also presents the adsorption-controlled growth of single-phase (0001)-oriented epitaxial films of charge ordered multiferroic, LuFe2O4, on (111) MgAl2O4, (111) MgO, and (0001) 6H-SiC substrates in an iron-rich environment at pressures and temperatures where excess iron desorbs from the film surface during growth. Scanning transmission electron microscopy reveals

  4. Quantification of chemotaxis-related alkane accumulation in Acinetobacter baylyi using Raman microspectroscopy.

    PubMed

    Li, Hanbing; L Martin, Francis Luke; Zhang, Dayi

    2017-03-03

    Alkanes are one of the most widespread contaminants in the natural environment, primarily as a consequence of biological synthesis and oil spills. Many indigenous microbes metabolize alkanes, and the chemotaxis and accumulation in some strains has been identified. For the first time, we apply Raman microspectroscopy to identify such chemotaxis-related affinity, and quantify the alkane concentrations via spectral alterations. Raman spectral alterations were only found for the alkane chemo-attractant bacteria Acinetobacter baylyi ADP1, not for Pseudomonas fluorescence, which exhibits limited chemotaxis towards alkane. The significant alterations were attributed to the strong chemotactic ability of A. baylyi enhancing the affinity and accumulation of alkane molecules on cell membranes or cellular internalization. Spectral fingerprints of A. baylyi significantly altered after 1-h exposure to pure alkanes (dodecane or tetradecane) and alkane mixtures (mineral oil or crude oil), but not monocyclic aromatic hydrocarbons (MAHs) or polycyclic aromatic hydrocarbons (PAHs). A semi-log linear regression relationship between Raman spectral alterations and alkane concentrations showed its feasibility in quantifying alkane concentration in environmental samples. Pure alkanes or alkane mixtures exhibited different limits of detection and regression slopes, indicating that the chemotaxis-related alkane accumulation in A. baylyi is dependent on the carbon chain length. This work provides a novel biospectroscopy approach to characterize the chemotaxis-related alkane bioaccumulation, and has immense potential for fast and high-throughput screening bacterial chemotaxis.

  5. Nanoporous TiO2/polyion thin-film-coated long-period grating sensors for the direct measurement of low-molecular-weight analytes.

    PubMed

    Yang, Rui-Zhu; Dong, Wen-Fei; Meng, Xiang; Zhang, Xu-Lin; Sun, Yun-Lu; Hao, Ya-Wei; Guo, Jing-Chun; Zhang, Wen-Yi; Yu, Yong-Sen; Song, Jun-Feng; Qi, Zhi-Mei; Sun, Hong-Bo

    2012-06-12

    We present novel nanoporous TiO(2)/polyion thin-film-coated long-period fiber grating (LPFG) sensors for the direct measurement of low-molecular-weight chemicals by monitoring the resonance wavelength shift. The hybrid overlay films are prepared by a simple layer-by-layer deposition approach, which is mainly based on the electrostatic interaction of TiO(2) nanoparticles and polyions. By the alternate immersion of LPFG into dispersions of TiO(2) nanoparticles and polyions, respectively, the so-formed TiO(2)/polyion thin film exhibits a unique nanoporous internal structure and has a relative higher refractive index than LPFG cladding. In particular, the porosity of the thin film reduces the diffusion coefficient and enhances the permeability retention of low-molecular-weight analytes within the porous film. The increases in the refractive index of the LPFG overlay results in a distinguished modulation of the resonance wavelength. Therefore, the detection sensitivity of LPFG sensors has been greatly improved, according to theoretical simulation. After the structure of the TiO(2)/polyion thin film was optimized, glucose solutions as an example with a low concentration of 10(-7) M was easily detected and monitored at room temperature.

  6. Fine-Tunable Absorption of Uniformly Aligned Polyurea Thin Films for Optical Filters Using Sequentially Self-Limited Molecular Layer Deposition.

    PubMed

    Park, Yi-Seul; Choi, Sung-Eun; Kim, Hyein; Lee, Jin Seok

    2016-05-11

    Development of methods enabling the preparation of uniformly aligned polymer thin films at the molecular level is a prerequisite for realizing their optoelectronic characteristics as innovative materials; however, these methods often involve a compromise between scalability and accuracy. In this study, we have grown uniformly aligned polyurea thin films on a SiO2 substrate using molecular layer deposition (MLD) based on sequential and self-limiting surface reactions. By integrating plane-polarized Fourier-transform infrared, Raman spectroscopic tools, and density functional theory calculations, we demonstrated the uniform alignment of polyurea MLD films. Furthermore, the selective-wavelength absorption characteristics of thickness-controlled MLD films were investigated by integrating optical measurements and finite-difference time-domain simulations of reflection spectra, resulting from their thickness-dependent fine resonance with photons, which could be used as color filters in optoelectronics.

  7. Angle-resolved photoemission spectroscopy of strontium lanthanum copper oxide thin films grown by molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Harter, John Wallace

    Among the multitude of known cuprate material families and associated structures, the archetype is "infinite-layer" ACuO2, where perfectly square and flat CuO2 planes are separated by layers of alkaline earth atoms. The infinite-layer structure is free of magnetic rare earth ions, oxygen chains, orthorhombic distortions, incommensurate superstructures, ordered vacancies, and other complications that abound among the other material families. Furthermore, it is the only cuprate that can be made superconducting by both electron and hole doping, making it a potential platform for decoding the complex many-body interactions responsible for high-temperature superconductivity. Research on the infinite-layer compound has been severely hindered by the inability to synthesize bulk single crystals, but recent progress has led to high-quality superconducting thin film samples. Here we report in situ angle-resolved photoemission spectroscopy measurements of epitaxially-stabilized Sr1-chiLa chiCuO2 thin films grown by molecular-beam epitaxy. At low doping, the material exhibits a dispersive lower Hubbard band typical of other cuprate parent compounds. As carriers are added to the system, a continuous evolution from Mott insulator to superconducting metal is observed as a coherent low-energy band develops on top of a concomitant remnant lower Hubbard band, gradually filling in the Mott gap. For chi = 0.10, our results reveal a strong coupling between electrons and (pi,pi) anti-ferromagnetism, inducing a Fermi surface reconstruction that pushes the nodal states below the Fermi level and realizing nodeless superconductivity. Electron diffraction measurements indicate the presence of a surface reconstruction that is consistent with the polar nature of Sr1-chiLachiCuO2. Most knowledge about the electron-doped side of the cuprate phase diagram has been deduced by generalizing from a single material family, Re2-chi CechiCuO4, where robust antiferromagnetism has been observed past chi

  8. Synthesis and modification of mesoporous silica and the preparation of molecular sieve thin films via pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Coutinho, Decio Heringer

    2001-07-01

    Hexagonal mesoporous DAM-1 (Dallas Amorphous Material-1) was prepared using Vitamin E TPGS as the structure-directing agent. Depending upon the temperature and gel composition, highly ordered and hydrothermally stable DAM-1 with various morphologies could be achieved including spheres, gyroids, discoid, hexagonal plates and rods. This synthesis was modified to prepare hybrid organic-inorganic amine and thiol bifunctionalized DAM-1 by direct co-condensation under acidic conditions. Patterned DAM-1 thin films were prepared on patterned transparencies utilizing pulsed laser deposition (PLD) and line patterning techniques. DAM-1 laser ablation onto the patterned substrate followed by hydrothermal treatment resulted in a densely packed film. Removal of the patterned lines by sonication revealed patterned DAM-1 films. Thin films of zeolite type X were also prepared using the PLD technique. Laser ablation of zeolite X onto TiN-coated silicon wafers followed by a hydrothermal treatment resulted in partially oriented, crystalline membranes. Hydrothermal treatment of PLD films on stainless steel mesh produced a coated wire mesh with a 3-mum thick zeolite X film. A novel strategy for imprinting mesoporous SBA-15 that combines a triblock copolymer template and a chiral ruthenium complex is reported. A chiral PEO helix was formed by the chiral ruthenium complex interaction with the block copolymer during the synthesis of SBA-15. Upon removal of the chiral ruthenium complex, a stereospecfic cavity was created. Preliminary results indicated stereoselective absorption of Delta or Λ-Ru(phen)3 2+ isomer from a racemic mixture could be achieved depending on the chirality of the PEO chain. Practicum Two. The industrial practicum report describes the process development unit (PDU) 3-pentenenitrile (3PN) refining operation. This distillation works was operated to refine crude 3PN product, which contained 3PN, 2-methyl-3-butenenitrile (2M3BN), and other byproducts. This report also

  9. Progressive Degradation of Crude Oil n-Alkanes Coupled to Methane Production under Mesophilic and Thermophilic Conditions

