WorldWideScience

Sample records for alkane monolayers studied

  1. Comparative study of normal and branched alkane monolayer films adsorbed on a solid surface. I. Structure

    DEFF Research Database (Denmark)

    Enevoldsen, Ann Dorrit; Hansen, Flemming Yssing; Diama, A.

    2007-01-01

    their backbone and squalane has, in addition, six methyl side groups. Upon adsorption, there are significant differences as well as similarities in the behavior of these molecular films. Both molecules form ordered structures at low temperatures; however, while the melting point of the two-dimensional (2D......The structure of a monolayer film of the branched alkane squalane (C30H62) adsorbed on graphite has been studied by neutron diffraction and molecular dynamics (MD) simulations and compared with a similar study of the n-alkane tetracosane (n-C24H52). Both molecules have 24 carbon atoms along...... temperature. The neutron diffraction data show that the translational order in the squalane monolayer is significantly less than in the tetracosane monolayer. The authors' MD simulations suggest that this is caused by a distortion of the squalane molecules upon adsorption on the graphite surface. When...

  2. Nanoscale Trapping and Squeeze-Out of Confined Alkane Monolayers.

    Science.gov (United States)

    Gosvami, N N; O'Shea, S J

    2015-12-01

    We present combined force curve and conduction atomic force microscopy (AFM) data for the linear alkanes CnH2n+2 (n = 10, 12, 14, 16) confined between a gold-coated AFM tip and a graphite surface. Solvation layering is observed in the force curves for all liquids, and conduction AFM is used to study in detail the removal of the confined (mono)layer closest to the graphite surface. The squeeze-out behavior of the monolayer can be very different depending upon the temperature. Below the monolayer melting transition temperatures the molecules are in an ordered state on the graphite surface, and fast and complete removal of the confined molecules is observed. However, above the melting transition temperature the molecules are in a disordered state, and even at large applied pressure a few liquid molecules are trapped within the tip-sample contact zone. These findings are similar to a previous study for branched alkanes [ Gosvami Phys. Rev. Lett. 2008, 100, 076101 ], but the observation for the linear alkane homologue series demonstrates clearly the dependence of the squeeze-out and trapping on the state of the confined material.

  3. Intramolecular diffusive motion in alkane monolayers studied by high-resolution quasielastic neutron scattering and molecular dynamics simulations

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Criswell, L.; Fuhrmann, D

    2004-01-01

    Molecular dynamics simulations of a tetracosane (n-C24H50) monolayer adsorbed on a graphite basal-plane surface show that there are diffusive motions associated with the creation and annihilation of gauche defects occurring on a time scale of similar to0.1-4 ns. We present evidence...... that these relatively slow motions are observable by high-energy-resolution quasielastic neutron scattering (QNS) thus demonstrating QNS as a technique, complementary to nuclear magnetic resonance, for studying conformational dynamics on a nanosecond time scale in molecular monolayers....

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

    DEFF Research Database (Denmark)

    Diama, A.; Matthies, B.; Herwig, K. W.

    2009-01-01

    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...... 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...

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

    Science.gov (United States)

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

    2009-08-01

    We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C24H50 denoted as C24) and dotriacontane (n-C32H66 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 Å=√3 ag, where ag=2.46 Å 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 ˜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.

  6. Fabrication and characterization of graphene/molecule/graphene vertical junctions with aryl alkane monolayers

    Science.gov (United States)

    Jeong, Inho; Song, Hyunwook

    2017-11-01

    In this study, we fabricated and characterized graphene/molecule/graphene (GMG) vertical junctions with aryl alkane monolayers. The constituent molecules were chemically self-assembled via electrophilic diazonium reactions into a monolayer on the graphene bottom electrode, while the other end physically contacted the graphene top electrode. A full understanding of the transport properties of molecular junctions is a key step in the realization of molecular-scale electronic devices and requires detailed microscopic characterization of the junction's active region. Using a multiprobe approach combining a variety of transport techniques, we elucidated the transport mechanisms and electronic structure of the GMG junctions, including temperature- and length-variable transport measurements, and transition voltage spectroscopy. These results provide criteria to establish a valid molecular junction and to determine the most probable transport characteristics of the GMG junctions.

  7. Intramolecular and Lattice Melting in n-Alkane Monolayers: An Analog of Melting in Lipid Bilayers

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Herwig, K.W.; Matthies, B.

    1999-01-01

    Molecular dynamics (MD) simulations and neutron diffraction experiments have been performed on n-dotriacontane (n-C32D66) monolayers adsorbed on a graphite basal-plane surface. The diffraction experiments show little change in the crystalline monolayer structure up to a temperature of similar to ...

  8. Formation of Underbrushes on thiolated Poly (ethylene glycol) PEG monolayers by Oligoethylene glycol (OEG) terminated Alkane Thiols on Gold

    DEFF Research Database (Denmark)

    Lokanathan, Arcot R.

    2011-01-01

    Adding underbrushes of oligoethylene glycol (OEG) to monolayers of long chain PEG molecules on a surface is one of the strategies [1] in designing a suitable platform for antifouling purpose, where it is possible to have high graft density and molecular conformational freedom[4] simultaneously......, there by maximal retention of activity of covalently immobilised antifouling enzyme [2] on PEG surfaces along with resistance to protein adsorption[3]. Here we present some our studies on the addition of OEG thiol molecules over a self assembled monolayer of PEG thiol on gold. The kinetics of addition of OEG thiol...

  9. Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

    Science.gov (United States)

    Devi, J Meena

    2017-06-01

    The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Theoretical study of n-alkane adsorption on metal surfaces

    DEFF Research Database (Denmark)

    Morikawa, Yoshitada; Ishii, Hisao; Seki, Kazuhiko

    2004-01-01

    The interaction between n-alkane and metal surfaces has been studied by means of density-functional theoretical calculations within a generalized gradient approximation (GGA). We demonstrate that although the GGA cannot reproduce the physisorption energy well, our calculations can reproduce the e...

  11. Alkane Metathesis

    KAUST Repository

    Basset, Jean-Marie

    2015-03-29

    Catalytic activation of alkanes which directly transforms light alkanes into higher homologs is a major area in organometallic chemistry and petrochemical chemistry. This transformation is a chemical challenge considering the inertness of the sp3 carbon-hydrogen bond. It is generally accepted that this catalytic process involves the formation of olefins. This reaction is defined as alkane metathesis. To date, two catalytic systems of alkane metathesis exist: (i) a single catalytic system prepared by surface organometallic chemistry, acting as multifunctional-supported catalyst which transforms any alkanes into a mixture of their lower and higher homologs and (ii) the other catalytic systems employing a tandem strategy with two different metals, one metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two classes of catalysts by looking at their specific reactivity of the catalysts towards alkanes, comparing their performances and studying the mechanism.

  12. Pulse radiolysis studies on liquid alkanes and related polymers

    International Nuclear Information System (INIS)

    Tagawa, S.; Hayashi, N.; Yoshida, Y.; Washio, M.; Tabata, Y.

    1989-01-01

    Absorption spectra of alkane radical cations, alkane excited states, and alkyl radicals and electrons in irradiated neat liquid alkanes at room temperature were assigned on subnanosecond and nanosecond time scale after an electron pulse. Two broad visible and near-infrared absorption bands of alkane excited states and radical cations, and UV absorption band of alkyl radicals was observed in neat n-alkanes. In neat cyclohezane and trans-decalin, very broad visible absorption band mainly due to alkane excited states and UV absorption band of alkyl radicals were observed. In neat neopentane and isooctane, visible absorption bands were not observed, although UV absorption bands of alkyl radicals were observed. The wavelengths of absorptive peaks of alkane radical cations and excited states become longer with increasing the number of carbon atoms of n-alkanes. The lifetimes of alkane radical cations become shorter with decreasing the number of carbon atoms of n-alkanes and are shorter than those of electrons in neat alkanes. The main processes of the alkyl radical formation finish within the time resolution of our system (about 20 ps). The alkyl radicals are produced mainly from excited radicals cations and partly from higher excited states, the lowest excited states, radical cations, and thermal hydrogen atoms, In irradiated ethylene-propylene copolymers, broad absorption bands of excited states and tail parts of absorption bands of radical cations and electrons were observed in visible and near-infrared region, although UV absorption of alkyl radicals was not confirmed lack of transparency of polymer films. (author)

  13. Study of factors that influence complex-formation of n-alkanes with crystal carbamide

    Energy Technology Data Exchange (ETDEWEB)

    Dorodnova, V.S.; Korzhov, Yu.A.; Martynenko, A.G.

    1982-01-01

    Studies effect of temperature, solid phase content in the suspension and amount of MeOH on extent of n-alkane extraction during carbamide deparaffinization. A most thorough extraction of n-alkanes is achieved with a graduated temperature regimen of complex-formation.

  14. Nonlinear optical studies of organic monolayers

    International Nuclear Information System (INIS)

    Shen, Y.R.

    1988-02-01

    Second-order nonlinear optical effects are forbidden in a medium with inversion symmetry, but are necessarily allowed at a surface where the inversion summary is broken. They are often sufficiently strong so that a submonolayer perturbation of the surface can be readily detected. They can therefore be used as effective tools to study monolayers adsorbed at various interfaces. We discuss here a number of recent experiments in which optical second harmonic generation (SHG) and sum-frequency generation (SFG) are employed to probe and characterize organic monolayers. 15 refs., 5 figs

  15. The fate of primary cations in radiolysis of alkanes as studied by ESR

    International Nuclear Information System (INIS)

    Iwasaki, M.; Toriyama, K.; Nunome, K.

    1983-01-01

    The structures and reactions of alkane cations (RH + ) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2 H 6 , C 3 H 8 , iso-C 4 H 10 and neo-C 5 H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6 , CFCl 2 CF 2 Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2 CF 2 Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers. (author)

  16. A MOLECULAR-DYNAMICS STUDY OF LECITHIN MONOLAYERS

    NARCIS (Netherlands)

    AHLSTROM, P; BERENDSEN, HJC

    1993-01-01

    Two monolayers of didecanoyllecithin at the air-water interface have been studied using molecular dynamics simulations. The model system consisted of two monolayers of 42 lecithin molecules each separated by a roughly 4 nm thick slab of SPC water. The area per lecithin molecule was 0.78 nm(2)

  17. Enhanced piezoelectricity of monolayer phosphorene oxides: a theoretical study.

    Science.gov (United States)

    Yin, Huabing; Zheng, Guang-Ping; Gao, Jingwei; Wang, Yuanxu; Ma, Yuchen

    2017-10-18

    Two-dimensional (2D) piezoelectric materials have potential applications in miniaturized sensors and energy conversion devices. In this work, using first-principles simulations at different scales, we systematically study the electronic structures and piezoelectricity of a series of 2D monolayer phosphorene oxides (POs). Our calculations show that the monolayer POs have tunable band gaps along with remarkable piezoelectric properties. The calculated piezoelectric coefficient d 11 of 54 pm V -1 in POs is much larger than those of 2D transition metal dichalcogenide monolayers and the widely used bulk α-quartz and AlN, and almost reaches the level of the piezoelectric effect in recently discovered 2D GeS. Furthermore, two other considerable piezoelectric coefficients, i.e., d 31 and d 26 with values of -10 pm V -1 and 21 pm V -1 , respectively, are predicted in some monolayer POs. We also examine the correlation between the piezoelectric coefficients and energy stability. The enhancement of piezoelectricity for monolayer phosphorene by oxidation will broaden the applications of phosphorene and phosphorene derivatives in nano-sized electronic and piezotronic devices.

  18. Alkane Metathesis

    KAUST Repository

    Basset, Jean-Marie; Callens, Emmanuel; Riache, Nassima

    2015-01-01

    metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two

  19. A QSPR STUDY OF NORMAL BOILING POINT OF ORGANIC COMPOUNDS (ALIPHATIC ALKANES USING MOLECULAR DESCRIPTORS

    Directory of Open Access Journals (Sweden)

    B. Souyei

    2013-12-01

    Full Text Available A quantitative structure–property relationship (QSPR study is carried out to develop correlations that relate the molecular structures of organic compounds (Aliphatic Alkanes to their normal boiling point (NBP and two correlations were proposed for constitutionals and connectivity indices Models. The correlations are simple in application with good accuracy, which provide an easy, direct and relatively accurate way to calculate NBP. Such calculation gives us a model that gives results in remarkable correlations with the descriptors of blokes constitutionals (CON, and connectivity indices (CI (R2 = 0.950, δ = 0.766 (R2 = 0.969, δ = 0.782 respectively.

  20. Molecular dynamics simulation studies of mid-size liquid n-Alkanes, C12–C160

    International Nuclear Information System (INIS)

    Kwon, Tae Woo; Lee, Song Hi

    2015-01-01

    In this study, we report the results of molecular dynamics simulations (MD) for model systems of mid-size liquid n-alkanes (C 12 –C 160 ) at several temperatures (⁓2700 K) in canonical ensembles to calculate structural and dynamic properties (viscosity η, self-diffusion constant D, and monomeric friction constant ζ). For the small n-alkanes for n ≤ 80, the chains are clearly ≥ 1, which leads to the conclusion that the liquid n-alkanes are far away from the Rouse regime, but for the n-alkanes for n ≥ 120, the chains are ⁓ 1 and they are Gaussian. It is found that the long chains of these n-alkanes at high temperatures show abnormalities in density, viscosity, and monomeric friction constant. The mass and temperature dependences of structural and dynamic properties (η, D, and ζ) are discussed

  1. Microculture system for studying monolayers of functional beta-cells.

    Science.gov (United States)

    Dobersen, M J; Scharff, J E; Notkins, A L

    1980-04-01

    A method is described for growing monolayers of newborn rat beta-cells in microculture trays. After disruption of the pancreas with collagenase, islets were isolated by Ficoll density gradient centrifugation, trypsinized to obtain individual cells, and plated in 96-well tissue culture trays. The cells were incubated for the first 3 days in growth medium containing 0.1 mM 3-isobutyl-1-methylxanthine to promote monolayer formation. The cultures could be maintained in a functional state, as defined by their responsiveness to known modulators of insulin secretion, for at least 2 weeks. As few as 1 X 10(3) islet cells/well gave results that were reproducible within +/- 10%. It is suggested that the microculture system for islet cells might prove to be a rapid and reproducible screening technique for studying drugs, viruses, or other agents that affect beta-cell function.

  2. Thermal stability of thiol and silane monolayers: A comparative study

    International Nuclear Information System (INIS)

    Chandekar, Amol; Sengupta, Sandip K.; Whitten, James E.

    2010-01-01

    The stability of self-assembled monolayers (SAMs) at elevated temperatures is of considerable technological importance. The thermal stability of 1-octadecanethiol (ODT), 16-mercaptohexadecanoic acid (MHDA) and 1H,1H,2H,2H-perfluorodecanethiol (PFDT) SAMs on gold surfaces, and of 4-aminobutyltriethoxysilane (ABTES) and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDS) assembled on hydroxylated silicon surfaces, was studied by X-ray photoelectron spectroscopy (XPS). The samples were heated in ultrahigh vacuum to temperatures in excess of that required for SAM degradation. ODT monolayers were stable to ca. 110 deg. C, while MHDA and PFDT SAMs were stable to ca. 145 deg. C. ABTES SAMs were found to be indefinitely stable to 250 deg. C, while PFDS SAMs were stable to 350 deg. C. These studies demonstrate the advantages of using silane monolayers for moderate to high temperature applications and illustrate differences that arise due to the nature of the tail group. To demonstrate the feasibility of silanes for template-directed patterning, a hydroxylated silicon oxide surface containing microcontact-printed PFDS patterns was spin-coated with a mainly hydrophilic block copolymer. Annealing the surface at 90 deg. C for 2 h caused the block copolymer to dewet the hydrophobic PFDS-patterned regions and adsorb exclusively on the unpatterned regions of the surface.

  3. Polycyclic aromatic hydrocarbons in model bacterial membranes - Langmuir monolayer studies.

    Science.gov (United States)

    Broniatowski, Marcin; Binczycka, Martyna; Wójcik, Aneta; Flasiński, Michał; Wydro, Paweł

    2017-12-01

    High molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) are persistent organic pollutants which due to their limited biodegradability accumulate in soils where their increased presence can lead to the impoverishment of the decomposer organisms. As very hydrophobic PAHs easily penetrate cellular membranes of soil bacteria and can be incorporated therein, changing the membrane fluidity and other functions which in consequence can lead to the death of the organism. The structure and size of PAH molecule can be crucial for its membrane activity; however the correlation between PAH structure and its interaction with phospholipids have not been investigated so far. In our studies we applied phospholipid Langmuir monolayers as model bacterial membranes and investigated how the incorporation of six structurally different PAH molecules change the membrane texture and physical properties. In our studies we registered surface pressure and surface potential isotherms upon the monolayer compression, visualized the monolayer texture with the application of Brewster angle microscopy and searched the ordering of the film-forming molecules with molecular resolution with the application of grazing incidence X-ray diffraction (GIXD) method. It turned out that the phospholipid-PAH interactions are strictly structure dependent. Four and five-ring PAHs of the angular or cluster geometry can be incorporated into the model membranes changing profoundly their textures and fluidity; whereas linear or large cluster PAHs cannot be incorporated and separate from the lipid matrix. The observed phenomena were explained based on structural similarities of the applied PAHs with membrane steroids and hopanoids. Copyright © 2017. Published by Elsevier B.V.

  4. Numerical and experimental studies of ethanol flames and autoignition theory for higher alkanes

    Science.gov (United States)

    Saxena, Priyank

    In order to enhance the fuel efficiency of an engine and to control pollutant formation, an improved understanding of the combustion chemistry of the fuels at a fundamental level is paramount. This knowledge can be gained by developing detailed reaction mechanisms of the fuels for various combustion processes and by studying combustion analytically employing reduced-chemistry descriptions. There is a need for small detailed reaction mechanisms for alkane and alcohol fuels with reduced uncertainties in their combustion chemistry that are computationally cheaper in multidimensional CFD calculations. Detailed mechanisms are the starting points in identifying reduced-chemistry descriptions of combustion processes to study problems analytically. This research includes numerical, experimental and analytical studies. The first part of the dissertation consists of numerical and experimental studies of ethanol flames. Although ethanol has gained popularity as a possible low-pollution source of renewable energy, significant uncertainties remain in its combustion chemistry. To begin to address ethanol combustion, first a relatively small detailed reaction mechanism, commonly known as the San Diego Mech, is developed for the combustion of hydrogen, carbon monoxide, formaldehyde, methane, methanol, ethane, ethylene, and acetylene, in air or oxygen-inert mixtures. This mechanism is tested for autoignition, premixed-flame burning velocities, and structures and extinction of diffusion flames and of partially premixed flames of many of these fuels. The reduction in uncertainties in the combustion chemistry can best be achieved by consistently updating a reaction mechanism with reaction rate data for the elementary steps based on newer studies in literature and by testing it against as many experimental conditions as available. The results of such a testing for abovementioned fuels are reported here along with the modifications of reaction-rate parameters of the most important

  5. A study of binuclear zirconium hydride catalysts of the hydrogenolysis of alkanes by the density functional theory method

    Science.gov (United States)

    Ustynyuk, L. Yu.; Fast, A. S.; Ustynyuk, Yu. A.; Lunin, V. V.

    2012-06-01

    Binuclear hydride centers containing two Zr(IV) atoms are suggested as promising catalysts for the hydrogenolysis of alkanes under mild conditions ( T model compounds L2(H)Zr(X)2Zr(H)L2 (X = H, L = OSi≡ ( 4a), X = L = OMe ( 4d)), L(H)Zr(O)2Zr(H)L (L = OSi≡ ( 4b), Cp( 4c)) and (≡SiO)2(H)Zr-O-Zr(H)(OSi≡)2 ( 4e and 4f) with the propane molecule were studied using the density functional theory method. The results show that centers of the 4a, 4e, and 4f types and especially 4b are promising catalysts of the hydrogenolysis of alkanes due to a high degree of unsaturation of two Zr atoms and their sequential participation in the splitting of the C-C bond and hydrogenation of ethylene formed as a result of splitting.

  6. Study of Liquid Alkanes Production from Biomass-Derived Carbohydrates by Aldol-Condensation and Hydrogenation Processes

    Directory of Open Access Journals (Sweden)

    Navadol Laosiripojana

    2010-10-01

    Full Text Available This research aims to synthesis liquid alkanes from biomass-derived hydroxyl methyl furfural (HMF and furfural by aldol-condensation and hydrogenation processes over several catalysts i.e. TiO2, TiO2-ZrO2, Pd/Al2O3 and Pd/CeO2. It was found that the catalysts make significant impact on the selectivity and yield of alkanes product. It is noted that Pd/Al2O3 provided the highest alkane yield and selectivity. The aldol-condensation and hydrogenation of HMF over Pd/Al2O3 provide high C12 selectivity whereas the aldol-condensation and hydrogenation of furfural over Pd/Al2O3 provide high C8 selectivity. The effects of reaction temperature, reaction pressure and reaction time were then studied. The effect of inlet furfural to acetone molar ratio was also determined. It was also found that the optimized conditions to maximize the yield of alkane production from the aldol-condensation/hydrogenation of HMF and furfural are (i at 53oC and 24 hr for aldol-condenstation of HMF, (ii 80oC and 24 hr for aldol-condenstation of furfural, and (iii 120oC for 6 hr with HMF to acetone molar ratio of 3:1 and furfural to acetone molar ratio of 4:1 in the presence of Pd/Al2O3 (calcined at 500oC for hydrogenation reaction.

  7. Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

    International Nuclear Information System (INIS)

    Shkrob, I.A.; Trifunac, A.D.

    1995-01-01

    Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

  8. The langmuir monolayer: an efficient model for studying interfacial properties of biomembranes

    International Nuclear Information System (INIS)

    Cirak, J.; Sokolsky, M.; Dobrocka, E.; Weis, M.

    2012-01-01

    In this communication, we describe aspects of monolayer technology by focusing on effects of calcium ions on physical properties of phospholipid monolayers using results of measurements of surface pressure, x-ray reflectivity and AFM. These experiments are motivated by the search for lipid-DNA complexes with high transfection efficiency but without toxicity which might be a promising tool in gene therapy. In each part methodological importance is stressed and its specificity for studying molecular interactions at a lipid monolayer. (authors)

  9. Studies of the structure and properties of organic monolayers, multilayers and superlattices

    International Nuclear Information System (INIS)

    Dutta, P.; Ketterson, J.B.

    1990-01-01

    Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this progress report, we describe our x-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension. 20 refs., 11 figs

  10. Flow reactor studies of non-equilibrium plasma-assisted oxidation of n-alkanes.

    Science.gov (United States)

    Tsolas, Nicholas; Lee, Jong Guen; Yetter, Richard A

    2015-08-13

    The oxidation of n-alkanes (C1-C7) has been studied with and without the effects of a nanosecond, non-equilibrium plasma discharge at 1 atm pressure from 420 to 1250 K. Experiments have been performed under nearly isothermal conditions in a flow reactor, where reactive mixtures are diluted in Ar to minimize temperature changes from chemical reactions. Sample extraction performed at the exit of the reactor captures product and intermediate species and stores them in a multi-position valve for subsequent identification and quantification using gas chromatography. By fixing the flow rate in the reactor and varying the temperature, reactivity maps for the oxidation of fuels are achieved. Considering all the fuels studied, fuel consumption under the effects of the plasma is shown to have been enhanced significantly, particularly for the low-temperature regime (T<800 K). In fact, multiple transitions in the rates of fuel consumption are observed depending on fuel with the emergence of a negative-temperature-coefficient regime. For all fuels, the temperature for the transition into the high-temperature chemistry is lowered as a consequence of the plasma being able to increase the rate of fuel consumption. Using a phenomenological interpretation of the intermediate species formed, it can be shown that the active particles produced from the plasma enhance alkyl radical formation at all temperatures and enable low-temperature chain branching for fuels C3 and greater. The significance of this result demonstrates that the plasma provides an opportunity for low-temperature chain branching to occur at reduced pressures, which is typically observed at elevated pressures in thermal induced systems. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

  11. Structural and Kinetic Studies of Novel Cytochrome P450 Small-Alkane Hydroxylases

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, Frances H.

    2012-02-27

    The goals of this project are to investigate (1) the kinetics and stabilities of engineered cytochrome P450 (P450) small alkane hydroxylases and their evolutionary intermediates, (2) the structural basis for catalytic proficiency on small alkanes of these engineered P450s, and (3) the changes in redox control resulting from protein engineering. To reach these goals, we have established new methods for determining the kinetics and stabilities of multicomponent P450s such as CYP153A6. Using these, we were able to determine that CYP153A6 is proficient for hydroxylation of alkanes as small as ethane, an activity that has never been observed previously in any natural P450. To elucidate the structures of the engineered P450s, we obtained x-ray diffraction data for two variants in the P450PMO (propane monooxygenase) lineage and a preliminary structure for the most evolved variant. This structure shows changes in the substrate binding regions of the enzyme and a reduction in active site volume that are consistent with the observed changes in substrate specificity from fatty acids in the native enzyme to small alkanes in P450PMO. We also constructed semi-rational designed libraries mutating only residues in the enzyme active site that in one round of mutagenesis and screening produced variants that achieved nearly half of the activity of the most evolved enzymes of the P450PMO lineage. Finally, we found that changes in redox properties of the laboratory-evolved P450 alkane hydroxylases did not reflect the improvement in their electron transfer efficiency. The heme redox potential remained constant throughout evolution, while activity increased and coupling efficiency improved from 10% to 90%. The lack of correlation between heme redox potential and enzyme activity and coupling efficiency led us to search for other enzyme properties that could be better predictors for activity towards small alkanes, specifically methane. We investigated the oxidation potential of the radical

  12. Cyclic voltammetry and scanning electrochemical microscopy studies of methylene blue immobilized on the self-assembled monolayer of n-dodecanethiol

    International Nuclear Information System (INIS)

    Salamifar, Seyed Ehsan; Mehrgardi, Masoud Ayatollahi; Kazemi, Sayed Habib; Mousavi, Mir Fazllollah

    2010-01-01

    Electron transfer (ET) kinetics through n-dodecanethiol (C 12 SH) self-assembled monolayer on gold electrode was studied using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). An SECM model for compensating pinhole contribution, was used to measure the ET kinetics of solution-phase probes of ferrocyanide/ferricyanide (Fe(CN) 6 4-/3- ) and ferrocenemethanol/ferrociniummethanol (FMC 0/+ ) through the C 12 SH monolayer yielding standard tunneling rate constant (k ET 0 ) of (4 ± 1) x 10 -11 and (3 ± 1) x 10 -10 cm s -1 for Fe(CN) 6 4-/3- and FMC 0/+ respectively. Decay tunneling constants (β) of 0.97 and 0.96 A -1 for saturated alkane thiol chains were obtained using Fe(CN) 6 4- and FMC respectively. Also, it was found that methylene blue (MB) molecules are effectively immobilized on the C 12 SH monolayer and can mediate the ET between the solution-phase probes and underlying gold substrate. SECM-mediated model was used to simultaneously measure the bimolecular ET between the solution-phase probes and the monolayer-immobilized MB molecules, as well as tunneling ET between the monolayer-immobilized MB molecules and the underlying gold electrode, allowing the measurement of k BI = (5 ± 1) x 10 6 and (4 ± 2) x 10 7 cm 3 mol -1 s -1 for the bimolecular ET and k ET/MB 0 =(1±0.3)x10 -3 and (7 ± 3) x 10 -2 s -1 for the standard tunneling rate constant of ET using Fe(CN) 6 4-/3- and FMC 0/+ probes respectively.

  13. Cyclic voltammetry and scanning electrochemical microscopy studies of methylene blue immobilized on the self-assembled monolayer of n-dodecanethiol

    Energy Technology Data Exchange (ETDEWEB)

    Salamifar, Seyed Ehsan [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mehrgardi, Masoud Ayatollahi [Department of Chemistry, University of Isfahan, Isfahan (Iran, Islamic Republic of); Kazemi, Sayed Habib [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of); Mousavi, Mir Fazllollah, E-mail: mousavim@modares.ac.i [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

    2010-12-30

    Electron transfer (ET) kinetics through n-dodecanethiol (C{sub 12}SH) self-assembled monolayer on gold electrode was studied using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). An SECM model for compensating pinhole contribution, was used to measure the ET kinetics of solution-phase probes of ferrocyanide/ferricyanide (Fe(CN){sub 6}{sup 4-/3-}) and ferrocenemethanol/ferrociniummethanol (FMC{sup 0/+}) through the C{sub 12}SH monolayer yielding standard tunneling rate constant (k{sub ET}{sup 0}) of (4 {+-} 1) x 10{sup -11} and (3 {+-} 1) x 10{sup -10} cm s{sup -1} for Fe(CN){sub 6}{sup 4-/3-} and FMC{sup 0/+} respectively. Decay tunneling constants ({beta}) of 0.97 and 0.96 A{sup -1} for saturated alkane thiol chains were obtained using Fe(CN){sub 6}{sup 4-} and FMC respectively. Also, it was found that methylene blue (MB) molecules are effectively immobilized on the C{sub 12}SH monolayer and can mediate the ET between the solution-phase probes and underlying gold substrate. SECM-mediated model was used to simultaneously measure the bimolecular ET between the solution-phase probes and the monolayer-immobilized MB molecules, as well as tunneling ET between the monolayer-immobilized MB molecules and the underlying gold electrode, allowing the measurement of k{sub BI} = (5 {+-} 1) x 10{sup 6} and (4 {+-} 2) x 10{sup 7} cm{sup 3} mol{sup -1} s{sup -1} for the bimolecular ET and k{sub ET/MB}{sup 0}=(1{+-}0.3)x10{sup -3} and (7 {+-} 3) x 10{sup -2} s{sup -1} for the standard tunneling rate constant of ET using Fe(CN){sub 6}{sup 4-/3-} and FMC{sup 0/+} probes respectively.

  14. Theoretical and experimental study of the vibrational excitations in ethane monolayers adsorbed on graphite (0001) surfaces

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Taub, H.

    1987-01-01

    The collective vibrational excitations of two different crystalline monolayer phases of ethane (C2H6) adsorbed on the graphite (0001) surface have been investigated theoretically and experimentally. The monolayer phases studied are the commensurate 7/8 ×4 structure in which the ethane molecules lie...

  15. Simulation studies of pore and domain formation in a phospholipid monolayer

    NARCIS (Netherlands)

    Knecht, Volker; Muller, M; Bonn, M; Marrink, SJ; Mark, AE

    2005-01-01

    Despite extensive study the phase behavior of phospholipid monolayers at an air-water interface is still not fully understood. In particular recent vibrational sum-frequency generation (VSFG) spectra of DPPC monolayers as a function of area density show a sharp transition in the order of the lipid

  16. Transcriptome response to alkane biofuels in Saccharomyces cerevisiae: identification of efflux pumps involved in alkane tolerance

    Science.gov (United States)

    2013-01-01

    Background Hydrocarbon alkanes have been recently considered as important next-generation biofuels because microbial production of alkane biofuels was demonstrated. However, the toxicity of alkanes to microbial hosts can possibly be a bottleneck for high productivity of alkane biofuels. To tackle this toxicity issue, it is essential to understand molecular mechanisms of interactions between alkanes and microbial hosts, and to harness these mechanisms to develop microbial host strains with improved tolerance against alkanes. In this study, we aimed to improve the tolerance of Saccharomyces cerevisiae, a model eukaryotic host of industrial significance, to alkane biofuels by exploiting cellular mechanisms underlying alkane response. Results To this end, we first confirmed that nonane (C9), decane (C10), and undecane (C11) were significantly toxic and accumulated in S. cerevisiae. Transcriptome analyses suggested that C9 and C10 induced a range of cellular mechanisms such as efflux pumps, membrane modification, radical detoxification, and energy supply. Since efflux pumps could possibly aid in alkane secretion, thereby reducing the cytotoxicity, we formed the hypothesis that those induced efflux pumps could contribute to alkane export and tolerance. In support of this hypothesis, we demonstrated the roles of the efflux pumps Snq2p and Pdr5p in reducing intracellular levels of C10 and C11, as well as enhancing tolerance levels against C10 and C11. This result provided the evidence that Snq2p and Pdr5p were associated with alkane export and tolerance in S. cerevisiae. Conclusions Here, we investigated the cellular mechanisms of S. cerevisiae response to alkane biofuels at a systems level through transcriptome analyses. Based on these mechanisms, we identified efflux pumps involved in alkane export and tolerance in S. cerevisiae. We believe that the results here provide valuable insights into designing microbial engineering strategies to improve cellular tolerance for

  17. Kinetics and mechanistic study of n-alkane hydroisomerization reaction on Pt-doped γ-alumina catalyst

    Directory of Open Access Journals (Sweden)

    Abhishek Dhar

    2017-12-01

    Full Text Available The catalysts γ-alumina (GA, the reference catalyst and Pt doped γ-alumina (PGA-s were synthesized using a simple sol-gel technique, in which at first preparation of porous base (GA, then impregnation of platinum salt over the base and finally reduction of platinum in the surface of the support were done. These catalysts prepared in different mole ratios of Pt:Al as 2:1, 1:1 and 1:2 are named as PGA-1, PGA-2 and PGA-3 respectively. The isomerization of n-alkanes (n-hexane, n-heptane and n-octane were investigated over the synthesized catalysts. The 2-methyl pentane (2-MP, 2,2-dimethyl pentane (2,2-DMP and 2,3-dimethyl hexane (2,3-DMH are the major products of respective isomerization of n-hexane, n-heptane and n-octane, besides a small amount of other branched isomers are also produced. The product distribution is comparable to that reported for Pt based other catalysts. The optimal mole ratios of Pt:Al is 1:1 (PGA-2 gives quite good catalytic activity for isomerization of n-alkane. Even through in reusability study, PGA-2 gives better performance than others. We have mainly focused on kinetic study, reaction mechanism behind isomerization and calculated the order of reactions and activation energies of the isomerization reactions in the present work. Keywords: Isomerization, n-alkanes, Catalyst, Reaction mechanism, Kinetics study, Activation energy

  18. Study of the ionization of alkane-electron scavenger reactant mixtures irradiated by 60Co gamma rays

    International Nuclear Information System (INIS)

    Bonnet, Jacques.

    1977-01-01

    This study deals with ionization of alkane-electron scavenger reactant mixtures, irradiated by 60 Co γ-rays. It is shown that the extrapolated free-ion yields (extrapolated yield method) decrease with the reactant concentration. On the basis of ONSAGER model and theoretical treatment of MOZUMDER, the cross sections of epithermal electron attachment in hexane, cyclohexane, 2,2-dimethylbutane, cyclopentane, 2,2,4-trimethylpentane for CCl 4 , C 7 F 14 , C 6 H 5 Br, C 6 H 5 Cl, C 6 F 14 , (C 6 H 5 ) 2 are determined. A comparison between gas-phase and liquid-phase cross sections is established [fr

  19. Lateral electron transport in monolayers of short chains at interfaces: A Monte Carlo study

    International Nuclear Information System (INIS)

    George, Christopher B.; Szleifer, Igal; Ratner, Mark A.

    2010-01-01

    Graphical abstract: Electron hopping between electroactive sites in a monolayer composed of redox-active and redox-passive molecules. - Abstract: Using Monte Carlo simulations, we study lateral electronic diffusion in dense monolayers composed of a mixture of redox-active and redox-passive chains tethered to a surface. Two charge transport mechanisms are considered: the physical diffusion of electroactive chains and electron hopping between redox-active sites. Results indicate that by varying the monolayer density, the mole fraction of electroactive chains, and the electron hopping range, the dominant charge transport mechanism can be changed. For high density monolayers in a semi-crystalline phase, electron diffusion proceeds via electron hopping almost exclusively, leading to static percolation behavior. In fluid monolayers, the diffusion of chains may contribute more to the overall electronic diffusion, reducing the observed static percolation effects.

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

    Science.gov (United States)

    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.

  1. Studies of lipid interactions in mixed Langmuir monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Gzyl-Malcher, Barbara [Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland)], E-mail: gzyl@chemia.uj.edu.pl; Paluch, Maria [Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland)

    2008-10-31

    The mixed monolayers of dipalmitoyl phosphatidylcholine (DPPC) with 3-monopalmitoyl glycerol (PG) and palmitic acid 4-methylumbelliferyl ester (4-MU) were compared. Relevant thermodynamic parameters such as excess area ({delta}A{sup E}) and excess free energy of mixing ({delta}G{sub mix}{sup E}) were derived from the surface pressure data obtained from compression measurements performed in a Langmuir trough. Generally, DPPC formed more condensed monolayers with PG and greater negative values of {delta}A{sup E} and {delta}G{sub mix}{sup E} were observed for DPPC/PG system than for DPPC/4-MU one. The positive values of the excess free entropy of mixing ({delta}S{sub mix}{sup E}) were calculated for DPPC/4-MU system at lower temperatures and for DPPC/PG system at higher temperatures.

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

    Directory of Open Access Journals (Sweden)

    Lisa eGieg

    2013-06-01

    Full Text Available 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 contibuting to modern-day detrimental effects such as oilfield souring, or may lead to more benefical 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.

  3. Molecular dynamics studies of the melting of butane and hexane monolayers adsorbed on the basal-plane surface of graphite

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Newton, J. C.; Taub, H.

    1993-01-01

    The effect of molecular steric properties on the melting of quasi-two-dimensional solids is investigated by comparing results of molecular dynamics simulations of the melting of butane and hexane monolayers adsorbed on the basal-plane surface of graphite. These molecules differ only in their length......, being members of the n-alkane series [CH3(CH2)n−2CH3] where n=4 for butane and n=6 for hexane. The simulations employ a skeletal model, which does not include the hydrogen atoms explicitly, to represent the intermolecular and molecule–substrate interactions. Nearest-neighbor intramolecular bonds...... are fixed in length, but the molecular flexibility is preserved by allowing the bend and dihedral torsion angles to vary. The simulations show a qualitatively different melting behavior for the butane and hexane monolayers consistent with neutron and x-ray scattering experiments. The melting of the low...

  4. Efficient Hydrogenolysis of Alkanes at Low Temperature and Pressure Using Tantalum Hydride on MCM-41, and a Quantum Chemical Study

    KAUST Repository

    Polshettiwar, Vivek

    2012-02-10

    Hydrogenolysis of hydrocarbons is of considerable technological importance for applications such as the hydroprocessing of petrochemical feedstocks to generate high-value and useful chemicals and fuels. We studied the catalytic activity of tantalum hydride supported on MCM-41 for the hydrogenolysis of alkanes at low temperature and low atmospheric pressure in a dynamic reactor. The reactions proceed with good turnover numbers, and the catalyst could be reused for several times, which makes the overall catalytic process sustainable. We derived the plausible mechanism by using DFT calculations and identified the preferred pathways by the analysis of potential energy surface. Our results and the proposed reaction mechanism demonstrate the viability of the "catalyst-by-design" approach. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Efficient Hydrogenolysis of Alkanes at Low Temperature and Pressure Using Tantalum Hydride on MCM-41, and a Quantum Chemical Study

    KAUST Repository

    Polshettiwar, Vivek; Pasha, Farhan Ahmad; De Mallmann, Aimery; Norsic, Sé bastien; Thivolle-Cazat, Jean; Basset, Jean-Marie

    2012-01-01

    Hydrogenolysis of hydrocarbons is of considerable technological importance for applications such as the hydroprocessing of petrochemical feedstocks to generate high-value and useful chemicals and fuels. We studied the catalytic activity of tantalum hydride supported on MCM-41 for the hydrogenolysis of alkanes at low temperature and low atmospheric pressure in a dynamic reactor. The reactions proceed with good turnover numbers, and the catalyst could be reused for several times, which makes the overall catalytic process sustainable. We derived the plausible mechanism by using DFT calculations and identified the preferred pathways by the analysis of potential energy surface. Our results and the proposed reaction mechanism demonstrate the viability of the "catalyst-by-design" approach. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. SAXS study of transient pre-melting in chain-folded alkanes

    International Nuclear Information System (INIS)

    Ungar, G.; Wills, H.H.

    1990-01-01

    A pronounced pre-melting effect is observed in chain-folded crystals of pure monodisperse n-alkane C 246 H 494 . The effect is reversible on a short time scale, but at longer times the once-folded chain crystals are irreversibly lost as slow chain extension proceeds by solid diffusion well below the melting point. The melting process is thus monitored by rapid time-resolved small-angle X-ray (SAXS) measurements, using synchrotron radiation. The results show that the observed pronounced broadening of the DSC melting endotherm for chain-folded crystals is entirely due to genuine pre-melting of lamellar surfaces. Although a significant portion of material is already molten below the final melting point of chain-folded crystals T F , no recrystallization in the chain-extended form can occur until the cores of the crystalline lamellae melt at T F . Pre-melting of extended chain crystals is significantly less pronounced than that of folded chain crystals

  7. Metal adsorption on monolayer blue phosphorene: A first principles study

    Science.gov (United States)

    Khan, Imran; Son, Jicheol; Hong, Jisang

    2018-01-01

    We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and 0.77 μB /impurity atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.

  8. Selectivity of alkyl radical formation from branched alkanes studied by electron spin resonance and electron spin echo spectroscopy

    International Nuclear Information System (INIS)

    Tsuneki, Ichikawa; Hiroshi, Yoshida

    1992-01-01

    Alkyl radicals generated from branched alkanes by γ radiation are being measuring by electron spin resonance and electron spin echo spectroscopy. This research is being conducted to determine the mechanism of selective alkyl radical formation in low-temperature solids

  9. Doping effect on monolayer MoS2 for visible light dye degradation - A DFT study

    Science.gov (United States)

    Cheriyan, Silpa; Balamurgan, D.; Sriram, S.

    2018-04-01

    The electronic and optical properties of, Nitrogen (N), Cobalt (Co), and Co-N co-doped monolayers of MoS2 has been studied by using density functional theory (DFT) for visible light photocatalytic activity. From the calculations, it has been observed that the band gap of monolayer MoS2 has been reduced while doping. However, the band gaps of pristine and N doped MoS2 monolayers only falls in the visible region while for Co and Co-N co-doped systems, the band gap shifted to IR region. The optical calculation also confirms the results. The formation energy values of the doped system reaveal that MoS2 monolayer drops its stability while doping. To evaluate the photocatalytic response, band edge potentials of pristine and N-MoS2 are calculated, and the observed results show that compared to N-doped MoS2 monolayer, pure MoS2 is highly suitable for visible light photocatalytic dye degradation.

  10. Atomic force microscopy studies of lateral phase separation in mixed monolayers of dipalmitoylphosphatidylcholine and dilauroylphosphatidylcholine

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez, Jacqueline; Badia, Antonella

    2003-09-01

    Atomic force microscopy imaging of dipalmitoylphosphatidylcholine (DPPC)/dilauroylphosphatidylcholine (DLPC) monolayers deposited onto alkanethiol modified-gold surfaces by the Langmuir-Schaefer technique was used to investigate domain formation in a binary system where phase separation arises from a difference in the alkyl chain lengths of the lipids. We have established how the condensed domain structure (shape and size) in DPPC/DLPC monolayers depends on the surface pressure and lipid composition. The mixed monolayers exhibit a positive deviation from an ideal mixing behavior at surface pressures of {<=}32 mN/m. Lateral compression to pressures greater than the liquid-expanded-to-liquid-condensed (LE-to-LC) phase transition pressure of the mixed monolayer ({approx}8-16 mN/m) induces extensive separation into condensed DPPC-rich domains and a fluid DLPC matrix. The condensed structures observed at a few milliNeutons per meter above the LE-to-LC transition pressure resemble those reported for pure DPPC monolayers in the LE/LC co-existence region. At a bilayer equivalence pressure of 32 mN/m and 20 deg. C, condensed domains exist between x{sub DPPC} {approx}0.25 and {approx}0.80, analogous to aqueous DPPC/DLPC dispersions. Compression from 32 to 40 mN/m results in either a striking distortion of the DPPC domain shape or a break-up of the microscopic DPPC domains into a network of nanoscopic islands (at higher DPPC mol fractions), possibly reflecting a critical mixing behavior. The results of this study provide a fundamental framework for understanding and controlling the formation of lateral domain structures in mixed phospholipid monolayers.

  11. Studying the influence of substrate conductivity on the optoelectronic properties of quantum dots langmuir monolayer

    Science.gov (United States)

    Al-Alwani, Ammar J.; Chumakov, A. S.; Begletsova, N. N.; Shinkarenko, O. A.; Markin, A. V.; Gorbachev, I. A.; Bratashov, D. N.; Gavrikov, M. V.; Venig, S. B.; Glukhovskoy, E. G.

    2018-04-01

    The formation of CdSe quantum dots (QDs) monolayers was studied by Langmuir Blodgett method. The fluorescence (PL) spectra of QD monolayers were investigated at different substrate type (glass, silicon and ITO glass) and the influence of graphene sheets layer (as a conductive surface) on the QDs properties has also been studied. The optoelectronic properties of QDs can be tuned by deposition of insulating nano-size layers of the liquid crystal between QDs and conductive substrate. The monolayer of QDs transferred on conductive surface (glass with ITO) has lowest intensity of PL spectra due to quenching effect. The PL intensity of QDs could be tuned by using various type of substrates or/and by transformed high conductive layer. Also the photooxidation processes of CdSe QDs monolayer on the solid surface can be controlled by selection of suitable substrate. The current-voltage (I–V) characteristics of QDs thin film on ITO surface was studied using scanning tunneling microscope (STM).

  12. Thermodynamic study of alkane-α,ω-diamines - evidence of odd-even pattern of sublimation properties

    Czech Academy of Sciences Publication Activity Database

    Fulem, Michal; Růžička, K.; Červinka, C.; Bazyleva, A.; Della Gatta, G.

    2014-01-01

    Roč. 371, Jun (2014), s. 93-105 ISSN 0378-3812 Institutional support: RVO:68378271 Keywords : alkane-diamines * odd–even effect * vapor pressure * sublimation and vaporization thermodynamic properties * statistical thermodynamics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.200, year: 2014

  13. Metathesis of alkanes and related reactions

    KAUST Repository

    Basset, Jean-Marie

    2010-02-16

    (Figure Presented) 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, (=SiO)2TaH, 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 aluminasupported tungsten hydride, W(H)3/Al 2O3, 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 of

  14. Metathesis of alkanes and related reactions.

    Science.gov (United States)

    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. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

    Directory of Open Access Journals (Sweden)

    Xiaoli Sun

    2017-12-01

    Full Text Available Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te. The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS2 and 2H-WSe2, which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries.

  16. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers.

    Science.gov (United States)

    Sun, Xiaoli; Wang, Zhiguo

    2017-01-01

    Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX 2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX 2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX 2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS 2 and 2H-WSe 2 , which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX 2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX 2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries.

  17. Study of the interaction of lactoferricin B with phospholipid monolayers and bilayers.

    Science.gov (United States)

    Arseneault, Marjolaine; Bédard, Sarah; Boulet-Audet, Maxime; Pézolet, Michel

    2010-03-02

    Bovine lactoferricin (LfcinB) is an antimicrobial peptide obtained from the pepsin cleavage of lactoferrin. The activity of LfcinB has been extensively studied on diverse pathogens, but its mechanism of action still has to be elucidated. Because of its nonspecificity, its mode of action is assumed to be related to interactions with membranes. In this study, the interaction of LfcinB with a negatively charged monolayer of dipalmitoylphosphatidylglycerol has been investigated as a function of the surface pressure of the lipid film using in situ Brewster angle and polarization modulation infrared reflection absorption spectroscopy and on transferred monolayers by atomic force microscopy and polarized attenuated total reflection infrared spectroscopy. The data show clearly that LfcinB forms stable films at the air-water interface. They also reveal that the interaction of LfcinB with the lipid monolayer is modulated by the surface pressure. At low surface pressure, LfcinB inserts within the lipid film with its long molecular axis oriented mainly parallel to the acyl chains, while at high surface pressure, LfcinB is adsorbed under the lipid film, the hairpin being preferentially aligned parallel to the plane of the interface. The threshold for which the behavior changes is 20 mN/m. At this critical surface pressure, LfcinB interacts with the monolayer to form discoidal lipid-peptide assemblies. This structure may actually represent the mechanism of action of this peptide. The results obtained on monolayers are correlated by fluorescent probe release measurements of dye-containing vesicles made of lipids in different phases and support the important role of the lipid fluidity and packing on the activity of LfcinB.

  18. First-principles study on the structure and electronic property of gas molecules adsorption on Ge2Li2 monolayer

    Science.gov (United States)

    Hu, Yiwei; Long, Linbo; Mao, Yuliang; Zhong, Jianxin

    2018-06-01

    Using first-principles methods, we have studied the adsorption of gas molecules (CO2, CH4, H2S, H2 and NH3) on two dimensional Ge2Li2 monolayer. The adsorption geometries, adsorption energies, charge transfer, and band structures of above mentioned gas molecules adsorption on Ge2Li2 monolayer are analyzed. It is found that the adsorption of CO2 on Ge2Li2 monolayer is a kind of strong chemisorption, while other gas molecules such as CH4, H2S, H2 and NH3 are physisorption. The strong covalent binding is formed between the CO2 molecule and the nearest Ge atom in Ge2Li2 monolayer. This adsorption of CO2 molecule on Ge2Li2 monolayer leads to a direct energy gap of 0.304 eV. Other gas molecules exhibit mainly ionic binding to the nearest Li atoms in Ge2Li2 monolayer, which leads to indirect energy gap after adsorptions. Furthermore, it is found that the work function of Ge2Li2 monolayer is sensitive with the variation of adsorbents. Our results reveal that the Ge2Li2 monolayer can be used as a kind of nano device for gas molecules sensor.

  19. Experimental evidence for an original two-dimensional phase structure: An antiparallel semifluorinated monolayer at the air-water interface

    International Nuclear Information System (INIS)

    El Abed, A.; Faure, M-C.; Pouzet, E.; Abillon, O.

    2002-01-01

    We show the spontaneous formation of an antiparallel monolayer of diblock semifluorinated n-alkane molecules spread at the air-water interface. We used simultaneous measurements of surface pressure and surface potential versus molecular area and performed grazing x-ray reflectivity experiments to characterize the studied monolayer, which is obtained at almost zero surface pressure and precedes the formation of a bilayer at higher surface pressure. Its thickness, equal to 2.7 nm, was found to be independent of the molecular area. This behavior may be explained by van der Waals and electrostatic interactions

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

    Science.gov (United States)

    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. Inelastic neutron scattering study on the polytypism of even-numbered n-alkanes

    Science.gov (United States)

    Kubota, Hideki; Kaneko, Fumitoshi; Kawaguchi, Tatsuya

    2005-02-01

    The thermodynamic properties of the two polytypes of n-hexatriacontane ( n- C36H74), single-layered structure Mon and double-layered structure Orth II, have been studied with incoherent inelastic neutron scattering and solubility measurements. The solubility measurements show that Orth II is more stable than Mon, because of its larger entropy. The neutron scattering measurements reveal that the vibrational modes of Orth II shift to the lower frequencies compared with those of Mon in the frequency region below 120 cm-1. The vibrational modes in this region make a dominant contribution to the vibrational entropy of a system, and the advantage of Orth II in vibrational entropy due to the low-frequency shifts is estimated to be 7.8 J K-1 mol-1 at 288 K under the harmonic approximation, which is in good agreement with the entropy difference between Mon and Orth II determined by solubility measurements. These results suggest that the relative stability of polytypic structures of long-chain compounds is mainly determined by the vibrational entropy of the low-frequency modes.

  2. Conformation, orientation and interaction in molecular monolayers: A surface second harmonic and sum frequency generation study

    International Nuclear Information System (INIS)

    Superfine, R.; Huang, J.Y.; Shen, Y.R.

    1988-12-01

    We have used sum frequency generation (SFG) to study the order in a silane monolayer before and after the deposition of a coadsorbed liquid crystal monolayer. We observe an increase in the order of the chain of the silane molecule induced by the interpenetration of the liquid crystal molecules. By using second harmonic generation (SHG) and SFG, we have studied the orientation and conformation of the liquid crystal molecule on clean and silane coated glass surfaces. On both surfaces, the biphenyl group is tilted by 70 degree with the alkyl chain end pointing away from the surface. The shift in the C-H stretch frequencies in the coadsorbed system indicates a significant interaction between molecules. 9 refs., 3 figs

  3. Possible doping strategies for MoS 2 monolayers: An ab initio study

    KAUST Repository

    Dolui, Kapildeb; Rungger, Ivan; Das Pemmaraju, Chaitanya; Sanvito, Stefano

    2013-01-01

    Density functional theory is used to systematically study the electronic properties of doped MoS2 monolayers, where the dopants are incorporated both via S/Mo substitution or as adsorbates. Among the possible substitutional dopants at the Mo site, Nb is identified as suitable p-type dopant, while Re is the donor with the lowest activation energy. When dopants are simply adsorbed on a monolayer we find that alkali metals shift the Fermi energy into the MoS2 conduction band, making the system n type. Finally, the adsorption of charged molecules is considered, mimicking an ionic liquid environment. We find that molecules adsorption can lead to both n- and p-type conductivity, depending on the charge polarity of the adsorbed species. © 2013 American Physical Society.

  4. Possible doping strategies for MoS 2 monolayers: An ab initio study

    KAUST Repository

    Dolui, Kapildeb

    2013-08-14

    Density functional theory is used to systematically study the electronic properties of doped MoS2 monolayers, where the dopants are incorporated both via S/Mo substitution or as adsorbates. Among the possible substitutional dopants at the Mo site, Nb is identified as suitable p-type dopant, while Re is the donor with the lowest activation energy. When dopants are simply adsorbed on a monolayer we find that alkali metals shift the Fermi energy into the MoS2 conduction band, making the system n type. Finally, the adsorption of charged molecules is considered, mimicking an ionic liquid environment. We find that molecules adsorption can lead to both n- and p-type conductivity, depending on the charge polarity of the adsorbed species. © 2013 American Physical Society.

  5. First-principles study of adsorption-induced magnetic properties of InSe monolayers

    Science.gov (United States)

    Fu, Zhaoming; Yang, Bowen; Zhang, Na; Ma, Dongwei; Yang, Zongxian

    2018-04-01

    In this work we studied the adsorption-induced magnetic behaviors on the two-dimensional InSe monolayer. Six kinds of adatoms (H, B, C, N, O and F) are taken into account. It is found that the InSe with adsorbing C and F have nonzero magnetic moments and good stability. Importantly, the magnetism of C and F modified InSe monolayers completely comes from p electrons of adatoms and substrates. The strength of magnetic exchange interaction can be controlled by changing the coverage of adsorbates. This p-electron magnetic material is thought to have obvious advantages compared to conventional d- or f-electron magnets. Our research is meaningful for practical applications in spintronic electronics and two dimensional magnetic semiconductors.

  6. Flash kinetics in liquefied noble gases: Studies of alkane activation and ligand dynamics at rhodium carbonyl centers, and a search for xenon-carbene adducts

    Energy Technology Data Exchange (ETDEWEB)

    Yeston, Jake Simon [Univ. of California, Berkeley, CA (United States)

    2001-01-01

    A general introduction is given to place the subsequent chapters in context for the nonspecialist. Results are presented from a low temperature infrared (IR) flash kinetic study of C-H bond activation via photoinduced reaction of Cp*Rh(CO)2 (1) with linear and cyclic alkanes in liquid krypton and liquid xenon solution. No reaction was observed with methane; for all other hydrocarbons studied, the rate law supports fragmentation of the overall reaction into an alkane binding step followed by an oxidative addition step. For the binding step, larger alkanes within each series (linear and cyclic) interact more strongly than smaller alkanes with the Rh center. The second step, oxidative addition of the C-H bond across Rh, exhibits very little variance in the series of linear alkanes, while in the cyclic series the rate decreases with increasing alkane size. Results are presented from an IR flash kinetic study of the photoinduced chemistry of Tp*Rh(CO)2 (5; Tp* = hydridotris(3,5-dimethylpyrazolyl)borato) in liquid xenon solution at –50 °C. IR spectra of the solution taken 2 μs after 308 nm photolysis exhibit two transient bands at 1972-1980 cm-1 and 1992-2000 cm-1, respectively. These bands were assigned to (η3-Tp*)Rh(CO)•Xe and (η2-Tp*)Rh(CO)•Xe solvates on the basis of companion studies using Bp*Rh(CO)2 (9; Bp* = dihydridobis(3,5-dimethyl pyrazolyl)borato). Preliminary kinetic data for reaction of 5 with cyclohexane in xenon solution indicate that both transient bands still appear and that their rates of decay correlate with formation of the product Tp*Rh(CO)(C6H11)(H). The preparation and reactivity of the new complex Bp*Rh(CO)(pyridine) (11) are described. The complex reacts with CH3I to yield the novel Rh carbene hydride complex HB(Me2pz)2Rh(H)(I)(C5H5N)(C(O)Me) (12), resulting from formal addition of CH

  7. Density functional study of CaN monolayer on Si(001)

    Energy Technology Data Exchange (ETDEWEB)

    Saati asr, Maryam; Zahedifar, Maedeh; Hashemifar, S. Javad; Akbarzadeh, Hadi

    2016-01-01

    In this work, the first-principles computations are performed to study the structural and magnetic properties of CaN/Si(001) interface. Bulk CaN in the zinc-blende (ZB) structure is argued to be an ionic magnetic compound with a total spin moment of 1 μ{sub B} per formula unit, originated from the p electrons of N ions. Various interface configurations of a ZB CaN monolayer on Si (001) surface are investigated and the lowest energy and the highest spin polarized interfaces are extracted. Then the minimum energy path between the lowest energy and the highest spin polarized interfaces are calculated by using the nudged elastic band method and it is argued that both these systems are unstable toward a nonmagnetic interface with a rock–salt arrangement of Ca and N atoms. - Highlights: • Ab-initio studies are done on various structures of CaN monolayer on Si (001). • The lowest energy system was found to be the N-top configuration interface, while the highest spin polarization was observed in the Ca-hollow termination. • Both Ca-hollow and N-top are unstable toward a nonmagnetic rock–salt CaN monolayer on silicon surface. • Realization of a magnetic CaN/Si (001) interface likely requires some buffer layer on silicon surface, prior to the thin film deposition.

  8. Density functional study of CaN monolayer on Si(001)

    International Nuclear Information System (INIS)

    Saati asr, Maryam; Zahedifar, Maedeh; Hashemifar, S. Javad; Akbarzadeh, Hadi

    2016-01-01

    In this work, the first-principles computations are performed to study the structural and magnetic properties of CaN/Si(001) interface. Bulk CaN in the zinc-blende (ZB) structure is argued to be an ionic magnetic compound with a total spin moment of 1 μ_B per formula unit, originated from the p electrons of N ions. Various interface configurations of a ZB CaN monolayer on Si (001) surface are investigated and the lowest energy and the highest spin polarized interfaces are extracted. Then the minimum energy path between the lowest energy and the highest spin polarized interfaces are calculated by using the nudged elastic band method and it is argued that both these systems are unstable toward a nonmagnetic interface with a rock–salt arrangement of Ca and N atoms. - Highlights: • Ab-initio studies are done on various structures of CaN monolayer on Si (001). • The lowest energy system was found to be the N-top configuration interface, while the highest spin polarization was observed in the Ca-hollow termination. • Both Ca-hollow and N-top are unstable toward a nonmagnetic rock–salt CaN monolayer on silicon surface. • Realization of a magnetic CaN/Si (001) interface likely requires some buffer layer on silicon surface, prior to the thin film deposition.

  9. An in situ study of the adsorption behavior of functionalized particles on selfassembled monolayers via different chemical interactions

    NARCIS (Netherlands)

    Ling, X.Y.; Malaquin, Laurent; Reinhoudt, David; Wolf, Heiko; Huskens, Jurriaan

    2007-01-01

    The formation of particle monolayers by convective assembly was studied in situ with three different kinds of particle-surface interactions: adsorption onto native surfaces, with additional electrostatic interactions, and with supramolecular host-guest interactions. In the first case

  10. A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

    International Nuclear Information System (INIS)

    Lu, Jinlian; Guo, Yanhua; Zhang, Yun; Tang, Yingru; Cao, Juexian

    2015-01-01

    A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%, 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.

  11. Study on Shale Adsorption Equation Based on Monolayer Adsorption, Multilayer Adsorption, and Capillary Condensation

    Directory of Open Access Journals (Sweden)

    Qing Chen

    2017-01-01

    Full Text Available Shale gas is an effective gas resource all over the world. The evaluation of pore structure plays a critical role in exploring shale gas efficiently. Nitrogen adsorption experiment is one of the significant approaches to analyze pore size structure of shale. Shale is extremely heterogeneous due to component diversity and structure complexity. Therefore, adsorption isotherms for homogeneous adsorbents and empirical isotherms may not apply to shale. The shape of adsorption-desorption curve indicates that nitrogen adsorption on shale includes monolayer adsorption, multilayer adsorption, and capillary condensation. Usually, Langmuir isotherm is a monolayer adsorption model for ideal interfaces; BET (Brunauer, Emmett, Teller adsorption isotherm is a multilayer adsorption model based on specific assumptions; Freundlich isotherm is an empirical equation widely applied in liquid phase adsorption. In this study, a new nitrogen adsorption isotherm is applied to simultaneously depict monolayer adsorption, multilayer adsorption, and capillary condensation, which provides more real and accurate representation of nitrogen adsorption on shale. In addition, parameters are discussed in relation to heat of adsorption which is relevant to the shape of the adsorption isotherm curve. The curve fitting results indicate that our new nitrogen adsorption isotherm can appropriately describe the whole process of nitrogen adsorption on shale.

  12. Diverse carrier mobility of monolayer BNCx: A combined density functional theory and Boltzmann transport theory study.

    Science.gov (United States)

    Wu, Tao; Deng, Kaiming; Deng, Wei-Qiao; Lu, Ruifeng

    2017-09-19

    BNCX monolayer as a kind of two-dimensional material has numerous chemical atomic ratios and arrangements with different electronic structures. Via calculations on the basis of density functional theory and Boltzmann transport theory under deformation potential approximation, the band structures and carrier mobilities of BNCX (x=1,2,3,4) nanosheets are systematically investigated. The calculated results show that BNC2-1 is a material with very small band gap (0.02 eV) among all the structures while other BNCX monolayers are semiconductors with band gap ranging from 0.51 to 1.32 eV. The carrier mobility of BNCX varies considerably from tens to millions of cm2 V-1 s-1. For BNC2-1, the hole mobility and electron mobility along both x and y directions can reach 105 orders of magnitude, which is similar to the carrier mobility of graphene. Besides, all studied BNCX monolayers obviously have anisotropic hole mobility and electron mobility. In particular, for semiconductor BNC4, its hole mobility along y direction and electron mobility along x direction unexpectedly reach 106 orders of magnitude, even higher than that of graphene. Our findings suggest that BNCX layered materials with proper ratio and arrangement of carbon atoms will possess desirable charge transport properties, exhibiting potential applications in nanoelectronic devices. © 2017 IOP Publishing Ltd.

  13. SFG and AFM Studies of Polymer Surface Monolayers

    Science.gov (United States)

    Somorjai, Gabor A.

    2003-03-01

    Sum frequency generation vibrational spectroscopy and atomic force microscopy techniques were utilized to study the structure and composition of polymer surfaces ranging from polyethylene and polypropylene to copolymers of polyurethane and polystyrene. The surface methyl groups aligned perpendicular to the surface above the glass transition temperature of polypropylene. Large side groups such as the phenyl group on polystyrene is also near the surface normal at the polymer-air interface. At the air interface hydrophobic groups are dominant on the polymer surface while at solid-water interface hydrophilic groups segregate to the surface. Minimizing surface energy is the cause of readjusting the surface composition at polymer-water interfaces as compared to polymer-air interfaces. Upon stretching the soft component of two-component polymer systems segregates to the surface and both the surface structure and the surface composition undergo reversible or irreversible changes depending on the magnitude of the stretch. Since the heart beat forces bio-polymers to stretch over 40 million times a year the molecular behavior due to stretching has important physiological consequences.

  14. Alkane dimers interaction

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Madsen, Georg Kent Hellerup; Hammer, Bjørk

    2010-01-01

    The interaction energies of a series of n-alkane dimers, from methane to decane, have been investigated with Density Functional Theory (DFT), using the MGGA-M06-L density functional. The results are compared both to the available wavefunction-based values as well as to dispersion corrected DFT...... values. The MGGA-M06-L density functional is a semi-local functional designed and has proven to provide accurate estimates of dispersion interactions for several systems at moderate computational cost. In the present application, it reproduces the trends obtained by the more expensive wavefunction...

  15. Vanadium impurity effects on optical properties of Ti3N2 mono-layer: An ab-initio study

    Directory of Open Access Journals (Sweden)

    Manuchehr Babaeipour

    2018-06-01

    Full Text Available The present work is investigated the effect of vanadium impurity on electronic and optical properties of Ti3N2 monolayer by using density function theory (DFT implemented in Wien2k code. In order to study optical properties in two polarization directions of photons, namely E||x and E||z, dielectric function, absorption coefficient, optical conductivity, refraction index, extinction index, reflectivity, and energy loss function of Ti3N2 and Ti3N2-V monolayer have been evaluated within GGA (PBE approximation. Although, Ti3N2 monolayer is a good infrared reflector and can be used as an infrared mirror, introducing V atom in the infrared area will decrease optical conductivity because optical conductivity of a pure form of a material is higher than its doped form. Keywords: Dielectric function, Optical conductivity, DFT, Ti3N2: V mono-layer

  16. Auger spectra of alkanes

    International Nuclear Information System (INIS)

    Rye, R.R.; Jennison, D.R.; Houston, J.E.

    1980-01-01

    The gas-phase Auger line shapes of the linear alkanes C 1 through C 6 and of neopentane are presented and analyzed. The general shape of the spectra are characteristic of carbon in a tetrahedral environment with the major feature in all cases occurring at approx.249 eV. The relatively large spectral changes found between methane and ethane results from the direct interaction of the terminal methyl groups in ethane, and the spectra of the higher alkanes are shown to be a composite of contributions from terminal methyl and interior methylene group carbon atoms. Theoretical analysis based on a one-electron approximation is shown to be capable of making a molecular orbital assignment by comparing calculated vertical transitions to features in the Auger spectra of ethane and propane, and, in the case of ethane, of differentiating between the 2 E/sub g/ and 2 A/sub 1g/ assignment of the ground state of (C 2 H 6 ) + . A one-electron based molecular orbital treatment, however, is shown to partially break down in propane and neopentane. Analysis of neopentane and the observed absence of any noticeable major peak energy shift with increasing molecular size (as predicted by the one-electron treatment) suggests that some Auger final states occur in which both valence holes are localized on the same subunit of the molecule

  17. Hydrogen Bonding to Alkanes: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen; Olesen, Solveig Gaarn

    2009-01-01

    The structural, vibrational, and energetic properties of adducts of alkanes and strong cationic proton donors were studied with composite ab initio calculations. Hydrogen bonding in [D-H+ H-alkyl] adducts contributes to a significant degree to the interactions between the two components, which is...

