WorldWideScience

Sample records for short polymer chain

  1. Folding of polymer chains with short-range binormal interactions

    International Nuclear Information System (INIS)

    Craig, A; Terentjev, E M

    2006-01-01

    We study the structure of chains which have anisotropic short-range contact interactions that depend on the alignment of the binormal vectors of chain segments. This represents a crude model of hydrogen bonding or 'stacking' interactions out of the plane of curvature. The polymers are treated as ribbon-like semi-flexible chains, where the plane of the ribbon is determined by the local binormal. We show that with dipole-dipole interactions between the binormals of contacting chain segments, mean-field theory predicts a first-order transition to a binormally aligned state. We describe the onset of this transition as a function of the temperature-dependent parameters that govern the chain stiffness and the strength of the binormal interaction, as well as the binormal alignment's coupling to chain collapse. We also examine a metastable state governing the folding kinetics. Finally, we discuss the possible mesoscopic structure of the aligned phase, and application of our model to secondary structure motifs like β-sheets and α-helices, as well as composite structures like β-(amyloid) fibrils

  2. Effect of short-chain branching on interfacial polymer structure and dynamics under shear flow.

    Science.gov (United States)

    Jeong, Sohdam; Kim, Jun Mo; Cho, Soowon; Baig, Chunggi

    2017-11-22

    We present a detailed analysis on the effect of short-chain branches on the structure and dynamics of interfacial chains using atomistic nonequilibrium molecular dynamics simulations of confined polyethylene melts in a wide range of shear rates. The intrinsically fast random motions of the short branches constantly disturb the overall chain conformation, leading to a more compact and less deformed chain structure of the short-chain branched (SCB) polymer against the imposed flow field in comparison with the corresponding linear polymer. Moreover, such highly mobile short branches along the backbone of the SCB polymer lead to relatively weaker out-of-plane wagging dynamics of interfacial chains, with highly curvy backbone structures in the intermediate flow regime. In conjunction with the contribution of short branches (as opposed to that of the backbone) to the total interfacial friction between the chains and the wall, the SCB polymer shows a nearly constant behavior in the degree of slip (d s ) with respect to shear rate in the weak-to-intermediate flow regimes. On the contrary, in the strong flow regime where irregular chain rotation and tumbling dynamics occur via intensive dynamical collisions between interfacial chains and the wall, an enhancement effect on the chain detachment from the wall, caused by short branches, leads to a steeper increase in d s for the SCB polymer than for the linear polymer. Remarkably, the SCB chains at the interface exhibit two distinct types of rolling mechanisms along the backbone, with a half-dumbbell mesoscopic structure at strong flow fields, in addition to the typical hairpin-like tumbling behavior displayed by the linear chains.

  3. Crystallization in melts of short, semiflexible hard polymer chains: An interplay of entropies and dimensions

    Science.gov (United States)

    Shakirov, T.; Paul, W.

    2018-04-01

    What is the thermodynamic driving force for the crystallization of melts of semiflexible polymers? We try to answer this question by employing stochastic approximation Monte Carlo simulations to obtain the complete thermodynamic equilibrium information for a melt of short, semiflexible polymer chains with purely repulsive nonbonded interactions. The thermodynamics is obtained based on the density of states of our coarse-grained model, which varies by up to 5600 orders of magnitude. We show that our polymer melt undergoes a first-order crystallization transition upon increasing the chain stiffness at fixed density. This crystallization can be understood by the interplay of the maximization of different entropy contributions in different spatial dimensions. At sufficient stiffness and density, the three-dimensional orientational interactions drive the orientational ordering transition, which is accompanied by a two-dimensional translational ordering transition in the plane perpendicular to the chains resulting in a hexagonal crystal structure. While the three-dimensional ordering can be understood in terms of Onsager theory, the two-dimensional transition can be understood in terms of the liquid-hexatic transition of hard disks. Due to the domination of lateral two-dimensional translational entropy over the one-dimensional translational entropy connected with columnar displacements, the chains form a lamellar phase. Based on this physical understanding, orientational ordering and translational ordering should be separable for polymer melts. A phenomenological theory based on this understanding predicts a qualitative phase diagram as a function of volume fraction and stiffness in good agreement with results from the literature.

  4. Influence of the ordered structure of short-chain polymer molecule all-trans-β-carotene on Raman scattering cross section in liquid

    International Nuclear Information System (INIS)

    Qu Guan-Nan; Li Zuo-Wei; Sun Cheng-Lin; Ou Yang Shun-Li; Wang Wei-Wei; Men Zhi-Wei

    2011-01-01

    We measured the resonant Raman spectra of all-trans-β-carotene in solvents with different densities and concentrations at different temperatures. The results demonstrated that the Raman scattering cross section (RSCS) of short-chain polymer all-trans-β-carotene is extremely high in liquid. Resonance and strong coherent weakly damped CC bond vibrating properties play important roles under these conditions. Coherent weakly damped CC bond vibration strength is associated with molecular ordered structure. All-trans-β-carotene has highly ordered structure and strong coherent weakly damped CC bond vibrating properties, which lead to large RSCS in the solvent with large density and low concentration at low temperature. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  5. Topology of polymer chains under nanoscale confinement.

    Science.gov (United States)

    Satarifard, Vahid; Heidari, Maziar; Mashaghi, Samaneh; Tans, Sander J; Ejtehadi, Mohammad Reza; Mashaghi, Alireza

    2017-08-24

    Spatial confinement limits the conformational space accessible to biomolecules but the implications for bimolecular topology are not yet known. Folded linear biopolymers can be seen as molecular circuits formed by intramolecular contacts. The pairwise arrangement of intra-chain contacts can be categorized as parallel, series or cross, and has been identified as a topological property. Using molecular dynamics simulations, we determine the contact order distributions and topological circuits of short semi-flexible linear and ring polymer chains with a persistence length of l p under a spherical confinement of radius R c . At low values of l p /R c , the entropy of the linear chain leads to the formation of independent contacts along the chain and accordingly, increases the fraction of series topology with respect to other topologies. However, at high l p /R c , the fraction of cross and parallel topologies are enhanced in the chain topological circuits with cross becoming predominant. At an intermediate confining regime, we identify a critical value of l p /R c , at which all topological states have equal probability. Confinement thus equalizes the probability of more complex cross and parallel topologies to the level of the more simple, non-cooperative series topology. Moreover, our topology analysis reveals distinct behaviours for ring- and linear polymers under weak confinement; however, we find no difference between ring- and linear polymers under strong confinement. Under weak confinement, ring polymers adopt parallel and series topologies with equal likelihood, while linear polymers show a higher tendency for series arrangement. The radial distribution analysis of the topology reveals a non-uniform effect of confinement on the topology of polymer chains, thereby imposing more pronounced effects on the core region than on the confinement surface. Additionally, our results reveal that over a wide range of confining radii, loops arranged in parallel and cross

  6. Liquid crystal polymers: evidence of hairpin defects in nematic main chains, comparison with side chain polymers

    Science.gov (United States)

    Li, M. H.; Brûlet, A.; Keller, P.; Cotton, J. P.

    1996-09-01

    This article describes the conformation of two species of liquid crystalline polymers as revealed by small angle neutron scattering. The results obtained with side chain polymers are recalled. The procedure used to analyze the scattering data of main chains in the nematic phase is reported in this paper. It permits a demonstration of the existence of hairpins. Comparison of both polymer species shows that in the isotropic phase, the two polymers adopt a random coil conformation. In the nematic phase, the conformations are very different; the side chains behave as a melt of penetrable random coils whereas the main chains behave as a nematic phase of non penetrable cylinders.

  7. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo; Bao, Zhenan

    2014-01-01

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer's physical properties, including absorption

  8. Adsorption of polymer chains at penetrable interfaces

    International Nuclear Information System (INIS)

    Gerasimchuk, I. V.; Sommer, J.-U.; Gerasimchuk, V. S.

    2011-01-01

    We investigate the problem of adsorption (localization) of polymer chains in the system of two penetrable interfaces within the mean-field approximation. The saturation of the polymer system in the limit case of zero bulk concentration is studied. We find the exact solution of this mean-field polymer adsorption problem that opens the possibility to treat various localization problems for polymer chains in such environments using appropriate boundary conditions. The exact solution is controlled by a single scaling variable that describes the coupling between the interfaces due to the polymer chains. We obtain a nonmonotonic behavior of the amount of adsorbed polymers as a function of the distance between the interfaces. This leads to a high-energy and a low-energy phase for the double layer with respect to the amount of polymers localized. At the saturation point, we find the total energy of the system and determine the force acting between the interfaces to be strictly attractive and to monotonically decay to zero when the interface distance increases.

  9. Development of water-repellent organic–inorganic hybrid sol–gel coatings on aluminum using short chain perfluoro polymer emulsion

    International Nuclear Information System (INIS)

    Wankhede, Ruchi Grover; Morey, Shantaram; Khanna, A.S.; Birbilis, N.

    2013-01-01

    The development of an organic–inorganic sol–gel coating system (thickness ∼ 2 μm) on aluminum is reported. The coating uses glycidoxytrimethoxysilane (GPTMS) and methyltrimethoxysilane (MTMS) as silane precursors, crosslinked with hexamethylmethoxymelamine (HMMM) and followed by hydrophobic modification using a water base short chain per-fluoro emulsion (FE). Such coating resulted in enhanced hydrophobicity with a contact angle of about 120° and sliding angle of 25° for a 20 μL water droplet. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements showed reduced corrosion upon coated substrates than the bare; correlated with both a higher degree of water repellency and formation of low permeable crosslinked sol–gel network. The structure of the coatings deposited was analyzed using Fourier transform infrared (FTIR) and X-ray photoelectron (XPS) spectroscopy, revealing replacement of hydrophillic surface hydroxyls groups with low energy per-fluoro groups.

  10. Buckling a Semiflexible Polymer Chain under Compression

    Directory of Open Access Journals (Sweden)

    Ekaterina Pilyugina

    2017-03-01

    Full Text Available Instability and structural transitions arise in many important problems involving dynamics at molecular length scales. Buckling of an elastic rod under a compressive load offers a useful general picture of such a transition. However, the existing theoretical description of buckling is applicable in the load response of macroscopic structures, only when fluctuations can be neglected, whereas membranes, polymer brushes, filaments, and macromolecular chains undergo considerable Brownian fluctuations. We analyze here the buckling of a fluctuating semiflexible polymer experiencing a compressive load. Previous works rely on approximations to the polymer statistics, resulting in a range of predictions for the buckling transition that disagree on whether fluctuations elevate or depress the critical buckling force. In contrast, our theory exploits exact results for the statistical behavior of the worm-like chain model yielding unambiguous predictions about the buckling conditions and nature of the buckling transition. We find that a fluctuating polymer under compressive load requires a larger force to buckle than an elastic rod in the absence of fluctuations. The nature of the buckling transition exhibits a marked change from being distinctly second order in the absence of fluctuations to being a more gradual, compliant transition in the presence of fluctuations. We analyze the thermodynamic contributions throughout the buckling transition to demonstrate that the chain entropy favors the extended state over the buckled state, providing a thermodynamic justification of the elevated buckling force.

  11. Elastic properties of a polymer chain

    International Nuclear Information System (INIS)

    Webman, I.; Lebowitz, J.L.; Kalos, M.H.

    1981-01-01

    We describe the results of computer simulations on a model polymer chain with excluded volume interactions in the presence of an external stretching force. For weak and moderate forces the response is linear while for strong forces the behavior is nonlinear, consistent with the non-Gaussian nature of the end-to-end vector R distribution for large R. In the vicinity of the THETA temperature the onset of nonlinearity occurs at larger forces

  12. The effect of chain flexibility and chain mobility on radiation crosslinking reactions of polymers

    International Nuclear Information System (INIS)

    Sun Jiazhen

    2003-01-01

    Flexibility of polymer chains is an important factor to effects of radiation crosslinking of the polymer. Polymers with flexible chains are easier to be crosslinked, with lower dose of gelation, than polymers with more rigid chains. And it is known that most polymers with abnormal rigidity can be radiation-crosslinked only at high temperatures when the molecular chains get enough mobility. The flexibility of polymer chains also influences the relationship between degree of degradation and radiation dose. A chain flexibility factor β has been introduced to modify the Charlesby-Pinner equation of sol-fraction and radiation dose. The new relationship equation applies to a wider range of polymers in radiation crosslinking. Studies also show that for flexible polymers with lower T g and molecular internal rotating factor, mechanism of radiation crosslinking is mainly in H type, whereas for rigid polymers with higher T g and molecular internal rotating factor, mechanism of radiation crosslinking is mainly in T type

  13. Side Chain Engineering in Solution-Processable Conjugated Polymers

    KAUST Repository

    Mei, Jianguo

    2014-01-14

    Side chains in conjugated polymers have been primarily utilized as solubilizing groups. However, these side chains have roles that are far beyond. We advocate using side chain engineering to tune a polymer\\'s physical properties, including absorption, emission, energy level, molecular packing, and charge transport. To date, numerous flexible substituents suitable for constructing side chains have been reported. In this Perspective article, we advocate that the side chain engineering approach can advance better designs for next-generation conjugated polymers. © 2013 American Chemical Society.

  14. Segregation of chain ends to polymer melt surfaces and interfaces

    International Nuclear Information System (INIS)

    Zhao, W.; Zhao, X.; Rafailovich, M.H.; Sokolov, J.; Composto, R.J.; Smith, S.D.; Satkowski, M.; Russell, T.P.; Dozier, W.D.; Mansfield, T.

    1993-01-01

    The conformation of polymer chains in the melt near an impenetrable boundary has recently been studied by molecular dynamics and off-lattice Monte Carlo simulations. Both types of calculations show an enhancement of the chain end density within a distance of approximately two polymer segment lengths of the interface relative to the bulk. In the absence of preferential interactions between monomers and the interface, the segregation arises from minimizing the loss of conformational entropy near an impenetrable boundary; i.e., by positioning an end near the surface, only one unit rather than two is reflected. In order to obtain an experimental measure of this effect, monodisperse polystyrene (PS) chains of molecular weight 63 000 with short blocks of deuterated polystyrene (dPS) at each end were prepared. The block length was kept as short as possible, while yet producing sufficient neutron scattering contrast in order to minimize any preferential surface segregation due to isotopic effects. The synthesis was carried out via living anionic polymerization of a purified styrene monomer in cyclohexane at 60 C, utilizing sec-butyllithium as the initiator. The process was terminated using degassed methanol

  15. Critical Casimir effect in a polymer chain in supercritical solvents.

    Science.gov (United States)

    Sumi, Tomonari; Imazaki, Nobuyuki; Sekino, Hideo

    2009-03-01

    Density fluctuation effects on the conformation of a polymer chain in a supercritical solvent were investigated by performing a multiscale simulation based on the density-functional theory. We found (a) a universal swelling of the polymer chain near the critical point, irrespective of whether the polymer chain is solvophilic or solvophobic, and (b) a characteristic collapse of the polymer chain having a strong solvophilicity at a temperature slightly higher than the critical point, where the isothermal compressibility becomes less than the ideal one.

  16. Improved power conversion efficiency of dye-sensitized solar cells using side chain liquid crystal polymer embedded in polymer electrolytes

    International Nuclear Information System (INIS)

    Cho, Woosum; Lee, Jae Wook; Gal, Yeong-Soon; Kim, Mi-Ra; Jin, Sung Ho

    2014-01-01

    Side chain liquid crystal polymer (SCLCP) embedded in poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based polymer electrolytes (PVdF-co-HFP:side chain liquid crystal polymer (SCLCP)) was prepared for dye-sensitized solar cell (DSSC) application. The polymer electrolytes contained tetrabutylammonium iodide (TBAI), iodine (I 2 ), and 8 wt% PVdF-co-HFP in acetonitrile. DSSCs comprised of PVdF-co-HFP:SCLCP-based polymer electrolytes displayed enhanced redox couple reduction and reduced charge recombination in comparison to those of the conventional PVdF-co-HFP-based polymer electrolyte. The significantly increased short-circuit current density (J sc , 10.75 mA cm −2 ) of the DSSCs with PVdF-co-HFP:SCLCP-based polymer electrolytes afforded a high power conversion efficiency (PCE) of 5.32% and a fill factor (FF) of 0.64 under standard light intensity of 100 mW cm −2 irradiation of AM 1.5 sunlight. - Highlights: • We developed the liquid crystal polymer embedded on polymer electrolyte for DSSCs. • We fabricated the highly efficient DSSCs using polymer electrolyte. • The best PCE achieved for P1 is 5.32% using polymer electrolyte

  17. Improved power conversion efficiency of dye-sensitized solar cells using side chain liquid crystal polymer embedded in polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Woosum [Department of Chemistry Education, and Department of Frontier Materials Chemistry, and Institute for Plastic Information and Energy Materials, Pusan National University, Busan 609-735 (Korea, Republic of); Lee, Jae Wook, E-mail: jlee@donga.ac.kr [Department of Chemistry, Dong-A University, Busan 604-714 (Korea, Republic of); Gal, Yeong-Soon [Polymer Chemistry Lab, College of General Education, Kyungil University, Hayang 712-701 (Korea, Republic of); Kim, Mi-Ra, E-mail: mrkim2@pusan.ac.kr [Department of Polymer Science and Engineering, Pusan National University, Busan 609-735 (Korea, Republic of); Jin, Sung Ho, E-mail: shjin@pusan.ac.kr [Department of Chemistry Education, and Department of Frontier Materials Chemistry, and Institute for Plastic Information and Energy Materials, Pusan National University, Busan 609-735 (Korea, Republic of)

    2014-02-14

    Side chain liquid crystal polymer (SCLCP) embedded in poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP)-based polymer electrolytes (PVdF-co-HFP:side chain liquid crystal polymer (SCLCP)) was prepared for dye-sensitized solar cell (DSSC) application. The polymer electrolytes contained tetrabutylammonium iodide (TBAI), iodine (I{sub 2}), and 8 wt% PVdF-co-HFP in acetonitrile. DSSCs comprised of PVdF-co-HFP:SCLCP-based polymer electrolytes displayed enhanced redox couple reduction and reduced charge recombination in comparison to those of the conventional PVdF-co-HFP-based polymer electrolyte. The significantly increased short-circuit current density (J{sub sc}, 10.75 mA cm{sup −2}) of the DSSCs with PVdF-co-HFP:SCLCP-based polymer electrolytes afforded a high power conversion efficiency (PCE) of 5.32% and a fill factor (FF) of 0.64 under standard light intensity of 100 mW cm{sup −2} irradiation of AM 1.5 sunlight. - Highlights: • We developed the liquid crystal polymer embedded on polymer electrolyte for DSSCs. • We fabricated the highly efficient DSSCs using polymer electrolyte. • The best PCE achieved for P1 is 5.32% using polymer electrolyte.

  18. Competing irreversible cooperative reactions on polymer chains

    International Nuclear Information System (INIS)

    Evans, J.W.; Hoffman, D.K.; Burgess, D.R.

    1984-01-01

    We analyze model processes involving competition between several irreversible reactions at the sites of a 1D, infinite, uniform polymer chain. These reactions can be cooperative, i.e., the corresponding rates depend on the state of the surrounding sites. An infinite hierarchy of rate equations is readily derived for the probabilities of various subconfigurations. By exploiting a shielding property of suitable blocks of unreacted sites, we show how exact hierarchy truncation and solution is sometimes possible. The behavior of solutions is illustrated in several cases by plotting families of ''reaction trajectories'' for varying ratios of reactant concentrations. As a specific application, we consider competition between coordination of ZnCl 2 to pairs of oxygen atoms and to single oxygen atoms in poly(propylene oxide). The observed glass transition temperature behavior is eludicated

  19. Record high hole mobility in polymer semiconductors via side-chain engineering.

    Science.gov (United States)

    Kang, Il; Yun, Hui-Jun; Chung, Dae Sung; Kwon, Soon-Ki; Kim, Yun-Hi

    2013-10-09

    Charge carrier mobility is still the most challenging issue that should be overcome to realize everyday organic electronics in the near future. In this Communication, we show that introducing smart side-chain engineering to polymer semiconductors can facilitate intermolecular electronic communication. Two new polymers, P-29-DPPDBTE and P-29-DPPDTSE, which consist of a highly conductive diketopyrrolopyrrole backbone and an extended branching-position-adjusted side chain, showed unprecedented record high hole mobility of 12 cm(2)/(V·s). From photophysical and structural studies, we found that moving the branching position of the side chain away from the backbone of these polymers resulted in increased intermolecular interactions with extremely short π-π stacking distances, without compromising solubility of the polymers. As a result, high hole mobility could be achieved even in devices fabricated using the polymers at room temperature.

  20. Phase transitions of single polymer chains and of polymer solutions: insights from Monte Carlo simulations

    International Nuclear Information System (INIS)

    Binder, K; Paul, W; Strauch, T; Rampf, F; Ivanov, V; Luettmer-Strathmann, J

    2008-01-01

    The statistical mechanics of flexible and semiflexible macromolecules is distinct from that of small molecule systems, since the thermodynamic limit can also be approached when the number of (effective) monomers of a single chain (realizable by a polymer solution in the dilute limit) is approaching infinity. One can introduce effective attractive interactions into a simulation model for a single chain such that a swollen coil contracts when the temperature is reduced, until excluded volume interactions are effectively canceled by attractive forces, and the chain conformation becomes almost Gaussian at the theta point. This state corresponds to a tricritical point, as the renormalization group theory shows. Below the theta temperature a fluid globule is predicted (at nonzero concentration then phase separation between dilute and semidilute solutions occurs), while at still lower temperature a transition to a solid phase (crystal or glass) occurs. Monte Carlo simulations have shown, however, that the fluid globule phase may become suppressed, when the range of the effective attractive forces becomes too short, with the result that a direct (ultimately first-order) transition from the swollen coil to the solid occurs. This behavior is analogous to the behavior of colloidal particles with a very short range of attractive forces, where liquid-vapor-type phase separation may be suppressed. Analogous first-order transitions from swollen coils to dense rodlike or toroidal structures occur for semiflexible polymers. Finally, the modifications of the behavior discussed when the polymers are adsorbed at surfaces are also mentioned, and possible relations to wetting behavior of polymer solutions are addressed.

  1. Capillary condensation of short-chain molecules.

    Science.gov (United States)

    Bryk, Paweł; Pizio, Orest; Sokolowski, Stefan

    2005-05-15

    A density-functional study of capillary condensation of fluids of short-chain molecules confined to slitlike pores is presented. The molecules are modeled as freely jointed tangent spherical segments with a hard core and with short-range attractive interaction between all the segments. We investigate how the critical parameters of capillary condensation of the fluid change when the pore width decreases and eventually becomes smaller than the nominal linear dimension of the single-chain molecule. We find that the dependence of critical parameters for a fluid of dimers and of tetramers on pore width is similar to that of the monomer fluid. On the other hand, for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. We attribute this behavior to the effect of conformational changes of molecules upon confinement.

  2. Effect of chain stiffness on the structure of single-chain polymer nanoparticles

    Science.gov (United States)

    Moreno, Angel J.; Bacova, Petra; Lo Verso, Federica; Arbe, Arantxa; Colmenero, Juan; Pomposo, José A.

    2018-01-01

    Polymeric single-chain nanoparticles (SCNPs) are soft nano-objects synthesized by purely intramolecular cross-linking of single polymer chains. By means of computer simulations, we investigate the conformational properties of SCNPs as a function of the bending stiffness of their linear polymer precursors. We investigate a broad range of characteristic ratios from the fully flexible case to those typical of bulky synthetic polymers. Increasing stiffness hinders bonding of groups separated by short contour distances and increases looping over longer distances, leading to more compact nanoparticles with a structure of highly interconnected loops. This feature is reflected in a crossover in the scaling behaviour of several structural observables. The scaling exponents change from those characteristic for Gaussian chains or rings in θ-solvents in the fully flexible limit, to values resembling fractal or ‘crumpled’ globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs.

  3. High Performance All-Polymer Solar Cell via Polymer Side-Chain Engineering

    KAUST Repository

    Zhou, Yan; Kurosawa, Tadanori; Ma, Wei; Guo, Yikun; Fang, Lei; Vandewal, Koen; Diao, Ying; Wang, Chenggong; Yan, Qifan; Reinspach, Julia; Mei, Jianguo; Appleton, Anthony Lucas; Koleilat, Ghada I.; Gao, Yongli; Mannsfeld, Stefan C. B.; Salleo, Alberto; Ade, Harald; Zhao, Dahui; Bao, Zhenan

    2014-01-01

    An average PCE of 4.2% for all-polymer solar cells from 20 devices with an average J SC of 8.8 mA cm-2 are obtained with a donor-acceptor pair despite a low LUMO-LUMO energy offset of less than 0.1 eV. Incorporation of polystyrene side chains into the donor polymer is found to assist in reducing the phase separation domain length scale, and results in more than 20% enhancement of PCE. We observe a direct correlation between the short circuit current (J SC) and the length scale of BHJ phase separation, which is obtained by resonance soft X-ray scattering. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. High Performance All-Polymer Solar Cell via Polymer Side-Chain Engineering

    KAUST Repository

    Zhou, Yan

    2014-03-24

    An average PCE of 4.2% for all-polymer solar cells from 20 devices with an average J SC of 8.8 mA cm-2 are obtained with a donor-acceptor pair despite a low LUMO-LUMO energy offset of less than 0.1 eV. Incorporation of polystyrene side chains into the donor polymer is found to assist in reducing the phase separation domain length scale, and results in more than 20% enhancement of PCE. We observe a direct correlation between the short circuit current (J SC) and the length scale of BHJ phase separation, which is obtained by resonance soft X-ray scattering. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. General approach to polymer chains confined by interacting boundaries.

    Science.gov (United States)

    Freed, Karl F; Dudowicz, Jacek; Stukalin, Evgeny B; Douglas, Jack F

    2010-09-07

    Polymer chains, confined to cavities or polymer layers with dimensions less than the chain radius of gyration, appear in many phenomena, such as gel chromatography, rubber elasticity, viscolelasticity of high molar mass polymer melts, the translocation of polymers through nanopores and nanotubes, polymer adsorption, etc. Thus, the description of how the constraints alter polymer thermodynamic properties is a recurrent theoretical problem. A realistic treatment requires the incorporation of impenetrable interacting (attractive or repulsive) boundaries, a process that introduces significant mathematical complications. The standard approach involves developing the generalized diffusion equation description of the interaction of flexible polymers with impenetrable confining surfaces into a discrete eigenfunction expansion, where the solutions are normally truncated at the first mode (the "ground state dominance" approximation). This approximation is mathematically well justified under conditions of strong confinement, i.e., a confinement length scale much smaller than the chain radius of gyration, but becomes unreliable when the polymers are confined to dimensions comparable to their typically nanoscale size. We extend a general approach to describe polymers under conditions of weak to moderate confinement and apply this semianalytic method specifically to determine the thermodynamics and static structure factor for a flexible polymer confined between impenetrable interacting parallel plate boundaries. The method is first illustrated by analyzing chain partitioning between a pore and a large external reservoir, a model system with application to chromatography. Improved agreement is found for the partition coefficients of a polymer chain in the pore geometry. An expression is derived for the structure factor S(k) in a slit geometry to assist in more accurately estimating chain dimensions from scattering measurements for thin polymer films.

  6. Stochastic entangled chain dynamics of dense polymer solutions.

    Science.gov (United States)

    Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

    2010-10-14

    We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

  7. Relaxation Dynamics of Nanoparticle-Tethered Polymer Chains

    KAUST Repository

    Kim, Sung A; Mangal, Rahul; Archer, Lynden A.

    2015-01-01

    © 2015 American Chemical Society. Relaxation dynamics of nanoparticle-tethered cis-1,4-polyisoprene (PI) are investigated using dielectric spectroscopy and rheometry. A model system composed of polymer chains densely grafted to spherical SiO2

  8. Nitroxide radicals formed in situ as polymer chain growth regulators

    International Nuclear Information System (INIS)

    Kolyakina, Elena V; Grishin, Dmitry F

    2009-01-01

    Published data on controlled synthesis of macromolecules using nitroxide radicals, formed in situ during polymerization, as polymer chain growth regulators are systematized and generalized. The attention is focused on the mechanism of polymer chain growth control during reversibly inhibited radical homopolymerization and the effect of structure of precursors and regulating additives on the polymerization kinetics of monomers of different nature and the molecular-mass characteristics of the polymers thus formed. The key methods for generation of nitroxide radicals directly during polymerization are considered. The prospects for development and practical use of these approaches for the synthesis of new polymeric materials are evaluated.

  9. Dynamics of dissolved polymer chains in isotropic turbulence

    International Nuclear Information System (INIS)

    Jin Shi; Collins, Lance R

    2007-01-01

    Polymers are remarkable molecules that have relaxation times that can span 15 orders of magnitude. The very longest of the relaxation times for high molecular weight polymers are sufficiently long to overlap with fluid mechanical times scales; under those circumstances, polymers can influence the flow. A well-known example that is still not fully understood is polymer drag reduction. It has been known since Toms (1949 Proc. 1st Int. Congress on Rheology 2 135-41) that parts per million (mass basis) concentrations of polymers can reduce the drag on a solid surface by as much as 80%. Understanding the mechanism of drag reduction requires an understanding of the dynamics of the dissolved polymer chain in response to local fluctuations in the turbulent flow field. We investigate this by using Brownian dynamics simulations of bead-spring models of polymers immersed in a turbulent solvent that is separately computed using direct numerical simulations. We observe that polymer chains with parameters that are effective for drag reduction generally remain stretched for long periods of time and only occasionally relax. The relatively restricted configuration space they sample makes it reasonable to represent their behavior with simpler dumbbell models. We also study the spatial structure of the polymer stresses using a Lagrangian strategy. The results explain the need for relatively high spatial resolution for numerical simulations of polymer flows

  10. Experimental studies of the dynamic mechanical response of a single polymer chain

    DEFF Research Database (Denmark)

    Thormann, Esben; Evans, Drew R.; Craig, Vincent S. J.

    2006-01-01

    The high-frequency and low-amplitude dynamic mechanical response from a single poly(vinyl alcohol) chain was investigated. Modification of a commercial atomic force microscope enabled high-frequency and low-amplitude periodic deformations of polymer chains during extension to be performed...... mechanical response from poly(vinyl alcohol) does not differ from its static response. This result is not unexpected as poly(vinyl alcohol) is a highly flexible polymer with intramolecular relaxation processes taking place on a short time scale. The choice of a polymer with a fast relaxation allows its...... static properties to be recovered from the dynamic measurements and enables the method suggested in this paper for decoupling the polymer response from the hydrodynamic response to be validated....

  11. Relaxation Dynamics of Nanoparticle-Tethered Polymer Chains

    KAUST Repository

    Kim, Sung A

    2015-09-08

    © 2015 American Chemical Society. Relaxation dynamics of nanoparticle-tethered cis-1,4-polyisoprene (PI) are investigated using dielectric spectroscopy and rheometry. A model system composed of polymer chains densely grafted to spherical SiO2 nanoparticles to form self-suspended suspensions facilitates detailed studies of slow global chain and fast segmental mode dynamics under surface and geometrical confinement-from experiments performed in bulk materials. We report that unentangled polymer molecules tethered to nanoparticles relax far more slowly than their tethered entangled counterparts. Specifically, at fixed grafting density we find, counterintuitively, that increasing the tethered polymer molecular weight up to values close to the entanglement molecular weight speeds up chain relaxation dynamics. Decreasing the polymer grafting density for a fixed molecular weight has the opposite effect: it dramatically slows down chain relaxation, increases interchain coupling, and leads to a transition in rheological response from simple fluid behavior to viscoelastic fluid behavior for tethered PI chains that are unentangled by conventional measures. Increasing the measurement temperature produces an even stronger elastic response and speeds up molecular relaxation at a rate that decreases with grafting density and molecular weight. These observations are discussed in terms of chain confinement driven by crowding between particles and by the existence of an entropic attractive force produced by the space-filling constraint on individual chains in a self-suspended material. Our results indicate that the entropic force between densely grafted polymer molecules couples motions of individual chains in an analogous manner to reversible cross-links in associating polymers.

  12. Renormalization group for centrosymmetric gauge transformations of the dynamic motion for a Markov-ordered polymer chain

    International Nuclear Information System (INIS)

    Mikhailov, I.D.; Zhuravskii, L.V.

    1987-01-01

    A method is proposed for calculating the vibrational-state density averaged over all configurations for a polymer chain with Markov disorder. The method is based on using a group of centrally symmetric gauge transformations that reduce the dynamic matrix for along polymer chain to renormalized dynamic matrices for short fragments. The short-range order is incorporated exactly in the averaging procedure, while the long-range order is incorporated in the self-consistent field approximation. Results are given for a simple skeletal model for a polymer containing tacticity deviations of Markov type

  13. Polymer ultrapermeability from the inefficient packing of 2D chains

    Science.gov (United States)

    Rose, Ian; Bezzu, C. Grazia; Carta, Mariolino; Comesaña-Gándara, Bibiana; Lasseuguette, Elsa; Ferrari, M. Chiara; Bernardo, Paola; Clarizia, Gabriele; Fuoco, Alessio; Jansen, Johannes C.; Hart, Kyle E.; Liyana-Arachchi, Thilanga P.; Colina, Coray M.; McKeown, Neil B.

    2017-09-01

    The promise of ultrapermeable polymers, such as poly(trimethylsilylpropyne) (PTMSP), for reducing the size and increasing the efficiency of membranes for gas separations remains unfulfilled due to their poor selectivity. We report an ultrapermeable polymer of intrinsic microporosity (PIM-TMN-Trip) that is substantially more selective than PTMSP. From molecular simulations and experimental measurement we find that the inefficient packing of the two-dimensional (2D) chains of PIM-TMN-Trip generates a high concentration of both small (Gas permeability data for PIM-TMN-Trip surpass the 2008 Robeson upper bounds for O2/N2, H2/N2, CO2/N2, H2/CH4 and CO2/CH4, with the potential for biogas purification and carbon capture demonstrated for relevant gas mixtures. Comparisons between PIM-TMN-Trip and structurally similar polymers with three-dimensional (3D) contorted chains confirm that its additional intrinsic microporosity is generated from the awkward packing of its 2D polymer chains in a 3D amorphous solid. This strategy of shape-directed packing of chains of microporous polymers may be applied to other rigid polymers for gas separations.

  14. Quantifying Short-Chain Chlorinated Paraffin Congener Groups

    NARCIS (Netherlands)

    Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A.; Alsberg, Tomas; Wit, de Cynthia A.

    2017-01-01

    Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are

  15. Linear rheology and structure of molecular bottlebrushes with short side chains

    International Nuclear Information System (INIS)

    López-Barrón, Carlos R.; Brant, Patrick; Crowther, Donna J.; Eberle, Aaron P. R.

    2015-01-01

    We investigate the microstructure and linear viscoelasticity of model molecular bottlebrushes (BBs) using rheological and small-angle X-ray and neutron scattering measurements. Our polymers have short atactic polypropylene (aPP) side chains of molecular weight ranging from 119 g/mol to 259 g/mol and narrow molecular weight distribution (M w /M n 1.02–1.05). The side chain molecular weights are a small fraction of the entanglement molecular weight of the corresponding linear polymer (M e,aPP = 7.05 kg/mol), and as such, they are unentangled. The morphology of the aPP BBs is characterized as semiflexible thick chains with small side chain interdigitation. Their dynamic master curves, obtained by time-temperature superposition, reveal two sequential relaxation processes corresponding to the segmental relaxation and the relaxation of the BB backbone. Due to the short length of the side chains, their fast relaxation could not be distinguished from the glassy relaxation. The fractional free volume is an increasing function of the side chain length (N SC ). Therefore, the glassy behavior of these polymers as well as their molecular friction and dynamic properties are influenced by their N SC values. The apparent flow activation energies are a decreasing function of N SC , and their values explain the differences in zero-shear viscosity measured at different temperatures

  16. Chain confinement, phase transitions, and lamellar structure in semicrystalline polymers, polymer blends and polymer nanocomposites

    Science.gov (United States)

    Chen, Huipeng

    and is applied to the iPS/atactic polystyrene, aPS, blends. The fractions of MAF inside and outside the lamellar stacks were quantified for the first time. For A/B binary polymer blends, it has been reported that if B is already crystalline, the crystalline fraction would serve as a restriction on the subsequent growth of the crystallizable partner A, while amorphous fraction could be diffused from the crystalline growth front of the crystallizing A component. Considering the effect of RAF on binary blends, a new concept is provided: like the crystals, the RAF of one polymer component may inhibit the growth of crystals of the other blend partner. The non-isothermal crystallization of PET/poly(lactic acid), PLA, blends were investigated and the results confirmed the new concept is correct: PET forms a large amount of RAF and inhibits crystal formation in PLA. Then, we broadened the concept of RAF and investigated the RAF in recent 'hot' materials, polymer nanocomposites. It was found the fraction of RAF greatly increased with a small amount of multi-wall carbon nanotubes, MWCNT, loading in PET electrospun, ES, fibers. A general model is given for polymer ES fibers with MWCNTs: the addition of MWCNTs causes polymer chains in the ES fibers to become more extended, (ie, more stretched), resulting in more confinement of PET chains and an increase in the RAF.

  17. New polymer systems: Chain extension by dianhydrides

    Science.gov (United States)

    Rhein, R. A.; Ingham, J. D.

    1974-01-01

    Three anhydrides provide effective chain extension of hydroxy-terminated polyalkylene oxides and polybutadienes. Novel feature of these anhydride reactants is that they are difunctional as anhydrides, but they are tetrafunctional if conditions are selected that lead to total esterification or reaction of all carboxyl groups.

  18. Synthesis and property characterization of two novel side-chain isoindigo copolymers for polymer solar cells

    Directory of Open Access Journals (Sweden)

    X. Liu

    2015-11-01

    Full Text Available Two novel side-chain conjugated polymers, PTBT-TID and PTBT-TTID, based on the new synthetic thiophene-benzne-thiophene (TBT unit, side-chain isoindigo (ID unit, and the introduced thiophene π-bridge, have been designed and synthesized. The photophysical, electrochemical and photovoltaic properties of the two polymers have been systematically investigated. The two polymers possess relatively good solubility as well as excellent thermal stability up to 380°C, and all of the polymer solar cell (PSC devices based on the two polymers obtain high open circuit voltage (Voc of about 0.8 V. The polymer solar cells based on the polymer PTBT-TID show relatively higher efficiencies than the PTBT-TTID-based ones, due to the broader absorption spectrum, a relatively higher hole mobility, a lower HOMO (the highest occupied molecular orbital energy level, a stronger IPCE (the incident photon to current conversion efficiency response and a better microphase separation, Consequently, the device based on PTBT-TID:PC61BM (1:2, by weight gives the best power conversion efficiency (PCE of 2.04%, with a short-circuit current density (Jsc of 5.39 mA·cm–2, an open-circuit voltage (Voc of 0.83 V, and a fill factor (FF of 0.45.

  19. Rouse mode analysis of chain relaxation in polymer nanocomposites.

    Science.gov (United States)

    Kalathi, Jagannathan T; Kumar, Sanat K; Rubinstein, Michael; Grest, Gary S

    2015-05-28

    Large-scale molecular dynamics simulations are used to study the internal relaxations of chains in nanoparticle (NP)/polymer composites. We examine the Rouse modes of the chains, a quantity that is closest in spirit to the self-intermediate scattering function, typically determined in an (incoherent) inelastic neutron scattering experiment. Our simulations show that for weakly interacting mixtures of NPs and polymers, the effective monomeric relaxation rates are faster than in a neat melt when the NPs are smaller than the entanglement mesh size. In this case, the NPs serve to reduce both the monomeric friction and the entanglements in the polymer melt, as in the case of a polymer-solvent system. However, for NPs larger than half the entanglement mesh size, the effective monomer relaxation is essentially unaffected for low NP concentrations. Even in this case, we observe a strong reduction in chain entanglements for larger NP loadings. Thus, the role of NPs is to always reduce the number of entanglements, with this effect only becoming pronounced for small NPs or for high concentrations of large NPs. Our studies of the relaxation of single chains resonate with recent neutron spin echo (NSE) experiments, which deduce a similar entanglement dilution effect.

  20. Statistical properties of multi-theta polymer chains

    Science.gov (United States)

    Uehara, Erica; Deguchi, Tetsuo

    2018-04-01

    We study statistical properties of polymer chains with complex structures whose chemical connectivities are expressed by graphs. The multi-theta curve of m subchains with two branch points connected by them is one of the simplest graphs among those graphs having closed paths, i.e. loops. We denoted it by θm , and for m  =  2 it is given by a ring. We derive analytically the pair distribution function and the scattering function for the θm -shaped polymer chains consisting of m Gaussian random walks of n steps. Surprisingly, it is shown rigorously that the mean-square radius of gyration for the Gaussian θm -shaped polymer chain does not depend on the number m of subchains if each subchain has the same fixed number of steps. For m  =  3 we show the Kratky plot for the theta-shaped polymer chain consisting of hard cylindrical segments by the Monte-Carlo method including reflection at trivalent vertices.

  1. Lattice cluster theory of associating polymers. I. Solutions of linear telechelic polymer chains.

    Science.gov (United States)

    Dudowicz, Jacek; Freed, Karl F

    2012-02-14

    The lattice cluster theory (LCT) for the thermodynamics of a wide array of polymer systems has been developed by using an analogy to Mayer's virial expansions for non-ideal gases. However, the high-temperature expansion inherent to the LCT has heretofore precluded its application to systems exhibiting strong, specific "sticky" interactions. The present paper describes a reformulation of the LCT necessary to treat systems with both weak and strong, "sticky" interactions. This initial study concerns solutions of linear telechelic chains (with stickers at the chain ends) as the self-assembling system. The main idea behind this extension of the LCT lies in the extraction of terms associated with the strong interactions from the cluster expansion. The generalized LCT for sticky systems reduces to the quasi-chemical theory of hydrogen bonding of Panyioutou and Sanchez when correlation corrections are neglected in the LCT. A diagrammatic representation is employed to facilitate the evaluation of the corrections to the zeroth-order approximation from short range correlations. © 2012 American Institute of Physics

  2. Single-Chain Folding of Synthetic Polymers: A Critical Update.

    Science.gov (United States)

    Altintas, Ozcan; Barner-Kowollik, Christopher

    2015-11-23

    The current contribution serves as a critical update to a previous feature article from us (Macromol. Rapid Commun. 2012, 33, 958-971), and highlights the latest advances in the preparation of single chain polymeric nanoparticles and initial-yet promising-attempts towards mimicking the structure of natural biomacromolecules via single-chain folding of well-defined linear polymers via so-called single chain selective point folding and repeat unit folding. The contribution covers selected examples from the literature published up to ca. September 2015. Our aim is not to provide an exhaustive review but rather highlight a selection of new and exciting examples for single-chain folding based on advanced macromolecular precision chemistry. Initially, the discussion focuses on the synthesis and characterization of single-chain folded structures via selective point folding. The second part of the feature article addresses the folding of well-defined single-chain polymers by means of repeat unit folding. The current state of the art in the field of single-chain folding indicates that repeat unit folding-driven nanoparticle preparation is well-advanced, while initial encouraging steps towards building selective point folding systems have been taken. In addition, a summary of the-in our view-open key questions is provided that may guide future biomimetic design efforts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The influence of polymer architectures on the dewetting behavior of thin polymer films: from linear chains to ring chains.

    Science.gov (United States)

    Wang, Lina; Xu, Lin; Liu, Binyuan; Shi, Tongfei; Jiang, Shichun; An, Lijia

    2017-05-03

    The dewetting behavior of ring polystyrene (RPS) film and linear polystyrene (LPS) film on silanized Si substrates with different grafting densities and PDMS substrate was investigated. Results showed that polymer architectures greatly influenced the dewetting behavior of the thin polymer film. On the silanized Si substrate with 69% grafting density, RPS chains exhibited stronger adsorption compared with LPS chains, and as a result the wetting layer formed more easily. For LPS films, with a decreased annealing temperature, the stability of the polymer film changed from non-slip dewetting via apparent slip dewetting to apparently stable. However, for RPS films, the polymer film stability switched from apparent slip dewetting to apparently stable. On the silanized Si substrate with 94% grafting density, the chain adsorption became weaker and the dewetting processes were faster than that on the substrate with 69% grafting density at the same experimental temperature for both the LPS and RPS films. Moreover, on the PDMS substrate, LPS films always showed non-slip dewetting, while the dewetting kinetics of RPS films switched from non-slip dewetting to slip dewetting behaviour. Forming the wetting layer strongly influenced the stability and dewetting behavior of the thin polymer films.

  4. SHORT COMMUNICATION Repellency property of long chain ...

    African Journals Online (AJOL)

    Repellency property of long chain aliphatic methyl ketones against Anopheles gambiae s.s ... tained from huge diversity of plant species are an important source of safe .... dry and then introduced with the hand covered by a glove in .... citronellal in repelling bees from basil (Oci- ... Journal of American Mosquito Control As-.

  5. Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

    International Nuclear Information System (INIS)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil

    2012-01-01

    We rationally designed and synthesized metallopolymers with organic 1,4-benzenedicarboxylic acid (BDC) linkers with different lengths of oxyethylene side chains in order to examine the influence of side chains on the coordination characteristics. While in a previous report the BDC linkers with alkyl side chains were found to form three-dimensional (3D) isoreticular metal-organic framework (IRMOF) structures or one-dimensional (1D) coordination polymeric structures with short -O(CH 2 ) 6 CH 3 or long -O(CH 2 ) 9 CH 3 side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH 2 CH 2 ) 2 CH 3 and -(OCH 2 CH 2 ) 3 CH 3 , form only 3D IRMOF structures. This result is attributed to the higher flexibility and smaller volume of oxyethylene side chains compared to alkyl side chains

  6. Controlling photophysical properties of ultrasmall conjugated polymer nanoparticles through polymer chain packing

    KAUST Repository

    Piwonski, Hubert Marek

    2017-05-16

    Applications of conjugated polymer nanoparticles (Pdots) for imaging and sensing depend on their size, fluorescence brightness and intraparticle energy transfer. The molecular design of conjugated polymers (CPs) has been the main focus of the development of Pdots. Here we demonstrate that proper control of the physical interactions between the chains is as critical as the molecular design. The unique design of twisted CPs and fine-tuning of the reprecipitation conditions allow us to fabricate ultrasmall (3.0–4.5 nm) Pdots with excellent photostability. Extensive photophysical and structural characterization reveals the essential role played by the packing of the polymer chains in the particles in the intraparticle spatial alignment of the emitting sites, which regulate the fluorescence brightness and the intraparticle energy migration efficiency. Our findings enhance understanding of the relationship between chain interactions and the photophysical properties of CP nanomaterials, providing a framework for designing and fabricating functional Pdots for imaging applications.

  7. Unconventional phase transitions in a constrained single polymer chain

    International Nuclear Information System (INIS)

    Klushin, L I; Skvortsov, A M

    2011-01-01

    Phase transitions were recognized among the most fascinating phenomena in physics. Exactly solved models are especially important in the theory of phase transitions. A number of exactly solved models of phase transitions in a single polymer chain are discussed in this review. These are three models demonstrating the second order phase transitions with some unusual features: two-dimensional model of β-structure formation, the model of coil–globule transition and adsorption of a polymer chain grafted on the solid surface. We also discuss models with first order phase transitions in a single macromolecule which admit not only exact analytical solutions for the partition function with explicit finite-size effects but also the non-equilibrium free energy as a function of the order parameter (Landau function) in closed analytical form. One of them is a model of mechanical desorption of a macromolecule, which demonstrates an unusual first order phase transition with phase coexistence within a single chain. Features of first and second order transitions become mixed here due to phase coexistence which is not accompanied by additional interfacial free energy. Apart from that, there exist several single-chain models belonging to the same class (adsorption of a polymer chain tethered near the solid surface or liquid–liquid interface, and escape transition upon compressing a polymer between small pistons) that represent examples of a highly unconventional first order phase transition with several inter-related unusual features: no simultaneous phase coexistence, and hence no phase boundary, non-concave thermodynamic potential and non-equivalence of conjugate ensembles. An analysis of complex zeros of partition functions upon approaching the thermodynamic limit is presented for models with and without phase coexistence. (topical review)

  8. Mouse myeloma cells that make short immunoglobulin heavy chains: pleiotropic effects on glycosylation and chain assembly

    OpenAIRE

    1984-01-01

    Two variants in immunoglobulin heavy chain production, derived from the MPC 11 mouse myeloma cell line, make short heavy (H) chains with identical precise deletions of the CH3 domain. The CH3 domain is expressed in the H chain mRNA from both variants. Although in vitro translation of this mRNA produces one H chain species, deleted heavy chains are secreted as heavy-light (HL) and H2L2 moieties in contrast to MPC 11, which secretes only H2L2 . The heavy chains of HL apparently contain more car...

  9. Developing Exchange in Short Local Foods Supply Chains

    Directory of Open Access Journals (Sweden)

    Per Engelseth

    2016-07-01

    Full Text Available The supply chain management of foods is commonly associated with modernistic large-scale production. This involves long transport distances of foods to reach consumers. In the case of local foods, supply chains are shorter. Based on a case study of five local foods producer's supply of their products to a common retailer, the supply chain of local foods is modelled conceptually and modes of development are pointed out based on contingency theory and supply chain management literature. Findings reveal that since these chains are transparent, reciprocal interdependency is abundant mainly because human perception creates a sufficient understanding of the operations management issues pertinent within this simple inter-organisational structure. Local foods supply chains are similar to service supply chains. This includes that both are short in nature and associated with bi-directional interaction between the customer and supplier. Developing short supply chains in local foods supply is associated with improving the exchange economy found in short supply chains. This also implies that development of local foods supply is associated with two paths which may be complementary. First, the use of improved intensive technology associated with reciprocal interdependency to develop efficiencies in the bi-directional and somewhat complex interaction. Alternatively local foods suppliers may seek to reduce this form of reciprocal interdependency thereby increasing the impact of pooled interdependencies and enabling using mediating technology involving standardising interaction such as through increased standardised products and packaging as well as automation of information connectivity.

  10. Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

    Institute of Scientific and Technical Information of China (English)

    Yuxiang Li; Seyeong Song; Song Yi Park; Jin Young Kim; Han Young Woo

    2017-01-01

    Three types of semi-cry stalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to(300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2 FBT devices showed a power conversion efficiency of 3.16%,4.40%and 5.65%,respectively,by blending with PC71BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density(JSC) and open-circuit voltage(VOc).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71 BM for further optimizing polymer solar cells.

  11. Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

    Institute of Scientific and Technical Information of China (English)

    Yuxiang Li; Seyeong Song; Song Yi Park; Jin Young Kim; Han Young Woo

    2017-01-01

    Three types of semi-crystalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents.A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra-and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization.The resulting polymers formed strongly agglomerated films with high roughness,suggesting strong intermolecular interactions.The optical band gap of ca.1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking.With increasing the fluorine substituents,the frontier energy levels decreased and preferential face-on orientation was observed.The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing,showing well resolved lamellar scatterings up to (300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements.The PPsiDTBT,PPsiDTFBT and PPsiDT2FBT devices showed a power conversion efficiency of 3.16%,4.40% and 5.65%,respectively,by blending with PC71BM.Langevin-type bimolecular charge recombination was similar for three polymeric solar cells.The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density (Jsc) and open-circuit voltage (Voc).Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71BM for further optimizing polymer solar cells.

  12. Communication: Polarizable polymer chain under external electric field in a dilute polymer solution.

    Science.gov (United States)

    Budkov, Yu A; Kolesnikov, A L; Kiselev, M G

    2015-11-28

    We study the conformational behavior of polarizable polymer chain under an external homogeneous electric field within the Flory type self-consistent field theory. We consider the influence of electric field on the polymer coil as well as on the polymer globule. We show that when the polymer chain conformation is a coil, application of external electric field leads to its additional swelling. However, when the polymer conformation is a globule, a sufficiently strong field can induce a globule-coil transition. We show that such "field-induced" globule-coil transition at the sufficiently small monomer polarizabilities goes quite smoothly. On the contrary, when the monomer polarizability exceeds a certain threshold value, the globule-coil transition occurs as a dramatic expansion in the regime of first-order phase transition. The developed theoretical model can be applied to predicting polymer globule density change under external electric field in order to provide more efficient processes of polymer functionalization, such as sorption, dyeing, and chemical modification.

  13. Brownian dynamics simulations of a flexible polymer chain which includes continuous resistance and multibody hydrodynamic interactions

    Science.gov (United States)

    Butler, Jason E.; Shaqfeh, Eric S. G.

    2005-01-01

    Using methods adapted from the simulation of suspension dynamics, we have developed a Brownian dynamics algorithm with multibody hydrodynamic interactions for simulating the dynamics of polymer molecules. The polymer molecule is modeled as a chain composed of a series of inextensible, rigid rods with constraints at each joint to ensure continuity of the chain. The linear and rotational velocities of each segment of the polymer chain are described by the slender-body theory of Batchelor [J. Fluid Mech. 44, 419 (1970)]. To include hydrodynamic interactions between the segments of the chain, the line distribution of forces on each segment is approximated by making a Legendre polynomial expansion of the disturbance velocity on the segment, where the first two terms of the expansion are retained in the calculation. Thus, the resulting linear force distribution is specified by a center of mass force, couple, and stresslet on each segment. This method for calculating the hydrodynamic interactions has been successfully used to simulate the dynamics of noncolloidal suspensions of rigid fibers [O. G. Harlen, R. R. Sundararajakumar, and D. L. Koch, J. Fluid Mech. 388, 355 (1999); J. E. Butler and E. S. G. Shaqfeh, J. Fluid Mech. 468, 204 (2002)]. The longest relaxation time and center of mass diffusivity are among the quantities calculated with the simulation technique. Comparisons are made for different levels of approximation of the hydrodynamic interactions, including multibody interactions, two-body interactions, and the "freely draining" case with no interactions. For the short polymer chains studied in this paper, the results indicate a difference in the apparent scaling of diffusivity with polymer length for the multibody versus two-body level of approximation for the hydrodynamic interactions.

  14. Dynamical behavior of a single polymer chain under nanometric confinement

    Science.gov (United States)

    Lagrené, K.; Zanotti, J.-M.; Daoud, M.; Farago, B.; Judeinstein, P.

    2010-10-01

    We address the dynamical behavior of a single polymer chain under nanometric confinement. We consider a polymer melt made of a mixture of hydrogenated and deuterated high molecular mass Poly(Ethylene Oxide) (PEO). The confining material is a membrane of Anodic Aluminum Oxide (AAO), a macroscopically highly ordered confining system made of parallel cylindrical channels. We use Neutron Spin-Echo (NSE) under the Zero Average Contrast (ZAC) condition to, all at once, i) match the intense porous AAO detrimental elastic SANS (Small Angle Neutron Scattering) contribution to the total intermediate scattering function I(Q,t) and ii) measure the Q dependence of the dynamical modes of a single chain under confinement. The polymer dynamics is probed on an extremely broad spacial ([2.2 10-2 Å-1, 0.2 Å-1]) and temporal ([0.1 ns, 600 ns]) ranges. We do not detect any influence of confinement on the polymer dynamics. This result is discussed in the framework of the debate on the existence of a "corset effect" recently suggested by NMR relaxometry data.

  15. Investigations of model polymers: Dynamics of melts and statics of a long chain in a dilute melt of shorter chains

    International Nuclear Information System (INIS)

    Bishop, M.; Ceperley, D.; Frisch, H.L.; Kalos, M.H.

    1982-01-01

    We report additional results on a simple model of polymers, namely the diffusion in concentrated polymer systems and the static properties of one long chain in a dilute melt of shorter chains. It is found, for the polymer sizes and time scales amenable to our computer calculations, that there is as yet no evidence for a ''reptation'' regime in a melt. There is some indication of reptation in the case of a single chain moving through fixed obstacles. No statistically significant effect of the change, from excluded volume behavior of the long chain to ideal behavior as the shorter chains grow, is observed

  16. Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

    KAUST Repository

    Zhang, Hefeng

    2015-05-01

    We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b-polystyrenyllithium (PI-. b-PSLi), to the main chain and subsequently to the branches in a divergent way. PI segment is short and serves as a precursor for multifunctional branching unit. The grafting reaction involves two successive steps: i) epoxidation of internal double bonds of PI segments, either in main chain or side chains; ii) ring-opening addition to the resulting epoxy group by the living PI-. b-PSLi. Repeating the two steps affords a series of cylindrical polymer brushes with up to 3rd generation and extremely high molecular weight. The branching multiplicity depends on the average number of oxirane groups per PI segment, usually ca. 8 in the present work. The high branching multiplicity leads to tremendous increase in molecular weights of the cylindrical products with generation growth. Several series of cylindrical polymer brushes with tunable aspect ratios are prepared using backbones and branches with controlled lengths. Shape anisotropy is investigated in dilute solution using light scattering technique. Worm-like single molecular morphology with large persistence length is observed on different substrates by atomic force microscopy.

  17. Application of dimensional regularization to single chain polymer static properties: Conformational space renormalization of polymers. III

    International Nuclear Information System (INIS)

    Oono, Y.; Ohta, T.; Freed, K.F.

    1981-01-01

    A dimensional regularization approach to the renormalization group treatment of polymer excluded volume is formulated in chain conformation space where monomers are specified by their spatial positions and their positions along the chain and the polymers may be taken to be monodisperse. The method utilizes basic scale invariance considerations. First, it is recognized that long wavelength macroscopic descriptions must be well defined in the limit that the minimum atomic or molecular scale L is set to zero. Secondly, the microscopic theory is independent of the conveniently chosen macroscopic scale of length k. The freedom of choice of k is exploited along with the assumed renormalizability of the theory to provide the renormalization group equations which directly imply the universal scaling laws for macroscopic properties. The renormalizability of the model implies the existence of the general relations between the basic macroparameters, such as chain length, excluded volume, etc., and their microscopic counterparts in the microscopic model for the system. These macro--micro relations are defined through the condition that macroscopic quantities be well defined for polymer chains for any spatial dimensionality. The method is illustrated by calculating the end vector distribution function for all values of end vectors R. The evaluation of this distribution function currently requires the use of expansions in e = 4-d. In this case our distribution reduces to known limits for R→0 or infinity. Subsequent papers will present calculations of the polymer coherent scattering function, the monomer spatial distribution function, and concentration dependent properties

  18. Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

    Science.gov (United States)

    Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

    2011-05-21

    with an equal number of short and long grafts at low to medium grafting density, the short grafts are in a more coiled up conformation (lower radius of gyration) than their monodisperse counterparts to provide a larger free volume to the longer grafts so they can gain conformational entropy. The longer grafts do not show much difference in conformation from their monodisperse counterparts at low grafting density, but at medium grafting density the longer grafts exhibit less stretched conformations (lower radius of gyration) as compared to their monodisperse counterparts. In the presence of an explicit homopolymer matrix, the longer grafts are more compressed by the matrix homopolymer chains than the short grafts. We observe that the potential of mean force between bidisperse grafted particles has features of the PMF of monodisperse grafted particles with short grafts and monodisperse grafted particles with long grafts. The value of the PMF at contact is governed by the short grafts and values at large inter-particle distances are governed by the longer grafts. Further comparison of the PMF for bidisperse and monodisperse polymer grafted particles in a homopolymer matrix at varying parameters shows that the effects of matrix chain length, matrix packing fraction, grafting density, and particle curvature on the PMF between bidisperse polymer grafted particles are similar to those seen between monodisperse polymer grafted particles. © 2011 American Institute of Physics.

  19. Charge photogeneration and transport in side-chain carbazole polymers and co-polymers

    KAUST Repository

    Li, Huawei; Termine, Roberto; Godbert, Nicolas; Angiolini, Luigi; Giorgini, Loris; Golemme, Attilio

    2011-01-01

    The photoconductivity, hole mobility and charge photogeneration efficiency of a series of side-chain carbazole homopolymers and copolymers (with azo side-chains) have been investigated. Cyclic voltammetry measurement of frontier orbitals energies show that the HOMO energy is determined by the nature and the position of attachment of the linker between the main chain and the carbazole, the azo-moiety being not relevant in this respect. Hole mobility is not influenced by the HOMO energy but seems to depend on the degree of conformational mobility of the side-chains, reaching values of the order of 10-3cm2V-1s-1 in the best cases. The HOMO energy is instead extremely important when considering photogeneration efficiency, that can change by 10 orders of magnitude depending on the density of the carbazole side-chains in co-polymers and on the linker nature and attachment position. © 2011 Elsevier B.V. All rights reserved.

  20. Charge photogeneration and transport in side-chain carbazole polymers and co-polymers

    KAUST Repository

    Li, Huawei

    2011-07-01

    The photoconductivity, hole mobility and charge photogeneration efficiency of a series of side-chain carbazole homopolymers and copolymers (with azo side-chains) have been investigated. Cyclic voltammetry measurement of frontier orbitals energies show that the HOMO energy is determined by the nature and the position of attachment of the linker between the main chain and the carbazole, the azo-moiety being not relevant in this respect. Hole mobility is not influenced by the HOMO energy but seems to depend on the degree of conformational mobility of the side-chains, reaching values of the order of 10-3cm2V-1s-1 in the best cases. The HOMO energy is instead extremely important when considering photogeneration efficiency, that can change by 10 orders of magnitude depending on the density of the carbazole side-chains in co-polymers and on the linker nature and attachment position. © 2011 Elsevier B.V. All rights reserved.

  1. On the chain length dependence of local correlations in polymer melts and a perturbation theory of symmetric polymer blends.

    Science.gov (United States)

    Morse, David C; Chung, Jun Kyung

    2009-06-14

    The self-consistent field (SCF) approach to the thermodynamics of dense polymer liquids is based on the idea that short-range correlations in a polymer liquid are almost independent of how monomers are connected into polymers over larger scales. Some limits of this idea are explored in the context of a perturbation theory for symmetric polymer blends. We consider mixtures of two structurally identical polymers, A and B, in which the AB monomer pair interaction differs slightly from the AA and BB interactions by an amount proportional to a parameter alpha. An expansion of the free energy to first order in alpha yields an excess free energy of mixing per monomer of the form alphaz(N)phi(A)phi(B) in both lattice and continuum models, where z(N) is a measure of the number of intermolecular near neighbors per monomer in a one-component (alpha=0) reference liquid with chains of length N. The quantity z(N) decreases slightly with increasing N because the concentration of intramolecular near neighbors is slightly higher for longer chains, creating a slightly deeper intermolecular correlation hole. We predict that z(N)=z(infinity)[1+betaN(-1/2)], where N is an invariant degree of polymerization and beta=(6/pi)(3/2) is a universal coefficient. This and related predictions about the slight N dependence of local correlations are confirmed by comparison to simulations of a continuum bead-spring model and to published lattice Monte Carlo simulations. We show that a renormalized one-loop theory for blends correctly describes this N dependence of local liquid structure. We also propose a way to estimate the effective interaction parameter appropriate for comparisons of simulation data to SCF theory and to coarse-grained theories of corrections to SCF theory, which is based on an extrapolation of perturbation theory to the limit N-->infinity.

  2. SANS study of polymer chains in confined space

    International Nuclear Information System (INIS)

    Hasegawa, Hirokazu; Tanaka, Hideaki; Hashimoto, Takeji; Han, C.C.

    1993-01-01

    The lateral and vertical components of the radius of gyration for a single block copolymer chain in the lamellar microdomain space formed by a mixture of diblock copolymers and homopolymers were investigated by means of small-angle neutron scattering (SANS), and the microdomain structures by small-angle X-ray scattering (SAXS). We used the homopolymers whose molecular weights are much smaller than that of the corresponding chains of the block copolymers so that the homopolymers are uniformly solubilized in the corresponding microdomains. The SANS result suggests that the block copolymer chains in the microdomain space are more compressed in the direction parallel to the interface and more stretched in the direction perpendicular to the interface than the corresponding unperturbed polymer chains with the same molecular weight. With increasing the volume fraction of the homopolymers the thickness of the lamellar microdomains increases. The block copolymer chains were found to undergo an isochoric affine deformation on addition of the homopolymers or with the change of the thickness of the lamellar microdomains. (author)

  3. Additive manufacturing of short and mixed fibre-reinforced polymer

    Science.gov (United States)

    Lewicki, James; Duoss, Eric B.; Rodriguez, Jennifer Nicole; Worsley, Marcus A.; King, Michael J.