    PubMed Central

    Cheng, Lei; Shi, Shengbao; Li, Qiang; Chen, Jianfa; Zhang, Hui; Lu, Yahai

    2014-01-01

    Although methanogenic degradation of hydrocarbons has become a well-known process, little is known about which crude oil tend to be degraded at different temperatures and how the microbial community is responded. In this study, we assessed the methanogenic crude oil degradation capacity of oily sludge microbes enriched from the Shengli oilfield under mesophilic and thermophilic conditions. The microbial communities were investigated by terminal restriction fragment length polymorphism (T-RFLP) analysis of 16S rRNA genes combined with cloning and sequencing. Enrichment incubation demonstrated the microbial oxidation of crude oil coupled to methane production at 35 and 55°C, which generated 3.7±0.3 and 2.8±0.3 mmol of methane per gram oil, respectively. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that crude oil n-alkanes were obviously degraded, and high molecular weight n-alkanes were preferentially removed over relatively shorter-chain n-alkanes. Phylogenetic analysis revealed the concurrence of acetoclastic Methanosaeta and hydrogenotrophic methanogens but different methanogenic community structures under the two temperature conditions. Candidate divisions of JS1 and WWE 1, Proteobacteria (mainly consisting of Syntrophaceae, Desulfobacteraceae and Syntrophorhabdus) and Firmicutes (mainly consisting of Desulfotomaculum) were supposed to be involved with n-alkane degradation in the mesophilic conditions. By contrast, the different bacterial phylotypes affiliated with Caldisericales, “Shengli Cluster” and Synergistetes dominated the thermophilic consortium, which was most likely to be associated with thermophilic crude oil degradation. This study revealed that the oily sludge in Shengli oilfield harbors diverse uncultured microbes with great potential in methanogenic crude oil degradation over a wide temperature range, which extend our previous understanding of methanogenic degradation of crude oil alkanes. PMID:25409013

  10. Progressive degradation of crude oil n-alkanes coupled to methane production under mesophilic and thermophilic conditions.

    PubMed

    Cheng, Lei; Shi, Shengbao; Li, Qiang; Chen, Jianfa; Zhang, Hui; Lu, Yahai

    2014-01-01

    Although methanogenic degradation of hydrocarbons has become a well-known process, little is known about which crude oil tend to be degraded at different temperatures and how the microbial community is responded. In this study, we assessed the methanogenic crude oil degradation capacity of oily sludge microbes enriched from the Shengli oilfield under mesophilic and thermophilic conditions. The microbial communities were investigated by terminal restriction fragment length polymorphism (T-RFLP) analysis of 16S rRNA genes combined with cloning and sequencing. Enrichment incubation demonstrated the microbial oxidation of crude oil coupled to methane production at 35 and 55°C, which generated 3.7±0.3 and 2.8±0.3 mmol of methane per gram oil, respectively. Gas chromatography-mass spectrometry (GC-MS) analysis revealed that crude oil n-alkanes were obviously degraded, and high molecular weight n-alkanes were preferentially removed over relatively shorter-chain n-alkanes. Phylogenetic analysis revealed the concurrence of acetoclastic Methanosaeta and hydrogenotrophic methanogens but different methanogenic community structures under the two temperature conditions. Candidate divisions of JS1 and WWE 1, Proteobacteria (mainly consisting of Syntrophaceae, Desulfobacteraceae and Syntrophorhabdus) and Firmicutes (mainly consisting of Desulfotomaculum) were supposed to be involved with n-alkane degradation in the mesophilic conditions. By contrast, the different bacterial phylotypes affiliated with Caldisericales, "Shengli Cluster" and Synergistetes dominated the thermophilic consortium, which was most likely to be associated with thermophilic crude oil degradation. This study revealed that the oily sludge in Shengli oilfield harbors diverse uncultured microbes with great potential in methanogenic crude oil degradation over a wide temperature range, which extend our previous understanding of methanogenic degradation of crude oil alkanes.

  11. Modeling the phase behavior of H2S+n-alkane binary mixtures using the SAFT-VR+D approach.

    PubMed

    dos Ramos, M Carolina; Goff, Kimberly D; Zhao, Honggang; McCabe, Clare

    2008-08-07

    A statistical associating fluid theory for potential of variable range has been recently developed to model dipolar fluids (SAFT-VR+D) [Zhao and McCabe, J. Chem. Phys. 2006, 125, 104504]. The SAFT-VR+D equation explicitly accounts for dipolar interactions and their effect on the thermodynamics and structure of a fluid by using the generalized mean spherical approximation (GMSA) to describe a reference fluid of dipolar square-well segments. In this work, we apply the SAFT-VR+D approach to real mixtures of dipolar fluids. In particular, we examine the high-pressure phase diagram of hydrogen sulfide+n-alkane binary mixtures. Hydrogen sulfide is modeled as an associating spherical molecule with four off-center sites to mimic hydrogen bonding and an embedded dipole moment (micro) to describe the polarity of H2S. The n-alkane molecules are modeled as spherical segments tangentially bonded together to form chains of length m, as in the original SAFT-VR approach. By using simple Lorentz-Berthelot combining rules, the theoretical predictions from the SAFT-VR+D equation are found to be in excellent overall agreement with experimental data. In particular, the theory is able to accurately describe the different types of phase behavior observed for these mixtures as the molecular weight of the alkane is varied: type III phase behavior, according to the scheme of classification by Scott and Konynenburg, for the H2S+methane system, type IIA (with the presence of azeotropy) for the H2S+ethane and+propane mixtures; and type I phase behavior for mixtures of H2S and longer n-alkanes up to n-decane. The theory is also able to predict in a qualitative manner the solubility of hydrogen sulfide in heavy n-alkanes.

  12. A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

    NASA Astrophysics Data System (ADS)

    Tang, Yongchun; Huang, Yongsong; Ellis, Geoffrey S.; Wang, Yi; Kralert, Paul G.; Gillaizeau, Bruno; Ma, Qisheng; Hwang, Rong

    2005-09-01

    A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C 13-C 21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ 13C values increase by ˜4‰ and δD values increase by ˜50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH ‡) and entropy (ΔΔS ‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C 20 ( n-icosane), the changes in enthalpy are calculated to be ˜1340 J mol -1 (320 cal mol -1) and 230 J mol -1 (55 cal mol -1) for D-H and 13C- 12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite

  13. An Observation of Diamond-Shaped Particle Structure in a Soya Phosphatidylcohline and Bacteriorhodopsin Composite Langmuir Blodgett Film Fabricated by Multilayer Molecular Thin Film Method

    NASA Astrophysics Data System (ADS)

    Tsujiuchi, Y.; Makino, Y.

    A composite film of soya phosphatidylcohline (soya PC) and bacteriorhodopsin (BR) was fabricated by the multilayer molecular thin film method using fatty acid and lipid on a quartz substrate. Direct Force Microscopy (DFM), UV absorption spectra and IR absorption spectra of the film were characterized on the detail of surface structure of the film. The DFM data revealed that many rhombus (diamond-shaped) particles were observed in the film. The spectroscopic data exhibited the yield of M-intermediate of BR in the film. On our modelling of molecular configuration indicate that the coexistence of the strong inter-molecular interaction and the strong inter-molecular interaction between BR trimmers attributed to form the particles.

  14. Structure, Energetics, and Dynamics of Screw Dislocations in Even n-Alkane Crystals.

    PubMed

    Olson, Isabel A; Shtukenberg, Alexander G; Hakobyan, Gagik; Rohl, Andrew L; Raiteri, Paolo; Ward, Michael D; Kahr, Bart

    2016-08-18

    Spiral hillocks on n-alkane crystal surfaces were observed immediately after Frank recognized the importance of screw dislocations for crystal growth, yet their structures and energies in molecular crystals remain ill-defined. To illustrate the structural chemistry of screw dislocations that are responsible for plasticity in organic crystals and upon which the organic electronics and pharmaceutical industries depend, molecular dynamics was used to examine heterochiral dislocation pairs with Burgers vectors along [001] in n-hexane, n-octane, and n-decane crystals. The cores were anisotropic and elongated in the (110) slip plane, with significant local changes in molecular position, orientation, conformation, and energy. This detailed atomic level picture produced a distribution of strain consistent with linear elastic theory, giving confidence in the simulations. Dislocations with doubled Burgers vectors split into pairs with elementary displacements. These results suggest a pathway to understanding the mechanical properties and failure associated with elastic and plastic deformation in soft crystals.

