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Sample records for a2b copolymer melts

  1. Melt structure and self-nucleation of ethylene copolymers

    NASA Astrophysics Data System (ADS)

    Alamo, Rufina G.

    A strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. These studies have been carried out by DSC, x-ray, TEM and optical microscopy on a large number of model, narrow, and broad copolymers with different comonomer types and contents. Melt memory is correlated with self-seeds that increase the crystallization rate of ethylene copolymers. The seeds are associated with molten ethylene sequences from the initial crystals that remain in close proximity and lower the nucleation barrier. Diffusion of all sequences to a randomized melt state is a slow process, restricted by topological chain constraints (loops, knots, and other entanglements) that build in the intercrystalline region during crystallization. Self-seeds dissolve above a critical melt temperature that demarcates homogeneity of the copolymer melt. There is a critical threshold level of crystallinity to observe the effect of melt memory on crystallization rate, thus supporting the correlation between melt memory and the change in melt structure during copolymer crystallization. Unlike binary blends, commercial ethylene-1-alkene copolymers with a range in inter-chain comonomer composition between 1 and about 15 mol % display an inversion of the crystallization rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. With decreasing the initial melt temperature, broadly distributed copolymers show enhanced crystallization followed by a decrease of crystallization rate. The inversion demarcates the onset of liquid-liquid phase separation (LLPS) and a reduction of self-nuclei due to the strong thermodynamic drive for molecular segregation inside the binodal. The strong effect of melt memory on crystallization rate can be used to identify liquid-liquid phase separation in broadly distributed copolymers, and offers strategies to control the state of copolymer melts in ways of

  2. On the Melting Behavior of Ethylene/alpha-olefin Copolymers

    NASA Astrophysics Data System (ADS)

    Marand, Herve; Alizadeh, Azar; Subramaniam, Chitra; Richardson, Ley

    1998-03-01

    The melting behavior of ethylene/a-olefin copolymers of well controlled microstructure and narrow molecular weight distribution will be discussed. Specifically, we will report results of investigations of the effect of crystallization temperature and time on the multiple melting behavior of ethylene copolymers of various contents in butene, pentene, hexene and octene comonomers. More importantly, it will be shown that the location of the low endotherm is independent of previous thermal history and initial degree of crystallinity at the beginning of the crystallization/annealing process which leads to that endotherm. The low endotherm is furthermore independent of the copolymer composition as long as the crystallization process leads to a fringed micellar crystal morphology. Implications of these new results and comparison of the effect of the nature of the short chain branches on the evolution of the melting behavior with crystallization time provides new venues to the understanding of the multiple endothermic behavior of semicrystalline polymers in general.

  3. Universality between Experiment and Simulation of a Diblock Copolymer Melt.

    PubMed

    Beardsley, Thomas M; Matsen, Mark W

    2016-11-18

    The equivalent behavior among analogous block copolymer systems involving chemically distinct molecules or mathematically different models has long hinted at an underlying universality, but only recently has it been rigorously demonstrated by matching results from different simulations. The profound implication of universality is that simple coarse-grained models can be calibrated so as to provide quantitatively accurate predictions to experiment. Here, we provide the first compelling demonstration of this by simulating a polyisoprene-polylactide diblock copolymer melt using a previously calibrated lattice model. The simulation successfully predicts the peak in the disordered-state structure function, the position of the order-disorder transition, and the latent heat of the transition in excellent quantitative agreement with experiment. This could mark a new era of precision in the field of block copolymer research.

  4. Universality between Experiment and Simulation of a Diblock Copolymer Melt

    NASA Astrophysics Data System (ADS)

    Beardsley, Thomas M.; Matsen, Mark W.

    2016-11-01

    The equivalent behavior among analogous block copolymer systems involving chemically distinct molecules or mathematically different models has long hinted at an underlying universality, but only recently has it been rigorously demonstrated by matching results from different simulations. The profound implication of universality is that simple coarse-grained models can be calibrated so as to provide quantitatively accurate predictions to experiment. Here, we provide the first compelling demonstration of this by simulating a polyisoprene-polylactide diblock copolymer melt using a previously calibrated lattice model. The simulation successfully predicts the peak in the disordered-state structure function, the position of the order-disorder transition, and the latent heat of the transition in excellent quantitative agreement with experiment. This could mark a new era of precision in the field of block copolymer research.

  5. Linear elasticity and phase behavior of block copolymer melts by self consistent field theory

    NASA Astrophysics Data System (ADS)

    Tyler, Christopher Austin

    Self Consistent Field Theory (SCFT) is a well established theory for describing the thermodynamics of block copolymer melts and blends. Although the theory is approximate, it has been quite successful in describing the phase behavior of diblock copolymers. We have applied SCFT to study the linear elastic behavior and the phase behavior of block copolymer melts. First, we calculate the linear elastic response of block copolymer melts ordered on a cubic lattice, with either body-centered or gyroid symmetry. We compare our results to experiments. A large, low-frequency plateau in the elastic storage modulus, corresponding to approximately 0.2kT per polymer chain, has been experimentally observed. By calculating the free energy of block copolymer melts on deformed lattices, we find that SOFT correctly predicts the elastic behavior of these three-dimensionally-ordered structures. We also investigate the phase behavior of triblock copolymer melts. Recent experimental work has identified a new, non-cubic, three-dimensional network phase, termed the O70 phase, in ABC triblock copolymers. We investigate the phase behavior of ABC triblock copolymer melts by calculating the free energy of several candidate phases, including the O70 phase. We find that O 70 is an equilibrium structure in triblock copolymer melts and that the SCFT and experimentally observed phase boundaries agree qualitatively. We also find that O70 is an equilibrium phase in diblock copolymer melts.

  6. Dynamics of a diblock copolymer melt studied via XPCS

    NASA Astrophysics Data System (ADS)

    Mochrie, Simon; Falus, Peter

    2003-03-01

    Measurements will be presented of the equilibrium dynamics of an entangled, asymmetric, PS-PDMS diblock copolymer melt. Specifically, the emerging technique of x-ray photon correlation spectroscopy (XPCS), employing beamline 8-ID of the Advanced Photon Source and a new fast CCD-based x-ray detector, was used to characterize the sample relaxation times for wavevectors spanning the peak of the diblock static structure factor. The results will be compared to available theory. (This work was supported by the NSF via DMR 0071755.)

  7. Lamellae orientation in dynamically sheared diblock copolymer melts

    NASA Astrophysics Data System (ADS)

    Koppi, Kurt A.; Tirrell, Matthew; Bates, Frank S.; Almdal, Kristoffer; Colby, Ralph H.

    1992-11-01

    Two distinct lamellae orientaitons have been identified by small-angle neutron scattering (SANS) in dynamically sheared poly(ethylene-propylene)-poly(ethylethylene) (PEP-PEE) diblock copolymer melts. Near the order-disorder transition temperature, Tto T_ODT, and at low shear frequencies, the lamellae arrange with unit normal perpendicular to the flow direction and parallel to the velocity gradient direction (parallel orientation). Higher frequency processing leads to lamellae with unit normal permendicular to both the flow and velocity gradient directions (perpendicular orientation). The crossover from low to high frequency behavior occurs at ω≈tau^{-1} where tau is the relaxation time for local domain deformations. At temperatures further from the ODT, T<copolymers. Nous avons identifié, par diffusion de neutrons aux petits angles, deux orientation différentes des lamelles dans des échantillons de copolymères séquencés poly(éthylène-propylène)- poly(éthylétylène) (PEP-PEE) qui ont été cisaillés dynamiquement. A des températures proches de la transition ordre-désordre et aux fréquences de cisaillement faibles, la normale aux couches est perpendiculaire à la direction d'écoulement et parallèle au gradient de vitesse (orientation parllèle). Aux fréquences plus élevées, la normale est perpendiculaire à la direction d'écoulement et au gradient de vitesse (orientation perpendiculaire). Le

  8. Molecular Simulation of Bicontinuous Phases in Diblock Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Martinez-Veracoechea, Francisco; Escobedo, Fernando

    2008-03-01

    Molecular simulations are used to study the stabilization of different bicontinuous phases in diblock copolymer (DBC) melts. The stabilization approach entails attempting to reduce the packing frustration inside the bicontinuous phases nodes by the addition of a ``filler'' with affinity for the A component. Two different strategies are considered: 1) addition of selective-solvent particles, and 2) addition of homopolymer. Approximate phase boundaries were found via free-energy calculations. A very dissimilar phase behavior is observed upon increasing the amount of the ``additive'' in the two different strategies. While with the first strategy (i.e., addition of selective solvent) we observed the progression Gyroid (G) -> Perforated Lamella -> Lamella -> Reversed-Gyroid. With the second strategy (i.e., addition of homopolymer) we observed the progression of morphologies G -> Cylinder -> Double Diamond (DD) -> Plumber's Nightmare (P). In both the DD and the P phases, the homopolymer concentrates preferentially in the nodes, suggesting the reduction of the nodes' packing frustration. In addition, a novel morphology was observed, wherein cylinders of two different diameters alternate in a tetragonal packing. The contrasting difference in the phase behavior observed for the two strategies is understood as a consequence of the difference in mixing entropy exhibited by the two additives.

  9. Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts

    SciTech Connect

    Banerjee, Debapriya; Schweizer, Kenneth S.

    2015-06-04

    The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non-microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials-of-mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption-strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degree of dispersion also depends strongly on nanoparticle diameter relative to the block contour length. Small particles in copolymers with longer block lengths experience a more homopolymer-like environment which renders them relatively insensitive to copolymer chemical heterogeneity and hinders dispersion. Larger particles (sufficiently larger than the monomer diameter) in copolymers of relatively short block lengths provide better dispersion than either a homopolymer or random copolymer. The theory also predicts a novel widening of the miscibility window for large particles upon increasing the overall molecular weight of copolymers composed of relatively long blocks. The influence of a positive chi-parameter in the pure copolymer melt is briefly studied. Quantitative application to fullerenes in specific copolymers of experimental interest is performed, and miscibility predictions are made.

  10. Dodecagonal quasicrystalline order in a diblock copolymer melt

    PubMed Central

    Gillard, Timothy M.; Lee, Sangwoo; Bates, Frank S.

    2016-01-01

    We report the discovery of a dodecagonal quasicrystalline state (DDQC) in a sphere (micelle) forming poly(isoprene-b-lactide) (IL) diblock copolymer melt, investigated as a function of time following rapid cooling from above the order–disorder transition temperature (TODT = 66 °C) using small-angle X-ray scattering (SAXS) measurements. Between TODT and the order–order transition temperature TOOT = 42 °C, an equilibrium body-centered cubic (BCC) structure forms, whereas below TOOT the Frank–Kasper σ phase is the stable morphology. At T < 40 °C the supercooled disordered state evolves into a metastable DDQC that transforms with time to the σ phase. The times required to form the DDQC and σ phases are strongly temperature dependent, requiring several hours and about 2 d at 35 °C and more than 10 and 200 d at 25 °C, respectively. Remarkably, the DDQC forms only from the supercooled disordered state, whereas the σ phase grows directly when the BCC phase is cooled below TOOT and vice versa upon heating. A transition in the rapidly supercooled disordered material, from an ergodic liquid-like arrangement of particles to a nonergodic soft glassy-like solid, occurs below ∼40 °C, coincident with the temperature associated with the formation of the DDQC. We speculate that this stiffening reflects the development of particle clusters with local tetrahedral or icosahedral symmetry that seed growth of the temporally transient DDQC state. This work highlights extraordinary opportunities to uncover the origins and stability of aperiodic order in condensed matter using model block polymers. PMID:27118844

  11. Investigation of Universal Behavior in Symmetric Diblock Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Medapuram, Pavani

    Coarse-grained theories of dense polymer liquids such as block copolymer melts predict a universal dependence of equilibrium properties on a few dimensionless parameters. For symmetric diblock copolymer melts, such theories predict a universal dependence on only chieN and N¯, where chie is an effective interaction parameter, N is the degree of polymerization, and N¯ is a measure of overlap. This thesis focuses on testing the universal behavior hypothesis by comparing results for various properties obtained from different coarse-grained simulation models to each other. Specifically, results from pairs of simulations of different models that have been designed to have matched values of N¯ are compared over a range of values of chiN. The use of vastly different simulation models allows us to cover a vast range of chi eN ≃ 200 - 8000 that includes most of the experimentally relevant range. Properties studied here include collective and single-chain correlations in the disordered phase, block and chain radii of gyration in the disordered phase, the value of chieN at the order-disorder transition (ODT), the free energy per chain, the latent heat of transition, the layer spacing, the composition profile, and compression modulus in the ordered phase. All results strongly support the universal scaling hypothesis, even for rather short chains, confirming that it is indeed possible to give an accurate universal description of simulation models that differ in many details. The underlying universality becomes apparent, however, only if data are analyzed using an adequate estimate of chie, which we obtained by fitting the structure factor S( q) in the disordered state to predictions of the recently developed renormalized one-loop (ROL) theory. The ROL theory is shown to provide an excellent description of the dependence of S(q on chain length and thermodynamic conditions for all models, even for very short chains, if we allow for the existence of a nonlinear dependence of

  12. Synthesis and characterization of A2B Miktoarm Star Copolymers Composed of Regioregular Poly(3-hexylthiophene) and Poly(methyl methacrylate) containing rigid core

    NASA Astrophysics Data System (ADS)

    Park, Jicheol; Moon, Hong Chul; Kim, Jin Kon

    2014-03-01

    The π- π interaction between P3HT arms in Miktoarm star copolymer composed of P3HT and PMMA ((P3HT)2PMMA) was strong enough to arrange two P3HT backbone chains in (P3HT)2PMMA to stack one by one along the nanofibril axis on thin film. This is because of very small π- π stacking distance between P3HT backbones compared with the size of the core. Here, we report a facile synthesis of (P3HT)2PMMA containing rigid core. First, we synthesized coupled P3HT having 1,3-diazidobenzylaldehyde at the center using click reaction between mono-ethynyl P3HT and 1,3-diazidobenzylaldehyde. The aldehyde at center in coupled P3HT was replaced by ethynyl group using Grignard reaction with ethynyl magnesiumbromide (P3HT-core-P3HT). Then, copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition click reaction between P3HT-core-P3HT and PMMA-N3 was performed to synthesize (P3HT)2PMMA. The optical property and self-assembly of (P3HT)2PMMA was investigated.

  13. Discovery of a Frank-Kasper sigma phase in sphere-forming block copolymer melts.

    PubMed

    Lee, Sangwoo; Bluemle, Michael J; Bates, Frank S

    2010-10-15

    Sphere-forming block copolymers are known to self-assemble into body-centered cubic crystals near the order-disorder transition temperature. Small-angle x-ray scattering and transmission electron microscopy experiments on diblock and tetrablock copolymer melts have revealed an equilibrium phase characterized by a large tetragonal unit cell containing 30 microphase-separated spheres. This structure, referred to as the sigma (σ) phase by Frank and Kasper more than 50 years ago, nucleates and grows from the body-centered cubic phase similar to its occurrence in metal alloys and is a crystal approximant to dodecagonal quasicrystals. Formation of the σ phase in undiluted linear block copolymers (and certain branched dendrimers) appears to be mediated by macromolecular packing frustration, an entropic contribution to the interparticle interactions that control the sphere-packing geometry.

  14. Synthesis and Melt Self-Assembly of PS-PMMA-PLA Triblock Bottlebrush Copolymers

    SciTech Connect

    Bolton, Justin; Rzayev, Javid

    2014-07-03

    Polystyrene–poly(methyl methacrylate)–polylactide (PS–PMMA–PLA) triblock bottlebrush copolymer with nearly symmetric volume fractions was synthesized by grafting from a symmetrical triblock backbone and the resulting melt was characterized by scanning electron microscopy and small-angle X-ray scattering. The copolymer backbone was prepared by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization of solketal methacrylate (SM), 2-(bromoisobutyryl)ethyl methacrylate (BIEM), and 5-(trimethylsilyl)-4-pentyn-1-ol methacrylate (TPYM). PMMA branches were grafted by atom transfer radical polymerization from the poly(BIEM) segment, PS branches were grafted by RAFT polymerization from the poly(TPYM) block after installment of the RAFT agents, while PLA side chains were grafted from the deprotected poly(SM) block. The resulting copolymer was found to exhibit a lamellae morphology with a domain spacing of 79 nm. Differential scanning calorimetry analysis indicated that PMMA was preferentially mixing with PS while phase separating from PLA domains.

  15. Local Dynamics of Acid- and Ion-containing Copolymer Melts

    NASA Astrophysics Data System (ADS)

    Winey, Karen; Middleton, Robert; Tarver, Jacob; Tyagi, Madhusudan; Soles, Christopher; Frischknecht, Amalie

    Interest in acid- and ion-containing polymers arises in part from applications as single-ion conductors for selectively transporting a counter ion for battery applications. Structurally, the low dielectric constant of organic polymers and strong ionic interactions leads to ionic aggregation. Here the polymer backbone motion was investigated through quasi-elastic neutron scattering measurements (QENS) and compared with fully atomistic molecular dynamic simulations of precise poly(ethylene-acrylic acid) copolymers and their ionomers (pxAA-y%Li). The effect of carbon spacer length (x =9, 15, 21) between the acid groups and the degree of neutralization (y) with Li on PE backbone dynamics were considered. Systematic slowing in chain dynamics were observed with increasing neutralization where polymer dynamics appear constrained due to anchoring effects. Simulations provide complementary viewpoints indicating a gradient in chain dynamics as a distance away from acid groups. These results indicate that the addition of pendant acid groups inhibit typical PE backbone motion and the neutralized forms strongly suppress the fraction of mobile PE chain.

  16. Melt and Solid-State Structures of Polydisperse Polyolefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Register, Richard; Li, Sheng

    2013-03-01

    Recent developments in coordinative chain transfer polymerization have enabled the synthesis of ethylene-co-octene block copolymers, where the blocks are either crystallizable (an ethylene-co-octene random copolymer block with low octene content) or amorphous (analogous block with high octene content). With a suitable choice of catalyst type(s) and reactor train configuration, accessible chain architectures include diblock, where each block ideally has the most-probable distribution of chain lengths, and multiblock, where both the individual blocks and the number of blocks per chain follow the most-probable distribution. With a sufficiently large interblock octene differential, block copolymers of both architectures, containing roughly equal masses of the two types of block, self-assemble in the melt into well-ordered lamellar structures, despite the large polydispersity. Interblock mixing, induced by the modest Flory interaction parameter and the broad distribution of block lengths, yields an enormous domain spacing (> 100 nm) despite the relatively low average block molecular weights (< 50 kg/mol). Extensive interblock mixing also allows the polyethylene crystals to grow freely and nearly isotropically across the domain interfaces, while preserving the domain structure present in the melt; in the solid state, the optical and x-ray contrasts between dissimilar domains are greatly enhanced due to their different levels of crystallinity. (Work conducted in collaboration with Jeffrey Weinhold, Philip Hustad, and Brian Landes of Dow Chemical Core R&D.) Support from the NSF Polymers Program (DMR-1003942).

  17. Melt and Solid-State Structures of Polydisperse Polyolefin Multiblock Copolymers

    SciTech Connect

    Li, Sheng; Register, Richard A.; Weinhold, Jeffrey D.; Landes, Brian G.

    2012-10-23

    Crystallization in polydisperse ethylene-octene multiblock copolymers, polymerized via chain shuttling chemistry, is examined using two-dimensional synchrotron small- and wide-angle X-ray scattering on flow-aligned specimens. The multiblocks are composed of alternating crystalline (hard) blocks of low 1-octene content and amorphous (soft) blocks of high 1-octene content; the block lengths and the number of blocks per chain are characterized by most-probable distributions. These polymers self-assemble into lamellar domain morphologies in the melt, and the melt morphology is retained in the solid state. Despite extensive mixing between hard and soft blocks, the high crystallinity (>50%) of the hard blocks leads to an alignment of the crystallites within the domain structure, with the orthorhombic polyethylene c-axis generally perpendicular to the lamellar domain normal. The interlamellar domain spacings exhibited by the multiblocks, which exceed 100 nm, are estimated to be 5 times larger than those in near-monodisperse block copolymers having a similar chemical composition and a number-average molecular weight equivalent to the multiblock's 'constituent diblock' repeating unit. This swelling factor exceeds the value of 3 previously reported for analogous polydisperse olefin diblock copolymers, due to the lower segregation strength and enhanced phase mixing of the multiblocks studied here.

  18. Kinetic pathways of sphere-to-cylinder transition in diblock copolymer melt under electric field.

    PubMed

    Ly, D Q; Pinna, M; Honda, T; Kawakatsu, T; Zvelindovsky, A V M

    2013-02-21

    Phase transition from body-centered-cubic spheres to cylinders in a diblock copolymer melt under an external electric field is investigated by means of real-space dynamical self-consistent field theory. Different phase transition kinetic pathways and different cylindrical domains arrangements of the final phase are observed depending on the strength and direction of the applied electric field. Various transient states have been identified depending on the electric field being applied along [111], [100], and [110] directions. The electric field should be above a certain threshold value in order the transition to occur. A "dynamic critical exponent" of the transition is found to be about 3/2, consistent with other order-order transitions in diblock copolymers under electric field.

  19. Well Ordered Melts from Low Molar Mass Pluronic Copolymers Blended with Poly (acrylic acid): Effect of Homopolymer Molar Mass

    NASA Astrophysics Data System (ADS)

    Daga, Vikram; Tirumala, Vijay; Romang, Alvin; Lin, Eric; Watkins, James

    2008-03-01

    The use of short chain block copolymer melts as nanostructured templates is often limited by their low segregation strength (χN). Since increasing molar mass to strengthen segregation also increases the interdomain spacing, it is more desirable to increase the segment-segment interaction parameter, χ to produce strong segregation. We have recently shown that block copolymer melts with a molar mass less than 15 kg/mol undergo disorder-to-order transition without a significant increase in interdomain spacing when blended with a selectively associating homopolymer, due to an apparent increase in effective χ. Here, we study the effect of homopolymer molar mass on the segregation of a disordered poly (oxyethylene-oxypropylene-oxyethylene) copolymer melt that forms lamellar microstructure in the ordered phase. Based on small-angle scattering measurements, we find that the melts remain ordered over a broad range of homopolymer chain lengths, ranging up to ten times that of the copolymer. This approach has many implications for the use of commodity block copolymer surfactants as inexpensive nanostructured templates for commercial applications.

  20. Phase diagram of rod-coil diblock copolymer melts by self-consistent field theory

    NASA Astrophysics Data System (ADS)

    Yan, Dadong; Tang, Jiuzhou; Jiang, Ying; Zhang, Xinghua; Chen, Jeff

    A unified phase diagram is presented for rod-coil diblock copolymer melts in the isotropic phase regime as a function of the asymmetric parameter. The study is based on free-energy calculation, which incorporates three-dimensional spatial variations of the volume fraction with angular dependence. The wormlike-chain model is used in a self-consistent field treatment. Body-centered cubic, A15, hexagonal, gyroid, and lamellar structures where the rod segments are packed inside the convex rod-coil interface are found stable. As the conformational asymmetric parameter increases, the A15 phase region expands and the gyroid phase region reduces. The stability of the structures is analyzed by concepts such as packing frustration, spinodal limit, and interfacial curvature.

  1. On the order-disorder transition of compressible diblock copolymer melts

    SciTech Connect

    Zong, Jing; Wang, Qiang

    2015-11-14

    We performed both the fast off-lattice Monte Carlo simulations of symmetric diblock copolymers (DBC) in an isothermal-isobaric ensemble and the self-consistent field calculations of asymmetric DBC to properly determine the order-disorder transition (ODT) of a model system of compressible DBC melts used in the literature when it is a first-order phase transition, and studied for the first time the co-existence of the two phases at ODT. We found that the co-existing region is quite small and decreases as the system becomes less compressible, which justifies the previous ODT results obtained by equating the Helmholtz free energy per chain of the two phases. We also found that for the most compressible system where there is no repulsion between the same type of segments, the self-consistent field theory predicts that ODT is a second-order phase transition even for asymmetric DBC melts due to its mean-field approximation.

  2. Melt-processable hydrophobic acrylonitrile-based copolymer systems with adjustable elastic properties designed for biomedical applications.

    PubMed

    Cui, J; Trescher, K; Kratz, K; Jung, F; Hiebl, B; Lendlein, A

    2010-01-01

    Acrylonitrile-based polymer systems (PAN) are comprehensively explored as versatile biomaterials having various potential biomedical applications, such as membranes for extra corporal devices or matrixes for guided skin reconstruction. The surface properties (e.g. hydrophilicity or charges) of such materials can be tailored over a wide range by variation of molecular parameters such as different co-monomers or their sequence structure. Some of these materials show interesting biofunctionalities such as capability for selective cell cultivation. So far, the majority of AN-based copolymers, which were investigated in physiological environments, were processed from the solution (e.g. membranes), as these materials are thermo-sensitive and might degrade when heated. In this work we aimed at the synthesis of hydrophobic, melt-processable AN-based copolymers with adjustable elastic properties for preparation of model scaffolds with controlled pore geometry and size. For this purpose a series of copolymers from acrylonitrile and n-butyl acrylate (nBA) was synthesized via free radical copolymerisation technique. The content of nBA in the copolymer varied from 45 wt% to 70 wt%, which was confirmed by 1H-NMR spectroscopy. The glass transition temperatures (Tg) of the P(AN-co-nBA) copolymers determined by differential scanning calorimetry (DSC) decreased from 58 degrees C to 20 degrees C with increasing nBA-content, which was in excellent agreement with the prediction of the Gordon-Taylor equation based on the Tgs of the homopolymers. The Young's modulus obtained in tensile tests was found to decrease significantly with rising nBA-content from 1062 MPa to 1.2 MPa. All copolymers could be successfully processed from the melt with processing temperatures ranging from 50 degrees C to 170 degrees C, whereby thermally induced decomposition was only observed at temperatures higher than 320 degrees C in thermal gravimetric analysis (TGA). Finally, the melt processed P

  3. Self-Assembly of Asymmetrically Interacting ABC Star Triblock Copolymer Melts.

    PubMed

    Jiang, Kai; Zhang, Juan; Liang, Qin

    2015-11-12

    The phase behavior of asymmetrically interacting ABC star triblock copolymer melts is investigated by the self-consistent field theory (SCFT). Motivated by the experimental systems, in this study, we focus on the systems in which the Flory-Huggins interaction parameters satisfy χAC > χ BC ≈ χAB. Using various initialization strategies, a large number of periodic structures have been obtained in our calculations. A fourth-order pseudospectral algorithm combined with Anderson mixing method is used to compute the free energy of candidate structures carefully. The stability has been analyzed in detail by splitting the free energy into internal and entropic parts. A complete and complex triangular phase diagram is presented for a model with χAC > χBC = χAB in which 15 ordered phases, including two- and three-dimensional structures, have been predicted to be stable from the SCFT calculations. Generally speaking, with the asymmetrical interactions, the hierarchical structures tend to be formed near the B-rich corner of the triangular phase diagram. This work broadens the previous theoretical results from equal interaction systems to unequal interaction systems. The predicted phase behavior is in good agreement with experimental observations and previous theoretical results.

  4. Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts

    SciTech Connect

    Scalfani, VF; Wiesenauer, EF; Ekblad, JR; Edwards, JP; Gin, DL; Bailey, TS

    2012-05-22

    The development of nanostructured polymeric systems containing directionally continuous poly(ionic liquid) (poly(IL)) domains has considerable implications toward a range of transport-dependent, energy-based technology applications. The controlled, synthetic integration of poly(IL)s into block copolymer (BCP) architectures provides a promising means to this end, based on their inherent ability to self-assemble into a range of defined, periodic morphologies. In this work, we report the melt-state phase behavior of an imidazolium-containing alkyl ionic BCP system, derived from the sequential ring-opening metathesis polymerization (ROMP) of imidazolium- and alkyl-substituted norbornene monomer derivatives. A series of 16 BCP samples were synthesized, varying both the relative volume fraction of the poly(norbornene dodecyl ester) block (f(DOD) = 0.42-0.96) and the overall molecular weights of the block copolymers (M-n values from 5000-20 100 g mol(-1)). Through a combination of small-angle X-ray scattering (SAXS) and dynamic rheology, we were able to delineate clear compositional phase boundaries for each of the classic BCP phases, including lamellae (Lam), hexagonally packed cylinders (Hex), and spheres on a body-centered-cubic lattice (S-BCC). Additionally, a liquid-like packing (LLP) of spheres was found for samples located in the extreme asymmetric region of the phase diagram, and a persistent coexistence of Lam and Hex domains was found in lieu of the bicontinuous cubic gyroid phase for samples located at the intersection of Hex and Lam regions. Thermal disordering was opposed even in very low molecular weight samples, detected only when the composition was highly asymmetric (f(DOD) = 0.96). Annealing experiments on samples exhibiting Lam and Hex coexistence revealed the presence of extremely slow transition kinetics, ultimately selective for one or the other but not the more complex gyroid phase. In fact, no evidence of the bicontinuous network was detected over

  5. Morphological Phase Behavior of Poly(RTIL)-Containing Diblock Copolymer Melts

    SciTech Connect

    Scalfani, Vincent F.; Wiesenauer, Erin F.; Ekblad, John R.; Edwards, Julian P.; Gin, Douglas L.; Bailey, Travis S.

    2012-10-23

    The development of nanostructured polymeric systems containing directionally continuous poly(ionic liquid) (poly(IL)) domains has considerable implications toward a range of transport-dependent, energy-based technology applications. The controlled, synthetic integration of poly(IL)s into block copolymer (BCP) architectures provides a promising means to this end, based on their inherent ability to self-assemble into a range of defined, periodic morphologies. In this work, we report the melt-state phase behavior of an imidazolium-containing alkyl-ionic BCP system, derived from the sequential ring-opening metathesis polymerization (ROMP) of imidazolium- and alkyl-substituted norbornene monomer derivatives. A series of 16 BCP samples were synthesized, varying both the relative volume fraction of the poly(norbornene dodecyl ester) block (f{sub DOD} = 0.42-0.96) and the overall molecular weights of the block copolymers (M{sub n} values from 5000-20,100 g mol{sup -1}). Through a combination of small-angle X-ray scattering (SAXS) and dynamic rheology, we were able to delineate clear compositional phase boundaries for each of the classic BCP phases, including lamellae (Lam), hexagonally packed cylinders (Hex), and spheres on a body-centered-cubic lattice (S{sub BCC}). Additionally, a liquid-like packing (LLP) of spheres was found for samples located in the extreme asymmetric region of the phase diagram, and a persistent coexistence of Lam and Hex domains was found in lieu of the bicontinuous cubic gyroid phase for samples located at the intersection of Hex and Lam regions. Thermal disordering was opposed even in very low molecular weight samples, detected only when the composition was highly asymmetric (f{sub DOD} = 0.96). Annealing experiments on samples exhibiting Lam and Hex coexistence revealed the presence of extremely slow transition kinetics, ultimately selective for one or the other but not the more complex gyroid phase. In fact, no evidence of the bicontinuous

  6. Simulation of the gyroid phase in off-lattice models of pure diblock copolymer melts

    NASA Astrophysics Data System (ADS)

    Martínez-Veracoechea, Francisco J.; Escobedo, Fernando A.

    2006-09-01

    Particle-based molecular simulations of pure diblock copolymer (DBC) systems were performed in continuum space via dissipative particle dynamics and Monte Carlo methods for a bead-spring chain model. This model consisted of chains of soft repulsive particles often used with dissipative particle dynamics. The gyroid phase was successfully simulated in DBC melts at selected conditions provided that the simulation box size was commensurate with the gyroid lattice spacing. Simulations were concentrated at conditions where the gyroid phase is expected to be stable which allowed us to outline approximate phase boundaries. When more than one phase was observed by varying simulation box size, thermodynamic stability was discerned by comparing the Helmholtz free energy of the competing phases. For this purpose, chemical potentials were efficiently simulated via an expanded ensemble that gradually inserts/deletes a target chain to/from the system. These simulations employed a novel combination of Bennett's [J. Comput. Phys. 22, 245 (1976)] acceptance-ratio method to estimate free-energy differences and a recently proposed method to get biasing weights that maximize the number of times that the target chain is regrown. The analysis of the gyroid nodes revealed clear evidence of packing frustration in the form of an (entropically) unfavorably overstretching of chains, a phenomenon that has been suggested to provide the structural basis for the limited region of stability of the gyroid phase in the DBC phase diagram. Finally, the G phase and nodal chain stretching were also found in simulations with a completely different DBC particle-based model.

  7. Rheological Evidence of Composition Fluctuations in an Unentangled Diblock Copolymer Melt near the Order-Disorder Transition

    SciTech Connect

    Kennemur, Justin G.; Hillmyer, Marc A.; Bates, Frank S.

    2014-02-13

    Rheological and small-angle X-ray scattering (SAXS) measurements were conducted on a symmetric, low molar mass (Mn = 17.6 kg/mol), poly(tert-butylstyrene-block-methyl methacrylate) (PtBS-PMMA) diblock copolymer near the order–disorder transition temperature (TODT = 193 ± 1 °C). Evidence of composition fluctuations is apparent in the low frequency elastic (G') and loss (G") moduli and in the temperature dependence of the peak scattering intensity, I(q*), up to 50 °C above the TODT. These findings demonstrate that chain entanglements are not responsible for the well-documented fluctuation mode in the terminal viscoelastic regime of block copolymer melts.

  8. Collective dynamics and self-diffusion in a diblock copolymer melt in the body-centered cubic phase.

    PubMed

    Papadakis, C M; Rittig, F; Almdal, K; Mortensen, K; Stĕpánek, P

    2004-12-01

    The structure and dynamics of a strongly asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) (PEP-PDMS) diblock copolymer in the melt have been studied over a wide temperature range. Small-angle neutron scattering reveals that the sample exhibits two stable phases in this temperature range: Above the order-to-disorder transition temperature, it is disordered, whereas the domain structure is body-centered cubic (bcc) below, being stable down to the lowest temperatures measured. In the disordered state, dynamic light scattering (DLS) in the polarized geometry reveals the heterogeneity mode and the cluster mode. In the bcc phase, the PEP and the PDMS blocks form the micellar cores and the matrix, respectively. Here, two modes are observed in DLS, and the diffusion coefficients measured using pulsed field gradient (PFG) NMR are broadly distributed with the most probable diffusion coefficient coinciding with the slow DLS mode. We attribute the fast process in the bcc state to concentration fluctuations of the micellar cores (PEP), relaxing by mutual diffusion of the micelles with copolymers dissolved in the PDMS matrix. The slower process in the bcc state is ascribed to activated long-range self-diffusion of single copolymers from micelle to micelle through the PDMS matrix. This assignment is corroborated by the good coincidence of the reduced diffusivities with the ones from the literature. However, this mode may also be assigned to the rearrangement of entire micelles.

  9. Crystal structure and melting behavior of homo-polypropylene and heterophasic ethylene-propylene copolymer after long time heat treatment

    NASA Astrophysics Data System (ADS)

    Wang, Shichao; Zhang, Jun; Chen, Shuangjun; Zhu, Han

    2012-09-01

    The homo-polypropylenes and heterophasic ethylene-propylene copolymers (EP-HECO) were prepared by the non-isothermal and isothermal crystallization methods. The crystal structure and crystal phase were detected by the wide-angle X-ray diffraction (WAXD). The morphology of the spherulite growth process was observed under a polarized optical microscope (POM) with a hot stage. The melting behavior was performed by the differential scanning calorimetry (DSC). It was found that the restricted ethylene segment in the long propylene sequences could act as a heterogeneous nucleating agent of β phase only when the crystallization temperature was very high. PP with long molecular chain had more polymer sequences entering crystal lattice to form large lamellar thickness. Nucleation and spherulitic growth occurred at the same time. Both the final spherulite size and the crystallinity of iPP were related to the melt flow rate. When samples crystallized isothermally at a very high temperature, shorter molecular chain would crystallize into some small-size defect crystals, and this resulted in a multiple melting behavior in the DSC endotherm.

  10. Molecular dynamics study on microstructures of diblock copolymer melts with soft potential and potential recovery

    NASA Astrophysics Data System (ADS)

    Ryu, Ji Ho; Wee, Han Sol; Lee, Won Bo

    2016-09-01

    Various microstructures are obtained through the self-assembly of block copolymers on the basis of the compositional fractions and repulsive interactions among different types of beads. The inhomogeneity of block copolymers can be studied by molecular dynamics. However, preparing initial configurations of various self-assembled structures directly by molecular dynamics requires extensive computational time because of topological constraints. Furthermore, manual preparation often becomes a complicated and time-consuming procedure even for the simplest structures, such as a lamellar phase, not to mention three-dimensional bicontinuous cubic phases such as a gyroid phase. In this paper, this difficulty is overcome by using a soft potential, which allows the system to reach a self-assembled state quickly (within 3 τd ). Once a self-assembled microstructure is obtained, the normal potential is restored and equilibration steps are performed to enable the calculation of various properties of the microstructures. Various equilibrated phase structures—including S (spherical), H (hexagonal), G (gyroid), and L (lamellar) phases—are obtained by this approach. To verify our method, static and dynamic properties of the lamellar phase are examined and compared with previous results.

  11. Theory of melt polyelectrolyte blends and block copolymers: Phase behavior, surface tension, and microphase periodicity

    SciTech Connect

    Sing, Charles E.; Zwanikken, Jos W.; Olvera de la Cruz, Monica

    2015-01-21

    Polymer mixtures such as blends or block copolymers are of great interest in energy applications and functional materials, and often, one or more of these species contain charges. The traditional fashion in which such materials are studied uses Self-Consistent Field Theory (SCFT) methods that incorporate electrostatics using Poisson-Boltzmann (PB) theory. We adapt a new and rigorous approach that does not rely on the mean-field assumptions inherent in the PB theory and instead uses Liquid State (LS) integral equation theory to articulate charge correlations that are completely neglected in PB. We use this theory to calculate phase diagrams for both blends and block copolyelectrolytes using SCFT-LS and demonstrate how their phase behavior is highly dependent on chain length, charge fraction, charge size, and the strength of Coulombic interactions. Beyond providing phase behavior of blends and block copolyelectrolytes, we can use this theory to investigate the interfacial properties such as surface tension and block copolyelectrolyte lamellar spacing. Lamellar spacing provides a way to directly compare the SCFT-LS theory to the results of experiments. SCFT-LS will provide conceptual and mathematical clarification of the role of charge correlations in these systems and aid in the design of materials based on charge polymers.

  12. Theory of melt polyelectrolyte blends and block copolymers: phase behavior, surface tension, and microphase periodicity.

    PubMed

    Sing, Charles E; Zwanikken, Jos W; Olvera de la Cruz, Monica

    2015-01-21

    Polymer mixtures such as blends or block copolymers are of great interest in energy applications and functional materials, and often, one or more of these species contain charges. The traditional fashion in which such materials are studied uses Self-Consistent Field Theory (SCFT) methods that incorporate electrostatics using Poisson-Boltzmann (PB) theory. We adapt a new and rigorous approach that does not rely on the mean-field assumptions inherent in the PB theory and instead uses Liquid State (LS) integral equation theory to articulate charge correlations that are completely neglected in PB. We use this theory to calculate phase diagrams for both blends and block copolyelectrolytes using SCFT-LS and demonstrate how their phase behavior is highly dependent on chain length, charge fraction, charge size, and the strength of Coulombic interactions. Beyond providing phase behavior of blends and block copolyelectrolytes, we can use this theory to investigate the interfacial properties such as surface tension and block copolyelectrolyte lamellar spacing. Lamellar spacing provides a way to directly compare the SCFT-LS theory to the results of experiments. SCFT-LS will provide conceptual and mathematical clarification of the role of charge correlations in these systems and aid in the design of materials based on charge polymers.

  13. Nucleation of the BCC phase from disorder in a diblock copolymer melt: Testing approximate theories through simulation

    NASA Astrophysics Data System (ADS)

    Spencer, Russell K. W.; Curry, Paul F.; Wickham, Robert A.

    2016-10-01

    We examine nucleation of the stable body-centred-cubic (BCC) phase from the metastable uniform disordered phase in an asymmetric diblock copolymer melt. Our comprehensive, large-scale simulations of the time-dependent, mean-field Landau-Brazovskii model find that spherical droplets of the BCC phase nucleate directly from disorder. Near the order-disorder transition, the critical nucleus is large and has a classical profile, attaining the bulk BCC phase in an interior that is separated from disorder by a sharp interface. At greater undercooling, the amplitude of BCC order in the interior decreases and the nucleus interface broadens, leading to a diffuse critical nucleus. This diffuse nucleus becomes large as the simulation approaches the disordered phase spinodal. We show that our simulation follows the same nucleation pathway that Cahn and Hilliard found for an incompressible two-component fluid, across the entire metastable region. In contrast, a classical nucleation theory calculation based on the free energy of a planar interface between coexisting BCC and disordered phases agrees with simulation only in the limit of very small undercooling; we can expand this region of validity somewhat by accounting for the curvature of the droplet interface. A nucleation pathway involving a classical droplet persists, however, to deep undercooling in our simulation, but this pathway is energetically unfavourable. As a droplet grows in the simulation, its interface moves with a constant speed, and this speed is approximately proportional to the undercooling.

  14. Nucleation of the BCC phase from disorder in a diblock copolymer melt: Testing approximate theories through simulation.

    PubMed

    Spencer, Russell K W; Curry, Paul F; Wickham, Robert A

    2016-10-14

    We examine nucleation of the stable body-centred-cubic (BCC) phase from the metastable uniform disordered phase in an asymmetric diblock copolymer melt. Our comprehensive, large-scale simulations of the time-dependent, mean-field Landau-Brazovskii model find that spherical droplets of the BCC phase nucleate directly from disorder. Near the order-disorder transition, the critical nucleus is large and has a classical profile, attaining the bulk BCC phase in an interior that is separated from disorder by a sharp interface. At greater undercooling, the amplitude of BCC order in the interior decreases and the nucleus interface broadens, leading to a diffuse critical nucleus. This diffuse nucleus becomes large as the simulation approaches the disordered phase spinodal. We show that our simulation follows the same nucleation pathway that Cahn and Hilliard found for an incompressible two-component fluid, across the entire metastable region. In contrast, a classical nucleation theory calculation based on the free energy of a planar interface between coexisting BCC and disordered phases agrees with simulation only in the limit of very small undercooling; we can expand this region of validity somewhat by accounting for the curvature of the droplet interface. A nucleation pathway involving a classical droplet persists, however, to deep undercooling in our simulation, but this pathway is energetically unfavourable. As a droplet grows in the simulation, its interface moves with a constant speed, and this speed is approximately proportional to the undercooling.

  15. Microphase Separation and Shear Alignment of Gradient Copolymers: Melt Rheology and Small-Angle X-Ray Scattering Analysis

    SciTech Connect

    Mok, Michelle M.; Pujari, Saswati; Burghardt, Wesley R.; Dettmer, Christine M.; Nguyen, SonBinh T.; Ellison, Christopher J.; Torkelson, John M.

    2008-10-24

    The degree of microphase or nanophase segregation in gradient copolymers with compositions varying across the whole copolymer backbone is studied via low-amplitude oscillatory shear (LAOS) measurements and small-angle X-ray scattering (SAXS). Studies are done as a function of comonomer segregation strength, molecular weight (MW), gradient architecture and temperature. Controlled radical polymerization is used to synthesize strongly segregating styrene/4-acetoxystyrene (S/AS) and the more weakly segregating S/n-butyl acrylate (S/nBA) gradient copolymers. Results are compared to those from S/AS and S/nBA random and block copolymers. The higher MW S/AS gradient copolymer exhibits LAOS behavior similar to the highly microphase segregated S/AS block copolymer, while the lower MW S/AS gradient copolymer exhibits complex, nonterminal behavior indicative of a lower degree of microphase segregation. The S/nBA gradient copolymers demonstrate more liquidlike behavior, with the lower MW sample exhibiting near-Newtonian behavior, indicative of a weakly segregating structure, while the higher MW, steeper gradient sample shows behavior ranging from solidlike to more liquidlike with increasing temperature. With the exception of the lower MW S/nBA case, the gradient copolymers exhibit temperature-dependent LAOS behavior over a wide temperature range, reflecting their temperature-dependent nanodomain composition amplitudes. The S/AS samples have SAXS results consistent with the degree of microphase segregation observed via rheology. Shear alignment studies are done on the higher MW S/AS gradient copolymer, which is the most highly microphase segregated gradient copolymer. Rheology and SAXS provide evidence of shear alignment, despite the gradual variation in composition profile across the nanodomains of such gradient copolymers. A short review of the nomenclature and behavior of linear copolymer architectures is also provided.

  16. The static structure and dynamics of cadmium sulfide nanoparticles within poly(styrene-block-isoprene) diblock copolymer melts

    DOE PAGES

    Jang, Woo -Sik; Koo, Peter; Bryson, Kyle; ...

    2015-12-20

    Here, the static structure and dynamic behavior of cadmium sulfide nanoparticles suspended in block copolymer matrix are investigated using transmission electron microscopy, small-angle X-ray scattering, and X-ray photon correlation spectroscopy. The transmission electron micro- scopy study shows that cadmium sulfide nanoparticles are preferentially segregated within the polyisoprene domain of a poly(styrene-block-isoprene) diblock copolymer. For the dynamics study, X-ray photon correlation spectroscopy captures the relaxation process of cadmium sulfide nanoparticles. The measured characteristic relaxation time reveals that the observed dynamics are hyperdiffusive. The characteristic velocity and corresponding activation energy, which are hallmarks of a hyperdiffusive system, are determined from the relationshipmore » between the characteristic relaxation time and the wavevector.« less

  17. The static structure and dynamics of cadmium sulfide nanoparticles within poly(styrene-block-isoprene) diblock copolymer melts

    SciTech Connect

    Jang, Woo -Sik; Koo, Peter; Bryson, Kyle; Narayanan, Suresh; Sandy, Alec R.; Russell, Thomas P.; Mochrie, Simon G.

    2015-12-20

    Here, the static structure and dynamic behavior of cadmium sulfide nanoparticles suspended in block copolymer matrix are investigated using transmission electron microscopy, small-angle X-ray scattering, and X-ray photon correlation spectroscopy. The transmission electron micro- scopy study shows that cadmium sulfide nanoparticles are preferentially segregated within the polyisoprene domain of a poly(styrene-block-isoprene) diblock copolymer. For the dynamics study, X-ray photon correlation spectroscopy captures the relaxation process of cadmium sulfide nanoparticles. The measured characteristic relaxation time reveals that the observed dynamics are hyperdiffusive. The characteristic velocity and corresponding activation energy, which are hallmarks of a hyperdiffusive system, are determined from the relationship between the characteristic relaxation time and the wavevector.

  18. Flory-Huggins parameter χ, from binary mixtures of Lennard-Jones particles to block copolymer melts.

    PubMed

    Chremos, Alexandros; Nikoubashman, Arash; Panagiotopoulos, Athanassios Z

    2014-02-07

    In this contribution, we develop a coarse-graining methodology for mapping specific block copolymer systems to bead-spring particle-based models. We map the constituent Kuhn segments to Lennard-Jones particles, and establish a semi-empirical correlation between the experimentally determined Flory-Huggins parameter χ and the interaction of the model potential. For these purposes, we have performed an extensive set of isobaric-isothermal Monte Carlo simulations of binary mixtures of Lennard-Jones particles with the same size but with asymmetric energetic parameters. The phase behavior of these monomeric mixtures is then extended to chains with finite sizes through theoretical considerations. Such a top-down coarse-graining approach is important from a computational point of view, since many characteristic features of block copolymer systems are on time and length scales which are still inaccessible through fully atomistic simulations. We demonstrate the applicability of our method for generating parameters by reproducing the morphology diagram of a specific diblock copolymer, namely, poly(styrene-b-methyl methacrylate), which has been extensively studied in experiments.

  19. Flory-Huggins parameter χ, from binary mixtures of Lennard-Jones particles to block copolymer melts

    SciTech Connect

    Chremos, Alexandros; Nikoubashman, Arash Panagiotopoulos, Athanassios Z.

    2014-02-07

    In this contribution, we develop a coarse-graining methodology for mapping specific block copolymer systems to bead-spring particle-based models. We map the constituent Kuhn segments to Lennard-Jones particles, and establish a semi-empirical correlation between the experimentally determined Flory-Huggins parameter χ and the interaction of the model potential. For these purposes, we have performed an extensive set of isobaric–isothermal Monte Carlo simulations of binary mixtures of Lennard-Jones particles with the same size but with asymmetric energetic parameters. The phase behavior of these monomeric mixtures is then extended to chains with finite sizes through theoretical considerations. Such a top-down coarse-graining approach is important from a computational point of view, since many characteristic features of block copolymer systems are on time and length scales which are still inaccessible through fully atomistic simulations. We demonstrate the applicability of our method for generating parameters by reproducing the morphology diagram of a specific diblock copolymer, namely, poly(styrene-b-methyl methacrylate), which has been extensively studied in experiments.

  20. Flory-Huggins parameter χ, from binary mixtures of Lennard-Jones particles to block copolymer melts

    NASA Astrophysics Data System (ADS)

    Chremos, Alexandros; Nikoubashman, Arash; Panagiotopoulos, Athanassios Z.

    2014-02-01

    In this contribution, we develop a coarse-graining methodology for mapping specific block copolymer systems to bead-spring particle-based models. We map the constituent Kuhn segments to Lennard-Jones particles, and establish a semi-empirical correlation between the experimentally determined Flory-Huggins parameter χ and the interaction of the model potential. For these purposes, we have performed an extensive set of isobaric-isothermal Monte Carlo simulations of binary mixtures of Lennard-Jones particles with the same size but with asymmetric energetic parameters. The phase behavior of these monomeric mixtures is then extended to chains with finite sizes through theoretical considerations. Such a top-down coarse-graining approach is important from a computational point of view, since many characteristic features of block copolymer systems are on time and length scales which are still inaccessible through fully atomistic simulations. We demonstrate the applicability of our method for generating parameters by reproducing the morphology diagram of a specific diblock copolymer, namely, poly(styrene-b-methyl methacrylate), which has been extensively studied in experiments.

  1. The Effect of Filler-Polymer Interactions on Cold-Crystallization Kinetics in Crosslinked, Silica Filled PDMS/PDPS Copolymer Melts.

    SciTech Connect

    Chien, A; DeTeresa, S; Thompson, L; Cohenour, R; Balazs, B; Maxwell, R S

    2006-04-21

    Crystallization in a series of variable crosslink density poly(dimethyl-diphenyl) siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and X-ray Diffraction (XRD). The silicone composite studied was composed of 94.6 mol% Dimethoylsiloxane, 5.1 mol% diphenylsiloxane, and 0.3 mol% methyl-vinyl siloxane (which formed crosslinking after a peroxide cure). The polymer was filled with a mixture of 21.6 wt. % fumed silica and 4.0 wt. % precipitated silica previously treated with 6.8 wt. % ethoxy-endblocked siloxane processing aid. The base composite was characterized by a molecular weight between crosslinks in the polymer network of {approx}24 kDa and an overall molecular weight (including the influence of the silica fillers) between crosslinks of {approx}11 kDa. Molecular weight between crosslinks and filler-polymer interaction strength were then modified by exposure to {gamma}-irradiation in either air or vacuum. The unirradiated material exhibited crystallization at -80 C as measured by DSC with a 16% crystallization as measured by XRD. Isothermal DMA experiments illustrated that crystallization at -85 C occurred over a 1.8 hour period in silica-filled systems and 2.2-2.6 hours in unfilled systems. The onset of crystallization typically occurred after a 30-minute incubation/nucleation period. The crystallization kinetics were dependent on crosslink density. Changes in molecular weight of a factor of two did not, however, change the amount of crystallization. Irradiation in vacuum resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface. Modulated differential scanning calorimetry contrasted the crystallization and melting behavior of pure PDMS versus the PDMS/PDPS base

  2. Polyether/Polyester Graft Copolymers

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

    1986-01-01

    Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

  3. Crystalline Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Hergenrother, Paul M.; Bass, Robert G.

    1991-01-01

    Series of imide/arylene ether block copolymers prepared by using arylene ether blocks to impart low melt viscosity, and imide blocks to provide high strength and other desirable mechanical properties. Work represents extension of LAR-14159 on imide/arylene ether copolymers in form of films, moldings, adhesives, and composite matrices. Copolymers potentially useful in variety of high-temperature aerospace and microelectronic applications.

  4. Hydrogen-bonded aggregates in precise acid copolymers

    SciTech Connect

    Lueth, Christopher A.; Bolintineanu, Dan S.; Stevens, Mark J. Frischknecht, Amalie L.

    2014-02-07

    We perform atomistic molecular dynamics simulations of melts of four precise acid copolymers, two poly(ethylene-co-acrylic acid) (PEAA) copolymers, and two poly(ethylene-co-sulfonic acid) (PESA) copolymers. The acid groups are spaced by either 9 or 21 carbons along the polymer backbones. Hydrogen bonding causes the acid groups to form aggregates. These aggregates give rise to a low wavevector peak in the structure factors, in agreement with X-ray scattering data for the PEAA materials. The structure factors for the PESA copolymers are very similar to those for the PEAA copolymers, indicating a similar distance between aggregates which depends on the spacer length but not on the nature of the acid group. The PEAA copolymers are found to form more dimers and other small aggregates than do the PESA copolymers, while the PESA copolymers have both more free acid groups and more large aggregates.

  5. Summary report on the fuel performance modeling of the AFC-2A, 2B irradiation experiments

    SciTech Connect

    Pavel G. Medvedev

    2013-09-01

    The primary objective of this work at the Idaho National Laboratory (INL) is to determine the fuel and cladding temperature history during irradiation of the AFC-2A, 2B transmutation metallic fuel alloy irradiation experiments containing transuranic and rare earth elements. Addition of the rare earth elements intends to simulate potential fission product carry-over from pyro-metallurgical reprocessing. Post irradiation examination of the AFC-2A, 2B rodlets revealed breaches in the rodlets and fuel melting which was attributed to the release of the fission gas into the helium gap between the rodlet cladding and the capsule which houses six individually encapsulated rodlets. This release is not anticipated during nominal operation of the AFC irradiation vehicle that features a double encapsulated design in which sodium bonded metallic fuel is separated from the ATR coolant by the cladding and the capsule walls. The modeling effort is focused on assessing effects of this unanticipated event on the fuel and cladding temperature with an objective to compare calculated results with the temperature limits of the fuel and the cladding.

  6. Role of adenosine A2b receptor overexpression in tumor progression.

    PubMed

    Sepúlveda, Cesar; Palomo, Iván; Fuentes, Eduardo

    2016-12-01

    The adenosine A2b receptor is a G-protein coupled receptor. Its activation occurs with high extracellular adenosine concentration, for example in inflammation or hypoxia. These conditions are generated in the tumor environment. Studies show that A2b receptor is overexpressed in various tumor lines and biopsies from patients with different cancers. This suggests that A2b receptor can be used by tumor cells to promote progression. Thus A2b participates in different events, such as angiogenesis and metastasis, besides exerting immunomodulatory effects that protect tumor cells. Therefore, adenosine A2b receptor appears as an interesting therapeutic target for cancer treatment.

  7. Polyether-polyester graft copolymer

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L. (Inventor)

    1987-01-01

    Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

  8. The Macrophage A2b Adenosine Receptor Regulates Tissue Insulin Sensitivity

    PubMed Central

    Koupenova, Milka; Carroll, Shannon; Ravid, Katya

    2014-01-01

    High fat diet (HFD)-induced type 2 diabetes continues to be an epidemic with significant risk for various pathologies. Previously, we identified the A2b adenosine receptor (A2bAR), an established regulator of inflammation, as a regulator of HFD-induced insulin resistance. In particular, HFD was associated with vast upregulation of liver A2bAR in control mice, and while mice lacking this receptor showed augmented liver inflammation and tissue insulin resistance. As the A2bAR is expressed in different tissues, here, we provide the first lead to cellular mechanism by demonstrating that the receptor's influence on tissue insulin sensitivity is mediated via its expression in macrophages. This was shown using a newly generated transgenic mouse model expressing the A2bAR gene in the macrophage lineage on an otherwise A2bAR null background. Reinstatement of macrophage A2bAR expression in A2bAR null mice fed HFD restored insulin tolerance and tissue insulin signaling to the level of control mice. The molecular mechanism for this effect involves A2bAR-mediated changes in cyclic adenosine monophosphate in macrophages, reducing the expression and release of inflammatory cytokines, which downregulate insulin receptor-2. Thus, our results illustrate that macrophage A2bAR signaling is needed and sufficient for relaying the protective effect of the A2bAR against HFD-induced tissue inflammation and insulin resistance in mice. PMID:24892847

  9. Crystallization in Ordered Polydisperse Polyolefin Diblock Copolymers

    SciTech Connect

    Li, Sheng; Register, Richard A.; Landes, Brian G.; Hustad, Phillip D.; Weinhold, Jeffrey D.

    2010-12-07

    The morphologies of polydisperse ethylene-octene diblock copolymers, synthesized via a novel coordinative chain transfer polymerization process, are examined using two-dimensional synchrotron small-angle and wide-angle X-ray scattering on flow-aligned specimens. The diblock copolymers comprise one amorphous block with high 1-octene content and one semicrystalline block with relatively low 1-octene content, and each block ideally exhibits the most-probable distribution. Near-symmetric diblocks with a sufficiently large octene differential between the amorphous and semicrystalline blocks show well-ordered lamellar domain structures with long periods exceeding 100 nm. Orientation of these domain structures persists through multiple melting/recrystallization cycles, reflecting a robust structure which self-assembles in the melt. The domain spacings are nearly 3-fold larger than those in near-monodisperse polyethylene block copolymers of similar molecular weights. Although the well-ordered lamellar domain structure established in the melt is preserved in the solid state, the crystallites are isotropic in orientation. These materials display crystallization kinetics consistent with a spreading growth habit, indicating that the lamellae do not confine or template the growing crystals. The exceptionally large domain spacings and isotropic crystal growth are attributed to interblock mixing resulting from the large polydispersity; short hard blocks dissolved in the soft-block-rich domains swell the domain spacing in the melt and allow hard block crystallization to proceed across the lamellar domain interfaces.

  10. Phase separations in a copolymer copolymer mixture

    NASA Astrophysics Data System (ADS)

    Zhang, Jin-Jun; Jin, Guojun; Ma, Yuqiang

    2006-01-01

    We propose a three-order-parameter model to study the phase separations in a diblock copolymer-diblock copolymer mixture. The cell dynamical simulations provide rich information about the phase evolution and structural formation, especially the appearance of onion-rings. The parametric dependence and physical reason for the domain growth of onion-rings are discussed.

  11. The A2B adenosine receptor modulates pulmonary hypertension associated with interstitial lung disease.

    PubMed

    Karmouty-Quintana, Harry; Zhong, Hongyan; Acero, Luis; Weng, Tingting; Melicoff, Ernestina; West, James D; Hemnes, Anna; Grenz, Almut; Eltzschig, Holger K; Blackwell, Timothy S; Xia, Yang; Johnston, Richard A; Zeng, Dewan; Belardinelli, Luiz; Blackburn, Michael R

    2012-06-01

    Development of pulmonary hypertension is a common and deadly complication of interstitial lung disease. Little is known regarding the cellular and molecular mechanisms that lead to pulmonary hypertension in patients with interstitial lung disease, and effective treatment options are lacking. The purpose of this study was to examine the adenosine 2B receptor (A(2B)R) as a regulator of vascular remodeling and pulmonary hypertension secondary to pulmonary fibrosis. To accomplish this, cellular and molecular changes in vascular remodeling were monitored in mice exposed to bleomycin in conjunction with genetic removal of the A(2B)R or treatment with the A(2B)R antagonist GS-6201. Results demonstrated that GS-6201 treatment or genetic removal of the A(2B)R attenuated vascular remodeling and hypertension in our model. Furthermore, direct A(2B)R activation on vascular cells promoted interleukin-6 and endothelin-1 release. These studies identify a novel mechanism of disease progression to pulmonary hypertension and support the development of A(2B)R antagonists for the treatment of pulmonary hypertension secondary to interstitial lung disease.