    2018-01-09

    Additive manufacturing of a fiber-reinforced polymer (FRP) product using an additive manufacturing print head; a reservoir in the additive manufacturing print head; short carbon fibers in the reservoir, wherein the short carbon fibers are randomly aligned in the reservoir; an acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin in the reservoir, wherein the short carbon fibers are dispersed in the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin; a tapered nozzle in the additive manufacturing print head operatively connected to the reservoir, the tapered nozzle produces an extruded material that forms the fiber-reinforced polymer product; baffles in the tapered nozzle that receive the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin with the short carbon fibers dispersed in the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin; and a system for driving the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin with the short carbon fibers dispersed in the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin from the reservoir through the tapered nozzle wherein the randomly aligned short carbon fibers in the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin are aligned by the baffles and wherein the extruded material has the short carbon fibers aligned in the acrylate, methacrylate, epoxy, cyanate ester or isocyanate resin that forms the fiber-reinforced polymer product.

  4. Flow boundary conditions for chain-end adsorbing polymer blends.

    Science.gov (United States)

    Zhou, Xin; Andrienko, Denis; Delle Site, Luigi; Kremer, Kurt

    2005-09-08

    Using the phenol-terminated polycarbonate blend as an example, we demonstrate that the hydrodynamic boundary conditions for a flow of an adsorbing polymer melt are extremely sensitive to the structure of the epitaxial layer. Under shear, the adsorbed parts (chain ends) of the polymer melt move along the equipotential lines of the surface potential whereas the adsorbed additives serve as the surface defects. In response to the increase of the number of the adsorbed additives the surface layer becomes thinner and solidifies. This results in a gradual transition from the slip to the no-slip boundary condition for the melt flow, with a nonmonotonic dependence of the slip length on the surface concentration of the adsorbed ends.

  5. Amphiphilic polymer based on fluoroalkyl and PEG side chains for fouling release coating

    Science.gov (United States)

    Cong, W. W.; Wang, K.; Yu, X. Y.; Zhang, H. Q.; Lv, Z.; Gui, T. J.

    2017-12-01

    Under static conditions, fouling release coating could not express good release property to marine organisms. Amphiphilic polymer with mixture of fluorinated monomer and short side group of polyethylene glycol (PEG) was synthesized. And also we studied the ability of amphiphilic polymer to influence the surface properties and how it controlled the adhesion of marine organisms to coated surfaces. By incorporating fluorinated monomer and PEG side chain into the polymer, the effect of incorporating both polar and non-polar groups on fouling-release coating could be studied. The dry surface was characterized by three-dimensional digital microscopy and scanning electron microscopy (SEM), and the morphology of the amphiphilic fouling release coating showed just like flaky petal. The amphiphilic polymer in fouling release coating tended to reconstruct in water, and the ability was examined by static contact angle, which was smaller than the PDMS (polydimethylsiloxane) fouling release coating. Also surface energy was calculated by three solvents, and surface energy of amphiphilic fouling release coating was higher than that of the PDMS fouling release coating. To understand more about its fouling release property, seawater exposure method was adopted in gulf of Qingdao port. Fewer diatoms Navicula were found in biofilm after using amphiphilic fouling release coating. In general, coating containing both PEG and fluorinated side chain possessed certain fouling release property.

  6. Polymer Chain Dynamics in a Random Environment: Heterogeneous Mobilities

    International Nuclear Information System (INIS)

    Niedzwiedz, K.; Wischnewski, A.; Monkenbusch, M.; Richter, D.; Strauch, M.; Straube, E.; Genix, A.-C.; Arbe, A.; Colmenero, J.

    2007-01-01

    We present a neutron scattering investigation on a miscible blend of two polymers with greatly different glass-transition temperatures T g . Under such conditions, the nearly frozen high-T g component imposes a random environment on the mobile chain. The results demand the consideration of a distribution of heterogeneous mobilities in the material and demonstrate that the larger scale dynamics of the fast component is not determined by the average local environment alone. This distribution of mobilities can be mapped quantitatively on the spectrum of local relaxation rates measured at high momentum transfers

  7. Enhancement of Short Chain Fatty Acid Production from Millet Fibres ...

    African Journals Online (AJOL)

    Pharmacotherapy Group, Faculty of Pharmacy, University of Benin, Benin City, 300001 Nigeria. ... Methods: The effect of millet dietary fibre fermentation on production of short chain fatty ... fildes PYF enrichment solution was used as the .... where Pa is the peak area of SCFA, Ps is the ..... enzymatic- gravimetric method.

  8. Structure factor of polymers interacting via a short range repulsive potential: Application to hairy wormlike micelles

    International Nuclear Information System (INIS)

    Massiera, Gladys; Ramos, Laurence; Ligoure, Christian; Pitard, Estelle

    2003-01-01

    We use the random phase approximation to compute the structure factor S(q) of a solution of chains interacting through a soft and short range repulsive potential V. Above a threshold polymer concentration, whose magnitude is essentially controlled by the range of the potential, S(q) exhibits a peak whose position depends on the concentration. We take advantage of the close analogy between polymers and wormlike micelles and apply our model, using a Gaussian function for V, to quantitatively analyze experimental small angle neutron scattering profiles of solutions of hairy wormlike micelles. These samples, which consist in surfactant self-assembled flexible cylinders decorated by amphiphilic copolymer, provide indeed an appropriate experimental model system to study the structure of sterically interacting polymer solutions

  9. A targeted metabolomic protocol for short-chain fatty acids and branched-chain amino acids

    OpenAIRE

    Zheng, Xiaojiao; Qiu, Yunping; Zhong, Wei; Baxter, Sarah; Su, Mingming; Li, Qiong; Xie, Guoxiang; Ore, Brandon M.; Qiao, Shanlei; Spencer, Melanie D.; Zeisel, Steven H.; Zhou, Zhanxiang; Zhao, Aihua; Jia, Wei

    2013-01-01

    Research in obesity and metabolic disorders that involve intestinal microbiota demands reliable methods for the precise measurement of the short-chain fatty acids (SCFAs) and branched-chain amino acids (BCAAs) concentration. Here, we report a rapid method of simultaneously determining SCFAs and BCAAs in biological samples using propyl chloroformate (PCF) derivatization followed by gas chromatography mass spectrometry (GC-MS) analysis. A one-step derivatization using 100 µL of PCF in a reactio...

  10. DMFC Performance of Polymer Electrolyte Membranes Prepared from a Graft-Copolymer Consisting of a Polysulfone Main Chain and Styrene Sulfonic Acid Side Chains

    Directory of Open Access Journals (Sweden)

    Nobutaka Endo

    2016-08-01

    Full Text Available Polymer electrolyte membranes (PEMs for direct methanol fuel cell (DMFC applications were prepared from a graft-copolymer (PSF-g-PSSA consisting of a polysulfone (PSF main chain and poly(styrene sulfonic acid (PSSA side chains with various average distances between side chains (Lav and side chain lengths (Lsc. The polymers were synthesized by grafting ethyl p-styrenesulfonate (EtSS on macro-initiators of chloromethylated polysulfone with different contents of chloromethyl (CM groups, and by changing EtSS content in the copolymers by using atom transfer radical polymerization (ATRP. The DMFC performance tests using membrane electrode assemblis (MEAs with the three types of the PEMs revealed that: a PSF-g-PSSA PEM (SF-6 prepared from a graft copolymer with short average distances between side chains (Lav and medium Lsc had higher DMFC performance than PEMs with long Lav and long Lsc or with short Lav and short Lsc. SF-6 had about two times higher PDmax (68.4 mW/cm2 than Nafion® 112 at 30 wt % of methanol concentration. Furthermore, it had 58.2 mW/cm2 of PDmax at 50 wt % of methanol concentration because of it has the highest proton selectivity during DMFC operation of all the PSF-g-PSSA PEMs and Nafion® 112.

  11. Surface relief gratings: experiments, physical scenarios, and photoinduced (anomalous) dynamics of functionalized polymer chains

    Science.gov (United States)

    Mitus, A. C.; Radosz, W.; Wysoczanski, T.; Pawlik, G.

    2017-10-01

    Surface Relief Gratings (SRG) were demonstrated experimentally more than 20 years ago. Despite many years of research efforts the underlying physical mechanisms remain unclear. In this paper we present a short overview of the main concepts related to SRG - photofluidization and its counterpart, the orientational approach - based on a seminal paper by Saphiannikova et al. Next, we summarize the derivation of the cos2 θ potential, following the lines of recent paper of this group. Those results validate the generic Monte Carlo model for the photoinduced build-up of the density and SRG gratings in a model polymer matrix functionalized with azo-dyes, presented in another part of the paper. The characterization of the photoinduced motion of polymer chains, based on our recent paper, is briefly discussed in the last part of the paper. This discussion offers a sound insight into the mechanisms responsible for inscription of SRG as well as for single functionalized nanoparticle studies.

  12. Quantifying Short-Chain Chlorinated Paraffin Congener Groups.

    Science.gov (United States)

    Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A; Alsberg, Tomas; de Wit, Cynthia A

    2017-09-19

    Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a "congener group" C n Cl m . Recently, we resolved individual C n Cl m by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying C n Cl m by introducing C n Cl m specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each C n Cl m are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were -0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. C n Cl m concentrations determined with the three instruments were highly correlated (R 2 > 0.90) with each other.

  13. Reduced viscosity for flagella moving in a solution of long polymer chains

    Science.gov (United States)

    Zhang, Yuchen; Li, Gaojin; Ardekani, Arezoo M.

    2018-02-01

    The bacterial flagellum thickness is smaller than the radius of gyration of long polymer chain molecules. The flow velocity gradient over the length of polymer chains can be nonuniform and continuum models of polymeric liquids break in this limit. In this work, we use Brownian dynamics simulations to study a rotating helical flagellum in a polymer solution and overcome this limitation. As the polymer size increases, the viscosity experienced by the flagellum asymptotically reduces to the solvent viscosity. The contribution of polymer molecules to the local viscosity in a solution of long polymer chains decreases with the inverse of polymer size to the power 1/2. The difference in viscosity experienced by the bacterial cell body and flagella can predict the nonmonotonic swimming speed of bacteria in polymer solutions.

  14. Interplay Between Side Chain Pattern, Polymer Aggregation, and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk-Heterojunction Solar Cells

    KAUST Repository

    Dyer-Smith, Clare

    2015-05-01

    Poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors with linear side-chains yield bulk-heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor, while a PBDTTPD polymer with a combination of branched and linear substituents yields a doubling of the PCE to 8%. Using transient optical spectroscopy it is shown that while the exciton dissociation and ultrafast charge generation steps are not strongly affected by the side chain modifications, the polymer with branched side chains exhibits a decreased rate of nongeminate recombination and a lower fraction of sub-nanosecond geminate recombination. In turn the yield of long-lived charge carriers increases, resulting in a 33% increase in short circuit current (J sc). In parallel, the two polymers show distinct grazing incidence X-ray scattering spectra indicative of the presence of stacks with different orientation patterns in optimized thin-film BHJ devices. Independent of the packing pattern the spectroscopic data also reveals the existence of polymer aggregates in the pristine polymer films as well as in both blends which trap excitons and hinder their dissociation.

  15. Effects of short-chain chlorinated paraffins on soil organisms.

    Science.gov (United States)

    Bezchlebová, Jitka; Cernohlávková, Jitka; Kobeticová, Klára; Lána, Jan; Sochová, Ivana; Hofman, Jakub

    2007-06-01

    Despite the fact that chlorinated paraffins have been produced in relatively large amounts, and high concentrations have been found in sewage sludge applied to soils, there is little information on their concentrations in soils and the effect on soil organisms. The aim of this study was to investigate the toxicity of chlorinated paraffins in soils. The effects of short-chain chlorinated paraffins (64% chlorine content) on invertebrates (Eisenia fetida, Folsomia candida, Enchytraeus albidus, Enchytraeus crypticus, Caenorhabditis elegans) and substrate-induced respiration of indigenous microorganisms were studied. Differences were found in the sensitivity of the tested organisms to short-chain chlorinated paraffins. F. candida was identified as the most sensitive organism with LC(50) and EC(50) values of 5733 and 1230 mg/kg, respectively. Toxicity results were compared with available studies and the predicted no effect concentration (PNEC) of 5.28 mg/kg was estimated for the soil environment, based on our data.

  16. Histone Deacetylase Inhibition and Dietary Short-Chain Fatty Acids

    OpenAIRE

    Licciardi, Paul V.; Ververis, Katherine; Karagiannis, Tom C.

    2011-01-01

    Changes in diet can also have dramatic effects on the composition of gut microbiota. Commensal bacteria of the gastrointestinal tract are critical regulators of health and disease by protecting against pathogen encounter whilst also maintaining immune tolerance to certain allergens. Moreover, consumption of fibre and vegetables typical of a non-Western diet generates substantial quantities of short-chain fatty acids (SCFAs) which have potent anti-inflammatory properties. Dietary interventions...

  17. Biodiesel production from triolein and short chain alcohols through biocatalysis.

    Science.gov (United States)

    Salis, Andrea; Pinna, Marcella; Monduzzi, Maura; Solinas, Vincenzo

    2005-09-29

    Oleic acid alkyl esters (biodiesel) were synthesised by biocatalysis in solvent-free conditions. Different commercial immobilised lipases, namely Candida antarctica B, Rizhomucor miehei, and Pseudomonas cepacia, were tested towards the reaction between triolein and butanol to produce butyl oleate. Pseudomonas cepacia lipase resulted to be the most active enzyme reaching 100% of conversion after 6h. Different operative conditions such as reaction temperature, water activity, and reagent stoichiometric ratio were investigated and optimised. These conditions were then used to investigate the effect of linear and branched short chain alcohols. Methanol and 2-butanol were the worst alcohols: the former, probably, due to its low miscibility with the oil and the latter because secondary alcohols usually are less reactive than primary alcohols. Conversely, linear and branched primary alcohols with short alkyl chains (C(2)--C(4)) showed high reaction rate and conversion. A mixture of linear and branched short chain alcohols that mimics the residual of ethanol distillation (fusel oil) was successfully used for oleic acid ester synthesis. These compounds are important in biodiesel mixtures since they improve low temperature properties.

  18. Stretching of a polymer chain anchored to a surface: the massive field theory approach

    International Nuclear Information System (INIS)

    Usatenko, Zoryana

    2014-01-01

    Taking into account the well-known correspondence between the field theoretical φ 4 O(n)-vector model in the limit n → 0 and the behaviour of long-flexible polymer chains, the investigation of stretching of an ideal and a real polymer chain with excluded volume interactions in a good solvent anchored to repulsive and inert surfaces is performed. The calculations of the average stretching force which arises when the free end of a polymer chain moves away from a repulsive or inert surface are performed up to one-loop order of the massive field theory approach in fixed space dimensions d = 3. The analysis of the obtained results indicates that the average stretching force for a real polymer chain anchored to a repulsive surface demonstrates different behaviour for the cases z-tilde ≪1 and z-tilde ≫1, where z-tilde =z ′ /R z . Besides, the results obtained in the framework of the massive field theory approach are in good agreement with previous theoretical results for an ideal polymer chain and results of a density functional theory approach for the region of small applied forces when deformation of a polymer chain in the direction of the applied force is not bigger than the linear extension of a polymer chain in this direction. The better agreement between these two methods is observed in the case where the number of monomers increases and the polymer chain becomes longer. (paper)

  19. Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain nder critical conditions

    NARCIS (Netherlands)

    Skvortsov, A.M.; Leermakers, F.A.M.; Fleer, G.J.

    2013-01-01

    In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of

  20. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui

    2013-06-26

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  1. Entanglement of conjugated polymer chains influences molecular self-assembly and carrier transport

    KAUST Repository

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Su, Yisong; Amassian, Aram

    2013-01-01

    The influence of polymer entanglement on the self-assembly, molecular packing structure, and microstructure of low-Mw (lightly entangled) and high-Mw (highly entangled) poly (3-hexylthiophene) (P3HT), and the carrier transport in thin-film transistors, are investigated. The polymer chains are gradually disentangled in a marginal solvent via ultrasonication of the polymer solution, and demonstrate improved diffusivity of precursor species (coils, aggregates, and microcrystallites), enhanced nucleation and crystallization of P3HT in solution, and self-assembly of well-ordered and highly textured fibrils at the solid-liquid interface. In low-Mw P3HT, reducing chain entanglement enhances interchain and intrachain ordering, but reduces the interconnectivity of ordered domains (tie molecules) due to the presence of short chains, thus deteriorating carrier transport even in the face of improving crystallinity. Reducing chain entanglement in high-Mw P3HT solutions increases carrier mobility up to ≈20-fold, by enhancing interchain and intrachain ordering while maintaining a sufficiently large number of tie molecules between ordered domains. These results indicate that charge carrier mobility is strongly governed by the balancing of intrachain and interchain ordering, on the one hand, and interconnectivity of ordered domains, on the other hand. In high-Mw P3HT, intrachain and interchain ordering appear to be the key bottlenecks to charge transport, whereas in low-Mw P3HT, the limited interconnectivity of the ordered domains acts as the primary bottleneck to charge transport. Conjugated polymer chains of poly(3-hexylthiophene) (P3HT) are gradually disentangled in solution and trends in carrier transport mechanisms in organic thin film transistors for low- and high-molecular weight P3HT are investigated. While intrachain and interchain ordering within ordered domains are the key bottlenecks to charge transport in high-Mw P3HT films, the limited interconnectivity of ordered

  2. Flory-type theories of polymer chains under different external stimuli

    Science.gov (United States)

    Budkov, Yu A.; Kiselev, M. G.

    2018-01-01

    In this Review, we present a critical analysis of various applications of the Flory-type theories to a theoretical description of the conformational behavior of single polymer chains in dilute polymer solutions under a few external stimuli. Different theoretical models of flexible polymer chains in the supercritical fluid are discussed and analysed. Different points of view on the conformational behavior of the polymer chain near the liquid-gas transition critical point of the solvent are presented. A theoretical description of the co-solvent-induced coil-globule transitions within the implicit-solvent-explicit-co-solvent models is discussed. Several explicit-solvent-explicit-co-solvent theoretical models of the coil-to-globule-to-coil transition of the polymer chain in a mixture of good solvents (co-nonsolvency) are analysed and compared with each other. Finally, a new theoretical model of the conformational behavior of the dielectric polymer chain under the external constant electric field in the dilute polymer solution with an explicit account for the many-body dipole correlations is discussed. The polymer chain collapse induced by many-body dipole correlations of monomers in the context of statistical thermodynamics of dielectric polymers is analysed.

  3. Equivalence of chain conformations in the surface region of a polymer melt and a single Gaussian chain under critical conditions.

    Science.gov (United States)

    Skvortsov, A M; Leermakers, F A M; Fleer, G J

    2013-08-07

    In the melt polymer conformations are nearly ideal according to Flory's ideality hypothesis. Silberberg generalized this statement for chains in the interfacial region. We check the Silberberg argument by analyzing the conformations of a probe chain end-grafted at a solid surface in a sea of floating free chains of concentration φ by the self-consistent field (SCF) method. Apart from the grafting, probe chain and floating chains are identical. Most of the results were obtained for a standard SCF model with freely jointed chains on a six-choice lattice, where immediate step reversals are allowed. A few data were generated for a five-choice lattice, where such step reversals are forbidden. These coarse-grained models describe the equilibrium properties of flexible atactic polymer chains at the scale of the segment length. The concentration was varied over the whole range from φ = 0 (single grafted chain) to φ = 1 (probe chain in the melt). The number of contacts with the surface, average height of the free end and its dispersion, average loop and train length, tail size distribution, end-point and overall segment distributions were calculated for a grafted probe chain as a function of φ, for several chain lengths and substrate∕polymer interactions, which were varied from strong repulsion to strong adsorption. The computations show that the conformations of the probe chain in the melt do not depend on substrate∕polymer interactions and are very similar to the conformations of a single end-grafted chain under critical conditions, and can thus be described analytically. When the substrate∕polymer interaction is fixed at the value corresponding to critical conditions, all equilibrium properties of a probe chain are independent of φ, over the whole range from a dilute solution to the melt. We believe that the conformations of all flexible chains in the surface region of the melt are close to those of an appropriate single chain in critical conditions, provided

  4. Fine-tuning blend morphology via alkylthio side chain engineering towards high performance non-fullerene polymer solar cells

    Science.gov (United States)

    Li, Ling; Feng, Liuliu; Yuan, Jun; Peng, Hongjian; Zou, Yingping; Li, Yongfang

    2018-03-01

    Two medium bandgap polymers (ffQx-TS1, ffQx-TS2) were designed and synthesized to investigate the influence of different alkylthio side chain on the morphology and photovoltaic performance of non-fullerene polymer solar cells (PSCs). Both polymers exhibit similar molecular weights and comparable the highest occupied molecular orbital (HOMO) energy level. However, the polymer with straight alkylthio chain delivers a root-mean-square (RMS) of 0.86 nm, which is slightly lower than that with branched chain (1.40 nm). The lower RMS benefits the ohmic contact between the active lay and interface layer, thus enhanced short circuit current (Jsc) (from 13.54 mA cm-1 to 15.25 mA cm-1) could be obtained. Due to the enhancement of Jsc, better power conversion efficiency (PCE) of 7.69% for ffQx-TS2 could be realized. These results indicated that alkylthio side chain engineering is a promising method to improve photovoltaic performance.

  5. Evaporation Kinetics in Short-Chain Alcohols by Optical Interference

    Science.gov (United States)

    Rosbrugh, Ian M.; Nishimura, S. Y.; Nishimura, A. M.

    2000-08-01

    The evaporation rates of volatile organic liquids may be determined through the observation of optical interference of spatially coincident light that is reflected from the top (air-liquid) and bottom (liquid-surface) of a liquid drop on a glass surface. As an example of what is possible with this technique, the evaporation for a series of short-chain alcohols and acetone was investigated. For 1-propanol, 2-propanol, 2-methyl-1-propanol, and acetone, the kinetics of evaporation was determined to be zero order. For methanol and ethanol, the process was significantly higher than zero order.

  6. Glycogen with short average chain length enhances bacterial durability

    Science.gov (United States)

    Wang, Liang; Wise, Michael J.

    2011-09-01

    Glycogen is conventionally viewed as an energy reserve that can be rapidly mobilized for ATP production in higher organisms. However, several studies have noted that glycogen with short average chain length in some bacteria is degraded very slowly. In addition, slow utilization of glycogen is correlated with bacterial viability, that is, the slower the glycogen breakdown rate, the longer the bacterial survival time in the external environment under starvation conditions. We call that a durable energy storage mechanism (DESM). In this review, evidence from microbiology, biochemistry, and molecular biology will be assembled to support the hypothesis of glycogen as a durable energy storage compound. One method for testing the DESM hypothesis is proposed.

  7. Phase separation in short-chain lecithin/gel-state long-chain lecithin aggregates

    International Nuclear Information System (INIS)

    Bian, J.; Roberts, M.F.

    1990-01-01

    Small bilayer particles for spontaneously from gel-state long-chain phospholipids such as dipalmitoylphosphatidylcholine and 0.2 mol fraction short-chain lecithins (e.g., diheptanoylphosphatidylcholine). When the particles are incubed at temperatures greater than the T m of the long-chain phosphatidylcholine (PC), the particles rapidly fuse (from 90-angstrom to ≥ 5,000-angstrom radius); this transition is reversible. A possible explanation for this behavior involves patching or phase separation of the short-chain component within the gel-state particle and randomization of both lipid species above T m . Differential scanning calorimetry, 1 H T 1 values of proteodiheptanoyl-PC in diheptanoyl-PC-d 26 /dipalmitoyl-PC-d 62 matrices of varying deuterium content, solid-state 2 H NMR spectroscopy as a function of temperature, and fluorescence pyrene excimer-to-monomer ratios as a function of mole fraction diheptanoyl-PC provide evidence that such phase separation must occur. These results are used to construct a phase diagram for the diheptanoyl-PC/dipalmitoyl-PC system, to propose detailed geometric models for the different lipid particles involved, and to understand phospholipase kinetics toward the different aggregates

  8. SUSTAINABILITY OF SHORT FOOD SUPPLY CHAINS: ANALYSIS OF RAW MATERIAL SUPPLY IN MILAN PUBLIC SCHOOL CATERING

    Directory of Open Access Journals (Sweden)

    G. D’Anna

    2009-09-01

    Full Text Available The demand of short food supply chains is becoming more pressing by consumers, especially in the largest school catering. The implementation of the short chain in a large catering company of Milan, is described in this practical contribution. Several aspects of short food chains sustainability: legal, commercial and economic sustainability, hygienic and gastronomic sustainability, are discussed.

  9. Effect of backbone structure on charge transport along isolated conjugated polymer chains

    International Nuclear Information System (INIS)

    Siebbeles, Laurens D.A.; Grozema, Ferdinand C.; Haas, Matthijs P. de; Warman, John M.

    2005-01-01

    Fast charge transport in conjugated polymers is essential for their application in opto-electronic devices. In the present paper, measurements and theoretical modeling of the mobility of excess charges along isolated chains of conjugated polymers in dilute solution are presented. Charge carriers were produced by irradiation of the polymer solution with 3-MeV electrons from a Van de Graaff accelerator. The mobilities of the charges along the polymer chains were obtained from time-resolved microwave conductivity measurements. The mobilities are strongly dependent on the chemical nature of the polymer backbone. Comparison of the experimental data with results from ab initio quantum mechanical calculations shows that the measured mobilities are strongly limited by torsional disorder, chemical defects and chain ends. Improvement of the structure of polymer backbones is therefore expected to significantly enhance the performance of these materials in 'plastic electronics'

  10. Polymer chain alignment and transistor properties of nanochannel-templated poly(3-hexylthiophene) nanowires

    Science.gov (United States)

    Oh, Seungjun; Hayakawa, Ryoma; Pan, Chengjun; Sugiyasu, Kazunori; Wakayama, Yutaka

    2016-08-01

    Nanowires of semiconducting poly(3-hexylthiophene) (P3HT) were produced by a nanochannel-template technique. Polymer chain alignment in P3HT nanowires was investigated as a function of nanochannel widths (W) and polymer chain lengths (L). We found that the ratio between chain length and channel width (L/W) was a key parameter as regards promoting polymer chain alignment. Clear dichroism was observed in polarized ultraviolet-visible (UV-Vis) absorption spectra only at a ratio of approximately L/W = 2, indicating that the L/W ratio must be optimized to achieve uniaxial chain alignment in the nanochannel direction. We speculate that an appropriate L/W ratio is effective in confining the geometries and conformations of polymer chains. This discussion was supported by theoretical simulations based on molecular dynamics. That is, the geometry of the polymer chains, including the distance and tilting angles of the chains in relation to the nanochannel surface, was dominant in determining the longitudinal alignment along the nanochannels. Thus prepared highly aligned polymer nanowire is advantageous for electrical carrier transport and has great potential for improving the device performance of field-effect transistors. In fact, a one-order improvement in carrier mobility was observed in a P3HT nanowire transistor.

  11. Molecular dynamics simulation of AFM studies of a single polymer chain

    International Nuclear Information System (INIS)

    Wang Wenhai; Kistler, Kurt A.; Sadeghipour, Keya; Baran, George

    2008-01-01

    Single polymer chain force-extension behavior measured by Atomic Force Microscopy (AFM) was interpreted by molecular dynamics (MD) simulation performed by applying a bead-spring (coarse-graining) model in which the bond potential function between adjacent beads is described by a worm-like chain (WLC) model. Simulation results indicate that caution should be applied when interpreting experimental AFM data, because the data vary depending on the point of AFM tip-polymer chain attachment. This approach offers an effective way for eventual analysis of the mechanical behavior of complex polymer networks

  12. Molecular dynamics simulation of AFM studies of a single polymer chain

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wenhai [Center for Bioengineering and Biomaterials, College of Engineering, Temple University, 1947 N. 12th Street, Philadelphia, PA 19122 (United States); Kistler, Kurt A. [Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, PA 19122 (United States); Sadeghipour, Keya [Center for Bioengineering and Biomaterials, College of Engineering, Temple University, 1947 N. 12th Street, Philadelphia, PA 19122 (United States); Baran, George [Center for Bioengineering and Biomaterials, College of Engineering, Temple University, 1947 N. 12th Street, Philadelphia, PA 19122 (United States)], E-mail: grbaran@temple.edu

    2008-11-24

    Single polymer chain force-extension behavior measured by Atomic Force Microscopy (AFM) was interpreted by molecular dynamics (MD) simulation performed by applying a bead-spring (coarse-graining) model in which the bond potential function between adjacent beads is described by a worm-like chain (WLC) model. Simulation results indicate that caution should be applied when interpreting experimental AFM data, because the data vary depending on the point of AFM tip-polymer chain attachment. This approach offers an effective way for eventual analysis of the mechanical behavior of complex polymer networks.

  13. Enzymatic hydrolysis of short-chain lecithin/long-chain phospholipid unilamellar vesicles: sensitivity of phospholipases to matrix phase state.

    Science.gov (United States)

    Gabriel, N E; Agman, N V; Roberts, M F

    1987-11-17

    Short-chain lecithin/long-chain phospholipid unilamellar vesicles (SLUVs), unlike pure long-chain lecithin vesicles, are excellent substrates for water-soluble phospholipases. Hemolysis assays show that greater than 99.5% of the short-chain lecithin is partitioned in the bilayer. In these binary component vesicles, the short-chain species is the preferred substrate, while the long-chain phospholipid can be treated as an inhibitor (phospholipase C) or poor substrate (phospholipase A2). For phospholipase C Bacillus cereus, apparent Km and Vmax values show that bilayer-solubilized diheptanoylphosphatidylcholine (diheptanoyl-PC) is nearly as good a substrate as pure micellar diheptanoyl-PC, although the extent of short-chain lecithin hydrolysis depends on the phase state of the long-chain lipid. For phospholipase A2 Naja naja naja, both Km and Vmax values show a greater range: in a gel-state matrix, diheptanoyl-PC is hydrolyzed with micellelike kinetic parameters; in a liquid-crystalline matrix, the short-chain lecithin becomes comparable to the long-chain component. Both enzymes also show an anomalous increase in specific activity toward diheptanoyl-PC around the phase transition temperature of the long-chain phospholipid. Since the short-chain lecithin does not exhibit a phase transition, this must reflect fluctuations in head-group area or vertical motions of the short-chain lecithin caused by surrounding long-chain lecithin molecules. These results are discussed in terms of a specific model for SLUV hydrolysis and a general explanation for the "interfacial activation" observed with water-soluble phospholipases.

  14. Single-molecule study on polymer diffusion in a melt state: Effect of chain topology

    KAUST Repository

    Habuchi, Satoshi; Fujiwara, Susumu; Yamamoto, Takuya; Vá cha, Martin; Tezuka, Yasuyuki

    2013-01-01

    We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction. © 2013 American Chemical Society.

  15. Single-molecule study on polymer diffusion in a melt state: Effect of chain topology

    KAUST Repository

    Habuchi, Satoshi

    2013-08-06

    We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction. © 2013 American Chemical Society.

  16. Specific heat study of quasi-one-dimensional antiferromagnetic model for an organic polymer chain

    International Nuclear Information System (INIS)

    Qu Shaohua; Zhu Lin

    2008-01-01

    The specific heat of an infinite one-dimensional polymer chain bearing periodically arranged side radicals connected to the even sites is studied by means of quantum transfer-matrix method based on a Ising-Heisenberg model. In the absence of the exchange interactions between side radicals and the main chain, the curves of specific heat show a round peak due to the antiferromagnetic excitations for the all antiferromagnetic interactions along the polymer chain. Considering the exchange interactions between the side radicals and the main chain, the curves of the specific heat show double-peak structure for ferromagnetic interactions between the radicals and main chain, indicating that a competition between ferromagnetic and antiferromagnetic interactions and the possibility of the occurrence of the stable ferrimagnetic state along the polymer chain

  17. Cylindrical polymer brushes with dendritic side chains by iterative anionic reactions

    KAUST Repository

    Zhang, Hefeng; Qu, Chengke; He, Junpo

    2015-01-01

    We report in this paper an easy method for the synthesis of cylindrical polymer brushes with dendritic side chains through anionic reaction. The synthesis is accomplished by iteratively grafting a living block copolymer, polyisoprene-. b

  18. Grafted polymers layers: neutral chains to charged chains; Couches de polymeres greffes: des chaines neutres aux chaines chargees

    Energy Technology Data Exchange (ETDEWEB)

    Mir, Y

    1995-09-29

    This work concerns an experimental study, by small angle neutrons scattering, of neutral or charged grafted polymers layers structures. The method consisted in exploiting the acknowledges got on neutral brushes, to reach the problem of grafted polyelectrolyte layers. The difficulty of charged layers making has been, until this day, an important obstacle to the experimental study of these systems. It has been partially resolved in the case of sodium sulfonate polystyrene layers, and allowed to study their structure. (N.C.). 72 refs., 74 figs., 24 tabs.

  19. Surface functionalization of quantum dots with fine-structured pH-sensitive phospholipid polymer chains.

    Science.gov (United States)

    Liu, Yihua; Inoue, Yuuki; Ishihara, Kazuhiko

    2015-11-01

    To add novel functionality to quantum dots (QDs), we synthesized water-soluble and pH-responsive block-type polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were composed of cytocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer segments, which contain a small fraction of active ester groups and can be used to conjugate biologically active compounds to the polymer, and pH-responsive poly(2-(N,N-diethylamino) ethyl methacrylate (DEAEMA)) segments. One terminal of the polymer chain had a hydrophobic alkyl group that originated from the RAFT initiator. This hydrophobic group can bind to the hydrophobic layer on the QD surface. A fluorescent dye was conjugated to the polymer chains via the active ester group. The block-type polymers have an amphiphilic nature in aqueous medium. The polymers were thus easily bound to the QD surface upon evaporation of the solvent from a solution containing the block-type polymer and QDs, yielding QD/fluorescence dye-conjugated polymer hybrid nanoparticles. Fluorescence resonance energy transfer (FRET) between the QDs (donors) and the fluorescent dye molecules (acceptors) was used to obtain information on the conformational dynamics of the immobilized polymers. Higher FRET efficiency of the QD/fluorescent dye-conjugated polymer hybrid nanoparticles was observed at pH 7.4 as compared to pH 5.0 due to a stretching-shrinking conformational motion of the poly(DEAEMA) segments in response to changes in pH. We concluded that the block-type MPC polymer-modified nanoparticles could be used to evaluate the pH of cells via FRET fluorescence based on the cytocompatibility of the MPC polymer. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. A possibility for generation of two species of charge carriers along main-chain and side-chains for a π-conjugated polymer

    International Nuclear Information System (INIS)

    Kudo, Yuki; Kawabata, Kohsuke; Goto, Hiromasa

    2013-01-01

    Iodide doping produces charge carriers in π-conjugated polymers. Solitons can be generated in the case of polyacetylene, and polarons in the case of aromatic-type conjugated polymers. We synthesized a conjugated main-chain/side-chain polymer, which consists of polyene in the main-chain and aromatic-type conjugated units in the side-chains. Based on the SSH (Su, Schrieffer, Heeger) theoretical model of solitons in one-dimensional conjugated polymers, we experimentally carried out chemical doping to the main-chain/side-chains conjugated polymer. Generation of the charge carriers was examined by electron spin resonance spectroscopy. This study may lead to realization of a dual doping system of solitons and polarons in π-conjugation expanded to two-dimensional directions in polymers.

  1. S2p core level spectroscopy of short chain oligothiophenes

    Science.gov (United States)

    Baseggio, O.; Toffoli, D.; Stener, M.; Fronzoni, G.; de Simone, M.; Grazioli, C.; Coreno, M.; Guarnaccio, A.; Santagata, A.; D'Auria, M.

    2017-12-01

    The Near-Edge X-ray-Absorption Fine-Structure (NEXAFS) and X-ray Photoemission Spectroscopy (XPS) of short-chain oligothiophenes (thiophene, 2,2'-bithiophene, and 2,2':5',2″-terthiophene) in the gas phase have been measured in the sulfur L2,3-edge region. The assignment of the spectral features is based on the relativistic two-component zeroth-order regular approximation time dependent density functional theory approach. The calculations allow us to estimate both the contribution of the spin-orbit splitting and of the molecular-field splitting to the sulfur binding energies and give results in good agreement with the experimental measurements. The deconvolution of the calculated S2p NEXAFS spectra into the two manifolds of excited states converging to the LIII and LII edges facilitates the attribution of the spectral structures. The main S2p NEXAFS features are preserved along the series both as concerns the energy positions and the nature of the transitions. This behaviour suggests that the electronic and geometrical environment of the sulfur atom in the three oligomers is relatively unaffected by the increasing chain length. This trend is also observed in the XPS spectra. The relatively simple structure of S2p NEXAFS spectra along the series reflects the localized nature of the virtual states involved in the core excitation process.

  2. Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization

    Directory of Open Access Journals (Sweden)

    Md. Masud Parvez

    2012-06-01

    Full Text Available Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylideneglycine tert-butyl ester.

  3. Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore

    Science.gov (United States)

    Wells, Craig C.; Melnikov, Dmitriy V.; Gracheva, Maria E.

    2017-08-01

    We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

  4. Well-defined single-chain polymer nanoparticles via thiol-Michael addition

    NARCIS (Netherlands)

    Kröger, A. Pia P.; Boonen, Roy J.E.A.; Paulusse, Jos M.J.

    2017-01-01

    A synthetic strategy has been developed giving facile access to well-defined single-chain polymer nanoparticles (SCNPs) from styrene-, acrylate- and methacrylate-based polymers. Random copolymers (polydispersity indices 1.10–1.15) of methyl (meth)acrylate, benzyl methacrylate or styrene containing

  5. Influence of polymer chain architecture of poly(vinyl alcohol) on the inhibition of ice recrystallization

    NARCIS (Netherlands)

    Olijve, L.L.C.; Hendrix, M.M.R.M.; Voets, I.K.

    2016-01-01

    Poly(vinyl alcohol) (PVA) is a water-soluble synthetic polymer well-known to effectively block the recrystallization of ice. The effect of polymer chain architecture on the ice recrystallization inhibition (IRI) by PVA remains unexplored. In this work, the synthesis of PVA molecular bottlebrushes is

  6. Real-time observation of conformational switching in single conjugated polymer chains.

    Science.gov (United States)

    Tenopala-Carmona, Francisco; Fronk, Stephanie; Bazan, Guillermo C; Samuel, Ifor D W; Penedo, J Carlos

    2018-02-01

    Conjugated polymers (CPs) are an important class of organic semiconductors that combine novel optoelectronic properties with simple processing from organic solvents. It is important to study CP conformation in solution to understand the physics of these materials and because it affects the properties of solution-processed films. Single-molecule techniques are unique in their ability to extract information on a chain-to-chain basis; however, in the context of CPs, technical challenges have limited their general application to host matrices or semiliquid environments that constrain the conformational dynamics of the polymer. We introduce a conceptually different methodology that enables measurements in organic solvents using the single-end anchoring of polymer chains to avoid diffusion while preserving polymer flexibility. We explore the effect of organic solvents and show that, in addition to chain-to-chain conformational heterogeneity, collapsed and extended polymer segments can coexist within the same chain. The technique enables real-time solvent-exchange measurements, which show that anchored CP chains respond to sudden changes in solvent conditions on a subsecond time scale. Our results give an unprecedented glimpse into the mechanism of solvent-induced reorganization of CPs and can be expected to lead to a new range of techniques to investigate and conformationally manipulate CPs.

  7. Capillary electrophoretic analysis of synthetic short-chain oligoribonucleotides.

    Science.gov (United States)

    Cellai, L; Onori, A M; Desiderio, C; Fanali, S

    1998-12-01

    Thirty synthetic oligoribonucleotides, 3 to 18 nucleotides (nt) long, were analyzed by capillary electrophoresis, under nondenaturing conditions, using a commercial kit. The migration time t(m) was dependent on nt length and composition, capillary length, operating temperature, and type of sieving polymer. Under fixed experimental conditions, the t(m) proved predictable by the equation: t(m) = [0.22(n-1) + 6.14A/n + 6.86G/n + 3.61 (C+U)/n] min, for n>3, where A/n, G/n, C/n, U/n is the frequency of each type of nt within the oligonucleotide (ONT). The equation accounts for the influence of charge-to-mass ratio on t(m), but not for structural effects, if present. This approximation is acceptable for short ONTs. The possibility of detecting n+1, n-1, n-2 impurities, having predicted the t(m), is of crucial importance in assessing the purity of synthetic ONTs dedicated to structural studies. This appears to be feasible. High resolution was shown among homologous series of ONTs of increasing length, and in some cases, even within groups of ONTs of the same length but different composition. The addition of 7 M urea to the buffer, as denaturing agent, accelerates the t(m) and significantly lowers the resolution for the shortest ONTs. It was also possible to monitor the state of association of mixtures of RNA and DNA sequence-complementary strands.

  8. Flow-induced correlation effects within a linear chain in a polymer melt

    NARCIS (Netherlands)

    Stepanyan, R.; Slot, J.J.M.; Molenaar, J.; Tchesnokov, M.A.

    2005-01-01

    A framework for a consistent description of the flow-induced correlation effects within a linear polymer chain in a melt is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The

  9. Restrictions in Model Reduction for Polymer Chain Models in Dissipative Particle Dynamics

    KAUST Repository

    Moreno Chaparro, Nicolas

    2014-06-06

    We model high molecular weight homopolymers in semidilute concentration via Dissipative Particle Dynamics (DPD). We show that in model reduction methodologies for polymers it is not enough to preserve system properties (i.e., density ρ, pressure p, temperature T, radial distribution function g(r)) but preserving also the characteristic shape and length scale of the polymer chain model is necessary. In this work we apply a DPD-model-reduction methodology for linear polymers recently proposed; and demonstrate why the applicability of this methodology is limited upto certain maximum polymer length, and not suitable for solvent coarse graining.

  10. Restrictions in Model Reduction for Polymer Chain Models in Dissipative Particle Dynamics

    KAUST Repository

    Moreno Chaparro, Nicolas; Nunes, Suzana Pereira; Calo, Victor M.

    2014-01-01

    We model high molecular weight homopolymers in semidilute concentration via Dissipative Particle Dynamics (DPD). We show that in model reduction methodologies for polymers it is not enough to preserve system properties (i.e., density ρ, pressure p, temperature T, radial distribution function g(r)) but preserving also the characteristic shape and length scale of the polymer chain model is necessary. In this work we apply a DPD-model-reduction methodology for linear polymers recently proposed; and demonstrate why the applicability of this methodology is limited upto certain maximum polymer length, and not suitable for solvent coarse graining.

  11. A stability study of polymer solar cells using conjugated polymers with different donor or acceptor side chain patterns

    DEFF Research Database (Denmark)

    Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

    2016-01-01

    -phenylethyl group. It is shown that the exchange of the hexyl chain on the DTBT moiety has a negative impact on the stability of the polymer as well as on the performance of the resulting PSCs. On the other hand, partial exchange of the 2-hexyldecyl side chain of the BDT unit by a 2-hydroxyethyl group results......)benzo[c][1,2,5]thiadiazole (DTBT), specifically selected because of its suitability for roll-coating in the ambient environment, is investigated in terms of operational stability via partial exchange (5 or 10%) of the alkyl side chain on either the donor or the acceptor monomer with a 2-hydroxyethyl or 2...

  12. Histone deacetylase inhibition and dietary short-chain Fatty acids.

    Science.gov (United States)

    Licciardi, Paul V; Ververis, Katherine; Karagiannis, Tom C

    2011-01-01

    Changes in diet can also have dramatic effects on the composition of gut microbiota. Commensal bacteria of the gastrointestinal tract are critical regulators of health and disease by protecting against pathogen encounter whilst also maintaining immune tolerance to certain allergens. Moreover, consumption of fibre and vegetables typical of a non-Western diet generates substantial quantities of short-chain fatty acids (SCFAs) which have potent anti-inflammatory properties. Dietary interventions such as probiotic supplementation have been investigated for their pleiotropic effects on microbiota composition and immune function. Probiotics may restore intestinal dysbiosis and improve clinical disease through elevated SCFA levels in the intestine. Although the precise mechanisms by which such dietary factors mediate these effects, SCFA metabolites such as butyrate also function as histone deacetylase inhibitors (HDACi), that can act on the epigenome through chromatin remodeling changes. The aim of this review is to provide an overview of HDAC enzymes and to discuss the biological effects of HDACi. Further, we discuss the important relationship between diet and the balance between health and disease and how novel dietary interventions such as probiotics could be alternative approach for the prevention and/or treatment of chronic inflammatory disease through modulation of the intestinal microbiome.

  13. Short chain molecular junctions: Charge transport versus dipole moment

    International Nuclear Information System (INIS)

    Ikram, I. Mohamed; Rabinal, M.K.

    2015-01-01

    Graphical abstract: - Highlights: • The role of dipole moment of organic molecules on molecular junctions has been studied. • Molecular junctions constituted using propargyl molecules of different dipole moments. • The electronic properties of the molecules were calculated using Gaussian software. • Junctions show varying rectification due to their varying dipole moment and orientation. - Abstract: The investigation of the influence of dipole moment of short chain organic molecules having three carbon atoms varying in end group on silicon surface was carried on. Here, we use three different molecules of propargyl series varying in dipole moment and its orientation to constitute molecular junctions. The charge transport mechanism in metal–molecules–semiconductor (MMS) junction obtained from current–voltage (I–V) characteristics shows the rectification behavior for two junctions whereas the other junction shows a weak rectification. The electronic properties of the molecules were calculated using Gaussian software package. The observed rectification behavior of these junctions is examined and found to be accounted to the orientation of dipole moment and electron cloud density distribution inside the molecules

  14. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

    DEFF Research Database (Denmark)

    Heckler, Ilona Maria; Kesters, Jurgen; Defour, Maxime

    2016-01-01

    ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio...... studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear......The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT) or thiazolo[5,4-d...

  15. Effect of Chain Conformation on the Single-Molecule Melting Force in Polymer Single Crystals: Steered Molecular Dynamics Simulations Study.

    Science.gov (United States)

    Feng, Wei; Wang, Zhigang; Zhang, Wenke

    2017-02-28

    Understanding the relationship between polymer chain conformation as well as the chain composition within the single crystal and the mechanical properties of the corresponding single polymer chain will facilitate the rational design of high performance polymer materials. Here three model systems of polymer single crystals, namely poly(ethylene oxide) (PEO), polyethylene (PE), and nylon-66 (PA66) have been chosen to study the effects of chain conformation, helical (PEO) versus planar zigzag conformation (PE, PA66), and chain composition (PE versus PA66) on the mechanical properties of a single polymer chain. To do that, steered molecular dynamics simulations were performed on those polymer single crystals by pulling individual polymer chains out of the crystals. Our results show that the patterns of force-extension curve as well as the chain moving mode are closely related to the conformation of the polymer chain in the single crystal. In addition, hydrogen bonds can enhance greatly the force required to stretch the polymer chain out of the single crystal. The dynamic breaking and reformation of multivalent hydrogen bonds have been observed for the first time in PA66 at the single molecule level.

  16. Nature of the Binding Interactions between Conjugated Polymer Chains and Fullerenes in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Ravva, Mahesh Kumar; Wang, Tonghui; Bredas, Jean-Luc

    2016-01-01

    Blends of π-conjugated polymers and fullerene derivatives are ubiquitous as the active layers of organic solar cells. However, a detailed understanding of the weak noncovalent interactions at the molecular level between the polymer chains

  17. State of mixing of deuterated and non-deuterated block polymer chains

    International Nuclear Information System (INIS)

    Hasegawa, Hirokazu; Hashimoto, Takeji

    1984-01-01

    Prior to the small-angle neutron scattering study on the conformation of block polymer chains in the domain space, the state of mixing of two block polymers, an ordinary polystyrene-polyisoprene diblock polymer and a poly(deuterated styrene)-polyisoprene diblock polymer with a different molecular weight and composition, was investigated by a small-angle X-ray scattering (SAXS) technique. Only one kind of domain structure was observed for each blend, and the domain spacings obtained by SAXS were proportional to the two-thirds power of the number-average molecular weight of the blends (reduced to non-deuterated block polymer). The volume fractions of polystyrene domain in the blends evaluated by computer simulation of SAXS profiles well agreed with the values estimated from blend composition. All these facts suggest the molecular mixing of the two block polymers in the domain space. (author)

  18. Defect-induced conductance oscillations in short atomic chains

    International Nuclear Information System (INIS)

    Wawrzyniak-Adamczewska, M; Kostyrko, T

    2012-01-01

    Electronic transport through a junction made of two gold electrodes connected with a gold chain containing a silver impurity is analyzed with a tight binding model and the density-functional theory. It is shown that the conductance depends in a simple way on the position of the impurity in the chain and the parity of the total number of atoms of the chain. For an odd chain the conductance takes on a higher value when the Ag impurity substitutes an even Au atom in the chain, and a lower one for an odd position of the Ag atom. In the case of an even chain the conductance hardly depends on the position of the Ag atom. This new kind of a defect-induced parity oscillation of the conductance is significantly more prominent than the well-known even-odd effect related to the dependence of the conductance on the parity of number of atoms in perfect chains. (paper)

  19. Parallelized event chain algorithm for dense hard sphere and polymer systems

    International Nuclear Information System (INIS)

    Kampmann, Tobias A.; Boltz, Horst-Holger; Kierfeld, Jan

    2015-01-01

    We combine parallelization and cluster Monte Carlo for hard sphere systems and present a parallelized event chain algorithm for the hard disk system in two dimensions. For parallelization we use a spatial partitioning approach into simulation cells. We find that it is crucial for correctness to ensure detailed balance on the level of Monte Carlo sweeps by drawing the starting sphere of event chains within each simulation cell with replacement. We analyze the performance gains for the parallelized event chain and find a criterion for an optimal degree of parallelization. Because of the cluster nature of event chain moves massive parallelization will not be optimal. Finally, we discuss first applications of the event chain algorithm to dense polymer systems, i.e., bundle-forming solutions of attractive semiflexible polymers

  20. Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers.

    Science.gov (United States)

    Chintapalli, Mahati; Timachova, Ksenia; Olson, Kevin R; Banaszak, Michał; Thelen, Jacob L; Mecham, Sue J; DeSimone, Joseph M; Balsara, Nitash P

    2017-06-07

    Incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE-PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ∼ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, R g . Over the temperature range 30-90 °C, the values of χ were determined to be very large (∼2-2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE-PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ∼ 2 nm -1 ) for relatively small polymer chains. Our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.

  1. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells.

    Science.gov (United States)

    Heckler, Ilona M; Kesters, Jurgen; Defour, Maxime; Madsen, Morten V; Penxten, Huguette; D'Haen, Jan; Van Mele, Bruno; Maes, Wouter; Bundgaard, Eva

    2016-03-09

    The stability of polymer solar cells (PSCs) can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyl)dialkoxybenzene donor and benzo[ c ][1,2,5]thiadiazole (BT) or thiazolo[5,4- d ]thiazole (TzTz) acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10%) of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable) TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs' lifetime.

  2. The Influence of Conjugated Polymer Side Chain Manipulation on the Efficiency and Stability of Polymer Solar Cells

    Directory of Open Access Journals (Sweden)

    Ilona M. Heckler

    2016-03-01

    Full Text Available The stability of polymer solar cells (PSCs can be influenced by the introduction of particular moieties on the conjugated polymer side chains. In this study, two series of donor-acceptor copolymers, based on bis(thienyldialkoxybenzene donor and benzo[c][1,2,5]thiadiazole (BT or thiazolo[5,4-d]thiazole (TzTz acceptor units, were selected toward effective device scalability by roll-coating. The influence of the partial exchange (5% or 10% of the solubilizing 2-hexyldecyloxy by alternative 2-phenylethoxy groups on efficiency and stability was investigated. With an increasing 2-phenylethoxy ratio, a decrease in solar cell efficiency was observed for the BT-based series, whereas the efficiencies for the devices based on the TzTz polymers remained approximately the same. The photochemical degradation rate for PSCs based on the TzTz polymers decreased with an increasing 2-phenylethoxy ratio. Lifetime studies under constant sun irradiance showed a diminishing initial degradation rate for the BT-based devices upon including the alternative side chains, whereas the (more stable TzTz-based devices degraded at a faster rate from the start of the experiment upon partly exchanging the side chains. No clear trends in the degradation behavior, linked to the copolymer structural changes, could be established at this point, evidencing the complex interplay of events determining PSCs’ lifetime.

  3. Phase behaviour of charged colloidal sphere dispersions with added polymer chains

    International Nuclear Information System (INIS)

    Fortini, Andrea; Dijkstra, Marjolein; Tuinier, Remco

    2005-01-01

    We study the stability of mixtures of highly screened repulsive charged spheres and non-adsorbing ideal polymer chains in a common solvent using free volume theory. The effective interaction between charged colloids in an aqueous salt solution is described by a screened Coulomb pair potential, which supplements the pure hard-sphere interaction. The ideal polymer chains are treated as spheres that are excluded from the colloids by a hard-core interaction, whereas the interaction between two ideal chains is set to zero. In addition, we investigate the phase behaviour of charged colloid-polymer mixtures in computer simulations, using the two-body (Asakura-Oosawa pair potential) approximation to the effective one-component Hamiltonian of the charged colloids. Both our results obtained from simulations and from free volume theory show similar trends. We find that the screened Coulomb repulsion counteracts the effect of the effective polymer-mediated attraction. For mixtures of small polymers and relatively large charged colloidal spheres, the fluid-crystal transition shifts to significantly larger polymer concentrations with increasing range of the screened Coulomb repulsion. For relatively large polymers, the effect of the screened Coulomb repulsion is weaker. The resulting fluid-fluid binodal is only slightly shifted towards larger polymer concentrations upon increasing the range of the screened Coulomb repulsion. In conclusion, our results show that the miscibility of dispersions containing charged colloids and neutral non-adsorbing polymers increases upon increasing the range of the screened Coulomb repulsion, or upon lowering the salt concentration, especially when the polymers are small compared to the colloids

  4. Mechanisms of chain adsorption on porous substrates and critical conditions of polymer chromatography.

    Science.gov (United States)

    Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

    2016-11-01

    Polymer adsorption is a ubiquitous phenomenon with numerous technological and healthcare applications. The mechanisms of polymer adsorption on surfaces and in pores are complex owing to a competition between various entropic and enthalpic factors. Due to adsorption of monomers to the surface, the chain gains in enthalpy yet loses in entropy because of confining effects. This competition leads to the existence of critical conditions of adsorption when enthalpy gain and entropy loss are in balance. The critical conditions are controlled by the confining geometry and effective adsorption energy, which depends on the solvent composition and temperature. This phenomenon has important implications in polymer chromatography, since the retention at the critical point of adsorption (CPA) is chain length independent. However, the mechanisms of polymer adsorption in pores are poorly understood and there is an ongoing discussion in the theoretical literature about the very existence of CPA for polymer adsorption on porous substrates. In this work, we examine the mechanisms of chain adsorption on a model porous substrate using Monte Carlo (MC) simulations. We distinguish three adsorption mechanisms depending on the chain location: on external surface, completely confined in pores, and also partially confined in pores in so-called "flower" conformations. The free energies of different conformations of adsorbed chains are calculated by the incremental gauge cell MC method that allows one to determine the partition coefficient as a function of the adsorption potential, pore size, and chain length. We confirm the existence of the CPA for chain length independent separation on porous substrates, which is explained by the dominant contributions of the chain adsorption at the external surface, in particular in flower conformations. Moreover, we show that the critical conditions for porous and nonporous substrates are identical and depend only on the surface chemistry. The theoretical

  5. Configurational statistics of a polymer chain with random sequence of elements

    International Nuclear Information System (INIS)

    Obukhov, S.P.

    1984-10-01

    It is shown that for a disordered polymer chain the upper critical dimension is d c =3. At d≤3 the effect of randomness increases on large scales due to the space correlations of attractive and repulsive monomers, but it can also be screened by repulsive two- or three-body interaction. The renorm group equations indicate that near the theta point it can be the large dispersion of sizes of polymers which differ only in sequences of elements. (orig.)

  6. Molecular dynamics simulation aiming at interfacial characteristics of polymer chains on nanotubes with different layers

    Science.gov (United States)

    Li, Kun; Gu, Boqin; Zhu, Wanfu

    2017-03-01

    A molecular dynamics (MD) simulations study is performed on multiwalled carbon nanotubes (MWNTs)/acrylonitrile-butadiene rubber (NBR) composites. The physisorption and interfacial characteristics between the various MWNTs and polymer macromolecular chains are identified. The effects of nanotube layers on the nanotubes/polymer interactions are examined. Each of the situation result and surface features is characterized by binding energy (Eb). It is shown that the binding energy (Eb) increase with the number of layers.

  7. A targeted metabolomic protocol for short-chain fatty acids and branched-chain amino acids.

    Science.gov (United States)

    Zheng, Xiaojiao; Qiu, Yunping; Zhong, Wei; Baxter, Sarah; Su, Mingming; Li, Qiong; Xie, Guoxiang; Ore, Brandon M; Qiao, Shanlei; Spencer, Melanie D; Zeisel, Steven H; Zhou, Zhanxiang; Zhao, Aihua; Jia, Wei

    2013-08-01

    Research in obesity and metabolic disorders that involve intestinal microbiota demands reliable methods for the precise measurement of the short-chain fatty acids (SCFAs) and branched-chain amino acids (BCAAs) concentration. Here, we report a rapid method of simultaneously determining SCFAs and BCAAs in biological samples using propyl chloroformate (PCF) derivatization followed by gas chromatography mass spectrometry (GC-MS) analysis. A one-step derivatization using 100 µL of PCF in a reaction system of water, propanol, and pyridine (v/v/v = 8:3:2) at pH 8 provided the optimal derivatization efficiency. The best extraction efficiency of the derivatized products was achieved by a two-step extraction with hexane. The method exhibited good derivatization efficiency and recovery for a wide range of concentrations with a low limit of detection for each compound. The relative standard deviations (RSDs) of all targeted compounds showed good intra- and inter-day (within 7 days) precision (< 10%), and good stability (< 20%) within 4 days at room temperature (23-25 °C), or 7 days when stored at -20 °C. We applied our method to measure SCFA and BCAA levels in fecal samples from rats administrated with different diet. Both univariate and multivariate statistics analysis of the concentrations of these target metabolites could differentiate three groups with ethanol intervention and different oils in diet. This method was also successfully employed to determine SCFA and BCAA in the feces, plasma and urine from normal humans, providing important baseline information of the concentrations of these metabolites. This novel metabolic profile study has great potential for translational research.

  8. Dependence of crystallite formation and preferential backbone orientations on the side chain pattern in PBDTTPD polymers

    KAUST Repository

    El Labban, Abdulrahman

    2014-11-26

    (Figure Presented) Alkyl substituents appended to the π-conjugated main chain account for the solution-processability and film-forming properties of most π-conjugated polymers for organic electronic device applications, including field-effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device performance. However, the factors that determine polymer crystallite orientation in thin-films, implying preferential backbone orientation relative to the device substrate, are a matter of some debate, and these structural changes remain difficult to anticipate. In this report, we show how systematic changes in the side-chain pattern of poly(benzo[1,2-b:4,5-b′]dithiophene-alt-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers can (i) influence the propensity of the polymer to order in the π-stacking direction, and (ii) direct the preferential orientation of the polymer crystallites in thin films (e.g., "face-on" vs "edge-on"). Oriented crystallites, specifically crystallites that are well-ordered in the π-stacking direction, are believed to be a key contributor to improved thin-film device performance in both FETs and BHJ solar cells.

  9. Investigation of the adsorption of polymer chains on amine-functionalized double-walled carbon nanotubes.

    Science.gov (United States)

    Ansari, R; Ajori, S; Rouhi, S

    2015-12-01

    Molecular dynamics (MD) simulations were used to study the adsorption of different polymer chains on functionalized double-walled carbon nanotubes (DWCNTs). The nanotubes were functionalized with two different amines: NH2 (a small amine) and CH2-NH2 (a large amine). Considering three different polymer chains, all with the same number of atoms, the effect of polymer type on the polymer-nanotube interaction was studied. In general, it was found that covalent functionalization considerably improved the polymer-DWCNT interaction. By comparing the results obtained with different polymer chains, it was observed that, unlike polyethylene and polyketone, poly(styrene sulfonate) only weakly interacts with the functionalized DWCNTs. Accordingly, the smallest radius of gyration was obtained with adsorbed poly(styrene sulfonate). It was also observed that the DWCNTs functionalized with the large amine presented more stable interactions with polyketone and poly(styrene sulfonate) than with polyethylene, whereas the DWCNTs functionalized with the small amine showed better interfacial noncovalent bonding with polyethylene.

  10. Synthesis and characterisation of new types of side chain cholesteryl polymers.

    Science.gov (United States)

    Wang, Bin; Du, Haiyan; Zhang, Junhua

    2011-01-01

    A series of cholesterol derivatives have been synthesised via the alkylation reaction of the 3-hydroxyl group with the aliphatic bromide compounds with different chain lengths, namely 3β-alkyloxy-cholesterol. The double bond between the C5 and C6 positions in these cholesterol derivatives was oxidised into epoxy, followed by an epoxy-ring-opening reaction with the treatment with acrylic acid, resulting in a series of 3β-alkyloxy-5α-hydroxy-6β-acryloyloxycholesterol, C(n)OCh (n=1, 2, 4, 6, 8, 10, 12), The acrylate group is connected to the C6 position, which is confirmed by the single crystal structure analysis. The corresponding polymers, PC(n)OCh, were prepared via free radical polymerisation. The structure of monomers and the resulting polymers were characterised with nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The thermal properties of PC(n)OCh were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). To determine the secondary structure of polymers, circular dichroism (CD) spectra were performed. It was found that not all monomers produce high-molecular-weight polymers because of steric hindrance. However, all polymers have a helical structure, which can be enhanced by increasing the alkoxy chain length. In addition, increasing the alkoxy chain length decreases the glass transition temperature and increases the decomposition temperature of the polymers. Copyright © 2010 Elsevier Inc. All rights reserved.

  11. Covalent bond force profile and cleavage in a single polymer chain

    Science.gov (United States)

    Garnier, Lionel; Gauthier-Manuel, Bernard; van der Vegte, Eric W.; Snijders, Jaap; Hadziioannou, Georges

    2000-08-01

    We present here the measurement of the single-polymer entropic elasticity and the single covalent bond force profile, probed with two types of atomic force microscopes (AFM) on a synthetic polymer molecule: polymethacrylic acid in water. The conventional AFM allowed us to distinguish two types of interactions present in this system when doing force spectroscopic measurements: the first interaction is associated with adsorption sites of the polymer chains onto a bare gold surface, the second interaction is directly correlated to the rupture process of a single covalent bond. All these bridging interactions allowed us to stretch the single polymer chain and to determine the various factors playing a role in the elasticity of these molecules. To obtain a closer insight into the bond rupture process, we moved to a force sensor stable in position when measuring attractive forces. By optimizing the polymer length so as to fulfill the elastic stability conditions, we were able for the first time to map out the entire force profile associated with the cleavage of a single covalent bond. Experimental data coupled with molecular quantum mechanical calculations strongly suggest that the breaking bond is located at one end of the polymer chain.

  12. Abnormal viscoelastic behavior of side-chain liquid-crystal polymers

    Science.gov (United States)

    Gallani, J. L.; Hilliou, L.; Martinoty, P.; Keller, P.

    1994-03-01

    We show that, contrary to what is commonly believed, the isotropic phase of side-chain liquid-crystal polymers has viscoelastic properties which are totally different from those of ordinary flexible melt polymers. The results can be explained by the existence of a transient network created by the dynamic association of mesogenic groups belonging to different chains. The extremely high sensitivity of the compound to the state of the surfaces with which it is in contact offers us an unexpected method of studying surface states.

  13. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.

    2015-07-02

    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  14. Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

    KAUST Repository

    Schroeder, Bob C.; Nielsen, Christian B.; Westacott, Paul; Smith, Jeremy; Rossbauer, Stephan; Anthopoulos, Thomas D.; Stingelin, Natalie; McCulloch, Iain

    2015-01-01

    Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors. Copyright © Materials Research Society 2015

  15. Chain propagator, mass, and universality in polymer solutions from Brownian relativity

    International Nuclear Information System (INIS)

    Mezzasalma, Stefano A.