  18. Reflectance spectroscopy of organic compounds: 1. Alkanes

    Science.gov (United States)

    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.

  19. Infrared Absorption Spectroscopic Study on Reaction between Self-Assembled Monolayers and Atmospheric-Pressure Plasma

    Directory of Open Access Journals (Sweden)

    Masanori Shinohara

    2015-01-01

    Full Text Available Plasma is becoming increasingly adopted in bioapplications such as plasma medicine and agriculture. This study investigates the interaction between plasma and molecules in living tissues, focusing on plasma-protein interactions. To this end, the reaction of air-pressure air plasma with NH2-terminated self-assembled monolayer is investigated by infrared spectroscopy in multiple internal reflection geometry. The atmospheric-pressure plasma decomposed the NH2 components, the characteristic units of proteins. The decomposition is attributed to water clusters generated in the plasma, indicating that protein decomposition by plasma requires humid air.

  20. Synthesis of Novel Amphiphilic Azobenzenes and X-ray Scattering Studies of Their Langmuir Monolayers

    DEFF Research Database (Denmark)

    Sørensen, Thomas Just; Kjær, Kristian; Breiby, Dag Werner

    2008-01-01

    . At the air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing...... synchrotron radiation. Compression beyond the collapse point does not change the XR data, showing that the film is unchanged at the molecular level, even at areas less than half of that of the collapse. This leads to the conclusion that few macroscopic collapse sites are responsible for reversibly removing...

  1. Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

    OpenAIRE

    Sun, Xiaoli; Wang, Zhiguo

    2017-01-01

    Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in bot...

  2. First-principles studies of chromium line-ordered alloys in a molybdenum disulfide monolayer

    Science.gov (United States)

    Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

    2017-08-01

    Density functional theory calculations have been performed to study the thermodynamic stability, structural and electronic properties of various chromium (Cr) line-ordered alloy configurations in a molybdenum disulfide (MoS2) hexagonal monolayer for band gap engineering. Only the molybdenum (Mo) sites were substituted at each concentration in this study. For comparison purposes, different Cr line-ordered alloy and random alloy configurations were studied and the most thermodynamically stable ones at each concentration were identified. The configurations formed by the nearest neighbor pair of Cr atoms are energetically most favorable. The line-ordered alloys are constantly lower in formation energy than the random alloys at each concentration. An increase in Cr concentration reduces the lattice constant of the MoS2 system following the Vegard’s law. From density of states analysis, we found that the MoS2 band gap is tunable by both the Cr line-ordered alloys and random alloys with the same magnitudes. The reduction of the band gap is mainly due to the hybridization of the Cr 3d and Mo 4d orbitals at the vicinity of the band edges. The band gap engineering and magnitudes (1.65 eV to 0.86 eV) suggest that the Cr alloys in a MoS2 monolayer are good candidates for nanotechnology devices.

  3. High-resolution ellipsometric study of an n-alkane film, dotriacontane, adsorbed on a SiO2 surface

    DEFF Research Database (Denmark)

    Volkmann, U.G.; Pino, M.; Altamirano, L.A.

    2002-01-01

    -crystal substrates. Our results suggest a model of a solid dotriacontane film that has a phase closest to the SiO2 surface in which the long-axis of the molecules is oriented parallel to the interface. Above this "parallel film" phase, a solid monolayer adsorbs in which the molecules are oriented perpendicular...... at higher coverages. In addition, we have performed high-resolution ellipsometry and stray-light measurements on dotriacontane films deposited from solution onto highly oriented pyrolytic graphite substrates. After film deposition, these substrates proved to be less stable in air than SiO2....

  4. The additional phase transition of DPPC monolayers at high surface pressure confirmed by GIXD study

    DEFF Research Database (Denmark)

    Shen, Chen; Serna, Jorge B. de la; Struth, Bernd

    Pulmonary surfactant forms the alveolar monolayer at the air/aqueous interface within the lung. During the breathing process, the surface pressure periodically varies from ~40mN/m up to ~70mN/m. The film is mechanically stable during this rapid and reversible expansion. The monolayer consists...... of the alveolae monolayer and at the same time allows reduction of the interfacial tension to ~0mN/m....

  5. First-principle study of single TM atoms X (X=Fe, Ru or Os) doped monolayer WS2 systems

    Science.gov (United States)

    Zhu, Yuan-Yan; Zhang, Jian-Min

    2018-05-01

    We report the structural, magnetic and electronic properties of the pristine and single TM atoms X (X = Fe, Ru or Os) doped monolayer WS2 systems based on first-principle calculations. The results show that the W-S bond shows a stronger covalent bond, but the covalency is obviously weakened after the substitution of W atom with single X atoms, especially for Ru (4d75s1) with the easily lost electronic configuration. The smaller total energies of the doped systems reveal that the spin-polarized states are energetically favorable than the non-spin-polarized states, and the smallest total energy of -373.918 eV shows the spin-polarized state of the Os doped monolayer WS2 system is most stable among three doped systems. In addition, although the pristine monolayer WS2 system is a nonmagnetic-semiconductor with a direct band gap of 1.813 eV, single TM atoms Fe and Ru doped monolayer WS2 systems transfer to magnetic-HM with the total moments Mtot of 1.993 and 1.962 μB , while single TM atom Os doped monolayer WS2 systems changes to magnetic-metal with the total moments Mtot of 1.569 μB . Moreover, the impurity states with a positive spin splitting energies of 0.543, 0.276 and 0.1999 eV near the Fermi level EF are mainly contributed by X-dxy and X-dx2-y2 states hybridized with its nearest-neighbor atom W-dz2 states for Fe, Ru and Os doped monolayer WS2 system, respectively. Finally, we hope that the present study on monolayer WS2 will provide a useful theoretical guideline for exploring low-dimensional spintronic materials in future experiments.

  6. Electrochemical deposition of the first Cd monolayer on polycrystalline Pt and Au electrodes: an Upd study

    Directory of Open Access Journals (Sweden)

    Santos Mauro C. dos

    1998-01-01

    Full Text Available The underpotential deposition of Cd on polycrystalline Pt and Au was studied by voltammetry at stationary and rotating ring-disc electrodes. On Pt, the Cd ads dissolution peaks overlap those related to the oxidation of Hads, thus hindering the precise evaluation of desorption charges. A model proposed to calculate such charges from voltammetry at stationary electrodes revealed a value of 285 muC cm-2 for the monolayer dissolution, which corresponds to a coverage of 90% with Cd ads presenting an electrosorption valence of 0.5. Rotating ring-disc experiments fully confirmed such values. The misfit between atomic radii of Cd and Pt justifies the less-than-100% coverage. On the other hand, on Au, the absence of Hads simplifies the procedure for determination of dissolution charges for the Cd monolayer. Here, a value of only 41 muC cm-2 was calculated, which corresponds to a maximum coverage of 15%, with the electrosorption valence of 0.5. The results obtained in the collecting experiments with the rotating electrode are in complete agreement with those values.

  7. Study of dithiol monolayer as the interface for controlled deposition of gold nanoparticles

    International Nuclear Information System (INIS)

    Cichomski, M.; Tomaszewska, E.; Kosla, K.; Kozlowski, W.; Kowalczyk, P.J.; Grobelny, J.

    2011-01-01

    Self-assembled monolayer of dithiol molecules, deposited on polycrystalline Au (111), prepared at room atmosphere, was studied using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Dithiols were used as interface, which chemically bonds to the deposited gold nanoparticles through strong covalent bonds. The size and size distribution of the deposited nanoparticles were measured using dynamic light scattering (DLS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The AFM results showed that nanoparticles are immobilized and stable during scanning procedure and do not contaminate the AFM tip. The size of monodisperse nanoparticles obtained from the DLS measurements is slightly higher than that obtained from the AFM and SEM measurements. This is due to the fact that the DLS measures the hydrodynamic radius, dependent on the protective chemical layer on nanoparticles. - Research Highlights: → Dithiols molecules create chemically bounded layers on a Au (111) surface. → Gold nanoparticles can be chemically bounded to a self-assembled monolayer. → Nanoparticles are stable during AFM probe interactions.

  8. Distribution and sources of n-alkanes in surface sediments of Taihu Lake, China

    Directory of Open Access Journals (Sweden)

    Yu Yunlong

    2016-03-01

    Full Text Available The last study on n-alkanes in surface sediments of Taihu Lake was in 2000, only 13 surface sediment samples were analysed, in order to have a comprehensive and up-to-date understanding of n-alkanes in the surface sediments of Taihu Lake, 41 surface sediment samples were analyzed by GC-MS. C10 to C37 were detected, the total concentrations of n-alkanes ranged from 2109 ng g−1 to 9096 ng g−1 (dry weight. There was strong odd carbon predominance in long chain n-alkanes and even carbon predominance in short chain n-alkanes. When this finding was combined with the analysis results of wax n-alkanes (WaxCn, carbon preference index (CPI, unresolved complex mixture (UCM, hopanes and steranes, it was considered that the long chain n-alkanes were mainly from terrigenous higher plants, and that the short chain n-alkanes mainly originated from bacteria and algae in the lake, compared with previous studies, there were no obvious anthropogenic petrogenic inputs. Terrestrial and aquatic hydrocarbons ratio (TAR and C21−/C25+ indicated that terrigenous input was higher than aquatic sources and the nearshore n-alkanes were mainly from land-derived sources. Moreover, the distribution of short chain n-alkanes presented a relatively uniform pattern, while the long chain n-alkanes presented a trend that concentrations dropped from nearshore places to the middle of lake.

  9. Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

    Directory of Open Access Journals (Sweden)

    Yongfeng Tong

    2016-02-01

    Full Text Available This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon–chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon–chalcogen atom-bond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the π-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

  10. Revisiting the Kinetics and Thermodynamics of the Low-Temperature Oxidation Pathways of Alkanes: A Case Study of the Three Pentane Isomers

    KAUST Repository

    Bugler, John

    2015-07-16

    © 2015 American Chemical Society. This paper describes our developing understanding of low-temperature oxidation kinetics. We have investigated the ignition of the three pentane isomers in a rapid compression machine over a wide range of temperatures and pressures, including conditions of negative temperature coefficient behavior. The pentane isomers are small alkanes, yet have structures that are complex enough to allow for the application of their kinetic and thermochemical rules to larger molecules. Updates to the thermochemistry of the species important in the low-temperature oxidation of hydrocarbons have been made based on a thorough literature review. An evaluation of recent quantum-chemically derived rate coefficients from the literature pertinent to important low-temperature oxidation reaction classes has been performed, and new rate rules are recommended for these classes. Several reaction classes have also been included to determine their importance with regard to simulation results, and we have found that they should be included when developing future chemical kinetic mechanisms. A comparison of the model simulations with pressure-time histories from experiments in a rapid compression machine shows very good agreement for both ignition delay time and pressure rise for both the first- and second-stage ignition events. We show that revisions to both the thermochemistry and the kinetics are required in order to replicate experiments well. A broader validation of the models with ignition delay times from shock tubes and a rapid compression machine is presented in an accompanying paper. The results of this study enhance our understanding of the combustion of straight- and branched-chained alkanes.

  11. Rectification of current responds to incorporation of fullerenes into mixed-monolayers of alkanethiolates in tunneling junctions.

    Science.gov (United States)

    Qiu, Li; Zhang, Yanxi; Krijger, Theodorus L; Qiu, Xinkai; Hof, Patrick Van't; Hummelen, Jan C; Chiechi, Ryan C

    2017-03-01

    This paper describes the rectification of current through molecular junctions comprising self-assembled monolayers of decanethiolate through the incorporation of C 60 fullerene moieties bearing undecanethiol groups in junctions using eutectic Ga-In (EGaIn) and Au conducting probe AFM (CP-AFM) top-contacts. The degree of rectification increases with increasing exposure of the decanethiolate monolayers to the fullerene moieties, going through a maximum after 24 h. We ascribe this observation to the resulting mixed-monolayer achieving an optimal packing density of fullerene cages sitting above the alkane monolayer. Thus, the degree of rectification is controlled by the amount of fullerene present in the mixed-monolayer. The voltage dependence of R varies with the composition of the top-contact and the force applied to the junction and the energy of the lowest unoccupied π-state determined from photoelectron spectroscopy is consistent with the direction of rectification. The maximum value of rectification R = | J (+)/ J (-)| = 940 at ±1 V or 617 at ±0.95 V is in agreement with previous studies on pure monolayers relating the degree of rectification to the volume of the head-group on which the frontier orbitals are localized.

  12. Studying electron transfer through alkanethiol self-assembled monolayers on a hanging mercury drop electrode using potentiometric measurements.

    Science.gov (United States)

    Cohen-Atiya, Meirav; Mandler, Daniel

    2006-10-14

    A new approach based on measuring the change of the open-circuit potential (OCP) of a hanging mercury drop electrode (HMDE), modified with alkanethiols of different chain length conducted in a solution containing a mixture of Ru(NH3)6(2+) and Ru(NH3)6(3+) is used for studying electron transfer across the monolayer. Following the time dependence of the OCP allowed the extraction of the kinetic parameters, such as the charge transfer resistance (R(ct)) and the electron transfer rate constant (k(et)), for different alkanethiol monolayers. An electron tunneling coefficient, beta, of 0.9 A(-1) was calculated for the monolayers on Hg.

  13. Vanadium impurity effects on optical properties of Ti3N2 mono-layer: An ab-initio study

    Science.gov (United States)

    Babaeipour, Manuchehr; Eslam, Farzaneh Ghafari; Boochani, Arash; Nezafat, Negin Beryani

    2018-06-01

    The present work is investigated the effect of vanadium impurity on electronic and optical properties of Ti3N2 monolayer by using density function theory (DFT) implemented in Wien2k code. In order to study optical properties in two polarization directions of photons, namely E||x and E||z, dielectric function, absorption coefficient, optical conductivity, refraction index, extinction index, reflectivity, and energy loss function of Ti3N2 and Ti3N2-V monolayer have been evaluated within GGA (PBE) approximation. Although, Ti3N2 monolayer is a good infrared reflector and can be used as an infrared mirror, introducing V atom in the infrared area will decrease optical conductivity because optical conductivity of a pure form of a material is higher than its doped form.

  14. A new tribological experimental setup to study confined and sheared monolayers.

    Science.gov (United States)

    Fu, L; Favier, D; Charitat, T; Gauthier, C; Rubin, A

    2016-03-01

    We have developed an original experimental setup, coupling tribology, and velocimetry experiments together with a direct visualization of the contact. The significant interest of the setup is to measure simultaneously the apparent friction coefficient and the velocity of confined layers down to molecular scale. The major challenge of this experimental coupling is to catch information on a nanometer-thick sheared zone confined between a rigid spherical indenter of millimetric radius sliding on a flat surface at constant speed. In order to demonstrate the accuracy of this setup to investigate nanometer-scale sliding layers, we studied a model lipid monolayer deposited on glass slides. It shows that our experimental setup will, therefore, help to highlight the hydrodynamic of such sheared confined layers in lubrication, biolubrication, or friction on solid polymer.

  15. Phases of phosphatidyl ethanolamine monolayers studied by synchrotron x-ray scattering

    DEFF Research Database (Denmark)

    Helm, C.A.; Tippmann-Krayer, P.; Möhwald, H.

    1991-01-01

    For the first time, phospholid monolayers at the air/water interface have been studied by x-ray diffraction and reflection all along the isotherm from the laterally isotropic fluid (the so-called LE phase) to the ordered phases. The model used to analyze the data, and the accuracy of the parameters...... deduced, were tested by comparing the results obtained with two lipids having the same head group but different chain lengths. Compression of the fluid phase leads predominantly to a change of thickness of the hydrophobic moiety, much less of its density, with the head group extension remaining constant....... The main transition involves a considerable increase (approximately 10%) of the electron density in the hydrophobic region, a dehydration of the head group and a positional ordering of the aliphatic tails, albeit with low coherence lengths (approximately 10 spacings). On further compression of the film...

  16. Spin polarized first principles study of Mn doped gallium nitride monolayer nanosheet

    Science.gov (United States)

    Sharma, Venus; Kaur, Sumandeep; Srivastava, Sunita; Kumar, Tankeshwar

    2017-05-01

    The structural, electronic and magnetic properties of gallium nitride nanosheet (GaNs) doped with Mn atoms have been studied using spin polarized density functional theory. The binding energy per atom, Energy Band gap, Fermi energy, magnetic moment, electric dipole moment have been found. The doped nanosheet is found to be more stable than pure GaN monolayer nanosheet. Adsorption of Mn atom has been done at four different sites on GaNs which affects the fermi level position. It is found that depending on the doping site, Mn can behave both like p-type semiconductor and also as n-type semiconductor. Also, it is ascertained that Mn doped GaNs (GaNs-Mn) exhibits ferromagnetic behavior.

  17. Atomic defects in monolayer WSe2 tunneling FETs studied by systematic ab initio calculations

    Science.gov (United States)

    Wu, Jixuan; Fan, Zhiqiang; Chen, Jiezhi; Jiang, Xiangwei

    2018-05-01

    Atomic defects in monolayer WSe2 tunneling FETs (TFETs) are studied through systematic ab initio calculations aiming at performance predictions and enhancements. The effects of various defect positions and different passivation atoms are characterized in WSe2 TFETs by rigorous ab initio quantum transport simulations. It is suggested that the Se vacancy (VSe) defect located in the gate-controlled channel region tends to increase the OFF current (I off), whereas it can be well suppressed by oxygen passivation. It is demonstrated that chlorine (Cl) passivation at the source-side tunneling region can largely suppress I off, leading to an impressively improved on–off ratio (I on/I off) compared with that without any defect. However, it is also observed that randomly positioned atomic defects tend to induce significant fluctuation of the TFET output. Further discussions are made with focus on the performance-variability trade-off for robust circuit design.

  18. Transepithelial transport of aliphatic carboxylic acids studied in Madin Darby canine kidney (MDCK) cell monolayers

    International Nuclear Information System (INIS)

    Cho, M.J.; Adson, A.; Kezdy, F.J.

    1990-01-01

    Transport of 14C-labeled acetic, propionic (PA), butyric, valeric, heptanoic (HA), and octanoic (OA) acids across the Madin Darby canine kidney (MDCK) epithelial cell monolayer grown on a porous polycarbonate membrane was studied in Hanks' balanced salt solution (HBSS) at 37 degrees C in both apical-to-basolateral and basolateral-to-apical directions. At micromolar concentrations of solutes, metabolic decomposition was significant as evidenced by [14C]CO2 production during the OA transport. The apparent permeability (Pe) indicates that as lipophilicity increases, diffusion across the unstirred boundary layer becomes rate limiting. In support of this notion, transport of OA and HA was enhanced by agitation, showed an activation energy of 3.7 kcal/mol for OA, and resulted in identical Pe values for both transport directions. Analysis of Pe changes with varying alkyl chain length resulted in a delta G of -0.68 +/- 0.09 kcal/mol for -CH2-group transfer from an aqueous phase to the MDCK cells. When the intercellular tight junctions were opened by the divalent chelator EGTA in Ca2+/Mg2(+)-free HBSS, transport of the fluid-phase marker Lucifer yellow greatly increased because of paracellular leakage. PA transport also showed a significant increase, but OA transport was independent of EGTA. Although albumin also undergoes paracellular transport in the presence of EGTA and OA binds strongly to albumin, OA transport in EGTA solution was unchanged by albumin. These observations indicate that transmembrane transport is the major mechanism for lipophilic substances. The present study, together with earlier work on the transport of polar substances, shows that the MDCK cell monolayer is an excellent model of the transepithelial transport barrier

  19. First principles study of optical properties of molybdenum disulfide: From bulk to monolayer

    Science.gov (United States)

    Hieu, Nguyen N.; Ilyasov, Victor V.; Vu, Tuan V.; Poklonski, Nikolai A.; Phuc, Huynh V.; Phuong, Le T. T.; Hoi, Bui D.; Nguyen, Chuong V.

    2018-03-01

    In this paper, we theoretically study the optical properties of both bulk and monolayer MoS2 using first-principles calculations. The optical characters such as: dielectric function, optical reflectivity, and electron energy-loss spectrum of MoS2 are observed in the energy region from 0 to 15 eV. At equilibrium state the dielectric constant in the parallel E∥ x and perpendicular E∥ z directions are of 15.01 and 8.92 for bulk while they are 4.95 and 2.92 for monolayer MoS2, respectively. In the case of bulk MoS2, the obtained computational results for both real and imaginary parts of the dielectric constant are in good agreement with the previous experimental data. In the energy range from 0 to 6 eV, the dielectric functions have highly anisotropic, whereas they become isotropic when the energy is larger than 7 eV. For the adsorption spectra and optical reflectivity, both the collective plasmon resonance and (π + σ) electron plasmon peaks are observed, in which the transition in E∥ x direction is accordant with the experiment data more than the transition in E∥ z direction is. The refractive index, extinction index, and electron energy-loss spectrum are also investigated. The observed prominent peak at 23.1 eV in the energy-loss spectra is in good agreement with experiment value. Our results may provide a useful potential application for the MoS2 structures in electronic and optoelectronic devices.

  20. Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study

    KAUST Repository

    Baksi, Ananya; Bootharaju, Megalamane Siddaramappa; Chhotaray, Pratap K.; Chakraborty, Papri; Mondal, Biswajit; Bhat, Shridevi; Gardas, Ramesh L.; Pradeep, Thalappil

    2017-01-01

    Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric

  1. Cholesterol Depletion from a Ceramide/Cholesterol Mixed Monolayer: A Brewster Angle Microscope Study

    KAUST Repository

    Mandal, Pritam

    2016-06-01

    Cholesterol is crucial to the mechanical properties of cell membranes that are important to cells’ behavior. Its depletion from the cell membranes could be dramatic. Among cyclodextrins (CDs), methyl beta cyclodextrin (MβCD) is the most efficient to deplete cholesterol (Chol) from biomembranes. Here, we focus on the depletion of cholesterol from a C16 ceramide/cholesterol (C16-Cer/Chol) mixed monolayer using MβCD. While the removal of cholesterol by MβCD depends on the cholesterol concentration in most mixed lipid monolayers, it does not depend very much on the concentration of cholesterol in C16-Cer/Chol monolayers. The surface pressure decay during depletion were described by a stretched exponential that suggested that the cholesterol molecules are unable to diffuse laterally and behave like static traps for the MβCD molecules. Cholesterol depletion causes morphology changes of domains but these disrupted monolayers domains seem to reform even when cholesterol level was low.

  2. Wetting of alkanes on water

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, E.; Bonn, D.; Meunier, J.; Shahidzadeh, N. [Ecole Normale Superieure, Laboratoire de Physique Statistique, 24 rue Lhomond, 75231, Cedex 05 Paris (France); Broseta, D.; Ragil, K. [Institut Francais du Petrole, 1-4 avenue de Bois Preau, 92852 Rueil-Malmaison Cedex (France); Dobbs, H.; Indekeu, J.O. [Katholieke Universiteit Leuven, Laboratorium voor Vaste-Stoffysica en Magnetisme, B-3001 Leuven (Belgium)

    2002-04-01

    The wetting behavior of oil on water (or brine) has important consequences for the transport properties of oil in water-containing porous reservoirs, and consequently for oil recovery. The equilibrium wetting behavior of model oils composed of pure alkanes or alkane mixtures on brine is reviewed in this paper. Intermediate between the partial wetting state, in which oil lenses coexist on water with a thin film of adsorbed alkane molecules, and the complete wetting state, in which a macroscopically thick oil layer covers the water, these systems display a third, novel wetting state, in which oil lenses coexist with a mesoscopic (a few-nanometers-thick) oil film. The nature and location of the transitions between these wetting regimes depend on oil and brine compositions, temperature and pressure.

  3. Anisotropic mechanical properties and Stone-Wales defects in graphene monolayer: A theoretical study

    International Nuclear Information System (INIS)

    Fan, B.B.; Yang, X.B.; Zhang, R.

    2010-01-01

    We investigate the mechanical properties of graphene monolayer via the density functional theoretical (DFT) method. We find that the strain energies are anisotropic for the graphene under large strain. We attribute the anisotropic feature to the anisotropic sp 2 hybridization in the hexagonal lattice. We further identify that the formation energies of Stone-Wales (SW) defects in the graphene monolayer are determined by the defect concentration and also the direction of applied tensile strain, correlating with the anisotropic feature.

  4. X-ray studies of the liquid/vapor interface: Water and polymer and fatty acid monolayers on water

    International Nuclear Information System (INIS)

    Schlossman, M.L.; Schwartz, D.K.; Kawamoto, E.H.; Kellogg, G.J.; Pershan, P.S.; Ocko, B.M.; Kim, M.W.; Chung, T.C.

    1989-01-01

    X-ray specular reflectivity is used to study the liquid-vapor interface of pure water and of fatty acid and polymer monolayers at that interface. For the pure water surface the reflectivity was measured for three different spectrometer resolutions and simultaneous fits with only one free parameter to all of the data are in excellent agreement with the prediction of capillary wave theory for the RMS surface roughness. Diffuse scattering away from the specular condition, at wavevectors corresponding to those of the capillary waves, yields intensities and line shapes in agreement with theory with no significant adjustable parameters. Reflectivity from separate monolayers of co-poly 1, 2-butadiene/butyl alcohol (50% random substitution) and lignoceric acid (CH 3 (CH 2 ) 22 COOH) at the water/vapor interface are interpreted to obtain profiles of the average electron density ρ(z) as a function of distance z along the surface normal. For the polymer monolayer we find the following: (1) a local maximum in the electron density approximately 10% larger than that of the bulk polymer and (2) the RMS roughness of the vapor/polymer interface agrees with capillary wave theory predictions for the lower surface pressures. For the highest surface pressure the RMS roughness exceeds the value predicted by the capillary wave model. Measurements of reflectivity from a lignoceric acid monolayer, as a function of surface pressure throughout an isotherm (near room temperature), reveal the following behavior: (1) the overall thickness of the monolayer increases with increasing pressure and (2) the head groups occupy a progressively larger region along the surface normal as the pressure increases, indicating that they rearrange normal to the interface. 15 refs., 5 figs., 2 tabs

  5. A systematic study of atmospheric pressure chemical vapor deposition growth of large-area monolayer graphene.

    Science.gov (United States)

    Liu, Lixin; Zhou, Hailong; Cheng, Rui; Chen, Yu; Lin, Yung-Chen; Qu, Yongquan; Bai, Jingwei; Ivanov, Ivan A; Liu, Gang; Huang, Yu; Duan, Xiangfeng

    2012-01-28

    Graphene has attracted considerable interest as a potential material for future electronics. Although mechanical peel is known to produce high quality graphene flakes, practical applications require continuous graphene layers over a large area. The catalyst-assisted chemical vapor deposition (CVD) is a promising synthetic method to deliver wafer-sized graphene. Here we present a systematic study on the nucleation and growth of crystallized graphene domains in an atmospheric pressure chemical vapor deposition (APCVD) process. Parametric studies show that the mean size of the graphene domains increases with increasing growth temperature and CH 4 partial pressure, while the density of domains decreases with increasing growth temperature and is independent of the CH 4 partial pressure. Our studies show that nucleation of graphene domains on copper substrate is highly dependent on the initial annealing temperature. A two-step synthetic process with higher initial annealing temperature but lower growth temperature is developed to reduce domain density and achieve high quality full-surface coverage of monolayer graphene films. Electrical transport measurements demonstrate that the resulting graphene exhibits a high carrier mobility of up to 3000 cm 2 V -1 s -1 at room temperature.

  6. Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study

    KAUST Repository

    Baksi, Ananya

    2017-10-31

    Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in presence of excess ligand, GSH using isothermal titration calorimetry (ITC). We have studied Ag11(SG)7 and Ag32(SG)19 clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity towards excess ligand com-pared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mech-anism of these silver clusters and nanoparticles. Effect of dissolved oxygen in the degradation process was studied in de-tail and found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirmation of the fact that functionalized metal clusters fall in-between NPs and atomic systems in their stability is obtained experimentally for the first time. Several other thermophysical parameters of these clusters were also determined including, density, speed of sound, isentropic compressibility and coefficient of thermal expansion.

  7. A structure study of copper oxide for monolayer dispersion of anatase supported

    International Nuclear Information System (INIS)

    Zi Fenlan; Yu Xiaofeng; Guo Hongyou; Cai Xiaohai; Yang Pengcheng; Wu Nianzu; Xie Yaning; Zang Jing; Hu Tiandou

    2002-01-01

    The monolayer dispersion of copper oxide on the surface of anatase and its effect on the properties have been studied by X-ray photoelectron spectroscopy (XPS) and X-ray extended absorption fine structure (EXAFS). XPS results give an utmost dispersion capacity of 7.2 mg/gTiO 2 . Strong interactions between copper oxide and anatase can be seen from EXAFS results. The structure of the supported CuO species is strongly dependent on the amount of CuO loading. When the content of CuO loading is below the utmost dispersion capacity, the surface of CuO/TiO 2 is dominated by the highly dispersed CuO species having no -Cu-O-Cu- chains. The copper ion is located in an octahedral coordination environment, and the Cu-O coordination distance is much longer than that in pure crystalline CuO. When CuO loading is exceeds the utmost dispersion capacity, crystalline CuO is formed on the surface of CuO/TiO 2 . From the result of the structure study, it is Cu-O octahedral coordination and coordination distance change in comparison with pure crystalline CuO on the surface CuO/TiO 2 that have catalytic activity

  8. First-principles study of intrinsic phononic thermal transport in monolayer C3N

    Science.gov (United States)

    Gao, Yan; Wang, Haifeng; Sun, Maozhu; Ding, Yingchun; Zhang, Lichun; Li, Qingfang

    2018-05-01

    Very recently, a new graphene-like crystalline, hole-free, 2D-single-layer carbon nitride C3N, has been fabricated by polymerization of 2,3-diaminophenazine and used to fabricate a field-effect transistor device with an on-off current ratio reaching 5. 5 ×1010 (Adv. Mater. 2017, 1605625). Heat dissipation plays a vital role in its practical applications, and therefore the thermal transport properties need to be explored urgently. In this paper, we perform first-principles calculations combined with phonon Boltzmann transport equation to investigate the phononic thermal transport properties of monolayer C3N, and meanwhile, a comparison with graphene is given. Our calculated intrinsic lattice thermal conductivity of C3N is 380 W/mK at room temperature, which is one order of magnitude lower than that of graphene (3550 W/mK at 300 K), but is greatly higher than many other typical 2D materials. The underlying mechanisms governing the thermal transport were thoroughly discussed and compared to graphene, including group velocities, phonon relax time, the contribution from phonon branches, phonon anharmonicity and size effect. The fundamental physics understood from this study may shed light on further studies of the newly fabricated 2D crystalline C3N sheets.

  9. Structures and shear response of lipid monolayers

    International Nuclear Information System (INIS)

    Dutta, P.; Ketterson, J.B.

    1993-02-01

    This report discusses our work during the last 3 years using x-ray diffraction and shear measurements to study lipid monolayers (membranes). The report is divided into: (1) structure: phase diagram of saturated fatty acid Langmuir monolayers, effect of head group interactions, studies of transferred monolayers (LB films); (2) mechanical properties: fiber=optic capillary wave probe and centrosymmetric trough, mechanical behavior of heneicosanoic acid monolayer phases

  10. Plant n-alkane production from litterfall altered the diversity and community structure of alkane degrading bacteria in litter layer in lowland subtropical rainforest in Taiwan

    Science.gov (United States)

    Huang, Tung-Yi; Hsu, Bing-Mu; Chao, Wei-Chun; Fan, Cheng-Wei

    2018-03-01

    n-Alkane and alkane-degrading bacteria have long been used as crucial biological indicators of paleoecology, petroleum pollution, and oil and gas prospecting. However, the relationship between n-alkane and alkane-degrading bacteria in natural forests is still poorly understood. In this study, long-chain n-alkane (C14-C35) concentrations in litterfall, litter layer, and topsoil as well as the diversity and abundance of n-alkane-degrading bacterial communities in litter layers were investigated in three habitats across a lowland subtropical rainforest in southern Taiwan: ravine, windward, and leeward habitats in Nanjenshan. Our results demonstrate that the litterfall yield and productivity of long-chain n-alkane were highest in the ravine habitats. However, long-chain n-alkane concentrations in all habitats were decreased drastically to a similar low level from the litterfall to the bulk soil, suggesting a higher rate of long-chain n-alkane degradation in the ravine habitat. Operational taxonomic unit (OTU) analysis using next-generation sequencing data revealed that the relative abundances of microbial communities in the windward and leeward habitats were similar and different from that in the ravine habitat. Data mining of community amplicon sequencing using the NCBI database revealed that alkB-gene-associated bacteria (95 % DNA sequence similarity to alkB-containing bacteria) were most abundant in the ravine habitat. Empirical testing of litter layer samples using semi-quantitative polymerase chain reaction for determining alkB gene levels confirmed that the ravine habitat had higher alkB gene levels than the windward and leeward habitats. Heat map analysis revealed parallels in pattern color between the plant and microbial species compositions of the habitats, suggesting a causal relationship between the plant n-alkane production and microbial community diversity. This finding indicates that the diversity and relative abundance of microbial communities in the

  11. An instrument for the examination of nucleation from solution and its applications to the study of precipitation from diesel fuels and solutions of n-alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Gerson, A R; Roberts, K J; Sherwood, J N [Strathclyde Univ., Glasgow (UK). Dept. of Pure and Applied Chemistry

    1991-03-01

    An automated apparatus has been designed and constructed to measure precipitation and dissolution of solids from solution at varying automatically predetermined rates of heating and cooling. The appearance and disappearance of crystals are detected by means of a fibre optic turbidity sensor attached to a Sybron/Brinkman colorimeter. Temperature is measured by a Pt resistance thermometer attached to a constant current source. Both of these measurements are recorded by a personal computer via an analog to digital converter. The temperature of the system and its variation is controlled from the personal computer via a digital to analog interface attached to the control head of a Haake F3Q cryostat. The system has been used for measurements of precipitation and dissolution temperatures for diesel waxes with and without nucleation additives. Studies have been made of the nucleation of a single n-alkane from solution. From these measurements, saturation curves, orders of reactions, interfacial tensions and the critical radii of nuclei can be assessed. (orig.).

  12. Electronic and magnetic properties of 3d-metal trioxides superhalogen cluster-doped monolayer MoS2: A first-principles study

    International Nuclear Information System (INIS)

    Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

    2014-01-01

    Utilizing first-principle calculations, the structural, electronic, and magnetic properties of monolayer MoS 2 doped with 3d transition-metal (TM) atoms and 3d-metal trioxides (TMO 3 ) superhalogen clusters are investigated. 3d-metal TMO 3 superhalogen cluster-doped monolayers MoS 2 almost have negative formation energies except CoO 3 and NiO 3 doped monolayer MoS 2 , which are much lower than those of 3d TM-doped structures. 3d-metal TMO 3 superhalogen clusters are more easily embedded in monolayer MoS 2 than 3d-metal atoms. MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic, and the total magnetic moments are approximately 1.0, 2.0, 3.0, and 4.0 μB per supercell, respectively. MnO 3 and FeO 3 incorporated into monolayer MoS 2 become semiconductors, whereas CoO 3 and NiO 3 incorporated into monolayer MoS 2 become half-metallic. Our studies demonstrate that the half-metallic ferromagnetic nature of 3d-metal TMO 3 superhalogen clusters-doped monolayer MoS 2 has a great potential for MoS 2 -based spintronic device applications. -- Highlights: •TMO 3 superhalogen clusters incorporated into monolayer MoS 2 were investigated. •TMO 3 doped structures have much lower formation energies than TM doped structures. •TMO 3 cluster-doped MoS 2 are thermodynamically favored. •Significant charge transfers between O atoms and Mo atoms in TMO 3 doped structures. •MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic.

  13. A study on the electronic and interfacial structures of monolayer ReS2-metal contacts.

    Science.gov (United States)

    Wang, Jin; Yang, Guofeng; Sun, Rui; Yan, Pengfei; Lu, Yanan; Xue, Junjun; Chen, Guoqing

    2017-10-11

    In this paper, we perform a systematic and rigorous study to evaluate the Ohmic nature of the top-contact formed by the monolayer ReS 2 (mReS 2 ) and metals (gold, silver, platinum, nickel, titanium, and scandium) by means of first-principles density functional theory calculations. We investigate the potential barrier, charge transfer and atomic orbital overlap at the mReS 2 -metal interface in consideration of van der Waals forces to understand how efficiently carriers could be injected from the metal contact to the mReS 2 channel. ReS 2 is physisorbed on Au and Ag, which leads to little perturbation of its electronic structures and forms a larger Schottky contact and a higher tunnel barrier at the interface. ReS 2 is chemisorbed on Ti and Sc, where the bonding strongly perturbs the electronic structures and is found to be purely Ohmic. The bonding of ReS 2 on Pt and Ni lies between these two extreme cases, demonstrating an intermediate behavior. These findings not only provide an insight into the mReS 2 -metal interfaces but may also prove to be instrumental in the future design of ReS 2 -based devices with good performance.

  14. Variation in n-Alkane Distributions of Modern Plants: Questioning Applications of n-Alkanes in Chemotaxonomy and Paleoecology

    Science.gov (United States)

    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

  15. Controlled assembly and single electron charging of monolayer protected Au144 clusters: an electrochemistry and scanning tunneling spectroscopy study

    Science.gov (United States)

    Bodappa, Nataraju; Fluch, Ulrike; Fu, Yongchun; Mayor, Marcel; Moreno-García, Pavel; Siegenthaler, Hans; Wandlowski, Thomas

    2014-11-01

    Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups exposed by the Au-MPCs enable their immobilization on Pt(111) substrates. By varying the humidity during their deposition, samples coated by stacks of compact monolayers of Au-MPCs or decorated with individual, laterally separated Au-MPCs are obtained. DPV experiments with stacked monolayers of Au144-MPCs and EC-STS experiments with laterally separated individual Au144-MPCs are performed both in aqueous and ionic liquid electrolytes. Lower capacitance values were observed for individual clusters compared to ensemble clusters. This trend remains the same irrespective of the composition of the electrolyte surrounding the Au144-MPC. However, the resolution of the energy level spacing of the single clusters is strongly affected by the proximity of neighboring particles.Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups

  16. 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.

    Science.gov (United States)

    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

  17. A novel growth mode of alkane films on a SiO2 surface

    DEFF Research Database (Denmark)

    Mo, H.; Taub, H.; Volkmann, U.G.

    2003-01-01

    on the SiO2 surface with the long-axis of the C32 molecules oriented parallel to the interface followed by a C32 monolayer with the long-axis perpendicular to it. Finally, preferentially oriented bulk particles nucleate having two different crystal structures. This growth model differs from that found...... previously for shorter alkanes deposited from the vapor phase onto solid surfaces....

  18. Data reduction and analysis programs for neutron reflection studies of monolayer adsorption at interfaces

    International Nuclear Information System (INIS)

    Penfold, J.

    1992-07-01

    Data reduction and analysis programs for neutron reflectivity data from monolayer adsorption at interfaces are described. The application of model fitting to the reflectivity data, and the determination of partial structure factors within the kinematic approximation are discussed. Recent data for the adsorption of surfactants at the air-solution interface are used to illustrate the programs described. (author)

  19. Dynamics of decanethiol self-assembled monolayers on Au(111) studied by Scanning tunnelling microscopy

    NARCIS (Netherlands)

    Wu, Hairong; Sotthewes, Kai; Kumar, Avijit; Vancso, Gyula J.; Schön, Peter Manfred; Zandvliet, Henricus J.W.

    2013-01-01

    We investigated the dynamics of decanethiol self-assembled monolayers on Au(111) surfaces using time-resolved scanning tunneling microscopy at room temperature. The expected ordered phases (β, δ, χ*, and ) and a disordered phase (ε) were observed. Current–time traces with the feedback loop disabled

  20. The Interface between Gd and Monolayer MoS2: A First-Principles Study

    KAUST Repository

    Zhang, Xuejing; Mi, Wenbo; Wang, Xiaocha; Cheng, Yingchun; Schwingenschlö gl, Udo

    2014-01-01

    We analyze the electronic structure of interfaces between two-, four- and six-layer Gd(0001) and monolayer MoS2 by first-principles calculations. Strong chemical bonds shift the Fermi energy of MoS2 upwards into the conduction band. At the surface

  1. Interaction between lipid monolayers and poloxamer 188: An X-ray reflectivity and diffraction study

    DEFF Research Database (Denmark)

    Wu, G.H.; Majewski, J.; Ege, C.

    2005-01-01

    The mechanism by which poloxamer 188 (P188) seals a damaged cell membrane is examined using the lipid monolayer as a model system. X-ray reflectivity and grazing-incidence x-ray diffraction results show that at low nominal lipid density, P188, by physically occupying the available area and phase ...

  2. Cholesterol Depletion from a Ceramide/Cholesterol Mixed Monolayer: A Brewster Angle Microscope Study

    KAUST Repository

    Mandal, Pritam; Noutsi, Bakiza Kamal; Chaieb, Saharoui

    2016-01-01

    to deplete cholesterol (Chol) from biomembranes. Here, we focus on the depletion of cholesterol from a C16 ceramide/cholesterol (C16-Cer/Chol) mixed monolayer using MβCD. While the removal of cholesterol by MβCD depends on the cholesterol concentration

  3. Immobilization of rhodium complexes at thiolate monolayers on gold surfaces : Catalytic and structural studies

    NARCIS (Netherlands)

    Belser, T; Stöhr, Meike; Pfaltz, A

    2005-01-01

    Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMS) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic

  4. Melting of short 1-alcohol monolayers on water: Thermodynamics and x-ray scattering studies

    DEFF Research Database (Denmark)

    Berge, B.; Konovalov, O.; Lajzerowicz, J.

    1994-01-01

    From surface tension measurements we extract the melting entropy Delta S-2D of fatty-alcohol monolayers on water. Delta S-2D is found to be 4(kB)/mol lower than in the bulk. Because of the role of the conformational entropy, the melting transition is discontinuous for long chains, but tends to be...

  5. Molecular structure of dipalmitoylphospatidylcholine Langmuir-Blodgett monolayers studied by atomic force microscopy.

    NARCIS (Netherlands)

    Zhai, X.; Kleijn, J.M.

    1997-01-01

    Monolayers of dipalmitoylphosphatidylcholine (DPPC) on the air-water interface have been transferred at various surface pressures onto quartz substrates using the Langmuir-Blodgett (LB) technique. The topography of these layers, on a molecular scale, has been examined by atomic force microscopy

  6. Neutron scattering study of 36 Ar monolayer films adsorbed on graphite

    DEFF Research Database (Denmark)

    Taub, H.; da Costa Carneiro, Kim; Kjems, Jørgen

    1977-01-01

    Diffraction of neutrons from 36 Ar monolayers adsorbed on graphite basal planes indicates that an ordered, two-dimensional (2D) triangular lattice is formed at low temperature. The lattice constant is found to be slightly larger than that of the bulk 3D solid but significantly smaller than that o...

  7. The (gas + liquid) critical properties and phase behaviour of some binary alkanol (C2-C5) + alkane (C5-C12) mixtures

    International Nuclear Information System (INIS)

    Morton, David W.; Lui, Matthew P.W.; Young, Colin L.

    2003-01-01

    Previously, the investigation of the (gas + liquid) critical properties of (alkanol + alkane) mixtures has focussed on (primary alkanol + straight chain alkane) mixtures. The experimental data available for (alkanol + alkane) mixtures, which include secondary or tertiary alcohols and/or branched chain alkanes, are extremely limited. This work extends the existing body of data on (alkanol + alkane) mixtures to include mixtures containing these components. Here the (gas + liquid) critical temperatures of 29 {alkanol (C 2 -C 5 ) + alkane (C 5 -C 12 )} mixtures are reported. All the (gas + liquid) critical lines for the binary mixtures studied are continuous, indicating they obey either Type I or Type II phase behaviour

  8. Surface plasmon resonance spectroscopic study of UV-addressable phenylalanine sensing based on a self-assembled spirooxazine derivative monolayer

    International Nuclear Information System (INIS)

    Suk, Shinae; Suh, Hee-Jung; Gun An, Won; Kim, Jae-Ho; Jin, Sung-Ho; Kim, Sung-Hoon; Gal, Yeong-Soon; Koh, Kwangnak

    2004-01-01

    Light-addressable compounds are very interesting due to the possibilities of their practical use such as optical switches and memories or variable transmission materials. For example, transportation of phenylalanine across liposomal bilayers mediated by a photoresponsive carrier like spirooxazine through electrostatic interaction between phenylalanine and spirooxazine derivative. Thus, the spirooxazine is expected to form a UV-addressable phenylalanine sensing interface. In this study, we prepared phenylalanine sensing interface of a spirooxazine derivative by self-assembly technique and evaluated interaction between a spirooxazine moiety and phenylalanine with a surface plasmon resonance (SPR). The refractive index change of monolayer caused by interaction between a spirooxazine derivative and phenylalanine led to the SPR angle shifts upon UV irradiation. The SPR angle shift increased with increasing the concentration of phenylalanine solution. These results indicated that the spirooxazine derivative self-assembled monolayer (SAM) has an application potential for UV-addressable phenylalanine sensing

  9. Study of structural order in porphyrin-fullerene dyad ZnDHD6ee monolayers by electron diffraction and atomic force microscopy

    Energy Technology Data Exchange (ETDEWEB)

    D' yakova, Yu. A.; Suvorova, E. I.; Orekhov, Andrei S.; Orekhov, Anton S. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Alekseev, A. S. [Russian Academy of Sciences, Prokhorov General Physics Institute (Russian Federation); Gainutdinov, R. V.; Klechkovskaya, V. V., E-mail: klechvv@ns.crys.ras.ru; Tereschenko, E. Yu. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Tkachenko, N. V.; Lemmetyinen, H. [Tampere University of Technology (Finland); Feigin, L. A.; Kovalchuk, M. V. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)

    2013-11-15

    The structure of porphyrin-fullerene dyad ZnDHD6ee monolayers formed on the surface of aqueous subphase in a Langmuir trough and transferred onto solid substrates has been studied. The data obtained are interpreted using simulation of the structure of isolated molecules and their packing in monolayer and modeling of diffraction patterns from molecular aggregates having different sizes and degrees of order. Experiments on the formation of condensed ZnDHD6ee monolayers are described. The structure of these monolayers on a water surface is analyzed using {pi}-A isotherms. The structure of the monolayers transferred onto solid substrates is investigated by electron diffraction and atomic force microscopy. The unit-cell parameters of two-dimensional domains, which are characteristic of molecular packing in monolayers and deposited films, are determined. Domains are found to be organized into a texture (the molecular axes are oriented by the [001] direction perpendicular to the substrate). The monolayers contain a limited number of small 3D domains.

  10. Surface structures of normal paraffins and cyclohexane monolayers and thin crystals grown on the (111) crystal face of platinum. A low-energy electron diffraction study

    International Nuclear Information System (INIS)

    Firment, L.E.; Somorjai, G.A.

    1977-01-01

    The surfaces of the normal paraffins (C 3 --C 8 ) and cyclohexane have been studied using low-energy electron diffraction (LEED). The samples were prepared by vapor deposition on the (111) face of a platinum single crystal in ultrahigh vacuum, and were studied both as thick films and as adsorbed monolayers. These molecules form ordered monolayers on the clean metal surface in the temperature range 100--220 K and at a vapor flux corresponding to 10 -7 Torr. In the adsorbed monolayers of the normal paraffins (C 4 --C 8 ), the molecules lie with their chain axes parallel to the Pt surface and Pt[110]. The paraffin monolayer structures undergo order--disorder transitions as a function of temperature. Multilayers condensed upon the ordered monolayers maintained the same orientation and packing as found in the monolayers. The surface structures of the growing organic crystals do not corresond to planes in their reported bulk crystal structures and are evidence for epitaxial growth of pseudomorphic crystal forms. Multilayers of n-octane and n-heptane condensed upon disordered monolayers have also grown with the (001) plane of the triclinic bulk crystal structures parallel to the surface. n-Butane has three monolayer structures on Pt(111) and one of the three is maintained during growth of the crystal. Cyclohexane forms an ordered monolayer, upon which a multilayer of cyclohexane grows exhibiting the (001) surface orientation of the monoclinic bulk crystal structure. Surface structures of saturated hydrocarbons are found to be very susceptible to electron beam induced damage. Surface charging interferes with LEED only at sample thicknesses greater than 200 A

  11. Adsorption of gas molecules on graphene-like InN monolayer: A first-principle study

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Xiang; Yang, Qun [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Meng, Ruishen [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Tan, Chunjian [Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Liang, Qiuhua [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Jiang, Junke [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Ye, Huaiyu [Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China); Chen, Xianping, E-mail: xianpingchen@cqu.edu.cn [Faculty of Mechanical and Electrical Engineering, Guilin University of Electronic Technology, 541004 Guilin (China); Key Laboratory of Optoelectronic Technology & Systems, Education Ministry of China, Chongqing University and College of Optoelectronic Engineering, Chongqing University, 400044 Chongqing (China)

    2017-05-15

    Highlights: • A comprehensive adsorption mechanism of InN monolayer is theoretical studied to distinguish the physic/chemi-sorption. • Different adsorption sites for different gases are systematically discussed. • The influence (enhanced or weakened) of external electric field to InN-gas system is well investigated. • The influences of gas adsorption to the optical properties (work function and light adsorption ability) of InN monolayer are also researched. - Abstract: Using first-principles calculation within density functional theory (DFT), we study the gas (CO, NH{sub 3}, H{sub 2}S, NO{sub 2}, NO, SO{sub 2}) adsorption properties on the surface of single-layer indium nitride (InN). Four different adsorption sites (Bridge, In, N, Hollow) are chosen to explore the most sensitive adsorption site. On the basis of the adsorption energy, band gap and charge transfer, we find that the most energetic favourable site is changeable between In site and N site for different gases. Moreover, our results reveal that InN is sensitive to NH{sub 3}, SO{sub 2}, H{sub 2}S and NO{sub 2}, by a physisorption or a chemisorption nature. We also perform a perpendicular electric field to the system and find that the applied electric field has a significant effect for the adsorption process. Besides, we also observed the desorption effects on NH{sub 3} adsorbed at the hollow site of InN when the electric field applied. In addition, the optical properties of InN monolayer affected by different gases are also discussed. Most of the gas adsorptions will cause the inhibition of light adsorption while the others can reduce the work function or enhance the adsorption ability in visible region. Our theoretical results indicate that monolayer InN is a promising candidate for gas sensing applications.

  12. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    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).

  13. Studying and controlling order within nanoparticle monolayers fabricated through electrophoretic deposition

    Science.gov (United States)

    Krejci, Alexander J.

    Langmuir Blodgett films can be used to create very thin NP films. Templated substrates in combination with spin coating have been used to order blockcopolymers; this could be adapted for NP arrays as well. Some of these techniques can be applied for forming ordered arrays of NPs in two-dimensions, creating nanoparticle monolayers (NPMs), the focus of this work. NPMs are attractive for many applications in devices such as magnetic storage, solar cells, and biosensors. One particularly attractive feature of NPMs is the high surface area to volume ratio of the films. For example, through collaboration, we are investigating PL properties of two monolayers, composed of two different types of NPs, stacked on top of one another. Although challenging, there now are a variety of techniques for the fabrication of NPMs. This dissertation introduces a new process by which one can fabricate monolayers, electrophoretic deposition (EPD). Literature exists on using EPD to fabricate NPMs, but this literature is very limited. One such study deposited films of Au NPs on carbon films and another Pt NPs on carbon films. To the best of our knowledge, only NPMs of metallic NPs on carbon have been fabricated. Of the EPD studies in which NPMs have been fabricated, the technique has not been investigated in depth or has not been generalized for deposition of many types of materials. If NPM formation via EPD could be generalized, the NPMs could be industrially attractive as EPD has many industrially advantageous properties. For instance, EPD is highly versatile in multiple ways: many types of particles can be deposited, the size of the electrodes can be varied over many orders of magnitude, and a large variety of solvents can be used to suspend NPs. For example, our group has deposited materials of different shapes including tubes, sheets, and spheres; different materials such as polymers, metals, semiconductors, and magnetic materials; and on a variety of substrates including steel, silicon

  14. Alkane inducible proteins in Geobacillus thermoleovorans B23

    Directory of Open Access Journals (Sweden)

    Kato Tomohisa

    2009-03-01

    Full Text Available Abstract Background Initial step of β-oxidation is catalyzed by acyl-CoA dehydrogenase in prokaryotes and mitochondria, while acyl-CoA oxidase primarily functions in the peroxisomes of eukaryotes. Oxidase reaction accompanies emission of toxic by-product reactive oxygen molecules including superoxide anion, and superoxide dismutase and catalase activities are essential to detoxify them in the peroxisomes. Although there is an argument about whether primitive life was born and evolved under high temperature conditions, thermophilic archaea apparently share living systems with both bacteria and eukaryotes. We hypothesized that alkane degradation pathways in thermophilic microorganisms could be premature and useful to understand their evolution. Results An extremely thermophilic and alkane degrading Geobacillus thermoleovorans B23 was previously isolated from a deep subsurface oil reservoir in Japan. In the present study, we identified novel membrane proteins (P16, P21 and superoxide dismutase (P24 whose production levels were significantly increased upon alkane degradation. Unlike other bacteria acyl-CoA oxidase and catalase activities were also increased in strain B23 by addition of alkane. Conclusion We first suggested that peroxisomal β-oxidation system exists in bacteria. This eukaryotic-type alkane degradation pathway in thermophilic bacterial cells might be a vestige of primitive living cell systems that had evolved into eukaryotes.

  15. A Quantitative Study of Tethered Chains in Various Solution Conditions Using Langmuir Diblock Copolymer Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Kent, Michael S.

    1999-08-13

    This article summarizes our investigations of tethered chain systems using Langmuir monolayer of polydimethysiloxane-poly styrene (PDMS-PS) diblock copolymers on organic liquids. In this system, the PDMS block adsorbs to the air surface while the PS block dangles into the subphase liquid. The air surface can be made either repulsive or attractive for the tethered PS chain segments by choosing a subphase liquid which has a surface tension lower or greater than that of PS, respectively. The segment profile of the PS block is determined by neutron reflection as a function of the surface density, the molecular weights of the PS and PDMS blocks, and the solution conditions. We cover the range of reduced surface density (SIGMA) characteristic of the large body of data in the literature for systems of chains tethered onto solid surfaces from dilute solution in good or theta solvent conditions (SIGMA < 12). We emphasize quantitative comparisons with analytical profile forms and scaling predictions. We find that the strong-stretching limit invoked in analytical SCF and scaling theories is not valid over this Z range. On the other hand, over a large portion of this range (SIGMA < 5) tethered layers are well described by a renormalization group theory addressing weakly interacting or noninteracting chains. Simultaneous with the study of the profile form, the free energy of the chains is examined through the surface tension. A strong increase in the surface pressure is observed with increasing surface density which determines the maximum surface density which can be achieved. This apparently nonequilibrium effect is attributed to steric interactions and limited lateral interpenetration. This effect may explain several outstanding discrepancies regarding the adsorption of end-functionalized chains and diblock copolymers onto solid surfaces.

  16. Magnetism of a Co monolayer on Pt(111) capped by overlayers of 5 d elements: A spin-model study

    Science.gov (United States)

    Simon, E.; Rózsa, L.; Palotás, K.; Szunyogh, L.

    2018-04-01

    Using first-principles calculations, we study the magnetic properties of a Co monolayer on a Pt(111) surface with a capping monolayer of selected 5 d elements (Re, Os, Ir, Pt, and Au). First we determine the tensorial exchange interactions and magnetic anisotropies characterizing the Co monolayer for all considered systems. We find a close relationship between the magnetic moment of the Co atoms and the nearest-neighbor isotropic exchange interaction, which is attributed to the electronic hybridization between the Co and the capping layers, in the spirit of the Stoner picture of ferromagnetism. The Dzyaloshinskii-Moriya interaction is decreased for all overlayers compared to the uncapped Co/Pt(111) system, while even the sign of the Dzyaloshinskii-Moriya interaction changes in the case of the Ir overlayer. We conclude that the variation of the Dzyaloshinskii-Moriya interaction is well correlated with the change of the magnetic anisotropy energy and of the orbital moment anisotropy. The unique influence of the Ir overlayer on the Dzyaloshinskii-Moriya interaction is traced by scaling the strength of the spin-orbit coupling of the Ir atoms in Ir/Co/Pt(111) and by changing the Ir concentration in the Au1 -xIrx /Co/Pt(111) system. Our spin dynamics simulations indicate that the magnetic ground state of Re/Co/Pt(111) thin film is a spin spiral with a tilted normal vector, while the other systems are ferromagnetic.

  17. Diverse carrier mobility of monolayer BNC x : a combined density functional theory and Boltzmann transport theory study.

    Science.gov (United States)

    Wu, Tao; Deng, Kaiming; Deng, Weiqiao; Lu, Ruifeng

    2017-10-19

    BNC x monolayer as a kind of two-dimensional material has numerous chemical atomic ratios and arrangements with different electronic structures. Via calculations on the basis of density functional theory and Boltzmann transport theory under deformation potential approximation, the band structures and carrier mobilities of BNC x (x  =  1,2,3,4) nanosheets are systematically investigated. The calculated results show that BNC 2 -1 is a material with very small band gap (0.02 eV) among all the structures while other BNC x monolayers are semiconductors with band gap ranging from 0.51 eV to 1.32 eV. The carrier mobility of BNC x varies considerably from tens to millions of cm 2 V -1 s -1 . For BNC 2 -1, the hole mobility and electron mobility along both x and y directions can reach 10 5 orders of magnitude, which is similar to the carrier mobility of graphene. Besides, all studied BNC x monolayers obviously have anisotropic hole mobility and electron mobility. In particular, for semiconductor BNC 4 , its hole mobility along the y direction and electron mobility along the x direction unexpectedly reach 10 6 orders of magnitude, even higher than that of graphene. Our findings suggest that BNC x layered materials with the proper ratio and arrangement of carbon atoms will possess desirable charge transport properties, exhibiting potential applications in nanoelectronic devices.

  18. The titration of carboxyl-terminated monolayers revisited: in situ calibrated fourier transform infrared study of well-defined monolayers on silicon.

    Science.gov (United States)

    Aureau, D; Ozanam, F; Allongue, P; Chazalviel, J-N

    2008-09-02

    The acid-base equilibrium at the surface of well-defined mixed carboxyl-terminated/methyl-terminated monolayers grafted on silicon (111) has been investigated using in situ calibrated infrared spectroscopy (attenuated total reflectance (ATR)) in the range of 900-4000 cm (-1). Spectra of surfaces in contact with electrolytes of various pH provide a direct observation of the COOH COO (-) conversion process. Quantitative analysis of the spectra shows that ionization of the carboxyl groups starts around pH 6 and extends over more than 6 pH units: approximately 85% ionization is measured at pH 11 (at higher pH, the layers become damaged). Observations are consistently accounted for by a single acid-base equilibrium and discussed in terms of change in ion solvation at the surface and electrostatic interactions between surface charges. The latter effect, which appears to be the main limitation, is qualitatively accounted for by a simple model taking into account the change in the Helmholtz potential associated with the surface charge. Furthermore, comparison of calculated curves with experimental titration curves of mixed monolayers suggests that acid and alkyl chains are segregated in the monolayer.

  19. Ecological response to climate change and human activities indicated by n-alkane proxy during the mid- to late Holocene: a case study from an alpine lake

    Science.gov (United States)

    Zhang, C.; Zhao, C.

    2017-12-01

    Paleolimonological records provide long-term dynamics information of past climate, environment, human activities and ecological variations and give evolutionary perspectives to understand responses process of ecological shift to internal or external trigger. In this study, a powerful biomarkers, n-alkanes, was used to reconstruct the past 5000 years organic matter sources and ecological evolution history of Beilianchi Lake in the southwestern of Loess Plateau after preliminary investigation of modern samples. Climate-environment change and human activities were also traced by total organic matter (TOC), magnetic susceptibility (MS) and relevant proxies. The results showed that the ecosystem related to organic matter composition in Beilianchi Lake might be mainly controlled by climate change before 1400 cal B.P., whereas after that, it was significantly influenced by soil erosion induced by increasing population and enhanced human activities. Lake ecosystem experienced periodical change from relatively stable stage with combination of allochthonous-autochthonous organic sources prior to 1400 cal B.P. to extremely instability and final return to steady state with allochthonous-dominant organic source since 300 cal B.P.. During the period of instability, organic matter composition during 1400-800 cal B.P. indicated a obvious bimodal distribution based on probability density distribution analysis, which reflected the lake ecosystem might stay at bistable state and switched repeatedly from more-macrophytes state (regime A with low ACL) towards less-macrophytes state (regime B with high ACL) controlled by disturbance of soil erosion. The flickering during this period could serve as the early warning signal of transition towards more-macrophytes state or less-macrophytes state in lake ecosystems.

  20. High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

    Science.gov (United States)

    Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

    2016-04-18

    One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Numerical study of friction of flake and adsorbed monolayer on atomically clean substrate

    International Nuclear Information System (INIS)

    Matsukawa, Hiroshi; Haraguchi, Kazuhiro; Ozaki, Shinsuke

    2007-01-01

    Frictional behaviors of flake and adsorbed monolayer on substrate can be observed by Frictional force microscope and Quartz crystal microbalance experiments and are typical problems in nano-friction. Computer simulations had been played important roles in understanding those behaviors, but in most of them the driving direction coincides with one of the crystal axes of the substrate. Here we report our numerical results of direction dependence of friction of flake and adsorbed monolayer. We found a new kind of dynamical phase transition in which flake and adsorbed monlayer change their structure relative to the substrate and make incommensurae structure to reduce kinetic frictional force after certain transition time. When the driving velocity is decreased the transition time tends to diverge at certain critical velocity for the flake. For the adsorbed monlayer the transition time tends to diverge at certain critical magnitudes of the external force or the interaction strength between adsorbates when they are decreased

  2. The Interface between Gd and Monolayer MoS2: A First-Principles Study

    KAUST Repository

    Zhang, Xuejing

    2014-12-08

    We analyze the electronic structure of interfaces between two-, four- and six-layer Gd(0001) and monolayer MoS2 by first-principles calculations. Strong chemical bonds shift the Fermi energy of MoS2 upwards into the conduction band. At the surface and interface the Gd f states shift to lower energy and new surface/interface Gd d states appear at the Fermi energy, which are strongly hybridized with the Mo 4d states and thus lead to a high spin-polarization (ferromagnetically ordered Mo magnetic moments of 0.15 μB). Gd therefore is an interesting candidate for spin injection into monolayer MoS2.

  3. A first-principles study on the magnetic properties of nonmetal atom doped phosphorene monolayers.

    Science.gov (United States)

    Zheng, Huiling; Zhang, Jianmin; Yang, Baishun; Du, Xiaobo; Yan, Yu

    2015-07-07

    In order to induce magnetism in two-dimensional semiconductors for their applications in spintronic devices and novel chemical and electronic properties of semiconducting phosphorene, the geometrical structure, electronic and magnetic properties of doped phosphorene monolayers with a series of nonmetal atoms, including H, F, Cl, Br, I, B, C, Si, N, As, O, S and Se, were systematically investigated using first-principles calculations. The results show that although the substitutional doping of H, F, Cl, Br, I, B, N, O, S or Se results in large structural deformation at the doping sites of phosphorene monolayers, all neutral nonmetal atom doped systems are stable. The calculated formation energies reveal that the substitutional doping of numerous nonmetal atoms in phosphorene monolayer are possible under appropriate experimental conditions, and the charged dopants C(-), Si(-), S(+) and Se(+) are stable. Moreover, the substitutional doping of H, F, Cl, Br, I, B, N, As, C(-), Si(-), S(+) or Se(+) cannot induce magnetism in phosphorene monolayer due to the saturation or pairing of valence electrons of dopant and its neighboring P atoms, whereas ground states of neutral C, Si, O, S or Se doped systems are magnetic due to the appearance of an unpaired valence electron of C and Si or the formation of a nonbonding 3p electron of a neighboring P atom around O, S and Se. Furthermore, the magnetic coupling between the moments induced by two Si, O, S or Se are long-range anti-ferromagnetic and the coupling can be attributed to the hybridization interaction involving polarized electrons, whereas the coupling between the moments induced by two C is weak.

  4. Literature study and experimental investigations into the production of organic iodine compounds from alkane-vapour/air mixtures with radioiodine in the radiation field

    International Nuclear Information System (INIS)

    Leskopf, W.; Holl, S.; Bleier, K.

    1992-01-01

    It was assumed in these investigations that these compounds originated in the gas phase by irradiation induced reactions with radioiodine. Alkane(methane, ethane, propane, n-butane) vapour/air mixtures were radiolysed with iodine in a Co-60 gamma source. The parameter varied were the concentrations of iodine (6.85 E-09 mol/ml - 3.43 E-06 mol/ml) and of the alkanes (1.81 E-05 mol/ml - 3.72 E-10 mol/ml) as well as the irradiation doses (4.45 E + 02 Gy - 1.17 E + 05 Gy). The gaseous reaction mixtures were analysed qualitatively and quantitatively by an ECD- and a MSD-detector for iodine compounds difficult to separate. (orig.) [de

  5. SUBSTRATE-SPECIFICITY OF THE ALKANE HYDROXYLASE SYSTEM OF PSEUDOMONAS-OLEOVORANS GPO1

    NARCIS (Netherlands)

    van Beilen, J.B.; Kingma, Jacob; Witholt, Bernard

    1994-01-01

    We have studied the hydroxylation of a wide range of linear, branched and cyclic alkanes and alkylbenzenes by the alkane hydroxylase system of Pseudomonas oleovorans GPo1 in vivo and in vitro. In vivo hydroxylation was determined with whole cells of the recombinant PpS8141; P. putida PpS81 carrying

  6. ESR study of n-alkane cation structure and photodecomposition in γ-irradiated frozen solutions of CF3CCl3

    International Nuclear Information System (INIS)

    Tabata, M.; Lund, A.