  15. Microstructural and Electrical Characterization of Silicon Carbide and Aluminum Nitride Thin Films Grown by Gas-Source Molecular Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Kern, Richard Scott

    1996-08-01

    Monocrystalline thin films, multilayered heterostructures and solid solutions of silicon carbide (SiC) and aluminum nitride (AlN) have been grown on alpha(6H) -SiC(0001) substrates by gas-source molecular beam epitaxy. Growth mechanisms, defect formation, donor and acceptor doping, metal-insulator-semiconductor diodes, pseudomorphic heterostructures and solid solutions in these materials have been studied. Monocrystalline films of beta(3C) -SiC(111) and alpha(6H)-SiC(0001) have been controllably deposited on the silicon face of 6H-SiC(0001) substrates. Polytype control was achieved via changes in the substrate orientation, substrate temperature and gas phase chemistry. Step flow growth was achieved on vicinal substrates at growth temperatures of at least 1350^circC using the SiH _4-rm C_2H_4 -H_2 system. Step bunching, cubic SiC nucleation and double positioning boundaries were observed at all temperatures when H_2 was removed from the system or the growth was performed at below 1350^circC. In both cases, growth rate was strongly dependent on temperature. Films doped using either a NH_3/H _2 mixture or pure N_2 were n-type; Al, p-type. Uniform, controllable doping levels between 10^{15} and 10^{19} cm ^{-3} were achieved for both polytypes. The measured mobility in the undoped 6H polytype, 434 cm ^2 V^{-1} s ^{-1}, is the highest reported in this polytype. Monocrystalline AlN was deposited using aluminum evaporated from a modified MBE effusion cell and either activated nitrogen derived from a compact electron cyclotron resonance plasma source or ammonia. Growth using each of the nitrogen sources was optimized with respect to substrate temperature, reactant flux and system pressure. In general, very thin films (<=q50 A) grown on vicinal 6H-SiC had a higher defect density than those grown on nominally on-axis substrates due to defect formation at or near the steps on the SiC surface. Full-width half maximum (FWHM) values of the (0002)_ {AlN} X-ray diffraction Bragg

  16. Variation in n-Alkane Distributions of Modern Plants: Questioning Applications of n-Alkanes in Chemotaxonomy and Paleoecology

    NASA Astrophysics Data System (ADS)

    Bush, R. T.; McInerney, F. A.

    2010-12-01

    Long chain n-alkanes (n-C21 to n-C37) are synthesized as part of the epicuticular leaf wax of terrestrial plants and are among the most recognizable and widely used plant biomarkers. n-Alkane distributions have been utilized in previous studies on modern plant chemotaxonomy, testing whether taxa can be identified based on characteristic n-alkane profiles. Dominant n-alkanes (e.g. n-C27 or n-C31) have also been ascribed to major plant groups (e.g. trees or grasses respectively) and have been used in paleoecology studies to reconstruct fluctuations in plant functional types. However, many of these studies have been based on relatively few modern plant data; with the wealth of modern n-alkane studies, a more comprehensive analysis of n-alkanes in modern plants is now possible and can inform the usefulness of n-alkane distributions as paleoecological indicators. The work presented here is a combination of measurements made using plant leaves collected from the Chicago Botanic Garden and a compilation of published literature data from six continents. We categorized plants by type: angiosperms, gymnosperms, woody plants, forbs, grasses, ferns and pteridophytes, and mosses. We then quantified n-alkane distribution parameters such as carbon preference index (CPI), average chain length (ACL), and dispersion (a measure of the spread of the profile over multiple chain lengths) and used these to compare plant groups. Among all plants, one of the emergent correlations is a decrease in dispersion with increasing CPI. Within and among plant groups, n-alkane distributions show a very large range of variation, and the results show little or no correspondence between broad plant groups and a single dominant n-alkane or a ratio of n-alkanes. These findings are true both when data from six continents are combined and when plants from a given region are compared (North America). We also compared the n-alkane distributions of woody angiosperms, woody gymnosperms, and grasses with one

  17. Comparative Study on Single-Molecule Junctions of Alkane- and Benzene-Based Molecules with Carboxylic Acid/Aldehyde as the Anchoring Groups

    NASA Astrophysics Data System (ADS)

    Chen, Fang; Peng, Lin-Lu; Hong, Ze-Wen; Mao, Jin-Chuan; Zheng, Ju-Fang; Shao, Yong; Niu, Zhen-Jiang; Zhou, Xiao-Shun

    2016-08-01

    We have measured the alkane and benzene-based molecules with aldehyde and carboxylic acid as anchoring groups by using the electrochemical jump-to-contact scanning tunneling microscopy break junction (ECSTM-BJ) approach. The results show that molecule with benzene backbone has better peak shape and intensity than those with alkane backbone. Typically, high junction formation probability for same anchoring group (aldehyde and carboxylic acid) with benzene backbone is found, which contributes to the stronger attractive interaction between Cu and molecules with benzene backbone. The present work shows the import role of backbone in junction, which can guide the design molecule to form effective junction for studying molecular electronics.

  18. Detailed chemical kinetic models for large n-alkanes and iso-alkanes found in conventional and F-T diesel fuels

    SciTech Connect

    Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

    2008-12-15

    Detailed chemical kinetic models are needed to simulate the combustion of current and future transportation fuels. These models should represent the various chemical classes in these fuels. Conventional diesel fuels are composed of n-alkanes, iso-alkanes, cycloalkanes and aromatics (Farrell et al. 2007). For future fuels, there is a renewed interest in Fischer-Tropsch (F-T) processes which can be used to synthesize diesel and other transportation fuels from biomass, coal and natural gas. F-T diesel fuels are expected to be similar to F-T jet fuels which are commonly comprised of iso-alkanes with some n-alkanes (Smith and Bruno, 2008). Thus, n-alkanes and iso-alkanes are common chemical classes in these conventional and future fuels. This paper reports on the development of chemical kinetic models of large n-alkanes and iso-alkanes to represent these chemical classes in conventional and future fuels. Two large iso-alkanes are 2,2,4,4,6,8,8-heptamethylnonane, which is a primary reference fuel for diesel, and isooctane, a primary reference fuel for gasoline. Other iso-alkanes are branched alkanes with a single methyl side chain, typical of most F-T fuels. The chemical kinetic models are then used to predict the effect of these fuel components on ignition characteristics under conditions found in internal combustion engines.

  19. Metabolism of Hydrocarbons in n-Alkane-Utilizing Anaerobic Bacteria.

    PubMed

    Wilkes, Heinz; Buckel, Wolfgang; Golding, Bernard T; Rabus, Ralf

    2016-01-01

    The glycyl radical enzyme-catalyzed addition of n-alkanes to fumarate creates a C-C-bond between two concomitantly formed stereogenic carbon centers. The configurations of the two diastereoisomers of the product resulting from n-hexane activation by the n-alkane-utilizing denitrifying bacterium strain HxN1, i.e. (1-methylpentyl)succinate, were assigned as (2S,1'R) and (2R,1'R). Experiments with stereospecifically deuterated n-(2,5-2H2)hexanes revealed that exclusively the pro-S hydrogen atom is abstracted from C2 of the n-alkane by the enzyme and later transferred back to C3 of the alkylsuccinate formed. These results indicate that the alkylsuccinate-forming reaction proceeds with an inversion of configuration at the carbon atom (C2) of the n-alkane forming the new C-C-bond, and thus stereochemically resembles a SN2-type reaction. Therefore, the reaction may occur in a concerted manner, which may avoid the highly energetic hex-2-yl radical as an intermediate. The reaction is associated with a significant primary kinetic isotope effect (kH/kD ≥3) for hydrogen, indicating that the homolytic C-H-bond cleavage is involved in the first irreversible step of the reaction mechanism. The (1-methylalkyl)succinate synthases of n-alkane-utilizing anaerobic bacteria apparently have very broad substrate ranges enabling them to activate not only aliphatic but also alkyl-aromatic hydrocarbons. Thus, two denitrifiers and one sulfate reducer were shown to convert the nongrowth substrate toluene to benzylsuccinate and further to the dead-end product benzoyl-CoA. For this purpose, however, the modified β-oxidation pathway known from alkylbenzene-utilizing bacteria was not employed, but rather the pathway used for n-alkane degradation involving CoA ligation, carbon skeleton rearrangement and decarboxylation. Furthermore, various n-alkane- and alkylbenzene-utilizing denitrifiers and sulfate reducers were found to be capable of forming benzyl alcohols from diverse alkylbenzenes

  20. Alkane desaturation by concerted double hydrogen atom transfer to benzyne.

    PubMed

    Niu, Dawen; Willoughby, Patrick H; Woods, Brian P; Baire, Beeraiah; Hoye, Thomas R

    2013-09-26

    The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists. In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids, eicosanoids, gibberellins and carotenoids. Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or σ-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cycloisomerization reaction of triyne substrates. We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.

  1. Determining and quantifying specific sources of light alkane

    NASA Astrophysics Data System (ADS)

    Bill, M.; Conrad, M. E.

    2015-12-01

    Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

  2. Growth, luminescence and magnetic properties of GaN:Er semiconductor thin films grown by molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Dasari, K.; Wu, J.; Huhtinen, H.; Jadwisienczak, W. M.; Palai, R.

    2017-05-01

    We report on the growth, surface, luminescence and magnetic properties of 180 nm thick Er-doped GaN thin films grown by molecular beam epitaxy (MBE) on c-sapphire substrates with no buffer layer and with different Er concentrations. In situ reflection high-energy electron diffraction (RHEED) patterns revealed crystalline and uniform growth of the films. The x-ray diffraction (XRD) pattern showed c-axis-oriented growth. Atomic force microscopy (AFM) analysis showed enhancement of surface morphology and smoothness with increasing Er doping, which could be due to minimization of surface defects because of the gettering effect of the rare earth. Scanning area-dependent surface morphology analysis showed a power law dependence indicating the fractal nature of the surface, which is confirmed by the observation of a non-integer D (fractal dimension) value. X-ray photoluminescence spectroscopy (XPS) revealed the formation of a GaN:Er phase and ruled out the presence of Ga and Er metallic and native oxide phases. The semi-quantitative elemental composition of the films was determined using N 1s, Ga 2p3/2 and Er 4d photoemission lines. The Er concentration was estimated from the x-ray photoelectron spectra and found to be between 3.0 and 9.0 at.% (˜1021 atoms cm-3). Photoluminescence (PL) and cathodoluminescence (CL) studies showed visible emission and concentration quenching of Er3+ ions in agreement with reported results. Excitation of the Er3+ ion might be affected by charge trapping due to Er-doping-induced defect complexes. The magnetic measurements carried out by a superconducting quantum interference device (SQUID) showed a ferromagnetic-paramagnetic phase transition at low temperature, contrary to the reported room temperature ferromagnetism in metalorganic chemical vapor deposition (MOCVD)-grown GaN:Er thick films of 550 nm.