    2005-01-01

    A Lagrangian theory for single chains in polymer solutions is addressed via a recent Brownian relativity. By employing generalized diffusive coordinates, statements of covariance and diffusivity invariance result into free particle Lagrangians, where mass turns out to rise as a universal spacetime property. It descends from lowering diffusivity (or curving spacetime), so identifying a mechanism which conceptually resemble those ruling macromolecular scaling laws. An extended chain propagator recovers the Gaussian end-to-end distribution and, in the limits of time-like and space-like orbits, the dualism for diffusive paths and polymer random-walks

  16. Primitive-path statistics of entangled polymers: mapping multi-chain simulations onto single-chain mean-field models

    International Nuclear Information System (INIS)

    Steenbakkers, Rudi J A; Schieber, Jay D; Tzoumanekas, Christos; Li, Ying; Liu, Wing Kam; Kröger, Martin

    2014-01-01

    We present a method to map the full equilibrium distribution of the primitive-path (PP) length, obtained from multi-chain simulations of polymer melts, onto a single-chain mean-field ‘target’ model. Most previous works used the Doi–Edwards tube model as a target. However, the average number of monomers per PP segment, obtained from multi-chain PP networks, has consistently shown a discrepancy of a factor of two with respect to tube-model estimates. Part of the problem is that the tube model neglects fluctuations in the lengths of PP segments, the number of entanglements per chain and the distribution of monomers among PP segments, while all these fluctuations are observed in multi-chain simulations. Here we use a recently proposed slip-link model, which includes fluctuations in all these variables as well as in the spatial positions of the entanglements. This turns out to be essential to obtain qualitative and quantitative agreement with the equilibrium PP-length distribution obtained from multi-chain simulations. By fitting this distribution, we are able to determine two of the three parameters of the model, which govern its equilibrium properties. This mapping is executed for four different linear polymers and for different molecular weights. The two parameters are found to depend on chemistry, but not on molecular weight. The model predicts a constant plateau modulus minus a correction inversely proportional to molecular weight. The value for well-entangled chains, with the parameters determined ab initio, lies in the range of experimental data for the materials investigated. (paper)

  17. Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

    KAUST Repository

    Abadi, Maram

    2015-08-24

    The motion and relaxation of linear and cyclic polymers under entangled conditions are investigated by means of a newly developed single-molecule tracking technique, cumulative-area (CA) tracking. CA tracking enables simultaneous quantitative characterization of the diffusion mode, diffusion rate, and relaxation time that have been impossible with a widely used conventional single-molecule localization and tracking method, by analyzing cumulative areas occupied by the moving molecule. Using the novel approach, we investigate the motion and relaxation of entangled cyclic polymers, which have been an important but poorly understood question. Fluorescently labeled 42 kbp linear or cyclic tracer dsDNAs in concentrated solutions of unlabeled linear or cyclic DNAs are used as model systems. We show that CA tracking can explicitly distinguish topology-dependent diffusion mode, rate, and relaxation time, demonstrating that the method provides an invaluable tool for characterizing topological interaction between the entangled chains. We further demonstrate that the current models proposed for the entanglement between cyclic polymers which are based on cyclic chains moving through an array of fixed obstacles cannot correctly describe the motion of the cyclic chain under the entangled conditions. Our results rather suggest the mutual relaxation of the cyclic chains, which underscore the necessity of developing a new model to describe the motion of cyclic polymer under the entangled conditions based on the mutual interaction of the chains.

  18. Single-Molecule Imaging Reveals Topology Dependent Mutual Relaxation of Polymer Chains

    KAUST Repository

    Abadi, Maram; Serag, Maged F.; Habuchi, Satoshi

    2015-01-01

    The motion and relaxation of linear and cyclic polymers under entangled conditions are investigated by means of a newly developed single-molecule tracking technique, cumulative-area (CA) tracking. CA tracking enables simultaneous quantitative characterization of the diffusion mode, diffusion rate, and relaxation time that have been impossible with a widely used conventional single-molecule localization and tracking method, by analyzing cumulative areas occupied by the moving molecule. Using the novel approach, we investigate the motion and relaxation of entangled cyclic polymers, which have been an important but poorly understood question. Fluorescently labeled 42 kbp linear or cyclic tracer dsDNAs in concentrated solutions of unlabeled linear or cyclic DNAs are used as model systems. We show that CA tracking can explicitly distinguish topology-dependent diffusion mode, rate, and relaxation time, demonstrating that the method provides an invaluable tool for characterizing topological interaction between the entangled chains. We further demonstrate that the current models proposed for the entanglement between cyclic polymers which are based on cyclic chains moving through an array of fixed obstacles cannot correctly describe the motion of the cyclic chain under the entangled conditions. Our results rather suggest the mutual relaxation of the cyclic chains, which underscore the necessity of developing a new model to describe the motion of cyclic polymer under the entangled conditions based on the mutual interaction of the chains.

  19. Effects of supercritical carbon dioxide on immobile bound polymer chains on solid substrates

    Science.gov (United States)

    Sen, Mani; Asada, Mitsunori; Jiang, Naisheng; Endoh, Maya K.; Akgun, Bulent; Satija, Sushil; Koga, Tadanori

    2013-03-01

    Adsorbed polymer layers formed on flat solid substrates have recently been the subject of extensive studies because it is postulated to control the dynamics of technologically relevant polymer thin films, for example, in lithography. Such adsorbed layers have been reported to hinder the mobility of polymer chains in thin films even at a large length scale. Consequently, this bound layer remains immobile regardless of processing techniques (i.e. thermal annealing, solvent dissolution, etc). Here, we investigate the use of supercritical carbon dioxide (scCO2) as a novel plasticizer for bound polystyrene layers formed on silicon substrates. In-situ swelling and interdiffusion experiments using neutron reflectivity were performed. As a result, we found the anomalous plasticization effects of scCO2 on the bound polymer layers near the critical point where the anomalous adsorption of CO2 molecules in polymer thin films has been reported previously. Acknowledgement: We acknowledge the financial support from NSF Grant No. CMMI-084626.

  20. Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

    Directory of Open Access Journals (Sweden)

    Ana Sanchez-Sanchez

    2015-01-01

    Full Text Available Single-chain technology (SCT allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful “click” chemistry driving force for SCNP construction. By employing poly(methyl methacrylate- (PMMA- based copolymers bearing β-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC, infrared (IR spectroscopy, proton nuclear magnetic resonance (1H NMR spectroscopy, dynamic light scattering (DLS, and elemental analysis (EA.

  1. Distortion of chain conformation and reduced entanglement in polymer-graphene oxide nanocomposites

    Science.gov (United States)

    Weir, Michael; Boothroyd, Stephen; Johnson, David; Thompson, Richard; Coleman, Karl; Clarke, Nigel

    Graphene and related two-dimensional materials are excellent candidates as filler materials in polymer nanocomposites due to their extraordinary physical properties and high aspect ratio. To explore the mechanism by which the filler affects the bulk properties of these unique systems, and to build understanding from the macromolecular level upwards, we use a combination of small-angle neutron scattering (SANS) and oscillatory rheology. Where a good dispersion is achieved in poly(methyl methacrylate)-graphene oxide (PMMA-GO) nanocomposites, we observe a reduction in the polymer radius of gyration with increasing GO concentration that is consistent with the predicted behavior of polymer melt chains at a solid interface. We use concepts from thin-film polymer physics to formulate a scaling relation for the reduction in entanglements caused by the GO interfaces. Using these scaling arguments, we utilize SANS results to directly estimate the changes to the elastic plateau modulus of the network of entangled polymer chains, and find a correlation with the measured bulk rheology. We present a direct link between interfacial confinement effects and the bulk polymer nanocomposite properties, whilst demonstrating a model system for measuring thin film polymer physics in the bulk.

  2. Vapor-liquid equilibrium and critical asymmetry of square well and short square well chain fluids.

    Science.gov (United States)

    Li, Liyan; Sun, Fangfang; Chen, Zhitong; Wang, Long; Cai, Jun

    2014-08-07

    The critical behavior of square well fluids with variable interaction ranges and of short square well chain fluids have been investigated by grand canonical ensemble Monte Carlo simulations. The critical temperatures and densities were estimated by a finite-size scaling analysis with the help of histogram reweighting technique. The vapor-liquid coexistence curve in the near-critical region was determined using hyper-parallel tempering Monte Carlo simulations. The simulation results for coexistence diameters show that the contribution of |t|(1-α) to the coexistence diameter dominates the singular behavior in all systems investigated. The contribution of |t|(2β) to the coexistence diameter is larger for the system with a smaller interaction range λ. While for short square well chain fluids, longer the chain length, larger the contribution of |t|(2β). The molecular configuration greatly influences the critical asymmetry: a short soft chain fluid shows weaker critical asymmetry than a stiff chain fluid with same chain length.

  3. Spatial Rearrangement and Mobility Heterogeneity of an Anionic Lipid Monolayer Induced by the Anchoring of Cationic Semiflexible Polymer Chains

    Directory of Open Access Journals (Sweden)

    Xiaozheng Duan

    2016-06-01

    Full Text Available We use Monte Carlo simulations to investigate the interactions between cationic semiflexible polymer chains and a model fluid lipid monolayer composed of charge-neutral phosphatidyl-choline (PC, tetravalent anionic phosphatidylinositol 4,5-bisphosphate (PIP2, and univalent anionic phosphatidylserine (PS lipids. In particular, we explore how chain rigidity and polymer concentration influence the spatial rearrangement and mobility heterogeneity of the monolayer under the conditions where the cationic polymers anchor on the monolayer. We find that the anchored cationic polymers only sequester the tetravalent PIP2 lipids at low polymer concentrations, where the interaction strength between the polymers and the monolayer exhibits a non-monotonic dependence on the degree of chain rigidity. Specifically, maximal anchoring occurs at low polymer concentrations, when the polymer chains have an intermediate degree of rigidity, for which the PIP2 clustering becomes most enhanced and the mobility of the polymer/PIP2 complexes becomes most reduced. On the other hand, at sufficiently high polymer concentrations, the anchoring strength decreases monotonically as the chains stiffen—a result that arises from the pronounced competitions among polymer chains. In this case, the flexible polymers can confine all PIP2 lipids and further sequester the univalent PS lipids, whereas the stiffer polymers tend to partially dissociate from the monolayer and only sequester smaller PIP2 clusters with greater mobilities. We further illustrate that the mobility gradient of the single PIP2 lipids in the sequestered clusters is sensitively modulated by the cooperative effects between anchored segments of the polymers with different rigidities. Our work thus demonstrates that the rigidity and concentration of anchored polymers are both important parameters for tuning the regulation of anionic lipids.

  4. Effect of side chain length on charge transport, morphology, and photovoltaic performance of conjugated polymers in bulk heterojunction solar cells

    NARCIS (Netherlands)

    Duan, C.; Willems, R.E.M.; van Franeker, J.J.; Bruijnaers, B.J.; Wienk, M.M.; Janssen, R.A.J.

    2016-01-01

    The effect of side chain length on the photovoltaic properties of conjugated polymers is systematically investigated with two sets of polymers that bear different alkyl side chain lengths based on benzodithiophene and benzo[2,1,3]thiadiazole or 5,6-difluorobenzo[2,1,3]thiadiazole. Characterization

  5. Adsorption of charged and neutral polymer chains on silica surfaces: The role of electrostatics, volume exclusion, and hydrogen bonding

    NARCIS (Netherlands)

    Spruijt, Evan; Biesheuvel, P.M.; de Vos, Wiebe Matthijs

    2015-01-01

    We develop an off-lattice (continuum) model to describe the adsorption of neutral polymer chains and polyelectrolytes to surfaces. Our continuum description allows taking excluded volume interactions between polymer chains and ions directly into account. To implement those interactions, we use a

  6. Beyond the Born approximation. The case of very long polymer chains adsorbed at an interface

    International Nuclear Information System (INIS)

    Guiselin, O.; Jannink, G.; Cloizeaux, J. des

    1991-01-01

    Two experimental evidences are discussed of the reflectance discontinuity associated with very long adsorbed polymer chains. It is shown that the Born approximation is not valid in this case. The anomalous low reflectivity is compared to the Ramsauer-Townsend effect in the scattering of slow electrons by rare-gas atoms. (author) 15 refs.; 6 figs

  7. Adsorption of flexible polymer chains on a surface: Effects of different solvent conditions

    Science.gov (United States)

    Martins, P. H. L.; Plascak, J. A.; Bachmann, M.

    2018-05-01

    Polymer chains undergoing a continuous adsorption-desorption transition are studied through extensive computer simulations. A three-dimensional self-avoiding walk lattice model of a polymer chain grafted onto a surface has been treated for different solvent conditions. We have used an advanced contact-density chain-growth algorithm, in which the density of contacts can be directly obtained. From this quantity, the order parameter and its fourth-order Binder cumulant are computed, as well as the corresponding critical exponents and the adsorption-desorption transition temperature. As the number of configurations with a given number of surface contacts and monomer-monomer contacts is independent of the temperature and solvent conditions, it can be easily applied to get results for different solvent parameter values without the need of any extra simulations. In analogy to continuous magnetic phase transitions, finite-size-scaling methods have been employed. Quite good results for the critical properties and phase diagram of very long single polymer chains have been obtained by properly taking into account the effects of corrections to scaling. The study covers all solvent effects, going from the limit of super-self-avoiding walks, characterized by effective monomer-monomer repulsion, to poor solvent conditions that enable the formation of compact polymer structures.

  8. Influence of structures of polymer backbones on cooperative photoreorientation behavior of p-cyanoazobenzene side chains

    DEFF Research Database (Denmark)

    Han, Mina; Kidowaki, Masatoshi; Ichimura, Kunihiro

    2001-01-01

    Photoinduced orientational behavior of a polymethacrylate (CN6) and a polyester (p6a12) with p-cyanoazobenzene side chains was studied to reveal the structural effect of the liquid crystalline polymer backbones. Irradiation with linearly polarized W light resulted in the reorientation of the azob...

  9. Chain length distribution and kinetic characteristics of an enzymatically produced polymer

    NARCIS (Netherlands)

    Mulders, K.J.M.; Beeftink, H.H.

    2013-01-01

    Non-processive enzymatic polymerization leads to a distribution of polymer chain lengths. A polymerization model was developed to investigate the relation between the extent of this distribution on one hand, and the polymerization start conditions and reaction kinetics on the other hand. The model

  10. Dependence of crystallite formation and preferential backbone orientations on the side chain pattern in PBDTTPD polymers

    KAUST Repository

    El Labban, Abdulrahman; Warnan, Julien; Cabanetos, Clement; Ratel, Olivier; Tassone, Christopher J.; Toney, Michael F.; Beaujuge, Pierre

    2014-01-01

    -effect transistors (FETs) and bulk-heterojunction (BHJ) solar cells. Beyond film-forming properties, recent work has emphasized the determining role that side-chain substituents play on polymer self-assembly and thin-film nanostructural order, and, in turn, on device

  11. The Role of Short-Chain Conjugated Poly-(R-3-Hydroxybutyrate (cPHB in Protein Folding

    Directory of Open Access Journals (Sweden)

    Rosetta N. Reusch

    2013-05-01

    Full Text Available Poly-(R-3-hydroxybutyrate (PHB, a linear polymer of R-3-hydroxybutyrate (R-3HB, is a fundamental constituent of biological cells. Certain prokaryotes accumulate PHB of very high molecular weight (10,000 to >1,000,000 residues, which is segregated within granular deposits in the cytoplasm; however, all prokaryotes and all eukaryotes synthesize PHB of medium-chain length (~100–200 residues which resides within lipid bilayers or lipid vesicles, and PHB of short-chain length (<12 residues which is conjugated to proteins (cPHB, primarily proteins in membranes and organelles. The physical properties of cPHB indicate it plays important roles in the targeting and folding of cPHB-proteins. Here we review the occurrence, physical properties and molecular characteristics of cPHB, and discuss its influence on the folding and structure of outer membrane protein A (OmpA of Escherichia coli.

  12. Nanoparticle amount, and not size, determines chain alignment and nonlinear hardening in polymer nanocomposites

    Science.gov (United States)

    Varol, H. Samet; Meng, Fanlong; Hosseinkhani, Babak; Malm, Christian; Bonn, Daniel; Bonn, Mischa; Zaccone, Alessio

    2017-01-01

    Polymer nanocomposites—materials in which a polymer matrix is blended with nanoparticles (or fillers)—strengthen under sufficiently large strains. Such strain hardening is critical to their function, especially for materials that bear large cyclic loads such as car tires or bearing sealants. Although the reinforcement (i.e., the increase in the linear elasticity) by the addition of filler particles is phenomenologically understood, considerably less is known about strain hardening (the nonlinear elasticity). Here, we elucidate the molecular origin of strain hardening using uniaxial tensile loading, microspectroscopy of polymer chain alignment, and theory. The strain-hardening behavior and chain alignment are found to depend on the volume fraction, but not on the size of nanofillers. This contrasts with reinforcement, which depends on both volume fraction and size of nanofillers, potentially allowing linear and nonlinear elasticity of nanocomposites to be tuned independently. PMID:28377517

  13. Self-interacting polymer chains terminally anchored to adsorbing surfaces of three-dimensional fractal lattices

    Science.gov (United States)

    Živić, I.; Elezović-Hadžić, S.; Milošević, S.

    2018-01-01

    We have studied the adsorption problem of self-attracting linear polymers, modeled by self-avoiding walks (SAWs), situated on three-dimensional fractal structures, exemplified by 3d Sierpinski gasket (SG) family of fractals as containers of a poor solvent. Members of SG family are enumerated by an integer b (b ≥ 2), and it is assumed that one side of each SG fractal is an impenetrable adsorbing surface. We calculate the critical exponents γ1 ,γ11, and γs, which are related to the numbers of all possible SAWs with one, both, and no ends anchored to the adsorbing boundary, respectively. By applying the exact renormalization group (RG) method (for the first three members of the SG fractal family, b = 2 , 3, and 4), we have obtained specific values of these exponents, for θ-chain and globular polymer phase. We discuss their mutual relations and relations with corresponding values pertinent to extended polymer chain phase.

  14. Main chain acid-degradable polymers for the delivery of bioactive materials

    Science.gov (United States)

    Frechet, Jean M. J. [Oakland, CA; Standley, Stephany M [Evanston, IL; Jain, Rachna [Milpitas, CA; Lee, Cameron C [Cambridge, MA

    2012-03-20

    Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

  15. Short-chain fatty acids and poly-beta-hydroxyalkanoates: (New) Biocontrol agents for a sustainable animal production.

    Science.gov (United States)

    Defoirdt, Tom; Boon, Nico; Sorgeloos, Patrick; Verstraete, Willy; Bossier, Peter

    2009-01-01

    Because of the risk of antibiotic resistance development, there is a growing awareness that antibiotics should be used more carefully in animal production. However, a decreased use of antibiotics could result in a higher frequency of pathogenic bacteria, which in its turn could lead to a higher incidence of infections. Short-chain fatty acids (SCFAs) have long been known to exhibit bacteriostatic activity. These compounds also specifically downregulate virulence factor expression and positively influence the gastrointestinal health of the host. As a consequence, there is currently considerable interest in SCFAs as biocontrol agents in animal production. Polyhydroxyalkanoates (PHAs) are polymers of beta-hydroxy short-chain fatty acids. Currently, PHAs are applied as replacements for synthetic polymers. These biopolymers can be depolymerised by many different microorganisms that produce extracellular PHA depolymerases. Interestingly, different studies provided some evidence that PHAs can also be degraded upon passage through the gastrointestinal tract of animals and consequently, adding these compounds to the feed might result in biocontrol effects similar to those described for SCFAs.

  16. Modelling the effect of nonplanarity on charge transport along conjugated polymer chains

    International Nuclear Information System (INIS)

    Correia, Helena M.G.; Ramos, Marta M.D.

    2007-01-01

    Conjugated polymers show interesting properties that make them appropriated for nanoelectronics. Several studies of poly(p-phenylene vinylene) (PPV) have suggested that each polymer chain consists of several planar segments, with conjugation length of nanoscale dimension, linked by twists or kinks. A pronounced twist between two planar segments in a PPV chain not only causes loss of main-chain conjugation but it may also alter electron and hole mobility along the chain, which has further implications for the percolation of charge through the polymer film. We used self-consistent quantum molecular dynamics calculations to provide information on the electric field needed to move the injected charges (either electrons or holes) along the planar segments of PPV and to cross the twist between two planar segments perpendicular to each other. Field-dependent charge mobility was also estimated for conjugated segments of various lengths. Our results suggest that electrons can cross the twist between adjacent planar segments for lower applied electric fields than holes if there is no more than one electronic charge (electron or hole) on the PPV chain, otherwise similar fields are needed

  17. Intra-chain organisation of hydrophobic residues controls inter-chain aggregation rates of amphiphilic polymers

    Science.gov (United States)

    Varilly, Patrick; Willard, Adam P.; Kirkegaard, Julius B.; Knowles, Tuomas P. J.; Chandler, David

    2017-04-01

    Aggregation of amphiphiles through the action of hydrophobic interactions is a common feature in soft condensed matter systems and is of particular importance in the context of biophysics as it underlies both the generation of functional biological machinery as well as the formation of pathological misassembled states of proteins. Here we explore the aggregation behaviour of amphiphilic polymers using lattice Monte Carlo calculations and show that the distribution of hydrophobic residues within the polymer sequence determines the facility with which dry/wet interfaces can be created and that such interfaces drive the aggregation process.

  18. Specific Interaction between Redox Phospholipid Polymers and Plastoquinone in Photosynthetic Electron Transport Chain.

    Science.gov (United States)

    Tanaka, Kenya; Kaneko, Masahiro; Ishikawa, Masahito; Kato, Souichiro; Ito, Hidehiro; Kamachi, Toshiaki; Kamiya, Kazuhide; Nakanishi, Shuji

    2017-04-19

    Redox phospholipid polymers added in culture media are known to be capable of extracting electrons from living photosynthetic cells across bacterial cell membranes with high cytocompatibility. In the present study, we identify the intracellular redox species that transfers electrons to the polymers. The open-circuit electrochemical potential of an electrolyte containing the redox polymer and extracted thylakoid membranes shift to positive (or negative) under light irradiation, when an electron transport inhibitor specific to plastoquinone is added upstream (or downstream) in the photosynthetic electron transport chain. The same trend is also observed for a medium containing living photosynthetic cells of Synechococcus elongatus PCC7942. These results clearly indicate that the phospholipid redox polymers extract photosynthetic electrons mainly from plastoquinone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Short bunch wake potentials for a chain of TESLA cavities

    International Nuclear Information System (INIS)

    Novokhatski, Alexander; Mosnier, Alban

    2014-01-01

    The modification of wake fields from a single cavity to a quasi-periodic structure of cavities is of great concern, especially for applications using very short bunches. We extend our former study (Novokhatski, 1997 [1]). A strong modification of wake fields along a train of cavities was clearly found for bunch lengths lower than 1 mm. In particular, the wakes induced by the bunch, as it proceeds down the successive cavities, decrease in amplitude and become more linear around the bunch center, with a profile very close to the integral of the charge density. The loss factor, decreasing also with the number of cells, becomes independent of bunch length for very short bunches and tends asymptotically to a finite value. This nice behavior of wake fields for short bunches presents good opportunity for application of very short bunches in Linear Colliders and X-ray Free Electron Lasers

  20. Bis(thienothiophenyl) diketopyrrolopyrrole-based conjugated polymers with various branched alkyl side chains and their applications in thin-film transistors and polymer solar cells.

    Science.gov (United States)

    Shin, Jicheol; Park, Gi Eun; Lee, Dae Hee; Um, Hyun Ah; Lee, Tae Wan; Cho, Min Ju; Choi, Dong Hoon

    2015-02-11

    New thienothiophene-flanked diketopyrrolopyrrole and thiophene-containing π-extended conjugated polymers with various branched alkyl side-chains were successfully synthesized. 2-Octyldodecyl, 2-decyltetradecyl, 2-tetradecylhexadecyl, 2-hexadecyloctadecyl, and 2-octadecyldocosyl groups were selected as the side-chain moieties and were anchored to the N-positions of the thienothiophene-flanked diketopyrrolopyrrole unit. All five polymers were found to be soluble owing to the bulkiness of the side chains. The thin-film transistor based on the 2-tetradecylhexadecyl-substituted polymer showed the highest hole mobility of 1.92 cm2 V(-1) s(-1) due to it having the smallest π-π stacking distance between the polymer chains, which was determined by grazing incidence X-ray diffraction. Bulk heterojunction polymer solar cells incorporating [6,6]-phenyl-C71-butyric acid methyl ester as the n-type molecule and the additive 1,8-diiodooctane (1 vol %) were also constructed from the synthesized polymers without thermal annealing; the device containing the 2-octyldodecyl-substituted polymer exhibited the highest power conversion efficiency of 5.8%. Although all the polymers showed similar physical properties, their device performance was clearly influenced by the sizes of the branched alkyl side-chain groups.

  1. Simulated glass-forming polymer melts: dynamic scattering functions, chain length effects, and mode-coupling theory analysis.

    Science.gov (United States)

    Frey, S; Weysser, F; Meyer, H; Farago, J; Fuchs, M; Baschnagel, J

    2015-02-01

    We present molecular-dynamics simulations for a fully flexible model of polymer melts with different chain length N ranging from short oligomers (N = 4) to values near the entanglement length (N = 64). For these systems we explore the structural relaxation of the supercooled melt near the critical temperature T c of mode-coupling theory (MCT). Coherent and incoherent scattering functions are analyzed in terms of the idealized MCT. For temperatures T > T c we provide evidence for the space-time factorization property of the β relaxation and for the time-temperature superposition principle (TTSP) of the α relaxation, and we also discuss deviations from these predictions for T ≈ T c. For T larger than the smallest temperature where the TTSP holds we perform a quantitative analysis of the dynamics with the asymptotic MCT predictions for the late β regime. Within MCT a key quantity, in addition to T c, is the exponent parameter λ. For the fully flexible polymer models studied we find that λ is independent of N and has a value (λ = 0.735 ) typical of simple glass-forming liquids. On the other hand, the critical temperature increases with chain length toward an asymptotic value T c (∞) . This increase can be described by T c (∞) - T c(N) ∼ 1/N and may be interpreted in terms of the N dependence of the monomer density ρ, if we assume that the MCT glass transition is ruled by a soft-sphere-like constant coupling parameter Γ c = ρ c T c (-1/4), where ρ c is the monomer density at T c. In addition, we also estimate T c from a Hansen-Verlet-like criterion and MCT calculations based on structural input from the simulation. For our polymer model both the Hansen-Verlet criterion and the MCT calculations suggest T c to decrease with increasing chain length, in contrast to the direct analysis of the simulation data.

  2. Brownian dynamics simulation of a polymer chain in a solid-state nanopore attached to a molecular stop

    Science.gov (United States)

    Wells, Craig; Hulings, Zachery; Melnikov, Dmitriy; Gracheva, Maria

    We study a nanopore inside a silicon dioxide membrane submerged in a KCl solution with a negatively charged polymer chain of varying lengths whose movement is described using Brownian dynamics. The polymer is attached to a molecule with a radius larger than that of the nanopore's which acts as a molecular stop, allowing the chain to thread the nanopore but preventing it from translocating. We found that the polymer chain's variation of movement along the nanopore decreased when increasing applied biases and chain lengths for portions of the chain closest to the molecular stop. The chain displacement within the pore is also compared to a freely translocating polymer where preliminary results show the free polymer having a greater variation in the radial direction. Overall, our preliminary results indicate that the radial direction of the polymer chain is dominated by the confinement in the narrow nanopore with restrictions imposed by the molecular stop and bias playing a lesser role. Understanding the interaction behavior of the polymer chain-stop molecule may lead to methods that decrease movement variation, facilitating an improvement on characterizing and identification of molecules. NSF DMR and CBET Grant No. 1352218.

  3. Pruned-enriched Rosenbluth method: Simulations of θ polymers of chain length up to 1000000

    International Nuclear Information System (INIS)

    Grassberger, P.

    1997-01-01

    We present an algorithm for simulating flexible chain polymers. It combines the Rosenbluth-Rosenbluth method with recursive enrichment. Although it can be applied also in more general situations, it is most efficient for three-dimensional θ polymers on the simple-cubic lattice. There it allows high statistics simulations of chains of length up to N=10 6 . For storage reasons, this is feasable only for polymers in a finite volume. For free θ polymers in infinite volume, we present very high statistics runs with N=10000. These simulations fully agree with previous simulations made by Hegger and Grassberger [J. Chem. Phys. 102, 6681 (1995)] with a similar but less efficient algorithm, showing that logarithmic corrections to mean field behavior are much stronger than predicted by field theory. But the finite volume simulations show that the density inside a collapsed globule scales with the distance from the θ point as predicted by mean field theory, in contrast to claims in the work mentioned above. In addition to the simple-cubic lattice, we also studied two versions of the bond fluctuation model, but with much shorter chains. Finally, we show that our method can be applied also to off-lattice models, and illustrate this with simulations of a model studied in detail by Freire et al. [Macromolecules 19, 452 (1986) and later work]. copyright 1997 The American Physical Society

  4. Boosting the ambipolar performance of solution-processable polymer semiconductors via hybrid side-chain engineering.

    Science.gov (United States)

    Lee, Junghoon; Han, A-Reum; Yu, Hojeong; Shin, Tae Joo; Yang, Changduk; Oh, Joon Hak

    2013-06-26

    Ambipolar polymer semiconductors are highly suited for use in flexible, printable, and large-area electronics as they exhibit both n-type (electron-transporting) and p-type (hole-transporting) operations within a single layer. This allows for cost-effective fabrication of complementary circuits with high noise immunity and operational stability. Currently, the performance of ambipolar polymer semiconductors lags behind that of their unipolar counterparts. Here, we report on the side-chain engineering of conjugated, alternating electron donor-acceptor (D-A) polymers using diketopyrrolopyrrole-selenophene copolymers with hybrid siloxane-solubilizing groups (PTDPPSe-Si) to enhance ambipolar performance. The alkyl spacer length of the hybrid side chains was systematically tuned to boost ambipolar performance. The optimized three-dimensional (3-D) charge transport of PTDPPSe-Si with pentyl spacers yielded unprecedentedly high hole and electron mobilities of 8.84 and 4.34 cm(2) V(-1) s(-1), respectively. These results provide guidelines for the molecular design of semiconducting polymers with hybrid side chains.

  5. Superhydrophilic surfaces from short and medium chain solvo-surfactants

    Directory of Open Access Journals (Sweden)

    Valentin Romain

    2013-01-01

    Full Text Available Pure monoglycerides (GM-Cs and glycerol carbonate esters (GCE-Cs are two families of oleochemical molecules composed of a polar part, glycerol for GM-Cs, glycerol carbonate for GCE-Cs, and a fatty acid lipophilic part. From a chemical point of view, GM-Cs include two free oxygen atoms in the hydroxyl functions and one ester function between the fatty acid and the glycerol parts. GCE-Cs contain two blocked oxygen atoms in the cyclic carbonate backbone and three esters functions: two endocyclic in the five-membered cyclic carbonate function, one exocyclic between the fatty acid and glycerol carbonate parts. At the physico-chemical level, GMCs and GCE-Cs are multifunctional molecules with amphiphilic structures: a common hydrophobic chain to the both families and a polar head, glycerol for GMs and glycerol carbonate for GCE-Cs. Physicochemical properties depend on chain lengths, odd or even carbon numbers on the chain, and glyceryl or cyclocarbonic polar heads. The solvo-surfactant character of GM-Cs and overall GCE-Cs were discussed through the measurements of critical micellar concentration (CMC or critical aggregation concentration (CAC. These surface active glycerol esters/glycerol carbonate esters were classified following their hydrophilic/hydrophobic character correlated to their chain length (LogPoctanol/water = f(atom carbon number. Differential scanning calorimetry and optical polarized light microscopy allow us to highlight the selfassembling properties of the glycerol carbonate esters alone and in presence of water. We studied by thermal analysis the polymorphic behaviour of GCE-Cs, and the correlation between their melting points versus the chain lengths. Coupling the self-aggregation and crystallization properties, superhydrophilic surfaces were obtained by formulating GM-Cs and GCE-Cs. An efficient durable water-repellent coating of various metallic and polymeric surfaces was allowed. Such surfaces coated by self-assembled fatty acid

  6. Ab initio I-V characteristics of short C-20 chains

    DEFF Research Database (Denmark)

    Roland, C.; Larade, B.; Taylor, Jeremy Philip

    2002-01-01

    We have calculated the I-V characteristics of short chains of C-20 molecular cages between Al and Au leads with an ab initio formalism. The results indicate that a linear chain of such molecules acts primarily as metallic nanowires. The transmission, however, depends sensitively both...

  7. Risk assessment of Short and Medium Chain Chlorinated Paraffin’s (SCCP and MCCP)

    DEFF Research Database (Denmark)

    Christensen, Frans Møller; Olsen, Stig Irving

    2002-01-01

    findings of the Short Chain Chlorinated Paraffin (SCCP) and the draft Medium Chain Chlorinated Paraffin (MCCP) risk assessments. The political actions taken as a consequence of the assessments are also described. The risk assessments have been prepared according to the EU Technical Guidance Document (TGD...

  8. Asymmetric Alkyl Side-Chain Engineering of Naphthalene Diimide-Based n-Type Polymers for Efficient All-Polymer Solar Cells.

    Science.gov (United States)

    Jia, Tao; Li, Zhenye; Ying, Lei; Jia, Jianchao; Fan, Baobing; Zhong, Wenkai; Pan, Feilong; He, Penghui; Chen, Junwu; Huang, Fei; Cao, Yong

    2018-02-13

    The design and synthesis of three n-type conjugated polymers based on a naphthalene diimide-thiophene skeleton are presented. The control polymer, PNDI-2HD, has two identical 2-hexyldecyl side chains, and the other polymers have different alkyl side chains; PNDI-EHDT has a 2-ethylhexyl and a 2-decyltetradecyl side chain, and PNDI-BOOD has a 2-butyloctyl and a 2-octyldodecyl side chain. These copolymers with different alkyl side chains exhibit higher melting and crystallization temperatures, and stronger aggregation in solution, than the control copolymer PNDI-2HD that has the same side chain. Polymer solar cells based on the electron-donating copolymer PTB7-Th and these novel copolymers exhibit nearly the same open-circuit voltage of 0.77 V. Devices based on the copolymer PNDI-BOOD with different side chains have a power-conversion efficiency of up to 6.89%, which is much higher than the 4.30% obtained with the symmetric PNDI-2HD. This improvement can be attributed to the improved charge-carrier mobility and the formation of favorable film morphology. These observations suggest that the molecular design strategy of incorporating different side chains can provide a new and promising approach to developing n-type conjugated polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. End-anchored polymers in good solvents from the single chain limit to high anchoring densities.

    Science.gov (United States)

    Whitmore, Mark D; Grest, Gary S; Douglas, Jack F; Kent, Michael S; Suo, Tongchuan

    2016-11-07

    An increasing number of applications utilize grafted polymer layers to alter the interfacial properties of solid substrates, motivating refinement in our theoretical understanding of such layers. To assess existing theoretical models of them, we have investigated end-anchored polymer layers over a wide range of grafting densities, σ, ranging from a single chain to high anchoring density limits, chain lengths ranging over two orders of magnitude, for very good and marginally good solvent conditions. We compare Monte Carlo and molecular dynamics simulations, numerical self-consistent field calculations, and experimental measurements of the average layer thickness, h, with renormalization group theory, the Alexander-de Gennes mushroom theory, and the classical brush theory. Our simulations clearly indicate that appreciable inter-chain interactions exist at all simulated areal anchoring densities so that there is no mushroom regime in which the layer thickness is independent of σ. Moreover, we find that there is no high coverage regime in which h follows the predicted scaling, h ∼ Nσ 1/3 , for classical polymer brushes either. Given that no completely adequate analytic theory seems to exist that spans wide ranges of N and σ, we applied scaling arguments for h as a function of a suitably defined reduced anchoring density, defined in terms of the solution radius of gyration of the polymer chains and N. We find that such a scaling approach enables a smooth, unified description of h in very good solvents over the full range of anchoring density and chain lengths, although this type of data reduction does not apply to marginal solvent quality conditions.

  10. Consistent model reduction of polymer chains in solution in dissipative particle dynamics: Model description

    KAUST Repository

    Moreno Chaparro, Nicolas

    2015-06-30

    We introduce a framework for model reduction of polymer chain models for dissipative particle dynamics (DPD) simulations, where the properties governing the phase equilibria such as the characteristic size of the chain, compressibility, density, and temperature are preserved. The proposed methodology reduces the number of degrees of freedom required in traditional DPD representations to model equilibrium properties of systems with complex molecules (e.g., linear polymers). Based on geometrical considerations we explicitly account for the correlation between beads in fine-grained DPD models and consistently represent the effect of these correlations in a reduced model, in a practical and simple fashion via power laws and the consistent scaling of the simulation parameters. In order to satisfy the geometrical constraints in the reduced model we introduce bond-angle potentials that account for the changes in the chain free energy after the model reduction. Following this coarse-graining process we represent high molecular weight DPD chains (i.e., ≥200≥200 beads per chain) with a significant reduction in the number of particles required (i.e., ≥20≥20 times the original system). We show that our methodology has potential applications modeling systems of high molecular weight molecules at large scales, such as diblock copolymer and DNA.

  11. Unlocking Chain Exchange in Highly Amphiphilic Block Polymer Micellar Systems: Influence of Agitation.

    Science.gov (United States)

    Murphy, Ryan P; Kelley, Elizabeth G; Rogers, Simon A; Sullivan, Millicent O; Epps, Thomas H

    2014-11-18

    Chain exchange between block polymer micelles in highly selective solvents, such as water, is well-known to be arrested under quiescent conditions, yet this work demonstrates that simple agitation methods can induce rapid chain exchange in these solvents. Aqueous solutions containing either pure poly(butadiene- b -ethylene oxide) or pure poly(butadiene- b -ethylene oxide- d 4 ) micelles were combined and then subjected to agitation by vortex mixing, concentric cylinder Couette flow, or nitrogen gas sparging. Subsequently, the extent of chain exchange between micelles was quantified using small angle neutron scattering. Rapid vortex mixing induced chain exchange within minutes, as evidenced by a monotonic decrease in scattered intensity, whereas Couette flow and sparging did not lead to measurable chain exchange over the examined time scale of hours. The linear kinetics with respect to agitation time suggested a surface-limited exchange process at the air-water interface. These findings demonstrate the strong influence of processing conditions on block polymer solution assemblies.

  12. Conformation and elasticity of a charged polymer chain bridging two nanoparticles

    International Nuclear Information System (INIS)

    Nowicki, W.; Nowicka, G.

    2013-01-01

    A complex composed of a charged flexible polymer chain irreversibly attached with its ends to surfaces of two nanoparticles was investigated using the Metropolis Monte Carlo method on a simple cubic lattice. The simulations were performed in the presence of explicit ions. The bridging chain and the nanoparticles bearing the same and the opposite sign charges were considered. Changes in the free energy of the complex upon its stretching or compression, together with the magnitude of the elastic force, were examined. The relative roles of energetic and entropic effects in determining the properties of the complex were identified. Also, the adsorption of charged monomers on the opposite-sign charged nanoparticles and its influence on the examined quantities was studied. Moreover, a simple semi-analytical approach to the thermodynamics of the polymer bridge was derived

  13. Solid state nuclear magnetic resonance spectroscopy of polymer thin films: chain conformation, dynamics, and morphology

    International Nuclear Information System (INIS)

    Nasreddine, V.F.

    2003-01-01

    This dissertation presents solid-state NMR studies of the chain conformation, dynamics and morphology of three adsorbed polymer systems: two random semi-crystalline copolymers, poly(ethylene-co-acrylic acid) (PEA) and poly(propylene-co-acrylic acid) (PPA), and an amorphous homopolymer, poly(n-butyl methacrylate) (PnBMA). Zirconia (ZrO 2 ) was chosen as the substrate for all three polymers since the binding of carboxylic acids to this metal oxide is well understood. The choice of polymers was based on their particular bulk conformational and dynamic properties as well as their common use in polymer coatings. These studies are motivated by the general lack of a microscopic picture of adsorbed polymers, which can be provided by NMR, and the relevance of chain conformation and dynamics to important polymer film properties such as adhesion. First the chain conformation and surface binding of adsorbed PEA as a function of acrylic acid content are characterized by 13 C cross polarization - magic angle spinning (CP-MAS), 2D 1 H- 13 C wideline separation (WISE) and 1 H spin diffusion NMR experiments and FTIR-PAS (Fourier transform infrared photoacoustic spectroscopy) measurements. The most important finding is that the chain conformation of adsorbed PEA is determined primarily by the sticker group density rather than the surface coverage. The second study of PEA concerns the chain dynamics in the bulk and adsorbed states. Variable temperature NMR experiments provide evidence that ethylene segments of adsorbed PEA form partially folded loops rather than flat extended trains. Finally 129 Xe NMR studies, used to probe the morphology of adsorbed PEA, show a bulk-like signal only for the highest loadings. The second system investigated, PPA, is another semi-crystalline random copolymer which binds to zirconia via carboxylate linkages. The 13 C CP-MAS NMR spectra of adsorbed PPAC unexpectedly show splittings normally associated with chain-chain packing in the crystalline regions

  14. Controlling photophysical properties of ultrasmall conjugated polymer nanoparticles through polymer chain packing

    KAUST Repository

    Piwonski, Hubert Marek; Michinobu, Tsuyoshi; Habuchi, Satoshi

    2017-01-01

    of the development of Pdots. Here we demonstrate that proper control of the physical interactions between the chains is as critical as the molecular design. The unique design of twisted CPs and fine-tuning of the reprecipitation conditions allow us to fabricate

  15. Single-chain statistics and the upper wave-vector cutoff in polymer blends

    International Nuclear Information System (INIS)

    Holyst, R.; Vilgis, T.A.

    1994-01-01

    We derive the equation for the single-chain correlation function in polymer blends. The chains in the incompressible blend have a radius of gyration smaller than the radius of gyration for ideal chains. The chains shrink progressively as we approach the critical temperature T c . The correction responsible for shrinking is proportional to 1/ √N , where N is the polymerization index. At T=T c and for N=1000, the size of the chain has been estimated to be 10% smaller than the size of the ideal coil. The estimate relies on the appropriate cutoff. In the limit of N→∞ the chains approach the random walk limit. Additionally, we propose in this paper a self-consistent determination of the radius of gyration and the upper wave-vector cutoff. Our model is free from any divergences such as were encountered in the previous mean-field studies; we make an estimate of the chain size at the true critical temperature and not the mean-field one

  16. Water Sorption and Hindered Diffusion with Different Chain Stiffness of Superabsorbent Polymer

    Energy Technology Data Exchange (ETDEWEB)

    Chun, Myung-Suk; Lee, Dae-Young [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2015-01-15

    Water sorption and diffusion are essential physicochemical properties of a high-performance superabsorbent polymer (SAP). We combine the Park model with the obstruction-scaling model and the water clustering in confined spaces of the polymer hydrogel. Special attention is focused on elucidating the effect of chain stiffness by considering the conformation of the polymer chain. Theoretical model parameters are determined from the best fits by simultaneous nonlinear regressions for both sorption and corrected diffusion data based on previous experiments with poly(acrylamide-co-sodium acrylate) hydrogel. Predictions show that the hindered water diffusivity leads to a sigmoid curve with relative humidity a{sub w}, where it increases monotonically up to aw{sub ≅} 0.6 due to the swelling but decreases at higher a{sub w} caused by water clustering. Water diffusion decreases with increasing chain stiffness, and the larger persistence length provides a smaller opening radius in void spaces regarding the weak elastic deformation of hydrogel under the applied stress.

  17. Microscopic theory of light-induced deformation in amorphous side-chain azobenzene polymers.

    Science.gov (United States)

    Toshchevikov, V; Saphiannikova, M; Heinrich, G

    2009-04-16

    We propose a microscopic theory of light-induced deformation of side-chain azobenzene polymers taking into account the internal structure of polymer chains. Our theory is based on the fact that interaction of chromophores with the polarized light leads to the orientation anisotropy of azobenzene macromolecules which is accompanied by the appearance of mechanical stress. It is the first microscopic theory which provides the value of the light-induced stress larger than the yield stress. This result explains a possibility for the inscription of surface relief gratings in glassy side-chain azobenzene polymers. For some chemical architectures, elongation of a sample demonstrates a nonmonotonic behavior with the light intensity and can change its sign (a stretched sample starts to be uniaxially compressed), in agreement with experiments. Using a viscoplastic approach, we show that the irreversible strain of a sample, which remains after the light is switched off, decreases with increasing temperature and can disappear at certain temperature below the glass transition temperature. This theoretical prediction is also confirmed by recent experiments.

  18. Location of radiation-induced grafted chains in polymers studied by solid-state NMR

    International Nuclear Information System (INIS)

    Whittacker, A.; Liu, H.

    1998-01-01

    In this study styrene and N-phenyl maleimide monomers were grafted onto poly(ethylene) (PE) chains using gamma radiation. Of main interest is the distribution of grafted chains within the polymer matrix, as this will determine the efficacy of mixing with the glassy polymers. It is expected that grafting will occur within the amorphous regions, and especially near the interface of the crystalline and amorphous regions. A suitable method for characterising the location of the grafted chains is solid-state 13 C NMR spectroscopy. The 13 C CPMAS spectrum of the blend of PE and N-phenyl maleimide mixed in the melt at 150 deg C , prior to reaction, is shown above. The spectrum shows the typical peaks for poly(ethylene) due to the amorphous and crystalline phase at 30.5 and 32.5 ppm, respectively. Peaks are also seen in the aromatic and carbonyl region due to the maleimide (not plotted). Experiments will be described where the NMR magnetisation is prepared in either the crystalline and amorphous regions of the poly(ethylene) prior to spin diffusion to the maleimide and styrene fractions. The location of the grafted monomers can then be determined by monitoring the changes in signal of polymer and graft with time

  19. Gamma-radiation induced polymerization of methyl methacrylate in aliphatic hydrocarbons: kinetics and evidence for incorporation of hydrocarbon in the polymer chain

    International Nuclear Information System (INIS)

    Mohan, H.; Iyer, R.M.

    1989-01-01

    On γ-radiolysis, the rate of polymerization of methyl methacrylate in hydrocarbon solvents is observed to decrease. It is explained by hydrocarbon entry into the polymer chains. The hydrocarbon entry into the polymer chains is observed to take place at later stages of polymerization and increases with hydrocarbon chain length. The extent of hydrocarbon entry into the polymer chains is estimated by NMR and GLC analysis. It is observed to be equal to ∼ 12% corresponding to ∼ 97 hexadecane molecules in each polymer chain. The IR, DSC, MW determination and radiation effects on the polymer showed evidences for hydrocarbon entry into the polymer. It is explained by chain transfer from the growing polymer radical to the hydrocarbon molecules. The chain transfer constant is determined to be equal to 1 x 10 -2 . (author)

  20. Synthesis and characterization of associating polymers which contain siloxanes chains; Synthese et caracterisation de polymeres associatifs porteurs de groupes siloxanes

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, V

    1999-01-11

    Polymers that associate via physical interactions in solutions have received much attention as viscosifiers. Such associating polymers are now used in variety of applications due to their unique theological properties coating, food thickeners, paints, enhanced oil recovery, water treatment). They contain a hydrophilic main chain with hydrophobic side chain that is generally constituted of hydrocarbon or fluorocarbon groups. Novel copolymers with sites of association in aqueous solution were prepared by co-polymerizing acrylamide with an hydrophobic monomer containing siloxane parts. Rheological properties were studied as a function of polymer concentration, microstructure, shear rate and frequency in order to show intra intermolecular associations between the hydrophobic parts. The polymer solution viscosity increases as a function of the hydrophobic group content. Tests of adsorption show a high affinity of these copolymers with clay and the amount absorbed increase with the quantity of hydrophobic entities containing in the chain. These properties are enhanced compared to copolymers containing hydrocarbon chains. (authors) 456 refs.

  1. A new series of two-ring-based side chain liquid crystalline polymers: synthesis and mesophase characterization

    CSIR Research Space (South Africa)

    Reddy, GSM

    2013-05-01

    Full Text Available A new series of side chain liquid crystalline polymers containing a core, a butamethylenoxy spacer, ester groups, and terminal alkoxy groups were synthesised and their structures were confirmed. The core was constructed with two phenyl rings...

  2. Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

    KAUST Repository

    Shivokhin, Maksim E.; Read, Daniel J.; Kouloumasis, Dimitris; Kocen, Rok; Zhuge, Flanco; Bailly, Christian; Hadjichristidis, Nikolaos; Likhtman, Alexei E.

    2017-01-01

    of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We

  3. Coulomb excitations for a short linear chain of metallic shells

    Energy Technology Data Exchange (ETDEWEB)

    Zhemchuzhna, Liubov, E-mail: lzhemchuzhna@unm.edu [Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States); Center for High Technology Materials, University of New Mexico, Albuquerque, New Mexico 87106 (United States); Gumbs, Godfrey [Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States); Donostia International Physics Center (DIPC), P de Manuel Lardizabal, 4, 20018 San Sebastian, Basque Country (Spain); Iurov, Andrii [Center for High Technology Materials, University of New Mexico, Albuquerque, New Mexico 87106 (United States); Huang, Danhong [Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117 (United States); Gao, Bo [Department of Physics and Astronomy, Hunter College of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States)

    2015-03-15

    A self-consistent-field theory is given for the electronic collective modes of a chain containing a finite number, N, of Coulomb-coupled spherical two-dimensional electron gases arranged with their centers along a straight line, for simulating electromagnetic response of a narrow-ribbon of metallic shells. The separation between nearest-neighbor shells is arbitrary and because of the quantization of the electron energy levels due to their confinement to the spherical surface, all angular momenta L of the Coulomb excitations, as well as their projections M on the quantization axis, are coupled. However, for incoming light with a given polarization, only one angular momentum quantum number is usually required. Therefore, the electromagnetic response of the narrow-ribbon of metallic shells is expected to be controlled externally by selecting different polarizations for incident light. We show that, when N = 3, the next-nearest-neighbor Coulomb coupling is larger than its value if they are located at opposite ends of a right-angle triangle forming the triad. Additionally, the frequencies of the plasma excitations are found to depend on the orientation of the line joining them with respect to the axis of quantization since the magnetic field generated from the induced oscillating electric dipole moment on one sphere can couple to the induced magnetic dipole moment on another. Although the transverse inter-shell electromagnetic coupling can be modeled by an effective dynamic medium, the longitudinal inter-shell Coulomb coupling, on the other hand, can still significantly modify the electromagnetic property of this effective medium between shells.

  4. Confinement Effects on Host Chain Dynamics in Polymer Nanocomposite Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Kyle J. [Department; Glynos, Emmanouil [Department; Maroulas, Serafeim-Dionysios [Department; Narayanan, Suresh [Advanced; Sakellariou, Georgios [Department; Green, Peter F. [Department; National

    2017-09-07

    Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g., sensing, energy conversion) of these materials influences other properties. One challenge is to understand the effects of nanoparticles on the viscosity of nanoscale thick polymer films. A new mechanism that contributes to an enhancement of the viscosity of nanoscale thick polymer/nanoparticle films is identified. We show that while the viscosities of neat homopolymer poly(2-vinylpyridine) (P2VP) films as thin as 50 nm remained the same as the bulk, polymer/nanoparticle films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were comparable to the bulk values. These results - NP proximities and suppression of their dynamics - suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for nanoscale applications.

  5. Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

    Directory of Open Access Journals (Sweden)

    Tahmina Haque

    2015-03-01

    Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

  6. Effect of chain rigidity on network architecture and deformation behavior of glassy polymer networks

    Science.gov (United States)

    Knowles, Kyler Reser

    Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of the polymer matrix in regards to strain storage and relaxation mechanisms which ultimately control composite performance throughout manufacturing and use. Through the use of a non-contact, full-field strain measurement technique known as digital image correlation (DIC), we describe and implement useful experiments which quantify matrix and composite parameters necessary for simulation efforts and failure models. The methods are compared to more traditional techniques and show excellent correlation. Further, we established relationships which represent matrix-fiber compatibility in regards to critical processing constraints. The second approach involves a systematic study of epoxy-amine networks which are chemically-similar but differ in chain segment rigidity. Prior research has investigated the isomer effect of glassy polymers, showing sizeable differences in thermal, volumetric, physical, and mechanical properties. This work builds on these themes and shows the apparent isomer effect is rather an effect of chain rigidity. Indeed, it was found that structurally-dissimilar polymer networks exhibit very similar properties as a consequence of their shared average network rigidity. Differences in chain packing, as a consequence of chain rigidity, were shown to

  7. Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations.

    Science.gov (United States)

    Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath; Narayanan, Suresh; Faraone, Antonio

    2017-11-08

    The effect of large deformation on the chain dynamics in attractive polymer nanocomposites was investigated using neutron scattering techniques. Quasi-elastic neutron backscattering measurements reveal a substantial reduction of polymer mobility in the presence of attractive, well-dispersed nanoparticles. In addition, large deformations are observed to cause a further slowing down of the Rouse rates at high particle loadings, where the interparticle spacings are slightly smaller than the chain dimensions, i.e. in the strongly confined state. No noticeable change, however, was observed for a lightly confined system. The reptation tube diameter, measured by neutron spin echo, remained unchanged after shear, suggesting that the level of chain-chain entanglements is not significantly affected. The shear-induced changes in the interparticle bridging reflect the slow nanoparticle motion measured by X-ray photon correlation spectroscopy. These results provide a first step for understanding how large shear can significantly affect the segmental motion in nanocomposites and open up new opportunities for designing mechanically responsive soft materials.

  8. New stochastic treatment of fermions with application to a double-chain polymer

    International Nuclear Information System (INIS)

    Kung, D.; Dahl, D.; Blankenbecler, R.; Deza, R.; Fulco, J.R.

    1985-01-01

    An extension of the stochastic algorithm as applied to Hamiltonian lattice field theories is developed. This new scheme will converge in problems that have intrinsic negative signs in the matrix elements. As an example, this scheme is applied to a two-chain polymer problem with (spinless) fermions that have a pairwise interaction. Because of the multiple connected structure of the double chain, this problem has intrinsic minus signs. It cannot be transformed into a bosonic problem with only positive matrix elements. Numerical results from this application of the new algorithm are presented for the energy and certain correlation functions for moderately long chains. A discussion of a modification of the method which will allow the treatment of much larger systems is discussed

  9. Efficient protein-repelling thin films regulated by chain mobility of low-Tg polymers with increased stability via crosslinking

    Science.gov (United States)

    Zhang, Jinghui; Huang, Zhiwei; Liu, Dan

    2017-12-01

    Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.

  10. Theoretical predictions for side-chain liquid-crystal polymers and comparison to experiment

    International Nuclear Information System (INIS)

    Dowell, F.

    1988-01-01

    This paper presents results from a new unique microscopic molecular theory for side-chain liquid-crystalline polymers (LCPs) in the nematic (N) and multiple smectic-A (SA) LC phases and the isotropic (I) liquid phase. There are no ad hoc or arbitrarily adjustable parameters in this theory. The agreement between the theoretical and experimental values for various properties (including transition temperatures and quadratic characteristic radii) is very good (relative deviations between 0% and less than 6.2%). The theoretical results also show--for the first time--that the N and I phases for these LCPs involve the packing of plate-like sections of backbones and side chains and that the local bilayer SA phase involves packing of side-chains within a plate-like section. This type of packing is predicted to be typical for side-chain LCPs. This theory can predict--for the first time--whether the side chains of a molecule pack on the same or alternating opposite sides of the backbone and whether side chains on different molecules interdigitate (overlap) with each other. 13 refs., 1 fig., 4 tabs

  11. Degradation behavior of polymer blend of isotactic polypropylenes with and without unsaturated chain end group

    International Nuclear Information System (INIS)

    Nakatani, Hisayuki; Kurniawan, Dodik; Taniike, Toshiaki; Terano, Minoru

    2008-01-01

    In this work, the relationship between the unsaturated chain end group content and the thermal oxidative degradation rate was systematically studied with binary polymer blends of isotactic polypropylene (iPP) with and without the unsaturated chain end group. The iPPs with and without the unsaturated chain end group were synthesized by a metallocene catalyst in the absence of hydrogen and by a Ziegler catalyst in the presence of one, respectively. The thermal oxidative degradation rate of the binary iPP blends was estimated from the molecular weight and the apparent activation energy (ΔE), which were obtained through size exclusion chromatography (SEC) and thermogravimetric analysis (TGA) measurements, respectively. These values exhibited a negative correlation against the mole content of the unsaturated chain end group. The thermal oxidative degradation rate apparently depends on the content of the unsaturated chain end group. This tendency suggests that the unsaturated chain end acts as a radical initiator of the iPP degradation reaction.

  12. Effect of chain stiffness on the structure of single-chain polymer nanoparticles

    DEFF Research Database (Denmark)

    Moreno, Angel J; Bacova, Petra; Lo Verso, Federica

    2018-01-01

    of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness...... or 'crumpled' globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour...... can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs. ....

  13. Long Range Polymer Chain Dynamics of Highly Flexible Polysiloxane in Solution Probed by Pyrene Excimer Fluorescence

    Directory of Open Access Journals (Sweden)

    Janine L. Thoma

    2018-03-01

    Full Text Available A poly(dimethylsiloxane-co-(3-aminopropylmethylsiloxane polymer (PDMS with 20.3 mol % of (3-aminopropylmethyl siloxane monomer has been labeled randomly with 1-pyreneacetyl groups to generate a series of polysiloxanes (Py-PDMS with pyrenyl contents ranging from 0.7 mol % to 5.2 mol % of the total number of structural units. The remainder of the amino groups were acetylated to avoid intra-chain quenching of the excited singlet states of pyrene via exciplex formation with free amino groups while allowing the formation of excimers to proceed. The fluorescence spectra and temporal decays of the Py-PDMS samples were acquired in tetrahydrofuran (THF, N,N-dimethylformamide (DMF, and dioxane. blob, the average rate constant for intra-chain pyrene excimer formation, was determined from the analysis of the fluorescence decays. blob was found to equal 1.16 (±0.13 × 109, 1.14 (±0.12 × 109, and 0.99 (±0.10 × 109 s−1 in THF, DMF, and dioxane, respectively, at room temperature. They are the largest values found to date for any polymeric backbone in these solvents. The qualitative relationship found here between blob and the chemical structures of the polymers indicates that the luminescence characteristics of randomly labeled polymers is a very useful method to probe the long range dynamics of chains of almost any polymer that is amenable to substitution by a lumophore.

  14. Multi-functionalized side-chain supramolecular polymers: A methodology towards tunable functional materials

    Science.gov (United States)

    Nair, Kamlesh Prabhakaran

    Even as we see a significant growth in the field of supramolecular polymers in the last ten years, multi-functionalized systems have been scarcely studied. Noncovalent multi-functionalization provides unique advantages such as rapid materials optimization via reversible functionalization as well as for the tuning of materials properties by exploiting the differences in the nature of these reversible interactions. This thesis involves the design principles, synthesis & methodology of supramolecular side-chain multi-functionalized polymers. The combination of a functionally tolerant & controlled polymerization technique such as ROMP with multiple noncovalent interactions such as hydrogen bonding, metal coordination and ionic interactions has been successfully used to synthesize these polymers. Furthermore, the orthogonality between the above interactions in block/random copolymers has been studied in detail. It has been found that the studied interactions were orthogonal to each other. To validate the viability of this methodology using multiple orthogonal interactions towards materials design noncovalent crosslinking of polymers has been used as a potential application. Three classes of networks have been studied: complementary multiple hydrogen bonded networks, metal crosslinked networks, & multi-functionalized hydrogen bonded and metal coordinated networks. The first room temperature decrosslinking by exclusive complementary hydrogen bonded interactions has been successfully achieved. Furthermore network properties have been successfully tuned by varying the network micro-structure which in turn was tuned by the hydrogen bonding motifs used for inter-chain crosslinking. By combining two different noncovalent interactions used for inter-chain crosslinking, it was possible to make multi-functionalized materials whose properties could be controlled by varying the crosslinking strategy. Hence by employing multi-functionalization methodology, important materials

  15. Statistical model of a flexible inextensible polymer chain: The effect of kinetic energy

    Science.gov (United States)

    Pergamenshchik, V. M.; Vozniak, A. B.

    2017-01-01

    Because of the holonomic constraints, the kinetic energy contribution in the partition function of an inextensible polymer chain is difficult to find, and it has been systematically ignored. We present the first thermodynamic calculation incorporating the kinetic energy of an inextensible polymer chain with the bending energy. To explore the effect of the translation-rotation degrees of freedom, we propose and solve a statistical model of a fully flexible chain of N +1 linked beads which, in the limit of smooth bending, is equivalent to the well-known wormlike chain model. The partition function with the kinetic and bending energies and correlations between orientations of any pair of links and velocities of any pair of beads are found. This solution is precise in the limits of small and large rigidity-to-temperature ratio b /T . The last exact solution is essential as even very "harmless" approximation results in loss of the important effects when the chain is very rigid. For very high b /T , the orientations of different links become fully correlated. Nevertheless, the chain does not go over into a hard rod even in the limit b /T →∞ : While the velocity correlation length diverges, the correlations themselves remain weak and tend to the value ∝T /(N +1 ). The N dependence of the partition function is essentially determined by the kinetic energy contribution. We demonstrate that to obtain the correct energy and entropy in a constrained system, the T derivative of the partition function has to be applied before integration over the constraint-setting variable.

  16. Fluorescence Correlation Spectroscopy to Study Diffusion of Polymer Chains within Layered Hydrogen-Bonded Polymer Films

    Science.gov (United States)

    Pristinski, Denis; Kharlampieva, Evguenia; Sukhishvili, Svetlana

    2002-03-01

    Fluorescence Correlation Spectroscopy (FCS) has been used to probe molecular motions within polymer multilayers formed by hydrogen-bonding sequential self-assembly. Polyethylene glycol (PEG) molecules were end-labeled with the fluorescent tags, and self-assembled with polymethacrylic acid (PMAA) using layer-by-layer deposition. We have found that molecules included in the top adsorbed layer have significant mobility at the millisecond time scale, probably due to translational diffusion. However, their dynamics deviate from classical Brownian motion with a single diffusion time. Possible reasons for the deviation are discussed. We found that motions were significantly slowed with increasing depth within the PEG/PMAA multilayer. This phenomena occured in a narrow pH range around 4.0 in which intermolecular interactions were relatively weak.

  17. Determination of Short-Chain Chlorinated Paraffins by Carbon Skeleton Gas Chromatography

    OpenAIRE

    PELLIZZATO FRANCESCA; RICCI MARINA; HELD ANDREA; EMONS HENDRIK

    2008-01-01

    Short-Chain Chlorinated Paraffins (SCCPs) are highly complex technical mixtures of polychlorinated n-alkanes with a chlorination degree between 50 and 70 % by mass, and a linear carbon chain length from C10 to C13, constituted by thousands of homologues, diastereomers and enantiomers. They have been used in many different applications, such as extreme pressure additives in lubricants and cutting fluids, plasticizers in PVC, and flame retardants in paints, adhesives and sealants. SCCPs are tox...

  18. Interference of a short-chain phospholipid with ion transport pathways in frog skin

    DEFF Research Database (Denmark)

    Unmack, M A; Frederiksen, O; Willumsen, N J

    1997-01-01

    The effects of mucosal application of the short-chain phospholipid didecanoyl-L-alpha-phosphatidylcholine (DDPC; with two saturated 10-carbon acyl chains) on active Na+ transport and transepithelial conductance (G) in the frog skin (Rana temporaria) were investigated. Active Na+ transport...... of the frog skin epithelium and opens a paracellular tight junction pathway. Both effects may be caused by incorporation of DDPC in the apical cell membrane....

  19. Barriers to the development of the short supply chain for local food producers in Romania

    Directory of Open Access Journals (Sweden)

    Lavinia DOVLEAC

    2017-07-01

    Full Text Available This article highlights the importance of short food supply chains for the development of rural areas in Romania, considering the increasing demand of the population for healthy food. A proper functionality of these local food supply chains brings benefits to producers, consumers and the local community, but some issues must be solved. This article presents the results of a qualitative marketing research study conducted for identifying the difficulties in this sector. The study aimed to identify the small producers’ opinions on the barriers to the development of these supply chains and how they could be helped to sell their products at a fair price.

  20. Orientational cross correlations between entangled branch polymers in primitive chain network simulations

    Science.gov (United States)

    Masubuchi, Yuichi; Pandey, Ankita; Amamoto, Yoshifumi; Uneyama, Takashi

    2017-11-01

    Although it has not been frequently discussed, contributions of the orientational cross-correlation (OCC) between entangled polymers are not negligible in the relaxation modulus. In the present study, OCC contributions were investigated for 4- and 6-arm star-branched and H-branched polymers by means of multi-chain slip-link simulations. Owing to the molecular-level description of the simulation, the segment orientation was traced separately for each molecule as well as each subchain composing the molecules. Then, the OCC was calculated between different molecules and different subchains. The results revealed that the amount of OCC between different molecules is virtually identical to that of linear polymers regardless of the branching structure. The OCC between constituent subchains of the same molecule is significantly smaller than the OCC between different molecules, although its intensity and time-dependent behavior depend on the branching structure as well as the molecular weight. These results lend support to the single-chain models given that the OCC effects are embedded into the stress-optical coefficient, which is independent of the branching structure.

  1. Adsorption of short-chain fluids at solid substrates from density functional theory

    International Nuclear Information System (INIS)

    Bryk, P.; Bucior, K.; Sokolowski, S.; Zukocinski, G.