    1984-01-01

    Cations of several n-alkanes produced by γ-irradiation at 77 K of a CF 3 CCl 3 matrix containing 0.1 to 2 mole% of solute have been investigated with special emphasis on their photo-induced decomposition. A general route of reaction of n-alkane cations containing 4 to 7 chain carbon atoms involves the formation of 2-butene cation probably in a process of the type Csub(n)H + sub(2n+2) -> 2-C 4 H 8 + + Csub(n-4)Hsub(2n-6). This reaction is exothermic, but does not occur thermally over the temperature interval 77 to 140 K. The variation of the ESR spectral data of the parent cations have been investigated over the temperature interval 4 to 140 K and have been compared with data obtained using other matrices. It is concluded that the assumption of an extended conformation of the n-alkane cation is not always valid and that the structure is sensitive to matrix and temperature effects. (author)

  7. Packing stress reduction in polymer-lipid monolayers at the air-water interface: An X-ray grazing-incidence diffraction and reflectivity study

    Energy Technology Data Exchange (ETDEWEB)

    Kuhl, T.L.; Majewski, J.; Howes, P.B.; Kjaer, K.; Nahmen, A. von; Lee, K.Y.C.; Ocko, B.; Israelachvili, J.N.; Smith, G.S.

    1999-08-25

    Using synchrotron grazing-incidence X-ray diffraction (GIXD) and reflectivity (XR), the authors have determined the in-plane and out-of-plane structure of phospholipid monolayers at the air-water interface as a function of hydrophilic lipid headgroup size. Di-stearoyl-phosphatidyl-ethanolamine (DSPE) lipid monolayers were systematically modified by chemically grafting hydrophilic poly(ethylene glycol) (PEG) chains of MW = 90 g/mol (2 ethylene oxide, EO, units), MW = 350 g/mol (8 EO units), and MW = 750 g/mol (17 EO units) to the lipid headgroups. The monolayers were studied in the solid phase at a surface pressure of 42 mN/m. At these high lipid packing densities, the PEG chains are submerged in the water subphase. The increased packing stresses from these bulky polymer headgroups distort the unit cell and the in-plane packing modes of the monolayers, leading to large out-of-plane alterations and staggering of the lipid molecules. Surprisingly, a change in the molecular packing of the monolayer toward higher packing densities (lower area per molecule) was observed on increasing the PEG MW to 750 g/mol (17 EO units). This rearrangement of the monolayer structure may be due to a conformational change in the PEG chains.

  8. First principles study of the electronic properties and band gap modulation of two-dimensional phosphorene monolayer: Effect of strain engineering

    Science.gov (United States)

    Phuc, Huynh V.; Hieu, Nguyen N.; Ilyasov, Victor V.; Phuong, Le T. T.; Nguyen, Chuong V.

    2018-06-01

    The effect of strain on the structural and electronic properties of monolayer phosphorene is studied by using first-principle calculations based on the density functional theory. The intra- and inter-bond length and bond angle for monolayer phosphorene is also evaluated. The intra- and inter-bond length and the bond angle for phosphorene show an opposite tendency under different directions of the applied strain. At the equilibrium state, monolayer phosphorene is a semiconductor with a direct band gap at the Γ-point of 0.91 eV. A direct-indirect band gap transition is found in monolayer phosphorene when both the compression and tensile strain are simultaneously applied along both zigzag and armchair directions. Under the applied compression strain, a semiconductor-metal transition for monolayer phosphorene is observed at -13% and -10% along armchair and zigzag direction, respectively. The direct-indirect and phase transition will largely constrain application of monolayer phosphorene to electronic and optical devices.

  9. Formation of Bimolecular Membranes from Lipid Monolayers and a Study of Their Electrical Properties

    Science.gov (United States)

    Montal, M.; Mueller, P.

    1972-01-01

    Bimolecular membranes are formed from two lipid monolayers at an air-water interface by the apposition of their hydrocarbon chains when an aperture in a Teflon partition separating two aqueous phases is lowered through the interface. Formation of the membrane is monitored by an increase of the electrical capacity, as measured with a voltage clamp. Electrical resistance of the unmodified membrane is analogous to that of conventional planar bilayers (black lipid membranes) prepared in the presence of a hydrocarbon solvent, i.e., 106-108 ohm cm2; the resistance can be lowered to values of 103 ohm cm2 by gramicidin, an antibiotic that modifies the conductance only when the membranes are of biomolecular thickness. In contrast to the resistance, there is a significant difference between the capacity of bilayers made from mono-layers and that of hydrocarbon-containing bilayers made by phase transition; the average values are 0.9 and 0.45 μF cm-2, respectively. The value of 0.9 μF cm-2 approximates that of biological membranes. Assuming a dielectric constant of 2.1 for the hydrocarbon region, the dielectric thickness, as calculated from a capacity of 0.9 μF cm-2, is 22 Å. This value is 6-10 Å smaller than the actual thickness of the hydrocarbon region of bilayers and cell membranes, as determined by x-ray diffraction. The difference may be due to a limited penetration of water into the hydrocarbon region near the ester groups that would lower the electrical resistance of this region and reduce the dielectric thickness. Asymmetric membranes have been formed by adjoining two lipid monolayers of different chemical composition. Images PMID:4509315

  10. Phase transitions in surfactant monolayers

    International Nuclear Information System (INIS)

    Casson, B.D.

    1998-01-01

    Two-dimensional phase transitions have been studied in surfactant monolayers at the air/water interface by sum-frequency spectroscopy and ellipsometry. In equilibrium monolayers of medium-chain alcohols C n H 2n+1 OH (n = 9-14) a transition from a two-dimensional crystalline phase to a liquid was observed at temperatures above the bulk melting point. The small population of gauche defects in the solid phase increased only slightly at the phase transition. A model of the hydrocarbon chains as freely rotating rigid rods allowed the area per molecule and chain tilt in the liquid phase to be determined. The area per molecule, chain tilt and density of the liquid phase all increased with increasing chain length, but for each chain length the density was higher than in a bulk liquid hydrocarbon. In a monolayer of decanol adsorbed at the air/water interface a transition from a two-dimensional liquid to a gas was observed. A clear discontinuity in the coefficient of ellipticity as a function of temperature showed that the transition is first-order. This result suggests that liquid-gas phase transitions in surfactant monolayers may be more widespread than once thought. A solid-liquid phase transition has also been studied in mixed monolayers of dodecanol with an anionic surfactant (sodium dodecyl sulphate) and with a homologous series of cationic surfactants (alkyltrimethylammonium bromides: C n TABs, n = 12, 14, 16). The composition and structure of the mixed monolayers was studied above and below the phase transition. At low temperatures the mixed monolayers were as densely packed as a monolayer of pure dodecanol in its solid phase. At a fixed temperature the monolayers under-went a first-order phase transition to form a phase that was less dense and more conformationally disordered. The proportion of ionic surfactant in the mixed monolayer was greatest in the high temperature phase. As the chain length of the C n TAB increased the number of conformational defects

  11. Thermodynamic parameters for the adsorption of volatile n-alkane ...

    African Journals Online (AJOL)

    alkanes hexane to nonane on ground dried water hyacinth (E. crassipes) root biomass were studied between 40 and 70°C column temperature using inverse gas chromatography, before and after treatment of the root biomass with mineral acid ...

  12. Synchrotron X-ray diffraction studies of phase transitions in physisorbed monolayers of rare gases on graphite

    International Nuclear Information System (INIS)

    Bohr, J.

    1984-01-01

    This study is an investigation of phase transition in monoatomic layers adsorbed on graphite. Such effects can be considered physical realizations of two-dimensional systems. The experimental technique used is synchrotron X-ray diffraction. Systems which have been investigated include the commensurate-incommensurate phase transition in krypton monolayer. By adjusting the spreading pressure in the krypton layer by means of a coadsorbent deuterium gas it has been unambiguously demonstrated that at low temperatures the phase transition is of first order. A melting study of incommensurate argon monolayers demonstrates an experimental verification of the possibility for having a continuous melting transition in two-dimensions. Mixtures of two-components have been investigated for their phases. No (chemical) order-disorder transition is seen. A discussion is given on this lack of a chemical order. This lack is utilized to study the commensurate-incommensurate phase transition driven by average particle size. Finally, a special low-temperature phase is identified in a xenon monlayer which is diluted with freon. (Auth.)

  13. Lower lattice thermal conductivity in SbAs than As or Sb monolayers: a first-principles study.

    Science.gov (United States)

    Guo, San-Dong; Liu, Jiang-Tao

    2017-12-06

    Phonon transport in group-VA element (As, Sb and Bi) monolayer semiconductors has been widely investigated in theory, and, of them, monolayer Sb (antimonene) has recently been synthesized. In this work, phonon transport in monolayer SbAs is investigated with a combination of first-principles calculations and the linearized phonon Boltzmann equation. It is found that the lattice thermal conductivity of monolayer SbAs is lower than those of both monolayer As and Sb, and the corresponding sheet thermal conductance is 28.8 W K -1 at room temperature. To understand the lower lattice thermal conductivity in monolayer SbAs than those in monolayer As and Sb, the group velocities and phonon lifetimes of monolayer As, SbAs and Sb are calculated. The calculated results show that the group velocities of monolayer SbAs are between those of monolayer As and Sb, but that the phonon lifetimes of SbAs are smaller than those of both monolayer As and Sb. Hence, the low lattice thermal conductivity in monolayer SbAs is attributed to very small phonon lifetimes. Unexpectedly, the ZA branch has very little contribution to the total thermal conductivity, only 2.4%, which is obviously different from those of monolayer As and Sb with very large contributions. This can be explained by very small phonon lifetimes for the ZA branch of monolayer SbAs. The lower lattice thermal conductivity of monolayer SbAs compared to that of monolayer As or Sb can be understood by the alloying of As (Sb) with Sb (As), which should introduce phonon point defect scattering. We also consider the isotope and size effects on the lattice thermal conductivity. It is found that isotope scattering produces a neglectful effect, and the lattice thermal conductivity with a characteristic length smaller than 30 nm can reach a decrease of about 47%. These results may offer perspectives on tuning the lattice thermal conductivity by the mixture of multiple elements for applications of thermal management and

  14. First-principles study on the electronic, optical, and transport properties of monolayer α - and β -GeSe

    Science.gov (United States)

    Xu, Yuanfeng; Zhang, Hao; Shao, Hezhu; Ni, Gang; Li, Jing; Lu, Hongliang; Zhang, Rongjun; Peng, Bo; Zhu, Yongyuan; Zhu, Heyuan; Soukoulis, Costas M.

    2017-12-01

    The extraordinary properties and the novel applications of black phosphorene induce the research interest in the monolayer group-IV monochalcogenides. Here using first-principles calculations, we systematically investigate the electronic, transport, and optical properties of monolayer α - and β -GeSe, revealing a direct band gap of 1.61 eV for monolayer α -GeSe and an indirect band gap of 2.47 eV for monolayer β -GeSe. For monolayer β -GeSe, the electronic/hole transport is anisotropic, with an extremely high electron mobility of 2.93 ×104cm2/Vs along the armchair direction, comparable to that of black phosphorene. Furthermore, for β -GeSe, robust band gaps nearly independent of the applied tensile strain along the armchair direction are observed. Both monolayer α - and β -GeSe exhibit anisotropic optical absorption in the visible spectrum.

  15. Study of the helium cross-section of unsymmetric disulfide self-assembled monolayers on Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Albayrak, Erol [Department of Materials and Metallurgical Engineering, Ahi Evran University, Kırşehir 40000 (Turkey); Karabuga, Semistan [Department of Chemistry, Kahramanmaraş Sütçü İmam University, Kahramanmaraş 46030 (Turkey); Bracco, Gianangelo [CNR-IMEM and Department of Physics, University of Genoa, Via Dodecaneso 33, Genoa 16146 (Italy); Danışman, M. Fatih, E-mail: danisman@metu.edu.tr [Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)

    2016-12-30

    Highlights: • Unsymmetrtic disulfide (HDD and HOD) self assembled monolayers were grown on Au(111) by supersonic molecular beam deposition. • Helium scattering cross sections for these two different unsymmetric disulfides were determined. • A common low temperature film phase was observed for the studied disulfides. - Abstract: We have investigated the formation of self-assembled monolayers (SAMs) of 11-hydroxyundecyl decyl disulfide (CH{sub 3}-(CH{sub 2}){sub 9}-S-S-(CH{sub 2}){sub 11}-OH, HDD) and 11-hydroxyundecyl octadecyl disulfide (CH{sub 3}-(CH{sub 2}){sub 17}-S-S-(CH{sub 2}){sub 11}-OH, HOD) produced by supersonic molecular beam deposition (SMBD). The study has been carried out by means of helium diffraction at very low film coverage. In this regime helium single molecule cross sections have been estimated in a temperature range between 100 K and 450 K. The results show a different behavior above 300 K that has been interpreted as the starting of mobility with the formation of two thiolate moieties either linked by a gold adatom or distant enough to prevent cross section overlapping. Finally, helium diffraction patterns measured at 80 K for the SAMs grown at 200 K are discussed and the results support the proposed hypothesis of molecular dissociation based on the cross section data.

  16. Comparing the accuracy of high-dimensional neural network potentials and the systematic molecular fragmentation method: A benchmark study for all-trans alkanes

    International Nuclear Information System (INIS)

    Gastegger, Michael; Kauffmann, Clemens; Marquetand, Philipp; Behler, Jörg

    2016-01-01

    Many approaches, which have been developed to express the potential energy of large systems, exploit the locality of the atomic interactions. A prominent example is the fragmentation methods in which the quantum chemical calculations are carried out for overlapping small fragments of a given molecule that are then combined in a second step to yield the system’s total energy. Here we compare the accuracy of the systematic molecular fragmentation approach with the performance of high-dimensional neural network (HDNN) potentials introduced by Behler and Parrinello. HDNN potentials are similar in spirit to the fragmentation approach in that the total energy is constructed as a sum of environment-dependent atomic energies, which are derived indirectly from electronic structure calculations. As a benchmark set, we use all-trans alkanes containing up to eleven carbon atoms at the coupled cluster level of theory. These molecules have been chosen because they allow to extrapolate reliable reference energies for very long chains, enabling an assessment of the energies obtained by both methods for alkanes including up to 10 000 carbon atoms. We find that both methods predict high-quality energies with the HDNN potentials yielding smaller errors with respect to the coupled cluster reference.

  17. Comparing the accuracy of high-dimensional neural network potentials and the systematic molecular fragmentation method: A benchmark study for all-trans alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Gastegger, Michael; Kauffmann, Clemens; Marquetand, Philipp, E-mail: philipp.marquetand@univie.ac.at [Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 17, Vienna (Austria); Behler, Jörg [Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Universitätsstraße 150, Bochum (Germany)

    2016-05-21

    Many approaches, which have been developed to express the potential energy of large systems, exploit the locality of the atomic interactions. A prominent example is the fragmentation methods in which the quantum chemical calculations are carried out for overlapping small fragments of a given molecule that are then combined in a second step to yield the system’s total energy. Here we compare the accuracy of the systematic molecular fragmentation approach with the performance of high-dimensional neural network (HDNN) potentials introduced by Behler and Parrinello. HDNN potentials are similar in spirit to the fragmentation approach in that the total energy is constructed as a sum of environment-dependent atomic energies, which are derived indirectly from electronic structure calculations. As a benchmark set, we use all-trans alkanes containing up to eleven carbon atoms at the coupled cluster level of theory. These molecules have been chosen because they allow to extrapolate reliable reference energies for very long chains, enabling an assessment of the energies obtained by both methods for alkanes including up to 10 000 carbon atoms. We find that both methods predict high-quality energies with the HDNN potentials yielding smaller errors with respect to the coupled cluster reference.

  18. First-principle study of hydrogenation on monolayer MoS2

    International Nuclear Information System (INIS)

    Xu, Yong; Li, Yin; Chen, Xi; Zhang, Ru; Zhang, Chunfang; Lu, Pengfei

    2016-01-01

    The structural and electronic properties of hydrogenation on 1H-MoS 2 and 1T-MoS 2 have been systematically explored by using density functional theory (DFT) calculations. Our calculated results indicate an energetically favorable chemical interaction between H and MoS 2 monolayer for H adsorption when increasing concentration of H atoms. For 1H-MoS 2 , single H atom adsorption creates midgap approaching the Fermi level which increases the n-type carrier concentration effectively. As a consequence, its electrical conductivity is expected to increase significantly. For 1T-MoS 2 , H atoms adsorption can lead to the opening of a direct gap of 0.13 eV compared to the metallic pristine 1T-MoS 2 .

  19. X-ray diffraction and molecular-dynamics studies: Structural analysis of phases in diglyceride monolayers

    DEFF Research Database (Denmark)

    Peters, Günther H.J.; Larsen, Niels Bent; Bjørnholm, T.

    1998-01-01

    We report a detailed structural analysis of the phases of 1,2-sn-dipalmitoylglycerol Langmuir monolayers at room temperature. Pressure-induced transitions have been investigated by combination of molecular-dynamics simulations and grazing-incidence x-ray diffraction (XRD). The diglyceride film...... undergoes two phase transitions occurring at 38.3 and 39.8 Angstrom(2)/molecule. Simulation indicates that the first transition involves a reorientation of the headgroups while simulation and XRD show that in the second transition the order parameter is the tilt angle of the alkyl chains. A methodology......; At the lowest pressure the tilt angle reaches approximate to 14 degrees in a direction close to a nearest neighbor direction. Both arrangements of the alkyl chains are confirmed by XRD. For higher order and fractional order Bragg peaks, simulations predict higher intensities than observed with XRD. This may...

  20. First-principle study of hydrogenation on monolayer MoS{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yong; Li, Yin [State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876 (China); School of science, Beijing University of Posts and Telecommunications, Beijing 100876 (China); Chen, Xi; Zhang, Ru [State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876 (China); School of Ethnic Minority Education, Beijing University of Posts and Telecommunications, Beijing 102209 (China); Zhang, Chunfang [Beijing Computational Science Research Center, Beijing 100094 (China); Lu, Pengfei, E-mail: photon.bupt@gmail.com [State Key Laboratory of Information Photonics and Optical Communications, Beijing University of Posts and Telecommunications, Beijing 100876 (China)

    2016-07-15

    The structural and electronic properties of hydrogenation on 1H-MoS{sub 2} and 1T-MoS{sub 2} have been systematically explored by using density functional theory (DFT) calculations. Our calculated results indicate an energetically favorable chemical interaction between H and MoS{sub 2} monolayer for H adsorption when increasing concentration of H atoms. For 1H-MoS{sub 2}, single H atom adsorption creates midgap approaching the Fermi level which increases the n-type carrier concentration effectively. As a consequence, its electrical conductivity is expected to increase significantly. For 1T-MoS{sub 2}, H atoms adsorption can lead to the opening of a direct gap of 0.13 eV compared to the metallic pristine 1T-MoS{sub 2}.

  1. A comparative study of post-irradiation growth kinetics of spheroids and monolayers

    International Nuclear Information System (INIS)

    Dertinger, J.; Luecke-Huhle, C.

    1975-01-01

    Post-irradiation growth kinetics of γ-irradiated spheroid and monolayer cells in exponential growth phase was investigated by means of dose-response curves based on cell counts after specified time intervals following irradiation. A mathematical model of cell-growth after irradiation was fitted to these curves. The model parameters (related to division delay and growth of non-surviving cells) obtained from this analysis consistently indicated increasing resistance to sub-lethal damage of cells cultured as multicellular spheroids under conditions of increasing three-dimensional contact. In contrast, no indication of an increased radiation-resistance was found with cells cultured on a substratum under a variety of conditions. (author)

  2. Self-assembled monolayers of alkyl-thiols on InAs: A Kelvin probe force microscopy study

    Science.gov (United States)

    Szwajca, A.; Wei, J.; Schukfeh, M. I.; Tornow, M.

    2015-03-01

    We report on the preparation and characterization of self-assembled monolayers from aliphatic thiols with different chain length and termination on InAs (100) planar surfaces. This included as first step the development and investigation of a thorough chemical InAs surface preparation step using a dedicated bromine/NH4OH-based etching process. Ellipsometry, contact angle measurements and atomic force microscopy (AFM) indicated the formation of smooth, surface conforming monolayers. The molecular tilt angles were obtained as 30 ± 10° with respect to the surface normal. Kelvin probe force microscopy (KPFM) measurements in hand with Parameterized Model number 5 (PM5) calculations of the involved molecular dipoles allowed for an estimation of the molecular packing densities on the surface. We obtained values of up to n = 1014 cm- 2 for the SAMs under study. These are close to what is predicted from a simple geometrical model that would calculate a maximum density of about n = 2.7 × 1014 cm- 2. We take this as additional conformation of the substrate smoothness and quality of our InAs-SAM hybrid layer systems.

  3. Crystallization features of normal alkanes in confined geometry.

    Science.gov (United States)

    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

  4. Structure and shear response of lipid monolayers

    International Nuclear Information System (INIS)

    Dutta, P.; Ketterson, J.B.

    1990-02-01

    Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this Progress Report, we describe our X-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension

  5. Magnetic monolayers on semiconducting substrates. An in situ FMR study of Fe-based heterostructures

    Energy Technology Data Exchange (ETDEWEB)

    Zakeri Lori, K.

    2007-10-18

    The growth, magnetic anisotropy, g-factor, and magnetization of Fe monolayers grown on GaAs(001), InAs(001), and InP(001) are investigated by a combination of in situ ferromagnetic resonance and SQUID magnetometry as a function of temperature and film thickness. The effect of stress caused by the lattice mismatch and the surface reconstruction on the magnetic anisotropy is quantified. An in-plane spin reorientation transition as a function of film thickness is observed at room temperature for all systems. A magneto-elastic model is used to explain the direction of the easy axis, the spin reorientation transition, and the contributions to the magnetic anisotropy terms using the stress components measured directly by in situ IV-low-energy electron diffraction. While the model gives a quantitative explanation of the out-of-plane magnetic anisotropy, changes of the electronic interface structure have to be taken into account for the in-plane magnetic anisotropy. The influence of Ag and Au buffer and cap layers on the magnetic anisotropy terms are determined. The temperature dependence of the total magnetic anisotropy, as well as the surface-interface and volume contribution to the magnetic anisotropy are determined for Fe monolayers on GaAs(001). It is demonstrated that the temperature dependence of the magnetic anisotropy is correlated with the temperature dependence of the magnetization according to the Callen-Callen model. The temperature dependence of the volume contribution to the perpendicular magnetic anisotropy is fully explained by the temperature dependence of the magneto-elastic anisotropy. A temperature-driven morphological transformation occurring at a temperature higher than 550 K depending on the film thickness is observed. The thin Fe3Si binary Heusler structure epitaxially grown on MgO(001) is investigated. In addition to the structural properties, magnetic anisotropy, magnetization, g-factor, spin, and orbital magnetism, the magnetic relaxation

  6. Al-Doped ZnO Monolayer as a Promising Transparent Electrode Material: A First-Principles Study

    Directory of Open Access Journals (Sweden)

    Mingyang Wu

    2017-03-01

    Full Text Available Al-doped ZnO has attracted much attention as a transparent electrode. The graphene-like ZnO monolayer as a two-dimensional nanostructure material shows exceptional properties compared to bulk ZnO. Here, through first-principle calculations, we found that the transparency in the visible light region of Al-doped ZnO monolayer is significantly enhanced compared to the bulk counterpart. In particular, the 12.5 at% Al-doped ZnO monolayer exhibits the highest visible transmittance of above 99%. Further, the electrical conductivity of the ZnO monolayer is enhanced as a result of Al doping, which also occurred in the bulk system. Our results suggest that Al-doped ZnO monolayer is a promising transparent conducting electrode for nanoscale optoelectronic device applications.

  7. Synthesis, crystal structures, computational studies and antimicrobial activity of new designed bis((5-aryl-1,3,4-oxadiazol-2-yl)thio)alkanes

    Science.gov (United States)

    Ahmed, Muhammad Naeem; Sadiq, Beenish; Al-Masoudi, Najim A.; Yasin, Khawaja Ansar; Hameed, Shahid; Mahmood, Tariq; Ayub, Khurshid; Tahir, Muhammad Nawaz

    2018-03-01

    A new series of bis((5-aryl-1,3,4-oxadiazol-2-yl)thio)alkanes 4-14 have been synthesized via nucleophilic substitution reaction of dihaloalkanes with respective 1,3,4-oxadiazole-2-thiols 3a-f, and characterized by spectroscopic techniques. The structures of 4 and 12 were unambiguously confirmed by single-crystal X-ray diffraction analysis. Density functional theory calculations at B3LYP/6-31 + G(d) level of theory were performed for comparison of X-ray geometric parameters, molecular electrostatic potential (MEP) and frontier molecular orbital analyses of synthesized compounds. MEP analysis revealed that these compounds are nucleophilic in nature. Frontier molecular orbitals (FMOs) analysis of 4-14 was performed for evaluation of kinetic stability. All synthesized compounds were screened in vitro for antimicrobial activity against three bacterial and three fungal strains and showed promising results.

  8. Comparative Study of Electroless Copper Film on Different Self-Assembled Monolayers Modified ABS Substrate

    Directory of Open Access Journals (Sweden)

    Jiushuai Xu

    2014-04-01

    Full Text Available Copper films were grown on (3-Mercaptopropyltrimethoxysilane (MPTMS, (3-Aminopropyltriethoxysilane (APTES and 6-(3-(triethoxysilylpropylamino-1,3,5- triazine-2,4-dithiol monosodium (TES self-assembled monolayers (SAMs modified acrylonitrile-butadiene-styrene (ABS substrate via electroless copper plating. The copper films were examined using scanning electron microscopy (SEM and X-ray diffraction (XRD. Their individual deposition rate and contact angle were also investigated to compare the properties of SAMs and electroless copper films. The results indicated that the formation of copper nuclei on the TES-SAMs modified ABS substrate was faster than those on the MPTMS-SAMs and APTES-SAMs modified ABS substrate. SEM images revealed that the copper film on TES-SAM modified ABS substrate was smooth and uniform, and the density of copper nuclei was much higher. Compared with that of TES-SAMs modified resin, the coverage of copper nuclei on MPTMS and APTES modified ABS substrate was very limited and the copper particle size was too big. The adhesion property test demonstrated that all the SAMs enhanced the interfacial interaction between copper plating and ABS substrate. XRD analysis showed that the copper film deposited on SAM-modified ABS substrate had a structure with Cu(111 preferred orientation, and the copper film deposited on TES-SAMs modified ABS substrate is better than that deposited on MPTMS-SAMs or APTES-SAMs modified ABS resins in electromigrtion resistance.

  9. Study of Alkylthiolate Self-assembled Monolayers on Au(111) Using a Semilocal meta-GGA Density Functional

    DEFF Research Database (Denmark)

    Ferrighi, Lara; Pan, Yun-xiang; Grönbeck, Henrik

    2012-01-01

    We present a density functional theory study of the structure and stability of self-assembled monolayers (SAMs) of alkylthiolate on Au(111) as a function of the alkyl chain length. The most favorable structure of the SAMs involves an RS–Au–SR complex (S being sulfur, R being an alkyl chain) forme....... In particular, the use of M06-L yields an increased stability of the SAMs with increasing alkyl chain length and an increased attractive interaction between RS–Au–SR complexes at shorter distances....... through sandwiching one Au adatom by two alkylthiolates (RSs). Comparing a generalized gradient (GGA-PBE) and a meta-GGA (MGGA-M06-L) exchange-correlation functional we find that only the meta-GGA functional predicts the experimentally observed attractive intermolecular interactions within the SAMs...

  10. A comprehensive study of piezomagnetic response in CrPS4 monolayer: mechanical, electronic properties and magnetic ordering under strains

    Science.gov (United States)

    Joe, Minwoong; Lee, Hosik; Menderes Alyörük, M.; Lee, Jinhwan; Youb Kim, Sung; Lee, Changgu; Lee, Jun Hee

    2017-10-01

    We performed first-principles calculations to investigate the magnetic, mechanical and electronic properties of the tetrachalcogenide CrPS4. Although bulk CrPS4 has been shown to exhibit a low-dimensional antiferromagnetic (AFM) ground state where ferromagnetic (FM) Cr-chains are coupled antiferromagnetically, our calculations indicated that the monolayer can be transformed to an FM material by applying a uniaxial tensile strain of  ⩾4% along the FM Cr-chain direction. The AFM-to-FM transition is explained to be driven by an increase of the exchange interaction induced by a decrease in the distance between the FM Cr-chains. A huge nonlinear piezomagnetism was predicted at the strain-induced magnetic phase boundary. Our study provides insight about rational design of single-layer magnetic materials for a wide range of spintronic devices and energy applications.

  11. Hydrothermal conversion of cellulose to alkanes with in-situ hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Sudong; Tan, Zhongchao [Department of Mechanical and Mechatronics Engineering, University of Waterloo (Canada)], Email: tanz@uwaterloo.ca

    2011-07-01

    A recently study examined the probability of hydrothermal conversion of cellulose to alkanes with in-situ H2 instead of external H2. This paper discusses the results of that study. The study researched the effects of volumetric ratios of initial input water to the reactor (W/R) and of selected catalysts on the alkane yields and composition. It was found that with the proper W/R ratios, the reforming of steam in the steam gas phase would automatically produce in-situ H2 and the key was to maintain the right balance of steam phase and liquid phase in the reactor. All the study results conclude that direct hydrothermal conversion of cellulose to alkanes with in-situ H2 is technically feasible. In addition, the application of this technology would protect the alkane bio-oil production biomass from the impact of unstable external supply of H2.

  12. Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

    International Nuclear Information System (INIS)

    Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia; Tavagnacco, Claudio; Borsari, Marco

    2011-01-01

    Highlights: → Denaturation involves intermediate and partially unfolded forms. → An unfolded species displaying the haem with Fe coordinated by two His is observed. → Under unfolding conditions the nature of the SAM influences conformation of protein. → Concentration of the unfolding agent affects redox properties of immobilized protein. - Abstract: The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The E o ' of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower E o ' value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.

  13. Unfolding of cytochrome c immobilized on self-assembled monolayers. An electrochemical study

    Energy Technology Data Exchange (ETDEWEB)

    Monari, Stefano; Ranieri, Antonio; Bortolotti, Carlo Augusto; Peressini, Silvia [Department of Chemistry, University of Modena and Reggio Emilia, via Campi 183, 41125 Modena (Italy); Tavagnacco, Claudio [Department of Chemistry, University of Trieste, via Giorgieri 1, 34127 Trieste (Italy); Borsari, Marco, E-mail: marco.borsari@unimore.it [Department of Chemistry, University of Modena and Reggio Emilia, via Campi 183, 41125 Modena (Italy)

    2011-08-01

    Highlights: > Denaturation involves intermediate and partially unfolded forms. > An unfolded species displaying the haem with Fe coordinated by two His is observed. > Under unfolding conditions the nature of the SAM influences conformation of protein. > Concentration of the unfolding agent affects redox properties of immobilized protein. - Abstract: The electron transfer (ET) process of progressively unfolded bovine cytochrome c immobilized on different self-assembled monolayers (SAMs) was investigated. Insight is gained on the role of the SAM surface on the functionality of the partially unfolded and non-native forms of the adsorbed protein. Direct electrochemical measurements were performed on cytochrome c adsorbed on mercaptopyridine (MP) and mixed 11-mercapto-1-undecanoic acid/11-mercapto-1-undecanol (MUA/MU) at varying temperature, in the presence of urea as unfolding agent. Under strongly unfolding conditions, a non-native form of cytochrome c, in which the methionine ligand is replaced by a histidine, was observed on both MP and MUA/MU SAMs. The E{sup o}' of the native form, in which the haem is axially coordinated by methionine and histidine, slightly shifts to negative values upon increasing urea concentration. However, the non-native bis-histidinate species shows a much lower E{sup o}' value (by approximately 0.4 V) which is by far enthalpic in origin and largely determined by axial ligand swapping. Analysis of the reduction enthalpies and entropies and of the ET rate constants indicate that the nature of the SAM (hydrophilic or anionic) results in changes in the conformational rearrangement of the cytochrome c under unfolding conditions.

  14. A raft-associated species of phosphatidylethanolamine interacts with cholesterol comparably to sphingomyelin. A Langmuir-Blodgett monolayer study.

    Directory of Open Access Journals (Sweden)

    Michal Grzybek

    Full Text Available BACKGROUND: Specific interactions between sphingomyelin (SM and cholesterol (Ch are commonly believed to play a key role in the formation of rafts in the biological membranes. A weakness of this model is the implication that these microdomains are confined to the outer bilayer leaflet. The cytoplasmic leaflet, which contains the bulk of phosphatidylethanolamine (PE, phosphatidylserine (PS and phosphatidylinositol (PI, is thought also to harbour half of the membrane cholesterol. Moreover, SLPE (1-stearoyl-2-linoleoyl-sn-glycero-3-phosphatidyl-ethanolamine has recently been shown to be enriched in isolated detergent-resistant membranes (DRM, and this enrichment was independent of the method of isolation of DRM. METHODOLOGY/PRINCIPAL FINDINGS: Here we present quantitative evidence coming from Langmuir-Blodgett monolayer experiments that SLPE forms complex with Ch similar to that between SM and Ch. The energies of these interactions as calculated form the monolayer studies are highly negative. FRAP analysis showed that NBD-Ch recovery was similar in liposomes composed of DOPC/Ch SM or SLPE but not DPPE, providing further evidence that SLPE may form an l(o phase in the presence of high Ch concentration. Experiments on the solubility of DOPC liposomes containing DPPE/Ch (1ratio1, SM/Ch (1ratio1 or SLPE/Ch (1ratio1 showed the presence of Triton X-100 insoluble floating fraction (TIFF in the case of SM/Ch or SLPE/Ch but not in DPPE/Ch containing liposomes. Quantitative determination of particular lipid species in the TIFF fraction confirms the conclusion that SLPE (or similar PE species could be an important constituent of the inner leaflet raft. CONCLUSION: Such interactions suggest a possible existence of inner-leaflet nanoscale assemblies composed of cholesterol complexes with SLPE or similar unsaturated PE species.

  15. Quantum chemical analysis of thermodynamics of 2D cluster formation of alkanes at the water/vapor interface in the presence of aliphatic alcohols.

    Science.gov (United States)

    Vysotsky, Yu B; Kartashynska, E S; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Miller, R

    2015-11-21

    Using the quantum chemical semi-empirical PM3 method it is shown that aliphatic alcohols favor the spontaneous clusterization of vaporous alkanes at the water surface due to the change of adsorption from the barrier to non-barrier mechanism. A theoretical model of the non-barrier mechanism for monolayer formation is developed. In the framework of this model alcohols (or any other surfactants) act as 'floats', which interact with alkane molecules of the vapor phase using their hydrophobic part, whereas the hydrophilic part is immersed into the water phase. This results in a significant increase of contact effectiveness of alkanes with the interface during the adsorption and film formation. The obtained results are in good agreement with the existing experimental data. To test the model the thermodynamic and structural parameters of formation and clusterization are calculated for vaporous alkanes C(n)H(2n+2) (n(CH3) = 6-16) at the water surface in the presence of aliphatic alcohols C(n)H(2n+1)OH (n(OH) = 8-16) at 298 K. It is shown that the values of clusterization enthalpy, entropy and Gibbs' energy per one monomer of the cluster depend on the chain lengths of corresponding alcohols and alkanes, the alcohol molar fraction in the monolayers formed, and the shift of the alkane molecules with respect to the alcohol molecules Δn. Two possible competitive structures of mixed 2D film alkane-alcohol are considered: 2D films 1 with single alcohol molecules enclosed by alkane molecules (the alcohols do not form domains) and 2D films 2 that contain alcohol domains enclosed by alkane molecules. The formation of the alkane films of the first type is nearly independent of the surfactant type present at the interface, but depends on their molar fraction in the monolayer formed and the chain length of the compounds participating in the clusterization, whereas for the formation of the films of the second type the interaction between the hydrophilic parts of the surfactant is

  16. Growth of n-alkane films on a single-crystal substrate

    DEFF Research Database (Denmark)

    Wu, Z. U.; Ehrlich, S. N.; Matthies, B.

    2001-01-01

    The structure and growth mode of alkane films (n-C/sub n/H/sub 2n+2/; n=4, 6, 7) adsorbed on a Ag(111) surface have been investigated by synchrotron X-ray scattering. New models are proposed for the butane (n=4) and hexane (n=6) monolayer and butane bilayer structures. Specular reflectivity scans...... reveal that growth of all films is preempted between two and three layers by nucleation of bulk particles oriented with a single bulk crystal plane parallel to the film. In the case of butane, the bulk particles also have a fixed azimuthal relationship with the film resulting in complete epitaxy....

  17. Molecular-dynamics study of the dynamical excitations in commensurate monolayer films of nitrogen molecules on graphite: A test of the corrugation in the nitrogen-graphite potential

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Bruch, Ludwig Walter

    1995-01-01

    The dynamical excitations in a commensurate monolayer solid of N2 molecules adsorbed on graphite have been studied using molecular-dynamics simulations. Velocity and rotational correlation functions as well as coherent intermediate scattering functions and dynamical structure factors have been ca...

  18. Structural Insights into Diversity and n-Alkane Biodegradation Mechanisms of Alkane Hydroxylases

    Directory of Open Access Journals (Sweden)

    Yurui eJi

    2013-03-01

    Full Text Available 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 analyses, 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.

  19. Lateral pressure profiles in lipid monolayers

    NARCIS (Netherlands)

    Baoukina, Svetlana; Marrink, Siewert J.; Tieleman, D. Peter

    2010-01-01

    We have used molecular dynamics simulations with coarse-grained and atomistic models to study the lateral pressure profiles in lipid monolayers. We first consider simple oil/air and oil/water interfaces, and then proceed to lipid monolayers at air/water and oil/water interfaces. The results are

  20. Quasielastic neutron scattering and molecular dynamics simulation studies of the melting transition in butane and hexane monolayers adsorbed on graphite

    DEFF Research Database (Denmark)

    Hervig, K.W.; Wu, Z.; Dai, P.

    1997-01-01

    Quasielastic neutron scattering experiments and molecular dynamics (MD) simulations have been used to investigate molecular diffusive motion near the melting transition of monolayers of flexible rod-shaped molecules. The experiments were conducted on butane and hexane monolayers adsorbed...... comparison with experiment, quasielastic spectra calculated from the MD simulations were analyzed using the same models and fitting algorithms as for the neutron spectra. This combination of techniques gives a microscopic picture of the melting process in these two monolayers which is consistent with earlier...... neutron diffraction experiments. Butane melts abruptly to a liquid phase where the molecules in the trans conformation translationally diffuse while rotating about their center of mass. In the case of the hexane monolayer, the MD simulations show that the appearance of quasielastic scattering below T...

  1. Evaluation of n-alkanes and their carbon isotope enrichments (d13C) as diet composition markers

    NARCIS (Netherlands)

    Derseh, M.B.; Pellikaan, W.F.; Tolera, A.; Hendriks, W.H.

    2011-01-01

    Plant cuticular n-alkanes have been successfully used as markers to estimate diet composition and intake of grazing herbivores. However, additional markers may be required under grazing conditions in botanically diverse vegetation. This study was conducted to describe the n-alkane profiles and the

  2. The Electronic Properties of O-Doped Pure and Sulfur Vacancy-Defect Monolayer WS₂: A First-Principles Study.

    Science.gov (United States)

    Wang, Weidong; Bai, Liwen; Yang, Chenguang; Fan, Kangqi; Xie, Yong; Li, Minglin

    2018-01-31

    Based on the density functional theory (DFT), the electronic properties of O-doped pure and sulfur vacancy-defect monolayer WS₂ are investigated by using the first-principles method. For the O-doped pure monolayer WS₂, four sizes (2 × 2 × 1, 3 × 3 × 1, 4 × 4 × 1 and 5 × 5 × 1) of supercell are discussed to probe the effects of O doping concentration on the electronic structure. For the 2 × 2 × 1 supercell with 12.5% O doping concentration, the band gap of O-doped pure WS₂ is reduced by 8.9% displaying an indirect band gap. The band gaps in 3 × 3 × 1 and 4 × 4 × 1 supercells are both opened to some extent, respectively, for 5.55% and 3.13% O doping concentrations, while the band gap in 5 × 5 × 1 supercell with 2.0% O doping concentration is quite close to that of the pure monolayer WS₂. Then, two typical point defects, including sulfur single-vacancy (V S ) and sulfur divacancy (V 2S ), are introduced to probe the influences of O doping on the electronic properties of WS₂ monolayers. The observations from DFT calculations show that O doping can broaden the band gap of monolayer WS₂ with V S defect to a certain degree, but weaken the band gap of monolayer WS₂ with V 2S defect. Doping O element into either pure or sulfur vacancy-defect monolayer WS₂ cannot change their band gaps significantly, however, it still can be regarded as a potential method to slightly tune the electronic properties of monolayer WS₂.

  3. Thermodynamic and structural study of two-dimensional melting within monolayers or rare gases or methane physically adsorbed upon the surface of layer-like solids

    International Nuclear Information System (INIS)

    Tessier, Christine

    1983-01-01

    The 2D (two-dimensional) melting of monolayers of rare gases or methane physically adsorbed on the basal face of lamellar solids (graphite, boron nitride and lamellar halides) has been studied. Two different experimental measurements have been made: i) adsorption isotherms; ii) neutron diffraction spectra. The main part of this report deals with the 2D liquid-incommensurate solid transition within monolayers of rare gases or methane adsorbed on the basal face of lamellar halides. This transition is first order. It is observed only if certain conditions of dimensional incompatibility between the substrate and the absorbate are fulfilled. It is little affected by the structure of the underlying substrate. A number of thermodynamic parameters associated with it, are constants once properly scaled. These constants agree well with theoretical estimates for 6-12 Lennard Jones particles adsorbed on a smooth surface. For the monolayer of Xe adsorbed on graphite the temperature of the tricritical point above which melting becomes a continuous transition has been measured. The isotope effect associated with 2D melting has been investigated by comparing the behaviour of monolayers of CH 4 and CD 4 adsorbed on boron nitride. The vapor pressure of Xe has been determined in the temperature range 101-120 K. (author) [fr

  4. Optimization of linear and branched alkane interactions with water to simulate hydrophobic hydration

    Science.gov (United States)

    Ashbaugh, Henry S.; Liu, Lixin; Surampudi, Lalitanand N.

    2011-08-01

    Previous studies of simple gas hydration have demonstrated that the accuracy of molecular simulations at capturing the thermodynamic signatures of hydrophobic hydration is linked both to the fidelity of the water model at replicating the experimental liquid density at ambient pressure and an accounting of polarization interactions between the solute and water. We extend those studies to examine alkane hydration using the transferable potentials for phase equilibria united-atom model for linear and branched alkanes, developed to reproduce alkane phase behavior, and the TIP4P/2005 model for water, which provides one of the best descriptions of liquid water for the available fixed-point charge models. Alkane site/water oxygen Lennard-Jones cross interactions were optimized to reproduce the experimental alkane hydration free energies over a range of temperatures. The optimized model reproduces the hydration free energies of the fitted alkanes with a root mean square difference between simulation and experiment of 0.06 kcal/mol over a wide temperature range, compared to 0.44 kcal/mol for the parent model. The optimized model accurately reproduces the temperature dependence of hydrophobic hydration, as characterized by the hydration enthalpies, entropies, and heat capacities, as well as the pressure response, as characterized by partial molar volumes.

  5. Transport properties in monolayer-bilayer-monolayer graphene planar junctions

    Institute of Scientific and Technical Information of China (English)

    Kai-Long Chu; Zi-Bo Wang; Jiao-Jiao Zhou; Hua Jiang

    2017-01-01

    The transport study of graphene based junctions has become one of the focuses in graphene research.There are two stacking configurations for monolayer-bilayer-monolayer graphene planar junctions.One is the two monolayer graphene contacting the same side of the bilayer graphene,and the other is the two-monolayer graphene contacting the different layers of the bilayer graphene.In this paper,according to the Landauer-Büttiker formula,we study the transport properties of these two configurations.The influences of the local gate potential in each part,the bias potential in bilayer graphene,the disorder and external magnetic field on conductance are obtained.We find the conductances of the two configurations can be manipulated by all of these effects.Especially,one can distinguish the two stacking configurations by introducing the bias potential into the bilayer graphene.The strong disorder and the external magnetic field will make the two stacking configurations indistinguishable in the transport experiment.

  6. Oxidative dehydrogenation of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany); Hartmann, D.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany)

    2012-07-01

    The demand of light olefins increases steadily and the current steam cracking production is highly energy demanding. This motivates the development of alternative production processes like the oxidative dehydrogenation (ODH) of light alkanes operating at comparably low temperatures. Multi-component oxides are reported to show excellent catalytic performance in the ODH. Especially, MoVTeNbO oxides present high activity and selectivity in ODH of ethane. Synthesis of MoVTeNb oxides was done by a hydrothermal method. Qualitative and quantitative phase analysis were performed by X-ray diffraction and Rietveld refinement. Surface compositions were determined by Low energy ion scattering (LEIS). Catalytic tests were carried out in a fixed bed plug flow reactor using ethane and oxygen diluted in helium, as gaseous feed. Based on laboratory investigations a first upscale to a bench-top-pilot unit was performed in order to evaluate the large scale and long term feasibility of the process under technically relevant conditions. MoVTeNb oxides show high activity combined with excellent selectivity in the ODH of ethane to ethylene (S > 95% at X < 40%). Phase analysis reveals the presence of M1, M2 and amorphous phases. Literature reports the crystalline M1 phase as essential for the performance. Indeed, the crystalline M1 phase impacts on the activity via exposing V on the surface being apparently vital to achieve an active material. A correlation of the apparent activation energy with the surface vanadium composition of the catalysts is noticed, however, surprisingly with no major impact on the ethene selectivity. As this material was identified as most promising for a technical application a scale up from less than 1g to 50g of catalyst was performed in a bench-top-pilot unit. The reaction has a significant adiabatic temperature rise and the handling of the reaction heat is a major challenge for process engineering. Furthermore different diluent media such as Helium, Nitrogen

  7. Thermodiffusion in multicomponent n-alkane mixtures.

    Science.gov (United States)

    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.

  8. Adsorption of gas molecules on Cu impurities embedded monolayer MoS{sub 2}: A first- principles study

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, B.; Li, C.Y. [Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan 430072 (China); Liu, L.L. [Key Lab for Special Functional Materials of Ministry of Eduaction, Henan Province, Henan University, Kaifeng 475004 (China); Zhou, B.; Zhang, Q.K. [Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan 430072 (China); Chen, Z.Q., E-mail: chenzq@whu.edu.cn [Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan 430072 (China); Tang, Z., E-mail: ztang@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education of China, East China Normal University, Shanghai 200241 (China)

    2016-09-30

    Highlights: • Embedded Cu atom is strongly constrained on the sulfur vacancy of monolayer MoS{sub 2}. • Transition-metal Cu atom can break the chemical inactivation of MoS{sub 2} surface. • MoS{sub 2}-Cu system is a promising for future application in gas molecules sensing. - Abstract: Adsorption of small gas molecules (O{sub 2}, NO, NO{sub 2} and NH{sub 3}) on transition-metal Cu atom embedded monolayer MoS{sub 2} was investigated by first-principles calculations based on the density-functional theory (DFT). The embedded Cu atom is strongly constrained on the sulfur vacancy of monolayer MoS{sub 2} with a high diffusion barrier. The stable adsorption geometry, charge transfer and electronic structures of these gas molecules on monolayer MoS{sub 2} embedded with transition-metal Cu atom are discussed in detail. It is found that the monolayer MoS{sub 2} with embedded Cu atom can effectively capture these gas molecules with high adsorption energy. The NH{sub 3} molecule acts as electron donor after adsorption, which is different from the other gas molecules (O{sub 2}, NO, and NO{sub 2}). The results suggest that MoS{sub 2}-Cu system may be promising for future applications in gas molecules sensing and catalysis, which is similar to those of the transition-metal embedded graphene.

  9. Enzymes and Genes Involved in Aerobic Alkane Degradation

    Directory of Open Access Journals (Sweden)

    Zongze eShao

    2013-05-01

    Full Text Available Alkanes are major constituents of crude oil. They are also present at low concentrations in diverse non-contaminated because many living organisms produce them as chemo-attractants or as protecting agents against water loss. Alkane degradation is a widespread phenomenon in nature. The numerous microorganisms, both prokaryotic and eukaryotic, capable of utilizing alkanes as a carbon and energy source, have been isolated and characterized. This review summarizes the current knowledge of how bacteria metabolize alkanes aerobically, with a particular emphasis on the oxidation of long-chain alkanes, including factors that are responsible for chemotaxis to alkanes , transport across cell membrane of alkanes , the regulation of alkane degradation gene and initial oxidation.

  10. A study of the inhibiton of copper corrosion by triethyl phosphate and triphenyl phosphate self-assembled monolayers

    Directory of Open Access Journals (Sweden)

    HOUYI MA

    2006-02-01

    Full Text Available Two kinds of phosphates, triethyl phosphate (TEP and triphenyl phosphate (TPP, were used to form self-assembled monolayers for the inhibition of the corrosion of copper in 0.2 mol dm–3 NaCl solution. Electrochemical impedance spectroscopy (EIS was applied to investigate the inhibition effects. The results showed that their inhibition ability first increased with increasing immersion time in ethanolic solutions of the corresponding compounds. However, when the immersion time was increased over some critical point, the inhibition effect decreased. For the same immersion time, the inhibition effect of the TPP monolayer was more pronounced than that of the TEP monolayer. Thus, ab initio calculations were used to interpret the relationship between the inhibition effects and the structures of the compounds.

  11. Self-assembled monolayers with different chemical group substrates for the study of MCF-7 breast cancer cell line behavior

    International Nuclear Information System (INIS)

    Yan, Hongji; Yin, Yanbin; Li, Yu; Tian, Weiming; Zhang, Song; Nie, Yongzhan; He, Jin; Wang, Xiumei; Cui, Fuzhai; Chen, Xiongbiao

    2013-01-01

    The interactions between cancer cells and the extracellular matrix (ECM) are important with respect to a number of cell behavoirs, yet remain unclear. In this study, self-assembled monolayers with different terminal chemical groups (hydroxyl (-OH), carboxyl (-COOH), animo (-NH 2 ), mercapto (-SH), and methyl (-CH 3 )) were employed as substrates for the culture of MCF-7 cells to examine effects on cell behavior. Cell spreading was investigated by scanning electron microscopy, tallin expression by immunofluorescence, proliferation rate by counting cell numbers, cell cycle by flow cytometry, metabolism by high-performance liquid chromatography and cell migration by live cell imaging. Annexin V-FITC (fluorescein isothiocyanate) and JC-1 assays were performed to determine cell apoptosis and mitochondrial membrane potential, respectively. Our results demonstrate the varied behaviors of MCF-7 cells in response to different chemical groups. Specifically, NH 2 and COOH terminal functional groups promote proliferation, the production of lactic acid and mobility of MCF-7 cells; SH and OH terminal groups enhance the expression and distribution of tallin but result in weak cell proliferation, metabolism, spreading and mobility. These results are meaningful for uncovering the interactions between the ECM and cancer cells; they are potentially useful for designing novel cancer treatment strategies. (paper)

  12. Adsorption of 3d transition metal atoms on graphene-like gallium nitride monolayer: A first-principles study

    Science.gov (United States)

    Chen, Guo-Xiang; Li, Han-Fei; Yang, Xu; Wen, Jun-Qing; Pang, Qing; Zhang, Jian-Min

    2018-03-01

    We study the structural, electronic and magnetic properties of 3d transition metal (TM) atoms (Cr, Mn, Fe, Co, Ni and Cu) adsorbed GaN monolayer (GaN-ML) using first-principles calculations. The results show that, for 6 different TM adatoms, the most stable adsorption sites are the same. The adsorption of TM atoms results in significant lattice distortions. A covalent chemical bonding character between TM adatom and GaN-ML is found in TM adsorbed systems. Except for Ni adsorbed system, all TM adsorbed systems show spin polarization implying that the adsorption of TM induces magnetization. The magnetic moments of the adsorbed systems are concentrated on the TM adatoms and the nearest-neighbor N atoms of the adsorption site contributed slightly. Our analysis shows that the GaN-ML properties can be effectively modulated by TM adsorption, and exhibit various electronic and magnetic properties, such as magnetic metals (Fe adsorption), half-metal (Co adsorption), and spin gapless semiconductor (Cu adsorption). These present properties of TM adsorbed GaN-ML may be of value in electronics and spintronics applications.

  13. A real-time Raman spectroscopy study of the dynamics of laser-thinning of MoS2 flakes to monolayers

    Science.gov (United States)

    Gu, Enyao; Wang, Qiyuan; Zhang, Youwei; Cong, Chunxiao; Hu, Laigui; Tian, Pengfei; Liu, Ran; Zhang, Shi-Li; Qiu, Zhi-Jun

    2017-12-01

    Transition metal dichalcogenides (TMDCs) in monolayer form have attracted a great deal of attention for electronic and optical applications. Compared to mechanical exfoliation and chemical synthesis, laser thinning is a novel and unique "on-demand" approach to fabricate monolayers or pattern desired shapes with high controllability and reproducibility. Its successful demonstration motivates a further exploration of the dynamic behaviour of this local thinning process. Here, we present an in-situ study of void formation by laser irradiation with the assistance of temporal Raman evolution. In the analysis of time-dependent Raman intensity, an empirical formula relating void size to laser power and exposure time is established. Void in thinner MoS2 flakes grows faster than in thicker ones as a result of reduced sublimation temperature in the two-dimensional (2D) materials. Our study provides useful insights into the laser-thinning dynamics of 2D TMDCs and guidelines for an effective control over the void formation.

  14. Transport mechanisms and wetting dynamics in molecularly thin films of long-chain alkanes at solid/vapour interface : relation to the solid-liquid phase transition

    OpenAIRE

    Lazar, Paul

    2005-01-01

    Wetting and phase transitions play a very important role our daily life. Molecularly thin films of long-chain alkanes at solid/vapour interfaces (e.g. C30H62 on silicon wafers) are very good model systems for studying the relation between wetting behaviour and (bulk) phase transitions. Immediately above the bulk melting temperature the alkanes wet partially the surface (drops). In this temperature range the substrate surface is covered with a molecularly thin ordered, solid-like alkane film (...

  15. A quasi-time-resolved CryoTEM study of the nucleation of CaCO3 under Langmuir monolayers

    NARCIS (Netherlands)

    Pichon, B.P.R.; Bomans, P.H.H.; Frederik, P.M.; Sommerdijk, N.A.J.M.

    2008-01-01

    Calcium carbonate biomineralization uses complex assemblies of macromolecules that control the nucleation, growth, and positioning of the mineral with great detail. To investigate the mechanisms involved in these processes, for many years Langmuir monolayers have been used as model systems. Here, we

  16. Phase transitions in diglyceride monolayers studied by computer simulations, pressure-area isotherms and x-ray diffraction

    DEFF Research Database (Denmark)

    Peters, Günther H.J.; Toxværd, S.; Larsen, N.B.

    1994-01-01

    1,2-sn-diglyceride monolayers exhibit unique and complex phase transitions as a function of surface pressure. The dynamical response of the layer on expanding the film has been investigated by computer simulations, (π-A) isotherms and grazing-incidence X-ray diffraction. Good agreement is found b...

  17. Dark excitations in monolayer transition metal dichalcogenides

    DEFF Research Database (Denmark)

    Deilmann, Thorsten; Thygesen, Kristian Sommer

    2017-01-01

    Monolayers of transition metal dichalcogenides (TMDCs) possess unique optoelectronic properties, including strongly bound excitons and trions. To date, most studies have focused on optically active excitations, but recent experiments have highlighted the existence of dark states, which are equally...

  18. Effect of dispersion on surface interactions of cobalt(II) octaethylporphyrin monolayer on Au(111) and HOPG(0001) substrates: a comparative first principles study.

    Science.gov (United States)

    Chilukuri, Bhaskar; Mazur, Ursula; Hipps, K W

    2014-07-21

    A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly to Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff-Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin-substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.

  19. Adsorption studies of alcohol molecules on monolayer MoS_2 nanosheet—A first-principles insights

    International Nuclear Information System (INIS)

    Nagarajan, V.; Chandiramouli, R.

    2017-01-01

    Highlights: • The adsorption of methanol, ethanol & 1-propanol on MoS_2 nanosheet are studied. • The PDOS & band structure confirms adsorption of alcohol vapors on MoS_2 nanosheet. • The adsorption of 1-propanol vapor on MoS_2 nanosheet is more favorable. • The alcohol molecules adsorption on MoS_2 nanosheet is explored in atomistic level. - Abstract: The electronic and adsorption properties of three different alcohol molecules namely methanol, ethanol and 1-propanol vapors on MoS_2 nanosheet is investigated using DFT method. The structural stability of MoS_2 nanosheet is ascertained with formation energy. The adsorption properties of alcohol molecules on MoS_2 base material is discussed in terms of average energy gap variation, Mulliken charge transfer, energy band gap and adsorption energy. The prominent adsorption sites of methanol, ethanol and 1-propanol vapors on MoS_2 nanosheet are studied in atomistic level. The projected density of states (PDOS) spectrum gives the clear insights on the electronic properties of MoS_2 nanosheet. The PDOS and energy band structure confirmed the adsorption of alcohol vapors on MoS_2 nanosheet. The variation in the band structure and PDOS is noticed upon adsorption of methanol, ethanol and 1-propanol molecules on MoS_2 nanosheet. The PDOS spectrum also reveals the variation in peak maxima owing to transfer of electron between alcohol molecules and MoS_2 base material. The adsorption of 1-propanol vapor on MoS_2 nanosheet is observed to be more favorable than other alcohol molecules. The findings confirm that monolayer MoS_2 nanosheet can be used to detect the presence of alcohol vapors in the environment.

  20. Adsorption studies of alcohol molecules on monolayer MoS{sub 2} nanosheet—A first-principles insights

    Energy Technology Data Exchange (ETDEWEB)

    Nagarajan, V.; Chandiramouli, R., E-mail: rcmoulii@gmail.com

    2017-08-15

    Highlights: • The adsorption of methanol, ethanol & 1-propanol on MoS{sub 2} nanosheet are studied. • The PDOS & band structure confirms adsorption of alcohol vapors on MoS{sub 2} nanosheet. • The adsorption of 1-propanol vapor on MoS{sub 2} nanosheet is more favorable. • The alcohol molecules adsorption on MoS{sub 2} nanosheet is explored in atomistic level. - Abstract: The electronic and adsorption properties of three different alcohol molecules namely methanol, ethanol and 1-propanol vapors on MoS{sub 2} nanosheet is investigated using DFT method. The structural stability of MoS{sub 2} nanosheet is ascertained with formation energy. The adsorption properties of alcohol molecules on MoS{sub 2} base material is discussed in terms of average energy gap variation, Mulliken charge transfer, energy band gap and adsorption energy. The prominent adsorption sites of methanol, ethanol and 1-propanol vapors on MoS{sub 2} nanosheet are studied in atomistic level. The projected density of states (PDOS) spectrum gives the clear insights on the electronic properties of MoS{sub 2} nanosheet. The PDOS and energy band structure confirmed the adsorption of alcohol vapors on MoS{sub 2} nanosheet. The variation in the band structure and PDOS is noticed upon adsorption of methanol, ethanol and 1-propanol molecules on MoS{sub 2} nanosheet. The PDOS spectrum also reveals the variation in peak maxima owing to transfer of electron between alcohol molecules and MoS{sub 2} base material. The adsorption of 1-propanol vapor on MoS{sub 2} nanosheet is observed to be more favorable than other alcohol molecules. The findings confirm that monolayer MoS{sub 2} nanosheet can be used to detect the presence of alcohol vapors in the environment.

  1. Diamondoid monolayers as electron emitters

    Science.gov (United States)

    Yang, Wanli [El Cerrito, CA; Fabbri, Jason D [San Francisco, CA; Melosh, Nicholas A [Menlo Park, CA; Hussain, Zahid [Orinda, CA; Shen, Zhi-Xun [Stanford, CA

    2012-04-10

    Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

  2. Experimental Investigation Of Microbially Induced Corrosion Of Test Samples And Effect Of Self-assembled Hydrophobic Monolayers. Exposure Of Test Samples To Continuous Microbial Cultures, Chemical Analysis, And Biochemical Studies

    CERN Document Server

    Laurinavichius, K S

    1998-01-01

    Experimental Investigation Of Microbially Induced Corrosion Of Test Samples And Effect Of Self-assembled Hydrophobic Monolayers. Exposure Of Test Samples To Continuous Microbial Cultures, Chemical Analysis, And Biochemical Studies

  3. Elastic properties of surfactant monolayers at liquid-liquid interfaces: A molecular dynamics study

    DEFF Research Database (Denmark)

    Laradji, Mohamed; Mouritsen, Ole G.

    2000-01-01

    Using a simple molecular model based on the Lennard-Jones potential, we systematically study the elastic properties of liquid-liquid interfaces containing surfactant molecules by means of extensive and large-scale molecular dynamics simulations. The main elastic constants of the interface, corres...

  4. Poly(diacetylene) Monolayers Studied with a Fluorescence Scanning Near-Field Optical Microscope

    NARCIS (Netherlands)

    Moers, Marco H.P.; Moers, M.H.P.; Gaub, Hermann E.; van Hulst, N.F.

    1994-01-01

    A novel and powerful method to study the optical properties of thin lipid films which a resolution superior to confocal microscopy is presented. With a scanning near-field optical microscope, fluorescence images of a Langmuir-Blodgett film of diethylene glycol diamine pentacosadiynoic amide are

  5. A comparative study of the growth of octadecyltrichlorosilane and 3-mercaptopropyltrimethoxysilane self-assembled monolayers on hydrophilic silicon surfaces

    International Nuclear Information System (INIS)

    Yang, S.-R.; Kolbesen, Bernd O.

    2008-01-01

    Self-assembled monolayers of two different organosilane precursors, methyl-terminated nonpolar n-octadecyltrichlorosilane (OTS, Cl 3 Si(CH 2 ) 17 CH 3 ) and thiol-terminated polar 3-mercaptopropyltrimethoxysilane (MPTMS, (CH 3 O) 3 SiCH 2 CH 2 CH 2 SH), were prepared separately on hydrophilic silicon surfaces by immersion in millimolar solutions of the respective precursors in toluene at room temperature. Ex situ atomic force microscopy (AFM), lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to study the growth and the properties of OTS and MPTMS SAMs. For OTS SAMs, generally speaking, small islands surrounded large dendrite-shaped islands. But for MPTMS SAMs, sporadic small round islands appeared, but no dendrites. The impact of the solution age was more significant on the growth of OTS SAMs than MPTMS SAMs. At the same precursor concentration and solution age, the growth of OTS SAMs was much faster than MPTMS SAMs due to the greater hydrolysis ability of Si-Cl bonds in OTS as compared with that of Si-OCH 3 bonds in MPTMS. The difference in hydrolysis ability was confirmed by the absence of a Cl signal in the XP spectrum of OTS SAMs and the existence of a C 1s peak corresponding to unhydrolyzed Si-OCH 3 bonds in the XP spectrum of MPTMS SAMs. This trend together with the difference in alkyl chain length had a strong influence on the surface morphology and coverage of these two SAMs. According to the individual adsorption behavior of the components, the predictable kinetic difficulty of preparing OTS/MPTMS mixed SAMs by co-adsorption is pointed out. Furthermore, a potential reaction condition for stepwise adsorption is suggested.

  6. Eukaryotic expression system Pichia pastoris affects the lipase catalytic properties: a monolayer study.

    Directory of Open Access Journals (Sweden)

    Madiha Bou Ali

    Full Text Available Recombinant DNA methods are being widely used to express proteins in both prokaryotic and eukaryotic cells for both fundamental and applied research purposes. Expressed protein must be well characterized to be sure that it retains the same properties as the native one, especially when expressed protein will be used in the pharmaceutical field. In this aim, interfacial and kinetic properties of native, untagged recombinant and tagged recombinant forms of a pancreatic lipase were compared using the monomolecular film technique. Turkey pancreatic lipase (TPL was chosen as model. A kinetic study on the dependence of the stereoselectivity of these three forms on the surface pressure was performed using three dicaprin isomers spread in the form of monomolecular films at the air-water interface. The heterologous expression and the N-His-tag extension were found to modify the pressure preference and decrease the catalytic hydrolysis rate of three dicaprin isomers. Besides, the heterologous expression was found to change the TPL regioselectivity without affecting its stereospecificity contrary to the N-tag extension which retained that regioselectivity and changed the stereospecificity at high surface pressures. The study of parameters, termed Recombinant expression Effects on Catalysis (REC, N-Tag Effects on Catalysis (TEC, and N-Tag and Recombinant expression Effects on Catalysis (TREC showed that the heterologous expression effects on the catalytic properties of the TPL were more deleterious than the presence of an N-terminal tag extension.

  7. Scanning tunneling microscopy studies of organic monolayers adsorbed on the rhodium(111) crystal surface

    Energy Technology Data Exchange (ETDEWEB)

    Cernota, Paul Davis [Univ. of California, Berkeley, CA (United States)

    1999-08-01

    Scanning Tunneling Microscopy studies were carried out on ordered overlayers on the (111) surface of rhodium. These adsorbates include carbon monoxide (CO), cyclohexane, cyclohexene, 1,4-cyclohexadiene, para-xylene, and meta-xylene. Coadsorbate systems included: CO with ethylidyne, CO with para- and meta-xylene, and para-xylene with meta-xylene. In the case of CO, the structure of the low coverage (2x2) overlayer has been observed. The symmetry of the unit cell in this layer suggests that the CO is adsorbed in the 3-fold hollow sites. There were also two higher coverage surface structures with (√7x√7) unit cells. One of these is composed of trimers of CO and has three CO molecules in each unit cell. The other structure has an additional CO molecule, making a total of four. This extra CO sits on a top site.

  8. First-Principles Study of Structure Property Relationships of Monolayer (Hydroxy)Oxide-Metal Bifunctional Electrocatalysts

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Kubal, Joseph; Greeley, Jeffrey Philip

    2015-01-01

    step towards accurate identification and prediction of a variety of oxide/electrode interfacial structure-properties relationships, but also provides the foundation for rational design and control of ‘targeted active phases’ at catalytic interfaces. The successful design of bifunctional......In the present study, on the basis of detailed density functional theory (DFT) calculations, and using Ni hydroxy(oxide) films on Pt(111) and Au(111) electrodes as model systems, we describe a detailed structural and electrocatalytic analysis of hydrogen evolution (HER) at three-phase boundaries...... under alkaline electrochemical conditions. We demonstrate that the structure and oxidation state of the films can be systematically tuned by changing the applied electrode potential and/or the nature of substrates. Structural features determined from the theoretical calculations provide a wealth...