  3. Carbon and hydrogen isotopic composition of methane and C2+ alkanes in electrical spark discharge: implications for identifying sources of hydrocarbons in terrestrial and extraterrestrial settings.

    PubMed

    Telling, Jon; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

    2013-05-01

    The low-molecular-weight alkanes--methane, ethane, propane, and butane--are found in a wide range of terrestrial and extraterrestrial settings. The development of robust criteria for distinguishing abiogenic from biogenic alkanes is essential for current investigations of Mars' atmosphere and for future exobiology missions to other planets and moons. Here, we show that alkanes synthesized during gas-phase radical recombination reactions in electrical discharge experiments have values of δ(2)H(methane)>δ(2)H(ethane)>δ(2)H(propane), similar to those of the carbon isotopes. The distribution of hydrogen isotopes in gas-phase radical reactions is likely due to kinetic fractionations either (i) from the preferential incorporation of (1)H into longer-chain alkanes due to the more rapid rate of collisions of the smaller (1)H-containing molecules or (ii) by secondary ion effects. Similar δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns may be expected in a range of extraterrestrial environments where gas-phase radical reactions dominate, including interstellar space, the atmosphere and liquid hydrocarbon lakes of Saturn's moon Titan, and the outer atmospheres of Jupiter, Saturn, Neptune, and Uranus. Radical recombination reactions at high temperatures and pressures may provide an explanation for the combined reversed δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns of terrestrial alkanes documented at a number of high-temperature/pressure crustal sites.

  4. A new approach to the non-oxidative conversion of gaseous alkanes in a barrier discharge and features of the reaction mechanism

    NASA Astrophysics Data System (ADS)

    Kudryashov, S.; Ryabov, A.; Shchyogoleva, G.

    2016-01-01

    A new approach to the non-oxidative conversion of C1-C4 alkanes into gaseous and liquid products in a barrier discharge is proposed. It consists in inhibiting the formation of deposits on the reactor electrode surfaces due to the addition of distilled water into the flow of hydrocarbon gases. The energy consumption on hydrocarbon conversion decreases from methane to n-butane from ~46 to 35 eV molecule-1. The main gaseous products of the conversion of light alkanes are hydrogen and C2-C4 hydrocarbons. The liquid reaction products contain C5+ alkanes with a predominantly isomeric structure. The results of modeling the kinetics of chemical reactions show that an increase in the molecular weight of the reaction products is mainly due to processes involving CH2 radical and the recombination of alkyl radicals.

  5. Investigation of the impact of water on the enantioselectivity displayed by CALB in the kinetic resolution of δ-functionalized alkan-2-ol derivatives.

    PubMed

    Yang, Bin; Lihammar, Richard; Bäckvall, Jan-E

    2014-10-13

    It is shown that the low enantioselectivity of Candida antarctica lipase B (CALB)-catalyzed transesterification of a δ-functionalized alkan-2-ol to its acetate does not correlate at all with the high enantioselectivity of the CALB-catalyzed hydrolysis of the corresponding acetate in water. This lack of correlation is unusual and for unfunctionalized alkan-2-ol derivatives there is a very good correlation between the enantioselectivity of transesterification of the alcohol and hydrolysis of the corresponding acetate (E>200 in both cases). The results confirm previous predictions from molecular modeling. The water effect was mimicked by CALB variant Ala281Ser, which showed an enhanced enantioselectivity in transesterification of δ-functionalized alkan-2-ols compared to wild-type CALB.

  6. Surface crystallization in normal-alkanes and alcohols

    SciTech Connect

    Deutsch, M.; Ocko, B.M.; Wu, X.Z. |; Sirota, E.B.; Sinha, S.K.

    1995-06-01

    A new, rare surface freezing, phenomenon is observed in molten normal-alkanes and their derivatives (alcohols, thiols, etc.). X-ray and surface tension measurements show the formation of a crystalline monolayer on the surface of the liquid alkane at temperatures up to 3 C above the bulk solidification temperature, T{sub f}. For alcohols, a single bilayer is formed. In both cases, the molecules in the layer are hexagonally packed and oriented normal to the surface for short chain lengths, and tilted for long ones. In both cases the single layer persists down to T{sub f}. In terms of wetting theory, this constitutes a very limited partial wetting of the liquid surface by the crystalline layer. The new surface phase is obtained only for chain lengths 14 < n {le} 50 in alkanes, and 16 < n < 30 in alcohols. The measurements are satisfactorily accounted for within a simple theory based on surface energy considerations.

  7. Infrared Spectroscopic Investigation on CH Bond Acidity in Cationic Alkanes

    NASA Astrophysics Data System (ADS)

    Matsuda, Yoshiyuki; Xie, Min; Fujii, Asuka

    2016-06-01

    We have demonstrated large enhancements of CH bond acidities in alcohol, ether, and amine cations through infrared predissociation spectroscopy based on the vacuum ultraviolet photoionization detection. In this study, we investigate for the cationic alkanes (pentane, hexane, and heptane) with different alkyl chain lengths. The σ electrons are ejected in the ionization of alkanes, while nonbonding electrons are ejected in ionization of alcohols, ethers, and amines. Nevertheless, the acidity enhancements of CH in these cationic alkanes have also been demonstrated by infrared spectroscopy. The correlations of their CH bond acidities with the alkyl chain lengths as well as the mechanisms of their acidity enhancements will be discussed by comparison of infrared spectra and theoretical calculations.

  8. Alkanes in shrimp from the Buccaneer Oil Field

    SciTech Connect

    Middleditch, B.S.; Basile, B.; Chang, E.S.

    1982-07-01

    A total of 36 samples of shrimp were examined from the region of the Buccaneer oil field, eighteen of which were representatives of the commercial species Penaeus aztecus and the rest were various other species: Penaeus duorarum (pink shrimp), Trachypenaeus duorarum (sugar shrimp), Squilla empusa (mantis shrimp), and Sicyonia dorsalis (chevron shrimp). The alkanes and deuteriated alkanes were completely separated by GC, so a mass spectrometer was not required for their detection and quantitation. To confirm the identities of individual compounds, however, some samples were examined by combined gas chromatography-mass spectrometry. Results show that only thirteen of the forty shrimp collected from the region of the Buccaneer oil field contained petroleum alkanes, and the majority of these were obtained from trawls immediately adjacent to the production platforms. It appears that shrimp caught in the region of the Buccaneer oil field are not appreciably tainted with hydrocarbons discharged from the production platforms. (JMT)

  9. Isolation and characterization of a novel oxygenase that catalyzes the first step of n-alkane oxidation in Acinetobacter sp. strain M-1.

    PubMed Central

    Maeng, J H; Sakai, Y; Tani, Y; Kato, N

    1996-01-01

    In the Finnerty pathway for n-alkane, oxidation in Acinetobacter sp., n-alkanes are postulated to be attacked by a dioxygenase and the product, n-alkyl hydroperoxide, is further metabolized to the corresponding aldehyde via the peroxy acid [W. R. Finnerty, P. 184-188, in A. H. Applewhite (ed.), Proceedings of the World Conference on Biotechnology for the Fats and Oil Industry, 1988]. However, no biochemical evidence regarding the first-step reaction is available. In this study, we found a novel n-alkane-oxidizing enzyme that requires only molecular oxygen, i.e., not NAD(P)H, in our isolate, Acinetobacter sp. strain M-1, and purified it to apparent homogeneity by gel electrophoresis. The purified enzyme is a homodimeric protein with a molecular mass of 134 kDa, contains 1 mol of flavin adenine dinucleotide per mol of subunit, and requires CU2+ for its activity. The enzyme uses n-alkanes ranging in length from 10 to 30 carbon atoms and is also active toward n-alkenes (C12 to C20) and some aromatic compounds with substituted alkyl groups but not toward a branched alkane, alcohol, or aldehyde. Transient accumulation of n-alkyl hydroperoxide was detected in the course of the reaction, and no oxygen radical scavengers affected the enzyme activity. From these properties, the enzyme is most probably a dioxygenase that catalyzes the introduction of two atoms of oxygen to the substrate, leading to the formation of the corresponding n-alkyl hydroperoxide. The enzymatic evidence strongly supports the existence of an n-alkane oxidation pathway, which is initiated by a dioxygenase reaction, in Acinetobacter spp. PMID:8682768

  10. Using volatile additives to alter the morphology and performance of active layers in thin-film molecular photovoltaic devices incorporating bulk heterojunctions.