    2005-01-01

    We use microscopic density functional theory to investigate the adsorption of short-chains at solid surfaces. The fluid is modeled as freely-jointed tangent spheres that interact via a short-ranged attractive potential. Within the framework of fundamental measure theory we study how the structure and surface phase behaviour of adsorbed fluid changes when the chain length is increased. We observe that the wetting temperature rescaled by the bulk critical temperature decreases with an increase of the chain length. For longer chains this temperature reaches a plateau. For the surface critical temperature an inverse effect is observed, i.e. the surface critical temperature increases with the chain length and then attains a plateau. Furthermore, we analyze how the layering transitions change with the change of the chain length and with relative strength of the fluid-solid interaction. The critical temperature of the first layering transition, rescaled by the bulk critical temperature increases slightly with an increase of the chain length. We have found that for longer chains the layering transitions within consecutive layers are shifted towards very low temperatures and that their sequence is finally replaced by a single transition. Finally we investigate capillary condensation of chain fluid in slit-like pores. We find that for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. (author)

  2. Polymer Main-Chain Substitution Effects on the Efficiency of Nonfullerene BHJ Solar Cells

    KAUST Repository

    Firdaus, Yuliar; Maffei, Luna Pratali; Cruciani, Federico; Mü ller, Michael A.; Liu, Shengjian; Lopatin, Sergei; Wehbe, Nimer; Ngongang Ndjawa, Guy Olivier; Amassian, Aram; Laquai, Fré dé ric; Beaujuge, Pierre

    2017-01-01

    “Nonfullerene” acceptors are proving effective in bulk heterojunction (BHJ) solar cells when paired with selected polymer donors. However, the principles that guide the selection of adequate polymer donors for high-efficiency BHJ solar cells with nonfullerene acceptors remain a matter of some debate and, while polymer main-chain substitutions may have a direct influence on the donor–acceptor interplay, those effects should be examined and correlated with BHJ device performance patterns. This report examines a set of wide-bandgap polymer donor analogues composed of benzo[1,2-b:4,5-b′]dithiophene (BDT), and thienyl ([2H]T) or 3,4-difluorothiophene ([2F]T) motifs, and their BHJ device performance pattern with the nonfullerene acceptor “ITIC”. Studies show that the fluorine- and ring-substituted derivative PBDT(T)[2F]T largely outperforms its other two polymer donor counterparts, reaching power conversion efficiencies as high as 9.8%. Combining several characterization techniques, the gradual device performance improvements observed on swapping PBDT[2H]T for PBDT[2F]T, and then for PBDT(T)[2F]T, are found to result from (i) notably improved charge generation and collection efficiencies (estimated as ≈60%, 80%, and 90%, respectively), and (ii) reduced geminate recombination (being suppressed from ≈30%, 25% to 10%) and bimolecular recombination (inferred from recombination rate constant comparisons). These examinations will have broader implications for further studies on the optimization of BHJ solar cell efficiencies with polymer donors and a wider range of nonfullerene acceptors.

  3. Polymer Main-Chain Substitution Effects on the Efficiency of Nonfullerene BHJ Solar Cells

    KAUST Repository

    Firdaus, Yuliar

    2017-07-21

    “Nonfullerene” acceptors are proving effective in bulk heterojunction (BHJ) solar cells when paired with selected polymer donors. However, the principles that guide the selection of adequate polymer donors for high-efficiency BHJ solar cells with nonfullerene acceptors remain a matter of some debate and, while polymer main-chain substitutions may have a direct influence on the donor–acceptor interplay, those effects should be examined and correlated with BHJ device performance patterns. This report examines a set of wide-bandgap polymer donor analogues composed of benzo[1,2-b:4,5-b′]dithiophene (BDT), and thienyl ([2H]T) or 3,4-difluorothiophene ([2F]T) motifs, and their BHJ device performance pattern with the nonfullerene acceptor “ITIC”. Studies show that the fluorine- and ring-substituted derivative PBDT(T)[2F]T largely outperforms its other two polymer donor counterparts, reaching power conversion efficiencies as high as 9.8%. Combining several characterization techniques, the gradual device performance improvements observed on swapping PBDT[2H]T for PBDT[2F]T, and then for PBDT(T)[2F]T, are found to result from (i) notably improved charge generation and collection efficiencies (estimated as ≈60%, 80%, and 90%, respectively), and (ii) reduced geminate recombination (being suppressed from ≈30%, 25% to 10%) and bimolecular recombination (inferred from recombination rate constant comparisons). These examinations will have broader implications for further studies on the optimization of BHJ solar cell efficiencies with polymer donors and a wider range of nonfullerene acceptors.

  4. Negative compressibility and non-equivalence of two statistical ensembles in the escape transition of a polymer chain

    NARCIS (Netherlands)

    Skvortsov, A.M.; Klushin, L.I.; Leermakers, F.A.M.

    2007-01-01

    An end-tethered polymer chain compressed between two pistons undergoes an abrupt transition from a confined coil state to an inhomogeneous flowerlike conformation partially escaped from the gap. This phase transition is first order in the thermodynamic limit of infinitely long chains. A rigorous

  5. Tuning the Mechanical Properties of Polymer Nanocomposites Filled with Grafted Nanoparticles by Varying the Grafted Chain Length and Flexibility

    Directory of Open Access Journals (Sweden)

    Zixuan Wang

    2016-08-01

    Full Text Available By employing coarse-grained molecular dynamics simulation, we simulate the spatial organization of the polymer-grafted nanoparticles (NPs in homopolymer matrix and the resulting mechanical performance, by particularly regulating the grafted chain length and flexibility. The morphologies ranging from the agglomerate, cylinder, sheet, and string to full dispersion are observed, by gradually increasing the grafted chain length. The radial distribution function and the total interaction energy between NPs are calculated. Meanwhile, the stress–strain behavior of each morphology and the morphological evolution during the uniaxial tension are simulated. In particular, the sheet structure exhibits the best mechanical reinforcement compared to other morphologies. In addition, the change of the grafted chain flexibility to semi-flexibility leads to the variation of the morphology. We also find that at long grafted chain length, the stress–strain behavior of the system with the semi-flexible grafted chain begins to exceed that of the system with the flexible grafted chain, attributed to the physical inter-locking interaction between the matrix and grafted polymer chains. A similar transition trend is as well found in the presence of the interfacial chemical couplings between grafted and matrix polymer chains. In general, this work is expected to help to design and fabricate high performance polymer nanocomposites filled with grafted NPs with excellent and controllable mechanical properties.

  6. Deformation and concentration fluctuations under stretching in a polymer network with free chains. The ''butterfly'' effect

    International Nuclear Information System (INIS)

    Ramzi, A.

    1994-06-01

    Small Angle Neutron Scattering gives access to concentration fluctuations of mobile labeled polymer chains embedded in a polymer network. At rest they appear progressively larger than for random mixing, with increasing ratio. Under uniaxial stretching, they decrease towards ideal mixing along the direction perpendicular to stretching, and can grow strongly along the parallel one, including the zero scattering vector q limit. This gives rise to intensity contours with double-winged patterns, in the shape of the figure '8', or of 'butterfly'. Random crosslinking and end-linking of monodisperse chains have both been studied. The strength of the 'butterfly' effect increases with the molecular weight of the free chains, the crosslinking ratio, the network heterogeneity, and the elongation ratio. Eventually, the signal collapses on an 'asymptotic' function I(q), of increasing correlation length with the elongation ratio. Deformation appears heterogeneous, maximal for soft areas, where the mobile chains localize preferentially. This could be due to spontaneous fluctuations, or linked to frozen fluctuations of the crosslink density. However, disagreement with the corresponding theoretical expressions makes it necessary to account for the spatial correlations of crosslink density, and their progressive unscreening as displayed by the asymptotic behavior. Networks containing pending labeled chains and free labeled stars lead to more precise understanding of the diffusion of free species and the heterogeneity of the deformation. It seems that the latter occurs even without diffusion for heterogeneous enough networks. In extreme cases (of the crosslinking parameters), the spatial correlations display on apparent fractal behavior, of dimensions 2 to 2.5, which is discussed here in terms of random clusters. 200 refs., 95 figs., 21 tabs., 10 appends

  7. Effect of the alkyl chain length of the ionic liquid anion on polymer electrolytes properties

    International Nuclear Information System (INIS)

    Leones, Rita; Sentanin, Franciani; Nunes, Sílvia Cristina; Esperança, José M.S.S.; Gonçalves, Maria Cristina

    2015-01-01

    New polymer electrolytes (PEs) based on chitosan and three ionic liquid (IL) families ([C 2 mim][C n SO 3 ], [C 2 mim][C n SO 4 ] and [C 2 mim][diC n PO 4 ]) were synthesized by the solvent casting method. The effect of the length of the alkyl chain of the IL anion on the thermal, morphological and electrochemical properties of the PEs was studied. The solid polymer electrolytes SPE membranes were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), polarized optical microscopy (POM), atomic force microscopy (AFM), complex impedance spectroscopy (ionic conductivity) and cyclic voltammetry (CV). The obtained results evidenced an influence of the alkyl chain length of the IL anion on the temperature of degradation, birefringence, surface roughness and ionic conductivity of the membranes. The DSC, XRD and CV results showed independency from the length of the IL-anion-alkyl chain. The PEs displayed an predominantly amorphous morphology, a minimum temperature of degradation of 135 °C, a room temperature (T = 25 °C) ionic conductivity of 7.78 × 10 −4 S cm −1 and a wide electrochemical window of ∼ 4.0 V.

  8. Dynamics of particle chain formation in a liquid polymer under ac electric field: modeling and experiments

    International Nuclear Information System (INIS)

    Belijar, G; Valdez-Nava, Z; Diaham, S; Laudebat, L; Lebey, T; Jones, T B

    2017-01-01

    Polymer/ceramic composite materials are of great interest for their many potential applications because of their ability to combine at least two properties of the constitutive elements: particles and matrix. In most cases, such enhanced properties are required only in one direction. Orthotropic materials can be elaborated by applying an ac electric field to form particle chain structures in the direction of the electric field due to the dielectrophoretic interactions affecting the particles. However, there is still a lack in the understanding of the impact of the structures on the properties of the material. The aim of this study is to propose a predictive model for the evolution of the permittivity during the chain formation, by including micro- and macroscopic phenomena. The chaining model is based on dipole–dipole interactions and the dielectric permittivity is computed through a finite element method. In parallel, an experimental study is performed with online permittivity measurements of composites during chaining. The developed model is able to predict the experimental results from 1 vol% while taking into account parameters such as the resin viscosity and permittivity and the transient evolution of the applied electric field. The formation of particle chains inside a material has applications in many domains such as electrorheological fluids, anisotropic composites, self-recovery materials etc. Such a developed model is a valuable tool for the tailoring of materials. (paper)

  9. A directed walk model of a long chain polymer in a slit with attractive walls

    International Nuclear Information System (INIS)

    Brak, R; Owczarek, A L; Rechnitzer, A; Whittington, S G

    2005-01-01

    We present the exact solutions of various directed walk models of polymers confined to a slit and interacting with the walls of the slit via an attractive potential. We consider three geometric constraints on the ends of the polymer and concentrate on the long chain limit. Apart from the general interest in the effect of geometrical confinement, this can be viewed as a two-dimensional model of steric stabilization and sensitized flocculation of colloidal dispersions. We demonstrate that the large width limit admits a phase diagram that is markedly different from the one found in a half-plane geometry, even when the polymer is constrained to be fixed at both ends on one wall. We are not able to find a closed form solution for the free energy for finite width, at all values of the interaction parameters, but we can calculate the asymptotic behaviour for large widths everywhere in the phase plane. This allows us to find the force between the walls induced by the polymer and hence the regions of the plane where either steric stabilization or sensitized flocculation would occur

  10. Concentration fluctuations in miscible polymer blends: Influence of temperature and chain rigidity

    International Nuclear Information System (INIS)

    Dudowicz, Jacek; Freed, Karl F.; Douglas, Jack F.

    2014-01-01

    In contrast to binary mixtures of small molecule fluids, homogeneous polymer blends exhibit relatively large concentration fluctuations that can strongly affect the transport properties of these complex fluids over wide ranges of temperatures and compositions. The spatial scale and intensity of these compositional fluctuations are studied by applying Kirkwood-Buff theory to model blends of linear semiflexible polymer chains with upper critical solution temperatures. The requisite quantities for determining the Kirkwood-Buff integrals are generated from the lattice cluster theory for the thermodynamics of the blend and from the generalization of the random phase approximation to compressible polymer mixtures. We explore how the scale and intensity of composition fluctuations in binary blends vary with the reduced temperature τ ≡ (T − T c )/T (where T c is the critical temperature) and with the asymmetry in the rigidities of the components. Knowledge of these variations is crucial for understanding the dynamics of materials fabricated from polymer blends, and evidence supporting these expectations is briefly discussed

  11. Contamination profiles of short-chain polychlorinated n-alkanes in foodstuff samples from Japan

    Energy Technology Data Exchange (ETDEWEB)

    Matsukami, Hidenori; Kurunthachalam, S; Ohi, Etsumasa; Takasuga, Takumi [Shimadzu Techno Research, Inc., Kyoto (Japan); Iino, Fukuya; Nakanishi, Junko [National Inst. of Advanced Industrial Science and Technology, Tsukuba (Japan)

    2004-09-15

    Polychlorinated n-alkanes (PCAs) are group of chemicals manufactured by chlorination of liquid n-paraffin or paraffin wax that contain 30 to 70% chlorine by weight. Large amounts of PCAs are widely used as plasticizers for vinyl chloride, lubricants, paints, and flame retardants and number of other industrial applications. Annual global production of PCAs is approximately 300 kilo tones, with a majority having medium-carbon-chain (C14-C19) length. According to the investigation made by Kagaku Kogyo Nippon-Sha, the annual consumption of PCAs in Japan was about 83,000 tons in between 1986-2001. Short-carbon-chain (C10-C13) has been placed on the Priority Substance List under Canadian Environmental Protection Act and on the Environmental Protection Agency Toxic Release Inventory in the USA due to its potential to act as tumor promoters in mammals. Data on environment levels of PCAs is meager, nevertheless, PCAs have been measured at relatively high concentrations in biota from Sweden, biota, sediment from Canada and marine biota and human milk from the Canadian Arctic. In our earlier study, we reported concentrations of short-chain PCAs from sewage treatment plant (STP) collected from Tama River, Tokyo and river water and sediment from Tokyo and Osaka. STP influent water contained greater shortchain PCAs concentrations than STP effluent. In addition, some river water and sediment samples contained detectable concentrations of short-chain PCAs, which was similar to other industrial countries. However, there is no study conducted to explore the contamination profiles of short-chain PCAs in human foodstuff samples. In the present study, we analyzed eleven foodstuff samples that were purchased from various supermarkets in order to know the short-chain PCAs concentrations in the foodstuff and possible human total daily intake (TDI) amounts.

  12. The Role of Chain Length in Nonergodicity Factor and Fragility of Polymers

    DEFF Research Database (Denmark)

    Dalle-Ferrie, Cecile; Niss, Kristine; Sokolov, Alexei

    2010-01-01

    The mechanism that leads to different fragility values upon approaching the glass transition remains a topic of active discussion. Many researchers are trying to find an answer in the properties of the frozen glassy state. Following this approach, we focus here on a previously proposed relationship...... between the fragility of glass-formers and their nonergodicity factor, determined by inelastic X-ray scattering (IXS) in the glass. We extend this molecular liquid study to two model polymers— polystyrene (PS) and polyisobutylene (PIB)—for which we change the molecular weight. Polymers offer...... the opportunity to change the fragility without altering the chemical structure, just by changing the chain length. Thus, we specifically chose PS and PIB because they exhibit opposite dependences of fragility with molecular weight. Our analysis for these two polymers reveals no unique correlation between...

  13. Controlled and selective placement of boron subphthalocyanines on either chain end of polymers synthesized by nitroxide mediated polymerization

    Directory of Open Access Journals (Sweden)

    Benoît H. Lessard

    2015-10-01

    Full Text Available In previous studies, we synthesized the first organic light emitting diode (OLED using boron subphthalocyanines (BsubPcs based polymers. When designing new polymer materials for organic electronic applications such as OLEDs or organic photovoltaic (OPV devices it is important to consider not only the contribution of each monomer but also the polymer chain ends. In this paper we establish a post-polymerization strategy to couple BsubPcs onto either the α- or the ω-chain end using chemically selective BsubPc derivatives. We outline how the chain ends of two representative polymers, poly(styrene (PS and poly(n-butylacrylate (BA, synthesized by nitroxide mediated polymerization (NMP, using BlocBuilder-MA as the initiating species, can be chemically modified by the incorporation of BsubPc chromophores. The addition of the BsubPc chromophore was confirmed through the use of a photodiode array detector (PDA connected in-line with a gel permeation chromatography (GPC setup. These findings represent the first reported method for the controlled and selective placement of a BsubPc chromophores on either end of a polymer produced by NMP. This strategy will therefore be utilized to make next generation BsubPc polymers for OLEDs and OPV devices. The extremely high molar extinction coefficient of BsubPc also make these polymers ideally suited for dye-labelling of polymers.

  14. Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

    KAUST Repository

    Mei, Jianguo

    2011-12-21

    We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm 2 V -1 s -1 (with a maximum mobility of 2.48 cm 2 V -1 s -1), was obtained from solution-processed thin-film transistors, one of the highest mobilities reported to date. In contrast, the reference polymer with a branched alkyl side chain gave an average hole mobility of 0.30 cm 2 V -1 s -1 and a maximum mobility of 0.57 cm 2 V -1 s -1. This is largely explained by the polymer packing: our new polymer exhibited a π-π stacking distance of 3.58 Å, while the reference polymer showed a distance of 3.76 Å. © 2011 American Chemical Society.

  15. Smectic order and backbone anisotropy of a side-chain liquid crystalline polymer by Small-Angle Neutron Scattering

    Science.gov (United States)

    Noirez, L.; Pépy, G.; Keller, P.; Benguigui, L.

    1991-07-01

    We have simultaneously measured, for the first time, the extension of the polymer backbone of a side-chain liquid crystalline polymer and the intensity of the 001 Bragg reflection, which gives the smectic order parameter Psi as a function of temperature in the smectic phase. We have qualitatively demonstrated that the more the smectic phase is ordered, the more the polymer backbone is localized between the mesogenic layers. It is shown that the Landau theory allows us to relate the radius of gyration parallel to the magnetic field of the polymer backbone to the smectic order parameter. We also show that the Renz-Warner theory is suitable at low temperatures.

  16. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    OpenAIRE

    Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

    2017-01-01

    We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient t...

  17. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Qianqian; Han, Ying [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Zhang, Yuanyuan; Duan, Chungang [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Peng, Hui, E-mail: hpeng@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi 030006 (China)

    2017-03-15

    One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.

  18. Hydrolysis of short-chain phosphatidylcholines by bee venom phospholipase A2.

    Science.gov (United States)

    Raykova, D; Blagoev, B

    1986-01-01

    In order to find out the aggregation state of the substrate, preferred by bee venom phospholipase A2 (EC 3.1.1.4), its action on short-chain phosphatidylcholines with two identical (C6-C10) fatty acids has been tested. The rate of hydrolysis as a function of acyl chain length showed a maximum at dioctanoylphosphatidylcholine. The effects of alcohols, NaCl and Triton X-100, which affect the aggregation state of phospholipids in water, were also studied. The addition of n-alcohol led to a significant inhibition of the hydrolysis of the substrates present in micellar form and activated the hydrolysis of substrates which form liposomes. The inhibitory effect increased with increasing length of the aliphatic carbon chain of the alcohol. Triton X-100 at low Triton/phospholipid molar ratios enhanced enzyme activity. These results do not agree with the accepted idea that bee venom phospholipase A2 hydrolyzes short-chain lecithins in their molecularly dispersed form and that micelles cannot act as substrates. The data indicate that short-chain lecithins in the aggregated state are hydrolyzed and that the requirements of bee venom phospholipase A2 for the aggregation state of the substrate are not strict.

  19. 2-ethylhydracrylic aciduria in short/branched-chain acyl-CoA dehydrogenase deficiency

    DEFF Research Database (Denmark)

    Korman, Stanley H; Andresen, Brage S; Zeharia, Avraham

    2005-01-01

    BACKGROUND: Isolated excretion of 2-methylbutyrylglycine (2-MBG) is the hallmark of short/branched-chain acyl-CoA dehydrogenase deficiency (SBCADD), a recently identified defect in the proximal pathway of L-isoleucine oxidation. SBCADD might be underdiagnosed because detection and recognition...

  20. Developments and interlaboratory study of the analysis of short-chain chlorinated paraffins

    NARCIS (Netherlands)

    van Mourik, L. M.; van der Veen, I.; Crum, S.; de Boer, J.

    To survey the conformity and quality of the results between laboratories for short-chain chlorinated paraffins (SCCPs) determination, we reviewed current and novel analytical methods and organized four worldwide laboratory exercises between 2011 and 2017. Participants were requested to analyse test

  1. Developments and interlaboratory study of the analysis of short-chain chlorinated paraffins

    NARCIS (Netherlands)

    Mourik, van L.M.; Veen, van der I.; Crum, S.; Boer, de J.

    2018-01-01

    To survey the conformity and quality of the results between laboratories for short-chain chlorinated paraffins (SCCPs) determination, we reviewed current and novel analytical methods and organized four worldwide laboratory exercises between 2011 and 2017. Participants were requested to analyse test

  2. Clinical aspects of short-chain acyl-CoA dehydrogenase deficiency

    NARCIS (Netherlands)

    Maldegem, B.T.; Wanders, R.J.A.; Wijburg, F.A.

    2010-01-01

    Short-chain acyl-CoA dehydrogenase deficiency (SCADD) is an autosomal recessive inborn error of mitochondrial fatty acid oxidation. SCADD is biochemically characterized by increased C4-carnitine in plasma and ethylmalonic acid in urine. The diagnosis of SCADD is confirmed by DNA analysis showing

  3. Gut-derived short-chain fatty acids are vividly assimilated into host carbohydrates and lipids

    NARCIS (Netherlands)

    den Besten, Gijs; Lange, Katja; Havinga, Rick; van Dijk, Theo H.; Gerding, Albert; van Eunen, Karen; Muller, Michael; Groen, Albert K.; Hooiveld, Guido J.; Bakker, Barbara M.; Reijngoud, Dirk-Jan

    2013-01-01

    Acetate, propionate, and butyrate are the main short-chain fatty acids (SCFAs) that arise from the fermentation of fibers by the colonic microbiota. While many studies focus on the regulatory role of SCFAs, their quantitative role as a catabolic or anabolic substrate for the host has received

  4. Effects of rough handling on short chain fatty acid production and ...

    African Journals Online (AJOL)

    The influence of stress due to rough handling (RH) on gastrointestinal tract (GIT) environmental pH, concentration of short chain fatty acids (SCFAs) and modulatory roles of two Lactobacillus strains was investigated in broiler chickens. Equal number of chicks was randomly assigned to one of the following treatment groups; ...

  5. Charge Injection and Transport in Metal/Polymer Chains/Metal Sandwich Structure

    International Nuclear Information System (INIS)

    Hai-Hong, Li; Dong-Mei, Li; Yuan, Li; Kun, Gao; De-Sheng, Liu; Shi-Jie, Xie

    2008-01-01

    Using the tight-binding Su–Schrieffer–Heeger model and a nonadiabatic dynamic evolution method, we study the dynamic processes of the charge injection and transport in a metal/two coupled conjugated polymer chains/metal structure. It is found that the charge interchain transport is determined by the strength of the electric field and the magnitude of the voltage bias applied on the metal electrode. The stronger electric field and the larger voltage bias are both in favour of the charge interchain transport. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  6. Topological derivation of black hole entropy by analogy with a chain polymer

    International Nuclear Information System (INIS)

    Siino, Masaru

    2002-01-01

    The generic crease set of an event horizon possesses anisotropic structure although most black holes are dynamically stable. This fact suggests that a generic almost spherical black hole has a very crumpled crease set on a microscopic scale although the crease set is similar to a pointwise crease set on a macroscopic scale. In the present article, we count the number of such microstates of an almost spherical black hole by analogy with an elastic chain polymer. This estimation of black hole entropy reproduces the well-known Bekenstein-Hawking entropy of a Schwarzschild black hole

  7. Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers

    DEFF Research Database (Denmark)

    Pedersen, T.G.; Johansen, P.M.

    1997-01-01

    . The theory provides an explanation for the high long-term stability of the photoinduced anisotropy as well as a theoretical prediction of the temporal behavior of photoinduced birefringence. The theoretical results agree favorably with measurements in the entire range of writing intensities used......A novel mean-field theory of photoinduced reorientation and optical anisotropy in liquid crystalline side-chain polymers is presented and compared with experiments, The reorientation mechanism is based on photoinduced trans cis isomerization and a multidomain model of the material is introduced...

  8. Mean-field theory of photoinduced formation of surface reliefs in side-chain azobenzene polymers

    DEFF Research Database (Denmark)

    Pedersen, Thomas Garm; Johansen, Per Michael; Holme, N.C.R.

    1998-01-01

    A mean-field model of photoinduced surface reliefs in dye containing side-chain polymers is presented. It is demonstrated that photoinduced ordering of dye molecules subject to anisotropic intermolecular interactions leads to mass transport even when the intensity of the incident light is spatially...... uniform. Theoretical profiles are obtained using a simple variational method and excellent agreement with experimental surface reliefs recorded under various polarization configurations is found. The polarization dependence of both period and shape of the profiles is correctly reproduced by the model....

  9. Molecular origin of urea driven hydrophobic polymer collapse and unfolding depending on side chain chemistry.

    Science.gov (United States)

    Nayar, Divya; Folberth, Angelina; van der Vegt, Nico F A

    2017-07-19

    Osmolytes affect hydrophobic collapse and protein folding equilibria. The underlying mechanisms are, however, not well understood. We report large-scale conformational sampling of two hydrophobic polymers with secondary and tertiary amide side chains using extensive molecular dynamics simulations. The calculated free energy of unfolding increases with urea for the secondary amide, yet decreases for the tertiary amide, in agreement with experiment. The underlying mechanism is rooted in opposing entropic driving forces: while urea screens the hydrophobic macromolecular interface and drives unfolding of the tertiary amide, urea's concomitant loss in configurational entropy drives collapse of the secondary amide. Only at sufficiently high urea concentrations bivalent urea hydrogen bonding interactions with the secondary amide lead to further stabilisation of its collapsed state. The observations provide a new angle on the interplay between side chain chemistry, urea hydrogen bonding, and the role of urea in attenuating or strengthening the hydrophobic effect.

  10. Effects of internal friction on contact formation dynamics of polymer chain

    Science.gov (United States)

    Bian, Yukun; Li, Peng; Zhao, Nanrong

    2018-04-01

    A theoretical framework is presented to study the contact formation dynamics of polymer chains, in accompany with an electron-transfer quenching. Based on a non-Markovian Smoluchowski equation supplemented with an exponential sink term, we derive the mean time of contact formation under Wilemski-Fixman approximation. Our particular attentions are paid to the effect of internal friction. We find out that internal friction induces a novel fractional viscosity dependence, which will become more remarkable as internal friction increases. Furthermore, we clarify that internal friction inevitably promotes a diffusion-controlled mechanism by slowing the chain relaxation. Finally, we apply our theory to rationalise the experimental investigation for contact formation of a single-stranded DNA. The theoretical results can reproduce the experimental data very well with quite reasonable estimation for the intrinsic parameters. Such good agreements clearly demonstrate the validity of our theory which has appropriately addressed the very role of internal friction to the relevant dynamics.

  11. Revealing the Supramolecular Nature of Side-Chain Terpyridine-Functionalized Polymer Networks

    Directory of Open Access Journals (Sweden)

    Jérémy Brassinne

    2015-01-01

    Full Text Available Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylaminoethyl methacrylate is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks.

  12. Adsorption of a single polymer chain on a surface: effects of the potential range.

    Science.gov (United States)

    Klushin, Leonid I; Polotsky, Alexey A; Hsu, Hsiao-Ping; Markelov, Denis A; Binder, Kurt; Skvortsov, Alexander M

    2013-02-01

    We investigate the effects of the range of adsorption potential on the equilibrium behavior of a single polymer chain end-attached to a solid surface. The exact analytical theory for ideal lattice chains interacting with a planar surface via a box potential of depth U and width W is presented and compared to continuum model results and to Monte Carlo (MC) simulations using the pruned-enriched Rosenbluth method for self-avoiding chains on a simple cubic lattice. We show that the critical value U(c) corresponding to the adsorption transition scales as W(-1/ν), where the exponent ν=1/2 for ideal chains and ν≈3/5 for self-avoiding walks. Lattice corrections for finite W are incorporated in the analytical prediction of the ideal chain theory U(c)≈(π(2)/24)(W+1/2)(-2) and in the best-fit equation for the MC simulation data U(c)=0.585(W+1/2)(-5/3). Tail, loop, and train distributions at the critical point are evaluated by MC simulations for 1≤W≤10 and compared to analytical results for ideal chains and with scaling theory predictions. The behavior of a self-avoiding chain is remarkably close to that of an ideal chain in several aspects. We demonstrate that the bound fraction θ and the related properties of finite ideal and self-avoiding chains can be presented in a universal reduced form: θ(N,U,W)=θ(NU(c),U/U(c)). By utilizing precise estimations of the critical points we investigate the chain length dependence of the ratio of the normal and lateral components of the gyration radius. Contrary to common expectations this ratio attains a limiting universal value /=0.320±0.003 only at N~5000. Finite-N corrections for this ratio turn out to be of the opposite sign for W=1 and for W≥2. We also study the N dependence of the apparent crossover exponent φ(eff)(N). Strong corrections to scaling of order N(-0.5) are observed, and the extrapolated value φ=0.483±0.003 is found for all values of W. The strong correction to scaling effects found here explain why

  13. Chain Gang-The Chemistry of Polymers (edited by Mickey Sarquis)

    Science.gov (United States)

    Collard, David M.

    1999-01-01

    Science in Our World, Vol. 5. Mickey Sarquis, series editor. Terrific Science Press: Middletown, OH, 1995. xiv + 149 pp. ISBN 1-883822-13-0. Spiral-bound, $13.95. Our familiarity with plastics makes polymers ideal examples of chemicals for discussion in K-12 science classes. Most importantly, polymers can be used as examples of chemicals that are safe to handle and of obvious use to society. The structures of polymers are easily represented by a number of models. These simple models go a long way in explaining the familiar physical properties of plastics. However, the introduction of polymers in the classroom relies on the availability of teaching material, experiments, and demonstrations that illustrate concepts in the current science curriculum. Chain Gang-The Chemistry of Polymers, one of the Science in Our World series published by the Center for Chemical Education at Miami University-Middletown (Ohio), will serve as a great resource for teachers interested in providing their students with a series of activities that can be related to their everyday experiences with these ubiquitous chemicals. After a brief introduction to some basic concepts, the book presents a series of 23 experiments. The collection of experiments presented here spans illustrations of chemistry, physical properties, analysis, and processing. Each experiment is recommended as either a hands-on activity or demonstration for various grade levels. A guide for the teacher suggests how the experiment can be used to illustrate topics in the science curriculum. The materials required for each activity are listed in detail, with quantities and sources (all materials are available from Flinn Scientific or hardware stores). There are detailed instructions for preparation of each experiment and how to introduce the experiment to students, and step-by-step instructions for activity. Very importantly, safety and disposal issues are clearly presented. Suggestions for cross-curriculum integration are also

  14. Modelling the short-circuit current of polymer bulk heterojunction solar cells

    International Nuclear Information System (INIS)

    Geens, Wim; Martens, Tom; Poortmans, Jef; Aernouts, Tom; Manca, Jean; Lutsen, Laurence; Heremans, Paul; Borghs, Staf; Mertens, Robert; Vanderzande, Dirk

    2004-01-01

    An analytical model has been developed to estimate the short-circuit current density of conjugated polymer/fullerene bulk heterojunction solar cells. The model takes into account the solvent-dependent molecular morphology of the donor/acceptor blend, which was revealed by transmission electron microscopy. Field-effect transistors based on single and composite organic layers were fabricated to determine values for the charge carrier mobilities of such films. These values served as input parameters of the model. It is shown that the difference in short-circuit current density that was measured between toluene-cast and chlorobenzene-cast conjugated polymer/fullerene photovoltaic cells (Appl. Phys. Lett. 78 (2001) 841) could be very well simulated with the model. Moreover, the calculations illustrate how increasing the hole and electron mobilities in the photoactive blend can improve the overall short-circuit current density of the solar cell

  15. Nanophase separation in side chain polymers: new evidence from structure and dynamics

    International Nuclear Information System (INIS)

    Hiller, S; Pascui, O; Budde, H; Kabisch, O; Reichert, D; Beiner, M

    2004-01-01

    New evidence for a nanophase separation of incompatible main and side chain parts in amorphous poly(n-alkyl methacrylates) with long alkyl groups are presented. Independent indications for the existence of alkyl nanodomains with a typical dimension in the 1 nm range from studies on dynamics and structure are reported. Results from nuclear magnetic resonance (NMR) experiments are compared with data from different relaxation spectroscopy methods on poly(n-decyl methacrylate). The NMR results in combination with relaxation spectroscopy data support the existence of an independent polyethylene-like glass transition, α PE , within the alkyl nanodomains in addition to the conventional glass transition a at higher temperatures. X-ray scattering data show that the situation in homopolymers is similar to that for random poly(n-alkyl methacrylate) copolymers with the same average length of the alkyl group in the side chains. Scattering data for a series of n-butyl methacrylate samples with polymerization degrees reaching from P=1 to 405 indicate that nanophase separation is chain-length independent above P=25, while the nanophase separation tends to disappear below P=6. Insensitivity of structural aspects in nanophase-separated poly(n-alkyl methacrylates) to changes in the molecular microstructure and consistency of NMR results with independent conclusions from relaxation spectroscopy underline the general importance of nanophase separation effects in a broad class of side chain polymers

  16. Development of Probiotic Fruit Juices Using Lactobacillus rhamnosus GR-1 Fortified with Short Chain and Long Chain Inulin Fiber

    Directory of Open Access Journals (Sweden)

    Jessica White

    2018-04-01

    Full Text Available Typically, probiotics are consumed in dairy based products such as yogurt. However, given the rise in various diet types, non-dairy alternatives have been developed, such as inoculating fruit juices with probiotics. Lactobacillus rhamnosus GR-1 is a probiotic strain exerting a number of human health benefits such as the prevention of urinary tract infections. Therefore, the objective of this study was to determine the viability of L. rhamnosus GR-1 in apple cider, orange, and grape juice when fortified with either 4% short chain or 4% long chain inulin fiber over 72 h of fermentation and 30 days of refrigerated storage. The secondary objective was to determine consumer acceptability of apple cider and orange juice samples using the hedonic scale. All of the fruit juice samples achieved a mean viable count of at least 107 CFU/mL during 72 h of fermentation and 30 days of refrigerated storage. According to the sensory evaluation, which evaluated samples according to appearance, flavor, texture, and overall acceptability, apple cider juice with long chain inulin fiber proved to have the highest score for all characteristics except appearance. Therefore, this study indicated a potential for probiotic fruit juices as a valid alternative to dairy based probiotic products.

  17. Randomised clinical study: inulin short-chain fatty acid esters for targeted delivery of short-chain fatty acids to the human colon.

    Science.gov (United States)

    Polyviou, T; MacDougall, K; Chambers, E S; Viardot, A; Psichas, A; Jawaid, S; Harris, H C; Edwards, C A; Simpson, L; Murphy, K G; Zac-Varghese, S E K; Blundell, J E; Dhillo, W S; Bloom, S R; Frost, G S; Preston, T; Tedford, M C; Morrison, D J

    2016-10-01

    Short-chain fatty acids (SCFA) produced through fermentation of nondigestible carbohydrates by the gut microbiota are associated with positive metabolic effects. However, well-controlled trials are limited in humans. To develop a methodology to deliver SCFA directly to the colon, and to optimise colonic propionate delivery in humans, to determine its role in appetite regulation and food intake. Inulin SCFA esters were developed and tested as site-specific delivery vehicles for SCFA to the proximal colon. Inulin propionate esters containing 0-61 wt% (IPE-0-IPE-61) propionate were assessed in vitro using batch faecal fermentations. In a randomised, controlled, crossover study, with inulin as control, ad libitum food intake (kcal) was compared after 7 days on IPE-27 or IPE-54 (10 g/day all treatments). Propionate release was determined using (13) C-labelled IPE variants. In vitro, IPE-27-IPE-54 wt% propionate resulted in a sevenfold increase in propionate production compared with inulin (P inulin (439.5 vs. 703.9 kcal, P = 0.025) and IPE-54 (439.5 vs. 659.3 kcal, P = 0.025), whereas IPE-54 was not significantly different from inulin control. IPE-27 significantly reduced food intake suggesting colonic propionate plays a role in appetite regulation. Inulin short-chain fatty acid esters provide a novel tool for probing the diet-gut microbiome-host metabolism axis in humans. © 2016 The Authors. Alimentary Pharmacology & Therapeutics Published by John Wiley & Sons Ltd.

  18. Confinement Effects on Host Chain Dynamics in Polymer Nanocomposite Thin Films

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Kyle J. [Department; Glynos, Emmanouil [Department; Maroulas, Serafeim-Dionysios [Department; Narayanan, Suresh [Advanced; Sakellariou, Georgios [Department; Green, Peter F. [Department; National

    2017-09-06

    Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g.: sensing, energy conversion) of these materials, introduces additional complications with regard to the processing-morphology-function behavior. A primary challenge is to understand and control the viscosity of a PNC with decreasing film thickness confinement for nanoscale applications. Using a combination of X-ray photon correlation spectroscopy (XPCS) and X-ray standing wave based resonance enhanced XPCS to study the dynamics of neat poly-2-vinyl pyridine (P2VP) chains and the nanoparticle dynamics, respectively, we identified a new mechanism that dictates the viscosity of PNC films in the nanoscale regime. We show that while the viscosities of neat P2VP films as thin as 50 nm remained the same as the bulk, PNC films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibited unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were equal to the bulk values. These results -NP proximities and suppression of their dynamics -suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for 2D and 3D nanoscale applications.

  19. A New 1D Chained Coordination Polymer: Synthesis, Crystal Structure, Antitumor Activity and Luminescent Property

    Directory of Open Access Journals (Sweden)

    Xi-Shi Tai

    2015-11-01

    Full Text Available A new 1D chained coordination polymer of Zn(II, {[Zn(L2(4,4′-bipy]·(H2O}n(1 (HL = N-acetyl-l-phenylalanine; 4,4′-bipy = 4,4′-bipyridine has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. Theresults show that each asymmetric unit of Zn(II complex belongs to monoclinic, space group P21 with a = 11.421(2 Å, b = 9.2213(17 Å, c = 15.188(3 Å,β = 106.112(3°, V = 1536.7(5 Å3, Z = 2, Dc = 1.444 g·cm−3, µ = 0.857 mm−1, F(000 = 696, and final R1 = 0.0439, ωR2 = 0.1013. The molecules form one-dimensional chained structure by its the bridging 4,4′-bipyridine ligands. The antitumor activities and luminescent properties of Zn(II coordination polymer have also been investigated.

  20. A Probabilistic Short-Term Water Demand Forecasting Model Based on the Markov Chain

    Directory of Open Access Journals (Sweden)

    Francesca Gagliardi

    2017-07-01

    Full Text Available This paper proposes a short-term water demand forecasting method based on the use of the Markov chain. This method provides estimates of future demands by calculating probabilities that the future demand value will fall within pre-assigned intervals covering the expected total variability. More specifically, two models based on homogeneous and non-homogeneous Markov chains were developed and presented. These models, together with two benchmark models (based on artificial neural network and naïve methods, were applied to three real-life case studies for the purpose of forecasting the respective water demands from 1 to 24 h ahead. The results obtained show that the model based on a homogeneous Markov chain provides more accurate short-term forecasts than the one based on a non-homogeneous Markov chain, which is in line with the artificial neural network model. Both Markov chain models enable probabilistic information regarding the stochastic demand forecast to be easily obtained.

  1. Conformational explosion: Understanding the complexity of short chain para-dialkylbenzene potential energy surfaces

    Science.gov (United States)

    Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.

    2018-05-01

    The single-conformation ultraviolet and infrared spectroscopy of three short-chain para-dialkylbenzenes (para-diethylbenzene, para-dipropylbenzene, and para-dibutylbenzene) is reported for the jet-cooled, isolated molecules. The present study builds off previous work on single-chain n-alkylbenzenes, where an anharmonic local mode Hamiltonian method was developed to account for stretch-bend Fermi resonance in the alkyl CH stretch region [D. P. Tabor et al., J. Chem. Phys. 144, 224310 (2016)]. The jet-cooled molecules are interrogated using laser-induced fluorescence (LIF) excitation, fluorescence dip infrared spectroscopy, and dispersed fluorescence. The LIF spectra in the S1 ← S0 origin region show a dramatic increase in the number of resolved transitions with increasing length of the alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an "egg carton" shaped potential energy surface. A combination of electronic frequency shift and alkyl CH stretch infrared spectra is used to generate a consistent set of conformational assignments. Using these experimental techniques in conjunction with computational methods, subsets of origin transitions in the LIF excitation spectrum can be classified into different conformational families. Two conformations are resolved in para-diethylbenzene, seven in para-dipropylbenzene, and about nineteen in para-dibutylbenzene. These chains are largely independent of each other as there are no new single-chain conformations induced by the presence of a second chain. A cursory LIF excitation scan of para-dioctylbenzene shows a broad congested spectrum at frequencies consistent with interactions of alkyl chains with the phenyl π cloud.

  2. Design and preparation of bi-functionalized short-chain modified zwitterionic nanoparticles.

    Science.gov (United States)

    Hu, Fenglin; Chen, Kaimin; Xu, Hong; Gu, Hongchen

    2018-05-01

    An ideal nanomaterial for use in the bio-medical field should have a distinctive surface capable of effectively preventing nonspecific protein adsorption and identifying target bio-molecules. Recently, the short-chain zwitterion strategy has been suggested as a simple and novel approach to create outstanding anti-fouling surfaces. In this paper, the carboxyl end group of short-chain zwitterion-coated silica nanoparticles (SiO 2 -ZWS) was found to be difficult to functionalize via a conventional EDC/NHS strategy due to its rapid hydrolysis side-reactions. Hence, a series of bi-functionalized silica nanoparticles (SiO 2 -ZWS/COOH) were designed and prepared by controlling the molar ratio of 3-aminopropyltriethoxysilane (APTES) to short-chain zwitterionic organosiloxane (ZWS) in order to achieve above goal. The synthesized SiO 2 -ZWS/COOH had similar excellent anti-fouling properties compared with SiO 2 -ZWS, even in 50% fetal bovine serum characterized by DLS and turbidimetric titration. Subsequently, SiO 2 -ZWS/COOH 5/1 was chosen as a representative and then demonstrated higher detection signal intensity and more superior signal-to-noise ratios compare with the pure SiO 2 -COOH when they were used as a bio-carrier for chemiluminescence enzyme immunoassay (CLEIA). These unique bi-functionalized silica nanoparticles have many potential applications in the diagnostic and therapeutic fields. Reducing nonspecific protein adsorption and enhancing the immobilized efficiency of specific bio-probes are two of the most important issues for bio-carriers, particularly for a nanoparticle based bio-carrier. Herein, we designed and prepared a bi-functional nanoparticle with anti-fouling property and bio conjugation capacity for further bioassay by improving the short-chain zwitterionic modification strategy we have proposed previously. The heterogeneous surface of this nanoparticle showed effective anti-fouling properties both in model protein solutions and fetal bovine serum

  3. Ethylmalonic aciduria is associated with an amino acid variant of short chain acyl-coenzyme A dehydrogenase

    DEFF Research Database (Denmark)

    Corydon, M J; Gregersen, N; Lehnert, W

    1996-01-01

    Ethylmalonic aciduria is a common biochemical finding in patients with inborn errors of short chain fatty acid beta-oxidation. The urinary excretion of ethylmalonic acid (EMA) may stem from decreased oxidation by short chain acyl-CoA dehydrogenase (SCAD) of butyryl-CoA, which is alternatively...

  4. Detachment of semiflexible polymer chains from a substrate: A molecular dynamics investigation

    Energy Technology Data Exchange (ETDEWEB)

    Paturej, J. [Leibniz-Institut of Poslymer Research Dresden, 01069 Dresden (Germany); Institute of Physics, University of Szczecin, Wielkopolska 15, 70451 Szczecin (Poland); Erbas, A. [Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208 (United States); Milchev, A. [Institute for Physical Chemistry, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Rostiashvili, V. G. [Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz (Germany)

    2014-12-07

    Using Molecular Dynamics simulations, we study the force-induced detachment of a coarse-grained model polymer chain from an adhesive substrate. One of the chain ends is thereby pulled at constant speed off the attractive substrate and the resulting saw-tooth profile of the measured mean force 〈f〉 vs height D of the end-segment over the plane is analyzed for a broad variety of parameters. It is shown that the observed characteristic oscillations in the 〈f〉-D profile depend on the bending and not on the torsional stiffness of the detached chains. Allowing for the presence of hydrodynamic interactions (HI) in a setup with explicit solvent and dissipative particle dynamics-thermostat, rather than the case of Langevin thermostat, one finds that HI have little effect on the 〈f〉-D profile. Also the change of substrate affinity with respect to the solvent from solvophilic to solvophobic is found to play negligible role in the desorption process. In contrast, a changing ratio ε{sub s}{sup B}/ε{sub s}{sup A} of the binding energies of A- and B-segments in the detachment of an AB-copolymer from adhesive surface strongly changes the 〈f〉-D profile whereby the B-spikes vanish when ε{sub s}{sup B}/ε{sub s}{sup A}<0.15. Eventually, performing an atomistic simulation of (bio)-polymers, we demonstrate that the simulation results, derived from our coarse-grained model, comply favorably with those from the all-atom simulation.

  5. Concentration and saturation effects of tethered polymer chains on adsorbing surfaces

    Science.gov (United States)

    Descas, Radu; Sommer, Jens-Uwe; Blumen, Alexander

    2006-12-01

    We consider end-grafted chains at an adsorbing surface under good solvent conditions using Monte Carlo simulations and scaling arguments. Grafting of chains allows us to fix the surface concentration and to study a wide range of surface concentrations from the undersaturated state of the surface up to the brushlike regime. The average extension of single chains in the direction parallel and perpendicular to the surface is analyzed using scaling arguments for the two-dimensional semidilute surface state according to Bouchaud and Daoud [J. Phys. (Paris) 48, 1991 (1987)]. We find good agreement with the scaling predictions for the scaling in the direction parallel to the surface and for surface concentrations much below the saturation concentration (dense packing of adsorption blobs). Increasing the grafting density we study the saturation effects and the oversaturation of the adsorption layer. In order to account for the effect of excluded volume on the adsorption free energy we introduce a new scaling variable related with the saturation concentration of the adsorption layer (saturation scaling). We show that the decrease of the single chain order parameter (the fraction of adsorbed monomers on the surface) with increasing concentration, being constant in the ideal semidilute surface state, is properly described by saturation scaling only. Furthermore, the simulation results for the chains' extension from higher surface concentrations up to the oversaturated state support the new scaling approach. The oversaturated state can be understood using a geometrical model which assumes a brushlike layer on top of a saturated adsorption layer. We provide evidence that adsorbed polymer layers are very sensitive to saturation effects, which start to influence the semidilute surface scaling even much below the saturation threshold.

  6. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    KAUST Repository

    Moia, Davide; Giovannitti, Alexander; Szumska, Anna A.; Schnurr, Martin; Rezasoltani, Elham; Maria, Iuliana P.; Barnes, Piers R. F.; McCulloch, Iain; Nelson, Jenny

    2017-01-01

    conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

  7. Biocompatible choline based ionic salts: Solubility in short-chain alcohols

    International Nuclear Information System (INIS)

    Lopes, Joana M.; Paninho, Ana B.; Môlho, Marta F.; Nunes, Ana V.M.; Rocha, Angelo; Lourenço, Nuno M.T.; Najdanovic-Visak, Vesna

    2013-01-01

    Highlights: • Biocompatible ionic liquids based on choline esters were synthesized in this work. • Solubility of choline and choline esters based ionic salt in alcohols were measured. • Activity coefficients were calculated. • Experimental data were correlated by means of the semi-empirical Grant equation. -- Abstract: In this work, we report data on solubility of choline chloride and choline acetate in short-chain linear alcohols (ethanol, 1-propanol and 1-butanol) at various temperatures. Furthermore, we synthesize two choline derivatives: hydrogen choline chloride glutarate ([CholGlut][Cl]) and hydrogen choline chloride succinate ([CholSucc][Cl]). Their characterization and solubility in short-chain alcohols as a function of temperature are also included. Activity coefficients were calculated and their comparisons with ideal solutions were discussed. The experimental data were correlated successfully by means of the semi-empirical Grant equation

  8. Gut microbiota–derived short-chain fatty acids and kidney diseases

    Directory of Open Access Journals (Sweden)

    Li L

    2017-12-01

    Full Text Available Lingzhi Li, Liang Ma, Ping Fu Kidney Research Institute, Department of Nephrology, West China Hospital of Sichuan University, Chengdu 610041, China Abstract: Gut microbiota and its metabolites play pivotal roles in host physiology and pathology. Short-chain fatty acids (SCFAs, as a group of metabolites, exert positive regulatory effects on energy metabolism, hormone secretion, immune inflammation, hypertension, and cancer. The functions of SCFAs are related to their activation of transmembrane G protein-coupled receptors and their inhibition of histone acetylation. Though controversial, growing evidence suggests that SCFAs, which regulate inflammation, oxidative stress, and fibrosis, have been involved in kidney disease through the activation of the gut–kidney axis; however, the molecular relationship among gut microbiota–derived metabolites, signaling pathways, and kidney disease remains to be elucidated. This review will provide an overview of the physiology and functions of SCFAs in kidney disease. Keywords: gut microbiome, short-chain fatty acids, kidney diseases, gut–kidney axis

  9. Structural organization of the human short-chain acyl-CoA dehydrogenase gene

    DEFF Research Database (Denmark)

    Corydon, M J; Andresen, B S; Bross, P

    1997-01-01

    Short-chain acyl-CoA dehydrogenase (SCAD) is a homotetrameric mitochondrial flavoenzyme that catalyzes the initial reaction in short-chain fatty acid beta-oxidation. Defects in the SCAD enzyme are associated with failure to thrive, often with neuromuscular dysfunction and elevated urinary excretion...... shown to be associated with ethylmalonic aciduria. From analysis of 18 unrelated Danish families, we show that the four SCAD gene polymorphisms constitute five allelic variants of the SCAD gene, and that the 625A variant together with the less frequent variant form of the three other polymorphisms (321C....... The evolutionary relationship between SCAD and five other members of the acyl-CoA dehydrogenase family was investigated by two independent approaches that gave similar phylogenetic trees....

  10. Proof of the identity between the depletion layer thickness and half the average span for an arbitrary polymer chain

    DEFF Research Database (Denmark)

    Wang, Yanwei; Peters, Günther H.J.; Hansen, Flemming Yssing

    2008-01-01

    point in the polymer chain (such as the center of mass, middle segment, and end segments) can be computed as a function of the confinement size solely based on a single sampling of the configuration space of a polymer chain in bulk. Through a simple analysis based on the CABS approach in the case...... of a single wall, we prove rigorously that (i) the depletion layer thickness delta is the same no matter which reference point is used to describe the depletion profile and (ii) the value of delta equals half the average span (the mean projection onto a line) of the macromolecule in free solution. Both...

  11. Calculation of Physicochemical Properties for Short- and Medium-Chain Chlorinated Paraffins

    Science.gov (United States)

    Glüge, Juliane; Bogdal, Christian; Scheringer, Martin; Buser, Andreas M.; Hungerbühler, Konrad

    2013-06-01

    Short- and medium-chain chlorinated paraffins are potential PBT chemicals (persistent, bioaccumulative, toxic) and short-chain chlorinated paraffins are under review for inclusion in the UNEP Stockholm Convention on Persistent Organic Pollutants. Despite their high production volume of more than one million metric tonnes per year, only few data on their physicochemical properties are available. We calculated subcooled-liquid vapor pressure, subcooled-liquid solubility in water and octanol, Henry's law constant for water and octanol, as well as the octanol-water partition coefficient with the property calculation methods COSMOtherm, SPARC, and EPI Suite™, and compared the results to experimental data from the literature. For all properties, good or very good agreement between calculated and measured data was obtained for COSMOtherm; results from SPARC were in good agreement with the measured data except for subcooled-liquid water solubility, whereas EPI Suite™ showed the largest discrepancies for all properties. After critical evaluation of the three property calculation methods, a final set of recommended property data for short- and medium-chain chlorinated paraffins was derived. The calculated property data show interesting relationships with chlorine content and carbon chain length. Increasing chlorine content does not cause pronounced changes in water solubility and octanol-water partition coefficient (KOW) as long as it is below 55%. Increasing carbon chain length leads to strong increases in KOW and corresponding decreases in subcooled-liquid water solubility. The present data set can be used in further studies to assess the environmental fate and human exposure of this relevant compound class.

  12. Endosulfan, pentachlorobenzene and short-chain chlorinated paraffins in background soils from Western Europe

    OpenAIRE

    Halse, Anne Karine; Schlabach, Martin; Schuster, Jasmin K; Jones, Kevin C; Steinnes, Eiliv; Breivik, Knut

    2015-01-01

    Soils are major reservoirs for many persistent organic pollutants (POPs). In this study, “newly” regulated POPs i.e. sum endosulfans (a-endosulfan, b-endosulfan, endosulfan sulfate), pentachlorobenzene (PeCB), and short-chain chlorinated paraffins (SCCPs) were determined in background samples from woodland (WL) and grassland (GL) surface soil, collected along an existing latitudinal UK-Norway transect. Statistical analysis, complemented with plots showing the predicted equilibrium distributio...

  13. Analysis of short-chain acids from anaerobic bacteria by high-performance liquid chromatography.

    OpenAIRE

    Guerrant, G O; Lambert, M A; Moss, C W

    1982-01-01

    A standard mixture of 25 short-chain fatty acids was resolved by high-performance liquid chromatography, using an Aminex HPX-87 column. The acids produced in culture media by anaerobic bacteria were analyzed by high-performance liquid chromatography after extraction with ether and reextraction into a small volume of 0.1 N NaOH. The presence of fumaric acid in culture extracts of Peptostreptococcus anaerobius was confirmed by gas chromatography-mass spectrometry analysis of the trapped eluent ...

  14. 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.

  15. Short supply chain: analysis of the competitiveness of organic horticultural farmers at Italian regional level

    OpenAIRE

    Bertazzoli, Aldo; Ruggeri, Arianna; Samoggia, Antonella

    2010-01-01

    The paper focuses on the competitiveness of organic horticultural farms implementing short food supply chain (SFSC), by analysing the organisational structures adopted by farmers and their economic performance. The collection of data based on face to face interviews with farmers and the review of the rural development plans of three central Italy regions. Results show that farms prefer a combination of organizational structures that involve both business to consumer and business to business s...

  16. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates

    2012-08-22

    While recent reports have established signifi cant miscibility in polymer:fullerene blends used in organic solar cells, little is actually known about why polymers and fullerenes mix and how their mixing can be controlled. Here, X-ray diffraction (XRD), differential scanning calorimetry (DSC), and molecular simulations are used to study mixing in a variety of polymer:molecule blends by systematically varying the polymer and smallmolecule properties. It is found that a variety of polymer:fullerene blends mix by forming bimolecular crystals provided there is suffi cient space between the polymer side chains to accommodate a fullerene. Polymer:tetrafl uoro-tetracyanoquinodimethane (F4-TCNQ) bimolecular crystals were also observed, although bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist, and the calculations point to van der Waals interactions as a signifi cant driving force for molecular mixing. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Quantitative characterization of short- and long-chain perfluorinated acids in solid matrices in Shanghai, China

    International Nuclear Information System (INIS)

    Li, Fei; Zhang, Chaojie; Qu, Yan; Chen, Jing; Chen, Ling; Liu, Ying; Zhou, Qi

    2010-01-01

    Perfluorinated acids (PFAs) have been recognized as emerging environmental pollutants because of their widespread occurrences, persistence, and bioaccumulative and toxicological effects. PFAs have been detected in aquatic environment and biota in China, but the occurrences of these chemicals have not been reported in solid matrices in China. In the present study, short- and long-chain PFAs (C2-C14) have been quantitatively determined in solid matrices including sediments, soils and sludge collected in Shanghai, China. The results indicate that sludge contains more PFAs than sediments and soils, and the total PFAs concentrations in sediments, soil and sludge are 62.5-276 ng g -1 , 141-237 ng g -1 and 413-755 ng g -1 , respectively. In most cases, trifluoroacetic acid was the major PFA and accounted for 22-90% of the total PFAs. Although the levels of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were not only lower than trifluoroacetic acid, but also lower than some short-chain PFCAs (< C8) in some individual cases, PFOA and PFOS were still the major pollution compounds in most cases and they constituted 2-34% and 1-9% of the total PFAs, respectively. Meanwhile, unlike previous studies, PFOS levels were not always higher than PFOA in solids collected in Shanghai, China. Given that some short-chain PFAs such as trifluoroacetic acid are mildly phytotoxic and their higher levels in solid matrices were collected in Shanghai, China, these chemicals should be included in future environmental monitoring efforts.

  18. Quantitative characterization of short- and long-chain perfluorinated acids in solid matrices in Shanghai, China.

    Science.gov (United States)

    Li, Fei; Zhang, Chaojie; Qu, Yan; Chen, Jing; Chen, Ling; Liu, Ying; Zhou, Qi

    2010-01-01

    Perfluorinated acids (PFAs) have been recognized as emerging environmental pollutants because of their widespread occurrences, persistence, and bioaccumulative and toxicological effects. PFAs have been detected in aquatic environment and biota in China, but the occurrences of these chemicals have not been reported in solid matrices in China. In the present study, short- and long-chain PFAs (C2-C14) have been quantitatively determined in solid matrices including sediments, soils and sludge collected in Shanghai, China. The results indicate that sludge contains more PFAs than sediments and soils, and the total PFAs concentrations in sediments, soil and sludge are 62.5-276 ng g(-1), 141-237 ng g(-1) and 413-755 ng g(-1), respectively. In most cases, trifluoroacetic acid was the major PFA and accounted for 22-90% of the total PFAs. Although the levels of perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were not only lower than trifluoroacetic acid, but also lower than some short-chain PFCAs (PFAs, respectively. Meanwhile, unlike previous studies, PFOS levels were not always higher than PFOA in solids collected in Shanghai, China. Given that some short-chain PFAs such as trifluoroacetic acid are mildly phytotoxic and their higher levels in solid matrices were collected in Shanghai, China, these chemicals should be included in future environmental monitoring efforts.

  19. Tunable Crystal-to-Crystal Phase Transition in a Cadmium Halide Chain Polymer

    Directory of Open Access Journals (Sweden)

    Ulli Englert

    2011-07-01

    Full Text Available The chain polymer [{Cd(μ-X2py2}1∞] (X = Cl, Br; py = pyridine undergoes a fully reversible phase transition between a monoclinic low-temperature and an orthorhombic high-temperature phase. The transformation can be directly monitored in single crystals and can be confirmed for the bulk by powder diffraction. The transition temperature can be adjusted by tuning the composition of the mixed-halide phase: Transition temperatures between 175 K up to the decomposition of the material at ca. 350 K are accessible. Elemental analysis, ion chromatography and site occupancy refinements from single-crystal X-ray diffraction agree with respect to the stoichiometric composition of the samples.

  20. Modeling the dynamics of polymer chains in water solution. Application to sensor design

    Science.gov (United States)

    Starovoitov, V. N.; Starovoitova, B. N.

    2017-10-01

    This paper is devoted to a mathematical model of a chaotic dynamics of a polymer chain in water. The model consists of a parabolic equation that is derived according to the self-consistent field approach. This model is employed for the numerical simulation of a biological sensor that detects the presence of a specific protein in the fluid. The sensor is absolutely simple and seems to be new. Besides that, the suggested equation is interesting from the mathematical point of view. It includes a non-local operator of integration not only over the past time interval as in the problems with memory but also over the future time interval. It is unusual for parabolic problems.

  1. Micro tooling technologies for polymer micro replication: direct, indirect and hybrid process chains

    DEFF Research Database (Denmark)

    Tosello, Guido; Hansen, Hans Nørgaard

    2009-01-01

    The increasing employment of micro products, of products containing micro parts and of products with micro-structured surfaces calls for mass fabrication technologies based on replication processes. In many cases, a suitable solution is given by the use of polymer micro products, whose production...... and performance of the corresponding micro mould. Traditional methods of micro tooling, such as various machining processes (e.g. micro milling, micro electrical discharge machining) have already reached their limitations with decreasing dimensions of mould inserts and cavities. To this respect, tooling process...... chains based on combination of micro manufacturing processes (defined as hybrid tooling) have been established in order to obtain further features miniaturization and increased accuracy. In this paper, examples and performance of different hybrid tooling approaches as well as challenges, opportunities...

  2. Polyurea with luminophor fragments in polymer chain: synthesis and spectral properties

    Science.gov (United States)

    Novikova, Tamara S.; Barashkov, Nikolay N.; Sakhno, Tamara V.

    2003-12-01

    A series of aliphatic polyureas with chromophore moieties in the polymer chain, such as 7-amino-2(4"-aminophenyl)benzoxazole, have been prepared. The absorption and fluorescence spectra of these polymers as well as corresponding chromophore-containing model urea (product of condensation of 7-amino-2(4"-amino-2"-hydroxyphenyl)benzoxazole and phenylisocyanate) were studied and compared. It was found that the special feature of the model compound and polyureas is the large value of Stokes shift due to the presence of a hydroxy group in the ortho-position to the nitrogen atom of the benzoxazole ring. The model of the excited-state proton transfer in molecules containing fragments of 2-(2"-hydroxyphenyl)benzoxazole has been used for the description of bathochromic shift in emission spectra of polymer solutions and films. According to this model, the proton remains predominantly on the phenol oxygen while in the ground state (enol form). Upon UV excitation, in the first excited singlet state, the phenol is a considerably stronger acid and the nitrogen is a stronger base. Thus, the proton is transferred from the oxygen site to the nitrogen site, and the isomer formed (S"1*) is more stable than the isomer before proton transfer (S1*) S"1* can be then regarded as a vibrationally excited form of S1*. Then the molecule de-excites to the ground state, emitting a photon. In the ground state the enol form is again the more stable form and the proton will then transfer back to the oxygen. S"o is also a vibrationally excited state of So. Because of this process the absorption and fluorescence spectra of model urea and polyureas do not intersect and the value of Stokes shift is about 6000 cm-1.

  3. Biogenesis and the growth of DNA-like polymer chains: a computer simulation

    International Nuclear Information System (INIS)

    Herrmann, H.J.; Tsallis, C.

    1987-01-01

    We study, through computer simulation, a crucial step of Biogenesis, namely the growth of self-replicating codified DNA-like polymers starting from a mixture of oligomers. We have adopted the growth scheme that has been recently proposed by Ferreira and Tsallis which incorporates usual ideas of autocatalysis through complementary pairs and within which a central role is played by the hydrogen-like links (characterized by the probabilities p AT and p CG of chemical bonding of the A-T and C-G pairs respectively) between the two chains of the growing polymer. We find that the average equilibrium polymeric length ξ diverges, for any fixed ratio (1-p AT )/(1-p sub (CG)), as ξ ∝ 1/r1-p AT . Selection of patterns may happen at all stages and in particular at chemical equilibrium. Selection occurs via two different mechanisms: (i) away from the critical point p AT = p CG = 1 if p AT ≠ p CG ; (ii) both on and away from the critical point if the initial concentrations of nucleotides (A, T, C and G or their precursors) are different. (author) [pt

  4. Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

    Science.gov (United States)

    Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

    2011-07-21

    In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

  5. Nature of the Binding Interactions between Conjugated Polymer Chains and Fullerenes in Bulk Heterojunction Organic Solar Cells

    KAUST Repository

    Ravva, Mahesh Kumar

    2016-10-24

    Blends of π-conjugated polymers and fullerene derivatives are ubiquitous as the active layers of organic solar cells. However, a detailed understanding of the weak noncovalent interactions at the molecular level between the polymer chains and fullerenes is still lacking and could help in the design of more efficient photoactive layers. Here, using a combination of long-range corrected density functional theory calculations and molecular dynamic simulations, we report a thorough characterization of the nature of binding between fullerenes (C60 and PC61BM) and poly(benzo[1,2-b:4,5-b′]dithiophene–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) chains. We illustrate the variations in binding strength when the fullerenes dock on the electron-rich vs electron-poor units of the polymer as well as the importance of the role played by the polymer and fullerene side chains and the orientations of the PC61BM molecules with respect to the polymer backbones.