  9. First-principles studies on the effects of halogen adsorption on monolayer antimony.

    Science.gov (United States)

    Yeoh, Keat Hoe; Yoon, Tiem Leong; Ong, Duu Sheng; Lim, Thong Leng; Zuntu Abdullahi, Yusuf

    2017-09-27

    Using first-principles calculations, we carry out systematic studies on the electronic, magnetic and structural properties of halogenated β-phase antimonene. We consider two different levels of halogen adatom coverage i.e. Θ = 1/8 and Θ = 1/18. It is found that F, Cl and Br adatoms act as acceptors whereas the I adatom acts as a donor. For a high coverage of Θ = 1/8, halogenated β-phase antimonene exhibits metallic characteristics. With a lower coverage of Θ = 1/18, through the adsorption of F, Cl and Br the semiconducting unstrained antimonene becomes metallic. In contrast, I-adsorbed antimonene remains semiconducting but exhibits magnetic behavior. We further investigate the effects of bi-axial strain on the halogenated β-phase antimonene. It is found that bi-axial strain can only induce ferromagnetism on the halogenated antimonene at Θ = 1/18. However, the ferromagnetism is suppressed when the applied strain is high. We uncover that the emergence of strain-dependent magnetism is attributed to the presence of localized states in the bandgap resulting from collective effects of bi-axial strain and the adsorption of halogen atoms.

  10. Saponin Interactions with Model Membrane Systems - Langmuir Monolayer Studies, Hemolysis and Formation of ISCOMs.

    Science.gov (United States)

    de Groot, Carolin; Müller-Goymann, Christel C

    2016-12-01

    Saponins are used in medicine due to their pharmacological and immunological effects. To better understand interactions of saponins with model membranes and natural membranes of, for example, erythrocytes, Langmuir film balance experiments are well established. For most saponins, a strong interaction with cholesterol was demonstrated in dependence of both the aglycone part and the sugar moieties and is suggested to be correlated with a strong hemolytic activity, high toxicity, and high surface activity, as was demonstrated for the steroid saponin digitonin. In general, changes in the sugar chain or in substituents of the aglycone result in a modification of the saponin properties. A promising saponin with regard to fairly low hemolytic activity and high adjuvant effect is α -tomatine, which still shows a high affinity for cholesterol. An interaction with cholesterol and lipids has also been proven for the Quillaja saponin from the bark of Quillaja saponaria Molina. This triterpene saponin was approved in marketed vaccines as an adjuvant due to the formation of immunostimulating complexes. Immunostimulating complexes consist of a Quillaja saponin, cholesterol, phospholipids, and a corresponding antigen. Recently, another saponin from Quillaja brasiliensis was successfully tested in immunostimulating complexes, too. Based on the results of interaction studies, the formation of drug delivery systems such as immunostimulating complexes or similar self-assembled colloids is postulated for a variety of saponins. Georg Thieme Verlag KG Stuttgart · New York.

  11. Alkanes as Components of Soil Hydrocarbon Status: Behavior and Indication Significance

    Science.gov (United States)

    Gennadiev, A. N.; Zavgorodnyaya, Yu. A.; Pikovskii, Yu. I.; Smirnova, M. A.

    2018-01-01

    Studies of soils on three key plots with different climatic conditions and technogenic impacts in Volgograd, Moscow, and Arkhangelsk oblasts have showed that alkanes in the soil exchange complex have some indication potential for the identification of soil processes. The following combinations of soil-forming factors and processes have been studied: (a) self-purification of soil after oil pollution; (b) accumulation of hydrocarbons coming from the atmosphere to soils of different land use patterns; and (c) changes in the soil hydrocarbon complex beyond the zone of technogenic impact due to the input of free hydrocarbon-containing gases. At the injection input of hydrocarbon pollutants, changes in the composition and proportions of alkanes allow tracing the degradation trend of pollutants in the soil from their initial content to the final stage of soil self-purification, when the background concentrations of hydrocarbons are reached. Upon atmospheric deposition of hydrocarbons onto the soil, from the composition and mass distribution of alkanes, conclusions can be drawn about the effect of toxicants on biogeochemical processes in the soil, including their manifestation under different land uses. Composition analysis of soil alkanes in natural landscapes can reveal signs of hydrocarbon emanation fluxes in soils. The indication potentials of alkanes in combination with polycyclic aromatic hydrocarbons and other components of soil hydrocarbon complex can also be used for the solution of other soil-geochemical problems.

  12. Leaf wax n-alkane distributions in and across modern plants: Implications for paleoecology and chemotaxonomy

    Science.gov (United States)

    Bush, Rosemary T.; McInerney, Francesca A.

    2013-09-01

    Long chain (C21 to C37) n-alkanes are among the most long-lived and widely utilized terrestrial plant biomarkers. Dozens of studies have examined the range and variation of n-alkane chain-length abundances in modern plants from around the world, and n-alkane distributions have been used for a variety of purposes in paleoclimatology and paleoecology as well as chemotaxonomy. However, most of the paleoecological applications of n-alkane distributions have been based on a narrow set of modern data that cannot address intra- and inter-plant variability. Here, we present the results of a study using trees from near Chicago, IL, USA, as well as a meta-analysis of published data on modern plant n-alkane distributions. First, we test the conformity of n-alkane distributions in mature leaves across the canopy of 38 individual plants from 24 species as well as across a single growing season and find no significant differences for either canopy position or time of leaf collection. Second, we compile 2093 observations from 86 sources, including the new data here, to examine the generalities of n-alkane parameters such as carbon preference index (CPI), average chain length (ACL), and chain-length ratios for different plant groups. We show that angiosperms generally produce more n-alkanes than do gymnosperms, supporting previous observations, and furthermore that CPI values show such variation in modern plants that it is prudent to discard the use of CPI as a quantitative indicator of n-alkane degradation in sediments. We also test the hypotheses that certain n-alkane chain lengths predominate in and therefore can be representative of particular plant groups, namely, C23 and C25 in Sphagnum mosses, C27 and C29 in woody plants, and C31 in graminoids (grasses). We find that chain-length distributions are highly variable within plant groups, such that chemotaxonomic distinctions between grasses and woody plants are difficult to make based on n-alkane abundances. In contrast

  13. Monolayer atomic crystal molecular superlattices

    Science.gov (United States)

    Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O.; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A., III; Huang, Yu; Duan, Xiangfeng

    2018-03-01

    Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 107, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

  14. Computational studies at the density functional theory (DFT) level about the surface functionalization of hexagonal monolayers by chitosan monomer

    Science.gov (United States)

    Ebrahimi, Javad; Ahangari, Morteza Ghorbanzadeh; Jahanshahi, Mohsen

    2018-05-01

    Theoretical investigations based on density functional theory have been carried out to understand the underlying interactions between the chitosan monomer and several types of hexagonal monolayers consisting of pristine and defected graphene and boron-nitride nanosheets. Based on the obtained results, it was found that the type of the interaction for all the systems is of non-covalent nature and the chitosan monomer physically interacts with the surface of mentioned nanostructures. The interaction strength was evaluated by calculating the adsorption energies for the considered systems and it was found that the adsorption of chitosan monomer accompanies by the release of about -0.67 and -0.66 eV energy for pristine graphene and h-BN monolayer, respectively. The role of structural defect has also been considered by embedding a Stone-Wales defect within the structure of mentioned monolayers and it was found that the introduced defect enhances the interactions between the chitosan monomer and nanostructures. The role of dispersion interactions has also been taken into account and it was found that these long-range interactions play the dominating role in the attachment of chitosan monomer onto the graphene sheet, while having strong contribution together with the electrostatic interactions for the stabilization of chitosan onto the surface of h-BN monolayer. For all the cases, the adsorption of chitosan monomer did not change the inherent electronic properties of the nanostructures based on the results of charge transfer analysis and energy gap calculations. The findings of the present work would be very useful in future investigations to explore the potential applications of these hybrid materials in materials science and bio-related fields.

  15. First-principles studies of Te line-ordered alloys in a MoS2 monolayer

    Science.gov (United States)

    Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

    2018-04-01

    The thermodynamic stability, structural and electronic properties of Te line-ordered alloys are investigated using density functional theory (DFT) methods. Thirty four possible Te line-ordered alloy configurations are found in a 5×5 supercell of a MoS2 monolayer. The calculated formation energies show that the Te line-ordered alloy configurations are thermodynamically stable at 0 K and agree very well with the random alloys. The lowest energy configurations at each concentration correspond to the configuration where the Te atom rows are far apart from each other (avoiding clustering) within the supercell. The variation of the lattice constant at different concentrations obey Vegard's law. The Te line-ordered alloys fine tune the band gap of a MoS2 monolayer although deviating from linearity behavior. Our results suggest that the Te line-ordered alloys can be an effective way to modulate the band gap of a MoS2 monolayer for nanoelectronic, optoelectronic and nanophotonic applications.

  16. Well-ordered structure of methylene blue monolayers on Au(111) surface: electrochemical scanning tunneling microscopy studies.

    Science.gov (United States)

    Song, Yonghai; Wang, Li

    2009-02-01

    Well-ordered structure of methylene blue (MB) monolayers on Au(111) surface has been successfully obtained by controlling the substrate potential. Electrochemical scanning tunneling microscopy (ECSTM) examined the monolayers of MB on Au(111) in 0.1 M HClO(4) and showed long-range ordered, interweaved arrays of MB with quadratic symmetry on the substrate in the potential range of double-layer charging. High-resolution ECSTM image further revealed the details of the MB monolayers structure of c(5 x 5 radical 3)rect and the flat-lying orientation of ad-molecules. The dependence of molecular organization on the substrate potential and the formation mechanism of well-ordered structure on Au(111) surface were investigated in detail. The obtained well-ordered structure at the interface between a metal and an aqueous electrolyte might possibly be used as high-density device for signal memory and templates for the advanced nanopatterning of surfaces. (c) 2008 Wiley-Liss, Inc.

  17. The wetting behavior of alkanes on water

    Energy Technology Data Exchange (ETDEWEB)

    Ragil, Karine; Broseta, Daniel; Kalaydjian, Francois [Institut Francais du Petrole, BP 311, 92852 Rueil Malmaison Cedex (France); Bonn, Daniel; Meunier, Jacques [ENS, Laboratoire de Physique Statistique, 24 rue Lhomond, 75231 Paris Cedex 05 (France); Indekeu, Joseph [Katholieke Universiteit Leuven, Laboratorium voor Vaste-Stoffysica en Magnetisme, B-3001 Leuven (Belgium)

    1998-06-06

    This paper presents recent experimental and theoretical results concerning the wetting behavior of n-alkanes on water as a function of thermodynamic conditions (i.e., temperature, pressure, etc.). The transition from lenses to a macroscopically thick film, that takes place when the temperature is increased, occurs for n-alkanes on water in a manner very different from that encountered in other fluid systems. For n-pentane on water, ellipsometric measurements reveal that the growth of the pentane layer to a macroscopically thick film occurs in a continuous manner, for a temperature ({approx}53C) corresponding to a change in the sign of the Hamaker constant. A theoretical approach based on the Cahn-Landau theory, which takes into account long-range (van der Waals) forces, enables us to explain the mechanism of this continuous wetting transition. This transition is preceded (at a lower temperature) by a discontinuous transition from a thin film (of adsorbed molecules) to a thick (but not macroscopically thick) film. The latter transition was not visible for pentane on water (it should occur below the freezing temperature for water), but we expect to observe it for longer alkanes (e.g., hexane) on water. Work is underway to examine the wetting behavior of oil/brine systems more representative of reservoir conditions

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

    Science.gov (United States)

    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. Ligand-accelerated activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI)-nitrido complex.

    Science.gov (United States)

    Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Yiu, Shek-Man; Lau, Tai-Chu

    2012-09-03

    Kinetic and mechanistic studies on the intermolecular activation of strong C-H bonds of alkanes by a (salen)ruthenium(VI) nitride were performed. The initial, rate-limiting step, the hydrogen atom transfer (HAT) from the alkane to Ru(VI)≡N, generates Ru(V)=NH and RC·HCH(2)R. The following steps involve N-rebound and desaturation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Hydration of Sulphobetaine (SB) and Tetra(ethylene glycol) (EG4)-Terminated Self-Assembled Monolayers Studied by Sum Frequency Generation (SFG) Vibrational Spectroscopy

    Science.gov (United States)

    Stein, M. Jeanette; Weidner, Tobias; McCrea, Keith; Castner, David G.; Ratner, Buddy D.

    2010-01-01

    Sum frequency generation (SFG) vibrational spectroscopy is used to study the surface and the underlying substrate of both homogeneous and mixed self-assembled monolayers (SAMs) of 11-mercaptoundecyl-1-sulphobetainethiol (HS(CH2)11N+(CH3)2(CH2)3SO3−, SB) and 1-mercapto-11-undecyl tetra(ethylene glycol) (HS(CH2)11O(CH2CH2O)4OH, EG4) with an 11-mercapto-1-undecanol (HS(CH2)11OH, MCU) diluent. SFG results on the C–H region of the dry and hydrated SAMs gave an in situ look into the molecular orientation and suggested an approach to maximize signal-to-noise ratio on these difficult to analyze hydrophilic SAMs. Vibrational fingerprint studies in the 3000–3600 cm−1 spectral range for the SAMs exposed serially to air, water, and deuterated water revealed that a layer of tightly-bound structured water was associated with the surface of a non-fouling monolayer but was not present on a hydrophobic N-undecylmercaptan (HS(CH2)10CH3, UnD) control. The percentage of water retained upon submersion in D2O correlated well with the relative amount of protein that was previously shown to absorb onto the monolayers. These results provide evidence supporting the current theory regarding the role of a tightly-bound vicinal water layer in the protein resistance of a non-fouling group. PMID:19639981

  1. Functional screening of aldehyde decarbonylases for long-chain alkane production by Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Kang, Min-Kyoung; Zhou, Yongjin J.; Buijs, Nicolaas A.

    2017-01-01

    Background: Low catalytic activities of pathway enzymes are often a limitation when using microbial based chemical production. Recent studies indicated that the enzyme activity of aldehyde decarbonylase (AD) is a critical bottleneck for alkane biosynthesis in Saccharomyces cerevisiae. We therefore...... detected in other AD expressed yeast strains. Dynamic expression of SeADO and CwADO under GAL promoters increased alkane production to 0.20 mg/L/OD600 and no fatty alcohols, with even number chain lengths from C8 to C14, were detected in the cells. Conclusions: We demonstrated in vivo enzyme activities...

  2. WSe2 Monolayer

    KAUST Repository

    Zhang, Shuai; Wang, Chen-Guang; Li, Ming-yang; Huang, Di; Li, Lain-Jong; Ji, Wei; Wu, Shiwei

    2017-01-01

    dichalcogenide materials, intrinsic defects in WSe2 arise surprisingly from single tungsten vacancies, leading to the hole (p-type) doping. Furthermore, we found these defects to dominate the excitonic emission of the WSe2 monolayer at low temperature. Our work

  3. Alkanes as markers in nutritional studies with wild ruminant and non-ruminant animals Alcanos como indicadores em estudos nutricionais com ruminantes selvagens e animais não-ruminantes

    Directory of Open Access Journals (Sweden)

    Dimas Estrasulas de Oliveira

    2007-12-01

    Full Text Available Knowledge of information relative to the digestibility, intake and botanical and morphological composition of the diet is important in nutritional studies, since it provides the basis for understanding aspects related to the ingestive behavior and selectivity of animals. N-alkanes have been used successfully as markers in studies with many species of animals, particularly domesticated ruminants, most of the times as replacements for conventional markers as chromium oxide for example. However, for wild ruminants and non-ruminant animals information on this technique is still scarce and, as a consequence, its potential for use unknown. This review reports the use of this technique in studies of feed digestibility, intake and diet composition with wild ruminants and non-ruminant animals, summarizing results and inferring on the feasibility and applicability of the technique.O conhecimento de informações relativas à digestibilidade, consumo, composição botânica e morfológica da dieta é importante em estudos de nutrição, pois fornece a base para a compreensão de aspectos relativos ao comportamento ingestivo e a seletividade dos animais. N-alcanos têm sido usados com sucesso como indicadores em estudos com várias espécies de animais, particularmente ruminantes domésticos, muitas vezes como substitutos a marcadores convencionais como o cromo por exemplo. No entanto, no caso de ruminantes selvagens e animais não-ruminantes as informações sobre essa técnica são ainda escassas e, consequentemente, seu potencial de uso desconhecido. Esta revisão borda o uso dessa metodologia em estudos de digestibilidade, consumo e estimativa da composição da dieta em ruminantes selvagens e animais não-ruminantes, sumarizando resultados e inferindo sobre a viabilidade e aplicabilidade da técnica.

  4. n-Alkane assimilation and tert-butyl alcohol (TBA) oxidation capacity in Mycobacterium austroafricanum strains.

    Science.gov (United States)

    Lopes Ferreira, Nicolas; Mathis, Hugues; Labbé, Diane; Monot, Frédéric; Greer, Charles W; Fayolle-Guichard, Françoise

    2007-06-01

    Mycobacterium austroafricanum IFP 2012, which grows on methyl tert-butyl ether (MTBE) and on tert-butyl alcohol (TBA), the main intermediate of MTBE degradation, also grows on a broad range of n-alkanes (C2 to C16). A single alkB gene copy, encoding a non-heme alkane monooxygenase, was partially amplified from the genome of this bacterium. Its expression was induced after growth on n-propane, n-hexane, n-hexadecane and on TBA but not after growth on LB. The capacity of other fast-growing mycobacteria to grow on n-alkanes (C1 to C16) and to degrade TBA after growth on n-alkanes was compared to that of M. austroafricanum IFP 2012. We studied M. austroafricanum IFP 2012 and IFP 2015 able to grow on MTBE, M. austroafricanum IFP 2173 able to grow on isooctane, Mycobacterium sp. IFP 2009 able to grow on ethyl tert-butyl ether (ETBE), M. vaccae JOB5 (M. austroaafricanum ATCC 29678) able to degrade MTBE and TBA and M. smegmatis mc2 155 with no known degradation capacity towards fuel oxygenates. The M. austroafricanum strains grew on a broad range of n-alkanes and three were able to degrade TBA after growth on propane, hexane and hexadecane. An alkB gene was partially amplified from the genome of all mycobacteria and a sequence comparison demonstrated a close relationship among the M. austroafricanum strains. This is the first report suggesting the involvement of an alkane hydroxylase in TBA oxidation, a key step during MTBE metabolism.

  5. Zitterbewegung in monolayer silicene in a magnetic field

    International Nuclear Information System (INIS)

    Romera, E.; Roldán, J.B.; Santos, F. de los

    2014-01-01

    We study the Zitterbewegung in monolayer silicene under a perpendicular magnetic field. Using an effective Hamiltonian, we have investigated the autocorrelation function and the density currents in this material. Moreover, we have analyzed other types of periodicities of the system (classical and revival times). Finally, the above results are compared with their counterparts in two other monolayer materials subject to a magnetic field: graphene and MoS 2 . - Highlights: • We study Zitterbewegung in monolayer silicene in a magnetic field. • We have analyzed other types of periodicities in silicene. • The above results are compared with other monolayer materials (graphene and MoS 2 )

  6. Zitterbewegung in monolayer silicene in a magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Romera, E. [Departamento de Física Atómica, Molecular y Nuclear and Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, Fuentenueva s/n, 18071 Granada (Spain); Roldán, J.B. [Departamento de Electrónica y Tecnología de Computadores and CITIC, Universidad de Granada, Fuentenueva s/n, 18071 Granada (Spain); Santos, F. de los [Departamento de Electromagnetismo y Física de la Materia, and Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, Fuentenueva s/n, 18071 Granada (Spain)

    2014-07-04

    We study the Zitterbewegung in monolayer silicene under a perpendicular magnetic field. Using an effective Hamiltonian, we have investigated the autocorrelation function and the density currents in this material. Moreover, we have analyzed other types of periodicities of the system (classical and revival times). Finally, the above results are compared with their counterparts in two other monolayer materials subject to a magnetic field: graphene and MoS{sub 2}. - Highlights: • We study Zitterbewegung in monolayer silicene in a magnetic field. • We have analyzed other types of periodicities in silicene. • The above results are compared with other monolayer materials (graphene and MoS{sub 2})

  7. Stable Organic Monolayers on Oxide-Free Silicon/Germanium in a Supercritical Medium: A New Route to Molecular Electronics.

    Science.gov (United States)

    Puniredd, Sreenivasa Reddy; Jayaraman, Sundaramurthy; Yeong, Sai Hooi; Troadec, Cedric; Srinivasan, M P

    2013-05-02

    Oxide-free Si and Ge surfaces have been passivated and modified with organic molecules by forming covalent bonds between the surfaces and reactive end groups of linear alkanes and aromatic species using single-step deposition in supercritical carbon dioxide (SCCO2). The process is suitable for large-scale manufacturing due to short processing times, simplicity, and high resistance to oxidation. It also allows the formation of monolayers with varying reactive terminal groups, thus enabling formation of nanostructures engineered at the molecular level. Ballistic electron emission microscopy (BEEM) spectra performed on the organic monolayer on oxide-free silicon capped by a thin gold layer reveals for the first time an increase in transmission of the ballistic current through the interface of up to three times compared to a control device, in contrast to similar studies reported in the literature suggestive of oxide-free passivation in SCCO2. The SCCO2 process combined with the preliminary BEEM results opens up new avenues for interface engineering, leading to molecular electronic devices.

  8. Effects of Odd–Even Side Chain Length of Alkyl-Substituted Diphenylbithiophenes on First Monolayer Thin Film Packing Structure

    KAUST Repository

    Akkerman, Hylke B.

    2013-07-31

    Because of their preferential two-dimensional layer-by-layer growth in thin films, 5,5′bis(4-alkylphenyl)-2,2′-bithiophenes (P2TPs) are model compounds for studying the effects of systematic chemical structure variations on thin-film structure and morphology, which in turn, impact the charge transport in organic field-effect transistors. For the first time, we observed, by grazing incidence X-ray diffraction (GIXD), a strong change in molecular tilt angle in a monolayer of P2TP, depending on whether the alkyl chain on the P2TP molecules was of odd or even length. The monolayers were deposited on densely packed ultrasmooth self-assembled alkane silane modified SiO2 surfaces. Our work shows that a subtle change in molecular structure can have a significant impact on the molecular packing structure in thin film, which in turn, will have a strong impact on charge transport of organic semiconductors. This was verified by quantum-chemical calculations that predict a corresponding odd-even effect in the strength of the intermolecular electronic coupling. © 2013 American Chemical Society.

  9. Effects of Odd–Even Side Chain Length of Alkyl-Substituted Diphenylbithiophenes on First Monolayer Thin Film Packing Structure

    KAUST Repository

    Akkerman, Hylke B.; Mannsfeld, Stefan C. B.; Kaushik, Ananth P.; Verploegen, Eric; Burnier, Luc; Zoombelt, Arjan P.; Saathoff, Jonathan D.; Hong, Sanghyun; Atahan-Evrenk, Sule; Liu, Xueliang; Aspuru-Guzik, Alá n; Toney, Michael F.; Clancy, Paulette; Bao, Zhenan

    2013-01-01

    Because of their preferential two-dimensional layer-by-layer growth in thin films, 5,5′bis(4-alkylphenyl)-2,2′-bithiophenes (P2TPs) are model compounds for studying the effects of systematic chemical structure variations on thin-film structure and morphology, which in turn, impact the charge transport in organic field-effect transistors. For the first time, we observed, by grazing incidence X-ray diffraction (GIXD), a strong change in molecular tilt angle in a monolayer of P2TP, depending on whether the alkyl chain on the P2TP molecules was of odd or even length. The monolayers were deposited on densely packed ultrasmooth self-assembled alkane silane modified SiO2 surfaces. Our work shows that a subtle change in molecular structure can have a significant impact on the molecular packing structure in thin film, which in turn, will have a strong impact on charge transport of organic semiconductors. This was verified by quantum-chemical calculations that predict a corresponding odd-even effect in the strength of the intermolecular electronic coupling. © 2013 American Chemical Society.

  10. Forces and electronic transport in a contact formed by a graphene tip and a defective MoS2 monolayer: a theoretical study

    Science.gov (United States)

    di Felice, D.; Dappe, Y. J.; González, C.

    2018-06-01

    A theoretical study of a graphene-like tip used in atomic force microscopy (AFM) is presented. Based on first principles simulations, we proved the low reactivity of this kind of tip, using a MoS2 monolayer as the testing sample. Our simulations show that the tip–MoS2 interaction is mediated through weak van der Waals forces. Even on the defective monolayer, the interaction is reduced by one order of magnitude with respect to the values obtained using a highly reactive metallic tip. On the pristine monolayer, the S atoms were imaged for large distances together with the substitutional defects which should be observed as brighter spots in non-contact AFM measurements. This result is in contradiction with previous simulations performed with Cu or Si tips where the metallic defects were imaged for much larger distances than the S atoms. For shorter distances, the Mo sites will be brighter even though a vacancy is formed. On the other hand, the largest conductance value is obtained over the defect formed by two Mo atoms occupying a S divacancy when the half-occupied p y -states of the graphene-like tip find a better coupling with d-orbitals of the highest substitutional atom. Due to the weak interaction, no conductance plateau is formed in any of the sites. A great advantage of this tip lies in the absence of atomic transfer between the tip and the sample leading to a more stable AFM measurement. Finally, and as previously shown, we confirm the atomic resolution in a scanning tunneling microscopy simulation using this graphene-based tip.

  11. Optimized reaction mechanism rate rules for ignition of normal alkanes

    KAUST Repository

    Cai, Liming

    2016-08-11

    The increasing demand for cleaner combustion and reduced greenhouse gas emissions motivates research on the combustion of hydrocarbon fuels and their surrogates. Accurate detailed chemical kinetic models are an important prerequisite for high fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules. Accurate and versatile rate rules are desirable to improve the predictive accuracy of kinetic models. A major contribution in the literature is the recent work by Bugler et al. (2015), which has significantly improved rate rules and thermochemical parameters used in kinetic modeling of alkanes. In the present study, it is demonstrated that rate rules can be used and consistently optimized for a set of normal alkanes including n-heptane, n-octane, n-nonane, n-decane, and n-undecane, thereby improving the predictive accuracy for all the considered fuels. A Bayesian framework is applied in the calibration of the rate rules. The optimized rate rules are subsequently applied to generate a mechanism for n-dodecane, which was not part of the training set for the optimized rate rules. The developed mechanism shows accurate predictions compared with published well-validated mechanisms for a wide range of conditions.

  12. Molecular beam epitaxy of quasi-freestanding transition metal disulphide monolayers on van der Waals substrates: a growth study

    Science.gov (United States)

    Hall, Joshua; Pielić, Borna; Murray, Clifford; Jolie, Wouter; Wekking, Tobias; Busse, Carsten; Kralj, Marko; Michely, Thomas

    2018-04-01

    Based on an ultra-high vacuum compatible two-step molecular beam epitaxy synthesis with elemental sulphur, we grow clean, well-oriented, and almost defect-free monolayer islands and layers of the transition metal disulphides MoS2, TaS2 and WS2. Using scanning tunneling microscopy and low energy electron diffraction we investigate systematically how to optimise the growth process, and provide insight into the growth and annealing mechanisms. A large band gap of 2.55 eV and the ability to move flakes with the scanning tunneling microscope tip both document the weak interaction of MoS2 with its substrate consisting of graphene grown on Ir(1 1 1). As the method works for the synthesis of a variety of transition metal disulphides on different substrates, we speculate that it could be of great use for providing hitherto unattainable high quality monolayers of transition metal disulphides for fundamental spectroscopic investigations.

  13. The effect of environmental factors on stable isotopic composition of n-alkanes in Mediterranean olive oils

    Science.gov (United States)

    Pedentchouk, Nikolai; Mihailova, Alina; Abbado, Dimitri

    2014-05-01

    Traceability of the geographic origin of olive oils is an important issue from both commercial and health perspectives. This study evaluates the impact of environmental factors on stable C and H isotope compositions of n-alkanes in extra virgin olive oils from Croatia, France, Greece, Italy, Morocco, Portugal, Slovenia, and Spain. The data are used to investigate the applicability of stable isotope methodology for olive oil regional classification in the Mediterranean region. Analysis of stable C isotope composition of n-C29 alkane showed that extra virgin olive oils from Portugal and Spain have the most positive n-C29 alkane delta13C values. Conversely, olive oils from Slovenia, northern and central Italy are characterized by the most negative values. Overall, the n-C29 alkane delta13C values show a positive correlation with the mean air temperature during August-December and a negative correlation with the mean relative humidity during these months. Analysis of stable H isotope composition of n-C29 alkane revealed that the deltaD values are the most positive in olive oils from Greece and Morocco and the most negative in oils from northern Italy. The deltaD values of oils show significant correlation with all the analyses geographical parameters: the mean air temperature and relative humidity during August-December, the total amount of rainfall (the same months) and the annual deltaD values of precipitation. As predictor variables in the Categorical Data Analysis, the n-C29 alkane deltaD values show the most significant discriminative power, followed by the n-C29 alkane delta13C values. Overall, 93.4% of olive oil samples have been classified correctly into one of the production regions. Our findings suggest that an integrated analysis of C and H isotope compositions of n-alkanes extracted from extra virgin olive oil could become a useful tool for geographical provenancing of this highly popular food commodity.

  14. Crystallisation and chain conformation of long chain n-alkanes

    International Nuclear Information System (INIS)

    Gorce, J.

    2000-06-01

    Hydrocarbon chains are a basic component in a number of systems as diverse as biological membranes, phospholipids and polymers. A better understanding of the physical properties of n-alkane chains should provide a better understanding of these more complex systems. With this aim, vibrational spectroscopy has been extensively used. This technique, sensitive to molecular details, is the only one able to both identify and quantify conformational disorder present in paraffinic systems. To achieve this, methyl deformations have been widely used as ''internal standards'' for the normalisation of peak areas. However, in the case of n-alkanes with short chain length, such as n-C 44 H 90 for example, the infrared spectra recorded at liquid nitrogen temperature and reported here show the sensitivity of these latter peaks to the various crystal structures formed. Indeed, the main frequencies of the symmetric methyl bending mode were found between 1384 cm -1 and 1368 cm -1 as a function of the crystal form. Changes in the frequency of the first order of the L.A.M. present in the Raman spectra were also observed. At higher temperatures, non all-trans conformers, inferred from different infrared bands present in the wagging mode region, were found to be essentially placed at the end of the n-alkane chains. At the monoclinic phase transition, the concentration of end-gauche conformers, proportional to the area of the infrared band at 1342 cm -1 , increases abruptly. On the contrary, in the spectra recorded at liquid nitrogen temperature no such band is observed. We also studied the degree of disorder in two purely monodisperse long chain n-alkanes, namely n-C 198 H 398 and n-C 246 H 494 . The chain conformation as well as the tilt angle of the chains from the crystal surfaces were determined by means of low frequency Raman spectroscopy and S.A.X.S. measurements on solution-crystallised samples. The increase in the number of end-gauche conformers which was expected to occur with

  15. Study of interfacial strain at the α-Al2O3/monolayer MoS2 interface by first principle calculations

    Science.gov (United States)

    Yu, Sheng; Ran, Shunjie; Zhu, Hao; Eshun, Kwesi; Shi, Chen; Jiang, Kai; Gu, Kunming; Seo, Felix Jaetae; Li, Qiliang

    2018-01-01

    With the advances in two-dimensional (2D) transition metal dichalcogenides (TMDCs) based metal-oxide-semiconductor field-effect transistor (MOSFET), the interface between the semiconductor channel and gate dielectrics has received considerable attention due to its significant impacts on the morphology and charge transport of the devices. In this study, first principle calculations were utilized to investigate the strain effect induced by the interface between crystalline α-Al2O3 (0001)/h-MoS2 monolayer. The results indicate that the 1.3 nm Al2O3 can induce a 0.3% tensile strain on the MoS2 monolayer. The strain monotonically increases with thicker dielectric layers, inducing more significant impact on the properties of MoS2. In addition, the study on temperature effect indicates that the increasing temperature induces monotonic lattice expansion. This study clearly indicates that the dielectric engineering can effectively tune the properties of 2D TMDCs, which is very attractive for nanoelectronics.

  16. Analysis of alkane-dependent methanogenic community derived from production water of a high-temperature petroleum reservoir

    Energy Technology Data Exchange (ETDEWEB)

    Mbadinga, Serge Maurice; Li, Kai-Ping; Zhou, Lei; Wang, Li-Ying; Yang, Shi-Zhong; Liu, Jin-Feng; Mu, Bo-Zhong [East China Univ. of Science and Technology, Shanghai (China). State Key Lab. of Bioreactor Engineering and Inst. of Applied Chemistry; Gu, Ji-Dong [Hong Kong Univ. (China). School of Biological Sciences

    2012-10-15

    Microbial assemblage in an n-alkanes-dependent thermophilic methanogenic enrichment cultures derived from production waters of a high-temperature petroleum reservoir was investigated in this study. Substantially higher amounts of methane were generated from the enrichment cultures incubated at 55 C for 528 days with a mixture of long-chain n-alkanes (C{sub 15}-C{sub 20}). Stoichiometric estimation showed that alkanes-dependent methanogenesis accounted for about 19.8% of the total amount of methane expected. Hydrogen was occasionally detected together with methane in the gas phase of the cultures. Chemical analysis of the liquid cultures resulted only in low concentrations of acetate and formate. Phylogenetic analysis of the enrichment revealed the presence of several bacterial taxa related to Firmicutes, Thermodesulfobiaceae, Thermotogaceae, Nitrospiraceae, Dictyoglomaceae, Candidate division OP8 and others without close cultured representatives, and Archaea predominantly related to uncultured members in the order Archaeoglobales and CO{sub 2}-reducing methanogens. Screening of genomic DNA retrieved from the alkanes-amended enrichment cultures also suggested the presence of new alkylsuccinate synthase alpha-subunit (assA) homologues. These findings suggest the presence of poorly characterized (putative) anaerobic n-alkanes degraders in the thermophilic methanogenic enrichment cultures. Our results indicate that methanogenesis of alkanes under thermophilic condition is likely to proceed via syntrophic acetate and/or formate oxidation linked with hydrogenotrophic methanogenesis. (orig.)

  17. Alkane-grown Beauveria bassiana produce mycelial pellets displaying peroxisome proliferation, oxidative stress, and cell surface alterations.

    Science.gov (United States)

    Huarte-Bonnet, Carla; Paixão, Flávia R S; Ponce, Juan C; Santana, Marianela; Prieto, Eduardo D; Pedrini, Nicolás

    2018-06-01

    The entomopathogenic fungus Beauveria bassiana is able to grow on insect cuticle hydrocarbons, inducing alkane assimilation pathways and concomitantly increasing virulence against insect hosts. In this study, we describe some physiological and molecular processes implicated in growth, nutritional stress response, and cellular alterations found in alkane-grown fungi. The fungal cytology was investigated using light and transmission electron microscopy while the surface topography was examined using atomic force microscopy. Additionally, the expression pattern of several genes associated with oxidative stress, peroxisome biogenesis, and hydrophobicity were analysed by qPCR. We found a novel type of growth in alkane-cultured B. bassiana similar to mycelial pellets described in other alkane-free fungi, which were able to produce viable conidia and to be pathogenic against larvae of the beetles Tenebrio molitor and Tribolium castaneum. Mycelial pellets were formed by hyphae cumulates with high peroxidase activity, exhibiting peroxisome proliferation and an apparent surface thickening. Alkane-grown conidia appeared to be more hydrophobic and cell surfaces displayed different topography than glucose-grown cells. We also found a significant induction in several genes encoding for peroxins, catalases, superoxide dismutases, and hydrophobins. These results show that both morphological and metabolic changes are triggered in mycelial pellets derived from alkane-grown B. bassiana. Copyright © 2017 British Mycological Society. Published by Elsevier Ltd. All rights reserved.

  18. Shale gas opportunities. Dehydrogenation of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Patcas, F.C.; Dieterle, M.; Rezai, A.; Asprion, N. [BASF SE, Ludwigshafen (Germany)

    2013-11-01

    The discovery and use of shale gas in North America has become a game changer for the chemical industry by access to a cheaper feedstock compared to conventional oil. Increased number of ethane crackers spurred increasing interest in light alkanes dehydrogenation. Several companies have announced their interest in new propane dehydrogenation units in North America. BASF is developing light alkanes dehydrogenation technologies for two decades now. BASF developed jointly with Linde the isothermal C3 dehydrogenation process. The latest dehydrogenation catalyst development at BASF focused on a supported and steam resistant Pt-Sn catalyst which yielded excellent selectivity and activity. Intense research work both internally as well as in cooperation with universities contributed to the understanding of the relationship between the surface structure and catalyst performances like activity, selectivity and coking resistance. Using such type of catalysts BASF developed an autothermal propane dehydrogenation as well as a butane dehydrogenation process. The most recent catalyst development was a dehydrogenation catalyst coated on a honeycomb monolith to improve catalyst usage and pressure drop. This will probably be the first industrial usage of catalytic monoliths in a chemical synthesis process. (orig.) (Published in summary form only)

  19. Squeezing molecularly thin alkane lubrication films: Layering transistions and wear

    DEFF Research Database (Denmark)

    Sivebæk, Ion Marius; Samoilov, V. N.; Persson, B. N. J.

    2004-01-01

    The properties of alkane lubricants confined between two approaching solids are investigated by a model that accounts for the curvature and the elastic properties of the solid surfaces. We consider linear alkane molecules of different chain lengths, C(3)H(8); C(4)H(10); C(8)H(18); C(9)H(20); C(10)H...

  20. Testing the effectiveness of monolayers under wind and wave conditions.

    Science.gov (United States)

    Palada, C; Schouten, P; Lemckert, C

    2012-01-01

    Monolayers are highly desirable for their evaporation reducing capabilities due to their relatively minimal cost and ease of application. Despite these positive attributes, monolayers have consistently failed to perform effectively due to the harsh wind and wave conditions prevalent across real-world water reserves. An exhaustive and consistent study testing the influence of wind and wave combinations on monolayer performance has yet to be presented in the literature. To remedy this, the effect of simultaneous wind and wave conditions on a benchmark high-performance monolayer (octadecanol suspension, CH(3)(CH(2))(16)CH(2)OH) has been analysed. Subjected only to waves, the monolayer remained intact due to its innate ability to compress and expand. However, the constant simultaneous application of wind and waves caused the monolayer to break up and gather down-wind where it volatilised over time. At wind speeds above 1.3 m s(-1) the monolayer was completely ineffective. For wind speeds below this threshold, the monolayer had an influence on the evaporation rate dependent on wind speed. From these results a series of application protocols can now be developed for the optimised deployment of monolayers in real-world water reserves. This will be of interest to private, commercial and government organisations involved in the storage and management of water resources.

  1. Structural, electronic and magnetic properties of 3d metal trioxide clusters-doped monolayer graphene: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Rafique, Muhammad [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China); M.U.E.T, S.Z.A.B, Campus Khairpur Mir' s, Sindh (Pakistan); Shuai, Yong, E-mail: shuaiyong1978@gmail.com [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China); Tan, He-Ping; Hassan, Muhammad [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China)

    2017-03-31

    Highlights: • First-principles calculations are performed for TMO{sub 3} cluster-doped and TM atoms adsorbed at three O atoms-doped graphene. • Significant magnetic coupling behavior is observed between TM atoms and neighboring C and O atoms for both cases. • The direction of charge transfer is always from monolayer graphene to TMO{sub 3} clusters incorporated into graphene. • TiO{sub 3} and VO{sub 3} doped structures display dilute magnetic semiconductor behavior. • Five different orbitals (d{sub xy}, d{sub yz}, d{sub z}{sup 2}, d{sub xz} and d{sub x}{sup 2}{sub -y}{sup 2}) of 3d TM atoms give rise to magnetic moments for both cases. - Abstract: We present first-principles density-functional calculations for the structural, electronic and magnetic properties of monolayer graphene doped with 3d (Ti, V, Cr, Fe, Co, Mn and Ni) metal trioxide TMO{sub 3} halogen clusters. In this paper we used two approaches for 3d metal trioxide clusters (i) TMO{sub 3} halogen cluster was embedded in monolayer graphene substituting four carbon (C) atoms (ii) three C atoms were substituted by three oxygen (O) atoms in one graphene ring and TM atom was adsorbed at the hollow site of O atoms substituted graphene ring. All the impurities were tightly bonded in the graphene ring. In first case of TMO{sub 3} doped graphene layer, the bond length between C−O atom was reduced and bond length between TM-O atom was increased. In case of Cr, Fe, Co and Ni atoms substitution in between the O atoms, leads to Fermi level shifting to conduction band thereby causing the Dirac cone to move into valence band, however a band gap appears at high symmetric K-point. In case of TiO{sub 3} and VO{sub 3} substitution, system exhibits semiconductor properties. Interestingly, TiO{sub 3}-substituted system shows dilute magnetic semiconductor behavior with 2.00 μ{sub B} magnetic moment. On the other hand, the substitution of CoO{sub 3}, CrO{sub 3}, FeO{sub 3} and MnO{sub 3} induced 1.015 μ{sub B}, 2

  2. The most stable mono-layers of (111)-Pt (fcc) on Graphene: A first-principles GGA study

    International Nuclear Information System (INIS)

    Otalora-Acevedo, J; Martínez, J A Rodríguez; Moreno-Armenta, G; Tan, N Takeuchi; Vera, E

    2016-01-01

    We investigate monolayers of planes (111) of Pt in the FCC structure located on graphene. The energy of formation showed that the most stable structure is √3×√3 — Pt on 2 × 2 — graphene. This system has a mismatch in the lattice constant of 0.45. The layers are completely flat, and its band structure shows that the new structure is metallic and the Dirac's cones are displaced 0.6eV above of the Fermi level. In this work we present the dependence of the enthalpy of formation of these structures and we calculated all structural parameters of their relaxation. (paper)

  3. Ab-initio study of electronic and magnetic properties of Co-doped Mo2C monolayer

    Science.gov (United States)

    Mehta, Veenu; Tankeshwar, K.; Saini, Hardev S.

    2018-05-01

    The spin polarized density functional theory (DFT) based calculations has been performed to investigate the electronic and magnetic properties of pristine and Co-doped Mo2C using VASP code. The calculated results show that the pristine Mo2C is found to be non-magnetic whereas the Co dopant at Mo-site in the Mo2C monolayer generates the ferromagnetism in the resultant compound. The total magnetic moment of the system has been found to be 1.2µB which increases to 2.03µB as the concentration of Co increase from 3% to 8%, respectively. The electronic structure calculations of the pristine and Co-doped Mo2C show its metallic behavior which may found its application in magnetic energy storage devices, magnetic tape etc.

  4. Monolayer Boron Nitride Substrate Interactions with Graphene Under In-Plane and Perpendicular Strains: A First-Principles Study

    Science.gov (United States)

    Behzad, Somayeh

    2018-04-01

    Effects of strain on the electronic and optical properties of graphene on monolayer boron nitride (BN) substrate are investigated using first-principle calculations based on density functional theory. Strain-free graphene/BN has a small band gap of 97 meV at the K point. The magnitude of band gap increases with in-plane biaxial strain while it decreases with the perpendicular uniaxial strain. The ɛ2 (ω ) spectrum of graphene/BN bilayer for parallel polarization shows red and blue shifts by applying the in-plane tensile and compressive strains, respectively. Also the positions of peaks in the ɛ2 (ω ) spectrum are not significantly changed under perpendicular strain. The calculated results indicate that graphene on the BN substrate has great potential in microelectronic and optoelectronic applications.

  5. Studies of the surface structures of molecular crystals and of adsorbed molecular monolayers on the (111) crystal faces of platinum and silver by low-energy electron diffraction

    International Nuclear Information System (INIS)

    Firment, L.E.

    1977-01-01

    The structures of molecular crystal surfaces were investigated for the first time by the use of low-energy electron diffraction (LEED). The experimental results from a variety of molecular crystals were examined and compared as a first step towards understanding the properties of these surfaces on a microscopic level. The method of sample preparation employed, vapor deposition onto metal single-crystal substrates at low temperatures in ultrahigh vacuum, allowed concurrent study of the structures of adsorbed monolayers on metal surfaces and of the growth processes of molecular films on metal substrates. The systems investigated were ice, ammonia, naphthalene, benzene, the n-paraffins (C 3 to C 8 ), cyclohexane, trioxane, acetic acid, propionic acid, methanol, and methylamine adsorbed and condensed on both Pt(111) and Ag(111) surfaces. Electron-beam-induced damage of the molecular surfaces was observed after electron exposures of 10 -4 A sec cm -2 at 20 eV. Aromatic molecular crystal samples were more resistant to damage than samples of saturated molecules. The quality and orientation of the grown molecular crystal films were influenced by substrate preparation and growth conditions. Forty ordered monolayer structures were observed. 110 figures, 22 tables, 162 references

  6. Temperature-Dependent Change of Packing Structure of Condensed-Phase in a Micro-Phase Separated Langmuir Monolayer Studied by Grazing-Incidence X-ray Diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Iimura, Ken-ichi [Department of Applied Chemisty, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Utsunomiya (Japan); Kato, Teiji [Department of Applied Chemisty, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Utsunomiya (Japan); Brezesinski, Gerald [Max-Planck Instutite of Colloids and Interfaces, Research Campus Golm, D-14476 Potsdam (Germany)

    2007-10-15

    Packing structure of condensed-phase in a binary mixed Langmuir monolayer of behenic acid (C22) and perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid (PFPE) on a cadmium acetate aqueous solution was studied by grazing incidence X-ray diffraction (GIXD) as a function of the subphase temperature. The measurements were made during temperature scan at a fixed molecular area to explain the morphological change of the condensed-phase domains due to a thermal treatment reported previously. Analysis of GIXD data implies that the condensed-phase domains are composed of only the C22 molecules perpendicularly oriented and very closely packed in a centered rectangular unit cell with orthorhombic distortion at low temperatures. As the temperature increases the area occupied by molecule increases, and above 25 deg. C the lattice becomes disordered, which would allow morphological transformation of the condensed-phase domains. The process of packing structure change is almost reversible except for non-equilibrium phases observed for the monolayer spread at a low temperature, 5.5 deg. C.

  7. Temperature-Dependent Change of Packing Structure of Condensed-Phase in a Micro-Phase Separated Langmuir Monolayer Studied by Grazing-Incidence X-ray Diffraction

    International Nuclear Information System (INIS)

    Iimura, Ken-ichi; Kato, Teiji; Brezesinski, Gerald

    2007-01-01

    Packing structure of condensed-phase in a binary mixed Langmuir monolayer of behenic acid (C22) and perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid (PFPE) on a cadmium acetate aqueous solution was studied by grazing incidence X-ray diffraction (GIXD) as a function of the subphase temperature. The measurements were made during temperature scan at a fixed molecular area to explain the morphological change of the condensed-phase domains due to a thermal treatment reported previously. Analysis of GIXD data implies that the condensed-phase domains are composed of only the C22 molecules perpendicularly oriented and very closely packed in a centered rectangular unit cell with orthorhombic distortion at low temperatures. As the temperature increases the area occupied by molecule increases, and above 25 deg. C the lattice becomes disordered, which would allow morphological transformation of the condensed-phase domains. The process of packing structure change is almost reversible except for non-equilibrium phases observed for the monolayer spread at a low temperature, 5.5 deg. C

  8. A theoretical and experimental XAS study of monolayer dispersive supported CuO/γ-Al2O3 catalysts

    International Nuclear Information System (INIS)

    Chen Dongliang; Wu Ziyu

    2006-01-01

    The local structures of supported CuO/γ-Al 2 O 3 monolayer dispersive catalysts with different CuO loadings have been investigated by EXAFS and multiple scattering XANES simulations. The EXAFS results show that the first nearest neighbors around the Cu atoms in the CuO/γ-Al 2 O 3 catalysts are similar to that of the polycrystalline CuO powder, which is independent of the CuO loadings. Moreover, the Cu K-XANES FEFF8 calculations for CuO reveal that the monolayer-dispersed CuO species are of small distorted (CuO 4 ) m n+ clusters, which is mainly composed of a distorted CuO 6 octahedron incorporated in the surface octahedral vacant sites of the γ-Al 2 O 3 support. We consider that the CuO species for the CuO/γ-Al 2 O 3 catalysts with loadings of 0.4 and 0.8 mmol/100 m 2 are distorted (CuO 4 ) m n+ clusters composed mainly of a distorted CuO 6 octahedron incorporated in the surface octahedral vacant sites of the γ-Al 2 O 3 support after calcinations at high temperature in air for a few hours. On the contrary, for the CuO/γ-Al 2 O 3 with loading of 1.2 mmol/100 m 2 , the local structure of Cu atoms in CuO/γ-Al 2 O 3 is similar to that of polycrystalline CuO powder

  9. n-Alkane adsorption to polar silica surfaces.

    Science.gov (United States)

    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.

  10. Study of the selective abstration reaction of the hydrogen atom in the radiolysis and photolysis of alkane mixture at 77 K

    International Nuclear Information System (INIS)

    Guedes, S.M.L.

    1979-01-01

    The occurence of the selective abstraction reaction of the solute hydrogen atom by hydrogen atom produced during radiolysis or photolysis of the systems such as neopentane/cyclo-hexane/HI, neopentane/2,3 dimethylbutane, n-pentane/HI/cyclo-hexane and cyclo-hexane/HI/n-pentane, at 77 K is studied. Experiments have been undertaken on the kinetics nature of the active species, the H atom, during radiolysis and photolysis of the neopentane/cyclo-hexane/HI system at 77 K, presenting competitive reactions. Studies have also been made on the occurrence of the selective abstraction reaction in inverted systems, in which the concentrations of the components of a system are so much altered that the solute becomes the solvent and vice-versa, in the other system. By means of photolysis at 77 K, it has been observed that for the two systems constitued by the cyclo-hexane and n-pentane the selective abstraction reaction occurs. However, for radiolysis of that same two systems it has been observed that only the hydrogen atom abstraction reaction corresponding to the solvent occurs. (Author) [pt

  11. Using n-alkane records to constrain carbon cycle - hydrological cycle coupling: Case study from the Northern Hemisphere mid-latitudes during the PETM

    Science.gov (United States)

    Krishnan, S.; Pagani, M.; Tipple, B. J.

    2010-12-01

    The early Eocene was a warmer world compared to the present and is characterized by rising temperatures interspersed with rapid hyperthermal events. During the largest of these rapid warming events; the Paleocene-Eocene Thermal Maximum (PETM), proxy records suggest that sea surface temperatures (SST) rose by 3-5 deg. C in the tropics (Zachos et al., 2003, Tripati and Elderfield, 2004), >5 deg. C in the Arctic (Sluijs et al., 2006) and perhaps has high as 9 deg. C in some sub-Antarctic regions (Kennett and Stott, 1991; Thomas et al., 1999). This warming is believed to be the result of massive input of 13C-depleted carbon into the ocean-atmosphere system, evidenced by the large negative carbon isotope excursion (CIE) and carbonate dissolution associated with the event. However, there are several questions regarding the exact mechanism of warming and feedbacks between the carbon cycle and climate. Did climate shift prior to the main event that led to the release of isotopically light carbon? Do we observe consistent leads or lags between changes in carbon isotopes and hydrological conditions during warm intervals? This study aims to reconstruct hydrological changes in the in the Northern Hemisphere mid-latitudes during the PETM using terrestrial biomarkers. Terrestrial biomarkers, such leaf-wax lipids stored in sediments, have the unique advantage of recording carbon and hydrogen isotopic compositions of atmospheric CO2 (modified by plant fractionation) and precipitation (modified by plant fractionation and evapotranspiration), allowing evaluation of the relative timing of carbon and hydrogen isotopic (i.e., climate) shifts. In this study, we compile and present three mid-latitude PETM records from the Northern Hemisphere, i.e. Alamedilla (Spain), Cicogna and Forada (Italy). The Cicogna and Forada sections are located in the Belluno basin (~12 km apart). Preliminary results do not indicate any significant pre-excursion hydrogen isotope changes at Cicogna, while at

  12. Cool-flame Extinction During N-Alkane Droplet Combustion in Microgravity

    Science.gov (United States)

    Nayagam, Vedha; Dietrich, Daniel L.; Hicks, Michael C.; Williams, Forman A.

    2014-01-01

    Recent droplet combustion experiments onboard the International Space Station (ISS) have revealed that large n-alkane droplets can continue to burn quasi-steadily following radiative extinction in a low-temperature regime, characterized by negative-temperaturecoefficient (NTC) chemistry. In this study we report experimental observations of n-heptane, n-octane, and n-decane droplets of varying initial sizes burning in oxygen/nitrogen/carbon dioxide and oxygen/helium/nitrogen environments at 1.0, 0.7, and 0.5 atmospheric pressures. The oxygen concentration in these tests varied in the range of 14% to 25% by volume. Large n-alkane droplets exhibited quasi-steady low-temperature burning and extinction following radiative extinction of the visible flame while smaller droplets burned to completion or disruptively extinguished. A vapor-cloud formed in most cases slightly prior to or following the "cool flame" extinction. Results for droplet burning rates in both the hot-flame and cool-flame regimes as well as droplet extinction diameters at the end of each stage are presented. Time histories of radiant emission from the droplet captured using broadband radiometers are also presented. Remarkably the "cool flame" extinction diameters for all the three n-alkanes follow a trend reminiscent of the ignition delay times observed in previous studies. The similarities and differences among the n-alkanes during "cool flame" combustion are discussed using simplified theoretical models of the phenomenon

  13. Unimolecular H2 elimination during the liquid phase radiolysis and photolysis of alkane - alkane mixtures

    International Nuclear Information System (INIS)

    Wojnarovits, L.; Foeldiak, G.

    1980-01-01

    Unimolecular H 2 elimination from alkanes was investigated in cyclopentane-cyclohexane, n-hexane-cyclohexane and cyclohexane-cyclooctane mixtures during fluradiolysis and 7.6 eV photolysis. During the radiolysis of all systems, and when the fluorescence shift law allowed it, during the photolysis as well, inhibited H 2 detachment was observed from the first component and sensitized hydrogen molecule elimination from the second. It has been concluded that the same excited state (the lowest singlet, S 1 ) is responsible for the H 2 elimination during radiolysis and photolysis and this is that one that gives rise to fluorescence in the experiments of other authors. The H 2 and H elimination from alkanes generally have different excited precursors. The direct population of S 1 by γ-irradiation is of limited importance and this intermediate is mainly produced in ''charge neutralization'' processes. (author)

  14. Characterization of self-assembled monolayers on a ruthenium surface

    NARCIS (Netherlands)

    Shaheen, Amrozia; Sturm, Jacobus Marinus; Ricciardi, R.; Huskens, Jurriaan; Lee, Christopher James; Bijkerk, Frederik

    2017-01-01

    We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on

  15. Langmuir monolayer formation of metal complexes from polymerizable amphiphilic ligands

    NARCIS (Netherlands)

    Werkman, P.J; Schouten, A.J.

    1996-01-01

    The monolayer behaviour of 4-(10,12-pentacosadiynoicamidomethyl)-pyridine at the air-water interface was studied by measuring the surface pressure-area isotherms. The amphiphile formed stable monolayers with a clear liquid-expanded (LE) to liquid-condensed phase transition at various temperatures.

  16. n-Alkane distributions as indicators of novel ecosystem development in western boreal forest soils

    Science.gov (United States)

    Norris, Charlotte; Dungait, Jennifer; Quideau, Sylvie

    2013-04-01

    Novel ecosystem development is occurring within the western boreal forest of Canada due to land reclamation following surface mining in the Athabasca Oil Sands Region. Sphagnum peat is the primary organic matter amendment used to reconstruct soils in the novel ecosystems. We hypothesised that ecosystem recovery would be indicated by an increasing similarity in the biomolecular characteristics of novel reconstructed soil organic matter (SOM) derived from peat to those of natural boreal ecosystems. In this study, we evaluated the use of the homologous series of very long chain (>C20) n-alkanes with odd-over-even predominance as biomarker signatures to monitor the re-establishment of boreal forests on reconstructed soils. The lipids were extracted from dominant vegetation inputs and SOM from a series of natural and novel ecosystem reference plots. We observed unique very long n-alkane signatures of the source vegetation, e.g. Sphagnum sp. was dominated by C31 and aspen (Populus tremuloides Michx.) leaves by C25. Greater concentrations of very long chain n-alkanes were extracted from natural than novel ecosystem SOM (puse of n-alkanes as biomarkers of ecosystem development is a promising method.

  17. Two cell circuits of oriented adult hippocampal neurons on self-assembled monolayers for use in the study of neuronal communication in a defined system.

    Science.gov (United States)

    Edwards, Darin; Stancescu, Maria; Molnar, Peter; Hickman, James J

    2013-08-21

    In this study, we demonstrate the directed formation of small circuits of electrically active, synaptically connected neurons derived from the hippocampus of adult rats through the use of engineered chemically modified culture surfaces that orient the polarity of the neuronal processes. Although synaptogenesis, synaptic communication, synaptic plasticity, and brain disease pathophysiology can be studied using brain slice or dissociated embryonic neuronal culture systems, the complex elements found in neuronal synapses makes specific studies difficult in these random cultures. The study of synaptic transmission in mature adult neurons and factors affecting synaptic transmission are generally studied in organotypic cultures, in brain slices, or in vivo. However, engineered neuronal networks would allow these studies to be performed instead on simple functional neuronal circuits derived from adult brain tissue. Photolithographic patterned self-assembled monolayers (SAMs) were used to create the two-cell "bidirectional polarity" circuit patterns. This pattern consisted of a cell permissive SAM, N-1[3-(trimethoxysilyl)propyl] diethylenetriamine (DETA), and was composed of two 25 μm somal adhesion sites connected with 5 μm lines acting as surface cues for guided axonal and dendritic regeneration. Surrounding the DETA pattern was a background of a non-cell-permissive poly(ethylene glycol) (PEG) SAM. Adult hippocampal neurons were first cultured on coverslips coated with DETA monolayers and were later passaged onto the PEG-DETA bidirectional polarity patterns in serum-free medium. These neurons followed surface cues, attaching and regenerating only along the DETA substrate to form small engineered neuronal circuits. These circuits were stable for more than 21 days in vitro (DIV), during which synaptic connectivity was evaluated using basic electrophysiological methods.

  18. Electrochemical behavior of monolayer and bilayer graphene.

    Science.gov (United States)

    Valota, Anna T; Kinloch, Ian A; Novoselov, Kostya S; Casiraghi, Cinzia; Eckmann, Axel; Hill, Ernie W; Dryfe, Robert A W

    2011-11-22

    Results of a study on the electrochemical properties of exfoliated single and multilayer graphene flakes are presented. Graphene flakes were deposited on silicon/silicon oxide wafers to enable fast and accurate characterization by optical microscopy and Raman spectroscopy. Conductive silver paint and silver wires were used to fabricate contacts; epoxy resin was employed as a masking coating in order to expose a stable, well-defined area of graphene. Both multilayer and monolayer graphene microelectrodes showed quasi-reversible behavior during voltammetric measurements in potassium ferricyanide. However, the standard heterogeneous charge transfer rate constant, k°, was estimated to be higher for monolayer graphene flakes. © 2011 American Chemical Society

  19. Antibiotic interaction with phospholipid monolayers

    International Nuclear Information System (INIS)

    Gambinossi, F.; Mecheri, B.; Caminati, G.; Nocentini, M.; Puggelli, M.; Gabrielli, G.

    2002-01-01

    We studied the interactions of tetracycline (TC) antibiotic molecules with phospholipid monolayers with the two-fold aim of elucidating the mechanism of action and providing a first step for the realization of bio-mimetic sensors for such drugs by means of the Langmuir-Blodgett technique. We examined spreading monolayers of three phospholipids in the presence of tetracycline in the subphase by means of surface pressure-area and surface potential-area isotherms as a function of bulk pH. We selected phospholipids with hydrophobic chains of the same length but polar head groups differing either in dimensions and protonation equilibria, i.e. dipalmitoylphosphatidylcholine (DPPC), dipalmitoylphosphatidylethanolamine (DPPE) and dipalmitoylphosphatidic acid (DPPA). The interaction of tetracycline with the three phospholipids was found to be highly dependent on the electric charge of the antibiotic and on the ionization state of the lipid. Significant interactions are established between the negatively charged form of dipalmitoylphosphatidic acid and the zwitterionic form of tetracycline. The drug was found to migrate at the interface where it is adsorbed underneath or/and among the head groups, depending on the surface pressure of the film, whereas penetration through the hydrophobic layer was excluded for all the three phospholipids

  20. Antibiotic interaction with phospholipid monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Gambinossi, F.; Mecheri, B.; Caminati, G.; Nocentini, M.; Puggelli, M.; Gabrielli, G

    2002-12-01

    We studied the interactions of tetracycline (TC) antibiotic molecules with phospholipid monolayers with the two-fold aim of elucidating the mechanism of action and providing a first step for the realization of bio-mimetic sensors for such drugs by means of the Langmuir-Blodgett technique. We examined spreading monolayers of three phospholipids in the presence of tetracycline in the subphase by means of surface pressure-area and surface potential-area isotherms as a function of bulk pH. We selected phospholipids with hydrophobic chains of the same length but polar head groups differing either in dimensions and protonation equilibria, i.e. dipalmitoylphosphatidylcholine (DPPC), dipalmitoylphosphatidylethanolamine (DPPE) and dipalmitoylphosphatidic acid (DPPA). The interaction of tetracycline with the three phospholipids was found to be highly dependent on the electric charge of the antibiotic and on the ionization state of the lipid. Significant interactions are established between the negatively charged form of dipalmitoylphosphatidic acid and the zwitterionic form of tetracycline. The drug was found to migrate at the interface where it is adsorbed underneath or/and among the head groups, depending on the surface pressure of the film, whereas penetration through the hydrophobic layer was excluded for all the three phospholipids.

  1. Arbuscular mycorrhizal wheat inoculation promotes alkane and polycyclic aromatic hydrocarbon biodegradation: Microcosm experiment on aged-contaminated soil

    International Nuclear Information System (INIS)

    Ingrid, Lenoir; Lounès-Hadj Sahraoui, Anissa; Frédéric, Laruelle; Yolande, Dalpé; Joël, Fontaine

    2016-01-01

    Very few studies reported the potential of arbuscular mycorrhizal symbiosis to dissipate hydrocarbons in aged polluted soils. The present work aims to study the efficiency of arbuscular mycorrhizal colonized wheat plants in the dissipation of alkanes and polycyclic aromatic hydrocarbons (PAHs). Our results demonstrated that the inoculation of wheat with Rhizophagus irregularis allowed a better dissipation of PAHs and alkanes after 16 weeks of culture by comparison to non-inoculated condition. These dissipations observed in the inoculated soil resulted from several processes: (i) a light adsorption on roots (0.5% for PAHs), (ii) a bioaccumulation in roots (5.7% for PAHs and 6.6% for alkanes), (iii) a transfer in shoots (0.4 for PAHs and 0.5% for alkanes) and mainly a biodegradation. Whereas PAHs and alkanes degradation rates were respectively estimated to 12 and 47% with non-inoculated wheat, their degradation rates reached 18 and 48% with inoculated wheat. The mycorrhizal inoculation induced an increase of Gram-positive and Gram-negative bacteria by 56 and 37% compared to the non-inoculated wheat. Moreover, an increase of peroxidase activity was assessed in mycorrhizal roots. Taken together, our findings suggested that mycorrhization led to a better hydrocarbon biodegradation in the aged-contaminated soil thanks to a stimulation of telluric bacteria and hydrocarbon metabolization in mycorrhizal roots. - Highlights: • Phytoremediation of aged-hydrocarbon polluted soils may be improved using arbuscular mycorrhizal fungi. • Inoculation of wheat with R. irregularis improved dissipation of PAH and alkanes. • Dissipation resulted from adsorption and bioaccumulation in wheat and mainly from biodegradation in soil. • Biodegradation was due to a stimulation of rhizosphere bacteria and an induction of root peroxidase. - Inoculation of wheat by an arbuscular mycorrhizal fungus improves biodegradation of alkanes and polycyclic aromatic hydrocarbons in an aged

  2. Investigating C4 Grass Contributions to N-alkane Based Paleoclimate Reconstructions

    Science.gov (United States)

    Doman, C. E.; Enders, S. K.; Chadwick, O.; Freeman, K. H.