    PubMed

    Dang, Minh Trung; Wuest, James D

    2013-12-07

    Thin-film photovoltaic devices composed of polymers or small molecules have an exciting future as sources of renewable energy because they can be made in large sizes on flexible surfaces by inexpensive techniques of fabrication. Significant progress in developing new molecular photovoltaic materials and device architectures has been achieved in the last decade. The identity of molecular components in active layers and their individual optoelectronic properties obviously help determine the properties of devices; in addition, however, the behavior of devices depends critically on the nature of the local organization of the components. Recent studies have shown that the morphology of active layers can be tuned by adjusting various parameters, including the solvent used to cast the layer, thermal annealing, and special processing additives. In this review, we summarize the effect of volatile additives on the nanoscale morphology of molecular blends, and we show how these effects can improve the performance of devices. Although we focus on the behavior of mixtures of the type used in current molecular thin-film photovoltaic devices, the subject of our review will interest researchers in all areas of science and technology requiring materials in which separate phases must form intimate long-lived intermixtures with defined structures.

  11. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    DOEpatents

    Koch, Daniel J.; Arnold, Frances H.

    2012-11-13

    AlkB from Pseudomonas putida was engineered using in-vivo directed evolution to hydroxylate small chain alkanes. Mutant AlkB-BMO1 hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. Mutant AlkB-BMO2 similarly hydroxylates propane and butane at the terminal carbon at a rate greater than the wild-type to form 1-propanol and 1-butanol, respectively. These biocatalysts are highly active for small chain alkane substrates and their regioselectivity is retained in whole-cell biotransformations.

  12. Assimilation of chlorinated alkanes by hydrocarbon-utilizing fungi

    SciTech Connect

    Murphy, G.L.; Perry, J.J.

    1984-12-01

    The fatty acid compositions of two filamentous fungi (Cunninghamella elegans and Penicillium zonatum) and a yeast (Candida lipolytica) were determined after the organisms were grown on 1-chlorohexadecane or 1-chlorooctadecane. These organisms utilized the chlorinated alkanes as sole sources of carbon and energy. Analyses of the fatty acids present after growth on the chlorinated alkanes indicated that 60 to 70% of the total fatty acids in C. elegans were chlorinated. Approximately 50% of the fatty acids in C. lipolytica were also chlorinated. P. zonatum contained 20% 1-chlorohexadecanoic acid after growth on either substrate but did not incorporate C/sub 18/ chlorinated fatty acids.

  13. Catalytic, mild, and selective oxyfunctionalization of linear alkanes: current challenges.

    PubMed

    Bordeaux, Mélanie; Galarneau, Anne; Drone, Jullien

    2012-10-22

    Selective catalysts for sustainable oxidation of alkanes are highly demanded because of the abundance of these molecules in the environment, the possibility to transform them into higher-value compounds, such as chemicals or synthetic fuels, and the fact that, kinetically speaking, this is a difficult reaction. Numerous chemical and biological catalysts have been developed in the lasts decades for this purpose, rendering the overview over this field of chemistry difficult. After giving a definition of the ideal catalyst for alkane oxyfunctionalization, this review aims to present the catalysts available today that are closest to ideal.

  14. Modeling of alkane emissions from a wood stain

    SciTech Connect

    Chang, J.C.S.; Guo, Z.

    1993-01-01

    The article discusses full-scale residential house tests to evaluate the effects of organic emissions from a wood finishing product--wood stain--on indoor air quality (IAQ). The test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a function of time after the application of the wood stain. It was found that the test house concentrations can be simulated by an integrated IAQ model which takes into consideration source, sink, and ventilation effects. The alkane emissions were controlled by an evaporation-like process.

  15. The effect of surface nano-corrugation on the squeeze-out of molecular thin hydrocarbon films between curved surfaces with long range elasticity

    NASA Astrophysics Data System (ADS)

    Sivebaek, I. M.; Persson, B. N. J.

    2016-11-01

    The properties of linear alkane lubricants confined between two approaching solids are investigated by a model that accounts for the roughness, curvature and elastic properties of the solid surfaces. We consider linear alkanes of different chain lengths from {{{C}}}3{{{H}}}8 to {{{C}}}16{{{H}}}34, confined between corrugated solid walls. The pressure necessary to squeeze out the lubricant increases rapidly with the alkane chain length, but is always much lower than in the case of smooth surfaces. The longest alkanes form domains of ordered chains and the squeeze-out appears to nucleate in the more disordered regions between these domains. The short alkanes stay fluid-like during the entire squeeze out process which result in a very small squeeze-out pressure which is almost constant during the squeeze-out of the last monolayer of the fluid. In all cases we observe lubricant trapped in the valley of the surface roughness, which cannot be removed independent of the magnitude of the squeezing pressures.

  16. The effect of surface nano-corrugation on the squeeze-out of molecular thin hydrocarbon films between curved surfaces with long range elasticity.

    PubMed

    Sivebaek, I M; Persson, B N J

    2016-11-04

    The properties of linear alkane lubricants confined between two approaching solids are investigated by a model that accounts for the roughness, curvature and elastic properties of the solid surfaces. We consider linear alkanes of different chain lengths from [Formula: see text] to [Formula: see text], confined between corrugated solid walls. The pressure necessary to squeeze out the lubricant increases rapidly with the alkane chain length, but is always much lower than in the case of smooth surfaces. The longest alkanes form domains of ordered chains and the squeeze-out appears to nucleate in the more disordered regions between these domains. The short alkanes stay fluid-like during the entire squeeze out process which result in a very small squeeze-out pressure which is almost constant during the squeeze-out of the last monolayer of the fluid. In all cases we observe lubricant trapped in the valley of the surface roughness, which cannot be removed independent of the magnitude of the squeezing pressures.

  17. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains

    SciTech Connect

    Jeong, Cheol; Douglas, Jack F.

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M{sup β}, is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from −1.8 to −2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature T{sub g} where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔH{sub a} and entropy ΔS{sub a} of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a “critical” chain length, n ≈ 17. A close examination of this phenomenon indicates that a “buckling transition” from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔS{sub a} ∝ ΔH{sub a}, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔH{sub a} and ΔS{sub a} with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  18. Mass dependence of the activation enthalpy and entropy of unentangled linear alkane chains.

    PubMed

    Jeong, Cheol; Douglas, Jack F

    2015-10-14

    The mass scaling of the self-diffusion coefficient D of polymers in the liquid state, D ∼ M(β), is one of the most basic characteristics of these complex fluids. Although traditional theories such as the Rouse and reptation models of unentangled and entangled polymer melts, respectively, predict that β is constant, this exponent for alkanes has been estimated experimentally to vary from -1.8 to -2.7 upon cooling. Significantly, β changes with temperature T under conditions where the chains are not entangled and at temperatures far above the glass transition temperature Tg where dynamic heterogeneity does not complicate the description of the liquid dynamics. Based on atomistic molecular dynamics simulations on unentangled linear alkanes in the melt, we find that the variation of β with T can be directly attributed to the dependence of the enthalpy ΔHa and entropy ΔSa of activation on the number of alkane backbone carbon atoms, n. In addition, we find a sharp change in the melt dynamics near a "critical" chain length, n ≈ 17. A close examination of this phenomenon indicates that a "buckling transition" from rod-like to coiled chain configurations occurs at this characteristic chain length and distinct entropy-enthalpy compensation relations, ΔSa ∝ ΔHa, hold on either side of this polymer conformational transition. We conclude that the activation free energy parameters exert a significant influence on the dynamics of polymer melts that is not anticipated by either the Rouse and reptation models. In addition to changes of ΔHa and ΔSa with M, we expect changes in these free energy parameters to be crucial for understanding the dynamics of polymer blends, nanocomposites, and confined polymers because of changes of the fluid free energy by interfacial interactions and geometrical confinement.

  19. Long-Wave Infrared (LWIR) Molecular Laser-Induced Breakdown Spectroscopy (LIBS) Emissions of Thin Solid Explosive Powder Films Deposited on Aluminum Substrates.

    PubMed

    Yang, Clayton S-C; Jin, Feng; Trivedi, Sudhir B; Brown, Ei E; Hommerich, Uwe; Tripathi, Ashish; Samuels, Alan C

    2017-04-01

    Thin solid films made of high nitro (NO2)/nitrate (NO3) content explosives were deposited on sand-blasted aluminum substrates and then studied using a mercury-cadmium-telluride (MCT) linear array detection system that is capable of rapidly capturing a broad spectrum of atomic and molecular laser-induced breakdown spectroscopy (LIBS) emissions in the long-wave infrared region (LWIR; ∼5.6-10 µm). Despite the similarities of their chemical compositions and structures, thin films of three commonly used explosives (RDX, HMX, and PETN) studied in this work can be rapidly identified in the ambient air by their molecular LIBS emission signatures in the LWIR region. A preliminary assessment of the detection limit for a thin film of RDX on aluminum appears to be much lower than 60 µg/cm(2). This LWIR LIBS setup is capable of rapidly probing and charactering samples without the need for elaborate sample preparation and also offers the possibility of a simultaneous ultraviolet visible and LWIR LIBS measurement.