  12. Protein based Block Copolymers

    PubMed Central

    Rabotyagova, Olena S.; Cebe, Peggy; Kaplan, David L.

    2011-01-01

    Advances in genetic engineering have led to the synthesis of protein-based block copolymers with control of chemistry and molecular weight, resulting in unique physical and biological properties. The benefits from incorporating peptide blocks into copolymer designs arise from the fundamental properties of proteins to adopt ordered conformations and to undergo self-assembly, providing control over structure formation at various length scales when compared to conventional block copolymers. This review covers the synthesis, structure, assembly, properties, and applications of protein-based block copolymers. PMID:21235251

  13. Field-theoretic simulations of random copolymers with structural rigidity.

    PubMed

    Mao, Shifan; MacPherson, Quinn; Qin, Jian; Spakowitz, Andrew J

    2017-04-12

    Copolymers play an important role in a range of soft-materials applications and biological phenomena. Prevalent works on block copolymer phase behavior use flexible chain models and incorporate interactions using a mean-field approximation. However, when phase separation takes place on length scales comparable to a few monomers, the structural rigidity of the monomers becomes important. In addition, concentration fluctuations become significant at short length scales, rendering the mean-field approximation invalid. In this work, we use simulation to address the role of finite monomer rigidity and concentration fluctuations in microphase segregation of random copolymers. Using a field-theoretic Monte-Carlo simulation of semiflexible polymers with random chemical sequences, we generate phase diagrams for random copolymers. We find that the melt morphology of random copolymers strongly depends on chain flexibility and chemical sequence correlation. Chemically anti-correlated copolymers undergo first-order phase transitions to local lamellar structures. With increasing degree of chemical correlation, this first-order phase transition is softened, and melts form microphases with irregular shaped domains. Our simulations in the homogeneous phase exhibit agreement with the density-density correlation from mean-field theory. However, conditions near a phase transition result in deviations between simulation and mean-field theory for the density-density correlation and the critical wavemode. Chain rigidity and sequence randomness lead to frustration in the segregated phase, introducing heterogeneity in the resulting morphologies.

  14. Immunodiagnosis of tumors in vivo using radiolabeled monoclonal antibody A2B5.

    PubMed

    Reintgen, D S; Shimizu, K; Coleman, E; Briner, W; Kitzmiller, J; Eisenbarth, G; Seigler, H F

    1983-07-01

    Recently a murine monoclonal antibody (A2B5) has been described that reacts with a membrane associated GQ ganglioside common to peptide secreting normal cells and tumors. In vitro binding data demonstrated the presence of this ganglioside on neurons, adrenal medulla, and pancreatic islets, along with neuroendocrine tumors such as insulinomas, pheochromocytomas, melanomas and neuroblastomas. Negative binding has previously been shown for tissue sections from liver, kidney, colon, lung, stomach, and tumors not derived from the neural crest. Because of the specificity at A2B5 in vitro, this monoclonal antibody was labeled with 131I for in vivo tumor localization studies. Daily radionuclear scans were obtained in 5 KX rats bearing the radiation induced rat insulinoma with disappearance of the label from the blood pool and concentration in the tumor so that by the fourth day, the only activity present by scan was in the insulinoma. Tissue-counting data showed tumor/blood ratios (av +/- SE, 1.29 +/- 0.25) of A2B5 activity two to ten times the average activity found in other organs (0.28 +/- 0.05). No tumor concentration of the control nonspecific monoclonal antibody P3X63 was evident (0.27 +/- 0.04). In addition A2B5 also localized to five different human melanoma cells lines grown in nude mice with high tumor/blood levels (1.04 +/- 0.27) compared to normal tissues (0.32 +/- 0.05) (P = .0005), while no localization is seen in nudes carrying osteosarcomas, colon, bladder, and renal cell carcinomas. In addition antibody A2B5 did not concentrate in any normal tissue though the antigen is present on several. The finding that A2B5 reacts across species lines (mouse, rat, man) lends itself to obvious diagnostic and therapeutic possibilities.

  15. Silicone/Acrylate Copolymers

    NASA Technical Reports Server (NTRS)

    Dennis, W. E.

    1982-01-01

    Two-step process forms silicone/acrylate copolymers. Resulting acrylate functional fluid is reacted with other ingredients to produce copolymer. Films of polymer were formed by simply pouring or spraying mixture and allowing solvent to evaporate. Films showed good weatherability. Durable, clear polymer films protect photovoltaic cells.

  16. Phase Behavior of Neat Triblock Copolymers and Copolymer/Homopolymer Blends Near Network Phase Windows

    SciTech Connect

    M Tureau; L Rong; B Hsiao; T Epps

    2011-12-31

    The phase behavior of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) copolymers near the styrene-rich network phase window was examined through the use of neat triblock copolymers and copolymer/homopolymer blends. Both end-block and middle-block blending protocols were employed using poly(isoprene) (PI), poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) homopolymers. Blended specimens exhibited phase transformations to well-ordered nanostructures (at homopolymer loadings up to 26 vol % of the total blend volume). Morphological consistency between neat and blended specimens was established at various locations in the ISM phase space. Copolymer/homopolymer blending permitted the refinement of lamellar, hexagonally packed cylinder, and disordered melt phase boundaries as well as the identification of double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), and orthorhombic (O{sup 70}) network regimes. Additionally, the experimental phase diagram exhibited similar trends to those found in a theoretical ABC triblock copolymer phase diagram with symmetric interactions and statistical segments lengths generated by Tyler et al.

  17. Block and Graft Copolymers of Polyhydroxyalkanoates

    NASA Astrophysics Data System (ADS)

    Marchessault, Robert H.; Ravenelle, François; Kawada, Jumpei

    2004-03-01

    Polyhydroxyalkanoates (PHAs) were modified for diblock copolymer and graft polymer by catalyzed transesterification in the melt and by chemical synthesis to extend the side chains of the PHAs, and the polymers were studied by transmission electron microscopy (TEM) X-ray diffraction, thermal analysis and nuclear magnetic resonance (NMR). Catalyzed transesterification in the melt is used to produce diblock copolymers of poly[3-hydroxybutyrate] (PHB) and monomethoxy poly[ethylene glycol] (mPEG) in a one-step process. The resulting diblock copolymers are amphiphilic and self-assemble into sterically stabilized colloidal suspensions of PHB crystalline lamellae. Graft polymer was synthesized in a two-step chemical synthesis from biosynthesized poly[3-hydroxyoctanoate-co-3-hydroxyundecenoate] (PHOU) containing ca. 25 mol chains. 11-mercaptoundecanoic acid reacts with the side chain alkenes of PHOU by the radical addition creating thioether linkage with terminal carboxyl functionalities. The latter groups were subsequently transformed into the amide or ester linkage by tridecylamine or octadecanol, respectively, producing new graft polymers. The polymers have different physical properties than poly[3-hydroxyoctanoate] (PHO) which is the main component of the PHOU, such as non-stickiness and higher thermal stability. The combination of biosynthesis and chemical synthesis produces a hybrid thermoplastic elastomer with partial biodegradability.

  18. Textbook Evaluation: An Analysis of Listening Comprehension Parts in Top Notch 2A & 2B

    ERIC Educational Resources Information Center

    Soori, Afshin; Haghani, Elham

    2015-01-01

    Textbooks are the instruments that assist both teachers and learners in process of second language learning. With respect to the importance of textbooks in a language course, evaluation of course books is a significant issue for most researchers. The present study investigated and analyzed Listening Comprehension parts in Top Notch 2A & 2B 2nd…

  19. The A2B adenosine receptor impairs the maturation and immunogenicity of dendritic cells.

    PubMed

    Wilson, Jeffrey M; Ross, William G; Agbai, Oma N; Frazier, Renea; Figler, Robert A; Rieger, Jayson; Linden, Joel; Ernst, Peter B

    2009-04-15

    The endogenous purine nucleoside adenosine is an important antiinflammatory mediator that contributes to the control of CD4(+) T cell responses. While adenosine clearly has direct effects on CD4(+) T cells, it remains to be determined whether actions on APC such as dendritic cells (DC) are also important. In this report we characterize DC maturation and function in BMDC stimulated with LPS in the presence or absence of the nonselective adenosine receptor agonist NECA (5'-N-ethylcarboxamidoadenosine). We found that NECA inhibited TNF-alpha and IL-12 in a concentration-dependent manner, whereas IL-10 production was increased. NECA-treated BMDC also expressed reduced levels of MHC class II and CD86 and were less effective at stimulating CD4(+) T cell proliferation and IL-2 production compared with BMDC exposed to vehicle control. Based on real-time RT-PCR, the A(2A) adenosine receptor (A(2A)AR) and A(2B)AR were the predominant adenosine receptors expressed in BMDC. Using adenosine receptor subtype selective antagonists and BMDC derived from A(2A)AR(-/-) and A(2B)AR(-/-)mice, it was shown that NECA modulates TNF-alpha, IL-12, IL-10, and CD86 responses predominantly via A(2B)AR. These data indicate that engagement of A(2B)AR modifies murine BMDC maturation and suggest that adenosine regulates CD4(+) T cell responses by selecting for DC with impaired immunogencity.

  20. Processible Polyaniline Copolymers and Complexes.

    NASA Astrophysics Data System (ADS)

    Liao, Yun-Hsin

    1995-01-01

    Polyaniline (PANI) is an intractable polymer due to the difficulty of melt processing or dissolving it in common solvents. The purpose of the present investigation was to prepare a new class of conducting polyanilines with better solubility both in base and dope forms by (1) adding external salt to break aggregated chains, (2) introducing ring substituted units onto the backbone without disturbing the coplanar structure, and (3) complexing with polymeric dopants to form a soluble polymer complex. Aggregation of PANI chains in dilute solution was investigated in N-methyl-2-pyrrolidinone (NMP) by light scattering, gel permeation chromatography, and viscosity measurements. The aggregation of chains resulted in a negative second virial coefficient in light scattering measurement, a bimodal molecular weight distribution in gel permeation chromatography, and concave reduced viscosity curves. The aggregates can be broken by adding external salt, which resulting in a higher reduced viscosity. The driving force for aggregation is assumed to be a combination of hydrogen bonding between the imine and amine groups, and the rigidity of backbone. The aggregation was modeled to occur via side-on packing of PANI chains. The ring substituted PANI copolymers, poly(aniline -co-phenetidine) were synthesized by chemical oxidation copolymerization using ammonium persulfate as an oxidant. The degree of copolymerization declined with an increasing feed of o-phenetidine in the reaction mixture. The o-phenetidine had a higher reactivity than aniline in copolymerization resulting in a higher content of o-phenetidine in copolymers. The resulting copolymers can be readily dissolved in NMP up to 20% (w/w), and other common solvents, and solutions possess a longer gelation time. The highly soluble copolymer with 20 mole % o-phenetidine in the backbone has same order of conductivity as the unsubstituted PANI after it is doped by HCl. Complexation of PANI and polymeric dopant, poly

  1. Mixing thermodynamics of block-random copolymers

    NASA Astrophysics Data System (ADS)

    Beckingham, Bryan Scott

    microphase-separated if they were connected as a diblock. However, attachment of the A block, and consequent localization of the A-B block junction to the A-B lamellar interface, induces extensive separation between the B and C blocks. The organization of the crystallized E block was also examined and it was found that in a weakly-segregated triblock, crystallization of the E block destroys the melt lamellar structure, but for more segregated triblocks, E crystallization is effectively confined by the melt structure, leading to an orientation wherein the E crystallites stack orthogonally to the lamellar microdomains, as observed previously in E-containing diblock copolymers exhibiting confined crystallization. Addditionally, the microphase separation of the two hydrogenated derivatives of an S-I-SrhI triblock, generating A-hI-ArhI triblocks, is also probed. While the two derivatives possess nearly identical block volume fractions, differences in the magnitudes of the block interaction energies results in the formation of two disparate ordered morphologies.

  2. Inosine attenuates spontaneous activity in the rat neurogenic bladder through an A2B pathway

    PubMed Central

    Doyle, Claire; Cristofaro, Vivian; Sack, Bryan S.; Lukianov, Stefan N.; Schäfer, Mattias; Chung, Yeun Goo; Sullivan, Maryrose P.; Adam, Rosalyn M.

    2017-01-01

    Neurogenic detrusor overactivity (NDO) is among the most challenging complications of spinal cord injury (SCI). A recent report by us demonstrated an improvement in NDO in SCI rats following chronic systemic treatment with the purine nucleoside inosine. The objective of this study was to investigate the mechanism of action of inosine underlying improvement of NDO. Male Sprague-Dawley rats underwent complete spinal cord transection at T8. Inosine (1 mM) delivered intravesically to SCI rats during conscious cystometry significantly decreased the frequency of spontaneous non-voiding contractions. In isolated tissue assays, inosine (1 mM) significantly decreased the amplitude of spontaneous activity (SA) in SCI bladder muscle strips. This effect was prevented by a pan-adenosine receptor antagonist CGS15943, but not by A1 or A3 receptor antagonists. The A2A antagonist ZM241385 and A2B antagonist PSB603 prevented the effect of inosine. The effect of inosine was mimicked by the adenosine receptor agonist NECA and the A2B receptor agonist BAY60-6583. The inhibition of SA by inosine was not observed in the presence of the BK antagonist, iberiotoxin, but persisted in the presence of KATP and SK antagonists. These findings demonstrate that inosine acts via an A2B receptor-mediated pathway that impinges on specific potassium channel effectors. PMID:28294142

  3. Catalytic production of olefin block copolymers via chain shuttling polymerization.

    PubMed

    Arriola, Daniel J; Carnahan, Edmund M; Hustad, Phillip D; Kuhlman, Roger L; Wenzel, Timothy T

    2006-05-05

    We report a catalytic system that produces olefin block copolymers with alternating semicrystalline and amorphous segments, achieved by varying the ratio of alpha-olefin to ethylene in the two types of blocks. The system uses a chain shuttling agent to transfer growing chains between two distinct catalysts with different monomer selectivities in a single polymerization reactor. The block copolymers simultaneously have high melting temperatures and low glass transition temperatures, and therefore they maintain excellent elastomeric properties at high temperatures. Furthermore, the materials are effectively produced in economically favorable, continuous polymerization processes.

  4. Hydrostatic pressure studies of polyvinylidine fluoride (PVDF) and its copolymers

    SciTech Connect

    Samara, G.A.; Bauer, F.

    1987-01-01

    The frequency, temperature and hydrostatic pressure (less than or equal to10 kbar) dependences of the dielectric properties, molecular relaxations and phase transitions in PVDF and a copolymer with a 30% trifluorethylene were investigated. For the copolymer, both the ferroelectric transition (T/sub c/) and dynamic melting (T/sub m/) temperatures exhibit large increases with pressure. PVDF itself does not exhibit a T/sub c/ below T/sub m/, but its T/sub m/ also shows a large increase with pressure. The pressure and frequency dependences suggest an explanation for why it is possible to use these polymers as piezoelectric shock wave gauges to relatively high shock pressures.

  5. Unexpected Consequences of Block Polydispersity on the Self-Assembly of ABA Triblock Copolymers

    SciTech Connect

    Widin, Joan M.; Schmitt, Adam K.; Schmitt, Andrew L.; Im, Kyuhyun; Mahanthappa, Mahesh K.

    2012-05-09

    Controlled/'living' polymerizations and tandem polymerization methodologies offer enticing opportunities to enchain a wide variety of monomers into new, functional block copolymer materials with unusual physical properties. However, the use of these synthetic methods often introduces nontrivial molecular weight polydispersities, a type of chain length heterogeneity, into one or more of the copolymer blocks. While the self-assembly behavior of monodisperse AB diblock and ABA triblock copolymers is both experimentally and theoretically well understood, the effects of broadening the copolymer molecular weight distribution on block copolymer phase behavior are less well-explored. We report the melt-phase self-assembly behavior of SBS triblock copolymers (S = poly(styrene) and B = poly(1,4-butadiene)) comprised of a broad polydispersity B block (M{sub w}/M{sub n} = 1.73-2.00) flanked by relatively narrow dispersity S blocks (M{sub w}/M{sub n} = 1.09-1.36), in order to identify the effects of chain length heterogeneity on block copolymer self-assembly. Based on synchrotron small-angle X-ray scattering and transmission electron microscopy analyses of seventeen SBS triblock copolymers with poly(1,4-butadiene) volume fractions 0.27 {le} f{sub B} {le} 0.82, we demonstrate that polydisperse SBS triblock copolymers self-assemble into periodic structures with unexpectedly enhanced stabilities that greatly exceed those of equivalent monodisperse copolymers. The unprecedented stabilities of these polydisperse microphase separated melts are discussed in the context of a complete morphology diagram for this system, which demonstrates that narrow dispersity copolymers are not required for periodic nanoscale assembly.

  6. Effects of hnRNP A2/B1 Knockdown on Inhibition of Glioblastoma Cell Invasion, Growth and Survival.

    PubMed

    Deng, Jinmu; Chen, Song; Wang, Feng; Zhao, Hongxin; Xie, Zongyi; Xu, Zhongye; Zhang, Qingtao; Liang, Ping; Zhai, Xuan; Cheng, Yuan

    2016-03-01

    Heterogeneous nuclear ribonucleoprotein A2/B1 (hnRNP A2/B1) plays an important role in influence of pre-messenger RNA (pre-mRNA) processing and mRNA metabolism and transportation in cells. Increasing evidence indicates that hnRNP A2/B1 played an important role in development and progression of various human cancers. Forty cases of normal and human glioma tissue samples were analyzed using immunohistochemistry to reveal the expression of hnRNP A2/B1 protein in the samples. Then, knockdown of hnRNP A2/B1 expression induced by RNA interference (RNAi) method was used to analyze the role of hnRNP A2/B1 in glioblastoma cell viability, adhesion, migration, invasion, and chemoresistance for temozolomide (TMZ). The data showed that hnRNP A2/B1 protein was overexpressed in glioma tissue specimens and associated with advanced glioma grades. Knockdown of hnRNP A2/B1 could reduce glioblastoma cell viability, adhesion, migration, invasion, and chemoresistance for TMZ capacity, but induced tumor cells to apoptosis and reactive oxygen species (ROS) generation in glioma U251 and SHG44 cells. Molecularly, hnRNP A2/B1 knockdown reduced expression of phospho-STAT3 and MMP-2. Detection of hnRNP A2/B1 expression may be useful as a biomarker for prediction of glioma progression and knockdown of hnRNP A2/B1 expression as a novel strategy in future control of glioblastoma in clinic.

  7. The impact of adenosine and A(2B) receptors on glucose homoeostasis.

    PubMed

    Rüsing, D; Müller, C E; Verspohl, E J

    2006-12-01

    Adenosine and adenosine receptor antagonists are involved in glucose homoeostasis. The participating receptors are not known, mainly due to a lack of specific agonists and antagonists, but are reasonable targets for anti-diabetic therapy. The stable, albeit nonselective, adenosine analogue NECA (5'-N-ethylcarboxamidoadenosine) (10 microM) reduced glucose-stimulated insulin release from INS-1 cells. This was mimicked by A(1)-(CHA), A(2A)-(CGS-21680) and A(3)-receptor agonists (Cl-IB-MECA). Two newly synthesized A(2B)-receptor antagonists, PSB-53 and PSB-1115, counteracted the inhibitory effect of NECA. These in-vitro effects were mirrored by in-vivo data with respect to CHA, CGS and Cl-IB-MECA. Distinct concentrations of either PSB-53 or PSB-1115 reversed the decrease in plasma insulin induced by NECA. This was not mimicked by a corresponding change in blood glucose. The effect of PSB-1115 was also obvious in diabetic GotoKakizaki rats: plasma insulin was increased whereas blood glucose was unchanged. During most experiments the effects on blood glucose were not impressive probably because of the physiologically necessary homoeostasis. The adenosine levels were not different in normal Wistar rats and in diabetic GotoKakzaki rats. Altogether the A(2B)-receptor antagonists showed an anti-diabetic potential mainly by increasing plasma insulin levels under conditions when the adenosine tonus was elevated in-vivo and increased insulin release in-vitro.

  8. Adenosine receptors and diabetes: Focus on the A(2B) adenosine receptor subtype.

    PubMed

    Merighi, Stefania; Borea, Pier Andrea; Gessi, Stefania

    2015-09-01

    Over the last two decades, diabetes mellitus has become one of the most challenging health problems worldwide. Diabetes mellitus, classified as type I and II, is a pathology concerning blood glucose level in the body. The nucleoside adenosine has long been known to affect insulin secretion, glucose homeostasis and lipid metabolism, through activation of four G protein coupled adenosine receptors (ARs), named A1, A2A, A2B and A3. Currently, the novel promising subtype to develop new drugs for diabetes treatment is the A2BAR subtype. The use of selective agonists and antagonists for A2BAR subtype in various diabetic animal models allowed us to identify several effects of A2BAR signaling in cell metabolism. In particular, the focus of this review is to summarize the studies on purinergic signaling associated with diabetes through A2BARs modulation.

  9. Adenosine A2B Receptor: From Cell Biology to Human Diseases

    PubMed Central

    Sun, Ying; Huang, Pingbo

    2016-01-01

    Extracellular adenosine is a ubiquitous signaling molecule that modulates a wide array of biological processes. Recently, significant advances have been made in our understanding of A2B adenosine receptor (A2BAR). In this review, we first summarize some of the general characteristics of A2BAR, and then we describe the multiple binding partners of the receptor, such as newly identified α-actinin-1 and p105, and discuss how these associated proteins could modulate A2BAR's functions, including certain seemingly paradoxical functions of the receptor. Growing evidence indicates a critical role of A2BAR in cancer, renal disease, and diabetes, in addition to its importance in the regulation of vascular diseases, and lung disease. Here, we also discuss the role of A2BAR in cancer, renal disease, and diabetes and the potential of the receptor as a target for treating these three diseases. PMID:27606311

  10. Adenosine A2B receptor: from cell biology to human diseases

    NASA Astrophysics Data System (ADS)

    Sun, Ying; Huang, Pingbo

    2016-08-01

    Extracellular adenosine is a ubiquitous signaling molecule that modulates a wide array of biological processes. Recently, significant advances have been made in our understanding of A2B adenosine receptor (A2BAR). In this review, we first summarize some of the general characteristics of A2BAR, and then we describe the multiple binding partners of the receptor, such as newly identified α-actinin-1 and p105, and discuss how these associated proteins could modulate A2BAR’s functions, including certain seemingly paradoxical functions of the receptor. Growing evidence indicates a critical role of A2BAR in cancer, renal disease, and diabetes, in addition to its importance in the regulation of vascular diseases and lung disease. Here, we also discuss the role of A2BAR in cancer, renal disease, and diabetes and the potential of the receptor as a target for treating these three diseases.

  11. Morphology of Novel Semicrystalline Ethylene-α-Olefin Block Copolymers

    NASA Astrophysics Data System (ADS)

    Li, Sheng; Register, Richard; Landes, Brian

    2009-03-01

    In semicrystalline block copolymers, the solid-state structure can be set either by block incompatibility or by crystallization of one or more blocks. Depending on the block interaction strength, a wide array of solid-state morphologies may be observed, ranging from spherulitic to confined crystallization within preexisting microphase-separated domains. Dow Chemical has recently developed a novel chain shuttling polymerization process to produce olefin block copolymers with alternating amorphous and semicrystalline chain segments, where each block exhibits the most-probable distribution. We examined the melt and solid-state morphologies of these novel olefin block copolymers, having a high octene content in the amorphous block, using two- dimensional synchrotron small-angle and wide-angle x-ray scattering on specimens oriented by channel die compression. Multiblock and diblock copolymers with near-symmetric compositions showed well-ordered lamellar structures at room temperature with long periods exceeding 100 nm, with little dependence on thermal history, indicating the presence of a mesophase-separated melt which templates crystallization.

  12. Synthesis of polytetrafluoroethylene based olefinic copolymer by gamma radiation grafting

    NASA Astrophysics Data System (ADS)

    Ferreto, H. F. R.; Lima, L. F. C. P.; Parra, D. F.; Zaia, V.; Lugão, A. B.

    2007-12-01

    High speed extrusion of linear low density polyethylene (LLDPE) is limited by processes shortcoming known as 'melt fracture' and 'sharkskin', which are surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and with poor surface properties. The fluoropolymer processing additives are used to eliminate the surface defect by coating the die wall and inducing slip at the coated fluoropolymer surface/LLDPE interface. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer grafted with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by grafting an olefinic monomer the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to allow recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. The olefinic monomer used was 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). The obtained copolymer (0.2-2.0 wt%) was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the developed process rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'.

  13. Ultraviolet absorbing copolymers

    DOEpatents

    Gupta, Amitava; Yavrouian, Andre H.

    1982-01-01

    Photostable and weather stable absorping copolymers have been prepared from acrylic esters such as methyl methacrylate containing 0.1 to 5% of an 2-hydroxy-allyl benzophenone, preferably the 4,4' dimethoxy derivative thereof. The pendant benzophenone chromophores protect the acrylic backbone and when photoexcited do not degrade the ester side chain, nor abstract hydrogen from the backbone.

  14. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G.; Matzger, Adam J.; Benin, Annabelle I.; Willis, Richard R.

    2012-12-04

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  15. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2012-11-13

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  16. Block coordination copolymers

    DOEpatents

    Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

    2014-11-11

    The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

  17. Crystallization studies of polyethylene -poly(ethylene glycol) graft copolymers

    NASA Astrophysics Data System (ADS)

    Mark, P. R.; Hovey, G. E.; Murthy, N. S.; Breitenkamp, K.; Kade, M.; Emerick, T.

    2006-03-01

    Structure and crystallization behavior of three copolymers obtained by grafting poly (ethylene glycol) (PEG) chains to polyethylene (PE) main chain was investigated by variable temperature x-ray diffraction and thermal analysis. The results show that PEG side chains and PE main chains crystallize into separate domains. This is especially true when grafted chains are long (50 and 100 repeat units), in which the PEG domains are same as in PEG homopolymer both in structure and in melting behavior. In the copolymer with shorter chains (25 repeat units), the PEG crystals are not distinct and melting is broad. The PEG domains can be dissolved in water or ethanol without altering the mechanical integrity of the film. PE crystallites in both samples are similar to that in PE homopolymer. For instance, the thermal expansion of the basal cell plane (a- and b-axes) of the PE domains agrees well with that of PE homopolymer over the entire temperature range from ambient to melt. However, the chain-axis dimension PE-lattice in the copolymer is shorter by ˜ 0.05 å and the basal dimensions are larger by ˜ 0.05 å. The changes in these dimensions due to the changes in the length of the grafted PEG chains were investigated.

  18. Adenosine A2B-receptor-mediated cyclic AMP accumulation in primary rat astrocytes.

    PubMed Central

    Peakman, M. C.; Hill, S. J.

    1994-01-01

    1. The effects of adenosine receptor agonists and antagonists on the accumulation of cyclic AMP have been investigated in primary cultures of rat astrocytes. 2. Adenosine A2-receptor stimulation caused a concentration-dependent increase in the accumulation of [3H]-cyclic AMP in cells prelabelled with [3H]-adenine. The rank order of agonist potencies was 5'-N-ethylcarboxamidoadenosine (NECA; EC50 = 1 microM) > adenosine (EC50 = 5 microM) > 2-chloroadenosine (EC50 = 20 microM) >> CGS 21680 (EC50 > 10 microM). The presence of 0.5 microM dipyridamole, an adenosine uptake blocker, had no effect on the potency of adenosine. 3. The response to 10 microM NECA was antagonized in a concentration-dependent manner by the non-selective adenosine receptor antagonists, xanthine amine congener (apparent KD = 12 nM), PD 115,199 (apparent KD = 134 nM) and 8-phenyltheophylline (apparent KD = 126 nM). However, the A1-receptor-selective antagonist, 8-cyclopentyl-1,3-dipropylxanthine, had no significant effect on the responses to NECA or 2-chloroadenosine at concentrations up to 1 microM. 4. Stimulation of A1-receptors with the selective agonist, N6-cyclopentyladenosine, did not alter the basal accumulation of [3H]-cyclic AMP but inhibited a forskolin-mediated elevation of [3H]-cyclic AMP accumulation by a maximal value of 42%. This inhibition was fully reversed in the presence of 0.1 microM, 8-cyclopentyl-1,3-dipropylxanthine. 5. The time course for NECA-mediated [3H]-cyclic AMP accumulation was investigated. The results suggest that there is a substantial efflux of cyclic AMP from the cells in addition to the rapid and sustained elevation of intracellular cyclic AMP (5 fold over basal) which was also observed. 6. These data indicate that rat astrocytes in primary culture express an A2B-adenosine receptor coupled positively to adenylyl cyclase. Furthermore, the presence of A1-receptors negatively coupled to adenylyl cyclase appears to have no significant effect on the A2B

  19. The A2B adenosine receptor modulates pulmonary hypertension associated with interstitial lung disease

    PubMed Central

    Karmouty-Quintana, Harry; Zhong, Hongyan; Acero, Luis; Weng, Tingting; Melicoff, Ernestina; West, James D.; Hemnes, Anna; Grenz, Almut; Eltzschig, Holger K.; Blackwell, Timothy S.; Xia, Yang; Johnston, Richard A.; Zeng, Dewan; Belardinelli, Luiz; Blackburn, Michael R.

    2012-01-01

    Development of pulmonary hypertension is a common and deadly complication of interstitial lung disease. Little is known regarding the cellular and molecular mechanisms that lead to pulmonary hypertension in patients with interstitial lung disease, and effective treatment options are lacking. The purpose of this study was to examine the adenosine 2B receptor (A2BR) as a regulator of vascular remodeling and pulmonary hypertension secondary to pulmonary fibrosis. To accomplish this, cellular and molecular changes in vascular remodeling were monitored in mice exposed to bleomycin in conjunction with genetic removal of the A2BR or treatment with the A2BR antagonist GS-6201. Results demonstrated that GS-6201 treatment or genetic removal of the A2BR attenuated vascular remodeling and hypertension in our model. Furthermore, direct A2BR activation on vascular cells promoted interleukin-6 and endothelin-1 release. These studies identify a novel mechanism of disease progression to pulmonary hypertension and support the development of A2BR antagonists for the treatment of pulmonary hypertension secondary to interstitial lung disease.—Karmouty-Quintana, H., Zhong, H., Acero, L., Weng, T., Melicoff, E., West, J. D., Hemnes, A., Grenz, A., Eltzschig, H. K., Blackwell, T. S., Xia, Y., Johnston, R. A., Zeng, D., Belardinelli, L., Blackburn, M. R. The A2B adenosine receptor modulates pulmonary hypertension associated with interstitial lung disease. PMID:22415303

  20. The A2B adenosine receptor protects against inflammation and excessive vascular adhesion

    PubMed Central

    Yang, Dan; Zhang, Ying; Nguyen, Hao G.; Koupenova, Milka; Chauhan, Anil K.; Makitalo, Maria; Jones, Matthew R.; Hilaire, Cynthia St.; Seldin, David C.; Toselli, Paul; Lamperti, Edward; Schreiber, Barbara M.; Gavras, Haralambos; Wagner, Denisa D.; Ravid, Katya

    2006-01-01

    Adenosine has been described as playing a role in the control of inflammation, but it has not been certain which of its receptors mediate this effect. Here, we generated an A2B adenosine receptor–knockout/reporter gene–knock-in (A2BAR-knockout/reporter gene–knock-in) mouse model and showed receptor gene expression in the vasculature and macrophages, the ablation of which causes low-grade inflammation compared with age-, sex-, and strain-matched control mice. Augmentation of proinflammatory cytokines, such as TNF-α, and a consequent downregulation of IκB-α are the underlying mechanisms for an observed upregulation of adhesion molecules in the vasculature of these A2BAR-null mice. Intriguingly, leukocyte adhesion to the vasculature is significantly increased in the A2BAR-knockout mice. Exposure to an endotoxin results in augmented proinflammatory cytokine levels in A2BAR-null mice compared with control mice. Bone marrow transplantations indicated that bone marrow (and to a lesser extent vascular) A2BARs regulate these processes. Hence, we identify the A2BAR as a new critical regulator of inflammation and vascular adhesion primarily via signals from hematopoietic cells to the vasculature, focusing attention on the receptor as a therapeutic target. PMID:16823489

  1. The A2B adenosine receptor promotes Th17 differentiation via stimulation of dendritic cell IL-6.

    PubMed

    Wilson, Jeffrey M; Kurtz, Courtney C; Black, Steven G; Ross, William G; Alam, Mohammed S; Linden, Joel; Ernst, Peter B

    2011-06-15

    Adenosine is an endogenous metabolite produced during hypoxia or inflammation. Previously implicated as an anti-inflammatory mediator in CD4(+) T cell regulation, we report that adenosine acts via dendritic cell (DC) A(2B) adenosine receptor (A(2B)AR) to promote the development of Th17 cells. Mouse naive CD4(+) T cells cocultured with DCs in the presence of adenosine or the stable adenosine mimetic 5'-(N-ethylcarboximado) adenosine resulted in the differentiation of IL-17- and IL-22-secreting cells and elevation of mRNA that encode signature Th17-associated molecules, such as IL-23R and RORγt. The observed response was similar when DCs were generated from bone marrow or isolated from small intestine lamina propria. Experiments using adenosine receptor antagonists and cells from A(2B)AR(-/-) or A(2A)AR(-/-)/A(2B)AR(-/-) mice indicated that the DC A(2B)AR promoted the effect. IL-6, stimulated in a cAMP-independent manner, is an important mediator in this pathway. Hence, in addition to previously noted direct effects of adenosine receptors on regulatory T cell development and function, these data indicated that adenosine also acts indirectly to modulate CD4(+) T cell differentiation and suggested a mechanism for putative proinflammatory effects of A(2B)AR.

  2. IFN-γ prevents adenosine receptor (A2bR) upregulation to sustain the macrophage activation response

    PubMed Central

    Cohen, Heather B.; Ward, Amanda; Hamidzadeh, Kajal; Ravid, Katya; Mosser, David M.

    2015-01-01

    The priming of macrophages with IFN-γ prior to TLR stimulation results in enhanced and prolonged inflammatory cytokine production. Here, we demonstrate that following TLR stimulation, macrophages up regulate the adenosine 2b receptor (A2bR) to enhance their sensitivity to immunosuppressive extracellular adenosine. This up-regulation of A2bR leads to the induction of a macrophage with an immunoregulatory phenotype and the down regulation of inflammation. IFN-γ priming of macrophages, selectively prevents the induction of the A2bR in macrophages to mitigate sensitivity to adenosine and prevent this regulatory transition. IFN-γ-mediated A2bR blockade leads to a prolonged production of TNFα and IL-12 in response to TLR ligation. The pharmacological inhibition or the genetic deletion of the A2bR results in a hyper-inflammatory response to TLR ligation, similar to IFN-γ treatment of macrophages. Conversely, the overexpression of A2bR on macrophages blunts the IFN-γ effects and promotes the development of immunoregulatory macrophages. Thus, we propose a novel mechanism whereby IFN-γ contributes to host defense, by desensitizing macrophages to the immunoregulatory effects of adenosine. This mechanism overcomes the transient nature of TLR activation, and prolongs the anti-microbial state of the classically activated macrophage. This study may offer promising new targets to improve the clinical outcome of inflammatory diseases in which macrophage activation is dysregulated. PMID:26355158

  3. Expression of Receptors for Tetanus Toxin and Monoclonal Antibody A2B5 by Pancreatic Islet Cells

    NASA Astrophysics Data System (ADS)

    Eisenbarth, G. S.; Shimizu, K.; Bowring, M. A.; Wells, S.

    1982-08-01

    Studies of the reaction of antibody A2B5 and tetanus toxin with pancreatic islet cells, islet cell tumors, and other human amine precursor uptake and decarboxylation (APUD) tumors are described. By indirect immunofluorescence, antibody A2B5 and tetanus toxin were shown to specifically bind to the plasma membrane of human, rat, chicken, and mouse islet cells. The binding of antibody A2B5 to the cell surface of living islet cells has allowed isolation of these cells from a suspension of pancreatic cells by using a fluorescence-activated cell sorter. In studies designed to determine whether tetanus toxin and antibody A2B5 bound to the same surface antigen, A2B5 and tetanus toxin did not compete for binding to normal islet cells, a human islet cell tumor, or a rat islet cell tumor. In addition to binding to islet cell tumors, antibody A2B5 reacts with frozen sections, isolated cells, and cell lines of neural, neural crest, and APUD origin.

  4. Imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

    1992-01-01

    Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties.

  5. Clickable Amphiphilic Triblock Copolymers.

    PubMed

    Isaacman, Michael J; Barron, Kathryn A; Theogarajan, Luke S

    2012-06-15

    Amphiphilic polymers have recently garnered much attention due to their potential use in drug-delivery and other biomedical applications. A modular synthesis of these polymers is extremely desirable since it offers precise individual block characterization and increased yields. We present here for the first time a modular synthesis of poly(oxazoline)-poly(siloxane)-poly(oxazoline) block copolymers that have been clicked together using the copper-catalyzed azide-alkyne cycloaddition reaction. Various click methodologies for the synthesis of these polymers have been carefully evaluated and optimized. The approach using copper nanoparticles was found to be the most optimal among the methods evaluated. Furthermore, these results were extended to allow for a reactive Si-H group-based siloxane middle block to be successfully clicked. This enables the design of more complex amphiphilic block copolymers that have additional functionality, such as stimuli responsiveness, to be synthesized via a simple hydrosilylation reaction.

  6. Baroplastic Block copolymers

    NASA Astrophysics Data System (ADS)

    Hewlett, Sheldon A.

    2005-03-01

    Block copolymers with rubbery and glassy components have been observed to have pressure induced miscibility. These microphase-separated materials, termed baroplastics, were able to flow and be processed at temperatures below the Tg of the glassy component by simple compression molding and extrusion. Diblock and triblock copolymers of polystyrene and poly(butyl acrylate) or poly(2-ethyl hexyl acrylate) were synthesized by atom transfer radical polymerization (ATRP) and processed at room temperature into well defined transparent objects. SAXS and SANS measurements demonstrated partial mixing between components as a result of pressure during processing. DSC results also show the presence of distinct domains even after several processing cycles. Their mechanical properties after processing were tested and compared with commercial thermoplastic elastomers.

  7. Block copolymer battery separator

    SciTech Connect

    Wong, David; Balsara, Nitash Pervez

    2016-04-26

    The invention herein described is the use of a block copolymer/homopolymer blend for creating nanoporous materials for transport applications. Specifically, this is demonstrated by using the block copolymer poly(styrene-block-ethylene-block-styrene) (SES) and blending it with homopolymer polystyrene (PS). After blending the polymers, a film is cast, and the film is submerged in tetrahydrofuran, which removes the PS. This creates a nanoporous polymer film, whereby the holes are lined with PS. Control of morphology of the system is achieved by manipulating the amount of PS added and the relative size of the PS added. The porous nature of these films was demonstrated by measuring the ionic conductivity in a traditional battery electrolyte, 1M LiPF.sub.6 in EC/DEC (1:1 v/v) using AC impedance spectroscopy and comparing these results to commercially available battery separators.

  8. Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Hergenrother, Paul M.; Bass, Robert G.

    1991-01-01

    New imide/arylene ether copolymers prepared by reacting anhydride-terminated poly(amic acids) with amine-terminated poly(arylene ethers) in polar aprotic solvents. Each resulting copolymer may have one glass-transition temperature or two, depending on chemical structure and/or compatibility of block units. Most of copolymers form tough, solvent-resistant films with high tensile properties. Films cast from solution tough and flexible, and exhibit useful thermal and mechanical properties. Potentially useful as moldings, adhesives, or composite matrices. Because of flexible arylene ether blocks, these copolymers easier to process than polyimides.

  9. Polyhydroxyalkanoate copolymers from forest biomass.

    PubMed

    Keenan, Thomas M; Nakas, James P; Tanenbaum, Stuart W

    2006-07-01

    The potential for the use of woody biomass in poly-beta-hydroxyalkanoate (PHA) biosynthesis is reviewed. Based on previously cited work indicating incorporation of xylose or levulinic acid (LA) into PHAs by several bacterial strains, we have initiated a study for exploring bioconversion of forest resources to technically relevant copolymers. Initially, PHA was synthesized in shake-flask cultures of Burkholderia cepacia grown on 2.2% (w/v) xylose, periodically amended with varying concentrations of levulinic acid [0.07-0.67% (w/v)]. Yields of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) [P(3HB-co-3HV)] from 1.3 to 4.2 g/l were obtained and could be modulated to contain from 1.0 to 61 mol% 3-hydroxyvalerate (3HV), as determined by 1H and 13C NMR analyses. No evidence for either the 3HB or 4HV monomers was found. Characterization of these P(3HB-co-3HV) samples, which ranged in molecular mass (viscometric, Mv) from 511-919 kDa, by differential scanning calorimetry and thermogravimetric analyses (TGA) provided data which were in agreement for previously reported P(3HB-co-3HV) copolymers. For these samples, it was noted that melting temperature (Tm) and glass transition temperature (Tg) decreased as a function of 3HVcontent, with Tm demonstrating a pseudoeutectic profile as a function of mol% 3HV content. In order to extend these findings to the use of hemicellulosic process streams as an inexpensive carbon source, a detoxification procedure involving sequential overliming and activated charcoal treatments was developed. Two such detoxified process hydrolysates (NREL CF: aspen and CESF: maple) were each fermented with appropriate LA supplementation. For the NREL CF hydrolysate-based cultures amended with 0.25-0.5% LA, P(3HB-co-3HV) yields, PHA contents (PHA as percent of dry biomass), and mol% 3HV compositions of 2.0 g/l, 40% (w/w), and 16-52 mol% were obtained, respectively. Similarly, the CESF hydrolysate-based shake-flask cultures yielded 1.6 g/l PHA, 39% (w

  10. Shallow oceanic crust: Full waveform tomographic images of the seismic layer 2A/2B boundary

    NASA Astrophysics Data System (ADS)

    Christeson, Gail L.; Morgan, Joanna V.; Warner, Michael R.

    2012-05-01

    We present results of full-waveform tomographic inversions of four profiles acquired over young intermediate- and fast spreading rate oceanic crust. The mean velocity-depth functions from our study include a 0.25-0.30 km-thick low-velocity, low-gradient region beneath the seafloor overlying a 0.24-0.28-km-thick high-gradient region; together these regions compose seismic layer 2A. Mean layer 2A interval velocities are 3.0-3.2 km/s. The mean depth to the layer 2A/2B boundary is 0.49-0.54 km, and mean velocities within the upper 0.25 km of layer 2B are 4.7-4.9 km/s. Previous velocity analyses of the study areas using 1-D ray tracing underestimate the thickness of the high-gradient region at the base of layer 2A. We observe differences in the waveform inversion velocity models that correspond to imaging of the layer 2A event; regions with a layer 2A event have higher velocity gradients at the base of layer 2A. Intermittent high velocities, which we interpret as massive flows, are observed in the waveform inversion velocity models at 0.05-0.10 km below the seafloor (bsf) over 10-25% of the intermediate-spreading profiles and 20-45% of the fast spreading profiles. The high-gradient region located 0.25-0.54 km bsf at the base of layer 2A may be associated with an increased prevalence of massive flows, the first appearance of dikes (lava-dike transition zone), or with increased crack sealing by hydrothermal products. The upper portion of layer 2B, which begins at 0.49-0.54 km bsf, may correspond to sheeted dikes or the top of the transition zone of lavas and dikes.

  11. Adenosine A2B receptor modulates intestinal barrier function under hypoxic and ischemia/reperfusion conditions

    PubMed Central

    Yang, Yang; Qiu, Yuan; Wang, Wensheng; Xiao, Weidong; Liang, Hongyin; Zhang, Chaojun; Yang, Hanwenbo; Teitelbaum, Daniel H; Sun, Li-Hua; Yang, Hua

    2014-01-01

    Background: Intestinal barrier function failure from ischemia/reperfusion (I/R) and acute hypoxia has been implicated as a critical determinant in the predisposition to intestinal inflammation and a number of inflammatory disorders. Here, we identified the role of Adenosine A2B receptor (A2BAR) in the regulation of intestinal barrier function under I/R and acute hypoxic conditions. Methods: C57BL/6J mice were used, and were randomized into three groups: Sham, I/R, IR+PSB1115 (a specific A2BAR antagonist) groups. After surgery, the small bowel was harvested for immunohistochemical staining, RNA and protein content, and intestinal permeability analyses. Using an epithelial cell culture model, we investigated the influence of hypoxia on the epithelial function, and the role of A2BAR in the expressions of tight junction and epithelial permeability. The expressions of Claudin-1, occludin and ZO-1 were detected by RT-PCR and Western-Blot. Epithelial barrier function was assessed with transepithelial resistance (TER). Results and conclusions: The A2BAR antagonist, PSB1115, significantly increased tight junction protein expression after intestinal I/R or acute hypoxia conditions. PSB1115 also attenuated the disrupted distribution of TJ proteins. Furthermore, inhibition of A2BAR attenuated the decrease in TER induced by I/R or acute hypoxic conditions, and maintained intestinal barrier function. Antagonism of A2BAR activity improves intestinal epithelial structure and barrier function in a mouse model of intestinal I/R and a cell model of acute hypoxia. These findings support a potentially destructive role for A2BAR under intestinal I/R and acute hypoxic conditions. PMID:24966910

  12. Analytic PRISM theory of structurally asymmetric polymer blends and copolymers

    SciTech Connect

    Schweizer, K.S. )

    1993-10-25

    Analytic PRISM theory with the new molecular closures is applied to determine the effective chi-parameters and spinodal instability curves for structurally asymmetric polymer alloys. Compressibility effects are found to be very important, and the use of a literal incompressible RPA-like approximation is shown to incur qualitative errors in most cases. A rich and nonadditive dependence of phase transition temperatures and apparent SANS chi-parameters on backbone stiffness asymmetry, attractive interaction potential asymmetry, and thermodynamic variables is found for binary homopolymer blends. A novel strategy for designing miscible mixtures based on a cancellation, or compensation, of the relevant asymmetries is identified. The influence of chain stiffness asymmetry in blends characterized by specific interactions is also studied. Generalization of the analytic PRISM theory to mixtures of random copolymers and periodic block copolymer melts is presented. All the rich behavior predicted for phase-separating homopolymer mixtures is again found for these systems, plus additional non mean field effects associated with random copolymer composition and block architecture. The theory is applied semiquantitatively to interpret recent experiments on polyolefin blends, diblock copolymers, and random copolymer alloys. Theoretical predictions are made which qualitatively account for recent experimental observations of a strong influence of stiffness asymmetry on phase separation temperatures, and the breakdown of the mean field random copolymer approach. Anomalous behavior is also predicted for deuterated mixtures due to an interference between the consequences of stiffness asymmetry and enthalipic interactions. The physical mechanism for the many non-Flory-Huggins effects predicted by the compressible PRISM theory is local, scalar density correlations, which appears to be different than the nematic fluctuation mechanism suggested by recent field theoretic work.

  13. Stereocomplex Crystallization of Linear Two-Armed Stereo Diblock Copolymers: Effects of Chain Directional Change, Coinitiator Moiety, and Terminal Groups.

    PubMed

    Tsuji, Hideto; Ogawa, Michiaki; Arakawa, Yuki

    2017-03-30

    Two-armed poly(l-lactide) (PLLA)-b-poly(d-lactide) (PDLA) (2-LD) copolymers with a wide-range of molecular weight were synthesized and the effect of coinitiator moiety, which functions as impurity and causes chain directional change in the middle of molecules (Effect A), and/or the additional effect of types of terminal groups (Effect B) on crystallization behavior of 2-LD copolymers were studied, in comparison with that reported for one-armed PLLA-b-PDLA (1-LD) copolymers. Formation of only stereocomplex (SC) crystallites in 2-LD and 1-LD copolymers indicates that neighboring PLLA and PDLA blocks facilitated SC crystallization and neither Effect A nor B affected the crystalline species. Effect A and/or B (both hydroxyl terminal groups) disturbed cold SC crystallization of 2-LD copolymers compared to that of 1-LD copolymers. Crystalline growth morphologies of 2-LD and 1-LD copolymers during cold SC crystallization were spherical and solid sheaf, respectively, exhibiting that crystalline growth morphology was influenced by Effects A and/or B. The melting temperature or crystalline thickness of SC crystallites were determined by number-average molecular weight per one block and not affected by Effect A or B. Maximum radial growth rates of spherulites of 2-LD copolymers compared to those of 1-LD copolymers were largely decreased by Effect A and/or B (both hydroxyl terminal groups).

  14. Interfacial Modification by Copolymers: The Importance of Copolymer Microstructure

    NASA Astrophysics Data System (ADS)

    Dadmun, Mark; Eastwood, Eric

    2002-03-01

    The dispersion of nanoscale particles or domains in a polymer matrix can readily lead to nonlinear enhancement of material properties. Our research group has been examining two primary methods to improve the properties of multicomponent polymer systems: compatibilization of a blend with an interfacial modifier or improving the miscibility and properties of polymer blends with specific interactions. In this talk, the importance of specific copolymer microstructure on its ability to strengthen a biphasic interface will be discussed. Atom transfer radical polymerization has been utilized to polymerize a series of multiblock copolymers containing styrene and methyl methacrylate. This, in turn, has allowed the synthesis of a series of copolymers with careful control of the sequence distribution. Subsequent experiments that determine the interfacial strength between two polymers in the presence and absence of these copolymers has provided critical information that documents the importance of copolymer sequence distribution on its ability to strengthen a biphasic interface.

  15. Transient Structures and Rheological Properties of SBS Block Copolymer Melts.

    DTIC Science & Technology

    1982-06-08

    Henderson and M.C. Williams, J. Polym. Sci., Polymer Letters, 17, 257 (1979). [111 E.V. Gouinlock and R.S. Porter , Polym. Eng. Sci., 17, 535 (1977...6, 277 (1974). II -16- [18] G. Akovali, J. Diamant , and M. Shen, J. Macromol. Sci., Phys. Ed., 13, 117 (1977). [191 Y.D.M. Chen and R.E. Cohen, J...Polym. Eng. Sci. [22] G. Kraus and R.W. Rollman, J. Polym. Sci., Polym. Phys. Ed., 14, 1133 (1976). [23] J. Diamant , D.S. Soong and M.C. Williams in

  16. Dynamics of Block Copolymer Nanocomposites

    SciTech Connect

    Mochrie, Simon G. J.

    2014-09-09

    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  17. Inducing Order from Disordered Copolymers: On Demand Generation of Triblock Morphologies Including Networks

    SciTech Connect

    Tureau, Maëva S.; Kuan, Wei-Fan; Rong, Lixia; Hsiao, Benjamin S.; Epps, III, Thomas H.

    2015-10-15

    Disordered block copolymers are generally impractical in nanopatterning applications due to their inability to self-assemble into well-defined nanostructures. However, inducing order in low molecular weight disordered systems permits the design of periodic structures with smaller characteristic sizes. Here, we have induced nanoscale phase separation from disordered triblock copolymer melts to form well-ordered lamellae, hexagonally packed cylinders, and a triply periodic gyroid network structure, using a copolymer/homopolymer blending approach, which incorporates constituent homopolymers into selective block domains. This versatile blending approach allows one to precisely target multiple nanostructures from a single disordered material and can be applied to a wide variety of triblock copolymer systems for nanotemplating and nanoscale separation applications requiring nanoscale feature sizes and/or high areal feature densities.

  18. Quantitative study of temperature-dependent order in thin films of cylindrical morphology block copolymer

    NASA Astrophysics Data System (ADS)

    Mishra, Vindhya; Kramer, Edward

    2010-03-01

    Disordering and defect generation in block copolymer systems at high temperatures is of significance to get a better understanding of the physics governing these systems, which can also direct efforts to minimize them. We have studied the smectic-nematic-isotropic transition in confined monolayers and bilayers of cylindrical morphology poly (styrene-b-2vinyl pyridine) diblock copolymer. Previous studies of melting phenomena in block copolymer thin films have relied on quantitative AFM studies alone. We have supplemented AFM studies with grazing incidence small angle X-ray diffraction lineshape analysis to quantify the decay of translational and orientational order with increasing temperature. The results have been interpreted in the context of the Toner-Nelson theory of melting for layered systems.

  19. Block copolymer morphologies confined by square-shaped particle: Hard and soft confinement

    NASA Astrophysics Data System (ADS)

    Zhang, Qiyi; Yang, Wenyan; Hu, Kaiyan

    2016-11-01

    The self-assembly of diblock copolymers confined around one square-shaped particle is studied systematically within two-dimensional self-consistent field theory (SCFT). In this model, we assume that the thin block copolymer film is confined in the vicinity of a square-shaped particle by a homopolymer melt, which is equivalent to the poor solvents. Multiple sequences of square-shaped particle-induced copolymer aggregates with different shapes and self-assembled internal morphologies are predicted as functions of the particle size, the structural portion of the copolymer, and the volume fraction of the copolymer. A rich variety of aggregates are found with complex internal self-assembled morphologies including complex structures of the vesicle, with one or several inverted micelle surrounded by the outer monolayer with the particle confined in the core. These results demonstrate that the assemblies of diblock copolymers formed around the square-shaped particle in poor solvents are of immediate interest to the assembly of copolymer and the morphology of biomembrane in the confined environment, as well as to the transitions of vesicles to micelles. Project supported by the National Natural Science Foundation of China (Grant No. 20804060) and the Research Foundation of Chongqing University of Science and Technology, China (Grant No. CK2013B16).

  20. How to Place Block Copolymer Molecules at the Interface of a Binary Blend

    NASA Astrophysics Data System (ADS)

    Chen, Zhong-Ren; Xu, Yuci; Zhong, Shuo

    2015-03-01

    Block copolymers have been used to reduce the domain size of immiscible polymer blends and thus improve the mechanical and other properties. The effectiveness of this method, however, depends on the percentage of these polymeric surfactants residing at the interface of the blend. In fact, theoretical as well as experimental work indicate that a large percentage of block copolymers form micelles in the bulk of one or both of the component polymers. These micelles may serve as weak spots initiating crack propagation. Previous work have been focused on the design of molecular architecture and synthesis of new block copolymers to address this problem. In this presentation, a simple mixing strategy is applied to make each block copolymer molecule stay at the interface. As one example, when this strategy is used to mix natural rubber (NR) with butadiene rubber (BR), a small amount of low molecular weight block copolymer (LIR) improves both processing characteristics such as melt viscosity and mechanical properties of cured samples, such as crack resistance. AFM micrographs show the much smaller domain size; and an original real-time monitoring system reveals the lowest crack growth rate. Using a model A/B/A-B binary blend, we have witnessed by microscopy that all block copolymer molecules form micelles at the first mixing step, and all of these micelles are disappeared and all block copolymer molecules stay at the interface after the second mixing step.

  1. ABSORPTION OF CO2 IN HIGH ACRYLONITRILE CONTENT COPOLYMERS: DEPENDENCE ON ACRYLONITRILE CONTENT. (R829555)

    EPA Science Inventory

    In continuation of our goal to determine the ability of CO2 to plasticize acrylonitrile (AN) copolymers and facilitate melt processing at temperatures below the onset of thermal degradation, a systematic study has been performed to determine the influence of AN cont...

  2. ABSORPTION OF CO2 AND SUBSEQUENT VISCOSITY REDUCTION OF AN ACRYLONITRILE COPOLYMER. (R829555)

    EPA Science Inventory

    Acrylonitrile (AN) copolymers (AN content greater than about 85 mol%) are traditionally solution processed to avoid a cyclization and crosslinking reaction that takes place at temperatures where melt processing would be feasible. It is well known that carbon dioxide (CO

  3. StyA1 and StyA2B from Rhodococcus opacus 1CP: a Multifunctional Styrene Monooxygenase System▿

    PubMed Central

    Tischler, Dirk; Kermer, René; Gröning, Janosch A. D.; Kaschabek, Stefan R.; van Berkel, Willem J. H.; Schlömann, Michael

    2010-01-01

    Two-component flavoprotein monooxygenases are emerging biocatalysts that generally consist of a monooxygenase and a reductase component. Here we show that Rhodococcus opacus 1CP encodes a multifunctional enantioselective flavoprotein monooxygenase system composed of a single styrene monooxygenase (SMO) (StyA1) and another styrene monooxygenase fused to an NADH-flavin oxidoreductase (StyA2B). StyA1 and StyA2B convert styrene and chemical analogues to the corresponding epoxides at the expense of FADH2 provided from StyA2B. The StyA1/StyA2B system presents the highest monooxygenase activity in an equimolar ratio of StyA1 and StyA2B, indicating (transient) protein complex formation. StyA1 is also active when FADH2 is supplied by StyB from Pseudomonas sp. VLB120 or PheA2 from Rhodococcus opacus 1CP. However, in both cases the reductase produces an excess of FADH2, resulting in a high waste of NADH. The epoxidation rate of StyA1 heavily depends on the type of reductase. This supports that the FADH2-induced activation of StyA1 requires interprotein communication. We conclude that the StyA1/StyA2B system represents a novel type of multifunctional flavoprotein monooxygenase. Its unique mechanism of cofactor utilization provides new opportunities for biotechnological applications and is highly relevant from a structural and evolutionary point of view. PMID:20675468

  4. Activation of DNA strand exchange by cationic comb-type copolymers: effect of cationic moieties of the copolymers

    PubMed Central

    Choi, Sung Won; Kano, Arihiro; Maruyama, Atsushi

    2008-01-01

    We have previously reported that poly(l-lysine)-graft-dextran cationic comb-type copolymers accelerate strand exchange reaction between duplex DNA and its complementary single strand by >4 orders of magnitude, while stabilizing duplex. However, the stabilization of the duplex is considered principally unfavourable for the accelerating activity since the strand exchange reaction requires, at least, partial melting of the initial duplex. Here we report the effects of different cationic moieties of cationic comb-type copolymers on the accelerating activity. The copolymer having guanidino groups exhibited markedly higher accelerating effect on strand exchange reactions than that having primary amino groups. The high accelerating effect of the former is considered to be due to its lower stabilizing effect on duplex DNA, resulting from its increased affinity to single-stranded DNA. The difference in affinity was clearly demonstrated by a fluorescence correlation spectroscopy study; the interaction of the former with single-stranded DNA still remained high even at 1 M NaCl, while that of the latter completely disappeared. These results suggest that some modes of interactions, such as hydrogen bonding, other than electrostatic interactions between the copolymers having guanidino groups and DNAs may be involved in strand exchange activation. PMID:18033803

  5. Second generation copolymers for EOR

    SciTech Connect

    McCormick, C.L.

    1988-05-01

    In this report, the authors review four types of acrylamide-based copolymers with distinctly different dilute solutions and rheological behavior. Each of these ''second generation'' systems possesses characteristics which, in theory, should be superior to conventional polymers under certain operational conditions. Type I copolymers are prepared from acrylamide (AM) and sodium-3-acrylamido-3-methylbutanoate (NaAMB). The high molecular weight, viscosity maintenance, and phase stability in the presence of divalent ions make these copolymers especially attractive for mobility control in EOR. Type II copolymers address the problems of entrapment, pore clogging, and shear degradation often encountered with ultrahigh molecular weight copolymers. The copolymers of this type are lower molecular weight than Type 1 but associate in a cooperative manner in semi-dilute solutions to enhance solution viscoscity. In this report, the authors discuss associative polymers of acrylamide/N-alkyl acrylamides which contain low mole percentages of C/sub 8/, C/sub 10/, or C/sub 12/ comonomers. In practice, a third charged comonomer such as carboxylated or sulfonated one, might be necessary to reduce adsorption to reservoir rock. Type III systems are relatively low molecular weight and hyrophibically modified in order to bring about intramolecular micelle-like association in aqueous solution. The aqueous solutions are non-viscous; viscosification occurs upon solubilization of hydrocarbons in the hydrophobic domains. Copolymers of acrylamide with N-propyl diacetone acrylamide are examples of Type III.