    2014-12-01

    Plant wax n-alkanes are long-chain, saturated hydrocarbons contained within the protective waxy cuticle on leaves. These lipids are pervasive and persistent in soils and sediments and thus are ideal biomarkers of ancient terrestrial organic matter. In ecosystems dominated by C3 plants, the relationship between the carbon isotopic value of whole leaves and lipids is fairly well documented, but this relationship has not been fully investigated for plants that use C4 photosynthesis. In both cases, it is unclear if the isotopic relationships are sensitive to environmental conditions, or reflect inherited characteristics. This study used a natural climate gradient on the Kohala peninsula of Hawaii to investigate relationships between climate and the δ13C and δ2H values of n-alkanes in C3 and C4 plants. δ13C of C3 leaves and lipids decreased 5 ‰ from the driest to the wettest sites, consistent with published data. Carbon isotope values of C4 plants showed no relationship to moisture up to 1000 mm mean annual precipitation (MAP). Above this threshold, δ 13C values were around 10‰ more depleted, likely due to a combination of canopy effects and C4 grasses growing in an uncharacteristically wet and cold environment. In C3 plants, the fractionation between leaf and lipid carbon isotopes did not vary with MAP, which allows estimations of δ13C leaf to be made from alkanes preserved in ancient sediments. Along this transect, C3 plants produce around twice the quantity of n-alkanes as C4 grasses. C4 grasses produce longer carbon chains. As a result, n-alkanes in the geologic record will be biased towards C3 plants, but the presence of alkanes C33 and C35 indicate the contributions of C4 grasses. In both C3 and C4 plants, average chain length increased with mean annual precipitation, but the taxonomic differences in chain length were greater than environmental differences. Hydrogen isotopes of n-alkanes show no trends with MAP, but do show clear differences between plant

  3. The effects of nonmetal dopants on the electronic, optical and chemical performances of monolayer g–C{sub 3}N{sub 4} by first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Lu, S. [Center for Coordination Bond Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Li, C., E-mail: canli1983@gmail.com [Center for Coordination Bond Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Li, H.H.; Zhao, Y.F.; Gong, Y.Y.; Niu, L.Y.; Liu, X.J. [Center for Coordination Bond Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Wang, T. [College of Electrical Engineering, Zhejiang University, Hangzhou 310027 (China)

    2017-01-15

    Highlights: • The electronic structures have been altered by the newly formed C−NM bonds and the relaxed chemical bonds around them. • The optical absorption edge (and intensity) in visible-light range red-shifts 10–75 nm (and increases about 14%–71%) except O– and S– doped specimens. • The separation of the HOMO and LUMO of H–, B–, O–, S–, F– and As– doped specimens can effectively enhance the photocatalytic efficiency.The electronic structures have been altered by the newly formed C−NM bonds and the relaxed chemical bonds around them. • The optical absorption edge (and intensity) in visible-light range red-shifts 10–75 nm (and increases about 14%–71%) except O– and S– doped specimens. • The separation of the HOMO and LUMO of H–, B–, O–, S–, F– and As– doped specimens can effectively enhance the photocatalytic efficiency. - Abstract: Doping is an effective means to alter the electronic behavior of materials by forming new chemical bond and relaxing the surrounding chemical bonds. With the aid of first-principle studies, the effects of a series of nonmetal (NM) dopants on the geometric, thermodynamic, electronic and optical performances of monolayer g–C{sub 3}N{sub 4} have been investigated. Results shown that, all considered NM atoms except Br and I atoms can be introduced into the monolayer g–C{sub 3}N{sub 4} on account of the thermal stability, the supercell parameter and film thickness have been altered by the newly formed C−NM bonds and the relaxed chemical bonds around them, which have affected their electronic structure. The band gap values were altered less than ±0.14 eV. The optical absorption edge (and intensity) in visible light of all doped specimens red-shift 10–75 nm (and increase about 14%–71%) except for O– and S–doped specimens, and thus the NM dopants can enhance the visible-light response capability. Moreover, the highest occupied molecular orbital and lowest unoccupied

  4. The effects of nonmetal dopants on the electronic, optical and chemical performances of monolayer g–C_3N_4 by first-principles study

    International Nuclear Information System (INIS)

    Lu, S.; Li, C.; Li, H.H.; Zhao, Y.F.; Gong, Y.Y.; Niu, L.Y.; Liu, X.J.; Wang, T.

    2017-01-01

    Highlights: • The electronic structures have been altered by the newly formed C−NM bonds and the relaxed chemical bonds around them. • The optical absorption edge (and intensity) in visible-light range red-shifts 10–75 nm (and increases about 14%–71%) except O– and S– doped specimens. • The separation of the HOMO and LUMO of H–, B–, O–, S–, F– and As– doped specimens can effectively enhance the photocatalytic efficiency.The electronic structures have been altered by the newly formed C−NM bonds and the relaxed chemical bonds around them. • The optical absorption edge (and intensity) in visible-light range red-shifts 10–75 nm (and increases about 14%–71%) except O– and S– doped specimens. • The separation of the HOMO and LUMO of H–, B–, O–, S–, F– and As– doped specimens can effectively enhance the photocatalytic efficiency. - Abstract: Doping is an effective means to alter the electronic behavior of materials by forming new chemical bond and relaxing the surrounding chemical bonds. With the aid of first-principle studies, the effects of a series of nonmetal (NM) dopants on the geometric, thermodynamic, electronic and optical performances of monolayer g–C_3N_4 have been investigated. Results shown that, all considered NM atoms except Br and I atoms can be introduced into the monolayer g–C_3N_4 on account of the thermal stability, the supercell parameter and film thickness have been altered by the newly formed C−NM bonds and the relaxed chemical bonds around them, which have affected their electronic structure. The band gap values were altered less than ±0.14 eV. The optical absorption edge (and intensity) in visible light of all doped specimens red-shift 10–75 nm (and increase about 14%–71%) except for O– and S–doped specimens, and thus the NM dopants can enhance the visible-light response capability. Moreover, the highest occupied molecular orbital and lowest unoccupied molecular orbital of H

  5. Strain tunable magnetic properties of 3d transition-metal ion doped monolayer MoS2: A first-principles study

    Science.gov (United States)

    Zhu, Yupeng; Liang, Xiao; Qin, Jun; Deng, Longjiang; Bi, Lei

    2018-05-01

    In this article, a systematic study on the magnetic properties and strain tunability of 3d transition metal ions (Mn, Fe, Co, Ni) doped MoS2 using first-principles calculations is performed. Antiferromagnetic coupling is observed between Mn, Fe ions and the nearest neighbor Mo ions; whereas ferromagnetic coupling is observed in Co and Ni systems. It is also shown that by applying biaxial tensile strain, a significant change of the magnetic moment is observed in all transition metal doped MoS2 materials with a strain threshold. The changes of total magnetic moment have different mechanisms for different doping systems including an abrupt change of the bond lengths, charge transfer and strain induced structural anisotropy. These results demonstrate applying strain as a promising method for tuning the magnetic properties in transition metal ion doped monolayer MoS2.

  6. Microbial communities in methane- and short chain alkane-rich hydrothermal sediments of Guaymas Basin

    Directory of Open Access Journals (Sweden)

    Frederick eDowell

    2016-01-01

    Full Text Available The hydrothermal sediments of Guaymas Basin, an active spreading center in the Gulf of California (Mexico, are rich in porewater methane, short-chain alkanes, sulfate and sulfide, and provide a model system to explore habitat preferences of microorganisms, including sulfate-dependent, methane- and short chain alkane-oxidizing microbial communities. In this study, sediments (above 60˚C covered with sulfur-oxidizing microbial mats surrounding a hydrothermal mound (termed Mat Mound were characterized by porewater geochemistry of methane, C2-C6 short-chain alkanes, sulfate, sulfide, sulfate reduction rate measurements, in-situ temperature gradients, bacterial and archaeal 16S rRNA gene clone libraries and V6 tag pyrosequencing. The most abundantly detected groups in the Mat mound sediments include anaerobic methane-oxidizing archaea of the ANME-1 lineage and its sister clade ANME-1Guaymas, the uncultured bacterial groups SEEP-SRB2 within the Deltaproteobacteria and the separately branching HotSeep-1 Group; these uncultured bacteria are candidates for sulfate-reducing alkane oxidation and for sulfate-reducing syntrophy with ANME archaea. The archaeal dataset indicates distinct habitat preferences for ANME-1, ANME-1-Guaymas and ANME-2 archaea in Guaymas Basin hydrothermal sediments. The bacterial groups SEEP-SRB2 and HotSeep-1 co-occur with ANME-1 and ANME-1Guaymas in hydrothermally active sediments underneath microbial mats in Guaymas Basin. We propose the working hypothesis that this mixed bacterial and archaeal community catalyzes the oxidation of both methane and short-chain alkanes, and constitutes a microbial community signature that is characteristic for hydrothermal and/or cold seep sediments containing both substrates.

  7. Enhanced biodegradation of alkane hydrocarbons and crude oil by mixed strains and bacterial community analysis.

    Science.gov (United States)

    Chen, Yu; Li, Chen; Zhou, Zhengxi; Wen, Jianping; You, Xueyi; Mao, Youzhi; Lu, Chunzhe; Huo, Guangxin; Jia, Xiaoqiang

    2014-04-01

    In this study, two strains, Acinetobacter sp. XM-02 and Pseudomonas sp. XM-01, were isolated from soil samples polluted by crude oil at Bohai offshore. The former one could degrade alkane hydrocarbons (crude oil and diesel, 1:4 (v/v)) and crude oil efficiently; the latter one failed to grow on alkane hydrocarbons but could produce rhamnolipid (a biosurfactant) with glycerol as sole carbon source. Compared with pure culture, mixed culture of the two strains showed higher capability in degrading alkane hydrocarbons and crude oil of which degradation rate were increased from 89.35 and 74.32 ± 4.09 to 97.41 and 87.29 ± 2.41 %, respectively. In the mixed culture, Acinetobacter sp. XM-02 grew fast with sufficient carbon source and produced intermediates which were subsequently utilized for the growth of Pseudomonas sp. XM-01 and then, rhamnolipid was produced by Pseudomonas sp. XM-01. Till the end of the process, Acinetobacter sp. XM-02 was inhibited by the rapid growth of Pseudomonas sp. XM-01. In addition, alkane hydrocarbon degradation rate of the mixed culture increased by 8.06 to 97.41 % compared with 87.29 % of the pure culture. The surface tension of medium dropping from 73.2 × 10(-3) to 28.6 × 10(-3) N/m. Based on newly found cooperation between the degrader and the coworking strain, rational investigations and optimal strategies to alkane hydrocarbons biodegradation were utilized for enhancing crude oil biodegradation.

  8. Effect of nickel monolayer deposition on the structural and electronic properties of the low miller indices of (bcc) iron: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Kwawu, Caroline R., E-mail: kwawucaroline@gmail.com [Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi (Ghana); Tia, Richard, E-mail: richtiagh@yahoo.com [Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi (Ghana); Adei, Evans [Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi (Ghana); Dzade, Nelson Y., E-mail: N.Y.Dzade@uu.nl [Department of Earth Sciences, Utrecht University, Princetonplein 9, 3584 CC, Utrecht (Netherlands); Catlow, C. Richard A. [Department of Chemistry, University College London, 20 Gordon Street, WC1H 0AJ, London (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park PI, Cardiff CF10 3AT (United Kingdom); Leeuw, Nora H. de, E-mail: DeLeeuwN@cardiff.ac.uk [Department of Earth Sciences, Utrecht University, Princetonplein 9, 3584 CC, Utrecht (Netherlands); Department of Chemistry, University College London, 20 Gordon Street, WC1H 0AJ, London (United Kingdom); School of Chemistry, Cardiff University, Main Building, Park PI, Cardiff CF10 3AT (United Kingdom)

    2017-04-01

    Highlights: • Thermodynamically, mono-layer deposition is exothermic on Fe (111) and (100) but endothermic on the Fe (110) facet. • The preferred adsorption site is the hollow site on all surface coverages except the 1 ML covered (110) surface, where the top site is most preferred. • Deposition leads to surface relaxation and no reconstruction, most profound on the stepped (111) surface, with the highest Ni-Fe interactions. • Work function of the bare (100), (110) and (111) surfaces were found to be 3.80 eV, 4.76 eV and 3.84 eV respectively. • Nickel monolayer deposition increases the work function on the (100) and (111) surfaces implying reduced corrosion tendencies. - Abstract: Metal clusters of both iron (Fe) and nickel (Ni) have been found in nature as active electro-catalytic sites, for example in the enzyme carbon mono-oxide dehydrogenase found in autotrophic organisms. Thus, surface modification of iron with nickel could improve the surface work function to enhance catalytic applications. The effects of surface modifications of iron by nickel on the structural and electronic properties have been studied using spin-polarised density functional theory calculations within the generalised gradient approximation. The thermodynamically preferred sites for Ni adsorption on the Fe (100), (110) and (111) surfaces have been studied at varying monolayer coverages (including 0.25 ML and 1 ML). The work function of the bare Fe surfaces is found to be of the order (100) ∼ (111) < (110) i.e. 3.80 eV ∼ 3.84 eV < 4.76 eV, which is consistent with earlier studies. The adsorption energies show that monolayer Ni deposition is thermodynamically favoured on the (100) and (111) surfaces, but not on the (110) surface. Expansion of the first interlayer spacing (d{sub 12}) of all three Fe surfaces is observed upon Ni deposition with the extent of expansion decreasing in the order (111) > (110) > (100), i.e. 6.78% > 5.76% > 1.99%. The extent of relaxation is magnified on

  9. Effect of nickel monolayer deposition on the structural and electronic properties of the low miller indices of (bcc) iron: A DFT study

    International Nuclear Information System (INIS)

    Kwawu, Caroline R.; Tia, Richard; Adei, Evans; Dzade, Nelson Y.; Catlow, C. Richard A.; Leeuw, Nora H. de

    2017-01-01

    Highlights: • Thermodynamically, mono-layer deposition is exothermic on Fe (111) and (100) but endothermic on the Fe (110) facet. • The preferred adsorption site is the hollow site on all surface coverages except the 1 ML covered (110) surface, where the top site is most preferred. • Deposition leads to surface relaxation and no reconstruction, most profound on the stepped (111) surface, with the highest Ni-Fe interactions. • Work function of the bare (100), (110) and (111) surfaces were found to be 3.80 eV, 4.76 eV and 3.84 eV respectively. • Nickel monolayer deposition increases the work function on the (100) and (111) surfaces implying reduced corrosion tendencies. - Abstract: Metal clusters of both iron (Fe) and nickel (Ni) have been found in nature as active electro-catalytic sites, for example in the enzyme carbon mono-oxide dehydrogenase found in autotrophic organisms. Thus, surface modification of iron with nickel could improve the surface work function to enhance catalytic applications. The effects of surface modifications of iron by nickel on the structural and electronic properties have been studied using spin-polarised density functional theory calculations within the generalised gradient approximation. The thermodynamically preferred sites for Ni adsorption on the Fe (100), (110) and (111) surfaces have been studied at varying monolayer coverages (including 0.25 ML and 1 ML). The work function of the bare Fe surfaces is found to be of the order (100) ∼ (111) < (110) i.e. 3.80 eV ∼ 3.84 eV < 4.76 eV, which is consistent with earlier studies. The adsorption energies show that monolayer Ni deposition is thermodynamically favoured on the (100) and (111) surfaces, but not on the (110) surface. Expansion of the first interlayer spacing (d 12 ) of all three Fe surfaces is observed upon Ni deposition with the extent of expansion decreasing in the order (111) > (110) > (100), i.e. 6.78% > 5.76% > 1.99%. The extent of relaxation is magnified on the

  10. Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

    Science.gov (United States)

    Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

    2006-11-23

    Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

  11. Fast on-line analysis of process alkane gas mixtures by NIR spectroscopy

    NARCIS (Netherlands)

    Boelens, H. F. M.; Kok, W. T.; de Noord, O. E.; Smilde, A. K.

    2000-01-01

    Proper operation of a molecular sieve process for the separation of iso- and cyclo-alkanes front normal alkanes requires the fast online detection of normal alkanes breaking through the column. The feasibility of using near-infrared (NIR) spectroscopy for this application was investigated. Alkane

  12. Biodegradation of n-alkanes on oil-seawater interfaces at different temperatures and microbial communities associated with the degradation.

    Science.gov (United States)

    Lofthus, Synnøve; Netzer, Roman; Lewin, Anna S; Heggeset, Tonje M B; Haugen, Tone; Brakstad, Odd Gunnar

    2018-04-01

    Oil biodegradation studies have mainly focused on microbial processes in dispersions, not specifically on the interfaces between the oil and the seawater in the dispersions. In this study, a hydrophobic adsorbent system, consisting of Fluortex fabrics, was used to investigate biodegradation of n-alkanes and microbial communities on oil-seawater interfaces in natural non-amended seawater. The study was performed over a temperature range from 0 to 20 °C, to determine how temperature affected biodegradation at the oil-seawater interfaces. Biodegradation of n-alkanes were influenced both by seawater temperature and chain-length. Biotransformation rates of n-alkanes decreased by reduced seawater temperature. Low rate coefficients at a seawater temperature of 0 °C were probably associated with changes in physical-chemical properties of alkanes. The primary bacterial colonization of the interfaces was predominated by the family Oceanospirillaceae at all temperatures, demonstrating the wide temperature range of these hydrocarbonoclastic bacteria. The mesophilic genus Oleibacter was predominant at the seawater temperature of 20 °C, and the psychrophilic genus Oleispira at 5 and 0 °C. Upon completion of n-alkane biotransformation, other oil-degrading and heterotrophic bacteria became abundant, including Piscirickettsiaceae (Cycloclasticus), Colwelliaceae (Colwellia), Altermonadaceae (Altermonas), and Rhodobacteraceae. This is one of a few studies that describe the biodegradation of oil, and the microbial communities associated with the degradation, directly at the oil-seawater interfaces over a large temperature interval.

  13. Emergence of chirality in hexagonally packed monolayers of hexapentyloxytriphenylene on Au(111): a joint experimental and theoretical study.

    Science.gov (United States)

    Sleczkowski, Piotr; Katsonis, Nathalie; Kapitanchuk, Oleksiy; Marchenko, Alexandr; Mathevet, Fabrice; Croset, Bernard; Lacaze, Emmanuelle

    2014-11-11

    We investigate the expression of chirality in a monolayer formed spontaneously by 2,3,6,7,10,11-pentyloxytriphenylene (H5T) on Au(111). We resolve its interface morphology by combining scanning tunneling microscopy (STM) with theoretical calculations of intermolecular and interfacial interaction potentials. We observe two commensurate structures. While both of them belong to a hexagonal space group, analogical to the triangular symmetry of the molecule and the hexagonal symmetry of the substrate surface, they surprisingly reveal a 2D chiral character. The corresponding breaking of symmetry arises for two reasons. First it is due to the establishment of a large molecular density on the substrate, which leads to a rotation of the molecules with respect to the molecular network crystallographic axes to avoid steric repulsion between neighboring alkoxy chains. Second it is due to the molecule-substrate interactions, leading to commensurable large crystallographic cells associated with the large size of the molecule. As a consequence, molecular networks disoriented with respect to the high symmetry directions of the substrate are induced. The high simplicity of the intermolecular and molecule-substrate van der Waals interactions leading to these observations suggests a generic character for this kind of symmetry breaking. We demonstrate that, for similar molecular densities, only two kinds of molecular networks are stabilized by the molecule-substrate interactions. The most stable network favors the interfacial interactions between terminal alkoxy tails and Au(111). The metastable one favors a specific orientation of the triphenylene core with its symmetry axes collinear to the Au⟨110⟩. This specific orientation of the triphenylene cores with respect to Au(111) appears associated with an energy advantage larger by at least 0.26 eV with respect to the disoriented core.

  14. Low temperature carrier transport study of monolayer MoS{sub 2} field effect transistors prepared by chemical vapor deposition under an atmospheric pressure

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xinke, E-mail: xkliu@szu.edu.cn, E-mail: wujing026@gmail.com; He, Jiazhu; Tang, Dan; Lu, Youming; Zhu, Deliang; Liu, Wenjun; Cao, Peijiang; Han, Sun [College of Materials Science and Engineering, Shenzhen Engineering Laboratory for Advanced Technology of Ceramics, Nanshan District Key Lab for Biopolymer and Safety Evaluation, Shenzhen University, 3688 Nanhai Ave, Shenzhen 518060 (China); Liu, Qiang; Wen, Jiao; Yu, Wenjie [State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, CAS, 865 Chang Ning Road, Shanghai 200050 (China); Liu, Wenjun [State Key Laboratory of ASIC and System, Department of Microelectronics, Fudan University, 220 Handan Road, Shanghai 200433 (China); Wu, Jing, E-mail: xkliu@szu.edu.cn, E-mail: wujing026@gmail.com [Department of Physics, National University of Singapore, 21 Lower Kent Ridge Road, 117576 Singapore (Singapore); He, Zhubing [Department of Materials Science and Engineering, South University of Science and Technology of China, 1088 Xueyuan Road, Shenzhen 518055 (China); Ang, Kah-Wee [Department of Electrical and Computer Engineering, National University of Singapore, 4 Engineering Drive 3, 117583 Singapore (Singapore)

    2015-09-28

    Large size monolayer Molybdenum disulphide (MoS{sub 2}) was successfully grown by chemical vapor deposition method under an atmospheric pressure. The electrical transport properties of the fabricated back-gate monolayer MoS{sub 2} field effect transistors (FETs) were investigated under low temperatures; a peak field effect mobility of 59 cm{sup 2}V{sup −1}s{sup −1} was achieved. With the assist of Raman measurement under low temperature, this work identified the mobility limiting factor for the monolayer MoS{sub 2} FETs: homopolar phonon scattering under low temperature and electron-polar optical phonon scattering at room temperature.

  15. Monolayer Superconductivity in WS2

    NARCIS (Netherlands)

    Zheliuk, Oleksandr; Lu, Jianming; Yang, Jie; Ye, Jianting

    Superconductivity in monolayer tungsten disulfide (2H-WS2) is achieved by strong electrostatic electron doping of an electric double-layer transistor (EDLT). Single crystals of WS2 are grown by a scalable method - chemical vapor deposition (CVD) on standard Si/SiO2 substrate. The monolayers are

  16. An in vitro and in silico study on the flavonoid-mediated modulation of the transport of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) through Caco-2 monolayers

    NARCIS (Netherlands)

    Schutte, M.E.; Freidig, A.P.; Sandt, J.J.M. van de; Alink, G.M.; Rietjens, I.M.C.M.; Groten, J.P.

    2006-01-01

    The present study describes the effect of different flavonoids on the absorption of the pro-carcinogen PhIP through Caco-2 monolayers and the development of an in silico model describing this process taking into account passive diffusion and active transport of PhIP. Various flavonoids stimulated

  17. Alkane oxidation by Pseudomonas oleovorans : genes and proteins

    NARCIS (Netherlands)

    van Beilen, Jan Berthold

    1994-01-01

    This thesis deals with the molecular genetics and biochemistry of oxidation of medium chainlength alkanes by P. oleovorans, as part of a program to develop biotechnological processes, based on oxygenases.

  18. Diversity of alkane degrading bacteria associated with plants in a petroleum oil-contaminated environment and expression of alkane monooxygenase (alkB) genes

    Science.gov (United States)

    Andria, V.; Yousaf, S.; Reichenauer, T. G.; Smalla, K.; Sessitsch, A.

    2009-04-01

    Among twenty-six different plant species, Italian ryegrass (Lolium multiflorum var. Taurus), Birdsfoot trefoil (Lotus corniculatus var. Leo), and the combination of both plants performed well in a petroleum oil contaminated soil. Hydrocarbon degrading bacteria were isolated from the rhizosphere, root interior and shoot interior and subjected to the analysis of 16S rRNA, the 16S and 23S rRNA intergenic spacer region and alkane hydroxylase genes. Higher numbers of culturable, degrading bacteria were associated with Italian ryegrass, which were also characterized by a higher diversity, particularly in the plant interior. Only half of the isolated bacteria hosted known alkane hydroxylase genes (alkB and cytochrome P153-like). Our results indicated that alkB genes have spread through horizontal gene transfer, particularly in the Italian ryegrass rhizosphere, and suggested mobility of catabolic genes between Gram-negative and Gram-positive bacteria. We furthermore studied the colonization behaviour of selected hydrocarbon-degrading strains (comprising an endopyhte and a rhizosphere strain) as well as the expression of their alkane monooxygenase genes in association with Italian ryegrass. Results showed that the endophyte strain better colonized the plant, particularly the plant interior, and also showed higher expression of alkB genes suggesting a more efficient degradation of the pollutant. Furthermore, plants inoculated with the endophyte were better able to grow in the presence of diesel. The rhizosphere strain colonized primarily the rhizosphere and showed low alkB gene expression in the plant interior.

  19. Arbuscular mycorrhizal wheat inoculation promotes alkane and polycyclic aromatic hydrocarbon biodegradation: Microcosm experiment on aged-contaminated soil.

    Science.gov (United States)

    Ingrid, Lenoir; Lounès-Hadj Sahraoui, Anissa; Frédéric, Laruelle; Yolande, Dalpé; Joël, Fontaine

    2016-06-01

    Very few studies reported the potential of arbuscular mycorrhizal symbiosis to dissipate hydrocarbons in aged polluted soils. The present work aims to study the efficiency of arbuscular mycorrhizal colonized wheat plants in the dissipation of alkanes and polycyclic aromatic hydrocarbons (PAHs). Our results demonstrated that the inoculation of wheat with Rhizophagus irregularis allowed a better dissipation of PAHs and alkanes after 16 weeks of culture by comparison to non-inoculated condition. These dissipations observed in the inoculated soil resulted from several processes: (i) a light adsorption on roots (0.5% for PAHs), (ii) a bioaccumulation in roots (5.7% for PAHs and 6.6% for alkanes), (iii) a transfer in shoots (0.4 for PAHs and 0.5% for alkanes) and mainly a biodegradation. Whereas PAHs and alkanes degradation rates were respectively estimated to 12 and 47% with non-inoculated wheat, their degradation rates reached 18 and 48% with inoculated wheat. The mycorrhizal inoculation induced an increase of Gram-positive and Gram-negative bacteria by 56 and 37% compared to the non-inoculated wheat. Moreover, an increase of peroxidase activity was assessed in mycorrhizal roots. Taken together, our findings suggested that mycorrhization led to a better hydrocarbon biodegradation in the aged-contaminated soil thanks to a stimulation of telluric bacteria and hydrocarbon metabolization in mycorrhizal roots. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Effect of biaxial strain and external electric field on electronic properties of MoS{sub 2} monolayer: A first-principle study

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Chuong V., E-mail: chuongnguyen11@gmail.com [Institute of Research and Development, Duy Tan University, Da Nang (Viet Nam); School of Mechanical Engineering, Le Quy Don Technical University, Ha Noi (Viet Nam); Hieu, Nguyen N. [Institute of Research and Development, Duy Tan University, Da Nang (Viet Nam)

    2016-04-01

    In this work, making use of density functional theory (DFT) computations, we systematically investigate the effect of biaxial strain engineering and external electric field applied perpendicular to the layers on the band gaps and electronic properties of monolayer MoS{sub 2}. The direct-to-indirect band gaps and semiconductor-to-metal transition are observed in monolayer MoS{sub 2} when strain and electric field are applied in our calculation. We show that when the biaxial strain and external electric field are introduced, the electronic properties including band gaps of monolayer MoS{sub 2} can be reduced to zero. Our results provide many useful insights for the wide applications of monolayer MoS{sub 2} in electronics and optoelectronics.

  1. Evaluation of monolayers and mixed monolayers formed from mercaptobenzothiazole and decanethiol as sensing platforms

    Energy Technology Data Exchange (ETDEWEB)

    Mary Vergheese, T.; Berchmans, Sheela

    2004-02-15

    In this investigation, the characterisation of monolayer and mixed monolayers formed from mercaptobenzothiazole (MBT) and decanethiol (DT) has been carried out with cyclic voltammetry. The SAMs have been tested for their stability and electron transfer blocking properties. The redox probes used in the present study are [Fe(China){sub 6}]{sup 4-}, [Ru(NH{sub 3}){sub 6}]{sup 2+} and Cu underpotential deposition (upd). The electron transfer kinetics is investigated in acid and neutral pH range. Electron transfer kinetics is altered by the nature of charge on the redox probe and the charge on the monolayer. Electron transfer kinetics of negatively charged redox probes like ferrocyanide ions is blocked when the surface pK{sub a}pH{sub medium} reversible features is observed for negatively charged probes. An exactly reverse effect is observed in the case of positively charged redox species like [Ru(NH{sub 3}){sub 6}]{sup 2+/3+}. Cu under potential deposition studies reflects the structural integrity and compactness of the SAM layer. The utility of these monolayers and mixed monolayer for selective sensing of dopamine is discussed based on their ability to discriminate between positively and negatively charged redox species at different pH.

  2. Evaluation of monolayers and mixed monolayers formed from mercaptobenzothiazole and decanethiol as sensing platforms

    International Nuclear Information System (INIS)

    Mary Vergheese, T.; Berchmans, Sheela

    2004-01-01

    In this investigation, the characterisation of monolayer and mixed monolayers formed from mercaptobenzothiazole (MBT) and decanethiol (DT) has been carried out with cyclic voltammetry. The SAMs have been tested for their stability and electron transfer blocking properties. The redox probes used in the present study are [Fe(China) 6 ] 4- , [Ru(NH 3 ) 6 ] 2+ and Cu underpotential deposition (upd). The electron transfer kinetics is investigated in acid and neutral pH range. Electron transfer kinetics is altered by the nature of charge on the redox probe and the charge on the monolayer. Electron transfer kinetics of negatively charged redox probes like ferrocyanide ions is blocked when the surface pK a medium and at pK a >pH medium reversible features is observed for negatively charged probes. An exactly reverse effect is observed in the case of positively charged redox species like [Ru(NH 3 ) 6 ] 2+/3+ . Cu under potential deposition studies reflects the structural integrity and compactness of the SAM layer. The utility of these monolayers and mixed monolayer for selective sensing of dopamine is discussed based on their ability to discriminate between positively and negatively charged redox species at different pH

  3. Relevance of carbon structure to formation of tar and liquid alkane during coal pyrolysis

    International Nuclear Information System (INIS)

    Liu, Peng; Le, Jiawei; Wang, Lanlan; Pan, Tieying; Lu, Xilan; Zhang, Dexiang

    2016-01-01

    Highlights: • Curve-fitting method was used to quantify the accurate contents of structural carbon. • Effect of carbon structure in coal with different rank on formation of pyrolysis tar was studied. • Numerical interrelation between carbon types in coal structure and tar yield is elaborated. • Effect of carbon structure on formation of liquid alkane during coal pyrolysis is discussed. - Abstract: The relevance of carbon structure to formation of tar and liquid alkane during coal pyrolysis were discussed extensively. The pyrolysis tests were carried out in a tube reactor at 873 K and keep 15 min. The carbon distribution in coals was investigated by solid state "1"3C nuclear magnetic resonance (N.M.R.). The curve-fitting method was used to quantify the accurate contents of structural carbon. The alkanes in coal tar were analyzed by Gas Chromatograph–Mass Spectrometer (GC–MS). The results show that oxygen-linked aromatic carbon decreases with the increasing of coal rank. The aliphatic carbon contents of Huainan (HN) coal are 44.20%, the highest among the four coals. The carbon types in coal structure have a significant influence on the formation of tar and liquid alkane. The coal tar yields are related to the aliphatic substituted aromatic carbon, CH_2/CH_3 ratio and oxygen-linked carbon in coal so that the increasing order of tar yield is Inner Mongolia lignite (IM, 6.30 wt.%) < Sinkiang coal (SK, 7.55 wt.%) < Shenmu coal (SM, 12.84 wt.%) < HN (16.29 wt.%). The highest contents of oxygen-linked aromatic carbon in IM lead to phenolic compound of 41.06% in IM-tar. The contents of alkane in SM-tar are the highest because the appropriate CH_2/CH_3 ratio and the highest aliphatic side chains on aromatic rings in SM leading to generate aliphatic hydrocarbon with medium molecular weight easily. The mechanism on formation of tar and liquid alkane plays an important role in guiding the industrialization of pyrolysis-based poly-generation producing tar with high

  4. A first-principles study of NbSe2 monolayer as anode materials for rechargeable lithium-ion and sodium-ion batteries

    Science.gov (United States)

    Lv, Xingshuai; Wei, Wei; Sun, Qilong; Huang, Baibiao; Dai, Ying

    2017-06-01

    There is a great desire to search for suitable anodes with good performance for rechargeable metal-ion batteries, which require not only large capacity but excellent rate performance and cycling stability. In this work, the electronic properties of NbSe2 monolayer were explored based on first-principles calculations. We performed a full geometry optimization for Li/Na-adsorbed structures and obtained favorable adsorption sites. The metallic character for both pristine NbSe2 monolayer and the Li/Na-adsorbed NbSe2 ensures good electrical conduction. In addition, we find that NbSe2 monolayer is more inclined to adsorb Li and Na atoms with smaller adsorption energy under Li/Na-rich condition, indicating the superiority of NbSe2 monolayer as an electrode. Then, we obtained a relatively low diffusion barrier of approximately 0.205 eV for Li and, in particular, a significantly small diffusion barrier of about 0.086 eV for Na, which ensures excellent cycling performance of NbSe2 monolayer as a battery electrode. Most importantly, the Li and Na adsorption density in NbSe2 monolayer can be as high as Li2NbSe2 and Na4NbSe2, corresponding to theoretical specific capacities of 203 and 312 mAh·g-1, respectively. And the average electrode potentials were predicted to be 0.51 V for the chemical stoichiometry of Li2NbSe2 and 0.22 V for Na4NbSe2. In view of these excellent properties, our work predicts that NbSe2 monolayer can be a promising anode material for the development of low-cost high-performance Li- and Na-ion batteries.

  5. Measurement and modelling of hydrogen bonding in 1-alkanol plus n-alkane binary mixtures

    DEFF Research Database (Denmark)

    von Solms, Nicolas; Jensen, Lars; Kofod, Jonas L.

    2007-01-01

    Two equations of state (simplified PC-SAFT and CPA) are used to predict the monomer fraction of 1-alkanols in binary mixtures with n-alkanes. It is found that the choice of parameters and association schemes significantly affects the ability of a model to predict hydrogen bonding in mixtures, eve...... studies, which is clarified in the present work. New hydrogen bonding data based on infrared spectroscopy are reported for seven binary mixtures of alcohols and alkanes. (C) 2007 Elsevier B.V. All rights reserved....... though pure-component liquid densities and vapour pressures are predicted equally accurately for the associating compound. As was the case in the study of pure components, there exists some confusion in the literature about the correct interpretation and comparison of experimental data and theoretical...

  6. Mechanism of trans-vinylene groups formation in the radiolysis of polyethylene and n-alkanes

    International Nuclear Information System (INIS)

    Borzov, S.M.; Sukhov, F.F.; Slovokhotova, N.A.

    1984-01-01

    Infrared spectra of polyethylene and some n-alkanes were studied after their irradiation at 20 K with 1-MeV electrons and subsequent heating to 160 K. The mechanism of trans-vinylene groups formation is suggested, which takes into account the decay of excited states of molecules in primary processes and the intra-chain recombination of free radicals in post-irradiation reactions. (author)

  7. Diversity of alkane hydroxylase genes on the rhizoplane of grasses planted in petroleum-contaminated soils

    OpenAIRE

    Tsuboi, Shun; Yamamura, Shigeki; Nakajima-Kambe, Toshiaki; Iwasaki, Kazuhiro

    2015-01-01

    The study investigated the diversity and genotypic features of alkane hydroxylase genes on rhizoplanes of grasses planted in artificial petroleum-contaminated soils to acquire new insights into the bacterial communities responsible for petroleum degradation in phytoremediation. Four types of grass (Cynodon dactylon, two phenotypes of Zoysia japonica, and Z. matrella) were used. The concentrations of total petroleum hydrocarbon effectively decreased in the grass-planted systems compared with t...

  8. Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air-water interface

    International Nuclear Information System (INIS)

    Panda, Amiya Kumar; Vasilev, Krasimir; Orgeig, Sandra; Prestidge, Clive A.

    2010-01-01

    Phospholipid monomolecular films at the air-water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)-area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)-dipalmitoylphosphatidylcholine (DPPC) and DoTAP-dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π-A isotherm. Associative interactions were identified in DPPC-DoTAP mixtures compared to the pure components, while DPPG-DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC-DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC-DoTAP mixtures with increasing X DoTAP . However, DPPG-DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.

  9. Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air-water interface

    Energy Technology Data Exchange (ETDEWEB)

    Panda, Amiya Kumar, E-mail: akpanda1@yahoo.com [Department of Chemistry, University of North Bengal, Darjeeling-734 013, West Bengal (India); Vasilev, Krasimir [Mawson Institute for Advanced Manufacturing, Mawson Lakes, University of South Australia, SA-5095 (Australia); Orgeig, Sandra [Sansom Institute for Health Research and School of Pharmacy and Medical Sciences, University of South Australia, Adelaide, SA 5000 (Australia); Prestidge, Clive A. [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia)

    2010-05-10

    Phospholipid monomolecular films at the air-water interface are useful model membranes to understand miscibility among various components. Surface pressure ({pi})-area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)-dipalmitoylphosphatidylcholine (DPPC) and DoTAP-dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous {pi}-A isotherm. Associative interactions were identified in DPPC-DoTAP mixtures compared to the pure components, while DPPG-DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC-DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X{sub DoTAP} values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC-DoTAP mixtures with increasing X{sub DoTAP}. However, DPPG-DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.

  10. The uptake of tritium-labelled carnitine by monolayer cultures of human fetal muscle and its potential as a label in cytotoxicity studies

    International Nuclear Information System (INIS)

    Cambridge, G.; Stern, C.M.M.

    1981-01-01

    As a novel approach to the investigation of immune responses directed against muscle antigens in inflammatory muscle disease, the use of tritium-labelled carnitine as a selective marker for myotubes in monolayer cultures was investigated. Tritium-labelled carnitine was incubated either with monolayer cultures of human fetal muscle or with syngeneic monolayer cultures of human fetal fibroblasts. The rate of uptake and loss of tritium-labelled carnitine by muscle cultures was compared with that shown by fibroblast cultures; values for the ratio Ksub(m)/Vsub(max) were 3.1 for muscle cultures and 0.46 for fibroblast cultures. Freeze-dried radioautographs of muscle monolayers, previously incubated with tritium-labelled carnitine confirmed the specific intra-tubular localization of the label. Fetal muscle monolayers, previously incubated with tritium-labelled carnitine, were used as targets in long-term cytotoxicity experiments into lymphocyte-mediated myotoxicity. Peripheral blood lymphocytes from patients with inflammatory muscle disease were shown to be myotoxic, but lymphocytes from normal individuals or those with non-inflammatory muscle disease were not. Carnitine-based measures of myotoxicity closely followed the clinical activity of the disease in one patient and the test shows considerable potential as a means of assessing myotube killing by lymphocytes on a per-cell basis. (author)

  11. Monolayer CS as a metal-free photocatalyst with high carrier mobility and tunable band structure: a first-principles study

    Science.gov (United States)

    Yang, Xiao-Le; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

    2018-02-01

    Producing hydrogen fuel using suitable photocatalysts from water splitting is a feasible method to harvest solar energy. A desired photocatalyst is expected to have suitable band gap, moderate band edge position, and high carrier mobility. By employing first-principles calculations, we explore a α-CS monolayer as a metal-free efficient photocatalyst. The α-CS monolayer shows good energetic, dynamic, and thermal stabilities and is insoluble in water, suggesting its experimental practicability. Monolayer and bilayer α-CS present not only appropriate band gaps for visible and ultraviolet light absorption but also moderate band alignments with water redox potentials in pH neutral water. Remarkably, the α-CS monolayer exhibits high (up to 8453.19 cm2 V-1s-1 for hole) and anisotropic carrier mobility, which is favorable to the migration and separation of photogenerated carriers. In addition, monolayer α-CS experiences an interesting semiconductor-metal transition by applying uniaxial strain and external electric field. Moreover, α-CS under certain strain and electric field is still dynamically stable with the absence of imaginary frequencies. Furthermore, we demonstrate that the graphite (0 0 1) surface is a potential substrate for the α-CS growth with the intrinsic properties of α-CS maintaining. Therefore, our results could pave the way for the application of α-CS as a promising photocatalyst.

  12. Metabolism of Hydrocarbons in n-Alkane-Utilizing Anaerobic Bacteria.

    Science.gov (United States)

    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

  13. Total internal reflection second-harmonic generation: probing the alkane water interface

    International Nuclear Information System (INIS)

    Conboy, J.C.; Daschbach, J.L.; Richmond, G.L.

    1994-01-01

    Total internal reflection Second-Harmonic Generation (SHG) has been used to study a series of neat n-alkane/water interfaces. Polarization and incident angular-dependent measurements of the SH response show good agreement with theoretical predictions. Analysis of the incident and polarization angular-dependent SH response allows for determination of the nonlinear optical properties of molecules comprising the interfacial region. Based on Kleinman symmetry, the measured surface nonlinear susceptibilities suggest a high degree of interfacial order for octane and decane with less order indicated by the odd carbon n-alkanes examined, heptane and nonane. The SH response in reflection and transmission has been measured under a Total Internal Reflection (TIR) of the fundamental. The measured nonlinear susceptibilities in each case are found to be identical. (orig.)

  14. High Selectivity of Alkanes Production by Calcium Basic Soap Thermal Decarboxylation

    Directory of Open Access Journals (Sweden)

    Neonufa Godlief F.

    2018-01-01

    Full Text Available Renewable fuel production from vegetable oil and fat or its fatty acids by direct decarboxylation has been widely reported. An innovative approach to produce drop-in fuel via thermal catalytic decarboxylation of basic soap derived from palm stearin reported in this research. The catalytic effect of the calcium and magnesium metals in the basic soap and its decarboxylation on drop-in fuel yield and product distribution was studied. The catalytic effect was tested in the temperature range up to 370°C and atmospheric pressure for 5 hours in a batch reactor. It has been proved that the calcium basic soap decarboxylation, effectively produce the drop-in fuel in carbon ranges C8 – C20, in which more than 78% selectivity toward alkane. Whereas, only 70% selectivity toward alkane has been resulted from the magnesium basic soap decarboxylation.

  15. C14–22 n-Alkanes in Soil from the Freetown Layered Intrusion, Sierra Leone: Products of Pt Catalytic Breakdown of Natural Longer Chain n-Alkanes?

    Directory of Open Access Journals (Sweden)

    John F. W. Bowles

    2018-03-01

    Full Text Available Soil above a platinum-group element (PGE-bearing horizon within the Freetown Layered Intrusion, Sierra Leone, contains anomalous concentrations of n-alkanes (CnH2n+2 in the range C14 to C22 not readily attributable to an algal or lacustrine origin. Longer chain n-alkanes (C23 to C31 in the soil were derived from the breakdown of leaf litter beneath the closed canopy humid tropical forest. Spontaneous breakdown of the longer chain n-alkanes to form C14–22 n-alkanes without biogenic or abiogenic catalysts is unlikely as the n-alkanes are stable. In the Freetown soil, the catalytic properties of the PGE (Pt in particular may lower the temperature at which oxidation of the longer chain n-alkanes can occur. Reaction between these n-alkanes and Pt species, such as Pt2+(H2O2(OH2 and Pt4+(H2O2(OH4 can bend and twist the alkanes, and significantly lower the Heat of Formation. Microbial catalysis is a possibility. Since a direct organic geochemical source of the lighter n-alkanes has not yet been identified, this paper explores the theoretical potential for abiogenic Pt species catalysis as a mechanism of breakdown of the longer n-alkanes to form C14–22 alkanes. This novel mechanism could offer additional evidence for the presence of the PGE in solution, as predicted by soil geochemistry.

  16. Wavepacket revivals in monolayer and bilayer graphene rings.

    Science.gov (United States)

    García, Trinidad; Rodríguez-Bolívar, Salvador; Cordero, Nicolás A; Romera, Elvira

    2013-06-12

    We have studied the existence of quantum revivals in graphene quantum rings within a simplified model. The time evolution of a Gaussian-populated wavepacket shows revivals in monolayer and bilayer graphene rings. We have also studied this behavior for quantum rings in a perpendicular magnetic field. We have found that revival time is an observable that shows different values for monolayer and bilayer graphene quantum rings. In addition, the revival time shows valley degeneracy breaking.

  17. Wavepacket revivals in monolayer and bilayer graphene rings

    International Nuclear Information System (INIS)

    García, Trinidad; Rodríguez-Bolívar, Salvador; Cordero, Nicolás A; Romera, Elvira

    2013-01-01

    We have studied the existence of quantum revivals in graphene quantum rings within a simplified model. The time evolution of a Gaussian-populated wavepacket shows revivals in monolayer and bilayer graphene rings. We have also studied this behavior for quantum rings in a perpendicular magnetic field. We have found that revival time is an observable that shows different values for monolayer and bilayer graphene quantum rings. In addition, the revival time shows valley degeneracy breaking. (paper)

  18. Soot emissions from turbulent diffusion flames burning simple alkane fuels

    Energy Technology Data Exchange (ETDEWEB)

    Canteenwalla, P.M.; Johnson, M.R. [Carleton Univ., Ottawa, ON (Canada). Dept. of Mechanical and Aerospace Engineering; Thomson, K.A.; Smallwood, G.J. [National Research Council of Canada, Ottawa, ON (Canada). Inst. for Chemical Process and Environmental Technology

    2007-07-01

    A classic problem in combustion involves measurement and prediction of soot emissions from turbulent diffusion flames. Very high-sensitivity measurements of particulate matter (PM) from very low-sooting diffusion flames burning methane and other simple alkane fuels have been enabled from recent advances in laser-induced incandescence (LII). In order to quantify soot emissions from a lab-scale turbulent diffusion flame burner, this paper presented a study that used LII to develop a sampling protocol. The purpose of the study was to develop an experimentally based model to predict PM emissions from flares used in industry using soot emissions from lab-scale flares. Quantitative results of mass of soot emitted per mass of fuel burned were presented across a range of flow conditions and fuels. The experiment used digital imaging to measure flame lengths and estimate flame residence times. Comparisons were also made between current measurements and results of previous researchers for soot in the overfire region. The study also considered the validity applicability of buoyancy based models for predicting and scaling soot emissions. The paper described the experimental setup including sampling system and flame length imaging. Background information on soot yield and a comparison of flame residence time definitions were provided. The results and discussion of results were also presented. It was concluded that the results highlighted the subjective nature of flame length measurements. 10 refs., 4 figs.

  19. Interaction of Soybean 7S Globulin Peptide with Cell Membrane Model via Isothermal Titration Calorimetry, Quartz Crystal Microbalance with Dissipation, and Langmuir Monolayer Study.

    Science.gov (United States)

    Zou, Yuan; Pan, Runting; Ruan, Qijun; Wan, Zhili; Guo, Jian; Yang, Xiaoquan

    2018-05-16

    To understand the underlying molecular mechanism of the cholesterol-lowering effect of soybean 7S globulins, the interactions of their pepsin-released peptides (7S-peptides) with cell membrane models consisting of dipalmitoylphosphatidylcholine (DPPC), dioleoylphosphatidylcholine (DOPC), and cholesterol (CHOL) were systematically studied. The results showed that 7S-peptides were bound to DPPC/DOPC/CHOL liposomes mainly through van der Waals forces and hydrogen bonds, and the presence of higher CHOL concentrations enhanced the binding affinity (e.g., DPPC/DOPC/CHOL = 1:1:0, binding ratio = 0.114; DPPC/DOPC/CHOL = 1:1:1, binding ratio = 2.02). Compression isotherms indicated that the incorporation of 7S-peptides increased the DPPC/DOPC/CHOL monolayer fluidity and the lipid raft size. The presence of CHOL accelerated the 7S-peptide accumulation on lipid rafts, which could serve as platforms for peptides to develop into β-sheet rich structures. These results allow us to hypothesize that 7S-peptides may indirectly influence membrane protein functions via altering the membrane organization in the enterocytes.

  20. Deposition of radiation energy in solids as visualized by the distribution, structure and properties of alkyl radicals in γ-irradiated n-alkane single crystals

    International Nuclear Information System (INIS)

    Gillbro, T.; Lund, A.

    1976-01-01

    This paper summarizes results obtained earlier from ESR studies of γ-irradiated n-alkane single crystals. It also contains some new experimental results that serve to give a more complete picture of the deposition of radiation energy in solid alkanes. The experiments performed with solid n-alkanes have thus far provided structural data that permit the nature and even the conformation of alkyl radicals to be clearly understood. Two types of radical exist namely, one where the unpaired electron is located next to the end methyl group and one with the unpaired electron in the interior of the chain. The first type has a conformation which differs from that of the undamaged molecule. Microwave saturation data show that there is a difference in relaxation properties of these radicals which can be understood in terms of a difference in mobility. Relative yield measurements give the distribution of isomeric alkyl, the result differing from that obtained using product analysis in liquids. For protiated n-alkanes n-alkyl is lacking and the 2-alkyl concentration is higher than expected. For deuterated n-alkanes the ESR spectrum is mainly that of radicals with the unpaired electron located in the interior of the carbon chain. This isotope effect is again contrary to observations in liquid n-alkanes. The broad lines observed in protiated alkanes irradiated at 77 K and deuterated alkanes irradiated at 4.2 K are not believed to arise from strong spin-spin interactions. They are thought instead to arise from distorted crystal and radical structures relating to the damaged regions of the crystals. (Auth.)

  1. Alkane and polycyclic aromatic hydrocarbons in sediments and benthic invertebrates of the northern Chukchi Sea

    Science.gov (United States)

    Harvey, H. Rodger; Taylor, Karen A.

    2017-10-01

    The Hanna Shoal region represents an important northern gateway for transport and deposition in the Chukchi Sea. This study determined the concentration and distribution of organic contaminants (aliphatic hydrocarbon and polycyclic aromatic hydrocarbons, PAHs) in surface sediments from 34 sites across Hanna Shoal. Up to 31 total PAHs, including parent and alkyl homologues were detected with total concentrations ranging from a low of 168 ng g-1 the western flank of Hanna Shoal (station H34) to 1147 ng g-1 at station in Barrow Canyon (station BarC5). Alkyl PAHs were more abundant than parent structures and accounted for 53-64% of the summed concentrations suggesting overall at background levels (< 1600 ng g-1) in sediments. Alkane (C15-C33) hydrocarbons ranged from 4.3 μg g-1 on the southern flank of Hanna shoal to 31 μg g-1 at a northern station. Sediments were often dominated by short chain (C15-C22) alkanes with overall terrestrial aquatic ratios (TAR) for the region averaging 0.20. Based on the ratio of Fl/(Fl+ Py) and BaF/(Baf+BeP) verses (BA/BA+Ch) in sediments, PAHs are largely derived from petrogenic sources with minor amounts of mixed combustion sources. A diversity of PAHs were detected in the northern whelk Neptunea heros foot muscle with total concentrations ranging from 0.14 to 1.5 μg g-1 dry tissue wt. Larger (and presumably older) animals showed higher levels of PAH per unit muscle tissue, suggesting that animals may bioaccumulate PAHs over time, with low but increasing concentrations also present in internal and external eggs. Alkane hydrocarbons were also higher in whelks with distributions similar to that seen in sediments. The mussel Muscularus discors collected in Barrow Canyon showed constrained distributions and substantially lower concentrations of both PAHs and alkanes than the surrounding surface sediments.

  2. Packing properties 1-alkanols and alkanes in a phospholipid membrane

    DEFF Research Database (Denmark)

    Westh, Peter

    2006-01-01

    We have used vibrating tube densitometry to investigate the packing properties of four alkanes and a homologous series of ten alcohols in fluid-phase membranes of dimyristoyl phosphatidylcholine (DMPC). It was found that the volume change of transferring these compounds from their pure states int...... into the membrane core, which is loosely packed. In this region, they partially occupy interstitial (or free-) volume, which bring about a denser molecular packing and generate a negative contribution to Vm(puremem)....... into the membrane, Vm(puremem), was positive for small (C4-C6) 1-alkanols while it was negative for larger alcohols and all alkanes. The magnitude of Vm(puremem) ranged from about +4 cm3/mol for alcohols with an alkyl chain about half the length of the fatty acids of DMPC, to -10 to -15 cm3/mol for the alkanes...

  3. Collective cell motion in endothelial monolayers

    International Nuclear Information System (INIS)

    Szabó, A; Ünnep, R; Méhes, E; Czirók, A; Twal, W O; Argraves, W S; Cao, Y

    2010-01-01

    Collective cell motility is an important aspect of several developmental and pathophysiological processes. Despite its importance, the mechanisms that allow cells to be both motile and adhere to one another are poorly understood. In this study we establish statistical properties of the random streaming behavior of endothelial monolayer cultures. To understand the reported empirical findings, we expand the widely used cellular Potts model to include active cell motility. For spontaneous directed motility we assume a positive feedback between cell displacements and cell polarity. The resulting model is studied with computer simulations and is shown to exhibit behavior compatible with experimental findings. In particular, in monolayer cultures both the speed and persistence of cell motion decreases, transient cell chains move together as groups and velocity correlations extend over several cell diameters. As active cell motility is ubiquitous both in vitro and in vivo, our model is expected to be a generally applicable representation of cellular behavior

  4. Electrochemical behaviour of monolayer and bilayer graphene

    OpenAIRE

    Valota, Anna T.; Kinloch, Ian A.; Novoselov, Kostya S.; Casiraghi, Cinzia; Eckmann, Axel; Hill, Ernie W.; Dryfe, Robert A. W.

    2011-01-01

    Results of a study on the electrochemical properties of exfoliated single and multilayer graphene flakes are presented. Graphene flakes were deposited on silicon/silicon oxide wafers to enable fast and accurate characterization by optical microscopy and Raman spectroscopy. Conductive silver paint and silver wires were used to fabricate contacts; epoxy resin was employed as masking coating in order to expose a stable, well defined area of graphene. Both multilayer and monolayer graphene microe...

  5. Regioselective alkane hydroxylation with a mutant AlkB enzyme

    Science.gov (United States)

    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.

  6. On the relation between Zenkevich and Wiener indices of alkanes

    Directory of Open Access Journals (Sweden)

    ZARKO BOSKOVIC

    2004-04-01

    Full Text Available A relatively complicated relation was found to exist between the quantity U, recently introduced by Zenkevich (providing a measure of internal molecular energy, and the Wiener index W (measuring molecular surface area and intermolecular forces. We now report a detailed analysis of this relation and show that, in the case of alkanes, its main features are reproduced by the formula U = –aW + b + gn1; where n1 is the number of methyl groups, and a, b and g are constants, depending only on the number of carbon atoms. Thus, for isomeric alkanes with the same number of methyl groups, U and W are linearly correlated.

  7. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

    KAUST Repository

    Szeto, Kaï Chung; Hardou, Lucie; Merle, Nicolas; Basset, Jean-Marie; Thivolle-Cazat, Jean; Papaioannou, Charalambos; Taoufik, Mostafa

    2012-01-01

    We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product

  8. Epitaxial growth by monolayer restricted galvanic displacement

    Directory of Open Access Journals (Sweden)

    Vasilić Rastko

    2012-01-01

    Full Text Available The development of a new method for epitaxial growth of metals in solution by galvanic displacement of layers pre-deposited by underpotential deposition (UPD was discussed and experimentally illustrated throughout the lecture. Cyclic voltammetry (CV and scanning tunneling microscopy (STM are employed to carry out and monitor a “quasi-perfect”, two-dimensional growth of Ag on Au(111, Cu on Ag(111, and Cu on Au(111 by repetitive galvanic displacement of underpotentially deposited monolayers. A comparative study emphasizes the displacement stoichiometry as an efficient tool for thickness control during the deposition process and as a key parameter that affects the deposit morphology. The excellent quality of layers deposited by monolayer-restricted galvanic displacement is manifested by a steady UPD voltammetry and ascertained by a flat and uniform surface morphology maintained during the entire growth process.

  9. Improving Charge Injection in Organic Electronic Devices Using Self-Assembled Monolayers

    Science.gov (United States)

    Campbell, I. H.; Kress, J. D.; Martin, R. L.; Smith, D. L.; Barashkov, N. N.; Ferraris, J. P.

    1997-03-01

    Organic electronic devices consist of one or more insulating organic layers contacted by metallic conductors. The Schottky energy barrier between the metal and the organic material is determined by the work function of the metal contact as described in the ideal Schottky model. The magnitude of the metal/organic Schottky energy barrier controls charge injection from the metal into the organic layer. Previously, polar alkane-thiol based self-assembled monolayers (SAMs) were used to change the Schottky energy barrier between the metal and an organic film by more than 1 eV. In these SAMs, the large energy gap of the alkane molecules blocks charge injection into the organic layer despite the decrease of the Schottky energy barrier. Here, we demonstrate improved charge injection into the organic material by using conjugated self-assembled monolayers. The conjugated SAMs have modest energy gaps which allow improved charge injection into the organic layer. We present measurements of current-voltage characteristics and metal/organic Schottky energy barriers for device structures both with and without conjugated SAMs.

  10. Extraction of pentylbenzene from high molar mass alkanes (C14 and C17) by N-methyl-2-pyrrolidone

    International Nuclear Information System (INIS)

    Fandary, Mohamed S.; Al-Jimaz, Adel S.; Al-Kandary, Jasem A.; Fahim, Mohamed A.

    2006-01-01

    Equilibrium tie line data have been determined for the two ternary liquid systems: {tetradecane, or heptadecane + pentylbenzene + N-methyl-2-pyrrolidone (NMP)} over a temperature range of (298 to 328) K. The two systems studied exhibit type I liquid + liquid phase diagram. The effect of temperature and n-alkane chain length upon solubility, selectivity, and distribution coefficients were investigated experimentally

  11. Monolayer Cu2Si as a potential gas sensor for NOx and COx (x = 1, 2): A first-principles study

    Science.gov (United States)

    Zhu, Hao-Hao; Ye, Xiao-Juan; Liu, Chun-Sheng; Yan, Xiao-Hong

    2018-02-01

    Although the metal-decoration can enhance the sensing properties of two-dimensional (2D) materials, the cyclic utilization of materials is hindered by the clustering tendency of metal atoms. Furthermore, there exists a risk of explosion of combustible gases with the electrical measure. Based on first-principles calculations, we investigate the adsorption of various gas molecules (O2, NO, NO2, NH3, N2, CO, CH4 and CO2) on the 2D Cu-Si extended system (Cu2Si). The NOx molecules are chemisorbed on the Cu2Si monolayer, while other gas molecules (except CH4 and N2) are held by an interaction intermediating between the physisorbed and chemisorbed states. The strong hybridizations between N 2p and Si 3p (Cu 4p) orbitals lead to the large adsorption energies. Interestingly, the adsorption of NOx (1 μB) and CO2 (2 μB) can induce magnetic moments on the intrinsically nonmagnetic Cu2Si monolayer. The magnetic moment of NO-Cu2Si mainly arises from the molecule, while the magnetic moments for the NO2 and CO2 adsorption almost origin from the monolayer. In addition, an antiferromagnetic coupling is found in CO-Cu2Si. The changes in magnetization upon the gas adsorption may be detected sensitively and safely, suggesting the Cu2Si monolayer is potential for gas sensing.

  12. A Study by Contact Angle of the Acid-Base Behavior of Monolayers Containing W-Mercaptocarboxylic Acids Absorbed on Gold: An Example of Reactive Spreading

    Science.gov (United States)

    1989-11-01

    1966,22, 138-143. 27 Joos, P. Bull. Soc. Chim. Belges 1971, 80, 277-281. 28 Patil, G. S.; Matthews, R. H.; Cornwell , D. G. In Monolayers; Goddard, E...Commanding Officer 1 Chief of Naval Research Naval Weapons Support Center Special Assistant Attn: Dr. Bernard E. Douda for Marine Corps Matters Crane

  13. Expression and functional activity of P-glycoprotein in passaged primary human nasal epithelial cell monolayers cultured by the air-liquid interface method for nasal drug transport study.

    Science.gov (United States)

    Cho, Hyun-Jong; Choi, Min-Koo; Lin, Hongxia; Kim, Jung Sun; Chung, Suk-Jae; Shim, Chang-Koo; Kim, Dae-Duk

    2011-03-01

    P-glycoprotein (P-gp) is an efflux transporter encoded by the multidrug resistance gene (MDR1), which is also known as the human ABCB1 gene (ATP-binding cassette, subfamily-B). The objectives of this study were to investigate the expression of P-gp in passaged primary human nasal epithelial (HNE) cell monolayer, cultured by the air-liquid interface (ALI) method, and to evaluate its feasibility as an in-vitro model for cellular uptake and transport studies of P-gp substrates. Reverse transcriptase-polymerase chain reaction (RT-PCR) was performed to verify the expression of the MDR1 gene. Transport and cellular uptake studies with P-gp substrate (rhodamine123) and P-gp inhibitors (verapamil and cyclosporin A) were conducted to assess the functional activity of P-gp in HNE cell monolayers cultured by the ALI method. MDR1 gene expression in primary HNE cell monolayers cultured by ALI method was confirmed by RT-PCR. The apparent permeability coefficient (P(app) ) of the P-gp substrate (rhodamine123) in the basolateral to apical (B to A) direction was 6.9 times higher than that in the apical to basolateral (A to B) direction. B to A transport was saturated at high rhodamine123 concentration, and the treatment of P-gp inhibitors increased cellular uptake of rhodamine123 in a time- and concentration-dependent manner. These results support the MDR1 gene expression and the functional activity of P-gp in primary HNE cell monolayers cultured by the ALI method. © 2011 The Authors. JPP © 2011 Royal Pharmaceutical Society.

  14. Trimethylamine (fishy odor) adsorption by biomaterials: effect of fatty acids, alkanes, and aromatic compounds in waxes.

    Science.gov (United States)

    Boraphech, Phattara; Thiravetyan, Paitip

    2015-03-02

    Thirteen plant leaf materials were selected to be applied as dried biomaterial adsorbents for polar gaseous trimethylamine (TMA) adsorption. Biomaterial adsorbents were efficient in adsorbing gaseous TMA up to 100% of total TMA (100 ppm) within 24 h. Sansevieria trifasciata is the most effective plant leaf material while Plerocarpus indicus was the least effective in TMA adsorption. Activated carbon (AC) was found to be lower potential adsorbent to adsorb TMA when compared to biomaterial adsorbents. As adsorption data, the Langmuir isotherm supported that the gaseous TMA adsorbed monolayer on the adsorbent surface and was followed pseudo-second order kinetic model. Wax extracted from plant leaf could also adsorb gaseous TMA up to 69% of total TMA within 24 h. Another 27-63% of TMA was adsorbed by cellulose and lignin that naturally occur in high amounts in plant leaf. Subsequently, the composition appearing in biomaterial wax showed a large quantity of short-chain fatty acids (≤C18) especially octadecanoic acid (C18), and short-chain alkanes (C12-C18) as well as total aromatic components dominated in the wax, which affected TMA adsorption. Hence, it has been demonstrated that plant biomaterial is a superior biosorbent for TMA removal.

  15. Monolayer arrangement of fatty hydroxystearic acids on graphite: Influence of hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Medina, S. [Laboratorio de Rayos-X, Centro de Investigación Tecnología e Innovación, de la Universidad de Sevilla (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes, 4B. 41012, Sevilla (Spain); Benítez, J.J.; Castro, M.A. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain); Cerrillos, C. [Servicio de Microscopía, Centro de Investigación Tecnología e Innovación, de la Universidad de Sevilla (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes, 4B. 41012, Sevilla (Spain); Millán, C. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain); Alba, M.D., E-mail: alba@icmse.csic.es [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain)

    2013-07-31

    Previous studies have indicated that long-chain linear carboxylic acids form commensurate packed crystalline monolayers on graphite even at temperatures above their melting point. This study examines the effect on the monolayer formation and structure of adding one or more secondary hydroxyl, functional groups to the stearic acid skeleton (namely, 12-hydroxystearic and 9,10-dihydroxystearic acid). Moreover, a comparative study of the monolayer formation on recompressed and monocrystalline graphite has been performed through X-ray diffraction (XRD) and Scanning Tunneling Microscopy (STM), respectively. The Differential Scanning Calorimetry (DSC) and XRD data were used to confirm the formation of solid monolayers and XRD data have provided a detailed structural analysis of the monolayers in good correspondence with obtained STM images. DSC and XRD have demonstrated that, in stearic acid and 12-hydroxystearic acid adsorbed onto graphite, the monolayer melted at a higher temperature than the bulk form of the carboxylic acid. However, no difference was observed between the melting point of the monolayer and the bulk form for 9,10-dihydroxystearic acid adsorbed onto graphite. STM results indicated that all acids on the surface have a rectangular p2 monolayer structure, whose lattice parameters were uniaxially commensurate on the a-axis. This structure does not correlate with the initial structure of the pure compounds after dissolving, but it is conditioned to favor a) hydrogen bond formation between the carboxylic groups and b) formation of hydrogen bonds between secondary hydroxyl groups, if spatially permissible. Therefore, the presence of hydroxyl functional groups affects the secondary structure and behavior of stearic acid in the monolayer. - Highlights: • Hydroxyl functional groups affect structure and behavior of acids in the monolayer. • Acids on the surface have a rectangular p2 monolayer structure. • Lattice parameters of acids are uniaxially

  16. Conformation, orientation and interaction in molecular monolayers

    International Nuclear Information System (INIS)

    Superfine, R.; Huang, J.Y.; Shen, Y.R.

    1989-01-01

    Knowledge of the conformation and ordering of molecular monolayers is essential for a detailed understanding of a wide variety of surface and interfacial phenomena. Over the past several years, surface second harmonic generation (SHG) has proven to be a valuable and versatile probe of monolayer systems. Our group has recently extended the technique to infrared-visible sum frequency generation (SFG) which has unique capabilities for surface vibrational spectroscopy. Like second harmonic generation, SFG is highly surface specific with submonolayer sensitivity at all interfaces accessible by light. The orientation of individual groups within an adsorbate molecule can be deduced by a polarization analysis of the SFG signal from the vibrational modes of the groups. The authors have used SHG and SFG to study orientations and conformations of surfactant and liquid crystal (LC) monolayers and their interaction on a substrate. The interfacial properties of LC are of great interest to many researchers for both basic science understanding and practical application to LC devices. It is well known that the bulk alignment of a liquid crystal in a cell is strongly affected by the surface treatment of the cell walls. The reason behind it is not yet clear. The theoretical background and experimental arrangement of SHG and SFG have been described elsewhere. In the setup, a 30 psec. Nd:YAG mode-locked laser system together with nonlinear accessories generates a visible beam at .532μm and an infrared beam tunable about 3.4μm. Both beams are focused to a common spot of 300μm dia. The typical signal off the surface from a compact ordered alkyl chain monolayer is ∼500 photons per pulse, easily detected with a photomultiplier tube

  17. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

    KAUST Repository

    Szeto, Kaï Chung

    2012-01-01

    We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product is unprecedented, asymmetrically distributed towards heavier alkanes. This journal is © 2012 The Royal Society of Chemistry.

  18. Nonequilibrium 2-hydroxyoctadecanoic acid monolayers: effect of electrolytes.

    Science.gov (United States)

    Lendrum, Conrad D; Ingham, Bridget; Lin, Binhua; Meron, Mati; Toney, Michael F; McGrath, Kathryn M

    2011-04-19

    2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position α to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of ∼6. The role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase. © 2011 American Chemical Society

  19. Pronounced Environmental Effects on Injection Currents in EGaIn Tunneling Junctions Comprising Self-Assembled Monolayers.