  20. Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

    PubMed

    Chen, Shasha; Jia, Wanglu; Peng, Ping'an

    2016-08-15

    Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Propagation and extinction of premixed C{sub 5}-C{sub 12}n-alkane flames

    SciTech Connect

    Ji, Chunsheng; Dames, Enoch; Wang, Yang L.; Wang, Hai; Egolfopoulos, Fokion N.

    2010-02-15

    Laminar flame speeds and extinction strain rates of premixed C{sub 5}-C{sub 12}n-alkane flames were determined at atmospheric pressure and elevated unburned mixture temperatures, over a wide range of equivalence ratios. Experiments were performed in the counterflow configuration and flow velocities were measured using Laser Doppler Velocimetry. The laminar flame speeds were obtained using a non-linear extrapolation technique utilizing numerical simulations of the counterflow experiments with detailed descriptions of chemical kinetics and molecular transport. Compared to linearly extrapolated values, the laminar flame speeds obtained using non-linear extrapolations were found to be 1-4 cm/s lower depending on the equivalence ratio. It was determined that the laminar flame speeds of all n-alkane/air mixtures considered in this investigation are similar to each other and sensitive largely to the H{sub 2}/CO and C{sub 1}-C{sub 4} hydrocarbon kinetics. Additionally, the resistance to extinction decreases as the fuel molecular weight increases. Simulations of the experiments were performed using the recently developed JetSurF 0.2 reaction model consisting of 194 species and 1459 reactions. The laminar flame speeds were predicted with good accuracy for all the n-alkane-air mixtures considered. The experimental extinction strain rates are well predicted by the model for fuel-lean mixtures. For stoichiometric and fuel-rich mixtures, the predicted extinction strain rates are approximately 10% lower than the experimental values. Insights into the physical and chemical processes that control the response of n-alkane flames are provided through detailed sensitivity analyses on both reaction rates and binary diffusion coefficients. (author)

  2. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  3. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  4. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  5. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  6. 40 CFR 721.785 - Halogenated alkane aromatic compound (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halogenated alkane aromatic compound... Specific Chemical Substances § 721.785 Halogenated alkane aromatic compound (generic name). (a) Chemical... as a halogenated alkane aromatic compound (PMN P-94-1747) is subject to reporting under this...

  7. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  8. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  9. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  10. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  11. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  12. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acryloxy alkanoic alkane derivative... Significant New Uses for Specific Chemical Substances § 721.10148 Acryloxy alkanoic alkane derivative with...) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  13. 40 CFR 721.10148 - Acryloxy alkanoic alkane derivative with mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acryloxy alkanoic alkane derivative... Significant New Uses for Specific Chemical Substances § 721.10148 Acryloxy alkanoic alkane derivative with...) The chemical substance identified generically as acryloxy alkanoic alkane derivative with mixed...

  14. Molecular beam epitaxy and characterization of thin Bi{sub 2}Se{sub 3} films on Al{sub 2}O{sub 3} (110)

    SciTech Connect

    Tabor, Phillip; Keenan, Cameron; Urazdhin, Sergei; Lederman, David

    2011-07-04

    The structural and electronic properties of thin Bi{sub 2}Se{sub 3} films grown on Al{sub 2}O{sub 3} (110) by molecular beam epitaxy are investigated. The epitaxial films grow in the Frank-van der Merwe mode and are c-axis oriented. They exhibit the highest crystallinity, the lowest carrier concentration, and optimal stoichiometry at a substrate temperature of 200 deg. C determined by the balance between surface kinetics and desorption of Se. The crystallinity of the films improves with increasing Se/Bi flux ratio. Our results enable studies of thin topological insulator films on inert, non-conducting substrates that allow optical access to both film surfaces.

  15. Magnetic properties of low-moment ferrimagnetic Heusler Cr 2 CoGa thin films grown by molecular beam epitaxy

    SciTech Connect

    Jamer, Michelle E.; Sterbinsky, George E.; Stephen, Gregory M.; DeCapua, Matthew C.; Player, Gabriel; Heiman, Don

    2016-10-31

    Recently, theorists have predicted many materials with a low magnetic moment and large spin-polarization for spintronic applications. These compounds are predicted to form in the inverse Heusler structure; however, many of these compounds have been found to phase segregate. In this study, ordered Cr2CoGa thin films were synthesized without phase segregation using molecular beam epitaxy. The present as-grown films exhibit a low magnetic moment from antiferromagnetically coupled Cr and Co atoms as measured with superconducting quantum interface device magnetometry and soft X-ray magnetic circular dichroism. Electrical measurements demonstrated a thermally-activated semiconductor-like resistivity component with an activation energy of 87 meV. These results confirm spin gapless semiconducting behavior, which makes these thin films well positioned for future devices.

  16. [Capacitive sensor for environmental monitoring based on thin films of molecularly imprinted polymers. Computer modeling for optimization of the composition of synthetic analogs of bioreceptors].

    PubMed

    Serheieva, T A; Panasiuk-Dileni, T L; Pilets'ka, O V; Pilets'kyĭ, S A; Iel's'ka, H V

    2006-01-01

    A capacitive sensor for environmental monitoring based on thin films of desmetryn-selective molecularly imprinted polymer (MIP) was developed. The method of modification of gold electrodes with the thin film of herbicide-selective MIP using the grafting polymerization approach was developed. The method of computational modeling was used to optimize the composition of desmetryn-selective MIPs. It was shown that 2-acrylamido-2-methyl-1-propan-sulfonic acid is the optimal functional monomer for desmetryn. Formation of synthetic binding sites in MIPs was demonstrated to be determined by the binding energy between the template and functional monomers as well as the number of functional groups taking part in the recognition of the template molecule. Electrochemical processes occurring at the MIP-modified electrode were analyzed. The detection limit for desmetryn comprised 100 nM. High selectivity of the capacitive sensor towards structural analogues of desmetryn as well as high operational and storage stabilities was demonstrated.

  17. Insight into the nanomechanical properties under indentation of β-Si3N4 nano-thin layers in the basal plane using molecular dynamics simulation.

    PubMed

    Lu, Xuefeng; Guo, Xin; La, Peiqing; Wei, Yupeng; Nan, Xueli; He, Ling

    2014-09-21

    Molecular dynamics simulations were performed to clarify the nanomechanical responses of β-Si3N4 nano-thin layers in the basal plane for indenters of various radii, different indentation velocities and at different temperatures. It was found that the maximum loading stress and indenter displacement both increase with increasing radius of the indenter. A large number of N(6h)-Si bond-breaking defects and one N(2c)-Si bond-breaking defects are responsible for the initiation of fracturing. With increasing loading velocity, the maximum loading stresses show almost no change; however, a high loading velocity can shorten the displacement of the indenter and contributes to the formation of new N(2c)-Si bond-breaking defects. Thermal fluctuations can decrease the mechanical properties of the thin layer. The maximum loading stresses and indenter displacements are sensitive to both the radius of the indenter and the loading temperature.

  18. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1995-01-17

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.

  19. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, P.E. Jr.; Lyons, J.E.

    1993-05-18

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.

  20. Crystallization and prevention of supercooling of microencapsulated n-alkanes.

    PubMed

    Zhang, Xing-xiang; Fan, Yao-feng; Tao, Xiao-ming; Yick, Kit-lun

    2005-01-15

    Microencapsulated n-alkanes (n-octadecane, n-nonadecane, and n-eicosane) were synthesized by in situ polymerization using urea-melamine-formaldehyde polymer as shells. Microcapsules 5.0 and 10.0 wt% of 1-tetradecanol, paraffin, and 1-octadecanol were used as nucleating agents. The fabrication was characterized using Fourier transform infrared, light microscopy, and scanning electron microscopy. The crystallization and prevention of supercooling of the microcapsules are studied using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction. The crystal system of the microencapsulated n-alkane is the same as that of the bulk. The enthalpies of the microcapsules containing 70 wt% n-alkanes are approximately 160 J/g. The melting temperature of the n-alkanes in the microcapsule is the same as that in the bulk. There are multiple peaks on the DSC cooling curves that are attributed to liquid-rotator, rotator-crystal, and liquid-crystal transitions. The DSC cooling behavior of microencapsulated n-octadecane is affected by the average diameters. The measured maximum degree of supercooling of the microencapsulated n-octadecane is approximately 26.0 degrees C at a heating and cooling rate of 10.0 degrees C/min. The degree of supercooling of microencapsulated n-octadecane is decreased by adding 10.0 wt% of 1-octadecanol as a nucleating agent.

  1. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1995-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  2. Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1993-01-01

    New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.