  6. Stabilization of Bicontinuous Phases in Diblock Copolymer Systems

    NASA Astrophysics Data System (ADS)

    Escobedo, Fernando; Martinez-Veracoechea, Francisco

    2009-03-01

    We used a coarse-grained description of the copolymer chains (i.e., dissipative particle dynamics fluid), together with continuum-space Monte Carlo and Molecular Dynamics methods, to study systems of diblock copolymers melts that have been ``filled'' with selective additives (i.e., homopolymer, and nanoparticles). Approximate phase boundaries were found via free-energy calculations. We focus on the stabilization of bi-continuous phases and the strikingly different phase behavior observed when the nature of the selective filler is changed. Our results elucidate the origins of the packing frustration that limits the viability of the gyroid, double-diamond, and plumber's nightmare phases and provide insights for overcoming it. Attention is also focused on directly determining the areas of phase diagram where macro- phase separation occurs. We compare the particle-based simulation results with the results obtained by means of self- consistent filed theory calculations.

  7. Inhibitory effects of benzodiazepines on the adenosine A(2B) receptor mediated secretion of interleukin-8 in human mast cells.

    PubMed

    Hoffmann, Kristina; Xifró, Rosa Altarcheh; Hartweg, Julia Lisa; Spitzlei, Petra; Meis, Kirsten; Molderings, Gerhard J; von Kügelgen, Ivar

    2013-01-30

    The activation of adenosine A(2B) receptors in human mast cells causes pro-inflammatory responses such as the secretion of interleukin-8. There is evidence for an inhibitory effect of benzodiazepines on mast cell mediated symptoms in patients with systemic mast cell activation disease. Therefore, we investigated the effects of benzodiazepines on adenosine A(2B) receptor mediated interleukin-8 production in human mast cell leukaemia (HMC1) cells by an enzyme linked immunosorbent assay. The adenosine analogue N-ethylcarboxamidoadenosine (NECA, 0.3-3 μM) increased interleukin-8 production about 5-fold above baseline. This effect was attenuated by the adenosine A(2B) receptor antagonist MRS1754 (N-(4-cyanophenyl)-2-{4-(2,3,6,7-tetrahydro-2,6-dioxo-1,3-dipropyl-1H-purin-8-yl)phenoxy}-acetamide) 1 μM. In addition, diazepam, 4'-chlorodiazepam and flunitrazepam (1-30 μM) markedly reduced NECA-induced interleukin-8 production in that order of potency, whereas clonazepam showed only a modest inhibition. The inhibitory effect of diazepam was not altered by flumazenil 10 μM or PK11195 (1-(2-chlorophenyl)-N-methyl-N-(1-methylpropyl)-3-isoquinolinecarboxamide) 10 μM. Diazepam attenuated the NECA-induced expression of mRNA encoding for interleukin-8. Moreover, diazepam and flunitrazepam reduced the increasing effects of NECA on cAMP-response element- and nuclear factor of activated t-cells-driven luciferase reporter gene activities in HMC1 cells. Neither diazepam nor flunitrazepam affected NECA-induced increases in cellular cAMP levels in CHO Flp-In cells stably expressing recombinant human adenosine A(2B) receptors, excluding a direct action of benzodiazepines on human adenosine A(2B) receptors. In conclusion, this is the first study showing an inhibitory action of benzodiazepines on adenosine A(2B) receptor mediated interleukin-8 production in human mast (HMC1) cells. The rank order of potency indicates the involvement of an atypical benzodiazepine binding site.

  8. A2a and a2b adenosine receptors affect HIF-1α signaling in activated primary microglial cells.

    PubMed

    Merighi, Stefania; Borea, Pier Andrea; Stefanelli, Angela; Bencivenni, Serena; Castillo, Carlos Alberto; Varani, Katia; Gessi, Stefania

    2015-05-15

    Microglia are central nervous system (CNS)-resident immune cells, that play a crucial role in neuroinflammation. Hypoxia-inducible factor-1 (HIF-1), the main transcription factor of hypoxia-inducible genes, is also involved in the immune response, being regulated in normoxia by inflammatory mediators. Adenosine is an ubiquitous nucleoside that has an influence on many immune properties of microglia through interaction with four receptor subtypes. The aim of this study was to investigate whether adenosine may affect microglia functions by acting on HIF-1α modulation. Primary murine microglia were activated with lipopolysaccharide (LPS) with or without adenosine, adenosine receptor agonists and antagonists and HIF-1α accumulation and downstream genes regulation were determined. Adenosine increased LPS-induced HIF-1α accumulation leading to an increase in HIF-1α target genes involved in cell metabolism [glucose transporter-1 (GLUT-1)] and pathogens killing [inducible nitric-oxide synthase (iNOS)] but did not induce HIF-1α dependent genes related to angiogenesis [vascular endothelial growth factor (VEGF)] and inflammation [tumor necrosis factor-α (TNF-α)]. The stimulatory effect of adenosine on HIF-1α and its target genes was essentially exerted by activation of A2A through p44/42 and A2B subtypes via p38 mitogen-activated protein kinases (MAPKs) and Akt phosphorylation. Furthermore the nucleoside raised VEGF and decreased TNF-α levels, by activating A2B subtypes. In conclusion adenosine increases GLUT-1 and iNOS gene expression in a HIF-1α-dependent way, through A2A and A2B receptors, suggesting their role in the regulation of microglial cells function following injury. However, inhibition of TNF-α adds an important anti-inflammatory effect only for the A2B subtype. GLIA 2015.

  9. Oxides of Nitrogen Emissions from the Testing of TF41-A-2B Engines at Naval Air Station, Lemoore, California

    DTIC Science & Technology

    1987-11-01

    for each engine test run. The procedure involves the use of a correlation coefficient which relates the weight (pounds) of NOx emissions to the...individual engines. This report establishes a correlation coefficient for the TF41-A-2B engine based on actual emissions data and the run sheets from 27...engine tests conducted in test cells at NAS Lemoore, CA. The correlation coefficient , equal to 0.01515 pounds of NOx formed per pound of fuel consumed

  10. Discovery and optimization of potent and selective functional antagonists of the human adenosine A2B receptor.

    PubMed

    Bedford, Simon T; Benwell, Karen R; Brooks, Teresa; Chen, Ijen; Comer, Mike; Dugdale, Sarah; Haymes, Tim; Jordan, Allan M; Kennett, Guy A; Knight, Anthony R; Klenke, Burkhard; LeStrat, Loic; Merrett, Angela; Misra, Anil; Lightowler, Sean; Padfield, Anthony; Poullennec, Karine; Reece, Mark; Simmonite, Heather; Wong, Melanie; Yule, Ian A

    2009-10-15

    We herein report the discovery of a novel class of antagonists of the human adenosine A2B receptor. This low molecular weight scaffold has been optimized to offer derivatives with potential utility for the alleviation of conditions associated with this receptor subtype, such as nociception, diabetes, asthma and COPD. Furthermore, preliminary pharmacokinetic analysis has revealed compounds with profiles suitable for either inhaled or systemic routes of administration.

  11. Clinical relevance of Helicobacter pylori babA2 and babA2/B in Costa Rica and Japan

    PubMed Central

    Con, Sergio A; Takeuchi, Hiroaki; Nishioka, Mitsuaki; Morimoto, Norihito; Sugiura, Tetsuro; Yasuda, Nobufumi; Con-Wong, Reinaldo

    2010-01-01

    AIM: To evaluate the prevalence of Helicobacter pylori (H. pylori) babA2, babB and a recombinant gene between babA2 and babB (babA2/B), and their role in the development of atrophic gastritis in Costa Rican and Japanese clinical isolates. METHODS: A total of 95 continuous H. pylori-positive Costa Rican (41 males and 54 females; mean age, 50.65 years; SD, ± 13.04 years) and 95 continuous H. pylori-positive Japanese (50 males and 45 females; mean age, 63.43; SD, ± 13.21 years) patients underwent upper endoscopy from October 2005 to July 2006. They were enrolled for the polymerase chain reaction (PCR)-based genotyping of the H. pylori babA2, babB and babA2/B genes. Statistical analysis was performed using the χ2 test and the Fisher’s exact probability test and multivariate analysis was performed by logistic regression adjusting for gender and age. P < 0.05 was regarded as statistically significant. RESULTS: The PCR-based genotyping of 95 Costa Rican and 95 Japanese isolates showed a higher prevalence of babA2 in Japan (96.8%) than in Costa Rica (73.7%), while that of babA2/B was higher in Costa Rica (11.6%) than in Japan (1.1%). In Costa Rican isolates only, babA2 was significantly associated with atrophic gastritis (P = 0.01). CONCLUSION: These results suggest that the status of babA2 and babA2/B shows geographic differences, and that babA2 has clinical relevance in Costa Rica. PMID:20101774

  12. Modulation of murine dendritic cell function by adenine nucleotides and adenosine: involvement of the A(2B) receptor.

    PubMed

    Ben Addi, Abduelhakem; Lefort, Anne; Hua, Xiaoyang; Libert, Frédérick; Communi, Didier; Ledent, Catherine; Macours, Pascale; Tilley, Stephen L; Boeynaems, Jean-Marie; Robaye, Bernard

    2008-06-01

    Adenosine triphosphate has previously been shown to induce semi-mature human monocyte-derived dendritic cells (DC). These are characterized by the up-regulation of co-stimulatory molecules, the inhibition of IL-12 and the up-regulation of some genes involved in immune tolerance, such as thrombospondin-1 and indoleamine 2,3-dioxygenase. The actions of adenosine triphosphate are mediated by the P2Y(11) receptor; since there is no functional P2Y(11) gene in the murine genome, we investigated the action of adenine nucleotides on murine DC. Adenosine 5'-(3-thiotriphosphate) and adenosine inhibited the production of IL-12p70 by bone marrow-derived DC (BMDC). These inhibitions were relieved by 8-p-sulfophenyltheophylline, an adenosine receptor antagonist. The use of selective ligands and A(2B) (-/-) BMDC indicated the involvement of the A(2B) receptor. A microarray experiment, confirmed by quantitative PCR, showed that, in presence of LPS, 5'-(N-ethylcarboxamido) adenosine (NECA, the most potent A(2B) receptor agonist) regulated the expression of several genes: arginase I and II, thrombospondin-1 and vascular endothelial growth factor were up-regulated whereas CCL2 and CCL12 were down-regulated. We further showed that NECA, in combination with LPS, increased the arginase I enzymatic activity. In conclusion, the described actions of adenine nucleotides on BMDC are mediated by their degradation product, adenosine, acting on the A(2B) receptor, and will possibly lead to an impairment of Th1 response or tolerance.

  13. Lignin-derived thermoplastic co-polymers and methods of preparation

    DOEpatents

    Naskar, Amit K.; Saito, Tomonori; Pickel, Joseph M.; Baker, Frederick S.; Eberle, Claude Clifford; Norris, Robert E.; Mielenz, Jonathan Richard

    2014-06-10

    The present invention relates to a crosslinked lignin comprising a lignin structure having methylene or ethylene linking groups therein crosslinking between phenyl ring carbon atoms, wherein said crosslinked lignin is crosslinked to an extent that it has a number-average molecular weight of at least 10,000 g/mol, is melt-processible, and has either a glass transition temperature of at least 100.degree. C., or is substantially soluble in a polar organic solvent or aqueous alkaline solution. Thermoplastic copolymers containing the crosslinked lignin are also described. Methods for producing the crosslinked lignin and thermoplastic copolymers are also described.

  14. Self-Consistent Field Approach for Cross-Linked Copolymer Materials

    NASA Astrophysics Data System (ADS)

    Schmid, Friederike

    2013-07-01

    A generalized self-consistent field approach for polymer networks with a fixed topology is developed. It is shown that the theory reproduces the localization of cross-links, which is characteristic for gels. The theory is then used to study the order-disorder transition in regular networks of end-linked diblock copolymers. Compared to diblock copolymer melts, the transition is shifted towards lower values of the incompatibility parameter χ (the Flory- Huggins parameter). Moreover, the transition becomes strongly first order already at the mean-field level. If stress is applied, the transition is further shifted and finally vanishes in a critical point.

  15. Potential therapeutic relevance of adenosine A2B and A2A receptors in the central nervous system.

    PubMed

    Popoli, Patrizia; Pepponi, Rita

    2012-09-01

    Adenosine A2B and, much more importantly, adenosine A2A receptors modulate many physiological and pathological processes in the brain. In this review, the most recent evidence concerning the role of such receptors and their potential therapeutic relevance is discussed. The low affinity of A2B receptors for adenosine implies that they might represent a good therapeutic target, since they are activated only under pathological conditions (when adenosine levels raise up to micromolar concentrations). The availability of selective ligands for A2B receptors would allow exploration of such an hypothesis. Since adenosine A2A receptors mediate both potentially neuroprotective and potentially neurotoxic effects, their role in neurodegenerative diseases is highly controversial. Nevertheless, A2A receptor antagonists have shown clear antiparkinsonian effects, and a great interest exists on the role of A2A receptors in Alzheimer's disease, brain ischaemia, spinal cord injury, drug addiction and other conditions. In order to establish whether such receptors represent a target for CNS diseases, at least two conditions are needed: the full comprehension of A2A-dependent mechanisms and the availability of ligands capable of discriminating among the different receptor populations.

  16. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... copolymer when extracted for 6 hours with distilled water at reflux temperature. (ii) Not to exceed 0.15 percent by weight of the copolymer when extracted for 6 hours with n-heptane at reflux temperature....

  17. Lignin poly(lactic acid) copolymers

    DOEpatents

    Olsson, Johan Vilhelm; Chung, Yi-Lin; Li, Russell Jingxian; Waymouth, Robert; Sattely, Elizabeth; Billington, Sarah; Frank, Curtis W.

    2017-02-14

    Provided herein are graft co-polymers of lignin and poly(lactic acid) (lignin-g-PLA copolymer), thermoset and thermoplastic polymers including them, methods of preparing these polymers, and articles of manufacture including such polymers.

  18. Viscoelastic Properties of Fluorinated Ethylene-Propylene (FEP) Random Copolymers

    NASA Astrophysics Data System (ADS)

    Curtin, Megan; Wright, Benjamin; Ozisik, Rahmi

    Florinated ethylene-propylene (FEP) random copolymers contain tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) repeat units. FEP is an excellent alternative to poly(tetrafluoroethylene), PTFE, which cannot be melt processed due to its high molecular weight and extensive crystallinity. On the other hand, FEP is a melt processible polymer and offers similar if not the same properties as PTFE. Many studies have been performed on FEP over the years, however, the properties of these polymers strongly depend on the HFP concentration and molecular weight (distribution). Just like PTFE, FEP cannot be dissolved in many solvents, therefore, obtaining molecular weight distribution of these polymers is not possible with commonly used methods. In the current study, we perform rheological analysis of various FEPs and obtain their molecular weight distributions by employing the Tuminello method. This material is based upon work supported by the National Science Foundation under Grant No. CMMI-1538730.

  19. Confinement effects on the miscibility of block copolymer blends.

    PubMed

    Spencer, Russell K W; Matsen, Mark W

    2016-04-01

    Thin films of long and short symmetric AB diblock copolymers are examined using self-consistent field theory (SCFT). We focus on hard confining walls with a preference for the A component, such that the lamellar domains orient parallel to the film with an even number ν of monolayers. For neat melts, confinement causes the lamellar period, D, to deviate from its bulk value, Db, in order to be commensurate with the film thickness, i.e., L = νD/2. For blends, however, the melt also has the option of macrophase separating into ν(l) large and ν((s)) small monolayers so as to provide a better fit, where L = ν(l)D(l)/2 + ν(s)D((s))/2. In addition to performing full SCFT calculations of the entire film, we develop a semi-analytical calculation for the coexistence of thick and thin monolayers that helps explain the complicated interplay between miscibility and commensurability.

  20. Yield Stress Enhancement in Glassy-Polyethylene Block Copolymers

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Polyethylene (PE) has the highest annual production volume of all synthetic polymers worldwide, and is valuable across many applications due to its low cost, toughness, processability, and chemical resistance. However, PE is not well suited to certain applications due to its modest yield stress and Young's modulus (approximately 30 MPa and 1 GPa, respectively for linear, high-density PE). Irreversible deformation of PE results from dislocation of crystal stems and eventual crystal fragmentation under applied stress. The liquid-like amorphous fraction provides no useful mechanical support to the crystal fold surface in a PE homopolymer, so the only method to enhance the force required for crystal slip, and hence the yield stress, is crystal thickening via thermal treatment. An alternative route towards modifying the mechanical properties of PE involves copolymerization of a minority high-glass transition temperature block into a majority-PE block copolymer. In this work, we investigate a system of glassy/linear-PE block copolymers prepared via ring-opening metathesis polymerization of cyclopentene and substituted norbornene monomers followed by hydrogenation. We demonstrate that a large change in mechanical properties can be achieved with the addition of a short glassy block (e.g. a doubling of the yield stress and Young's modulus versus PE homopolymer with the addition of 25 percent glassy block). Furthermore, owing to the low interaction energy between PE and the substituted polynorbornene blocks employed, these high-yield PE block copolymers can exhibit single-phase melts for ease of processability.

  1. 21 CFR 173.65 - Divinylbenzene copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... CONSUMPTION Polymer Substances and Polymer Adjuvants for Food Treatment § 173.65 Divinylbenzene copolymer. Divinylbenzene copolymer may be used for the removal of organic substances from aqueous foods under the following... contacting the polymer is maintained at 79.4 °C (175 °F) or less. (d) The copolymer may be used in...

  2. Imidazolium-containing, hydrophobic-ionic-hydrophilic ABC triblock copolymers: synthesis, ordered phase-separation, and supported membrane fabrication

    SciTech Connect

    Wiesenauer, EF; Nguyen, PT; Newell, BS; Bailey, TS; Nobleb, RD; Gin, DL

    2013-01-01

    Novel ABC triblock copolymers containing hydrophobic, imidazolium ionic liquid (IL)-based ionic, and non-charged hydrophilic blocks were synthesized by direct sequential, ring-opening metathesis polymerization (ROMP) of three chemically immiscible norborene monomers. The resulting ABC triblock copolymers were found by small-angle X-ray scattering to phase-separate into different nanostructures in their pure melt states, depending on their block sequence and compositions. Supported composite membranes of these triblock copolymers were successfully fabricated with defect-free, <= 20 microns thick top coatings. Preliminary CO2/light gas transport studies demonstrated the potential of this new type of IL-based block copolymer material for gas separation applications.

  3. Copolymers For Capillary Gel Electrophoresis

    SciTech Connect

    Liu, Changsheng; Li, Qingbo

    2005-08-09

    This invention relates to an electrophoresis separation medium having a gel matrix of at least one random, linear copolymer comprising a primary comonomer and at least one secondary comonomer, wherein the comonomers are randomly distributed along the copolymer chain. The primary comonomer is an acrylamide or an acrylamide derivative that provides the primary physical, chemical, and sieving properties of the gel matrix. The at least one secondary comonomer imparts an inherent physical, chemical, or sieving property to the copolymer chain. The primary and secondary comonomers are present in a ratio sufficient to induce desired properties that optimize electrophoresis performance. The invention also relates to a method of separating a mixture of biological molecules using this gel matrix, a method of preparing the novel electrophoresis separation medium, and a capillary tube filled with the electrophoresis separation medium.

  4. Effect of chain microstructure on physical properties of olefin copolymers

    NASA Astrophysics Data System (ADS)

    Poon, Benjamin Chunman

    The effect of chain microstructure on various physical properties was studied in polyethylene and polypropylene copolymers. Adhesion of Ziegler-Natta (ZNPE) and metallocene (mPE) catalyzed ethylene-octene copolymers to polypropylene (PP) were studied by measuring the delamination toughness G of coextruded microlayers using the T-peel test. It was found that the heterogeneous ZNPE exhibited poor adhesion to polypropylene. It was proposed that the low molecular weight, highly branched ZNPE fractions migrate to the interface to form an amorphous layer. The homogeneous mPE with the same short chain branch content showed very high G. Blending ZNPE with an mPE increased G. Atomic force microscopy revealed that blending mPE into ZNPE reduced or eliminated the amorphous interfacial layer. It was hypothesized that mPE increased miscibility of low molecular weight, highly branched fractions of ZNPE and prevented their segregation at the interface. The solid state structure and properties of homogeneous propylene-octene copolymers were examined. Based on the combined observations from melting behavior, dynamic mechanical response, morphology with primarily atomic force microscopy, X-ray diffraction, and tensile deformation, a classification scheme with 4 distinct categories is proposed. The homopolymer with 60 wt% crystallinity constitutes Type IV. It is characterized by large alpha-positive spherulite. Copolymers with up to 5 mol% octene, with at least 35 wt% crystallinity, are classified as Type III. They crystallize as alpha-positive spherulites that are smaller than the homopolymer. Both Type IV and Type III materials exhibit thermoplastic behavior. Copolymers classified as Type II have between 5 and 10 mol% octene with crystallinity in the range of 20--35%. Type II materials have smaller impinging spherulites than Type III copolymers and they are negative. The materials in this category have plastomeric behavior. Type I copolymers have more than 10 mol% octene and less

  5. Phylogeography of Y-chromosome haplogroup O3a2b2-N6 reveals patrilineal traces of Austronesian populations on the eastern coastal regions of Asia.

    PubMed

    Wei, Lan-Hai; Yan, Shi; Teo, Yik-Ying; Huang, Yun-Zhi; Wang, Ling-Xiang; Yu, Ge; Saw, Woei-Yuh; Ong, Rick Twee-Hee; Lu, Yan; Zhang, Chao; Xu, Shu-Hua; Jin, Li; Li, Hui

    2017-01-01

    Austronesian diffusion is considered one of the greatest dispersals in human history; it led to the peopling of an extremely vast region, ranging from Madagascar in the Indian Ocean to Easter Island in Remote Oceania. The Y-chromosome haplogroup O3a2b*-P164(xM134), a predominant paternal lineage of Austronesian populations, is found at high frequencies in Polynesian populations. However, the internal phylogeny of this haplogroup remains poorly investigated. In this study, we analyzed -seventeen Y-chromosome sequences of haplogroup O3a2b*-P164(xM134) and generated a revised phylogenetic tree of this lineage based on 310 non-private Y-chromosome polymorphisms. We discovered that all available O3a2b*-P164(xM134) samples belong to the newly defined haplogroup O3a2b2-N6 and samples from Austronesian populations belong to the sublineage O3a2b2a2-F706. Additionally, we genotyped a series of Y-chromosome polymorphisms in a large collection of samples from China. We confirmed that the sublineage O3a2b2a2b-B451 is unique to Austronesian populations. We found that O3a2b2-N6 samples are widely distributed on the eastern coastal regions of Asia, from Korea to Vietnam. Furthermore, we propose- that the O3a2b2a2b-B451 lineage represents a genetic connection between ancestors of Austronesian populations and ancient populations in North China, where foxtail millet was domesticated about 11,000 years ago. The large number of newly defined Y-chromosome polymorphisms and the revised phylogenetic tree of O3a2b2-N6 will be helpful to explore the origin of proto-Austronesians and the early diffusion process of Austronesian populations.

  6. Crystalline imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

    1995-01-01

    Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

  7. Purification and characterization of Yersinia enterocolitica and Yersinia pestis LcrV–cholera toxin A2/B chimeras

    PubMed Central

    Davis, Chadwick T.; Arlian, Britni M.

    2010-01-01

    Yersinia pestis is a virulent human pathogen and potential biological weapon. Despite a long history of research on this organism, there is no licensed vaccine to protect against pneumonic forms of Y. pestis disease. In the present study, plasmids were constructed to express cholera toxin A2/B chimeric molecules containing the LcrV protective antigen from Y. enterocolitica and Y. pestis. These chimeras were expressed and purified to high yields from the supernatant of transformed E. coli. Western and GM1 ELISA assays were used to characterize the composition, receptor-binding and relative stability of the LcrV-CTA2/B chimera in comparison to cholera toxin. In addition, we investigated the ability of the Y. pestis LcrV-CTA2/B chimera to bind to and internalize into cultured epithelial cells and macrophages by confocal microscopy. These studies indicate that the uptake and trafficking of the LcrV antigen from the chimera is comparable to the trafficking of native toxin. Together these findings report that stable, receptor-binding, non-toxic LcrV-cholera toxin A2/B chimeras can be expressed at high levels in E. coli and purified from the supernatant. In addition, the internalization of antigen in vitro reported here supports the development of these molecules as novel mucosal vaccine candidates. PMID:20438844

  8. Biological materials: Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. Biobased nanomaterials

    NASA Astrophysics Data System (ADS)

    Chen, Ning

    The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery "wastes": lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization (≤ 5-10 μm), but it was concluded that cellulose was not a suitable binder. Cellulose lignin fibers before carbonization showed up to 90% decrease in moisture uptake compared to pure cellulose. Peptidoglycan (a bacterial cell wall

  9. Liquid ethylene-propylene copolymers

    NASA Technical Reports Server (NTRS)

    Rhein, R. A.; Ingham, J. D.; Humphrey, M. F.

    1975-01-01

    Oligomers are prepared by heating solid ethylene-propylene rubber in container that retains solid and permits liquid product to flow out as it is formed. Molecular weight and viscosity of liquids can be predetermined by process temperature. Copolymers have low viscosity for given molecular weight.

  10. Electrochemical Deposition Of Conductive Copolymers

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesan; Distefano, Salvador; Liang, Ranty H.

    1991-01-01

    Experiments show electrically conductive films are deposited on glassy carbon or indium tin oxide substrates by electrochemical polymerization of N-{(3-trimethoxy silyl) propyl} pyrrole or copolymerization with pyrrole. Copolymers of monomer I and pyrrole exhibit desired electrical conductivity as well as desired adhesion and other mechanical properties. When fully developed, new copolymerization process useful in making surface films of selectable conductivity.

  11. Structural Studies of Ethylene-1-Octene and Ethylene-Norbornene Random Copolymers by NMR and WAXD

    NASA Astrophysics Data System (ADS)

    Mowery, Daniel; Carrilero, Isabel; Alamo, Rufina

    2003-03-01

    The properties of two series of melt-quenched, random ethylene copolymers (comonomer content < 15 moldiscussed. Changes in the crystallite properties with increasing comonomer content, including crystallite thickness reduction from ^13C T1 NMR relaxation times and chain packing from the line widths of crystal NMR spectra, were found to be independent of comonomer type. Analyses of the non-crystalline regions revealed differences. Copolymers with norbornene showed a larger reduction in the peak position of the WAXD amorphous halo relative to copolymers with the same content of 1-octene. The NMR resonance of the amorphous CH2 backbone units was broader in the copolymers with norbornene. Both observations are due to significant conformational differences in the non-crystalline chains with different comonomer type. Interestingly, the overall decrease in ^13C T1 times of the amorphous CH2 backbone units with increasing comonomer content was the same for both copolymer systems. Hence, in the range of comonomer content studied, the rates of fast motions for ethylene segments in the backbone are independent of comonomer type.

  12. Molecular Simulation and Microstructure Characterization of Poly(p-phenylene/m-phenylene) Copolymers

    NASA Astrophysics Data System (ADS)

    Bubeck, Robert; Keinath, Steven

    2014-03-01

    Molecular simulation and characterization of the molecular structure and microstructure of poly(p-phenylene/m-phenylene) copolymers were carried out. Tensile modulus, yield stress, and entanglement molecular weight were modeled as amorphous polymers as a function of m-phenylene content. Significant biphasic character, however, was observed for two copolymers in the melt (environs of 300°C) using variable temperature synchrotron-based WAXS. Precise experimental determinations of entanglement molecular weights were frustrated by the occurrence of significant amounts of nematic mesophasic order in the rubbery and melt regimes of two commercial poly(p-phenylene/m-phenylene) examples. Nonetheless, entanglement molecular weights obtained by molecular modeling are useful for future experimental guidance because the level of order in the glassy phase near ambient temperature was found to be low (approx. 5%) regardless of melt processing history. The biphasic nature of the melt may also be a contributor to more difficult melt processing. Based on both the modeling and WAXS measurements, it is believed that increasing m-phenylene content might improve toughness and processibility relative to the interrogated samples. Beam time at the Cornell High Energy Synchrotron Source is gratefully acknowledged.

  13. Characterization and Molecular Simulation of Poly(p-phenylene/m-phenylene) Copolymers

    NASA Astrophysics Data System (ADS)

    Bubeck, Robert; Keinath, Steven

    Characterization and molecular simulation of the molecular structure and microstructure of poly(p-phenylene/m-phenylene) copolymers were carried out. Tensile modulus, yield stress, and entanglement molecular weight were modeled as amorphous polymers as a function of m-phenylene content. Significant biphasic character, however, was observed for two copolymers in the melt near 300ºC using variable temperature synchrotron-based WAXS. The biphasic nature of the melt may be a contributor to difficulty in melt processing. Precise experimental determinations of entanglement molecular weights were frustrated by the occurrence of significant amounts of nematic mesophasic order in the rubbery and melt regimes of two commercial poly(p-phenylene/m-phenylene) examples. Nonetheless, entanglement molecular weights obtained by molecular modeling can be useful for experimental guidance because the level of order in the glassy phase near ambient temperature was found to be low (5 %) regardless of melt processing history. Based on both the modeling and WAXS measurements, it is believed that increasing m-phenylene content reduces modulus, and improves toughness and processibility. Beamtime at the Cornell High Energy Synchrotron Source is gratefully acknowledged.

  14. Strain rate effects on symmetric diblock copolymer liquid bridges: order-induced stability of polymer fibres.

    PubMed

    Peters, Robert D; Dalnoki-Veress, Kari

    2014-10-01

    Optical microscopy is used to study the effect of lamellar order on the evolution of polymer-melt bridges. Measurements are performed on symmetric diblock copolymers and linear homopolymers in the melt state. Diblock copolymer bridges measured in the disordered phase are shown to exhibit the same strain rate response as their homopolymer counterparts: shear thinning at low strain rates and shear thickening at high strain rates. However, when measured in the ordered phase, copolymer-melt bridges demonstrate an increased effective viscosity due to the lamellar order and a shear thinning response over the entire range of strain rates probed. The increased viscosity demonstrates an enhanced stability in lamellae forming diblock liquid bridges, presumed to be caused by the isotropic orientational order of lamellar domains that provide energy barriers to flow within the bridge. The shear thinning can be understood as an alignment of lamellae along the axis of the bridge due to flow, facilitating unimpeded diffusion of polymer out of the liquid bridge along lamellar boundaries.

  15. Impacts of Repeat Unit Structure and Copolymer Architecture on Thermal and Solution Properties in Homopolymers, Copolymers, and Copolymer Blends

    NASA Astrophysics Data System (ADS)

    Marrou, Stephen Raye

    Gradient copolymers are a relatively new type of copolymer architecture in which the distribution of comonomers gradually varies over the length of the copolymer chain, resulting in a number of unusual properties derived from the arrangement of repeat units. For example, nanophase-segregated gradient copolymers exhibit extremely broad glass transition temperatures (Tgs) resulting from the wide range of compositions present in the nanostructure. This dissertation presents a number of studies on how repeat unit structure and copolymer architecture dictate bulk and solution properties, specifically taking inspiration from the gradient copolymer architecture and comparing the response from this compositionally heterogeneous material to other more conventional materials. The glass transition behavior of a range of common homopolymers was studied to determine the effects of subunit structure on Tg breadth, observing a significant increase in T g breadth with increasing side chain length in methacrylate-based homopolymers and random copolymers. Additionally, increasing the composition distribution of copolymers, either by blending individual random copolymers of different overall composition or synthesizing random copolymers to high conversion, resulted in significant increases to Tg breadth. Plasticization of homopolymers and random copolymers with low molecular weight additives also served to increase the Tg breadth; the most dramatic effect was observed in the selective plasticization of a styrene/4-vinylpyridine gradient copolymer with increases in T g breadth to values above 100 °C. In addition, the effects of repeat unit structure and copolymer architecture on other polymer properties besides Tg were also investigated. The intrinsic fluorescence of styrene units in styrene-containing copolymers was studied, noting the impact of repeat unit structure and copolymer architecture on the resulting fluorescence spectra in solution. The impact of repeat unit structure on

  16. Bioinspired catecholic copolymers for antifouling surface coatings.

    PubMed

    Cho, Joon Hee; Shanmuganathan, Kadhiravan; Ellison, Christopher J

    2013-05-01

    We report here a synthetic approach to prepare poly(methyl methacrylate)-polydopamine diblock (PMMA-PDA) and triblock (PDA-PMMA-PDA) copolymers combining mussel-inspired catecholic oxidative chemistry and atom transfer radical polymerization (ATRP). These copolymers display very good solubility in a range of organic solvents and also a broad band photo absorbance that increases with increasing PDA content in the copolymer. Spin-cast thin films of the copolymer were stable in water and showed a sharp reduction (by up to 50%) in protein adsorption compared to those of neat PMMA. Also the peak decomposition temperature of the copolymers was up to 43°C higher than neat PMMA. The enhanced solvent processability, thermal stability and low protein adsorption characteristics of this copolymer makes it attractive for variety of applications including antifouling coatings on large surfaces such as ship hulls, buoys, and wave energy converters.

  17. Melt containment member

    SciTech Connect

    Rieken, Joel R.; Heidloff, Andrew J.

    2014-09-09

    A tubular melt containment member for transient containment of molten metals and alloys, especially reactive metals and alloys, includes a melt-contacting layer or region that comprises an oxygen-deficient rare earth oxide material that is less reactive as compared to the counterpart stoichiometric rare earth oxide. The oxygen-deficient (sub-stoichiometric) rare earth oxide can comprise oxygen-deficient yttria represented by Y.sub.2O.sub.3-x wherein x is from 0.01 to 0.1. Use of the oxygen-deficient rare earth oxide as the melt-contacting layer or region material reduces reaction with the melt for a given melt temperature and melt contact time.

  18. Copolymers of fluorinated polydienes and sulfonated polystyrene

    DOEpatents

    Mays, Jimmy W.; Gido, Samuel P.; Huang, Tianzi; Hong, Kunlun

    2009-11-17

    Copolymers of fluorinated polydienes and sulfonated polystyrene and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization.

  19. Self-assembly of Random Copolymers

    PubMed Central

    Li, Longyu; Raghupathi, Kishore; Song, Cunfeng; Prasad, Priyaa; Thayumanavan, S.

    2014-01-01

    Self-assembly of random copolymers has attracted considerable attention recently. In this feature article, we highlight the use of random copolymers to prepare nanostructures with different morphologies and to prepare nanomaterials that are responsive to single or multiple stimuli. The synthesis of single-chain nanoparticles and their potential applications from random copolymers are also discussed in some detail. We aim to draw more attention to these easily accessible copolymers, which are likely to play an important role in translational polymer research. PMID:25036552

  20. Shape memory rubber bands & supramolecular ionic copolymers

    NASA Astrophysics Data System (ADS)

    Brostowitz, Nicole

    The primary focus of this dissertation is to understand the thermo-mechanical properties that govern shape memory in rubber blends. An ideal shape memory polymer (SMP) has a large entropic component that drives shape recovery with a distinct transition mechanism to control the recovery conditions. Polyisoprene rubber is highly elastic and shows shape memory behavior through strain induced crystallization above its glass transition temperature. However, this transition temperature is below 0°C and not suitable for most applications. Shape memory blends can tailor the transition temperature through selection of the switching phase. Most SMP blends require complicated synthesis routes or intensive compounding which would be inhibitive for production. A facile method was developed for fabrication of a robust shape memory polymer by swelling cross-linked natural rubber with stearic acid. Thermal, microscopic studies showed that stearic acid formed a percolated network of crystalline platelets within the natural rubber. Further investigation of the material interactions was carried out with a low molecular weight polyisoprene analog, squalene, and stearic acid gel. Tensile tests on the rubber band demonstrated the thermo-mechanical effect of swelling with stearic acid. Low hysteresis was observed under cyclic loading which indicated viability for the stearic acid swollen rubber band as an SMP. The microscopic crystals and the cross-linked rubber produce a temporary network and a permanent network, respectively. These two networks allow thermal shape memory cycling with deformation and recovery above the melting point of stearic acidand fixation below that point. Under manual, strain-controlled tensile deformation, the shape memory rubber bands exhibited fixity and recovery of 100% +/- 10%. The recovery properties of the SMP were studied under various loading conditions and a model was fit to describe the potential recovery with relation to the fixation. An additional

  1. Elevated adenosine signaling via adenosine A2B receptor induces normal and sickle erythrocyte sphingosine kinase 1 activity.

    PubMed

    Sun, Kaiqi; Zhang, Yujin; Bogdanov, Mikhail V; Wu, Hongyu; Song, Anren; Li, Jessica; Dowhan, William; Idowu, Modupe; Juneja, Harinder S; Molina, Jose G; Blackburn, Michael R; Kellems, Rodney E; Xia, Yang

    2015-03-05

    Erythrocyte possesses high sphingosine kinase 1 (SphK1) activity and is the major cell type supplying plasma sphingosine-1-phosphate, a signaling lipid regulating multiple physiological and pathological functions. Recent studies revealed that erythrocyte SphK1 activity is upregulated in sickle cell disease (SCD) and contributes to sickling and disease progression. However, how erythrocyte SphK1 activity is regulated remains unknown. Here we report that adenosine induces SphK1 activity in human and mouse sickle and normal erythrocytes in vitro. Next, using 4 adenosine receptor-deficient mice and pharmacological approaches, we determined that the A2B adenosine receptor (ADORA2B) is essential for adenosine-induced SphK1 activity in human and mouse normal and sickle erythrocytes in vitro. Subsequently, we provide in vivo genetic evidence that adenosine deaminase (ADA) deficiency leads to excess plasma adenosine and elevated erythrocyte SphK1 activity. Lowering adenosine by ADA enzyme therapy or genetic deletion of ADORA2B significantly reduced excess adenosine-induced erythrocyte SphK1 activity in ADA-deficient mice. Finally, we revealed that protein kinase A-mediated extracellular signal-regulated kinase 1/2 activation functioning downstream of ADORA2B underlies adenosine-induced erythrocyte SphK1 activity. Overall, our findings reveal a novel signaling network regulating erythrocyte SphK1 and highlight innovative mechanisms regulating SphK1 activity in normal and SCD.

  2. Targeted Segment Transfer from Rye Chromosome 2R to Wheat Chromosomes 2A, 2B, and 7B.

    PubMed

    Ren, Tianheng; Li, Zhi; Yan, Benju; Tan, Feiquan; Tang, Zongxiang; Fu, Shulan; Yang, Manyu; Ren, Zhenglong

    2017-03-10

    Increased chromosome instability was induced by a rye (Secale cereale L.) monosomic 2R chromosome into wheat (Triticum aestivum L.). Centromere breakage and telomere dysfunction result in high rates of chromosome aberrations, including breakages, fissions, fusions, deletions, and translocations. Plants with target traits were sequentially selected to produce a breeding population, from which 3 translocation lines with target traits have been selected. In these lines, wheat chromosomes 2A, 2B, and 7B recombined with segments of the rye chromosome arm 2RL. This was detected by FISH analysis using repeat sequences pSc119.2, pAs1 and genomic DNA of rye together as probes. The translocation chromosomes in these lines were named as 2ASMR, 2BSMR, and 7BSMR. The small segments that were transferred into wheat consisted of pSc119.2 repeats and other chromatin regions that conferred resistance to stripe rust and expressed target traits. These translocation lines were highly resistant to stripe rust, and expressed several typical traits that were associated with chromosome arm 2RL, which are better than those of its wheat parent, disomic addition, and substitution lines that show agronomic characteristics. The integration of molecular methods and conventional techniques to improve wheat breeding schemes are discussed.

  3. Epithelial-specific A2B adenosine receptor signaling protects the colonic epithelial barrier during acute colitis

    PubMed Central

    Aherne, CM; Saeedi, B; Collins, CB; Masterson, JC; McNamee, EN; Perrenoud, L; Rapp, CR; Curtis, VF; Bayless, A; Fletcher, A; Glover, LE; Evans, CM; Jedlicka, P; Furuta, GT; de Zoeten, EF; Colgan, SP; Eltzschig, HK

    2015-01-01

    Central to inflammatory bowel disease (IBD) pathogenesis is loss of mucosal barrier function. Emerging evidence implicates extracellular adenosine signaling in attenuating mucosal inflammation. We hypothesized that adenosine-mediated protection from intestinal barrier dysfunction involves tissue-specific signaling through the A2B adenosine receptor (Adora2b) at the intestinal mucosal surface. To address this hypothesis, we combined pharmacologic studies and studies in mice with global or tissue-specific deletion of the Adora2b receptor. Adora2b−/− mice experienced a significantly heightened severity of colitis, associated with a more acute onset of disease and loss of intestinal epithelial barrier function. Comparison of mice with Adora2b deletion on vascular endothelial cells (Adora2bfl/flVeCadCre+) or intestinal epithelia (Adora2bfl/flVillinCre+) revealed a selective role for epithelial Adora2b signaling in attenuating colonic inflammation. In vitro studies with Adora2b knockdown in intestinal epithelial cultures or pharmacologic studies highlighted Adora2b-driven phosphorylation of vasodilator-stimulated phosphoprotein (VASP) as a specific barrier repair response. Similarly, in vivo studies in genetic mouse models or treatment studies with an Adora2b agonist (BAY 60-6583) recapitulate these findings. Taken together, our results suggest that intestinal epithelial Adora2b signaling provides protection during intestinal inflammation via enhancing mucosal barrier responses. PMID:25850656

  4. Synthesis, photophysical, electrochemical and electrochemiluminescence properties of A2B2 zinc porphyrins: the effect of π-extended conjugation.

    PubMed

    Galván-Miranda, Elizabeth K; Castro-Cruz, Hiram M; Arturo Arias-Orea, J; Iurlo, Matteo; Valenti, Giovanni; Marcaccio, Massimo; Macías-Ruvalcaba, Norma A

    2016-06-01

    The synthesis of two A2B2 porphyrins, {5,15-bis-[4-(octyloxy)phenyl]-porphyrinato}zinc(ii) () and {5,15-bis-(carbazol-3-yl-ethynyl)-10,20-bis-[4-(octyloxy)phenyl]-porphinato}-zinc(ii) (), is reported. Their photophysical properties were studied by steady-state absorption and emission. Substituting the carbazolylethynyl moieties at two of the meso positions results in a large bathochromic shift of all the absorption bands, a notable increase in the absorption coefficient of the Q(0,0) band, and higher fluorescence quantum yield compared to porphyrin , with two unsubstituted meso positions. Cyclic voltammetry and digital simulation show that electrogenerated radical ions of are more stable than those of . The lack of substituents at the meso positions of leads to dimerization reactions of the radical cation. Despite this, the annihilation reaction of and produces very similar electrogenerated chemiluminescence (ECL) intensity. Spectroelectrochemical experiments demonstrate that the electroreduction of leads to a strong absorption band that might quench the ECL.

  5. a Nonthermal Model for Catalytic Surface Reaction of the Type A2+B2→2AB:

    NASA Astrophysics Data System (ADS)

    Khan, K. M.; Ahmad, W.; Iqbal, K.

    The kinetics of irreversible dimer-dimer reaction of the type A2+B2→2AB has already been studied through Monte Carlo simulation via a model based on Langmuir-Hinshelwood (thermal) mechanism. The results of this study are well known. There is single transition point (yC) at yB=0.5 (where yB is partial pressure of B2 dimer in gas phase), which separates the two poisoned states from each other. Here, we have studied this reaction on the basis of a nonthermal model, which involves the precursor motion of B2 molecule. The most interesting feature of this model is that it yields a steady reactive window. The phase diagram is similar to the ZGB model. The reactive window is separated by continuous and discontinuous irreversible phase transitions. The width of the reactive window depends upon the mobility of the precursors. The dependence of production rate on partial pressure of B2 is shown by simple mathematical equations in our model. Some interesting results are observed when reaction between precursors and chemisorbed B atoms is considered.

  6. Melt inclusions: Chapter 6

    USGS Publications Warehouse

    ,; Lowenstern, J. B.

    2014-01-01

    Melt inclusions are small droplets of silicate melt that are trapped in minerals during their growth in a magma. Once formed, they commonly retain much of their initial composition (with some exceptions) unless they are re-opened at some later stage. Melt inclusions thus offer several key advantages over whole rock samples: (i) they record pristine concentrations of volatiles and metals that are usually lost during magma solidification and degassing, (ii) they are snapshots in time whereas whole rocks are the time-integrated end products, thus allowing a more detailed, time-resolved view into magmatic processes (iii) they are largely unaffected by subsolidus alteration. Due to these characteristics, melt inclusions are an ideal tool to study the evolution of mineralized magma systems. This chapter first discusses general aspects of melt inclusions formation and methods for their investigation, before reviewing studies performed on mineralized magma systems.

  7. Continuous concentric lamellar block copolymer nanofibers with long range order.

    PubMed

    Ma, Minglin; Titievsky, Kirill; Thomas, Edwin L; Rutledge, Gregory C

    2009-04-01

    Fibers with long-range ordered internal structures have applications in various areas such as photonic band gap fibers, optical waveguides, wearable power, sensors, and sustained drug release. Up to now, such fibers have been formed by melt extrusion or drawing from a macroscopic preformed rod and were typically limited to diameters >10 microm with internal features >1 microm (Abouraddy, A. F.; et al. Nat. Mater. 2007, 6, 336). We describe a new class of continuous fibers and fibrous membranes with long-range ordered concentric lamellar structure that have fiber diameters and feature sizes 2-3 orders of magnitude smaller than those made by conventional methods. These fibers are created through confined self-assembly of block copolymers within core-shell electrospun filaments. In contrast to the copolymer in bulk or thin films, the domains of the concentric lamellar structure are shown here to vary quantitatively with (radial) position and to exhibit a novel dislocation that accommodates variations in fiber diameter robustly, permitting for the first time the realization of long-range order in technologically meaningful, continuous fibers with approximately 300 nm diameter and 50 nm radial period.

  8. Customized PEG-derived copolymers for tissue-engineering applications.

    PubMed

    Tessmar, Joerg K; Göpferich, Achim M

    2007-01-05

    PEG-containing copolymers play a prominent role as biomaterials for different applications ranging from drug delivery to tissue engineering. These custom-designed materials offer enormous possibilities to change the overall characteristics of biomaterials by improving their biocompatibility and solubility, as well as their ability to crystallize in polymer blends and to resist protein adsorption. This article demonstrates various principles of PEG-based material design that are applied to fine tune the properties of biomaterials for different tissue engineering applications. More specifically, strategies are described to develop PEG copolymers with various block compositions and specific bulk properties, including low melting points and improved surface hydrophilicity. Highly hydrated polymer gel networks for promoting cellular growth or suppressing protein adsorption and cell adhesion are introduced. By incorporating selectively cleavable cross-links, these hydrophilic polymers can also serve as smart hydrogel scaffolds, mimicking the natural extracellular matrix for cell cultivation and tissue growth. Ultimately, these developments lead to the creation of biomimetic materials to immobilize bioactive compounds, allowing precise control of cellular adhesion and tissue growth. [image: see text

  9. Ordered phases of diblock copolymers in selective solvent.

    PubMed

    Grason, Gregory M

    2007-03-21

    The authors propose a mean-field model to explore the equilibrium coupling between micelle aggregation and lattice choice in neutral copolymer and selective solvent mixtures. They find both thermotropic and lyotropic transitions from face-centered cubic to body-centered cubic ordered phases of spherical micelles, in agreement with experimental observations of these systems over a broad range of conditions. The stability of the nonclosed packed phase can be attributed to two physical mechanisms: the large entropy of lattice phonons near crystal melting and the preference of the intermicelle repulsions for the body-centered cubic structure when the lattice becomes sufficiently dense at higher solution concentrations. Both mechanisms are controlled by the decrease of micelle aggregation and subsequent increase of lattice density as solvent selectivity is reduced. These results shed new light on the relationship between micelle structure--"crewcut" or "hairy"--and long-range order in micelle solutions.

  10. A2B adenosine receptors stimulate IL-6 production in primary murine microglia through p38 MAPK kinase pathway.

    PubMed

    Merighi, Stefania; Bencivenni, Serena; Vincenzi, Fabrizio; Varani, Katia; Borea, Pier Andrea; Gessi, Stefania

    2017-03-01

    The hallmark of neuroinflammation is the activation of microglia, the immunocompetent cells of the CNS, releasing a number of proinflammatory mediators implicated in the pathogenesis of neuronal diseases. Adenosine is an ubiquitous autacoid regulating several microglia functions through four receptor subtypes named A1, A2A, A2B and A3 (ARs), that represent good targets to suppress inflammation occurring in CNS. Here we investigated the potential role of ARs in the modulation of IL-6 secretion and cell proliferation in primary microglial cells. The A2BAR agonist 2-[[6-Amino-3,5-dicyano-4-[4-(cyclopropylmethoxy)phenyl]-2-pyridinyl]thio]-acetamide (BAY60-6583) stimulated IL-6 increase under normoxia and hypoxia, in a dose- and time-dependent way. In cells incubated with the blockers of phospholipase C (PLC), protein kinase C epsilon (PKC-ε) and PKC delta (PKC-δ) the IL-6 increase due to A2BAR activation was strongly reduced, whilst it was not affected by the inhibitor of adenylyl cyclase (AC). Investigation of cellular signalling involved in the A2BAR effect revealed that only the inhibitor of p38 mitogen activated protein kinase (MAPK) was able to block the agonist's effect on IL-6 secretion, whilst inhibitors of pERK1/2, JNK1/2 MAPKs and Akt were not. Stimulation of p38 by BAY60-6583 was A2BAR-dependent, through a pathway affecting PLC, PKC-ε and PKC-δ but not AC, in both normoxia and hypoxia. Finally, BAY60-6583 increased microglial cell proliferation involving A2BAR, PLC, PKC-ε, PKC-δ and p38 signalling. In conclusion, A2BARs activation increased IL-6 secretion and cell proliferation in murine primary microglial cells, through PLC, PKC-ε, PKC-δ and p38 pathways, thus suggesting their involvement in microglial activation and neuroinflammation.

  11. A2B adenosine receptor blockade enhances macrophage-mediated bacterial phagocytosis and improves polymicrobial sepsis survival in mice.

    PubMed

    Belikoff, Bryan G; Hatfield, Stephen; Georgiev, Peter; Ohta, Akio; Lukashev, Dmitriy; Buras, Jon A; Remick, Daniel G; Sitkovsky, Michail

    2011-02-15

    Antimicrobial treatment strategies must improve to reduce the high mortality rates in septic patients. In noninfectious models of acute inflammation, activation of A2B adenosine receptors (A2BR) in extracellular adenosine-rich microenvironments causes immunosuppression. We examined A2BR in antibacterial responses in the cecal ligation and puncture (CLP) model of sepsis. Antagonism of A2BR significantly increased survival, enhanced bacterial phagocytosis, and decreased IL-6 and MIP-2 (a CXC chemokine) levels after CLP in outbred (ICR/CD-1) mice. During the CLP-induced septic response in A2BR knockout mice, hemodynamic parameters were improved compared with wild-type mice in addition to better survival and decreased plasma IL-6 levels. A2BR deficiency resulted in a dramatic 4-log reduction in peritoneal bacteria. The mechanism of these improvements was due to enhanced macrophage phagocytic activity without augmenting neutrophil phagocytosis of bacteria. Following ex vivo LPS stimulation, septic macrophages from A2BR knockout mice had increased IL-6 and TNF-α secretion compared with wild-type mice. A therapeutic intervention with A2BR blockade was studied by using a plasma biomarker to direct therapy to those mice predicted to die. Pharmacological blockade of A2BR even 32 h after the onset of sepsis increased survival by 65% in those mice predicted to die. Thus, even the late treatment with an A2BR antagonist significantly improved survival of mice (ICR/CD-1) that were otherwise determined to die according to plasma IL-6 levels. Our findings of enhanced bacterial clearance and host survival suggest that antagonism of A2BRs offers a therapeutic target to improve macrophage function in a late treatment protocol that improves sepsis survival.

  12. Involvement of 5-HT(2A/2B/2C) receptors on memory formation: simple agonism, antagonism, or inverse agonism?

    PubMed

    Meneses, Alfredo

    2002-12-01

    1. The 5-HT2 receptors subdivision into the 5-HT(2A/2B/2C) subtypes along with the advent of the selective antagonists has allowed a more detailed investigation on the role and therapeutic significance of these subtypes in cognitive functions. The present study further analyzed the 5-HT2 receptors role on memory consolidation. 2. The SB-200646 (a selective 5-HT(2B/2C) receptor antagonist) and LY215840 (a nonselective 5-HT(2/7) receptor antagonist) posttraining administration had no effect on an autoshaped memory consolidation. However, both drugs significantly and differentially antagonized the memory impairments induced by 1-(3-chlorophenyl)piperazine (mCPP), 1-naphtyl-piperazine (1-NP), mesulergine, or N-(3-trifluoromethylphenyl) piperazine (TFMPP). 3. In contrast, SB-200646 failed to modify the facilitatory procognitive effect produced by (+/-)-2.5-dimethoxy-4-iodoamphetamine (DOI) or ketanserin, which were sensitive to MDL100907 (a selective 5-HT2A receptor antagonist) and to a LY215840 high dose. 4. Finally, SB-200646 reversed the learning deficit induced by dizocilpine, but not that by scopolamine: while SB-200646 and MDL100907 coadministration reversed memory deficits induced by both drugs. 5. It is suggested that 5-HT(2B/2C) receptors might be involved on memory formation probably mediating a suppressive or constraining action. Whether the drug-induced memory impairments in this study are explained by simple agonism, antagonism, or inverse agonism at 5-HT2 receptors remains unclear at this time. 6. Notably, the 5-HT2 receptor subtypes blockade may provide some benefit to reverse poor memory consolidation conditions associated with decreasedcholinergic, glutamatergic, and/or serotonergic neurotransmission.

  13. High-pressure behavior of A2B2O7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

    NASA Astrophysics Data System (ADS)

    Rittman, Dylan R.; Turner, Katlyn M.; Park, Sulgiye; Fuentes, Antonio F.; Yan, Jinyuan; Ewing, Rodney C.; Mao, Wendy L.

    2017-01-01

    In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A2B2O7 pyrochlore (A = Eu, Dy; B = Ti, Zr) up to ˜50 GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ˜41 GPa for B = Ti and ˜16 GPa B = Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A = Dy, proceeding faster than those with a larger ionic radii, i.e., A = Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B = Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A = Eu than A = Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu2Zr2O7 as compared with the initially defect-fluorite structured Dy2Zr2O7.

  14. Transcriptional regulation of heat shock proteins and ascorbate peroxidase by CtHsfA2b from African bermudagrass conferring heat tolerance in Arabidopsis

    PubMed Central

    Wang, Xiuyun; Huang, Wanlu; Yang, Zhimin; Liu, Jun; Huang, Bingru

    2016-01-01

    Heat stress transcription factor A2s (HsfA2s) are key regulators in plant response to high temperature. Our objectives were to isolate an HsfA2 gene (CtHsfA2b) from a warm-season grass species, African bermudagrass (Cynodon transvaalensis Burtt-Davy), and to determine the physiological functions and transcriptional regulation of HsfA2 for improving heat tolerance. Gene expression analysis revealed that CtHsfA2b was heat-inducible and exhibited rapid response to increasing temperature. Ectopic expression of CtHsfA2b improved heat tolerance in Arabidopsis and restored heat-sensitive defects of Arabidopsis hsfa2 mutant, which was demonstrated by higher survival rate and photosynthetic parameters, and lower electrolyte leakage in transgenic plants compared to the WT or hsfa2 mutant. CtHsfA2b transgenic plants showed elevated transcriptional regulation of several downstream genes, including those encoding ascorbate peroxidase (AtApx2) and heat shock proteins [AtHsp18.1-CI, AtHsp22.0-ER, AtHsp25.3-P and AtHsp26.5-P(r), AtHsp70b and AtHsp101-3]. CtHsfA2b was found to bind to the heat shock element (HSE) on the promoter of AtApx2 and enhanced transcriptional activity of AtApx2. These results suggested that CtHsfA2b could play positive roles in heat protection by up-regulating antioxidant defense and chaperoning mechanisms. CtHsfA2b has the potential to be used as a candidate gene to genetically modify cool-season species for improving heat tolerance. PMID:27320381

  15. Dimensionally Stable Ether-Containing Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Fay, Catharine C. (Inventor); St.Clair, Anne K. (Inventor)

    1999-01-01

    Novel polyimide copolymers containing ether linkages were prepared by the reaction of an equimolar amount of dianhydride and a combination of diamines. The polyimide copolymers described herein possess the unique features of low moisture uptake, dimensional stability, good mechanical properties, and moderate glass transition temperatures. These materials have potential application as encapsulants and interlayer dielectrics.

  16. Thermochemical characteristics of chitosan-polylactide copolymers

    NASA Astrophysics Data System (ADS)

    Goruynova, P. E.; Larina, V. N.; Smirnova, N. N.; Tsverova, N. E.; Smirnova, L. A.

    2016-05-01

    The energies of combustion of chitosan and its block-copolymers with different polylactide contents are determined in a static bomb calorimeter. Standard enthalpies of combustion and formation are calculated for these substances. The dependences of the thermochemical characteristics on block-copolymer composition are determined and discussed.

  17. Process-Accessible States of Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sun, De-Wen; Müller, Marcus

    2017-02-01

    Process-directed self-assembly of block copolymers refers to thermodynamic processes that reproducibly direct the kinetics of structure formation from a starting, unstable state into a selected, metastable mesostructure. We investigate the kinetics of self-assembly of linear A C B triblock copolymers after a rapid transformation of the middle C block from B to A . This prototypical process (e.g., photochemical transformation) converts the initial, equilibrium mesophase of the A B B copolymer into a well-defined but unstable, starting state of the A A B copolymer. The spontaneous structure formation that ensues from this unstable state becomes trapped in a metastable mesostructure, and we systematically explore which metastable mesostructures can be fabricated by varying the block copolymer composition of the initial and final states. In addition to the equilibrium mesophases of linear A B diblock copolymers, this diagram of process-accessible states includes 7 metastable periodic mesostructures, inter alia, Schoen's F-RD periodic minimal surface. Generally, we observe that the final, metastable mesostructure of the A A B copolymer possesses the same symmetry as the initial, equilibrium mesophase of the A B B copolymer.

  18. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ....2470 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended...

  19. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ....2470 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended...

  20. 21 CFR 177.2470 - Polyoxymethylene copolymer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ....2470 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED... Components of Articles Intended for Repeated Use § 177.2470 Polyoxymethylene copolymer. Polyoxymethylene copolymer identified in this section may be safely used as an article or component of articles intended...

  1. Chiral Block Copolymer Structures for Metamaterial Applications

    DTIC Science & Technology

    2015-01-27

    Final 3. DATES COVERED (From - To) 25-August-2011 to 24-August-2014 4. TITLE AND SUBTITLE Chiral Block Copolymer Structures for...researchers focused o synthesis and processing, morphology and physical characterization of chiral block copolymer (BCP) materials. Such materials a...valuable for both their optical and mechanical properties, particularly for their potential as chiral metamaterials and lightweig energy absorbing

  2. Nanostructured high-performance dielectric block copolymers.

    PubMed

    Liu, Wenmei; Liao, Xiaojuan; Li, Yawei; Zhao, Qiuhua; Xie, Meiran; Sun, Ruyi

    2015-10-25

    A new type of insulating-conductive block copolymer was synthesized by metathesis polymerization. The copolymer can self-assemble into unique nanostructures of micelles or hollow spheres. It exhibits a high dielectric constant, low dielectric loss, and high stored/released energy density due to the strong dipolar and nano-interfacial polarization contributions.