  6. Free-radical-induced chain scission and cross-linking of polymers in aqueous solution. An overview

    International Nuclear Information System (INIS)

    Von Sonntag, C.

    2002-01-01

    Complete text of publication follows. In the radiolysis of N 2 O-saturated aqueous solutions OH are generated. In their reactions with polymers, they give rise to polymer-derived radicals. The kinetics of the formation and decay of these radicals are reviewed. The rate of reaction of a polymer with a reactive free radical is noticeably lower than that of an equivalent concentration of monomer due to the non-random distribution of the reaction sites. Once a larger number of radicals are formed on one polymer molecule, e.g. upon pulse radiolysis, close-by radicals recombine more rapidly while the more distant ones survive for much longer times than an equivalent concentration of freely diffusing radicals. Intermolecular cross-linking (between two polymer chains, increase in molecular weight) and intramolecular cross-linking (formation of small loops, no increase in polymer weight) are competing processes, and their relative yields thus depend on the dose rate and polymer concentration. Hydrogen-transfer reactions within the polymer, e.g. transformation of a secondary radical into a tertiary one, are common and facilitated by the high local density of reactive sites. Due to repulsive forces, the lifetime of radicals of charged polymers is substantially increased. This enables even relatively slow b-fragmentation reactions to become of importance. In the case of poly(methacrylic acid), where β-fragmentation is comparatively fast, this even leads to an unzipping, and as a consequence of the efficient release of methacrylic acid the situation of equilibrium polymerization is approached. Heterolytic β-fragmentation is possible when adequate leaving groups are available, e.g. in polynucleotides and DNA. In the presence of O 2 , chain scission occurs via oxyl radicals as intermediates. Some implications for technical applications are discussed

  7. Segment-scale, force-level theory of mesoscopic dynamic localization and entropic elasticity in entangled chain polymer liquids

    Science.gov (United States)

    Dell, Zachary E.; Schweizer, Kenneth S.

    2017-04-01

    We develop a segment-scale, force-based theory for the breakdown of the unentangled Rouse model and subsequent emergence of isotropic mesoscopic localization and entropic elasticity in chain polymer liquids in the absence of ergodicity-restoring anisotropic reptation or activated hopping motion. The theory is formulated in terms of a conformational N-dynamic-order-parameter generalized Langevin equation approach. It is implemented using a universal field-theoretic Gaussian thread model of polymer structure and closed at the level of the chain dynamic second moment matrix. The physical idea is that the isotropic Rouse model fails due to the dynamical emergence, with increasing chain length, of time-persistent intermolecular contacts determined by the combined influence of local uncrossability, long range polymer connectivity, and a self-consistent treatment of chain motion and the dynamic forces that hinder it. For long chain melts, the mesoscopic localization length (identified as the tube diameter) and emergent entropic elasticity predictions are in near quantitative agreement with experiment. Moreover, the onset chain length scales with the semi-dilute crossover concentration with a realistic numerical prefactor. Distinctive novel predictions are made for various off-diagonal correlation functions that quantify the full spatial structure of the dynamically localized polymer conformation. As the local excluded volume constraint and/or intrachain bonding spring are softened to allow chain crossability, the tube diameter is predicted to swell until it reaches the radius-of-gyration at which point mesoscopic localization vanishes in a discontinuous manner. A dynamic phase diagram for such a delocalization transition is constructed, which is qualitatively consistent with simulations and the classical concept of a critical entanglement degree of polymerization.

  8. Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxyalkanoates) as the polymer binder

    NARCIS (Netherlands)

    Walle, van der G.A.M.; Buisman, F.J.H.; Weusthuis, R.A.; Eggink, G.

    1999-01-01

    Unsaturated medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) produced by Pseudomonas putida from linseed oil fatty acids (LOFA) and tall oil fatty acids (TOFA), were used as the polymer binder in the formulation of high solid alkyd-like paints. The relatively high concentration of

  9. Interplay Between Side Chain Pattern, Polymer Aggregation, and Charge Carrier Dynamics in PBDTTPD:PCBM Bulk-Heterojunction Solar Cells

    KAUST Repository

    Dyer-Smith, Clare; Howard, Ian A.; Cabanetos, Clement; El Labban, Abdulrahman; Beaujuge, Pierre; Laquai, Fré dé ric

    2015-01-01

    Poly(benzo[1,2-b:4,5-b′]dithiophene–alt–thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymer donors with linear side-chains yield bulk-heterojunction (BHJ) solar cell power conversion efficiencies (PCEs) of about 4% with phenyl-C71-butyric acid methyl

  10. Siloxane-Terminated Solubilizing Side Chains: Bringing Conjugated Polymer Backbones Closer and Boosting Hole Mobilities in Thin-Film Transistors

    KAUST Repository

    Mei, Jianguo; Kim, Do Hwan; Ayzner, Alexander L.; Toney, Michael F.; Bao, Zhenan

    2011-01-01

    We introduce a novel siloxane-terminated solubilizing group and demonstrate its effectiveness as a side chain in an isoindigo-based conjugated polymer. An average hole mobility of 2.00 cm 2 V -1 s -1 (with a maximum mobility of 2.48 cm 2 V -1 s -1

  11. Extensional Strain Hardening Induced by π -π Interactions in Barely Entangled Polymer Chains: The Curious Case of Poly(4-vinylbiphenyl)

    Science.gov (United States)

    López-Barrón, Carlos R.; Zhou, Huaxing

    2017-12-01

    Aromatic π -π interactions between phenyl groups of adjacent chains in poly(4-vinylbiphenyl) (PVBP) have profound effects on the dynamics of this polymer. We report two unexpected nonlinear viscoelastic responses of PVBP when subjected to uniaxial flow. One is the unprecedented observation of extensional strain hardening (SH) in a barely entangled polymer melt. An even more intriguing finding is that SH of lightly (or even barely) entangled melts occurs at strain rates one order of magnitude below the coil-stretch transition predicted by Rouse theory (ɛ˙ H=0.5 /τR ).We postulate that this behavior is due to a molecular rearrangement mechanism (supported by x-ray diffraction measurements) that involves flow-induced π -π stacking of the phenyl groups, which results in an enhancement of the friction coefficient between polymer chains.

  12. A salt water battery with high stability and charging rates made from solution processed conjugated polymers with polar side chains

    KAUST Repository

    Moia, Davide

    2017-11-28

    We report a neutral salt water based battery which uses p-type and n-type solution processed polymer films as the cathode and the anode of the cell. The specific capacity of the electrodes (approximately 30 mAh cm-3) is achieved via formation of bipolarons in both the p-type and n-type polymers. By engineering ethylene glycol and zwitterion based side chains attached to the polymer backbone we facilitate rapid ion transport through the non-porous polymer films. This, combined with efficient transport of electronic charge via the conjugated polymer backbones, allowed the films to maintain constant capacity at high charge and discharge rates (>1000 C-rate). The electrodes also show good stability during electrochemical cycling (less than 30% decrease in capacity over >1000 cycles) and an output voltage up to 1.4 V. The performance of these semiconducting polymers with polar side-chains demonstrates the potential of this material class for fast-charging, water based electrochemical energy storage devices.

  13. Molecular Orientation of Conjugated Polymer Chains in Nanostructures and Thin Films: Review of Processes and Application to Optoelectronics

    Directory of Open Access Journals (Sweden)

    Varun Vohra

    2017-01-01

    Full Text Available Semiconducting polymers are composed of elongated conjugated polymer backbones and side chains with high solubility and mechanical properties. The combination of these two features results in a high processability and a potential to orient the conjugated backbones in thin films and nanofibers. The thin films and nanofibers are usually composed of highly crystalline (high charge transport and amorphous parts. Orientation of conjugated polymer can result in enhanced charge transport or optical properties as it induces increased crystallinity or preferential orientation of the crystallites. After summarizing the potential strategies to exploit molecular order in conjugated polymer based optoelectronic devices, we will review some of the fabrication processes to induce molecular orientation. In particular, we will review the cases involving molecular and interfacial interactions, unidirectional deposition processes, electrospinning, and postdeposition mechanical treatments. The studies presented here clearly demonstrate that process-controlled molecular orientation of the conjugated polymer chains can result in high device performances (mobilities over 40 cm2·V−1·s−1 and solar cells with efficiencies over 10%. Furthermore, the peculiar interactions between molecularly oriented polymers and polarized light have the potential not only to generate low-cost and low energy consumption polarized light sources but also to fabricate innovative devices such as solar cell integrated LCDs or bipolarized LEDs.

  14. Amide side chain amphiphilic polymers disrupt surface established bacterial bio-films and protect mice from chronic Acinetobacter baumannii infection.

    Science.gov (United States)

    Uppu, Divakara S S M; Samaddar, Sandip; Ghosh, Chandradhish; Paramanandham, Krishnamoorthy; Shome, Bibek R; Haldar, Jayanta

    2016-01-01

    Bacterial biofilms represent the root-cause of chronic or persistent infections in humans. Gram-negative bacterial infections due to nosocomial and opportunistic pathogens such as Acinetobacter baumannii are more difficult to treat because of their inherent and rapidly acquiring resistance to antibiotics. Due to biofilm formation, A. baumannii has been noted for its apparent ability to survive on artificial surfaces for an extended period of time, therefore allowing it to persist in the hospital environment. Here we report, maleic anhydride based novel cationic polymers appended with amide side chains that disrupt surface established multi-drug resistant A. baumannii biofilms. More importantly, these polymers significantly (p polymers also show potent antibacterial efficacy against methicillin resistant Staphylococcus aureus (MRSA), vancomycin resistant Enterococci (VRE) and multi-drug resistant clinical isolates of A. baumannii with minimal toxicity to mammalian cells. We observe that optimal hydrophobicity dependent on the side chain chemical structure of these polymers dictate the selective toxicity to bacteria. Polymers interact with the bacterial cell membranes by causing membrane depolarization, permeabilization and energy depletion. Bacteria develop rapid resistance to erythromycin and colistin whereas no detectable development of resistance occurs against these polymers even after several passages. These results suggest the potential use of these polymeric biomaterials in disinfecting biomedical device surfaces after the infection has become established and also for the topical treatment of chronic bacterial infections. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander

    2018-04-24

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  16. The Role of the Side Chain on the Performance of N-type Conjugated Polymers in Aqueous Electrolytes

    KAUST Repository

    Giovannitti, Alexander; Maria, Iuliana P.; Hanifi, David; Donahue, Mary J.; Bryant, Daniel; Barth, Katrina J.; Makdah, Beatrice E.; Savva, Achilleas; Moia, Davide; Zetek, Matyá š; Barnes, Piers R.F.; Reid, Obadiah G.; Inal, Sahika; Rumbles, Garry; Malliaras, George G.; Nelson, Jenny; Rivnay, Jonathan; McCulloch, Iain

    2018-01-01

    We report a design strategy that allows the preparation of solution processable n-type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol-based side chain. A series of random copolymers was prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90, and 100 with respect to the alkyl side chains. These were characterized to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions, and performance in OECTs when operated in aqueous electrolytes. We observed that glycol side chain percentages of >50% are required to achieve volumetric charging, while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

  17. Fixed-bed column study for hexavalent chromium removal and recovery by short-chain polyaniline synthesized on jute fiber

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Potsangbam Albino [Department of Civil Engineering, Indian Institute of Technology Guwahati, Assam 781039 (India); Chakraborty, Saswati [Department of Civil Engineering, Indian Institute of Technology Guwahati, Assam 781039 (India)], E-mail: saswati@iitg.ernet.in

    2009-03-15

    Fixed-bed column studies were conducted to evaluate performance of a short-chain polymer, polyaniline, synthesized on the surface of jute fiber (PANI-jute) for the removal of hexavalent chromium [Cr(VI)] in aqueous environment. Influent pH, column bed depth, influent Cr(VI) concentrations and influent flow rate were variable parameters for the present study. Optimum pH for total chromium removal was observed as 3 by electrostatic attraction of acid chromate ion (HCrO{sub 4}{sup -}) with protonated amine group (NH{sub 3}{sup +}) of PANI-jute. With increase in column bed depth from 40 to 60 cm, total chromium uptake by PANI-jute increased from 4.14 to 4.66 mg/g with subsequent increase in throughput volume from 9.84 to 12.6 L at exhaustion point. The data obtained for total chromium removal were well described by BDST equation till 10% breakthrough. Adsorption rate constant and dynamic bed capacity at 10% breakthrough were observed as 0.01 L/mg h and 1069.46 mg/L, respectively. Adsorbed total chromium was recovered back from PANI-jute as non-toxic Cr(III) after ignition with more than 97% reduction in weight, minimizing the problem of solid waste disposal.

  18. Small angle neutron scattering study on short and long chain phosphatidylcholine mixture in trehalose solution

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Hiroshi [Department of Physics, Gunma University, Maebashi, Gunma (Japan)

    2001-03-01

    Trehalose protects cells and proteins against various stresses due to low temperatures or dryness. In order to clarify the molecular mechanism of cryoprotective function of trehalose, we have studied the interaction between trehalose and phosphatidylcholine (PC) which is a main lipid component of cell membranes. In this study, the structural change of a binary PC mixture by the presence of trehalose was investigated by means of small angle neutron scattering. The PC binary mixture studied contains dihexanoyl-PC (diC{sub 6}PC) and dihexadecy-PC (DHPC). The former has short hydrocarbon chains and the latter has long hydrocarbon chains. The scattering profiles from the DHPC/diC{sub 6}PC mixture were changed, depending on trehalose concentrations. This change can be interpreted as suggesting that the presence of trehalose reduces the interfacial area between water and PCs. (author)

  19. Dechlorination of short chain chlorinated paraffins by nanoscale zero-valent iron.

    Science.gov (United States)

    Zhang, Zhi-Yong; Lu, Mang; Zhang, Zhong-Zhi; Xiao, Meng; Zhang, Min

    2012-12-01

    In this study, nanoscale zero-valent iron (NZVI) particles were synthesized and used for the reductive dehalogenation of short chain chlorinated paraffins (SCCPs) in the laboratory. The results show that the dechlorination rate of chlorinated n-decane (CP(10)) by NZVI increased with decreased solution pH. Increasing the loading of NZVI enhanced the dechlorination rate of CP(10). With an increase in temperature, the degradation rate increased. The reduction of CP(10) by NZVI was accelerated with increasing the concentration of humic acid up to 15 mg/L but then was inhibited. The dechlorination of CP(10) within the initial 18 h followed pseudo-first order rate model. The formation of intermediate products indicates a stepwise dechlorination pathway of SCCPs by NZVI. The carbon chain length and chlorination degree of SCCPs have a polynominal impact on dechlorination reactions. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Distribution of short block copolymer chains in Binary Blends of Block Copolymers Having Hydrogen Bonding

    Science.gov (United States)

    Kwak, Jongheon; Han, Sunghyun; Kim, Jin Kon

    2014-03-01

    A binary mixture of two block copolymers whose blocks are capable of forming the hydrogen bonding allows one to obtain various microdomains that could not be expected for neat block copolymer. For instance, the binary blend of symmetric polystyrene-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) and polystyrene-block-polyhydroxystyrene copolymer (PS-b-PHS) blends where the hydrogen bonding occurred between P2VP and PHS showed hexagonally packed (HEX) cylindrical and body centered cubic (BCC) spherical microdomains. To know the exact location of short block copolymer chains at the interface, we synthesized deuterated polystyrene-block-polyhydroxystyrene copolymer (dPS-b-PHS) and prepared a binary mixture with PS-b-P2VP. We investigate, via small angle X-ray scattering (SAXS) and neutron reflectivity (NR), the exact location of shorter dPS block chain near the interface of the microdomains.

  1. A Novel Protocol to Analyze Short- and Long-Chain Fatty Acids Using Nonaqueous Microchip Capillary Electrophoresis

    Science.gov (United States)

    Cable, M. L.; Stockton, A. M.; Mora, Maria F; Willis, P. A.

    2013-01-01

    We propose a new protocol to identify and quantify both short- and long-chain saturated fatty acids in samples of astrobiological interest using non-aqueous microchip capillary electrophoresis (micronNACE) with laser induced fluorescence (LIF).

  2. Degradation of amino acids to short-chain fatty acids in humans. An in vitro study

    DEFF Research Database (Denmark)

    Rasmussen, H S; Holtug, K; Mortensen, P B

    1988-01-01

    Short-chain fatty acids (SCFA) originate mainly in the colon through bacterial fermentation of polysaccharides. To test the hypothesis that SCFA may originate from polypeptides as well, the production of these acids from albumin and specific amino acids was examined in a faecal incubation system....... Albumin was converted to all C2-C5-fatty acids, whereas amino acids generally were converted to specific SCFA, most often through the combination of a deamination and decarboxylation of the amino acids, although more complex processes also took place. This study indicates that a part of the intestinal...

  3. 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

  4. Volatile Short-chain Chlorinated Hydrocarbons in the Groundwater of the City of Zagreb

    OpenAIRE

    Marijanović-Rajčić, M.; Senta, A.

    2008-01-01

    The aim of the study was to assess the quality of the groundwater sampled from private wells and the public water-supply system in terms of estimating the contamination caused by short-chain chlorinated hydrocarbons, as well as to estimate the exposure of the citizens dwelling in different suburbs to these pollutants of their drinking water (Fig. 1). The aim of the study was also to determine which suburb is supplied through the public water-supply system with water originating from the Sašna...

  5. Emission control strategies for short-chain chloroparaffins in two semi-hypothetical case cities

    DEFF Research Database (Denmark)

    Eriksson, Eva; Revitt, M.; Lützhøft, Hans-Christian Holten

    2012-01-01

    The short-chain chloroparaffins (SCCP), (C10-13 chloroalkanes) are identified in the European Water Framework Directive, as priority hazardous substances. Within the ScorePP project, the aim is to develop emission control strategies that can be employed to reduce emissions from urban areas...... into receiving waters. Six different scenarios for mitigating SCCP emissions in two different semi-hypothetical case cities representing eastern inland and northern coastal conditions have been evaluated. The analysis, associated with scenario uncertainty, indicates that the EU legislation, Best Available...

  6. Novel short chain chloroquine analogues retain activity against chloroquine resistant K1 Plasmodium falciparum.

    Science.gov (United States)

    Stocks, Paul A; Raynes, Kaylene J; Bray, Patrick G; Park, B Kevin; O'Neill, Paul M; Ward, Stephen A

    2002-11-07

    A series of short chain chloroquine (CQ) derivatives have been synthesized in one step from readily available starting materials. The diethylamine function of CQ is replaced by shorter alkylamine groups (4-9) containing secondary or tertiary terminal nitrogens. Some of these derivatives are significantly more potent than CQ against a CQ resistant strain of Plasmodium falciparum in vitro. We conclude that the ability to accumulate at higher concentrations within the food vacuole of the parasite is an important parameter that dictates their potency against CQ sensitive and the chloroquine resistant K1 P. falciparum.

  7. Antibiotic-associated diarrhoea, Clostridium difficile, and short-chain fatty acids

    DEFF Research Database (Denmark)

    Hove, H; Tvede, M; Mortensen, P B

    1996-01-01

    BACKGROUND: It has been hypothesized that Clostridium difficile and decreased colonic production of short-chain fatty acids (SCFAs) cause the development of antibiotic-associated diarrhoea. We therefore wanted to investigate the effects of an intensive and uniform antibiotic therapy on faecal SCFAs...... concentrations. C. difficile, and extent of diarrhoea. METHODS: Fifteen liver-transplanted patients who received oral bowel flora suppression therapy (6.3 g cefuroxime, 0.6 g tobramycin, and 0.5 g nystatin three times daily) were studied for 12 days before and 12 days after discontinuation of therapy. RESULTS...

  8. Ion solvation in polymer blends and block copolymer melts: effects of chain length and connectivity on the reorganization of dipoles.

    Science.gov (United States)

    Nakamura, Issei

    2014-05-29

    We studied the thermodynamic properties of ion solvation in polymer blends and block copolymer melts and developed a dipolar self-consistent field theory for polymer mixtures. Our theory accounts for the chain connectivity of polymerized monomers, the compressibility of the liquid mixtures under electrostriction, the permanent and induced dipole moments of monomers, and the resultant dielectric contrast among species. In our coarse-grained model, dipoles are attached to the monomers and allowed to rotate freely in response to electrostatic fields. We demonstrate that a strong electrostatic field near an ion reorganizes dipolar monomers, resulting in nonmonotonic changes in the volume fraction profile and the dielectric function of the polymers with respect to those of simple liquid mixtures. For the parameter sets used, the spatial variations near an ion can be in the range of 1 nm or larger, producing significant differences in the solvation energy among simple liquid mixtures, polymer blends, and block copolymers. The solvation energy of an ion depends substantially on the chain length in block copolymers; thus, our theory predicts the preferential solvation of ions arising from differences in chain length.

  9. Self-assembly of the hydrogel polymer chain consisting of chitosan and chondroitin sulphate in the presence of theophylline

    International Nuclear Information System (INIS)

    Lopes, Lais C.; Piai, Juliana F.; Fajardo, Andre R.; Rubira, Adley F.; Muniz, Edvani C.

    2009-01-01

    In this work, polyelectronic complex (PEC) consisting of two polysaccharides were developed. One is chitosan (QT), cationic polymer, produced by the chitin deacetylation and the other is chondroitin sulphate (CS), anionic polymer, extracted from bovine or porcine aorta. The PECs were prepared in the presence of theophylline (TEO) for evaluating the influence of this drug in the polymer chains reorganization, as well as, studying the mechanical properties and release of SC and TEO in aqueous solutions on different pH conditions. By the obtained results, it was observed that the 84QT/15SC/TEO (% in weight) hydrogel is pH responsive because the CS releasing is more effective at pH 8, while the release of the TEO is higher at pH 2. The hydrogel showed mechanical properties more resistant to pH 2, 8 and 10 and this was attributed to interactions between the polymer chains. Finally, the X-rays profile showed the presence of peaks associated to reorganization of the chains in the hydrogel is at times larger than the hydrogel in the absence of solute. (author)

  10. Controlling morphology and chain aggregation in semiconducting conjugated polymers: the role of solvent on optical gain in MEH-PPV.

    Science.gov (United States)

    Lampert, Zach E; Reynolds, C Lewis; Papanikolas, John M; Aboelfotoh, M Osama

    2012-10-25

    We report the results of a detailed investigation that addresses the influence of polymer morphology and chain aggregation, as controlled by the chemical nature of the solvent, on the optical gain properties of the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV). Using the variable stripe length technique in the picosecond regime, we have extensively studied the optical gain performance of asymmetric planar waveguides formed with thin MEH-PPV films spin-cast from concentrated chlorobenzene (CB) and tetrahydrofuran (THF) solutions onto thermally oxidized silicon substrates. CB and THF solvents were chosen based on their known ability to promote and effectively limit aggregate formation, respectively. Very large net gain coefficients are demonstrated, reaching values of 330 and 365 cm(-1), respectively, when optically pumping the waveguides with a maximum energy density of 85 μJ/cm(2). Our results clearly demonstrate that polymer morphology, and hence, the chain conformation dependence of the degree of aggregation in the films as controlled by the solvent, has minimal impact on the net gain. Moreover, the waveguides exhibit low loss coefficients of 10-20 cm(-1) at the ASE wavelength. These results question the importance of polymer morphology and aggregate formation in polymer-based optical devices operating at high excitation densities in the stimulated emission regime as would be characteristic of lasers and optical amplifiers.

  11. Polarized Emission from Conjugated Polymer Chains Aligned by Epitaxial Growth during Off-Center Spin-Coating

    Directory of Open Access Journals (Sweden)

    Takuya Anzai

    2017-01-01

    Full Text Available Due to their macromolecular nature, conjugated polymers can be relatively easily aligned by applying a variety of processes resulting in either elongation or ordering of their conjugated backbones. Processes that induce chain alignment include electrospinning, mechanical rubbing, epitaxial growth, and nanoconfinement and unidirectional deposition techniques such as off-center spin-coating. In this study, we compare these deposition techniques by applying them to a green-emitting conjugated polymer material that exhibits liquid crystalline phase behavior. Our study reveals that while methods such as electrospinning and mechanical rubbing can be useful to locally generate polymer chain alignment, the combination of epitaxial growth using 1,3,5-trichlorobenzene as crystallizing agent with off-center spin-coating results in the formation of anisotropic nanofiber-like structures with enhanced crystallinity degree and polarized light-emission properties. The unidirectional epitaxial growth was also applied to a red-emitting polymer that exhibits polarization ratios up to 4.1. Our results emphasize that this simple solution formulation and process can be used for the fabrication of polarized thin films of a variety of conjugated polymers with potential applications in the advanced display technologies or analytical equipment fields.

  12. 乳酸扩链聚合物的降解性能%DEGRADABLE BEHAVIORS OF LACTIDE CHAIN-EXTENED POLYMERS

    Institute of Scientific and Technical Information of China (English)

    封瑞江

    2001-01-01

    In this paper,the effects of change of degradable rate and relative molecular mass on the degradable behaviors of four lactide chain-extened polymers are contrasted with those of lactide polymers.The results indicated that the four lactide chain-extened polymers could degrade in this experiment and their degradable rate were lower than that of P-LA.LA-SDI has the highest degradable rates among the four lactide chain-extened polymers,but there was no significant difference among aromatic and aliphatic lactide chain-extened polymers.The results showed that the degradable rates were dependent on experiment methods and condition and also indicated that the relative molecular mass became smaller and smaller with the progress of degradation time.

  13. Side chain engineering of fused aromatic thienopyrazine based low band-gap polymers for enhanced charge carrier mobility

    KAUST Repository

    Mondal, Rajib

    2011-01-01

    A strategic side-chain engineering approach leads to the two orders of magnitude enhancement of charge carrier mobility in phenanthrene based fused aromatic thienopyrazine polymers. Hole carrier mobility up to 0.012 cm 2/Vs can be obtained in thin film transistor devices. Polymers were also utilized to fabricate bulk heterojunction photovoltaic devices and the maximum PCE obtained in these OPV\\'s was 1.15%. Most importantly, performances of the devices were correlated with thin morphological analysis performed by atomic force microscopy and grazing incidence X-ray scattering. © 2011 The Royal Society of Chemistry.

  14. Identification and Funtional Characterization of Three Postsynaptic Short-chain Neurotoxins from Hydrophiinae, Lapemis hardwickii Gray.

    Science.gov (United States)

    Zhong, Xiao-Fen; Peng, Li-Sheng; Wu, Wen-Yan; Wei, Jian-Wen; Yang, Hong; Yang, Yan-Zhen; Xu, An-Long

    2001-01-01

    Three cDNA clones, sn12, sn36 and sn160, encoding isoforms of postsynaptic short-chain neurotoxins, were cloned by screening a cDNA library of the venom from Hydrophiinae, Lapemis hardwickii Gray. The sequences of three cDNA clones encoded proteins consisting of 60 amino acid residues. There was only one amino acid substitution among the three isoforms SN12, SN36 and SN160 at the position 46 of mature proteins, and they were Pro(46), His(46) and Arg(46), respectively. The three molecules were expressed in Escherichia coli and the recombinant proteins were characterized. Different LD(50) were obtained, namely 0.0956 mg/kg, 0.3467 mg/kg and 0.2192 mg/kg, when the SN12, SN36 and SN160 were injected into Kunming mice(i.p.). In analgesic effect assayed by the acetic acid-induced writhing method, SN12 and SN160 showed similar analgesic effect, but SN36 had effects significantly different with the other two. Our studies suggested that the amino acid residues on position 46 could affect the combination between the postsynaptic short-chain neurotoxins and the nicotinic acetylchoine receptor, since different amino acid substitution resulted in different biological activities.

  15. Engineered Production of Short-Chain Acyl-Coenzyme A Esters in Saccharomyces cerevisiae

    DEFF Research Database (Denmark)

    Krink-Koutsoubelis, Nicolas; Loechner, Anne C.; Lechner, Anna

    2018-01-01

    Short-chain acyl-coenzyme A esters serve as intermediate compounds in fatty acid biosynthesis, and the production of polyketides, biopolymers and other value-added chemicals. S. cerevisiae is a model organism that has been utilized for the biosynthesis of such biologically and economically valuable...... compounds. However, its limited repertoire of short-chain acyl-CoAs effectively prevents its application as a production host for a plethora of natural products. Therefore, we introduced biosynthetic metabolic pathways to five different acyl-CoA esters into S. cerevisiae. Our engineered strains provide......-CoA at 0.5 μM; and isovaleryl-CoA, n-butyryl-CoA, and n-hexanoyl-CoA at 6 μM each. The acyl-CoAs produced in this study are common building blocks of secondary metabolites and will enable the engineered production of a variety of natural products in S. cerevisiae. By providing this toolbox of acyl...

  16. Gut microbiota alterations and dietary modulation in childhood malnutrition - The role of short chain fatty acids.

    Science.gov (United States)

    Pekmez, Ceyda Tugba; Dragsted, Lars Ove; Brahe, Lena Kirchner

    2018-02-17

    The gut microbiome affects the health status of the host through different mechanisms and is associated with a wide variety of diseases. Both childhood undernutrition and obesity are linked to alterations in composition and functionality of the gut microbiome. One of the possible mechanisms underlying the interplay between microbiota and host metabolism is through appetite-regulating hormones (including leptin, ghrelin, glucagon-like peptide-1). Short chain fatty acids, the end product of bacterial fermentation of non-digestible carbohydrates, might be able to alter energy harvest and metabolism through enteroendocrine cell signaling, adipogenesis and insulin-like growth factor-1 production. Elucidating these mechanisms may lead to development of new modulation practices of the gut microbiota as a potential prevention and treatment strategy for childhood malnutrition. The present overview will briefly outline the gut microbiota development in the early life, gut microbiota alterations in childhood undernutrition and obesity, and whether this relationship is causal. Further we will discuss possible underlying mechanisms in relation to the gut-brain axis and short chain fatty acids, and the potential of probiotics, prebiotics and synbiotics for modulating the gut microbiota during childhood as a prevention and treatment strategy against undernutrition and obesity. Copyright © 2018 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

  17. Short-term droughts forecast using Markov chain model in Victoria, Australia

    Science.gov (United States)

    Rahmat, Siti Nazahiyah; Jayasuriya, Niranjali; Bhuiyan, Muhammed A.

    2017-07-01

    A comprehensive risk management strategy for dealing with drought should include both short-term and long-term planning. The objective of this paper is to present an early warning method to forecast drought using the Standardised Precipitation Index (SPI) and a non-homogeneous Markov chain model. A model such as this is useful for short-term planning. The developed method has been used to forecast droughts at a number of meteorological monitoring stations that have been regionalised into six (6) homogenous clusters with similar drought characteristics based on SPI. The non-homogeneous Markov chain model was used to estimate drought probabilities and drought predictions up to 3 months ahead. The drought severity classes defined using the SPI were computed at a 12-month time scale. The drought probabilities and the predictions were computed for six clusters that depict similar drought characteristics in Victoria, Australia. Overall, the drought severity class predicted was quite similar for all the clusters, with the non-drought class probabilities ranging from 49 to 57 %. For all clusters, the near normal class had a probability of occurrence varying from 27 to 38 %. For the more moderate and severe classes, the probabilities ranged from 2 to 13 % and 3 to 1 %, respectively. The developed model predicted drought situations 1 month ahead reasonably well. However, 2 and 3 months ahead predictions should be used with caution until the models are developed further.

  18. Changes in short-chain fatty acid plasma profile incurred by dietary fiber composition

    DEFF Research Database (Denmark)

    Knudsen, Knud Erik Bach; Jørgensen, Henry Johs. Høgh; Theil, Peter Kappel

    2016-01-01

    Pigs were used as model for humans to study the impact of dietary fiber (DF), the main substrate for microbial fermentation, on plasma profile of short-chain fatty acids (SCFA; acetate, propionate, and butyrate). Six female pigs fitted with catheters in the portal vein and mesenteric artery and w...... higher net absorption of butyrate (2.4–4.0 vs. 1.6 mmol/h; P ...Pigs were used as model for humans to study the impact of dietary fiber (DF), the main substrate for microbial fermentation, on plasma profile of short-chain fatty acids (SCFA; acetate, propionate, and butyrate). Six female pigs fitted with catheters in the portal vein and mesenteric artery...... >> arabinoxylan >> β-glucan, whereas in the WWG, WAF, and RAF, diets it was arabinoxylan >> cellulose > β-glucan. The diets were fed to the pigs during 3 wk in a crossover design. Within an experimental week, WFL was supplied on Days 1 through 3 and WWG, WAF, or RAF was supplied during Days 4 through 7. Fasting...

  19. Social-economic and environmental sustainability of short supply chains: opportunities for development rural territories

    Directory of Open Access Journals (Sweden)

    Mykola Babych

    2018-03-01

    Full Text Available The paper substantiates the expediency of developing short supply chains at the local level. The focus of this paper is to determine opportunities for developing rural territories in Ukraine on the basis of the development of short supply chains in terms of ensuring social, economic and environmental sustainability. It is established that such an approach provides stability of development of rural territory, in particular, it promotes: social interaction (trust, justice, solidarity and common values between consumers and producers, community development (just relationships, pride, social cohesion and community affiliation, strengthening local culture and identity, health and well-being of the population (healthy diet; access to healthy food, health improvement, which ensures social sustainability of the system; rural development and economic recovery (increase of workplaces, tourism development, increase of local incomes, development of small and medium-sized farms, achievement of economic benefits to farms (reduction of overheads, fixed margin and premium for quality, increase of competitiveness and economic viability, sustainable use resources, which ensures economic stability of the system; reducing energy consumption and carbon dioxide emissions (reducing transport and storage time; using alternative technologies; maximizing manual labor; reducing the use of plastic packaging; reducing food losses; sustainability of agro-systems (promoting agro-biodiversity; using local varieties; highlighting ecological and organic production, which ensures the ecological stability of the system.

  20. [Contamination characteristics of short-chain chlorinated paraffins in edible fish of Shanghai].

    Science.gov (United States)

    Jiang, Guo; Chen, Lai-guo; He, Qiu-sheng; Meng, Xiang-zhou; Feng, Yong-bin; Huang, Yu-mei; Tang, Cai-ming

    2013-09-01

    According to the local habit of eating fish, in a total of 68 samples, 8 kinds of different trophic levels of edible fish collected in Shanghai were determined in terms of concentration and distribution profile of short chain chlorinated paraffin (SCCPs) in muscles to investigate the pollution status of SCCPs in edible fish from the Yangtze River Delta region. The results indicated that the concentrations (dw) of SCCPs in edible fish were in the range of 36-801 ng x g(-1). With the increase in carbon chain length, the concentration of SCCPs decreased. In addition, lower chlorinated (Cl6-Cl8) and shorter chain (Cl10, C11) congeners were the dominant chlorine and carbon homologues groups, respectively, contributing a total relative abundance of 61.46%-82.50% to the total abundance of SCCPs. The levels of SCCPs in fish of Shanghai were in the medium level worldwide, and the distribution pattern was in line with those of the domestic and foreign studies.

  1. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    International Nuclear Information System (INIS)

    Freire, J J

    2008-01-01

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches

  2. Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

    Energy Technology Data Exchange (ETDEWEB)

    Freire, J J [Departamento de Ciencias y Tecnicas FisicoquImicas, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia (UNED), Senda del Rey 9, 28040 Madrid (Spain)], E-mail: jfreire@invi.uned.es

    2008-07-16

    The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, two distinct values of B have been considered for alternate bonds in linear chains. In the case of the branched chains, mixed models with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of ordering or crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of the abrupt change in the curves associated with a thermodynamic transition. It is concluded that ordering is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves, which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches.

  3. Chain networking revealed by molecular dynamics simulation

    Science.gov (United States)

    Zheng, Yexin; Tsige, Mesfin; Wang, Shi-Qing

    Based on Kremer-Grest model for entangled polymer melts, we demonstrate how the response of a polymer glass depends critically on the chain length. After quenching two melts of very different chain lengths (350 beads per chain and 30 beads per chain) into deeply glassy states, we subject them to uniaxial extension. Our MD simulations show that the glass of long chains undergoes stable necking after yielding whereas the system of short chains is unable to neck and breaks up after strain localization. During ductile extension of the polymer glass made of long chain significant chain tension builds up in the load-bearing strands (LBSs). Further analysis is expected to reveal evidence of activation of the primary structure during post-yield extension. These results lend support to the recent molecular model 1 and are the simulations to demonstrate the role of chain networking. This work is supported, in part, by a NSF Grant (DMR-EAGER-1444859)

  4. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan; Honmou, Yoshihiro; Komiyama, Hideaki; Furumaki, Shu; Iyoda, Tomokazu; Vacha, Martin

    2013-01-01

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Conjugated Polymer Chains Confined in Vertical Nanocylinders of a Block-Copolymer Film: Preparation, Characterization, and Optoelectronic Function

    KAUST Repository

    Dong, Ban Xuan

    2013-01-15

    Hybrid materials composed of phase-separated block copolymer films and conjugated polymers of the phenylenevinylene family (PPV) are prepared. The PPV chains are embedded in vertical cylinders of nanometer diameter in the block-copolymer films. The cylinders span continuously the whole film thickness of 70 nm. Incorporation of the PPV chains into the one-dimensional cylinders leads to modified photoluminescence spectra and to large absorption anisotropy. The hybrid films show electroluminescence from the PPV chains in a simple light-emitting device at minute doping concentrations, and also exhibit a factor of 19 increase in electron transport efficiency along the single PPV chains. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Impact of charge carrier injection on single-chain photophysics of conjugated polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, Felix J.; Vogelsang, Jan, E-mail: jan.vogelsang@physik.uni-regensburg.de; Lupton, John M. [Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg (Germany)

    2016-06-27

    Charges in conjugated polymer materials have a strong impact on the photophysics and their interaction with the primary excited state species has to be taken into account in understanding device properties. Here, we employ single-molecule spectroscopy to unravel the influence of charges on several photoluminescence (PL) observables. The charges are injected either stochastically by a photochemical process or deterministically in a hole-injection sandwich device configuration. We find that upon charge injection, besides a blue-shift of the PL emission and a shortening of the PL lifetime due to quenching and blocking of the lowest-energy chromophores, the non-classical photon arrival time distribution of the multichromophoric chain is modified towards a more classical distribution. Surprisingly, the fidelity of photon antibunching deteriorates upon charging, whereas one would actually expect the opposite: the number of chromophores to be reduced. A qualitative model is presented to explain the observed PL changes. The results are of interest to developing a microscopic understanding of the intrinsic charge-exciton quenching interaction in devices.

  7. Small-angle neutron scattering of short-segment block polymers

    International Nuclear Information System (INIS)

    Cooper, S.L.; Miller, J.A.; Homan, J.G.

    1988-01-01

    Small-angle neutron scattering has been used to investigate the chain conformation of the hard and soft segments in short-segment polyether-polyester and polyether-polyurethane materials. The method of phase-contrast matching was used to eliminate the coherent neutron scattering due to the two-phase microstructure in these materials. The partial deutero-labelling necessary for this technique also provides a neutron scattering contrast between labelled and unlabelled segments. The structure factor for each segment type is determined from the coherent scattering from such deuterolabelled materials. In all of the materials examined, the poly(tetramethylene oxide) (PTMO) soft segment was found to be in a slightly extended conformation relative to bulk PTMO at room temperature. Upon heating, the PTMO segments contracted to a more relaxed conformation. In one polyether-polyurethane sample, the radius of gyration of the PTMO segment increased again at high temperatures, indicating phase mixing. The hardsegment radii of gyration in the polyether-polyester materials were found to increase with temperature, indicating a transition from a chain-folded conformation at room temperature to a more extended conformation at higher temperatures. The radius of gyration of the whole polyether-polyester chain first decreased then increased with temperature, indicative of the combined effects of the component hard- and soft-segment chain conformation changes. The hard-segment radius of gyration in a polyether-polyurethane was observed to decrease with temperature. (orig.)

  8. Development of environmentally friendly coatings and paints using medium-chain-length poly(3-hydroxyalkanoates) as the polymer binder.

    Science.gov (United States)

    van der Walle, G A; Buisman, G J; Weusthuis, R A; Eggink, G

    1999-01-01

    Unsaturated medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) produced by Pseudomonas putida from linseed oil fatty acids (LOFA) and tall oil fatty acids (TOFA), were used as the polymer binder in the formulation of high solid alkyd-like paints. The relatively high concentration of unsaturated alkyl side chains incorporated into the PHA resins resulted in oxidative drying PHA paints having excellent coating properties. The homogeneously pigmented PHA coatings yielded high-gloss, smooth and strong films upon curing and showed an excellent flexibility, a good adhesion to different substrates, cohesive film properties and resistance to chipping.

  9. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

    Energy Technology Data Exchange (ETDEWEB)

    He, Tian [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhao, Yi-xing; Chen, San-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn [Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000 (China); Yan, Ni [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)

    2016-07-15

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC

  10. Lactobacillus rhamnosus GR-1 in Fermented Rice Pudding Supplemented with Short Chain Inulin, Long Chain Inulin, and Oat as a Novel Functional Food

    Directory of Open Access Journals (Sweden)

    Maja Williams

    2017-10-01

    Full Text Available Lactobacillus rhamnosus GR-1 is a probiotic that has been shown to reduce the risk of urogenital problems and urinary tract infections. Rice pudding is a popular gluten-free dairy product, and could be a vehicle to deliver L. rhamnosus GR-1 to a broader population. The purpose of this study was to investigate the growth and viability of L. rhamnosus GR-1 in six fermented rice pudding samples, each one supplemented with one type of prebiotic (short-chain inulin-2% w/w, 4% w/w; long-chain inulin-2% w/w, 4% w/w and oat-0.5% w/w, 1% w/w, along with control, over a 21-day storage period. The objective was to determine if the supplementation would have a positive effect on the microbial viability of L. rhamnosus GR-1, and to evaluate the sensory properties of the samples. All of the samples had viable levels of L. rhamnosus GR-1. Bacterial counts were at least 1 × 108 CFU/mL over the 21-day storage period. The probiotic rice pudding sample supplemented with 4% w/w short-chain inulin had the highest hedonic score for flavour, sweetness, texture, and overall acceptability. This study shows that the addition of short-chain inulin, long-chain inulin, and oat had no adverse supplementation effects on the viability of L. Rhamnosus GR-1. There is the potential for the production of a novel functional food.

  11. The Impact of Short-Sale Constraints on Asset Allocation Strategies via the Backward Markov Chain Approximation Method

    OpenAIRE

    Carl Chiarella; Chih-Ying Hsiao

    2005-01-01

    This paper considers an asset allocation strategy over a finite period under investment uncertainty and short-sale constraints as a continuous time stochastic control problem. Investment uncertainty is characterised by a stochastic interest rate and inflation risk. If there are no short-sale constraints, the optimal asset allocation strategy can be solved analytically. We consider several kinds of short-sale constraints and employ the backward Markov chain approximation method to explore the ...

  12. The Relationship between the Monomer Chain Length and the Electro-Optical Properties of Polymer Dispersed Liquid Crystals

    Directory of Open Access Journals (Sweden)

    Liu J.

    2016-03-01

    Full Text Available Five polymers dispersed liquid crystalline (LC films were fabricated using photo-polymerizable monomers with different lengths of carbon chains. These LC films have shown different electro-optical (EO properties. Through their SEM pictures, the relationship between the linear electro-optical effect and the mesh size of the polymer network was explored. With the increase of number of photo-polymerizable monomers, the mesh size of the polymer network would become larger. So the liquid crystal molecules would be easily oriented in the electric field and therefore, the threshold voltage and saturation voltage would decrease. The open state response times were also reduced and the off state response times would be extended. The DFT simulations have shown principal role of the ground state dipole moments in the observed electro-optical efficiency.

  13. Small-angle x-ray scattering study on conformation of amorphous polymer chain in the bulk

    International Nuclear Information System (INIS)

    Hayashi, Hisao; Hamada, Fumiyuki; Nakajima, Akio

    1975-01-01

    In a previous paper, the new method for the determination of the conformation of polymer chains in concentrated solution and in bulk by small angle X-ray scattering was reported. The purpose of this paper is to estimate the dimension and conformation of polystyrene chains in bulk by this method. The tagged polymer used was the copolymer of styrene and p-iodostyrene. Excess scattering was obtained by subtracting the intensity of polystyrene matrix from that of a mixture containing polystyrene and a small fraction of the tagged polystyrene. Since the excess scattering originates from the group of iodine atoms in the tagged polystyrene, the radius of gyration of the tagged polystyrene is estimated by Guinier plot. Measurement was made with a Kratky camera, and in order to obtain high scattering intensity, the primary beam with line-shaped cross section was used. The intercepts of two limiting curves in the plotted radius of gyration diagram showed good agreement, and the measured molecular dimension agreed with the unperturbed dimension of this polymer. It was concluded that the molecular chains in bulk are mutually penetrable, and the centers of gravity of the molecules distribute almost randomly. It was suggested from the plot of the excess scattering intensity that the conformation of the tagged molecules is a random coil. The present results did not support the ordered structure revealed by bundle model and meander model. (Kako, I.)

  14. Biomedical applications of polymers derived by reversible addition - fragmentation chain-transfer (RAFT).

    Science.gov (United States)

    Fairbanks, Benjamin D; Gunatillake, Pathiraja A; Meagher, Laurence

    2015-08-30

    RAFT- mediated polymerization, providing control over polymer length and architecture as well as facilitating post polymerization modification of end groups, has been applied to virtually every facet of biomedical materials research. RAFT polymers have seen particularly extensive use in drug delivery research. Facile generation of functional and telechelic polymers permits straightforward conjugation to many therapeutic compounds while synthesis of amphiphilic block copolymers via RAFT allows for the generation of self-assembled structures capable of carrying therapeutic payloads. With the large and growing body of literature employing RAFT polymers as drug delivery aids and vehicles, concern over the potential toxicity of RAFT derived polymers has been raised. While literature exploring this complication is relatively limited, the emerging consensus may be summed up in three parts: toxicity of polymers generated with dithiobenzoate RAFT agents is observed at high concentrations but not with polymers generated with trithiocarbonate RAFT agents; even for polymers generated with dithiobenzoate RAFT agents, most reported applications call for concentrations well below the toxicity threshold; and RAFT end-groups may be easily removed via any of a variety of techniques that leave the polymer with no intrinsic toxicity attributable to the mechanism of polymerization. The low toxicity of RAFT-derived polymers and the ability to remove end groups via straightforward and scalable processes make RAFT technology a valuable tool for practically any application in which a polymer of defined molecular weight and architecture is desired. Copyright © 2015. Published by Elsevier B.V.

  15. Diversion procto-colitis: response to treatment with short-chain fatty acids.

    Science.gov (United States)

    Kiely, E M; Ajayi, N A; Wheeler, R A; Malone, M

    2001-10-01

    Diversion procto-colitis (DPC) results from a deficiency of luminal short-chain fatty acids (SCFAs). Endoscopic and histopathologic features of the disorder are almost universally present in defunctioned bowel, but symptomatic DPC is less common. Five children with symptomatic DPC underwent endoscopy and rectosigmoid biopsies. An endoscopic index (EI) was used to quantify disease severity. An SCFA mixture was administered into the defunctioned bowel. A good clinical response and improvement in the endoscopic index occurred in all children. Undiversion or rectal excision was carried out in 4 and was curative in each case. One child is awaiting a redo pull through. DPC should be considered in children with a defunctioned colon presenting with evidence of colitis. Histopathology provides supportive evidence and SCFAs may provide effective relief of symptoms. Stoma reversal or rectal excision is curative. Copyright 2001 by W.B. Saunders Company.

  16. Long-term physical ageing in As-Se glasses with short chalcogen chains

    International Nuclear Information System (INIS)

    Golovchak, R; Shpotyuk, O; Kozdras, A; Vlcek, M; Bureau, B; Kovalskiy, A; Jain, H

    2008-01-01

    Long-term physical ageing of chalcogenide glasses, which occurs over tens of years, is much less understood than the short-term ageing. With Se-rich underconstrained As 30 Se 70 glass as a model composition (consisting of Se n chains with n≤3 on average), a microscopic model is developed for this phenomenon by combining information from differential scanning calorimetry, extended x-ray absorption fine structure, Raman, and 77 Se solid state nuclear magnetic resonance spectroscopies. The accompanying changes in the electronic structure of these glasses are investigated by x-ray photoelectron spectroscopy. The data suggest ageing from cooperative relaxation, presumably involving bond switching or reconfiguration of As-Se-Se-As fragments

  17. Long-term physical ageing in As-Se glasses with short chalcogen chains

    Energy Technology Data Exchange (ETDEWEB)

    Golovchak, R; Shpotyuk, O [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska street, Lviv, UA-79031 (Ukraine); Kozdras, A [Faculty of Physics of Opole University of Technology, 75, Ozimska street, Opole, 45370 (Poland); Vlcek, M [Department of General and Inorganic Chemistry, Faculty of Chemistry, University of Pardubice, 532 10 Pardubice (Czech Republic); Bureau, B [Verres et Ceramiques, UMR CNRS 6226 Sciences Chimiques de Rennes, University of Rennes, 1, Campus de Beaulieu, Rennes, 35042 (France); Kovalskiy, A; Jain, H [Department of Materials Science and Engineering, Lehigh University, 5, East Packer Avenue, Bethlehem, PA 18015-3195 (United States)

    2008-06-18

    Long-term physical ageing of chalcogenide glasses, which occurs over tens of years, is much less understood than the short-term ageing. With Se-rich underconstrained As{sub 30}Se{sub 70} glass as a model composition (consisting of Se{sub n} chains with n{<=}3 on average), a microscopic model is developed for this phenomenon by combining information from differential scanning calorimetry, extended x-ray absorption fine structure, Raman, and {sup 77}Se solid state nuclear magnetic resonance spectroscopies. The accompanying changes in the electronic structure of these glasses are investigated by x-ray photoelectron spectroscopy. The data suggest ageing from cooperative relaxation, presumably involving bond switching or reconfiguration of As-Se-Se-As fragments.

  18. Retention of short chain fatty acids under drying and storage conditions

    Directory of Open Access Journals (Sweden)

    Alexandre Santos Souza

    2011-09-01

    Full Text Available Cheese whey permeate was used as a substrate for the fermentation of Propionibacterium freudenreichi PS1 for the production of short chain fatty acids, components of the bio-aroma of Swiss cheese. The liquid bio-aroma was encapsulated by spray drying under different conditions of air inlet temperature and feed rate. A study was carried out on the stability of the bio-aroma during storage in laminated packages at 30 °C for 96 days using the product showing the greatest retention of acetic and propionic acids. The results showed that the best drying conditions were an air entrance temperature of 180 °C and a feed rate of 24 g/min resulting in particles with a smooth surface and few invaginations and micro-fissures. However, 72% of the acetic acid and 80% of the propionic acid were lost during storage showing that the wall material used was inadequate to guarantee product stability.

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

    Science.gov (United States)

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

    2012-12-01

    Global geochemical analyses suggest that C2-C4 short chain alkanes are a common component of the utilizable carbon pool in deep-sea sediments worldwide and have been found in diverse ecosystems. From a thermodynamic standpoint, the anaerobic microbial oxidation of these aliphatic hydrocarbons is more energetically yielding than the anaerobic oxidation of methane (AOM). Therefore, the preferential degradation of these hydrocarbons may compete with AOM for the use of oxidants such as sulfate, or other potential oxidants. Such processes could influence the fate of methane in the deep-sea. Sulfate-reducing bacteria (SRB) from hydrocarbon seep sediments of the Gulf of Mexico and Guaymas Basin have previously been enriched that anaerobically oxidize short chain alkanes to generate CO2 with the preferential utilization of 12C-enriched alkanes (Kniemeyer et al. 2007). Different temperature regimens along with multiple substrates were tested and a pure culture (deemed BuS5) was isolated from mesophilic enrichments with propane or n-butane as the sole carbon source. Through comparative sequence analysis, strain BuS5 was determined to cluster with the metabolically diverse Desulfosarcina / Desulfococcus cluster, which also contains the SRB found in consortia with anaerobic, methane-oxidizing archaea in seep sediments. Enrichments from a terrestrial, low temperature sulfidic hydrocarbon seep also corroborated that propane degradation occurred with most bacterial phylotypes surveyed belonging to the Deltaproteobacteria, particularly Desulfobacteraceae (Savage et al. 2011). To date, no microbes capable of ethane oxidation or anaerobic C2-C4 alkane oxidation at thermophilic temperature have been isolated. The sediment-covered, hydrothermal vent systems found at Middle Valley (Juan de Fuca Ridge, eastern Pacific Ocean) are a prime environment for investigating mesophilic to thermophilic anaerobic oxidation of short-chain alkanes, given the elevated temperatures and dissolved

  20. The effect of short-chain fatty acids on human monocyte-derived dendritic cells

    DEFF Research Database (Denmark)

    Nastasi, Claudia; Candela, Marco; Bonefeld, Charlotte Menné

    2015-01-01

    negligible effects, while both butyrate and propionate strongly modulated gene expression in both immature and mature human monocyte-derived DC. An Ingenuity pathway analysis based on the differentially expressed genes suggested that propionate and butyrate modulate leukocyte trafficking, as SCFA strongly......The gut microbiota is essential for human health and plays an important role in the pathogenesis of several diseases. Short-chain fatty acids (SCFA), such as acetate, butyrate and propionate, are end-products of microbial fermentation of macronutrients that distribute systemically via the blood....... The aim of this study was to investigate the transcriptional response of immature and LPS-matured human monocyte-derived DC to SCFA. Our data revealed distinct effects exerted by each individual SCFA on gene expression in human monocyte-derived DC, especially in the mature ones. Acetate only exerted...

  1. Enantiocomplementary Yarrowia lipolytica Oxidoreductases: Alcohol Dehydrogenase 2 and Short Chain Dehydrogenase/Reductase

    Directory of Open Access Journals (Sweden)

    Margit Winkler

    2013-08-01

    Full Text Available Enzymes of the non-conventional yeast Yarrowia lipolytica seem to be tailor-made for the conversion of lipophilic substrates. Herein, we cloned and overexpressed the Zn-dependent alcohol dehydrogenase ADH2 from Yarrowia lipolytica in Escherichia coli. The purified enzyme was characterized in vitro. The substrate scope for YlADH2 mediated oxidation and reduction was investigated spectrophotometrically and the enzyme showed a broader substrate range than its homolog from Saccharomyces cerevisiae. A preference for secondary compared to primary alcohols in oxidation direction was observed for YlADH2. 2-Octanone was investigated in reduction mode in detail. Remarkably, YlADH2 displays perfect (S-selectivity and together with a highly (R-selective short chain dehydrogenase/ reductase from Yarrowia lipolytica it is possible to access both enantiomers of 2-octanol in >99% ee with Yarrowia lipolytica oxidoreductases.

  2. Enantiocomplementary Yarrowia lipolytica Oxidoreductases: Alcohol Dehydrogenase 2 and Short Chain Dehydrogenase/Reductase.

    Science.gov (United States)

    Napora-Wijata, Kamila; Strohmeier, Gernot A; Sonavane, Manoj N; Avi, Manuela; Robins, Karen; Winkler, Margit

    2013-08-12

    Enzymes of the non-conventional yeast Yarrowia lipolytica seem to be tailor-made for the conversion of lipophilic substrates. Herein, we cloned and overexpressed the Zn-dependent alcohol dehydrogenase ADH2 from Yarrowia lipolytica in Escherichia coli. The purified enzyme was characterized in vitro. The substrate scope for YlADH2 mediated oxidation and reduction was investigated spectrophotometrically and the enzyme showed a broader substrate range than its homolog from Saccharomyces cerevisiae. A preference for secondary compared to primary alcohols in oxidation direction was observed for YlADH2. 2-Octanone was investigated in reduction mode in detail. Remarkably, YlADH2 displays perfect (S)-selectivity and together with a highly (R)-selective short chain dehydrogenase/ reductase from Yarrowia lipolytica it is possible to access both enantiomers of 2-octanol in >99% ee with Yarrowia lipolytica oxidoreductases.

  3. Lithiated short side chain perfluorinated sulfonic ionomeric membranes: Water content and conductivity

    Science.gov (United States)

    Navarrini, Walter; Scrosati, Bruno; Panero, Stefania; Ghielmi, Alessandro; Sanguineti, Aldo; Geniram, Giuliana

    In view of possible applications as single-ion electrolyte for lithium batteries, some aspects of the lithium form of Hyflon Ion ionomer, a sulfonic short side chain (SSC) electrolyte, have been investigated. The synthesis of the ionomer and the successive membrane preparation is reported. An appropriate methodology for the direct salification of the ionomeric membrane from the SO 2F form to lithium salt, using lithium hydroxide in absence of organic solvent has been found. Utilizing these SSC lithium ionomer membranes and though a particular methodology for the dehydration of the lithium ion membrane in non-aqueous media, it has been possible to achieve an ionic conductivity of 10 -3 S cm -1 at room temperature [W. Navarrini, S. Panero, B. Scrosati, A. Sanguineti, European Patent 1,403,958 A1 (2003)]. Surprisingly it was observed that the membrane ionic conductivity depends on the dehydration methodologies adopted.

  4. Biodiesel production by esterification of oleic acid with short-chain alcohols under ultrasonic irradiation condition

    Energy Technology Data Exchange (ETDEWEB)

    Hanh, Hoang Duc; Okitsu, Kenji; Nishimura, Rokuro; Maeda, Yasuaki [Department of Applied Material Science, Graduate School of Engineering, Osaka Prefecture University, Gakuen-cho 1-1, Sakai, Osaka 599-8531 (Japan); Dong, Nguyen The [Institute of Environmental Technology, Vietnamese Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Hanoi (Viet Nam)

    2009-03-15

    Production of fatty acid ethyl ester (FAEE) from oleic acid (FFA) with short-chain alcohols (ethanol, propanol, and butanol) under ultrasonic irradiation was investigated in this work. Batch esterification of oleic acid was carried out to study the effect of: test temperatures of 10-60 C, molar ratios of alcohol to oleic acid of 1:1-10:1, quantity of catalysts of 0.5-10% (wt of sulfuric acid/wt of oleic acid) and irradiation times of 10 h. The optimum condition for the esterification process was molar ratio of alcohol to oleic acid at 3:1 with 5 wt% of H{sub 2}SO{sub 4} at 60 C with an irradiation time of 2 h. (author)

  5. Enhancing the specificity of polymerase chain reaction by graphene oxide through surface modification: zwitterionic polymer is superior to other polymers with different charges

    Science.gov (United States)

    Zhong, Yong; Huang, Lihong; Zhang, Zhisen; Xiong, Yunjing; Sun, Liping; Weng, Jian

    2016-01-01

    Graphene oxides (GOs) with different surface characteristics, such as size, reduction degree and charge, are prepared, and their effects on the specificity of polymerase chain reaction (PCR) are investigated. In this study, we demonstrate that GO with a large size and high reduction degree is superior to small and nonreduced GO in enhancing the specificity of PCR. Negatively charged polyacrylic acid (PAA), positively charged polyacrylamide (PAM), neutral polyethylene glycol (PEG) and zwitterionic polymer poly(sulfobetaine) (pSB) are used to modify GO. The PCR specificity-enhancing ability increases in the following order: GO-PAA Pfu DNA polymerase. Our data demonstrate that the size, reduction degree and surface charge of GO affect the specificity of PCR. Based on our results, zwitterionic polymer-modified GO may be used as an efficient additive for enhancing the specificity of PCR. PMID:27956830

  6. A Catalase-related Hemoprotein in Coral Is Specialized for Synthesis of Short-chain Aldehydes

    Science.gov (United States)

    Teder, Tarvi; Lõhelaid, Helike; Boeglin, William E.; Calcutt, Wade M.; Brash, Alan R.; Samel, Nigulas

    2015-01-01

    In corals a catalase-lipoxygenase fusion protein transforms arachidonic acid to the allene oxide 8R,9-epoxy-5,9,11,14-eicosatetraenoic acid from which arise cyclopentenones such as the prostanoid-related clavulones. Recently we cloned two catalase-lipoxygenase fusion protein genes (a and b) from the coral Capnella imbricata, form a being an allene oxide synthase and form b giving uncharacterized polar products (Lõhelaid, H., Teder, T., Tõldsepp, K., Ekins, M., and Samel, N. (2014) PloS ONE 9, e89215). Here, using HPLC-UV, LC-MS, and NMR methods, we identify a novel activity of fusion protein b, establishing its role in cleaving the lipoxygenase product 8R-hydroperoxy-eicosatetraenoic acid into the short-chain aldehydes (5Z)-8-oxo-octenoic acid and (3Z,6Z)-dodecadienal; these primary products readily isomerize in an aqueous medium to the corresponding 6E- and 2E,6Z derivatives. This type of enzymatic cleavage, splitting the carbon chain within the conjugated diene of the hydroperoxide substrate, is known only in plant cytochrome P450 hydroperoxide lyases. In mechanistic studies using 18O-labeled substrate and incubations in H218O, we established synthesis of the C8-oxo acid and C12 aldehyde with the retention of the hydroperoxy oxygens, consistent with synthesis of a short-lived hemiacetal intermediate that breaks down spontaneously into the two aldehydes. Taken together with our initial studies indicating differing gene regulation of the allene oxide synthase and the newly identified catalase-related hydroperoxide lyase and given the role of aldehydes in plant defense, this work uncovers a potential pathway in coral stress signaling and a novel enzymatic activity in the animal kingdom. PMID:26100625

  7. Yoghurt from short supply chain: preliminary study of microbiological and physicochemical characteristics during shelf life

    Directory of Open Access Journals (Sweden)

    Virginia Carfora

    2013-04-01

    Full Text Available Yoghurt is one of very popular flavorful and healthful dairy product obtained by fermentation of lactic acid bacteria including Lactobacillus delbrueckii bulgaricus and Streptococcus thermophilus. Its production and consumption is growing continuously due to its therapeutic properties beside its high nutritive value. Thirty samples of yoghurt from short supply chain produced in 2 factory localized in Lazio region were analyzed with the aim of determining how certain microbiological and physicochemical characteristics change during their shelf life. Different types of yoghurt were studied: plain (12, fruit (14 and cereal yoghurt (4 produced with cow (8 and goat milk (22.The obtained results show: no presence of Enterobacteria, occasional presence of moulds and a considerable presence of yeasts. On the other hand, all the products analyzed have shown an almost constant amount of lactic acid bacteria during their shelf life. Lactic acid bacteria were identified by a biochemical and polymerase chain reaction assay. The presence of undesired microorganisms like yeasts was found. However, the quality of products was satisfying for the concentration of lactic acid bacteria detected in their shelf life.

  8. Intestinal short chain fatty acids and their link with diet and human health

    Directory of Open Access Journals (Sweden)

    David eRios-Covian

    2016-02-01

    Full Text Available The colon is inhabited by a dense population of microorganisms, the so-called gut microbiota, able to ferment carbohydrates and proteins that escape absorption in the small intestine during digestion. This microbiota produces a wide range of metabolites, including short chain fatty acids (SCFA. These compounds are absorbed in the large bowel and are defined as 1-6 carbon volatile fatty acids which can present straight or branched-chain conformation. Their production is influenced by the pattern of food intake and diet-mediated changes in the gut microbiota. SCFA have distinct physiological effects: they contribute to shaping the gut environment, influence the physiology of the colon, they can be used as energy sources by host cells and the intestinal microbiota and they also participate in different host-signalling mechanisms. We summarize the current knowledge about the production of SCFA, including bacterial cross-feedings interactions, and the biological properties of these metabolites with impact on the human health

  9. Phase separation of a Lennard-Jones fluid interacting with a long, condensed polymer chain: implications for the nuclear body formation near chromosomes.

    Science.gov (United States)

    Oh, Inrok; Choi, Saehyun; Jung, YounJoon; Kim, Jun Soo

    2015-08-28

    Phase separation in a biological cell nucleus occurs in a heterogeneous environment filled with a high density of chromatins and thus it is inevitably influenced by interactions with chromatins. As a model system of nuclear body formation in a cell nucleus filled with chromatins, we simulate the phase separation of a low-density Lennard-Jones (LJ) fluid interacting with a long, condensed polymer chain. The influence of the density variation of LJ particles above and below the phase boundary and the role of attractive interactions between LJ particles and polymer segments are investigated at a fixed value of strong self-interaction between LJ particles. For a density of LJ particles above the phase boundary, phase separation occurs and a dense domain of LJ particles forms irrespective of interactions with the condensed polymer chain whereas its localization relative to the polymer chain is determined by the LJ-polymer attraction strength. Especially, in the case of moderately weak attractions, the domain forms separately from the polymer chain and subsequently associates with the polymer chain. When the density is below the phase boundary, however, the formation of a dense domain is possible only when the LJ-polymer attraction is strong enough, for which the domain grows in direct contact with the interacting polymer chain. In this work, different growth behaviors of LJ particles result from the differences in the density of LJ particles and in the LJ-polymer interaction, and this work suggests that the distinct formation of activity-dependent and activity-independent nuclear bodies (NBs) in a cell nucleus may originate from the differences in the concentrations of body-specific NB components and in their interaction with chromatins.