  3. Diverse alkane hydroxylase genes in microorganisms and environments

    PubMed Central

    Nie, Yong; Chi, Chang-Qiao; Fang, Hui; Liang, Jie-Liang; Lu, She-Lian; Lai, Guo-Li; Tang, Yue-Qin; Wu, Xiao-Lei

    2014-01-01

    AlkB and CYP153 are important alkane hydroxylases responsible for aerobic alkane degradation in bioremediation of oil-polluted environments and microbial enhanced oil recovery. Since their distribution in nature is not clear, we made the investigation among thus-far sequenced 3,979 microbial genomes and 137 metagenomes from terrestrial, freshwater, and marine environments. Hundreds of diverse alkB and CYP153 genes including many novel ones were found in bacterial genomes, whereas none were found in archaeal genomes. Moreover, these genes were detected with different distributional patterns in the terrestrial, freshwater, and marine metagenomes. Hints for horizontal gene transfer, gene duplication, and gene fusion were found, which together are likely responsible for diversifying the alkB and CYP153 genes adapt to the ubiquitous distribution of different alkanes in nature. In addition, different distributions of these genes between bacterial genomes and metagenomes suggested the potentially important roles of unknown or less common alkane degraders in nature. PMID:24829093

  4. Modular and selective biosynthesis of gasoline-range alkanes.

    PubMed

    Sheppard, Micah J; Kunjapur, Aditya M; Prather, Kristala L J

    2016-01-01

    Typical renewable liquid fuel alternatives to gasoline are not entirely compatible with current infrastructure. We have engineered Escherichia coli to selectively produce alkanes found in gasoline (propane, butane, pentane, heptane, and nonane) from renewable substrates such as glucose or glycerol. Our modular pathway framework achieves carbon-chain extension by two different mechanisms. A fatty acid synthesis route is used to generate longer chains heptane and nonane, while a more energy efficient alternative, reverse-β-oxidation, is used for synthesis of propane, butane, and pentane. We demonstrate that both upstream (thiolase) and intermediate (thioesterase) reactions can act as control points for chain-length specificity. Specific free fatty acids are subsequently converted to alkanes using a broad-specificity carboxylic acid reductase and a cyanobacterial aldehyde decarbonylase (AD). The selectivity obtained by different module pairings provides a foundation for tuning alkane product distribution for desired fuel properties. Alternate ADs that have greater activity on shorter substrates improve observed alkane titer. However, even in an engineered host strain that significantly reduces endogenous conversion of aldehyde intermediates to alcohol byproducts, AD activity is observed to be limiting for all chain lengths. Given these insights, we discuss guiding principles for pathway selection and potential opportunities for pathway improvement. Copyright © 2015 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  5. Cyano- and polycyanometalloporphyrins as catalysts for alkane oxidation

    DOEpatents

    Ellis, Jr., Paul E.; Lyons, James E.

    1992-01-01

    Alkanes are oxidized by contact with oxygen-containing gas in the presence as catalyst of a metalloporphyrin in which hydrogen atoms in the porphyrin ring have been substituted with one or more cyano groups. Hydrogen atoms in the porphyrin ring may also be substituted with halogen atoms.

  6. Improving alkane synthesis in Escherichia coli via metabolic engineering.

    PubMed

    Song, Xuejiao; Yu, Haiying; Zhu, Kun

    2016-01-01

    Concerns about energy security and global petroleum supply have made the production of renewable biofuels an industrial imperative. The ideal biofuels are n-alkanes in that they are chemically and structurally identical to the fossil fuels and can "drop in" to the transportation infrastructure. In this work, an Escherichia coli strain that produces n-alkanes was constructed by heterologous expression of acyl-acyl carrier protein (ACP) reductase (AAR) and aldehyde deformylating oxygenase (ADO) from Synechococcus elongatus PCC7942. The accumulation of alkanes ranged from 3.1 to 24.0 mg/L using different expressing strategies. Deletion of yqhD, an inherent aldehyde reductase in E. coli, or overexpression of fadR, an activator for fatty acid biosynthesis, exhibited a nearly twofold increase in alkane titers, respectively. Combining yqhD deletion and fadR overexpression resulted in a production titer of 255.6 mg/L in E. coli, and heptadecene was the most abundant product.

  7. MODELING OF ALKANE EMISSIONS FROM A WOOD STAIN

    EPA Science Inventory

    The article discusses full-scale residential house tests to evaluate the effects of organic emissions from a wood finishing product--wood stain--on indoor air quality (IAQ). The test house concentrations of three alkane species, nonane, decane, and undecane, were measured as a fu...

  8. Synthesis of a photo-caged aminooxy alkane thiol.

    PubMed

    Mancini, Rock J; Li, Ronald C; Tolstyka, Zachary P; Maynard, Heather D

    2009-12-07

    A photo-caged aminooxy alkane thiol synthesized in 7 steps and 15% overall yield was used to form a self-assembled monolayer (SAM). Photo-deprotection on the surface was confirmed by FT-IR spectroscopy and contact angle goniometry. Conjugation of a small molecule ketone, ethyl levulinate, further confirmed the presence of aminooxy groups on the surface.

  9. Johari-Goldstein secondary relaxation in methylated alkanes

    NASA Astrophysics Data System (ADS)

    Ngai, K. L.

    2005-06-01

    Dielectric relaxation measurements of the methylated alkanes, 3-methylpentane, 3-methylheptane, 4-methylheptane, 2,3-dimethylpentane, and 2,4,6-trimethylheptane by S. Shahriari, A. Mandanici, L-M Wang, and R. Richert [J. Chem. Phys. 121, 8960 (2004)] have found a primary α relaxation of these glass-forming liquids and a slow secondary β relaxation that are in close proximity to each other on the frequency scale. These glass formers have one or more methyl groups individually attached to various carbons on the alkane chain. They cannot contribute to such a slow secondary relaxation. Hence the observed secondary relaxations is not intramolecular in origin and, similar to secondary relaxations found in rigid molecules by Johari and Goldstein, they are potentially important in the consideration of a mechanism for the glass transition. These secondary relaxations in the methylated alkanes are special and belong to the class of Johari-Goldstein in a generalized sense. The coupling model has predicted that its primitive relaxation time should be approximately the same as the relaxation time of the secondary relaxation if the latter is of the Johari-Goldstein kind. This prediction has been shown to hold in many other glass formers. The published data of the methylated alkanes provide an opportunity to test this prediction once more. The results of this work confirm the prediction.

  10. Integrated process for preparing a carboxylic acid from an alkane

    SciTech Connect

    Benderly, Abraham; Chadda, Nitin; Sevon, Douglass

    2011-12-20

    The present invention relates to an integrated process for producing unsaturated carboxylic acids from the corresponding C.sub.2-C.sub.4 alkane. The process begins with performance of thermally integrated dehydrogenation reactions which convert a C.sub.2-C.sub.4 alkane to its corresponding C.sub.2-C.sub.4 alkene, and which involve exothermically converting a portion of an alkane to its corresponding alkene by oxidative dehydrogenation in an exothermic reaction zone, in the presence of oxygen and a suitable catalyst, and then feeding the products of the exothermic reaction zone to an endothermic reaction zone wherein at least a portion of the remaining unconverted alkane is endothermically dehydrogenated to form an additional quantity of the same corresponding alkene, in the presence of carbon dioxide and an other suitable catalyst. The alkene products of the thermally integrated dehydrogenation reactions are then provided to a catalytic vapor phase partial oxidation process for conversion of the alkene to the corresponding unsaturated carboxylic acid or nitrile. Unreacted alkene and carbon dioxide are recovered from the oxidation product stream and recycled back to the thermally integrated dehydrogenation reactions.

  11. Roaming radical pathways for the decomposition of alkanes.

    SciTech Connect

    Harding, L. B.; Klippenstein, S. J.

    2010-01-01

    CASPT2 calculations predict the existence of roaming radical pathways for the decomposition of propane, n-butane, isobutane and neopentane. The roaming radical paths lead to the formation of an alkane and an alkene instead of the expected radical products. The predicted barriers for the roaming radical paths lie {approx}1 kcal/mol below the corresponding radical asymptotes.

  12. Catalytic oxidation of light alkanes in presence of a base

    DOEpatents

    Bhinde, Manoj V.; Bierl, Thomas W.

    1998-01-01

    The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol.

  13. Catalytic oxidation of light alkanes in presence of a base

    DOEpatents

    Bhinde, M.V.; Bierl, T.W.

    1998-03-03

    The presence of a base in the reaction mixture in a metal-ligand catalyzed partial oxidation of alkanes results in sustained catalyst activity, and in greater percent conversion as compared with oxidation in the absence of base, while maintaining satisfactory selectivity for the desired oxidation, for example the oxidation of isobutane to isobutanol. 1 fig.