  3. Process-Accessible States of Block Copolymers.

    PubMed

    Sun, De-Wen; Müller, Marcus

    2017-02-10

    Process-directed self-assembly of block copolymers refers to thermodynamic processes that reproducibly direct the kinetics of structure formation from a starting, unstable state into a selected, metastable mesostructure. We investigate the kinetics of self-assembly of linear ACB triblock copolymers after a rapid transformation of the middle C block from B to A. This prototypical process (e.g., photochemical transformation) converts the initial, equilibrium mesophase of the ABB copolymer into a well-defined but unstable, starting state of the AAB copolymer. The spontaneous structure formation that ensues from this unstable state becomes trapped in a metastable mesostructure, and we systematically explore which metastable mesostructures can be fabricated by varying the block copolymer composition of the initial and final states. In addition to the equilibrium mesophases of linear AB diblock copolymers, this diagram of process-accessible states includes 7 metastable periodic mesostructures, inter alia, Schoen's F-RD periodic minimal surface. Generally, we observe that the final, metastable mesostructure of the AAB copolymer possesses the same symmetry as the initial, equilibrium mesophase of the ABB copolymer.

  4. Synthesis and Characterization of Block Copolymers.

    DTIC Science & Technology

    1987-07-01

    Polyether-Polyimide Block Copolymers; Three series of Polyether-Polyimide (PEPI) block copolymers were synthesized. Soft segments were poly( propylene ... glycol ) (PPO) Mn = 2,000 and 4,000. Hard segments were pyromellitic dianhydride (PMDA) and di-(2-hydroxyethyl)-dimethylhydantoin (H). The hard

  5. Responsive copolymers for enhanced petroleum recovery

    SciTech Connect

    McCormick, C.; Hester, R.

    1992-01-01

    The overall goal of this research is the development of advanced water-soluble copolymers for use in enhanced oil recovery which rely on reversible microheterogeneous associations for mobility control and reservoir conformance. Technical progress is summarized for the following tasks: advanced copolymer synthesis; characterization of macromolecular structure and properties; and solution rheology in a porous media.

  6. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  7. Signatures of nonthermal melting

    PubMed Central

    Zier, Tobias; Zijlstra, Eeuwe S.; Kalitsov, Alan; Theodonis, Ioannis; Garcia, Martin E.

    2015-01-01

    Intense ultrashort laser pulses can melt crystals in less than a picosecond but, in spite of over thirty years of active research, for many materials it is not known to what extent thermal and nonthermal microscopic processes cause this ultrafast phenomenon. Here, we perform ab-initio molecular-dynamics simulations of silicon on a laser-excited potential-energy surface, exclusively revealing nonthermal signatures of laser-induced melting. From our simulated atomic trajectories, we compute the decay of five structure factors and the time-dependent structure function. We demonstrate how these quantities provide criteria to distinguish predominantly nonthermal from thermal melting. PMID:26798822

  8. PAR1 inhibition suppresses the self-renewal and growth of A2B5-defined glioma progenitor cells and their derived gliomas in vivo

    PubMed Central

    Auvergne, R; Wu, C; Connell, A; Au, S; Cornwell, A; Osipovitch, M; Benraiss, A; Dangelmajer, S; Guerrero-Cazares, H; Quinones-Hinojosa, A; Goldman, SA

    2016-01-01

    Glioblastoma (GBM) remains the most common and lethal intracranial tumor. In a comparison of gene expression by A2B5-defined tumor-initiating progenitor cells (TPCs) to glial progenitor cells derived from normal adult human brain, we found that the F2R gene encoding PAR1 was differentially overexpressed by A2B5-sorted TPCs isolated from gliomas at all stages of malignant development. In this study, we asked if PAR1 is causally associated with glioma progression. Lentiviral knockdown of PAR1 inhibited the expansion and self-renewal of human GBM-derived A2B5+ TPCs in vitro, while pharmacological inhibition of PAR 1 similarly slowed both the growth and migration of A2B5+ TPCs in culture. In addition, PAR1 silencing potently suppressed tumor expansion in vivo, and significantly prolonged the survival of mice following intracranial transplantation of human TPCs. These data strongly suggest the importance of PAR1 to the self-renewal and tumorigenicity of A2B5-defined glioma TPCs; as such, the abrogation of PAR1-dependent signaling pathways may prove a promising strategy for gliomas. PMID:26616854

  9. The Effect of Adenosine A2A and A2B Antagonists on Tracheal Responsiveness, Serum Levels of Cytokines and Lung Inflammation in Guinea Pig Model of Asthma

    PubMed Central

    Pejman, Laleh; Omrani, Hasan; Mirzamohammadi, Zahra; Shahbazfar, Amir Ali; Khalili, Majid; Keyhanmanesh, Rana

    2014-01-01

    Purpose: Nowadays adenosine is specified as an important factor in the pathophysiology of asthma. For determining the effect of different A2 receptors, in this investigation the effect of single dose of selective adenosine A2A and A2B antagonists (ZM241385 and MRS1706) on different inflammatory parameters; tracheal responsiveness to methacholine and ovalbumin, total and differential cell count in bronchoalveolar lavage (BAL), blood levels of IL-4 and IFN-γ and lung pathology of guinea pig model of asthma were assessed. Methods: All mentioned parameters were evaluated in two sensitized groups of guinea pigs pretreated with A2A and A2B antagonists (S+Anta A2A, S+Anta A2B) compared with sensitized (S) and control (C) groups. Results: The tracheal responsiveness to methacholine and OA, total cell and eosinophil and basophil count in BAL, blood IL-4 level and pathological changes in pre-treated group with MRS1706 (S+Anta A2B) was significantly lower than those of sensitized group (p<0.01 to p<0.05). In pretreated group with Anta A2A(S+Anta A2A), all the above changes were reversed. Conclusion: These results showed a preventive effect of A2B antagonist (MRS1706) on tracheal responsiveness to methacholine and OA, total and differential cell count in bronchoalveolar lavage, blood cytokines and pathological changes. Administration of ZM241385, selective A2A antagonist, deteriorated the induction effect of ovalbumin. PMID:24511476

  10. Hybridization of Block Copolymer Micelles

    DTIC Science & Technology

    1993-01-01

    J. Macromol. Sci., Part A 1973, 7,601. (10) Tiara, M.; Ramireddy, C.; Webber, S. K; Munk,P. Collect. Czer" (14) 0snford, C. In The Hydrophobic Effect ...equilibrate In the first series of experiments we have studied the within 20 min, similarly as ASA-10 micelles do. However, effect of the copolymer...high. This may happen after a sudden The Johnston-Ogston effect 2’ 6- also may play a role in jump in temperature or in the composition of the mixed

  11. 21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false n-Alkylglutarimide/acrylic copolymers. 177.1060... Use Food Contact Surfaces § 177.1060 n-Alkylglutarimide/acrylic copolymers. n-Alkylglutarimide/acrylic...) Identity. For the purpose of this section, n-alkylglutarimide/acrylic copolymers are copolymers obtained...

  12. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Acrylate ester copolymer coating. 175.210 Section... Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as... prepared food, subject to the provisions of this section: (a) The acrylate ester copolymer is a...

  13. Rapid self-assembly of block copolymers to photonic crystals

    DOEpatents

    Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

    2016-07-05

    The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

  14. Melt fracture revisited

    SciTech Connect

    Greenberg, J. M.

    2003-07-16

    In a previous paper the author and Demay advanced a model to explain the melt fracture instability observed when molten linear polymer melts are extruded in a capillary rheometer operating under the controlled condition that the inlet flow rate was held constant. The model postulated that the melts were a slightly compressible viscous fluid and allowed for slipping of the melt at the wall. The novel feature of that model was the use of an empirical switch law which governed the amount of wall slip. The model successfully accounted for the oscillatory behavior of the exit flow rate, typically referred to as the melt fracture instability, but did not simultaneously yield the fine scale spatial oscillations in the melt typically referred to as shark skin. In this note a new model is advanced which simultaneously explains the melt fracture instability and shark skin phenomena. The model postulates that the polymer is a slightly compressible linearly viscous fluid but assumes no slip boundary conditions at the capillary wall. In simple shear the shear stress {tau}and strain rate d are assumed to be related by d = F{tau} where F ranges between F{sub 2} and F{sub 1} > F{sub 2}. A strain rate dependent yield function is introduced and this function governs whether F evolves towards F{sub 2} or F{sub 1}. This model accounts for the empirical observation that at high shears polymers align and slide more easily than at low shears and explains both the melt fracture and shark skin phenomena.

  15. Microphase separation in random multiblock copolymers

    NASA Astrophysics Data System (ADS)

    Govorun, E. N.; Chertovich, A. V.

    2017-01-01

    Microphase separation in random multiblock copolymers is studied with the mean-field theory assuming that long blocks of a copolymer are strongly segregated, whereas short blocks are able to penetrate into "alien" domains and exchange between the domains and interfacial layer. A bidisperse copolymer with blocks of only two sizes (long and short) is considered as a model of multiblock copolymers with high polydispersity in the block size. Short blocks of the copolymer play an important role in the microphase separation. First, their penetration into the "alien" domains leads to the formation of joint long blocks in their own domains. Second, short blocks localized at the interface considerably change the interfacial tension. The possibility of penetration of short blocks into the "alien" domains is controlled by the product χ Nsh (χ is the Flory-Huggins interaction parameter and Nsh is the short block length). At not very large χ Nsh , the domain size is larger than that for a regular copolymer consisting of the same long blocks as in the considered random copolymer. At a fixed mean block size, the domain size grows with an increase in the block size dispersity, the rate of the growth being dependent of the more detailed parameters of the block size distribution.

  16. Impact property enhancement of poly (lactic acid) with different flexible copolymers

    NASA Astrophysics Data System (ADS)

    Likittanaprasong, N.; Seadan, M.; Suttiruengwong, S.

    2015-07-01

    The objective of this work was to improve the impact property of Poly (lactic acid) (PLA) by blending with different copolymers. Six flexible copolymers, namely, acrylonitrile butadiene styrene (ABS) powder, Biomax, polybutyrate adipate co-terephthalate (PBAT), polyether block amide (PEBAX), ethylene-vinyl acetate (EVA) and ethylene acrylic elastomer (EAE), with loading less than 20wt% were used and compared. The rheological, mechanical and morphological properties of samples were investigated by melt flow index, tensile testing, impact testing and scanning electron microscope (SEM), respectively. It was found that PLA added 20wt% EAE showed the highest impact strength (59.5 kJ/m2), which was 22 times higher than neat PLA. The elongation at break was also increased by 12 folds compared to neat PLA. The SEM images showed good interface and distribution for PLA containing 20wt% EAE, 15 phr Biomax and 20 wt% PEBAX.

  17. Microbial degradation of linseed oil-based elastomer and subsequent accumulation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer.

    PubMed

    Pramanik, Nilkamal; Das, Rakesh; Rath, Tanmoy; Kundu, P P

    2014-10-01

    The microbial synthesis of environment-friendly poly(3-hydroxybutyrate--co-3-hydroxyvalerate), PHBV, has been performed by using an alkaliphilic microorganism, Alkaliphilus oremlandii OhILAs strain (GenBank Accession number NR_043674.1), at pH 8 and at a temperature of 30-32 °C through the biodegradation of linseed oil-based elastomer. The yield of the copolymer on dry cell weight basis is 90 %. The elastomers used for the biodegradation have been synthesized by cationic polymerization technique. The yield of the PHBV copolymer also varies with the variation of linseed oil content (30-60 %) in the elastomer. Spectroscopic characterization ((1)H NMR and FTIR) of the accumulated product through biodegradation of linseed oil-based elastomers indicates that the accumulated product is a PHBV copolymer consisting of 13.85 mol% of 3-hydroxyvalerate unit. The differential scanning calorimetry (DSC) results indicate a decrease in the melting (T m) and glass transition temperature (T g) of PHBV copolymer with an increase in the content of linseed oil in the elastomer, which is used for the biodegradation. The gel permeation chromatography (GPC) results indicate that the weight average molecular weight (M w) of PHBV copolymer decreases with an increasing concentration of linseed oil in the elastomer. The surface morphology of the elastomer before and after biodegradation is observed under scanning electron microscope (SEM) and atomic force microscope (AFM); these results indicate about porous morphology of the biodegraded elastomer.

  18. Block Copolymer Membranes for Biofuel Purification

    NASA Astrophysics Data System (ADS)

    Evren Ozcam, Ali; Balsara, Nitash

    2012-02-01

    Purification of biofuels such as ethanol is a matter of considerable concern as they are produced in complex multicomponent fermentation broths. Our objective is to design pervaporation membranes for concentrating ethanol from dilute aqueous mixtures. Polystyrene-b-polydimethylsiloxane-b-polystyrene block copolymers were synthesized by anionic polymerization. The polydimethylsiloxane domains provide ethanol-transporting pathways, while the polystyrene domains provide structural integrity for the membrane. The morphology of the membranes is governed by the composition of the block copolymer while the size of the domains is governed by the molecular weight of the block copolymer. Pervaporation data as a function of these two parameters will be presented.

  19. Injectible bodily prosthetics employing methacrylic copolymer gels

    DOEpatents

    Mallapragada, Surya K.; Anderson, Brian C.

    2007-02-27

    The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

  20. Stereocomplexes of enantiomeric lactic acid and sebacic acid ester-anhydride triblock copolymers.

    PubMed

    Slivniak, Raia; Domb, Abraham J

    2002-01-01

    A systematic study on the synthesis, characterization, degradation, and drug release of d-, l-, and dl-poly(lactic acid) (PLA)-terminated poly(sebacic acid) (PSA) and their stereocomplexes is reported. PLA-terminated sebacic acid polymers were synthesized by melt condensation of the acetate anhydride derivatives of PLA oligomers and sebacic anhydride oligomers to yield ABA triblock copolymers of molecular weights between 3000 and 9000 that melt at temperatures between 35 and 80 degrees C. Pairs of the corresponding enantiomeric ABA copolymers composed of l-PLA-PSA-l-PLA and d-PLA-PSA-d-PLA were solvent mixed to form stereocomplexes. The formed stereocomplexes exhibited higher crystalline melting temperature than the enantiomeric polymers, which indicate stereocomplex formulation. The PLA terminals had a significant effect on the polymer degradation and drug release rate. PSA with up to 20% w/w of PLA terminals degraded and released the incorporated drug for more than 3 weeks as compared with 10 days for PSA homopolymer.

  1. The effects of adenosine A2B receptor inhibition on VEGF and nitric oxide axis-mediated renal function in diabetic nephropathy.

    PubMed

    Patel, Leena; Thaker, Aswin

    2014-07-01

    Diabetic nephropathy (DN) is the most common cause of end-stage renal disease worldwide. The pathophysiologic mechanisms of diabetic nephropathy are incompletely understood but include overproduction of various growth factors and cytokines. Upregulation of vascular endothelial growth factor (VEGF) is a pathogenic event occurring in most forms of podocytopathy; however, the mechanisms that regulate this growth factor induction are not clearly identified. A2B receptors have been found to regulate VEGF expression under hypoxic environment in different tissues. One proposed hypothesis in mediating diabetic nephropathy is the modulation of VEGF-NO balance in renal tissue. We determined the role of adenosine A2B receptor in mediating VEGF overproduction and nitrite in diabetic nephropathy. The renal content of A2B receptors and VEGF was increased after 8 weeks of diabetes induction. The renal and plasma nitrite levels were also reduced in these animals. In vivo administration of A2B adenosine receptor antagonist (MRS1754) inhibited the renal over expression of VEGF and adverse renal function parameters. The antagonist administration also improved the kidney tissue nitrite levels. In conclusion, we demonstrated that VEGF induction via adenosine signaling might be the critical event in regulating VEGF-NO axis in diabetic nephropathy.

  2. Morphological structure and properties relationship for rubber modified polypropylene-g-polystyrene copolymer blends

    SciTech Connect

    Adewole, A.; Mascia, L.; Gogos, C.

    1996-12-31

    As produced reactor copolymer, obtained by in-reactor grafting polymerization technology is a two-phase rigid copolymer which combines the best attributes of semi-crystalline polypropylene and those of amorphous polystyrene. In the process, the compatibilizer, PP-g-PS and the non-olefinic polymer component, PS are simultaneously generated from the monomer styrene. The reactor product, which has higher modulus but lower impact-resistance is further toughened by incorporation of EPR (ethylene propylene rubber) and SEBS (styrene-ethylene-butylene-styrene) triblock copolymer, via intensive melt-mixing downstream extruder operation. A similarly produced graft copolymer, PP-g-LLDPE has been shown to be an effective compatibilizer for recycled polyolefinic streams. Hence, the motivation to assess the efficacy of the PP-g-PS copolymer as a compatibilizer for commingled polyolefinic and polystyrene recycled streams. Therefore, we have formulated both {open_quotes}physical{close_quotes} analogues and {open_quotes}model{close_quotes} blends of the reactor product, aiming to determine the influence on blend properties, of the critical components, such as the free polystyrene (PS), the grafted polystyrene (g-PS) or chemical compatibilizer, SEBS or physical compatibilizer and the EPR rubber modifier. In mixing experiments off-line, hot stage microscopy on polymer carcass samples was used to monitor morphology evolution and dispersion rate. Using fracture mechanics approach, material properties such as critical stress intensity factor, Kc and critical strain energy release rate, Gc were determined to elucidate the rubber toughening process for the polyblend. Characterization techniques such as DMA (Dynamic Mechanical Analysis), SEM (Scanning Electron Microscopy), TEM (Transmission Electron Microscopy) and DSC (Differential Scanning Calorimetry) were used to examine samples before and after annealing.

  3. Synthesis of biocompatible poly(ɛ-caprolactone)- block-poly(propylene adipate) copolymers appropriate for drug nanoencapsulation in the form of core-shell nanoparticles.

    PubMed

    Nanaki, Stavroula G; Pantopoulos, Kostas; Bikiaris, Dimitrios N

    2011-01-01

    Poly(propylene adipate)-block-poly(ɛ-caprolactone) copolymers were synthesized using a combination of polycondensation and ring-opening polymerization of ɛ-caprolactone in the presence of poly(propylene adipate). Gel permeation chromatography was used for molecular weight determination, whereas hydrogen-1 nuclear magnetic resonance and carbon-13 nuclear magnetic resonance spectroscopy were employed for copolymer characterization and composition evaluation. The copolymers were found to be block while their composition was similar to the feeding ratio. They formed semicrystalline structures, while only poly(ɛ-caprolactone) formed crystals, as shown by wide angle X-ray diffraction. Differential scanning calorimetry data suggest that the melting point and heat of fusion of copolymers decreased by increasing the poly(propylene adipate) amount. The synthesized polymers exhibited low cytotoxicity and were used to encapsulate desferrioxamine, an iron-chelating drug. The desferrioxamine nanoparticles were self-assembled into core shell structures, had mean particle size <250 nm, and the drug remained in crystalline form. Further studies revealed that the dissolution rate was mainly related to the melting temperature, as well as to the degree of crystallinity of copolymers.

  4. Curable polyphosphazene copolymers and terpolymers

    NASA Technical Reports Server (NTRS)

    Reynard, Kennard A. (Inventor); Rose, Selwyn H. (Inventor)

    1976-01-01

    Copolymers and terpolymers comprising randomly repeating units represented by the general formulae ##EQU1## wherein the R' radicals contain OH functionality and R being at least one member of the group of monovalent radicals selected from alkyl, substituted alkyl, aryl, substituted aryl and arylalkyl, and R' is represented by ##EQU2## wherein Q represents either --(CH.sub.2).sub. n or --C.sub.6 H.sub.4 X(CH.sub.2).sub. m, the --X(CH.sub.2).sub. m group being either meta or para and n is an integer from 1 to 6, m is an integer from 1 to 3, X is O or CH.sub.2, and R is H or a lower alkyl radical with up to four carbon atoms (methyl, ethyl, etc.). The ratio of R to R' is between 99.5 to 0.5 and 65 to 35.

  5. Organosilane Polymers. III. Block Copolymers.

    DTIC Science & Technology

    1980-04-01

    5446 (1969) 9) R. West, J. Polym. Sci., C, 29, 65 (1970) 10) V.F. Traven and R. West, J. Am. Chem. Soc., 95, 6824 (1973) 11) W.G. Boberski and-A.L...COMPOSITION Alkyl H/Aryl H (2 ) Copolymer Method,1 , Calculated Found 111-3 A 0.72 0.73 B 0.72 0.73 111-5 A 0.80 0.85 B 0.80 0.80 111-8 A 1.0 1.4 B 1.0...1.1 (1) A: Chloro-oligomer added to lithio-oligomer. B : Lithio-oligomer added to chloro-oligomer. (2) By HI-NMR TABLE 2 INFRA-RED ABSORPTIONS

  6. Electrostatic control of block copolymer morphology

    NASA Astrophysics Data System (ADS)

    Sing, Charles E.; Zwanikken, Jos W.; Olvera de La Cruz, Monica

    2014-07-01

    Energy storage is at present one of the foremost issues society faces. However, material challenges now serve as bottlenecks in technological progress. Lithium-ion batteries are the current gold standard to meet energy storage needs; however, they are limited owing to the inherent instability of liquid electrolytes. Block copolymers can self-assemble into nanostructures that simultaneously facilitate ion transport and provide mechanical stability. The ions themselves have a profound, yet previously unpredictable, effect on how these nanostructures assemble and thus the efficiency of ion transport. Here we demonstrate that varying the charge of a block copolymer is a powerful mechanism to predictably tune nanostructures. In particular, we demonstrate that highly asymmetric charge cohesion effects can induce the formation of nanostructures that are inaccessible to conventional uncharged block copolymers, including percolated phases desired for ion transport. This vastly expands the design space for block copolymer materials and is informative for the versatile design of battery electrolyte materials.

  7. Block copolymer structures in nano-pores

    NASA Astrophysics Data System (ADS)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei

    2010-03-01

    We present results of coarse-grained computer modelling of block copolymer systems in cylindrical and spherical nanopores on Cell Dynamics Simulation. We study both cylindrical and spherical pores and systematically investigate structures formed by lamellar, cylinders and spherical block copolymer systems for various pore radii and affinity of block copolymer blocks to the pore walls. The obtained structures include: standing lamellae and cylinders, ``onions,'' cylinder ``knitting balls,'' ``golf-ball,'' layered spherical, ``virus''-like and mixed morphologies with T-junctions and U-type defects [1]. Kinetics of the structure formation and the differences with planar films are discussed. Our simulations suggest that novel porous nano-containers can be formed by confining block copolymers in pores of different geometries [1,2]. [4pt] [1] M. Pinna, X. Guo, A.V. Zvelindovsky, Polymer 49, 2797 (2008).[0pt] [2] M. Pinna, X. Guo, A.V. Zvelindovsky, J. Chem. Phys. 131, 214902 (2009).

  8. Arbitrary lattice symmetries via block copolymer nanomeshes

    PubMed Central

    Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.; Yager, Kevin G.

    2015-01-01

    Self-assembly of block copolymers is a powerful motif for spontaneously forming well-defined nanostructures over macroscopic areas. Yet, the inherent energy minimization criteria of self-assembly give rise to a limited library of structures; diblock copolymers naturally form spheres on a cubic lattice, hexagonally packed cylinders and alternating lamellae. Here, we demonstrate multicomponent nanomeshes with any desired lattice symmetry. We exploit photothermal annealing to rapidly order and align block copolymer phases over macroscopic areas, combined with conversion of the self-assembled organic phase into inorganic replicas. Repeated photothermal processing independently aligns successive layers, providing full control of the size, symmetry and composition of the nanoscale unit cell. We construct a variety of symmetries, most of which are not natively formed by block copolymers, including squares, rhombuses, rectangles and triangles. In fact, we demonstrate all possible two-dimensional Bravais lattices. Finally, we elucidate the influence of nanostructure on the electrical and optical properties of nanomeshes. PMID:26100566

  9. Salt Complexation in Block Copolymer Thin Films

    SciTech Connect

    Kim,S.; Misner, M.; Yang, L.; Gang, O.; Ocko, B.; Russell, T.

    2006-01-01

    Ion complexation within cylinder-forming block copolymer thin films was found to affect the ordering process of the copolymer films during solvent annealing, significantly enhancing the long-range positional order. Small amounts of alkali halide or metal salts were added to PS-b-PEO, on the order of a few ions per chain, where the salt complexed with the PEO block. The orientation of the cylindrical microdomains strongly depended on the salt concentration and the ability of the ions to complex with PEO. The process shows large flexibility in the choice of salt used, including gold or cobalt salts, whereby well-organized patterns of nanoparticles can be generated inside the copolymer microdomains. By further increasing the amount of added salts, the copolymer remained highly ordered at large degrees of swelling and demonstrated long-range positional correlations of the microdomains in the swollen state, which holds promise as a route to addressable media.

  10. Reactivity ratios for organotin copolymer systems.

    PubMed

    El-Newehy, Mohamed H; Al-Deyab, Salem S; Al-Hazmi, Ali Mohsen Ali

    2010-04-15

    Di(tri-n-butyltin) itaconate (DTBTI) and monoethyl tributyltin fumarate (METBTF) were synthesized as organotin monomers. The organotin monomers were copolymerized with styrene (ST) and methyl methacrylate (MMA) via a free radical polymerization technique. The overall conversion was kept low (copolymer composition was determined from tin analysis. The synthesized monomers and copolymers were characterized by elemental analysis, 1H- and 13C-NMR, and FTIR spectroscopy.

  11. Method for making block siloxane copolymers

    DOEpatents

    Butler, N.L.; Jessop, E.S.; Kolb, J.R.

    1981-02-25

    A method for synthesizing block polysiloxane copolymers is disclosed. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  12. Responsive Copolymers for Enhanced Petroleum Recovery

    SciTech Connect

    McCormick, C.; Hester, R.

    2001-02-27

    The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

  13. Method for making block siloxane copolymers

    DOEpatents

    Butler, Nora; Jessop, Edward S.; Kolb, John R.

    1982-01-01

    A method for synthesizing block polysiloxane copolymers. Diorganoscyclosiloxanes and an end-blocking compound are interacted in the presence of a ring opening polymerization catalyst, producing a blocked prepolymer. The prepolymer is then interacted with a silanediol, resulting in condensation polymerization of the prepolymers. A second end-blocking compound is subsequently introduced to end-cap the polymers and copolymers formed from the condensation polymerization.

  14. Low melting mesophase pitches

    SciTech Connect

    Diefendorf, R.J.; Chen, S.H.

    1984-04-17

    A low melting point, low molecular weight, heptane insoluble, 1,2,4-trichlorobenzene soluble mesophase pitch useful in carbon fiber spinning as such or as a plasticizer in a carbon fiber spinning composition is obtained by heating chrysene, triphenylene or paraterphenyl as well as mixtures thereof and hydrocarbon fractions containing the same, dissolving the resulting heat treated material with 1,2,4-trichlorobenzene, and separating the insolubles, and then contacting the 1,2,4-trichlorobenzene soluble fraction with a sufficient amount of heptane to precipitate the low melting point, low molecular weight mesophase pitch.

  15. Effects of Process Parameters on Replication Accuracy of Microinjection Molded Cyclic Olefins Copolymers Parts

    NASA Astrophysics Data System (ADS)

    Lin, Hsuan-Liang; Chen, Chun-Sheng; Lee, Ruey-Tsung; Chen, Shia-Chung; Chien, Rean-Der; Jeng, Ming-Chang; Hwang, Jiun-Ren

    2013-04-01

    In this study, the effects of various processing parameters of microinjection molding on the replication accuracy of the micro featured fluidic platform used for DNA/RNA tests are investigated. LIGA-like processes were utilized to prepare a silicon-based SU-8 photoresist, followed by electroforming to make a Ni-Co-based stamp. A cyclic olefin copolymer (COC) was used as the injection molding material. The molding parameters associated with the replication accuracy of micro channel parts were investigated. It was found that for microinjection molded devices, the replication accuracies of the imprint width and depth increase with increasing of mold temperature, melt temperature, injection velocity, and packing pressure.

  16. Diffusion of copolymers composed of monomers with drastically different friction factors in copolymer/homopolymer blends

    NASA Astrophysics Data System (ADS)

    Duranty, Edward R.; Baschnagel, Jörg; Dadmun, Mark

    2017-02-01

    Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this work, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary the connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. The results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer's local volume.

  17. 180-Nucleotide Duplication in the G Gene of Human metapneumovirus A2b Subgroup Strains Circulating in Yokohama City, Japan, since 2014

    PubMed Central

    Saikusa, Miwako; Kawakami, Chiharu; Nao, Naganori; Takeda, Makoto; Usuku, Shuzo; Sasao, Tadayoshi; Nishimoto, Kimiko; Toyozawa, Takahiro

    2017-01-01

    Human metapneumovirus (HMPV), a member of the family Paramyxoviridae, was first isolated in 2001. Seroepidemiological studies have shown that HMPV has been a major etiological agent of acute respiratory infections in humans for more than 50 years. Molecular epidemiological, genetic, and antigenetic evolutionary studies of HMPV will strengthen our understanding of the epidemic behavior of the virus and provide valuable insight for the control of HMPV and the development of vaccines and antiviral drugs against HMPV infection. In this study, the nucleotide sequence of and genetic variations in the G gene were analyzed in HMPV strains prevalent in Yokohama City, in the Kanto area, Japan, between January 2013 and June 2016. As a part of the National Epidemiological Surveillance of Infectious Diseases, Japan, 1308 clinical specimens (throat swabs, nasal swabs, nasal secretions, and nasal aspirate fluids) collected at 24 hospitals or clinics in Yokohama City were screened for 15 major respiratory viruses with a multiplex reverse transcription–PCR assay. HMPV was detected in 91 specimens, accounting for 7.0% of the total specimens, and the nucleotide sequences of the G genes of 84 HMPV strains were determined. Among these 84 strains, 6, 43, 10, and 25 strains were classified into subgroups A2a, A2b, B1, and B2, respectively. Approximately half the HMPV A2b subgroup strains detected since 2014 had a 180-nucleotide duplication (180nt-dup) in the G gene and clustered on a phylogenic tree with four classical 180nt-dup-lacking HMPV A2b strains prevalent between 2014 and 2015. The 180nt-dup causes a 60-amino-acid duplication (60aa-dup) in the G protein, creating 23–25 additional potential acceptor sites for O-linked sugars. Our data suggest that 180nt-dup occurred between 2011 and 2013 and that HMPV A2b strains with 180nt-dup (A2b180nt-dup HMPV) became major epidemic strains within 3 years. The detailed mechanism by which the A2b180nt-dup HMPV strains gained an advantage

  18. Viscosity Measurement for Tellurium Melt

    NASA Technical Reports Server (NTRS)

    Lin, Bochuan; Li, Chao; Ban, Heng; Scripa, Rosalia N.; Su, Ching-Hua; Lehoczky, Sandor L.

    2006-01-01

    The viscosity of high temperature Te melt was measured using a new technique in which a rotating magnetic field was applied to the melt sealed in a suspended ampoule, and the torque exerted by rotating melt flow on the ampoule wall was measured. Governing equations for the coupled melt flow and ampoule torsional oscillation were solved, and the viscosity was extracted from the experimental data by numerical fitting. The computational result showed good agreement with experimental data. The melt velocity transient initiated by the rotating magnetic field reached a stable condition quickly, allowing the viscosity and electrical conductivity of the melt to be determined in a short period.

  19. Thermoacoustic Streaming and Ultrasonic Processing of Low Melting Melts

    NASA Technical Reports Server (NTRS)

    Trinh, E. H.

    1997-01-01

    Ultrasonic levitation allows the processing of low melting materials both in 1 G as well as in microgravity. The free suspension of the melts also facilitates undercooling, permitting the measurements of the physical properties of the metastable liquids.

  20. Crystalline free energies of micelles of diblock copolymer solutions.

    PubMed

    D'Adamo, Giuseppe; Pierleoni, Carlo

    2010-11-28

    We report a characterization of the relative stability and structural behavior of various micellar crystals of an athermal model of AB-diblock copolymers in solution. We adopt a previously developed coarse-graining representation of the chains which maps each copolymer on a soft dumbbell. Thanks to this strong reduction of degrees of freedom, we are able to investigate large aggregated systems and for a specific length ratio of the blocks f = M(A)∕(M(A) + M(B)) = 0.6, to locate the order-disorder transition of the system of micelles. Above the transition, mechanical and thermal properties are found to depend on the number of particles per lattice site in the simulation box, and the application of a recent methodology for multiple occupancy crystals [B. M. Mladek et al., Phys. Rev. Lett. 99, 235702 (2007)] is necessary to correctly define the equilibrium state. Within this scheme we have performed free energy calculations at two reduced density ρ∕ρ∗ = 4, 5 and for several cubic structures such as fcc, bcc, and A15. At both densities, the bcc symmetry is found to correspond to the minimum of the unconstrained free energy, that is to the stable symmetry among the few considered, while the A15 structure is almost degenerate, indicating that the present system prefers to crystallize in less packed structures. At ρ∕ρ∗ = 4 close to melting, the Lindemann ratio is fairly high (∼0.29) and the concentration of vacancies is roughly 6%. At ρ∕ρ∗ = 5 the mechanical stability of the stable bcc structure increases and the concentration of vacancies accordingly decreases. The ratio of the corona layer thickness to the core radius is found to be in good agreement with experimental data for poly(styrene-b-isoprene)(22-12) in isoprene selective solvent which is also reported to crystallize in the bcc structure.

  1. Downregulation of A(1) and A(2B) adenosine receptors in human trisomy 21 mesenchymal cells from first-trimester chorionic villi.

    PubMed

    Gessi, Stefania; Merighi, Stefania; Stefanelli, Angela; Mirandola, Prisco; Bonfatti, Alessandra; Fini, Sergio; Sensi, Alberto; Marci, Roberto; Varani, Katia; Borea, Pier Andrea; Vesce, Fortunato

    2012-11-01

    Human reproduction is complex and prone to failure. Though causes of miscarriage remain unclear, adenosine, a proangiogenic nucleoside, may help determine pregnancy outcome. Although adenosine receptor (AR) expression has been characterized in euploid pregnancies, no information is available for aneuploidies, which, as prone to spontaneous abortion (SA), are a potential model for shedding light on the mechanism regulating this event. AR expression was investigated in 71 first-trimester chorionic villi (CV) samples and cultured mesenchymal cells (MC) from euploid and TR21 pregnancies, one of the most frequent autosomal aneuploidy, with a view to elucidating their potential role in the modulation of vascular endothelial growth factor (VEGF) and nitric oxide (NO). Compared to euploid cells, reduced A(1) and A(2B) expression was revealed in TR21 CV and MCs. The non-selective adenosine agonist 5'-N-ethylcarboxamidoadenosine (NECA) increased NO, by activating, predominantly, A(1)AR and A(2A)AR through a molecular pathway involving hypoxia-inducible-factor-1 (HIF-1α), and increased VEGF, mainly through A(2B). In conclusion the adenosine transduction cascade appears to be disturbed in TR21 through reduced expression of A(2B) and A(1)ARs. These anomalies may be implicated in complications such as fetal growth restriction, malformation and/or SA, well known features of aneuploid pregnancies. Therefore A(1) and A(2B)ARs could be potential biomarkers able to provide an early indication of SA risk and their stimulation may turn out to improve fetoplacental perfusion by increasing NO and VEGF.

  2. The cellular protein hnRNP A2/B1 enhances HIV-1 transcription by unfolding LTR promoter G-quadruplexes

    PubMed Central

    Scalabrin, Matteo; Frasson, Ilaria; Ruggiero, Emanuela; Perrone, Rosalba; Tosoni, Elena; Lago, Sara; Tassinari, Martina; Palù, Giorgio; Richter, Sara N.

    2017-01-01

    G-quadruplexes are four-stranded conformations of nucleic acids that act as cellular epigenetic regulators. A dynamic G-quadruplex forming region in the HIV-1 LTR promoter represses HIV-1 transcription when in the folded conformation. This activity is enhanced by nucleolin, which induces and stabilizes the HIV-1 LTR G-quadruplexes. In this work by a combined pull-down/mass spectrometry approach, we consistently found hnRNP A2/B1 as an additional LTR-G-quadruplex interacting protein. Surface plasmon resonance confirmed G-quadruplex specificity over linear sequences and fluorescence resonance energy transfer analysis indicated that hnRNP A2/B1 is able to efficiently unfold the LTR G-quadruplexes. Evaluation of the thermal stability of the LTR G-quadruplexes in different-length oligonucleotides showed that the protein is fit to be most active in the LTR full-length environment. When hnRNP A2/B1 was silenced in cells, LTR activity decreased, indicating that the protein acts as a HIV-1 transcription activator. Our data highlight a tightly regulated control of transcription based on G-quadruplex folding/unfolding, which depends on interacting cellular proteins. These findings provide a deeper understanding of the viral transcription mechanism and may pave the way to the development of drugs effective against the integrated HIV-1, present both in actively and latently infected cells. PMID:28338097

  3. Initiator Effects in Reactive Extrusion of Starch Graft Copolymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Graft copolymers of starch with water-soluble polymers such as polyacrylamide have potential applications including hydrogels, superabsorbents, and thickening agents. Reactive extrusion is a rapid, continuous method for production of starch graft copolymers with high reaction and grafting efficienc...

  4. Thermodynamics of Oligonucleotide Duplex Melting

    ERIC Educational Resources Information Center

    Schreiber-Gosche, Sherrie; Edwards, Robert A.

    2009-01-01

    Melting temperatures of oligonucleotides are useful for a number of molecular biology applications, such as the polymerase chain reaction (PCR). Although melting temperatures are often calculated with simplistic empirical equations, application of thermodynamics provides more accurate melting temperatures and an opportunity for students to apply…

  5. Charge Transport in Conjugated Block Copolymers

    NASA Astrophysics Data System (ADS)

    Smith, Brandon; Le, Thinh; Lee, Youngmin; Gomez, Enrique

    Interest in conjugated block copolymers for high performance organic photovoltaic applications has increased considerably in recent years. Polymer/fullerene mixtures for conventional bulk heterojunction devices, such as P3HT:PCBM, are severely limited in control over interfaces and domain length scales. In contrast, microphase separated block copolymers self-assemble to form lamellar morphologies with alternating electron donor and acceptor domains, thereby maximizing electronic coupling and local order at interfaces. Efficiencies as high as 3% have been reported in solar cells for one block copolymer, P3HT-PFTBT, but the details concerning charge transport within copolymers have not been explored. To fill this gap, we probed the transport characteristics with thin-film transistors. Excellent charge mobility values for electron transport have been observed on aluminum source and drain contacts in a bottom gate, bottom contact transistor configuration. Evidence of high mobility in ordered PFTBT phases has also been obtained following thermal annealing. The insights gleaned from our investigation serve as useful guideposts, revealing the significance of the interplay between charge mobility, interfacial order, and optimal domain size in organic block copolymer semiconductors.

  6. Lamellar Morphology of Metallocene Random Propylene Copolymers studied by Atomic Force Microscopy

    NASA Astrophysics Data System (ADS)

    Hosier, Ian; Alamo, Rufina

    2003-03-01

    Four sets of propylene based random copolymers with co-units of ethylene, 1-butene, 1-hexene and 1-octene, in a wide range of co-monomer contents up to 10 mol percent (including co-unit and other defects), were studied after both rapid and isothermal crystallization from the melt. Etched film surfaces were imaged so as to minimize catalyst and co-catalyst residues. As the concentration of the gamma polymorph increases with increasing comonomer content or increasing crystallization temperature, the thickness and lateral extension of the observed lamellae decreases rapidly. Spherulites are formed in copolymers with non-crystallizable units (1-hexene and 1-octene) up to 3 mol percent total defect content, and were observed right up to 7 mol percent total defect content in those with partially crystallizable co-monomers (ethylene and 1-butene). However, lamellae were observed in the surfaces of all copolymers analyzed, even in the most defective ones, highlighting the importance of the gamma polymorph in propagating lamellar crystallites in polypropylenes with a high concentration of defects. The morphology of equivalent microtomed bulk specimens will be comparatively discussed.

  7. Poly(lactide)-block-poly([epsilon]-caprolactone-co-[epsilon]-decalactone)-block-poly(lactide) copolymer elastomers

    SciTech Connect

    Schneiderman, Deborah K.; Hill, Erin M.; Martello, Mark T.; Hillmyer, Marc A.

    2015-08-28

    Batch ring opening transesterification copolymerization of ε-caprolactone and ε-decalactone was used to generate statistical copolymers over a wide range of compositions and molar masses. Reactivity ratios determined for this monomer pair, rCL = 5.9 and rDL = 0.03, reveal ε-caprolactone is added preferentially regardless of the propagating chain end. Relative to poly(ε-caprolactone) the crystallinity and melting point of these statistical copolymers were depressed by the addition of ε-decalactone; copolymers containing greater than 31 mol% (46 wt%) ε-decalactone were amorphous. Poly(lactide)-block-poly(ε-caprolactone-co-ε-decalactone)-block-poly(lactide) triblock polymers were also prepared and used to explore the influence of midblock composition on the temperature dependent Flory-Huggins interaction parameter (χ). In addition, uniaxial extension tests were used to determine the effects of midblock composition, poly(lactide) content, and molar mass on the mechanical properties of these new elastomeric triblocks.

  8. Controlling Miscibility in Polyethylene-Polynorbornene Block Copolymers via Side-Group Chemistry

    NASA Astrophysics Data System (ADS)

    Mulhearn, William; Register, Richard

    Block copolymers containing a crystallizable block, such as polyethylene (PE), and an amorphous block with high glass transition temperature (Tg) are an interesting class of materials since the rigid glassy block can improve the mechanical response of the article under strain by reinforcing the crystal fold surface. However, to prepare an easily processable PE-containing block copolymer it is necessary to avoid microphase separation in the melt by selection of amorphous blocks with weak repulsive interactions against PE (low Flory interaction parameter χ or interaction energy density X) . Most such low- χ polymers are chemically similar to PE, such as copolymers of ethylene and a small amount of an α-olefin, and therefore exhibit similarly low glass transition temperatures. This work investigates a series of low- and high-Tg polymers based on substituted norbornene monomers, polymerized via ring-opening metathesis polymerization (ROMP). Hydrogenated polynorbornene derivatives possess a wide range of glass transition temperatures, and miscibility with PE can be readily tuned by the choice of substituents on the monomers (e.g. aromatic vs. aliphatic groups). Two species investigated, hydrogenated poly(cyclohexyl norbornene) and hydrogenated poly(norbornyl norbornene), have high Tg and also remain miscible with polyethylene to high molecular weight. Furthermore, we develop a set of mixing rules to qualitatively predict the solubility behavior of substituted ROMP polynorbornenes as a function of their side-groups.

  9. Synthesis and Characterization of a Poly(ethylene glycol)-Poly(simvastatin) Diblock Copolymer

    PubMed Central

    Asafo-Adjei, Theodora A.; Dziubla, Thomas D.; Puleo, David A.

    2014-01-01

    Biodegradable polyesters are commonly used as drug delivery vehicles, but their role is typically passive, and encapsulation approaches have limited drug payload. An alternative drug delivery method is to polymerize the active agent or its precursor into a degradable polymer. The prodrug simvastatin contains a lactone ring that lends itself to ring-opening polymerization (ROP). Consequently, simvastatin polymerization was initiated with 5 kDa monomethyl ether poly(ethylene glycol) (mPEG) and catalyzed via stannous octoate. Melt condensation reactions produced a 9.5 kDa copolymer with a polydispersity index of 1.1 at 150 °C up to a 75 kDa copolymer with an index of 6.9 at 250 °C. Kinetic analysis revealed first-order propagation rates. Infrared spectroscopy of the copolymer showed carboxylic and methyl ether stretches unique to simvastatin and mPEG, respectively. Slow degradation was demonstrated in neutral and alkaline conditions. Lastly, simvastatin, simvastatin-incorporated molecules, and mPEG were identified as the degradation products released. The present results show the potential of using ROP to polymerize lactone-containing drugs such as simvastatin. PMID:25431653

  10. 21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true n-Alkylglutarimide/acrylic copolymers. 177.1060... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1060 n-Alkylglutarimide/acrylic copolymers. n-Alkylglutarimide/acrylic copolymers identified in this section may be safely used as...

  11. 21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false n-Alkylglutarimide/acrylic copolymers. 177.1060... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1060 n-Alkylglutarimide/acrylic copolymers. n-Alkylglutarimide/acrylic copolymers identified in this section may be safely used as...

  12. 21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false n-Alkylglutarimide/acrylic copolymers. 177.1060... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1060 n-Alkylglutarimide/acrylic copolymers. n-Alkylglutarimide/acrylic copolymers identified in this section may be safely used as...

  13. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as a food-contact surface of articles intended for...

  14. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as a food-contact surface of articles intended for...

  15. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as a food-contact surface of articles intended for...

  16. 21 CFR 175.210 - Acrylate ester copolymer coating.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate ester copolymer coating may safely be used as a food-contact surface of articles intended for...

  17. Structure Confirmation and Properties of Poly(Dimethylsiloxaneco-diethylsiloxane) Copolymer

    NASA Astrophysics Data System (ADS)

    Gao, Li-Juan; Ma, De-Peng; Feng, Sheng-Yu

    2016-05-01

    High molecular weight poly (dimethylsiloxane-co-diethylsiloxane) (PMES) copolymer was synthesized by anionic ring opening polymerization. Its composition and structures was determined by 29Si NMR spectroscopy. A random microstructure of copolymer was observed in the 29Si NMR spectrum. Further, PMES was characterized by GPC and DSC. The results show that PMES is crystallization-free copolymer with low glass transition temperatures.

  18. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Styrene-maleic anhydride copolymers. 177.1820... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1820 Styrene-maleic anhydride copolymers. Styrene-maleic anhydride copolymers identified in paragraph (a) of this section may be...

  19. pH-sensitive methacrylic copolymers and the production thereof

    SciTech Connect

    Mallapragada, Surya K.; Anderson, Brian C.; Bloom, Paul D.; Sheares Ashby, Valerie V.

    2007-01-09

    The present invention provides novel multi-functional methacrylic copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility under acidic conditions. The copolymers are constructed from tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates. The copolymers are useful as gene vectors, pharmaceutical carriers, and in protein separation applications.

  20. pH-sensitive methacrylic copolymers and the production thereof

    DOEpatents

    Mallapragada, Surya K.; Anderson, Brian C.; Bloom, Paul D.; Sheares Ashby, Valerie V.

    2006-02-14

    The present invention provides novel multi-functional methacrylic copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility under acidic conditions. The copolymers are constructed from tertiary amine methacrylates and poly(ethylene glycol) containing methacrylates. The copolymers are useful as gene vectors, pharmaceutical carriers, and in protein separation applications.

  1. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be...

  2. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be...

  3. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene-carbon monoxide copolymers. 177.1312... Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide... of this section, ethylene-carbon monoxide copolymers (CAS Reg. No. 25052-62-4) consist of the...

  4. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be...

  5. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be...

  6. 40 CFR 721.484 - Fluorinated acrylic copolymer (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated acrylic copolymer (generic... Specific Chemical Substances § 721.484 Fluorinated acrylic copolymer (generic name). (a) Chemical substance... fluorinated acrylic copolymer (PMN P-95-1208) is subject to reporting under this section for the...

  7. 40 CFR 721.484 - Fluorinated acrylic copolymer (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fluorinated acrylic copolymer (generic... Specific Chemical Substances § 721.484 Fluorinated acrylic copolymer (generic name). (a) Chemical substance... fluorinated acrylic copolymer (PMN P-95-1208) is subject to reporting under this section for the...

  8. 21 CFR 177.1060 - n-Alkylglutarimide/acrylic copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false n-Alkylglutarimide/acrylic copolymers. 177.1060... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1060 n-Alkylglutarimide/acrylic copolymers. n-Alkylglutarimide/acrylic copolymers identified in this section may be safely used as...

  9. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials,...

  10. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-vinyl acetate copolymers. 177.1350... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of...

  11. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate copolymers. 177.1350 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of...

  12. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be...

  13. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be...

  14. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-vinyl acetate copolymers. 177.1350... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of...

  15. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be...

  16. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be...

  17. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-vinyl acetate copolymers. 177.1350... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of...

  18. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be...

  19. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials,...

  20. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials,...

  1. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene-vinyl acetate copolymers. 177.1350... Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate... with the following prescribed conditions: (a)(1) Ethylene-vinyl acetate copolymers consist of...

  2. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be...

  3. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be...

  4. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be...

  5. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the...

  6. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the...

  7. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... HUMAN CONSUMPTION Other Specific Usage Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may be safely used in food in accordance with the...

  8. 21 CFR 172.775 - Methacrylic acid-divinylbenzene copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Methacrylic acid-divinylbenzene copolymer. 172.775... Additives § 172.775 Methacrylic acid-divinylbenzene copolymer. Methacrylic acid-divinylbenzene copolymer may... produced by the polymerization of methacrylic acid and divinylbenzene. The divinylbenzene functions as...

  9. Block copolymer blend phase behavior: Binary diblock blends and amphiphilic block copolymer/epoxy mixtures

    NASA Astrophysics Data System (ADS)

    Lipic, Paul Martin

    The phase behavior of block copolymers and block copolymer blends has provided an extensive amount of exciting research and industrial applications for over thirty years. However, the unique nanoscale morphologies of microphase separated block copolymer systems is still not completely understood. This thesis examines the phase behavior of diblock copolymers and binary diblock copolymer blends in the strong segregation limit (SSL), and blends of an amphiphilic diblock copolymer with an epoxy resin. Studies of high molecular weight (˜84,000 g/mole) poly(ethylene)-poly(ethyl ethylene) (PE-PEE) diblock copolymers probed the ability of block copolymers to reach equilibrium in the SSL. Samples of pure diblocks or binary diblock blends prepared using different preparation techniques (solvent casting or precipitation) had different phase behaviors, as identified with transmission electron microscopy (TEM) and small-angle x-ray scattering (SAXS), confirming non-equilibrium phase behavior. This non-equilibrium behavior was metastable, and these results identify the caution that should be used when claiming equilibrium phase behavior in the SSL. Blends of an amphiphilic diblock copolymer, poly(ethylene oxide)-poly(ethylene-alt-propylene) (PEO-PEP) with a polymerizable epoxy resin selectively miscible with PEO, poly(Bisphenol-A-co-epichlorohydrin), supported theoretical calculations and increased the understanding of block copolymer/homopolymer blends. These blends formed different ordered structures (lamellae, bicontinuous cubic gyroid, hexagonally packed cylinders, cubic and hexagonally packed spheres) as well as a disordered spherical micellar structure, identified with SAXS and rheological measurements. Addition of hardener, methylene dianiline, to the system resulted in cross-linking of the epoxy resin and formation of a thermoset material. Macrophase separation between the epoxy and block copolymer did not occur, but local expulsion of the PEO from the epoxy was

  10. Structure-property relationships in block copolymers

    NASA Technical Reports Server (NTRS)

    Mcgrath, J. E.

    1976-01-01

    Block copolymers are a class of relatively new materials which contain long sequences of two (or more) chemically different repeat units. Unlike random copolymers, each segment may retain some properties which are characteristic of its homopolymer. It is well known that most physical blends of two different homopolymers are incompatible on a macro-scale. By contrast most block copolymers display only a microphase (eg. 100-200 A domains) separation. Complete separation is restricted because of a loss in configurational entropy. The latter is due to presence of chemical bond(s) between the segments. Novel physical properties can be obtained because it is possible to prepare any desired combination of rubber-like, glassy, or crystalline blocks. The architecture and sequential arrangement of the segments can strongly influence mechanical behavior.

  11. Optical properties of coumarins containing copolymers

    NASA Astrophysics Data System (ADS)

    Skowronski, L.; Krupka, O.; Smokal, V.; Grabowski, A.; Naparty, M.; Derkowska-Zielinska, B.

    2015-09-01

    We investigate the optical properties such as absorption coefficient, refractive index, real and imaginary parts of dielectric function and energy band gap of coumarin-containing copolymers thin films by means of spectroscopic ellipsometry (SE) combined with transmittance measurements (T) and atomic force microscopy (AFM). We found that the optical properties of coumarin-containing copolymers strongly depend from length of alkyl spacer as well as the type of substitution in coumarin moiety. In our case the refractive index as well as the energy band gap of coumarin-containing copolymer decrease with increase the length of alkyl spacer. Additionally, the lengthening of the alkyl spacer brings the bathochromic shifts of the absorption spectra towards longer wavelengths.

  12. Nanoscale Ionic Aggregate Morphology in Zwitterionic Copolymers

    NASA Astrophysics Data System (ADS)

    Choi, Jae-Hong; Huyck, Rebecca; Salas-de La Cruz, David; Long, Timothy E.; Winey, Karen I.

    2009-03-01

    The morphology of two different zwitterionic copolymers, poly(sulfobetaine methacrylate-ran-butyl acrylate), and poly(sulfobetaine methacrylamide-ran-butyl acrylate) are investigated as a function of the mol % content of SBMA (7 and 9 mol %) and SBMAm (6, 10 and 13 mol %), respectively. In both copolymers, X-ray scattering results show a new structure in the material arising from ionic aggregates. The sizes of the ionic aggregates are obtained through the scattering model. The sizes of the ionic aggregates increase as the ion content increases. The application of scanning transmission electron microscopy to the study of ionomer morphology has enabled direct, model-independent visualization of the ionic aggregates. The correlation between X-ray scattering results and the real space imaging for morphology of these zwitterionic copolymers will be presented.

  13. Microbial Cometabolism and Polyhydroxyalkanoate Co-polymers.

    PubMed

    Ray, Subhasree; Kalia, Vipin Chandra

    2017-03-01

    Polyhydroxyalkanoate (PHAs) are natural, biodegradable biopolymers, which can be produced from renewable materials. PHAs have potential to replace petroleum derived plastics. Quite a few bacteria can produce PHA under nutritional stress. They generally produce homopolymers of butyrate i.e., polyhydroxybutyrate (PHB), as a storage material. The biochemical characteristics of PHB such as brittleness, low strength, low elasticity, etc. make these unsuitable for commercial applications. Co-polymers of PHA, have high commercial value as they overcome the limitations of PHBs. Co-polymers can be produced by supplementing the feed with volatile fatty acids or through hydrolysates of different biowastes. In this review, we have listed the potential bacterial candidates and the substrates, which can be co-metabolized to produce PHA co-polymers.

  14. Microphase segregation in molten randomly grafted copolymers

    NASA Astrophysics Data System (ADS)

    Qi, Shuyan; Chakraborty, Arup K.; Balsara, Nitash P.

    2001-08-01

    We study microphase ordering of molten randomly grafted copolymers (RGCs) by using a mean field theory and the replica method to calculate the quenched average. Our results illustrate that in the weak segregation limit (WSI), the optimal wave vector q* of the lamellar phase formed by molten RGCs, has a temperature dependence different from either linear random copolymers (LRCs) or diblock copolymers (DCPs): when close, but below the microphase separation transition (MST) temperature, q* increases sharply with decreasing temperature; then q* gradually acquires an asymptotic value determined by the length of the branch and the average distance between branch points on the backbone. Our results are compared with recent experiments, and the effects of chain architecture on the microphase separation characteristics of RGCs are delineated. Our results suggest a new method for controlling the microphase spacing by exploiting quenched disorder.

  15. Rod-Coil Block Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B. (Inventor); Kinder, James D. (Inventor)

    2005-01-01

    This invention is a series of rod-coil block polyimide copolymers that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consist of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

  16. Additive-driven assembly of block copolymers

    NASA Astrophysics Data System (ADS)

    Lin, Ying; Daga, Vikram; Anderson, Eric; Watkins, James

    2011-03-01

    One challenge to the formation of well ordered hybrid materials is the incorporation of nanoscale additives including metal, semiconductor and dielectric nanoparticles at high loadings while maintaining strong segregation. Here we describe the molecular and functional design of small molecule and nanoparticle additives that enhance phase segregation in their block copolymer host and enable high additive loadings. Our approach includes the use of hydrogen bond interactions between the functional groups on the additive or particle that serve as hydrogen bond donors and one segment of the block copolymer containing hydrogen bond acceptors. Further, the additives show strong selectively towards the targeted domains, leading to enhancements in contrast between properties of the phases. In addition to structural changes, we explore how large changes in the thermal and mechanical properties occur upon incorporation of the additives. Generalization of this additive-induced ordering strategy to various block copolymers will be discussed.

  17. [Hydrodynamic properties of exopolysaccharide-acrylamide copolymer].

    PubMed

    Votselko, S K

    2000-01-01

    The method for producing copolymer EPAA of exopolysaccharide (EPS)--polyacrylamide (PAA) has been presented which was based on microbial exopolysaccharides (enposane, xampane), their mixture and model EPS (xanthane sigma, rodopol P-23). The copolymer was produced by acrylamide polymerization in 1-2% water solutions of polysaccharides, the concentration of acrylamide in the reaction mixture being 4.7-2% and that of polysaccharides 0.1-1% of the weight. Hydrodynamic parameters of the studied polymers have been determined, their heterogenity as to molecular-weight characteristics has been demonstrated. Molecular-weight distribution of copolymers showed that the content of low-molecular fractions decreased, thus the Mw values were (0.08-0.2) x 10(6) Da in contrast to that of exopolysaccharides possessing Mw (1.2-0.4) x 10(6) Da and of polyacrylamide possessing Mw within (2-30) x 10(6) Da. The value of efficient viscosity of copolymers ranged from 120 to 131 mPa.s that was lower than that of polyacrylamide (500 mPa.s), and higher than that of exopolysaccharides (42 mPa.s), and it depended on the sample, raw material, production conditions. A possibility has been shown to produce a new copolymer based on microbial polysaccharides enposane and xampane in the process of acrylamide polymerization. It has been found out that the studied copolymers EPAA differ from initial ones as to their hydrodynamical properties, which determines their preference: better solubility, good glueing properties, prolonged term of preservation, resistance to bacterial pollution.

  18. hnRNP A2/B1 interacts with influenza A viral protein NS1 and inhibits virus replication potentially through suppressing NS1 RNA/protein levels and NS1 mRNA nuclear export

    SciTech Connect

    Wang, Yimeng; Zhou, Jianhong; Du, Yuchun

    2014-01-20

    The NS1 protein of influenza viruses is a major virulence factor and exerts its function through interacting with viral/cellular RNAs and proteins. In this study, we identified heterogeneous nuclear ribonucleoprotein A2/B1 (hnRNP A2/B1) as an interacting partner of NS1 proteins by a proteomic method. Knockdown of hnRNP A2/B1 by small interfering RNA (siRNA) resulted in higher levels of NS vRNA, NS1 mRNA, and NS1 protein in the virus-infected cells. In addition, we demonstrated that hnRNP A2/B1 proteins are associated with NS1 and NS2 mRNAs and that knockdown of hnRNP A2/B1 promotes transport of NS1 mRNA from the nucleus to the cytoplasm in the infected cells. Lastly, we showed that knockdown of hnRNP A2/B1 leads to enhanced virus replication. Our results suggest that hnRNP A2/B1 plays an inhibitory role in the replication of influenza A virus in host cells potentially through suppressing NS1 RNA/protein levels and NS1 mRNA nucleocytoplasmic translocation. - Highlights: • Cellular protein hnRNP A2/B1 interacts with influenza viral protein NS1. • hnRNP A2/B1 suppresses the levels of NS1 protein, vRNA and mRNA in infected cells. • hnRNP A2/B1 protein is associated with NS1 and NS2 mRNAs. • hnRNP A2/B1 inhibits the nuclear export of NS1 mRNAs. • hnRNP A2/B1 inhibits influenza virus replication.