  10. Screening of short- and medium-chain chlorinated paraffins in selected riverine sediments and sludge from the Czech Republic.

    Science.gov (United States)

    Pribylová, Petra; Klánová, Jana; Holoubek, Ivan

    2006-11-01

    Wide distribution of chlorinated paraffins in the environment has already been demonstrated in several studies; however, information about their levels in the Central Europe is still very limited. First study focused on the SCCP contamination of the Czech aquatic environment have been performed recently, and its results motivated the authors to analyze sediments from a wide set of the Czech rivers in order to obtain more detailed information. Thirty-six sediment samples from eleven rivers and five drainage vents neighboring the chemical factories were analyzed; special attention was paid to the industrial areas. For the first time in the Czech Republic, medium-chain in addition to short-chain chlorinated paraffins were analyzed using GC-ECNI-MS. Chlorinated paraffins were detected in sediment samples on the concentration levels up to 347 ngg(-1) for short-chain chlorinated paraffins, and 5575 ngg(-1) for medium-chain chlorinated paraffins. Average chlorination degree of SCCPs was 65%.

  11. New theories for smectic and nematic liquid-crystal polymers: Backbone LCPs [liquid crystalline polymers] and their mixtures and side-chain LCPs

    International Nuclear Information System (INIS)

    Dowell, F.

    1987-01-01

    A summary of predictions and explanations from statistical-physics theories for both backbone and side-chain liquid crystalline polymers (LCPs) and for mixtures with backbone LCPs are presented. Trends in the thermodynamic and molecular ordering properties have been calculated as a function of pressure, density, temperature, and molecule chemical structures (including degree of polymerization and the following properties of the chemical structures of the repeat units: lengths and shapes, intra-chain rotation energies, dipole moments, site-site polarizabilities and Lennard-Jones potentials, etc.) in nematic and multiple smectic-A LC phases and in the isotropic liquid phase. The theoretical results are found to be in good agreement with existing experimental data. These theories can also be applied to combined LCPs. Since these theories have no ad hoc or arbitrarily adjustable parameters, these theories can be used to design new LCPs and new solvents as well as to predict and explain properties. 27 refs., 4 tabs

  12. Process development of short-chain polyols synthesis from corn stover by combination of enzymatic hydrolysis and catalytic hydrogenolysis

    Directory of Open Access Journals (Sweden)

    Zhen-Hong Fang

    2014-09-01

    Full Text Available Currently short-chain polyols such as ethanediol, propanediol, and butanediol are produced either from the petroleum feedstock or from the starch-based food crop feedstock. In this study, a combinational process of enzymatic hydrolysis with catalytic hydrogenolysis for short-chain polyols production using corn stover as feedstock was developed. The enzymatic hydrolysis of the pretreated corn stover was optimized to produce stover sugars at the minimum cost. Then the stover sugars were purified and hydrogenolyzed into polyols products catalyzed by Raney nickel catalyst. The results show that the yield of short-chain polyols from the stover sugars was comparable to that of the corn-based glucose. The present study provided an important prototype for polyols production from lignocellulose to replace the petroleum- or corn-based polyols for future industrial applications.

  13. Bioaccumulation and biomagnification of short and medium chain polychlorinated paraffins in different species of fish from Liaodong Bay, North China

    OpenAIRE

    Huang, Huiting; Gao, Lirong; Xia, Dan; Qiao, Lin

    2017-01-01

    Chlorinated paraffins (CPs) are highly complex technical mixtures, and the short chain chlorinated paraffins (SCCPs) are classed as persistent and have been included in the Stockholm Convention. However, there have been few studies of SCCPs and medium chain chlorinated paraffins (MCCPs) and their bioaccumulation and biomagnification in different species of fish. The present study investigated the levels, congener group profiles, bioaccumulation, and biomagnification of SCCPs and MCCPs in diff...

  14. Isolation and amino acid sequence of a short-chain neurotoxin from an Australian elapid snake, Pseudechis australis.

    OpenAIRE

    Takasaki, C; Tamiya, N

    1985-01-01

    A short-chain neurotoxin Pseudechis australis a (toxin Pa a) was isolated from the venom of an Australian elapid snake Pseudechis australis (king brown snake) by sequential chromatography on CM-cellulose, Sephadex G-50 and CM-cellulose columns. Toxin Pa a has an LD50 (intravenous) value of 76 micrograms/kg body wt. in mice and consists of 62 amino acid residues. The amino acid sequence of Pa a shows considerable homology with those of short-chain neurotoxins of elapid snakes, especially of tr...

  15. Volatile Short-chain Chlorinated Hydrocarbons in the Groundwater of the City of Zagreb

    Directory of Open Access Journals (Sweden)

    Marijanović-Rajčić, M.

    2008-01-01

    Full Text Available The aim of the study was to assess the quality of the groundwater sampled from private wells and the public water-supply system in terms of estimating the contamination caused by short-chain chlorinated hydrocarbons, as well as to estimate the exposure of the citizens dwelling in different suburbs to these pollutants of their drinking water (Fig. 1. The aim of the study was also to determine which suburb is supplied through the public water-supply system with water originating from the Sašnak spring that is contaminated with volatile chlorinated short-chain hydrocarbons.Drinking water samples were taken from 3 private wells and 1 public water-supply system situated in 3 Zagreb suburbs - Pešćenica, Trnje, and Trešnjevka. The sampling was carried out during 2003 and was undertaken on a seasonal basis. Short-chain chlorinated hydrocarbons - 1,1,1-trichloroethane, carbon tetrachloride, 1,1,2-trichloroethene and 1,1,2,2-tetrachloroethene - were determined by gas chromatography, following "liquid-liquid extraction" in pentane. For that purpose, we applied the gas chromatograph equipped with an electron-capture detector, thermo-programmable operations, and a suitable capillary column. The technique applied was that of split-injection.The groundwater of the City of Zagreb was found to be contaminated with volatile chlorinated hydrocarbons. The concentration level of 1,1,1-trichloroethane, determined in most of the samples, was found to be low (Fig. 2. On the other hand, 1,1,2-trichloroethene was present in all samples in concentrations of about 1 µg l-1- (Fig. 3. Only the drinking water samples taken from private wells in the suburb of Trnje contained somewhat higher mass concentrations of 1,1,1-trichloroethane, with the peak value of 19.03 µg l-1, measured in the winter season. In the samples taken from private wells in Trnje, the mass concentrations of 1,1,2,2-tetrachloroethene rangedfrom 15.30 µg l-1 to 18.65 µg l-1, as measured in autumn

  16. Strain hardening in startup shear of long-chain branched polymer solutions.

    Science.gov (United States)

    Liu, Gengxin; Cheng, Shiwang; Lee, Hyojoon; Ma, Hongwei; Xu, Hongde; Chang, Taihyun; Quirk, Roderic P; Wang, Shi-Qing

    2013-08-09

    We show for the first time that entangled polymeric liquids containing long-chain branching can exhibit strain hardening upon startup shear. As the significant long-chain branching impedes chain disentanglement, Gaussian coils between entanglements can deform to reach the finite extensibility limit where the intrachain retraction force exceeds the value expected from the usual conformational entropy loss evaluated based on Gaussian chain statistics. The phenomenon is expected to lead to further theoretical understanding.

  17. Oral Lichen Planus and Features in the Short Chain Fatty Acid Pattern Produced by Colonic Fermentation

    Directory of Open Access Journals (Sweden)

    Umida A. Shukurova

    2016-03-01

    Full Text Available The aim of the study was to assess the content of short chain fatty acids (SCFAs in feces of patients with different clinical forms of oral lichen planus (OLP. Materials and Methods: The study included 139 patients with different clinical forms of OLP in the acute stage. The diagnosis of OLP was performed according to both clinical and histopathological criteria. Patients were distributed in four groups according to the clinical form of OLP. Group 1 included 36 patients with the reticular form of OLP; Group 2 included 34 patients with the exudative-hyperemic form of OLP; Group 3 included 27 patients with the erosive-ulcerative form of OLP; Group 4 included 42 patients with the bullous form of OLP. The four groups to be compared were randomized by sex and age. The control group consisted of 40 healthy, age-matched, randomly selected persons without clinical and instrumental signs of OLP and other diseases of the oral cavity. The concentration of SCFAs in feces was evaluated by gas-liquid chromatography. The profiles (specific concentration of C2, C3, and C4 acids, the ratio of iso-acids to straight-chain acids (iso-Cn/Cn and iso-C5/C5 were also calculated. Results: Three types of SCFA changes reflecting the activity of certain groups of microorganisms were found. For all types of the SCFA disorders, we found a marked increase in the iso-C5/C5 ratio. The severity of dysbiosis increased with the severity of clinical forms of OLP. Changes in the qualitative and quantitative contents of SCFAs reflect the disturbances in gut microbiocenosis in LPO patients, which may be one cause for aggravation of the pathological process.

  18. Analysis of the oxidation of short chain alkynes by flavocytochrome P450 BM3.

    Science.gov (United States)

    Waltham, Timothy N; Girvan, Hazel M; Butler, Christopher F; Rigby, Stuart R; Dunford, Adrian J; Holt, Robert A; Munro, Andrew W

    2011-04-01

    Bacillus megaterium flavocytochrome P450 BM3 (BM3) is a high activity fatty acid hydroxylase, formed by the fusion of soluble cytochrome P450 and cytochrome P450 reductase modules. Short chain (C6, C8) alkynes were shown to be substrates for BM3, with productive outcomes (i.e. alkyne hydroxylation) dependent on position of the carbon-carbon triple bond in the molecule. Wild-type P450 BM3 catalyses ω-3 hydroxylation of both 1-hexyne and 1-octyne, but is suicidally inactivated in NADPH-dependent turnover with non-terminal alkynes. A F87G mutant of P450 BM3 also undergoes turnover-dependent heme destruction with the terminal alkynes, pointing to a key role for Phe87 in controlling regioselectivity of alkyne oxidation. The terminal alkynes access the BM3 heme active site led by the acetylene functional group, since hydroxylated products are not observed near the opposite end of the molecules. For both 1-hexyne and 1-octyne, the predominant enantiomeric product formed (up to ∼90%) is the (S)-(-)-1-alkyn-3-ol form. Wild-type P450 BM3 is shown to be an effective oxidase catalyst of terminal alkynes, with strict regioselectivity of oxidation and potential biotechnological applications. The absence of measurable octanoic or hexanoic acid products from oxidation of the relevant 1-alkynes is also consistent with previous studies suggesting that removal of the phenyl group in the F87G mutant does not lead to significant levels of ω-oxidation of alkyl chain substrates.

  19. Can Structural Timber Foster Short Procurement Chains within Mediterranean Forests? A Research Case in Sardinia

    Directory of Open Access Journals (Sweden)

    Massimo Fragiacomo

    2015-06-01

    Full Text Available Background and Purpose: The aim of this paper is to present the idea of a timber short procurement chain as a means to provide an increased value to Mediterranean forests. It is based on the evidence that timber buildings are increasingly used for a number of reasons including sustainability, the speed of erection, and excellent structural and seismic performance. However, most of the timber currently used around the Mediterranean is imported from outside this area. Materials and Methods: The idea is to use the best part of the tree to produce timber boards, while all the remaining part of the tree including the production waste is used for energy production. Important issues to address are the generally low mechanical properties of locally-grown timber such as maritime pine in Sardinia, which would make some wood-based products such as glue-laminated timber not technically viable. Cross-laminated timber panels are a possible solution to this problem because this wood-based product is manufactured in such a way that even with low-quality timber boards it is possible to obtain a medium quality panel. The panel is made of layers of timber boards with the adjacent layers glued under pressure at a right angle. Another issue is the need to grade the local timber, for which a number of specimens must be tested to destruction in order to identify a visual or a machine-stress grading procedure. Last but not least, the panels must be tested to destruction to correlate their mechanical properties to the properties of the boards. Results: The preliminary mechanical tests carried out on Sardinia maritime pine confirm that the material is low-grade because it is characterized by large knots and a significant grain deviation. Nevertheless, when used in the cross-laminated panels, the properties are significantly improved due to the layout of the panel which reduces the influence of defects in the boards on the mechanical properties of the panel. Conclusions

  20. Proteomic analysis of the response of Escherichia coli to short-chain fatty acids.

    Science.gov (United States)

    Rodríguez-Moyá, María; Gonzalez, Ramon

    2015-06-03

    Given their simple and easy-to-manipulate chemical structures, short-chain fatty acids (SCFAs) are valuable feedstocks for many industrial applications. While the microbial production of SCFAs by engineered Escherichia coli has been demonstrated recently, productivity and yields are limited by their antimicrobial properties. In this work, we performed a comparative proteomic analysis of E. coli under octanoic acid stress (15 mM) and identified the underlying mechanisms of SCFA toxicity. Out of a total of 33 spots differentially expressed at a p-value ≤ 0.05, nine differentially expressed proteins involved in transport and structural roles (OmpF, HPr, and FliC), oxidative stress (SodA, SodB, and TrxA), protein synthesis (PPiB and RpsA) and metabolic functions (HPr, PflB) were selected for further investigation. Our studies suggest that membrane damage and oxidative stress are the main routes of inhibition by SCFAs in E. coli. The outer membrane porin OmpF had the greatest impact on SCFA tolerance. Intracellular pH analysis on ompF mutants grown under octanoic acid stress indicated that this porin facilitates transport of SCFAs into the cell. The same response was observed under hexanoic acid stress, further supporting the role of OmpF in response to the presence of SCFAs. Furthermore, analysis of membrane protein expression revealed that other outer membrane porins are also involved in the response of E. coli to SCFAs. This work covers the first known proteomic analysis to assess the inhibitory effect of SCFAs in E. coli. SCFAs are molecules of great interest in the industry, but their microbial production is limited by their antimicrobial properties. This work allowed identification of differentially expressed proteins in response to SCFA stress and demonstrated the relevance of short- and medium-chain FA transport across the cell membrane via outer membrane porins, providing valuable insights on the toxicity mechanism of SCFAs in E. coli. These results could

  1. Understanding Effect of Constraint Release Environment on End-to-End Vector Relaxation of Linear Polymer Chains

    KAUST Repository

    Shivokhin, Maksim E.

    2017-05-30

    We propose and verify methods based on the slip-spring (SSp) model [ Macromolecules 2005, 38, 14 ] for predicting the effect of any monodisperse, binary, or ternary environment of topological constraints on the relaxation of the end-to-end vector of a linear probe chain. For this purpose we first validate the ability of the model to consistently predict both the viscoelastic and dielectric response of monodisperse and binary mixtures of type A polymers, based on published experimental data. We also report the synthesis of new binary and ternary polybutadiene systems, the measurement of their linear viscoelastic response, and the prediction of these data by the SSp model. We next clarify the relaxation mechanisms of probe chains in these constraint release (CR) environments by analyzing a set of "toy" SSp models with simplified constraint release rates, by examining fluctuations of the end-to-end vector. In our analysis, the longest relaxation time of the probe chain is determined by a competition between the longest relaxation times of the effective CR motions of the fat and thin tubes and the motion of the chain itself in the thin tube. This picture is tested by the analysis of four model systems designed to separate and estimate every single contribution involved in the relaxation of the probe\\'s end-to-end vector in polydisperse systems. We follow the CR picture of Viovy et al. [ Macromolecules 1991, 24, 3587 ] and refine the effective chain friction in the thin and fat tubes based on Read et al. [ J. Rheol. 2012, 56, 823 ]. The derived analytical equations form a basis for generalizing the proposed methodology to polydisperse mixtures of linear and branched polymers. The consistency between the SSp model and tube model predictions is a strong indicator of the compatibility between these two distinct mesoscopic frameworks.

  2. A Comprehensive study of the Effects of Chain Morphology on the Transport Properties of Amorphous Polymer Films

    Science.gov (United States)

    Mendels, Dan; Tessler, Nir

    2016-07-01

    Organic semiconductors constitute one of the main components underlying present-day paradigm shifting optoelectronic applications. Among them, polymer based semiconductors are deemed particularly favorable due to their natural compatibility with low-cost device fabrication techniques. In light of recent advances in the syntheses of these classes of materials, yielding systems exhibiting charge mobilities comparable with those found in organic crystals, a comprehensive study of their charge transport properties is presented. Among a plethora of effects arising from these systems morphological and non morphological attributes, it is shown that a favorable presence of several of these attributes, including that of rapid on-chain carrier propagation and the presence of elongated conjugation segments, can lead to an enhancement of the system’s mobility by more than 5 orders of magnitude with respect to ‘standard’ amorphous organic semiconductors. New insight for the formulation of new engineering strategies for next generation polymer based semiconductors is thus gathered.

  3. Influence of Side Chain Position on the Electrical Properties of Organic Solar Cells Based on Dithienylbenzothiadiazole-alt-phenylene Conjugated Polymers

    DEFF Research Database (Denmark)

    Livi, Francesco; Zawacka, Natalia Klaudia; Angmo, Dechan

    2015-01-01

    backbone for polymer solar cells. All the polymers were roll slot die coated under ambient conditions on flexible ITO-free plastic substrates to give inverted polymer solar cell devices with an upscaled active area of 1 cm2. The best characteristics were found for the polymer carrying alkoxy side chains...... showed excellent performance under constant illumination and high temperature (exhibiting stable photovoltaic properties even after 670 h under conditions similar to ISOS-L-2 lifetime protocol). This makes P7 a good candidate for further upscaling and device optimization. The photovoltaic performance...

  4. Impact of the Nature of the Side-Chains on the Polymer-Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

    KAUST Repository

    Wang, Tonghui; Ravva, Mahesh Kumar; Bredas, Jean-Luc

    2016-01-01

    Polymer-fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton-dissociation, charge-separation, and charge-recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side-chains on the polymer-fullerene packing in mixed regions. The focus is on poly-benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione (PBDTTPD) as electron-donating material and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as electron-accepting material. Three polymer side-chain patterns are considered: i) linear side-chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side-chains on BDT and a branched side-chain on TPD; and iii) two branched side-chains on BDT and a linear side-chain on TPD. Increasing the number of branched side-chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC61 BM mixing. The nature and location of side-chains are found to play a determining role in the probability of finding PC61BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton-dissociation and charge-recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC61BM solar-cell performance as a function of side-chain patterns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  5. Impact of the Nature of the Side-Chains on the Polymer-Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

    KAUST Repository

    Wang, Tonghui

    2016-06-20

    Polymer-fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton-dissociation, charge-separation, and charge-recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side-chains on the polymer-fullerene packing in mixed regions. The focus is on poly-benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione (PBDTTPD) as electron-donating material and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as electron-accepting material. Three polymer side-chain patterns are considered: i) linear side-chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side-chains on BDT and a branched side-chain on TPD; and iii) two branched side-chains on BDT and a linear side-chain on TPD. Increasing the number of branched side-chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC61 BM mixing. The nature and location of side-chains are found to play a determining role in the probability of finding PC61BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton-dissociation and charge-recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC61BM solar-cell performance as a function of side-chain patterns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  6. Fasting serum concentration of short-chain fatty acids in subjects with microscopic colitis and celiac disease

    DEFF Research Database (Denmark)

    Jakobsdottir, Greta; Bjerregaard, Jens Holst; Skovbjerg, Hanne

    2013-01-01

    Short-chain fatty acids (SCFAs), particularly propionic and butyric acids, have been shown to have many positive health effects. The amount and type of SCFAs formed from dietary fibre by the colonic microbiota depends on the substrate available and is reflected in blood. The total intake and type...

  7. Urea and short-chain fatty acids metabolism in Holstein cows fed a low-nitrogen grass-based diet

    DEFF Research Database (Denmark)

    Røjen, B A; Lund, P; Kristensen, N B

    2008-01-01

    Three ruminally cannulated and multicatheterised lactating dairy cows were used to investigate the effect of different supplement strategies to fresh clover grass on urea and short-chain fatty acid (SCFA) metabolism in a zero-grazing experiment with 24-h blood and ruminal samplings....

  8. Differential modulation of enterocyte-like Caco-2 cells after exposure to short-chain fatty acids

    NARCIS (Netherlands)

    Malago, J.J.; Koninkx, J.F.J.G.; Douma, P.M.; Dirkzwager, A.; Veldman, K.T.; Hendriks, H.G.C.J.M.; Dijk, van J.E.

    2003-01-01

    The response of intestinal epithelial cells to short-chain fatty acids, which are increasingly used as food additives, was investigated. Human small intestinal epithelial cell model Caco-2 cells were exposed to formate, propionate and butyrate to assess their effect on cellular growth, metabolism,

  9. Expression of the short chain fatty acid receptor GPR41/FFAR3 in autonomic and somatic sensory ganglia

    DEFF Research Database (Denmark)

    Nøhr, Mark Klitgaard; Egerod, K L; Christiansen, S H

    2015-01-01

    G-protein-coupled receptor 41 (GPR41) also called free fatty acid receptor 3 (FFAR3) is a Gαi-coupled receptor activated by short-chain fatty acids (SCFAs) mainly produced from dietary complex carbohydrate fibers in the large intestine as products of fermentation by microbiota. FFAR3 is expressed...

  10. Colonic infusions of short-chain fatty acid mixtures promote energy metabolism in overweight/obese men

    DEFF Research Database (Denmark)

    Canfora, Emanuel E; van der Beek, Christina M; Jocken, Johan W E

    2017-01-01

    Short-chain fatty acids (SCFA), formed by microbial fermentation, are believed to be involved in the aetiology of obesity and diabetes. This study investigated the effects of colonic administration of physiologically relevant SCFA mixtures on human substrate and energy metabolism...

  11. The importance of stakeholder-initiatives for business models in short food supply chains: the case of the Netherlands

    NARCIS (Netherlands)

    Wubben, E.F.M.; Fondse, M.; Pascucci, S.

    2013-01-01

    While the interest in Short Food Supply Chains (SFSCs) is growing, we still await management studies that explore the impact of stakeholders of SFSCs in substantial numbers. This article investigates the differences in the business models of SFSCs that may be attributed to the initiator-stakeholder,

  12. Extending our knowledge of fermentable, short-chain carbohydrates for managing gastrointestinal symptoms.

    Science.gov (United States)

    Barrett, Jacqueline S

    2013-06-01

    The Monash University low FODMAP (fermentable oligosaccharides, disaccharides, monosaccharides, and polyols) diet is now accepted as an effective strategy for managing symptoms of irritable bowel syndrome (IBS) in Australia, with interest expanding across the world. These poorly absorbed, short-chain carbohydrates have been shown to induce IBS symptoms of diarrhea, bloating, abdominal pain, and flatus due to their poor absorption, osmotic activity, and rapid fermentation. Four clinical trials have been published to date, all with significant symptomatic response to the low FODMAP diet. Up to 86% of patients with IBS have achieved relief of overall gastrointestinal symptoms and, more specifically, bloating, flatus, abdominal pain, and altered bowel habit from the approach. This review provides an overview of the low FODMAP diet and summarizes the research to date, emerging concepts, and limitations. FODMAPs are known to be beneficial to bowel health; the importance of this and how this should be considered in the clinical management of IBS is also discussed. A clinical management flowchart is provided to assist nutrition professionals in the use of this approach.

  13. Role of colonic short-chain fatty acid transport in diarrhea.

    Science.gov (United States)

    Binder, Henry J

    2010-01-01

    Short-chain fatty acids (SCFA) are the major anion in stool and are synthesized from nonabsorbed carbohydrate by the colonic microbiota. Nonabsorbed carbohydrate are not absorbed in the colon and induce an osmotically mediated diarrhea; in contrast, SCFA are absorbed by colonic epithelial cells and stimulate Na-dependent fluid absorption via a cyclic AMP-independent process involving apical membrane Na-H, SCFA-HCO(3), and Cl-SCFA exchanges. SCFA production represents an adaptive process to conserve calories, fluid, and electrolytes. Inhibition of SCFA synthesis by antibiotics and administration of PEG, a substance that is not metabolized by colonic microbiota, both result in diarrhea. In contrast, increased production of SCFA as a result of providing starch that is relatively resistant to amylase digestion [so-called resistant starch (RS)] to oral rehydration solution (RS-ORS) improves the efficacy of ORS and represents an important approach to improve the effectiveness of ORS in the treatment of acute diarrhea in children under five years of age.

  14. DFT-based prediction of reactivity of short-chain alcohol dehydrogenase

    Science.gov (United States)

    Stawoska, I.; Dudzik, A.; Wasylewski, M.; Jemioła-Rzemińska, M.; Skoczowski, A.; Strzałka, K.; Szaleniec, M.

    2017-06-01

    The reaction mechanism of ketone reduction by short chain dehydrogenase/reductase, ( S)-1-phenylethanol dehydrogenase from Aromatoleum aromaticum, was studied with DFT methods using cluster model approach. The characteristics of the hydride transfer process were investigated based on reaction of acetophenone and its eight structural analogues. The results confirmed previously suggested concomitant transfer of hydride from NADH to carbonyl C atom of the substrate with proton transfer from Tyr to carbonyl O atom. However, additional coupled motion of the next proton in the proton-relay system, between O2' ribose hydroxyl and Tyr154 was observed. The protonation of Lys158 seems not to affect the pKa of Tyr154, as the stable tyrosyl anion was observed only for a neutral Lys158 in the high pH model. The calculated reaction energies and reaction barriers were calibrated by calorimetric and kinetic methods. This allowed an excellent prediction of the reaction enthalpies (R2 = 0.93) and a good prediction of the reaction kinetics (R2 = 0.89). The observed relations were validated in prediction of log K eq obtained for real whole-cell reactor systems that modelled industrial synthesis of S-alcohols.

  15. Impact of short-chain galactooligosaccharides on the gut microbiome of lactose-intolerant individuals.

    Science.gov (United States)

    Azcarate-Peril, M Andrea; Ritter, Andrew J; Savaiano, Dennis; Monteagudo-Mera, Andrea; Anderson, Carlton; Magness, Scott T; Klaenhammer, Todd R

    2017-01-17

    Directed modulation of the colonic bacteria to metabolize lactose effectively is a potentially useful approach to improve lactose digestion and tolerance. A randomized, double-blind, multisite placebo-controlled trial conducted in human subjects demonstrated that administration of a highly purified (>95%) short-chain galactooligosaccharide (GOS), designated "RP-G28," significantly improved clinical outcomes for lactose digestion and tolerance. In these individuals, stool samples were collected pretreatment (day 0), after GOS treatment (day 36), and 30 d after GOS feeding stopped and consumption of dairy products was encouraged (day 66). In this study, changes in the fecal microbiome were investigated using 16S rRNA amplicon pyrosequencing and high-throughput quantitative PCR. At day 36, bifidobacterial populations were increased in 27 of 30 of GOS subjects (90%), demonstrating a bifidogenic response in vivo. Relative abundance of lactose-fermenting Bifidobacterium, Faecalibacterium, and Lactobacillus were significantly increased in response to GOS. When dairy was introduced into the diet, lactose-fermenting Roseburia species increased from day 36 to day 66. The results indicated a definitive change in the fecal microbiome of lactose-intolerant individuals, increasing the abundance of lactose-metabolizing bacteria that were responsive to dietary adaptation to GOS. This change correlated with clinical outcomes of improved lactose tolerance.

  16. Short chain and polyunsaturated fatty acids in host gut health and foodborne bacterial pathogen inhibition.

    Science.gov (United States)

    Peng, Mengfei; Biswas, Debabrata

    2017-12-12

    As a major source of microbes and their numerous beneficial effects, the gut microflora/microbiome is intimately linked to human health and disease. The exclusion of enteric pathogens by these commensal microbes partially depends upon the production of bioactive compounds such as short-chain fatty acids (SCFAs) and polyunsaturated fatty acids (PUFAs). These key intestinal microbial byproducts are crucial to the maintenance of a healthy gut microbial community. Moreover, SCFAs and PUFAs play multiple critical roles in host defense and immunity, including anti-cancer, anti-inflammation, and anti-oxidant activities, as well as out-competition of enteric bacterial pathogens. In this review article, we hereby aim to highlight the importance of SCFAs and PUFAs and the microbes involved in production of these beneficial intestinal components, and their biological functions, specifically as to their immunomodulation and interactions with enteric bacterial pathogens. Finally, we also advance potential applications of these fatty acids with regards to food safety and human gut health.

  17. The pea SAD short-chain dehydrogenase/reductase: quinone reduction, tissue distribution, and heterologous expression.

    Science.gov (United States)

    Scherbak, Nikolai; Ala-Häivälä, Anneli; Brosché, Mikael; Böwer, Nathalie; Strid, Hilja; Gittins, John R; Grahn, Elin; Eriksson, Leif A; Strid, Åke

    2011-04-01

    The pea (Pisum sativum) tetrameric short-chain alcohol dehydrogenase-like protein (SAD) family consists of at least three highly similar members (SAD-A, -B, and -C). According to mRNA data, environmental stimuli induce SAD expression. The aim of this study was to characterize the SAD proteins by examining their catalytic function, distribution in pea, and induction in different tissues. In enzyme activity assays using a range of potential substrates, the SAD-C enzyme was shown to reduce one- or two-ring-membered quinones lacking long hydrophobic hydrocarbon tails. Immunological assays using a specific antiserum against the protein demonstrated that different tissues and cell types contain small amounts of SAD protein that was predominantly located within epidermal or subepidermal cells and around vascular tissue. Particularly high local concentrations were observed in the protoderm of the seed cotyledonary axis. Two bow-shaped rows of cells in the ovary and the placental surface facing the ovule also exhibited considerable SAD staining. Ultraviolet-B irradiation led to increased staining in epidermal and subepidermal cells of leaves and stems. The different localization patterns of SAD suggest functions both in development and in responses to environmental stimuli. Finally, the pea SAD-C promoter was shown to confer heterologous wound-induced expression in Arabidopsis (Arabidopsis thaliana), which confirmed that the inducibility of its expression is regulated at the transcriptional level.

  18. Microbial Production of Short Chain Fatty Acids from Lignocellulosic Biomass: Current Processes and Market

    Directory of Open Access Journals (Sweden)

    Ivan Baumann

    2016-01-01

    Full Text Available Biological production of organic acids from conversion of biomass derivatives has received increased attention among scientists and engineers and in business because of the attractive properties such as renewability, sustainability, degradability, and versatility. The aim of the present review is to summarize recent research and development of short chain fatty acids production by anaerobic fermentation of nonfood biomass and to evaluate the status and outlook for a sustainable industrial production of such biochemicals. Volatile fatty acids (VFAs such as acetic acid, propionic acid, and butyric acid have many industrial applications and are currently of global economic interest. The focus is mainly on the utilization of pretreated lignocellulosic plant biomass as substrate (the carbohydrate route and development of the bacteria and processes that lead to a high and economically feasible production of VFA. The current and developing market for VFA is analyzed focusing on production, prices, and forecasts along with a presentation of the biotechnology companies operating in the market for sustainable biochemicals. Finally, perspectives on taking sustainable product of biochemicals from promise to market introduction are reviewed.

  19. Endosulfan, pentachlorobenzene and short-chain chlorinated paraffins in background soils from Western Europe.

    Science.gov (United States)

    Halse, Anne Karine; Schlabach, Martin; Schuster, Jasmin K; Jones, Kevin C; Steinnes, Eiliv; Breivik, Knut

    2015-01-01

    Soils are major reservoirs for many persistent organic pollutants (POPs). In this study, "newly" regulated POPs i.e. Σendosulfans (α-endosulfan, β-endosulfan, endosulfan sulfate), pentachlorobenzene (PeCB), and short-chain chlorinated paraffins (SCCPs) were determined in background samples from woodland (WL) and grassland (GL) surface soil, collected along an existing latitudinal UK-Norway transect. Statistical analysis, complemented with plots showing the predicted equilibrium distribution and mobility potential, was then explored to discuss factors controlling their spatial distribution. SCCPs were detected with the highest average concentrations (35 ± 100 ng/g soil organic matter (SOM)), followed by Σendosulfans (3 ± 3 ng/g SOM) and PeCB (1 ± 1 ng/g SOM). PeCB and Σendosulfans share many similarities in their distribution in these background soils as well as with several legacy POPs. A steep decline in concentrations of SCCPs with increasing latitude indicates that their occurrence is dictated by proximity to source regions, while concentrations of Σendosulfans peaked in regions experiencing elevated precipitation rates. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Short-chain alkanes synergise responses of moth pests to their sex pheromones.

    Science.gov (United States)

    Gurba, Alexandre; Guerin, Patrick M

    2016-05-01

    The use of sex pheromones for mating disruption of moth pests of crops is increasing worldwide. Efforts are under way to augment the efficiency and reliability of this control method by adding molecules derived from host plants to the sex attractants in dispensers. We show how attraction of the European grapevine moth, Lobesia botrana Den. & Schiff., and the codling moth, Cydia pomonella L., males to underdosed levels of their sex pheromones is increased by adding heptane or octane over a range of release rates. Pheromone-alkane mixtures enhance male recruitment by up to 30%, reaching levels induced by calling females, and shorten the flight time to the sex attractant by a factor of 2. The findings show the promise of using short-chain alkanes as pheromone synergists for mating disruption of insect pests of food crops. Alkane-pheromone combinations are expected to increase the competitiveness of dispensers with females, and to reduce the amount of pheromone needed for the control of these pests. © 2015 Society of Chemical Industry.

  1. Short-Chain Chlorinated Paraffins in Zurich, Switzerland--Atmospheric Concentrations and Emissions.

    Science.gov (United States)

    Diefenbacher, Pascal S; Bogdal, Christian; Gerecke, Andreas C; Glüge, Juliane; Schmid, Peter; Scheringer, Martin; Hungerbühler, Konrad

    2015-08-18

    Short-chain chlorinated paraffins (SCCPs) are of concern due to their potential for adverse health effects, bioaccumulation, persistence, and long-range transport. Data on concentrations of SCCPs in urban areas and underlying emissions are still scarce. In this study, we investigated the levels and spatial distribution of SCCPs in air, based on two separate, spatially resolved sampling campaigns in the city of Zurich, Switzerland. SCCP concentrations in air ranged from 1.8 to 17 ng·m(-3) (spring 2011) and 1.1 to 42 ng·m(-3) (spring 2013) with medians of 4.3 and 2.7 ng·m(-3), respectively. Both data sets show that atmospheric SCCP levels in Zurich can vary substantially and may be influenced by a number of localized sources within this urban area. Additionally, continuous measurements of atmospheric concentrations performed at one representative sampling site in the city center from 2011 to 2013 showed strong seasonal variations with high SCCP concentrations in summer and lower levels in winter. A long-term dynamic multimedia environmental fate model was parametrized to simulate the seasonal trends of SCCP concentrations in air and to back-calculate urban emissions. Resulting annual SCCP emissions in the city of Zurich accounted for 218-321 kg, which indicates that large SCCP stocks are present in urban areas of industrialized countries.

  2. [Levels and distribution of short chain chlorinated paraffins in seafood from Dalian, China].

    Science.gov (United States)

    Yu, Jun-Chao; Wang, Thanh; Wang, Ya-Wei; Meng, Mei; Chen, Ru; Jiang, Gui-Bin

    2014-05-01

    Seafood samples were collected from Dalian, China to study the accumulation and distribution characteristics of short chain chlorinated paraffins (SCCPs) by GC/ECNI-LRMS. Sum of SCCPs (dry weight) were in the range of 77-8 250 ng.g-1, with the lowest value in Scapharca subcrenata and highest concentration in Neptunea cumingi. The concentrations of sum of SCCPs (dry weight) in fish, shrimp/crab and shellfish were in the ranges of 100-3 510, 394-5 440, and 77-8 250 ng.g-1 , respectively. Overall, the C10 and C11 homologues were the most predominant carbon groups of SCCPs in seafood from this area,and a relatively higher proportion of C12-13 was observed in seafood with higher concentrations of sum of SCCPs . With regard to chlorine content, Cl1,, CI8 and CI6 were the major groups. Significant correlations were found among concentrations of different SCCP homologues (except C1, vs. Cl10 ) , which indicated that they might share the same sources and/or have similar accumulation, migration and transformation processes.

  3. Gridded emission inventory of short-chain chlorinated paraffins and its validation in China.

    Science.gov (United States)

    Jiang, Wanyanhan; Huang, Tao; Mao, Xiaoxuan; Wang, Li; Zhao, Yuan; Jia, Chenhui; Wang, Yanan; Gao, Hong; Ma, Jianmin

    2017-01-01

    China produces approximately 20%-30% of the total global chlorinated paraffins (CPs). The establishment of a short-chain CP (SCCP) emission inventory is a significant step toward risk assessment and regulation of SCCPs in China and throughout the globe. This study developed a gridded SCCPs emission inventory with a 1/4° longitude by 1/4° latitude resolution from 2008 to 2012 for China, which was based on the total annual CPs emissions for the nation. The total national SCCPs emission during this 5-year period was 5651.5 tons. An additive in metal cutting fluids was a major emission source in China, contributing 2680.2 tons to the total atmospheric emissions of SCCPs from 2008 to 2012, followed by the production of CPs (2281.8 tons), plasticizers (514.3 tons), flame retardants (108.6 tons), and net import (66.6 tons). Most of these emission sources are located along the eastern seaboard of China and southern China. A coupled atmospheric transport model was employed to simulate environmental contamination by SCCPs using the gridded emission inventory of SCCPs from 2008 to 2012 as the model initial conditions. Simulated atmospheric and soil concentrations were compared with field monitoring data to validate the emission inventory. The results showed good consistency between modeled and field sampling data, supporting the reliability and credibility of the gridded SCCPs emission inventory that was developed in the present study. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Novel short chain fatty acids restore chloride secretion in cystic fibrosis

    International Nuclear Information System (INIS)

    Nguyen, Toan D.; Kim, Ug-Sung; Perrine, Susan P.

    2006-01-01

    Phenylalanine deletion at position 508 of the cystic fibrosis transmembrane conductance regulator (ΔF508-CFTR), the most common mutation in cystic fibrosis (CF), causes a misfolded protein exhibiting partial chloride conductance and impaired trafficking to the plasma membrane. 4-Phenylbutyrate corrects defective ΔF508-CFTR trafficking in vitro, but is not clinically efficacious. From a panel of short chain fatty acid derivatives, we showed that 2,2-dimethyl-butyrate (ST20) and α-methylhydrocinnamic acid (ST7), exhibiting high oral bioavailability and sustained plasma levels, correct the ΔF508-CFTR defect. Pre-incubation (≥6 h) of CF IB3-1 airway cells with ≥1 mM ST7 or ST20 restored the ability of 100 μM forskolin to stimulate an 125 I - efflux. This efflux was fully inhibited by NPPB, DPC, or glibenclamide, suggesting mediation through CFTR. Partial inhibition by DIDS suggests possible contribution from an additional Cl - channel regulated by CFTR. Thus, ST7 and ST20 offer treatment potential for CF caused by the ΔF508 mutation

  5. Bifidobacteria, Lactobacilli, and Short Chain Fatty Acids of Vegetarians and Omnivores

    Directory of Open Access Journals (Sweden)

    Bunešová Věra

    2017-03-01

    Full Text Available The intestinal microbiota represents the largest and the most complex microbial community inhabiting the human body. Bifidobacteria and lactobacilli represent important commensal bacteria with the ability to utilize complex carbohydrates. The main fermentation products from the breakdown of complex dietary carbohydrates are short chain fatty acids (SCFAs. We examined faecal samples of vegetarians (n = 10 and conventional omnivores (n = 10 to evaluate the counts and occurrence of cultivable bacteria, especially bifidobacteria and lactobacilli, using cultivation on selective media, and matrix-assisted laser desorption/ionization time-of-flight. Moreover, concentrations and molar proportion of SCFAs in faecal samples were measured. Total counts of Gram-negative anaerobic bacteria were significantly lower (P 0.05 between the diet groups. In total, six Bifidobacterium spp. and thirteen Lactobacillus spp. were detected via culture-dependent methods. Bifidobacteria counts and species composition in faecal samples of both groups were found to be relatively similar, regardless of the diet. Lactobacillus species varied more by individual diet.

  6. Occurrence of fatty acid short-chain-alkyl esters in fruits of Celastraceae plants.

    Science.gov (United States)

    Sidorov, Roman A; Zhukov, Anatoly V; Pchelkin, Vasily P; Vereshchagin, Andrei G; Tsydendambaev, Vladimir D

    2013-06-01

    Small amounts of a mixture of fatty acid short-chain-alkyl esters (FASCAEs) were obtained from the fruits of twelve plant species of Celastraceae family, and in five of them the FASCAEs were present not only in the arils but also in the seeds. These mixtures contained 32 individual FASCAE species, which formed four separate fractions, viz. FA methyl, ethyl, isopropyl, and butyl esters (FAMEs, FAEEs, FAIPEs, and FABEs, resp.). The FASCAE acyl components included the residues of 16 individual C₁₄-C₂₄ saturated, mono-, di-, and trienoic FAs. Linoleic, oleic, and palmitic acids, and, in some cases, also α-linolenic acid predominated in FAMEs and FAEEs, while myristic acid was predominant in FAIPEs. It can be suggested that, in the fruit arils of some plant species, FAMEs and FAEEs were formed at the expense of a same FA pool characteristic of a given species and were strongly different from FAIPEs and FABEs esters regarding the mechanism of their biosynthesis. However, as a whole, the qualitative and quantitative composition of various FASCAE fractions, as well as their FA composition, varied considerably depending on various factors. Therefore, separate FASCAE fractions seem to be synthesized from different FA pools other than those used for triacylglycerol formation. Copyright © 2013 Verlag Helvetica Chimica Acta AG, Zürich.

  7. Characterization of short chain fatty acid microcapsules produced by spray drying

    International Nuclear Information System (INIS)

    Teixeira, Maria Ines; Andrade, Leonardo R.; Farina, Marcos; Rocha-Leao, Maria Helena M.

    2004-01-01

    Microcapsules containing short chain fatty acids (SCFA) were produced by spray drying technique using different proportions of gum arabic and maltodextrin as wall materials. Proportions of 5% and 10% of gum arabic and maltodextrin isolated, and a mixture of 5% of maltodextrin and 5% of gum arabic were added to samples of fermented permeate containing SCFA, and spray dried. The microstructure of microcapsules was studied by scanning electron microscopy (SEM) and the size distribution was obtained by laser diffraction. SEM observations showed that the microcapsules structures were affected by type and proportion of wall material tested. Most of the microcapsules containing gum arabic as wall material had surface dents or invaginations. Microcapsules containing maltodextrin were spherical with few surface dents and some of them had pores. The larger microcapsule sizes were observed in those containing maltodextrin. Our results show that microstructure and size of microcapsules are affected by type and proportion of biomaterial used. The samples containing 5% of maltodextrin and the mixture of 5% of gum arabic with 5% of maltodextrin presented smooth surfaces and homogenous size distributions. The corresponding microcapsules are considered optimal to food industrial uses due to the flowability property. Besides, these capsules were found to present a homogenous distribution of diameters, which may give a homogenous flavor distribution to the food products

  8. Fecal short-chain fatty acids at different time points after ceftriaxone administration in rats

    Directory of Open Access Journals (Sweden)

    Yu. V. Holota

    2017-02-01

    Full Text Available Short-chain fatty acids (SCFAs are major products of the microbial fermentation of dietary fiber in the colon. Recent studies suggest that these products of microbial metabolism in the gut act as signaling molecules, influence host energy homeostasis and play major immunological roles. In the present study, defined the long-term effects of ceftriaxone administration on the fecal SCFAs concentration in Wistar rats. Ceftriaxone (300 mg/kg, i.m. was administered daily for 14 days. Rats were euthanized in 1, 15 and 56 days after ceftriaxone withdrawal. Caecal weight and fecal concentration of SCFAs by gas chromatography were measured. Ceftriaxone administration induced time-dependent rats’ caecal enlargement through accumulation of undigestable substances. In 1 day after ceftriaxone withdrawal, the concentrations of acetic, propionic, butyric acids and total SCFAs were decreased 2.9-, 13.8-, 8.5-, 4.8-fold (P < 0.05, respectively. Concentration of valeric, isovaleric and caproic acids was below the detectable level. That was accompanied by decreased 4.3-fold anaerobic index and increased the relative amount of acetic acid (P < 0.05. In 56 days, concentration of SCFAs was still below control value but higher than in 1 day (except propionic acid. Anaerobic index was lower 1.3-fold (P < 0.05 vs. control. Conclusion: antibiotic therapy induced long-term disturbance in colonic microbiota metabolic activity.

  9. Delineating Substrate Diversity of Disparate Short-Chain Dehydrogenase Reductase from Debaryomyces hansenii.

    Directory of Open Access Journals (Sweden)

    Arindam Ghatak

    Full Text Available Short-chain dehydrogenase reductases (SDRs have been utilized for catalyzing the reduction of many aromatic/aliphatic prochiral ketones to their respective alcohols. However, there is a paucity of data that elucidates their innate biological role and diverse substrate space. In this study, we executed an in-depth biochemical characterization and substrate space mapping (with 278 prochiral ketones of an unannotated SDR (DHK from Debaryomyces hansenii and compared it with structurally and functionally characterized SDR Synechococcus elongatus. PCC 7942 FabG to delineate its industrial significance. It was observed that DHK was significantly more efficient than FabG, reducing a diverse set of ketones albeit at higher conversion rates. Comparison of the FabG structure with a homology model of DHK and a docking of substrate to both structures revealed the presence of additional flexible loops near the substrate binding site of DHK. The comparative elasticity of the cofactor and substrate binding site of FabG and DHK was experimentally substantiated using differential scanning fluorimetry. It is postulated that the loop flexibility may account for the superior catalytic efficiency of DHK although the positioning of the catalytic triad is conserved.

  10. A wormlike chain model of forced desorption of a polymer adsorbed on an attractive wall

    International Nuclear Information System (INIS)

    Lam, Pui-Man; Zhen, Yi

    2014-01-01

    Forced desorption of a semiflexible polymer chain on a solid substrate is theoretically investigated. The pulling force versus displacement is studied for varying adsorption energy ε and persistence length P. It is found that the relationships between pulling force and cantilever displacement show a series of characteristic force spikes at different persistence lengths P. These force spikes become more pronounced but the average magnitude of this force decreases as P grows. Our results are of relevance to the forced desorption of DNA on an attractive wall in single-molecule pulling experiments. (paper)

  11. A combined theoretical and experimental study of the polymer inter-chain structure in poly(phenylene vinylene) derivatives

    International Nuclear Information System (INIS)

    Sumpter, B G; Drummond, M L; Shelton, W A; Valeev, E F; Barnes, M D

    2008-01-01

    The structures and photophysical properties of single molecule MEH-PPV (2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylenevinylene) and CN-PPV (2,5,2' ,5'-tetrahexyloxy-7,8'-dicyano-p-phenylenevinylene) nanoparticles are investigated using electronic structure theory and high resolution fluorescence experiments. It is shown that electron withdrawing substituents, such as CN, on the vinyl group of the PPV polymer backbone cause substantial change in the π electronic structure which subsequently decreases the inter-chain distance. Not only does CN-PPV have a smaller inter-chain separation compared to MEH-PPV, but also an increased binding energy and more efficient charge transport (carrier mobility) due to larger electronic coupling (charge transfer integrals). These changes help explain the enhanced luminescence quantum yield, photo-stability, and lifetime for CN-PPV versus MEH-PPV observed in experimental high resolution fluorescence imaging of individual single molecule nanoparticles

  12. Efficient sampling of reversible cross-linking polymers: Self-assembly of single-chain polymeric nanoparticles

    Science.gov (United States)

    Oyarzún, Bernardo; Mognetti, Bortolo Matteo

    2018-03-01

    We present a new simulation technique to study systems of polymers functionalized by reactive sites that bind/unbind forming reversible linkages. Functionalized polymers feature self-assembly and responsive properties that are unmatched by the systems lacking selective interactions. The scales at which the functional properties of these materials emerge are difficult to model, especially in the reversible regime where such properties result from many binding/unbinding events. This difficulty is related to large entropic barriers associated with the formation of intra-molecular loops. In this work, we present a simulation scheme that sidesteps configurational costs by dedicated Monte Carlo moves capable of binding/unbinding reactive sites in a single step. Cross-linking reactions are implemented by trial moves that reconstruct chain sections attempting, at the same time, a dimerization reaction between pairs of reactive sites. The model is parametrized by the reaction equilibrium constant of the reactive species free in solution. This quantity can be obtained by means of experiments or atomistic/quantum simulations. We use the proposed methodology to study the self-assembly of single-chain polymeric nanoparticles, starting from flexible precursors carrying regularly or randomly distributed reactive sites. We focus on understanding differences in the morphology of chain nanoparticles when linkages are reversible as compared to the well-studied case of irreversible reactions. Intriguingly, we find that the size of regularly functionalized chains, in good solvent conditions, is non-monotonous as a function of the degree of functionalization. We clarify how this result follows from excluded volume interactions and is peculiar of reversible linkages and regular functionalizations.

  13. Flexible multimode polymer waveguides for high-speed short-reach communication links

    Science.gov (United States)

    Bamiedakis, N.; Shi, F.; Chu, D.; Penty, R. V.; White, I. H.

    2018-02-01

    Multimode polymer waveguides have attracted great interest for use in high-speed short-reach communication links as they can be cost-effectively integrated onto standard PCBs using conventional methods of the electronics industry and provide low loss (30 GHz×m) interconnection. The formation of such waveguides on flexible substrates can further provide flexible low-weight low-thickness interconnects and offer additional freedom in the implementation of high-speed short-reach optical links. These attributes make these flexible waveguides particularly attractive for use in low-cost detachable chip-to-chip links and in environments where weight and shape conformity become important, such as in cars and aircraft. However, the highly-multimoded nature of these waveguides raises important questions about their performance under severe flex due to mode loss and mode coupling. In this work therefore, we investigate the loss, crosstalk and bandwidth performance of such waveguides under out-of plane bending and in-plane twisting under different launch conditions and carry out data transmission tests at 40 Gb/s on a 1 m long spiral flexible waveguide under flexure. Excellent optical transmission characteristics are obtained while robust loss, crosstalk and bandwidth performance are demonstrated under flexure. Error-free (BER<10-12) 40 Gb/s data transmission is achieved over the 1 m long spiral waveguide for a 180° bend with a 4 mm radius. The obtained results demonstrate the excellent optical and mechanical properties of this technology and highlight its potential for use in real-world systems.

  14. Phase stability and dynamics of entangled polymer-nanoparticle composites.

    KAUST Repository

    Mangal, Rahul

    2015-06-05

    Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.

  15. Phase stability and dynamics of entangled polymer-nanoparticle composites.

    KAUST Repository

    Mangal, Rahul; Srivastava, Samanvaya; Archer, Lynden A

    2015-01-01

    Nanoparticle-polymer composites, or polymer-nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.

  16. Permeability of a Fluid Lipid Bilayer to Short-Chain Alcohols from First Principles.

    Science.gov (United States)

    Comer, Jeffrey; Schulten, Klaus; Chipot, Christophe

    2017-06-13

    Computational prediction of membrane permeability to small molecules requires accurate description of both the thermodynamics and kinetics underlying translocation across the lipid bilayer. In this contribution, well-converged, microsecond-long free-energy calculations are combined with a recently developed subdiffusive kinetics framework to describe the membrane permeation of a homologous series of short-tail alcohols, from methanol to 1-butanol, with unprecedented fidelity to the underlying molecular models. While the free-energy profiles exhibit barriers for passage through the center of the bilayer in all cases, the height of these barriers decreases with the length of the aliphatic chain of the alcohol, in quantitative agreement with experimentally determined differential solvation free energies in water and oil. A unique aspect of the subdiffusive model employed herein, which was developed in a previous article, is the determination of a position-dependent fractional order which quantifies the degree to which the motion of the alcohol deviates from classical diffusion along the thickness of the membrane. In the aqueous medium far from the bilayer, this quantity approaches 1.0, the asymptotic limit for purely classical diffusion, whereas it dips below 0.75 near the center of the membrane irrespective of the permeant. Remarkably, the fractional diffusivity near the center of membrane, where its influence on the permeability is the greatest, is similar among the four permeants despite the large difference in molecular weight and lipophilicity between methanol and 1-butanol. The relative permeabilities, which are estimated from the free-energy and fractional diffusivity profiles, are therefore determined predominantly by differences in the former rather than the latter. The predicted relative permeabilities are highly correlated with existing experimental results, albeit they do not agree quantitatively with them. On the other hand, quite unexpectedly, the

  17. Short-chain fatty acid fermentation products of the gut microbiome: implications in autism spectrum disorders

    Science.gov (United States)

    MacFabe, Derrick F.

    2012-01-01

    Recent evidence suggests potential, but unproven, links between dietary, metabolic, infective, and gastrointestinal factors and the behavioral exacerbations and remissions of autism spectrum disorders (ASDs). Propionic acid (PPA) and its related short-chain fatty acids (SCFAs) are fermentation products of ASD-associated bacteria (Clostridia, Bacteriodetes, Desulfovibrio). SCFAs represent a group of compounds derived from the host microbiome that are plausibly linked to ASDs and can induce widespread effects on gut, brain, and behavior. Intraventricular administration of PPA and SCFAs in rats induces abnormal motor movements, repetitive interests, electrographic changes, cognitive deficits, perseveration, and impaired social interactions. The brain tissue of PPA-treated rats shows a number of ASD-linked neurochemical changes, including innate neuroinflammation, increased oxidative stress, glutathione depletion, and altered phospholipid/acylcarnitine profiles. These directly or indirectly contribute to acquired mitochondrial dysfunction via impairment in carnitine-dependent pathways, consistent with findings in patients with ASDs. Of note, common antibiotics may impair carnitine-dependent processes by altering gut flora favoring PPA-producing bacteria and by directly inhibiting carnitine transport across the gut. Human populations that are partial metabolizers of PPA are more common than previously thought. PPA has further bioactive effects on neurotransmitter systems, intracellular acidification/calcium release, fatty acid metabolism, gap junction gating, immune function, and alteration of gene expression that warrant further exploration. These findings are consistent with the symptoms and proposed underlying mechanisms of ASDs and support the use of PPA infusions in rats as a valid animal model of the condition. Collectively, this offers further support that gut-derived factors, such as dietary or enteric bacterially produced SCFAs, may be plausible environmental

  18. Short-chain fatty acid fermentation products of the gut microbiome: implications in autism spectrum disorders

    Directory of Open Access Journals (Sweden)

    Derrick F. MacFabe

    2012-08-01

    Full Text Available Recent evidence suggests potential, but unproven, links between dietary, metabolic, infective, and gastrointestinal factors and the behavioral exacerbations and remissions of autism spectrum disorders (ASDs. Propionic acid (PPA and its related short-chain fatty acids (SCFAs are fermentation products of ASD-associated bacteria (Clostridia, Bacteriodetes, Desulfovibrio. SCFAs represent a group of compounds derived from the host microbiome that are plausibly linked to ASDs and can induce widespread effects on gut, brain, and behavior. Intraventricular administration of PPA and SCFAs in rats induces abnormal motor movements, repetitive interests, electrographic changes, cognitive deficits, perseveration, and impaired social interactions. The brain tissue of PPA-treated rats shows a number of ASD-linked neurochemical changes, including innate neuroinflammation, increased oxidative stress, glutathione depletion, and altered phospholipid/acylcarnitine profiles. These directly or indirectly contribute to acquired mitochondrial dysfunction via impairment in carnitine-dependent pathways, consistent with findings in patients with ASDs. Of note, common antibiotics may impair carnitine-dependent processes by altering gut flora favoring PPA-producing bacteria and by directly inhibiting carnitine transport across the gut. Human populations that are partial metabolizers of PPA are more common than previously thought. PPA has further bioactive effects on neurotransmitter systems, intracellular acidification/calcium release, fatty acid metabolism, gap junction gating, immune function, and alteration of gene expression that warrant further exploration. These findings are consistent with the symptoms and proposed underlying mechanisms of ASDs and support the use of PPA infusions in rats as a valid animal model of the condition. Collectively, this offers further support that gut-derived factors, such as dietary or enteric bacterially produced SCFAs, may be plausible

  19. Evidence for greater production of colonic short-chain fatty acids in overweight than lean humans.

    Science.gov (United States)

    Rahat-Rozenbloom, S; Fernandes, J; Gloor, G B; Wolever, T M S

    2014-12-01

    Short-chain fatty acids (SCFA) are produced by colonic microbiota from dietary carbohydrates and proteins that reach the colon. It has been suggested that SCFA may promote obesity via increased colonic energy availability. Recent studies suggest obese humans have higher faecal SCFA than lean, but it is unclear whether this difference is due to increased SCFA production or reduced absorption. To compare rectal SCFA absorption, dietary intake and faecal microbial profile in lean (LN) versus overweight and obese (OWO) individuals. Eleven LN and eleven OWO individuals completed a 3-day diet record, provided a fresh faecal sample and had SCFA absorption measured using the rectal dialysis bag method. The procedures were repeated after 2 weeks. Age-adjusted faecal SCFA concentration was significantly higher in OWO than LN individuals (81.3±7.4 vs 64.1±10.4 mmol kg(-1), P=0.023). SCFA absorption (24.4±0.8% vs 24.7±1.2%, respectively, P=0.787) and dietary intakes were similar between the groups, except for a higher fat intake in OWO individuals. However, fat intake did not correlate with SCFAs or bacterial abundance. OWO individuals had higher relative Firmicutes abundance (83.1±4.1 vs 69.5±5.8%, respectively, P=0.008) and a higher Firmicutes:Bacteriodetes ratio (P=0.023) than LN individuals. There was a positive correlation between Firmicutes and faecal SCFA within the whole group (r=0.507, P=0.044), with a stronger correlation after adjusting for available carbohydrate (r=0.615, P=0.005). The higher faecal SCFA in OWO individuals is not because of differences in SCFA absorption or diet. Our results are consistent with the hypothesis that OWO individuals produce more colonic SCFA than LN individuals because of differences in colonic microbiota. However, further studies are needed to prove this.

  20. Short-chain C6 ceramide sensitizes AT406-induced anti-pancreatic cancer cell activity

    International Nuclear Information System (INIS)

    Zhao, Xiaoguang; Sun, Baoyou; Zhang, Jingjing; Zhang, Ruishen; Zhang, Qing

    2016-01-01

    Our previous study has shown that AT406, a first-in-class small molecular antagonist of IAPs (inhibitor of apoptosis proteins), inhibits pancreatic cancer cell proliferation in vitro and in vivo. The aim of this research is to increase AT406's sensitivity by adding short-chain C6 ceramide. We show that co-treatment of C6 ceramide dramatically potentiated AT406-induced caspase/apoptosis activation and cytotoxicity in established (Panc-1 and Mia-PaCa-2 lines) and primary human pancreatic cancer cells. Reversely, caspase inhibitors largely attenuated C6 ceramide plus AT406-induced above cancer cell death. Molecularly, C6 ceramide downregulated Bcl-2 to increase AT406's sensitivity in pancreatic cancer cells. Intriguingly, C6 ceramide-mediated AT406 sensitization was nullified with Bcl-2 shRNA knockdown or pretreatment of the Bcl-2 inhibitor ABT-737. In vivo, liposomal C6 ceramide plus AT406 co-administration dramatically inhibited Panc-1 xenograft tumor growth in severe combined immunodeficient (SCID) mice. The combined anti-tumor activity was significantly more potent than either single treatment. Expressions of IAPs (cIAP1/XIAP) and Bcl-2 were downregulated in Panc-1 xenografts with the co-administration. Together, we demonstrate that C6 ceramide sensitizes AT406-mediated anti-pancreatic cancer cell activity possibly via downregulating Bcl-2. - Highlights: • C6 ceramide dramatically potentiates AT406-induced pancreatic cancer cell death. • C6 ceramide facilitates AT406-induced pancreatic cancer cell apoptosis. • C6 ceramide downregulates Bcl-2 to increase AT406's sensitivity in pancreatic cancer cells. • Liposomal C6 ceramide enhances AT406-induced anti-pancreatic cancer activity in vivo.

  1. Effect of foamability index of short chain alkyl amines on flotation of quartz

    Directory of Open Access Journals (Sweden)

    Szczerkowska Sabina

    2016-01-01

    Full Text Available Amines can be used for flotation of various minerals, especially quartz. The flotation efficiency of quartz depends on the amine type and dose. It was proved that the shorter alkyl amine, higher amine concentration has to be used to recover quartz at the same level. In flotation amines play a role of both collectors and frothers. The ability of a amine to collect particles can be expressed in the form of contact angle, while the foaming properties by different parameters including dynamic foamability index (DFI and critical coalescence concentration (CCC. Determination of DFI and CCC requires advanced techniques and methods. Therefore, in this paper a rapid and facile method for determination of foaming properties of amines and also other surfactants was used. It was based on measuring the initial foam and froth heights in a conventional flotation machine at different concentrations of surfactants. The foam height-concentration curve was described by utilizing an empirical equation which was based on one-adjustable parameter called the foamability index (FI. In this work the foamability index was determined for butylamine (ButNH2, hexylamine (HexNH2 and octylamine (OctNH2 as examples of short chain alkyl amines. The determined foamability indices were 92, 12 and 4 mg/dm3 for ButNH2, HexNH2 and OctNH2, respectively. It was shown that when the flotation results of quartz were presented in the form of recovery versus normalized amine concentration in relation to the foamability index (c/FI, all the experimental data points converged to one curve. It indicates that amines act similarly but at different concentrations expressed as FI. The foamability index seems to be a useful parameter for characterizing any flotation frother.

  2. Quantification of in Vivo Colonic Short Chain Fatty Acid Production from Inulin.

    Science.gov (United States)

    Boets, Eef; Deroover, Lise; Houben, Els; Vermeulen, Karen; Gomand, Sara V; Delcour, Jan A; Verbeke, Kristin

    2015-10-28

    Short chain fatty acids (SCFA), including acetate, propionate, and butyrate, are produced during bacterial fermentation of undigested carbohydrates in the human colon. In this study, we applied a stable-isotope dilution method to quantify the in vivo colonic production of SCFA in healthy humans after consumption of inulin. Twelve healthy subjects performed a test day during which a primed continuous intravenous infusion with [1-(13)C]acetate, [1-(13)C]propionate and [1-(13)C]butyrate (12, 1.2 and 0.6 μmol·kg(-1)·min(-1), respectively) was applied. They consumed 15 g of inulin with a standard breakfast. Breath and blood samples were collected at regular times during the day over a 12 h period. The endogenous rate of appearance of acetate, propionate, and butyrate was 13.3 ± 4.8, 0.27 ± 0.09, and 0.28 ± 0.12 μmol·kg(-1)·min(-1), respectively. Colonic inulin fermentation was estimated to be 137 ± 75 mmol acetate, 11 ± 9 mmol propionate, and 20 ± 17 mmol butyrate over 12 h, assuming that 40%, 10%, and 5% of colonic derived acetate, propionate, and butyrate enter the systemic circulation. In conclusion, inulin is mainly fermented into acetate and, to lesser extents, into butyrate and propionate. Stable isotope technology allows quantifying the production of the three main SCFA in vivo and proved to be a practical tool to investigate the extent and pattern of SCFA production.

  3. Enhanced mucosal re-epithelialization induced by short chain fatty acids in experimental colitis

    Directory of Open Access Journals (Sweden)

    Aguilar-Nascimento J.E.

    1999-01-01

    Full Text Available The short chain fatty acids (SCFA are the best nutrients for the colonocytes. Glucose is poorly used as a fuel but may be transformed into SCFA by colonic bacteria. The aim of this study was to investigate the effect of SCFA or glucose on experimental colitis. Colitis was induced in 30 Wistar rats by colonic instillation of 4% acetic acid. Five days later they were randomized to receive twice a day colonic lavage containing saline (controls, N = 10, 10% hypertonic glucose (N = 10 or SCFA (N = 10 until day 8 when they were killed. At autopsy, the colon was removed and weighed and the mucosa was evaluated macro- and microscopically and stripped out for DNA assay. Data are reported as mean ± SD or median [range] as appropriate. All animals lost weight but there was no difference between groups. Colon weight was significantly lower in the SCFA group (3.8 ± 0.5 g than in the control (5.3 ± 2.1 g and glucose (5.2 ± 1.3 g groups (P<0.05. Macroscopically, the severity of inflammation was less in SCFA (grade 2 [1-5] than in control (grade 9 [4-10] and glucose-treated (grade 9 [2-10] animals (P<0.01. Microscopically, ulceration of the mucosa was more severe in the glucose and control groups than in the SCFA group. The DNA content of the mucosa of SCFA-treated animals (8.2 [5.0-20.2] mg/g of tissue was higher than in glucose-treated (5.1 [4.2-8.5] mg/g of tissue; P<0.01 and control (6.2 [4.5-8.9] mg/g of tissue; P<0.05 animals. We conclude that SCFA may enhance mucosal re-epithelialization in experimental colitis, whereas hypertonic glucose is of no benefit.