    Science.gov (United States)

    Carlotti, Marco; Degen, Maarten; Zhang, Yanxi; Chiechi, Ryan C

    2016-09-15

    Large-area tunneling junctions using eutectic Ga-In (EGaIn) as a top contact have proven to be a robust, reproducible, and technologically relevant platform for molecular electronics. Thus far, the majority of studies have focused on saturated molecules with backbones consisting mainly of alkanes in which the frontier orbitals are either highly localized or energetically inaccessible. We show that self-assembled monolayers of wire-like oligophenyleneethynylenes (OPEs), which are fully conjugated, only exhibit length-dependent tunneling behavior in a low-O 2 environment. We attribute this unexpected behavior to the sensitivity of injection current on environment. We conclude that, contrary to previous reports, the self-limiting layer of Ga 2 O 3 strongly influences transport properties and that the effect is related to the wetting behavior of the electrode. This result sheds light on the nature of the electrode-molecule interface and suggests that adhesive forces play a significant role in tunneling charge-transport in large-area molecular junctions.

  20. Exploring atomic defects in molybdenum disulphide monolayers

    KAUST Repository

    Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

    2015-01-01

    Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 10 13 cm '2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

  1. Exploring atomic defects in molybdenum disulphide monolayers

    KAUST Repository

    Hong, Jinhua

    2015-02-19

    Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 10 13 cm \\'2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

  2. Affinity of serum apolipoproteins for lipid monolayers

    International Nuclear Information System (INIS)

    Ibdah, J.A.

    1987-01-01

    The effects of lipid composition and packing as well as the structure of the protein on the affinities of apolipoproteins for lipid monolayers have been investigated. The adsorption of 14 C-reductively methylated human apolipoproteins A-I and A-II at saturating subphase concentrations to monolayers prepared with synthetic lipids or lipoprotein surface lipids spread at various initial surface pressures has been studied. The adsorption of apolipoproteins is monitored by following the surface radioactivity using a gas flow counter and Wilhelmy plate, respectively. The physical states of the lipid monolayers are evaluated by measurement of the surface pressure-molecular area isotherms using a Langmuir-Adam surface balance. The probable helical regions in various apolipoproteins have been predicted using a secondary structure analysis computer program. The mean residue hydrophobicity and mean residue hydrophobic moment for the predicted helical segments have been calculated. The surface properties of synthetic peptides which are amphipathic helix analogs have been investigated at the air-water and lipid-water interfaces

  3. Nonlinear optical characteristics of monolayer MoSe{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Le, Chinh Tam; Ullah, Farman; Senthilkumar, Velusamy; Kim, Yong Soo [Department of Physics and Energy Harvest Storage Research Center, University of Ulsan (Korea, Republic of); Clark, Daniel J.; Jang, Joon I. [Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, NY (United States); Sim, Yumin; Seong, Maeng-Je [Department of Physics, Chung-Ang University, Seoul (Korea, Republic of); Chung, Koo-Hyun [School of Mechanical Engineering, University of Ulsan (Korea, Republic of); Park, Hyoyeol [Electronics, Communication and Semiconductor Applications Department, Ulsan College (Korea, Republic of)

    2016-08-15

    In this study, we utilized picosecond pulses from an Nd:YAG laser to investigate the nonlinear optical characteristics of monolayer MoSe{sub 2}. Two-step growth involving the selenization of pulsed-laser-deposited MoO{sub 3} film was employed to yield the MoSe{sub 2} monolayer on a SiO{sub 2}/Si substrate. Raman scattering, photoluminescence (PL) spectroscopy, and atomic force microscopy verified the high optical quality of the monolayer. The second-order susceptibility χ{sup (2)} was calculated to be ∝50 pm V{sup -1} at the second harmonic wavelength λ{sub SHG} ∝810 nm, which is near the optical gap of the monolayer. Interestingly, our wavelength-dependent second harmonic scan can identify the bound excitonic states including negatively charged excitons much more efficiently, compared with the PL method at room temperature. Additionally, the MoSe{sub 2} monolayer exhibits a strong laser-induced damage threshold ∝16 GW cm{sup -2} under picosecond-pulse excitation{sub .} Our findings suggest that monolayer MoSe{sub 2} can be considered as a promising candidate for high-power, thin-film-based nonlinear optical devices and applications. (copyright 2016 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Surface Charge Transfer Doping of Monolayer Phosphorene via Molecular Adsorption.

    Science.gov (United States)

    He, Yuanyuan; Xia, Feifei; Shao, Zhibin; Zhao, Jianwei; Jie, Jiansheng

    2015-12-03

    Monolayer phosphorene has attracted much attention owing to its extraordinary electronic, optical, and structural properties. Rationally tuning the electrical transport characteristics of monolayer phosphorene is essential to its applications in electronic and optoelectronic devices. Herein, we study the electronic transport behaviors of monolayer phosphorene with surface charge transfer doping of electrophilic molecules, including 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), NO2, and MoO3, using density functional theory combined with the nonequilibrium Green's function formalism. F4TCNQ shows optimal performance in enhancing the p-type conductance of monolayer phosphorene. Static electronic properties indicate that the enhancement is originated from the charge transfer between adsorbed molecule and phosphorene layer. Dynamic transport behaviors demonstrate that additional channels for hole transport in host monolayer phosphorene were generated upon the adsorption of molecule. Our work unveils the great potential of surface charge transfer doping in tuning the electronic properties of monolayer phosphorene and is of significance to its application in high-performance devices.

  5. Stable hydrogen isotopic composition of n-alkanes in atmospheric aerosols as a tracer for the source region of terrestrial plant waxes

    Science.gov (United States)

    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

  6. Solid acid catalysts in heterogeneous n-alkanes hydroisomerisation ...

    African Journals Online (AJOL)

    As the current global environmental concerns have prompted regulations to reduce the level of aromatic compounds, particularly benzene and its derivatives in gasoline, ydroisomerisation of n-alkanes is becoming a major alternative for enhancing octane number. Series of solid acid catalysts comprising of Freidel crafts, ...

  7. 40 CFR 721.10163 - Chloro fluoro alkane (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chloro fluoro alkane (generic). 721.10163 Section 721.10163 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC...)(2) of this section. (2) The significant new uses are: (i) Industrial, commercial, and consumer...

  8. Surface sealing using self-assembled monolayers and its effect on metal diffusion in porous low-k dielectrics studied using monoenergetic positron beams

    International Nuclear Information System (INIS)

    Uedono, Akira; Armini, Silvia; Zhang, Yu; Kakizaki, Takeaki; Krause-Rehberg, Reinhard; Anwand, Wolfgang; Wagner, Andreas

    2016-01-01

    Graphical abstract: - Highlights: • Pores with cubic pore side lengths of 1.1 and 3.1 nm coexisted in the low-k film. • For the sample without the SAM sealing process, metal atoms diffused from the top Cu/MnN layer into the OSG film and were trapped by the pores. Almost all pore interiors were covered by those metals. • For the sample damaged by a plasma etch treatment before the SAM sealing process, self-assembled molecules diffused into the OSG film, and they were preferentially trapped by larger pores. - Abstract: Surface sealing effects on the diffusion of metal atoms in porous organosilicate glass (OSG) films were studied by monoenergetic positron beams. For a Cu(5 nm)/MnN(3 nm)/OSG(130 nm) sample fabricated with pore stuffing, C_4F_8 plasma etch, unstuffing, and a self-assembled monolayer (SAM) sealing process, it was found that pores with cubic pore side lengths of 1.1 and 3.1 nm coexisted in the OSG film. For the sample without the SAM sealing process, metal (Cu and Mn) atoms diffused from the top Cu/MnN layer into the OSG film and were trapped by the pores. As a result, almost all pore interiors were covered with those metals. For the sample damaged by an Ar/C_4F_8 plasma etch treatment before the SAM sealing process, SAMs diffused into the OSG film, and they were preferentially trapped by larger pores. The cubic pore side length in these pores containing self-assembled molecules was estimated to be 0.7 nm. Through this work, we have demonstrated that monoenergetic positron beams are a powerful tool for characterizing capped porous films and the trapping of atoms and molecules by pores.

  9. Stability and magnetic properties of SnSe monolayer doped by transition metal atom (Mn, Fe, and Co): a first-principles study

    Science.gov (United States)

    Tang, Chao; Li, Qinwen; Zhang, Chunxiao; He, Chaoyu; Li, Jin; Ouyang, Tao; Li, Hongxing; Zhong, Jianxin

    2018-06-01

    Two dimensional (2D) tin selenium (SnSe) is an intriguing material with desired thermal and electric properties in nanoelectronics. In this paper, we carry on a density functional theory study on the stability and dilute magnetism of the 3d TM (Mn, Fe, and Co) doped 2D SnSe. Both the adsorption and substitution are in consideration here. We find that all the defects are electrically active and the cation substitutional doping (TM@Sn) is energetically favorable. The TM@Sn prefers to act as accepters and exhibits high-spin state with nonzero magnetic moment. The magnetic moment is mainly contributed by the spin-polarized charge density of the TM impurities. The magnetism is determined by the arrangement of the TM-3d orbitals, which is the result of the crystal field splitting and spin exchange splitting under specific symmetry. The magnetic and electronic properties of the TM@Sn are effectively modulated by external electric field (Eext) and charge doping. The Eext shifts the TM impurities relative to the SnSe host and then modifies the crystal field splitting. In particular, the magnetic moment is sensitive to the Eext in the Fe@Sn because the Eext induces distinct structure transformation. Based on the formation energy, doping electrons is a viable way to modulate the magnetic moment of TM@Sn. Doping electrons shift the 3d states towards low energy level, which induces the occupation of more 3d states and then the reduction of magnetism. These results render SnSe monolayer a promising 2D material for applications in future spintronics.

  10. Orientational epitaxy in adsorbed monolayers

    International Nuclear Information System (INIS)

    Novaco, A.D.; McTague, J.P.

    1977-01-01

    The ground state for adsorbed monolayers on crystalline substrates is shown to involve a definite relative orientation of the substrate and adsorbate crystal axes, even when the relative lattice parameters are incommensurate. The rotation angle which defines the structure of the monolayer-substrate system is determined by the competition between adsorbate-substrate and adsorbate-adsorbate energy terms, and is generally not a symmetry angle. Numerical predictions are presented for the rare gas-graphite systems, whose interaction potentials are rather well known. Recent LEED data for some of these systems appear to corroborate these predictions

  11. Polymer Adsorption on Graphite and CVD Graphene Surfaces Studied by Surface-Specific Vibrational Spectroscopy.

    Science.gov (United States)

    Su, Yudan; Han, Hui-Ling; Cai, Qun; Wu, Qiong; Xie, Mingxiu; Chen, Daoyong; Geng, Baisong; Zhang, Yuanbo; Wang, Feng; Shen, Y R; Tian, Chuanshan

    2015-10-14

    Sum-frequency vibrational spectroscopy was employed to probe polymer contaminants on chemical vapor deposition (CVD) graphene and to study alkane and polyethylene (PE) adsorption on graphite. In comparing the spectra from the two surfaces, it was found that the contaminants on CVD graphene must be long-chain alkane or PE-like molecules. PE adsorption from solution on the honeycomb surface results in a self-assembled ordered monolayer with the C-C skeleton plane perpendicular to the surface and an adsorption free energy of ∼42 kJ/mol for PE(H(CH2CH2)nH) with n ≈ 60. Such large adsorption energy is responsible for the easy contamination of CVD graphene by impurity in the polymer during standard transfer processes. Contamination can be minimized with the use of purified polymers free of PE-like impurities.

  12. Studies of endothelial monolayer formation on irradiated poly-L-lactide acid with ions of different stopping power and velocity

    Energy Technology Data Exchange (ETDEWEB)

    Arbeitman, Claudia R. [CONICET – Consejo Nacional de Investigaciones Científicas y Técnicas (Argentina); Gerencia de Investigación y Aplicaciones, TANDAR-CNEA (Argentina); UNQ – IMBICE – CCT – CONICET – LA PLATA (Argentina); Grosso, Mariela F. del [CONICET – Consejo Nacional de Investigaciones Científicas y Técnicas (Argentina); Gerencia de Investigación y Aplicaciones, TANDAR-CNEA (Argentina); Ibañez, Irene L. [CONICET – Consejo Nacional de Investigaciones Científicas y Técnicas (Argentina); Behar, Moni [Instituto de Física, UFRGS, Porto Alegre, RS (Brazil); Grasselli, Mariano [UNQ – IMBICE – CCT – CONICET – LA PLATA (Argentina); Bermúdez, Gerardo García [Gerencia de Investigación y Aplicaciones, TANDAR-CNEA (Argentina)

    2015-12-15

    In this work we study cell viability, proliferation and morphology of bovine aortic endothelial cells (BAEC) cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. In a previous study comparing ions beams with the same stopping power we observed an increase in cell density and a better cell morphology at higher ion velocities. In the present work we continued this study using heavy ions beam with different stopping power and ion velocities. To this end thin films of 50 μm thickness were irradiated with 2 MeV/u and 0.10 MeV/u ion beams provided the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The results suggest that a more dense and elongated cell shapes, similar to the BAEC cells on the internal surface of bovine aorta, was obtained for stopping power of 18.2–22.1 MeV cm{sup 2} mg{sup −1} and ion velocity of 2 MeV/u. On the other hand, for low ion velocity 0.10 MeV/u the cells present a more globular shapes.

  13. Studies of endothelial monolayer formation on irradiated poly-L-lactide acid with ions of different stopping power and velocity

    International Nuclear Information System (INIS)

    Arbeitman, Claudia R.; Grosso, Mariela F. del; Ibañez, Irene L.; Behar, Moni; Grasselli, Mariano; Bermúdez, Gerardo García

    2015-01-01

    In this work we study cell viability, proliferation and morphology of bovine aortic endothelial cells (BAEC) cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. In a previous study comparing ions beams with the same stopping power we observed an increase in cell density and a better cell morphology at higher ion velocities. In the present work we continued this study using heavy ions beam with different stopping power and ion velocities. To this end thin films of 50 μm thickness were irradiated with 2 MeV/u and 0.10 MeV/u ion beams provided the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The results suggest that a more dense and elongated cell shapes, similar to the BAEC cells on the internal surface of bovine aorta, was obtained for stopping power of 18.2–22.1 MeV cm 2 mg −1 and ion velocity of 2 MeV/u. On the other hand, for low ion velocity 0.10 MeV/u the cells present a more globular shapes.

  14. A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal

    Science.gov (United States)

    Solowey, Douglas P.; Mane, Manoj V.; Kurogi, Takashi; Carroll, Patrick J.; Manor, Brian C.; Baik, Mu-Hyun; Mindiola, Daniel J.

    2017-11-01

    Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community. Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CHtBu(CH3) (PNP=N[2-P(CHMe2)2-4-methylphenyl]2-), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C4 to C8 to terminal olefins under mild conditions. This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst. We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.

  15. Phase Behavior and Evaporation Profile of Tween 20 - Eugenol System. Effect of Different Alkane Chain Length and Solvent System

    International Nuclear Information System (INIS)

    Kassim, A.; Lim, W.H.; Kuangl, D.; Rusmawati, W.W.M.; Abdullah, A.H.; Teoh, S.P.

    2003-01-01

    The isotropic region of Tween 20/eugenol/n-alkane in aqueous systems was determined. The solubilisation trend of isotropic solution formed in the presence of eugenol was studied as a function of different alkyl chain length of n-alkane. The solubility of solvent in surfactant solution is dependent on their molecular polarity. An increase in n-alkane chain length (lower polarity) lead to smaller isotropic region which will affect the surfactant partitioning between the interface, the oil phase and the aqueous phase of the microemulsion as the oil chain length is varied. The changes of evaporation behaviour were affected strongly by the types of phases existed in the systems. The increment of n-alkane and water content led to higher evaporation rate. But the formation of w/o microemulsion would lower the evaporation rate because water molecules were trapped in the core of aggregates. In solubilisation system, evaporation rate is dependent on the solvent content and the interaction between Tween 20 and solvent molecules in the mixed composition. (author)

  16. Paleoclimate and Asian monsoon variability inferred from n-alkanes and their stable isotopes at lake Donggi Cona, NE Tibetan Plateau

    Science.gov (United States)

    Saini, Jeetendra; Guenther, Franziska; Mäusbacher, Roland; Gleixner, Gerd

    2015-04-01

    The Tibetan Plateau is one of the most extensive and sensitive region of elevated topography affecting global climate. The interplay between the Asian summer monsoon and the westerlies greatly influences the lake systems at the Tibetan Plateau. Despite a considerable number of research efforts in last decade, possible environmental reactions to change in monsoon dynamics are still not well understood. Here we present results from a sediment core of lake Donggi Cona, which dates back to late glacial period. Distinct organic geochemical proxies and stable isotopes are used to study the paleoenvironmental and hydrological changes in late glacial and Holocene period. Sedimentary n-alkanes of lake Donggi Cona are used as a proxy for paleoclimatic and monsoonal reconstruction. The hydrogen (δD) and carbon (δ13C) isotopes of n-alkanes are used as proxy for hydrological and phytoplankton productivity, respectively . Qualitative and quantitative analysis were performed for n-alkanes over the sediment core. δD proxy for sedimentary n-alkanes is used to infer lake water and rainfall signal. δD of (n-alkane C23) records the signal of the lake water, whereas δD of (n-alkane C29) record the precipitation signal, hence act as an appropriate proxy to track Asian monsoon. Long chain n-alkanes dominate over the sediment core while unsaturated mid chain n-alkenes have high abundance in some samples. From 18.4-13.8 cal ka BP, sample shows low organic productivity due to cold and arid climate. After 13.8-11.8 cal ka BP, slight increase in phytoplankton productivity indicate onset of weaker monsoon. From 11.8-6.8 cal ka BP, high content of organic matter indicates rise in productivity and strong monsoon with high inflow. After 6.8 cal ka BP, decrease in phytoplankton productivity indicating cooler climate and show terrestrial signal. Our results provide new insight into the variability of east Asian monsoon and changes in phytoplankton productivity for last 18.4 ka. Keywords: n-alkanes

  17. Subcellular topological effect of particle monolayers on cell shapes and functions.

    Science.gov (United States)

    Miura, Manabu; Fujimoto, Keiji

    2006-12-01

    We studied topological effects of subcellular roughness displayed by a closely packed particle monolayer on adhesion and growth of endothelial cells. Poly(styrene-co-acrylamide) (SA) particles were prepared by soap-free emulsion copolymerization. Particle monolayers were prepared by Langmuir-Blodgett deposition using particles, which were 527 (SA053) and 1270 nm (SA127) in diameter. After 24-h incubation, cells tightly adhered on a tissue culture polystyrene dish and randomly spread. On the other hand, cells attached on particle monolayers were stretched into a narrow stalk-like shape. Lamellipodia spread from the leading edge of cells attached on SA053 monolayer to the top of the particles and gradually gathered to form clusters. This shows that cell-cell adhesion became stronger than cell-substrate interaction. Cells attached to SA127 monolayer extended to the reverse side of a particle monolayer and engulfed particles. They remained immobile without migration 24h after incubation. This shows that the inhibition of extensions on SA127 monolayer could inhibit cell migration and cell proliferation. Cell growth on the particle monolayers was suppressed compared with a flat TCPS dish. The number of cells on SA053 gradually increased, whereas that on SA127 decreased with time. When the cell seeding density was increased to 200,000 cells cm(-2), some adherent cells gradually became into contact with adjacent cells. F-actin condensations were formed at the frame of adherent cells and the thin filaments grew from the edges to connect each other with time. For the cell culture on SA053 monolayer, elongated cells showed a little alignment. Cells showed not arrangement of actin stress fibers but F-actin condensation at the contact regions with neighboring cells. Interestingly, the formed cell monolayer could be readily peeled from the particle monolayer. These results indicate that endothelial cells could recognize the surface roughness displayed by particle monolayers and

  18. Solution-processable septithiophene monolayer transistor

    NARCIS (Netherlands)

    Defaux, M.; Gholamrezaie, F.; Wang, J.; Kreyes, A.; Ziener, U.; Anokhin, D.V.; Ivanov, D.A.; Moser, A.; Neuhold, A.; Salzmann, I.; Resel, R.; Leeuw, de D.M.; Meskers, S.C.J.; Moeller, M.; Mourran, A.

    2012-01-01

    Septithiophene with endgroups designed to form liquid crystalline phases and allows controlled deposition of an electrically connected monolayer. Field effect mobilies mobilities of charge carriers and spectroscopic properties of the monolayer provide evidence of sustainable transport and

  19. Solution-Processable Septithiophene Monolayer Transistor

    NARCIS (Netherlands)

    Defaux, Matthieu; Gholamrezaie, Fatemeh; Wang, Jingbo; Kreyes, Andreas; Ziener, Ulrich; Anokhin, Denis V.; Ivanov, Dimitri A.; Moser, Armin; Neuhold, Alfred; Salzmann, Ingo; Resel, Roland; de Leeuw, Dago M.; Meskers, Stefan C. J.; Moeller, Martin; Mourran, Ahmed

    2012-01-01

    Septithiophene with endgroups designed to form liquid crystalline phases and allows controlled deposition of an electrically connected monolayer. Field effect mobilies mobilities of charge carriers and spectroscopic properties of the monolayer provide evidence of sustainable transport and

  20. Monte Carlo studies of thermalization of electron-hole pairs in spin-polarized degenerate electron gas in monolayer graphene

    Science.gov (United States)

    Borowik, Piotr; Thobel, Jean-Luc; Adamowicz, Leszek

    2018-02-01

    Monte Carlo method is applied to the study of relaxation of excited electron-hole (e-h) pairs in graphene. The presence of background of spin-polarized electrons, with high density imposing degeneracy conditions, is assumed. To such system, a number of e-h pairs with spin polarization parallel or antiparallel to the background is injected. Two stages of relaxation: thermalization and cooling are clearly distinguished when average particles energy and its standard deviation σ _E are examined. At the very beginning of thermalization phase, holes loose energy to electrons, and after this process is substantially completed, particle distributions reorganize to take a Fermi-Dirac shape. To describe the evolution of and σ _E during thermalization, we define characteristic times τ _ {th} and values at the end of thermalization E_ {th} and σ _ {th}. The dependence of these parameters on various conditions, such as temperature and background density, is presented. It is shown that among the considered parameters, only the standard deviation of electrons energy allows to distinguish between different cases of relative spin polarizations of background and excited electrons.

  1. Variation in the Apparent Biosynthetic Fractionation for N-alkane δD Among Terrestrial Plants: Patterns, Mechanisms, and Implications

    Science.gov (United States)

    Johnson, J. E.; Tipple, B. J.; Betancourt, J. L.; Ehleringer, J. R.; Leavitt, S. W.; Monson, R. K.

    2016-12-01

    Long-chain normal alkanes (n-alkanes) are a component of the leaf cuticle of all terrestrial plants. Since the hydrogen in the n-alkanes is derived from the hydrogen in plants' water sources and is non-exchangeable, the stable hydrogen isotopic composition (δD) of the n-alkanes provides information about the δD of environmental waters. While this relationship creates opportunities for using n-alkane δD for process-based reconstructions of δD of environmental waters, progress in this direction is currently constrained by the observation that terrestrial plants exhibit a startlingly wide range of apparent biosynthetic fractionations. To understand the mechanisms responsible for variation in the apparent biosynthetic fractionations, we compared measurements and models of δD for n-C29 in a water-limited ecosystem where the timing of primary and secondary cuticle deposition is closely coupled to water availability (Tumamoc Hill, Tucson, Arizona, USA). During the 2014-2015 hydrologic year, the most widespread and abundant plant species at this site exhibited δD for n-C29 varying over a total range of 102‰. Discrete samples of leaf water collected at the same time as the n-C29 samples exhibited δD varying over a total range of only 53‰, but a continuous model of leaf water through the annual cycle predicted δD varying over a total range of 190‰. These results indicate that the observed variation in the apparent biosynthetic fractionation for n-C29 δD could be primarily attributable to leaf water dynamics that are temporally uncoupled from primary and secondary cuticle deposition. If a single biosynthetic fractionation does describe the relationship between the δD of n-alkanes and leaf water during intervals of cuticle deposition, it will facilitate process-based interpretations of n-alkane δD values in ecological, hydrological, and climatological studies of modern and ancient terrestrial environments.

  2. Production of liquid alkanes by controlling reactivity of sorbitol hydrogenation with a Ni/HZSM-5 catalyst in water

    International Nuclear Information System (INIS)

    Zhang, Qing; Wang, Tiejun; Xu, Ying; Zhang, Qi; Ma, Longlong

    2014-01-01

    Graphical abstract: MCM-41-modified Ni/HZSM-5 catalyst was developed by impregnation method with high catalytic performance for sorbitol hydrogenation in water. Appropriate amount of MCM-41 addition can distinctly promote the improvement in the surface structure and modulation of acidic sites of the catalyst. The scission of C–O bond in the sorbitol molecule into liquid alkanes was easily carried out on the catalyst containing more Lewis acidic sites. - Highlights: • Ni/HZSM-5 promoted with MCM-41 is active for sorbitol hydrogenation to liquid alkanes. • Lewis acidic sites of Ni/HZSM-5 can be modulated by pure silica MCM-41. • MCM-41 added can distinctly decrease carbon deposition on the catalyst surface. - Abstract: Liquid fuels derived from renewable biomass are of great importance on the potential substitution for diminishing fossil fuels. The conversion of sorbitol (a product of biomass-derived glucose hydrogenation) into liquid alkanes such as pentane and hexane over the Ni/HZSM-5 catalysts with or without MCM-41 addition was investigated in the presence of hydrogen in water medium. The production distribution of sorbitol hydrogenation can be controlled by adjusting the acidity of the catalyst. The scission of C–C bond in the sorbitol molecule into light C 1 –C 4 alkanes was mainly carried out over Ni/HZSM-5 containing strong Brønsted acid sites, while C–O bond scission into heavier alkanes was dominated over the catalysts added by MCM-41 containing weak Lewis acid sites. The sorbitol conversion and total liquid alkanes selectivity were found to be 67.1% and 98.7% over 2%Ni/HZSM-5 modified by 40 wt% of MCM-41, whereas the corresponding value was 40% and 35.6% over 2%Ni/HZSM-5 in the absence of MCM-41. The effect of MCM-41 on the structure, acidity, and reducibility of Ni/HZSM-5 was investigated by using XRD, Py-IR, IR, and H 2 -TPR. Meanwhile, the resistance of carbon deposition over the catalyst modified by MCM-41 was studied by using TG

  3. Density functional study on the mechanism for the highly active palladium monolayer supported on titanium carbide for the oxygen reduction reaction

    International Nuclear Information System (INIS)

    Mao, Jianjun; Zhang, Yanxing; Chu, Xingli; Li, Shasha; Yang, Zongxian

    2016-01-01

    The adsorption, diffusion, and dissociation of O 2 on the palladium monolayer supported on TiC(001) surface, MLPd/TiC(001), are investigated using ab initio density functional theory calculations. Strong adhesion of palladium monolayer to the TiC(001) support, accompanied by a modification of electronic structure of the supported palladium, is evidenced. Compared with Pt(111) surface, the MLPd/TiC(001) can enhance the adsorption of O 2 , leading to comparable dissociation barrier and a smaller diffusion barrier of O 2 . Whilst the adsorption strength of atomic O (the dissociation product of O 2 ) on MLPd/TiC(001) is similar to that on the Pt(111) surface, possessing high mobility, our theoretical results indicate that MLPd/TiC(001) may serve as a good catalyst for the oxygen reduction reaction.

  4. Phase transitions in polymer monolayers

    NARCIS (Netherlands)

    Deschênes, Louise; Lyklema, J.; Danis, Claude; Saint-Germain, François

    2015-01-01

    In this paper we investigate the application of the two-dimensional Clapeyron law to polymer monolayers. This is a largely unexplored area of research. The main problems are (1) establishing if equilibrium is reached and (2) if so, identifying and defining phases as functions of the temperature.

  5. Crystallography and Molecular Arrangement of Polymorphic Monolayer J-Aggregates of a Cyanine Dye: Multiangle Polarized Light Fluorescence Optical Microscopy Study.

    Science.gov (United States)

    Prokhorov, Valery V; Pozin, Sergey I; Perelygina, Olga M; Mal'tsev, Eugene I

    2018-04-24

    The molecular orientation in monolayer J-aggregates of 3,3-di(γ-sulfopropyl)-5,5-dichlorotiamonomethinecyanine dye has been precisely estimated using improved linear polarization measurements in the fluorescence microscope in which a multiangle set of polarization data is obtained using sample rotation. The estimated molecular orientation supplemented with the previously established crystallographic constraints based on the analysis of the well-developed two-dimensional J-aggregate shapes unambiguously indicate the staircase type of molecular arrangement for striplike J-aggregates with the staircases oriented along strips. The molecular transition dipoles are inclined at an angle of ∼25° to the strip direction, whereas the characteristic strip vertex angle ∼45° is formed by the [100] and [1-10] directions of the monoclinic unit cell. Measurements of the geometry of partially unwound tubes and their polarization properties support the model of tube formation by close-packed helical winding of flexible monolayer strips. In the tubes, the long molecular axes are oriented at a small angle in the range of 5-15° to the normal to the tube axis providing low bending energy. At a nanoscale, high-resolution atomic force microscopy imaging of J-aggregate monolayers reveals a complex quasi-one-dimensional organization.

  6. Stability of defects in monolayer MoS_2 and their interaction with O_2 molecule: A first-principles study

    International Nuclear Information System (INIS)

    Zhao, B.; Shang, C.; Qi, N.; Chen, Z.Y.; Chen, Z.Q.

    2017-01-01

    Highlights: • Defects can exist steadily in monolayer MoS_2 and break surface chemical inertness. • Activated surfaces are beneficial to the adsorption of O_2 through the introduction of defect levels. • Adsorbed O_2 on defective surface can dissociate with low activation energy barrier. • Defective system may be a potential substrate to design MoS_2-based gas sensor or catalysts. - Abstract: The stability of various defects in monolayer MoS_2, as well as their interactions with free O_2 molecules were investigated by density functional theory (DFT) calculations coupled with the nudged elastic band (NEB) method. The defects including S vacancy (monosulfur and disulfue vacancies), antisite defect (Mo_S) and external Mo atom can exist steadily in monolayer MoS_2, and introduce defect levels in these defective systems, which breaks the surface chemical inertness and significantly enhances the adsorption capacity for free O_2. The adsorption energy calculations and electronic properties analysis suggest that there is a strong interaction between O_2 molecule and defective system. The adsorbed O_2 on the defective surface can dissociate with a lower activation energy barrier, which produce two active oxygen atoms. Especially, two Mo atoms can occupy one Mo lattice site, and adsorbed O_2 on the top of the Mo atom can then dissociate directly with the lowest activation energy barrier. Hence, our work may provide useful information to design MoS_2-based gas sensor or catalysts.

  7. Neutrophil-endothelial cell interactions on endothelial monolayers grown on micropore filters.

    Science.gov (United States)

    Taylor, R F; Price, T H; Schwartz, S M; Dale, D C

    1981-01-01

    We have developed a technique for growing endothelial monolayers on micropore filters. These monolayers demonstrate confluence by phase and electron microscopy and provide a functional barrier to passage of radiolabeled albumin. Neutrophils readily penetrate the monolayer in response to chemotaxin, whereas there is little movement in the absence of chemotaxin. This system offers unique advantages over available chemotaxis assays and may have wider applications in the study of endothelial function. Images PMID:7007441

  8. Interferon induction in bovine and feline monolayer cultures by four bluetongue virus serotypes.

    OpenAIRE

    Fulton, R W; Pearson, N J

    1982-01-01

    The interferon inducing ability of bluetongue viruses was studied in bovine and feline monolayer cultures inoculated with each of four bluetongue virus serotypes. Interferon was assayed by a plaque reduction method in monolayer cultures with vesicular stomatitis virus as challenge virus. Interferon was produced by bovine turbinate, Georgia bovine kidney, and Crandell feline kidney monolayer cultures in response to bluetongue virus serotypes 10, 11, 13 and 17. The antiviral substances produced...

  9. Image Charge Effects in the Wetting Behavior of Alkanes on Water with Accounting for Water Solubility

    Directory of Open Access Journals (Sweden)

    Kirill A. Emelyanenko

    2016-03-01

    Full Text Available 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.

  10. Active cell-matrix coupling regulates cellular force landscapes of cohesive epithelial monolayers

    Science.gov (United States)

    Zhao, Tiankai; Zhang, Yao; Wei, Qiong; Shi, Xuechen; Zhao, Peng; Chen, Long-Qing; Zhang, Sulin

    2018-03-01

    Epithelial cells can assemble into cohesive monolayers with rich morphologies on substrates due to competition between elastic, edge, and interfacial effects. Here we present a molecularly based thermodynamic model, integrating monolayer and substrate elasticity, and force-mediated focal adhesion formation, to elucidate the active biochemical regulation over the cellular force landscapes in cohesive epithelial monolayers, corroborated by microscopy and immunofluorescence studies. The predicted extracellular traction and intercellular tension are both monolayer size and substrate stiffness dependent, suggestive of cross-talks between intercellular and extracellular activities. Our model sets a firm ground toward a versatile computational framework to uncover the molecular origins of morphogenesis and disease in multicellular epithelia.

  11. Critical wetting of n-alkanes on water; Mouillage critique des alcanes sur l`eau

    Energy Technology Data Exchange (ETDEWEB)

    Ragil, K

    1996-10-18

    This study concerns the wetting properties of n-alkanes on water under thermodynamic equilibrium conditions, a problem that is interesting for the petroleum industry as well as for the fundamental understanding of wetting phenomena. An experimental study using ellipsometry reveals that pentane on water undergoes a continuous or critical wetting transition at a temperature equal to 53.1 deg. C. This is the first experimental observation of such a transition, confirming theoretical predictions made on this subject over ten years. This transition is characterized by a continuous and reversible evolution of the thickness of the film of pentane with temperature from a thick (but finite film) to a macroscopic film. The critical wetting transition occurs when the Hamaker constant of the system, which gives the net interaction between the two interfaces bounding the wetting layer of pentane in terms of the van der Waals forces, changes sign. A theoretical approach based on the Cahn-Landau theory, which takes into account long range forces (van der Waals forces), enables us to explain the mechanism of the critical wetting transition and to show that a first-order wetting transition should precede it. Because of their similar dispersive properties, linear alkanes could all be able to show such a succession of transitions. An ellipsometry study performed on a brine/hexane/vapor system confirms that a discontinuous transition from a thin microscopic film to a thick but finite adsorbed film takes place. THis study demonstrates that the wetting of alkanes on water is determined by subtle interplay between short range and long range forces, which can lead to an intermediary state between partial and complete wetting. (author)

  12. Controlled synthesis of high-quality crystals of monolayer MoS2 for nanoelectronic device application

    DEFF Research Database (Denmark)

    Yang, Xiaonian; Li, Qiang; Hu, Guofeng

    2016-01-01

    . Monolayer MoS2 so far can be obtained by mechanical exfoliation or chemical vapor deposition (CVD). However, controllable synthesis of large area monolayer MoS2 with high quality needs to be improved and their growth mechanism requires more studies. Here we report a systematical study on controlled...... synthesis of high-quality monolayer MoS2 single crystals using low pressure CVD. Large-size monolayer MoS2 triangles with an edge length up to 405 mu m were successfully synthesized. The Raman and photoluminescence spectroscopy studies indicate high homogenous optical characteristic of the synthesized...... monolayer MoS2 triangles. The transmission electron microscopy results demonstrate that monolayer MoS2 triangles are single crystals. The back-gated field effect transistors (FETs) fabricated using the as-grown monolayer MoS2 show typical n-type semiconductor behaviors with carrier mobility up to 21.8 cm(2...

  13. Flash Points of Secondary Alcohol and n-Alkane Mixtures.

    Science.gov (United States)

    Esina, Zoya N; Miroshnikov, Alexander M; Korchuganova, Margarita R

    2015-11-19

    The flash point is one of the most important characteristics used to assess the ignition hazard of mixtures of flammable liquids. To determine the flash points of mixtures of secondary alcohols with n-alkanes, it is necessary to calculate the activity coefficients. In this paper, we use a model that allows us to obtain enthalpy of fusion and enthalpy of vaporization data of the pure components to calculate the liquid-solid equilibrium (LSE) and vapor-liquid equilibrium (VLE). Enthalpy of fusion and enthalpy of vaporization data of secondary alcohols in the literature are limited; thus, the prediction of these characteristics was performed using the method of thermodynamic similarity. Additionally, the empirical models provided the critical temperatures and boiling temperatures of the secondary alcohols. The modeled melting enthalpy and enthalpy of vaporization as well as the calculated LSE and VLE flash points were determined for the secondary alcohol and n-alkane mixtures.

  14. Alkane Biosynthesis Genes in Cyanobacteria and Their Transcriptional Organization

    International Nuclear Information System (INIS)

    Klähn, Stephan; Baumgartner, Desirée; Pfreundt, Ulrike; Voigt, Karsten; Schön, Verena; Steglich, Claudia; Hess, Wolfgang R.

    2014-01-01

    In cyanobacteria, alkanes are synthesized from a fatty acyl-ACP by two enzymes, acyl–acyl carrier protein reductase and aldehyde deformylating oxygenase. Despite the great interest in the exploitation for biofuel production, nothing is known about the transcriptional organization of their genes or the physiological function of alkane synthesis. The comparison of 115 microarray datasets indicates the relatively constitutive expression of aar and ado genes. The analysis of 181 available genomes showed that in 90% of the genomes both genes are present, likely indicating their physiological relevance. In 61% of them they cluster together with genes encoding acetyl-CoA carboxyl transferase and a short-chain dehydrogenase, strengthening the link to fatty acid metabolism and in 76% of the genomes they are located in tandem, suggesting constraints on the gene arrangement. However, contrary to the expectations for an operon, we found in Synechocystis sp. PCC 6803 specific promoters for the two genes, sll0208 (ado) and sll0209 (aar), which give rise to monocistronic transcripts. Moreover, the upstream located ado gene is driven by a proximal as well as a second, distal, promoter, from which a third transcript, the ~160 nt sRNA SyR9 is transcribed. Thus, the transcriptional organization of the alkane biosynthesis genes in Synechocystis sp. PCC 6803 is of substantial complexity. We verified all three promoters to function independently from each other and show a similar promoter arrangement also in the more distant Nodularia spumigena, Trichodesmium erythraeum, Anabaena sp. PCC 7120, Prochlorococcus MIT9313, and MED4. The presence of separate regulatory elements and the dominance of monocistronic mRNAs suggest the possible autonomous regulation of ado and aar. The complex transcriptional organization of the alkane synthesis gene cluster has possible metabolic implications and should be considered when manipulating the expression of these genes in cyanobacteria.

  15. Alkane biosynthesis genes in cyanobacteria and their transcriptional organization

    Directory of Open Access Journals (Sweden)

    Stephan eKlähn

    2014-07-01

    Full Text Available In cyanobacteria, alkanes are synthesized from a fatty acyl-ACP by two enzymes, acyl-acyl carrier protein reductase (AAR and aldehyde deformylating oxygenase (ADO. Despite the great interest in the exploitation for biofuel production, nothing is known about the transcriptional organization of their genes or the physiological function of alkane synthesis. The comparison of 115 microarray datasets indicates the relatively constitutive expression of aar and ado genes. The analysis of 181 available genomes showed that in 90% of the genomes both genes are present, likely indicating their physiological relevance. In 61% of them they cluster together with genes encoding acetyl-CoA carboxyl transferase and a short chain dehydrogenase, strengthening the link to fatty acid metabolism and in 76% of the genomes they are located in tandem, suggesting constraints on the gene arrangement. However, contrary to the expectations for an operon, we found in Synechocystis sp. PCC 6803 specific promoters for the two genes, sll0208 (ado and sll0209 (aar, that give rise to monocistronic transcripts. Moreover, the upstream located ado gene is driven by a proximal as well as a second, distal, promoter, from which a third transcript, the ~160 nt sRNA SyR9 is transcribed. Thus, the transcriptional organization of the alkane biosynthesis genes in Synechocystis sp. PCC 6803 is of substantial complexity. We verified all three promoters to function independently from each other and show a similar promoter arrangement also in the more distant Nodularia spumigena, Trichodesmium erythraeum, Anabaena sp. PCC 7120, Prochlorococcus MIT9313 and MED4. The presence of separate regulatory elements and the dominance of monocistronic mRNAs suggest the possible autonomous regulation of ado and aar. The complex transcriptional organization of the alkane synthesis gene cluster has possible metabolic implications and should be considered when manipulating the expression of these genes in

  16. Alkane Biosynthesis Genes in Cyanobacteria and Their Transcriptional Organization

    Energy Technology Data Exchange (ETDEWEB)

    Klähn, Stephan; Baumgartner, Desirée; Pfreundt, Ulrike; Voigt, Karsten; Schön, Verena; Steglich, Claudia; Hess, Wolfgang R., E-mail: wolfgang.hess@biologie.uni-freiburg.de [Genetics and Experimental Bioinformatics, Institute of Biology 3, Faculty of Biology, University of Freiburg, Freiburg (Germany)

    2014-07-14

    In cyanobacteria, alkanes are synthesized from a fatty acyl-ACP by two enzymes, acyl–acyl carrier protein reductase and aldehyde deformylating oxygenase. Despite the great interest in the exploitation for biofuel production, nothing is known about the transcriptional organization of their genes or the physiological function of alkane synthesis. The comparison of 115 microarray datasets indicates the relatively constitutive expression of aar and ado genes. The analysis of 181 available genomes showed that in 90% of the genomes both genes are present, likely indicating their physiological relevance. In 61% of them they cluster together with genes encoding acetyl-CoA carboxyl transferase and a short-chain dehydrogenase, strengthening the link to fatty acid metabolism and in 76% of the genomes they are located in tandem, suggesting constraints on the gene arrangement. However, contrary to the expectations for an operon, we found in Synechocystis sp. PCC 6803 specific promoters for the two genes, sll0208 (ado) and sll0209 (aar), which give rise to monocistronic transcripts. Moreover, the upstream located ado gene is driven by a proximal as well as a second, distal, promoter, from which a third transcript, the ~160 nt sRNA SyR9 is transcribed. Thus, the transcriptional organization of the alkane biosynthesis genes in Synechocystis sp. PCC 6803 is of substantial complexity. We verified all three promoters to function independently from each other and show a similar promoter arrangement also in the more distant Nodularia spumigena, Trichodesmium erythraeum, Anabaena sp. PCC 7120, Prochlorococcus MIT9313, and MED4. The presence of separate regulatory elements and the dominance of monocistronic mRNAs suggest the possible autonomous regulation of ado and aar. The complex transcriptional organization of the alkane synthesis gene cluster has possible metabolic implications and should be considered when manipulating the expression of these genes in cyanobacteria.

  17. Short-chain alkane cycling in deep Gulf of Mexico cold-seep sediments

    Science.gov (United States)

    Sibert, R.; Joye, S. B.; Hunter, K.

    2015-12-01

    Mixtures of light hydrocarbon gases are common in deep Gulf of Mexico cold-seep sediments, and are typically dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is usually methane (>80% C1), but ethane (C2) and propane (C3) are nearly always present in trace amounts (95% of the methane produced at depth never reaches the water column. Production of C1 and C2 in deep-sea sediments has been historically attributed only to thermocatalytic processes, though limited data suggests production of C2/C3 compounds through the activity of archaea at depth. Furthermore, carbon isotopic data on ethane and propane from deep cores of Gulf of Mexico sediments suggest alkanogenesis at >3 m depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Additional studies have also isolated microorganisms capable of oxidizing ethane and propane in the laboratory, but field studies of microbial-driven dynamics of C2/C3 gases in cold-seep sediments are rare. Here, we present the results of a series of incubation experiments using sediment slurries culled from surface sediments from one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of alkane oxidation were measured under a variety of conditions to assess the surface-driven microbial controls on C2/C3 cycling in cold-seep environments. Such microbial processes are important in terms of the possible 'oxidative overprinting' of alkane isotopic signatures produced at depth, possibly obscuring typical microbial isotopic signals.

  18. Stability of defects in monolayer MoS{sub 2} and their interaction with O{sub 2} molecule: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, B. [Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan, 430072 (China); Shang, C. [Wuhan National High Magnetic Field Center, Huazhong University of Science and Technology, Wuhan, 430074 (China); Qi, N. [Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan, 430072 (China); Chen, Z.Y. [School of Nuclear Technology and Chemistry & Biology, Hubei University of Science and Technology, Xianning, 437100 (China); Chen, Z.Q., E-mail: chenzq@whu.edu.cn [Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan, 430072 (China)

    2017-08-01

    Highlights: • Defects can exist steadily in monolayer MoS{sub 2} and break surface chemical inertness. • Activated surfaces are beneficial to the adsorption of O{sub 2} through the introduction of defect levels. • Adsorbed O{sub 2} on defective surface can dissociate with low activation energy barrier. • Defective system may be a potential substrate to design MoS{sub 2}-based gas sensor or catalysts. - Abstract: The stability of various defects in monolayer MoS{sub 2}, as well as their interactions with free O{sub 2} molecules were investigated by density functional theory (DFT) calculations coupled with the nudged elastic band (NEB) method. The defects including S vacancy (monosulfur and disulfue vacancies), antisite defect (Mo{sub S}) and external Mo atom can exist steadily in monolayer MoS{sub 2}, and introduce defect levels in these defective systems, which breaks the surface chemical inertness and significantly enhances the adsorption capacity for free O{sub 2}. The adsorption energy calculations and electronic properties analysis suggest that there is a strong interaction between O{sub 2} molecule and defective system. The adsorbed O{sub 2} on the defective surface can dissociate with a lower activation energy barrier, which produce two active oxygen atoms. Especially, two Mo atoms can occupy one Mo lattice site, and adsorbed O{sub 2} on the top of the Mo atom can then dissociate directly with the lowest activation energy barrier. Hence, our work may provide useful information to design MoS{sub 2}-based gas sensor or catalysts.

  19. Influence of compost amendments on the diversity of alkane degrading bacteria in hydrocarbon contaminated soils

    Directory of Open Access Journals (Sweden)

    Michael eSchloter

    2014-03-01

    Full Text Available Alkane degrading microorganisms play an important role for bioremediation of petrogenic contaminated environments. In this study, we investigated the effects of compost addition on the diversity of alkane monooxygenase gene (alkB harboring bacteria in oil-contaminated soil originated from an industrial zone in Celje, Slovenia, to improve our understanding about the bacterial community involved in alkane degradation and the effects of amendments. Soil without any amendments (control soil and soil amended with compost of different maturation stages, i 1 year and ii 2 weeks, were incubated under controlled conditions in a microcosm experiment and sampled after 0, 6, 12 and 36 weeks of incubation. By using quantitative real-time PCR higher number of alkB genes could be detected in soil samples with compost compared to the control soil after 6, 12 and 36 weeks mainly if the less maturated compost was added. To get an insight into the composition of the alkB harboring microbial communities, we performed next generation sequencing of alkB gene fragment amplicons. Richness and diversity of alkB gene harboring prokaryotes was higher in soil mixed with compost compared to control soil after 6, 12 and 36 weeks again with stronger effects of the less maturated compost. Comparison of communities detected in different samples and time points based on principle component analysis revealed that the addition of compost in general stimulated the abundance of alkB harboring Actinobacteria during the experiment independent from the maturation stage of the compost compared to the control soils. In addition alkB harboring proteobacteria like Shewanella or Hydrocarboniphaga as well as proteobacteria of the genus Agrobacterium responded positively to the addition of compost to soil The amendment of the less maturated compost resulted in addition in a large increase of alkB harboring bacteria of the Cytophaga group (Microscilla mainly at the early sampling

  20. Evidence of indirect gap in monolayer WSe2

    KAUST Repository

    Hsu, Wei-Ting

    2017-10-09

    Monolayer transition metal dichalcogenides, such as MoS2 and WSe2, have been known as direct gap semiconductors and emerged as new optically active materials for novel device applications. Here we reexamine their direct gap properties by investigating the strain effects on the photoluminescence of monolayer MoS2 and WSe2. Instead of applying stress, we investigate the strain effects by imaging the direct exciton populations in monolayer WSe2–MoS2 and MoSe2–WSe2 lateral heterojunctions with inherent strain inhomogeneity. We find that unstrained monolayer WSe2 is actually an indirect gap material, as manifested in the observed photoluminescence intensity–energy correlation, from which the difference between the direct and indirect optical gaps can be extracted by analyzing the exciton thermal populations. Our findings combined with the estimated exciton binding energy further indicate that monolayer WSe2 exhibits an indirect quasiparticle gap, which has to be reconsidered in further studies for its fundamental properties and device applications.

  1. Piezoelectric effect on the thermal conductivity of monolayer gallium nitride

    Science.gov (United States)

    Zhang, Jin

    2018-01-01

    Using molecular dynamics and density functional theory simulations, in this work, we find that the heat transport property of the monolayer gallium nitride (GaN) can be efficiently tailored by external electric field due to its unique piezoelectric characteristic. As the monolayer GaN possesses different piezoelectric properties in armchair and zigzag directions, different effects of the external electric field on thermal conductivity are observed when it is applied in the armchair and zigzag directions. Our further study reveals that due to the elastoelectric effect in the monolayer GaN, the external electric field changes the Young's modulus and therefore changes the phonon group velocity. Also, due to the inverse piezoelectric effect, the applied electric field induces in-plane stress in the monolayer GaN subject to a length constraint, which results in the change in the lattice anharmonicity and therefore affects the phonon mean free path. Furthermore, for relatively long GaN monolayers, the in-plane stress may trigger the buckling instability, which can significantly reduce the phonon mean free path.

  2. Triptycene-terminated thiolate and selenolate monolayers on Au(111

    Directory of Open Access Journals (Sweden)

    Jinxuan Liu

    2017-04-01

    Full Text Available To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs, triptycyl thiolates and selenolates with and without methylene spacers on Au(111 surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se–Au binding energy in the investigated SAMs was found to be higher than the S–Au binding energy.

  3. Binding of the GTPase Sar1 to a Lipid Membrane Monolayer: Insertion and Orientation Studied by Infrared Reflection–Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    Christian Schwieger

    2017-11-01

    Full Text Available Membrane-interacting proteins are polyphilic polymers that engage in dynamic protein–protein and protein–lipid interactions while undergoing changes in conformation, orientation and binding interfaces. Predicting the sites of interactions between such polypeptides and phospholipid membranes is still a challenge. One example is the small eukaryotic GTPase Sar1, which functions in phospholipid bilayer remodeling and vesicle formation as part of the multimeric coat protein complex (COPII. The membrane interaction of Sar1 is strongly dependent on its N-terminal 23 amino acids. By monolayer adsorption experiments and infrared reflection-absorption spectroscopy (IRRAS, we elucidate the role of lipids in inducing the amphipathicity of this N-terminal stretch, which inserts into the monolayer as an amphipathic helix (AH. The AH inserting angle is determined and is consistent with the philicities and spatial distribution of the amino acid monomers. Using an advanced method of IRRAS data evaluation, the orientation of Sar1 with respect to the lipid layer prior to the recruitment of further COPII proteins is determined. The result indicates that only a slight reorientation of the membrane-bound Sar1 is needed to allow coat assembly. The time-course of the IRRAS analysis corroborates a role of slow GTP hydrolysis in Sar1 desorption from the membrane.

  4. Temperature-dependent Raman spectroscopy studies of the interface coupling effect of monolayer ReSe2 single crystals on Au foils

    Science.gov (United States)

    Jiang, Shaolong; Zhao, Liyun; Shi, Yuping; Xie, Chunyu; Zhang, Na; Zhang, Zhepeng; Huan, Yahuan; Yang, Pengfei; Hong, Min; Zhou, Xiebo; Shi, Jianping; Zhang, Qing; Zhang, Yanfeng

    2018-05-01

    Rhenium diselenide (ReSe2), which bears in-plane anisotropic optical and electrical properties, is of considerable interest for its excellent applications in novel devices, such as polarization-sensitive photodetectors and integrated polarization-controllers. However, great challenges to date in the controllable synthesis of high-quality ReSe2 have hindered its in-depth investigations and practical applications. Herein, we report a feasible synthesis of monolayer single-crystal ReSe2 flakes on the Au foil substrate by using a chemical vapor deposition route. Particularly, we focus on the temperature-dependent Raman spectroscopy investigations of monolayer ReSe2 grown on Au foils, which present concurrent red shifts of Eg-like and Ag-like modes with increasing measurement temperature from 77–290 K. Linear temperature dependences of both modes are revealed and explained from the anharmonic vibration of the ReSe2 lattice. More importantly, the strong interaction of ReSe2 with Au, with respect to that with SiO2/Si, is further confirmed by temperature-dependent Raman characterization. This work is thus proposed to shed light on the optical and thermal properties of such anisotropic two-dimensional three-atom-thick materials.

  5. The influence of chromatin structure on the frequency of radiation-induced DNA strand breaks: a study using nuclear and nucleoid monolayers

    International Nuclear Information System (INIS)

    Ljungman, M.

    1991-01-01

    To assess the influence of chromatin structure on the frequency of radiation-induced DNA strand breaks, the alkaline unwinding technique was applied to nuclear and nucleoid monolayers. These chromatin substrates were prepared by treating human fibroblasts grown as monolayers with the nonionic detergent Triton X-100 and varying concentrations of cations. The chromatin structure was modified either by a stepwise removal of DNA-bound proteins by extraction in increasing concentrations of monovalent salt, or by the addition or deletion of mono- and divalent cations to condense or decondense the chromatin, respectively. It was found that the stepwise removal of DNA-bound proteins from the chromatin dramatically increased the frequency of radiation-induced DNA strand breaks. The DNA-bound proteins showed a qualitative difference in their ability to protect the DNA where proteins removed by salt concentrations above 1.0 M exerted the greatest protection. Furthermore, the frequency of radiation-induced DNA strand breaks was found to be 6 times lower in condensed chromatin than in decondensed chromatin and about 80 times lower than in protein-depleted chromatin. It is concluded that the presence of DNA-bound proteins and the folding of the chromatin into higher-order structures protect the DNA against radiation-induced strand breaks

  6. Resonance Raman spectra of phthalocyanine monolayers on different supports. A normal mode analysis of zinc phthalocyanine by means of the MNDO method

    NARCIS (Netherlands)

    Palys, Barbara J.; van den Ham, Dirk M.W.; van den Ham, D.M.W.; Briels, Willem J.; Feil, D.; Feil, Dirk

    1995-01-01

    Resonance Raman spectra of monolayers of transition metal phthalocyanines reveal specific interaction with the support. To elucidate its mechanism, Raman spectra of zinc phthalocyanine monolayers were studied. The analysis was based largely on the results of MNDO calculations. Calculated wavenumbers

  7. Biomimetic Oxidation Studies. 11. Alkane Functionalization in Aqueous Solution Utilizing in Situ Formed [Fe(2)O(eta(1)-H(2)O)(eta(1)-OAc)(TPA)(2)](3+), as an MMO Model Precatalyst, Embedded in Surface-Derivatized Silica and Contained in Micelles.

    Science.gov (United States)

    Neimann, Karine; Neumann, Ronny; Rabion, Alain; Buchanan, Robert M.; Fish, Richard H.

    1999-07-26

    The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe(2)O(eta(1)-H(2)O)(eta(1)-OAc)(TPA)(2)](3+) (TPA = tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe(2)O(&mgr;-OAc)(TPA)(2)](3+), 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O(2) in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of approximately 3:1:2. The balance between poly(ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O(2) in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of approximately 2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO(*)() and t-BuOO(*)()( )()radicals. The t-BuO(*)()( )()radical initiates the C-H functionalization reaction to form the carbon radical, followed by O(2) trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO(*)() and cyclohexyl radicals. A discussion concerning both approaches for

  8. N-Type self-assembled monolayer field-effect transistors for flexible organic electronics

    NARCIS (Netherlands)

    Ringk, A.; Roelofs, Christian; Smits, E.C.P.; van der Marel, C.; Salzmann, I.; Neuhold, A.; Gelinck, G.H.; Resel, R.; de Leeuw, D.M.; Strohriegl, P.

    Within this work we present n-type self-assembled monolayer field-effect transistors (SAMFETs) based on a novel perylene bisimide. The molecule spontaneously forms a covalently fixed monolayer on top of an aluminium oxide dielectric via a phosphonic acid anchor group. Detailed studies revealed an

  9. The effect of gauche molecular conformations on the phase diagram of a Langmuir monolayer

    NARCIS (Netherlands)

    Zangi, R; Rice, SA

    2003-01-01

    Experimental and simulation studies have shown that the gauche conformational degrees of freedom of long-chain amphiphile molecules assembled in a dense Langmuir monolayer play an important role in determining the structures of the several phases that the monolayer supports. Nevertheless, for

  10. SYNCHROTRON X-RAY OBSERVATIONS OF A MONOLAYER TEMPLATE FOR MINERALIZATION

    International Nuclear Information System (INIS)

    Dimasi, E.; Gower, L.B.

    2000-01-01

    Mineral nucleation at a Langmuir film interface has been studied by synchrotron x-ray scattering. Diluted calcium bicarbonate solutions were used as subphases for arachidic and stearic acid monolayers, compressed in a Langmuir trough. Self-assembly of the monolayer template is observed directly, and subsequent crystal growth monitored in-situ

  11. Fundamental Flame Velocities of Pure Hydrocarbons I : Alkanes, Alkenes, Alkynes Benzene, and Cyclohexane

    Science.gov (United States)

    Gerstein, Melvin; Levine, Oscar; Wong, Edgar L

    1950-01-01

    The flame velocities of 37 pure hydrocarbons including normal and branched alkanes, alkenes, and alkynes; as well as benzene and cyclohexane, together with the experimental technique employed are presented. The normal alkanes have about the same flame velocity from ethane through heptane with methane being about 16 percent lower. Unsaturation increases the flame velocity in the order of alkanes, alkenes, and alkynes. Branching reduces the flame velocity.

  12. Cavity plasmon polaritons in monolayer graphene

    International Nuclear Information System (INIS)

    Kotov, O.V.; Lozovik, Yu.E.

    2011-01-01

    Plasmon polaritons in a new system, a monolayer doped graphene embedded in optical microcavity, are studied here. The dispersion law for lower and upper cavity plasmon polaritons is obtained. Peculiarities of Rabi splitting for the system are analyzed; particularly, role of Dirac-like spinor (envelope) wave functions in graphene and corresponding angle factors are considered. Typical Rabi frequencies for maximal (acceptable for Dirac-like electron spectra) Fermi energy and frequencies of polaritons near polariton gap are estimated. The plasmon polaritons in considered system can be used for high-speed information transfer in the THz region. -- Highlights: → Plasmon polaritons in a monolayer doped graphene embedded in optical microcavity, are studied here. → The dispersion law for lower and upper cavity plasmon polaritons is obtained. → Peculiarities of Rabi splitting for the system are analyzed. → Role of Dirac-like wave functions in graphene and corresponding angle factors are considered. → Typical Rabi frequencies and frequencies of polaritons near polariton gap are estimated.

  13. Even-odd alternation of the formation of dimer isomers in irradiated polycrystalline alkanes: evidence from product analysis

    International Nuclear Information System (INIS)

    Baudson, T.; Tilquin, B.

    1984-01-01

    Recent ESR studies on n-alkanes from n-C 11 to n-C 25 have shown that a prominent chain end (-CH 2 -CH 2 ) alkyl radical is formed in odd members of the series. In this preliminary discussion of our study, we shall report the capillary chromatogram in the dimer isomers range for n-alkanes ranging from n-C 11 to n-C 17 irradiated at 80 kGy. Dimer isomers, produced in part by the combination of chain end radicals, are eluted at the end chromatogram. The combination of two chain end radicals gives the dimer (D 11 ) isomer eluted at the last place. It is shown that dimers produced by the combination of chain end alkyl radicals are more important for the odd members of the series than for the even members. (author)

  14. Disorder-dependent valley properties in monolayer WSe2

    KAUST Repository

    Tran, Kha

    2017-07-19

    We investigate the effect of disorder on exciton valley polarization and valley coherence in monolayer WSe2. By analyzing the polarization properties of photoluminescence, the valley coherence (VC) and valley polarization (VP) are quantified across the inhomogeneously broadened exciton resonance. We find that disorder plays a critical role in the exciton VC, while affecting VP less. For different monolayer samples with disorder characterized by their Stokes shift (SS), VC decreases in samples with higher SS while VP does not follow a simple trend. These two methods consistently demonstrate that VC as defined by the degree of linearly polarized photoluminescence is more sensitive to disorder, motivating further theoretical studies.

  15. High frequency of Thermodesulfovibrio spp. and Anaerolineaceae in association with Methanoculleus spp. in a long-term incubation of n-alkanes-degrading methanogenic enrichment culture

    Directory of Open Access Journals (Sweden)

    Bo Liang

    2016-09-01

    Full Text Available 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.

  16. Packing of ganglioside-phospholipid monolayers

    DEFF Research Database (Denmark)

    Majewski, J.; Kuhl, T.L.; Kjær, K.

    2001-01-01

    Using synchrotron grazing-incidence x-ray diffraction (GIXD) and reflectivity, the in-plane and out-of-plane structure of mixed ganglioside-phospholipid monolayers was investigated at the air-water interface. Mixed monolayers of 0, 5, 10, 20, and 100 mol% ganglioside GM, and the phospholipid...... monolayers did not affect hydrocarbon tail packing (fluidization or condensation of the hydrocarbon region). This is in contrast to previous investigations of lipopolymer-lipid mixtures, where the packing structure of phospholipid monolayers was greatly altered by the inclusion of lipids bearing hydrophilic...

  17. Nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives

    International Nuclear Information System (INIS)

    Taggart, Audrey M.

    1996-01-01

    A detailed study has been performed on the nucleation, growth and habit modification of n-alkanes and homologous mixtures in the absence and presence of flow improving additives in an attempt to gain a clearer appreciation of the interaction mechanisms behind wax / additive crystallisation. Kinetic and structural assessment of melt phase n-alkanes illustrate the different crystallographic forms present within the homologous series. Studies demonstrate the alternating behaviour of the even and odd numbered homologues which converges as a function of increasing molecular weight. Greater crystal lattice stabilities were found for those n-alkanes which have an even carbon number and which crystallise into the triclinic crystal structure. Solid state phase behaviour of the n-alkanes was found to vary depending on the number and parity of n. Nucleation kinetic studies of n-alkanes and homologous mixtures from model diesel fuel solvents (dodecane, m-xylene, decalin, pristane and a dewaxed fuel) are assessed using turbidity as the method of crystallite detection. Saturation temperatures are found to be related to both alkane structure and molecular chain length for all solvent systems. N-alkane solubilities are lower for n-alkane like solvents. The width of the meta stable zone varies as a function of solvent in order of dodecane ≅ pristane 19 H 40 and solvent m-xylene. Wax precipitation from distillate fuels in the presence of flow improving additives (di-alkyl di-amino xylene, phthalic acid and sulphobenzene acid derivatives and high molecular weight polymers) reveal responsive wax crystal nucleator and growth inhibitor additives. The crystal morphology of heptacosane, C 27 H 56 to simulate a model wax crystal is assessed in addition to its response to blocker 'tailor made' additives: methyl substituted C 27 H 56 and di-alkyl substituted phenyl additives [additive (A) and (B)]. Pure C 27 H 56 reveals a thin lozenge shaped platelet. All additives studied induce growth

  18. Polycyclic aromatic hydrocarbons (PAHs) and n-Alkanes in beaked sea snake Enhydrina schistose (Daudin, 1803) from the Mandovi Estuary, Goa

    Digital Repository Service at National Institute of Oceanography (India)

    Mote, S.; RanjeetKumar; Naik, B.G.; Ingole, B.S.

    , occur in high abundances (Voris H K 1985; Aaron Lobo et al. 2004) Present study demonstrates the tissue specific distribution of 15 EPA priority PAHs and 27 n-alkanes compounds in two individuals of E. schistose. We used GC-MS for analysis, which... in 20 ml dichloromethane/hexane (1:3 v/v) with surrogate internal standard (SIS) 20 ppm-200μl Tetracosane-d50 for alkane, 5ppm-200μl Chrysene-d12 for PAHs were spiked and transferred to 5% H2O deactivated silica gel column (1 cm i.dx 9 cm). Elution...

  19. Recombinant albumin monolayers on latex particles.

    Science.gov (United States)

    Sofińska, Kamila; Adamczyk, Zbigniew; Kujda, Marta; Nattich-Rak, Małgorzata

    2014-01-14

    The adsorption of recombinant human serum albumin (rHSA) on negatively charged polystyrene latex micro-particles was studied at pH 3.5 and the NaCl concentration range of 10(-3) to 0.15 M. The electrophoretic mobility of latex monotonically increased with the albumin concentration in the suspension. The coverage of adsorbed albumin was quantitatively determined using the depletion method, where the residual protein concentration was determined by electrokinetic measurements and AFM imaging. It was shown that albumin adsorption was irreversible. Its maximum coverage on latex varied between 0.7 mg m(-2) for 10(-3) M NaCl to 1.3 mg m(-2) for 0.15 M NaCl. The latter value matches the maximum coverage previously determined for human serum albumin on mica using the streaming potential method. The increase in the maximum coverage was interpreted in terms of reduced electrostatic repulsion among adsorbed molecules. These facts confirm that albumin adsorption at pH 3.5 is governed by electrostatic interactions and proceeds analogously to colloid particle deposition. The stability of albumin monolayers was measured in additional experiments where changes in the latex electrophoretic mobility and the concentration of free albumin in solutions were monitored over prolonged time periods. Based on these experimental data, a robust procedure of preparing albumin monolayers on latex particles of well-controlled coverage and molecule distribution was proposed.

  20. Effect of lipid composition and packing on the adsorption of apolipoproteins to lipid monolayers

    International Nuclear Information System (INIS)

    Ibdah, J.A.; Lund-Katz, S.; Phillips, M.C.

    1987-01-01

    The monolayer system has been used to study the effects of lipoprotein surface lipid composition and packing on the affinities of apolipoproteins for the surfaces of lipoprotein particles. The adsorption of apolipoproteins injected beneath lipid monolayers prepared with pure lipids or lipoprotein surface lipids is evaluated by monitoring the surface pressure of the film and the surface concentration (Gamma) of 14 C-labelled apolipoprotein. At a given initial film pressure (π/sub i/) there is a higher adsorption of human apo A-I to unsaturated phosphatidylcholine (PC) monolayers compared to saturated PC monolayers (e.g., at π/sub i/ = 10 mN/m, Gamma = 0.35 and 0.06 mg/m 2 for egg PC and distearoyl PC, respectively, with 3 x 10 -4 mg/ml apo A-I in the subphase). In addition, adsorption of apo A-I is less to an egg sphingomyelin monolayer than to an egg PC monolayer. The adsorption of apo A-I to PC monolayers is decreased by addition of cholesterol. Generally, apo A-I adsorption diminishes as the lipid molecular area decreases. Apo A-I adsorbs more to monolayers prepared with HDL 3 surface lipids than with LDL surface lipids. These studies suggest that lipoprotein surface lipid composition and packing are crucial factors influencing the transfer and exchange of apolipoproteins among various lipoprotein classes during metabolism of lipoprotein particles

  1. Seasonal variation of the particle size distribution of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) in urban aerosol of Guangzhou, China.