  19. Structure of Poly(3-(2'-ethyl)hexylthiophene) (P3EHT) Containing Diblock Copolymers Controlled via Thermal Processing

    NASA Astrophysics Data System (ADS)

    Davidson, Emily; Segalman, Rachel

    Poly(3-alkylthiophene)s with modified alkyl side chains crystallize confined within block copolymer microphases, serving as a good model system for the confined crystallization of semiflexible polymers. We hypothesize that the diblock structure may impose an equilibrium degree of crystalline conjugated chain folding which here is only accessible for small degrees of undercooling. Crystallization of these P3ATs in soft confinement drives microdomain expansion; here, we show that this expansion is minimized for crystallization at small degrees of undercooling. Upon heating, domains return to their melt structure over three distinct regimes. These regimes directly correspond to thermal features we assign to the relaxation of a rigid-amorphous fraction at the diblock interface, melt-recrystallization which reorganizes the degree of chain folding, and a final complete melting transition.

  20. Characterization of the copolymer poly(ethyleneglycol-g-vinylalcohol) as a potential carrier in the formulation of solid dispersions.

    PubMed

    Guns, Sandra; Kayaert, Pieterjan; Martens, Johan A; Van Humbeeck, Jan; Mathot, Vincent; Pijpers, Thijs; Zhuravlev, Evgeny; Schick, Christoph; Van den Mooter, Guy

    2010-02-01

    In order to fully exploit the graft copolymer poly(ethyleneglycol-g-vinylalcohol) (EG/VA) in the formulation of solid dispersions, a characterization of its phase behavior before, during and after spray-drying and hot-melt extrusion is performed. Solid state characterization was performed using MDSC and XRPD. The effect of heating/cooling rate on the degree of crystallinity was studied using HPer DSC and ultra-fast chip calorimetry. EG/VA consists of two semi-crystalline fractions, one corresponding to the polyethyleneglycol (PEG) fraction (T(g)=-57 degrees C, T(m)=15 degrees C) and one corresponding to the polyvinylalcohol (PVA) fraction (T(g)=45 degrees C, T(m)=212 degrees C). XRPD analysis confirmed its semi-crystallinity, and EG/VA showed Bragg reflections comparable to those of PVA. Spray-drying at a temperature lower than 170 degrees C resulted in amorphization of the PVA fraction, while after hot-melt extrusion at different temperatures, the crystallinity of this fraction increases. In both cases, the PEG fraction is not influenced. Plasticization of the amorphous domains of the PEG or PVA fraction of the copolymer was dependent on the type and concentration of plasticizer, suggesting that also other small organic molecules like drugs may not homogeneously mix with both amorphous domains. A controlled cooling rate of 3000 degrees C/s was necessary to make the copolymer completely amorphous.

  1. Biodegradable blends of poly (lactic acid) (PLA) / polyhydroxybutrate (PHB) copolymer and its effects on rheological, thermal and mechanical properties

    NASA Astrophysics Data System (ADS)

    Sood, Nitin K.

    Poly (Lactic acid) is the most important plastic derived from the renewable resources. PLA based products have extensively been used in the medical industry. However, PLA has a few disadvantages such as inherent brittleness and low toughness despite a high modulus. A focus of this experiment was to study the improvement in toughness of PLA and to study the changes in thermal and rheological properties by blending PLA with a PHB copolymer. Where, PLA and PHB copolymer were melt blended using a twin screw Brabender extruder in the ratios of 100/0, 70/30, 50/50, 30/70, 0/100. Further, the blends were injection molded into tensile bar and impact bars for mechanical testing. Rheological properties were studied using a Galaxy capillary rheometer for melt viscosities and temperature dependence indicated a shear-thinning behavior along with power law model and consistency index. Blends were characterized to study the phase model using a differential scanning calorimetric (DSC), showed two separate phases. Mechanical properties were analyzed using a Tensile and Izod impact test indicating decrease in elastic modulus with increase in toughness and elongation as the PHB copolymer content was increased in the blend.

  2. Phase diagram of selectively cross-linked block copolymers shows chemically microstructured gel

    NASA Astrophysics Data System (ADS)

    von der Heydt, Alice; Zippelius, Annette

    2015-02-01

    We study analytically the intricate phase behavior of cross-linked AB diblock copolymer melts, which can undergo two main phase transitions due to quenched random constraints. Gelation, i.e., spatially random localisation of polymers forming a system-spanning cluster, is driven by increasing the number parameter μ of irreversible, type-selective cross-links between random pairs of A blocks. Self-assembly into a periodic pattern of A/B-rich microdomains (microphase separation) is controlled by the AB incompatibility χ inversely proportional to temperature. Our model aims to capture the system's essential microscopic features, including an ensemble of random networks that reflects spatial correlations at the instant of cross-linking. We identify suitable order parameters and derive a free-energy functional in the spirit of Landau theory that allows us to trace a phase diagram in the plane of μ and χ. Selective cross-links promote microphase separation at higher critical temperatures than in uncross-linked diblock copolymer melts. Microphase separation in the liquid state facilitates gelation, giving rise to a novel gel state whose chemical composition density mirrors the periodic AB pattern.

  3. Synthesis of comb-like copolymers from renewable resources: Itaconic anhydride, stearyl methacrylate and lactic acid

    NASA Astrophysics Data System (ADS)

    Shang, Shurui

    The synthesis and properties of comb-like copolymers and ionomers derived from renewable resources: itaconic anhydride (ITA), stearyl methacrylate (SM) and lactic acid (LA) are described. The copolymers based on ITA and SM (ITA-SM) were nearly random with a slight alternating tendency. The copolymers exhibited a nanophase-separated morphology, with the stearate side-chains forming a bilayer, semi-crystalline structure. The crystalline side-chains suppressed molecular motion of the main-chain, so that a glass transition temperature (Tg) was not resolved unless the ITA concentration was sufficiently high so that Tg > the melting point (Tm). The softening point and modulus of the copolymers increased with the increasing ITA concentration, but the thermal stability decreased. The ITA moiety along the main chain of the copolymers was neutralized with metal acetates to produce Na-, Ca- and Zn- random ionomers with comb-like architectures. In general, the incorporation of the ionic groups increased the Tg and suppressed the crystallinity of the side-chain packing. Ionomers with high SM side-chain density had two competing driving forces for self-assembled nano-phase separation: ionic aggregation and side-chain crystalline packing. Upon neutralization, a morphological transition from semi-crystalline lamella to spherical ionic aggregation was observed by small angle X-ray scattering (SAXS) analysis and transmission electron microscopy (TEM). Thermomechanical analysis revealed an increasing resistance to penetration deformation with an increasing degree of neutralization and an apparent rubbery plateau was observed above Tg. A controlled transesterification of PLA in glassware was an effective way to prepare a methacrylate functionalized PLA macromonomer with controlled molecular weight, which was used to synthesize a variety of copolymers. The copolymerization of this functionalized PLA macromonomer with ITA totally suppressed the side-chain crystallinity for the PLA chain

  4. Co-polymer Films for Sensors

    NASA Technical Reports Server (NTRS)

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

    2012-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  5. Co-polymer films for sensors

    NASA Technical Reports Server (NTRS)

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)

    2010-01-01

    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  6. The versatility in morphology and physical properties offered by chain shuttled olefin block copolymers

    NASA Astrophysics Data System (ADS)

    Weinhold, Jeffrey

    2014-03-01

    Chain shuttling catalysis enables the production of olefin block copolymers (OBCs) with a wide range of block compositions. Unique morphology and property combinations can be achieved with highly crystalline hard blocks and low crystallinity or fully amorphous soft blocks. The effect of the amount of comonomer in the soft blocks on phase behavior, morphology and properties will be the focus of this presentation. In one class of materials, the soft blocks contain just enough octene comonomer to give elastic behavior but, unlike a random copolymer-based olefin elastomer, the soft segments are held together by thick crystals formed by the hard blocks. In addition to strengthening the network, these crystals provide temperature resistance and, by solidifying at higher temperature, they allow faster product fabrication. Increasing the soft block's octene content yields the next class of materials which have improved compatibility with polypropylene. This property allows the formation of fine, uniformly-dispersed OBC elastomer particles in PP. Since the impact strength of toughened PP increases as the particle size is reduced, a lower amount of elastomer is required to achieve an application's target for toughness. The direct benefit of lower elastomer loading is an increase in modulus, which enables lightweighting in applications. With further increases in the soft block's octene content, the incompatibility between the hard and soft blocks becomes large enough to cause the OBCs to form ordered melt morphologies. In the solid state, the alternating crystalline and amorphous regions have surprisingly large domain spacings and, due to the difference in refractive index between the domains, the periodicity results in a partial photonic band gap for frequencies in the visible spectrum. Comparisons to the morphology of monodisperse block copolymers and the predictions of theories will be presented. Also, the results of an extension to strong segregation theory will be shown

  7. Improved nerve regeneration through piezoelectric vinylidenefluoride-trifluoroethylene copolymer guidance channels.

    PubMed

    Fine, E G; Valentini, R F; Bellamkonda, R; Aebischer, P

    1991-10-01

    Piezoelectric materials generating electrical charges in response to mechanical strain may be used to stimulate axonal regeneration following nerve injury. Tubular nerve guidance channels were extruded from a vinylidenefluoride-trifluoroethylene copolymer using a melt-extrusion process. Unlike vinylidenefluoride homopolymer, the copolymer does not need mechanical stretching to achieve a dipole-containing crystal structure, enabling the fabrication of complex piezoelectric devices. Selected tubes were rendered piezoelectric in a high voltage corona poling apparatus. Crystal structure changes induced by poling were evaluated with differential scanning calorimetry. In contrast to unpoled samples, poled ones displayed a sharp endothermic peak and a greater heat of transition at the Curie temperature, indicative of an increase in crystal order and size. The piezoelectric output of poled tubes was characterized using a laser-monitored deflection system interfaced with a charge amplifier and oscilloscope. Poled tubes generated significant voltages in response to slight mechanical deformations. The magnitude of electrical output was independent of the poling polarity. Unpoled tubes showed no electrical output. Positive, negative and unpoled vinylidenefluoride-trifluoroethylene copolymer tubes were used to repair a 10 mm gap in transected sciatic nerves of adult rats. Nerves regenerated in positively poled channels had a significantly greater number of myelinated axons than those regenerated in unpoled channels 4 wk post-implantation. Negatively poled channels contained an intermediate number of myelinated axons. We concluded that piezoelectrically active vinylidenefluoride-trifluoroethylene copolymer tubes significantly enhance nerve regeneration as compared to chemically identical, unpoled tubes and that the polarity of the corona poling procedure used to fabricate piezoelectric materials may play a role in determining biological responses.

  8. New functionalized block copolymers for bonding copper to epoxy

    SciTech Connect

    Kent, M.; Saunders, R.; Emerson, J.; Hurst, M.

    1995-11-01

    The authors are exploring the use of functionalized block copolymers for bonding copper to epoxy in printed wiring boards. The program involves four key elements: (i) synthesis of suitable functionalized block copolymers; (ii) characterization of the conformation of the copolymers at the relevant interfaces by neutron reflectivity; (iii) spectroscopic measurements of chemical bonding, and (iv) measurement of the mechanical properties of the interfaces. The copolymers are synthesized by living, ring-opening metathesis polymerization. This relatively new technique allows great flexibility for synthesis of functionalized block copolymers in that the initiators are relatively insensitive to a wide range of functional groups. Significant adhesion enhancement has been observed in lap shear tests.

  9. Remifentanil-induced preconditioning has cross-talk with A1 and A2B adenosine receptors in ischemic-reperfused rat heart.

    PubMed

    Lee, Yong-Cheol; Jung, Jiyoon; Park, Sang-Jin

    2016-01-01

    The purpose of this study was to determine whether there is a cross-talk between opioid receptors (OPRs) and adenosine receptors (ADRs) in remifentanil preconditioning (R-Pre) and, if so, to investigate the types of ADRs involved in the cross-talk. Isolated rat hearts received 30 min of regional ischemia followed by 2 hr of reperfusion. OPR and ADR antagonists were perfused from 10 min before R-Pre until the end of R-Pre. The heart rate, left ventricular developed pressure (LVDP),velocity of contraction (+dP/dtmax), and coronary flow (CF) were recorded. The area at risk and area of necrosis were measured. After reperfusion, the LVDP, +dP/dtmax,and CF showed a significant increase in the R-Pre group compared with the control group (no intervention before or after regional ischemia). These increases in the R-Pre group were blocked by naloxone, a nonspecific ADR antagonist, an A1 ADR antagonist, and an A2B ADR antagonist. The infarct size was reduced significantly in the R-Pre group compared with the control group. The infarct-reducing effect in the R-Pre group was blocked by naloxone, the nonspecific ADR antagonist, the A1 ADR antagonist, and the A2B ADR antagonist. The results of this study demonstrate that there is cross-talk between ADRs and OPRs in R-Pre and that A1 ADR and A2B ADR appear to be involved in the cross-talk.

  10. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors

    NASA Astrophysics Data System (ADS)

    Cho, Junhan

    2014-03-01

    Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

  11. Melting the Divide

    NASA Astrophysics Data System (ADS)

    Gibson, S. M.

    2014-12-01

    Presenting Quaternary Environmental Change to students who fall into Widening Participation criteria at the University of Cambridge, gives a unique opportunity to present academic debate in an approachable and entertaining way. Literally by discussing the melting of our ice caps, melts the divide Cambridge has between its reputation and the reality for the brightest, underprivileged, students. There is a balance between presenting cutting edge research with the need to come across as accessible (and importantly valuable to "learning"). Climate change over the Quaternary lends itself well to this aim. By lecturing groups of potential students through the entire Quaternary in an hour, stopping to discuss how our ancestors interacted with past Interglacials and what are the mechanisms driving change (in generalized terms), you are able to introduce cutting edge research (such as the latest NEEM ice core) to the students. This shows the evolution and importance of higher education and academic research. The lecture leads well onto group discussions (termed "supervisions" in Cambridge), to explore their opinions on the concern for present Anthropogenic Climate Change in relation to Past Climate Change after being presented with images that our ancestors "made it". Here discussion thrives off students saying obvious things (or sarcastic comments!) which quickly can lead into a deep technical discussion on their terms. Such discussions give the students a zest for higher education, simply throwing Ruddiman's (2003) "The Anthroprocene Started Several Thousand Years Ago" at them, questions in a second their concept of Anthropogenic Climate Change. Supervisions lend themselves well to bright, articulate, students and by offering these experiences to students of Widening Participation criteria we quickly melt the divide between the reputation of Cambridge ( and higher education as a whole) and the day to day practice. Higher education is not for the privileged, but a free and

  12. Melting and Crystalline Properties of Isotactic Poly(propylenes) with 1,3 Defects

    NASA Astrophysics Data System (ADS)

    Ruiz-Orta, Carolina; Fernandez-Blazquez, Juan P.; Alamo, Rufina G.; Anderson, Amelia M.; Coates, Geoffrey W.

    2010-03-01

    Polypropylenes synthesized with a chiral diimine Ni(II) catalyst and MAO produce isotactic poly(propylenes) with random 1,3 enchainments and offer the opportunity to study the effect of this defect on iPP crystallization in reference to the effect given by 1-alkene comonomers. The type and content of 1,3 insertions was obtained from high resolution 13 C NMR spectra. Both, the 1,3 insertion and the ethylene comonomer add similar methylene sequences to the isotactic iPP chain; however, iPP with isolated 1,3 defects melt and crystallize at lower temperatures than matched propylene ethylene copolymers. The melting behavior is similar to propylene 1-octene copolymers, reflecting the exclusion of the 1,3 defect from the crystals. Compared to copolymers with 1-octene or 1-hexene units, the methylene enchainment and change in chirality caused by the 1,3 defect leads to a lower degree of crystallinity and different polymorphic behavior.

  13. Acrylamide/acrylic acid copolymers for cement fluid loss control

    SciTech Connect

    McKenzie, L.F.; McElfresh, P.M.

    1982-01-01

    Acrylamide/acrylic acid copolymers are considered as effective fluid loss control additives in a wide range of oil well cements. Unlike HEC based fluid loss aditives, these copolymers can be used with calcium chloride accelerator without significantly influencing fluid loss control. Another advantage of the copolymers is that the amount of fluid loss for a given concentration of polymer remains relatively constant over a wide range of temperatures. The use of acrylamide/acrylic acid copolymers has generally been restricted to wells below 60 degree C BHCT. Above that temperature chemical changes in the copolymer often lead to retardation of the cement. This paper presents data related to the use of acrylamide/acrylic acid copolymers as fluid loss control agents in oil well cementing. A comparison of these polymers with HEC based fluid loss control additives is made. In addition, data related to the cause of acrylamide/acrylic acid copolymer retarding effects is presented. 4 refs.

  14. Block copolymer nanolithography for the fabrication of patterned media.

    SciTech Connect

    Warke, Vishal V; Bakker, Martin G; Hong, Kunlun; Mays, Jimmy; Britt, Phillip F; Li, Xuefa; Wang, Jin

    2008-01-01

    Abstract Bit patterned perpendicular media has the potential to increase the density of magnetic recording beyond what can be achieved by granular media. Self assembling diblock copolymers are of interest as templates for patterned media, as they potentially provide a low cost fabrication route. A method to fabricate the desired pattern using cylinder forming diblock copolymers of (PS-b-PMMA) as template is reported. Upon phase separation hexagonally packed cylinders of the minority phase (PMMA) surrounded by the continuous majority phase (PS) are obtained. The processing sequence began with spin coating the block copolymer on a suitable substrate, followed by annealing the block copolymer thin film in vacuum to orient it perpendicular to the substrate. Block copolymer templates were obtained by glacial acetic acid treatment which opened the pores in the block copolymer thin film. Ni was electrodeposited in the block copolymer templates and this pattern was then transferred onto the underlying substrate by ion milling

  15. Melt Heterogeneity and Degassing at MT Etna from Melt Inclusions

    NASA Astrophysics Data System (ADS)

    Salem, L. C.; Edmonds, M.; Maclennan, J.; Corsaro, R. A.

    2014-12-01

    The melts feeding Mt Etna, Italy, are rich in volatiles and drive long-lasting powerful eruptions of basaltic magma in both effusive and explosive styles of activity. The volatile systematics of the volcanic system are well understood through melt inclusion and volcanic gas studies. Etna's melts are generated from a complex mantle setting, with subduction-related chemical modifications as well as OIB-type features, and then the melts must travel through thick carbonate-rich crust. The continual influx of mantle-derived volatile-rich magma controls the major compositional and eruptive features of Mount Etna and magma mixing has been recognized as an important process driving large eruptions [Kamenetsky, 2007]. Our study focusses on the 1669 eruption, the largest in historical times. Olivine-hosted melt inclusions were analyzed for volatile, trace and major elements using electron microprobe and ion probe (SIMS). We use volatile systematics and geochemical data to deconvolve mantle-derived heterogeneity from melt mixing and crystal fractionation. Our data are well described by a mixing trend between two distinct melts: a CO2-rich (CO2~1000ppm), incompatible trace element depleted melt (La/Yb~16), and a CO2-poor, enriched melt. The mixing also generates a strong correlation between Sr and CO2 in the melt inclusions dataset, reflecting the presence of a strong Sr anomaly in one of the end-member melts. We investigate the origin of this Sr anomaly by considering plagioclase dissolution and crustal assimilation. We also investigate degassing processes in the crust and plumbing system of the volcano. We compare our results with similar studies of OIB and arc-related basalts elsewhere and assess the implications for linking eruption size and style with the nature of the mantle-derived melts. Kamenetsky et al. (2007) Geology 35, 255-258.

  16. Thermal Conductivity of Ethylene Vinyl Acetate Copolymer/Nanofiller Blends

    NASA Technical Reports Server (NTRS)

    Ghose, S.; Watson, K. A.; Working, D. C.; Connell, J. W.; Smith, J. G., Jr.; Lin, Y.; Sun, Y. P.

    2007-01-01

    To reduce weight and increase the mobility, comfort, and performance of future spacesuits, flexible, thermally conductive fabrics and plastic tubes are needed for the Liquid Cooling and Ventilation Garment. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As an approach to raise the thermal conductivity (TC) of an ethylene vinyl acetate copolymer (Elvax 260), it was compounded with three types of carbon based nanofillers: multi-walled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNFs), and expanded graphite (EG). In addition, other nanofillers including metallized CNFs, nickel nanostrands, boron nitride, and powdered aluminum were also compounded with Elvax 260 in the melt at various loading levels. In an attempt to improve compatibility between Elvax 260 and the nanofillers, MWCNTs and EG were modified by surface coating and through noncovalent and covalent attachment of organic molecules containing alkyl groups. Ribbons of the nanocomposites were extruded to form samples in which the nanofillers were aligned in the direction of flow. Samples were also fabricated by compression molding to yield nanocomposites in which the nanofillers were randomly oriented. Mechanical properties of the aligned samples were determined by tensile testing while the degree of dispersion and alignment of nanoparticles were investigated using high-resolution scanning electron microscopy. TC measurements were performed using a laser flash (Nanoflash ) technique. TC of the samples was measured in the direction of, and perpendicular to, the alignment direction. Additionally, tubing was also extruded from select nanocomposite compositions and the TC and mechanical flexibility measured.

  17. Interplay between cubic and hexagonal phases in block copolymer solutions.

    PubMed

    Park, Moon Jeong; Char, Kookheon; Bang, Joona; Lodge, Timothy P

    2005-02-15

    The phase behavior of a symmetric styrene-isoprene (SI) diblock copolymer in a styrene-selective solvent, diethylphthalate, was investigated by in situ small-angle X-ray scattering on isotropic and shear-oriented solutions and by rheology and birefringence. A remarkable new feature in this phase diagram is the coexistence of both body-centered cubic (bcc) and hexagonally close-packed (hcp) sphere phases, in a region between close-packed spheres (cps) and hexagonally packed cylinders (hex) over the concentration range phi approximately 0.33-0.45. By focusing on the transitions among these various ordered phases during heating and cooling cycles, we observed a strong hysteresis: supercooled cylinders persisted upon cooling. The stability of these supercooled cylinders is quite dependent on concentration, and for phi > or = 0.40, the supercooled cylinders do not revert to spheres even after quiescent annealing for 1 month. The spontaneous formation of spheres due to the dissociation of cylinders is kinetically hindered in this case, and the system is apparently not amenable to any pretransitional fluctuations of cylinders prior to the cylinder-to-sphere transition. This contrasts with the case of cylinders transforming to spheres upon heating in the melt. The application of large amplitude shear to the supercooled cylinders is effective in restoring the equilibrium sphere phases.

  18. Solid-supported block copolymer membranes through interfacial adsorption of charged block copolymer vesicles.

    PubMed

    Rakhmatullina, Ekaterina; Meier, Wolfgang

    2008-06-17

    The properties of amphiphilic block copolymer membranes can be tailored within a wide range of physical parameters. This makes them promising candidates for the development of new (bio)sensors based on solid-supported biomimetic membranes. Here we investigated the interfacial adsorption of polyelectrolyte vesicles on three different model substrates to find the optimum conditions for formation of planar membranes. The polymer vesicles were made from amphiphilic ABA triblock copolymers with short, positively charged poly(2,2-dimethylaminoethyl methacrylate) (PDMAEMA) end blocks and a hydrophobic poly( n-butyl methacrylate) (PBMA) middle block. We observed reorganization of the amphiphilic copolymer chains from vesicular structures into a 1.5+/-0.04 nm thick layer on the hydrophobic HOPG surface. However, this film starts disrupting and dewetting upon drying. In contrast, adsorption of the vesicles on the negatively charged SiO2 and mica substrates induced vesicle fusion and formation of planar, supported block copolymer films. This process seems to be controlled by the surface charge density of the substrate and concentration of the block copolymers in solution. The thickness of the copolymer membrane on mica was comparable to the thickness of phospholipid bilayers.

  19. Melting in Martian Snowbanks

    NASA Technical Reports Server (NTRS)

    Zent, A. P.; Sutter, B.

    2005-01-01

    Precipitation as snow is an emerging paradigm for understanding water flow on Mars, which gracefully resolves many outstanding uncertainties in climatic and geomorphic interpretation. Snowfall does not require a powerful global greenhouse to effect global precipitation. It has long been assumed that global average temperatures greater than 273K are required to sustain liquid water at the surface via rainfall and runoff. Unfortunately, the best greenhouse models to date predict global mean surface temperatures early in Mars' history that differ little from today's, unless exceptional conditions are invoked. Snowfall however, can occur at temperatures less than 273K; all that is required is saturation of the atmosphere. At global temperatures lower than 273K, H2O would have been injected into the atmosphere by impacts and volcanic eruptions during the Noachian, and by obliquity-driven climate oscillations more recently. Snow cover can accumulate for a considerable period, and be available for melting during local spring and summer, unless sublimation rates are sufficient to remove the entire snowpack. We decided to explore the physics that controls the melting of snow in the high-latitude regions of Mars to understand the frequency and drainage of snowmelt in the high martian latitudes.

  20. 21 CFR 173.65 - Divinylbenzene copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Divinylbenzene copolymer. 173.65 Section 173.65 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED...-benzene, and no more than 4 weight-percent nonpolymerizable impurities. (b) In accordance with...

  1. 21 CFR 173.65 - Divinylbenzene copolymer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Divinylbenzene copolymer. 173.65 Section 173.65 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... weight-percent ethyl-vinyl-benzene, and no more than 4 weight-percent nonpolymerizable impurities. (b)...

  2. Copolymer sealant compositions and method for making

    NASA Technical Reports Server (NTRS)

    Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor); Krabbenhoft, Herman Otto (Inventor)

    2003-01-01

    Condensation curable poly(fluoroorgano)siloxane-poly(silarylene)siloxane block copolymer compositions having a glass transition temperature not exceeding about -54.degree. C. and excellent solvent resistance have been found useful as sealants. Polyalkoxysilylorgano compounds, such as 1,4-bis[trimethoxysilyl(ethyl)]benzene have been found to be effective as cross-linkers.

  3. Copolymer sealant compositions and method for making

    NASA Technical Reports Server (NTRS)

    Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor); Krabbenhoft, Herman Otto (Inventor)

    2004-01-01

    Condensation curable poly(fluoroorgano)siloxane-poly(silarylene)siloxane block copolymer compositions having a glass transition temperature not exceeding about -54.degree. C. and excellent solvent resistance have been found useful as sealants. Polyalkoxysilylorgano compounds, such as 1,4-bis[trimethoxysilyl(ethyl)]benzene have been found to be effective as cross-linkers.

  4. Copolymer sealant compositions and method for making

    NASA Technical Reports Server (NTRS)

    Singh, Navjot (Inventor); Leman, John Thomas (Inventor); Whitney, John M. (Inventor); Krabbenhoft, Herman Otto (Inventor)

    2002-01-01

    Condensation curable poly(fluoroorgano)siloxane-poly(silarylene)siloxane block copolymer compositions having a glass transition temperature not exceeding about -54.degree. C. and excellent solvent resistance have been found useful as sealants. Polyalkoxysilylorgano compounds, such as 1,4-bis[trimethoxysilyl(ethyl)]benzene have been found to be effective as cross-linkers.

  5. A2B and A3 Adenosine Receptors Modulate Vascular Endothelial Growth Factor and Interleukin-8 Expression in Human Melanoma Cells Treated with Etoposide and Doxorubicin

    PubMed Central

    Merighi, Stefania; Simioni, Carolina; Gessi, Stefania; Varani, Katia; Mirandola, Prisco; Tabrizi, Mojgan Aghazadeh; Baraldi, Pier Giovanni; Borea, Pier Andrea

    2009-01-01

    Cancer patients undergoing treatment with systemic cancer chemotherapy drugs often have abnormal growth factor and cytokine profiles. Thus, serum levels of interleukin-8 (IL-8) are elevated in patients with malignant melanoma. In addition to IL-8, aggressive melanoma cells secrete, through its transcriptional regulator hypoxia-inducible factor 1 (HIF-1), vascular endothelial growth factor (VEGF), which promotes angiogenesis and metastasis of human cancerous cells. Whether these responses are related to adenosine, a ubiquitous mediator expressed at high concentrations in cancer and implicated in numerous inflammatory processes, is not known and is the focus of this study. We have examined whether the DNA-damaging agents etoposide (VP-16) and doxorubicin can affect IL-8, VEGF, and HIF-1 expressions in human melanoma cancer cells. In particular, we have investigated whether these responses are related to the modulation of the adenosine receptor subtypes, namely, A1, A2A, A2B, and A3. We have demonstrated that A2B receptor blockade can impair IL-8 production, whereas blocking A3 receptors, it is possible to further decrease VEGF secretion in melanoma cells treated with VP-16 and doxorubicin. This understanding may present the possibility of using adenosine antagonists to reduce chemotherapy-induced inflammatory cytokine production and to improve the ability of chemotherapeutic drugs to block angiogenesis. Consequently, we conclude that adenosine receptor modulation may be useful for refining the use of chemotherapeutic drugs to treat human cancer more effectively. PMID:19794965

  6. A widespread sequence-specific mRNA decay pathway mediated by hnRNPs A1 and A2/B1

    PubMed Central

    Geissler, Rene; Simkin, Alfred; Floss, Doreen; Patel, Ravi; Fogarty, Elizabeth A.; Scheller, Jürgen; Grimson, Andrew

    2016-01-01

    3′-untranslated regions (UTRs) specify post-transcriptional fates of mammalian messenger RNAs (mRNAs), yet knowledge of the underlying sequences and mechanisms is largely incomplete. Here, we identify two related novel 3′ UTR motifs in mammals that specify transcript degradation. These motifs are interchangeable and active only within 3′ UTRs, where they are often preferentially conserved; furthermore, they are found in hundreds of transcripts, many encoding regulatory proteins. We found that degradation occurs via mRNA deadenylation, mediated by the CCR4–NOT complex. We purified trans factors that recognize the motifs and identified heterogeneous nuclear ribonucleoproteins (hnRNPs) A1 and A2/B1, which are required for transcript degradation, acting in a previously unknown manner. We used RNA sequencing (RNA-seq) to confirm hnRNP A1 and A2/B1 motif-dependent roles genome-wide, profiling cells depleted of these factors singly and in combination. Interestingly, the motifs are most active within the distal portion of 3′ UTRs, suggesting that their role in gene regulation can be modulated by alternative processing, resulting in shorter 3′ UTRs. PMID:27151978

  7. Synthesis of Diblock copolymer poly-3-hydroxybutyrate -block-poly-3-hydroxyhexanoate [PHB-b-PHHx] by a β-oxidation weakened Pseudomonas putida KT2442

    PubMed Central

    2012-01-01

    Background Block polyhydroxyalkanoates (PHA) were reported to be resistant against polymer aging that negatively affects polymer properties. Recently, more and more attempts have been directed to make PHA block copolymers. Diblock copolymers PHB-b-PHHx consisting of poly-3-hydroxybutyrate (PHB) block covalently bonded with poly-3-hydroxyhexanoate (PHHx) block were for the first time produced successfully by a recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. Results The chloroform extracted polymers were characterized by nuclear magnetic resonance (NMR), thermo- and mechanical analysis. NMR confirmed the existence of diblock copolymers consisting of 58 mol% PHB as the short chain length block with 42 mol% PHHx as the medium chain length block. The block copolymers had two glass transition temperatures (Tg) at 2.7°C and −16.4°C, one melting temperature (Tm) at 172.1°C and one cool crystallization temperature (Tc) at 69.1°C as revealed by differential scanning calorimetry (DSC), respectively. This is the first microbial short-chain-length (scl) and medium-chain-length (mcl) PHA block copolymer reported. Conclusions It is possible to produce PHA block copolymers of various kinds using the recombinant Pseudomonas putida KT2442 with its β-oxidation cycle deleted to its maximum. In comparison to a random copolymer poly-3-hydroxybutyrate-co-3-hydroxyhexanoate (P(HB-co-HHx)) and a blend sample of PHB and PHHx, the PHB-b-PHHx showed improved structural related mechanical properties. PMID:22480145

  8. Melting of Ice under Pressure

    SciTech Connect

    Schwegler, E; Sharma, M; Gygi, F; Galli, G

    2008-07-31

    The melting of ice under pressure is investigated with a series of first principles molecular dynamics simulations. In particular, a two-phase approach is used to determine the melting temperature of the ice-VII phase in the range of 10 to 50 GPa. Our computed melting temperatures are consistent with existing diamond anvil cell experiments. We find that for pressures between 10 to 40 GPa, ice melts as a molecular solid. For pressures above {approx}45 GPa there is a sharp increase in the slope of the melting curve due to the presence of molecular dissociation and proton diffusion in the solid, prior to melting. The onset of significant proton diffusion in ice-VII as a function of increasing temperature is found to be gradual and bears many similarities to that of a type-II superionic solid.

  9. Melting of ice under pressure.

    PubMed

    Schwegler, Eric; Sharma, Manu; Gygi, François; Galli, Giulia

    2008-09-30

    The melting of ice under pressure is investigated with a series of first-principles molecular dynamics simulations. In particular, a two-phase approach is used to determine the melting temperature of the ice-VII phase in the range of 10-50 GPa. Our computed melting temperatures are consistent with existing diamond anvil cell experiments. We find that for pressures between 10 and 40 GPa, ice melts as a molecular solid. For pressures above approximately 45 Gpa, there is a sharp increase in the slope of the melting curve because of the presence of molecular dissociation and proton diffusion in the solid before melting. The onset of significant proton diffusion in ice-VII as a function of increasing temperature is found to be gradual and bears many similarities to that of a type-II superionic solid.

  10. Block copolymer/ferroelectric nanoparticle nanocomposites

    NASA Astrophysics Data System (ADS)

    Pang, Xinchang; He, Yanjie; Jiang, Beibei; Iocozzia, James; Zhao, Lei; Guo, Hanzheng; Liu, Jin; Akinc, Mufit; Bowler, Nicola; Tan, Xiaoli; Lin, Zhiqun

    2013-08-01

    Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were first synthesized by exploiting amphiphilic unimolecular star-like poly(acrylic acid)-block-polystyrene (PAA-b-PS) diblock copolymers as nanoreactors. Subsequently, PS-functionalized BaTiO3 NPs were preferentially sequestered within PS nanocylinders in the linear cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer upon mixing the BaTiO3 NPs with PS-b-PMMA. The use of PS-b-PMMA diblock copolymers, rather than traditional homopolymers, offers the opportunity for controlling the spatial organization of PS-functionalized BaTiO3 NPs in the PS-b-PMMA/BaTiO3 NP nanocomposites. Selective solvent vapor annealing was utilized to control the nanodomain orientation in the nanocomposites. Vertically oriented PS nanocylinders containing PS-functionalized BaTiO3 NPs were yielded after exposing the PS-b-PMMA/BaTiO3 NP nanocomposite thin film to acetone vapor, which is a selective solvent for PMMA block. The dielectric properties of nanocomposites in the microwave frequency range were investigated. The molecular weight of PS-b-PMMA and the size of BaTiO3 NPs were found to exert an apparent influence on the dielectric properties of the resulting nanocomposites.Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were

  11. Block copolymer/ferroelectric nanoparticle nanocomposites.

    PubMed

    Pang, Xinchang; He, Yanjie; Jiang, Beibei; Iocozzia, James; Zhao, Lei; Guo, Hanzheng; Liu, Jin; Akinc, Mufit; Bowler, Nicola; Tan, Xiaoli; Lin, Zhiqun

    2013-09-21

    Nanocomposites composed of diblock copolymer/ferroelectric nanoparticles were formed by selectively constraining ferroelectric nanoparticles (NPs) within diblock copolymer nanodomains via judicious surface modification of ferroelectric NPs. Ferroelectric barium titanate (BaTiO3) NPs with different sizes that are permanently capped with polystyrene chains (i.e., PS-functionalized BaTiO3NPs) were first synthesized by exploiting amphiphilic unimolecular star-like poly(acrylic acid)-block-polystyrene (PAA-b-PS) diblock copolymers as nanoreactors. Subsequently, PS-functionalized BaTiO3 NPs were preferentially sequestered within PS nanocylinders in the linear cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer upon mixing the BaTiO3 NPs with PS-b-PMMA. The use of PS-b-PMMA diblock copolymers, rather than traditional homopolymers, offers the opportunity for controlling the spatial organization of PS-functionalized BaTiO3 NPs in the PS-b-PMMA/BaTiO3 NP nanocomposites. Selective solvent vapor annealing was utilized to control the nanodomain orientation in the nanocomposites. Vertically oriented PS nanocylinders containing PS-functionalized BaTiO3 NPs were yielded after exposing the PS-b-PMMA/BaTiO3 NP nanocomposite thin film to acetone vapor, which is a selective solvent for PMMA block. The dielectric properties of nanocomposites in the microwave frequency range were investigated. The molecular weight of PS-b-PMMA and the size of BaTiO3 NPs were found to exert an apparent influence on the dielectric properties of the resulting nanocomposites.

  12. Melting line of polymeric nitrogen

    NASA Astrophysics Data System (ADS)

    Yakub, L. N.

    2013-05-01

    We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

  13. Cycloolefin effect in cycloolefin-(meth)acryl copolymer

    NASA Astrophysics Data System (ADS)

    Lim, Hyun Soon; Seo, Dong Chul; Lee, Chang Soo; Park, Sang Wok; Kim, Sang Jin; Shin, Dae Hyeon; Shin, Jin Bong; Park, Joo Hyun

    2008-11-01

    One of the most important factors in ArF resist development is a resin platform, which dominates a lot of parts of resist characteristics. It has been much changed in order to improve their physical properties such as resolution, pattern profile, etch resistance and line edge roughness. Through the low etch resistance in ArF initial (meth)acryl type copolymer and low transmittance in COMA type copolymer most researchers were interested in developing of (meth)acryl type copolymer again for ArF photoresist. On the other hand, we have studied various polymer platforms suitable ArF photoresist except for meth(acryl) type copolymer. As a result of this study we had developed ROMA type polymers and cycloolefin-(meth)acryl type copolymers. Among the polymers cycloolefin-(meth)acryl type copolymer has many attractions such as etch roughness, resist reflow which needs low glass transition temperature and solvent solubility. In this study, we intend to find out cycloolefin-(meth)acryl copolymer characteristics compared with (meth)acryl copolymer. And, we have tried to find out any differences between acrylate type copolymer and cycloolefin-(meth)acrylate type copolymer with various evaluation results. As a result of this study we are going to talk about the reason that the resist using acrylate type copolymer and cycloolefin-(meth)acryl type copolymer show good pattern profile while acrylate type copolymer show poor pattern profile. We also intend to explain the role of cycloolefin as a function of molecular weight variation and substitution ratio variation of cycloolefin in cycloolefin-(meth)acrylate resin.One of the most important factors in ArF resist development is a resin platform, which dominates a lot of parts of resist characteristics. It has been much changed in order to improve their physical properties such as resolution, pattern profile, etch resistance and line edge roughness. Through the low etch resistance in ArF initial (meth)acryl type copolymer and low

  14. Phase morphology and orientation development of polymer blends in melt processing

    NASA Astrophysics Data System (ADS)

    Yang, Jinhai

    In this dissertation, we studied phase morphology development of various polymer blends in both extrusion and melt spinning using scanning electron microscopy (SEM) assisted with appropriate etching techniques. Various processing conditions, for example shear or elongation rate, shear or elongation stress, and extrusion die length/diameter ratio were considered. The effects of material characteristics, such as viscosity ratio, miscibility and interfacial tension, were studied. To do this, polymer blends were carefully selected. One isotactic polypropylene was blended with two ethylene butene copolymers (EBM), which had different butene contents. One of the blends was miscible and the other was immiscible. The polypropylene was also blended two ethylene octene copolymers (EOM). The above blends had low interfacial tension and different viscosity ratios. One EBM was blended with two polyamide 12 (PA12) materials. These blends had high interfacial tension and different viscosity ratios. One maleic anhydride grafted ethylene octene copolymer was added into the EBM/PA12 blends to decrease their interfacial tension. Studies were focused on a phenomenon that the dispersed phases in these blends could coalesce into a surface layer in both extrusion and melt spinning. This process was controlled by viscosity ratio, interfacial tension and processing conditions. The orientation development of melt spun fibers of these blends was studied by both wide angle X-ray diffraction (WAXD) and birefringence techniques. The orientation was affected by both blend morphologies and solidification order of the blend individual phases. The phase, which solidifies later in the spinline, did not affect the orientation of the first solidified phase. However, the first solidified phase, if it was continuous phase, could largely suppress the orientation of the second solidified phase. Composite stress analysis explained the different orientation behaviors. Extrusion of a PA12 material through a

  15. Solvent-free melt electrospinning for preparation of fast dissolving drug delivery system and comparison with solvent-based electrospun and melt extruded systems.

    PubMed

    Nagy, Zsombor Kristóf; Balogh, Attlia; Drávavölgyi, Gábor; Ferguson, James; Pataki, Hajnalka; Vajna, Balázs; Marosi, György

    2013-02-01

    The solvent-free melt electrospinning (MES) method was developed to prepare a drug delivery system with fast release of carvedilol (CAR), a drug with poor water solubility. To the authors knowledge, this is the first report for preparing drug-loaded melt electrospun fibers. Cationic methacrylate copolymer of Eudragit® E type was used as a fiber forming polymer matrix. For comparison, ethanol-based electrospinning and melt extrusion (EX) methods were used to produce samples that had the same composition as the melt electrospun system. According to the results of scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, and Fourier transformed infrared spectrometry investigations, amorphous solid nanodispersions/solutions of CAR in Eudragit® E matrix were obtained in all cases with 20 m/m % drug content. In vitro drug release in acidic media from the extrudates was significantly faster (5 min) than that from crystalline CAR. Moreover, ultrafast drug release was achieved from the solvent-free melt and ethanol-based electrospun samples because of their huge surface area and the soluble polymer matrix in the acidic media. These results demonstrate that solvent-free MES is a promising, novel technique for the production of drug delivery systems with enhanced dissolution because it can combine the advantages of EX (e.g., solvent-free, continuous process, and effective amorphization) and solvent-based electrospinning (huge product surface area).

  16. In Brief: Melting glaciers

    NASA Astrophysics Data System (ADS)

    Showstack, Randy; Tretkoff, Ernie

    2010-12-01

    Glaciers in Patagonia and Alaska have been losing their mass, and for longer than glaciers elsewhere in the world, according to a 7 December report compiled by the United Nations Environment Programme (UNEP). “Climate change is causing significant mass loss of glaciers in high mountains worldwide,” notes the report, which calls for accelerated research, monitoring, and modeling of glaciers and snow and their role in water supplies. The report “also highlights the vulnerability and exposure of people dependent upon [glacier-fed] rivers to floods, droughts and eventually shortages as a result of changes in the melting and freezing cycles linked with climate change and other pollution impacts,” according to UNEP executive director Achim Steiner. For more information, visit http://www.grida.no/publications/high­mountain-glaciers/.

  17. Waste glass melting stages

    SciTech Connect

    Anderson, L.D.; Dennis, T.; Elliott, M.L.; Hrma, P.

    1993-04-01

    Three different simulated nuclear waste glass feeds, consisting of dried waste and glass frit, were heat treated for 1 hour in a gradient furnace at temperatures ranging from approximately 600[degrees]C--1000[degrees]C. Simulated melter feeds from the Hanford Waste Vitrification Plant (HWVP), the Defense Waste Processing Facility (DWPF), and Kernforschungszentrum Karlsruhe (KfK) in Germany were used. The samples were thin-sectioned and examined by optical microscopy to investigate the stages of the conversion from feed to glass. Various phenomena were seen, such as frit softening, bubble formation, foaming, bubble motion and removal, convective mixing, and homogenization. Behavior of different feeds was similar, although the degree of gas generation and melt homogenization varied.

  18. Waste glass melting stages

    SciTech Connect

    Anderson, L.D.; Dennis, T.; Elliott, M.L.; Hrma, P.

    1993-04-01

    Three different simulated nuclear waste glass feeds, consisting of dried waste and glass frit, were heat treated for 1 hour in a gradient furnace at temperatures ranging from approximately 600{degrees}C--1000{degrees}C. Simulated melter feeds from the Hanford Waste Vitrification Plant (HWVP), the Defense Waste Processing Facility (DWPF), and Kernforschungszentrum Karlsruhe (KfK) in Germany were used. The samples were thin-sectioned and examined by optical microscopy to investigate the stages of the conversion from feed to glass. Various phenomena were seen, such as frit softening, bubble formation, foaming, bubble motion and removal, convective mixing, and homogenization. Behavior of different feeds was similar, although the degree of gas generation and melt homogenization varied.

  19. Tin in silicate melts

    NASA Astrophysics Data System (ADS)

    Paparoni, Guido

    An experimental technique that uses Re metal capsules as containers for tin-bearing systems has been developed and successfully used in the study of the compositional dependence of SnO2 solubility in silicate melts. These experiments have been performed in the absence of an aqueous fluid phase and oxygen fugacity (fO2) has been established by the addition of tin-metal to SnO2. This approach solves three long-standing problems in the study of SnO 2 solubility in silicate melts: (1) Alloying of noble-metal crucibles and corrosion of ceramic crucibles is avoided; (2) fO 2 is established by direct contact of a metal-oxide oxygen buffer; (3) Gaseous SnO is not lost to the furnace atmosphere. The Re-capsule technique, combined with evacuated silica-tube experiments, has been applied to the study of the system SnO-SiO2 at pressures of 1 atm and 10 kbar. SnO2 solubilities of up to 95 wt% SnO are reported. The system SnO-SiO2 is found to be a pseudo-binary of the ternary system Sn°-SnO2-SiO2. A revised phase diagram for the system SnO-SiO2 at a pressure ≈1 atm is provided, and a new phase diagram for the system SnOSiO2 at a pressure = 10 kbar has been constructed. These results are used to suggest the topology of the ternary system Sn°-SnO2SiO2. The Re-capsule technique has also been applied to the study of the subaluminous haplogranite system (SiO2NaAlSi3O8-KAlSi 3O8) at T = 1100°C, P = 10 kbar and fO 2 at Sn°-SnO2. Solubilities span the range of 41 to 80 wt% SnO. In the haplogranite system, the solubility of SnO2 increases with the proportion of normative SiO2, and SnO is found to expand the stability field of SiO2. In the feldspar join, Na-based melts dissolve a larger proportion of SnO than K-based melts. This effect is lost as SiO2 is progressively added to the feldspar join. Small amounts of F (1 wt%) are found to increase the solubility of SnO 2 by an equivalent 15 wt% normative quartz as shown with the Spor Mountain rhyolite. A comparison of SnO2 solubilities

  20. Melting and melt-movement in the Earth

    NASA Astrophysics Data System (ADS)

    White, Robert S.

    Researchers came together to discuss melting and melt-movement in the Earth at a 2-day Royal Society Discussion Meeting held in March 1992 at the Royal Society, London.In recent years, many new tools have become available to geologists studying igneous and metamorphic rocks. They can be examined at ever-higher magnifications: the composition within individual crystals can be measured; their isotopic, trace, and rare-earth element concentrations can be determined; and measurements of partition coefficients and melting behavior can be made in the laboratory at pressures and temperatures appropriate to in-situ rocks. Along with these improvements in instrumentation and experimental techniques, advances have been made in understanding the physics of melt generation and separation, and computers have been developed that are sufficiently powerful to model theoretical formulations of the behavior of melt in the Earth.

  1. Solvent enhanced block copolymer ordering in thin films

    NASA Astrophysics Data System (ADS)

    Misner, Matthew J.

    Diblock copolymer self-assembly of materials is emerging as a key element in the fabrication of functional nanostructured materials. By solvent casting or solvent annealing block copolymer thin films, we have demonstrated methods to produce diblock copolymer films with highly oriented, close-packed arrays of nanoscopic cylindrical domains with a high degree of long-range lateral order with few defects. The solvent imparts a high degree of mobility in the microphase-separated copolymer that enables a rapid removal of defects and a high degree of lateral order. Though the use of a selective cosolvent during solvent casting, it was found that the microdomain size and spacing could be increased, leading to a size-tunable system. Additionally, the presence of water also led to the ability to control the microdomain orientation during solvent annealing. Ionic complexation within cylinder-forming PS- b-EO block copolymer thin films was also investigated, where added salts bind PEO block as the minor component. Small amounts of added salts, on the order a few ions per chain, show large effects on the ordering of the copolymer films during solvent annealing. By using gold or cobalt salts, well-organized patterns of nanoparticles can be generated in the copolymer microdomains. Topographically and chemically patterned surfaces were used as a route to sectorizing and controlling the lattice orientation of copolymer films. Topographically patterned surfaces allow well-defined boundaries to confine the copolymer microdomains on a surface and effectively direct the ordering and grain orientation of the copolymer microdomains. Chemically patterned surfaces provide a route to direct the block copolymer ordering on completely flat surface, which may have advantages in applications where adding additional topography may be undesirable. To generate nanoporous templates from PS-b-PEO bases materials several routs were followed. The first route was through the addition and selective

  2. Combination of TREF, high-temperature HPLC, FTIR and HPer DSC for the comprehensive analysis of complex polypropylene copolymers.

    PubMed

    Cheruthazhekatt, Sadiqali; Pijpers, Thijs F J; Mathot, Vincent B F; Pasch, Harald

    2013-11-01

    A novel, powerful analytical technique, preparative temperature rising elution fractionation (prep TREF)/high-temperature (HT)-HPLC/Fourier transform infrared spectroscopy (FTIR)/high-performance differential scanning calorimetry (HPer DSC)), has been introduced to study the correlation between the polymer chain microstructure and the thermal behaviour of various components in a complex impact polypropylene copolymer (IPC). For the comprehensive analysis of this complex material, in a first step, prep TREF is used to produce less complex but still heterogeneous fractions. These chemically heterogeneous fractions are completely separated by using a highly selective chromatographic separation method--high-temperature solvent gradient HPLC. The detailed structural and thermal analysis of the HPLC fractions was conducted by offline coupling of HT-HPLC with FTIR spectroscopy and a novel DSC method--HPer DSC. Three chemically different components were identified in the mid-elution temperature TREF fractions. For the first component, identified as isotactic polypropylene homopolymer by FTIR, the macromolecular chain length is found to be an important factor affecting the melting and crystallisation behaviour. The second component relates to ethylene-propylene copolymer molecules with varying ethylene monomer distributions and propylene tacticity distributions. For the polyethylene component (last eluting component in all semi-crystalline TREF fractions), it was found that branching produced defects in the long crystallisable ethylene sequences that affected the thermal properties. The different species exhibit distinctively different melting and crystallisation behaviour, as documented by HPer DSC. Using this novel approach of hyphenated techniques, the chain structure and melting and crystallisation behaviour of different components in a complex copolymer were investigated systematically.

  3. MicroRNA signatures predict dysregulated vitamin D receptor and calcium pathways status in limb girdle muscle dystrophies (LGMD) 2A/2B.

    PubMed

    Aguennouz, M; Lo Giudice, C; Licata, N; Rodolico, C; Musumeci, O; Fanin, M; Migliorato, A; Ragusa, M; Macaione, V; Di Giorgio, R M; Angelini, C; Toscano, A

    2016-08-01

    miRNA expression profile and predicted pathways involved in selected limb-girdle muscular dystrophy (LGMD)2A/2B patients were investigated. A total of 187 miRNAs were dysregulated in all patients, with six miRNAs showing opposite regulation in LGMD2A versus LGMD2B patients. Silico analysis evidence: (1) a cluster of the dysregulated miRNAs resulted primarily involved in inflammation and calcium metabolism, and (2) two genes predicted as controlled by calcium-assigned miRNAs (Vitamin D Receptor gene and Guanine Nucleotide Binding protein beta polypeptide 1gene) showed an evident upregulation in LGMD2B patients, in accordance with miRNA levels. Our data support alterations in calcium pathway status in LGMD 2A/B, suggesting myofibre calcium imbalance as a potential therapeutic target. Copyright © 2016 John Wiley & Sons, Ltd.

  4. Synthesis and characterization of monoisomeric 1,8,15,22-substituted (A3B and A2B2) phthalocyanines and phthalocyanine-fullerene dyads.

    PubMed

    Ranta, Jenni; Kumpulainen, Tatu; Lemmetyinen, Helge; Efimov, Alexander

    2010-08-06

    Synthesis and characterization of three phthalocyanine-fullerene (Pc-C(60)) dyads, corresponding monoisomeric phthalocyanines (Pc), and building blocks, phthalonitriles, are described. Six novel bisaryl phthalonitriles were prepared by the Suzuki-Miyaura coupling reaction from trifluoromethanesulfonic acid 2,3-dicyanophenyl ester and various oxaborolanes. Two phthalonitriles were selected for the synthesis of A(3)B- and A(2)B(2)-type phthalocyanines. Phthalonitrile 4 has a bulky 3,5-di-tert-butylphenyl substituent at the alpha-phthalo position, which forces only one regioisomer to form and greatly increases the solubility of phthalocyanine. Phthalonitrile 8 has a 3-phenylpropanol side chain at the alpha-position making further modifications of the side group possible. Synthesized monoisomeric A(3)B- and A(2)B(2)-type phthalocyanines are modified by attachment of malonic residues. Finally, fullerene is covalently linked to phthalocyanine with one or two malonic bridges to produce Pc-C(60) dyads. Due to the monoisomeric structure and increased solubility of phthalocyanines, the quality of NMR spectra of the compounds is enhanced significantly, making detailed NMR analysis of the structures possible. The synthesized dyads have different orientations of phthalocyanine and fullerene, which strongly influence the electron transfer (ET) from phthalocyanine to fullerene moiety. Fluorescence quenchings of the dyads were measured in both polar and nonpolar solvents, and in all cases, the quenching was more efficient in the polar environment. As expected, most efficient fluorescence quenching was observed for dyad 20b, with two linkers and phthalocyanine and fullerene in face-to-face orientation.

  5. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification... adhesive is a device composed of polyvinylmethylether maleic anhydride, acid copolymer,...

  6. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  7. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  8. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  9. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  10. 40 CFR 721.10523 - Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (generic). 721... Substances § 721.10523 Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl... methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (PMN...

  11. 40 CFR 721.10523 - Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (generic). 721... Substances § 721.10523 Perfluoroalkylethyl methacrylate copolymer with hydroxymethyl acrylamide, vinyl... methacrylate copolymer with hydroxymethyl acrylamide, vinyl chloride and long chain fatty alkyl acrylate (PMN...

  12. Amphiphilic block copolymer membrane for vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

    2013-11-01

    An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

  13. Interaction of poloxamine block copolymers with lipid membranes: Role of copolymer structure and membrane cholesterol content.

    PubMed

    Sandez-Macho, Isabel; Casas, Matilde; Lage, Emilio V; Rial-Hermida, M Isabel; Concheiro, Angel; Alvarez-Lorenzo, Carmen

    2015-09-01

    Interactions of X-shaped poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers with cell membranes were investigated recording the π-A isotherms of monolayer systems of dipalmitoylphosphatidylcholine (DPPC):cholesterol 100:0; 80:20 and 60:40 mol ratio and evaluating the capability of the copolymers to trigger haemolysis or to protect from haemolytic agents. Four varieties of poloxamine (Tetronic 904, 908, 1107 and 1307) were chosen in order to cover a wide range of EO and PO units contents and molecular weights, and compared to a variety of poloxamer (Pluronic P85). The π-A isotherms revealed that the greater the content in cholesterol, the stronger the interaction of the block copolymers with the lipids monolayer. The interactions were particularly relevant at low pressures and low lipid proportions, mimicking the conditions of damaged membranes. Relatively hydrophobic copolymers bearing short PEO blocks (e.g., T904 and P85) intercalated among the lipids expanding the surface area (ΔGexc) but not effectively sealing the pores. These varieties showed haemolytic behavior. Oppositely, highly hydrophilic copolymers bearing long PEO blocks (e.g., T908, T1107 and T1307) caused membrane contraction and outer leaflet sealing due to strong interactions of PEO with cholesterol and diamine core with phospholipids. These later varieties were not haemolytic and exerted a certain protective effect against spontaneous haemolysis for both intact erythrocytes and cholesterol-depleted erythrocytes.

  14. Polymer-organoclay nanocomposites by melt processing

    NASA Astrophysics Data System (ADS)

    Cui, Lili

    2009-12-01

    Polymer-layered silicate nanocomposites based on a variety of polymer matrices and several organoclays were prepared by melt processing. A detailed characterization of the thermal degradation of several commercial and experimental organoclays often used to form polymer nanocomposites was reported. The surfactant type, loading, and purification level of organoclay significantly affect their thermal stability; however, broadly speaking, the results suggest that these differences in thermal stability do not appear to have much effect on the morphology and properties of the nanocomposites formed from them. It seems that the thermal stability of organoclays is not the key factor in organoclay exfoliation in melt processed polymer nanocomposites, since the exfoliation/dispersion process may have been completed on a time scale before the degradation of surfactant progresses to a detrimental level. Polymer nanocomposites have been made from a variety of polymers; however, few matrices have demonstrated the ability to readily exfoliate the organoclay as well as nylon 6, especially for highly hydrophobic materials like polyolefins. Hence, a significant part of this research work was devoted to explore various routes to improve polyolefin-organoclay interactions, and thus, organoclay exfoliation in these systems. Amine grafted polypropylenes and a conventionally used maleic anhydride grafted polypropylene were used as compatibilizers for polypropylene based nanocomposites to improve the organoclay exfoliation. A series of ethylene vinyl acetate copolymers, the polarity of which can be adjusted by varying their vinyl acetate contents, based nanocomposites were prepared as the model system to address the relationship between the polarity of the polymers and their preferences over various organoclay structures. Attempts were made to explore the effect of degree of neutralization of acid groups in ionomers on the morphology and properties of nanocomposites, and it seems that the

  15. Fault rheology beyond frictional melting

    PubMed Central

    Lavallée, Yan; Hirose, Takehiro; Kendrick, Jackie E.; Hess, Kai-Uwe; Dingwell, Donald B.

    2015-01-01

    During earthquakes, comminution and frictional heating both contribute to the dissipation of stored energy. With sufficient dissipative heating, melting processes can ensue, yielding the production of frictional melts or “pseudotachylytes.” It is commonly assumed that the Newtonian viscosities of such melts control subsequent fault slip resistance. Rock melts, however, are viscoelastic bodies, and, at high strain rates, they exhibit evidence of a glass transition. Here, we present the results of high-velocity friction experiments on a well-characterized melt that demonstrate how slip in melt-bearing faults can be governed by brittle fragmentation phenomena encountered at the glass transition. Slip analysis using models that incorporate viscoelastic responses indicates that even in the presence of melt, slip persists in the solid state until sufficient heat is generated to reduce the viscosity and allow remobilization in the liquid state. Where a rock is present next to the melt, we note that wear of the crystalline wall rock by liquid fragmentation and agglutination also contributes to the brittle component of these experimentally generated pseudotachylytes. We conclude that in the case of pseudotachylyte generation during an earthquake, slip even beyond the onset of frictional melting is not controlled merely by viscosity but rather by an interplay of viscoelastic forces around the glass transition, which involves a response in the brittle/solid regime of these rock melts. We warn of the inadequacy of simple Newtonian viscous analyses and call for the application of more realistic rheological interpretation of pseudotachylyte-bearing fault systems in the evaluation and prediction of their slip dynamics. PMID:26124123

  16. Fault rheology beyond frictional melting.

    PubMed

    Lavallée, Yan; Hirose, Takehiro; Kendrick, Jackie E; Hess, Kai-Uwe; Dingwell, Donald B

    2015-07-28

    During earthquakes, comminution and frictional heating both contribute to the dissipation of stored energy. With sufficient dissipative heating, melting processes can ensue, yielding the production of frictional melts or "pseudotachylytes." It is commonly assumed that the Newtonian viscosities of such melts control subsequent fault slip resistance. Rock melts, however, are viscoelastic bodies, and, at high strain rates, they exhibit evidence of a glass transition. Here, we present the results of high-velocity friction experiments on a well-characterized melt that demonstrate how slip in melt-bearing faults can be governed by brittle fragmentation phenomena encountered at the glass transition. Slip analysis using models that incorporate viscoelastic responses indicates that even in the presence of melt, slip persists in the solid state until sufficient heat is generated to reduce the viscosity and allow remobilization in the liquid state. Where a rock is present next to the melt, we note that wear of the crystalline wall rock by liquid fragmentation and agglutination also contributes to the brittle component of these experimentally generated pseudotachylytes. We conclude that in the case of pseudotachylyte generation during an earthquake, slip even beyond the onset of frictional melting is not controlled merely by viscosity but rather by an interplay of viscoelastic forces around the glass transition, which involves a response in the brittle/solid regime of these rock melts. We warn of the inadequacy of simple Newtonian viscous analyses and call for the application of more realistic rheological interpretation of pseudotachylyte-bearing fault systems in the evaluation and prediction of their slip dynamics.