  4. Quantification of in Vivo Colonic Short Chain Fatty Acid Production from Inulin

    Directory of Open Access Journals (Sweden)

    Eef Boets

    2015-10-01

    Full Text Available Short chain fatty acids (SCFA, including acetate, propionate, and butyrate, are produced during bacterial fermentation of undigested carbohydrates in the human colon. In this study, we applied a stable-isotope dilution method to quantify the in vivo colonic production of SCFA in healthy humans after consumption of inulin. Twelve healthy subjects performed a test day during which a primed continuous intravenous infusion with [1-13C]acetate, [1-13C]propionate and [1-13C]butyrate (12, 1.2 and 0.6 μmol·kg−1·min−1, respectively was applied. They consumed 15 g of inulin with a standard breakfast. Breath and blood samples were collected at regular times during the day over a 12 h period. The endogenous rate of appearance of acetate, propionate, and butyrate was 13.3 ± 4.8, 0.27 ± 0.09, and 0.28 ± 0.12 μmol·kg−1·min−1, respectively. Colonic inulin fermentation was estimated to be 137 ± 75 mmol acetate, 11 ± 9 mmol propionate, and 20 ± 17 mmol butyrate over 12 h, assuming that 40%, 10%, and 5% of colonic derived acetate, propionate, and butyrate enter the systemic circulation. In conclusion, inulin is mainly fermented into acetate and, to lesser extents, into butyrate and propionate. Stable isotope technology allows quantifying the production of the three main SCFA in vivo and proved to be a practical tool to investigate the extent and pattern of SCFA production.

  5. Free Fatty Acids Profiles Are Related to Gut Microbiota Signatures and Short-Chain Fatty Acids

    Directory of Open Access Journals (Sweden)

    Javier Rodríguez-Carrio

    2017-07-01

    Full Text Available A growing body of evidence highlights the relevance of free fatty acids (FFA for human health, and their role in the cross talk between the metabolic status and immune system. Altered serum FFA profiles are related to several metabolic conditions, although the underlying mechanisms remain unclear. Recent studies have highlighted the link between gut microbiota and host metabolism. However, although most of the studies have focused on different clinical conditions, evidence on the role of these mediators in healthy populations is lacking. Therefore, we have addressed the analysis of the relationship among gut microbial populations, short-chain fatty acid (SCFA production, FFA levels, and immune mediators (IFNγ, IL-6, and MCP-1 in 101 human adults from the general Spanish population. Levels of selected microbial groups, representing the major phylogenetic types present in the human intestinal microbiota, were determined by quantitative PCR. Our results showed that the intestinal abundance of Akkermansia was the main predictor of total FFA serum levels, displaying a negative association with total FFA and the pro-inflammatory cytokine IL-6. Similarly, an altered FFA profile, identified by cluster analysis, was related to imbalanced levels of Akkermansia and Lactobacillus as well as increased fecal SCFA, enhanced IL-6 serum levels, and higher prevalence of subclinical metabolic alterations. Although no differences in nutritional intakes were observed, divergent patterns in the associations between nutrient intakes with intestinal microbial populations and SCFA were denoted. Overall, these findings provide new insights on the gut microbiota–host lipid metabolism axis and its potential relevance for human health, where FFA and SCFA seem to play an important role.

  6. Markov Chain Modelling for Short-Term NDVI Time Series Forecasting

    Directory of Open Access Journals (Sweden)

    Stepčenko Artūrs

    2016-12-01

    Full Text Available In this paper, the NDVI time series forecasting model has been developed based on the use of discrete time, continuous state Markov chain of suitable order. The normalised difference vegetation index (NDVI is an indicator that describes the amount of chlorophyll (the green mass and shows the relative density and health of vegetation; therefore, it is an important variable for vegetation forecasting. A Markov chain is a stochastic process that consists of a state space. This stochastic process undergoes transitions from one state to another in the state space with some probabilities. A Markov chain forecast model is flexible in accommodating various forecast assumptions and structures. The present paper discusses the considerations and techniques in building a Markov chain forecast model at each step. Continuous state Markov chain model is analytically described. Finally, the application of the proposed Markov chain model is illustrated with reference to a set of NDVI time series data.

  7. Short Term Cyber Attacks with Long Term Effects and Degradation of Supply Chain Capability

    Science.gov (United States)

    2016-09-01

    Artificial Intelligence Research Society Conference, 271–275, St. Augustine: Florida. Goetschalckx, Marc. 2011. Supply Chain Engineering. New York: Springer...term risks in a network supply chain to establish the existence of black swan events. 14. SUBJECT TERMS cybersecurity , supply chain risk...Mission, and Information System View (NIST SP 800–39) .....50 6. Cybersecurity Instruction for the DOD (DODI 8500.01) .........51 7. Risk Management

  8. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Ling, E-mail: qinling@hfut.edu.cn [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China); Jiangsu Engineering Technology Research Center of Environmental Cleaning Materials (CEM), School of Environmental Sciences and Engineering, Nanjing University of Information Science and Technology (China); State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China); Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China)

    2016-07-15

    Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub n} (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.

  9. Fermentation to short-chain fatty acids and lactate in human faecal batch cultures. Intra- and inter-individual variations versus variations caused by changes in fermented saccharides

    DEFF Research Database (Denmark)

    Mortensen, P B; Hove, H; Clausen, M R

    1991-01-01

    in homogenates pooled from three individuals increased short-chain fatty acid production linearly. Amounts and ratios of short-chain fatty acids formed were highly dependent on the type of substrate fermented. Fermentable saccharides increased ammonia assimilation, in contrast to the metabolic inert cellulose...

  10. Process chain for fabrication of anisotropic optical functional surfaces on polymer components

    DEFF Research Database (Denmark)

    Li, Dongya; Zhang, Yang; Regi, Francesco

    2017-01-01

    . In order to implement the traceability ofthe manufacturing process, the geometry and dimension of the micro structure on the tool and the replica were assessed viametrological methods. The functionality of the anisotropic surfaces on the polymer replicas were evaluated by a gonioreflectometerand image...

  11. Conformational Behavior of Polymer Chains of Different Architectures in Strongly Endothermic Solvent Mixtures: Specific Solvation Effects.

    Czech Academy of Sciences Publication Activity Database

    Suchá, L.; Limpouchová, Z.; Procházka, Karel

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1391-1403 ISSN 0303-402X R&D Projects: GA ČR GA15-19542S Institutional support: RVO:67985858 Keywords : cononsolvency * preferential solvation * star polymer Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  12. Synthesis and Crosslinking of Polyether-Based Main Chain Benzoxazine Polymers and Their Gas Separation Performance

    Directory of Open Access Journals (Sweden)

    Muntazim Munir Khan

    2018-02-01

    Full Text Available The poly(ethylene glycol-based benzoxazine polymers were synthesized via a polycondensation reaction between Bisphenol-A, paraformaldehyde, and poly(ether diamine/(Jeffamine®. The structures of the polymers were confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR, indicating the presence of a cyclic benzoxazine ring. The polymer solutions were casted on the glass plate and cross-linked via thermal treatment to produce tough and flexible films without using any external additives. Thermal properties and the crosslinking behaviour of these polymers were studied by thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. Single gas (H2, O2, N2, CO2, and CH4 transport properties of the crosslinked polymeric membranes were measured by the time-lag method. The crosslinked PEG-based polybenzoxazine membranes show improved selectivities for CO2/N2 and CO2/CH4 gas pairs. The good separation selectivities of these PEG-based polybenzoxazine materials suggest their utility as efficient thin film composite membranes for gas and liquid membrane separation technology.

  13. Molecular current modulator consisting of conjugated polymer chain with chemically attached photoactive side groups

    Czech Academy of Sciences Publication Activity Database

    Nešpůrek, Stanislav; Sworakowski, J.

    2001-01-01

    Roč. 393, 1-2 (2001), s. 168-176 ISSN 0040-6090 R&D Projects: GA AV ČR IAA1050901; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : molecular electronics * photoconductivity * polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.266, year: 2001

  14. Schiff base polymer based on triphenylamine moieties in the main chain. Characterization and studies in solar cells

    International Nuclear Information System (INIS)

    Sánchez, C.O.; Bèrnede, J.C.; Cattin, L.; Makha, M.; Gatica, N.

    2014-01-01

    Polytriphenylamine (PTPA), a Schiff base polymer containing triphenylamine (TPA) segments and whose monomer contains triphenylamine and thiophene end groups, was synthesized. The monomer structure enabled the polymerization to be performed under conditions similar to those of thiophene. Oxidative coupling using FeCl 3 as oxidizing agent in anhydrous CHCl 3 medium was employed for the polymer synthesis. Scanning electron microscopy, fluorescence spectroscopy, and cyclic voltammetry were used to characterize the polymer. PTPA exhibited high thermal stability with a mass loss of 13.3 % at 546.5 °C. The fluorescence spectrum showed emission at 300–550 nm and the optical band gap was found to be 2.6 eV. It was also established that PTPA forms complexes with Lewis acids, e.g. MoO 3 and CuI. Its absorption band widened and extended up to the near-IR. It was seen that PTPA is rich in π-electrons and thus can act as electron donor. The value of the Highest Occupied Molecular Orbital (HOMO) was − 5.35 eV indicating its potential application in optoelectronic devices. An attempt was also made to investigate the photovoltaic potential of PTPA. Organic photovoltaic devices with various buffer layer structures, namely ITO/CuI/PTPA/C 60 /BCP/Al, ITO/MoO 3 /PTPA/C 60 /BCP/Al, and ITO/MoO 3 /CuI/PTPA/C 60 /BCP/Al, where ITO stands for indium tin oxide and BCP for bathocuproine, were utilized for the studies. Power conversion efficiency of these devices ranged between 0.21 and 0.43% under simulated AM 1.5 illumination (100 mW cm −2 ). This result proved that polymers containing TPA in the main chain hold promising properties that would allow their use in photovoltaic devices. - Highlights: • A Schiff base polymer with triphenylamine and thiophene segments was synthesized. • In organic cells, the highest efficiency was obtained in a MoO 3 /CuI double layer. • Polymer exhibited a power conversion efficiency between 0.21 and 0.43 %

  15. Schiff base polymer based on triphenylamine moieties in the main chain. Characterization and studies in solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez, C.O. [Instituto de Ciencias Químicas, Facultad de Ciencias, Universidad Austral de Chile, Avda. Las Encinas 220, Campus Isla Teja, Valdivia (Chile); Bèrnede, J.C. [L' UNAM, Moltech Anjou, UMR 6200, 2 rue de la Houssinière, BP 92208, Nantes F-44000 (France); Cattin, L. [L' UNAM, Institut Jean Rouxel (IMN), UMR 6502, 2 rue de la Houssinière, BP 92208, Nantes F-44000 (France); Makha, M. [L' UNAM, Moltech Anjou, UMR 6200, 2 rue de la Houssinière, BP 92208, Nantes F-44000 (France); Gatica, N. [Departamento de Polímeros, Facultad de Ciencias, Universidad de Concepción, Avda. Edmundo Larenas 129, Concepción (Chile)

    2014-07-01

    Polytriphenylamine (PTPA), a Schiff base polymer containing triphenylamine (TPA) segments and whose monomer contains triphenylamine and thiophene end groups, was synthesized. The monomer structure enabled the polymerization to be performed under conditions similar to those of thiophene. Oxidative coupling using FeCl{sub 3} as oxidizing agent in anhydrous CHCl{sub 3} medium was employed for the polymer synthesis. Scanning electron microscopy, fluorescence spectroscopy, and cyclic voltammetry were used to characterize the polymer. PTPA exhibited high thermal stability with a mass loss of 13.3 % at 546.5 °C. The fluorescence spectrum showed emission at 300–550 nm and the optical band gap was found to be 2.6 eV. It was also established that PTPA forms complexes with Lewis acids, e.g. MoO{sub 3} and CuI. Its absorption band widened and extended up to the near-IR. It was seen that PTPA is rich in π-electrons and thus can act as electron donor. The value of the Highest Occupied Molecular Orbital (HOMO) was − 5.35 eV indicating its potential application in optoelectronic devices. An attempt was also made to investigate the photovoltaic potential of PTPA. Organic photovoltaic devices with various buffer layer structures, namely ITO/CuI/PTPA/C{sub 60}/BCP/Al, ITO/MoO{sub 3}/PTPA/C{sub 60}/BCP/Al, and ITO/MoO{sub 3}/CuI/PTPA/C{sub 60}/BCP/Al, where ITO stands for indium tin oxide and BCP for bathocuproine, were utilized for the studies. Power conversion efficiency of these devices ranged between 0.21 and 0.43% under simulated AM 1.5 illumination (100 mW cm{sup −2}). This result proved that polymers containing TPA in the main chain hold promising properties that would allow their use in photovoltaic devices. - Highlights: • A Schiff base polymer with triphenylamine and thiophene segments was synthesized. • In organic cells, the highest efficiency was obtained in a MoO{sub 3}/CuI double layer. • Polymer exhibited a power conversion efficiency between 0.21 and 0.43 %.

  16. Short Chain Fatty Acids in the Colon and Peripheral Tissues: A Focus on Butyrate, Colon Cancer, Obesity and Insulin Resistance

    Directory of Open Access Journals (Sweden)

    Sean M. McNabney

    2017-12-01

    Full Text Available Increased dietary fiber consumption has been associated with many beneficial effects, including amelioration of obesity and insulin resistance. These effects may be due to the increased production of short chain fatty acids, including propionate, acetate and butyrate, during fermentation of the dietary fiber in the colon. Indeed, oral and dietary supplementation of butyrate alone has been shown to prevent high fat-diet induced obesity and insulin resistance. This review focuses on sources of short chain fatty acids, with emphasis on sources of butyrate, mechanisms of fiber and butyrate metabolism in the gut and its protective effects on colon cancer and the peripheral effects of butyrate supplementation in peripheral tissues in the prevention and reversal of obesity and insulin resistance.

  17. Self-consistent field theoretic simulations of amphiphilic triblock copolymer solutions: Polymer concentration and chain length effects

    Directory of Open Access Journals (Sweden)

    X.-G. Han

    2014-06-01

    Full Text Available Using the self-consistent field lattice model, polymer concentration φP and chain length N (keeping the length ratio of hydrophobic to hydrophilic blocks constant the effects on temperature-dependent behavior of micelles are studied, in amphiphilic symmetric ABA triblock copolymer solutions. When chain length is increased, at fixed φP, micelles occur at higher temperature. The variations of average volume fraction of stickers φcos and the lattice site numbers Ncols at the micellar cores with temperature are dependent on N and φP, which demonstrates that the aggregation of micelles depends on N and φP. Moreover, when φP is increased, firstly a peak appears on the curve of specific heat CV for unimer-micelle transition, and then in addition a primary peak, the secondary peak, which results from the remicellization, is observed on the curve of CV. For a long chain, in intermediate and high concentration regimes, the shape of specific heat peak markedly changes, and the peak tends to be a more broad peak. Finally, the aggregation behavior of micelles is explained by the aggregation way of amphiphilic triblock copolymer. The obtained results are helpful in understanding the micellar aggregation process.

  18. Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

    Science.gov (United States)

    Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

    2015-08-01

    Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Effects of Short-Term Jump Squat Training With and Without Chains on Strength and Power in Recreational Lifters

    Directory of Open Access Journals (Sweden)

    David C. Archer

    2016-10-01

    Full Text Available Background: The use of chains in resistance training is a way to accommodate the muscular strength curve. Short-term training and jump squats have been shown to increase back squat strength, but not in conjunction with each other or with chains. Jump squats have also been used to increase jump height and power. Objectives: The purpose of this study was to investigate the effects of short-term jump squat training with and without chains on strength and power. Methods: Thirty-one resistance-trained men volunteered to participate (age = 23.87 ± 2.2 years, height=174.87 ± 6.94 cm, mass = 82.74 ± 14.95 kg and were randomly assigned to one of three groups [control (C = 10, no chains (NC =10, or chains (CH = 11]. Participants had their jump height (VJ and back squat strength (BS tested before and after a week of training. The NC and CH groups performed three training sessions consisting of five sets of three reps of jump squats at 30% 1RM with 30s rest between sets. The CH group had 20% of their load added by chains when standing erect. The C group did not train. Results: A 3 (group: CH, NC, C x 2 (time: pre, post mixed factor ANOVA revealed a significant (p = 0.006 interaction for back squat 1RM. Both the CH (pre 142.56 ± 20.40 kg; post 145.66 ± 19.59 kg and NC (pre 150.00 ± 15.23 kg; post 154.77 ± 15.09 kg groups significantly increased while the C (pre 157.27 ± 25.35 kg; post 156.36 ± 24.85 kg group showed no difference. There were no significant interactions (p =0.32 or main effects for VJ (C = pre 50.59 ± 9.39cm; post 51.29 ± 9.68cm; NC = pre 55.29 ± 5.23cm; post 57.39 ± 5.22cm; CH = pre 46.19 ± 5.02; post 47.45 ± 4.62. Conclusions: The CH group was able to increase strength while lifting less overall weight. Coaches may use short-term training with chains to yield a similar increase in back squat strength as without chains. Keywords: variable resistance, back squats, novel, vertical jump

  20. Short-chain fatty acids induced autophagy serves as an adaptive strategy for retarding mitochondria-mediated apoptotic cell death

    OpenAIRE

    Tang, Y; Chen, Y; Jiang, H; Nie, D

    2010-01-01

    Short-chain fatty acids (SCFAs) are the major by-products of bacterial fermentation of undigested dietary fibers in the large intestine. SCFAs, mostly propionate and butyrate, inhibit proliferation and induce apoptosis in colon cancer cells, but clinical trials had mixed results regarding the anti-tumor activities of SCFAs. Herein we demonstrate that propionate and butyrate induced autophagy in human colon cancer cells to dampen apoptosis whereas inhibition of autophagy potentiated SCFA induc...

  1. Evaluating the Environmental Fate of Short-Chain Chlorinated Paraffins (SCCPs) in the Nordic Environment Using a Dynamic Multimedia Model

    OpenAIRE

    Krogseth, Ingjerd Sunde; Breivik, Knut; Arnot, Jon A; Wania, Frank; Borgen, Anders; Schlabach, Martin

    2013-01-01

    Short chain chlorinated paraffins (SCCPs) raise concerns due to their potential for persistence, bioaccumulation, long-range transport and adverse effects. An understanding of their environmental fate remains limited, partly due to the complexity of the mixture. The purpose of this study was to evaluate whether a mechanistic, integrated, dynamic environmental fate and bioaccumulation multimedia model (CoZMoMAN) can reconcile what is known about environmental emissions and human exposure of SC...

  2. Relative developmental toxicity of short-chain chlorinated paraffins in Zebrafish (Danio rerio) embryos.

    Science.gov (United States)

    Liu, Lihua; Li, Yifan; Coelhan, Mehmet; Chan, Hing Man; Ma, Wanli; Liu, Liyan

    2016-12-01

    Short-chain chlorinated paraffins (SCCPs) are ubiquitous in the environment and might cause adverse environmental and human health effects. Little is known about the relative toxicity of different SCCP compounds especially during development. The objective of this study was to characterize and compare effects of seven SCCP groups at environmentally relevant levels, using a zebrafish (Danio rerio) model. Observations on malformation, survival rates at 96 h post fertilization (hpf), and hatching rates at 72 hpf indicated that the C 10- groups (C 10 H 18 Cl 4 , 1,2,5,6,9,10-C 10 H 16 Cl 6 and C 10 H 15 Cl 7 ) were more toxic than the C 12- groups (C 12 H 22 Cl 4 , C 12 H 19 Cl 7 and 1,1,1,3,10,12,12,12-C 12 H 18 Cl 8 ) and Cereclor 63L. The C 10- groups were also more potent than C 12- groups and Cereclor 63L in decreasing thyroid hormone levels. Among the three compounds within the C 10- group, the compounds with less chlorine content had stronger effects on sub-lethal malformations but less effects on triiodothyronine (T3) and tetraiodothyronine (T4). Only C 10 H 18 Cl 4 significantly decreased the mRNA expression of tyr, ttr, dio2 and dio3 at a dose-dependent manner suggesting that the specific mode of actions differ with different congeners. The mechanisms of disruption of thyroid status by different SCCPs could be different. C 10 H 18 Cl 4 might inhibit T3 production through the inhibition effect on dio2. These results indicate that SCCP exposure could alter gene expression in the hypothalamic-pituitary-thyroid (HPT) axis and thyroid hormone levels. The mechanisms of disruption of thyroid status by different SCCPs could be different. Our results on the relative developmental toxicities of SCCPs will be useful to reach a better understanding of SCCP toxicity supporting environmental risk evaluation and regulation and used as a guidance for environmental monitoring of SCCPs in the future. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Screening of short- and medium-chain chlorinated paraffins in selected riverine sediments and sludge from the Czech Republic

    International Nuclear Information System (INIS)

    Pribylova, Petra; Klanova, Jana; Holoubek, Ivan

    2006-01-01

    Wide distribution of chlorinated paraffins in the environment has already been demonstrated in several studies; however, information about their levels in the Central Europe is still very limited. First study focused on the SCCP contamination of the Czech aquatic environment have been performed recently, and its results motivated the authors to analyze sediments from a wide set of the Czech rivers in order to obtain more detailed information. Thirty-six sediment samples from eleven rivers and five drainage vents neighboring the chemical factories were analyzed; special attention was paid to the industrial areas. For the first time in the Czech Republic, medium-chain in addition to short-chain chlorinated paraffins were analyzed using GC-ECNI-MS. Chlorinated paraffins were detected in sediment samples on the concentration levels up to 347 ng g -1 for short-chain chlorinated paraffins, and 5575 ng g -1 for medium-chain chlorinated paraffins. Average chlorination degree of SCCPs was 65%. - Data on contamination of sediments from industrial areas fill the informational gap in the field of contamination of the Central Europe by chlorinated paraffins

  4. FUNCTIONAL SHORT FOOD SUPPLY CHAINS IN THE FIELD OF ROMANIAN RURAL TOURISM. CASE STUDY: HARGHITA AND NEAMȚ COUNTIES

    Directory of Open Access Journals (Sweden)

    Lucian TANASA

    2015-08-01

    Full Text Available Nowadays, one cannot talk about an authentic rural tourism within a certain destination without emphasizing the local cultural heritage (cultural landscape, customs and traditions, gastronomy and so on. In the existing context, the local gastronomy is perceived as a marketing instrument efficient in differentiating the rural touristic destinations. A special place in the development of the traditional cuisine is represented by the setting up and the promotion of the short food supply chains which can be achieved by sustaining the small local producers and by putting into practice an environment-friendly traditional agriculture. Sustaining the partnerships between the owners of accommodation units and the small local agricultural producers represents an essential element in putting into practice a sustainable and qualitative rural tourism. Romania has a substantial potential as regards the enhancement of short food supply chains thanks to: the large number of semi-subsistence agricultural farms (with an area under 5 hectares, the „village-town connection” as regards the food procurement, especially from acquaintances and relatives and the carrying on of a traditional agriculture at a large scale in the rural households.The case studies emphasized in the current paper (Harghita and Neamţ Counties focus on the existence of short food supply chains, functional in the rural tourism sector under very different ways: touristic sheepfolds, trout farms, inns, authentic holiday villages, peasant guest houses etc.

  5. 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.

  6. On the Wrapping of Polyglycolide, Poly(Ethylene Oxide), and Polyketone Polymer Chains Around Single-Walled Carbon Nanotubes Using Molecular Dynamics Simulations

    Science.gov (United States)

    Rouhi, S.; Alizadeh, Y.; Ansari, R.

    2015-02-01

    By using molecular dynamics simulations, the interaction between a single-walled carbon nanotube and three different polymers has been studied in this work. The effects of various parameters such as the nanotube geometry and temperature on the interaction energy and radius of gyration of polymers have been explored. By studying the snapshots of polymers along the single-walled carbon nanotube, it has been shown that 50 ps can be considered as a suitable time after which the shape of polymer chains around the nanotube remains almost unchanged. It is revealed that the effect of temperature on the interaction energy and radius of gyration of polymers in the range of 250 to 500 K is not significant Also, it is shown that the interaction energy depends on the nanotube diameter.

  7. Molecular weight kinetics and chain scission models for dextran polymers during ultrasonic degradation.

    Science.gov (United States)

    Pu, Yuanyuan; Zou, Qingsong; Hou, Dianzhi; Zhang, Yiping; Chen, Shan

    2017-01-20

    Ultrasonic degradation of six dextran samples with different initial molecular weights (IMW) has been performed to investigate the degradation behavior and chain scission mechanism of dextrans. The weight-average molecular weight (Mw) and polydispersity index (D value) were monitored by High Performance Gel Permeation Chromatography (HPGPC). Results showed that Mw and D value decreased with increasing ultrasonic time, resulting in a more homologous dextran solution with lower molecular weight. A significant degradation occurred in dextrans with higher IMW, particularly at the initial stage of the ultrasonic treatment. The Malhotra model was found to well describe the molecular weight kinetics for all dextran samples. Experimental data was fitted into two chain scission models to study dextran chain scission mechanism and the model performance was compared. Results indicated that the midpoint scission model agreed well with experimental results, with a linear regression factor of R 2 >0.99. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Side-Chain Supramolecular Polymers Employing Conformer Independent Triple Hydrogen Bonding Arrays

    OpenAIRE

    Gooch, Adam; Murphy, Natasha S.; Thomson, Neil H.; Wilson, Andrew J.

    2013-01-01

    Derivatives of thymine have been extensively used to promote supramolecular materials assembly. Such derivatives can be synthetically challenging to access and may be susceptible to degradation. The current article uses a conformer-independent acceptor-donor-acceptor array (ureidopyrimidine) which forms moderate affinity interactions with diamidopyridine derivatives to effect supramolecular blend formation between polystyrene and poly(methyl methacrylate) polymers obtained by RAFT which have ...

  9. Silver-tellurolate polynuclear complexes: from isolated cluster units to extended polymer chains

    International Nuclear Information System (INIS)

    Corrigan, J.F.; Fenske, D.; Power, W.P.

    1997-01-01

    In the presence of tertiary phosphanes, AgCl reacts readily with the reagent Te(Ph)SiMe 3 to yield silver - tellurolate polynuclear complexes. In the case of PMe 3 , the polymer [Ag 10 (μ 3 -TePh) 10 (PMe 3 ) 2 ] ∞ (shown below) is formed, in which the TePh ligands seve as both inter- and intracluster bridges. (orig.)

  10. Self-Assembly of Block Copolymer Chains To Promote the Dispersion of Nanoparticles in Polymer Nanocomposites

    Science.gov (United States)

    2017-01-01

    In this paper we adopt molecular dynamics simulations to study the amphiphilic AB block copolymer (BCP) mediated nanoparticle (NP) dispersion in polymer nanocomposites (PNCs), with the A-block being compatible with the NPs and the B-block being miscible with the polymer matrix. The effects of the number and components of BCP, as well as the interaction strength between A-block and NPs on the spatial organization of NPs, are explored. We find that the increase of the fraction of the A-block brings different dispersion effect to NPs than that of B-block. We also find that the best dispersion state of the NPs occurs in the case of a moderate interaction strength between the A-block and the NPs. Meanwhile, the stress–strain behavior is probed. Our simulation results verify that adopting BCP is an effective way to adjust the dispersion of NPs in the polymer matrix, further to manipulate the mechanical properties. PMID:28892620

  11. 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.

  12. Diketopyrrolopyrrole-Based Conjugated Polymer Entailing Triethylene Glycols as Side Chains with High Thin-Film Charge Mobility without Post-Treatments

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Si-Fen [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Liu, Zi-Tong [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Cai, Zheng-Xu [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Dyson, Matthew J. [Department of Materials and Centre for Plastic Electronics, Imperial College London, London SW72AZ UK; Stingelin, Natalie [Department of Materials and Centre for Plastic Electronics, Imperial College London, London SW72AZ UK; Chen, Wei [Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Institute for Molecular Engineering, The University of Chicago, 5640 South Ellis Avenue Chicago IL 60637 USA; Ju, Hua-Jun [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Zhang, Guan-Xin [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; Zhang, De-Qing [Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China

    2017-04-18

    Side chain engineering of conjugated donor-acceptor polymers is a new way to manipulate their optoelectronic properties. Two new diketopyrrolopyrrole (DPP)-terthiophene-based conjugated polymers PDPP3T-1 and PDPP3T-2, with both hydrophilic triethylene glycol (TEG) and hydrophobic alkyl chains, are reported. It is demonstrated that the incorporation of TEG chains has a significant effect on the interchain packing and thin-film morphology with noticeable effect on charge transport. Polymer chains of PDPP3T-1 in which TEG chains are uniformly distributed can self-assemble spontaneously into a more ordered thin film. As a result, the thin film of PDPP3T-1 exhibits high saturated hole mobility up to 2.6 cm(2) V-1 s(-1) without any post-treatment. This is superior to those of PDPP3T with just alkyl chains and PDPP3T-2. Moreover, the respective field effect transistors made of PDPP3T-1 can be utilized for sensing ethanol vapor with high sensitivity (down to 100 ppb) and good selectivity.

  13. Elevated levels of short carbon-chain PFCAs in breast milk among Korean women: Current status and potential challenges.

    Science.gov (United States)

    Kang, Habyeong; Choi, Kyungho; Lee, Haeng-Shin; Kim, Do-Hee; Park, Na-Youn; Kim, Sunmi; Kho, Younglim

    2016-07-01

    Breast milks can be contaminated with perfluoroalkyl substances (PFASs). Exposure to PFASs during early stages of life may lead to adverse health effects among breastfed infants. To date, perfluorootanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been most frequently measured PFASs in breast milks worldwide. Information on shorter carbon-chain PFASs in breast milk is scarce. In this study, breast milks were sampled from 264 Korean lactating women, and measured for seventeen PFASs, including ten perfluoroalkyl carboxylates (PFCAs), four perfluoroalkyl sulfonates, and three perfluoroalkyl sulfonamides. PFOA and PFOS were detected in 98.5% of the breast milk samples, with median concentrations of 0.072 and 0.050ng/mL, respectively. Perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), and perfluoroheptanoic acid (PFHpA) were detected in higher frequencies, ranging between 67.4% and 81.8%. The concentrations of short carbon-chain PFCAs in breast milk such as PFPeA and PFHxA were the highest ever reported to date, and were comparable to that of PFOS. Concentrations of shorter chain PFCA in breast milk tended to be higher among the women with longer lactation period, while those of PFOA showed the opposite trend, suggesting a possibility that breastfeeding might be an important route of excretion for PFOA among lactating women. Fish consumption and the use of consumer products, e.g., skin care products, cosmetics and non-stick coated cooking utensils, were identified as significant predictors of PFAS concentrations in breast milk. Health risks associated with PFOA and PFOS exposure through breastfeeding were estimated negligible, however, risks of the short carbon-chain PFCAs could not be assessed because of lack of relevant toxicological information. Further efforts for source identification and exposure management measures for shorter chain PFCAs are necessary. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Polymer nanocomposites: polymer and particle dynamics

    KAUST Repository

    Kim, Daniel; Srivastava, Samanvaya; Narayanan, Suresh; Archer, Lynden A.

    2012-01-01

    Polymer nanocomposites containing nanoparticles smaller than the random coil size of their host polymer chains are known to exhibit unique properties, such as lower viscosity and glass transition temperature relative to the neat polymer melt. It has

  15. Silica-filled elastomers polymer chain and filler characterization by a SANS-SAXS approach

    CERN Document Server

    Botti, A; Richter, D; Urban, V; Ipns, A 6 4; Kohlbrecher, J; Straube, E

    2002-01-01

    A study of composites based upon commercially available silica fillers and networks of blends of protonated and deuterated anionically prepared polyisoprene is presented. The extraction of the single chain structure factor for SANS in the polymeric soft phase in isotropic and deformed state has been performed for the first time. The quasi three-component system could not be compositionally matched due to the internal structures of the activated fillers. For this, a parallel SAXS investigation provided the neccessary information on the filler structure which was lacking in the SANS analysis. Whereas mechanically clear reinforcement at low strains and filler-networking can be observed, the microscopic characterization of the chain deformation in the framework of the network tube model agrees with the estimates for hydrodynamic reinforcement of fractal fillers. (orig.)

  16. Silica-filled elastomers: polymer chain and filler characterization by a SANS-SAXS approach

    International Nuclear Information System (INIS)

    Botti, A.; Pyckhout-Hintzen, W.; Richter, D.; Urban, V.; Kohlbrecher, J.; Straube, E.

    2002-01-01

    A study of composites based upon commercially available silica fillers and networks of blends of protonated and deuterated anionically prepared polyisoprene is presented. The extraction of the single chain structure factor for SANS in the polymeric soft phase in isotropic and deformed state has been performed for the first time. The quasi three-component system could not be compositionally matched due to the internal structures of the activated fillers. For this, a parallel SAXS investigation provided the neccessary information on the filler structure which was lacking in the SANS analysis. Whereas mechanically clear reinforcement at low strains and filler-networking can be observed, the microscopic characterization of the chain deformation in the framework of the network tube model agrees with the estimates for hydrodynamic reinforcement of fractal fillers. (orig.)

  17. NOR and nitroxide-based HAS in accelerated photooxidation of carbon-chain polymers; comparison with secondary HAS: an ESRI and ATR FTIR study

    Czech Academy of Sciences Publication Activity Database

    Pilař, Jan; Michálková, Danuše; Šeděnková, Ivana; Pfleger, Jiří; Pospíšil, Jan

    2011-01-01

    Roč. 96, č. 5 (2011), s. 847-862 ISSN 0141-3910 R&D Projects: GA AV ČR IAA400500804 Institutional research plan: CEZ:AV0Z40500505 Keywords : commodity carbon-chain polymers * photodegradation * accelerated weathering Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.769, year: 2011

  18. Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors

    KAUST Repository

    Nam, Sungho; Hahm, Suk Gyu; Khim, Dongyoon; Kim, Hwajeong; Sajoto, Tissa; Ree, Moonhor; Marder, Seth R.; Anthopoulos, Thomas D.; Bradley, Donal D.C.; Kim, Youngkyoo

    2018-01-01

    on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO

  19. From Short Food Supply Chains to Sustainable Agriculture in Urban Food Systems: Food Democracy as a Vector of Transition

    Directory of Open Access Journals (Sweden)

    Yuna Chiffoleau

    2016-10-01

    Full Text Available In industrialized nations, local food networks have generally been analyzed through alternative food systems, in spite of the fact that they are much more diverse than this would imply. In France, ‘short food chains’ are both a continuation of a long tradition and a recent trend which now extends beyond activists, to consumers and producers as well. This paper will explore the conditions under which these chains can change the practices and knowledge of ordinary actors in urban food systems, from producers to urban consumers and policy-makers, in the area of agriculture and sustainability. It will consider the case study of the creation and development of an urban open-air market which has been analyzed using intervention research with input from economic sociology. We will highlight how personal relations, which are encouraged by a participatory context, support the evolution of practices and knowledge. We will also illustrate how a system of produce labelling has emerged as a mediation resource, and has increased changes as well as participation within the re-territorialization of the urban food system. By describing a concrete expression of food democracy which is spreading in France via a free collective trademark, and by showing its role in the transition of ‘ordinary’ actors towards a more sustainable agriculture, this paper will shine new light onto local food chains as well as traditional short food chains, and will call for more research on the subject.

  20. Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

    Science.gov (United States)

    Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

    2018-05-02

    Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular

  1. Enhanced performance and durability of low catalyst loading PEM water electrolyser based on a short-side chain perfluorosulfonic ionomer

    International Nuclear Information System (INIS)

    Siracusano, Stefania; Baglio, Vincenzo; Van Dijk, Nicholas; Merlo, Luca; Aricò, Antonino Salvatore

    2017-01-01

    Graphical abstract: Tripling current density (>3 A·cm"−"2) with respect to the state of the art of commercial PEM electrolyser can be achieved also in the presence of a significant reduction, about 4-fold, of the total noble metal loading (0.5 mg·cm"−"2) while achieving high efficiency (>80%) and proper durability. - Highlights: • Current density >3 A·cm"−"2 is achieved in electrolysis cells with efficiency >80%. • A 4-fold reduction of noble metal loading is demonstrated in electrolysis cells. • Degradation rate <5 μV/h is achieved in a 1000 h durability test at 1 A·cm"−"2. • Degradation associated to a change in Lewis acidity characteristics is observed. - Abstract: Water electrolysis supplied by renewable energy is the foremost technology for producing “green” hydrogen for fuel cell vehicles. In addition, the ability to rapidly follow an intermittent load makes electrolysis an ideal solution for grid-balancing caused by differences in supply and demand for energy generation and consumption. Membrane-electrode assemblies (MEAs) designed for polymer electrolyte membrane (PEM) water electrolysis, based on a novel short-side chain (SSC) perfluorosulfonic acid (PFSA) membrane, Aquivion®, with various cathode and anode noble metal loadings, were investigated in terms of both performance and durability. Utilizing a nanosized Ir_0_._7Ru_0_._3O_x solid solution anode catalyst and a supported Pt/C cathode catalyst, in combination with the Aquivion® membrane, gave excellent electrolysis performances exceeding 3.2 A·cm"−"2 at 1.8 V terminal cell voltage (∼80% efficiency) at 90 °C in the presence of a total catalyst loading of 1.6 mg⋅cm"−"2. A very small loss of efficiency, corresponding to 30 mV voltage increase, was recorded at 3 A⋅cm"−"2 using a total noble metal catalyst loading of less than 0.5 mg·cm"−"2 (compared to the industry standard of 2 mg·cm"−"2). Steady-state durability tests, carried out for 1000 h at 1 A

  2. Detection of adenovirus hexon sequence in a cat by polymerase chain reaction(short communication)

    NARCIS (Netherlands)

    Horzinek, M.C.; Lakatos, B.; Farkas, J.; Egberink, H.F.; Vennema, H.; Benko, M.

    1999-01-01

    Adenoviral nucleic acid was detected by polymerase chain reaction (PCR) in pharyngeal and rectal swab samples of a cat seropositive for adenovirus and suffering from transient hepatic failure. The samples were taken at a one-year interval, and both faecal samples as well as the second pharyngeal

  3. Influence of short chain organic acids and bases on the wetting properties and surface energy of submicrometer ceramic powders.

    Science.gov (United States)

    Neirinck, Bram; Soccol, Dimitri; Fransaer, Jan; Van der Biest, Omer; Vleugels, Jef

    2010-08-15

    The effect of short chained organic acids and bases on the surface energy and wetting properties of submicrometer alumina powder was assessed. The surface chemistry of treated powders was determined by means of Diffuse Reflectance Infrared Fourier Transform spectroscopy and compared to untreated powder. The wetting of powders was measured using a modified Washburn method, based on the use of precompacted powder samples. The geometric factor needed to calculate the contact angle was derived from measurements of the porous properties of the powder compacts. Contact angle measurements with several probe liquids before and after modification allowed a theoretical estimation of the surface energy based on the surface tension component theory. Trends in the surface energy components were linked to observations in infrared spectra. The results showed that the hydrophobic character of the precompacted powder depends on both the chain length and polar group of the modifying agent. Copyright 2010 Elsevier Inc. All rights reserved.

  4. Activation of Short and Long Chain Fatty Acid Sensing Machinery in the Ileum Lowers Glucose Production in Vivo.

    Science.gov (United States)

    Zadeh-Tahmasebi, Melika; Duca, Frank A; Rasmussen, Brittany A; Bauer, Paige V; Côté, Clémence D; Filippi, Beatrice M; Lam, Tony K T

    2016-04-15

    Evidence continues to emerge detailing the myriad of ways the gut microbiota influences host energy homeostasis. Among the potential mechanisms, short chain fatty acids (SCFAs), the byproducts of microbial fermentation of dietary fibers, exhibit correlative beneficial metabolic effects in humans and rodents, including improvements in glucose homeostasis. The underlying mechanisms, however, remain elusive. We here report that one of the main bacterially produced SCFAs, propionate, activates ileal mucosal free fatty acid receptor 2 to trigger a negative feedback pathway to lower hepatic glucose production in healthy rats in vivo We further demonstrate that an ileal glucagon-like peptide-1 receptor-dependent neuronal network is necessary for ileal propionate and long chain fatty acid sensing to regulate glucose homeostasis. These findings highlight the potential to manipulate fatty acid sensing machinery in the ileum to regulate glucose homeostasis. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  5. Dendrite short-circuit and fuse effect on Li/polymer/Li cells

    International Nuclear Information System (INIS)

    Rosso, Michel; Brissot, Claire; Teyssot, Anna; Dolle, Mickael; Sannier, Lucas; Tarascon, Jean-Marie; Bouchet, Renaud; Lascaud, Stephane

    2006-01-01

    We report on experimental and theoretical studies of dendritic growth in Li/polymer/Li symmetric cells. Potential evolution with time, impedance and in situ microscopy experiments enable to characterise the onset and evolution of dendrites. In particular we observe that dendrites may burn when a high enough current goes through them, a thermo-fusible effect predicted in a previous paper and confirmed by SEM experiments. We present a calculation that gives a quantitative description of this effect: our results enable to understand a series of experimental data published in the literature concerning impedance variations observed while cycling lithium-polymer cells

  6. Effect of Areal Density of Polymer Chains on Gold Nanoparticles on Nanoparticle Location in a Block Copolymer Template

    Science.gov (United States)

    Kim, B. J.; Bang, J.; Hawker, C. J.; Kramer, E. J.

    2006-03-01

    It is well established that one block of a copolymer can interact preferentially with an inorganic substrate to produce wetting and domain orientation. We take advantage of this preferential interaction to control the location of 2.5 nm diameter Au nanoparticles coated with short thiol-terminated polystyrene (Mn=3.4 kg/mol) chains (PS-SH) in a symmetric poly(styrene-b-2 vinyl-pyridine) (PS-b-P2VP) diblock copolymer (Mn=196 kg/mol) by changing the areal density σ of the PS-SH on the Au. If σ >= 1.6 chains/nm^2, the preferential interaction between the P2VP of the PS-b-P2VP and the Au surface is screened and the Au localizes in the center of the PS domains. If σ <= 1.4 chains/nm^2 , the Au particles are localized at the PS-P2VP interface. Au nanoparticles coated with thiol terminated P2VP (Mn=3 kg/mol) localize in the center of the P2VP domain of the PS-P2VP over the entire range of σ, demonstrating the localization of the PS coated Au nanoparticles at the interface at low values of σ is due to the unscreened Au-P2VP interaction.

  7. Enhancement of short-circuit current density in polymer bulk heterojunction solar cells comprising plasmonic silver nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yuzhao; Lin, Xiaofeng; Ou, Jiemei; Chen, Xudong, E-mail: cescxd@mail.sysu.edu.cn, E-mail: stszx@mail.sysu.edu.cn, E-mail: chenyj69@mail.sysu.edu.cn [Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education of China, Sun Yat-sen University, Guangzhou 510275 (China); Qing, Jian; Zhong, Zhenfeng; Zhou, Xiang, E-mail: cescxd@mail.sysu.edu.cn, E-mail: stszx@mail.sysu.edu.cn, E-mail: chenyj69@mail.sysu.edu.cn; Chen, Yujie, E-mail: cescxd@mail.sysu.edu.cn, E-mail: stszx@mail.sysu.edu.cn, E-mail: chenyj69@mail.sysu.edu.cn [State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275 (China); Hu, Chenglong [Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education, Jianghan University, Wuhan 430056 (China)

    2014-03-24

    We demonstrate that the influence of plasmonic effects based on silver nanowires (Ag NWs) on the characteristics of polymer solar cells (PSCs). The solution-processed Ag NWs are situated at the interface of anode buffer layer and active layer, which could enhance the performance especially the photocurrent of PSCs by scattering, localized surface plasmon resonance, and surface plasmon polaritons. Plasmonic effects are confirmed by the enhancement of extinction spectra, external quantum efficiency, and steady state photoluminescence. Consequently, the short-circuit current density (J{sub sc}) and power conversion efficiency enhance about 24% and 18%, respectively, under AM1.5 illumination when Ag NWs plasmonic nanostructure incorporated into PSCs.

  8. Small-bandgap polymer solar cells with unprecedented short-circuit current density and high fill factor.

    Science.gov (United States)

    Choi, Hyosung; Ko, Seo-Jin; Kim, Taehyo; Morin, Pierre-Olivier; Walker, Bright; Lee, Byoung Hoon; Leclerc, Mario; Kim, Jin Young; Heeger, Alan J

    2015-06-03

    Small-bandgap polymer solar cells (PSCs) with a thick bulk heterojunction film of 340 nm exhibit high power conversion efficiencies of 9.40% resulting from high short-circuit current density (JSC ) of 20.07 mA cm(-2) and fill factor of 0.70. This remarkable efficiency is attributed to maximized light absorption by the thick active layer and minimized recombination by the optimized lateral and vertical morphology through the processing additive. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Use of isothermal titration calorimetry to study the interaction of short-chain alcohols with lipid membranes

    DEFF Research Database (Denmark)

    Trandum, Christa; Westh-Andersen, Peter; Jørgensen, Kent

    1999-01-01

    of short-chain alcohols on Lipid bilayers. isothermal titration calorimetry (ITC) has been used to determine the energy involved in the association of the alcohols with lipid bilayers. Pure unilamellar DMPC liposomes and DMPC liposomes incorporated with different amounts of cholesterol, sphingomyelin...... dependent on the lipid bilayer composition. In the presence of high concentrations of cholesterol, the binding enthalpy of ethanol is decreased, whereas the presence of ceramides enhances the enthalpic response of the lipid bilayer to ethanol. Isothermal titration calorimetry offers a new methodology...

  10. Structure of the conversion laws in quantum integrable spin chains with short range interactions

    International Nuclear Information System (INIS)

    Grabowski, M.P.; Mathieu, P.

    1995-01-01

    The authors present a detailed analysis of the structure of the conservation laws in quantum integrable chains of the XYZ-type and in the Hubbard model. The essential tool for the former class of models is the boost operator, which provides a recursive way of calculating the integrals of motion. With its help, they establish the general form of the XYZ conserved charges in terms of simple polynomials in spin variables and derive recursion relations for the relative coefficients of these polynomials. Although these relations are difficult to solve in general, a subset of the coefficients can be determined. Moreover, for two submodels of the XYZ chain, namely the XXX and XY cases, all the charges can be calculated in closed form. Using this approach, the authors rederive the known expressions for the XY charges in a novel way. For the XXX case. a simple description of conserved charges is found in terms of a Catalan tree. This construction is generalized for the su(M) invariant integrable chain. They also investigate the circumstances permitting the existence of a recursive (ladder) operator in general quantum integrable systems. They indicate that a quantum ladder operator can be traced back to the presence of a Hamiltonian mastersymmetry of degree one in the classical continuous version of the model. In this way, quantum chains endowed with a recursive structure can be identified from the properties of their classical relatives. The authors also show that in the quantum continuous limits of the XYZ model, the ladder property of the boost operator disappears. For the Hubbard model they demonstrate the nonexistence of a ladder operator. Nevertheless, the general structure of the conserved charges is indicated, and the expression for the terms linear in the model's free parameter for all charges is derived in closed form. 62 refs., 4 figs

  11. Evaluation of short-chain-length polyhydroxyalkanoate accumulation in Bacillus aryabhattai

    Directory of Open Access Journals (Sweden)

    Aneesh Balakrishna Pillai

    Full Text Available Abstract This study was focused on the polyhydroxybutyrate (PHB accumulation property of Bacillus aryabhattai isolated from environment. Twenty-four polyhydroxyalkanoate (PHA producers were screened out from sixty-two environmental bacterial isolates based on Sudan Black B colony staining. Based on their PHA accumulation property, six promising isolates were further screened out. The most productive isolate PHB10 was identified as B. aryabhattai PHB10. The polymer production maxima were 3.264 g/L, 2.181 g/L, 1.47 g/L, 1.742 g/L and 1.786 g/L in glucose, fructose, maltose, starch and glycerol respectively. The bacterial culture reached its stationary and declining phases at 18 h and 21 h respectively and indicated growth-associated PHB production. Nuclear Magnetic Resonance (NMR spectra confirmed the material as PHB. The material has thermal stability between 30 and 140 °C, melting point at 170 °C and maximum thermal degradation at 287 °C. The molecular weight and poly dispersion index of the polymer were found as 199.7 kDa and 2.67 respectively. The bacterium B. aryabhattai accumulating PHB up to 75% of cell dry mass utilizing various carbon sources is a potential candidate for large scale production of bacterial polyhydroxybutyrate.

  12. The Role of Morphology and Electronic Chain Aggregation on the Optical Gain Properties of Semiconducting Conjugated Polymers

    Science.gov (United States)

    Lampert, Zachary Evan

    Conjugated polymers (CPs) are a novel class of materials that exhibit the optical and electrical properties of semiconductors while still retaining the durability and processability of plastics. CPs are also intrinsically 4-level systems with high luminescence quantum efficiencies making them particularly attractive as organic gain media for solid-state laser applications. However, before CPs can emerge as a commercially available laser technology, a more comprehensive understanding of the morphological dependence of the photophysics is required. In this thesis, the morphology and chain conformation dependence of amplified spontaneous emission (ASE) and optical gain in thin films of poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) was investigated. By changing the chemical nature of the solvent from which films were cast, as well as the temperature at which films were annealed, CP films with different morphologies, and hence different degrees of interchain interactions were achieved. Contrary to the common perception that polymer morphology plays a decisive role in determining the ASE behavior of thin CP films, we found that chromophore aggregation and degree of conformational order have minimal impact on optical gain. In fact, experimental results indicated that an extremely large fraction of interchain aggregate species and/or exciton dissociating defects are required to significantly alter the optical properties and suppress stimulated emission. These results are pertinent to the fabrication and optimization of an electrically pumped laser device, as improvements in charge carrier mobility through controlled increases in chain aggregation may provide a viable means of optimizing injection efficiency without significantly degrading optical gain. To offset charge-induced absorption losses under electrical pumping, and to enable the use of more compact and economical sources under optical pumping, conjugated polymers exhibiting low lasing

  13. Short wave infrared hyperspectral imaging for recovered post-consumer single and mixed polymers characterization

    Science.gov (United States)

    Bonifazi, Giuseppe; Palmieri, Roberta; Serranti, Silvia

    2015-03-01

    Postconsumer plastics from packing and packaging represent about the 60% of the total plastic wastes (i.e. 23 million of tons) produced in Europe. The EU Directive (2014/12/EC) fixes as target that the 60%, by weight, of packaging waste has to be recovered, or thermally valorized. When recovered, the same directive established that packaging waste has to be recycled in a percentage ranging between 55% (minimum) and 60% (maximum). The non-respect of these rules can produce that large quantities of end-of-life plastic products, specifically those utilized for packaging, are disposed-off, with a strong environmental impact. The application of recycling strategies, finalized to polymer recovery, can represent an opportunity to reduce: i) not renewable raw materials (i.e. oil) utilization, ii) carbon dioxide emissions and iii) amount of plastic waste disposed-off. Aim of this work was to perform a full characterization of different end-of-life polymers based products, constituted not only by single polymers but also of mixtures, in order to realize their identification for quality control and/or certification assessment. The study was specifically addressed to characterize the different recovered products as resulting from a recycling plant where classical processing flow-sheets, based on milling, classification and separation, are applied. To reach this goal, an innovative sensing technique, based on the utilization of a HyperSpectral[b] I[/b]maging (HSI) device working in the SWIR region (1000-2500 nm), was investigated. Following this strategy, single polymers and/or mixed polymers recovered were correctly recognized. The main advantage of the proposed approach is linked to the possibility to perform "on-line" analyses, that is directly on the different material flow streams, as resulting from processing, without any physical sampling and classical laboratory "off-line" determination.

  14. Vortex-assisted liquid-liquid microextraction for the rapid screening of short-chain chlorinated paraffins in water.

    Science.gov (United States)

    Chang, Chia-Yu; Chung, Wu-Hsun; Ding, Wang-Hsien

    2016-01-01

    The rapid screening of trace levels of short-chain chlorinated paraffins in various aqueous samples was performed by a simple and reliable procedure based on vortex-assisted liquid-liquid microextraction combined with gas chromatography and electron capture negative ionization mass spectrometry. The optimal vortex-assisted liquid-liquid microextraction conditions for 20 mL water sample were as follows: extractant 400 μL of dichloromethane; vortex extraction time of 1 min at 2500 × g; centrifugation of 3 min at 5000 × g; and no ionic strength adjustment. Under the optimum conditions, the limit of quantitation was 0.05 μg/L. Precision, as indicated by relative standard deviations, was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was above 91%. The vortex-assisted liquid-liquid microextraction with gas chromatography and electron capture negative ionization mass spectrometry method was successfully applied to quantitatively extract short-chain chlorinated paraffins from samples of river water and the effluent of a wastewater treatment plant, and the concentrations ranged from 0.8 to 1.6 μg/L. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Short-chain chlorinated paraffins (SCCPs) in surface soil from a background area in China: occurrence, distribution, and congener profiles.

    Science.gov (United States)

    Wang, Xue-Tong; Zhang, Yuan; Miao, Yi; Ma, Ling-Ling; Li, Yuan-Cheng; Chang, Yue-Ya; Wu, Ming-Hong

    2013-07-01

    Short-chain chlorinated paraffins (SCCPs) are extremely complex technical mixtures of polychlorinated n-alkanes with carbon chain lengths from C10 to C13 and chlorine content between 49 and 70%. SCCPs are under consideration for inclusion in the Stockholm Convention on persistent organic pollutants. SCCPs have been used extensively in industrial production, but little is known about the pollution level in soil environment in China. In this study, levels and distribution of SCCPs in soil samples from Chongming Island were analyzed. Concentrations of total SCCPs in soil samples ranged from 0.42 to 420 ng g(-1), with a median of 9.6 ng g(-1). The ubiquitous occurrence of SCCPs in Chongming Island implied that long-range atmospheric transport and soil-air exchange may be the most important pathways for SCCP contamination in the background area. The localized SCCP contamination could be derived from an unidentified source. Hierarchical cluster analysis indicated that C13- and C11-congeners were predominant in most soils and C10- and C12-congeners dominated in the remaining soils. Cl7- and Cl8-congeners were on the average the most dominant chlorine congeners in nearly all soils. Principal component analysis suggested that the separation of even and odd carbon chain congeners occurred during long-range atmospheric transport and aging in soil in the study area.

  16. Trapping social wasps (Hymenoptera: Vespidae) with acetic acid and saturated short chain alcohols.

    Science.gov (United States)

    Landolt, P J; Smithhisler, C S; Reed, H C; McDonough, L M

    2000-12-01

    Nineteen compounds were evaluated in combination with a solution of acetic acid as baits for trapping the German yellowjacket, Vespula germanica (F.), the western yellowjacket Vespula pensylvanica (Sausssure), and the golden paper wasp Polistes aurifer Saussure. Compounds with three to six carbon chains or branched chains and with a hydroxy functional group were selected for testing based on their similarity to isobutanol. They were compared with isobutanol with acetic acid, which is a known wasp attractant. None of the compounds tested were superior to isobutanol when presented with acetic acid as a lure for these species of wasps. However, traps baited with either the S-(-)- or the racemic mixture of 2-methyl-1-butanol in combination with acetic acid captured similar numbers of both species of yellowjackets, compared with isobutanol with acetic acid. Polistes aurifer responded strongly to the S-(-)-enantiomer and to the racemic mixture of 2-methyl-1-butanol with acetic acid and not to the R-(+)-enantiomer with acetic acid.

  17. Effects of molecular structure on microscopic heat transport in chain polymer liquids

    International Nuclear Information System (INIS)

    Matsubara, Hiroki; Kikugawa, Gota; Ohara, Taku; Bessho, Takeshi; Yamashita, Seiji

    2015-01-01

    In this paper, we discuss the molecular mechanism of the heat conduction in a liquid, based on nonequilibrium molecular dynamics simulations of a systematic series of linear- and branched alkane liquids, as a continuation of our previous study on linear alkane [T. Ohara et al., J. Chem. Phys. 135, 034507 (2011)]. The thermal conductivities for these alkanes in a saturated liquid state at the same reduced temperature (0.7T c ) obtained from the simulations are compared in relation to the structural difference of the liquids. In order to connect the thermal energy transport characteristics with molecular structures, we introduce the new concept of the interatomic path of heat transfer (atomistic heat path, AHP), which is defined for each type of inter- and intramolecular interaction. It is found that the efficiency of intermolecular AHP is sensitive to the structure of the first neighbor shell, whereas that of intramolecular AHP is similar for different alkane species. The dependence of thermal conductivity on different lengths of the main and side chain can be understood from the natures of these inter- and intramolecular AHPs

  18. Effects of molecular structure on microscopic heat transport in chain polymer liquids

    Energy Technology Data Exchange (ETDEWEB)

    Matsubara, Hiroki, E-mail: matsubara@microheat.ifs.tohoku.ac.jp; Kikugawa, Gota; Ohara, Taku [Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Bessho, Takeshi; Yamashita, Seiji [Higashifuji Technical Center, Toyota Motor Corporation, 1200 Mishuku, Susono, Shizuoka 410-1193 (Japan)

    2015-04-28

    In this paper, we discuss the molecular mechanism of the heat conduction in a liquid, based on nonequilibrium molecular dynamics simulations of a systematic series of linear- and branched alkane liquids, as a continuation of our previous study on linear alkane [T. Ohara et al., J. Chem. Phys. 135, 034507 (2011)]. The thermal conductivities for these alkanes in a saturated liquid state at the same reduced temperature (0.7T{sub c}) obtained from the simulations are compared in relation to the structural difference of the liquids. In order to connect the thermal energy transport characteristics with molecular structures, we introduce the new concept of the interatomic path of heat transfer (atomistic heat path, AHP), which is defined for each type of inter- and intramolecular interaction. It is found that the efficiency of intermolecular AHP is sensitive to the structure of the first neighbor shell, whereas that of intramolecular AHP is similar for different alkane species. The dependence of thermal conductivity on different lengths of the main and side chain can be understood from the natures of these inter- and intramolecular AHPs.

  19. Polymer chain dynamics in epoxy based composites as investigated by broadband dielectric spectroscopy

    Directory of Open Access Journals (Sweden)

    Mohammad K. Hassan

    2016-03-01

    Full Text Available Epoxy networks of the diglycidyl ether of bisphenol A (DGEBA were prepared using 3,3′- and 4,4′-diaminodiphenyl sulfone isomer crosslinkers. Secondary relaxations and the glass transitions of resultant networks were probed using broadband dielectric spectroscopy (BDS. A sub-Tg γ relaxation peak for both networks shifts to higher frequencies (f with increasing temperature in Arrhenius fashion, both processes having the same activation energy and being assigned to phenyl ring flipping in DGEBA chains. A β relaxation is assigned to local motions of dipoles that were created during crosslinking reactions. 4,4′-based networks exhibited higher Tg relative to 3,3′-based networks as per dynamic mechanical as well as BDS analyses. The Vogel–Fulcher–Tammann–Hesse equation fitted well to relaxation time vs. temperature data and comparison of Vogel temperatures suggests lower free volume per mass for the 3,3′-based network. The Kramers–Krönig transformation was used to directly calculate dc-free ɛ″ vs. f data from experimental ɛ′ vs. f data. Distribution of relaxation times (DRT curves are bi-modal for the 3,3′-crosslinked resin suggesting large-scale microstructural heterogeneity as opposed to homogeneity for the 4,4′-based network whose DRT consists of a single peak.

  20. Quantum critical scaling for field-induced quantum phase transition in a periodic Anderson-like model polymer chain

    Energy Technology Data Exchange (ETDEWEB)

    Ding, L.J., E-mail: dinglinjie82@126.com; Zhong, Y.

    2017-07-15

    Highlights: • The quantum critical scaling is investigated by Green’s function theory. • The obtained power-law critical exponents (β, δ and α) obey the critical scaling relation α + β(1 + δ) = 2. • The scaling hypothesis equations are proposed to verify the scaling analysis. - Abstract: The quantum phase transition and thermodynamics of a periodic Anderson-like polymer chain in a magnetic field are investigated by Green’s function theory. The T-h phase diagram is explored, wherein a crossover temperature T{sup ∗} denoting the gapless phase crossover into quantum critical regimes, smoothly connects near the critical fields to the universal linear line T{sup ∗} ∼ (h − h{sub c,s}), and ends at h{sub c,s}, providing a new route to capture quantum critical point (QCP). The quantum critical scaling around QCPs is demonstrated by analyzing magnetization, specific heat and Grüneisen parameter Γ{sub h}, which provide direct access to distill the power-law critical exponents (β, δ and α) obeying the critical scaling relation α + β(1 + δ) = 2, analogous to the quantum spin system. Furthermore, scaling hypothesis equations are proposed to check the scaling analysis, for which all the data collapse onto a single curve or two independent branches for the plot against an appropriate scaling variable, indicating the self-consistency and reliability of the obtained critical exponents.

  1. Rod like attapulgite/poly(ethylene terephthalate nanocomposites with chemical bonding between the polymer chain and the filler

    Directory of Open Access Journals (Sweden)

    Q. Fu

    2012-08-01

    Full Text Available Poly(ethylene terephthalate (PET nanocomposites containing rod-like silicate attapulgite (AT were prepared via in situ polymerization. It is presented that PET chains identical to the matrix have been successfully grafted onto simple organically pre-modified AT nanorods (MAT surface during the in situ polymerization process. The covalent bonding at the interface was confirmed by Fourier transform infrared spectroscopy (FTIR and thermogravimetric analysis (TGA. The content of grafted PET polymer on the surface of MAT was about 26 wt%. This high grafting density greatly improved the dispersion of fillers, interfacial adhesion as well as the significant confinement of the segmental motion of PET, as compared to the nanocomposites of PET/pristine AT (PET/AT. Owing to the unique interfacial structure in PET/MAT composites, their thermal and mechanical properties have been greatly improved. Compared with neat PET, the elastic modulus and the yield strength of PET/MAT were significantly improved by about 39.5 and 36.8%, respectively, by incorporating only 2 wt % MAT. Our work provides a novel route to fabricate advanced PET nanocomposites using rod-like attapulgite as fillers, which has great potential for industrial applications.

  2. Interactions of short chain phenylalkanoic acids within ionic surfactant micelles in aqueous media

    Directory of Open Access Journals (Sweden)

    Naeem Kashif

    2012-01-01

    Full Text Available % SDS KR nema Solubilization and interactions of phenylalkanoic acids induced by cationic surfactant, cetyltrimethylammonium bromide (CTAB and an anionic surfactant, sodium dodecyl sulfate (SDS was investigated spectrophotometrically at 25.0°C. The UV spectra of the additives (acids were measured with and without surfactant above and below critical micelle concentration (cmc of the surfactant. The presence of alkyl chain in phenylalkanoic acids is responsible for hydrophobic interaction resulting in shift of the spectra towards longer wavelength (red shift. The value of partition coefficient (Kx between the bulk water and surfactant micelles and in turn standard free energy change of solubilization (ΔGpº were also estimated by measuring the differential absorbance (ΔA of the additives in micellar solutions.

  3. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates; Cho, Eunkyung; Gysel, Roman; Risko, Chad; Coropceanu, Veaceslav; Miller, Chad E.; Sweetnam, Sean; Sellinger, Alan; Heeney, Martin; McCulloch, Iain; Bré das, Jean-Luc; Toney, Michael F.; McGehee, Michael D.

    2012-01-01

    bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist

  4. Polymer reaction engineering, an integrated approach

    NARCIS (Netherlands)

    Meyer, T.; Keurentjes, J.T.F.; Meyer, T.; Keurentjes, J.T.F.