  14. Isolating the non-polar contributions to the intermolecular potential for water-alkane interactions.

    PubMed

    Ballal, Deepti; Venkataraman, Pradeep; Fouad, Wael A; Cox, Kenneth R; Chapman, Walter G

    2014-08-14

    Intermolecular potential models for water and alkanes describe pure component properties fairly well, but fail to reproduce properties of water-alkane mixtures. Understanding interactions between water and non-polar molecules like alkanes is important not only for the hydrocarbon industry but has implications to biological processes as well. Although non-polar solutes in water have been widely studied, much less work has focused on water in non-polar solvents. In this study we calculate the solubility of water in different alkanes (methane to dodecane) at ambient conditions where the water content in alkanes is very low so that the non-polar water-alkane interactions determine solubility. Only the alkane-rich phase is simulated since the fugacity of water in the water rich phase is calculated from an accurate equation of state. Using the SPC/E model for water and TraPPE model for alkanes along with Lorentz-Berthelot mixing rules for the cross parameters produces a water solubility that is an order of magnitude lower than the experimental value. It is found that an effective water Lennard-Jones energy ε(W)/k = 220 K is required to match the experimental water solubility in TraPPE alkanes. This number is much higher than used in most simulation water models (SPC/E-ε(W)/k = 78.2 K). It is surprising that the interaction energy obtained here is also higher than the water-alkane interaction energy predicted by studies on solubility of alkanes in water. The reason for this high water-alkane interaction energy is not completely understood. Some factors that might contribute to the large interaction energy, such as polarizability of alkanes, octupole moment of methane, and clustering of water at low concentrations in alkanes, are examined. It is found that, though important, these factors do not completely explain the anomalously strong attraction between alkanes and water observed experimentally.

  15. Computational study on hole conduction in normal alkanes: Anisotropy and effect of dynamic disorder

    NASA Astrophysics Data System (ADS)

    Sato, M.; Kumada, A.; Hidaka, K.; Hirano, T.; Sato, F.

    2017-02-01

    Despite its importance, carrier conduction in electrical insulators is poorly understood. This work presents a computational study of hole conduction in single crystalline alkanes (n-C18H38 and n-C36H74). Hole mobilities are computed with the combination of molecular dynamics simulation, quantum chemical calculation, and the kinetic Monte Carlo method. The hole hopping rate is computed by the Fermi golden rule rate kernel without high temperature approximation. A strong correlation between the anisotropy of hole mobility and crystalline morphology is found. Hole mobilities in the direction of the c axis are more than an order of magnitude larger than those in the a - b plane. At room temperature, hole mobility is increased by roughly a factor of 10 due to the thermal motion of molecules. Computed anisotropic hole mobilities are in reasonable agreement with experimental values when the effect of dynamic disorder is taken into account. The results strongly indicate that hole transfer in crystalline alkane occurs in the phonon-assisted transport regime.

  16. High Frequency of Thermodesulfovibrio spp. and Anaerolineaceae in Association with Methanoculleus spp. in a Long-Term Incubation of n-Alkanes-Degrading Methanogenic Enrichment Culture

    PubMed Central

    Liang, Bo; Wang, Li-Ying; Zhou, Zhichao; Mbadinga, Serge M.; Zhou, Lei; Liu, Jin-Feng; Yang, Shi-Zhong; Gu, Ji-Dong; Mu, Bo-Zhong

    2016-01-01

    In the present study, the microbial community and functional gene composition of a long-term active alkane-degrading methanogenic culture was established after two successive enrichment culture transfers and incubated for a total period of 1750 days. Molecular analysis was conducted after the second transfer (incubated for 750 days) for both the active alkanes-degrading methanogenic enrichment cultures (T2-AE) and the background control (T2-BC). A net increase of methane as the end product was detected in the headspace of the enrichment cultures amended with long-chain n-alkanes and intermediate metabolites, including octadecanoate, hexadecanoate, isocaprylate, butyrate, isobutyrate, propionate, acetate, and formate were measured in the liquid cultures. The composition of microbial community shifted through the successive transfers over time of incubation. Sequences of bacterial and archaeal 16S rRNA gene (16S rDNA) and mcrA functional gene indicated that bacterial sequences affiliated to Thermodesulfovibrio spp. and Anaerolineaceae and archaeal sequences falling within the genus Methanoculleus were the most frequently encountered and thus represented the dominant members performing the anaerobic degradation of long-chain n-alkanes and methanogenesis. In addition, the presence of assA functional genes encoding the alkylsuccinate synthase α subunit indicated that fumarate addition mechanism could be considered as a possible initial activation step of n-alkanes in the present study. The succession pattern of microbial communities indicates that Thermodesulfovibrio spp. could be a generalist participating in the metabolism of intermediates, while Anaerolineaceae plays a key role in the initial activation of long-chain n-alkane biodegradation. PMID:27695441

  17. Physiological function of the Pseudomonas putida PpG6 (Pseudomonas oleovorans) alkane hydroxylase: monoterminal oxidation of alkanes and fatty acids.

    PubMed Central

    Nieder, M; Shapiro, J

    1975-01-01

    Pseudomonas putida PpG6 is able to utilize purified n-alkanes of six to ten carbon atoms for growth. It can also grow on the primary terminal oxidation products of these alkanes and on 1-dodecanol but not on the corresponding 2-ketones or 1,6-hexanediol, adipic acid, or pimelic acid. Revertible point mutants can be isolated which have simultaneously lost the ability to grow on all five n-alkane growth substrates but which can still grow on octanol or nonanol. An acetate-negative mutant defective in isocitrate lysase activity is unable to grow on even-numbered alkanes and fatty acids. Analysis of double mutants defective in acetate and propionate or in acetate and glutarate metabolism shows that alkane carbon is assimilated only via acetyl-coenzyme A and propionyl-coenzyme A. These results support the following conclusions: (i) The n-alkane growth specificity of P. putida PpG6 is due to the substrate specificity of whole-cell alkane hydroxylation; (ii) there is a single alkane hydroxylase enzyme complex; (iii) the physiological role of this complex is to initiate the monoterminal oxidation of alkane chains; and (iv) straight-chain fatty acids from butyric through nonanoic are degraded exclusively by beta-oxidation from the carboxyl end of the molecule. PMID:804473

  18. Reconstitution of plant alkane biosynthesis in yeast demonstrates that Arabidopsis ECERIFERUM1 and ECERIFERUM3 are core components of a very-long-chain alkane synthesis complex.

    PubMed

    Bernard, Amélie; Domergue, Frédéric; Pascal, Stéphanie; Jetter, Reinhard; Renne, Charlotte; Faure, Jean-Denis; Haslam, Richard P; Napier, Johnathan A; Lessire, René; Joubès, Jérôme

    2012-07-01

    In land plants, very-long-chain (VLC) alkanes are major components of cuticular waxes that cover aerial organs, mainly acting as a waterproof barrier to prevent nonstomatal water loss. Although thoroughly investigated, plant alkane synthesis remains largely undiscovered. The Arabidopsis thaliana ECERIFERUM1 (CER1) protein has been recognized as an essential element of wax alkane synthesis; nevertheless, its function remains elusive. In this study, a screen for CER1 physical interaction partners was performed. The screen revealed that CER1 interacts with the wax-associated protein ECERIFERUM3 (CER3) and endoplasmic reticulum-localized cytochrome b5 isoforms (CYTB5s). The functional relevance of these interactions was assayed through an iterative approach using yeast as a heterologous expression system. In a yeast strain manipulated to produce VLC acyl-CoAs, a strict CER1 and CER3 coexpression resulted in VLC alkane synthesis. The additional presence of CYTB5s was found to enhance CER1/CER3 alkane production. Site-directed mutagenesis showed that CER1 His clusters are essential for alkane synthesis, whereas those of CER3 are not, suggesting that CYTB5s are specific CER1 cofactors. Collectively, our study reports the identification of plant alkane synthesis enzymatic components and supports a new model for alkane production in which CER1 interacts with both CER3 and CYTB5 to catalyze the redox-dependent synthesis of VLC alkanes from VLC acyl-CoAs.

  19. Image Charge Effects in the Wetting Behavior of Alkanes on Water with Accounting for Water Solubility

    PubMed Central

    Emelyanenko, Kirill A.; Emelyanenko, Alexandre M.; Boinovich, Ludmila B.

    2016-01-01

    Different types of surface forces, acting in the films of pentane, hexane, and heptane on water are discussed. It is shown that an important contribution to the surface forces originates from the solubility of water in alkanes. The equations for the distribution of electric potential inside the film are derived within the Debye-Hückel approximation, taking into account the polarization of the film boundaries by discrete charges at water-alkane interface and by the dipoles of water molecules dissolved in the film. On the basis of above equations we estimate the image charge contribution to the surface forces, excess free energy, isotherms of water adsorption in alkane film, and the total isotherms of disjoining pressure in alkane film. The results indicate the essential influence of water/alkane interface charging on the disjoining pressure in alkane films, and the wettability of water surface by different alkanes is discussed. PMID:28773305

  20. Genetically assembled fluorescent biosensor for in situ detection of bio-synthesized alkanes.

    PubMed

    Wu, Wei; Zhang, Lei; Yao, Lun; Tan, Xiaoming; Liu, Xufeng; Lu, Xuefeng

    2015-06-03

    Construction of highly efficient microbial cell factories producing drop-in biofuel alkanes is severely limited due to the lack of a fast detection method against alkanes. Here we first developed a sensitive fluorescent biosensor for rapid and in situ monitoring of intracellular alkane synthesis. Using GFP as reporter, the biosensor could actively respond to the intracellular alkane products, especially for the mid- and long-chain alkanes synthesized in the recombinant Escherichia coli and give a concentration-dependent fluorescence response. Our results also suggested the feasibility of developing high-throughput strategies basing on the alkane biosensor device in E. coli, and thus will greatly facilitate the application of directed evolution strategies to further improve the alkane-producing microbial cell factories.