  17. hnRNP A2/B1 interacts with influenza A viral protein NS1 and inhibits virus replication potentially through suppressing NS1 RNA/protein levels and NS1 mRNA nuclear export.

    PubMed

    Wang, Yimeng; Zhou, Jianhong; Du, Yuchun

    2014-01-20

    The NS1 protein of influenza viruses is a major virulence factor and exerts its function through interacting with viral/cellular RNAs and proteins. In this study, we identified heterogeneous nuclear ribonucleoprotein A2/B1 (hnRNP A2/B1) as an interacting partner of NS1 proteins by a proteomic method. Knockdown of hnRNP A2/B1 by small interfering RNA (siRNA) resulted in higher levels of NS vRNA, NS1 mRNA, and NS1 protein in the virus-infected cells. In addition, we demonstrated that hnRNP A2/B1 proteins are associated with NS1 and NS2 mRNAs and that knockdown of hnRNP A2/B1 promotes transport of NS1 mRNA from the nucleus to the cytoplasm in the infected cells. Lastly, we showed that knockdown of hnRNP A2/B1 leads to enhanced virus replication. Our results suggest that hnRNP A2/B1 plays an inhibitory role in the replication of influenza A virus in host cells potentially through suppressing NS1 RNA/protein levels and NS1 mRNA nucleocytoplasmic translocation.

  18. Reversible geling co-polymer and method of making

    DOEpatents

    Gutowska, Anna

    2005-12-27

    The present invention is a thereapeutic agent carrier having a thermally reversible gel or geling copolymer that is a linear random copolymer of an [meth-]acrylamide derivative and a hydrophilic comonomer, wherein the linear random copolymer is in the form of a plurality of linear chains having a plurality of molecular weights greater than or equal to a minimum geling molecular weight cutoff and a therapeutic agent.

  19. On the birefringence of multilayered symmetric diblock copolymer films

    SciTech Connect

    Kim, J.; Chin, I.; Smith, B.A.; Russell, T.P. ); Mays, J.W. . Dept. of Chemistry)

    1993-09-27

    The chain extension at lamellar interfaces was studied in thin films of symmetric diblock copolymers on gold substrates. The first copolymer consisted of blocks of polystyrene (PS) and poly(2-vinylpyridine) (P2VP), denoted P(S-b-2VP). The second was a diblock copolymer of PS and poly(methyl methacrylate) (PMMA), denoted P(S-b-MMA), on a gold substrate. Using attenuated total reflectance spectroscopy, the refractive indices parallel, n[sub [parallel

  20. ROMP from ROMP: A New Approach to Graft Copolymer Synthesis

    PubMed Central

    Allen, Matthew J.; Wangkanont, Kittikhun; Raines, Ronald T.; Kiessling, Laura L.

    2009-01-01

    A new strategy is presented for the synthesis of graft copolymers using only the ring-opening metathesis polymerization (ROMP). From a ROMP-derived main chain, pendant maleimide functional groups are converted into norbornene moieties via a Diels–Alder reaction with cyclopentadiene. The norbornene groups serve as sites of initiation, and subsequent ROMP from the main chain yields graft copolymers with both main and side chains derived from ROMP. This strategy offers ready access to defined graft copolymers. PMID:20161406

  1. Structure-property relationships in multilayered polymeric system and olefinic block copolymers

    NASA Astrophysics Data System (ADS)

    Khariwala, Devang

    diffusion. Subsequently, the oxygen permeability was directly related to the composition profile in each layer and changed as the interdiffusion proceeded. This methodology enabled the extraction of the mutual diffusion co-efficient, D, for the Nylon-6/EVOH system. The effect of comonomer content in EVOH on the mutual diffusion coefficient was also studied by comparing the kinetics of interdiffusion of Nylon-6 with two EVOHs containing 24 and 44 mole % ethylene. Chapter 3. Exciting new developments in polyolefin synthesis give rise to olefinic block copolymers with properties typical of thermoplastic elastomers. The block copolymers synthesized by chain shuttling technology consist of crystallizable ethylene-octene blocks with low comonomer content and high melting temperature (hard blocks), alternating with amorphous ethylene-octene blocks with high comonomer content and low glass transition temperature (soft blocks). This study describes the material science of these unique polymers as characterized by thermal analysis, X-ray diffraction, microscopy, and tensile deformation. The crystallizable blocks are long enough to form well-organized lamellar crystals with the orthorhombic unit cell and high melting temperature. The lamellae are organized into space-filling spherulites in all compositions even in copolymers with only 18 wt% hard block. The morphology is consistent with crystallization from a miscible melt. Crystallization of the hard blocks forces segregation of the noncrystallizable soft blocks into the interlamellar regions. Good separation of hard and soft blocks in the solid state is confirmed by distinct and separate beta- and alpha-relaxations in all the block copolymers. Compared to statistical ethylene-octene copolymers, the blocky architecture imparts a substantially higher crystallization temperature, a higher melting temperature and a better organized crystalline morphology, while maintaining a lower glass transition temperature. The differences between

  2. Formation of Anisotropic Block Copolymer Gels

    NASA Astrophysics Data System (ADS)

    Liaw, Chya Yan; Shull, Kenneth; Henderson, Kevin; Joester, Derk

    2011-03-01

    Anisotropic, fibrillar gels are important in a variety of processes. Biomineralization is one example, where the mineralization process often occurs within a matrix of collagen or chitin fibers that trap the mineral precursors and direct the mineralization process. We wish to replicate this type of behavior within block copolymer gels. Particularly, we are interested in employing gels composed of cylindrical micelles, which are anisotropic and closely mimic biological fibers. Micelle geometry is controlled in our system by manipulating the ratio of molecular weights of the two blocks and by controlling the detailed thermal processing history of the copolymer solutions. Small-Angle X-ray Scattering and Dynamic Light Scattering are used to determine the temperature dependence of the gel formation process. Initial experiments are based on a thermally-reversible alcohol-soluble system, that can be subsequently converted to a water soluble system by hydrolysis of a poly(t-butyl methacrylate) block to a poly (methacrylic acid) block. MRSEC.

  3. Defect trapping in ABC block copolymers

    NASA Astrophysics Data System (ADS)

    Corte, Laurent; Yamauchi, Kazuhiro; Court, Francois; Cloitre, Michel; Hashimoto, Takeji; Leibler, Ludwik

    2004-03-01

    Equilibrium morphologies in molten ABC triblock terpolymers are much more difficult to attain than in AB diblocks. In practice, it is important to know whether and how synthesis conditions influence the morphology and properties of copolymer materials. It is also relevant to understand the mechanisms of defect formation and annihilation. Indeed, a potential use of copolymers in new applications such as lithography highly depends on the ability to produce regular structures with no or few defects. We show that even the simplest lamellar structures exhibit high sensitivity to preparation conditions and that strongly trapped structural defects inherent to ABC triblock architecture cannot be removed by long annealing. Annealing can induce a transition from a lamellar structure in which A and C blocks are mixed to a lamellar structure where A, B and C are segregated. We propose reorganization mechanisms that are at the origin of some characteristic defects.

  4. Rapid ordering of block copolymer thin films

    DOE PAGES

    Majewski, Pawel W.; Yager, Kevin G.

    2016-08-18

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times—hours or days—required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. Here, wemore » also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems.« less

  5. Rapid ordering of block copolymer thin films

    SciTech Connect

    Majewski, Pawel W.; Yager, Kevin G.

    2016-08-18

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times—hours or days—required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. Here, we also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems.

  6. "Clickable" PEG-dendritic block copolymers.

    PubMed

    Fernandez-Megia, Eduardo; Correa, Juan; Riguera, Ricardo

    2006-11-01

    Three generations of azido-terminated PEG-dendritic block copolymers have been synthesized and completely characterized by NMR and MALDI-TOF. A radial decrease of density, leading to more mobile protons at the outermost periphery, and an increasingly higher compactness of the core with generation have been determined by T(1) and T(2) relaxation time studies. The efficient surface decoration of these dendritic polymers by means of click chemistry has been demonstrated by the incorporation of unprotected carbohydrate units in very good to excellent yields. The reaction proceeds at room temperature, under aqueous conditions, and requires just catalytic amounts of Cu. The modified block copolymers are conveniently purified by ultrafiltration. The glycodendrimers functionalized with alpha-mannose form aggregates with concanavalin A as determined by absorbance experiments at 400 nm. This aggregation ability increases with generation.

  7. Photothermal degradation of ethylene/vinylacetate copolymer

    NASA Technical Reports Server (NTRS)

    Liang, R. H.; Chung, S.; Clayton, A.; Di Stefano, S.; Oda, K.; Hong, S. D.; Gupta, A.

    1983-01-01

    Photothermal degradation studies were conducted on a 'stabilized' formulation of ethylene/vinyl acetate copolymer (EVA) in the temperature range 25-105 C under three different oxygen environments (in open air, with limited access to O2, and in a dark closed stagnant oven). These studies were performed in order to evaluate the utility of EVA as an encapsulation material for photovoltaic modules. Results showed that at low temperature (25 C), slow photooxidation of the polymer occurred via electronic energy transfer involving the UV absorber incorporated in the polymer. However, no changes in the physical properties of the bulk polymer were detected up to 1500 hours of irradiation. At elevated temperatures, leaching and evaporation of the additives occurred, which ultimately resulted in the chemical crosslinking of the copolymer and the formation of volatile photoproducts such as acetic acid.

  8. Rapid ordering of block copolymer thin films

    NASA Astrophysics Data System (ADS)

    Majewski, Pawel W.; Yager, Kevin G.

    2016-10-01

    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times—hours or days—required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems.

  9. Amine-reactive biodegradable diblock copolymers.

    PubMed

    Tessmar, Jörg K; Mikos, Antonios G; Göpferich, Achim

    2002-01-01

    A new class of diblock copolymers was synthesized from biodegradable poly(lactic acid) and poly(ethylene glycol)minus signmonoamine. These polymers were activated by covalently attaching linkers such as disuccinimidyl tartrate or disuccinimidyl succinate to the hydrophilic polymer chain. The polymers were characterized by (1)H NMR spectroscopy, (13)C NMR spectroscopy and gel permeation chromatography (GPC). These investigations indicated that the polymers were obtained with the correct composition, in high purities, and the expected molecular weight. By using dyes containing primary amine groups such as 5-aminoeosin as model substrates, it was possible to show that the polymers are able to bind such compounds covalently. The diblock copolymers were developed to suppress unspecific protein adsorption and allow the binding of bioactive molecules by instant surface modification. The polymers are intended to be used for tissue engineering applications where surface immobilized cell adhesion peptides or growth factors are needed to control cell behavior.

  10. Multigraft Copolymer Superelastomers: Synthesis Morphology, and Properties

    SciTech Connect

    Uhrig, David; Schlegel, Ralf; Weidisch, Roland; Mays, Jimmy

    2011-01-01

    The synthesis of well-defined multigraft copolymers having a polydiene backbone with polystyrene side chains is briefly reviewed, with particular focus on controlling branch point spacing and branch point functionality. Use of living anionic polymerization and chlorosilane linking chemistry has led to the synthesis of series of materials having regularly spaced trifunctional (comb), tetrafunctional (centipede), and hexafunctional (barbwire) branch points. The morphologies of these materials were characterized by transmission electron microscopy and small-angle X-ray scattering, and it was found that the morphologies were controlled by the local architectural asymmetry associated with each branch point. Mechanical properties studies revealed that such multigraft copolymers represent a new class of thermoplastic elastomers (TPEs) with superior elongation at break and low residual strains as compared to conventional TPEs.

  11. Block-copolymer-based plasmonic nanostructures.

    PubMed

    Mistark, Peter A; Park, Soojin; Yalcin, Sibel Ebru; Lee, Dong Hyun; Yavuzcetin, Ozgur; Tuominen, Mark T; Russell, Thomas P; Achermann, Marc

    2009-12-22

    We report on the fabrication and optical characterization of dense and ordered arrays of metal nanoparticles. The metal arrays are produced by reducing metal salts in block copolymer (BCP) templates made by solvent annealing of poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) or poly(styrene-b-ethylene oxide) (PS-b-PEO) diblock copolymer thin films in mixed solvents. The gold and gold/silver composite nanoparticle arrays show characteristic surface plasmon resonances in the visible wavelength range. The patterning can be applied over large areas onto various substrates. We demonstrate that these metal nanoparticle arrays on metal thin films interact with surface plasmon polaritons (SPPs) that propagate at the film/nanoparticle interface and, therefore, modify the dispersion relation of the SPPs.

  12. Hierarchical porous polymer scaffolds from block copolymers.

    PubMed

    Sai, Hiroaki; Tan, Kwan Wee; Hur, Kahyun; Asenath-Smith, Emily; Hovden, Robert; Jiang, Yi; Riccio, Mark; Muller, David A; Elser, Veit; Estroff, Lara A; Gruner, Sol M; Wiesner, Ulrich

    2013-08-02

    Hierarchical porous polymer materials are of increasing importance because of their potential application in catalysis, separation technology, or bioengineering. Examples for their synthesis exist, but there is a need for a facile yet versatile conceptual approach to such hierarchical scaffolds and quantitative characterization of their nonperiodic pore systems. Here, we introduce a synthesis method combining well-established concepts of macroscale spinodal decomposition and nanoscale block copolymer self-assembly with porosity formation on both length scales via rinsing with protic solvents. We used scanning electron microscopy, small-angle x-ray scattering, transmission electron tomography, and nanoscale x-ray computed tomography for quantitative pore-structure characterization. The method was demonstrated for AB- and ABC-type block copolymers, and resulting materials were used as scaffolds for calcite crystal growth.

  13. Steps in the transition of an entangled polymer melt to the partially crystalline state

    NASA Astrophysics Data System (ADS)

    Heck, B.; Hugel, T.; Iijima, M.; Sadiku, E.; Strobl, G.

    1999-11-01

    For s-polypropylene, three different s-poly(propene-co-octene)s, two poly(ethylene-co-octene)s and poly(ɛ-caprolactone) we determined the relationships between the crystallization temperature Tc, the crystal thickness dc and the melting peak temperature Tf by carrying out time- and temperature-dependent small-angle x-ray scattering experiments. As a general law, dc is found to be inversely proportional to the supercooling below a characteristic temperature, Tc∞, which is always located above the equilibrium melting point following from an application of the Gibbs-Thomson equation. Tc∞ is not (for the polypropylene-based copolymers) or only weakly (for the polyethylene-based copolymers) dependent on the co-unit content. The `crystallization line' Tc versus dc-1 and the Gibbs-Thomson melting line Tf versus dc-1 limit the range of the accessible partially crystalline states. The occurrence of two well defined independent boundary lines may be understood as indicating that the transformation from the melt into the partially crystalline state is generally, for homopolymers and copolymerized derivatives likewise, a two-step process, beginning with the building up of an initial form of lower order at the crystallization line which then becomes stabilized to end up in the state with layer-like morphology melting at Tf. Stabilization is achieved without a change in dc. AFM and TEM observations suggest that the initial structure could be composed of crystal blocks in planar assemblies. The stabilization then would result from their merging into a continuous lamella. It is proposed that the size of the blocks represents the minimum necessary to retain intrinsic stability. As a further result it was found that crystallinities reached at the end of isothermal crystallization processes remain invariant over larger ranges of Tc, in contrast to the changing length scales of the structure.

  14. Melt Production in Oblique Impacts

    NASA Astrophysics Data System (ADS)

    Pierazzo, E.; Melosh, H. J.

    2000-05-01

    Hydrocode modeling is a fundamental tool for the study of melt production in planetary impact events. Until recently, however, numerical modeling of impacts for melt production studies has been limited to vertical impacts. We present the first results of the investigation of melt production in oblique impacts. Simulations were carried out using Sandia's three-dimensional hydrocode CTH, coupled to the SESAME equation of state. While keeping other impact parameters constant, the calculations span impact angles (measured from the surface) from 90° (vertical impact) to 15°. The results show that impact angle affects the strength and distribution of the shock wave generated in the impact. As a result, both the isobaric core and the regions of melting in the target appear asymmetric and concentrated in the downrange, shallower portion of the target. The use of a pressure-decay power law (which describes pressure as function of linear distance from the impact point) to reconstruct the region of melting and vaporization is therefore complicated by the asymmetry of the shock wave. As an analog to the pressure decay versus distance from the impact point, we used a "volumetric pressure decay," where the pressure decay is modeled as a function of volume of target material shocked at or above the given shock pressure. We find that the volumetric pressure decay exponent is almost constant for impact angles from 90° to 30°, dropping by about a factor of two for a 15° impact. In the range of shock pressures at which most materials of geologic interest melt or begin to vaporize, we find that the volume of impact melt decreases by at most 20% for impacts from 90° down to 45°. Below 45°, however, the amount of melt in the target decreases rapidly with impact angle. Compared to the vertical case, the reduction in volume of melt is about 50% for impacts at 30° and more than 90% for a 15° impact. These estimates do not include possible melting due to shear heating, which can

  15. Nanostructured Block Copolymer Coatings for Biofouling Inhibition

    DTIC Science & Technology

    2015-06-30

    despite similar contact angles) indicating that the amphiphilic nature and patterning of the coating was deterring spore settlement . The two PS-P2VP-PEO...involved settlement and release of algal spores/sporelings, barnacle cyprids/adults, and tubeworm adults, against these phase segregated block...Our previous studies investigated the antifouling properties of a triblock copolymer system PS-b-P2VP-b- PEO in the field in Florida. No settlement of

  16. Asymmetric block copolymers for supramolecular templating of inorganic nanospace materials.

    PubMed

    Bastakoti, Bishnu Prasad; Li, Yunqi; Kimura, Tatsuo; Yamauchi, Yusuke

    2015-05-06

    This review focuses on polymeric micelles consisting of asymmetric block copolymers as designed templates for several inorganic nanospace materials with a wide variety of compositions. The presence of chemically distinct domains of asymmetric triblock and diblock copolymers provide self-assemblies with more diverse morphological and functional features than those constructed by EOn POm EOn type symmetric triblock copolymers, thereby affording well-designed nanospace materials. This strategy can produce unprecedented nanospace materials, which are very difficult to prepare through other conventional organic templating approaches. Here, the recent development on the synthesis of inorganic nanospace materials are mainly focused on, such as hollow spheres, tubes, and porous oxides, using asymmetric triblock copolymers.

  17. Critical adsorption of copolymer tethered on selective surfaces

    NASA Astrophysics Data System (ADS)

    Li, Hong; Qian, Chang-Ji; Luo, Meng-Bo

    2016-04-01

    Critical adsorption behaviors of flexible copolymer chains tethered to a flat homogeneous surface are studied by using Monte Carlo simulations. We have compared the critical adsorption temperature Tc, estimated by a finite-size scaling method, for different AB copolymer sequences with A the attractive monomer and B the inert monomer. We find that Tc increases with an increase in the fraction of monomers A, fA, in copolymers, and it increases with an increase in the length of block A for the same fA. In particular, Tc of copolymer (AnBn)r can be expressed as a function of the block length, n, and Tc of copolymer (AnB)r and (ABm)r can be expressed as a linear function of fA. Tc of random copolymer chains also can be expressed as a linear function of fA and it can be estimated by using weight-average of Tc of different diblocks in the random copolymer. However, the crossover exponent is roughly independent of AB sequence distributions either for block copolymers or for random copolymers.

  18. Sulfur copolymers for infrared optical imaging

    NASA Astrophysics Data System (ADS)

    Namnabat, S.; Gabriel, J. J.; Pyun, J.; Norwood, R. A.; Dereniak, E. L.; van der Laan, J.

    2014-06-01

    The development of organic polymers with low infrared absorption has been investigated as a possible alternative to inorganic metal oxide, semiconductor, or chalcogenide-based materials for a variety of optical devices and components, such as lenses, goggles, thermal imaging cameras and optical fibers. In principle, organic-based polymers are attractive for these applications because of their low weight, ease of processing, mechanical toughness, and facile chemical variation using commercially available precursors. Herein we report on the optical characterization of a new class of sulfur copolymers that are readily moldable, transparent above 500 nm, possess high refractive index (n > 1.8) and take advantage of the low infrared absorption of S-S bonds for potential use in the mid-infrared at 3-5 microns. These materials are largely made from elemental sulfur by an inverse vulcanization process; in the current study we focus on the properties of a chemically stable, branched copolymer of poly(sulfur-random-1,3-diisopropenylbenzene) (poly(S-r- DIB). Copolymers with elemental sulfur content ranging from 50% to 80% by weight were studied by UV-VIS spectroscopy, FTIR, and prism coupling for refractive index measurement. Clear correlation between material composition and the optical properties was established, confirming that the high polarizability of the sulfur atom leads to high refractive index while also maintaining low optical loss in the infrared.

  19. Cavitation in block copolymer modified epoxy

    NASA Astrophysics Data System (ADS)

    Declet-Perez, Carmelo; Francis, Lorraine; Bates, Frank

    2013-03-01

    Today, brittleness in epoxy networks limits most commercial applications. Significant toughness can be imparted by adding small amounts of micelle forming block copolymers (BCP) without compromising critical properties such as high use temperature and modulus. Curing the network locks in the self-assembled BCP micellar structures formed in the monomer resin providing control of the resulting morphology. Despite significant research over the last decade, a complete description of the parameters influencing toughness in block copolymer modified epoxies is still lacking. In this presentation we compare the ultimate mechanical behavior of epoxies modified with spherical micelle forming BCP's containing rubbery and glassy cores using real-time in-situ small-angle X-ray scattering (SAXS) performed during tensile deformation. Striking differences in the 2D SAXS patterns were documented for epoxies modified with rubbery (PEP) versus glassy (PS) micelle cores. Rubbery cores dilate by 100% in volume upon specimen yielding, while the glassy micelle cores deform at approximately constant volume. These results provide direct evidence of a cavitation mediated mechanism for toughness in block copolymer modified epoxies. We further interpret characteristic butterfly features in the 2D SAXS patterns in terms of epoxy network deformation. Support was provided by the NSF sponsored MRSEC at the University of Minnesota

  20. Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

    PubMed Central

    Vukovic, Ivana; Punzhin, Sergey; Voet, Vincent S. D.; Vukovic, Zorica; de Hosson, Jeff Th. M.; ten Brinke, Gerrit; Loos, Katja

    2014-01-01

    Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template's channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology. PMID:24797367

  1. Gyroid nickel nanostructures from diblock copolymer supramolecules.

    PubMed

    Vukovic, Ivana; Punzhin, Sergey; Voet, Vincent S D; Vukovic, Zorica; de Hosson, Jeff Th M; ten Brinke, Gerrit; Loos, Katja

    2014-04-28

    Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template's channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

  2. Comparing Fluid and Elastic Block Copolymer Shells

    NASA Astrophysics Data System (ADS)

    Rozairo, Damith; Croll, Andrew B.

    2014-03-01

    Emulsions can be stabilized with the addition of an amphiphilic diblock copolymer, resulting in droplets surrounded and protected by a polymer monolayer. Such droplets show considerable promise as advanced cargo carriers in pharmaceuticals or cosmetics due to their strength and responsiveness. Diblock copolymer interfaces remain mostly fluid and may not be able to attain the mechanical performance desired by industry. To strengthen block copolymer emulsion droplets we have developed a novel method for creating thin elastic shells using polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS). Characterization of the fluid filled elastic shells is difficult with traditional means which lead us to develop a new and general method of mechanical measurement. Specifically, we use laser scanning confocal microscopy to achieve a high resolution measure of the deformation of soft spheres under the influence of gravity. To prove the resilience of the technique we examine both a polystyrene-b-poly(ethylene oxide) (PS-PEO) stabilized emulsion and the PS-PAA-PS emulsion. The mechanical measurement allows the physics of the polymer at the interface to be examined, which will ultimately lead to the rational development of these technologies.

  3. Thermodynamics of Oligonucleotide Duplex Melting

    NASA Astrophysics Data System (ADS)

    Schreiber-Gosche, Sherrie; Edwards, Robert A.

    2009-05-01

    Melting temperatures of oligonucleotides are useful for a number of molecular biology applications, such as the polymerase chain reaction (PCR). Although melting temperatures are often calculated with simplistic empirical equations, application of thermodynamics provides more accurate melting temperatures and an opportunity for students to apply rigorous thermodynamic analysis to an important biochemical problem. Because the stacking of base pairs on top of one another is a significant factor in the energetics of oligonucleotide melting, several investigators have applied van't Hoff analysis to melting temperature data using a nearest-neighbor model and have obtained entropies and enthalpies for the stacking of bases. The present article explains how the equilibrium constant for the dissociation of strands from double-stranded oligonucleotides can be expressed in terms of the total strand concentration and thus how the total strand concentration influences the melting temperature. It also presents a simplified analysis based on the entropies and enthalpies of stacking that is manually tractable so that students can work examples to help them understand the thermodynamics of oligonucleotide melting.

  4. Are block copolymer worms more effective Pickering emulsifiers than block copolymer spheres?

    PubMed

    Thompson, K L; Mable, C J; Cockram, A; Warren, N J; Cunningham, V J; Jones, E R; Verber, R; Armes, S P

    2014-11-21

    RAFT-mediated polymerisation-induced self-assembly (PISA) is used to prepare six types of amphiphilic block copolymer nanoparticles which were subsequently evaluated as putative Pickering emulsifiers for the stabilisation of n-dodecane-in-water emulsions. It was found that linear poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) diblock copolymer spheres and worms do not survive the high shear homogenisation conditions used for emulsification. Stable emulsions are obtained, but the copolymer acts as a polymeric surfactant; individual chains rather than particles are adsorbed at the oil-water interface. Particle dissociation during emulsification is attributed to the weakly hydrophobic character of the PHPMA block. Covalent stabilisation of these copolymer spheres or worms can be readily achieved by addition of ethylene glycol dimethacrylate (EGDMA) during the PISA synthesis. TEM studies confirm that the resulting cross-linked spherical or worm-like nanoparticles survive emulsification and produce genuine Pickering emulsions. Alternatively, stabilisation can be achieved by either replacing or supplementing the PHPMA block with the more hydrophobic poly(benzyl methacrylate) (PBzMA). The resulting linear spheres or worms also survive emulsification and produce stable n-dodecane-in-water Pickering emulsions. The intrinsic advantages of anisotropic worms over isotropic spheres for the preparation of Pickering emulsions are highlighted. The former particles are more strongly adsorbed at similar efficiencies compared to spheres and also enable smaller oil droplets to be produced for a given copolymer concentration. The scalable nature of PISA formulations augurs well for potential applications of anisotropic block copolymer nanoparticles as Pickering emulsifiers.

  5. High-performance dual-action polymer-TiO2 nanocomposite films via melting processing.

    PubMed

    Kubacka, Anna; Serrano, Cristina; Ferrer, Manuel; Lünsdorf, Heinrich; Bielecki, Piotr; Cerrada, María Luisa; Fernández-García, Marta; Fernández-García, Marcos

    2007-08-01

    The incorporation of TiO2 nanoparticles into (ethylene-vinyl alcohol)-based food packaging copolymers affords an opportunity to synthesize polymer-based nanocomposite materials with novel and powerful biocidal and photodegradability properties, resulting in the production of an advanced, environmentally friendly system prepared using a cost-effective synthesis method via a simple melt compounding without the need of a coupling agent incorporation. The presented materials display an unprecedented performance in the killing of both Gram positive and negative bacteria without the necessity of being release to the media and an easy degradation under sunlight which favorably competes with biodegradation procedures.

  6. Hot melt adhesive attachment pad

    NASA Technical Reports Server (NTRS)

    Fox, R. L.; Frizzill, A. W.; Little, B. D.; Progar, D. J.; Coultrip, R. H.; Couch, R. H.; Gleason, J. R.; Stein, B. A.; Buckley, J. D.; St.clair, T. L. (Inventor)

    1984-01-01

    A hot melt adhesive attachment pad for releasably securing distinct elements together is described which is particularly useful in the construction industry or a spatial vacuum environment. The attachment pad consists primarily of a cloth selectively impregnated with a charge of hot melt adhesive, a thermo-foil heater, and a thermo-cooler. These components are securely mounted in a mounting assembly. In operation, the operator activates the heating cycle transforming the hot melt adhesive to a substantially liquid state, positions the pad against the attachment surface, and activates the cooling cycle solidifying the adhesive and forming a strong, releasable bond.

  7. Plasma arc melting of zirconium

    SciTech Connect

    Tubesing, P.K.; Korzekwa, D.R.; Dunn, P.S.

    1997-12-31

    Zirconium, like some other refractory metals, has an undesirable sensitivity to interstitials such as oxygen. Traditionally, zirconium is processed by electron beam melting to maintain minimum interstitial contamination. Electron beam melted zirconium, however, does not respond positively to mechanical processing due to its large grain size. The authors undertook a study to determine if plasma arc melting (PAM) technology could be utilized to maintain low interstitial concentrations and improve the response of zirconium to subsequent mechanical processing. The PAM process enabled them to control and maintain low interstitial levels of oxygen and carbon, produce a more favorable grain structure, and with supplementary off-gassing, improve the response to mechanical forming.

  8. Thermal Conductivity of Ethylene Vinyl Acetate Copolymer/Nanofiller Blends

    NASA Technical Reports Server (NTRS)

    Ghose, Sayata; Watson, Kent A.; Working, Dennis C.; Connell, John W.; Smith, Joseph G., Jr.; Lin, Y.; Sun, Y. P.

    2007-01-01

    To reduce weight and increase the mobility, comfort, and performance of future spacesuits, flexible, thermally conductive fabrics and plastic tubes are needed for the Liquid Cooling and Ventilation Garment. Such improvements would allow astronauts to operate more efficiently and safely for extended extravehicular activities. As an approach to raise the thermal conductivity (TC) of an ethylene vinyl acetate copolymer (Elvax(TM)260), it was compounded with three types of carbon based nanofillers: multi-walled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNFs), and expanded graphite (EG). In addition, other nanofillers including metallized CNFs, nickel nanostrands, boron nitride, and powdered aluminum were also compounded with Elvax(TM) 260 in the melt at various loading levels. In an attempt to improve compatibility between Elvax 260 and the nanofillers, MWCNTs and EG were modified by surface coating and through noncovalent and covalent attachment of organic molecules containing alkyl groups. Ribbons of the nanocomposites were extruded to form samples in which the nanofillers were aligned in the direction of flow. Samples were also fabricated by compression molding to yield nanocomposites in which the nanofillers were randomly oriented. Mechanical properties of the aligned samples were determined by tensile testing while the degree of dispersion and alignment of nanoparticles were investigated using high-resolution scanning electron microscopy. TC measurements were performed using a laser flash (Nanoflash(TM)) technique. TC of the samples was measured in the direction of, and perpendicular to, the alignment direction. Additionally, tubing was also extruded from select nanocomposite compositions and the TC and mechanical flexibility measured.

  9. The Role of Aromatic Structural Units of Conjugated Copolymers in Reaching High Solid-State Order and Optoelectronic Performances

    NASA Astrophysics Data System (ADS)

    Wang, Chien-Lung; Hsu, Chain-Shu; Wu, Kuan-Yi; Lee, Tien-Hsin

    2014-03-01

    Solid-state order of conjugated polymers is determinative in converting molecular properties into useful optoelectronic performances. The rapid development in donor-acceptor conjugated copolymers not only prompted device performances of polymeric optoelectronics, but also created wide varieties of complicate aromatic structural units, whose role in the solid-state order remains under studied. The roles of two widely used axisymmetrical aromatic units- 5,6-difluorobenzo-2,1,3-thiadiazole, and dithienocyclopentacarbazole will be discussed in this presentation. 2-dimensional X-ray diffraction, electron diffraction and theoretical molecular simulation showed that ordered solid-state structures were reached in copolymers with strong interchain interaction and good backbone linearity. The enhanced interchain interaction was supported by higher melting temperature and dis-aggregation temperature in the solution. High mobility of 0.29 cm2/Vs and power conversion efficiency of 6.82% were reached in copolymers possess ordered solid-state structure with long correlation lengths. This work is supported by the National Science Council and ``ATP'' of the National Chiao Tung University and Ministry of Education, Taiwan.

  10. Controlled synthesis of biodegradable lactide polymers and copolymers using novel in situ generated or single-site stereoselective polymerization initiators.

    PubMed

    Zhong, Zhiyuan; Dijkstra, Pieter J; Feijen, Jan

    2004-01-01

    Polylactides and their copolymers are key biodegradable polymers used widely in biomedical, pharmaceutical and ecological applications. The development of synthetic pathways and catalyst/initiator systems to produce pre-designed polylactides, as well as the fundamental understanding of the polymerization reactions, has continuously been an important topic. Here, we will address the recent advances in the ring-opening polymerization of lactides, with an emphasis on the highly versatile in situ generated initiator systems and single-site stereoselective initiators. The in situ generated initiators including in situ formed yttrium, calcium and zinc alkoxides all have been shown to bring about a rapid and living polymerization of lactides under mild conditions, which facilitated the preparation of a variety of advanced lactide-based biomaterials. For example, well-defined di- and tri-block copolymers consisting of hydrophilic poly(ethylene glycol) blocks and hydrophobic polyester blocks, which form novel biodegradable polymersomes or biodegradable thermosensitive hydrogels, have been prepared. In the past few years, significant progress has also been made in the area of stereoselective polymerization of lactides. This new generation of initiators has enabled the production of polylactide materials with novel microstructures and/or properties, such as heterotactic (--RRSSRRSSRRSS--) polylactide, crystalline syndiotactic (--RSRSRSRSRSRS--) polylactide and isotactic stereoblock (--Rn Sn Rn Sn--) polylactide, exhibiting a high melting temperature. The recently developed polymerizations using in situ generated initiators and stereoselective polymerizations have no doubt opened a brand-new avenue for the design and exploration of polylactides and their copolymers.

  11. Actuator based on sulfonated comb copolymer of poly (ethylene-co-vinyl alcohol) grafted by poly (ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Gong, Guifen; Li, Lei; Zhang, Yujun

    2007-07-01

    Comb copolymer consisting of poly (ethylene-co-vinyl alcohol) (EVAL) as backbone and poly (ethylene glycol) (PEG) as side chains (EVAL-g-PEG) has been synthesized, then it was sulfonated by 1,3-propane sultone to get the final ionomer (EVAL-g-SPEG), and ionic polymer-metal composite (IPMC) based on EVAL-g-SPEG was prepared through electroless deposition of platinum onto the surfaces of EVAL-g-SPEG membrane. The graft copolymers were characterized with respect to molecular weight using gel permeation chromatography (GPC) and composition using 1H-NMR. The results showed that the No. of PEG graft of the side chains is n=1, 2 and others. Thermal properties were examined by DSC and TG. The melt temperature (T m) and glass transition temperature (T g) of the comb copolymer increase with the increasing length and the number of the side chains. Moreover, the deformation performance of IPMC material was tested and its results show that the starting response voltage of IPMC actuator decreases with the increasing IEC value. On the other hand, the starting response voltage increases with the decreased side chain length. The IPMC with n=2 side chain length of PEG has the maximum tip displacement, and the maximum tip displacement of IPMC membrane generally decreases with the side chain length of EVAL-g-SPEG. This feature may be the reflection of two opposite effects, namely the decreasing ion densities and increasing water sorption of the membrane.

  12. Impact of structural changes on dielectric and thermal properties of vinylidene fluoride-trifluoroethylene-based terpolymer/copolymer blends

    NASA Astrophysics Data System (ADS)

    Casar, G.; Li, X.; Malič, B.; Zhang, Q. M.; Bobnar, V.

    2015-03-01

    We report dielectric and thermal properties of the poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer [P(VDF-TrFE-CFE), a member of the relaxor polymer family that exhibits fast response speeds, giant electrostriction, high electric energy density, and large electrocaloric effect] blended with the ferroelectric poly(vinylidene fluoride-trifluoroethylene) copolymer, P(VDF-TrFE). Although the differential scanning calorimetry (DSC) clearly reveals that both components form separate crystalline phases, at low copolymer content blends entirely exhibit a relaxorlike linear dielectric response, since the interfacial couplings to the bulky defects in the terpolymer convert the normal ferroelectric copolymer into a relaxor. On the other hand, dielectric experiments evidence that in blends with 20-50 wt% of P(VDF-TrFE) the ferroelectric and relaxor states coexist. This coexistence is confirmed by DSC results, which further reveal the influence of blending on the terpolymer crystallinity and melting point. At last, the crystallinity data appropriately explain the variation of the dielectric constant in P(VDF-TrFE-CFE)/P(VDF-TrFE) blends.

  13. Study of iron nanoparticle melting

    NASA Astrophysics Data System (ADS)

    Fedorov, A. V.; Shulgin, A. V.; Lavruk, S. A.

    2016-10-01

    In paper melting process of iron nanoparticles was investigated with molecular dynamics method. Melting temperatures was found for particles with radius from 1.5 to 4 nm. Results match with data of other authors. Heat capacity was calculated based on investigation of caloric curves. Dependence between heat capacity and temperature for different size of nanoparticles was approximated. Heat conductivity of iron nanoparticles was calculated.

  14. Basic physical properties/structure of polystyrene-polyisobutylene-polystyrene triblock copolymers

    SciTech Connect

    Kaszas, G.

    1993-12-31

    Polystyrene-b-polyisobutylene-b-polystyrene (PSt-PIB-PSt) triblock copolymers, with various molecular architectures, have been synthesized to establish basic physical properties/structure correlations for this novel thermoplastics elastomer (TPE). The test results have confirmed that these triblock copolymers have a unique combination of physical properties which is currently unavailable on the TPE market. The fully saturated character of the PIB backbone provides excellent ozone resistance. Barrier, electrical, and low-temperature properties, were measured, and found to be equivalent to those of conventional butyl vulcanizates. The low initial modules of PIB, and the fact that the PSt content can be kept low without significant loss in tensile properties, renders the material soft. The high incompatibility of PIB and PSt allows the overall chain length and, therefore, the melt viscosity, to be kept low. This could bring an important advantage, in processing, over other TPE`s. The combination of the above properties, and the inherent properties of PIB, makes this material in excellent candidate for wire and cable coating, seal and gasket, adhesive and vibration damping applications.

  15. Unexpected Temperature Behavior of Polyethylene Glycol Spacers in Copolymer Dendrimers in Chloroform

    PubMed Central

    Markelov, Denis A.; Matveev, Vladimir V.; Ingman, Petri; Nikolaeva, Marianna N.; Penkova, Anastasia V.; Lahderanta, Erkki; Boiko, Natalia I.; Chizhik, Vladimir I.

    2016-01-01

    We have studied copolymer dendrimer structure: carbosilane dendrimers with terminal phenylbenzoate mesogenic groups attached by poly(ethylene) glycol (PEG) spacers. In this system PEG spacers are additional tuning to usual copolymer structure: dendrimer with terminal mesogenic groups. The dendrimer macromolecules were investigated in a dilute chloroform solution by 1H NMR methods (spectra and relaxations). It was found that the PEG layer in G = 5 generations dendrimer is “frozen” at high temperatures (above 260 K), but it unexpectedly becomes “unfrozen” at temperatures below 250 K (i.e., melting when cooling). The transition between these two states occurs within a small temperature range (~10 K). Such a behavior is not observed for smaller dendrimer generations (G = 1 and 3). This effect is likely related to the low critical solution temperature (LCST) of PEG and is caused by dendrimer conformations, in which the PEG group concentration in the layer increases with growing G. We suppose that the unusual behavior of PEG fragments in dendrimers will be interesting for practical applications such as nanocontainers or nanoreactors. PMID:27052599

  16. Real-space evidence of the equilibrium ordered bicontinuous double diamond structure of a diblock copolymer.

    PubMed

    Chu, C Y; Jiang, X; Jinnai, H; Pei, R Y; Lin, W F; Tsai, J C; Chen, H L

    2015-03-14

    The ordered bicontinuous double diamond (OBDD) structure has long been believed to be an unstable ordered network nanostructure, which is relative to the ordered bicontinuous double gyroid (OBDG) structure for diblock copolymers. Using electron tomography, we present the first real-space observation of the thermodynamically stable OBDD structure in a diblock copolymer composed of a stereoregular block, syndiotactic polypropylene-block-polystyrene (sPP-b-PS), in which the sPP tetrapods are interconnected via a bicontinuous network with Pn3̄m symmetry. The OBDD structure underwent a thermally reversible order-order transition (OOT) to OBDG upon heating, and the transition was accompanied with a slight reduction of domain spacing, as demonstrated both experimentally and theoretically. The thermodynamic stability of the OBDD structure was attributed to the ability of the configurationally regular sPP block to form helical segments, even above its melting point, as the reduction of internal energy associated with the helix formation may effectively compensate the greater packing frustration in OBDD relative to that in the tripods of OBDG.

  17. Bulk and mechanical properties of the Paintbrush tuff recovered from boreholes UE25 NRG-2, 2A, 2B, and 3: Data report

    SciTech Connect

    Boyd, P.J.; Martin, R.J.; Noel, J.S.; Price, R.H.

    1996-09-01

    An integral part of the licensing procedure for the potential nuclear waste repository at Yucca Mountain, Nevada, involves characterization of the in situ rheology for the design and construction of the facility and the emplacement of canisters containing radioactive waste. The data used to model the thermal and mechanical behavior of the repository and surrounding lithologies include dry and saturated bulk densities, average grain density, porosity, compressional and shear wave velocities, elastic moduli, and compressional and tensional fracture strengths. In this study, a suite of experiments was performed on cores recovered from boreholes UE25 NRG-2, 2A, 2B, and 3 drilled in support of the Exploratory Studies Facility (ESF) at Yucca Mountain. The holes penetrated the Timber Mountain tuff and two thermal/mechanical units of the Paintbrush tuff. The thermal/mechanical stratigraphy was defined by Ortiz to group rock horizons of similar properties for the purpose of simplifying modeling efforts. The relationship between the geologic stratigraphy and the thermal/mechanical stratigraphy for each borehole is presented. The tuff samples in this study have a wide range of welding characteristics (usually reflected in sample porosity), and a smaller range of mineralogy and petrology characteristics. Generally, the samples are silicic, ash-fall tuffs that exhibit large variability in their elastic and strength properties.

  18. Excess adenosine A2B receptor signaling contributes to priapism through HIF-1α mediated reduction of PDE5 gene expression.

    PubMed

    Ning, Chen; Wen, Jiaming; Zhang, Yujin; Dai, Yingbo; Wang, Wei; Zhang, Weiru; Qi, Lin; Grenz, Almut; Eltzschig, Holger K; Blackburn, Michael R; Kellems, Rodney E; Xia, Yang

    2014-06-01

    Priapism is featured with prolonged and painful penile erection and is prevalent among males with sickle cell disease (SCD). The disorder is a dangerous urological and hematological emergency since it is associated with ischemic tissue damage and erectile disability. Here we report that phosphodiesterase-5 (PDE5) gene expression and PDE activity is significantly reduced in penile tissues of two independent priapic models: SCD mice and adenosine deaminase (ADA)-deficient mice. Moreover, using ADA enzyme therapy to reduce adenosine or a specific antagonist to block A(2B) adenosine receptor (ADORA2B) signaling, we successfully attenuated priapism in both ADA(-/-) and SCD mice by restoring penile PDE5 gene expression to normal levels. This finding led us to further discover that excess adenosine signaling via ADORA2B activation directly reduces PDE5 gene expression in a hypoxia-inducible factor-1α (HIF-1α)-dependent manner. Overall, we reveal that excess adenosine-mediated ADORA2B signaling underlies reduced penile PDE activity by decreasing PDE5 gene expression in a HIF-1α-dependent manner and provide new insight for the pathogenesis of priapism and novel therapies for the disease.

  19. Molecular motor KIF17 is fundamental for memory and learning via differential support of synaptic NR2A/2B levels.

    PubMed

    Yin, Xiling; Takei, Yosuke; Kido, Mizuho A; Hirokawa, Nobutaka

    2011-04-28

    Kinesin superfamily motor protein 17 (KIF17) is a candidate transporter of N-methyl-D-aspartate (NMDA) receptor subunit 2B (NR2B). Disruption of the murine kif17 gene inhibits NR2B transport, accompanied by decreased transcription of nr2b, resulting in a loss of synaptic NR2B. In kif17(-/-) hippocampal neurons, the NR2A level is also decreased because of accelerated ubiquitin-proteasome system-dependent degradation. Accordingly, NMDA receptor-mediated synaptic currents, early and late long-term potentiation, long-term depression, and CREB responses are attenuated in kif17(-/-) neurons, concomitant with a hippocampus-dependent memory impairment in knockout mice. In wild-type neurons, CREB is activated by synaptic inputs, which increase the levels of KIF17 and NR2B. Thus, KIF17 differentially maintains the levels of NR2A and NR2B, and, when synapses are stimulated, the NR2B/KIF17 complex is upregulated on demand through CREB activity. These KIF17-based mechanisms for maintaining NR2A/2B levels could underlie multiple phases of memory processes in vivo.

  20. DFT+ U study of electronic structure and Curie temperature of A2 B ReO6 (A=Sr, Ca and B=Cr, Fe)

    NASA Astrophysics Data System (ADS)

    Lee, Alex; Marianetti, Chris

    Re-based double perovskites (DPs) have attracted much attention due to their high Curie temperature (TC) and colossal magneto resistance with large potential for spintronic applications. Here we investigate the electronic and magnetic properties of the Re-based DPs A2 B ReO6 (A=Sr, Ca and B=Cr, Fe) using density functional theory + U (DFT+ U) calculations. While monoclinic Ca2CrReO6 and Ca2FeReO6 (monoclinic) are insulating within GGA+ U, tetragonal Sr2CrReO6 (a0a0c0) and Sr2FeReO6 (a0a0c-) remain metallic. We show that both on-site interaction U and octahedral tilting are critical to obtain the insulating phases. The a0a0c- -phase of Sr2CrReO6 is most stable and insulating with nonzero U, suggesting that the high quality Sr2CrReO6 film on STO substrate can be a semiconductor as reported in recent experiments. We explain that the insulator-to-metal transition (MIT) of Ca2FeReO6 at 140K is predominantly due to a structural phase transition which drives the insulating state. Curie temperatures of Re-based DPs are calculated using the classical Monte Carlo simulations based on the Heisenberg model.

  1. Self-consistent field theory simulations of block copolymer assembly on a sphere

    NASA Astrophysics Data System (ADS)

    Chantawansri, T. L.; Bosse, A. W.; Hexemer, A.; Ceniceros, H. D.; Garcia-Cervera, C. J.; Kramer, E. J.; Fredrickson, G. H.

    2007-03-01

    Using a self-consistent field theory (SCFT) framework, we explore the topic of self-assembly in a thin AB diblock copolymer melt confined to the surface of the sphere. This model is numerically simulated by spectral collocation with a spherical harmonic basis. The method allows us to investigate the lamellar and cylindrical phases on the surface of a sphere as a function of sphere radius. For thin cylinder-forming films, with uniform radial composition, we have found that the number of microdomains in the ground state configuration is determined by a delicate competition between chain stretching and topological constraints. Notably, our SCFT simulations have shown the absence of configurations with 11 and 13 domains in the ground state. For thin lamellar films, we examined the stability of three lamellar configurations: spiral, hedgehog, and quasi-baseball phases. The spiral and hedgehog morphologies are found to alternate in stability over a range of sphere radii.

  2. Mechanical properties and heat shrinkability of electron beam crosslinked polyethylene octene copolymer

    NASA Astrophysics Data System (ADS)

    Mishra, Joy K.; Chang, Young-Wook; Lee, Byung Chul; Ryu, Sung Hun

    2008-05-01

    The mechanical properties and heat shrinkability of electron beam crosslinked polyethylene-octene copolymer were studied. It was found that gel content increases with increased radiation dose. The analysis of results by the Charlesby-Pinner equation revealed that crosslinking was dominant over chain scission upon irradiation. Formation of a crosslinked structure in the electron beam irradiated sample was confirmed by the presence of a plateau of dynamic storage modulus above the melting point of the polymer. Wide-angle X-ray diffraction revealed that there was little change in crystallinity for the irradiated samples, indicating that radiation crosslinking occurs in the amorphous region of the polymer. The tensile modulus increases, whereas the elongation at break decreases with increased radiation dose. The heat shrinkability of the material increased with an increased radiation dose because the radiation-induced crosslinks serve as memory points during the shrinking process.

  3. Laser melting of uranium carbides

    NASA Astrophysics Data System (ADS)

    Utton, C. A.; De Bruycker, F.; Boboridis, K.; Jardin, R.; Noel, H.; Guéneau, C.; Manara, D.

    2009-03-01

    In the context of the material research aimed at supporting the development of nuclear plants of the fourth Generation, renewed interest has recently arisen in carbide fuels. A profound understanding of the behaviour of nuclear materials in extreme conditions is of prime importance for the analysis of the operation limits of nuclear fuels, and prediction of possible nuclear reactor accidents. In this context, the main goal of the present paper is to demonstrate the feasibility of laser induced melting experiments on stoichiometric uranium carbides; UC, UC1.5 and UC2. Measurements were performed, at temperatures around 3000 K, under a few bars of inert gas in order to minimise vaporisation and oxidation effects, which may occur at these temperatures. Moreover, a recently developed investigation method has been employed, based on in situ analysis of the sample surface reflectivity evolution during melting. Current results, 2781 K for the melting point of UC, 2665 K for the solidus and 2681 K for the liquidus of U2C3, 2754 K for the solidus and 2770 K for the liquidus of UC2, are in fair agreement with early publications where the melting behaviour of uranium carbides was investigated by traditional furnace melting methods. Further information has been obtained in the current research about the non-congruent (solidus-liquidus) melting of certain carbides, which suggest that a solidus-liquidus scheme is followed by higher ratio carbides, possibly even for UC2.

  4. Synthesis and Self-Assembly of Rod2Coil Miktoarm Star Copolymers of Poly(3-dodecxylthiophene) and Poly(methyl methacrylate) with high rod fractions

    NASA Astrophysics Data System (ADS)

    Park, Jicheol; Moon, Hong Chul; Choi, Chung-Royng; Kim, Jin Kon

    2015-03-01

    Poly(3-dodecylthiophene)-b-poly(methyl methacrylate) diblock copolymer (P3DDT- b-PMMA) can self-assembled into various microdomains such as spheres, cylinders, and lamellae depending on weight fraction of P3DDT. However, only filbril morphology was formed when weight fraction of P3DDT (wP 3 DDT) was major (wP 3 DDT ~ 0.76). Here, we introduce a new approach to obtain microdomain structures even at high wP 3 DDT by using well-defined A2B miktoarm star copolymer composed of P3DDT and PMMA ((P3DDT)2PMMA. We found via small angle X-ray scattering and transmission electron microscopy that (P3DDT)2PMMA showed PMMA cylinder packed hexagonally in the matrix of P3DDT and body-centered-cubic spheres of PMMA for wP 3 DDT of 0.66 and 0.75, respectively. This because of much reduction of the rod-rod interaction in (P3DDT)2PMMA compared with P3DDT- b-PMMA diblock copolymers.

  5. 40 CFR 721.10213 - Polyether polyester copolymer phosphate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... phosphate (generic). 721.10213 Section 721.10213 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10213 Polyether polyester copolymer phosphate (generic). (a) Chemical... as polyether polyester copolymer phosphate (PMN P-09-253) is subject to reporting under this...

  6. 40 CFR 721.10213 - Polyether polyester copolymer phosphate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... phosphate (generic). 721.10213 Section 721.10213 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10213 Polyether polyester copolymer phosphate (generic). (a) Chemical... as polyether polyester copolymer phosphate (PMN P-09-253) is subject to reporting under this...

  7. 40 CFR 721.10213 - Polyether polyester copolymer phosphate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... phosphate (generic). 721.10213 Section 721.10213 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10213 Polyether polyester copolymer phosphate (generic). (a) Chemical... as polyether polyester copolymer phosphate (PMN P-09-253) is subject to reporting under this...

  8. 40 CFR 721.10213 - Polyether polyester copolymer phosphate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... phosphate (generic). 721.10213 Section 721.10213 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10213 Polyether polyester copolymer phosphate (generic). (a) Chemical... as polyether polyester copolymer phosphate (PMN P-09-253) is subject to reporting under this...

  9. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... blended with polyethylene or with one or more olefin copolymers complying with § 177.1520 or with a mixture of polyethylene and one or more olefin copolymers, in such proportions that the ethyl acrylate... prescribed in paragraph (c)(2) of this section, when tested by the methods prescribed for polyethylene...

  10. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... percent by weight unless it is blended with polyethylene or with one or more olefin copolymers complying with § 177.1520 or with a mixture of polyethylene and one or more olefin copolymers, in such... prescribed for polyethylene in § 177.1520. (1) Specifications—(i) Infrared identification....

  11. Alternation and tunable composition in hydrogen bonded supramolecular copolymers.

    PubMed

    Felder, Thorsten; de Greef, Tom F A; Nieuwenhuizen, Marko M L; Sijbesma, Rint P

    2014-03-07

    Sequence control in supramolecular copolymers is limited by the selectivity of the associating monomer end groups. Here we introduce the use of monomers with aminopyrimidinone and aminohydroxynaphthyridine quadruple hydrogen bonding end groups, which both homodimerize, but form even stronger heterodimers. These features allow the formation of supramolecular copolymers with a tunable composition and a preference for alternating sequences.

  12. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  13. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  14. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  15. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... weight of aqueous sodium chloride solution at 20 °C for 24 hours. The low molecular weight extractives... applied mass). The solvent used shall be at least 60 milliliters aqueous sodium chloride solution per gram... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified...

  16. Morphological studies on block copolymer modified PA 6 blends

    NASA Astrophysics Data System (ADS)

    Poindl, M.; Bonten, C.

    2014-05-01

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  17. Piezoelectric Properties of Non-Polar Block Copolymers

    SciTech Connect

    Pester, Christian; Ruppel, Markus A; Schoberth, Heiko; Schmidt, K.; Liedel, Clemens; Van Rijn, Patrick; Littrell, Ken; Schindler, Kerstin; Hiltl, Stephanie; Czubak, Thomas; Mays, Jimmy; Urban, Volker S; Boker, Alexander

    2011-01-01

    Piezoelectric properties in non-polar block copolymers are a novelty in the field of electroactive polymers. The piezoelectric susceptibility of poly(styrene-b-isoprene) block copolymer lamellae is found to be up to an order of magnitude higher when compared to classic piezoelectric materials. The electroactive response increases with temperature and is found to be strongest in the disordered phase.

  18. Morphological studies on block copolymer modified PA 6 blends

    SciTech Connect

    Poindl, M. E-mail: christian.bonten@ikt.uni-stuttgart.de; Bonten, C. E-mail: christian.bonten@ikt.uni-stuttgart.de

    2014-05-15

    Recent studies show that compounding polyamide 6 (PA 6) with a PA 6 polyether block copolymers made by reaction injection molding (RIM) or continuous anionic polymerization in a reactive extrusion process (REX) result in blends with high impact strength and high stiffness compared to conventional rubber blends. In this paper, different high impact PA 6 blends were prepared using a twin screw extruder. The different impact modifiers were an ethylene propylene copolymer, a PA PA 6 polyether block copolymer made by reaction injection molding and one made by reactive extrusion. To ensure good particle matrix bonding, the ethylene propylene copolymer was grafted with maleic anhydride (EPR-g-MA). Due to the molecular structure of the two block copolymers, a coupling agent was not necessary. The block copolymers are semi-crystalline and partially cross-linked in contrast to commonly used amorphous rubbers which are usually uncured. The combination of different analysis methods like atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) gave a detailed view in the structure of the blends. Due to the partial cross-linking, the particles of the block copolymers in the blends are not spherical like the ones of ethylene propylene copolymer. The differences in molecular structure, miscibility and grafting of the impact modifiers result in different mechanical properties and different blend morphologies.

  19. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene-acrylic acid copolymers. 177.1310 Section... Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid... for use in contact with food subject to the provisions of this section. (a) The ethylene-acrylic...

  20. Preparation, Characterization and Pharmacodynamic Evaluation of Fused Dispersions of Simvastatin using PEO-PPO Block Copolymer.

    PubMed

    Singh, Harjeet; Philip, Betty; Pathak, Kamla

    2012-01-01

    The solubility enhancement of poorly soluble compounds is an important task in pharmaceutical technology as it leads to better bioavailability and a more efficient application. Fused dispersions (FDs) of simvastatin (SIM) using PEO-PPO block copolymer were prepared which paved the way for the formation of an amorphous product with enhanced dissolution and bioavailability. The accumulative solubility of simvastatin (SIM) from PEO-PPO block copolymer (Lutrol NF 127 prill surfactant) was found to be superior to the drug alone which may be due to the increased oxyethylene content that played the major role in solubility enhancement. A 3(2) full factorial approach was used for optimization wherein the temperature to which the melt-drug mixture cooled (X1) and the drug-to-polymer ratio (X2) were selected as the independent variables and the time required for 90% drug dissolution (t90%) was selected as the dependent variable. A low level of X1 and a high level of X2 were suitable for obtaining higher dissolution of SIM from SIM FDs. On increasing melt to cool drug temperature, t90% increased thus improving dissolution rate of FD2 batch with the maximum drug release (99.63%) in 120 min. The optimized FDs were characterized by saturation solubility study, drug content, in-vitro dissolution, fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, x-ray diffraction, (1)HNMR spectroscopy and pharmacodynamic evaluation. Capsules containing optimized FDs were prepared and compared with marketed brand (SIMVOTIN®). Finally, it can be concluded that the optimized FDs of SIM ameliorate the solubility and dissolution of drug with improved pharmacodynamic activity.

  1. Light-emitting block copolymers composition, process and use

    DOEpatents

    Ferraris, John P.; Gutierrez, Jose J.

    2006-11-14

    Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

  2. N-halamine copolymers for use in antimicrobial paints.

    PubMed

    Kocer, Hasan B; Cerkez, Idris; Worley, S D; Broughton, R M; Huang, T S

    2011-08-01

    A series of copolymers containing units of a novel hydantoinylacrylamide and the sodium salt of 2-(acrylamido)-2-methylpropanesulfonic acid have been synthesized. The homopolymer of the hydantoinylacrylamide compound was insoluble in water, while the copolymers with the sulfonic acid sodium salt were water-dispersible/soluble, with the solution becoming completely transparent when the feed ratio for the copolymer contained 7 parts of the hydantoin moiety to 3 parts of the sodium sulfonate moiety. The polymers were added into a commercial water-based latex paint, and upon drying, the painted surfaces treated with the water-miscible copolymers were rendered antimicrobial following chlorination with dilute household bleach. The chlorinated homopolymer failed to provide an antimicrobial property for the paint because of its tendency to isolate into aggregates in the paint, while the completely miscible copolymers were capable of 6-log inactivation of Staphylococcus aureus and Escherichia coli O157:H7 within 5 min of contact time.

  3. Block Copolymer Metastability: Scientific Nightmare or Engineering Dream?

    NASA Astrophysics Data System (ADS)

    Bates, Frank S.