    Science.gov (United States)

    Tang, X L; Bi, X H; Sheng, G Y; Tan, J H; Fu, J M

    2006-06-01

    Seasonal aerosol samples have been collected by Andersen Hi-Vol pumping system equipped with a five stage cascade impactor and a backup filter (size range: 10-7.2 microm, 7.2-3.0 microm, 3.0-1.5 microm, 1.5-0.95 microm, 0.95-0.49 microm, gas chromatography and PAHs were measured using gas chromatography/mass spectrometry analysis. The bimodal log-normal distributions of n-alkanes and semi-volatile PAHs were found, while for non-volatile PAHs that was unimodal, so much as the mode of semi-volatile PAHs was similar with that of the particles. The n-alkanes and PAHs were preferably associated with fine particles. C (max) (carbon number maximum) (C(22)-C(26)), CPI (carbon preference index) (1.12-1.21), U/R (unresolved to resolved components ratio) (7.42-10.7), wax% (0.9-3.12%) and the diagnostic ratios for PAHs revealed that vehicular emission was the major source of these organic compounds during the study periods, while the contribution of epicuticular waxes emitted by terrestrial plants was minor. CPI(2) (values for petrogenic hydrocarbons), CPI(3) (values for biogenic n-alkanes) and wax% revealed that the natural preferentially accumulated in the larger aerosol while the anthropogenic in the smaller. In addition, the different MMDs (mass median diameters) for n-alkanes and PAHs were observed in different seasons. The MMDs for n-alkanes and PAHs were higher in autumn/winter than those in spring/summer. The seasonal effect was related to the hydrocarbon content in the individual particulate fractions, showing a preferential association of n-alkanes and PAHs with larger particles in the autumn/winter season.

  2. Screening the best catalyst with group 9, 10 and 11 metals monolayer loading on NbC(001) from first-principles study

    Science.gov (United States)

    Kan, Dongxiao; Zhang, Xilin; Zhang, Yanxing; Yang, Zongxian

    2018-02-01

    The supported catalysts have received great attentions due to their high catalytic activity, low cost and good stability. Here we report the stability, wetting ability, corrosion resistance and catalytic activity of the supported catalysts with group 9, 10 and 11 metals (M = Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) monolayers (ML) deposited on NbC(001), denoted as MML/NbC(001). The PdML/NbC(001) and PtML/NbC(001) are testified as the most stable and active ones with the former even better on the whole. The catalytic activities toward oxygen reduction reactions (ORR) are clarified by the dissociation and the change in Gibbs free energies for the elementary reaction steps of O2 on PdML/NbC(001).

  3. Ignition of alkane-rich FACE gasoline fuels and their surrogate mixtures

    KAUST Repository

    Sarathy, Mani

    2015-01-01

    Petroleum derived gasoline is the most used transportation fuel for light-duty vehicles. In order to better understand gasoline combustion, this study investigated the ignition propensity of two alkane-rich FACE (Fuels for Advanced Combustion Engines) gasoline test fuels and their corresponding PRF (primary reference fuel) blend in fundamental combustion experiments. Shock tube ignition delay times were measured in two separate facilities at pressures of 10, 20, and 40 bar, temperatures from 715 to 1500 K, and two equivalence ratios. Rapid compression machine ignition delay times were measured for fuel/air mixtures at pressures of 20 and 40 bar, temperatures from 632 to 745 K, and two equivalence ratios. Detailed hydrocarbon analysis was also performed on the FACE gasoline fuels, and the results were used to formulate multi-component gasoline surrogate mixtures. Detailed chemical kinetic modeling results are presented herein to provide insights into the relevance of utilizing PRF and multi-component surrogate mixtures to reproduce the ignition behavior of the alkane-rich FACE gasoline fuels. The two FACE gasoline fuels and their corresponding PRF mixture displayed similar ignition behavior at intermediate and high temperatures, but differences were observed at low temperatures. These trends were mimicked by corresponding surrogate mixture models, except for the amount of heat release in the first stage of a two-stage ignition events, when observed. © 2014 The Combustion Institute.

  4. Biosynthesis of medium chain length alkanes for bio-aviation fuel by metabolic engineered Escherichia coli.

    Science.gov (United States)

    Wang, Meng; Nie, Kaili; Cao, Hao; Xu, Haijun; Fang, Yunming; Tan, Tianwei; Baeyens, Jan; Liu, Luo

    2017-09-01

    The aim of this work was to study the synthesis of medium-chain length alkanes (MCLA), as bio-aviation product. To control the chain length of alkanes and increase the production of MCLA, Escherichia coli cells were engineered by incorporating (i) a chain length specific thioesterase from Umbellularia californica (UC), (ii) a plant origin acyl carrier protein (ACP) gene and (iii) the whole fatty acid synthesis system (FASs) from Jatropha curcas (JC). The genetic combination was designed to control the product spectrum towards optimum MCLA. Decanoic, lauric and myristic acid were produced at concentrations of 0.011, 0.093 and 1.657mg/g, respectively. The concentration of final products nonane, undecane and tridecane were 0.00062mg/g, 0.0052mg/g, and 0.249mg/g respectively. Thioesterase from UC controlled the fatty acid chain length in a range of 10-14 carbons and the ACP gene with whole FASs from JC significantly increased the production of MCLA. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. The structure of n-alkane binary mixtures adsorbed on graphite

    International Nuclear Information System (INIS)

    Espeau, Philippe; White, John W.; Papoular, Robert J.

    2005-01-01

    The thermodynamics and structure of the surface adsorbed phase in binary C15-C16 and C15-C17 n-alkane mixtures confined in graphite pores have been studied by differential scanning calorimetry and small-angle X-ray scattering. The previously observed selective adsorption of the longer alkane for chain length differences greater than five carbon atoms is verified but reduced for chain length differences less than or equal to two. With a difference in chain length of one carbon atom, Vegard's law is followed for the melting points of the adsorbed mixture and the (0 2) d-spacing is a continuous function of the mole fraction x. With a two-carbon atom difference, samples aged for 1 week have a lamellar structure for which the entities A 1-x B x try to be commensurate with the substrate. The same samples aged for 1 month show a continuous parabolic x-dependence for both the melting points and the d-spacings. An explanation in terms of selective probability of adsorption is proposed based on crystallographic considerations

  6. The structure of n-alkane binary mixtures adsorbed on graphite

    Energy Technology Data Exchange (ETDEWEB)

    Espeau, Philippe [Laboratoire de Chimie Physique et Minerale, Faculte de Pharmacie, Universite Rene Descartes-Paris V, F-75006 Paris (France)]. E-mail: philippe.espeau@univ-paris5.fr; White, John W. [Research School of Chemistry, Australian National University, Canberra, ACT 0200 (Australia); Papoular, Robert J. [Laboratoire Leon Brillouin, CEA-CEN Saclay, F-91191 Gif-sur-Yvette Cedex (France)

    2005-12-15

    The thermodynamics and structure of the surface adsorbed phase in binary C15-C16 and C15-C17 n-alkane mixtures confined in graphite pores have been studied by differential scanning calorimetry and small-angle X-ray scattering. The previously observed selective adsorption of the longer alkane for chain length differences greater than five carbon atoms is verified but reduced for chain length differences less than or equal to two. With a difference in chain length of one carbon atom, Vegard's law is followed for the melting points of the adsorbed mixture and the (0 2) d-spacing is a continuous function of the mole fraction x. With a two-carbon atom difference, samples aged for 1 week have a lamellar structure for which the entities A{sub 1-x}B {sub x} try to be commensurate with the substrate. The same samples aged for 1 month show a continuous parabolic x-dependence for both the melting points and the d-spacings. An explanation in terms of selective probability of adsorption is proposed based on crystallographic considerations.

  7. Prediction of the Flash Point of Binary and Ternary Straight-Chain Alkane Mixtures

    Directory of Open Access Journals (Sweden)

    X. Li

    2014-01-01

    Full Text Available The flash point is an important physical property used to estimate the fire hazard of a flammable liquid. To avoid the occurrence of fire or explosion, many models are used to predict the flash point; however, these models are complex, and the calculation process is cumbersome. For pure flammable substances, the research for predicting the flash point is systematic and comprehensive. For multicomponent mixtures, especially a hydrocarbon mixture, the current research is insufficient to predict the flash point. In this study, a model was developed to predict the flash point of straight-chain alkane mixtures using a simple calculation process. The pressure, activity coefficient, and other associated physicochemical parameters are not required for the calculation in the proposed model. A series of flash points of binary and ternary mixtures of straight-chain alkanes were determined. The results of the model present consistent experimental results with an average absolute deviation for the binary mixtures of 0.7% or lower and an average absolute deviation for the ternary mixtures of 1.03% or lower.

  8. A theoretical and experimental XAS study of monolayer dispersive supported CuO/{gamma}-Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chen Dongliang [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); Wu Ziyu [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China)]. E-mail: wuzy@ihep.ac.cn

    2006-11-15

    The local structures of supported CuO/{gamma}-Al{sub 2}O{sub 3} monolayer dispersive catalysts with different CuO loadings have been investigated by EXAFS and multiple scattering XANES simulations. The EXAFS results show that the first nearest neighbors around the Cu atoms in the CuO/{gamma}-Al{sub 2}O{sub 3} catalysts are similar to that of the polycrystalline CuO powder, which is independent of the CuO loadings. Moreover, the Cu K-XANES FEFF8 calculations for CuO reveal that the monolayer-dispersed CuO species are of small distorted (CuO{sub 4}) {sub m} {sup n+} clusters, which is mainly composed of a distorted CuO{sub 6} octahedron incorporated in the surface octahedral vacant sites of the {gamma}-Al{sub 2}O{sub 3} support. We consider that the CuO species for the CuO/{gamma}-Al{sub 2}O{sub 3} catalysts with loadings of 0.4 and 0.8 mmol/100 m{sup 2} are distorted (CuO{sub 4}) {sub m} {sup n+} clusters composed mainly of a distorted CuO{sub 6} octahedron incorporated in the surface octahedral vacant sites of the {gamma}-Al{sub 2}O{sub 3} support after calcinations at high temperature in air for a few hours. On the contrary, for the CuO/{gamma}-Al{sub 2}O{sub 3} with loading of 1.2 mmol/100 m{sup 2}, the local structure of Cu atoms in CuO/{gamma}-Al{sub 2}O{sub 3} is similar to that of polycrystalline CuO powder.

  9. Improvement of gas-adsorption performances of Ag-functionalized monolayer MoS2 surfaces: A first-principles study

    Science.gov (United States)

    Song, Jian; Lou, Huan

    2018-05-01

    Investigations of the adsorptions of representative gases (NO2, NH3, H2S, SO2, CO, and HCHO) on different Ag-functionalized monolayer MoS2 surfaces were performed by first principles methods. The adsorption configurations, adsorption energies, electronic structure properties, and charge transfer were calculated, and the results show that the adsorption activities to gases of monolayer MoS2 are dramatically enhanced by the Ag-modification. The Ag-modified perfect MoS2 (Ag-P) and MoS2 with S-vacancy (Ag-Vs) substrates exhibit a more superior adsorption activity to NO2 than other gases, which is consistent with the experimental reports. The charge transfer processes of different molecules adsorbed on different surfaces exhibit various characteristics, with potential benefits to gas selectivity. For instance, the NO2 and SO2 obtain more electrons from both Ag-P and Ag-Vs substrates but the NH3 and H2S donate more electrons to materials than others. In addition, the CO and HCHO possess totally opposite charge transfer directs on both substrates, respectively. The BS and PDOS calculations show that semiconductor types of gas/Ag-MoS2 systems are more determined by the metal-functionalization of material, and the directs and numbers of charge transfer process between gases and adsorbents can cause the increase or decline of material resistance theoretically, which is helpful to gas detection and distinction. The further analysis indicates suitable co-operation between the gain-lost electron ability of gas and metallicity of featuring metal might adjust the resistivity of complex and contribute to new thought for metal-functionalization. Our works provide new valuable ideas and theoretical foundation for the potential improvement of MoS2-based gas sensor performances, such as sensitivity and selectivity.

  10. Langmuir-Blodgett and X-ray diffraction studies of isolated photosystem II reaction centers in monolayers and multilayers: physical dimensions of the complex.

    Science.gov (United States)

    Uphaus, R A; Fang, J Y; Picorel, R; Chumanov, G; Wang, J Y; Cotton, T M; Seibert, M

    1997-04-01

    The photosystem II (PSII) reaction center (RC) is a hydrophobic intrinsic protein complex that drives the water-oxidation process of photosynthesis. Unlike the bacterial RC complex, an X-ray crystal structure of the PSII RC is not available. In order to determine the physical dimensions of the isolated PSII RC complex, we applied Langmuir techniques to determine the cross-sectional area of an isolated RC in a condensed monolayer film. Low-angle X-ray diffraction results obtained by examining Langmuir-Blodgett multilayer films of alternating PSII RC/Cd stearate monolayers were used to determine the length (or height; z-direction, perpendicular to the plane of the original membrane) of the complex. The values obtained for a PSII RC monomer were 26 nm2 and 4.8 nm, respectively, and the structural integrity of the RC in the multilayer film was confirmed by several approaches. Assuming a cylindrical-type RC structure, the above dimensions lead to a predicted volume of about 125 nm3. This value is very close to the expected volume of 118 nm3, calculated from the known molecular weight and partial specific volume of the PSII RC proteins. This same type of comparison was also made with the Rhodobacter sphaeroides RC based on published data, and we conclude that the PSII RC is much shorter in length and has a more regular solid geometric structure than the bacterial RC. Furthermore, the above dimensions of the PSII RC and those of PSII core (RC plus proximal antenna) proteins protruding outside the plane of the PSII membrane into the lumenal space as imaged by scanning tunneling microscopy (Seibert, Aust. J. Pl. Physiol. 22, 161-166, 1995) fit easily into the known dimensions of the PSII core complex visualized by others as electron-density projection maps. From this we conclude that the in situ PSII core complex is a dimeric structure containing two copies of the PSII RC.

  11. Heritability of the Structures and 13C Fractionation in Tomato Leaf Wax Alkanes: A Genetic Model System to Inform Paleoenvironmental Reconstructions

    Directory of Open Access Journals (Sweden)

    Amanda L. D. Bender

    2017-06-01

    Full Text Available Leaf wax n-alkanes are broadly used to reconstruct paleoenvironmental information. However, the utility of n-alkanes as a paleoenvironmental proxy may be modulated by the extent to which biological as well as environmental factors influence the structural and isotopic variability of leaf waxes. In paleoclimate applications, there is usually an implicit assumption that most variation of leaf wax traits through a time series can be attributed to environmental change and that biological sources of variability within plant communities are small. For example, changes in hydrology affect the δ2H of waxes via rainwater and the δ13C of leaf waxes by changing plant communities. We measured the degree of genetic control over δ13C variation in leaf waxes within closely related species with an experimental greenhouse growth study. We measured the proportion of variability in structural and isotopic leaf wax traits that is attributable to genetic variation using a set of 76 introgression lines (ILs between two interfertile Solanum (tomato species: S. lycopersicum cv M82 (hereafter cv M82 and S. pennellii. Leaves of S. pennellii, a wild desert tomato relative, produced significantly more iso-alkanes than cv M82, a domesticated tomato cultivar adapted to water-replete conditions. We report a methylation index to summarize the ratio of branched (iso- and anteiso- to total alkanes. Between Solanum pennellii and cv M82, the iso-alkanes were found to be enriched in 13C by 1.2–1.4‰ over n-alkanes. The broad-sense heritability values (H2 of leaf wax traits describe the degree to which genetic variation contributes to variation of these traits. Variation of individual carbon isotopic compositions of alkanes were of low heritability (H2 = 0.13–0.19, suggesting that most variation in δ13C of leaf waxes in this study can be attributed to environmental variance. This supports the interpretation that variation in the δ13C of wax compounds recorded in sediments

  12. Heritability of the structures and 13C fractionation in tomato leaf wax alkanes: a genetic model system to inform paleoenvironmental reconstructions

    Science.gov (United States)

    Bender, Amanda L. D.; Chitwood, Daniel H.; Bradley, Alexander S.

    2017-06-01

    Leaf wax n-alkanes are broadly used to reconstruct paleoenvironmental information. However, the utility of n-alkanes as a paleoenvironmental proxy may be modulated by the extent to which biological as well as environmental factors influence the structural and isotopic variability of leaf waxes. In paleoclimate applications, there is usually an implicit assumption that most variation of leaf wax traits through a time series can be attributed to environmental change and that biological sources of variability within plant communities are small. For example, changes in hydrology affect the δ2H of waxes via rainwater and the δ13C of leaf waxes by changing plant communities. We measured the degree of genetic control over δ13C variation in leaf waxes within closely related species with an experimental greenhouse growth study. We measured the proportion of variability in structural and isotopic leaf wax traits that is attributable to genetic variation using a set of 76 introgression lines (ILs) between two interfertile Solanum (tomato) species: S. lycopersicum cv M82 (hereafter cv M82) and S. pennellii. Leaves of S. pennellii, a wild desert tomato relative, produced significantly more iso-alkanes than cv M82, a domesticated tomato cultivar adapted to water-replete conditions. We report a methylation index to summarize the ratio of branched (iso- and anteiso-) to total alkanes. Between S. pennellii and cv M82, the iso-alkanes were found to be enriched in 13C by 1.2-1.4‰ over n-alkanes. The broad-sense heritability values (H2) of leaf wax traits describe the degree to which genetic variation contributes to variation of these traits. Variation of individual carbon isotopic compositions of alkanes were of low heritability (H2 = 0.13-0.19), suggesting that most variation in δ13C of leaf waxes in this study can be attributed to environmental variance. This supports the interpretation that variation in the δ13C of wax compounds recorded in sediments reflects

  13. Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation.

    Science.gov (United States)

    Summers, Andrew Z; Iacovella, Christopher R; Cummings, Peter T; McCabe, Clare

    2017-10-24

    Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

  14. DPPC Monolayers Exhibit an Additional Phase Transition at High Surface Pressure

    DEFF Research Database (Denmark)

    Shen, Chen; de la Serna, Jorge B.; Struth, Bernd

    2015-01-01

    Pulmonary surfactant forms a monolayer at the air/aqueous interface within the lung. During the breath process, the surface pressure (Π) periodically varies from ~40mN/m up to ~70mN/m. The film is mechanically stable during this rapid and reversible expansion. Pulmonary surfactant consists of ~90......% of lipid with 10% integrated proteins. Among its lipid compounds, di-palmitoyl-phosphatidylcholine (DPPC) dominates (~45wt%). DPPC is the only known lipid that can be compressed to very high surface pressure (~70mN/m) before its monolayer collapses. Most probably, this feature contributes to the mechanical...... stability of the alveoli monolayer. Still, to the best of our knowledge, some details of the compression isotherm presented here and the related structures of the DPPC monolayer were not studied so far. The liquid-expanded/liquid-condensed phase transition of the DPPC monolayer at ~10mN/m is well known...

  15. Melting mechanism in monolayers of flexible rod-shaped molecules

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Taub, H.

    1992-01-01

    The melting of butane and hexane monolayers adsorbed on a graphite basal-plane surface has been studied by molecular-dynamics simulations and experimentally by neutron diffraction. The simulation results are qualitatively consistent with the observed diffraction patterns and suggest a general...

  16. Formation and optical characterisation of colloidal gold monolayers

    NARCIS (Netherlands)

    Kooij, Ernst S.; Brouwer, E.A.M.; Wormeester, Herbert; Poelsema, Bene

    2003-01-01

    We study the deposition of charge-stabilised gold nanocolloids on silicon substrates, which have been derivatised with (aminopropyl)triethoxysilane. Atomic force microscopy (AFM) and spectroscopic ellipsometry are employed to investigate the nanocrystal monolayers ex situ. Analysis of AFM images

  17. Thermodynamic modeling of saturated liquid compositions and densities for asymmetric binary systems composed of carbon dioxide, alkanes and alkanols

    International Nuclear Information System (INIS)

    Bayestehparvin, Bita; Nourozieh, Hossein; Kariznovi, Mohammad; Abedi, Jalal

    2015-01-01

    Highlights: • Phase behavior of the binary systems containing largely different components. • Equation of state modeling of binary polar and non-polar systems by utilizing different mixing rules. • Three different mixing rules (one-parameter, two-parameters and Wong–Sandler) coupled with Peng–Robinson equation of state. • Two-parameter mixing rule shows promoting results compared to one-parameter mixing rule. • Wong–Sandler mixing rule is unable to predict saturated liquid densities with sufficient accuracy. - Abstract: The present study mainly focuses on the phase behavior modeling of asymmetric binary mixtures. Capability of different mixing rules and volume shift in the prediction of solubility and saturated liquid density has been investigated. Different binary systems of (alkane + alkanol), (alkane + alkane), (carbon dioxide + alkanol), and (carbon dioxide + alkane) are considered. The composition and the density of saturated liquid phase at equilibrium condition are the properties of interest. Considering composition and saturated liquid density of different binary systems, three main objectives are investigated. First, three different mixing rules (one-parameter, two parameters and Wong–Sandler) coupled with Peng–Robinson equation of state were used to predict the equilibrium properties. The Wong–Sandler mixing rule was utilized with the non-random two-liquid (NRTL) model. Binary interaction coefficients and NRTL model parameters were optimized using the Levenberg–Marquardt algorithm. Second, to improve the density prediction, the volume translation technique was applied. Finally, Two different approaches were considered to tune the equation of state; regression of experimental equilibrium compositions and densities separately and spontaneously. The modeling results show that there is no superior mixing rule which can predict the equilibrium properties for different systems. Two-parameter and Wong–Sandler mixing rule show promoting

  18. Quaternary (liquid + liquid) equilibrium data for the extraction of toluene from alkanes using the ionic liquid [EMim][MSO4

    International Nuclear Information System (INIS)

    Corderí, Sandra; Calvar, Noelia; Gómez, Elena; Domínguez, Ángeles

    2014-01-01

    Highlights: • EMim[MSO 4 ] was proposed as solvent for the extraction of toluene from alkanes. • The quaternary system {heptane + cyclohexane + toluene + [EMim][MSO 4 ]} was evaluated. • The extraction of toluene would be facilitated in the presence of one alkane. • Experimental LLE data were successfully correlated with the NRTL model. - Abstract: (Liquid + liquid) equilibrium (LLE) studies for the extraction of aromatics from alkanes present in the petroleum fractions are important to develop theoretical/semiempirical (liquid + liquid) equilibrium models, which are used in the design of extraction processes. In this work, the ionic liquid 1-ethyl-3-methylimidazolium methylsulfate, [EMim][MSO 4 ], was evaluated as potential solvent for the separation of toluene from heptane and cyclohexane. The LLE data for the quaternary system {heptane (1) + cyclohexane (2) + toluene (3) + [EMim][MSO 4 ] (4)} were experimentally determined at T = 298.15 K and atmospheric pressure. Moreover, the LLE data for the ternary systems {heptane or cyclohexane (1) + toluene (2) + [EMim][MSO 4 ] (3)} were also determined. Solute distribution ratios and selectivities were calculated and analysed in order to evaluate the capability of the ionic liquid to accomplish the separation target. A comparison between the solute distribution ratios and selectivities for the quaternary and the ternary systems was also made. Finally, the experimental tie-line data were correlated with the NRTL model

  19. Pd/NbOPO₄ multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans.

    Science.gov (United States)

    Xia, Qi-Neng; Cuan, Qian; Liu, Xiao-Hui; Gong, Xue-Qing; Lu, Guan-Zhong; Wang, Yan-Qin

    2014-09-08

    Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbO(x)-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90% throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbO(x) species play the key role in C-O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbO(x) species help to cleave the C-O bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Short-chain alkanes fuel mussel and sponge Cycloclasticus symbionts from deep-sea gas and oil seeps.

    Science.gov (United States)

    Rubin-Blum, Maxim; Antony, Chakkiath Paul; Borowski, Christian; Sayavedra, Lizbeth; Pape, Thomas; Sahling, Heiko; Bohrmann, Gerhard; Kleiner, Manuel; Redmond, Molly C; Valentine, David L; Dubilier, Nicole

    2017-06-19

    Cycloclasticus bacteria are ubiquitous in oil-rich regions of the ocean and are known for their ability to degrade polycyclic aromatic hydrocarbons (PAHs). In this study, we describe Cycloclasticus that have established a symbiosis with Bathymodiolus heckerae mussels and poecilosclerid sponges from asphalt-rich, deep-sea oil seeps at Campeche Knolls in the southern Gulf of Mexico. Genomic and transcriptomic analyses revealed that, in contrast to all previously known Cycloclasticus, the symbiotic Cycloclasticus appears to lack the genes needed for PAH degradation. Instead, these symbionts use propane and other short-chain alkanes such as ethane and butane as carbon and energy sources, thus expanding the limited range of substrates known to power chemosynthetic symbioses. Analyses of short-chain alkanes in the environment of the Campeche Knolls symbioses revealed that these are present at high concentrations (in the μM to mM range). Comparative genomic analyses revealed high similarities between the genes used by the symbiotic Cycloclasticus to degrade short-chain alkanes and those of free-living Cycloclasticus that bloomed during the Deepwater Horizon oil spill. Our results indicate that the metabolic versatility of bacteria within the Cycloclasticus clade is higher than previously assumed, and highlight the expanded role of these keystone species in the degradation of marine hydrocarbons.

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

    Science.gov (United States)

    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.

  2. Preparation and Photoluminescence of Tungsten Disulfide Monolayer

    Directory of Open Access Journals (Sweden)

    Yanfei Lv

    2018-05-01

    Full Text Available Tungsten disulfide (WS2 monolayer is a direct band gap semiconductor. The growth of WS2 monolayer hinders the progress of its investigation. In this paper, we prepared the WS2 monolayer through chemical vapor transport deposition. This method makes it easier for the growth of WS2 monolayer through the heterogeneous nucleation-and-growth process. The crystal defects introduced by the heterogeneous nucleation could promote the photoluminescence (PL emission. We observed the strong photoluminescence emission in the WS2 monolayer, as well as thermal quenching, and the PL energy redshift as the temperature increases. We attribute the thermal quenching to the energy or charge transfer of the excitons. The redshift is related to the dipole moment of WS2.

  3. Potential of amino acid/dipeptide monoester prodrugs of floxuridine in facilitating enhanced delivery of active drug to interior sites of tumors: a two-tier monolayer in vitro study.

    Science.gov (United States)

    Tsume, Yasuhiro; Hilfinger, John M; Amidon, Gordon L

    2011-10-01

    To evaluate the advantages of amino acid/dipeptide monoester prodrugs for cancer treatments by assessing the uptake and cytotoxic effects of floxuridine prodrugs in a secondary cancer cell monolayer following permeation across a primary cancer cell monolayer. The first Capan-2 monolayer was grown on membrane transwell inserts; the second monolayer was grown at the bottom of a plate. The permeation of floxuridine and its prodrugs across the first monolayer and the uptake and cell proliferation assay on secondary layer were sequentially determined. All floxuridine prodrugs exhibited greater permeation across the first Capan-2 monolayer than the parent drug. The correlation between uptake and growth inhibition in the second monolayer with intact prodrug permeating the first monolayer suggests that permeability and enzymatic stability are essential for sustained action of prodrugs in deeper layers of tumors. The correlation of uptake and growth inhibition were vastly superior for dipeptide prodrugs to those obtained with mono amino acid prodrugs. Although a tentative general overall correlation between intact prodrug and uptake or cytotoxic action was obtained, it appears that a mixture of floxuridine prodrugs with varying beneficial characteristics may be more effective in treating tumors.

  4. Abundance of macroalgal organic matter in biofilms: Evidence from n-alkane biomarkers

    Digital Repository Service at National Institute of Oceanography (India)

    Garg, A; Bhosle, N.B.

    carbon (OC), organic nitrogen (ON), chlorophyll a, diatoms and bacterial numbers on the titanium panels generally increased over the period of immersion. Total lipids and n-alkane concentration also showed similar trends. n-alkanes from C sub(12) to C sub...

  5. The use of n-alkane markers to estimate the intake and apparent ...

    African Journals Online (AJOL)

    However, the effect of the higher recovery of the dosed marker needs further investigation. The estimates of apparent dry matter digestibility corresponded well with measured values, provided the factor for the incomplete faecal recovery of the internal alkanes was included in the calculation. It was concluded that the alkane ...

  6. Thermal, Catalytic Conversion of Alkanes to Linear Aldehydes and Linear Amines.

    Science.gov (United States)

    Tang, Xinxin; Jia, Xiangqing; Huang, Zheng

    2018-03-21

    Alkanes, the main constituents of petroleum, are attractive feedstocks for producing value-added chemicals. Linear aldehydes and amines are two of the most important building blocks in the chemical industry. To date, there have been no effective methods for directly converting n-alkanes to linear aldehydes and linear amines. Here, we report a molecular dual-catalyst system for production of linear aldehydes via regioselective carbonylation of n-alkanes. The system is comprised of a pincer iridium catalyst for transfer-dehydrogenation of the alkane using t-butylethylene or ethylene as a hydrogen acceptor working sequentially with a rhodium catalyst for olefin isomerization-hydroformylation with syngas. The system exhibits high regioselectivity for linear aldehydes and gives high catalytic turnover numbers when using ethylene as the acceptor. In addition, the direct conversion of light alkanes, n-pentane and n-hexane, to siloxy-terminated alkyl aldehydes through a sequence of Ir/Fe-catalyzed alkane silylation and Ir/Rh-catalyzed alkane carbonylation, is described. Finally, the Ir/Rh dual-catalyst strategy has been successfully applied to regioselective alkane aminomethylation to form linear alkyl amines.

  7. Pronounced Environmental Effects on Injection Currents in EGaln Tunneling Junctions Comprising Self-Assembled Monolayers

    NARCIS (Netherlands)

    Carlotti, Marco; Degen, Maarten; Zhang, Yanxi; Chiechi, Ryan C.

    2016-01-01

    Large-area tunneling junctions using eutectic Ga-In (EGaIn) as a top contact have proven to be a robust, reproducible, and technologically relevant platform for molecular electronics. Thus far, the majority of studies have focused on saturated molecules with backbones consisting mainly of alkanes in

  8. Photocarrier dynamics in monolayer phosphorene and bulk black phosphorus.

    Science.gov (United States)

    Zereshki, Peymon; Wei, Yaqing; Ceballos, Frank; Bellus, Matthew Z; Lane, Samuel D; Pan, Shudi; Long, Run; Zhao, Hui

    2018-06-13

    We report a combined theoretical and experimental study on photocarrier dynamics in monolayer phosphorene and bulk black phosphorus. Samples of monolayer phosphorene and bulk black phosphorus were fabricated by mechanical exfoliation, identified according to their reflective contrasts, and protected by covering them with hexagonal boron nitride layers. Photocarrier dynamics in these samples was studied by an ultrafast pump-probe technique. The photocarrier lifetime of monolayer phosphorene was found to be about 700 ps, which is about 9 times longer than that of bulk black phosphorus. This trend was reproduced in our calculations based on ab initio nonadiabatic molecular dynamics combined with time-domain density functional theory in the Kohn-Sham representation, and can be attributed to the smaller bandgap and stronger nonadiabatic coupling in bulk. The transient absorption response was also found to be dependent on the sample orientation with respect to the pump polarization, which is consistent with the previously reported anisotropic absorption of phosphorene. In addition, an oscillating component of the differential reflection signal at early probe delays was observed in the bulk sample and was attributed to the layer-breathing phonon mode with an energy of about 1 meV and a decay time of about 1.35 ps. These results provide valuable information for application of monolayer phosphorene in optoelectronics.

  9. Geomicrobiological linkages between short-chain alkane consumption and sulfate reduction rates in seep sediments.

    Directory of Open Access Journals (Sweden)

    Arpita eBose

    2013-12-01

    Full Text Available Marine hydrocarbon seeps are ecosystems that are rich in methane, and, in some cases, short-chain (C2-C5 and longer alkanes. C2-C4 alkanes such as ethane, propane and butane can be significant components of seeping fluids. Some sulfate-reducing microbes oxidize short-chain alkanes anaerobically, and may play an important role in both the competition for sulfate and the local carbon budget. To better understand the anaerobic oxidation of short-chain n-alkanes coupled with sulfate-reduction, hydrocarbon-rich sediments from the Gulf of Mexico were amended with artificial, sulfate-replete seawater and one of four n-alkanes (C1-C4 then incubated under strict anaerobic conditions. Measured rates of alkane oxidation and sulfate reduction closely follow stoichiometric predictions that assume the complete oxidation of alkanes to CO2 (though other sinks for alkane carbon likely exist. Changes in the δ13C of all the alkanes in the reactors show enrichment over the course of the incubation, with the C3 and C4 incubations showing the greatest enrichment (4.4‰ and 4.5‰ respectively. The concurrent depletion in the δ13C of dissolved inorganic carbon (DIC implies a transfer of carbon from the alkane to the DIC pool (-3.5 and -6.7‰ for C3 and C4 incubations, respectively. Microbial community analyses reveal that certain members of the class Deltaproteobacteria are selectively enriched as the incubations degrade C1-C4 alkanes. Phylogenetic analyses indicate that distinct phylotypes are enriched in the ethane reactors, while phylotypes in the propane and butane reactors align with previously identified C3-C4 alkane-oxidizing sulfate-reducers. These data further constrain the potential influence of alkane oxidation on sulfate reduction rates in cold hydrocarbon-rich sediments, provide insight into their contribution to local carbon cycling, and illustrate the extent to which short-chain alkanes can serve as electron donors and govern microbial community

  10. Theory of lithium islands and monolayers: Electronic structure and stability

    International Nuclear Information System (INIS)

    Quassowski, S.; Hermann, K.

    1995-01-01

    Systematic calculations on planar clusters and monolayers of lithium are performed to study geometries and stabilities of the clusters as well as their convergence behavior with increasing cluster size. The calculations are based on ab initio methods using density-functional theory within the local-spin-density approximation for exchange and correlation. The optimized nearest-neighbor distances d NN of the Li n clusters, n=1,...,25, of both hexagonal and square geometry increase with cluster size, converging quite rapidly towards the monolayer results. Further, the cluster cohesive energies E c increase with cluster size and converge towards the respective monolayer values that form upper bounds. Clusters of hexagonal geometry are found to be more stable than square clusters of comparable size, consistent with the monolayer results. The size dependence of the cluster cohesive energies can be described approximately by a coordination model based on the concept of pairwise additive nearest-neighbor binding. This indicates that the average binding in the Li n clusters and their relative stabilities can be explained by simple geometric effects which derive from the nearest-neighbor coordination

  11. Monolayer II-VI semiconductors: A first-principles prediction

    Science.gov (United States)

    Zheng, Hui; Chen, Nian-Ke; Zhang, S. B.; Li, Xian-Bin

    A systematic study of 32 honeycomb monolayer II-VI semiconductors is carried out by first-principles methods. It appears that BeO, MgO, CaO, ZnO, CdO, CaS, SrS, SrSe, BaTe, and HgTe honeycomb monolayers have a good dynamic stability which is revealed by phonon calculations. In addition, from the molecular dynamic (MD) simulation of other unstable candidates, we also find two extra monolayers dynamically stable, which are tetragonal BaS and orthorhombic HgS. The honeycomb monolayers exist in form of either a planar perfect honeycomb or a low-buckled 2D layer, all of which possess a band gap and most of them are in the ultraviolet region. Interestingly, the dynamically stable SrSe has a gap near visible light, and displays exotic electronic properties with a flat top of the valence band, and hence has a strong spin polarization upon hole doping. The honeycomb HgTe has been reported to achieve a topological nontrivial phase under appropriate in-plane tensile strain and spin-orbital coupling (SOC). Some II-VI partners with less than 5% lattice mismatch may be used to design novel 2D heterojunction devices. If synthesized, potential applications of these 2D II-VI families could include optoelectronics, spintronics, and strong correlated electronics. Distinguished Student (DS) Program of APS FIP travel funds.

  12. Topography and instability of monolayers near domain boundaries

    International Nuclear Information System (INIS)

    Diamant, H.; Witten, T. A.; Ege, C.; Gopal, A.; Lee, K. Y. C.

    2001-01-01

    We theoretically study the topography of a biphasic surfactant monolayer in the vicinity of domain boundaries. The differing elastic properties of the two phases generally lead to a nonflat topography of 'mesas,' where domains of one phase are elevated with respect to the other phase. The mesas are steep but low, having heights of up to 10 nm. As the monolayer is laterally compressed, the mesas develop overhangs and eventually become unstable at a surface tension of about K(δc 0 ) 2 (δc 0 being the difference in spontaneous curvature and K a bending modulus). In addition, the boundary is found to undergo a topography-induced rippling instability upon compression, if its line tension is smaller than about Kδc 0 . The effect of diffuse boundaries on these features and the topographic behavior near a critical point are also examined. We discuss the relevance of our findings to several experimental observations related to surfactant monolayers: (i) small topographic features recently found near domain boundaries; (ii) folding behavior observed in mixed phospholipid monolayers and model lung surfactants; (iii) roughening of domain boundaries seen under lateral compression; (iv) the absence of biphasic structures in tensionless surfactant films

  13. In situ and real-time atomic force microscopy studies of the stability of oligothiophene langmuir-blodgett monolayers in liquid

    KAUST Repository

    Yin, Naining

    2014-03-20

    Oligothiophene thin films have been considered as promising material for molecular electronics due to their desirable electronic properties and high structural stability under ambient conditions. To ensure performance in devices the functional structures, such as individual ordered domains, must be stable under practical and operational conditions or environments including exposure to various media. This work investigates the structure of oligothiophene Langmuir-Blodgett (LB) films upon exposure to liquid media such as water, ethanol (EtOH), and mixed tetrahydrofuran (THF)/EtOH solutions. The LB films form islands ranging from 500 nm up to 1 μm consisting of densely packed oligothiophene molecules. These islands are surrounded by bare substrate and loosely packed adsorbates. In situ and time-dependent AFM images were acquired to reveal the structural evolution, from which degradation pathways and kinetics are extracted. Degradation of these LB films initiates and propagates from intraisland defect sites, such as cracks and pin holes, whereas the edges of islands remain intact on the surface. The observations appear to be in contrast to the known degradation mechanism among self-assembled monolayers, such as alkanethiols on gold, which initiates and progresses at domain boundaries. Rationale for the observed degradation processes will also be discussed. © 2014 American Chemical Society.

  14. Self-assembled organic monolayers on gold nanoparticles: A study by sum-frequency generation combined with UV-vis spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Humbert, C. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France) and Laboratoire de Spectroscopie Moleculaire de Surface, University of Namur, 61 Rue de Bruxelles, B-5000 Namur (Belgium)]. E-mail: christophe.humbert@fundp.ac.be; Busson, B. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France); Abid, J.-P. [Ecole Polytechnique Federale de Lausanne, Laboratoire d' Electrochimie Physique et Analytique, CH-1015 Lausanne (Switzerland); Six, C. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France); Girault, H.H. [Ecole Polytechnique Federale de Lausanne, Laboratoire d' Electrochimie Physique et Analytique, CH-1015 Lausanne (Switzerland); Tadjeddine, A. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France)

    2005-05-20

    We use sum-frequency generation spectroscopy (SFG) in the infrared 2800-3000 cm{sup -1} spectral range and UV-vis spectroscopy (transmission) in the 450-650 nm spectral range in order to characterize vibrational and electronic properties of various interfaces composed of organic monolayers adsorbed on gold nanoparticles (AuNPs) with 19 nm average diameter. SFG signal is observed for AuNPs films deposited on glass substrates using the following silane intermediates: 3-(aminopropyl) triethoxysilane and 3-(mercaptopropyl) trimethoxysilane. The density of AuNPs and their aggregates are measured with a scanning electron microscope. For the samples showing a strong well-defined surface plasmon resonance (SPR), we also observe an enhancement of their non-linear optical properties. Furthermore, the SFG measurements show that 1-dodecanethiol films are rather well ordered on specific AuNPs substrates. In this way, the presence of the SFG signal, which comes from both the bulk electronic s-d interband transition and the vibrational states of the adsorbed molecules, depends on a SPR process. This phenomenon is evidenced on the AuNPs by the incident visible beam located at 532 nm, i.e. near the SPR energy maximum of these interfaces. These results open the door to experiments involving macromolecular and biological materials networks deposited on ultrathin metal electrodes in a controlled electrochemical environment.

  15. Self-assembled organic monolayers on gold nanoparticles: A study by sum-frequency generation combined with UV-vis spectroscopy

    International Nuclear Information System (INIS)

    Humbert, C.; Busson, B.; Abid, J.-P.; Six, C.; Girault, H.H.; Tadjeddine, A.

    2005-01-01

    We use sum-frequency generation spectroscopy (SFG) in the infrared 2800-3000 cm -1 spectral range and UV-vis spectroscopy (transmission) in the 450-650 nm spectral range in order to characterize vibrational and electronic properties of various interfaces composed of organic monolayers adsorbed on gold nanoparticles (AuNPs) with 19 nm average diameter. SFG signal is observed for AuNPs films deposited on glass substrates using the following silane intermediates: 3-(aminopropyl) triethoxysilane and 3-(mercaptopropyl) trimethoxysilane. The density of AuNPs and their aggregates are measured with a scanning electron microscope. For the samples showing a strong well-defined surface plasmon resonance (SPR), we also observe an enhancement of their non-linear optical properties. Furthermore, the SFG measurements show that 1-dodecanethiol films are rather well ordered on specific AuNPs substrates. In this way, the presence of the SFG signal, which comes from both the bulk electronic s-d interband transition and the vibrational states of the adsorbed molecules, depends on a SPR process. This phenomenon is evidenced on the AuNPs by the incident visible beam located at 532 nm, i.e. near the SPR energy maximum of these interfaces. These results open the door to experiments involving macromolecular and biological materials networks deposited on ultrathin metal electrodes in a controlled electrochemical environment

  16. Defect-Tolerant Monolayer Transition Metal Dichalcogenides

    DEFF Research Database (Denmark)

    Pandey, Mohnish; Rasmussen, Filip Anselm; Kuhar, Korina

    2016-01-01

    Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with a lower tendency to form defect induced deep gap states are termed defect-tolerant. Here we provide a systematic first...... the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to nonpolar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within......-principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only...

  17. Beam damage of self-assembled monolayers

    International Nuclear Information System (INIS)

    Rieke, P.C.; Baer, D.R.; Fryxell, G.E.; Engelhard, M.H.; Porter, M.S.

    1993-01-01

    X-ray and electron beam damage studies were performed on Br-terminated and methyl-terminated alkylsilane self-assembled monolayers. X-ray beam initiated damage was primarily limited to removal of the labile Br group and did not significantly damage the hydrocarbon chain. Some of the x-ray beam damage could be attributed to low-energy electrons emitted by the non-monochromatic source, but further damage was attributed to secondary electrons produced in the sample by x-ray exposure. Electron beams caused significant damage to the hydrocarbon chains. Maximum damage occurred with a beam energy of 600 eV and a dosage of 6x10 -3 C/cm 2

  18. Geochemical Tracers and Rates of Short-Chain Alkane Production in Gulf of Mexico Cold Seep Sediments

    Science.gov (United States)

    Sibert, R.; Bernard, B. B.; Brooks, J. M.; Hunter, K.; Joye, S. B.

    2014-12-01

    The organic-rich cold seep sediments in the deep Gulf of Mexico commonly contain mixtures of light hydrocarbon gases either dissolved in pore fluids, adsorbed to sediment particles, trapped in methane ice, or as free gas. The dominant component in these natural gas mixtures is typically methane (C1), but ethane (C2) and propane (C3) are nearly always present in trace or major amounts. The ratio of C1:C2:C3 varies but C2 and C3 are typically present at single digit percent levels, whereas methane usually dominates at >80%. Methane production proceeds by at least two well-studied mechanisms: either 1) by thermocatalytic cracking of fossil organic matter, or 2) as a direct product of microbial metabolism, methanogenesis. In contrast, ethane and propane production in deep-sea sediments has been historically attributed only to thermocatalytic processes. However, limited data suggests production of C2/C3 compounds through the activity of archaea. Such studies of microbial- driven dynamics of C2/C3 gases (i.e. 'alkanogenesis') in cold seep sediments are rare. Furthermore, the identities of potential substrates are poorly constrained and no attempt has been made to quantify production rates of C2/C3 gases. However, carbon isotopic data on ethane and propane from deep cores from the Gulf of Mexico suggest alkanogenesis at depth in the sediment column and alkane oxidation in uppermost oxidant-rich sediments. Here, we present the results of a series of incubation experiments using sediment slurries culled from GC600, one of the most prolific natural oil and gas seeps in the Gulf of Mexico. Rates of both alkane production and oxidation were measured under a variety of conditions to assess the net rates of alkane production and elucidate the driving microbiological mechanisms and controls on the central processes of >C1 alkane cycling in cold seep sediments. Microbial processes are important both in terms of alkane production and oxidation, raising many questions as to the

  19. Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies

    Science.gov (United States)

    Suhr, Matthias; Raff, Johannes; Pollmann, Katrin

    2016-01-01

    In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These biomolecules arrange in paracrystalline two-dimensional arrays on surfaces, bind metals, and are thus interesting for several biotechnical applications, such as biosorptive materials for the removal or recovery of different elements from the environment and industrial processes. The deposition of Au(0) nanoparticles on S-layers, either by S-layer directed synthesis 1 or adsorption of nanoparticles, opens new possibilities for diverse sensory applications. Although numerous studies have described the biosorptive properties of S-layers 2-5, a deeper understanding of protein-protein and protein-metal interaction still remains challenging. In the following study, inductively coupled mass spectrometry (ICP-MS) was used for the detection of metal sorption by suspended S-layers. This was correlated to measurements of quartz crystal microbalance with dissipation monitoring (QCM-D), which allows the online detection of proteinaceous monolayer formation and metal deposition, and thus, a more detailed understanding on metal binding. The ICP-MS results indicated that the binding of Au(III) to the suspended S-layer polymers is pH dependent. The maximum binding of Au(III) was obtained at pH 4.0. The QCM-D investigations enabled the detection of Au(III) sorption as well as the deposition of Au(0)-NPs in real-time during the in situ experiments. Further, this method allowed studying the influence of metal binding on the protein lattice stability of Slp1. Structural properties and protein layer stability could be visualized directly after QCM-D experiment using atomic force microscopy (AFM). In conclusion, the combination of these different methods provides a deeper understanding of metal binding by bacterial S-layer proteins in suspension or as monolayers on either bacterial cells or recrystallized surfaces. PMID:26863150

  20. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    Energy Technology Data Exchange (ETDEWEB)

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

  1. A class of monolayer metal halogenides MX{sub 2}: Electronic structures and band alignments

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Feng; Wang, Weichao; Luo, Xiaoguang; Cheng, Yahui; Dong, Hong; Liu, Hui; Wang, Wei-Hua, E-mail: whwangnk@nankai.edu.cn [Department of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin 300071 (China); Xie, Xinjian [School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130 (China)

    2016-03-28

    With systematic first principles calculations, a class of monolayer metal halogenides MX{sub 2} (M = Mg, Ca, Zn, Cd, Ge, Pb; M = Cl, Br, I) has been proposed. Our study indicates that these monolayer materials are semiconductors with the band gaps ranging from 2.03 eV of ZnI{sub 2} to 6.08 eV of MgCl{sub 2}. Overall, the band gap increases with the increase of the electronegativity of the X atom or the atomic number of the metal M. Meanwhile, the band gaps of monolayer MgX{sub 2} (X = Cl, Br) are direct while those of other monolayers are indirect. Based on the band edge curvatures, the derived electron (m{sub e}) and hole (m{sub h}) effective masses of MX{sub 2} monolayers are close to their corresponding bulk values except that the m{sub e} of CdI{sub 2} is three times larger and the m{sub h} for PbI{sub 2} is twice larger. Finally, the band alignments of all the studied MX{sub 2} monolayers are provided using the vacuum level as energy reference. These theoretical results may not only introduce the monolayer metal halogenides family MX{sub 2} into the emerging two-dimensional materials, but also provide insights into the applications of MX{sub 2} in future electronic, visible and ultraviolet optoelectronic devices.

  2. Proton and hydrogen transport through two-dimensional monolayers

    International Nuclear Information System (INIS)

    Seel, Max; Pandey, Ravindra

    2016-01-01

    Diffusion of protons and hydrogen atoms in representative two-dimensional materials is investigated. Specifically, density functional calculations were performed on graphene, hexagonal boron nitride (h-BN), phosphorene, silicene, and molybdenum disulfide (MoS 2 ) monolayers to study the surface interaction and penetration barriers for protons and hydrogen atoms employing finite cluster models. The calculated barrier heights correlate approximately with the size of the opening formed by the three-fold open sites in the monolayers considered. They range from 1.56 eV (proton) and 4.61 eV (H) for graphene to 0.12 eV (proton) and 0.20 eV (H) for silicene. The results indicate that only graphene and h-BN monolayers have the potential for membranes with high selective permeability. The MoS 2 monolayer behaves differently: protons and H atoms become trapped between the outer S layers in the Mo plane in a well with a depth of 1.56 eV (proton) and 1.5 eV (H atom), possibly explaining why no proton transport was detected, suggesting MoS 2 as a hydrogen storage material instead. For graphene and h-BN, off-center proton penetration reduces the barrier to 1.38 eV for graphene and 0.11 eV for h-BN. Furthermore, Pt acting as a substrate was found to have a negligible effect on the barrier height. In defective graphene, the smallest barrier for proton diffusion (1.05 eV) is found for an oxygen-terminated defect. Therefore, it seems more likely that thermal protons can penetrate a monolayer of h-BN but not graphene and defects are necessary to facilitate the proton transport in graphene. (paper)

  3. Proton and hydrogen transport through two-dimensional monolayers

    Science.gov (United States)

    Seel, Max; Pandey, Ravindra

    2016-06-01

    Diffusion of protons and hydrogen atoms in representative two-dimensional materials is investigated. Specifically, density functional calculations were performed on graphene, hexagonal boron nitride (h-BN), phosphorene, silicene, and molybdenum disulfide (MoS2) monolayers to study the surface interaction and penetration barriers for protons and hydrogen atoms employing finite cluster models. The calculated barrier heights correlate approximately with the size of the opening formed by the three-fold open sites in the monolayers considered. They range from 1.56 eV (proton) and 4.61 eV (H) for graphene to 0.12 eV (proton) and 0.20 eV (H) for silicene. The results indicate that only graphene and h-BN monolayers have the potential for membranes with high selective permeability. The MoS2 monolayer behaves differently: protons and H atoms become trapped between the outer S layers in the Mo plane in a well with a depth of 1.56 eV (proton) and 1.5 eV (H atom), possibly explaining why no proton transport was detected, suggesting MoS2 as a hydrogen storage material instead. For graphene and h-BN, off-center proton penetration reduces the barrier to 1.38 eV for graphene and 0.11 eV for h-BN. Furthermore, Pt acting as a substrate was found to have a negligible effect on the barrier height. In defective graphene, the smallest barrier for proton diffusion (1.05 eV) is found for an oxygen-terminated defect. Therefore, it seems more likely that thermal protons can penetrate a monolayer of h-BN but not graphene and defects are necessary to facilitate the proton transport in graphene.

  4. Shock tube measurements of the rate constants for seven large alkanes+OH

    KAUST Repository

    Badra, Jihad

    2015-01-01

    Reaction rate constants for seven large alkanes + hydroxyl (OH) radicals were measured behind reflected shock waves using OH laser absorption. The alkanes, n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethyl-butane, 2,3-dimethyl-butane, 2-methyl-heptane, and 4-methyl-heptane, were selected to investigate the rates of site-specific H-abstraction by OH at secondary and tertiary carbons. Hydroxyl radicals were monitored using narrow-line-width ring-dye laser absorption of the R1(5) transition of the OH spectrum near 306.7 nm. The high sensitivity of the diagnostic enabled the use of low reactant concentrations and pseudo-first-order kinetics. Rate constants were measured at temperatures ranging from 880 K to 1440 K and pressures near 1.5 atm. High-temperature measurements of the rate constants for OH + n-hexane and OH + 2,2-dimethyl-butane are in agreement with earlier studies, and the rate constants of the five other alkanes with OH, we believe, are the first direct measurements at combustion temperatures. Using these measurements and the site-specific H-abstraction measurements of Sivaramakrishnan and Michael (2009) [1,2], general expressions for three secondary and two tertiary abstraction rates were determined as follows (the subscripts indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon): S20=1.58×10-11exp(-1550K/T)cm3molecule-1s-1(887-1327K)S30=2.37×10-11exp(-1850K/T)cm3molecule-1s-1(887-1327K)S21=4.5×10-12exp(-793.7K/T)cm3molecule-1s-1(833-1440K)T100=2.85×10-11exp(-1138.3K/T)cm3molecule-1s-1(878-1375K)T101=7.16×10-12exp(-993K/T)cm3molecule-1s-1(883-1362K) © 2014 The Combustion Institute.

  5. Modeling of Alkane Oxidation Using Constituents and Species

    Science.gov (United States)

    Bellan, Jasette; Harstad, Kenneth G.

    2010-01-01

    It is currently not possible to perform simulations of turbulent reactive flows due in particular to complex chemistry, which may contain thousands of reactions and hundreds of species. This complex chemistry results in additional differential equations, making the numerical solution of the equation set computationally prohibitive. Reducing the chemical kinetics mathematical description is one of several important goals in turbulent reactive flow modeling. A chemical kinetics reduction model is proposed for alkane oxidation in air that is based on a parallel methodology to that used in turbulence modeling in the context of the Large Eddy Simulation. The objective of kinetic modeling is to predict the heat release and temperature evolution. This kinetic mechanism is valid over a pressure range from atmospheric to 60 bar, temperatures from 600 K to 2,500 K, and equivalence ratios from 0.125 to 8. This range encompasses diesel, HCCI, and gas-turbine engines, including cold ignition. A computationally efficient kinetic reduction has been proposed for alkanes that has been illustrated for n-heptane using the LLNL heptane mechanism. This model is consistent with turbulence modeling in that scales were first categorized into either those modeled or those computed as progress variables. Species were identified as being either light or heavy. The heavy species were decomposed into defined 13 constituents, and their total molar density was shown to evolve in a quasi-steady manner. The light species behave either in a quasi-steady or unsteady manner. The modeled scales are the total constituent molar density, Nc, and the molar density of the quasi-steady light species. The progress variables are the total constituent molar density rate evolution and the molar densities of the unsteady light species. The unsteady equations for the light species contain contributions of the type gain/loss rates from the heavy species that are modeled consistent with the developed mathematical

  6. Distribution and origins of n-alkanes, hopanes, and steranes in rivers and marine sediments from Southwest Caspian coast, Iran: implications for identifying petroleum hydrocarbon inputs.

    Science.gov (United States)

    Shirneshan, Golshan; Bakhtiari, Alireza Riyahi; Memariani, Mahmoud

    2016-09-01

    The occurrence of n-alkanes and biomarkers (hopane and sterane) in surface sediments from Southwestern coasts of Caspian Sea and 28 rivers arriving to this lake, determined with a gas chromatography-mass spectrometry method, was used to assess the impacts of anthropogenic activities in the studied area. The concentrations of total n-alkanes (Σ21 n-alkane) in costal and riverine sediments varied from 249.2 to 3899.5 and 56 to 1622.4 μg g(-1), respectively. An evaluation of the source diagnostic indices indicated that petroleum related sources (petrogenic) were mainly contributed to n-alkanes in costal and most riverine sediments. Only the hydrocarbons in sediment of 3 rivers were found to be mainly of biogenic origin. Principal component analysis using hopane diagnostic ratios in costal and riverine sediments, and Anzali, Turkmenistan, and Azerbaijan oils were used to identify the sources of hydrocarbons in sediments. It was indicated that the anthropogenic contributions in most of the costal sediment samples are dominated with inputs of oil spills from Turkmenistan and Azerbaijan countries.

  7. Surface Electrostatic Potential and Water Orientation in the presence of Sodium Octanoate Dilute Monolayers Studied by Means of Molecular Dynamics Simulations.

    Science.gov (United States)

    Bernardino, Kalil; de Moura, André F

    2015-10-13

    A series of atomistic molecular dynamics simulations were performed in the present investigation to assess the spontaneous formation of surfactant monolayers of sodium octanoate at the water-vacuum interface. The surfactant surface coverage increased until a saturation threshold was achieved, after which any further surfactant addition led to the formation of micellar aggregates within the solution. The saturated films were not densely packed, as might be expected for short-chained surfactants, and all films regardless of the surface coverage presented surfactant molecules with the same ordering pattern, namely, with the ionic heads toward the aqueous solution and the tails lying nearly parallel to the interface. The major contributions to the electrostatic surface potential came from the charged heads and the counterion distribution, which nearly canceled out each other. The balance between the oppositely charged ions rendered the electrostatic contributions from water meaningful, amounting to ca. 10% of the contributions arising from the ionic species. And even the aliphatic tails, whose atoms bear relatively small partial atomic charges as compared to the polar molecules and molecular fragments, contributed with ca. 20% of the total electrostatic surface potential of the systems under investigation. Although the aliphatic tails were not so orderly arranged as in a compact film, the C-H bonds assumed a preferential orientation, leading to an increased contribution to the electrostatic properties of the interface. The most prominent feature arising from the partitioning of the electrostatic potential into individual contributions was the long-range ordering of the water molecules. This ordering of the water molecules produced a repulsive dipole-dipole interaction between the two interfaces, which increased with the surface coverage. Only for a water layer wider than 10 nm was true bulk behavior observed, and the repulsive dipole-dipole interaction faded away.

  8. An in vitro and in silico study on the flavonoid-mediated modulation of the transport of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) through Caco-2 monolayers

    International Nuclear Information System (INIS)

    Schutte, Maaike E.; Freidig, Andreas P.; Sandt, Johannes J.M. van de; Alink, Gerrit M.; Rietjens, Ivonne M.C.M.; Groten, John P.

    2006-01-01

    The present study describes the effect of different flavonoids on the absorption of the pro-carcinogen PhIP through Caco-2 monolayers and the development of an in silico model describing this process taking into account passive diffusion and active transport of PhIP. Various flavonoids stimulated the apical to basolateral PhIP transport. Using the in silico model for flavone, kaempferol and chrysoeriol, the apparent Ki value for inhibition of the active transport to the apical side was estimated to be below 53 μM and for morin, robinetin and taxifolin between 164 and 268 μM. For myricetin, luteolin, naringenin and quercetin, the apparent Ki values were determined more accurately and amounted to 37.3, 12.2, 11.7 and 5.6 μM respectively. Additional experiments revealed that the apical to basolateral PhIP transport was also increased in the presence of a typical BCRP or MRP inhibitor with apparent Ki values in the same range as those of the flavonoids. This observation together with the fact that flavonoids are known to be inhibitors of MRPs and BCRP, corroborates that inhibition of these apical membrane transporters is involved in the flavonoid-mediated increased apical to basolateral PhIP transport. Based on the apparent Ki values obtained, it is concluded that the flavonols, at the levels present in the regular Western diet, are capable of stimulating the transport of PhIP through Caco-2 monolayers from the apical to the basolateral compartment. This points to flavonoid-mediated stimulation of the bioavailability of PhIP and, thus, a possible adverse effect of these supposed beneficial food ingredients

  9. Using a chemiresistor-based alkane sensor to distinguish exhaled breaths of lung cancer patients from subjects with no lung cancer.

    Science.gov (United States)

    Tan, Jiunn-Liang; Yong, Zheng-Xin; Liam, Chong-Kin

    2016-10-01

    Breath alkanes are reported to be able to discriminate lung cancer patients from healthy people. A simple chemiresistor-based sensor was designed to respond to alkanes by a change in resistance measured by a digital multimeter connected to the sensor. In preclinical experiments, the sensor response was found to have a strong positive linear relationship with alkane compounds and not responsive to water. This study aimed to determine the ability of the alkane sensor to distinguish the exhaled breaths of lung cancer patients from that of chronic obstructive pulmonary disease (COPD) patients and control subjects without lung cancer. In this cross-sectional study, 12 treatment-naive patients with lung cancer, 12 ex- or current smokers with COPD and 13 never-smokers without lung disease were asked to exhale through a drinking straw into a prototype breath-in apparatus made from an empty 125 mL Vitagen ® bottle with the chemiresistor sensor attached at its inside bottom to measure the sensor peak output (percentage change of baseline resistance measured before exhalation to peak resistance) and the time taken for the baseline resistance to reach peak resistance. Analysis of multivariate variance and post-hoc Tukey test revealed that the peak output and the time to peak values for the lung cancer patients were statistically different from that for both the COPD patients and the controls without lung disease, Pillai's Trace =0.393, F=3.909, df = (4, 64), P=0.007. A 2.20% sensor peak output and a 90-s time to peak gave 83.3% sensitivity and 88% specificity in diagnosing lung cancer. Tobacco smoking did not affect the diagnostic accuracy of the sensor. The alkane sensor could discriminate patients with lung cancer from COPD patients and people without lung disease. Its potential utility as a simple, cheap and non-invasive test for early lung cancer detection needs further studies.

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

    Science.gov (United States)

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

    2016-11-28

    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.

  11. Density and Compressibility of Multicomponent n-Alkane Mixtures up to 463 K and 140 MPa

    DEFF Research Database (Denmark)

    Regueira, Teresa; Glykioti, Maria-Lito; Stenby, Erling Halfdan

    2017-01-01

    Density measurements of two ternary alkane mixtures (methane/n-butane/n-decane and methane/n-butane/n-dodecane) and two multicomponent mixtures composed of methane/n-butane/n-octane/n-dodecane/n-hexadecane/n-eicosane were performed in the temperature range from (278.15 to 463.15) K and pressures ......–Redlich–Kwong (SRK), Peng–Robinson (PR), Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT), and Soave-Benedict-Webb-Rubin (Soave-BWR) were used for predicting the experimental density values as well as the excess volumes....... to 140 MPa. The isothermal compressibility values of these mixtures were obtained by differentiation from a Tait-type fitting of experimental densities as a function of temperature and pressure. Excess volume of the studied mixtures was also determined. Four different equations of state, that is, Soave...

  12. Topological Phase Diagrams of Bulk and Monolayer TiS2−xTex

    KAUST Repository

    Zhu, Zhiyong; Cheng, Yingchun; Schwingenschlö gl, Udo

    2013-01-01

    With the use of ab initio calculations, the topological phase diagrams of bulk and monolayer TiS2−xTex are established. Whereas bulk TiS2−xTex shows two strong topological phases [1;(000)] and [1;(001)] for 0.44monolayer is topologically nontrivial for 0.48monolayer, TiS2−xTex is a unique system for studying topological phases in three and two dimensions simultaneously.

  13. Topological Phase Diagrams of Bulk and Monolayer TiS2−xTex

    KAUST Repository

    Zhu, Zhiyong

    2013-02-12

    With the use of ab initio calculations, the topological phase diagrams of bulk and monolayer TiS2−xTex are established. Whereas bulk TiS2−xTex shows two strong topological phases [1;(000)] and [1;(001)] for 0.44monolayer is topologically nontrivial for 0.48monolayer, TiS2−xTex is a unique system for studying topological phases in three and two dimensions simultaneously.

  14. Large Friction Anisotropy of a Polydiacetylene Monolayer

    International Nuclear Information System (INIS)

    Burns, A.R.; Carpick, R.W.; Sasaki, D.Y.

    1999-01-01

    Friction force microscopy measurements of a polydiacetylene monolayer film reveal a 300% friction anisotropy that is correlated with the film structure. The film consists of a monolayer of the red form of N-(2-ethanol)- 10,12 pentacosadiynamide, prepared on a Langmuir trough and deposited on a mica substrate. As confirmed by atomic force microscopy and fluorescence microscopy, the monolayer consists of domains of linearly oriented conjugated backbones with pendant hydrocarbon side chains above and below the backbones. Maximum friction occurs when the sliding direction is perpendicular to the backbone. We propose that the backbones impose anisotropic packing of the hydrocarbon side chains which leads to the observed friction anisotropy. Friction anisotropy is therefore a sensitive, optically-independent indicator of polymer backbone direction and monolayer structural properties

  15. Molecular diffusion in monolayer and submonolayer nitrogen

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Bruch, Ludwig Walter

    2001-01-01

    The orientational and translational motions in a monolayer fluid of physisorbed molecular nitrogen are treated using molecular dynamics simulations. Dynamical response functions and several approximations to the coefficient of translational diffusion are determined for adsorption on the basal plane...

  16. Method to synthesize metal chalcogenide monolayer nanomaterials

    Science.gov (United States)

    Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

    2016-12-13

    Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

  17. Janus Monolayer Transition-Metal Dichalcogenides.

    Science.gov (United States)

    Zhang, Jing; Jia, Shuai; Kholmanov, Iskandar; Dong, Liang; Er, Dequan; Chen, Weibing; Guo, Hua; Jin, Zehua; Shenoy, Vivek B; Shi, Li; Lou, Jun

    2017-08-22

    The crystal configuration of sandwiched S-Mo-Se structure (Janus SMoSe) at the monolayer limit has been synthesized and carefully characterized in this work. By controlled sulfurization of monolayer MoSe 2 , the top layer of selenium atoms is substituted by sulfur atoms, while the bottom selenium layer remains intact. The structure of this material is systematically investigated by Raman, photoluminescence, transmission electron microscopy, and X-ray photoelectron spectroscopy and confirmed by time-of-flight secondary ion mass spectrometry. Density functional theory (DFT) calculations are performed to better understand the Raman vibration modes and electronic structures of the Janus SMoSe monolayer, which are found to correlate well with corresponding experimental results. Finally, high basal plane hydrogen evolution reaction activity is discovered for the Janus monolayer, and DFT calculation implies that the activity originates from the synergistic effect of the intrinsic defects and structural strain inherent in the Janus structure.