    2005-01-01

    Summary This chapter contains sections titled: Polymer Materials A Short History of Polymer Reaction Engineering The Position of Polymer Reaction Engineering Toward Integrated Polymer Reaction Engineering The Disciplines in Polymer Reaction Engineering The Future: Product-inspired Polymer Reaction

  5. Comparison of the Photovoltaic Characteristics and Nanostructure of Fullerenes Blended with Conjugated Polymers with Siloxane-Terminated and Branched Aliphatic Side Chains

    KAUST Repository

    Kim, Do Hwan

    2013-02-12

    All-organic bulk heterojunction solar cells based on blends of conjugated polymers with fullerenes have recently surpassed the 8% efficiency mark and are well on their way to the industrially relevant ∼15% threshold. Using a low band-gap conjugated polymer, we have recently shown that polymer side chain engineering can lead to dramatic improvement in the in-plane charge carrier mobility. In this article, we investigate the effectiveness of siloxy side chain derivatization in controlling the photovoltaic performance of polymer:[6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM) blends and hence its influence on charge transport in the out-of-plane direction relevant for organic solar cells. We find that, in neat blends, the photocurrent of the polymer with siloxy side chains (PII2T-Si) is 4 times greater than that in blends using the polymer with branched aliphatic side chains (PII2T-ref). This difference is due to a larger out-of-plane hole mobility for PII2T-Si brought about by a largely face-on crystallite orientation as well as more optimal nanoscale polymer:PC71BM mixing. However, upon incorporating a common processing additive, 1,8-diiodooctane (DIO), into the spin-casting blend solution and following optimization, the PII2T-ref:PC71BM OPV device performance undergoes a large improvement and becomes the better-performing device, almost independent of DIO concentration (>1%). We find that the precise amount of DIO plays a larger role in determining the efficiency of PII2T-Si:PC71BM, and even at its maximum, the device performance lags behind optimized PII2T-ref:PC71BM blends. Using a combination of atomic force microscopy and small- and wide-angle X-ray scattering, we are able to elucidate the morphological modifications associated with the DIO-induced changes in both the nanoscale morphology and the molecular packing in blend films. © 2012 American Chemical Society.

  6. Short-wavelength ablation of polymers in the high-fluence regime

    Czech Academy of Sciences Publication Activity Database

    Liberatore, Chiara; Mann, K.; Müller, M.; Pina, L.; Juha, Libor; Vyšín, Luděk; Rocca, J.J.; Endo, Akira; Mocek, Tomáš

    T161, MAY (2014), "014066-1"-"014066-4" ISSN 0031-8949 R&D Projects: GA MŠk ED2.1.00/01.0027; GA MŠk EE2.3.20.0143 Grant - others:HILASE(XE) CZ.1.05/2.1.00/01.0027; OP VK 6(XE) CZ.1.07/2.3.00/20.0143 Institutional support: RVO:68378271 Keywords : extreme ultraviolet * soft x-ray * ablation * polymers Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 1.126, year: 2014

  7. The effect of side-chain substitution and hot processing on diketopyrrolopyrrole-based polymers for organic solar cells

    NARCIS (Netherlands)

    Heintges, G.H.L.; Leenaers, P.J.; Janssen, R.A.J.

    2017-01-01

    The effects of cold and hot processing on the performance of polymer-fullerene solar cells are investigated for diketopyrrolopyrrole (DPP) based polymers that were specifically designed and synthesized to exhibit a strong temperature-dependent aggregation in solution. The polymers, consisting of

  8. Short (

    NARCIS (Netherlands)

    Telleman, Gerdien; den Hartog, Laurens

    2013-01-01

    Aim: This systematic review assessed the implant survival rate of short (<10 mm) dental implants installed in partially edentulous patients. A case report of a short implant in the posterior region have been added. Materials and methods: A search was conducted in the electronic databases of MEDLINE

  9. A novel temperature control method for shortening thermal cycling time to achieve rapid polymerase chain reaction (PCR) in a disposable polymer microfluidic device

    DEFF Research Database (Denmark)

    Bu, Minqiang; R. Perch-Nielsen, Ivan; Sørensen, Karen Skotte

    steps to achieve a rapid ramping between the temperature steps for DNA denaturation, annealing and extension. The temperature dynamics within the microfluidic PCR chamber was characterized and the overshooting and undershooting parameters were optimized using the temperature dependent fluorescence......We present a new temperature control method capable of effectively shortening the thermal cycling time of polymerase chain reaction (PCR) in a disposable polymer microfluidic device with external heater and temperature sensor. The method employs optimized temperature overshooting and undershooting...

  10. A temperature control method for shortening thermal cycling time to achieve rapid polymerase chain reaction (PCR) in a disposable polymer microfluidic device

    DEFF Research Database (Denmark)

    Bu, Minqiang; Perch-Nielsen, Ivan R.; Sørensen, Karen Skotte

    2013-01-01

    steps to achieve a rapid ramping between the temperature steps for DNA denaturation, annealing and extension. The temperature dynamics within the microfluidic PCR chamber was characterized and the overshooting and undershooting parameters were optimized using the temperature-dependent fluorescence......We present a temperature control method capable of effectively shortening the thermal cycling time of polymerase chain reaction (PCR) in a disposable polymer microfluidic device with an external heater and a temperature sensor. The method employs optimized temperature overshooting and undershooting...

  11. Soliton scatterings by impurities in a short-length sine-Gordon chain

    International Nuclear Information System (INIS)

    Dikande, A.M.; Kofane, T.C.

    1995-07-01

    The scattering of soliton by impurities at the frontiers of a finite-length region of an infinite sine-Gordon chain is analyzed. The impurities consist of two isotopic inhomogeneities installed at the boundaries of the finite-length region. The soliton solution in the region is found in term of snoidal sine-Gordon soliton which properly takes into account the effects of the boundaries. By contrast, the soliton solutions in the neighboring sides of the region are obtained in terms of the so-called large-amplitude, localized kinks with limiting spatial extensions at x → ± ∞, which is equal ±π. Using the continuity of these soliton solutions at the frontiers as well as appropriate boundary conditions, it is shown that the soliton may be either i) reflected by the incident impurity; ii) trapped (with oscillating motions) between the two impurities (i.e. inside the infinite region); or iii) transmitted by the second impurity into the third, infinitely extended region. The threshold velocities for the reflection and transmission into different regions are found and shown to vary exponentially as a function of the length of the bounded region. The frequency of soliton oscillations between the impurities has also been calculated in some acceptable limit. (author). 28 refs, 1 fig

  12. In vitro batch fecal fermentation comparison of gas and short-chain fatty acid production using "slowly fermentable" dietary fibers.

    Science.gov (United States)

    Kaur, Amandeep; Rose, Devin J; Rumpagaporn, Pinthip; Patterson, John A; Hamaker, Bruce R

    2011-01-01

    Sustained colonic fermentation supplies beneficial fermentative by-products to the distal colon, which is particularly prone to intestinal ailments. Blunted/delayed initial fermentation may also lead to less bloating. Previously, we reported that starch-entrapped alginate-based microspheres act as a slowly fermenting dietary fiber. This material was used in the present study to provide a benchmark to compare to other "slowly fermentable" fibers. Dietary fibers with previous reports of slow fermentation, namely, long-chain inulin, psyllium, alkali-soluble corn bran arabinoxylan, and long-chain β-glucan, as well as starch-entrapped microspheres were subjected to in vitro upper gastrointestinal digestion and human fecal fermentation and measured over 48 h for pH, gas, and short-chain fatty acids (SCFA). The resistant fraction of cooked and cooled potato starch was used as another form of fermentable starch and fructooligosaccharides (FOS) served as a fast fermenting control. Corn bran arabinoxylan and long-chain β-glucan initially appeared slower fermenting with comparatively low gas and SCFA production, but later fermented rapidly with little remaining in the final half of the fermentation period. Long-chain inulin and psyllium had slow and moderate, but incomplete, fermentation. The resistant fraction of cooked and cooled potato starch fermented rapidly and appeared similar to FOS. In conclusion, compared to the benchmark slowly fermentable starch-entrapped microspheres, a number of the purported slowly fermentable fibers fermented fairly rapidly overall and, of this group, only the starch-entrapped microspheres appreciably fermented in the second half of the fermentation period. Consumption of dietary fibers, particularly commercial prebiotics, leads to uncomfortable feelings of bloating and flatulence due to their rapid degradation in our large intestine. This article employs claimed potential slowly fermenting fibers and compares their fermentation rates

  13. Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

    KAUST Repository

    Yiu, Alan T.; Beaujuge, Pierre; Lee, Olivia P.; Woo, Claire; Toney, Michael F.; Frechet, Jean

    2012-01-01

    The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells. © 2011 American Chemical Society.

  14. INVERSION SYMMETRY, ARCHITECTURE AND DISPERSITY, AND THEIR EFFECTS ON THERMODYNAMICS IN BULK AND CONFINED REGIONS: FROM RANDOMLY BRANCHED POLYMERS TO LINEAR CHAINS, STARS AND DENDRIMERS

    Directory of Open Access Journals (Sweden)

    P.D.Gujrati

    2002-01-01

    Full Text Available Theoretical evidence is presented in this review that architectural aspects can play an important role, not only in the bulk but also in confined geometries by using our recursive lattice theory, which is equally applicable to fixed architectures (regularly branched polymers, stars, dendrimers, brushes, linear chains, etc. and variable architectures, i.e. randomly branched structures. Linear chains possess an inversion symmetry (IS of a magnetic system (see text, whose presence or absence determines the bulk phase diagram. Fixed architectures possess the IS and yield a standard bulk phase diagram in which there exists a theta point at which two critical lines C and C' meet and the second virial coefficient A2 vanishes. The critical line C appears only for infinitely large polymers, and an order parameter is identified for this criticality. The critical line C' exists for polymers of all sizes and represents phase separation criticality. Variable architectures, which do not possess the IS, give rise to a topologically different phase diagram with no theta point in general. In confined regions next to surfaces, it is not the IS but branching and monodispersity, which becomes important in the surface regions. We show that branching plays no important role for polydisperse systems, but become important for monodisperse systems. Stars and linear chains behave differently near a surface.

  15. Side-chain tunability of furan-containing low-band-gap polymers provides control of structural order in efficient solar cells

    KAUST Repository

    Yiu, Alan T.

    2012-02-01

    The solution-processability of conjugated polymers in organic solvents has classically been achieved by modulating the size and branching of alkyl substituents appended to the backbone. However, these substituents impact structural order and charge transport properties in thin-film devices. As a result, a trade-off must be found between material solubility and insulating alkyl content. It was recently shown that the substitution of furan for thiophene in the backbone of the polymer PDPP2FT significantly improves polymer solubility, allowing for the use of shorter branched side chains while maintaining high device efficiency. In this report, we use PDPP2FT to demonstrate that linear alkyl side chains can be used to promote thin-film nanostructural order. In particular, linear side chains are shown to shorten π-π stacking distances between backbones and increase the correlation lengths of both π-π stacking and lamellar spacing, leading to a substantial increase in the efficiency of bulk heterojunction solar cells. © 2011 American Chemical Society.

  16. Synthesis, structure and optical limiting effect of a novel inorganic-organic hybrid polymer containing mixed chains of copper(I)/iodine

    International Nuclear Information System (INIS)

    Li Haohong; Chen Zhirong; Li Junqian; Zhan Hongbing; Zhang Wenxuan; Huang Changcang; Ma Cheng; Zhao Bin

    2006-01-01

    In this paper, treatment of N-ethyl-benzo[f]quinolium (ebq) iodide and CuI with excess KI afforded an unusual coordination polymer [(ebq) 2 (Cu 3 I 4 )(CuI 2 )] n (1). 1 crystallizes in tetragonal system, space group P4(2)bc with cell parameters of a=23.2040(6)A, c=6.7393(3)A, V=3628.6(2)A 3 , Z=8, D c =2.622g/c 3 , R 1 =0.0447 and wR 2 =0.0974. A highly interesting feature of 1 is its presence of mixed types of chains [(Cu 3 I 4 ) n - and (CuI 2 ) n - chain] in one crystal lattice based on supramolecular self-assembly directed by cations. The infinite chains (Cu 3 I 4 ) n - and (CuI 2 ) n - in 1 could be described as the edge-sharing arrangement of CuI 4 tetrahedron. Furthermore, IR, EA, UV-Vis, thermal analysis and optical limiting measurements were adopted to characterize polymer 1. The optical limiting experiment shows that the present polymer exhibits a large optical limiting capacity

  17. Beneficial effects on host energy metabolism of short-chain fatty acids and vitamins produced by commensal and probiotic bacteria.

    Science.gov (United States)

    LeBlanc, Jean Guy; Chain, Florian; Martín, Rebeca; Bermúdez-Humarán, Luis G; Courau, Stéphanie; Langella, Philippe

    2017-05-08

    The aim of this review is to summarize the effect in host energy metabolism of the production of B group vitamins and short chain fatty acids (SCFA) by commensal, food-grade and probiotic bacteria, which are also actors of the mammalian nutrition. The mechanisms of how these microbial end products, produced by these bacterial strains, act on energy metabolism will be discussed. We will show that these vitamins and SCFA producing bacteria could be used as tools to recover energy intakes by either optimizing ATP production from foods or by the fermentation of certain fibers in the gastrointestinal tract (GIT). Original data are also presented in this work where SCFA (acetate, butyrate and propionate) and B group vitamins (riboflavin, folate and thiamine) production was determined for selected probiotic bacteria.

  18. Microbial degradation of whole-grain complex carbohydrates and impact on short-chain fatty acids and health

    DEFF Research Database (Denmark)

    Knudsen, Knud Erik Bach

    2015-01-01

    Whole-grain cereals have a complex dietary fiber (DF) composition consisting of oligosaccharides (mostly fructans), resistant starch, and nonstarch polysaccharides (NSPs); the most important are arabinoxylans, mixed-linkage β(1,3; 1,4)-d-glucan (β-glucan), and cellulose and the noncarbohydrate...... to the intake of DF. The type and composition of cereal DF can consequently be used to modulate the microbial composition and activity as well as the production and molar ratios of short-chain fatty acids (SCFAs). Arabinoxylans and β-glucan in whole-grain cereals and cereal ingredients have been shown...... on the concentration in peripheral blood was less because the majority of propionate and butyrate is cleared in the liver. Active microbial fermentation with increased SCFA production reduced the exposure of potentially toxic compounds to the epithelium, potentially stimulating anorectic hormones and acting...

  19. Misfolding, degradation, and aggregation of variant proteins. The molecular pathogenesis of short chain acyl-CoA dehydrogenase (SCAD) deficiency

    DEFF Research Database (Denmark)

    Pedersen, Christina Bak; Bross, P.; Winter, V.S.

    2003-01-01

    and aggregation of variant SCAD proteins. In this study we investigated the processing of a set of disease-causing variant SCAD proteins (R22W, G68C, W153R, R359C, and Q341H) and two common variant proteins (R147W and G185S) that lead to reduced SCAD activity. All SCAD proteins, including the wild type, associate...... proteolytic degradation by mitochondrial proteases or, especially at elevated temperature, aggregation of non-native conformers. The latter finding may indicate that accumulation of aggregated SCAD proteins may play a role in the pathogenesis of SCAD deficiency.......Short chain acyl-CoA dehydrogenase (SCAD) deficiency is an inborn error of the mitochondrial fatty acid metabolism caused by rare variations as well as common susceptibility variations in the SCAD gene. Earlier studies have shown that a common variant SCAD protein (R147W) was impaired in folding...

  20. Uptake and metabolism of the short-chain fatty acid butyrate, a critical review of the literature.

    Science.gov (United States)

    Astbury, Stuart M; Corfe, Bernard M

    2012-07-01

    Butyrate is a short-chain fatty acid (SCFA) formed by bacterial fermentation of fibre in the colon, and serves as an energy source for colonocytes. The action of butyrate as a histone deacetylase inhibitor (HDACi) has led to a number of clinical trials testing its effectiveness as a potential treatment for cancer. The biology of butyrate transport is therefore relevant to both its physiological and pharmacological benefits. This review of the literature was carried out to assess the evidence for both the uptake and metabolism of butyrate, in an attempt to determine possible mechanism (s) by which butyrate can act as an HDACi. It is noted that although uptake and metabolism are well characterised, there are still significant gaps in the knowledgebase around the intracellular handing of butyrate, where assumptions or dated evidence are relied upon.

  1. Esterification of Fatty Acids with Short-Chain Alcohols over Commercial Acid Clays in a Semi-Continuous Reactor

    Directory of Open Access Journals (Sweden)

    Mohamed H. Frikha

    2009-11-01

    Full Text Available Production of fatty acid esters from stearic, oleic, and palmitic acids and short-chain alcohols (methanol, ethanol, propanol, and butanol for the production of biodiesel was investigated in this work. A series of montmorillonite-based clays catalysts (KSF, KSF/0, KP10, and K10 were used as acidic catalysts. The influence of the specific surface area and the acidity of the catalysts on the esterification rate were investigated. The best catalytic activities were obtained with KSF/0 catalyst. The esterification reaction has been carried out efficiently in a semi-continuous reactor at 150°C temperature higher than the boiling points of water and alcohol. The reactor used enabled the continuous removal of water and esterification with hydrated alcohol (ethanol 95% without affecting the original activity of the clay.

  2. Molecular structure stability of short-chain chlorinated paraffins (SCCPs): Evidence from lattice compatibility and Simha-Somcynsky theories

    Science.gov (United States)

    Yumak, A.; Boubaker, K.; Petkova, P.; Yahsi, U.

    2015-10-01

    In is known that short-chain chlorinated paraffins (SCCPs) are highly complex technical mixtures of polychlorinated n-alkanes with single chlorine content. Due to their physical properties (viscosity, flame resistance) they are used in many different applications, such as lubricant additives, metal processing, leather fat-liquoring, plastics softening, PVC plasticizing and flame retardants in paints, adhesives and sealants. SCCPs are studied here in terms of processing-linked molecular structure stability, under Simha and Somcynsky-EOS theory calculations and elements from Simha-Somcynsky-related Lattice Compatibility Theory. Analyses were carried out on 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro 2-methylane, and 2-chloro 2-methylane as (SCCPs) universal representatives. This paper gives evidence to this stability and reviews the current state of knowledge and highlights the need for further research in order to improve future (SCCPs) monitoring efforts.

  3. The emergence of sarcomeric, graded-polarity and spindle-like patterns in bundles of short cytoskeletal polymers and two opposite molecular motors

    International Nuclear Information System (INIS)

    Craig, E M; Dey, S; Mogilner, A

    2011-01-01

    We use linear stability analysis and numerical solutions of partial differential equations to investigate pattern formation in the one-dimensional system of short dynamic polymers and one (plus-end directed) or two (one is plus-end, another minus-end directed) molecular motors. If polymer sliding and motor gliding rates are slow and/or the polymer turnover rate is fast, then the polymer-motor bundle has mixed polarity and homogeneous motor distribution. However, if motor gliding is fast, a sarcomeric pattern with periodic bands of alternating polymer polarity separated by motor aggregates evolves. On the other hand, if polymer sliding is fast, a graded-polarity bundle with motors at the center emerges. In the presence of the second, minus-end directed motor, the sarcomeric pattern is more ubiquitous, while the graded-polarity pattern is destabilized. However, if the minus-end motor is weaker than the plus-end directed one, and/or polymer nucleation is autocatalytic, and/or long polymers are present in the bundle, then a spindle-like architecture with a sorted-out polarity emerges with the plus-end motors at the center and minus-end motors at the edges. We discuss modeling implications for actin-myosin fibers and in vitro and meiotic spindles.

  4. Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors

    KAUST Repository

    Nam, Sungho

    2018-03-23

    Three triple bond-conjugated naphthalene diimide (NDI) copolymers, poly{[N,N′-bis(2-R1)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-[(2,5-bis(2-R2)-1,4-phenylene)bis(ethyn-2,1-diyl)]} (PNDIR1-R2), were synthesized via Sonogashira coupling polymerization with varying alkyl side chains at the nitrogen atoms of the imide ring and 2,5-positions of the 1,4-diethynylbenzene moiety. Considering their identical polymer backbone structures, the side chains were found to have a strong influence on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO) chain at the 2,5-positions of 1,4-diethynylbenzene, P(NDIOD-HO), exhibited the highest electron mobility of 0.016 cm2 V–1 s–1, as compared to NDI-based copolymers with an ethylhexyl chain at the 2,5-positions of 1,4-diethynylbenzene. The enhanced charge mobility in the P(NDIOD-HO) layers is attributed to the well-aligned nano-fiber-like surface morphology and highly ordered packing structure with a dominant edge-on orientation, thus enabling efficient in-plane charge transport. Our results on the molecular structure–charge transport property relationship in these materials may provide an insight into novel design of n-type conjugated polymers for applications in the organic electronics of the future.

  5. Characterization of Lactobacillus salivarius alanine racemase: short-chain carboxylate-activation and the role of A131.

    Science.gov (United States)

    Kobayashi, Jyumpei; Yukimoto, Jotaro; Shimizu, Yasuhiro; Ohmori, Taketo; Suzuki, Hirokazu; Doi, Katsumi; Ohshima, Toshihisa

    2015-01-01

    Many strains of lactic acid bacteria produce high concentrations of d-amino acids. Among them, Lactobacillus salivarius UCC 118 produces d-alanine at a relative concentration much greater than 50 % of the total d, l-alanine (100d/d, l-alanine). We characterized the L. salivarius alanine racemase (ALR) likely responsible for this d-alanine production and found that the enzyme was activated by carboxylates, which is an unique characteristic among ALRs. In addition, alignment of the amino acid sequences of several ALRs revealed that A131 of L. salivarius ALR is likely involved in the activation. To confirm that finding, an L. salivarius ALR variant with an A131K (ALR(A131K)) substitution was prepared, and its properties were compared with those of ALR. The activity of ALR(A131K) was about three times greater than that of ALR. In addition, whereas L. salivarius ALR was strongly activated by low concentrations (e.g., 1 mM) of short chain carboxylates, and was inhibited at higher concentrations (e.g., 10 mM), ALR(A131K) was clearly inhibited at all carboxylate concentrations tested (1-40 mM). Acetate also increased the stability of ALR such that maximum activity was observed at 35 °C and pH 8.0 without acetate, but at 50 °C in the presence of 1 mM acetate. On the other hand, maximum ALR(A131K) activity was observed at 45 °C and around pH 9.0 with or without acetate. It thus appears that A131 mediates the activation and stabilization of L. salivarius ALR by short chain carboxylates.

  6. Effects of dietary inulin on bacterial growth, short-chain fatty acid production and hepatic lipid metabolism in gnotobiotic mice.

    Science.gov (United States)

    Weitkunat, Karolin; Schumann, Sara; Petzke, Klaus Jürgen; Blaut, Michael; Loh, Gunnar; Klaus, Susanne

    2015-09-01

    In literature, contradictory effects of dietary fibers and their fermentation products, short-chain fatty acids (SCFA), are described: On one hand, they increase satiety, but on the other hand, they provide additional energy and promote obesity development. We aimed to answer this paradox by investigating the effects of fermentable and non-fermentable fibers on obesity induced by high-fat diet in gnotobiotic C3H/HeOuJ mice colonized with a simplified human microbiota. Mice were fed a high-fat diet supplemented either with 10% cellulose (non-fermentable) or inulin (fermentable) for 6 weeks. Feeding the inulin diet resulted in an increased diet digestibility and reduced feces energy, compared to the cellulose diet with no differences in food intake, suggesting an increased intestinal energy extraction from inulin. However, we observed no increase in body fat/weight. The additional energy provided by the inulin diet led to an increased bacterial proliferation in this group. Supplementation of inulin resulted further in significantly elevated concentrations of total SCFA in cecum and portal vein plasma, with a reduced cecal acetate:propionate ratio. Hepatic expression of genes involved in lipogenesis (Fasn, Gpam) and fatty acid elongation/desaturation (Scd1, Elovl3, Elovl6, Elovl5, Fads1 and Fads2) were decreased in inulin-fed animals. Accordingly, plasma and liver phospholipid composition were changed between the different feeding groups. Concentrations of omega-3 and odd-chain fatty acids were increased in inulin-fed mice, whereas omega-6 fatty acids were reduced. Taken together, these data indicate that, during this short-term feeding, inulin has mainly positive effects on the lipid metabolism, which could cause beneficial effects during obesity development in long-term studies. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Differential effects of short chain fatty acids on endothelial Nlrp3 inflammasome activation and neointima formation: Antioxidant action of butyrate

    Directory of Open Access Journals (Sweden)

    Xinxu Yuan

    2018-06-01

    Full Text Available Short chain fatty acids (SCFAs, a family of gut microbial metabolites, have been reported to promote preservation of endothelial function and thereby exert anti-atherosclerotic action. However, the precise mechanism mediating this protective action of SCFAs remains unknown. The present study investigated the effects of SCFAs (acetate, propionate and butyrate on the activation of Nod-like receptor pyrin domain 3 (Nlrp3 inflammasome in endothelial cells (ECs and associated carotid neointima formation. Using a partial ligated carotid artery (PLCA mouse model fed with the Western diet (WD, we found that butyrate significantly decreased Nlrp3 inflammasome formation and activation in the carotid arterial wall of wild type mice (Asc+/+, which was comparable to the effect of gene deletion of the adaptor protein apoptosis-associated speck-like protein gene (Asc-/-. Nevertheless, both acetate and propionate markedly enhanced the formation and activation of the Nlrp3 inflammasome as well as carotid neointima formation in the carotid arteries with PLCA in Asc+/+, but not Asc-/- mice. In cultured ECs (EOMA cells, butyrate was found to significantly decrease the formation and activation of Nlrp3 inflammasomes induced by 7-ketocholesterol (7-Ket or cholesterol crystals (CHC, while acetate did not inhibit Nlrp3 inflammasome activation induced by either 7-Ket or CHC, but itself even activated Nlrp3 inflammsomes. Mechanistically, the inhibitory action of butyrate on the Nlrp3 inflammasome was attributed to a blockade of lipid raft redox signaling platforms to produce O2•- upon 7-Ket or CHC stimulations. These results indicate that SCFAs have differential effects on endothelial Nlrp3 inflammasome activation and associated carotid neointima formation. Keywords: Arterial endothelium, Short chain fatty acids, Inflammation, Neointima, Atherosclerosis

  8. Levels and distribution patterns of short chain chlorinated paraffins in sewage sludge of wastewater treatment plants in China

    International Nuclear Information System (INIS)

    Zeng Lixi; Wang Thanh; Ruan Ting; Liu Qian; Wang Yawei; Jiang Guibin

    2012-01-01

    Short chain chlorinated paraffins (SCCPs) are listed as persistent organic pollutant candidates in the Stockholm Convention and are receiving more and more attentions worldwide. In general, concentrations of contaminants in sewage sludge can give an important indication on their pollution levels at a local/regional basis. In this study, SCCPs were investigated in sewage sludge samples collected from 52 wastewater treatment plants in China. Concentrations of total SCCPs (ΣSCCPs) in sludge were in the range of 0.80–52.7 μg/g dry weight (dw), with a mean value of 10.7 μg/g dw. Most of SCCPs in the sludge samples showed a similar congener distribution patterns, and C 11 and Cl 7,8 were identified as the dominant carbon and chlorine congener groups. Significant linear relationships were found among different SCCP congener groups (r 2 ≥ 0.9). High concentrations of SCCPs in sewage sludge imply that SCCPs are widely present in China. - Highlights: ► Levels and distribution patterns of SCCPs were studied in sewage sludge in China. ► Concentrations of total SCCPs in sludge ranged from 0.8 to 52.7 μg/g dry weight. ► C 11 and Cl 7,8 were identified as the dominant congener groups within SCCPs. ► Significant linear relationships were found among SCCP congener groups (r 2 ≥ 0.9). ► SCCPs are present in household products and can be exposing to human. - High levels of short chain chlorinated paraffins in sewage sludge of wastewater treatment plants in China have been found.

  9. Butyrate and other short-chain fatty acids increase the rate of lipolysis in 3T3-L1 adipocytes

    Directory of Open Access Journals (Sweden)

    John M. Rumberger

    2014-10-01

    Full Text Available We determined the effect of butyrate and other short-chain fatty acids (SCFA on rates of lipolysis in 3T3-L1 adipocytes. Prolonged treatment with butyrate (5 mM increased the rate of lipolysis approximately 2–3-fold. Aminobutyric acid and acetate had little or no effect on lipolysis, however propionate stimulated lipolysis, suggesting that butyrate and propionate act through their shared activity as histone deacetylase (HDAC inhibitors. Consistent with this, the HDAC inhibitor trichostatin A (1 µM also stimulated lipolysis to a similar extent as did butyrate. Western blot data suggested that neither mitogen-activated protein kinase (MAPK activation nor perilipin down-regulation are necessary for SCFA-induced lipolysis. Stimulation of lipolysis with butyrate and trichostatin A was glucose-dependent. Changes in AMP-activated protein kinase (AMPK phosphorylation mediated by glucose were independent of changes in rates of lipolysis. The glycolytic inhibitor iodoacetate prevented both butyrate- and tumor necrosis factor-alpha-(TNF-α mediated increases in rates of lipolysis indicating glucose metabolism is required. However, unlike TNF-α– , butyrate-stimulated lipolysis was not associated with increased lactate release or inhibited by activation of pyruvate dehydrogenase (PDH with dichloroacetate. These data demonstrate an important relationship between lipolytic activity and reported HDAC inhibitory activity of butyrate, other short-chain fatty acids and trichostatin A. Given that HDAC inhibitors are presently being evaluated for the treatment of diabetes and other disorders, more work will be essential to determine if these effects on lipolysis are due to inhibition of HDAC.

  10. Quantification of fructans, galacto-oligosacharides and other short-chain carbohydrates in processed grains and cereals.

    Science.gov (United States)

    Biesiekierski, J R; Rosella, O; Rose, R; Liels, K; Barrett, J S; Shepherd, S J; Gibson, P R; Muir, J G

    2011-04-01

    Wholegrain grains and cereals contain a wide range of potentially protective factors that are relevant to gastrointestinal health. The prebiotics best studied are fructans [fructooligosaccharides (FOS), inulin] and galactooligosaccharides (GOS). These and other short-chain carbohydrates can also be poorly absorbed in the small intestine (named fermentable oligo-, di- and monosaccharides and polyols; FODMAPs) and may have important implications for the health of the gut. In the present study, FODMAPs, including fructose in excess of glucose, FOS (nystose, kestose), GOS (raffinose, stachyose) and sugar polyols (sorbitol, mannitol), were quantified using high-performance liquid chromatography with an evaporative light scattering detector. Total fructan was quantified using an enzymic hydrolysis method. Fifty-five commonly consumed grains, breakfast cereals, breads, pulses and biscuits were analysed. Total fructan were the most common short-chain carbohydrate present in cereal grain products and ranged (g per portion as eaten) from 1.12 g in couscous to 0 g in rice; 0.6 g in dark rye bread to 0.07 g in spelt bread; 0.96 g in wheat-free muesli to 0.11 g in oats; and 0.81 g in muesli fruit bar to 0.05 g in potato chips. Raffinose and stachyose were most common in pulses.   Composition tables including FODMAPs and prebiotics (FOS and GOS) that are naturally present in food will greatly assist research aimed at understanding their physiological role in the gut. © 2011 The Authors. Journal compilation © 2011 The British Dietetic Association Ltd.

  11. Dietary Cerebroside from Sea Cucumber (Stichopus japonicus): Absorption and Effects on Skin Barrier and Cecal Short-Chain Fatty Acids.

    Science.gov (United States)

    Duan, Jingjing; Ishida, Marina; Aida, Kazuhiko; Tsuduki, Tsuyoshi; Zhang, Jin; Manabe, Yuki; Hirata, Takashi; Sugawara, Tatsuya

    2016-09-21

    Sphingolipids from marine sources have attracted more attention recently because of their distinctive structures and expected functions. In this study, the content and components of cerebroside from sea cucumber Stichopus japonicus were analyzed. The absorption of cerebroside from S. japonicus was investigated with an in vivo lipid absorption assay. The result revealed that S. japonicus is a rich source of cerebroside that contained considerable amounts of odd carbon chain sphingoid bases. The cumulative recoveries of d17:1- and d19:2-containing cerebrosides were 0.31 ± 0.16 and 0.32 ± 0.10%, respectively, for 24 h after administration. To the best of the authors' knowledge, this is the first work that shows sphingolipids from a marine source could be absorbed in vivo and incorporated into ceramides. In addition, dietary supplementation with sea cucumber cerebroside to hairless mouse improved the skin barrier function and increased short-chain fatty acids in cecal contents, which have shown beneficial effects on the host.

  12. [Determination of short chain chlorinated paraffins in polyvinyl chloride plastics by gas chromatography-negative chemical ion/mass spectrometry].

    Science.gov (United States)

    Xing, Yuanna; Lin, Zhihui; Feng, Anhong; Wang, Xin; Gong, Yemeng; Chen, Zeyong

    2015-02-01

    A novel method was established to determine short chain chlorinated paraffins (SC-CPs) in polyvinyl chloride (PVC) plastics by gas chromatography-negative chemical ion/mass spectrometry (GC-NCI/MS). Ultrasonic extraction was used to extract SCCPs from PVC plastics. The optimal extraction time was 1.5 h, and concentrated sulfuric acid was adopted to purify the extracted solution. Finally, SCCPs in a sample were detected by GC-NCI/MS at 160 C and with methane reagent gas at 1. 5 mL/min. This method was not influenced by medium chain chlorinated paraffins (MCCPs) in the sample, and accurate quantitation was made for SCCPs. Twelve batches of samples were analyzed and SCCPs were detected in each batch with the contents from 0. 3 x 10(2)mg/kg to 3. 5 x 10(4)mg/kg. With respect to European limitation of SC-CPs (1%), four batches of samples did not comply with the European regulation, and they accounted for 33. 3%. Obviously, high SCCPs risk was presented in PVC plastics.

  13. Tracking Dietary Sources of Short- and Medium-Chain Chlorinated Paraffins in Marine Mammals through a Subtropical Marine Food Web.

    Science.gov (United States)

    Zeng, Lixi; Lam, James C W; Chen, Hui; Du, Bibai; Leung, Kenneth M Y; Lam, Paul K S

    2017-09-05

    Our previous study revealed an elevated accumulation of short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) in marine mammals from Hong Kong waters in the South China Sea. To examine the bioaccumulation potential and biomagnification in these apex predators, we sampled the dietary items of marine mammals and tracked the sources of SCCPs and MCCPs through a marine food web in this region. Sixteen fish species, seven crustacean species, and four mollusk species were collected, and the main prey species were identified for two species of marine mammals. Concentrations of ∑SCCPs and ∑MCCPs in these collected species suggested a moderate pollution level in Hong Kong waters compared to the global range. Lipid content was found to mediate congener-specific bioaccumulation in these marine species. Significantly positive correlations were observed between trophic levels and concentrations of ∑SCCPs or ∑MCCPs (p mammals was observed. This is the first report of dietary source tracking of SCCPs and MCCPs in marine mammals. The elevated biomagnification between prey and marine mammals raises environmental concerns about these contaminants.

  14. Short-chain analogs of luteinizing hormone-releasing hormone containing cytotoxic moieties.

    Science.gov (United States)

    Janáky, T; Juhász, A; Rékási, Z; Serfözö, P; Pinski, J; Bokser, L; Srkalovic, G; Milovanovic, S; Redding, T W; Halmos, G

    1992-11-01

    Five hexapeptide and heptapeptide analogs of luteinizing hormone-releasing hormone (LH-RH) were synthesized for use as carriers for cytotoxic compounds. These short analogs were expected to enhance target selectivity of the antineoplastic agents linked to them. Native LH-RH-(3-9) and LH-RH-(4-9) containing D-lysine and D-ornithine at position 6 were amidated with ethylamine and acylated on the N terminus. The receptor-binding affinity of one hexapeptide carrier AJ-41 (Ac-Ser-Tyr-D-Lys-Leu-Arg-Pro-NH-Et) to human breast cancer cell membranes was similar to that of [D-Trp6]LH-RH. Alkylating nitrogen mustards (melphalan, Ac-melphalan), anthraquinone derivatives including anticancer antibiotic doxorubicin, antimetabolite (methotrexate), and cisplatin-like platinum complex were linked to these peptides through their omega-amino group at position 6. The hybrid molecules showed no LH-RH agonistic activity in vitro and in vivo but had nontypical antagonistic effects on pituitary cells in vitro at the doses tested. These analogs showed a wide range of receptor-binding affinities to rat pituitaries and cell membranes of human breast cancer and rat Dunning prostate cancer. Several of these conjugates exerted some cytotoxic effects on MCF-7 breast cancer cell line.

  15. An anisotropic elasto-viscoplastic model for short-fiber reinforced polymers

    NARCIS (Netherlands)

    Amiri Rad, A.; Govaert, L.E.; van Dommelen, J.A.W.

    2017-01-01

    The influence of flow on the fiber orientation in injection molding of short-fiber composites leads to both anisotropy and inhomogeneity of the mechanical response. An anisotropic elasto-viscoplastic constitutive model is developed to capture the anisotropic and time-dependent behavior and

  16. An Anisotropic Elasto-Viscoplastic Model for Short-Fiber Reinforced Polymers

    NARCIS (Netherlands)

    Amiri Rad, A.; Govaert, L.E.; van Dommelen, J.A.W.

    2018-01-01

    The influence of flow on the fiber orientation in injection molding of short-fiber composites leads to both anisotropy and inhomogeneity of the mechanical response. An anisotropic elasto-viscoplastic constitutive model is developed to capture the anisotropic and time-dependent behavior and

  17. Thermal analysis studies of doping effects on the conformational motions of polymer chains in solid solutions with lasing molecules

    Science.gov (United States)

    Kalogeras, Ioannis M.; Pallikari, Fotini; Vassilikou-Dova, Aglaia; Neagu, Eugen R.

    2007-05-01

    The advancement of the solid-state dye laser performance largely depends on the systematic study of the dye-matrix interactions at the nanoscopic scale. The current work deals with blends of a comparatively inert dye host, poly(methyl methacrylate) (PMMA), with nonionic/apolar (substituted perylenes) and ionic/polar (rhodamine 6G, pyrromethene 567) dyes at ≈10-4 mol L-1 loading. Differential scanning calorimetry (DSC) and thermally stimulated currents (TSC) were used to explore the relative strength of inter- and intramolecular guest-host interactions by monitoring blending-induced modifications of the high-temperature signals: the segmental relaxation, the space-charge relaxation, and the liquid-liquid transition. Both techniques revealed the antiplasticizing role of the oligomeric organics on the relaxation dynamics of polymer segments, evidenced by clear glass-transition temperature upshifts. It becomes apparent that this effect is independent of the size, polarity, and ionicity of the dopant, signifying a common mechanism underway. It is suggested that, at least for the dyes under investigation, the chromophores simply fill the voids within the matrix, imposing strong steric hindrances on the rearrangement of the long-range structure. A comparison between the present results and earlier low-temperature dielectric data reveals that the large-scale relaxation dynamics show stronger perturbations due to blending, in comparison to the localized rotational motion of the pendant groups. DSC provided estimates for the unconverted monomer percentages in the solid blends. These were also determined more accurately by nuclear magnetic resonance (NMR), which additionally confirmed that the tacticity of the chains is not affected by the presence of the dye.

  18. A pilot, short-term dietary manipulation of branched chain amino acids has modest influence on fasting levels of branched chain amino acids.

    Science.gov (United States)

    Cavallaro, Nicole Landa; Garry, Jamie; Shi, Xu; Gerszten, Robert E; Anderson, Ellen J; Walford, Geoffrey A

    2016-01-01

    Elevated fasting levels of branched chain amino acids (BCAAs: valine, isoleucine, leucine) in venous blood are associated with a variety of metabolic impairments, including increased risk of type 2 diabetes (T2D). Fasting BCAA levels are influenced by non-dietary factors. However, it is unknown whether fasting BCAAs can be altered through manipulation of dietary intake alone. To test whether a specific dietary intervention, using differences in BCAA intake, alters fasting BCAA levels independent of other factors. Five healthy male volunteers underwent 4 days of a low and 4 days of a high BCAA content dietary intervention (ClinicalTrials.gov [NCT02110602]). All food and supplements were provided. Fasting BCAAs were measured from venous blood samples by mass spectrometry at baseline and after each intervention. Diets were isocaloric; contained equal percentages of calories from carbohydrate, fats, and protein; and differed from each other in BCAA content (1.5±0.1 vs. 14.0±0.6 g for valine; 4.5±0.9 g vs. 13.8±0.5 g for isoleucine; 2.1±0.2 g vs. 27.1±1.0 g for leucine; pBCAA content vs. the high BCAA content diet levels. The inter-individual response to the dietary interventions was variable and not explained by adherence. Short-term dietary manipulation of BCAA intake led to modest changes in fasting levels of BCAAs. The approach from our pilot study can be expanded to test the metabolic implications of dietary BCAA manipulation.

  19. A pilot, short-term dietary manipulation of branched chain amino acids has modest influence on fasting levels of branched chain amino acids

    Directory of Open Access Journals (Sweden)

    Nicole Landa Cavallaro

    2016-01-01

    Full Text Available Background: Elevated fasting levels of branched chain amino acids (BCAAs: valine, isoleucine, leucine in venous blood are associated with a variety of metabolic impairments, including increased risk of type 2 diabetes (T2D. Fasting BCAA levels are influenced by non-dietary factors. However, it is unknown whether fasting BCAAs can be altered through manipulation of dietary intake alone. Objective: To test whether a specific dietary intervention, using differences in BCAA intake, alters fasting BCAA levels independent of other factors. Design: Five healthy male volunteers underwent 4 days of a low and 4 days of a high BCAA content dietary intervention (ClinicalTrials.gov [NCT02110602]. All food and supplements were provided. Fasting BCAAs were measured from venous blood samples by mass spectrometry at baseline and after each intervention. Results: Diets were isocaloric; contained equal percentages of calories from carbohydrate, fats, and protein; and differed from each other in BCAA content (1.5±0.1 vs. 14.0±0.6 g for valine; 4.5±0.9 g vs. 13.8±0.5 g for isoleucine; 2.1±0.2 g vs. 27.1±1.0 g for leucine; p<0.0001 for all. Fasting valine was significantly lower (p=0.02 and fasting isoleucine and leucine were numerically lower following the low BCAA content vs. the high BCAA content diet levels. The inter-individual response to the dietary interventions was variable and not explained by adherence. Conclusion: Short-term dietary manipulation of BCAA intake led to modest changes in fasting levels of BCAAs. The approach from our pilot study can be expanded to test the metabolic implications of dietary BCAA manipulation.

  20. A viscoelastic-viscoplastic model for short-fibre reinforced polymers with complex fibre orientations

    Directory of Open Access Journals (Sweden)

    Nciri M.

    2015-01-01

    Full Text Available This paper presents an innovative approach for the modelling of viscous behaviour of short-fibre reinforced composites (SFRC with complex distributions of fibre orientations and for a wide range of strain rates. As an alternative to more complex homogenisation methods, the model is based on an additive decomposition of the state potential for the computation of composite’s macroscopic behaviour. Thus, the composite material is seen as the assembly of a matrix medium and several linear elastic fibre media. The division of short fibres into several families means that complex distributions of orientation or random orientation can be easily modelled. The matrix behaviour is strain-rate sensitive, i.e. viscoelastic and/or viscoplastic. Viscoelastic constitutive laws are based on a generalised linear Maxwell model and the modelling of the viscoplasticity is based on an overstress approach. The model is tested for the case of a polypropylene reinforced with short-glass fibres with distributed orientations and subjected to uniaxial tensile tests, in different loading directions and under different strain rates. Results demonstrate the efficiency of the model over a wide range of strain rates.

  1. Deformation and concentration fluctuations under stretching in a polymer network with free chains. The ``butterfly`` effect; Fluctuations de deformation et de concentration sous etirement dans un reseau polymere contenant des chaines libres. L`effet ``papillon``

    Energy Technology Data Exchange (ETDEWEB)

    Ramzi, A

    1994-06-01

    Small Angle Neutron Scattering gives access to concentration fluctuations of mobile labeled polymer chains embedded in a polymer network. At rest they appear progressively larger than for random mixing, with increasing ratio. Under uniaxial stretching, they decrease towards ideal mixing along the direction perpendicular to stretching, and can grow strongly along the parallel one, including the zero scattering vector q limit. This gives rise to intensity contours with double-winged patterns, in the shape of the figure `8`, or of `butterfly`. Random crosslinking and end-linking of monodisperse chains have both been studied. The strength of the `butterfly` effect increases with the molecular weight of the free chains, the crosslinking ratio, the network heterogeneity, and the elongation ratio. Eventually, the signal collapses on an `asymptotic` function I(q), of increasing correlation length with the elongation ratio. Deformation appears heterogeneous, maximal for soft areas, where the mobile chains localize preferentially. This could be due to spontaneous fluctuations, or linked to frozen fluctuations of the crosslink density. However, disagreement with the corresponding theoretical expressions makes it necessary to account for the spatial correlations of crosslink density, and their progressive unscreening as displayed by the asymptotic behavior. Networks containing pending labeled chains and free labeled stars lead to more precise understanding of the diffusion of free species and the heterogeneity of the deformation. It seems that the latter occurs even without diffusion for heterogeneous enough networks. In extreme cases (of the crosslinking parameters), the spatial correlations display on apparent fractal behavior, of dimensions 2 to 2.5, which is discussed here in terms of random clusters. 200 refs., 95 figs., 21 tabs., 10 appends.

  2. Four Novel Zn (II Coordination Polymers Based on 4′-Ferrocenyl-3,2′:6′,3′′-Terpyridine: Engineering a Switch from 1D Helical Polymer Chain to 2D Network by Coordination Anion Modulation

    Directory of Open Access Journals (Sweden)

    Lufei Xiao

    2017-11-01

    Full Text Available Four novel ZnII coordination polymers, [(ZnCl22(L2]n (1, [(ZnBr22(L2]n (2, and [(ZnI22(L2]n (3 and {[Zn(SCN2]1.5(L3}n (4, have been synthesized based on 4′-ferrocenyl-3,2′:6′,3′′-terpyridine with ZnII ions and different coordination anions under similar ambient conditions. Their structures have been confirmed using single crystal X-ray diffraction analysis, showing that complexes 1–3 are one-dimensional (1D double-stranded metal ion helical polymer chains and complex 4 is of a two-dimensional (2D network. The structural transformations of them from a 1D polymer chain to a 2D network under the influence of the coordination anions has been systematic investigated. Furthermore, the optical band gaps have been measured by optical diffuse reflectance spectroscopy, revealing that the ligand and the complexes should have semiconductor properties.

  3. Evaluating the environmental fate of short-chain chlorinated paraffins (SCCPs) in the Nordic environment using a dynamic multimedia model.

    Science.gov (United States)

    Krogseth, Ingjerd S; Breivik, Knut; Arnot, Jon A; Wania, Frank; Borgen, Anders R; Schlabach, Martin

    2013-12-01

    Short chain chlorinated paraffins (SCCPs) raise concerns due to their potential for persistence, bioaccumulation, long-range transport and adverse effects. An understanding of their environmental fate remains limited, partly due to the complexity of the mixture. The purpose of this study was to evaluate whether a mechanistic, integrated, dynamic environmental fate and bioaccumulation multimedia model (CoZMoMAN) can reconcile what is known about environmental emissions and human exposure of SCCPs in the Nordic environment. Realistic SCCP emission scenarios, resolved by formula group, were estimated and used to predict the composition and concentrations of SCCPs in the environment and the human food chain. Emissions at the upper end of the estimated range resulted in predicted total concentrations that were often within a factor of 6 of observations. Similar model performance for a complex group of organic contaminants as for the well-known polychlorinated biphenyls strengthens the confidence in the CoZMoMAN model and implies a relatively good mechanistic understanding of the environmental fate of SCCPs. However, the degree of chlorination predicted for SCCPs in sediments, fish, and humans was higher than observed and poorly established environmental half-lives and biotransformation rate constants contributed to the uncertainties in the predicted composition and ∑SCCP concentrations. Improving prediction of the SCCP composition will also require better constrained estimates of the composition of SCCP emissions. There is, however, also large uncertainty and lack of coherence in the existing observations, and better model-measurement agreement will require improved analytical methods and more strategic sampling. More measurements of SCCP levels and compositions in samples from background regions are particularly important.

  4. The Role of Short-Chain Fatty Acids, Produced by Anaerobic Bacteria, in the Cystic Fibrosis Airway.

    Science.gov (United States)

    Mirković, Bojana; Murray, Michelle A; Lavelle, Gillian M; Molloy, Kevin; Azim, Ahmed Abdul; Gunaratnam, Cedric; Healy, Fiona; Slattery, Dubhfeasa; McNally, Paul; Hatch, Joe; Wolfgang, Matthew; Tunney, Michael M; Muhlebach, Marianne S; Devery, Rosaleen; Greene, Catherine M; McElvaney, Noel G

    2015-12-01

    Anaerobic bacteria are present in large numbers in the airways of people with cystic fibrosis (PWCF). In the gut, anaerobes produce short-chain fatty acids (SCFAs) that modulate immune and inflammatory processes. To investigate the capacity of anaerobes to contribute to cystic fibrosis (CF) airway pathogenesis via SCFAs. Samples of 109 PWCF were processed using anaerobic microbiological culture with bacteria present identified by 16S RNA sequencing. SCFA levels in anaerobic supernatants and bronchoalveolar lavage (BAL) were determined by gas chromatography. The mRNA and/or protein expression of two SCFA receptors, GPR41 and GPR43, in CF and non-CF bronchial brushings and 16HBE14o(-) and CFBE41o(-) cells were evaluated using reverse transcription polymerase chain reaction, Western blot analysis, laser scanning cytometry, and confocal microscopy. SCFA-induced IL-8 secretion was monitored by ELISA. Fifty-seven (52.3%) of 109 PWCF were anaerobe positive. Prevalence increased with age, from 33.3% to 57.7% in PWCF younger (n = 24) and older (n = 85) than 6 years of age. All evaluated anaerobes produced millimolar concentrations of SCFAs, including acetic, propionic, and butyric acids. SCFA levels were higher in BAL samples of adults than in those of children. GPR41 levels were elevated in CFBE41o(-) versus 16HBE14o(-) cells; CF versus non-CF bronchial brushings; and 16HBE14o(-) cells after treatment with cystic fibrosis transmembrane conductance regulator inhibitor CFTR(inh)-172, CF BAL, or inducers of endoplasmic reticulum stress. SCFAs induced a dose-dependent and pertussis toxin-sensitive IL-8 response in bronchial epithelial cells, with a higher production of IL-8 in CFBE41o(-) than in 16HBE14o(-) cells. This study illustrates that SCFAs contribute to excessive production of IL-8 in CF airways colonized with anaerobes via up-regulated GPR41.

  5. Xenoestrogenic short ethoxy chain nonylphenol is oxidized by a flavoprotein alcohol dehydrogenase from Ensifer sp. strain AS08.

    Science.gov (United States)

    Liu, Xin; Tani, Akio; Kimbara, Kazuhide; Kawai, Fusako

    2007-01-01

    The ethoxy chains of short ethoxy chain nonylphenol (NPEO(av2.0), containing average 2.0 ethoxy units) were dehydrogenated by cell-free extracts from Ensifer sp. strain AS08 grown on a basal medium supplemented with NPEO(av2.0). The reaction was coupled with the reduction in 3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide and phenazine methosulfate. The enzyme (NPEO(av2.0) dehydrogenase; NPEO-DH) was purified to homogeneity with a yield of 20% and a 56-fold increase in specific activity. The molecular mass of the native enzyme was 120 kDa, consisting of two identical monomer units (60 kDa). The gene encoding NPEO-DH was cloned, which consisted of 1,659 bp, corresponding to a protein of 553 amino acid residues. The deduced amino acid sequence agreed with the N-terminal amino acid sequence of the purified NPEO-DH. The presence of a flavin adenine dinucleotide (FAD)-binding motif and glucose-methanol-choline (GMC) oxidoreductase signature motifs strongly suggested that the enzyme belongs to the GMC oxidoreductase family. The protein exhibited homology (40-45% identity) with several polyethylene glycol dehydrogenases (PEG-DHs) of this family, but the identity was lower than those (approximately 58%) among known PEG-DHs. The substrate-binding domain was more hydrophobic compared with those of glucose oxidase and PEG-DHs. The recombinant protein had the same molecular mass as the purified NPEO-DH and dehydrogenated PEG400-2000, NPEO(av2.0) and its components, and NPEOav10, but only slight or no activity was found using diethylene glycol, triethylene glycol, and PEG200.

  6. Microbiota-Derived Short-Chain Fatty Acids Modulate Expression of Campylobacter jejuni Determinants Required for Commensalism and Virulence.

    Science.gov (United States)

    Luethy, Paul M; Huynh, Steven; Ribardo, Deborah A; Winter, Sebastian E; Parker, Craig T; Hendrixson, David R

    2017-05-09

    Campylobacter jejuni promotes commensalism in the intestinal tracts of avian hosts and diarrheal disease in humans, yet components of intestinal environments recognized as spatial cues specific for different intestinal regions by the bacterium to initiate interactions in either host are mostly unknown. By analyzing a C. jejuni acetogenesis mutant defective in converting acetyl coenzyme A (Ac-CoA) to acetate and commensal colonization of young chicks, we discovered evidence for in vivo microbiota-derived short-chain fatty acids (SCFAs) and organic acids as cues recognized by C. jejuni that modulate expression of determinants required for commensalism. We identified a set of C. jejuni genes encoding catabolic enzymes and transport systems for amino acids required for in vivo growth whose expression was modulated by SCFAs. Transcription of these genes was reduced in the acetogenesis mutant but was restored upon supplementation with physiological concentrations of the SCFAs acetate and butyrate present in the lower intestinal tracts of avian and human hosts. Conversely, the organic acid lactate, which is abundant in the upper intestinal tract where C. jejuni colonizes less efficiently, reduced expression of these genes. We propose that microbiota-generated SCFAs and lactate are cues for C. jejuni to discriminate between different intestinal regions. Spatial gradients of these metabolites likely allow C. jejuni to locate preferred niches in the lower intestinal tract and induce expression of factors required for intestinal growth and commensal colonization. Our findings provide insights into the types of cues C. jejuni monitors in the avian host for commensalism and likely in humans to promote diarrheal disease. IMPORTANCE Campylobacter jejuni is a commensal of the intestinal tracts of avian species and other animals and a leading cause of diarrheal disease in humans. The types of cues sensed by C. jejuni to influence responses to promote commensalism or

  7. Linear side chains in benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c] pyrrole-4,6-dione polymers direct self-assembly and solar cell performance

    KAUST Repository

    Cabanetos, Clement; El Labban, Abdulrahman; Bartelt, Jonathan A.; Douglas, Jessica D.; Mateker, William R.; Frechet, Jean; McGehee, Michael D.; Beaujuge, Pierre

    2013-01-01

    role that linear side-chain substituents play in poly(benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers for bulk heterojunction (BHJ) solar cell applications. We show that replacing branched side chains by linear ones

  8. Polymer Brush Grafted Nanoparticles and Their Impact on the Morphology Evolution of Polymer Blend Films

    Science.gov (United States)

    Chung, Hyun-Joong; Ohno, Kohji; Composto, Russell

    2013-03-01

    We present an novel pathway to control the location of nanoparticles (NPs) in phase-separating polymer blend films containing poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN). Because hydrophobic polymer phases have a small interfacial energy, ~1 mJ/m2, subtle changes in the NP surface functionality can be used to guide NPs to either the interface between immiscible polymers or into one of the phases. Based on this idea, we designed a class of NPs grafted with PMMA brushes. These PMMA brushes were grown from the NP surface by atom transfer radical polymerization (ATRP), which results in chains terminated with chlorine atoms. The chain end can be substituted with protons (H) by dehalogenation. As a result, the NPs are strongly segregated at the interface when grafted PMMA chains are short (Mn =1.8K) and the end group is Cl, whereas NPs partition into PMMA-rich phase when chains are long (Mn =160K) and/or when chains are terminated with hydrogen. The Cl end groups and shorter chain length cause an increase in surface energy for the NPs. The increase in surface energy of short-chained NPs can be attributed to (i) an extended brush conformation (entropic) and/or (ii) a high density of ``unfavorable'' end groups (enthalpic). Finally, the impact of NPs on the morphological evolution of the polymer blend films will be discussed. Ref: H.-J.Chung et al., ACS Macro Lett. 1(1), 252-256 (2012).

  9. Atomistic simulation of graphene-based polymer nanocomposites

    International Nuclear Information System (INIS)

    Rissanou, Anastassia N.; Bačová, Petra; Harmandaris, Vagelis

    2016-01-01

    Polymer/graphene nanostructured systems are hybrid materials which have attracted great attention the last years both for scientific and technological reasons. In the present work atomistic Molecular Dynamics simulations are performed for the study of graphene-based polymer nanocomposites composed of pristine, hydrogenated and carboxylated graphene sheets dispersed in polar (PEO) and nonpolar (PE) short polymer matrices (i.e., matrices containing chains of low molecular weight). Our focus is twofold; the one is the study of the structural and dynamical properties of short polymer chains and the way that they are affected by functionalized graphene sheets while the other is the effect of the polymer matrices on the behavior of graphene sheets.

  10. Influence of the strength of the smectic order on the backbone anisotropy of side-chain liquid crystal polymers as revealed by SANS

    Science.gov (United States)

    Noirez, L.; Keller, P.; Cotton, J. P.

    1992-06-01

    It is proposed that the strength of the smectic order determines the backbone anisotropy of side-chain liquid crystal polymers. Here this strength increases with the length of the alkyl terminal group of the mesogens. Two liquid crystal polymethacrylates differing only by the mesogenic tails —OCH3 and —OC4H9 are considered. The backbone anisotropy of these polymers is measured by small angle neutron scattering (SANS) whereas the smectic order is evaluated from the intensity of the 001 Bragg peak. Il est proposé que la qualité de l'ordre smectique détermine l'anisotropie du squelette de polymères mésomorphes en peigne confinés dans les lamelles. Ici l'ordre smectique est augmenté en allongeant le groupe alkyl terminal des mésogènes. Nous étudions deux polyméthacrylates cristal liquide qui ne différent que par leurs groupes terminaux : —OCH3 et —OC4H9. L'anisotropie du squellete est mesurée par diffusion de neutrons aux petits angles tandis que l'ordre smectique est évalué à l'aide de l'intensité du pic de Bragg 001.

  11. Short-chain Acyl-CoA dehydrogenase deficiency: studies in a large family adding to the complexity of the disorder

    NARCIS (Netherlands)

    Bok, Levinus A.; Vreken, Peter; Wijburg, Frits A.; Wanders, Ronald J. A.; Gregersen, Niels; Corydon, Morten J.; Waterham, Hans R.; Duran, Marinus

    2003-01-01

    OBJECTIVE: To understand the expanding clinical and biochemical spectrum of short-chain acyl-CoA dehydrogenase (SCAD) deficiency, the impact of which is not fully understood. STUDY DESIGN: We studied a family with SCAD deficiency and determined urinary ethylmalonic acid excretion, plasma

  12. Protection against the Metabolic Syndrome by Guar Gum-Derived Short-Chain Fatty Acids Depends on Peroxisome Proliferator-Activated Receptor. and Glucagon-Like Peptide-1

    NARCIS (Netherlands)

    den Besten, Gijs; Gerding, Albert; van Dijk, Theo H.; Ciapaite, Jolita; Bleeker, Aycha; van Eunen, Karen; Havinga, Rick; Groen, Albert K.; Reijngoud, Dirk-Jan; Bakker, Barbara M.

    2015-01-01

    The dietary fiber guar gum has beneficial effects on obesity, hyperglycemia and hypercholesterolemia in both humans and rodents. The major products of colonic fermentation of dietary fiber, the short-chain fatty acids (SCFAs), have been suggested to play an important role. Recently, we showed that

  13. Cost and time models for the evaluation of intermodal chains by using short sea shipping in the North Sea Region: the Rosyth-Zeebrugge route

    DEFF Research Database (Denmark)

    Lopez, Alba Martínez; Kronbak, Jacob; Jiang, Liping

    2015-01-01

    This paper is framed in the context of the EU Interreg IVB North Sea Region project Food Port. In line with this project, this paper aims to define mathematically cost and time models able to provide realistic information about the performances of road haulage and of intermodal chains using short...

  14. Effect of acute exposure to ergot alkaloids on short-chain fatty acid absorption and barrier function of isolated bovine ruminal epithelium

    Science.gov (United States)

    Ergot alkaloids present in endophyte-infected tall fescue are the causative agents for fescue toxicosis in cattle. Ergot alkaloids have been shown to cause a reduction in blood flow to the rumen epithelium as well as a decrease in short-chain fatty acid (SCFA) absorption from the washed rumen of ste...

  15. Different effects of short- and long-chained fructans on large intestinal physiology and carcinogen-induced aberrant crypt foci in rats

    DEFF Research Database (Denmark)

    Poulsen, Morten; Molck, Anne-Marie; Jacobsen, Bodil Lund

    2002-01-01

    Inulin-type fructans, which are nondigestible carbohydrates, have been shown to modulate the number of induced preneoplastic lesions in the colon as well as the colonic microflora in laboratory animals. The present study was designed to investigate the effect of a short- and long-chained inulin...

  16. Flavin Adenine Dinucleotide Status and the Effects of High-Dose Riboflavin Treatment in Short-Chain Acyl-CoA Dehydrogenase Deficiency

    NARCIS (Netherlands)

    van Maldegem, Bianca T.; Duran, Marinus; Wanders, Ronald J. A.; Waterham, Hans R.; Wijburg, Frits A.

    2010-01-01

    Short-chain acyl-CoA dehydrogenase deficiency (SCADD) is an inborn error, biochemically characterized by increased plasma butyrylcarnitine (C4-C) concentration and increased ethylmalonic acid (EMA) excretion and caused by rare mutations and/or common gene variants in the SCAD encoding gene. Although

  17. Application of liquid chromatography-mass spectrometry to measure the concentrations and study the synthesis of short chain fatty acids following stable isotope infusions

    NARCIS (Netherlands)

    Meesters, R.J.W.; Eijk, H.M.H. van; Have, G.A.M. ten; Graaf, A.A. de; Venema, K.; Rossum, B.E.J. van; Deutz, N.E.P.

    2007-01-01

    A new method involving zinc sulphate deproteinization was developed to study short chain fatty acids (SCFA) production in the colon and subsequent occurrence of SCFA in blood. SCFA were baseline separated in a 30 min cycle using ion-exclusion chromatography and detected by mass spectrometry.

  18. Lethal neonatal case and review of primary short-chain enoyl-CoA hydratase (SCEH) deficiency associated with secondary lymphocyte pyruvate dehydrogenase complex (PDC) deficiency

    NARCIS (Netherlands)

    Bedoyan, Jirair K.; Yang, Samuel P.; Ferdinandusse, Sacha; Jack, Rhona M.; Miron, Alexander; Grahame, George; DeBrosse, Suzanne D.; Hoppel, Charles L.; Kerr, Douglas S.; Wanders, Ronald J. A.

    2017-01-01

    Mutations in ECHS1 result in short-chain enoyl-CoA hydratase (SCEH) deficiency which mainly affects the catabolism of various amino acids, particularly valine. We describe a case compound heterozygous for ECHS1 mutations c.836T>C (novel) and c.8C>A identified by whole exome sequencing of proband and

  19. Comprehensive in Vitro Analysis of Acyltransferase Domain Exchanges in Modular Polyketide Synthases and Its Application for Short-Chain Ketone Production

    DEFF Research Database (Denmark)

    Yuzawa, Satoshi; Deng, Kai; Wang, George

    2017-01-01

    AT domain replacements in most type I PKS modules. To further demonstrate the utility of the optimized AT domain boundary, we have constructed hybrid PKSs to produce industrially important short-chain ketones. Our in vitro and in vivo analysis demonstrated production of predicted ketones without significant...

  20. Short-chain fatty acids production and microbial community in sludge alkaline fermentation: Long-term effect of temperature.

    Science.gov (United States)

    Yuan, Yue; Liu, Ye; Li, Baikun; Wang, Bo; Wang, Shuying; Peng, Yongzhen

    2016-07-01

    Sludge alkaline fermentation has been reported to achieve efficient short-chain fatty acids (SCFAs) production. Temperature played important role in further improved SCFAs production. Long-term SCFAs production from sludge alkaline fermentation was compared between mesotherm (30±2°C) and microtherm (15±2°C). The study of 90days showed that mesotherm led to 2.2-folds production of SCFAs as microtherm and enhanced the production of acetic acid as major component of SCFAs. Soluble protein and carbohydrate at mesotherm was 2.63-folds as that at microtherm due to higher activities of protease and α-glucosidase, guaranteeing efficient substrates to produce SCFAs. Illumina MiSeq sequencing revealed that microtherm increased the abundance of Corynebacterium, Alkaliflexus, Pseudomonas and Guggenheimella, capable of enhancing hydrolysis. Hydrolytic bacteria, i.e. Alcaligenes, Anaerolinea and Ottowia, were enriched at mesotherm. Meanwhile, acidogenic bacteria showed higher abundance at mesotherm than microtherm. Therefore, enrichment of functional bacteria and higher microbial activities resulted in the improved SCFAs at mesotherm. Copyright © 2016 Elsevier Ltd. All rights reserved.