    1997-03-01

    Most experimental studies and almost all theories that deal with block copolymers, or mixtures of block copolymers and homopolymers, have been designed from an equilibrium perspective. Yet a myriad of factors conspire to retard approach to equilibrium in these systems, including: subtle features in the free energy surface that are controlled by ordered state symmetry; a coupling between microphase separation and entanglement dynamics; complex molecular architectures such as multiblock, starblock, and miktoarm. Even unentangled low molecular weight diblock copolymers, the simplest and dynamically least encumbered materials, exhibit long-lived metastable states that confound attempts to validate equilibrium theories. However, this apparent dilemma can be exploited through clever processing strategies. This lecture will address two opposing consequences of block copolymer metastability. The first is a potential nightmare: Can we ever establish universal block copolymer phase diagrams? The second is the stuff of dreams: Self-assembled thermoset nanocomposites.

  4. Electric Field Induced Selective Disordering in Lamellar Block Copolymers

    SciTech Connect

    Ruppel, Markus A; Pester, Christian W; Langner, Karol M; Sevink, Geert; Schoberth, Heiko; Schmidt, Kristin; Urban, Volker S; Mays, Jimmy; Boker, Alexander

    2013-01-01

    External electric fields align nanostructured block copolymers by either rotation of grains or nucleation and growth depending on how strongly the chemically distinct block copolymer components are segregated. In close vicinity to the orderdisorder transition, theory and simulations suggest a third mechanism: selective disordering. We present a time-resolved small-angle X-ray scattering study that demonstrates how an electric field can indeed selectively disintegrate ill-aligned lamellae in a lyotropic block copolymer solution, while lamellae with interfaces oriented parallel to the applied field prevail. The present study adds an additional mechanism to the experimentally corroborated suite of mechanistic pathways, by which nanostructured block copolymers can align with an electric field. Our results further unveil the benefit of electric field assisted annealing for mitigating orientational disorder and topological defects in block copolymer mesophases, both in close vicinity to the orderdisorder transition and well below it.

  5. Electric field induced selective disordering in lamellar block copolymers.

    PubMed

    Ruppel, Markus; Pester, Christian W; Langner, Karol M; Sevink, Geert J A; Schoberth, Heiko G; Schmidt, Kristin; Urban, Volker S; Mays, Jimmy W; Böker, Alexander

    2013-05-28

    External electric fields align nanostructured block copolymers by either rotation of grains or nucleation and growth depending on how strongly the chemically distinct block copolymer components are segregated. In close vicinity to the order-disorder transition, theory and simulations suggest a third mechanism: selective disordering. We present a time-resolved small-angle X-ray scattering study that demonstrates how an electric field can indeed selectively disintegrate ill-aligned lamellae in a lyotropic block copolymer solution, while lamellae with interfaces oriented parallel to the applied field prevail. The present study adds an additional mechanism to the experimentally corroborated suite of mechanistic pathways, by which nanostructured block copolymers can align with an electric field. Our results further unveil the benefit of electric field assisted annealing for mitigating orientational disorder and topological defects in block copolymer mesophases, both in close vicinity to the order-disorder transition and well below it.

  6. Poly(methyl methacrylate)-cellulose nitrate copolymers. I. Preparation

    SciTech Connect

    Badran, B.M.; Sherif, S.; Abu-Sedira, A.A.

    1981-03-01

    Poly(methyl methacrylate)-cellulose nitrate copolymers were prepared in the form of rods and sheets by bulk polymerization using benzoyl peroxide as initiator. Suspension polymerization did not succeed in preparing poly(methyl methacrylate)-cellulose nitrate copolymers, especially when cellulose nitrate of 11.4% nitrogen content was used. The parameters such as cellulose nitrate concentration, nitrogen content of cellulose nitrate, the amount of initiator and the reaction time, and the temperature are discussed. The prepared copolymers were irradiated for specified periods of up to 11.83 Mrad. It was found that poly(methyl methacrylate)-cellulose nitrate copolymers did not dissolve in any conventional solvent, but they swelled. Swelling decreases with increasing cellulose nitrate concentrations, nitrogen content of cellulose nitrate, and irradiation dose, indicating the crosslinked structure of the prepared copolymers.

  7. Quantifying melting and mobilistaion of interstitial melts in crystal mushes

    NASA Astrophysics Data System (ADS)

    Veksler, Ilya; Dobson, Katherine; Hess, Kai-Uwe; Ertel-Ingrisch, Werner; Humphreys, Madeleine

    2015-04-01

    The deformation of crystals mushes and separation of melts and crystals in is critical to understanding the development of physical and chemical heterogeneity in magma chambers and has been invoked as an eruption trigger mechanism. Here we investigate the behaviour of the melt in the well characterised, classic crystal mush system of the Skaergaard intrusion by combining experimental petrology and the non-destructive 3D imaging methods. Starting materials for partial melting experiments were four samples from the upper Middle Zone of the Layered Series. Cylinders, 15 mm in diameter and 20 mm in length, were drilled out of the rock samples, placed in alumina crucibles and held for 5 days in electric furnaces at atmospheric pressure and 1050-1100 °C. Redox conditions set by the CO-CO2 gas mixture were kept close to those of the FMQ buffer. We then use spatially registered 3D x-ray computed tomography images, collected before and after the experiment, to determine the volume and distribution of the crystal framework and interstitial phases, and the volume, distribution and connectivity the interstitial phases that undergo melting and extraction while at elevated temperature. Image analysis has allowed us to quantify these physical changes with high spatial resolution. Our work is a first step towards quantitative understanding of the melt mobilisation and migration processes operating in notionally locked crystal rich magmatic systems.

  8. Ionization of amphiphilic acidic block copolymers.

    PubMed

    Colombani, Olivier; Lejeune, Elise; Charbonneau, Céline; Chassenieux, Christophe; Nicolai, Taco

    2012-06-28

    The ionization behavior of an amphiphilic diblock copolymer poly(n-butyl acrylate(50%)-stat-acrylic acid(50%))(100)-block-poly(acrylic acid)(100) (P(nBA(50%)-stat-AA(50%))(100)-b-PAA(100), DH50) and of its equivalent triblock copolymer P(nBA(50%)-stat-AA(50%))(100)-b-PAA(200)-b-P(nBA(50%)-stat-AA(50%))(100) (TH50) were studied by potentiometric titration either in pure water or in 0.5 M NaCl. These polymers consist of a hydrophilic acidic block (PAA) connected to a hydrophobic block, P(nBA(50%)-stat-AA(50%))(100), whose hydrophobic character has been mitigated by copolymerization with hydrophilic units. We show that all AA units, even those in the hydrophobic block could be ionized. However, the AA units within the hydrophobic block were less acidic than those in the hydrophilic block, resulting in the preferential ionization of the latter block. The preferential ionization of PAA over that of P(nBA(50%)-stat-AA(50%))(100) was stronger at higher ionic strength. Remarkably, the covalent bonds between the PAA and P(nBA(50%)-stat-AA(50%))(100) blocks in the diblock or the triblock did not affect the ionization of each block, although the self-association of the block copolymers into spherical aggregates modified the environment of the PAA blocks compared to when PAA was molecularly dispersed.

  9. Methods for Melting Temperature Calculation

    NASA Astrophysics Data System (ADS)

    Hong, Qi-Jun

    Melting temperature calculation has important applications in the theoretical study of phase diagrams and computational materials screenings. In this thesis, we present two new methods, i.e., the improved Widom's particle insertion method and the small-cell coexistence method, which we developed in order to capture melting temperatures both accurately and quickly. We propose a scheme that drastically improves the efficiency of Widom's particle insertion method by efficiently sampling cavities while calculating the integrals providing the chemical potentials of a physical system. This idea enables us to calculate chemical potentials of liquids directly from first-principles without the help of any reference system, which is necessary in the commonly used thermodynamic integration method. As an example, we apply our scheme, combined with the density functional formalism, to the calculation of the chemical potential of liquid copper. The calculated chemical potential is further used to locate the melting temperature. The calculated results closely agree with experiments. We propose the small-cell coexistence method based on the statistical analysis of small-size coexistence MD simulations. It eliminates the risk of a metastable superheated solid in the fast-heating method, while also significantly reducing the computer cost relative to the traditional large-scale coexistence method. Using empirical potentials, we validate the method and systematically study the finite-size effect on the calculated melting points. The method converges to the exact result in the limit of a large system size. An accuracy within 100 K in melting temperature is usually achieved when the simulation contains more than 100 atoms. DFT examples of Tantalum, high-pressure Sodium, and ionic material NaCl are shown to demonstrate the accuracy and flexibility of the method in its practical applications. The method serves as a promising approach for large-scale automated material screening in which

  10. The influence of comonomer on ethylene/α-olefin copolymers prepared using [bis(N-(3-tert butylsalicylidene)anilinato)] titanium (IV) dichloride complex.

    PubMed

    Kaivalchatchawal, Patcharaporn; Suttipitakwong, Pattiya; Samingprai, Sutheerawat; Praserthdam, Piyasan; Jongsomjit, Bunjerd

    2011-02-15

    We describe the synthesis of [bis(N-(3-tert-butylsalicylidene)anilinato)] titanium (IV) dichloride (Ti-FI complex) and examine the effects of comonomer (feed concentration and type) on its catalytic performance and properties of the resulting polymers. Ethylene/1-hexene and ethylene/1-octene copolymers were prepared through copolymerization using Ti-FI catalyst, activated by MAO cocatalyst at 323 K and 50 psi ethylene pressure at various initial comonomer concentrations. The obtained copolymers were characterized by DSC, GPC and 13C-NMR. The results indicate that Ti-FI complex performs as a high potential catalyst, as evidenced by high activity and high molecular weight and uniform molecular weight distribution of its products. Nevertheless, the bulky structure of FI catalyst seems to hinder the insertion of α-olefin comonomer, contributing to the pretty low comonomer incorporation into the polymer chain. The catalytic activity was enhanced with the comonomer feed concentration, but the molecular weight and melting temperature decreased. By comparison both sets of catalytic systems, namely ethylene/1-hexene and ethylene/1-octene copolymerization, the first one afforded better activity by reason of easier insertion of short chain comonomer. Although 1-hexene copolymers also exhibited higher molecular weight than 1-octene, no significant difference in both melting temperature and crystallinity can be noticed between these comonomers.

  11. Corrugational Instabilities of Thin Copolymer Films

    NASA Astrophysics Data System (ADS)

    Williams, D. R. M.

    1995-07-01

    We study the equilibrium configurations of thin films of diblock copolymers, in the strong segregation limit, resting on a flat surface. The top surface is free. Such films are geometrically frustrated and possess an inherent strain. Here we show how this strain induces an undulational instability in the film. The existence of this instability is very sensitive to the chain end distribution within the bilayers, and a macroscopic observation of this instability on a length scale of 1000 Å gives an indication of the chain end distribution on the scale of 5 Å.

  12. 21 CFR 177.1340 - Ethylene-methyl acrylate copolymer resins.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Ethylene-methyl acrylate copolymer resins. 177... Repeated Use Food Contact Surfaces § 177.1340 Ethylene-methyl acrylate copolymer resins. Ethylene-methyl... section, the ethylene-methyl acrylate copolymer resins consist of basic copolymers produced by...

  13. Primary structures of the heterogeneous nuclear ribonucleoprotein A2, B1, and C2 proteins: a diversity of RNA binding proteins is generated by small peptide inserts.

    PubMed Central

    Burd, C G; Swanson, M S; Görlach, M; Dreyfuss, G

    1989-01-01

    We have isolated cDNAs for the major heterogeneous nuclear ribonucleoprotein (hnRNP) A2, B1, and C2 proteins and determined their nucleotide and deduced amino acid sequences. The A2 and B1 cDNAs are identical except for a 36-nucleotide in-frame insert in B1. Similarly, the sequence of the C2 protein cDNA is related to that of C1 in that C2 contains an extra 39 in-frame nucleotides. Therefore, the B1 amino acid sequence is identical to A2 except for the insertion of 12 amino acids near its amino terminus, and C1 and C2 are also identical to each other except for an extra 13 amino acids near the middle of C2. All three proteins are members of a large family of RNA binding proteins that contain the consensus sequence-type RNA binding domain (CS-RBD). The A2 and B1 proteins have a modular structure similar to that of the hnRNP protein A1: they contain two CS-RBDs and a glycine-rich auxiliary domain at the carboxyl terminus. The CS-RBDs of A2 and B1 have approximately 80% amino acid identity with those of A1, whereas the glycine-rich auxiliary domain is considerably more divergent with less than 30% of the amino acids being identical. These findings indicate that the addition of small peptides, probably by alternative pre-mRNA splicing, generates some of the diversity apparent among hnRNP proteins. Images PMID:2557628

  14. Activation of the A2B adenosine receptor in B16 melanomas induces CXCL12 expression in FAP-positive tumor stromal cells, enhancing tumor progression

    PubMed Central

    Sorrentino, Claudia; Miele, Lucio; Porta, Amalia; Pinto, Aldo; Morello, Silvana

    2016-01-01

    The A2B receptor (A2BR) can mediate adenosine-induced tumor proliferation, immunosuppression and angiogenesis. Targeting the A2BR has proved to be therapeutically effective in some murine tumor models, but the mechanisms of these effects are still incompletely understood. Here, we report that pharmacologic inhibition of A2BR with PSB1115, which inhibits tumor growth, decreased the number of fibroblast activation protein (FAP)-expressing cells in tumors in a mouse model of melanoma. This effect was associated with reduced expression of fibroblast growth factor (FGF)-2. Treatment of melanoma-associated fibroblasts with the A2BR agonist Bay60-6583 enhanced CXCL12 and FGF2 expression. This effect was abrogated by PSB1115. The A2AR agonist CGS21680 did not induce CXCL12 or FGF2 expression in tumor associated fibroblasts. Similar results were obtained under hypoxic conditions in skin-derived fibroblasts, which responded to Bay60-6583 in an A2BR-dependent manner, by stimulating pERK1/2. FGF2 produced by Bay60-6583-treated fibroblasts directly enhanced the proliferation of melanoma cells. This effect could be reversed by PSB1115 or an anti-FGF2 antibody. Interestingly, melanoma growth in mice receiving Bay60-6583 was attenuated by inhibition of the CXCL12/CXCR4 pathway with AMD3100. CXCL12 and its receptor CXCR4 are involved in angiogenesis and immune-suppression. Treatment of mice with AMD3100 reduced the number of CD31+ cells induced by Bay60-6583. Conversely, CXCR4 blockade did not affect the accumulation of tumor-infiltrating MDSCs or Tregs. Together, our data reveal an important role for A2BR in stimulating FGF2 and CXCL12 expression in melanoma-associated fibroblasts. These factors contribute to create a tumor-promoting microenvironment. Our findings support the therapeutic potential of PSB1115 for melanoma. PMID:27590504

  15. Multidimensional chromatographic techniques for hydrophilic copolymers II. Analysis of poly(ethylene glycol)-poly(vinyl acetate) graft copolymers.

    PubMed

    Knecht, Daniela; Rittig, Frank; Lange, Ronald F M; Pasch, Harald

    2006-10-13

    A large variety of hydrophilic copolymers is applied in different fields of chemical industry including bio, pharma and pharmaceutical applications. For example, poly(ethylene glycol)-poly(vinyl alcohol) graft copolymers that are used as tablet coatings are responsible for the controlled release of the active compounds. These copolymers are produced by grafting of vinyl acetate onto polyethylene glycol (PEG) and subsequent hydrolysis of the poly(ethylene glycol)-poly(vinyl acetate) graft copolymers. The poly(ethylene glycol)-poly(vinyl acetate) copolymers are distributed with regard to molar mass and chemical composition. In addition, they frequently contain the homopolymers polyethylene glycol and polyvinyl acetate. The comprehensive analysis of such complex systems requires hyphenated analytical techniques, including two-dimensional liquid chromatography and combined LC and nuclear magnetic resonance spectroscopy. The development and application of these techniques are discussed in the present paper.

  16. Human natural killer cell microRNA: differential expression of MIR181A1B1 and MIR181A2B2 genes encoding identical mature microRNAs.

    PubMed

    Presnell, S R; Al-Attar, A; Cichocki, F; Miller, J S; Lutz, C T

    2015-01-01

    Natural killer (NK) and T lymphocytes share many properties, yet only NK cells respond rapidly to infection and cancer without pre-activation. We found that few microRNAs (miRNAs) differed significantly between human NK and T cells. Among those miRNAs, miR-181a and miR-181b levels rose during NK cell differentiation. Prior studies indicate that miR-181a and miR-181b are critical for human NK cell development and are co-transcribed from genes on chromosome 1 (MIR181A1B1) and on chromosome 9 (MIR181A2B2). We mapped human MIR181A1B1 and MIR181A2B2 transcription start sites to 78.3 kb and 34.0 kb upstream of the mature miRNAs, generating predominantly unspliced transcripts of 80-127 kb and ~60 kb, respectively. Unlike mouse thymocytes, human T cells expressed both MIR181A1B1 and MIR181A2B2. We tested the hypothesis that NK cells differentially transcribe the two genes during development and in response to immune regulatory cytokines. During NK-cell differentiation, MIR181A2B2 expression rose markedly and exceeded that of MIR181A1B1. TGF-β treatment increased NK-cell MIR181A2B2 transcription, whereas IL-2, IL-15 and IL-12/IL-18 treatments upregulated MIR181A1B1. The MIR181A2B2 promoter was strongly transactivated by SMAD3 and SMAD4 transcription factors, suggesting that TGF-β signaling upregulates MIR181A2B2 expression, at least in part, through SMAD-dependent promoter activation.

  17. Improved capacitive melting curve measurements

    NASA Astrophysics Data System (ADS)

    Sebedash, Alexander; Tuoriniemi, Juha; Pentti, Elias; Salmela, Anssi

    2009-02-01

    Sensitivity of the capacitive method for determining the melting pressure of helium can be enhanced by loading the empty side of the capacitor with helium at a pressure nearly equal to that desired to be measured and by using a relatively thin and flexible membrane in between. This way one can achieve a nanobar resolution at the level of 30 bar, which is two orders of magnitude better than that of the best gauges with vacuum reference. This extends the applicability of melting curve thermometry to lower temperatures and would allow detecting tiny anomalies in the melting pressure, which must be associated with any phenomena contributing to the entropy of the liquid or solid phases. We demonstrated this principle in measurements of the crystallization pressure of isotopic helium mixtures at millikelvin temperatures by using partly solid pure 4He as the reference substance providing the best possible universal reference pressure. The achieved sensitivity was good enough for melting curve thermometry on mixtures down to 100 μK. Similar system can be used on pure isotopes by virtue of a blocked capillary giving a stable reference condition with liquid slightly below the melting pressure in the reference volume. This was tested with pure 4He at temperatures 0.08-0.3 K. To avoid spurious heating effects, one must carefully choose and arrange any dielectric materials close to the active capacitor. We observed some 100 pW loading at moderate excitation voltages.

  18. Anomalous Micellization of Pluronic Block Copolymers

    NASA Astrophysics Data System (ADS)

    Leonardi, Amanda; Ryu, Chang Y.

    2014-03-01

    Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

  19. Controlling Structure in Sulfonated Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Truong, Phuc; Stein, Gila; Strzalka, Joe

    2015-03-01

    In many ionic block copolymer systems, the strong incompatibility between ionic and non-ionic segments will trap non-equilibrium structures in the film, making it difficult to engineer the optimal domain sizes and transport pathways. The goal of this work is to establish a framework for controlling the solid-state structure of sulfonated pentablock copolymer membranes. They have ABCBA block sequence, where A is poly(t-butyl styrene), B is poly(hydrogenated isoprene), and C is poly(styrene sulfonate). To process into films, the polymer is dissolved in toluene/n-propanol solvent mixtures, where the solvent proportions and the polymer loading were both varied. Solution-state structure was measured with small angle X-ray scattering (SAXS). We detected micelles with radii that depend on the solvent composition and polymer loading. Film structure was measured with grazing-incidence SAXS, which shows (i) domain periodicity is constant throughout film thickness; (ii) domain periodicity depends on solvent composition and polymer loading, and approximately matches the micelle radii in solutions. The solid-state packing is consistent with a hard sphere structure factor. Results suggest that solid-state structure can be tuned by manipulating the solution-state self-assembly.

  20. Interface-enforced complexation between copolymer blocks.

    PubMed

    Steinschulte, Alexander A; Xu, Weinan; Draber, Fabian; Hebbeker, Pascal; Jung, Andre; Bogdanovski, Dimitri; Schneider, Stefanie; Tsukruk, Vladimir V; Plamper, Felix A

    2015-05-14

    Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering.

  1. Partial Melting of the Indarch (EH4) Meteorite : A Textural, Chemical and Phase Relations View of Melting and Melt Migration

    NASA Technical Reports Server (NTRS)

    McCoy, Timothy J.; Dickinson, Tamara L.; Lofgren, Gary E.

    2000-01-01

    To Test whether Aubrites can be formed by melting of enstatite Chondrites and to understand igneous processes at very low oxygen fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000-1500 C. Silicate melting begins at 1000 C. Substantial melt migration occurs at 1300-1400 C and metal migrates out of the silicate change at 1450 C and approx. 50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts 9Si-, and C-rich), two immiscible sulfide melts(Fe-and FeMgMnCa-rich) and Silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite Chondrite suggest that igneous processes at low fO2 exhibit serveral unique features. The complete melting of sulfides at 1000 C suggest that aubritic sulfides are not relicts. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO2. This exchange may help explain the formation of aubrites from known enstatite chondrites.

  2. Thermodynamics of freezing and melting.

    PubMed

    Pedersen, Ulf R; Costigliola, Lorenzo; Bailey, Nicholas P; Schrøder, Thomas B; Dyre, Jeppe C

    2016-08-17

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature-pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system.

  3. Thermodynamics of freezing and melting

    PubMed Central

    Pedersen, Ulf R.; Costigliola, Lorenzo; Bailey, Nicholas P.; Schrøder, Thomas B.; Dyre, Jeppe C.

    2016-01-01

    Although the freezing of liquids and melting of crystals are fundamental for many areas of the sciences, even simple properties like the temperature–pressure relation along the melting line cannot be predicted today. Here we present a theory in which properties of the coexisting crystal and liquid phases at a single thermodynamic state point provide the basis for calculating the pressure, density and entropy of fusion as functions of temperature along the melting line, as well as the variation along this line of the reduced crystalline vibrational mean-square displacement (the Lindemann ratio), and the liquid's diffusion constant and viscosity. The framework developed, which applies for the sizable class of systems characterized by hidden scale invariance, is validated by computer simulations of the standard 12-6 Lennard-Jones system. PMID:27530064

  4. Benzodithiophene and Imide-Based Copolymers for Photovoltaic; Applications

    SciTech Connect

    Braunecker, W. A.; Owczarczyk, Z. R.; Garcia, A.; Kopidakis, N.; Larsen, R. E.; Hammond, S. R.; Ginley, D. S.; Olson, D. C.

    2012-04-10

    Conjugated alternating copolymers were designed with low optical band gaps for organic photovoltaic (OPV) applications by considering quinoid resonance stabilization. Copolymers of thienoisoindoledione (TID) and benzodithiophene (BDT) had appreciably lower band gaps (by {approx}0.4 eV) than copolymers of thienopyrroledione (TPD) and BDT. In addition to intramolecular charge transfer stabilization (i.e., the 'push-pull' effect), the former copolymer's quinoid resonance structure is stabilized by a gain in aromatic resonance energy in the isoindole unit. Additionally, the HOMO levels of the copolymers could be tuned with chemical modifications to the BDT monomer, resulting in open circuit voltages of greater than 1 V in photovoltaic devices. Despite the optimized band gap, TID containing polymers displayed lower photoconductance, as determined by time-resolved microwave conductivity, and decreased device efficiency (2.1% vs 4.8%) as compared with TPD analogues. These results were partially attributed to morphology, as computational modeling suggests TID copolymers have a twisted backbone, and X-ray diffraction data indicate the polymer films do not form ordered domains, whereas TPD copolymers are considerably more planar and are shown to form partially ordered domains.

  5. Effects of Blockiness on the phase behavior of random copolymers

    NASA Astrophysics Data System (ADS)

    Vanderwoude, Gordon; Shi, An-Chang

    Theoretical study of random block copolymers remains a challenging topic due in part to the sheer enormity of their phase space. In this study we use the self-consistent field theory to investigate the phase behaviour of linear (AB)n-type and (AB)n-C-type multiblock copolymers with randomly distributed A and B blocks. In particular, we examine the effect of ``blockiness'' of the random copolymers on the formation of ordered phases. The blockiness can be quantified by the average length of individual A or B blocks, which can be taken as a measure of the heterogeneity of the random copolymers. We observed that the critical value of the χ parameter, at which the order-disorder transition occurs, decreases with increasing blockiness in the (AB)n copolymers. We also observed that the phase behaviour of the (AB)n-C copolymers depends strongly on the blockiness of the random chain. In particular, the blockiness governs whether or not the A/B blocks can phase separate within the A/B domains, thus dictating whether the (AB)n-C behaves as A/B-C diblock copolymers or as ABC terpolymers. The theoretical phase diagrams will be compared with available experiments.

  6. Nanopatterning of recombinant proteins and viruses using block copolymer templates

    NASA Astrophysics Data System (ADS)

    Cresce, Arthur Von Wald

    The study of interfaces is important in understanding biological interactions, including cellular signaling and virus infection. This thesis is an original effort to examine the interaction between a block copolymer and both a protein and a virus. Block copolymers intrinsically form nanometer-scale structures over large areas without expensive processing, making them ideal for the synthesis of the nanopatterned surfaces used in this study. The geometry of these nanostructures can be easily tuned for different applications by altering the block ratio and composition of the block copolymer. Block copolymers can be used for controlled uptake of metal ions, where one block selectively binds metal ions while the other does not. 5-norbornene-2,3-dicarboxylic acid is synthesized through ring-opening metathesis polymerization. It formed spherical domains with spheres approximately 30 nm in diameter, and these spheres were then subsequently loaded with nickel ion. This norbornene block copolymer was tested for its ability to bind histidine-tagged green fluorescent protein (hisGFP), and it was found that the nickel-loaded copolymer was able to retain hisGFP through chelation between the histidine tag and the metal-containing portions of the copolymer surface. Poly(styrene-b-4-vinylpyridine) (PS/P4VP) was also loaded with nickel, forming a cylindrical microstructure. The binding of Tobacco mosaic virus and Tobacco necrosis virus was tested through Tween 20 detergent washes. Electron microscopy allowed for observation of both block copolymer nanostructures and virus particles. Results showed that Tween washes could not remove bound Tobacco mosaic virus from the surface of PS/P4VP. It was also seen that the size and tunability of block copolymers and the lack of processing needed to attain different structures makes them attractive for many applications, including microfluidic devices, surfaces to influence cellular signaling and growth, and as a nanopatterning surface for

  7. Electrochemically controlled self-assembly of block copolymer nanostructures

    NASA Astrophysics Data System (ADS)

    Eitouni, Hany Basam

    Organometallic block copolymers, wherein one block is composed of alternating ferrocene and dialkylsilane units in the main chain, undergo self-assembly to form microphase-separated ordered structures similarly to typical organic block copolymers. The 1,1'-dimethylsilylferrocenophane monomer was synthesized and polymerized anionically with other monomers to make a variety of different organometallic block copolymers. The phase behavior and thermodynamic interactions of anionically synthesized poly(styrene-block-ferrocenyldimethylsilane) (SF) and poly(isoprene-block-ferrocenyldimethylsilane) (IF) copolymers were examined using depolarized light scattering, small angle x-ray and neutron scattering (SAXS and SANS), and transmission electron microscopy. The temperature-dependence of the Flory-Huggins parameter, chi, and the statistical segment lengths of SF and IF copolymers were determined by SAXS and SANS using the random phase approximation. The thermodynamic interactions in poly(ferrocenyldimethylsilane) diblock copolymers were systematically adjusted by oxidizing the ferrocene moieties with silver salts and examined using SAXS and depolarized light scattering. The polymers retained microphase separated ordered structures upon oxidation and showed systematic changes in the location of the order-disorder transition as a function of extent of oxidation. By controlling the redox properties of the ferrocene moiety in the backbone of the polymer, we present a method for controlling the self-assembled microstructure and hence bulk material properties. Using electrochemical techniques, a novel means of controlling the order-disorder transition of block copolymers was discovered. By applying very small electrical potentials to disordered solutions of organometallic block copolymers, oriented ordered grains were formed near one electrode, the result of electrochemical reactions. After reversing the electrical bias on the system, the ordered grains disappeared and new

  8. In vitro digestion of purified β-casein variants A(1), A(2), B, and I: effects on antioxidant and angiotensin-converting enzyme inhibitory capacity.

    PubMed

    Petrat-Melin, B; Andersen, P; Rasmussen, J T; Poulsen, N A; Larsen, L B; Young, J F

    2015-01-01

    Genetic polymorphisms of bovine milk proteins affect the protein profile of the milk and, hence, certain technological properties, such as casein (CN) number and cheese yield. However, reports show that such polymorphisms may also affect the health-related properties of milk. Therefore, to gain insight into their digestion pattern and bioactive potential, β-CN was purified from bovine milk originating from cows homozygous for the variants A(1), A(2), B, and I by a combination of cold storage, ultracentrifugation, and acid precipitation. The purity of the isolated β-CN was determined by HPLC, variants were verified by mass spectrometry, and molar extinction coefficients at λ=280nm were determined. β-Casein from each of the variants was subjected to in vitro digestion using pepsin and pancreatic enzymes. Antioxidant and angiotensin-converting enzyme (ACE) inhibitory capacities of the hydrolysates were assessed at 3 stages of digestion and related to that of the undigested samples. Neither molar extinction coefficients nor overall digestibility varied significantly between these 4 variants; however, clear differences in digestion pattern were indicated by gel electrophoresis. In particular, after 60min of pepsin followed by 5min of pancreatic enzyme digestion, one ≈4kDa peptide with the N-terminal sequence (106)H-K-E-M-P-F-P-K- was absent from β-CN variant B. This is likely a result of the (122)Ser to (122)Arg substitution in variant B introducing a novel trypsin cleavage site, leading to the changed digestion pattern. All investigated β-CN variants exhibited a significant increase in antioxidant capacity upon digestion, as measured by the Trolox-equivalent antioxidant capacity assay. After 60min of pepsin + 120min of pancreatic enzyme digestion, the accumulated increase in antioxidant capacity was ≈1.7-fold for the 4 β-CN variants. The ACE inhibitory capacity was also significantly increased by digestion, with the B variant reaching the highest inhibitory

  9. Stabilization of fenofibrate in low molecular weight hydroxypropylcellulose matrices produced by hot-melt extrusion.

    PubMed

    Deng, Weibin; Majumdar, Soumyajit; Singh, Abhilasha; Shah, Sejal; Mohammed, Noorullah Naqvi; Jo, Seongbong; Pinto, Elanor; Tewari, Divya; Durig, Thomas; Repka, Michael A

    2013-02-01

    The objective of this study was to improve the dissolution rate and to enhance the stability of a poorly water-soluble and low glass-trasition temperature (T(g)) model drug, fenofibrate, in low molecular weight grades of hydroxypropylcellulose matrices produced by hot-melt extrusion (HME). Percent drug loading had a significant effect on the extrudability of the formulations. Dissolution rate of fenofibrate from melt extruded pellets was faster than that of the pure drug (p < 0.05). Incorporation of sugars within the formulation further increased the fenofibrate release rates. Differential scanning calorimetry results revealed that the crystalline drug was converted into an amorphous form during the HME process. Fenofibrate is prone to recrystallization due to its low T(g). Various polymers were evaluated as stabilizing agents among which polyvinylpyrrolidone 17PF and amino methacrylate copolymer exhibited a significant inhibitory effect on fenofibrate recrystallization in the hot-melt extrudates. Subsequently immediate-release fenofibrate tablets were successfully developed and complete drug release was achieved within 5 min. The dissolution profile was comparable to that of a currently marketed formulation. The hot-melt extruded fenofibrate tablets were stable, and exhibited an unchanged drug release profile after 3-month storage at 40°C/75% RH.

  10. Thin membranes of new hard/soft segment copolymers

    SciTech Connect

    Ho, W.S.; Sartori, G.; Thaler, W.A.

    1996-12-31

    Thin membranes of new hard/soft segment copolymers have been synthesized for the separation of aromatics from saturates through high temperature pervaporation. In the membranes, hard segments provide temperature stability and solvent resistance, while soft segments govern aromatic/saturate selectivity and flux. We have synthesized new chlorinated polyurethane/polyester and polyimide/polyester copolymers. Based on a polyimide copolymer membrane, a new technology has been developed recently to separate heavy catalytically cracked naphtha into an aromatics-rich permeate and an aromatics-lean retentate.

  11. Photocrosslinkable copolymers for non-linear optical applications

    SciTech Connect

    Kawatsuki, N.; Pakbaz, K.; Schmidt, H.W.

    1993-12-31

    New photocrosslinkable copolymers have been synthesized and applied as non-linear optical materials. The copolymers are based on methyl methacrylate, a photo-excitable benzophenone monomer, a non-linear optical active 4`-[(2-hydroxyethyl)ethylamino]-4-nitro-azobenzene (disperse red 1) side chain monomer and a crosslinkable 2-butenyl monomer. These copolymers can be crosslinked by UV light at 366 nm in the poled state and show a stable alignment of NLO chromophore by monitoring the adsorption spectra. The crosslinked and poled film did not change its alignment after storing 4 weeks at room temperature.

  12. Microphase Separated Block Copolymers in Pervaporation Membranes for Biofuels Processing

    NASA Astrophysics Data System (ADS)

    Greer, Douglas; Shin, Chae-Young; Ozcam, Evren; Skerker, Jeffrey; Basso, Thalita; Leon, Dacia; Bauer, Stefan; Balsara, Nitash; Energy Biosciences Institute Collaboration

    2014-03-01

    The production of transportation biofuels requires numerous continuous separation processes. We designed block copolymer membranes for pervaporation as a means to achieve these separations. These block copolymers contain a glassy structure block for support and a rubbery transport block for sorption and diffusion. We create membranes with nanoscale conducting channels using the unique trait of block copolymers to assemble into ordered morphologies. We have previously used nanostructured membranes to separate ethanol/water binary mixtures [J. Membr. Sci. 373, 112 (2011)], [J. Membr. Sci. 401, 125 (2012)]. We report this type of membranes is effective in other, more complex separations important to biofuel production. These separations increase yield and decrease process time.

  13. Electrically conductive doped block copolymer of polyacetylene and polyisoprene

    DOEpatents

    Aldissi, Mahmoud

    1985-01-01

    An electrically conductive block copolymer of polyisoprene and polyacetyl and a method of making the same are disclosed. The polymer is prepared by first polymerizing isoprene with n-butyllithium in a toluene solution to form an active isoprenyllithium polymer. The active polymer is reacted with an equimolar amount of titanium butoxide and subsequently exposed to gaseous acetylene. A block copolymer of polyisoprene and polyacetylene is formed. The copolymer is soluble in common solvents and may be doped with I.sub.2 to give it an electrical conductivity in the metallic regime.

  14. Effect of water uptake on morphology of polymerized ionic liquid block copolymers and random copolymers

    NASA Astrophysics Data System (ADS)

    Wang, Tsen-Shan; Ye, Yuesheng; Elabd, Yossef; Winey, Karen

    2012-02-01

    Dynamic studies of polymer morphology probe how the physical properties of polymerized ionic liquids are affected by the environment, such as temperature or moisture. For a series of poly(methyl methacrylate-b-1-[2-(methacryloyloxy)ethyl]-3-Butylimidazolium X^-) block and random copolymers with hydrophilic counterions (X^- = Br^-, HCO3^-, OH^-), the introduction of water vapor to the system can swell the ionic liquid block, causing enlarged hydrophilic domains and swollen channels for ion conduction. This expected expansion of ionic liquid domains in humid environments can be used to intelligently design these copolymers for use in technological applications. The effect of water vapor exposure in these imidazolium-based acrylate polymers is studied by small-angle X-ray scattering. These morphology results will be discussed alongside complementary studies of water uptake and ion conductivity.

  15. No evidence for priming response in Galleria mellonella larvae exposed to toxin protein PirA2B2 from Photorhabdus luminescens TT01: An association with the inhibition of the host cellular immunity.

    PubMed

    Wu, Gongqing; Yi, Yunhong; Sun, Jianyu; Li, Mei; Qiu, Lihong

    2015-11-17

    There is accumulating evidence that many invertebrates including insects can acquire enhanced immune protection against subsequently pathogens infection through immune priming. However, whether the toxin protein from pathogenic bacteria can induce such priming response remains unclear. Here we cloned, expressed and purified the toxin Photorhabdus insect-related proteins A2B2 (PirA2B2) from Photorhabdus luminescens TT01. We primed Galleria mellonella with sublethal dose of PirA2B2 and then challenged the larvae with viable P. luminescens TT01 at 48 h after priming. We found no evidence for immune priming in G. mellonella larvae exposed to PirA2B2. Priming the larvae with PirA2B2 did not improve their resistance in a subsequent challenge with P. luminescens TT01. Whereas a robust priming response was observed when the larvae exposed to lipopolysaccharide (LPS) extracted from P. luminescens TT01. Because the larvae primed with LPS showed significant higher resistance against P. luminescens TT01 infection than those of the PBS and BSA controls. Furthermore, we investigated the changes of the cellular immune parameters, such as hemocyte counts, phagocytic activity and encapsulation ability of the hemocytes, after priming. We found that the toxin PirA2B2 significantly decreased the cellular immunity of the larvae, whereas the LPS significantly increased them. These results indicated that the degree of priming response in G. mellonella correlated positively to the levels of cellular immune parameters, and the underlying mechanism in regulating the immune priming of invertebrates was not homologous to that of the immunological memory of vertebrates.

  16. Characterization of copolymer latexes by capillary electrophoresis.

    PubMed

    Anik, Nadia; Airiau, Marc; Labeau, Marie-Pierre; Bzducha, Wojciech; Cottet, Hervé

    2010-02-02

    Latexes are widely used for industrial applications, including decorative paints, binders for the papermaking industry, and drilling fluids for oil-field applications. In this work, the interest of capillary zone electrophoresis (CE) for the characterization of hydrophobic block copolymer latexes obtained by the conventional emulsion polymerization technique consisting of a core of polystyrene (PS) surrounded by a layer of poly(ethyl acrylate) (PEA) has been investigated. The PEA part of the copolymer can be partially hydrolyzed in poly(acrylic acid) (PAA) leading to PS-PEA-AA water-soluble amphiphilic copolymer having high viscosifying properties. The main purpose of this work was to evaluate the potential of CE for the characterization of the latexes at the different stages of the synthesis (PS core, PS-PEA diblock latex, and hydrolyzed PS-PEA-AA gel). The main analytical issues were to state (i) if there was free PS or PEA homopolymer latexes in the PS-PEA latex sample and (ii) if there was free PS, PEA, PS-PEA latexes, or free PAA chains in the PS-PEA-AA gel. Within this scope, this work describes the optimization of the selectivity of the separation between the different species (PS, PEA particles in the not hydrolyzed diblock latex and PS, PEA, PS-PEA particles as well as the polymer PAA chains in the PS-PEA-AA diblock gel sample obtained by latter latex hydrolysis). For that purpose, several experimental parameters were investigated such as pH and ionic strength of the background electrolyte (BGE) or the concentration of neutral surfactant added in the BGE. A challenging issue was to overcome the high viscosity of the PS-PEA-AA gel. This was resolved by the addition of 10 mM neutral surfactant in the gel sample and in the BGE. Finally, it is demonstrated that, within the detection limits, CE is a suitable analytical tool for controlling and monitoring the syntheses of these latexes and for intrinsically characterizing the distribution in charge density of

  17. Magnetic Biocomposites for Remote Melting.

    PubMed

    Zhou, Mengbo; Liebert, Tim; Müller, Robert; Dellith, Andrea; Gräfe, Christine; Clement, Joachim H; Heinze, Thomas

    2015-08-10

    A new approach toward the fabrication of biocompatible composites suitable for remote melting is presented. It is shown that magnetite nanoparticles (MNP) can be embedded into a matrix of biocompatible thermoplastic dextran esters. For that purpose, fatty acid esters of dextran with adjustable melting points in the range of 30-140 °C were synthesized. Esterification of the polysaccharide by activation of the acid as iminium chlorides guaranteed mild reaction conditions leading to high quality products as confirmed by FTIR- and NMR spectroscopy as well as by gel permeation chromatography (GPC). A method for the preparation of magnetically responsive bionanocomposites was developed consisting of combined dissolution/suspension of the dextran ester and hydrophobized MNPs in an organic solvent followed by homogenization with ultrasonication, casting of the solution, drying and melting of the composite for a defined shaping. This process leads to a uniform distribution of MNPs in nanocomposite as revealed by scanning electron microscope. Samples of different geometries were exposed to high frequency alternating magnetic field. It could be shown that defined remote melting of such biocompatible nanocomposites is possible for the first time. This may lead to a new class of magnetic remote control systems, which are suitable for controlled release applications or self-healing materials.

  18. Transcrystalline melt migration in clinopyroxene

    NASA Astrophysics Data System (ADS)

    Sonzogni, Yann; Provost, Ariel; Schiano, Pierre

    2011-03-01

    Glass inclusions in clinopyroxene phenocrysts from La Sommata (Vulcano Island, Aeolian Arc) were reheated and submitted to a sustained thermal gradient. Each remelted inclusion undergoes a transient textural and chemical reequilibration and concomitantly begins to migrate along a crystallographic direction, at a small angle with the thermal gradient. The completion of morphological evolution requires a characteristic time that is governed by chemical diffusion. Chemical reequilibration results in the formation of a colored halo that delineates the former location and shape of the inclusion after it has migrated away. Transcrystalline migration proceeds by dissolution of the host clinopyroxene ahead and precipitation astern. Its rate is not limited by Fick's law, but by the crystal-melt interface kinetics. Clinopyroxene dissolution and growth are slower than for olivine in similar conditions but obey the same analytical law, which can be transposed to equally or more sluggish melting or crystallization events in nature. When a gas bubble is initially present, it responds to elastic forces by quickly shifting toward the cold end of the inclusion, where it soon becomes engulfed as an isolated fluid inclusion in the reprecipitated crystal. This study confirms that transcrystalline melt migration, beside its possible implications for small-scale melt segregation and fluid-inclusion generation in the Earth's mantle, provides an experimental access to interfacial kinetic laws in near-equilibrium conditions.

  19. Cationic vinyl pyridine copolymers and products thereof

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor)

    1978-01-01

    Quaternized, cross-linked, insoluble copolymers of unsubstituted and substituted vinyl pyridines and a dihalo organic compound are spontaneously formed at ambient temperature on mixing the two monomers in bulk, in solution or in suspension. The amount of cross-linking may be varied according to the composition and reaction conditions. The polymer product exhibits ion exchange capacity and undergoes a reversible color change from black at a pH above 7 to yellow at a pH below 7. The polymer may be formed in the presence of preformed polymers, substrates such as porous or impervious particles or films to deposit an ion exchange film in situ or on the surface of the substrate. The coated or resin impregnated substrate may be utilized for separation of anionic species from aqueous solution.

  20. Computational engineering of low bandgap copolymers

    PubMed Central

    Wykes, Michael; Milián-Medina, Begoña; Gierschner, Johannes

    2013-01-01

    We present a conceptual approach to low bandgap copolymers, in which we clarify the physical parameters which control the optical bandgap, develop a fundamental understanding of bandgap tuning, unify the terminology, and outline the minimum requirements for accurate prediction of polymer bandgaps from those of finite length oligomers via extrapolation. We then test the predictive power of several popular hybrid and long-range corrected (LC) DFT functionals when applied to this task by careful comparison to experimental studies of homo- and co-oligomer series. These tests identify offset-corrected M06HF, with 100% HF exchange, as a useful alternative to the poor performance of tested hybrid and LC functionals with lower fractions of HF exchange (B3LYP, CAM-B3LYP, optimally-tuned LC-BLYP, BHLYP), which all significantly overestimate changes in bandgap as a function of system size. PMID:24790963

  1. Block and graft copolymers and NanoGel copolymer networks for DNA delivery into cell.

    PubMed

    Lemieux, P; Vinogradov, S V; Gebhart, C L; Guérin, N; Paradis, G; Nguyen, H K; Ochietti, B; Suzdaltseva, Y G; Bartakova, E V; Bronich, T K; St-Pierre, Y; Alakhov, V Y; Kabanov, A V

    2000-01-01

    Self-assembling complexes from nucleic acids and synthetic polymers are evaluated for plasmid and oligonucleotide (oligo) delivery. Polycations having linear, branched, dendritic. block- or graft copolymer architectures are used in these studies. All these molecules bind to nucleic acids due to formation of cooperative systems of salt bonds between the cationic groups of the polycation and phosphate groups of the DNA. To improve solubility of the DNA/polycation complexes, cationic block and graft copolymers containing segments from polycations and non-ionic soluble polymers, for example, poly(ethylene oxide) (PEO) were developed. Binding of these copolymers with short DNA chains, such as oligos, results in formation of species containing hydrophobic sites from neutralized DNA polycation complex and hydrophilic sites from PEO. These species spontaneously associate into polyion complex micelles with a hydrophobic core from neutralized polyions and a hydrophilic shell from PEO. Such complexes are very small (10-40 nm) and stable in solution despite complete neutralization of charge. They reveal significant activity with oligos in vitro and in vivo. Binding of cationic copolymers to plasmid DNA forms larger (70-200 nm) complexes. which are practically inactive in cell transfection studies. It is likely that PEO prevents binding of these complexes with the cell membranes ("stealth effect"). However attaching specific ligands to the PEO-corona can produce complexes, which are both stable in solution and bind to target cells. The most efficient complexes were obtained when PEO in the cationic copolymer was replaced with membrane-active PEO-b-poly(propylene oxide)-b-PEO molecules (Pluronic 123). Such complexes exhibited elevated levels of transgene expression in liver following systemic administration in mice. To increase stability of the complexes, NanoGel carriers were developed that represent small hydrogel particles synthesized by cross-linking of PEI with double end

  2. Electrode coating composed of copolymers derived from diacetone acrylamide

    SciTech Connect

    Rampel, G.

    1981-01-13

    An improved electrode coating and separator coating derived from a copolymer of diacetone acrylamide and a polymerizable monomer are disclosed. This invention relates to novel rechargeable electrodes, separators and processes for preparing same.

  3. Crystalline Morphology of Propylene 1-Octene Random Copolymers

    NASA Astrophysics Data System (ADS)

    Jeon, Keesu; Alamo, Rufina G.

    2008-03-01

    The morphology of isotactic propylene 1-octene random copolymers has been studied by AFM, DSC, WAXS, and FTIR in an octene range of 10-20 mol %. Different morphologies were observed below and above 15 mol %. The morphological components in the higher counit copolymers are not of the lamellae-type, thicker than lamellae observed below 15 mol %, connected and isotropic in their orientation. Their global morphology is developed via nucleation and growth (NG) of spherulitic aggregates. The evolution of heat of fusion with time is also sigmoidal shape, typical of NG-type crystallization mechanism. WAXS diffractograms for the higher counit copolymers are devoid of crystalline reflections, except for small and broad peaks suggesting mesomorphic-like structures, which by FTIR show small contents of the 840 cm-1, 12 and higher units regularity bands, and hence formed of short helical sequences. The PO morphology is additionally compared with copolymers with ethylene, 1-butene and 1-hexene counits at matched contents.

  4. Insensitive explosive composition of halogenated copolymer and triaminotrinitrobenzene

    DOEpatents

    Benziger, Theodore M.

    1976-01-01

    A highly insensitive and heat resistant plastic-bonded explosive containing 90 wt % triaminotrinitrobenzene and 10 wt % of a fully saturated copolymer of chlorotrifluoroethylene and vinylidene fluoride is readily manufactured by the slurry process.

  5. Nanostructured photovoltaic materials using conjugated block copolymer assemblies

    NASA Astrophysics Data System (ADS)

    Mastroianni, Sarah E.; Epps, Thomas H., III

    2011-03-01

    Block copolymers containing a conjugated block offer attractive possibilities for creating nanostructured organic photovoltaic (OPV) devices. Current OPV materials suffer from efficiency losses primarily due to a size-scale discrepancy between exciton diffusion length and domain sizes; excitons that do not reach the interface between electron and hole-conducting materials recombine, preventing charge carrier separation. The inherent nature of block-copolymers to self-assemble into well-defined nanoscale structures with domain spacings on the order of exciton diffusion length offers a potential solution for reducing exciton recombination. In this work, allyl-terminated poly(3-hexyl thiophene) or poly(3-decyl thiophene) acting as electron donors are incorporated into the block copolymer chain via a coupling reaction with poly(styrene) or poly(isoprene- b -styrene) derivatives synthesized by anionic polymerization. The resulting block copolymer morphologies are characterized by small angle X-ray scattering and transmission electron microscopy.

  6. Electrode coating composed of copolymers derived from diacetone acrylamide

    SciTech Connect

    Rampel, G.

    1985-07-23

    An improved electrode coating and separator coating derived from a copolymer of diacetone acrylamide and a polymerizable monomer. This invention relates to novel rechargeable electrodes, separators and processes for preparing same.

  7. Surface Characterization of Aliphatic Polyester -g- Phosphorylcholine Copolymers

    NASA Astrophysics Data System (ADS)

    Zhang, Xiongfei; Emrick, Todd; Hsu, Shaw L.

    2007-03-01

    In order to control biodegradation behavior of a class of polyesters, hydrophilic functional groups were grafted onto the main chains. Phosphorylcholine (PC) molecules with azide attached at the end were synthesized. Due to their excellent biocompatibility and hydrophilicity, they have been covalently coupled to biodegradable aliphatic polyesters via a ``click'' cycloaddition reaction to produce amphiphilic graft copolymers. A series of copolymers were prepared by varying the molar incorporation of PC groups. Surface properties of the copolymers were examined to further explore their applications in drug delivery systems. Grazing angle reflection infrared spectroscopy was employed to determine segmental orientation at the film surface. XPS was used to verify surface composition. A water adsorption experiment was carried out to determine the water permeation rate. The improvement in hydrophilicity was confirmed by a water contact experiment. Results indicate that the graft copolymers were promising in drug delivery systems.

  8. Self-Assembly of Block Copolymers in an Ionic Liquid

    NASA Astrophysics Data System (ADS)

    He, Yiyong; Li, Zhibo; Lodge, Timothy P.

    2006-03-01

    Amphiphilic diblock copolymers poly((1,2-butadiene)-b-ethylene oxide) (PB-PEO) were shown to aggregate and form well-defined micelles in an ionic liquid, 1-butyl-3-methyl imidazolium hexafluorophosphate ([BMIM][PF6]). The universal sequence of micellar structures (spherical micelle, wormlike micelle, and bilayered vesicle) were all resolved by varying the block copolymer composition. For the first time, the nanostructures of PB-PEO micelles formed in an ionic liquid were directly visualized by cryogenic transmission electron microscopy (cryo-TEM). The detailed micelle structure information was extracted from cryo-TEM and dynamic light scattering (DLS) measurements, and compared to their aqueous counterparts. The work demonstrates the feasibility of controlling micellar nanostructures of amphiphilic block copolymers in ionic liquids, and also provides important knowledge for further applications of copolymers for forming microemulsions and ion gels.

  9. Stepwise Activation of Switchable Glazing by Compositional Gradient of Copolymers.

    PubMed

    Lee, Eunsu; Kim, Dowan; Yoon, Jinhwan

    2016-10-05

    Thermotropic glazing is one of the most promising developments for adaptive solar control; however, a monotonic transparent-opaque transition limits its practical application. In this work, to render stepwise activation of the switchable glazing, we prepared multicomposition copolymers having a compositional gradient. By slow addition of the monomers in the reaction mixture during free-radical polymerization, the blend of copolymers with each polymer having different compositions of the monomers could be prepared. We found that the developed copolymers exhibit different thermal behaviors according to the monomer composition, yielding the nearly linear transmittance change over a wide temperature range due to the gradient hydrophilic-hydrophobic balances. By combining prepared copolymers with photothermal graphene oxide as a heat transducer, we demonstrated gradual solar control of the smart window in response to sunlight intensity in outdoor testing.

  10. Interfacial properties of semifluorinated alkane diblock copolymers

    NASA Astrophysics Data System (ADS)

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

    2008-06-01

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

  11. Block Copolymer Thin Films: Patterns and Patterning

    NASA Astrophysics Data System (ADS)

    Register, Richard A.

    2001-03-01

    The nanostructures ("microdomains") in thin block copolymer films make excellent contact masks for surface patterning on the nanoscale. Using these thin films as templates, we have developed techniques based on reactive ion etching to uniformly and completely pattern the underlying substrate with a dense periodic pattern of dots, holes, or lines, with widths of order 20 nm. In addition, we have fabricated arrays of metal dots by backfilling these holes, and GaAs quantum dots by regrowth onto patterned GaAs substrates. A key issue in this nanopatterning approach is controlling the pattern which forms within the mask. While the local structure of the pattern (e.g., spheres vs. cylinders) is easily controlled through block copolymer composition, the long-range order ("grain size") is more difficult to manipulate. For cylinder-forming diblocks, we find that the correlation length of the microdomains grows as a weak power of annealing time, approximately 1/4. The principal types of defects which destroy the long-range order of the microdomains are disclinations. Sequential AFM images taken on the same region of the film after varying annealing times can be strung together into "movies" (to be shown at the talk) which directly show that the principal mode of defect annihilation (and hence grain growth) is the annihilation of disclination quadrupoles (pairs of +1/2 and -1/2 disclinations). We propose a model for quadrupole annihilation which reproduces the 1/4 exponent. Preliminary results for sphere-forming systems suggest that the exponent there is even lower than 1/4, making it difficult to achieve a significant degree of coarsening by extending the annealing time. * in collaboration with D.H. Adamson, P.M. Chaikin, Z. Cheng, P.D. Dapkus (USC), C.K. Harrison, D.A. Huse, R.R. Li (USC), and M. Park.

  12. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, Michael S.; Saunders, Randall

    1997-01-01

    Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

  13. Thermoreversible, epitaxial fcc<-->bcc transitions in block copolymer solutions.

    PubMed

    Bang, Joona; Lodge, Timothy P; Wang, Xiaohui; Brinker, Kristin L; Burghardt, Wesley R

    2002-11-18

    Uncharged block copolymer micelles display thermoreversible transitions between close-packed and bcc lattices for a range of concentration, solvent selectivity, and copolymer composition. Using small-angle x-ray scattering on shear-oriented solutions, highly aligned fcc crystals are seen to transform epitaxially to bcc crystals, with fcc/bcc orientational relationships that are well established in martensitic transformations in metals. The transition is driven by decreasing solvent selectivity with increasing temperature, inducing solvent penetration of the micellar core.

  14. Photooxidative degradation of clear ultraviolet absorbing acrylic copolymer surfaces

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Liang, R. H.; Vogl, O.; Pradellok, W.; Huston, A. L.; Scott, G. W.

    1983-01-01

    Photodegradation of copolymer of methyl methacrylate and 2(2'-hydroxy 5'vinyl-phenyl) 2H-benzotriazole has been investigated in order to determine the changes in the chemical composition of the surface of the copolymer on photooxidation. An electronic energy transfer mechanism has been postulated in order to interpret the observed photochemical changes in the polymer. Preliminary examination of the photophysical properties of the chromophore provides support for such a mechanism.

  15. Carboxymethylbetaine copolymer layer covalently fixed to a glass substrate.

    PubMed

    Suzuki, Hisatomo; Li, Lifu; Nakaji-Hirabayashi, Tadashi; Kitano, Hiromi; Ohno, Kohji; Matsuoka, Kazuyoshi; Saruwatari, Yoshiyuki

    2012-06-01

    A random copolymer of zwitterionic monomer, carboxymethylbetaine (CMB), and 3-methacryloyloxypropyl trimethoxysilane was prepared in ethanol using 2,2'-azobisisobutyronitrile as initiator. The incubation of ethanol solution of the copolymer with a glass plate gave a layer of the copolymer with a thickness of about 2-3 nm. The copolymer-modified glass substrate became highly hydrophilic upon immersion in water, and showed a resistance against non-specific adsorption of proteins, and the degree of resistance increased with the content of CMB residues in the copolymer and leveled off. The adhesion of various cells to the glass substrate was also strongly suppressed by the surface modification with the copolymer layer. Further introduction of PolyCMB graft chains on the surface of the layer enhanced the suppression of cell adhesion due to the steric hindrance for the cells to approach the layer. The usefulness of the combination of zwitterionic polymer layer and graft chains to afford anti-biofouling properties to a solid surface of metal oxides was shown.

  16. Theory for the aggregation of proteins and copolymers

    SciTech Connect

    Fields, G.B.; Alonso, D.O.V.; Stigter, D.; Dill, K.A.

    1992-05-14

    We develop mean-field lattice statistical mechanics theory for the equilibrium between denatured and aggregated states of proteins and other random copolymers of hydrophobic and polar monomers in aqueous solution. We suppose that the aggregated state is a mixture of amorphous polymer plus solvent and that the driving forces are the hydrophobic interaction, which favors aggregation, and conformational and translational entropies, which favor disaggregation. The theory predicts that the phase diagram for thermal aggregation is an asymmetric closed loop, and for denaturants (guanidinium hydrochloride of urea) it is asymmetric with an upper consolute point. The theory predicts that a copolymer in a poor solvent will expand with increasing polymer concentration because of {open_quotes}screening{close_quotes} of the solvent interactions by the other chains; the chain ultimately reaches a theta-like state in the absence of solvent. The screening concentration depends strongly on the copolymer composition. We find two striking features of these copolymer phase diagrams. First, they are extraordinarily sensitive to the copolymer composition; a change of one amino acid can substantially change the aggregation behavior. Second, relative to homopolymers, copolymers should be stable against aggregation at concentrations that are higher by many orders of magnitude. 43 refs., 13 figs.

  17. Antimicrobial activity of poly(acrylic acid) block copolymers.

    PubMed

    Gratzl, Günther; Paulik, Christian; Hild, Sabine; Guggenbichler, Josef P; Lackner, Maximilian

    2014-05-01

    The increasing number of antibiotic-resistant bacterial strains has developed into a major health problem. In particular, biofilms are the main reason for hospital-acquired infections and diseases. Once formed, biofilms are difficult to remove as they have specific defense mechanisms against antimicrobial agents. Antimicrobial surfaces must therefore kill or repel bacteria before they can settle to form a biofilm. In this study, we describe that poly(acrylic acid) (PAA) containing diblock copolymers can kill bacteria and prevent from biofilm formation. The PAA diblock copolymers with poly(styrene) and poly(methyl methacrylate) were synthesized via anionic polymerization of tert-butyl acrylate with styrene or methyl methacrylate and subsequent acid-catalyzed hydrolysis of the tert-butyl ester. The copolymers were characterized via nuclear magnetic resonance spectroscopy (NMR), size-exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and acid-base titrations. Copolymer films with a variety of acrylic acid contents were produced by solvent casting, characterized by atomic force microscopy (AFM) and tested for their antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. The antimicrobial activity of the acidic diblock copolymers increased with increasing acrylic acid content, independent of the copolymer-partner, the chain length and the nanostructure.

  18. Radical-cured block copolymer-modified thermosets

    SciTech Connect

    Redline, Erica M.; Francis, Lorraine F.; Bates, Frank S.

    2013-01-10

    Poly(ethylene-alt-propylene)-b-poly(ethylene oxide) (PEP-PEO) diblock copolymers were synthesized and added at 4 wt % to 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane (BisGMA), a monomer that cures using free radical chemistry. In separate experiments, poly(ethylene glycol) dimethacrylate (PEGDMA) was combined as a secondary monomer with BisGMA and the monomers were loaded with 4 wt % PEP-PEO. The diblock copolymers self-assembled into well-dispersed spherical micelles with PEP cores and PEO coronas. No appreciable change in the final extent of cure of the thermosets was caused by the addition of diblock copolymer, except in the case of BisGMA, where the addition of the block copolymer increased extent of cure by 12%. Furthermore, the extent of cure was increased by 29% and 37% with the addition of 25 and 50 wt % PEGDMA, respectively. Elastic modulus and fracture resistance were also determined, and the values indicate that the addition of block copolymers does not significantly toughen the thermoset materials. This finding is surprising when compared with the large increase in fracture resistance seen in block copolymer-modified epoxies, and an explanation is proposed.