  18. Nanotubes based on monolayer blue phosphorus

    KAUST Repository

    Montes Muñ oz, Enrique; Schwingenschlö gl, Udo

    2016-01-01

    We demonstrate structural stability of monolayer zigzag and armchair blue phosphorus nanotubes by means of molecular dynamics simulations. The vibrational spectrum and electronic band structure are determined and analyzed as functions of the tube

  19. Heterointerface Screening Effects between Organic Monolayers and Monolayer Transition Metal Dichalcogenides

    KAUST Repository

    Zheng, Yu Jie; Huang, Yu Li; Chen, Yifeng; Zhao, Weijie; Eda, Goki; Spataru, Catalin D.; Zhang, Wenjing; Chang, Yung-Huang; Li, Lain-Jong; Chi, Dongzhi; Quek, Su Ying; Wee, Andrew Thye Shen

    2016-01-01

    © 2016 American Chemical Society. The nature and extent of electronic screening at heterointerfaces and their consequences on energy level alignment are of profound importance in numerous applications, such as solar cells, electronics etc. The increasing availability of two-dimensional (2D) transition metal dichalcogenides (TMDs) brings additional opportunities for them to be used as interlayers in "van der Waals (vdW) heterostructures" and organic/inorganic flexible devices. These innovations raise the question of the extent to which the 2D TMDs participate actively in dielectric screening at the interface. Here we study perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) monolayers adsorbed on single-layer tungsten diselenide (WSe2), bare graphite, and Au(111) surfaces, revealing a strong dependence of the PTCDA HOMO-LUMO gap on the electronic screening effects from the substrate. The monolayer WSe2 interlayer provides substantial, but not complete, screening at the organic/inorganic interface. Our results lay a foundation for the exploitation of the complex interfacial properties of hybrid systems based on TMD materials.

  20. Heterointerface Screening Effects between Organic Monolayers and Monolayer Transition Metal Dichalcogenides

    KAUST Repository

    Zheng, Yu Jie

    2016-01-21

    © 2016 American Chemical Society. The nature and extent of electronic screening at heterointerfaces and their consequences on energy level alignment are of profound importance in numerous applications, such as solar cells, electronics etc. The increasing availability of two-dimensional (2D) transition metal dichalcogenides (TMDs) brings additional opportunities for them to be used as interlayers in "van der Waals (vdW) heterostructures" and organic/inorganic flexible devices. These innovations raise the question of the extent to which the 2D TMDs participate actively in dielectric screening at the interface. Here we study perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) monolayers adsorbed on single-layer tungsten diselenide (WSe2), bare graphite, and Au(111) surfaces, revealing a strong dependence of the PTCDA HOMO-LUMO gap on the electronic screening effects from the substrate. The monolayer WSe2 interlayer provides substantial, but not complete, screening at the organic/inorganic interface. Our results lay a foundation for the exploitation of the complex interfacial properties of hybrid systems based on TMD materials.

  1. Enhancement of Hole Confinement by Monolayer Insertion in Asymmetric Quantum-Barrier UVB Light Emitting Diodes

    KAUST Repository

    Janjua, Bilal; Alyamani, Ahmed Y.; El-Desouki, M. M.; Ng, Tien Khee; Ooi, Boon S.

    2014-01-01

    We study the enhanced hole confinement by having a large bandgap AlGaN monolayer insertion (MLI) between the quantum well (QW) and the quantum barrier (QB). The numerical analysis examines the energy band alignment diagrams, using a self

  2. Spin-orbit-induced spin splittings in polar transition metal dichalcogenide monolayers

    KAUST Repository

    Cheng, Yingchun; Zhu, Zhiyong; Tahir, Muhammad; Schwingenschlö gl, Udo

    2013-01-01

    . We present ab initio electronic structure, phonon, and molecular-dynamics calculations to study the structural stability and spin-orbit-induced spin splitting in the transition metal dichalcogenide monolayers MXY (M = Mo, W and X, Y = S, Se, Te

  3. Piezoelectric effect in chemical vapour deposition-grown atomic-monolayer triangular molybdenum disulfide piezotronics

    KAUST Repository

    Qi, Junjie; Lan, Yann-Wen; Stieg, Adam Z.; Chen, Jyun-Hong; Zhong, Yuan-Liang; Li, Lain-Jong; Chen, Chii-Dong; Zhang, Yue; Wang, Kang L.

    2015-01-01

    High-performance piezoelectricity in monolayer semiconducting transition metal dichalcogenides is highly desirable for the development of nanosensors, piezotronics and photo-piezotransistors. Here we report the experimental study

  4. Exciton Binding Energy of Monolayer WS2

    Science.gov (United States)

    Zhu, Bairen; Chen, Xi; Cui, Xiaodong

    2015-03-01

    The optical properties of monolayer transition metal dichalcogenides (TMDC) feature prominent excitonic natures. Here we report an experimental approach to measuring the exciton binding energy of monolayer WS2 with linear differential transmission spectroscopy and two-photon photoluminescence excitation spectroscopy (TP-PLE). TP-PLE measurements show the exciton binding energy of 0.71 +/- 0.01 eV around K valley in the Brillouin zone.

  5. Critical constants and acentric factors for long-chain alkanes suitable for corresponding states applications

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios; Dimitrios, Tassios

    1997-01-01

    Several methods for the estimation of the critical temperature T-c, the critical pressure P-c, and the acentric factor omega for long-chain n-alkanes are reviewed and evaluated for the prediction of vapor pressures using Corresponding States (CS) methods, like the Lee-Kesler equation and the cubic....... Anselme, Correlation of the critical properties of alkanes and alkanols, Fluid Phase Equilibria, 56 (1990) 153-169; W. Hu, J. Lovland and P. Vonka. Generalized vapor pressure equations for n-alkanes, 1-alkenes, and 1-alkanols, Presented at the 11th Int. Congress of Chemical Engineering, Chemical Equipment...

  6. Integrated quantitative fractal polarimetric analysis of monolayer lung cancer cells

    Science.gov (United States)

    Shrestha, Suman; Zhang, Lin; Quang, Tri; Farrahi, Tannaz; Narayan, Chaya; Deshpande, Aditi; Na, Ying; Blinzler, Adam; Ma, Junyu; Liu, Bo; Giakos, George C.

    2014-05-01

    Digital diagnostic pathology has become one of the most valuable and convenient advancements in technology over the past years. It allows us to acquire, store and analyze pathological information from the images of histological and immunohistochemical glass slides which are scanned to create digital slides. In this study, efficient fractal, wavelet-based polarimetric techniques for histological analysis of monolayer lung cancer cells will be introduced and different monolayer cancer lines will be studied. The outcome of this study indicates that application of fractal, wavelet polarimetric principles towards the analysis of squamous carcinoma and adenocarcinoma cancer cell lines may be proved extremely useful in discriminating among healthy and lung cancer cells as well as differentiating among different lung cancer cells.

  7. [Bis(TrimethylsilylMethyl]Lithium and -Sodium: Solubility in Alkanes and Complexes with O- and N- Donor Ligands

    Directory of Open Access Journals (Sweden)

    Markus von Pilgrim

    2017-06-01

    Full Text Available In contrast to alkyl compounds of lithium, which play an important role in organometallic chemistry, the corresponding heavier alkali metal compounds are less investigated. These compounds are mostly insoluble in inert solvents or undergo solvolysis in coordinating solvents due to their high reactivity. An exception from this typical behavior is demonstrated by bis(trimethylsilylmethylsodium. This study examines alkane solutions of bis(trimethylsilylmethyllithium and -sodium by NMR spectroscopic and cryoscopic methods. In addition, structural studies by X-ray crystallography of the corresponding compounds coordinated by O- and N- ligands (tetrahydrofuran and tetramethylethylenediamine present possible structural motifs of the uncoordinated compounds in solution.

  8. ELECTROCATALYSIS ON SURFACES MODIFIED BY METAL MONOLAYERS DEPOSITED AT UNDERPOTENTIALS.

    Energy Technology Data Exchange (ETDEWEB)

    ADZIC,R.

    2000-12-01

    The remarkable catalytic properties of electrode surfaces modified by monolayer amounts of metal adatoms obtained by underpotential deposition (UPD) have been the subject of a large number of studies during the last couple of decades. This interest stems from the possibility of implementing strictly surface modifications of electrocatalysts in an elegant, well-controlled way, and these bi-metallic surfaces can serve as models for the design of new catalysts. In addition, some of these systems may have potential for practical applications. The UPD of metals, which in general involves the deposition of up to a monolayer of metal on a foreign substrate at potentials positive to the reversible thermodynamic potential, facilitates this type of surface modification, which can be performed repeatedly by potential control. Recent studies of these surfaces and their catalytic properties by new in situ surface structure sensitive techniques have greatly improved the understanding of these systems.

  9. Biobased production of alkanes and alkenes through metabolic engineering of microorganisms

    DEFF Research Database (Denmark)

    Kang, Min Kyoung; Nielsen, Jens

    2017-01-01

    Advancement in metabolic engineering of microorganisms has enabled bio-based production of a range of chemicals, and such engineered microorganism can be used for sustainable production leading to reduced carbon dioxide emission there. One area that has attained much interest is microbial...... hydrocarbon biosynthesis, and in particular, alkanes and alkenes are important high-value chemicals as they can be utilized for a broad range of industrial purposes as well as ‘drop-in’ biofuels. Some microorganisms have the ability to biosynthesize alkanes and alkenes naturally, but their production level...... is extremely low. Therefore, there have been various attempts to recruit other microbial cell factories for production of alkanes and alkenes by applying metabolic engineering strategies. Here we review different pathways and involved enzymes for alkane and alkene production and discuss bottlenecks...

  10. Molecular dynamics and energy landscape of decanethiolates in self-assembled monolayers on Au(111) by STM

    NARCIS (Netherlands)

    Sotthewes, Kai; Wu, Hairong; Kumar, Avijit; Vancso, Gyula J.; Schön, Peter Manfred; Zandvliet, Henricus J.W.

    2013-01-01

    The energetics and dynamics of the various phases of decanethiolate self-assembled monolayers on Au(111) surfaces were studied with scanning tunneling microscopy. We have observed five different phases of the decanethiolate monolayer on Au(111): four ordered phases (β, δ, χ*, and ) and one

  11. Liquid–liquid extraction of toluene from alkane with pyridinium based ionic liquid ([BPy][NO3] and [HPy][NO3]) at 298.15 K and atmospheric pressure

    International Nuclear Information System (INIS)

    Enayati, Mobin; Mokhtarani, Babak; Sharifi, Ali; Anvari, Sanam; Mirzaei, Mojtaba

    2016-01-01

    Highlights: • Extraction of toluene from alkane with pyridinium based ionic liquid was studied. • The ionic liquids [BPy][NO 3 ] and [HPy][NO 3 ] were used. • The effect of alkane chain length on selectivity of toluene was evaluated. • The effect of alkyl chain length of ionic liquids on toluene selectivity was investigated. • The experimental data were correlated with the NRTL model. - Abstract: The focus of this paper is to study the liquid−liquid extraction process for the separation of toluene from alkane employing the ionic liquids N-butylpyridinium nitrate, [BPy][NO 3 ], and N-hexylpyridinium nitrate, [HPy][NO 3 ], as a new solvents. New experimental data for the ternary systems of {[BPy][NO 3 ] (1) + heptane, or octane, or decane (2) + toluene (3)} and {[HPy][NO 3 ] (1) + heptane, or octane, or decane (2) + toluene (3)} at T = 298.15 K and atmospheric pressure are reported. The Othmer-Tobias and Hand correlation are examined to check the reliability of the experimental LLE data. The toluene distribution ratios and selectivity were calculated form the experimental data. The selectivity values are higher than unity which indicates the ILs, [BPy][NO 3 ] and [HPy][NO 3 ], used in this work are potential solvents to separate toluene from alkane. Besides, the effect of the alkane chain length in the selectivity values was evaluated. In addition, the result of the NRTL thermodynamic modeling shows, the experimental data were satisfactorily correlated.

  12. Quantum chemical study of hydroxylation of alkanes by hypofluorous acid

    Czech Academy of Sciences Publication Activity Database

    Ončák, Milan; Srnec, Martin; Zahradník, Rudolf

    2008-01-01

    Roč. 82, č. 4 (2008), s. 649-659 ISSN 0137-5083 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40550506 Keywords : electronic structure * nonheme iron * basis-set Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.518, year: 2008

  13. Nuclear magnetic resonance study of alkane conformational statistics

    Science.gov (United States)

    Burnell, E. Elliott; Weber, Adrian C. J.; de Lange, Cornelis A.; Meerts, W. Leo; Dong, Ronald Y.

    2011-12-01

    NMR spectra of ethane, propane, and n-butane as solutes in the nematic liquid crystals 4-n-pentyl-4'-cyanobiphenyl (5CB) and Merck ZLI 1132 (1132) are investigated over a wide temperature range. The ratios of dipolar couplings of ethane to propane are constant over the entire temperature range. Assuming that this constancy applies to the butane conformers facilitates the separation of probability from order parameter. This separation allows the investigation of conformational distribution without the need of invoking any model for the anisotropic intermolecular potential. The results give an order matrix that is consistent with that predicted from model potentials that describe the orientational potential in terms of short-range size and shape effects. The isotropic intermolecular potential contribution to the trans-gauche energy difference Etg is found to be temperature dependent with the values and variation in agreement with that found when the same results are analyzed using the chord model for anisotropic interactions [A. C. J. Weber and E. E. Burnell, Chem. Phys. Lett. 506, 196 (2011)]. The fit obtained for 9 spectra in 5CB (63 dipolar couplings) has an RMS difference between experimental and calculated dipolar couplings of 2.7 Hz, while that for the 16 spectra in 1132 (112 couplings) is 6.2 Hz; this excellent fit with nine adjustable parameters suggests that the assumption of equal temperature dependencies of the order parameters for ethane, propane, and each conformer of butane is correct. Also the fit parameters (Etg and the methyl angle increase) obtained for 1132 and 5CB agree. The results indicate that the chord model, which was designed to treat hydrocarbon chains, is indeed the model of choice for these chains. The temperature variation of Etg provides a challenge for theoreticians. Finally, even better fits to the experimental dipolar couplings are obtained when the energy in the Boltzmann factor is used for scaling ethane to butane results. However, in this case the values obtained for Etg differ between 1132 and 5CB.

  14. Electronic, magnetic and optical properties of B, C, N and F doped MgO monolayer

    Science.gov (United States)

    Moghadam, A. Dashti; Maskane, P.; Esfandiari, S.

    2018-06-01

    MgO as one of the alkaline earth oxides has various applications in industry. In this work, we aim to investigate the electronic, optical and magnetic properties of MgO monolayers. Furthermore, monolayer structures with substituted B, N, C and F atoms instead of O atom are studied. These results indicate that MgO layer has possessed potential application in optoelectronic and spintronic nano-devices.

  15. Exciton-dominant Electroluminescence from a Diode of Monolayer MoS2

    Science.gov (United States)

    2014-05-14

    injected electrons and holes, is a reliable technique to study exciton recombination processes in monolayer MoS2, including val- ley and spin excitation...temperature. After superimposing a white light scattering image of the de - vice, we find that the electroluminescence is localized at the edge of the...We find the emerged feature (labeled NX) peaks at 550 nm with energy of 2.255 eV. In low dimensional system, like monolayer MoS2, Coulomb interactions

  16. Characterization and Two-Dimensional Crystallization of Membrane Component AlkB of the Medium-Chain Alkane Hydroxylase System from Pseudomonas putida GPo1

    OpenAIRE

    Alonso, Hernan; Roujeinikova, Anna

    2012-01-01

    The alkane hydroxylase system of Pseudomonas putida GPo1 allows it to use alkanes as the sole source of carbon and energy. Bacterial alkane hydroxylases have tremendous potential as biocatalysts for the stereo- and regioselective transformation of a wide range of chemically inert unreactive alkanes into valuable reactive chemical precursors. We have produced and characterized the first 2-dimensional crystals of the integral membrane component of the P. putida alkane hydroxylase system, the no...

  17. The quantitative significance of Syntrophaceae and syntrophic partnerships in methanogenic degradation of crude oil alkanes.

    Science.gov (United States)

    Gray, N D; Sherry, A; Grant, R J; Rowan, A K; Hubert, C R J; Callbeck, C M; Aitken, C M; Jones, D M; Adams, J J; Larter, S R; Head, I M

    2011-11-01

    Libraries of 16S rRNA genes cloned from methanogenic oil degrading microcosms amended with North Sea crude oil and inoculated with estuarine sediment indicated that bacteria from the genera Smithella (Deltaproteobacteria, Syntrophaceace) and Marinobacter sp. (Gammaproteobacteria) were enriched during degradation. Growth yields and doubling times (36 days for both Smithella and Marinobacter) were determined using qPCR and quantitative data on alkanes, which were the predominant hydrocarbons degraded. The growth yield of the Smithella sp. [0.020 g(cell-C)/g(alkane-C)], assuming it utilized all alkanes removed was consistent with yields of bacteria that degrade hydrocarbons and other organic compounds in methanogenic consortia. Over 450 days of incubation predominance and exponential growth of Smithella was coincident with alkane removal and exponential accumulation of methane. This growth is consistent with Smithella's occurrence in near surface anoxic hydrocarbon degrading systems and their complete oxidation of crude oil alkanes to acetate and/or hydrogen in syntrophic partnership with methanogens in such systems. The calculated growth yield of the Marinobacter sp., assuming it grew on alkanes, was [0.0005 g(cell-C)/g(alkane-C)] suggesting that it played a minor role in alkane degradation. The dominant methanogens were hydrogenotrophs (Methanocalculus spp. from the Methanomicrobiales). Enrichment of hydrogen-oxidizing methanogens relative to acetoclastic methanogens was consistent with syntrophic acetate oxidation measured in methanogenic crude oil degrading enrichment cultures. qPCR of the Methanomicrobiales indicated growth characteristics consistent with measured rates of methane production and growth in partnership with Smithella. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

  18. Application of a Crossover Equation of State to Describe Phase Equilibrium and Critical Properties of n-Alkanes and Methane/n-Alkane Mixtures

    DEFF Research Database (Denmark)

    P. C. M. Vinhal, Andre; Yan, Wei; Kontogeorgis, Georgios M.

    2018-01-01

    and the asymptotic one near the critical point. Although several crossover EOSs have been developed in the last decades their use in modeling industrial processes is rather limited. In this work, we use the crossover Soave–Redlich–Kwong (CSRK) to describe phase equilibrium and critical properties of pure n......-alkanes and methane/n-alkane binary mixtures and compare the results to two other modeling approaches of the SRK EOS. In the case of the pure fluids, CSRK gives an accurate overall description of the phase equilibrium and critical properties; nevertheless, a minor increase in the deviation of the saturation pressure...

  19. Platinum monolayer electrocatalysts for oxygen reduction: effect of substrates, and long-term stability

    Directory of Open Access Journals (Sweden)

    J. ZHANG

    2005-03-01

    Full Text Available We describe a novel concept for a Ptmonolayer electrocatalyst and present the results of our electrochemical, X-ray absorption spectroscopy, and scanning tunneling microscopy studies. The electrocatalysts were prepared by a new method for depositing Pt monolayers involving the galvanic displacement by Pt of an underpotentially deposited Cu monolayer on substrates of Au (111, Ir(111, Pd(111, Rh(111 and Ru(0001 single crylstals, and Pd nanoparticles. The kinetics of O2 reduction showed significant enhancement with Pt monolayers on Pd(111 and Pd nanoparticle surfaces in comparisonwith the reaction on Pt(111 and Pt nanoparticles, respectively. This increase in catalytic activity is attributed partly to the decreased formation of PtOH, as shown by in situ X-ray absorption spectroscopy. The results illustrate that placing a Pt monolayer on a suitable substrate of metal nanoparticles is an attractive way of designing better O2 reduction electrocatalysts with very low Pt contents.

  20. Bidisperse silica nanoparticles close-packed monolayer on silicon substrate by three step spin method

    Science.gov (United States)

    Khanna, Sakshum; Marathey, Priyanka; Utsav, Chaliawala, Harsh; Mukhopadhyay, Indrajit

    2018-05-01

    We present the studies on the structural properties of monolayer Bidisperse silica (SiO2) nanoparticles (BDS) on Silicon (Si-100) substrate using spin coating technique. The Bidisperse silica nanoparticle was synthesised by the modified sol-gel process. Nanoparticles on the substrate are generally assembled in non-close/close-packed monolayer (CPM) form. The CPM form is obtained by depositing the colloidal suspension onto the silicon substrate using complex techniques. Here we report an effective method for forming a monolayer of bidisperse silica nanoparticle by three step spin coating technique. The samples were prepared by mixing the monodisperse solutions of different particles size 40 and 100 nm diameters. The bidisperse silica nanoparticles were self-assembled on the silicon substrate forming a close-packed monolayer film. The scanning electron microscope images of bidisperse films provided in-depth film structure of the film. The maximum surface coverage obtained was around 70-80%.

  1. Analysis of final products from the liquid alkanes radiolysis at low dose, low temperature and high dose rate

    International Nuclear Information System (INIS)

    Tilquin, B.; Doncker, J. de.

    1991-01-01

    Yields of final products (dimers) from the radiolysis of n-hexane and 2,3-dimethylbutane are studied by capillary chromatographic techniques for trace analysis. Reaction of intermediates with the products, the alkane molecules or impurities, is reduced by using low dose (1 kGy), low temperature (195 K) and high dose rate (LINAC). Temperature is the most important experiment variable; by reducing the temperature, reactions with significant activation energies do not compete with radical-radical termination reactions. Products from LINAC radiolysis provide information about active species (reactive fragment, allylic radical...) which deserve a more detailed examination by direct methods [fr

  2. Intact penetratin metabolite permeates across Caco-2 monolayers

    DEFF Research Database (Denmark)

    Birch, Ditlev; Christensen, Malene Vinther; Stærk, Dan

    . Previous studies have demonstrated that cell-penetrating peptides (CPPs) may be used as carriers in order to improve the bioavailability of a therapeutic cargo like insulin after oral administration. Penetratin, a commonly used CPP, has been shown to increase the uptake of insulin across Caco-2 cell......-2 cells cultured on permeable filter inserts and in cell lysates, respectively. The epithelial permeation of penetratin and the formed metabolites was assessed by using Caco-2 monolayers cultured on permeable filter inserts. Results Preliminary data revealed that at least one specific metabolite...... is formed upon both intracellular and extracellular degradation of penetratin (figure 1A). Following incubation with epithelium for 4 hours, the metabolite permeated the Caco-2 monolayer and the concentration increased approximately 10-fold when compared to a sample collected following 15 minutes...

  3. MgO monolayer epitaxy on Ni (100)

    Science.gov (United States)

    Sarpi, B.; Putero, M.; Hemeryck, A.; Vizzini, S.

    2017-11-01

    The growth of two-dimensional oxide films with accurate control of their structural and electronic properties is considered challenging for engineering nanotechnological applications. We address here the particular case of MgO ultrathin films grown on Ni (100), a system for which neither crystallization nor extended surface ordering has been established previously in the monolayer range. Using Scanning Tunneling Microscopy and Auger Electron Spectroscopy, we report on experiments showing MgO monolayer (ML) epitaxy on a ferromagnetic nickel surface, down to the limit of atomic thickness. Alternate steps of Mg ML deposition, O2 gas exposure, and ultrahigh vacuum thermal treatment enable the production of a textured film of ordered MgO nano-domains. This study could open interesting prospects for controlled epitaxy of ultrathin oxide films with a high magneto-resistance ratio on ferromagnetic substrates, enabling improvement in high-efficiency spintronics and magnetic tunnel junction devices.

  4. Acoustic analog of monolayer graphene and edge states

    International Nuclear Information System (INIS)

    Zhong, Wei; Zhang, Xiangdong

    2011-01-01

    Acoustic analog of monolayer graphene has been designed by using silicone rubber spheres of honeycomb lattices embedded in water. The dispersion of the structure has been studied theoretically using the rigorous multiple-scattering method. The energy spectra with the Dirac point have been verified and zigzag edge states have been found in ribbons of the structure, which are analogous to the electronic ones in graphene nanoribbons. The guided modes along the zigzag edge excited by a point source have been numerically demonstrated. The open cavity and 'Z' type edge waveguide with 60 o corners have also been realized by using such edge states. -- Highlights: → Acoustic analog of monolayer graphene has been designed. → The energy spectra with the Dirac point have been verified. → The zigzag edge states have been found in ribbons of the structure. → The guided modes excited by a point source have been demonstrated. → The open cavity and 'Z' type edge waveguide have been realized.

  5. Bidirectional gene sequences with similar homology to functional proteins of alkane degrading bacterium pseudomonas fredriksbergensis DNA

    International Nuclear Information System (INIS)

    Megeed, A.A.

    2011-01-01

    The potential for two overlapping fragments of DNA from a clone of newly isolated alkanes degrading bacterium Pseudomonas frederiksbergensis encoding sequences with similar homology to two parts of functional proteins is described. One strand contains a sequence with high homology to alkanes monooxygenase (alkB), a member of the alkanes hydroxylase family, and the other strand contains a sequence with some homology to alcohol dehydrogenase gene (alkJ). Overlapping of the genes on opposite strands has been reported in eukaryotic species, and is now reported in a bacterial species. The sequence comparisons and ORFS results revealed that the regulation and the genes organization involved in alkane oxidation represented in Pseudomonas frederiksberghensis varies among the different known alkane degrading bacteria. The alk gene cluster containing homologues to the known alkane monooxygenase (alkB), and rubredoxin (alkG) are oriented in the same direction, whereas alcohol dehydrogenase (alkJ) is oriented in the opposite direction. Such genomes encode messages on both strands of the DNA, or in an overlapping but different reading frames, of the same strand of DNA. The possibility of creating novel genes from pre-existing sequences, known as overprinting, which is a widespread phenomenon in small viruses. Here, the origin and evolution of the gene overlap to bacteriophages belonging to the family Microviridae have been investigated. Such a phenomenon is most widely described in extremely small genomes such as those of viruses or small plasmids, yet here is a unique phenomenon. (author)

  6. Analysis of polychlorinated n-alkanes in environmental samples.

    Science.gov (United States)

    Santos, F J; Parera, J; Galceran, M T

    2006-10-01

    Polychlorinated n-alkanes (PCAs), also known as chlorinated paraffins (CPs), are highly complex technical mixtures that contain a huge number of structural isomers, theoretically more than 10,000 diastereomers and enantiomers. As a consequence of their persistence, tendency to bioaccumulation, and widespread and unrestricted use, PCAs have been found in aquatic and terrestrial food webs, even in rural and remote areas. Recently, these compounds have been included in regulatory programs of several international organizations, including the US Environmental Protection Agency and the European Union. Consequently, there is a growing demand for reliable methods with which to analyze PCAs in environmental samples. Here, we review current trends and recent developments in the analysis of PCAs in environmental samples such as air, water, sediment, and biota. Practical aspects of sample preparation, chromatographic separation, and detection are covered, with special emphasis placed on analysis of PCAs using gas chromatography-mass spectrometry. The advantages and limitations of these techniques as well as recent improvements in quantification procedures are discussed.

  7. Parallel studies of His-DTrp-Ala-Trp-DPhe-Lys-NH2 and human pancreatic growth hormone-releasing factor-44-NH2 in rat primary pituitary cell monolayer culture.

    Science.gov (United States)

    Sartor, O; Bowers, C Y; Chang, D

    1985-03-01

    His-DTrp-Ala-Trp-DPhe-Lys-NH2 (GH-RP-6) is a synthetic hexapeptide that specifically releases GH both in vivo and in vitro in pituitary incubates. In this study, for the first time, GH-RP-6 was studied in primary pituitary cell monolayer culture. Parallel studies were performed with human pancreatic GH-releasing factor-44 (hpGRF-44). Culture conditions optimal for GH-RP-6 were not optimal for hpGRF-44. Both peptides released GH in a dose- and time-dependent manner. In this assay system, the ED50 for GH-RP-6 was 9 nM, and the ED50 for hp-GRF-44 was 1.6 nM. Calcium-blocking agents inhibited the GH responses of both peptides as well as basal GH release. Pretreatment with GH-RP-6 decreased the subsequent response to both GH-RP-6 and hpGRF-44. hpGRF-44 down regulated itself but not GH-RP-6. Rat sera potentiated the GH response of hpGRF-44 but not that of GH-RP-6. GH-RP-6 and hpGRF-44 GH responses were additive. These results suggest that GH-RP-6 and hpGRF-44 stimulate GH release via different somatotroph receptors.

  8. The detection and phylogenetic analysis of the alkane 1-monooxygenase gene of members of the genus Rhodococcus.

    Science.gov (United States)

    Táncsics, András; Benedek, Tibor; Szoboszlay, Sándor; Veres, Péter G; Farkas, Milán; Máthé, István; Márialigeti, Károly; Kukolya, József; Lányi, Szabolcs; Kriszt, Balázs

    2015-02-01

    Naturally occurring and anthropogenic petroleum hydrocarbons are potential carbon sources for many bacteria. The AlkB-related alkane hydroxylases, which are integral membrane non-heme iron enzymes, play a key role in the microbial degradation of many of these hydrocarbons. Several members of the genus Rhodococcus are well-known alkane degraders and are known to harbor multiple alkB genes encoding for different alkane 1-monooxygenases. In the present study, 48 Rhodococcus strains, representing 35 species of the genus, were investigated to find out whether there was a dominant type of alkB gene widespread among species of the genus that could be used as a phylogenetic marker. Phylogenetic analysis of rhodococcal alkB gene sequences indicated that a certain type of alkB gene was present in almost every member of the genus Rhodococcus. These alkB genes were common in a unique nucleotide sequence stretch absent from other types of rhodococcal alkB genes that encoded a conserved amino acid motif: WLG(I/V/L)D(G/D)GL. The sequence identity of the targeted alkB gene in Rhodococcus ranged from 78.5 to 99.2% and showed higher nucleotide sequence variation at the inter-species level compared to the 16S rRNA gene (93.9-99.8%). The results indicated that the alkB gene type investigated might be applicable for: (i) differentiating closely related Rhodococcus species, (ii) properly assigning environmental isolates to existing Rhodococcus species, and finally (iii) assessing whether a new Rhodococcus isolate represents a novel species of the genus. Copyright © 2014 Elsevier GmbH. All rights reserved.

  9. Electrical Contacts in Monolayer Arsenene Devices.

    Science.gov (United States)

    Wang, Yangyang; Ye, Meng; Weng, Mouyi; Li, Jingzhen; Zhang, Xiuying; Zhang, Han; Guo, Ying; Pan, Yuanyuan; Xiao, Lin; Liu, Junku; Pan, Feng; Lu, Jing

    2017-08-30

    Arsenene, arsenic analogue of graphene, as an emerging member of two-dimensional semiconductors (2DSCs), is quite promising in next-generation electronic and optoelectronic applications. The metal electrical contacts play a vital role in the charge transport and photoresponse processes of nanoscale 2DSC devices and even can mask the intrinsic properties of 2DSCs. Here, we present a first comprehensive study of the electrical contact properties of monolayer (ML) arsenene with different electrodes by using ab initio electronic calculations and quantum transport simulations. Schottky barrier is always formed with bulk metal contacts owing to the Fermi level pinning (pinning factor S = 0.33), with electron Schottky barrier height (SBH) of 0.12, 0.21, 0.25, 0.35, and 0.50 eV for Sc, Ti, Ag, Cu, and Au contacts and hole SBH of 0.75 and 0.78 eV for Pd and Pt contacts, respectively. However, by contact with 2D graphene, the Fermi level pinning effect can be reduced due to the suppression of metal-induced gap states. Remarkably, a barrier free hole injection is realized in ML arsenene device with graphene-Pt hybrid electrode, suggestive of a high device performance in such a ML arsenene device. Our study provides a theoretical foundation for the selection of favorable electrodes in future ML arsenene devices.

  10. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yongli [Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou 730000 (China)] [Institute of Tibetan and Plateau Research, Chinese Academy of Sciences, Beijing 100085 (China); Fang Xiaomin, E-mail: fangxm@itpcas.ac.cn [Institute of Tibetan and Plateau Research, Chinese Academy of Sciences, Beijing 100085 (China)] [Key Laboratory of Western Resources and Environment of Education Ministry, College at Earth and Environment Sciences, University of Lanzhou, Lanzhou 730000 (China); Zhang Tongwei [Key Laboratory of Western Resources and Environment of Education Ministry, College at Earth and Environment Sciences, University of Lanzhou, Lanzhou 730000 (China); Li Yuanmao; Wu Yingqin; He Daxiang; Wang Youxiao [Key Laboratory of Petroleum Resources Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou 730000 (China)

    2010-10-15

    Research highlights: {yields} This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. {yields} Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. {yields} These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. {yields} A close correspondence among the low ratio of n-C{sub 27}/n-C{sub 31}, the heavy {delta}{sup 13}C values of TOC and a strong even carbon-number predominance (low OEP{sub 16-20} values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C{sub 16}-n-C{sub 20} with maximum values at n-C{sub 18} and n-C{sub 27}-n-C{sub 31} as well as at n-C{sub 29}. The first mode shows a strong even C-number predominance (OEP{sub 16-20} 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP{sub 27-31} 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded

  11. Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin, NE Tibetan Plateau: Implications for climate change

    International Nuclear Information System (INIS)

    Wang Yongli; Fang Xiaomin; Zhang Tongwei; Li Yuanmao; Wu Yingqin; He Daxiang; Wang Youxiao

    2010-01-01

    Research highlights: → This study reports the first observation of predominant even carbon-numbered n-alkanes of sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. → Certain types of special autochthonous bacteria are a possible source for the special distribution of even carbon-numbered n-alkanes in lacustrine sediments. → These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change. → A close correspondence among the low ratio of n-C 27 /n-C 31 , the heavy δ 13 C values of TOC and a strong even carbon-number predominance (low OEP 16-20 values) from approximately 6.5 to 4.4 Ma and at approximately 8 Ma in the studied section suggests that n-alkanes with a high predominance of even carbon-numbers may be treated as geochemical proxies for arid climate. - Abstract: This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13-4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C 16 -n-C 20 with maximum values at n-C 18 and n-C 27 -n-C 31 as well as at n-C 29 . The first mode shows a strong even C-number predominance (OEP 16-20 0.34-0.66). In contrast, the second mode has a strong odd C-number predominance (OEP 27-31 1.20-2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic-anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change.

  12. Influence of calcium on ceramide-1-phosphate monolayers

    Directory of Open Access Journals (Sweden)

    Joana S. L. Oliveira

    2016-02-01

    Full Text Available Ceramide-1-phosphate (C1P plays an important role in several biological processes, being identified as a key regulator of many protein functions. For instance, it acts as a mediator of inflammatory responses. The mediation of the inflammation process happens due to the interaction of C1P with the C2 domain of cPLA2α, an effector protein that needs the presence of submicromolar concentrations of calcium ions. The aim of this study was to determine the phase behaviour and structural properties of C1P in the presence and absence of millimolar quantities of calcium in a well-defined pH environment. For that purpose, we used monomolecular films of C1P at the soft air/liquid interface with calcium ions in the subphase. The pH was varied to change the protonation degree of the C1P head group. We used surface pressure versus molecular area isotherms coupled with other monolayer techniques as Brewster angle microscopy (BAM, infrared reflection–absorption spectroscopy (IRRAS and grazing incidence X-ray diffraction (GIXD. The isotherms indicate that C1P monolayers are in a condensed state in the presence of calcium ions, regardless of the pH. At higher pH without calcium ions, the monolayer is in a liquid-expanded state due to repulsion between the negatively charged phosphate groups of the C1P molecules. When divalent calcium ions are added, they are able to bridge the highly charged phosphate groups, enhancing the regular arrangement of the head groups. Similar solidification of the monolayer structure can be seen in the presence of a 150 times larger concentration of monovalent sodium ions. Therefore, calcium ions have clearly a strong affinity for the phosphomonoester of C1P.

  13. Combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) studies of glucose oxidase (GOx) immobilised onto self-assembled monolayer on the gold film

    International Nuclear Information System (INIS)

    Losic, D.; Shapter, J.; Gooding, J.; Erokin, P.; Short, K.

    1999-01-01

    In fabrication of biosensors, self-assembled monolayers (SAM) are an attractive method of immobilising enzymes at electrode surface since it allows precise control over the amount and spatial distribution of the immobilized enzyme. The covalent attachment of glucose oxidase (GOx) to a carboxylic terminated SAM chemisorbed onto gold films was achieved via carbodiimide activation of the carboxylic acids to a reactive intermediate susceptible to nucleophilic attack by amines on free lysine chains of the enzyme. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) measurements were used for characterisation of GOx modified gold surfaces. Tapping mode AFM studies have revealed that GOx molecules form slightly disordered arrays of pentagonal or hexagonal clusters. Observed features of immobilised GOx are distributed as a submonolayer on the SAM surface which has allowed visualisation of native and unfolded enzyme structure. The presence of the SAM and enzyme on the gold surface was detected by XPS spectroscopy. Spectra show typical peaks for the C 1s, O 1s and N 1s regions. A kinetic study of the adsorption of GOx onto activated SAM using in-situ QCM allowed determination the amount of immobilised GOx on the layer and consequently the optimal immobilisation conditions. Performance parameters of the biosensor such as sensitivity to glucose concentration as a function of enzyme loading were evaluated amperometrically using the redox mediator p-benzoquinone

  14. Analysis of the induction of the myelin basic protein binding to the plasma membrane phospholipid monolayer

    International Nuclear Information System (INIS)

    Zhang Lei; Hao Changchun; Feng Ying; Gao Feng; Lu Xiaolong; Li Junhua; Sun Runguang

    2016-01-01

    Myelin basic protein (MBP) is an essential structure involved in the generation of central nervous system (CNS) myelin. Myelin shape has been described as liquid crystal structure of biological membrane. The interactions of MBP with monolayers of different lipid compositions are responsible for the multi-lamellar structure and stability of myelin. In this paper, we have designed MBP-incorporated model lipid monolayers and studied the phase behavior of MBP adsorbed on the plasma membrane at the air/water interface by thermodynamic method and atomic force microscopy (AFM). By analyzing the pressure–area ( π – A ) and pressure–time ( π – T ) isotherms, univariate linear regression equation was obtained. In addition, the elastic modulus, surface pressure increase, maximal insertion pressure, and synergy factor of monolayers were detected. These parameters can be used to modulate the monolayers binding of protein, and the results show that MBP has the strongest affinity for 1,2-dipalmitoyl-sn-glycero-3- phosphoserine (DPPS) monolayer, followed by DPPC/DPPS mixed and 1,2-dipalmitoyl-sn-glycero-3-phospho-choline (DPPC) monolayers via electrostatic and hydrophobic interactions. AFM images of DPPS and DPPC/DPPS mixed monolayers in the presence of MBP (5 nM) show a phase separation texture at the surface pressure of 20 mN/m and the incorporation of MBP put into the DPPC monolayers has exerted a significant effect on the domain structure. MBP is not an integral membrane protein but, due to its positive charge, interacts with the lipid head groups and stabilizes the membranes. The interaction between MBP and phospholipid membrane to determine the nervous system of the disease has a good biophysical significance and medical value. (special topic)

  15. Thermal ripples in model molybdenum disulfide monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Remsing, Richard C.; Klein, Michael L. [Institute for Computational Molecular Science, Center for the Computational, Design of Functional Layered Materials, and Department of Chemistry, Temple University, 1925 N. 12th St., 19122, Philadelphia, PA (United States); Waghmare, Umesh V. [Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, 560 064, Jakkur, Bangalore (India)

    2017-01-15

    Molybdenum disulfide (MoS{sub 2}) monolayers have the potential to revolutionize nanotechnology. To reach this potential, it will be necessary to understand the behavior of this two-dimensional (2D) material on large length scales and under thermal conditions. Herein, we use molecular dynamics (MD) simulations to investigate the nature of the rippling induced by thermal fluctuations in monolayers of the 2H and 1T phases of MoS{sub 2}. The 1T phase is found to be more rigid than the 2H phase. Both monolayer phases are predicted to follow long wavelength scaling behavior typical of systems with anharmonic coupling between vibrational modes as predicted by classic theories of membrane-like systems. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Platinum Monolayer Electrocatalysts for Anodic Oxidation of Alcohols.

    Science.gov (United States)

    Li, Meng; Liu, Ping; Adzic, Radoslav R

    2012-12-06

    The slow, incomplete oxidation of methanol and ethanol on platinum-based anodes as well as the high price and limited reserves of Pt has hampered the practical application of direct alcohol fuel cells. We describe the electrocatalysts consisting of one Pt monolayer (one atom thick layer) placed on extended or nanoparticle surfaces having the activity and selectivity for the oxidation of alcohol molecules that can be controlled with platinum-support interaction. The suitably expanded Pt monolayer (i.e., Pt/Au(111)) exhibits a factor of 7 activity increase in catalyzing methanol electrooxidation relative to Pt(111). Sizable enhancement is also observed for ethanol electrooxidation. Furthermore, a correlation between substrate-induced lateral strain in a Pt monolayer and its activity/selectivity is established and rationalized by experimental and theoretical studies. The knowledge we gained with single-crystal model catalysts was successfully applied in designing real nanocatalysts. These findings for alcohols are likely to be applicable for the oxidation of other classes of organic molecules.

  17. Immobilization of Colloidal Monolayers at Fluid–Fluid Interfaces

    Directory of Open Access Journals (Sweden)

    Peter T. Bähler

    2016-07-01

    Full Text Available Monolayers of colloidal particles trapped at an interface between two immiscible fluids play a pivotal role in many applications and act as essential models in fundamental studies. One of the main advantages of these systems is that non-close packed monolayers with tunable inter-particle spacing can be formed, as required, for instance, in surface patterning and sensing applications. At the same time, the immobilization of particles locked into desired structures to be transferred to solid substrates remains challenging. Here, we describe three different strategies to immobilize monolayers of polystyrene microparticles at water–decane interfaces. The first route is based on the leaking of polystyrene oligomers from the particles themselves, which leads to the formation of a rigid interfacial film. The other two rely on in situ interfacial polymerization routes that embed the particles into a polymer membrane. By tracking the motion of the colloids at the interface, we can follow in real-time the formation of the polymer membranes and we interestingly find that the onset of the polymerization reaction is accompanied by an increase in particle mobility determined by Marangoni flows at the interface. These results pave the way for future developments in the realization of thin tailored composite polymer-particle membranes.

  18. A trough for improved SFG spectroscopy of lipid monolayers

    Science.gov (United States)

    Franz, Johannes; van Zadel, Marc-Jan; Weidner, Tobias

    2017-05-01

    Lipid monolayers are indispensable model systems for biological membranes. The main advantage over bilayer model systems is that the surface pressure within the layer can be directly and reliably controlled. The sensitive interplay between surface pressure and temperature determines the molecular order within a model membrane and consequently determines the membrane phase behavior. The lipid phase is of crucial importance for a range of membrane functions such as protein interactions and membrane permeability. A very reliable method to probe the structure of lipid monolayers is sum frequency generation (SFG) vibrational spectroscopy. Not only is SFG extremely surface sensitive but it can also directly access critical parameters such as lipid order and orientation, and it can provide valuable information about protein interactions along with interfacial hydration. However, recent studies have shown that temperature gradients caused by high power laser beams perturb the lipid layers and potentially obscure the spectroscopic results. Here we demonstrate how the local heating problem can be effectively reduced by spatially distributing the laser pulses on the sample surface using a translating Langmuir trough for SFG experiments at lipid monolayers. The efficiency of the trough is illustrated by the detection of enhanced molecular order due to reduced heat load.

  19. Strain engineering on transmission carriers of monolayer phosphorene.

    Science.gov (United States)

    Zhang, Wei; Li, Feng; Hu, Junsong; Zhang, Ping; Yin, Jiuren; Tang, Xianqiong; Jiang, Yong; Wu, Bozhao; Ding, Yanhuai

    2017-11-22

    The effects of uniaxial strain on the structure, band gap and transmission carriers of monolayer phosphorene were investigated by first-principles calculations. The strain induced semiconductor-metal as well as direct-indirect transitions were studied in monolayer phosphorene. The position of CBM which belonged to indirect gap shifts along the direction of the applied strain. We have concluded the change rules of the carrier effective mass when plane strains are applied. In band structure, the sudden decrease of band gap or the new formation of CBM (VBM) causes the unexpected change in carrier effective mass. The effects of zigzag and armchair strain on the effective electron mass in phosphorene are different. The strain along zigzag direction has effects on the electrons effective mass along both zigzag and armchair direction. By contrast, armchair-direction strain seems to affect only on the free electron mass along zigzag direction. For the holes, the effective masses along zigzag direction are largely affected by plane strains while the effective mass along armchair direction exhibits independence in strain processing. The carrier density of monolayer phosphorene at 300 K is calculated about [Formula: see text] cm -2 , which is greatly influenced by the temperature and strain. Strain engineering is an efficient method to improve the carrier density in phosphorene.

  20. Specific Ion Effects in Cholesterol Monolayers

    Directory of Open Access Journals (Sweden)

    Teresa Del Castillo-Santaella

    2016-05-01

    Full Text Available The interaction of ions with interfaces and, in particular, the high specificity of these interactions to the particular ions considered, are central questions in the field of surface forces. Here we study the effect of different salts (NaI, NaCl, CaCl2 and MgCl2 on monolayers made of cholesterol molecules, both experimentally (surface area vs. lateral pressure isotherms measured by a Langmuir Film Balance and theoretically (molecular dynamics (MD all-atomic simulations. We found that surface isotherms depend, both quantitatively and qualitatively, on the nature of the ions by altering the shape and features of the isotherm. In line with the experiments, MD simulations show clear evidences of specific ionic effects and also provide molecular level details on ion specific interactions with cholesterol. More importantly, MD simulations show that the interaction of a particular ion with the surface depends strongly on its counterion, a feature ignored so far in most theories of specific ionic effects in surface forces.

  1. Monolayer-by-monolayer growth of platinum films on complex carbon fiber paper structure

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Liuqing; Zhang, Yunxia [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Liu, Shengzhong, E-mail: szliu@dicp.ac.cn [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Dalian National Laboratory for Clean Energy, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

    2017-06-15

    Graphical abstract: A controlled monolayer-by-monolayer deposition process has been developed to fabricate Pt coating on carbon fiber paper with complex network structures using a dual buffer strategy. This development may pave a way to fabricate superior Pt catalysts with the minimal Pt usage. In fact, the present Pt group metal loading is 25 times lower than the U.S. DOE 2017 target value. - Highlights: • Developed a controlled monolayer-by-monolayer Pt deposition using a dual buffer strategy. • The present Pt group metal loading is 25 times lower than the U.S. DOE 2017 target value. • This development may pave a way to fabricate superior Pt catalysts with the minimal Pt usage. - Abstract: A controlled monolayer-by-monolayer deposition process has been developed to fabricate Pt coating on carbon fiber paper with complex network structures using a dual buffer (Au/Ni) strategy. The X-ray diffraction, electrochemical quartz crystal microbalance, current density analyses, and X-ray photoelectron spectroscopy results conclude that the monolayer deposition process accomplishes full coverage on the substrate and that the thickness of the deposition layer can be controlled on a single atom scale. This development may pave a way to fabricate superior Pt catalysts with the minimal Pt usage. In fact, the present Pt group metal loading is 25 times lower than the U.S. DOE 2017 target value.

  2. Connexin 26-mediated gap junctional intercellular communication suppresses paracellular permeability of human intestinal epithelial cell monolayers

    International Nuclear Information System (INIS)

    Morita, Hidekazu; Katsuno, Tatsuro; Hoshimoto, Aihiro; Hirano, Noriaki; Saito, Yasushi; Suzuki, Yasuo

    2004-01-01

    In some cell types, gap junctional intercellular communication (GJIC) is associated with tight junctions. The present study was performed to determine the roles of GJIC in regulation of the barrier function of tight junctions. Caco-2 human colonic cells were used as a monolayer model, and barrier function was monitored by measuring mannitol permeability and transepithelial electrical resistance (TER). The monolayers were chemically disrupted by treatment with oleic acid and taurocholic acid. Western blotting analyses were performed to evaluate the protein levels of connexins, which are components of gap junctional intercellular channels. Cx26 expression was detected in preconfluent Caco-2 cells, and its level increased gradually after the monolayer reached confluency. These results prompted us to examine whether overexpression of Cx26 affects barrier function. Monolayers of Caco-2 cells stably expressing Cx26 showed significantly lower mannitol permeability and higher TER than mock transfectants when the monolayers were chemically disrupted. The levels of claudin-4, an important component of tight junctions, were significantly increased in the stable Cx26 transfectant. These results suggest that Cx26-mediated GJIC may play a crucial role in enhancing the barrier function of Caco-2 cell monolayers

  3. NO2 decreases paracellular resistance to ion and solute flow in alveolar epithelial monolayers

    International Nuclear Information System (INIS)

    Cheek, J.M.; Kim, K.J.; Crandall, E.D.

    1990-01-01

    Primary cultured monolayers of rat alveolar epithelial cells grown on tissue culture-treated Nuclepore filters were exposed to 2.5 ppm nitrogen dioxide NO 2 for 2-20 min. Changes in monolayer bioelectric properties and solute permeabilities were subsequently measured. Exposure to NO 2 produced a dose-dependent decrease in monolayer transepithelial electrical resistance (Rt), whereas monolayer short-circuit current was unaffected. Post-exposure monolayer permeability to 14 C-sucrose (which primarily crosses alveolar epithelium via the paracellular pathway) increased markedly. That for 3 H-glycerol (which permeates through both paracellular and transcellular pathways) increased to a lesser extent. Partial recovery of Rt and solute permeabilities was noted by 48-h post-exposure. The time courses of the decrease in Rt and increase in solute permeabilities were similar. These results suggest that NO 2 primarily impairs passive alveolar epithelial barrier functions in vitro, probably by altering intercellular junctions, and does not appear to directly affect cell membrane active ion transport processes. When correlated with results obtained from experimental approaches, studies of in vitro alveolar epithelial monolayers may facilitate investigations of dosimetry, sites, and mechanisms of oxidant injury in the lung

  4. Conformations and orientations of a signal peptide interacting with phospholipid monolayers

    International Nuclear Information System (INIS)

    Cornell, D.G.; Dluhy, R.A.; Briggs, M.S.; McKnight, C.J.; Gierasch, L.M.

    1989-01-01

    The interaction of a chemically synthesized 25-residue signal peptide of LamB protein from Escherichia coli with phospholipids has been studied with a film balance technique. The conformation, orientation, and concentration of the peptides in lipid monolayers have been determined from polarized infrared spectroscopy, ultraviolet spectroscopy, and assay of 14 C-labeled peptide in transferred films. When the LamB signal peptide in injected into the subphase under a phosphatidylethanolamine-phosphatidylglycerol monolayer at low initial pressure, insertion of a portion of the peptide into the lipid film is evidenced by a rapid rise in film pressure. Spectroscopic results obtained on films transferred to quartz plates and Ge crystals show that the peptide is a mixture of α-helix and β-conformation where the long axis of the α-helix penetrates the monolayer plane and the β-structure which is coplanar with the film. By contrast, when peptide is injected under lipid at high initial pressure, no pressure rise is observed, and the spectroscopic results show the presence of only β-structure which is coplanar with the monolayer. The spectroscopic and radioassay results are all consistent with the picture of a peptide anchored to the monolayer through electrostatic binding with a helical portion inserted into the lipid region of the monolayer and a β-structure portion resident in the aqueous phase. The negative charges on the lipid molecules are roughly neutralized by the positive charges of the peptide

  5. Identification and use of an alkane transporter plug-in for application in biocatalysis and whole-cell biosensing of alkanes

    DEFF Research Database (Denmark)

    Grant, Chris; Deszcz, Dawid; Wei, Yu-Chia

    2014-01-01

    Effective application of whole-cell devices in synthetic biology and biocatalysis will always require consideration of the uptake of molecules of interest into the cell. Here we demonstrate that the AlkL protein from Pseudomonas putida GPo1 is an alkane import protein capable of industrially rele...

  6. Sub-THz Characterisation of Monolayer Graphene

    Directory of Open Access Journals (Sweden)

    Ehsan Dadrasnia

    2014-01-01

    Full Text Available We explore the optical and electrical characteristics of monolayer graphene by using pulsed optoelectronic terahertz time-domain spectroscopy in the frequency range of 325–500 GHz based on fast direct measurements of phase and amplitude. We also show that these parameters can, however, be measured with higher resolution using a free space continuous wave measurement technique associated with a vector network analyzer that offers a good dynamic range. All the scattering parameters (both magnitude and phase are measured simultaneously. The Nicholson-Ross-Weir method is implemented to extract the monolayer graphene parameters at the aforementioned frequency range.

  7. Low temperature photoresponse of monolayer tungsten disulphide

    Directory of Open Access Journals (Sweden)

    Bingchen Cao

    2014-11-01

    Full Text Available High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup, while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

  8. Thermodynamic properties of (an ester+an alkane). XVII. Experimental HmE and VmE values for (an alkyl propanoate+an alkane) at 318.15K

    International Nuclear Information System (INIS)

    Ortega, J.; Espiau, F.; Toledo, F.J.; Dieppa, R.

    2005-01-01

    In this article, we record the experimental values of H m E and V m E , obtained at a temperature of T=318.15K and atmospheric pressure for a set of 30 binary mixtures comprised of five alkyl propanoates (methyl to pentyl) with six odd alkanes (heptane to heptadecane). The net values obtained for these properties are the result of different effects of the selected compounds on the mixing process. These effects and the variation with temperature are studied. The H m E are positive in all cases and increase with the saturated hydrocarbon chain and diminish with the alkanolic portion of the ester. The variation in V m E is similar to that occurring in the H m E . For the data correlation, a new form of polynomial equation is used in which the variable is the so-called active fraction which, in turn, is a function of the concentration of the mixture, giving acceptable estimations for simultaneous correlations between the values of Gibbs function obtained in the isobaric (liquid+vapour) equilibria and the enthalpies of the mixture, for some of the mixtures studied. The results are explained with the molecular model proposed for (ester+alkane) mixtures. Finally, the application of two versions of the UNIFAC groups contribution method to estimate enthalpies of the mixtures does not give satisfactory results, although the modified UNIFAC gives somewhat better results

  9. Preparation of porous monolayer film by immersing the stearic acid Langmuir-Blodgett monolayer on mica in salt solution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, S. [Institute of Near-Field Optics and Nano Technology, School of Physics and Optoelectronic Technology, Dalian University of Technology, Street No. 2 Linggong Road, Dalian 116024 (China); Li, Y.L.; Zhao, H.L.; Liang, H. [Institute of Photo-Biophysics, School of Physics and Electronic, Henan University, Jinming, Kaifeng 475004, Henan (China); Liu, B., E-mail: boliu@henu.edu.cn [Institute of Photo-Biophysics, School of Physics and Electronic, Henan University, Jinming, Kaifeng 475004, Henan (China); Pan, S., E-mail: span@dlut.edu.cn [Institute of Near-Field Optics and Nano Technology, School of Physics and Optoelectronic Technology, Dalian University of Technology, Street No. 2 Linggong Road, Dalian 116024 (China)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Porous film has been prepared by immersing the stearic acid Langmuir-Blodgett monolayer on mica in salt solution. Black-Right-Pointing-Pointer The mechanism relies on the electrostatic screening effect of the cations in salt solution. Black-Right-Pointing-Pointer The factors influencing the size and area of the pores were investigated. - Abstract: Porous materials have drawn attention from scientists in many fields such as life sciences, catalysis and photonics since they can be used to induce some materials growth as expected. Especially, porous Langmuir-Blodgett (LB) film is an ideal material with controlled thickness and flat surface. In this paper, stearic acid (SA), which has been extensively explored in LB film technique, is chosen as the template material with known parameters to prepare the LB film, and then the porous SA monolayer film is obtained by means of etching in salt solution. The main etching mechanism is suggested that the cations in the solution block the electrostatic interaction between the polar carboxyl group of SA and the electronegative mica surface. The influencing factors (such as concentration of salt solution, valence of cation and surface pressure) of the porous SA film are systematically studied in this work. The novel method proposed in this paper makes it convenient to prepare porous monolayer film for designed material growth or cell culture.

  10. Thermal analysis as an aid to forensics: Alkane melting and oxidative stability of wool

    International Nuclear Information System (INIS)

    Alan Riga, D.

    1998-01-01

    Interdisciplinary methods and thermal analytical techniques in particular are effective tools in aiding the identification and characterization of materials in question involved in civil or criminal law. Forensic material science uses systematic knowledge of the physical or material world gained through analysis, observation and experimentation. Thermal analytical data can be used to aid the legal system in interpreting technical variations in quite often a complex system.Calorimetry and thermal microscopic methods helped define a commercial product composed of alkanes that was involved in a major law suit. The solid-state structures of a number of normal alkanes have unique crystal structures. These alkanes melt and freeze below room temperature to more than 60C below zero. Mixtures of specific alkanes have attributes of pure chemicals. The X-ray diffraction structure of a mixture of alkanes is the same as a pure alkane, but the melting and freezing temperature are significantly lower than predicted. The jury ruled that the product containing n-alkanes had the appropriate melting characteristics. The thermal-physical properties made a commercial fluid truly unique and there was no advertising infringement according to the law and the jury trialA combination of thermogravimetry, differential thermal analysis, infrared spectroscopy and macrophotography were used to conduct an extensive modeling and analysis of physical evidence obtained in a mobile home fire and explosion. A person's death was allegedly linked to the misuse of a kerosene space heater. The thermal analytical techniques showed that external heating was the cause of the space heater's deformation, not a firing of the heater with gasoline and kerosene. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  11. Thermal analysis as an aid to forensics: Alkane melting and oxidative stability of wool

    Energy Technology Data Exchange (ETDEWEB)

    Alan Riga, D. [Professor of Chemistry, Cleveland State University and TechCon Inc., 6325 Aldenham Dr., Cleveland, OH 44143-3331 (United States)

    1998-12-21

    Interdisciplinary methods and thermal analytical techniques in particular are effective tools in aiding the identification and characterization of materials in question involved in civil or criminal law. Forensic material science uses systematic knowledge of the physical or material world gained through analysis, observation and experimentation. Thermal analytical data can be used to aid the legal system in interpreting technical variations in quite often a complex system.Calorimetry and thermal microscopic methods helped define a commercial product composed of alkanes that was involved in a major law suit. The solid-state structures of a number of normal alkanes have unique crystal structures. These alkanes melt and freeze below room temperature to more than 60C below zero. Mixtures of specific alkanes have attributes of pure chemicals. The X-ray diffraction structure of a mixture of alkanes is the same as a pure alkane, but the melting and freezing temperature are significantly lower than predicted. The jury ruled that the product containing n-alkanes had the appropriate melting characteristics. The thermal-physical properties made a commercial fluid truly unique and there was no advertising infringement according to the law and the jury trialA combination of thermogravimetry, differential thermal analysis, infrared spectroscopy and macrophotography were used to conduct an extensive modeling and analysis of physical evidence obtained in a mobile home fire and explosion. A person's death was allegedly linked to the misuse of a kerosene space heater. The thermal analytical techniques showed that external heating was the cause of the space heater's deformation, not a firing of the heater with gasoline and kerosene. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

  12. Alkane Hydroxylase Gene (alkB Phylotype Composition and Diversity in Northern Gulf of Mexico Bacterioplankton

    Directory of Open Access Journals (Sweden)

    Conor Blake Smith

    2013-12-01

    Full Text Available Natural and anthropogenic activities introduce alkanes into marine systems where they are degraded by alkane hydroxylases expressed by phylogenetically diverse bacteria. Partial sequences for alkB, one of the structural genes of alkane hydroxylase, have been used to assess the composition of alkane-degrading communities, and to determine their responses to hydrocarbon inputs. We present here the first spatially extensive analysis of alkB in bacterioplankton of the northern Gulf of Mexico (nGoM, a region that experiences numerous hydrocarbon inputs. We have analyzed 401 partial alkB gene sequences amplified from genomic extracts collected during March 2010 from 17 water column samples that included surface waters and bathypelagic depths. Previous analyses of 16S rRNA gene sequences for these and related samples have shown that nGoM bacterial community composition and structure stratify strongly with depth, with distinctly different communities above and below 100 m. Although we hypothesized that alkB gene sequences would exhibit a similar pattern, PCA analyses of operational protein units (OPU indicated that community composition did not vary consistently with depth or other major physical-chemical variables. We observed 22 distinct OPUs, one of which was ubiquitous and accounted for 57% of all sequences. This OPU clustered with alkB sequences from known hydrocarbon oxidizers (e.g., Alcanivorax and Marinobacter. Some OPUs could not be associated with known alkane degraders, however, and perhaps represent novel hydrocarbon-oxidizing populations or genes. These results indicate that the capacity for alkane hydrolysis occurs widely in the nGoM, but that alkane degrader diversity varies substantially among sites and responds differently than bulk communities to physical-chemical variables.

  13. Some aspects of electron dynamics in solid alkanes

    International Nuclear Information System (INIS)

    Cheng, I.I.; Funabashi, K.

    1975-01-01

    The excess electron mobility in 3-methylpentane (3MP) is in the range of 0.02-0.1 cm 2 /v.s. for 4.2-85 0 K. The mobility is nearly independent of temperature below 35 0 K, while the activation energy is about 0.01 eV for 35 0 K-85 0 K. The magnitude of mobility and its temperature dependence are consistent with the hopping and tunneling motion of electron between trapped (or localized) states. The decay kinetics of the absorption spectrum of trapped electrons in 3MP also suggest the presence of many trapping sites, and a small mean free path of retrapping for a quasi-free electron. It is conjectured that the electron-transport in 3MP glass is the phonon-assisted hopping or tunneling and the mean free path (or the mobility) at the quasi-free state is not as large as 100 A (or 150 cm 2 /v.s.). The mean free path of scattering for an excess electron at the quasi-free level in various alkane glasses can be found approximately from measurement of attenuation constants for electron beams (Chang and Berry). The relationship of these attenuation constants with V 0 (quasi-free state) will be discussed. The effect of electron-phonon coupling on the effective mass of excess electrons will also be discussed in terms of a simple model. The effective mass is a sensitive function of the ratio of the relaxation energy to the phonon energy

  14. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  15. Extraction of pentylbenzene from high molar mass alkanes (C{sub 14} and C{sub 17}) by N-methyl-2-pyrrolidone

    Energy Technology Data Exchange (ETDEWEB)

    Fandary, Mohamed S. [Chemical Engineering Department, College of Technological Studies, P.O. Box 3242, Salmyiah 22033 (Kuwait)]. E-mail: mfandary@yahoo.com; Al-Jimaz, Adel S. [Chemical Engineering Department, College of Technological Studies, P.O. Box 3242, Salmyiah 22033 (Kuwait); Al-Kandary, Jasem A. [Chemical Engineering Department, College of Technological Studies, P.O. Box 3242, Salmyiah 22033 (Kuwait); Fahim, Mohamed A. [Chemical Engineering Department, University of Kuwait, P.O. Box 5969, Safat 13060 (Kuwait)

    2006-04-15

    Equilibrium tie line data have been determined for the two ternary liquid systems: {l_brace}tetradecane, or heptadecane + pentylbenzene + N-methyl-2-pyrrolidone (NMP){r_brace} over a temperature range of (298 to 328) K. The two systems studied exhibit type I liquid + liquid phase diagram. The effect of temperature and n-alkane chain length upon solubility, selectivity, and distribution coefficients were investigated experimentally.

  16. Onset wear in self-assembled monolayers

    International Nuclear Information System (INIS)

    D'Acunto, Mario

    2006-01-01

    Self-assembled monolayers (SAMs) are very useful for the systematic modification of the physical, chemical and structural properties of a surface by varying the chain length, tail group and composition. Many of these properties can be studied making use of atomic force microscopy (AFM), and the interaction between the AFM probe tip and the SAMs can also be considered an excellent reference to study the fundamental properties of dissipation phenomena and onset wear for viscoelastic materials on the nanoscale. We have performed a numerical study showing that the fundamental mechanism for the onset wear is a process of nucleation of domains starting from initial defects. An SAM surface repeatedly sheared by an AFM probe tip with enough applied loads shows the formation of progressive damages nucleating in domains. The AFM induced surface damages involve primarily the formation of radicals from the carbon chain backbones, but the deformations of the chains resulting in changes of period lattice also have to be taken into consideration. The nucleation of the wear domains generally starts at the initial surface defects where the energy cohesion between chains is lower. Moreover, the presence of surface defects is consistent with the changes in lateral force increasing the probability of the activation for the removal of carbon debris from the chain backbone. The quantification of the progressive worn area is performed making use of the Kolmogorov-Johnson-Mehl-Avrami (KJMA) theory for phase transition kinetic processes. The advantage of knowing the general conditions for onset wear on the SAM surfaces can help in studying the fundamental mechanisms for the tribological properties of viscoelastic materials, in solid lubrication applications and biopolymer mechanics

  17. Imidazolide monolayers for versatile reactive microcontact printing

    NARCIS (Netherlands)

    Hsu, S.H.; Reinhoudt, David; Huskens, Jurriaan; Velders, Aldrik

    2008-01-01

    Imidazolide monolayers prepared from the reaction of amino SAMs with N,N-carbonyldiimidazole (CDI) are used as a versatile platform for surface patterning with amino-, carboxyl- and alcohol-containing compounds through reactive microcontact printing (µCP). To demonstrate the surface reactivity of

  18. Nanotubes based on monolayer blue phosphorus

    KAUST Repository

    Montes Muñoz, Enrique

    2016-07-08

    We demonstrate structural stability of monolayer zigzag and armchair blue phosphorus nanotubes by means of molecular dynamics simulations. The vibrational spectrum and electronic band structure are determined and analyzed as functions of the tube diameter and axial strain. The nanotubes are found to be semiconductors with a sensitive indirect band gap that allows flexible tuning.

  19. Integrated circuits based on conjugated polymer monolayer.

    Science.gov (United States)

    Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo; Carpenter, Joshua H; Yan, Hongping; Ade, Harald; Yan, He; Müllen, Klaus; Blom, Paul W M; Pisula, Wojciech; de Leeuw, Dago M; Asadi, Kamal

    2018-01-31

    It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2  V -1  s -1 . The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.

  20. Shadow mask evaporation through monolayer modified nanostencils

    NARCIS (Netherlands)

    Kolbel, M.; Tjerkstra, R.W.; Brugger, J.P.; van Rijn, C.J.M.; Nijdam, W.; Huskens, Jurriaan; Reinhoudt, David

    2002-01-01

    Gradual clogging of the apertures of nanostencils used as miniature shadow masks in metal evaporations can be reduced by coating the stencil with self-assembled monolayers (SAM). This is quantified by the dimensions (height and volume) of gold features obtained by nanostencil evaporation as measured