  19. Complex copolymers for mobility control, water purification, and surface activity

    SciTech Connect

    Meister, J.J.

    1988-05-01

    Many processes that are basic to the extraction of natural resources are facilitated by addition of polymers. To be useful, the polymers must meet an interrelated list of chemical and physical properties as well as economic criteria. Two important properties demanded of the polymers are: 1. Rheology. Polymers are often added to change solvent or process flow properties. The addition of polymers almost always causes non-Newtonian flow behavior in the resulting fluid. Methods of controlling surface behavior are to: 1) create polar and nonpolar regions in the molecule thus producing a hydrophilic-lipophilic balance in the molecule, 2) charge the molecule by introducing ionic sites with the same or opposite charge as the boundary, or 3) introduce or remove functional groups in the molecule which produce binding reactions, such as a) hydrogen bond creation of b) nitrogen lone-pair donation, with the surface. This multitude of properties the polymer must possess dictate that better polymer performance is obtained from materials with complicated structures. Such polymers are complex polymers: random copolymers, block copolymers, graft copolymers, micellizing copolymers, and network copolymers. There has been a dramatic increase in the past decade in the number and complexity of these copolymers and it is these newly discovered polymers and their chemistry which will be described here. The synthesis, analysis, and testing of these polymers, with particular emphasis on those polymers designed for enhanced oil recovery, is presented.

  20. Thermodynamics of block copolymers with and without salt.

    PubMed

    Teran, Alexander A; Balsara, Nitash P

    2014-01-09

    Ion-containing block copolymers are of interest for applications such as electrolytes in rechargeable lithium batteries. The addition of salt to these materials is necessary to make them conductive; however, even small amounts of salt can have significant effects on the phase behavior of these materials and consequently on their ion-transport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the past decade. This feature article describes a comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations, and temperatures. The Flory-Huggins interaction parameter was determined by fitting small-angle X-ray scattering data of disordered systems to predictions based on the random phase approximation. Experiments on neat block copolymers revealed that the Flory-Huggins parameter is a strong function of chain length. Experiments on block copolymer/salt mixtures revealed a highly nonlinear dependence of the Flory-Huggins parameter on salt concentration. These findings are a significant departure from previous results and indicate the need for improved theories for describing thermodynamic interactions in neat and salt-containing block copolymers.

  1. Properties of radiation cured vinyl-divinyl copolymers. [Gamma rays

    SciTech Connect

    Micko, M.M.; Paszner, L.

    1980-04-01

    Analysis of compression stress-strain curves of radiation-cured vinyl methacrylate copolymers shows that addition of small concentrations of vinyl comonomers significantly alter all mechanical strength properties in compression. Stress-strain behavior is found to be a function of the copolymer composition. Best strength results are limited to a narrow comonomer concentration region; between 5 to 10% of divinyl monomer (DVM) for the four systems studied. This concentration range broadens with increasing molecular bridge length of the crosslinking agent being narrowest for ethylene glycol dimethylacrylate and broadest for tetraethylene glycol dimethacrylate. Copolymer connection number (CN/sub co/), as introduced earlier, is found to be useful structural parameter for crosslinked copolymers in that it correlates quantitatively mechanical or thermomechanical properties with crosslink densities within copolymers. The Methyl methacrylate-TEGDMA comonomer system was found to be the most suitable and economically attractive. It represents a well balanced compromise of improved polymerization parameters and copolymer properties desirable in many polymeric products. 9 figures, 2 tables.

  2. Direct writing by way of melt electrospinning.

    PubMed

    Brown, Toby D; Dalton, Paul D; Hutmacher, Dietmar W

    2011-12-15

    Melt electrospun fibers of poly(ϵ-caprolactone) are accurately deposited using an automated stage as the collector. Matching the translation speed of the collector to the speed of the melt electrospinning jet establishes control over the location of fiber deposition. In this sense, melt electrospinning writing can be seen to bridge the gap between solution electrospinning and direct writing additive manufacturing processes.

  3. Thermodynamics of glass forming polymeric melts

    NASA Astrophysics Data System (ADS)

    Pandya, Prapti B.; Patel, Ashmi T.; Pratap, Arun

    2013-06-01

    The temperature dependence of the Gibbs free energy difference (ΔG) between the under cooled melt and the corresponding equilibrium solid has been analyzed for two samples of glass forming polymeric melts; polyamid-6 (PA-6), polypropylene oxide (PPO) in the entire temperature range: i.e. Tm (melting temperature) to Tg (glass transition temperature).

  4. Functional Polymers and Sequential Copolymers by Phase Transfer Catalysis. 30. Synthesis of Liquid Crystalline Poly(epichlorohydrin) and Copolymers.

    DTIC Science & Technology

    1986-10-01

    Copolymers K0 By Coleen Pugh and V. Percec Department of Macromolecular Science Case Western Reserve University Cleveland, OH 44106 Submitted for... Coleen Pugh and V. Percec Department of Macromolecular Science Case Western Reserve University Cleveland, OH 44106 f ABSTRACT/ -Poly(epichlotohydrin...Catalysis. 30. Synthesis of Liquid Crystalline Poly(epichlorohydrin) and Copolymers 12 PERSONAL AUTIIOR(S C Coleen Pugh and V. Percec 13a TYPE OF

  5. Water freezing and ice melting

    DOE PAGES

    Malolepsza, Edyta; Keyes, Tom

    2015-10-12

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubic ice↔liquid,more » with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.« less

  6. Water freezing and ice melting

    SciTech Connect

    Malolepsza, Edyta; Keyes, Tom

    2015-10-12

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubic ice↔liquid, with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.

  7. Viscoelastic properties of Ionomer Melt

    NASA Astrophysics Data System (ADS)

    Goswami, Monojoy; Kumar, Sanat

    2007-03-01

    Viscoelastic prperties of a model telechelic ionomer, i.e., a melt of non-polar polymers with a charge at each chain end along with neutralizing counterions, have been examined using molecular dynamics simulation. Equlibrium calculation of the loss modulus G^''(φ) and storage modulus G^'(φ) shows plateau at lower temperatures when the systems are not relaxed. In this situation the specific heat (Cv) peak corresponds to the self-assembly of the system, at lower temperatures the specific heat begins to plateau. Similarities of the dynamic features found for telechelic melts with those observed in glass-forming liquids and entangled polymers have been shown. Furthremore, using an athermal 'probe', the properties of these materials is being distinctly classified as 'strong' glass or physical gels.

  8. Water Freezing and Ice Melting.

    PubMed

    Małolepsza, Edyta; Keyes, Tom

    2015-12-08

    The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to the freezing of liquid water and the melting of hexagonal and cubic ice. It is confirmed that coexisting states are well-sampled. The statistical temperature as a function of enthalpy, TS(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice ↔ liquid and cubic ice ↔ liquid with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. Pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.

  9. Failure behavior after stepwise uniaxial extension of entangled polymer melts

    SciTech Connect

    Sun, Hao; Lin, Panpan; Liu, Gengxin; Ntetsikas, Konstantinos; Misichronis, Konstantinos; Kang, Namgoo; Liu, Jianning; Avgeropoulos, Apostolos; Mays, Jimmy; Wang, Shi-Qing

    2015-04-20

    This paper studies how stepwise extension of various well-entangled polymer melts produce mechanical/structural breakdowns during stress relaxation. Depending on how stepwise extension is imposed on five different styrene-butadiene random copolymers, two different forms of specimen failure are observed. When a step extension is produced with a low Hencky rate or to a low strain below some thresholds, the sample breaks up rather sharply after an appreciable period of induction during which the stress relaxes quiescently. After step extension, the sample draws and undergoes unsustainable necking due to shear yielding, if the step extension is produced with a Hencky rate higher than the Rouse relaxation rate and the magnitude is beyond a Hencky strain of 1.5. Moreover, introduction of long-chain branching suppresses the elastic breakup, postponing it to Hencky strains beyond 2.5. The clearly identifiable characteristics of the elastic yielding may be understood in terms of some speculative interpretations. Finally, more convincing explanations have yet to come from future computer experiments that hopefully the present work is able to motivate.

  10. On the Multiple Melting Behavior of Semicrystalline Polymers

    NASA Astrophysics Data System (ADS)

    Marand, Herve; Velikov, Vesselin; Alizadeh, Azar

    1998-03-01

    When semicrystalline polymers of low to moderate crystallinity (i.e. less than 75-80 crystallization temperature, their subsequent heating in a differential scanning calorimeter generally leads to the observation of a multiple endothermic behavior. Interestingly, the characteristics of this multiple melting behavior appear to be universal. For example, independent of the annealing temperature, an endothermic peak appears at temperatures 10 to 30 K above the annealing/crystallization temperature. Upon increasing annealing/crystallization time, this "low endotherm" shifts reproducibly to higher temperatures, the increase in peak temperature always being a linear function of the logarithm of annealing/crystallization time. Whereas close to Tg the rate of upward shift seems to increase with temperature, at higher temperatures it appears to be independent of temperature. A summary of experimental data gathered in our laboratory on PEEK, PET, PBT, it-PS, it-PP and various ethylene copolymers will be discussed and some "new" speculation as to the origin of the low endotherm proposed. The possible role of fringe micellar crystallization will be discussed.

  11. Melting And Purification Of Niobium

    NASA Astrophysics Data System (ADS)

    Moura, Hernane R. Salles; de Moura, Lourenço

    2007-08-01

    The aspects involved in the purification of niobium in Electron Beam Furnaces will be outlined and correlated with practical experience accumulated over 17 years of continuously producing high purity niobium metal and niobium-zirconium ingots at CBMM, meeting the needs for a wide range of uses. This paper also reports some comments regarding raw material requirements, the experience on cold hearth operation melting niobium and the production of large grains niobium ingots by CBMM with some comments of their main characteristics.

  12. Melting And Purification Of Niobium

    SciTech Connect

    Salles Moura, Hernane R.; Moura, Lourenco de

    2007-08-09

    The aspects involved in the purification of niobium in Electron Beam Furnaces will be outlined and correlated with practical experience accumulated over 17 years of continuously producing high purity niobium metal and niobium-zirconium ingots at CBMM, meeting the needs for a wide range of uses. This paper also reports some comments regarding raw material requirements, the experience on cold hearth operation melting niobium and the production of large grains niobium ingots by CBMM with some comments of their main characteristics.

  13. Crystal growing from the melt

    NASA Technical Reports Server (NTRS)

    Davis, S. H.

    1987-01-01

    The mechanical and electrical properties of crystals produced by a unidirectional process depend strongly on the temperature and flow fields since these control the concentration of solute at the melt-crystal interface. The solute gradient there drives morphological instabilities that lead to cellular or dendritic interfaces. In the presentation several features of flow-solidification interactions will be discussed. These will include the effects of convection driven by density changes and buoyancy and the imposition of forced flow.

  14. Melt Spinning of Crystalline Alloys.

    DTIC Science & Technology

    1980-01-01

    manufactoring iron-based amorphous alloys for magnetic appli- cations (2). Liebermann and Graham (3) and Kavesh (-)’have discussed the effect of melt spinning...and Mn. The main objectige was to determine whether the conclusions of Liebermann and Graham and Kavesh can be applied over a wide range of materials...length, width and thickness, p is density (2.71.103 Kgm-3 ), and W is the measured weight. Liebermann and Graham (3) applied Bernoulli’s equation

  15. The influence of melting and melt drainage on crustal rheology during orogenesis

    NASA Astrophysics Data System (ADS)

    Diener, Johann F. A.; Fagereng, Åke

    2014-08-01

    Partial melting significantly weakens crustal rocks by introducing a low-viscosity liquid phase. However, near-concomitant melt drainage can remove this weak phase, potentially reversing the rheological effects such that the strength of a specific lithology depends on when the prograde pressure-temperature path intersects a melting reaction, how much melt is produced, and how long this melt is retained before it is lost. Phase equilibria and mixed rheology modeling of typical metapelite and metagreywacke compositions indicate that these rocks undergo continuous but pulsed melt production during prograde metamorphism. Depending on whether melt removal is continuous or episodic, and assuming geological strain rates, the lithologies can retain a very low strength less than 1 MPa or transiently strengthen to ˜5 MPa following melt loss. Lithologies undergoing episodic melt loss can therefore cycle between being relatively weak and relatively strong components within a composite crustal section. Melt production, retention, and weakening in the middle to lower crust as a whole is more sustained during heating and melt production, consistent with geodynamic inferences of weak, melt-bearing lower crust. However, the long-term consequence of melting and melt loss is a 50-400% increase in the strength of residual lithologies. The strengthening is more pronounced in metapelite than metagreywacke and is achieved through a combination of dehydration and the removal of the weak mica framework coupled to increased proportions of strong feldspars and garnet. Despite prolonged weakness, melting and melt loss therefore ultimately result in a dry and elastic lower crust.

  16. A universal criterion of melting.

    PubMed

    Lubchenko, Vassiliy

    2006-09-28

    Melting is analyzed dynamically as a problem of localization at a liquid-solid interface. A Lindemann-like criterion of melting is derived in terms of particular vibrational amplitudes, which turn out to equal a universal quotient (about one-tenth) of the molecular spacing, at the interface. The near universality of the Lindemann ratio apparently arises owing to strongly overdamped dynamics near melting, and despite the anharmonic interactions being system-specific. A similar criterion is derived for structural displacements in the bulk of the solid, in particular the premelted layer; the criterion is no longer strictly universal, but still depends only on the harmonic properties of the solid. We further compute the dependence of the magnitude of the elemental molecular translations, in deeply supercooled fluids, on the temperature and the high frequency elastic constants. We show explicitly that the surface tension between distinct liquid states, near the glass transition of a supercooled liquid, is nearly evenly split between entropic and energetic contributions.

  17. Melting Behaviour of Ferronickel Slags

    NASA Astrophysics Data System (ADS)

    Sagadin, Christoph; Luidold, Stefan; Wagner, Christoph; Wenzl, Christine

    2016-12-01

    The industrial manufacturing of ferronickel in electric furnaces produces large amounts of slag with strong acidic character and high melting points, which seriously stresses the furnace refractory lining. In this study, the melting behavior of synthetically produced ferronickel slags on magnesia as refractory material was determined by means of a hot stage microscope. Therefore, slags comprising the main oxides SiO2 (35-70 wt.%), MgO (15-45 wt.%) and Fe2O3 (5-35 wt.%) were melted in a graphite crucible and afterwards analyzed by a hot stage microscope. The design of experiments, which was created by the statistic software MODDE®, included 20 experiments with varying slag compositions as well as atmospheres. The evaluation of the test results occurred at three different characteristic states of the samples like the softening point according to DIN 51730 and the temperatures at which the area of residual cross-section of the samples amounted to 30% and 40%, respectively, of the original value depending of their SiO2/MgO ratio and iron oxide content. Additionally, the thickness of the zone influenced by the slag was measured and evaluated.

  18. Compositional convection in viscous melts

    NASA Astrophysics Data System (ADS)

    Tait, Stephen; Jaupart, Claude

    1989-04-01

    DURING solidification of multi-component melts, gradients in temperature and composition develop on different scales because of the large difference between their respective molecular diffusivities. Two consequences are the development of double-diffusive convection1 and the creation of mushy zones in which solid and liquid intimately coexist with a complex small-scale geometry2,3. Theoretical analysis requires simplifying assumptions that must be verified by laboratory experiments. Hitherto, experiments have been carried out with aqueous solutions which do not accurately represent the dynamics of melts with high Prandtl numbers, such as magmas. Here we describe the characteristics of compositional convection using a new experimental technique which allows the viscosity of the solution to be varied independently of chemical composition and liquidus temperature. A supereutectic melt was cooled from below, causing the growth of a horizontal layer of crystals. Convective instability occurred when the local solutal Rayleigh number of the compositional boundary layer ahead of the advancing crystallization front attained a value of ~3 on average. We observed a novel regime of convection in which the thermal boundary layer above the crystallization front was essentially unmodified by the motion of the plumes. The plumes carried a small heat flux and did not mix the fluid to a uniform temperature.

  19. Coatings with Thermally Switchable Surface Energy Produced From Block Copolymer Films

    NASA Astrophysics Data System (ADS)

    Davis, Raleigh; Register, Richard

    2015-03-01

    Polymer-based coatings are employed across a wide array of sectors. One application of such coatings is to impart a prescribed surface energy, i . e . hydrophilic or hydrophobic character. The present work explores an approach to create surfaces with thermally switchable wetting behavior by employing coatings based on block copolymers which possess both hydrophilic and hydrophobic segments. The amphiphilic block copolymers were synthesized by coupling allyl-ended poly(ethylene oxide) (PEO) and hydride-ended poly(dimethylsiloxane) (PDMS) oligomers via a Pt catalyst. One PEO-PDMS diblock possessed an order-disorder-transition-temperature (TODT) of 64°C as characterized by small angle x-ray scattering. Above the TODT the polymer is a disordered melt, but below this temperature it self-assembles into alternating lamellae with a repeat spacing of 7.7 nm. When cooled through the TODT in vacuum or dry air, the PDMS-enriched domains wet the film's surface, producing a hydrophobic surface with a contact angle (CA) ~ 90° as measured from CA goniometry. However, when cooled under water or in humid air, a PEO-rich hydrophilic surface is produced, yielding CAs ranging from 20-40°. The coatings can then be reversibly switched between the two states by reheating above the TODT, exposing to the appropriate environment, and re-cooling, ideally ``locking in'' the structure until the next processing cycle. The TODT, and thus the switching temperature, can be continuously tuned by blending with PEO-PDMS diblocks of different molecular weights.

  20. Photonic and opto-electronic applications of polydiacetylene films photodeposited from solution and polydiacetylene copolymer networks

    NASA Astrophysics Data System (ADS)

    Paley, Mark S.; Frazier, Donald O.; Smith, David D.; Witherow, William K.; Abdeldayem, Hossin A.; Wolfe, Daniel B.

    1998-08-01

    Polydiacetylenes (PDAs) are attractive materials for both electronic and photonic applications because of their highly conjugated electronic structures. They have been investigated for applications as both 1D conductors and nonlinear optical (NLO) materials. One of the chief limitations to the use of PDAs has been the inability to readily process them into useful forms such as films and fibers. In our laboratory we have developed a novel process for obtaining amorphous films of a PDA derived from 2- methyl-4-nitroaniline using photodeposition with UV light from monomer solutions onto transparent substrates. Photodeposition from solution provides a simple technique for obtaining PDA films in any desired pattern with good optical quality. This technique has been used to produce PDA films that show potential for optical applications such as holographic memory storage and optical limiting, as well as third-order NLO applications such as all-optical refractive index modulation, phase modulation and switching. Additionally, copolymerization of diacetylenes with other monomers such as methacrylates provides a means to obtain materials with good processibility. Such copolymers can be spin cast to form films, or drawn by either melt or solution extrusion into fibers. These films or fibers can then be irradiated with UV to photopolymerize the diacetylene units to form a highly stable cross-linked PDA-copolymer network. If such films are electrically poled while being irradiated, they can achieve the asymmetry necessary for second-order NLO applications such as electro-optic switching. On Earth, formation of PDAs by the above mentioned techniques suffers from defects and inhomogeneities caused by convective flows that can arise during processing. By studying the formation of these materials in the reduced-convection, diffusion- controlled environment of space we hope to better understand the factors that affect their processing, and thereby, their nature and properties

  1. Photonic and Opto-Electronic Applications of Polydiacetylene Films Photodeposited from Solution and Polydiacetylene Copolymer Networks

    NASA Technical Reports Server (NTRS)

    Paley, Mark S.; Frazier, Donald O.; Smith, David D.; Witherow, William K.; Addeldeyem, Hossin A.; Wolfe, Daniel B.

    1998-01-01

    Polydiacetylenes (PDAS) are attractive materials for both electronic and photonic applications because of their highly conjugated electronic structures. They have been investigated for applications as both one-dimensional (linear chain) conductors and nonlinear optical (NLO) materials. One of the chief limitations to the use of PDAs has been the inability to readily process them into useful forms such as films and fibers. In our laboratory we have developed a novel process for obtaining amorphous films of a PDA derived from 2-methyl4-nitroaniline using photodeposition with Ultraviolet (UV) light from monomer solutions onto transparent substrates. Photodeposition from solution provides a simple technique for obtaining PDA films in any desired pattern with good optical quality. This technique has been used to produce PDA films that show potential for optical applications such as holographic memory storage and optical limiting, as well as third-order NLO applications such as all-optical refractive index modulation, phase modulation and switching. Additionally, copolymerization of diacetylenes with other monomers such as methacrylates provides a means to obtain materials with good processibility. Such copolymers can be spin cast to form films, or drawn by either melt or solution extrusion into fibers. These films or fibers can then be irradiated with UV to photopolymerize the diacetylene units to form a highly stable cross-linked PDA-copolymer network. If such films are electrically poled while being irradiated, they can achieve the asymmetry necessary for second-order NLO applications such as electro-optic switching. On Earth, formation of PDAs by the above mentioned techniques suffers from defects and inhomogeneities caused by convective flows that can arise during processing. By studying the formation of these materials in the reduced-convection, diffusion-controlled environment of space we hope to better understand the factors that affect their processing, and

  2. Synthesis and Characterization of Poly(3-alkylthiophene)-containing Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ho, Victor

    temperatures can be used to directly manipulate, and thereby balance, the competition between the driving forces for crystallization and self-assembly. As evidence, the nanoscale structure is shown to be directly controlled via synthesis of block copolymers in which one block is the low melting temperature semiconducting polymer, poly(3-(2-ethylhexyl)thiophene). A wide range of morphologies with curved interfaces are observed which, in the past, have been precluded by the crystallization of poly(3-alkylthiophenes) with unbranched aliphatic side chains such as poly(3-hexylthiophene). Importantly, confinement of the conjugated polymer to nanoscale domains is not detrimental to the crystallinity or to charge transport over device-scale dimensions. Additionally, this approach is shown to be effective for a number of different chemistries providing a flexible methodology for obtaining periodic, semiconducting domains on the nanoscale. Together, these simple synthetic strategies can be used to tune the morphology of various length scales of thin film active layers and provide synthetic rules for design of novel semiconducting polymer systems.

  3. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there

  4. Martian mantle primary melts - An experimental study of iron-rich garnet lherzolite minimum melt composition

    NASA Technical Reports Server (NTRS)

    Bertka, Constance M.; Holloway, John R.

    1988-01-01

    The minimum melt composition in equilibrium with an iron-rich garnet lherzolite assemblage is ascertained from a study of the liquidus relations of iron-rich basaltic compositions at 23 kb. The experimentally determined primary melt composition and its calculated sodium content reveal that Martian garnet lherzolite minimum melts are picritic alkali olivine basalts. Martian primary melts are found to be more picritic than terrestrial garnet lherzolite primary melts.

  5. Melting by temperature-modulated calorimetry

    SciTech Connect

    Wunderlich, B.; Okazaki, Iwao; Ishikiriyama, Kazuhiko; Boller, A. |

    1997-09-01

    Well-crystallized macromolecules melt irreversibly due to the need of molecular nucleation, while small molecules melt reversibly as long as crystal nuclei are present to assist crystallization. Furthermore, imperfect crystals of low-molar-mass polymers may have a sufficiently small region of metastability between crystallization and melting to show a reversing heat-flow component due to melting of poor crystals followed by crystallization of imperfect crystals which have insufficient time to perfect before the modulation switches to heating and melts the imperfect crystals. Many metals, in turn. melt sharply and reversibly as long as nuclei remain after melting for subsequent crystallization during the cooling cycle. Their analysis is complicated, however, due to thermal conductivity limitations of the calorimeters. Polymers of sufficiently high molar mass, finally, show a small amount of reversible. local melting that may be linked to partial melting of individual molecules. Experiments by temperature-modulated calorimetry and model calculations are presented. The samples measured included poly(ethylene terephthalate)s, poly(ethylene oxide)s, and indium. Two unsolved problems that arose from this research involve the origin of a high, seemingly stable, reversible heat capacity of polymers in the melting region, and a smoothing of melting and crystallization into a close-to-elliptical Lissajous figure in a heat-flow versus sample-temperature plot.

  6. Disulfide-Functionalized Diblock Copolymer Worm Gels.

    PubMed

    Warren, Nicholas J; Rosselgong, Julien; Madsen, Jeppe; Armes, Steven P

    2015-08-10

    Two strategies for introducing disulfide groups at the outer surface of RAFT-synthesized poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA, or Gx-Hy for brevity) diblock copolymer worms are investigated. The first approach involved statistical copolymerization of GMA with a small amount of disulfide dimethacrylate (DSDMA, or D) comonomer to afford a G54-D0.50 macromolecular chain transfer agent (macro-CTA); this synthesis was conducted in relatively dilute solution in order to ensure mainly intramolecular cyclization and hence the formation of linear chains. Alternatively, a new disulfide-based bifunctional RAFT agent (DSDB) was used to prepare a G45-S-S-G45 (or (G45-S)2) macro-CTA. A binary mixture of a non-functionalized G55 macro-CTA was utilized with each of these two disulfide-based macro-CTAs in turn for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). By targeting a PHPMA DP of 130 and systematically varying the molar ratio of the two macro-CTAs, a series of disulfide-functionalized diblock copolymer worm gels were obtained. For both formulations, oscillatory rheology studies confirmed that higher disulfide contents led to stronger gels, presumably as a result of inter-worm covalent bond formation via disulfide/thiol exchange. Using the DSDB-based macro-CTA led to the strongest worm gels, and this formulation also proved to be more effective in suppressing the thermosensitive behavior that is observed for the nondisulfide-functionalized control worm gel. However, macroscopic precipitation occurred when the proportion of DSDB-based macro-CTA was increased to 50 mol %, whereas the DSDMA-based macro-CTA could be utilized at up to 80 mol %. Finally, the worm gel modulus could be reduced to that of a nondisulfide-containing worm gel by reductive cleavage of the inter-worm disulfide bonds using excess tris(2-carboxyethyl)phosphine (TCEP) to yield thiol groups. These new biomimetic worm gels are

  7. Small particle melting of pure metals

    NASA Technical Reports Server (NTRS)

    Allen, G. L.; Bayles, R. A.; Gile, W. W.; Jesser, W. A.

    1986-01-01

    Submicron-sized crystallites of lead, tin, indium and bismuth were melted in situ in the modified specimen chamber of a Siemens transmission e lectron microscope. Melting point and size determinations were made directly from the dark field images of the crystallites. Particles exhibited melting points that decreased with decreasing particle size. A near-linear relationship was observed for the melting point as a function of the reciprocal of the radius. Thermodynamnic expressions based on the significant contributions of the surface energy to the free energy of the system also suggest a linear relation. Other factors, such as shape and surface contamination, were also observed to affect the size-dependent melting of particles. Crystallites of extended platelet shape did not exhibit a significant depression in melting point. Elevated residual gas pressures were found to lessen the melting point depression of spherical particles.

  8. New adhesive systems based on functionalized block copolymers

    SciTech Connect

    Kent, M.; Saunders, R.; Hurst, M.; Small, J.; Emerson, J.; Zamora, D.

    1997-05-01

    The goal of this work was to evaluate chemically-functionalized block copolymers as adhesion promoters for metal/thermoset resin interfaces. Novel block copolymers were synthesized which contain pendant functional groups reactive toward copper and epoxy resins. In particular, imidazole and triazole functionalities that chelate with copper were incorporated onto one block, while secondary amines were incorporated onto the second block. These copolymers were found to self-assemble from solution onto copper surfaces to form monolayers. The structure of the adsorbed monolayers were studied in detail by neutron reflection and time-of-flight secondary ion mass spectrometry. The monolayer structure was found to vary markedly with the solution conditions and adsorption protocol. Appropriate conditions were found for which the two blocks form separate layers on the surface with the amine functionalized block exposed at the air surface. Adhesion testing of block copolymer-coated copper with epoxy resins was performed in both lap shear and peel modes. Modest enhancements in bond strengths were observed with the block copolymer applied to the native oxide. However, it was discovered that the native oxide is the weak link, and that by simply removing the native oxide, and then applying an epoxy resin before the native oxide can reform, excellent bond strength in the as-prepared state as well as excellent retention of bond strength after exposure to solder in ambient conditions are obtained. It is recommended that long term aging studies be performed with and without the block copolymer. In addition, the functionalized block copolymer method should be evaluated for another system that has inherently poor bonding, such as the nickel/silicone interface, and for systems involving metals and alloys which form oxides very rapidly, such as aluminum and stainless steel, where bonding strategies involve stabilizing the native oxide.

  9. A novel transflectance near infrared spectroscopy technique for monitoring hot melt extrusion.

    PubMed

    Kelly, A L; Halsey, S A; Bottom, R A; Korde, S; Gough, T; Paradkar, A

    2015-12-30

    A transflectance near infra red (NIR) spectroscopy approach has been used to simultaneously measure drug and plasticiser content of polymer melts with varying opacity during hot melt extrusion. A high temperature reflectance NIR probe was mounted in the extruder die directly opposed to a highly reflective surface. Carbamazepine (CBZ) was used as a model drug, with polyvinyl pyrollidone-vinyl acetate co-polymer (PVP-VA) as a matrix and polyethylene glycol (PEG) as a plasticiser. The opacity of the molten extrudate varied from transparent at low CBZ loading to opaque at high CBZ loading. Particulate amorphous API and voids formed around these particles were found to cause the opacity. The extrusion process was monitored in real time using transflectance NIR; calibration and validation runs were performed using a wide range of drug and plasticiser loadings. Once calibrated, the technique was used to simultaneously track drug and plasticiser content during applied step changes in feedstock material. Rheological and thermal characterisations were used to help understand the morphology of extruded material. The study has shown that it is possible to use a single NIR spectroscopy technique to monitor opaque and transparent melts during HME, and to simultaneously monitor two distinct components within a formulation.

  10. Molecular Transfer Printing Using Block Copolymers

    NASA Astrophysics Data System (ADS)

    Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang; Nealey, Paul

    2009-03-01

    We report a new parallel patterning technique, molecular transfer printing (MTP), for replicating geometrically complex patterns over macroscopic areas with sub-15 nm feature dimensions, and the ability to replicate the same pattern multiple times. In MTP, inks are mixed with block copolymers (BCPs) and deposited as films on a substrate. The inks are compatible with only one block of the BCP, and sequestered into domains of nanometer scale dimensions after microphase separation. A second substrate is then placed in contact with the surface of the film. By designing the inks to react, adsorb, or otherwise interact with the second substrate, inks are transferred to the second substrate in the exact pattern of domains present at the surface of the ``master'' BCP film. Here we demonstrate high degrees of perfection on both line and dot patterns. We also show that 1) the master template can be regenerated, 2) the resultant replica can be used to direct the assembly of BCPs and as a daughter master for MTP, and 3) the master and daughter templates can be reused tens of times.

  11. Nanoscale buckling deformation in layered copolymer materials

    PubMed Central

    Makke, Ali; Perez, Michel; Lame, Olivier; Barrat, Jean-Louis

    2012-01-01

    In layered materials, a common mode of deformation involves buckling of the layers under tensile deformation in the direction perpendicular to the layers. The instability mechanism, which operates in elastic materials from geological to nanometer scales, involves the elastic contrast between different layers. In a regular stacking of “hard” and “soft” layers, the tensile stress is first accommodated by a large deformation of the soft layers. The inhibited Poisson contraction results in a compressive stress in the direction transverse to the tensile deformation axis. The hard layers sustain this transverse compression until buckling takes place and results in an undulated structure. Using molecular simulations, we demonstrate this scenario for a material made of triblock copolymers. The buckling deformation is observed to take place at the nanoscale, at a wavelength that depends on strain rate. In contrast to what is commonly assumed, the wavelength of the undulation is not determined by defects in the microstructure. Rather, it results from kinetic effects, with a competition between the rate of strain and the growth rate of the instability. PMID:22203970

  12. Rotation of melting ice disks due to melt fluid flow

    NASA Astrophysics Data System (ADS)

    Dorbolo, S.; Adami, N.; Dubois, C.; Caps, H.; Vandewalle, N.; Darbois-Texier, B.

    2016-03-01

    We report experiments concerning the melting of ice disks (85 mm in diameter and 14 mm in height) at the surface of a thermalized water bath. During the melting, the ice disks undergo translational and rotational motions. In particular, the disks rotate. The rotation speed has been found to increase with the bath temperature. We investigated the flow under the bottom face of the ice disks by a particle image velocimetry technique. We find that the flow goes downwards and also rotates horizontally, so that a vertical vortex is generated under the ice disk. The proposed mechanism is the following. In the vicinity of the bottom face of the disk, the water eventually reaches the temperature of 4°C for which the water density is maximum. The 4°C water sinks and generates a downwards plume. The observed vertical vorticity results from the flow in the plume. Finally, by viscous entrainment, the horizontal rotation of the flow induces the solid rotation of the ice block. This mechanism seems generic: any vertical flow that generates a vortex will induce the rotation of a floating object.

  13. Rotation of melting ice disks due to melt fluid flow.

    PubMed

    Dorbolo, S; Adami, N; Dubois, C; Caps, H; Vandewalle, N; Darbois-Texier, B

    2016-03-01

    We report experiments concerning the melting of ice disks (85 mm in diameter and 14 mm in height) at the surface of a thermalized water bath. During the melting, the ice disks undergo translational and rotational motions. In particular, the disks rotate. The rotation speed has been found to increase with the bath temperature. We investigated the flow under the bottom face of the ice disks by a particle image velocimetry technique. We find that the flow goes downwards and also rotates horizontally, so that a vertical vortex is generated under the ice disk. The proposed mechanism is the following. In the vicinity of the bottom face of the disk, the water eventually reaches the temperature of 4 °C for which the water density is maximum. The 4 °C water sinks and generates a downwards plume. The observed vertical vorticity results from the flow in the plume. Finally, by viscous entrainment, the horizontal rotation of the flow induces the solid rotation of the ice block. This mechanism seems generic: any vertical flow that generates a vortex will induce the rotation of a floating object.

  14. Copolymers for Drag Reduction in Marie Propulsion: New Molecular Structures with Enhanced Effectiveness

    DTIC Science & Technology

    1991-05-31

    the in the solution viscosity is observed due to repulsive neutral sulfonic acid moiety to the charged sodium sulfonate electrostatic interactions...34Water-Soluble Copolymers. 26. Fluorescence Probe Studies of Hydrophobically- Modified Maleic Acid -Ethyl Vinyl Ether Copolymers," Charles. L...Chem., A27(5), 539 (1990). "Water-Soluble Copolymers. XXXV. Photophysical and Rheological Studies of the Copolymer of Methacrylic Acid with 2-(1

  15. Synthesis and Structure - Property Relationships for Regular Multigraft Copolymers

    SciTech Connect

    Mays, Jimmy; Uhrig, David; Gido, Samuel; Zhu, Yuqing; Weidisch, Roland; Iatrou, Hermis; Hadjichristidis, Nikos; Hong, Kunlun; Beyer, Frederick; Lach, Ralph

    2004-01-01

    Multigraft copolymers with polyisoprene backbones and polystyrene branches, having multiple regularly spaced branch points, were synthesized by anionic polymerization high vacuum techniques and controlled chlorosilane linking chemistry. The functionality of the branch points (1, 2 and 4) can be controlled, through the choice of chlorosilane linking agent. The morphologies of the various graft copolymers were investigated by transmission electron microscopy and X-ray scattering. It was concluded that the morphology of these complex architectures is governed by the behavior of the corresponding miktoarm star copolymer associated with each branch point (constituting block copolymer), which follows Milner's theoretical treatment for miktoarm stars. By comparing samples having the same molecular weight backbone and branches but different number of branches it was found that the extent of long range order decreases with increasing number of branch points. The stress-strain properties in tension were investigated for some of these multigraft copolymers. For certain compositions thermoplastic elastomer (TPE) behavior was observed, and in many instances the elongation at break was much higher (2-3X) than that of conventional triblock TPEs.

  16. A Solid-State NMR Investigation of MQ Silicone Copolymers.

    PubMed

    Vasil'ev, Sergey G; Volkov, Vitaly I; Tatarinova, Elena A; Muzafarov, Aziz M

    2013-01-01

    The structure of MQ copolymers of the general chemical formula [(CH3)3SiO0.5]m [SiO2]n was characterized by means of solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The MQ copolymers are highly branched polycyclic compounds (densely cross-linked nanosized networks). MQ copolymers were prepared by hydrolytic polycondensation in active medium. (29)Si NMR spectra were obtained by single pulse excitation (or direct polarization, DP) and cross-polarization (CP) (29)Si{(1)H} techniques in concert with MAS. It was shown that material consist of monofunctional M (≡SiO Si (CH3)3) and two types of tetrafunctional Q units: Q(4) ((≡SiO)4Si) and Q(3) ((≡SiO)3SiOH). Spin-lattice relaxation times T1 measurements of (29)Si nuclei and analysis of (29)Si{(1)H} variable contact time signal intensities allowed us to obtain quantitative data on the relative content of different sites in copolymers. These investigations indicate that MQ copolymers represent dense structure with core and shell.

  17. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    SciTech Connect

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.

    2016-03-08

    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  18. Preparation and icephobic properties of polymethyltrifluoropropylsiloxane-polyacrylate block copolymers

    NASA Astrophysics Data System (ADS)

    Li, Xiaohui; Zhao, Yunhui; Li, Hui; Yuan, Xiaoyan

    2014-10-01

    Five polymethyltrifluoropropylsiloxane (PMTFPS)-polyacrylate block copolymers (PMTFPS-b-polyacrylate) were synthesized by free radical polymerization of methyl methacrylate, n-butyl acrylate and hydroxyethyl methacrylate using PMTFPS macroazoinitiator (PMTFPS-MAI) in range of 10-50 mass percentages. The morphology, surface chemical composition and wettability of the prepared copolymer films were investigated by transmission electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy, and water contact angle measurement. Delayed icing time and ice shear strength of the films were also detected for the icephobic purpose. The surface morphologies of the copolymers were different from those of the bulk because of the migration of the PMTFPS segments to the air interface during the film formation. Maximal delayed icing time (186 s at -15 °C) and reduction of the ice shear strength (301 ± 10 kPa) which was significantly lower than that of polyacrylates (804 ± 37 kPa) were achieved when the content of PMTFPS-MAI was 20 wt%. The icephobicity of the copolymers was attributed primarily to the enrichment of PMTFPS on the film surface and synergistic effect of both silicone and fluorine. Thus, the results show that the PMTFPS-b-polyacrylate copolymer can be used as icephobic coating materials potentially.

  19. Controlling block copolymer phase behavior using ionic surfactant

    NASA Astrophysics Data System (ADS)

    Ray, D.; Aswal, V. K.

    2016-05-01

    The phase behavior of poly(ethylene oxide)-poly(propylene oxide-poly(ethylene oxide) PEO-PPO-PEO triblock copolymer [P85 (EO26PO39EO26)] in presence of anionic surfactant sodium dodecyl sulfate (SDS) in aqueous solution as a function of temperature has been studied using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The measurements have been carried out for fixed concentrations (1 wt%) of block copolymer and surfactants. Each of the individual components (block copolymer and surfactant) and the nanoparticle-surfactant mixed system have been examined at varying temperature. The block copolymer P85 forms spherical micelles at room temperature whereas shows sphere-to-rod like micelle transition at higher temperatures. On the other hand, SDS surfactant forms ellipsoidal micelles over a wide temperature range. Interestingly, it is found that phase behavior of mixed micellar system (P85 + SDS) as a function of temperature is drastically different from that of P85, giving the control over the temperature-dependent phase behavior of block copolymers.

  20. Chain bridging in a model of semicrystalline multiblock copolymers

    NASA Astrophysics Data System (ADS)

    Shah, Manas; Ganesan, Venkat

    2009-02-01

    Recent experimental observations have suggested an intimate connection between the chain conformations and mechanical properties of semicrystalline multiblock copolymers. Motivated by these studies, we present a theoretical study evaluating the bridging/looping fractions in a model of semicrystalline multiblock copolymers. We model the noncrystalline block (A) as a flexible Gaussian chain and the crystalline block (B) as a semiflexible chain with a temperature dependent rigidity and interactions that favor the formation of parallel oriented bonds. Using self-consistent field theory, the bridging fractions of the various domains in different multiblock copolymers (ABA, BAB, ABABA, and BABAB) are evaluated and compared with their flexible counterparts. In general, we observe that for both triblock and pentablock copolymers, rendering one of the blocks crystallizable promotes bridging in that component while reducing the bridging in the other noncrystallizable component. Moreover, the bridging fractions in tri- and pentablock copolymers were seen to be quantitatively similar except insofar as being normalized by the volume fraction of bridgeable units.

  1. Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer

    NASA Astrophysics Data System (ADS)

    Xu, Binbin; Yao, Wenqiang; Li, Yongjun; Zhang, Sen; Huang, Xiaoyu

    2016-12-01

    A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

  2. Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer

    PubMed Central

    Xu, Binbin; Yao, Wenqiang; Li, Yongjun; Zhang, Sen; Huang, Xiaoyu

    2016-01-01

    A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents. PMID:28000757

  3. Effects of copolymer component on the properties of phosphorylcholine micelles.

    PubMed

    Wu, Zhengzhong; Cai, Mengtan; Cao, Jun; Zhang, Jiaxing; Luo, Xianglin

    2017-01-01

    Zwitterionic polymers have unique features, such as good compatibility, and show promise in the application of drug delivery. In this study, the zwitterionic copolymers, poly(ε-caprolactone)-b-poly(2-methacryloyloxyethyl phosphorylcholine) with disulfide (PCL-ss-PMPC) or poly(ε-caprolactone)-b-poly(2-methacryloyloxyethyl phosphorylcholine) or without disulfide (PCL-PMPC) and with different block lengths in PCL-ss-PMPC, were designed. The designed copolymers were obtained by a combination of ring-opening polymerization and atom transferring radical polymerization. The crystallization properties of these polymers were investigated. The micelles were prepared based on the obtained copolymers with zwitterionic phosphorylcholine as the hydrophilic shell and PCL as the hydrophobic core. The size distributions of the blank micelles and the doxorubicin (DOX)-loaded micelles were uniform, and the micelle diameters were <100 nm. In vitro drug release and intracellular drug release results showed that DOX-loaded PCL-ss-PMPC micelles could release drugs faster responding to the reduction condition and the intracellular microenvironment in contrast to PCL-PMPC micelles. Moreover, in vitro cytotoxicity evaluation revealed that the designed copolymers possessed low cell toxicity, and the inhibiting effect of DOX-loaded phosphorylcholine micelles to tumor cells was related to the components of these copolymers. These results reveal that the reduction-responsive phosphorylcholine micelles with a suitable ratio of hydrophilic/hydrophobic units can serve as promising drug carriers.

  4. Ion Transport in Polymerized Ionic Liquid Block and Random Copolymers

    NASA Astrophysics Data System (ADS)

    Elabd, Yossef; Ye, Yuesheng; Choi, Jae-Hong; Winey, Karen

    2012-02-01

    Polymerized ionic liquid (PIL) block copolymers, a new type of solid-state polymer electrolyte, are of interest for energy conversion and storage devices, such as fuel cells, batteries, supercapacitors, and solar cells. In this study, a series of PIL diblock and random copolymers with various PIL compositions were synthesized. These consisted of an IL monomer and a non-ionic monomer, 1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (MEBIm-TFSI) and methyl methacrylate (MMA), and 1-[(2-acryloyloxy)ethyl]-3-butylimidazolium bis(trifluoromethanesulfonyl)imide (AEBIm-TFSI) and styrene (S), respectively, were synthesized. The anion conductivity (ion transport) and morphology were measured in all of the polymers with EIS, SAXS/WAXS, and TEM. Ion transport in block copolymers are significantly higher than random copolymers at the same PIL composition and are highly dependent on the block copolymer nanostructure. The relationship between ion transport mechanisms and the phase behavior of these materials will be discussed.

  5. Effects of copolymer component on the properties of phosphorylcholine micelles

    PubMed Central

    Wu, Zhengzhong; Cai, Mengtan; Cao, Jun; Zhang, Jiaxing; Luo, Xianglin

    2017-01-01

    Zwitterionic polymers have unique features, such as good compatibility, and show promise in the application of drug delivery. In this study, the zwitterionic copolymers, poly(ε-caprolactone)-b-poly(2-methacryloyloxyethyl phosphorylcholine) with disulfide (PCL-ss-PMPC) or poly(ε-caprolactone)-b-poly(2-methacryloyloxyethyl phosphorylcholine) or without disulfide (PCL-PMPC) and with different block lengths in PCL-ss-PMPC, were designed. The designed copolymers were obtained by a combination of ring-opening polymerization and atom transferring radical polymerization. The crystallization properties of these polymers were investigated. The micelles were prepared based on the obtained copolymers with zwitterionic phosphorylcholine as the hydrophilic shell and PCL as the hydrophobic core. The size distributions of the blank micelles and the doxorubicin (DOX)-loaded micelles were uniform, and the micelle diameters were <100 nm. In vitro drug release and intracellular drug release results showed that DOX-loaded PCL-ss-PMPC micelles could release drugs faster responding to the reduction condition and the intracellular microenvironment in contrast to PCL-PMPC micelles. Moreover, in vitro cytotoxicity evaluation revealed that the designed copolymers possessed low cell toxicity, and the inhibiting effect of DOX-loaded phosphorylcholine micelles to tumor cells was related to the components of these copolymers. These results reveal that the reduction-responsive phosphorylcholine micelles with a suitable ratio of hydrophilic/hydrophobic units can serve as promising drug carriers. PMID:28138244

  6. Plastic Deformation and Morphological Evolution of Precise Acid Copolymers

    NASA Astrophysics Data System (ADS)

    Middleton, L. Robert; Azoulay, Jason; Murtagh, Dustin; Cordaro, Joseph; Winey, Karen

    2014-03-01

    Acid- and ion-containing polymers have specific interactions that produce complex and hierarchical morphologies that provide remarkable mechanical properties. Historically, correlating the hierarchical structure and the mechanical properties of these polymers has been challenging due to the random arrangements of the polar groups along the backbone, ex situ characterization and the difficulty in deconvolution the effects of crystalline and amorphous regions along with secondary interactions between polymer chains. We address these challenges through in situ deformation of precise acid copolymers and relate the structural evolution to bulk properties by considering a series of copolymers with 9, 15 or 21 carbons between acid groups. Simultaneous synchrotron X-ray scattering and room temperature uniaxial tensile experiments of these precise acid copolymers were conducted. The different deformation mechanisms are compared and the microstructural evolution during deformation is discussed. For example, the liquid-like distribution of acid aggregates within the bulk copolymer transitions into a layered structure concurrent to a dramatic increase in tensile strength. Overall, we evaluate the effect and control of introducing acid groups on mechanical deformation of the bulk copolymers.

  7. Drug release from pH-responsive thermogelling pentablock copolymers.

    PubMed

    Determan, Michael D; Cox, James P; Mallapragada, Surya K

    2007-05-01

    A novel pH-dependent injectable sustained delivery system was developed by utilizing a cationic pentablock copolymer that exhibits a thermoreversible sol-gel transition. Aqueous solutions of the pentablock copolymer, consisting of poly(2-diethylaminoethyl-methyl methacrylate)-poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-poly(2-diethylaminoethyl-methyl methacrylate) (PDEAEM(25)-PEO(100)-PPO(65)-PEO(100)-PDEAEM(25)) exhibit temperature and pH dependent micellization due to the lower critical solution temperature of the PPO blocks and the polyelectrolyte character of the PDEAEM blocks, respectively. Aqueous solutions of the copolymers above 12 wt % are free flowing liquids at room temperature and form elastic physical hydrogels reversibly above 37 degrees C. Hydrophobic probe absorbance studies indicate that pentablock copolymer micelles increase the solubility of sparingly soluble drugs. Solutions of the pentablock copolymer that form gels at body temperature exhibit sustained zero-order release in in vitro experiments. The release rates of model drugs and proteins were significantly influenced by the pH of the release media, thereby making these polymers ideal candidates for modulated drug delivery.

  8. Relaxation processes in a lower disorder order transition diblock copolymer

    SciTech Connect

    Sanz, Alejandro; Ezquerra, Tiberio A.; Nogales, Aurora

    2015-02-14

    The dynamics of lower disorder-order temperature diblock copolymer leading to phase separation has been observed by X ray photon correlation spectroscopy. Two different modes have been characterized. A non-diffusive mode appears at temperatures below the disorder to order transition, which can be associated to compositional fluctuations, that becomes slower as the interaction parameter increases, in a similar way to the one observed for diblock copolymers exhibiting phase separation upon cooling. At temperatures above the disorder to order transition T{sub ODT}, the dynamics becomes diffusive, indicating that after phase separation in Lower Disorder-Order Transition (LDOT) diblock copolymers, the diffusion of chain segments across the interface is the governing dynamics. As the segregation is stronger, the diffusive process becomes slower. Both observed modes have been predicted by the theory describing upper order-disorder transition systems, assuming incompressibility. However, the present results indicate that the existence of these two modes is more universal as they are present also in compressible diblock copolymers exhibiting a lower disorder-order transition. No such a theory describing the dynamics in LDOT block copolymers is available, and these experimental results may offer some hints to understanding the dynamics in these systems. The dynamics has also been studied in the ordered state, and for the present system, the non-diffusive mode disappears and only a diffusive mode is observed. This mode is related to the transport of segment in the interphase, due to the weak segregation on this system.

  9. Chitosan-glutaraldehyde copolymers and their sorption properties.

    PubMed

    Poon, Louis; Wilson, Lee D; Headley, John V

    2014-08-30

    This study reports the preparation of chitosan-glutaraldehyde (Chi-Glu) copolymers at modified reaction conditions such as the temperature prior to gelation, pH, and reagent ratios. The chitosan copolymers were characterized using infrared spectroscopy (FT-IR), CHN elemental analysis, and thermal gravimetric analysis (TGA). Evidence of self-polymerized glutaraldehyde was supported by CHN and TGA results. The sorption properties of Chi-Glu copolymers were evaluated in aqueous solutions containing p-nitrophenol at variable pH (4.6, 6.6, and 9.0). The sorption properties of the copolymers correlated with the level of the accessibility of the sorption sites in accordance with the relative cross-linker content. The relative sorption capacity of the Chi-Glu copolymers increases as the level of cross-linking increases. Chitosan displays the lowest sorptive uptake while an optimal sorption capacity was concluded at the 4:1 glutaraldehyde:chitosan monomer mole ratio, in close agreement with the three reactive sites (i.e. OH/NH) per glucosamine monomer. The PNP dye probe was determined to bind to chitosan through an electrostatic interaction due to the increased sorption capacity of the phenolate anion, as evidenced by the change in pH from 4.6 to 9.0.

  10. Quantum melting of spin ice

    NASA Astrophysics Data System (ADS)

    Onoda, Shigeki; Tanaka, Yoichi

    2010-03-01

    A quantum melting of the spin ice is proposed for pyrochlore-lattice magnets Pr2TM2O7 (TM =Ir, Zr, and Sn). The quantum pseudospin-1/2 model is derived from the strong-coupling perturbation of the f-p electron transfer in the basis of atomic non-Kramers magnetic doublets. The ground states are characterized by a cooperative ferroquadrupole and pseudospin chirality in the cubic unit cell, forming a magnetic analog of smectic liquid crystals. Then, pinch points observed in spin correlations for dipolar spin-ice systems are replaced with the minima. The relevance to experiments is discussed.

  11. Time-resolved SAXS studies of morphological changes in a blend of linear polyethylene with homogeneous ethylene-1-octene copolymer

    NASA Astrophysics Data System (ADS)

    Ślusarczyk, Czesław

    2015-12-01

    Isothermal melt crystallization in the 15/85 (m/m) blend of a high density polyethylene (HDPE) and a homogeneous ethylene copolymer with 5.5 mol% 1-octene was studied by time-resolved SAXS method with synchrotron radiation over a wide-range of crystallization temperatures. The SAXS profile was analyzed by means of the correlation function which allows to elucidate the evolution of the morphological parameters of polyethylene lamellar structure (long period (LP), thicknesses of crystalline (LC) and amorphous (LA) layers) during a crystallization process. It was found that for the samples crystallized at 100 °C, 120 °C and 122 °C LC increases with time. The lamellar thickening rate strongly depends on crystallization temperature. At 40 °C thickening of the crystalline layers does not occur. The time evolution of the lamellar structure in the blend studied confirms the role of hexyl branches of homogeneous copolymer in the crystallization process of polyethylene. The branches introduce steric constraints which hinder the crystallization of HDPE, thus decreasing the size of the HDPE lamellar crystals.

  12. Production of copolymer, poly (hydroxybutyrate-co-hydroxyvalerate) by Halomonas campisalis MCM B-1027 using agro-wastes.

    PubMed

    Kulkarni, S O; Kanekar, P P; Jog, J P; Sarnaik, S S; Nilegaonkar, S S

    2015-01-01

    For cost effective production of PHA, agro-wastes like fruit peels, bagasse and deoiled cakes were screened as a sole source of carbon. Halomonas campisalis MCM B-1027, which was isolated from one of the extreme environment, i.e. Lonar Lake, India, was explored for the production of PHA using fruit peels and bagasse having fermentable sugars. Among the agro-wastes tested, 1% (v/v) aqueous extract of bagasse was found to be the optimum carbon source with 47% PHA production on dry cell weight basis. Significant amount of total sugars are utilized and converted into cell mass and PHA, e.g. 62% sugar utilized from bagasse extract, 84% from orange peel extract and 71% from banana peel extract as compared to 51% in case of maltose. Hence the cost of production would be positively reduced. The detailed characterization of PHA formed by H. campisalis using bagasse extract as sole carbon source revealed that the organism produces a copolymer of PHB-co-PHV (94.4:5.6) having molecular weight M(w) 1.394 × 10(6) and melting temperature 168.9 °C. Production of PHA by H. campisalis using aqueous extract of fruit peels and a copolymer PHB-co-PHV using aqueous extract of bagasse is presumably the first report.

  13. Crystallization Behavior of Isotactic Propylene-1-Hexene Random Copolymer Investigated by Time-Resolved SAXS/WAXD Techniques

    SciTech Connect

    Mao, Y.; Zuo, F; Keum, J; Hsiao, B; Thurman, D; Tsou, A

    2010-01-01

    The crystallization behavior of isotactic propylene-1-hexene (PH) random copolymer having 5.7% mole fraction of hexene content was investigated using simultaneous time-resolved small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. For this copolymer, the hexene component cannot be incorporated into the unit cell structure of isotactic polypropylene (iPP). Only {alpha}-phase crystal form of iPP was observed when samples were melt crystallized at temperatures of 40 C, 60 C, 80 C, and 100 C. Comprehensive analysis of SAXS and WAXD profiles indicated that the crystalline morphology is correlated with crystallization temperature. At high temperatures (e.g., 100 C) the dominant morphology is the lamellar structure; while at low temperatures (e.g., 40 C) only highly disordered small crystal blocks can be formed. These morphologies are kinetically controlled. Under a small degree of supercooling (the corresponding iPP crystallization rate is slow), a segmental segregation between iPP and hexene components probably takes place, leading to the formation of iPP lamellar crystals with a higher degree of order. In contrast, under a large degree of supercooling (the corresponding iPP crystallization rate is fast), defective small crystal blocks are favored due to the large thermodynamic driving force and low chain mobility.

  14. On the mechanical and thermomechanical properties of low-density polyethylene/ethylene-α-octene copolymer blends

    NASA Astrophysics Data System (ADS)

    Pizele, D.; Kalkis, V.; Merijs Meri, R.; Ivanova, T.; Zicans, J.

    2008-03-01

    Blends of low-density polyethylene (LDPE) and ethylene-octene copolymer (EOC) were obtained. The effect of EOC content and absorbed radiation dose on the mechanical and thermomechanical properties of LDPE/EOC blends are investigated. Particular attention is given to a tensile stress-strain analysis and the "form-memory" effect of the blends. With growing LDPE content, the elastic modulus, the yield stress, and the thermorelaxation and residual stresses of the blends increase, but the ultimate elongation at break decreases, which is caused by the higher crystallinity of polyethylene. As a result of radiation-induced cross-linking, the elastic modulus, the yield stress (at a 1% strain), the ultimate yield strength, and the thermorelaxation and residual stresses increase, while the ultimate elongation at break and the melt flow-behavior index decrease, which is confirmed by the growing gel fraction in the blend.

  15. Impact melt in small lunar highland craters

    NASA Astrophysics Data System (ADS)

    Plescia, J. B.; Cintala, M. J.

    2012-03-01

    Impact melt deposits have been identified in small, simple impact craters within the lunar highlands. Such deposits are rare, but have been observed in craters as small as 170 m diameter. The melt occurs as well-defined pools on the crater floor, as well as veneers on the inner crater wall and stringers of material extending over the rim and away from the crater. Model calculations indicate that the amount of melt formed in craters 100-2000 m diameter would amount to a few to ˜106 m3, representing <1% of the crater volume. Thus, significant, visible impact melt deposits would not be expected in such small craters as most of the melt material that was formed would be ejected. Variations in the properties of the projectile or the target cannot account for the amount of observed melt; the amount of melt produced is largely insensitive to such variations. Rather, we suggest that these small melt-containing craters represent near-vertical impacts in which the axes of melting and melt motion are essentially straight down, toward the base of the transient cavity. For a given event energy under vertical impact conditions, the volume of melt produced would be greater than in an oblique impact and the momentum of the material would be directed vertically downward with minimal lateral momentum such that most of the melt is retained within the crater interior. Since vertical impacts are relatively rare, such small craters with visible, interior melt deposits are rare. While we focus here on the highlands, such craters also occur on the maria.

  16. 40 CFR 180.1162 - Acrylate polymers and copolymers; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Acrylate polymers and copolymers... RESIDUES IN FOOD Exemptions From Tolerances § 180.1162 Acrylate polymers and copolymers; exemption from the requirement of a tolerance. (a) Acrylate polymers and copolymers are exempt from the requirement of...

  17. 40 CFR 721.10419 - Tetrafluoroethylene chlorotrifluoroethylene copolymer (generic) (P-11-561).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... chlorotrifluoroethylene copolymer (generic) (P-11-561). 721.10419 Section 721.10419 Protection of Environment... chlorotrifluoroethylene copolymer (generic) (P-11-561). (a) Chemical substance and significant new uses subject to... copolymer (PMN P-11-561) is subject to reporting under this section for the significant new uses...

  18. 40 CFR 721.10419 - Tetrafluoroethylene chlorotrifluoroethylene copolymer (generic) (P-11-561).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... chlorotrifluoroethylene copolymer (generic) (P-11-561). 721.10419 Section 721.10419 Protection of Environment... chlorotrifluoroethylene copolymer (generic) (P-11-561). (a) Chemical substance and significant new uses subject to... copolymer (PMN P-11-561) is subject to reporting under this section for the significant new uses...

  19. 40 CFR 721.10419 - Tetrafluoroethylene chlorotrifluoroethylene copolymer (generic) (P-11-561).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... chlorotrifluoroethylene copolymer (generic) (P-11-561). 721.10419 Section 721.10419 Protection of Environment... chlorotrifluoroethylene copolymer (generic) (P-11-561). (a) Chemical substance and significant new uses subject to... copolymer (PMN P-11-561) is subject to reporting under this section for the significant new uses...

  20. 40 CFR 721.10179 - Copolymers of phenol and aromatic hydocarbon (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Copolymers of phenol and aromatic... Specific Chemical Substances § 721.10179 Copolymers of phenol and aromatic hydocarbon (generic). (a... generically as copolymers of phenol and aromatic hydocarbon (PMNs P-04-346 and P-04-347) are subject...